摘要:

ABSTRACTS H. M. DAWSON D.Sc. B.Sc. Ph.D. H. W. DUDLEY O.B.E. M Sc. P11.D. A. A. ELDRIDOE B.Sc. W. E. GARNER KSc. OF CHEMICAL PAPERS BUREAU OF CHEMICAL ABSTRACTS ISSUED BY THE H. J. PAGE M.B.E. B.Sc. A.I.C. E. H. RODD D.Sc. E. E. TURNER M.A. D.Sc. H. WREN M.A. D.Sc. P1i.D. A. PURE CHEMISTRY ORGANIC CHEMISTRY AND BIOCHEMISTRY. BUREAU dJpiirnrrrn J. C. PHILIP O.R.E. D.Sc. F.R.S. @Jminattb IYg flp &i’pticaI Siacittc C. S. GIBSON O.B.E. M.A. M.Sc. G. T. MOBOAN O.B.E. D.Sc. F.R.S. J. F. TROBPE C.B.E. D.Sc. F.R.S. W. P. WYNNE D.Sc. F.R.S. &miirateb IYg tbt Sotiaf~ of Q ~ t m i t n I Birbnstrg! E. F. ARMSTRONG D.Sc. F.R.S. J. L. BAKER. E. V. EVANS O.B.E. Sir W. J. L’OPE K. B. E. F.R.8. 1924. VoL CXXVI. Part I. OFFICES OF THE BUREAU CENTRAT. HOUSE 46 FINSRURY SQlIARH LONDON E.C.RJ. W. BAKEB M.Sc. Ph.D. G. BARGER M.A. D.Sc. F.R.S. S. BARRATT M.A. W. T. K. BRAUNEOLTZ X.A. Ph.D. J. F. BRIGGS. R. BKIGHTMAN M.Sc. F. BRINSLEY M.Sc. M. S. BURR D.8c. A. COULTHARD Ph.D. B.Sc. H. J. EVANS B.Sc. W. E. GARNER KSc. C!. R. HARINGTON B.A. Ph.D. A. 2. HALL. W. HUME-ROTHERY B. A. H. HUNTER 31.S~. C. IRWIN. K. KASHIMA RgS. W. 0. KEKMACK M.A. R.Sc. G . A. R KON M.A. D.Sc. S. I. LEVY M.A. P1i.D. F. A. MA~OK M.A. P1i.D. S. 8. MIBOLI~ Ph.D. L. J. HUDLESTON R.Sc. D. B. NANJI M.Sc. W. S. Noimrs Ph.D. J. P. OGILVIE. A. G. POLLARD B.Sc. D.I.C. A. R. POWELL. T. H. POPE. B.Sc. J. PRYDE B.Sc. H. c. REYNAKD. G. W. ROBINSON M.A. E. H. RODD D.Sc. W. A. SILVESTER M.Sc. W. P. SKERTCHLT. J. F. SPENCER D.Sc.. Ph.D. L. J. SPENCER M.A. Sc.D. S. SUGDEN D.Sc. A.Et.C.Sc. J. S. G. THOXAS D.Sc. E. E. TURNER M. A. D.Sc. S. K. TWEEDY B.Sc. D. F. Twiss D.Sc. H. WREN M.A. D.Sc. P1i.D. S. S. ZILVA D.Sc. Ph.D. E. STEDMAN P11.D. PRINTED IN GREAT BRITAIN BY RICHARD CLAY & SOKS LIXITED BUNGAY YUE’FOLK.

ISSN:0368-1769    

DOI:10.1039/CA92426FP001

出版商:RSC    

年代:1924

数据来源: RSC

摘要:

ABSTRACTS H. W. DUDLEY O.R.E. &I.&. P11.D. A. A. ELDRIDGE B.Sc. W. E. GARNER M.Sc. OF E. H. RODD D.Sc. E. E. TURNER M.A. D.Sc. H. WREN M.A. D.Sc. P1i.D. CIHEM1CA.L PAPERS ISSUED BY THE BUREAU OF CHEMICAL ABSTRACTS A. PURE CHEMISTRY PHYSICAL INORGANIC MINERALOGICAL ANALYTICAL CHEMISTRY. AND BUREAU a ipirtntrn J. C. PHILIP O.R.E. D.Sc. F.R.S. 8amintrteb Xrg ibe Qkemicd Sorietg c. s. GIBSON o.B.E. M.A. Br.sc. G. T. MORGAN O.B.E.. D.Sc. F.R.S. J. F. THOEPE C.B.E. D.Sc. F.R.S. W. P. WYNNE D.Sc. F.1t.S. $jhttilrattb bg tke SutEetg of a;emica:L 3nbu0trg E. F. ARMSTRONG D.Sc. F.R.S. J. L. BAKER. E. V. EVANS O.B.E. Sir W. J. POPE K.B.E. F.R.S. 1924. Vol. CXXVI. Part 11. ~- OFFICES OF THE BUREAU CENTRAL HOUSE 46 FINSBURY SQUARE LONDON E.C. 2J. W. BAKER M.Sc. Ph.D. G.BARGER M.A. D.Sc. F.R.S. S. BARRATT M.A. W. T. I(. BRAUNHOLTZ M.A. Ph.D. J. F. BRIGGS. R. RRIOHTIMAN M.Sc. F. BXINSLEY M.Sc. M. S. BURR D.Sc. A. COULTHARD Ph.D. B.Sc. H. J. EVANS B.Sc. W. E. GARNER M.Sc. C. R. HARIKGTON B. A. Ph. D. A. J . HALL. W. HUME-ROTHERY B.A. H. HUNTER M.Sc. C. IRWIN. I(. KABHIMA Rg.S. W. 0. KEKMACK M. A. BSc. 0. A. R. KON M.A. D.Sc. S. I. LEVY M.A. Ph.D. F. A. MASON b!.A. Ph.D. S. S. MIHOLIC' Ph.l). r,. J. HUDLRSTON B.SC. D. R. NANJI M.Sc. W. S. NORRIS Ph.D. J. P. OGILVIE. A. G. POLLARD B.Sc. D.I.C. A. R. POWELL. T. H. POPE B.Sc. J. PRYDE B.Sc. H. C. REYNARD. G. W. ROBINSON b1.A. E. H. RODD D.Sc. W. A. SILVESTER M.Sc. W. P. SKERTCHLY. J. F. SPENCER D.Sc. Ph.D. L. J. SPENCER M.A. Sc.D. E. STEDMAN Ph.D. S. SUUDEN D.Sc. A.R.C.So. J. S. G. THOMAS D.Sc. E. E. TURNEE M.A. D.Sc. 6. K. TWEEDY B.Sc. D. F. TWISS D.Sc. H. WREN M.A. D.Sc. Ph.D. S. S. ZILVA D.Sc. Ph.D.

ISSN:0368-1769    

DOI:10.1039/CA92426FP003

出版商:RSC    

年代:1924

数据来源: RSC

摘要:

ii. 34 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry Electrolytic Production of Active Hydrogen. Y. VENKA- TARAMAIAH and B. S. V. R. RAO ( J . Xci. Assoc. Vixianagaram 1923,1 45-46 ; cf. A. 1923 ii 235,482 ; Wendt and Landauer A. 1922 ii 369; Grubb A. 1923 ii 403).-By electrolysing dilute sul- phuric acid with a current of 3 to 15 amperes in a cell with platinum electrodes one being a perforated tube of length 30 mm. internal diameter 1.0 mm. and external diameter 1.5 mm while a current of nitrogen is passed through the perforated electrodeIN ORGANIC CHEMISTRY. ii. 35 into the solution ammonia is formed. In another form of apparatus the permeability of iron to nascent hydrogen a t the ordinary temperature is utilised; a small quantity of triatomic hydrogen present in the atomic hydrogen reacts with sulphur and forms hydrogen sulphide . Revision of the Atomic Weight of Bromine by the Complete Synthesis of Silver Bromide.0. HONIGSCHMID and E. ZINTL (Annulen 1923,433,201-230).-The stoicheiometrical relationship between silver and the halogens has hitherto always been found in modern work on atomic weights by measuring the ratio Ag AgHal. The results now communicated are theref ore novel since in addition to the ratio Br AgBr the ratio Br Ag is determined directly. An apparatus constructed entirely of glass is described by means of which specially purified bromine is distilled under reduced pressure into glass bulbs in which it is weighed. It is then reduced by means of ammoniacal ammonium arsenite solution an excess of which does not matter and the solution treated with a weighed quantity of silver dissolved in nitric acid.Equivalence of the bromine and silver is determined nephelometrically ; also the silver bromide is weighed. As the mean of ten determinations of the ratio Br Ag and nine of the ratio Br AgBr the atomic weight of bromine is found to be 79.916 on the basis Ag = 1074380. It is agreed with Baxter (A. 1922 ii 377) that contrary to the results of Guye and Germann (A 1914 ii 727) the purity of atomic weight silver is fully adequate. Hypobromous Acid and the Determination of Hypobromous Acid and Bromic Acid. E. BIILMANN and E. RIMBERT (Bull. Soc. chim. 1923 33 [iv] 1465-1473).-Hypobromous acid may be prepared by the action of bromine water on silver nitrate solution or on silver oxide the equations given being Br2+AgN03+H20 -+ HBrO +AgBr +HNO and 2Br2+Ag20 +H20 + 2HBrO + 2AgBr and the acid is then distilled under reduced pressure at 30-35".Various experimental difficulties and the methods of obviating them are discussed. Both reactions are reversible ; this may be shown by removal of free bromine on passing a current of air through the mixture when it becomes clear by solution of the precipitated silver bromide. Hypobromous acid even after distillation always contains bromic acid although the latter is not volatile under the conditions of distillation. The bromic acid may be determined by adding excess of phenol which removes the hypobromous acid then titrating with sodium thiosulphate after addition of dilute sulphuric acid and potassium iodide.If the titration is carried out without the addition of phenol the total of hypobromous and bromic acids is obtained and from this the former is estimated by difference. Mechanism of Oxidation Processes. VI. H. WIELAND (Annalen 1923 434 185-203).-I. [With A. WINGLER and H. RAU.] The Activation of Oxygen by Metallic Copper.-When A. A. E. W. S. N. H. J. E. 2-2ii. 36 ABSTRACTS OF CHEMICAL PAPERS. dilute aqueous solutions of carboxylic acids (acetic pyruvic succinic malic benzoic or better oxalic lact,ic malonic fumaric and citric) are shaken with copper powder in an atmosphere of oxygen the latter is rapidly absorbed (with oxalic acid 3Cu absorbs 20,) and the acids are converted into carbon dioxide; the metal passes into solution and thc action which is therefore not a catalytic oiie ceases when dissolution is complete.Neutral substances (alcohol dextrose etc.) are only oxidised when acid is present since the autoxidation of copper depends on its dissolution to form a salt and the metal cannot therefore alone activate molecular oxygen. The sodium salts of the above acids for example are not oxidised by copper and oxygen. As is shown by experiments conducted in an atmosphere of nitrogen the hydrogen acceptor molecular oxygen may be replaced by p-benzoquinone Methylene-blue or potassium persulphate. The copper dissolves and equivalent reduction (to quinol etc .) occurs but there is no oxidation when copper passes into solution in absence of molecular oxygen. An oxidation process similar to that observed with copper and oxygen occurs with cuprous salts and hydrogen peroxide.Similar COz:O relations are observed (potassium cyanide acts as a strong anticatalyst). An ice-cold suspension of cuprous chloride with hydrogen peroxide gives a strongly oxidising brownish-yellow precipitate probably identical with Moser’s copper peroxite (A. 1914 ii 467) which since it is formed by the direct combination of cupric oxide and hydrogen peroxide is probably OH*Cu*O*O*Cu*OH. With acids it affords a cupric salt and hydrogen peroxide and its oxidising properties are simply those of the latter substance. It plays no part in the autoxidations under discussion in which the active intermediary is probably produced (R = acid radical) thus CUR +HO*OH -+ R*CuH-O*OH + R*H +Cu*O*OH or O:Cu*OH (again possibly a basic salt R*Cu:O functions as the intermediary).Cuprous salts like copper also activate molecular oxygen. Cuprous chloride (2 mols.) effects similarly the reduction of 1 mol. of p-benzoquinone in presence of aqueous oxalic acid in absence of oxygen 2CuC1+2CLH +O:O (or O:C,H,:O) -+ 2CuC1 +KO-OH (or OH*C,H,*OH). Hydrogen peroxide so formed during an autoxidation cannot however be detected since it is a t once destroyed (cf. Traube A. 1882 795) but both with copper and with cuprous salts a cuprous-hydrogen peroxide intermediary complex is responsible for the autoxidations observed. [With A. wrn~LE~.]-The Oxidation of Phosphorous Acid.- Aqueous solutions of phosphorous acid do not absorb oxygen but do so in presence of palladium black phosphoric acid resulting.For oxygen may be substituted p-benzoquinone etc. oxygen being excluded. Bromine does not react in dry ethereal solutions with anhydrous phosphorous acid nor does dry palladium black cause absorption of oxygen in dry ether whereas on admitting traces of water both reactions proceed rapidly. Similarly palladium black p-benzo- quinone and phosphorous acid do not interact in absence of water 11. Charcoal does not act like palladium.IXORCAMC (XIEMISTRY. ii. 37 It is therefore concluded that the reducing action of phosphorous acid is due not to its absorption of oxygen but to the loss of hydro- gen from a hydrate which is the active form O:PH(OH) -+ PH(HO),-+ 2H+O:P(OH) (cf. Mitchell T. 1923,123 629 etc.). E. E. T. Diffusion of Sulphur Vapour in Air at the Ordinary Tem- perature. CHAVASTELON (Cmpt.rend. 1923 177 1040-1041 1217-1218).-1f small pieces of rhombic sulphur are kept in confact with or very near to sheets of silver copper or lead a circular sulphide film forms on the metal round the sulphur. Temperature time and presence or absence of light affect the result slightly. The effect is due to sulphur possessing an appreciable vapour pressure a t the ordinary temperature. Silver lead or copper wire was wound round a quartz tube closed a t one end and containing sulphur. The whole was placed (open end inwards) inside a similar but larger tube. With dry air inside the apparatus which was kept closed no metallic sulphide formed a t the ordinary temperature during nineteen months' exposure to light.With moist air a faint tarnishing was noticed. E. E. T. Pyrosulphates and Acid Sulphates. L. CAMBI and G. BOZZA (Ann. Chim. Applicata 1923 13 221-238).-None of the methods proposed for the preparation of pyrosulphates yields the pure salts with the exception of the direct synthesis from anhydrous sulphates and sulphur trioxide. Dehydration of the hydrogen sulphates does not proceed to completion even under reduced pressure or in a current of sulphur trioxide. Sodium pyrosulphate solidifies in lustrous translucent white crystals m. p. 400.9" dy 2.668 begins to exhibit evident dissocia- tion a t about 460" and in moist air is rapidly converted into concentrated sodium hydrogen sulphate solution. The system Na,H,S,O,-Na,S,O with which supercooling is common forms an eutectic containing 6.8 l u 0 1 .~ ~ of the pyrosulphate a t 182.7". Sodium hydrogen sulphate has m. p. 185.7" (cf. ICendall and Landon A. 1921 ii 45). The pure pyrosulphate and also all the mixtures containing it in greater proportion than 10% are greenish-yellow in the liquid state. The dissociation of sodium hydrogen sulphate has been investigated by measuring the pressure of the water vapour emitted a t different temperatures; this pressure is very slight a t 180" and becomes equal to 1 atmosphere a t a little above 320". Potassium pyrosulphate crystallises in transparent colourless prisms m. p. 414.2" di5 2.512 and absorbs moisture from the air only very slowly. The solid undergoes a polymorphic transform- ation at 315" assuming an opaque porcelain-like appearance and a second transformation may be detected thermally at 225"; both changes are frequently accompanied by marked supercooling and usually proceed slowly.The eutectic temperature for the system K,H,S,08-K2S,0 is 201 -2" and the corresponding composition 14 mol. yo of the pyrosulphate. The polymorphic transformations of the pyrosulphate in the mixtures generally escape the thermalii. 38 ABSTRACTS OF CHEMICAL PAPERS analysis owing to the sluggishness with which they occur at low temperatures. The divergent results for the system Na,SO,-H,SO obtained by Pascal and Ero (A. 1919 ii 154) and by Kendall and Landon (loc. cit.) depend on the fact that the former authors fused the mixtures in open tubes and followed the crystallisation during the cooling whilst the latter melted the mixtures in sealed tubes.The curve of unstable crystallisation at 0-25 mol.yo of Na,SO is observed (cf. Kendall and Landon) and the transition point between the compounds Na2S0,,2H,SO and 2Na,S04,9H,S0 fixed a t 54.6". In the range 25-60 mol.% of Na,SO anomalies are manifested owing to dehydration of the sodium hydrogen sulphates occurring in the mixtures melting at the higher temperatures. The non-existence of any compound of sodium pyrosulphate with sodium hydrogen sulphate and the existence of the compounds 2Na,S04,9H,S0 Na2S0,,2H2S04 and Na,S0,,H,S04 are confirmed. The results obtained for the system K,#O,-H,SO differ little from those of Kendall and Landon (loc. cit.). Less dehydration occurs than with the sodium sulphate system but anomalies occur at temperatures above 120".The results indicate potassium hydrogen sulphate to be tetramorphous (cf. Bridgman Proc. Nat. A d . Sci. 1916 52 124). The double salts K2S0,,3H,S04 and &SO,,H,SO are formed. The results obtained with the system (NH,),SO,-H,SO coincide with those of Kendall and Landon. The Preparation of Pure Ammonia. L. MOSER and R. HERZNER (Monutsh. 1923 44 115-122).-Pure magnesium and calcium nitrides readily yield pure ammonia if allowed to fall gradually into gas-free water. On account of the highly exothermal nature of the reaction decomposition of the gas always occurs if water is allowed to fall on the nitride. The only impurity present in the gas obtained by allowing the nitride to fall slowly into water is hydrogen traces of which are formed from the traces of metal always present in the nitride. Commercial ammonium salts always contain organic matter the carbon dioxide obtained by oxidation corresponding with 0-39-0.62 yo of carbon in the samples examined. By oxidation with nitric acid or permanganate a t high temperatures the organic matter may be completely destroyed and pure ammonia obtained from the residues.Ammonia from technical salts may be completely freed from pyridine and other organic impurities by being passed over prepared wood charcoal. s. I. L. Decomposition of Nitric Oxide by Heating with Metals. E. MULLER and H. BARCK (2. anorg. Chem. 1923,129,309-320).- The action of metals on nitric oxide at high temperatures is studied. Copper a t 500" decomposes 99.7% of the gas but the action at lower temperatures depends on the purity of the metal.Silver is without action up to 700" ; iron if reduced in hydrogen is better than copper for decomposing nitric oxide whilst brass is without action a t 600" and decomposes only 29% at 700". Tin has no action up to 4W" T. H. P.INORGANIC CHEMISTRY. ii. 39 but then commences to act rapidly forming a nitride which may be completely decomposed a t 600". Zinc has no action below 350"; at; 600" the action is slow but the decomposition is complete. Bismuth decomposes 74% at 400" forming bismuth trioxide. Magnesium and calcium decompose the gas at 500" with the form- ation of metallic oxide and nitride. Aluminium has little action below 600". Manganese decomposes 68% of the ga,s a t 400" all of it a t 500" manganese nitride being formed.Chromium has no action below 700" and ferrochrome (60% Cr) only 19% at 650". Lead peroxide absorbs nitric oxide at laboratory temperature form- ing lead nitrite. On heating the gas is liberated but at 200" oxygen is liberated as well and nitrogen peroxide is formed. Litharge is practically without action on nitric oxide even a t 650". Red lead has no action on nitric oxide at laboratory temperature but at 200" absorbs it almost completely forming lead nitride ( '2 nitrite). Vanadium trioxide decomposes the gas completely at 500" forming vanadium tetroxide. H. H. The Intermittent Glow of Phosphorus. K. R. KRISHNA IYER (Chem. News 1923 127 321).-The author states that the pheno- mena of intermittent luminosity and the propagation of luminous pulses exhibited by phosphorus contained in an exhausted vessel into which air is allowed to leak (Lord Rayleigh A.1921 ii 546; 1923 ii 755) may be produced in an open vessel containing traces of inhibitors e.g. naphthalene carbon disulphide turpentine and light petroleum. A simple method of exhibiting the effect as a lecture experiment is described. P. PASCAL (Compt. rend. 1923 177 1298-1300) .-Hexametaphosphate is the name usually given to the product of the action of heat (with subsequent rapid cooling) of an acid pyrophosphate or metal dihydrogen phosphate. If the rapid cooling is omitted trimetaphosphate is also formed and some colloidal products Hexametaphosphates are also supposed to result from the interaction of alkali sulphides and the metaphos- phates of heavy metals.The products however are mixtures of trimetaphosphates hexametaphosphates and colloidal meta- phosphates. To obtain a pure alkali hexametaphosphate a pure trimetaphos- phate is fused (at 700") in a platinum crucible and the latter then rapidly placed in cold water. The vitreous product is free from colloidal material and from trimetaphosphate. Tri- and hexa-metaphosphates are interconverted a t a definite temperature (607" & 2" for the sodium salts). The hexameta- phosphate is the form stable at high temperatures. Interconversion is almost instantaneous at one definite temperature being slower as the temperature falls until at the ordinary temperature no change occurs. The identity of the melting points of the two sodium salts (638") is thus explained as are also the details necessary for obtaining " Graham's soluble salt.'' After their formation hexametaphosphates undergo slight J.S. G. T. Hexametaphosphates.ii. 40 ABSTRACTS OF CHEMICAL PAPERS. changes (complete in sixteen hours at 648" or in six hours at 835"). The viscosity of t,heir solutions increases slightly owing to the formation of a little colloidal salt (1.8% and 1.2% at 648" and 835" respectively). The hexametaphosphates are distinguished by the formation of complex salts of the types M,[Fe(PO,),$ M,[Pe(PO,),] and M,[UO,(PO,) s]. Thus an excess of an alkali hexametaphosphate decolorises ferric thiocyanate and prevents the formation of a colour when uranyl salts and ferrocyanides are mixed.The Vapour Pressure of Arsenious Oxide. P. SMELLIE ( J . SOC Chm. Ind. 1923 42 466468~).-Experiments were made to extend the work of Schwers (A. 1920 ii 247) on the vapour pressure of arsenic in sulphuric acid solution Using the same method as Schwers but taking special precautions to prevent sulphuric acid being carried over mechanically much lower results were obtained than those recorded by Schwers. At 60-64" the vapour pressure found was 2.7 to 9 x mm. of mercury. Using a similar method the vapour pressure of pure arsenious oxide was found to be at 60-61" 2.4 x ; a t 81-86" 2-5 x ; a t 101-105" 4.6 x ; at 117-124" 1-9 x lop3 ; at 119-126" 2.2 x ; a t 149-152" 2.6 x 10-2 mm. To obtain hydrochloric acid free from arsenic for the Marsh test it is recommended to dilute the acid to d 1.10 and boil it gently with precipitated copper for several hours using a reflux condenser.The copper is prepared from pure granulated zinc and cuprous chloride dissolved in hydrochloric acid. The acid is then distilled over fresh precipitated copper and stored in Jena glass vessels. It is also recommended to use electrolytic hydrogen for the Marsh test. P. GAUBERT (Compt. rend. 1923 177 1123-1 125).-Very thin graphite laminae result when a lamina (obtained by cleavage) is rubbed between two microscope slides. The lamin= are trans- parent (if sufficiently thin) green in transmitt'ed light give complete extinction between crossed Nicols and in convergent light give a black cross without coloured rings. The crystals are optically negative and have a refractive index bctween 1.93 and 2.07.Graphitic oxide (green) obtained by treating graphite lamina? with fuming nitric acid and potassium chlorate has a crystalline structure (crystals optically negative ; black cross distinct). The oxide is stable while it contains a little nitric acid but after washing with water becomes brown grey or yellow when it also deflagrates on heating giving pyrographitic acid i.e. graphite. The dried oxide has a refractive index of 1-93-2. E. E. T. E. E. T. E. H. R. Optical Properties of Graphite and Graphitic Oxide. Azido-carbondisulphide. I. Formation Preparation and General Properties. A. W. BROWNE A. B. HOEL G. B. L. SMITH and F. H. SWEZEY [with Microscopical Studies by C. W. MASON] ( J . Amer. Chem. soc. 1923 45 2541-2550).-The action of oxidising agents on a 30/6 aqueous solution of potassium szido-INORGANIC CHEMISTRY.ii. 41 ditbiocarbonate (A. 1922 ii 847) has been investigated; in each case a 1% solution of the oxidising agent was used with 5 C.C. of the azido-salt (cf. Sommer A. 1916 ii 29). It is found that hydrogen peroxide after producing a green colour gives a precipitate of azido- carbondisulphide ( S*CS*N,) ; ozonised oxygen potassium chlorate potassium chromate potassium persulphate mercuric chloride ferric chloride (acidified) stannic chloride acidified potassium permanganate solid manganese dioxide cerium dioxide sodium nitrite chlorine bromine and iodine all produce the same substance in greater or lesser yields. It can also be prepared by the electrolysis of a 20 yo solution of potassium azido-dithiocarbonate between a rotating platinum anode of 30 sq.cm. total area and a stationary platinum cathode enclosed in a parchment thimble with an anode current density of 18.6 amperes/dcm.2 when relatively large yields a're obtained. The best method of preparation consists in taking 5 C.C. of the clear concentrated solution of potassium azido- dithiocarbonate obtained by filtering the liquid resulting from the interaction of 6 g. of potassium azide and 6 g. of carbon disulphide in 25 C.C. of water. This is diluted to 55 C.C. with water and treated drop by drop with a normal solution of iodine in potassium iodide and continually stirred until the precipitation of azido-carbon- disulphide is complete. The precipitate is washed wit,h water dried by suction and transferred to porous plates by a boiie spatula pressure and tapping being avoided and placed in a desiccator over phosphoric oxide a t 10" or lower.It is a white crystalline solid soluble to the extent of 3 parts in 10,000 of water at 25" ; it is very unstable and particularly sensitive to impact and heat more so than potassium azido-dithiocarbonate. It explodes with the liberation of heat and with more smoke and less flame than the azido-dithiocarbonate. It undergoes spontaneous decomposition at the ordinary temperature giving nitrogen sulphur and a polythiocyanogen ( S*CS*N3),=2N,+2S + (SCN),. Examin- ation of the rate of decomposition shows that the spontaneous decomposition probably takes place in the two stages (SCSN,),= N,+S+SCSN,*SCN ; SCSN,*SCN=S+N,+(SCN),.In the spon- taneous decomposition the colour changes to dark orange passing through various yellow shades. The crystals are tetragonal or orthorhombic and have a refractive index about 1.8. It is soluble in the commoner organic solvents but decomposes slowly in them. Dilute sulphuric acid (1 6) has little action on azido-carbondisulphide until the temperature is raised above 40° but more concentrated acid decomposes it at all temperatures ; hydrochloric and nitric acids both decompose it. It reacts with potassium hydroxide in much the same manner as a halogen to form the potassium salts of azido-dithiocarbonic acid and azido-oxydithiocarbonate (S*CS*N,) + 2KOH = KSCSN + KOSCSN,. It reduces potassium permanganate potassium iodate and potassium iodide.On the basis of the reactions of azido-carbondisulphide the authors adopt the formula NiN:N*CS.S*S*CS*N:NIN suggested by Sommer. J. F. S. An excess of iodine must be avoided. 2"ii. 42 ABSTRACTS OF CHEMICAL PAPERS. Azido-dithiocarbonic Acid. I. Formation Preparation and Properties. G. B . L. SMITH and F. WILCOXON [with A. W. BROWNE and with Microscopical Studies by C. W. MASON] ( J . Arner. Chem. Xoc. 1923 45 2604-2613).-Axido-dithiocarbolzic acid HS-CS-N a new halogenoid hydracid has been prepared by treat- ment of concentrated solutions of the sodium salt with concentrated hydrochloric acid. It is a white or very pale yellow crystalline solid; it crystallises in the monoclinic system has a strong double refraction and is readily soluble in non-aqueous solvents. It has the characteristic properties of it strong acid and its strength approaches that of hydrochloric acid.It is easily oxidised by various oxidising agents yielding the free halogenoid (S*CS*N,),. In the solid form the acid is very sensitive to both shock and to heat. It undergoes spontaneous decomposition at the ordinary temperature in keeping with the laws of unimolecular change. In the dry state this reaction is catalysed by an intermediate product or by the thiocyanic acid formed but not in aqueous solution. The decomposition may be represented by the equation HS*CS*N,=HSCN+S+N,. The solid product formed consists of polymerised thiocyanic acid and free sulphur. Diffusibility of Helium through Crystalline Septa. A.PIUTTI and E. BOOGIO-LERA (Rend. Accad. Xci. Fis. Mat. Napoli 1923 [iii] 29 111-115; cf. A. 1923 ii 20).-At 480” helium is unable to traverse plates of laevo- or dextrorotatory quartz cut either parallel or perpendicular to the optic axis and having the thickness 0.3-1 mm. although the gas is able to penetrate ordinary or quartz glass a t this temperahre (cf. Williams and Ferguson A. 1922 ii 841). V. CHLOPINE (Bull. Xoc. chim. 1923 [iv] 33,1547-1551).-The values obtained by Engel (A 1894 ii 40) and by Masson (T. 1911 99 1132) for the solu- bility of barium chloride in hydrochloric acid of various concentra- tions were used as the basis of a method of separating the chlorides of radium and barium from one another. Gaseous hydrogen chloride is passed into a solution containing the mixed chlorides until the optimum concentration of the acid has been attained.This value depends on the “coefficient of enrichment,” which is the ratio of the percentage of total radium precipitated to the percentage of total barium precipitated. This coefficient is a regular function of the percentage of the barium salt precipitated and varies from 3.7 to 1.3 with a corresponding precipitation of 7-8% to 55-57% of t’he total barium present. The presence of other chlorides with the exception of that of lead does not interfere with the efficiency of the method which may therefore be carried out without pre- liminary purification of the mixed chlorides. Solubility of Potassium Perchlorate in Salt Solutions and the Corresponding Activity Relations.R. M. BOZORTH ( J . Amer. Chem. Xoc. 1923,45 2653-2657).-The solubility of potass- ium perchlorate has been determined in O-lN 0*3N and 0.6N J. F. S. T. H. P. The Separation of Radium and Barium. H. J. E.INORGANIC CHEMISTRY. ii. 43 solutions of potassium chloride nitrate and sulphate sodium chloride nitrate perchlorate and sulphate and barium chloride and nitrate. The individual effects of the separate ions on the activity coefficient product of the potassium- and perchlorate-ions have been compared and at the concentrations involved (0.25- 0.75N) have been found to be markedly specific and additive. J. F. S. The Third Form of the Amwonia-soda Process. P. P. FEDOTBEV and A. KOLOSSOV (2. anorg. Chem. 1923 130 3 9 4 5 ; cf. A. 1914 ii 268).-A third form of the ammonia-soda process involves the reaction between sodium sulphate and ammonium hydrogen carbonate which is complicated by the existence of the double salt NaNH,SO,,aq now shown to crystallise with 3H,O.The equilibrium conditions for this salt pair have been studied a t 35" under a pressure of 3 atm. of carbon dioxide. Measurements were made of the solubility of ammonium sulphate in sodium sulphate solution and of sodium sulphate in ammonium sulphate solution (these at 15" as well as 35") of ammonium hydrogen car- bonate in ammonium sulphate and vice versa of sodium hydrogen carbonate in ammonium hydrogen carbonate and of sodium hydrogen carbonate in sodium sulphate solution. Three solutions are possible saturated simultaneously with three salts namely (1) NaHCO NH,*HCO and (NH,),SO ; (2) NaHCO NaNH4S0,,3H,O (NH,),SO ; (3) NaHCO NaNH4S0,,3H,0 and Na,SO,.The solubility of sodium sulphate in ammonia solutions a t 35" was also determined. The disadvantage of this form of the ammonia-soda process is the low solubility of sodium sulphate in ammonia solutions. A Caesium Cupric Mercuric Chloride Cs,CuHgCl ; the Failure to Prepare Cs-Cu-Cd or Cs-Cu-Zn Chlorides ; and the varying Complexity of certain Triple Salts. H. L. WELLS (Amer. J. Sci. 1923 6 521-525).-The addition of strong hydro- chloric acid to mixed solutions of cesium cupric and mercuric chlorides with subsequent concentration and cooling causes the separation of the triple salt Cs,CuHgCl in the form of black cubes which when broken show a pale brownish-red colour and thus appear to be strongly dichroic or pleochroic.Triple chlorides of cmium and copper with cadmium or zinc could not be obtained. A comparison of the formulze of various triple salts of the metals of groups I and I1 shows that ammonium and the alkali metals of lower atomic weight than that of cesium tend to form more complex triple salts than cesium itself; this may be attributed to the more electro-positive character of cesium which gives it a E. J. WEEKS and W. V. LLOYD (Chem. News 1923,127,362) .-When stibine prepared as previously described (T. 1923 123 456) is washed dried and passed into a cold N/2-solution of silver nitrate pure silver antimonide is deposited. E. H. R. greater combining power. s. I. L. Preparation of Pure Silver htimonide. J. S. G.T. 2'-2ii. 44 ABSTRACTS OF CHEMICAL PAPERS. Solubility and Surface Energy of Calcium Sulphate. M. L. DUNDON and E. MACK jun. ( J . Amer. Chem. SOC. 1923 45 2479- 2485).-Some of Hulett's experiments (A. 1901 ii 493; 1904 ii 321) on the variation of solubility with the size of the particles have been repeated and further experiments have been carried out with calcium sulphate of different sizes of particles with the object of obtaining trustworthy values of the surface energy. The method of working consisted in adding finely powdered calcium sulphate to a saturated solution a t 25" in equilibrium with large crystals and measuring the increase in concentration and the return to the original concentration by conductivity measurements. On adding particles of average size 0 .3 ~ to a solution in equilibrium with particles 20-5Op long the electrical conductivity rose from 2208 x 10-6 to 2616 x 10-6 in a minute ; aftcr ~ W O days it had rcturned to 2276 x This represents an increased concentration of 24%. It was found that grinding gypsum and precipitated calcium sulphate causes them to lose water and since the particles added in the above experiment con- tained only 12% of watcr instead of 21-17( it is possible that some of the increased solubility is due to this cause. The concentration can be increased if the dehydrated salt is added to the saturated solution without any previous fine powdering. Thus a solution saturated as above rose in conductivity to 2450 x 10-6 in one day and to 2520~10-6 in two days on adding dehydrated crystals of the same sort as those with which the original solution was in equilibrium. Calculations from the results obtained with particles of calcium sulphate 0.2 and 0 .5 ~ in diameter give a value 370 ergs/ cm .z for the surface energy of the dihydrate of calcium sulphate. J. F. S. and a,fter six days to-2213 x Action of Silica and Alumina on Calcium Sulphate. (MLLE) G. MARCHAL (Compt. rend. 1923,177,1300-1302).-Using a method similar to that employed previously (cf. A. 1923 ii 139) the author has studied the reactions (1) CaS0,fSi02=CaSi0,+S02~+O~60 and (2) CaS0,+A1203=CaAl,0,tS0,+0~502 by measuring the equilibrium pressures at difterent temperatures (the systems being univariant). The first reaction begins a t 870" the second at 940-950" both being studied up to 1,250". Both are very rapid thus if gas is removed at 1,230" equilibrium is restored in a few seconds.Por the first reaction the total gas pressure becomes 760 mm. at 1,273" for the second at 1,363" (extrapolation value). E. E. T. New Reaction pmducing Strontium. C. MATIGNON (Cumpt. rend. 1923 177 1116-1118).-The method previously used for the preparation of barium (A. 1913 ii 504) has been successfully applied to the case of strontium which is obtained in a pure state by heating silicon (2.5 parts) with strontium oxide (20 parts) in an exhausted iron tube at 1,250" for three hours (2.1 grams of strontium were actually obtained). Ferro-silicon if sufficienkly rich in silicon may be used instead of silicon. E. E. T.INORGANIC C€IEMISTRY. ii.45 The Technical Electrolysis of Fused Carnallite. P. P. FEDOTBEV~W~~~ N. WORONIN] (2. anorg. Chem. 1923,130,25-38). -A study of the conditions favourable for the preparation of magnesium by the electrolysis of carnallite. [Cf. B. 19.1 E. H. R. The Preparation of Zinc by Electrolysis of Sulphate Solutions. P. P. FEDOT~EV and W. W. STENDER (2. anorg. Chem. 1923 130 51-62).-This paper records the results of a study of the influence of different factors (concentration of electrolyte concentration of acid current density temperature and impurities) on the efficiency of the electrolysis of zinc sulphate. [Cf. B. 18.1 E. H. R. Zinc Halide Ammines. W. BILTZ and C. MESSERKNECHT (2. nnorg. C'hem. 1923 129 161-175).-Compounds of the zinc halides with ammonia have been prepared and their vapour tensions determined. From these measurements the isothermals have been plotted.The halides all form monoammines diammines tetra-ammines and hexa-ammines whilst the chloride in addition forms a deca-ammine. By plotting the heats of formation of the ammines against the valency of the halide it is found that for the hexa-ammines and tetra-ammines the heats of formation are in the order C1< Br < I whilst for the diammines and monoammines the reverse is the case. Lead Acetato- (Oxalato-)complexes and Basic Lead Salts. R. WEINLANU and F. PAUL (2. anorg. Chem. 1923 129 243-262; cf. A. 1922 i 981 ; ii 767).-By means of replacement reactions carried out with the lead acetatoperchlorates previously prepared some other salts have been obtained notably the dithionate picrate nitrate and bromate. Further it has been found possible to prepare lead oxalato-salts in a similar way having kations of the structure Pb,Ox (I) and Pb,Ox (11).H. H. (Ox=C2O4.) Pb- ** Yb ! 1; ox 'Ox" ox (11.) ;I / \ I! -Pb (I ) [Pb -' o=(;-o\'.h]'* ! i I *-.. [ l i b \O"-O .*' 1- Basic lead salts have also been prepared these are considered to be aquo-salts of the types LPb<EE>Pb] (C10J2,H20 and [ P b ( gg>Pb) ] (ClO3),. Of these many examples including dithionates nickelicyanides and a nitroprusside have been prepared. Other basic salts have been prepared derived from the kation [Pb3(OH),]" by elimination of water to give [Pb,( OH),O]" or 1 Pb=O--Pb*$,H>Pb] OH . Salts with tervalent ions (111) 2 .. -J -~ L ~ < ~ ~ ~ ; * P b - O H - - - - P b ~ ~ ~ ~ g ~ > P b ] " ' or [Yb,(OH),]"' and (IV) [(Pb<gE>:.) 2 P b - O H - - - P b ~ ~ ~ ~ > P b ) ~ * * * or [Pb,( OH),]"' arcii.46 ABSTRACTS OF CHEMICAL PAPERS. also described. Finally are described salts containing the phos- phito-plumbo-kations (V) [Pb--O=PH<O-pbl and (VI) O-pb .*'. The following salts are new diacetatodiplumbo-dithionate [Pb,( OAc),]S,O irregular greasy platelets ; picrate lemon-yellow long tablets ; bromate irregular very thin platelets ; diacetutotri- plumbo-nitrate [Pb,(OAc),](NO,) granular crystalline masses. Omlatodiplumbo-perchlorate [Pb,Ox]( C10,),,3H20 long thin tablets ; nitrate thick irregular platelets (2H,O) ; trioxalatotetraplumbo- perchlorate [ Pb,Ox2](C10,),,5H,O prismatic six-sided crystals ; dioldiplumbo-chlorate [Pb,( OH),](C1O3),,H,O large greasy well- defined prisms dithionate (1 H,O) irregular pearly plates bromide (anhy.) whitish microcrystalline powder nitroprusside (2H,O) red cubes nickelicyanide (anhy.) microcrystalline pale yellow powder bromate (anhy.). Tetroltriplumbo-chlorate [Pb,( OH),](ClO,) sharp spiky crystals dithionate (0-5H2O) rods and truncated prisms bromide (anhy.) microcrystalline powder darkening in the light niclelicyanide (anhy.) irregular platelets bromate (anhy.) light orange needles basic bromate [Pb,( OH) ,]( Bra,) lustrous irregular six-sided platelets.Dioloxotriplumbo-bromate Pb(BrO3),,2PbO,H2O yellow microcrystalline powder trioxotetraplumbo-dichromate 4Pb0,2Cr03 fiery red powder dioxotriplumbo-dichromate 3Pb0,2Cr03 deep orange-red powder basic nitrite (06H,O) orange-yellow tufted prisms.Di(dioldip1umbo)chlorate ferricyanide exists in a brown and black form the bromateferricyanide (lH,O) forms reddish-brown irregular tablets the hypophosphite ferricyanzde (anhy.) bright yellowish-green powder. Di(dioldip1umbo)tetroltri- phmbo-tribromate f erricyanide [ Pb,( OH) J( BrO,),[Fe( CN) ,I bright yellow irregular platelets dioldiplumbotetroltriplumbo-nitrateferri- cyanide [Pb5(oH),]No,[Fe(CN),] minute cubes. Dioldiplumbo-p- oldioldiplumbo- f erric yanide olive- green and red forms. Tetroltriplumbo-~-oltetroltri~lumbo-ferricyanide dirty violet powder olacetatodiplumbo-chlorate dioldiacetatotri- plumbo-chlorate phosphitotriplumbo-bromide phosphitodiplumbo- chloride lead chlorate monohydrate and dileadthiocyanate mono- hydrate.H. H. [Pb,(OH),I(ClO,)[Fe(CN) 61 [Pb,( OH),]( H,PO,)[ E'e( CN) ,] Metallisation of Organisms. N. D. ZELINSKI ( C m p t . rend. 1923 177 1041-1043).-A bee placed in a platinum boat and lightly covered with cupric oxide was heated in a glass tube in a current of carbon dioxide. On removing the excess of cupric oxide a copper replica of the bee was obtained the minutest details of the structure being preserved. Beneath the metal was a coke- like mass containing nitrogen and hydrogen. The metallised bee contained 48.8470 of copper. Vegetable products e.g. leaves undergo similar metallisation. The effect is ascribed to the volatility of cupric oxide (cf. following abstract). E. E. T.INORGANIC CHEMISTRY. ii.47 Transportation of Copper in the Gaseous State and Copper Carbonyl. G. BERTRAND (Compt. rend. 1923 177 997-999).- Zelinski's results in connexion with the effect of heat on organisms which have previously been covered with cupric oxide (preceding abstract) are most readily explained on the assumption that copper curbonyE is formed being decomposed almost immediately but being sufliciently stable to account for the alleged volatility of copper oxide. Ignition of animal or vegetable matter not con- taining copper using copper or brass gas burners causes the introduction of traces of copper into the ash obtained this result being observed in absence of halogen compounds. If carbon dioxide is passed over heated cupric oxide in a glass tube no unusual effect is observed but if before passing over the cupric oxide the gas first passes over red hot carbon a red mirror-like deposit of copper is produced presumably owing to the inter- mediate formation of copper carbonyl.Formation of Sulphides Selenides and Tellurides of certain Metals. I. Copper Compounds. F. GARELLI ( A t t i R. Accud. Sci. Torino 1923 58 193-200).-The author confirms the observation made by Wicke (Annulen 1852 82 145) who found that a piece of sulphur wrapped in clean copper wire and immersed in saturated copper sulphate solution at the ordinary temperature gradually becomes coated with indigo-coloured crystalline copper sulphide. The copper sulphate solution which need not be saturated does not change in composition during the reaction. Very pure cupric sulphide may be prepared in con- siderable quantities by adding copper together with rather more than the atomic proportion of sulphur to neutral aqueous cupric sulphate or nitrate kept boiling by means of a current of ,steam.If the proportion of sulphur added is halved pure cuprous sulphide is obtained. I n a similar manner by the interaction of copper and selenium in copper sulphate solution the selenides Cu,Se CuSe and Cu3Se2 may be obtained in pure condition. The copper telluride Cu4Te may be prepared similarly. Basic Copper Sulphate. F. S . WILLIAMSON ( J . Physicul Chem. 1923 2'7 789-797) .-The formation of basic sulphates of copper has been investigated by adding various definite molecular qyan- tities of sodium hydroxide to copper sulphate solution and analysing the precipitates. The results of Pickering (A.1883 853) have been confirmed namely that the precipitate obtained by adding varying amounts of sodium hydroxide not exceeding 1.5 mols. per mol. of copper sulphate is practically constant in composition. This precipitate has the composition CuS04,3Cu0,4H20 which may be written (Cu0,H2)3CuS0,,H,0. By precipitating with alkali as in the above case the compound CuS0,,2Cu0,2H20 is not obtained as postulated by Stearn and Young (Phil. Mag. 1843 [3] 23 501). Since copper sulphate will peptise hydrated copper oxide and be carried down by it there is no certainty that the basic salts may not contain adsorbed copper sulphate. E. E. T. T. H. P. J. F. S.ii. 48 ABSTRACTS OF CBEMXCAL PdPERS. Absorption of Halogens by Mercurous Salts.K. G. NAIK and M. D. AVASARE (J. Arner. Chem. Xoc. 1923,45,2769-2770).- Mercurous chloride sulphate and nitrate are treated with an alcoholic solution of iodine or bromine in excess. Mercurous chloride yields mercuric iodochloride HgIC1 and mercuric bromo- chloride HgBrCl. The sulphate yields di-iodomercuric sulphate (IHg),SO and a perbromide (BrHg),X04,Br2. The latter reacts with dry chlorine to give dichloromercuric sulphate (ClHg),SO,. The nitrate gives a periodide (IHgNO,),,I and a perbromide (BrHgNO,),,Br,. The periodide when treated with chlorine gives a perchloride (ClHgNO,),,Cl,. Separation of Rare Earths by Basic Precipitation. VI. W PRANDTL and J. RAUCHENBERGER (2. anorg. Chem. 1923 129 176-180 ; cf. A. 1922 ii 769).-The influence of mercuric cyanide and of nickel nitrate on the precipitation of the rare earth oxides from solutions of their nitrates by means of ammonia has been studied.The authors conclude that although these and other salts tend to keep t'he rare earths especially lanthanum in solution in the presence of ammonia the most effective for this purpose is cadmium nitrate. H. H. Action of High Temperatures on some Refractory Sub- stances. C. MATICNON (Cmpt. rend. 1923 177 1290-1293).- Various substances have been heated in the form of pellets in an electric furnace in an atmosphere of nitrogen. Sodium aluminate Pu'a,O,Al,O (m. p. 1,660') is prepared by heating the appropriate mixture of aluminium oxide and sodium carbonate a t 1,100-1,200" a pure product also being obtained using a slight excess of the oxide.Aluminates of the type A1 O,,(n+l)Na,O dissociate below 1,650'; sodium oxide being lost until the simple aluminate is formed. Zircon used in the natural crystalline form does not melt a t 2,126'. At 1,800' some dissociation occurs dense white fumes of silicon dioxide being formed a t 1,900". The residue melts a t about 2,600'. Zirkite (that is zircon containing excess of silica and some ferric oxide) does not melt a t 1,950'. Tungstic oxide does not melt a t 2,130'. In presence of carbon it is converted into tungsten and a carbide. Aluminium nitride (AN) does not melt at 2,200". At a higher temperature it dissociates into its elements but is under these conditions only slowly affected by oxygen. E. E. T. Composition of the Precipitate from Partially Alkalinised Alum Solutions. L.B. MILLER (U.S. Pub. Health Repts. 1923 38 1995-2004 ; cf. Theriault and Clark ibid. 181 ; Williamson A. 1923 ii 324).-Varying amounts of sodium hydroxide were added to 0.005 and 0-02M- (in aluminium) alum solutions a t room temperature and to the latter at 100". After precipitates had settled for half an hour the pH value of the liquid was determined colorimetrically . After using a centrifuge and decanting the precipitate was treated in a centrifuge with successive 200 C.C. portions of water until nearly free from sulphate-ion. At this \V. S. N.INORGANIC CHEBfISTRY. ii. 49 point dispersion of the precipitate commenced. Bringing the pE of the wash-water to that of the solution had little effect on the composition of the precipitate.For additions of sodium hydroxide up to 2.5 mols. per mol. of aluminium at room temperature the composition of the precipitate was constant and approximate to 5A1,0,,3S03. Increasing concentration of sulphate-ion over a wide range (by addition of potassium or ammonium sulphate) or increasing concentration of aluminium up to 0.1M had no effect on the composition of a precipitate formed at a definite p E value. For pH 4-0-5.5 the ratio of aluminium to sulphate in the pre- cipitate is constant; at higher p values the sulphate rapidly disappears. When three or more mols. of sodium hydroxide are added for each mol. of aluminium the precipitate can be washed free from sulphate. The precipitate appears to consist of two components of nearly equal solubility.For 0.005M-aluminium the greatest insolubility of the precipitate was found at pH 6.7-7*0 at which point 2.75 mols. of sodium hydroxide have been added. On both sides of this however pH 54-8.5 are zones of great insolubility. Theriault and Clark's (Eoc. cit.) point of greatest flocculation pa 5.5 (2.4 mols. of sodium hydroxide added) is the point where precipitation of aluminium first approaches completion and is in the region where the greatest amount of sulphate is found in the precipitate. In Blum's method for the determination of aluminium it is essential that sulphate should be absent or present only in small amount; otherwise a second precipitation from hydrochloric acid solution is necessary. Chloride is satisfactorily removed by ignition over a MBker burner for ten minutes.Experi- ments with solutions of aluminium chloride were abandoned on account of the formation of colloidal suspensions not flocculated by the prolonged use of a centrifuge. The Production of Manganese by Electrolysis of Aqueous Solutions of its Salts. P. I?. FEDOT~EV (2. anorg. Chem. 1923 130 18-24) .-Attempts to obtain pure manganese by electrolysis of manganous chloride or sulphate under dserent conditions were unsuccessful. Under the most favourable conditions using a neutral or weakly acid 6.5N solution of the chloride at 5" with a current density of 20 amperes per sq. dcm. the deposit on the copper cathode contained only about 65% of metallic manganese the remainder being hydroxide. [a. B. 19.1 E. H. R. Formation of Manganese Carbide from Carbon Dioxide and Manganese.E. MULLER and H. BARCK (2. anorg. Chem. 1923 129 321-322) .-When a mixture of carbon dioxide and hydrogen is passed over manganese at SOO" some of the manganese is con- verted into manganous oxide and some into manganese carbide; the latter yielded methane when treated with water. The gaseous mixture was found to contain carbon monoxide. H. H. Polymorphic Transformation of Iron at 370" and the Possiblity of Dissolution of Cementite in a1-Iron. G. SIROVICH (Gaxxettn 1923 53 674-688) .-The existence at 370" CHEMICAL ABSTRACTS.ii. 50 ABSTRACTS OF CHEMICAL PAPERS. of the point A corresponding with the polymorphic transformation of al- into ct,-iron (La Metall. Ital. 1922 16 3) is confirmed by the results of dilatometric measurements which exhibit anomalous behaviour a t that point.Both the al- and the a,-modifications of iron possess characteristic coefficients of expansion so that the conclusions of Le Chatelier of Charpy and Grenet and of Driesen with regard to the way in which the coefficient of expansion of iron varies below 700" require revision. The possibility of effecting dissolution of cementite in ccl-iron by means of maturation in the field of stability of this iron on pearlitic steels must be admitted and such maturation certainly induces in the metal abnormal hardness which indicates the occurrence of phenomena not yet observed. T. H. P. Ferric Salt as the " Solution Link " in the Stability of Ferric Oxide Hydrosol. A. W. THOMAS and A. FRIEDEN ( J . Amer.Chem. Xoc. 1923,45,2522-2532) .-Ferric oxide hydrosols prepared from ferric chloride have been investigated with the object of ascertaining the quantitative relationships between the substances constituting the colloid and of determining the amount of electro- lyte required to keep the colloidal particles dispersed. It is found that precipitation of the sol is imminent when the ratio Fe,O,,/FeCl is about 21 and that this value is unaffected by dilution. It is shown that the stability of ferric oxide sol stabilised by ferric chloride is due to the solubility or the solution forces of the adsorbed ferric chloride in the dispersion medium rather than to the mutual repulsive forces of the particles presumed to reside in their electrical charges of like sign. The so-called " meta-iron '' sol of Pkan de St.Gilles ( J . pr. Chem. 1855 [l] 66 137) is one in which the particles of the dispersed phase are less hydrated than those in Graham's ferric oxide hydrosol. J. I?. S. Mechanism of the Mutual Precipitation of certain Hydrosols. A. W. TIIonus and L. JOHNSON ( J . Amer. Chem. SOC. 1923 45 2532-2541) .-The mutual precipitation of ferric oxide and silicic acid sols and ferric oxide and arsenic trisulphide sols has been investigated. It is shown that the precipitating ratios depend on the peptising agent. There is chemical equivalence between the peptising agents of ferric oxide hydrosol peptised by ferric chloride and silicic acid sols peptised by sodium silicate provided the ratio of peptising agent to the dispersed phase falls within a certain range. Outside this range the precipitation is erratic.Ferric oxide-silicic acid sol precipitations showing chemical equivalence between the peptising agents at maximum precipitation exhibit little variance in precipitation ratios with dilution whilst those showing a divergence from chemical equivalence approach the chemical equivalence on dilution. The mutual precipitation of ferric oxide-silicic acid sols is due to the removal of the peptising agents by chemical action between them. Qualitative experiment shows that the mutual precipitation of arsenious sulphide hydrosol and ferric oxide hydrosol may be due to the chemical reactionINORGANIC CHEMISTRY. ii. 51 S"+2Fe"* -+ S+2Fe". This however has not been confirmed quantitatively. J. F.S. Solubility of Nickel Sulphate by the Floating Equilibrium Method. F. C. VILBRANDT and J. A. BENDER (Ind. Eng. Chem. 1923 15 967-969) .-The method for determining solubility described by Dundon and Henderson (A. 1922 ii 552) was used for measuring the solubility at different temperatures of hydrated nickel sulphates. The new method gives results in good agreement with those obtained by the gravimetric method and is much more rapid. The following results in g. of anhydrous nickel sulphate per 100 g. of water were obtained NiS0,,7H20 -4.25' 27.335; 40.594 ; 30" 43368 ; NiSO,,GH,O (blue) 31-71' 45-299 ; 40" 47.528 ; 50° 52.166 ; 53-26" 54.041 ; NiSO,,GH,O (green) 58-21" 55.389 ; 60*ll" 55.557 ; 79.75" 64.476 ; 94*22" 72.597. -2.O" 23.366; 0" 26.189; 6" 30.282; 15*65" 35.491; 25" E.H. R. System Chromium-Carbon. 0. RUFF (2. Elektrochem. 1923 29 469474).-A criticism of Nischk's paper (A. 1923 ii 762) in which it is stated that the carbide of chromium richest in chromium has the formula Cr,C. In an earlier paper (A. 1918 ii 399) Ruff and Foehr have shown that a carbide Cr5C2 exists and can be prepared in quantity. After a discussion of the data furnished in both papers the author maintains his assertion as to the existence of Cr5C,. Iso- and Hetero-poly-acids. XIX. Molybdi-phosphites and -pyrophosphates. The Structure of Phosphorous Acid. A ROSENHEIM and M. SCHAPIRO (2. anorg. Chem. 1923 129 196-205 ; cf. this vol. ii 54 ; Rosenheim Weinberg and Pinsker A. 1914 ii 58) .-Heteropolymolybdates similar to the hetero- polyvanadates have been obtained of the general formulae 2R20,P,03,12Mo03,xH20 (ammonium potassium sodium and lit hzum) and 2R,O P,O 5Mo0 ,xH20 (potassium ammonium and guanidinium) for the phosphites and 2R,0,P,0,,12M00,,xH20 (sodium and lithium) for the pyrophosphates.[With A. ITALIENER.]-By measurements of depression of freezing point and elevation of boiling points of aqueous solutions of phos- phorous acid it is concluded that phosphorous acid may be repre- sented as H,(P,O,H,) in complete analogy with H4(P,0,) for pyrophosphoric acid. There is thus a complete series of ions containing phosphorus (PO,) + + + (HPO,) + (H,PO,) + H,PO and (pH,)-. J. P. S. phosphate phosphite hypophosphite phosphine oxide H. H. phosphonium Complex Chlorotungstates. 0. COUENBERG and K.SANDVED (2. anorg. Chem. 1923 130 l-l7).-The only derivatives of tervalent tungsten known are the potassium salt K,W,Cl and the corresponding ammonium rubidium cesium and thallium salts prepared from it by double decomposition (A. 1913 ii 328; 1914 i 944). It is now shown that in these salts the tungsten is present as part of a complex anion and a number of new com-ii. 52 ABSTRACTS OF CHEMICAL PUERS. pounds have been prepared from the potassium salt by double decomposition with cliff ereiit chlorides. The complex character of the potassium salt was proved qualitatively by ion migration experiments. The freezing point depression in aqueous solutions of the salt K3WgCl indicated that not more than four ions are formed by dissociation of the salt and conductivity experiments were confirmatory.The complex chlorotungstates are strong reducing agents ; solutions of gold silver mercury and copper salts are readily reduced and powerful oxidising agents oxidise the tervalent tungsten to tungstic acid. With ferric salts this reaction is quantitative and can be used for the analysis of the complex salts of tervalent tungsten. The stability of the complex ion W2C$"' is shown by the fact that the potassium salt interacts with cadmium copper and silver salts in presence of strong ammonia to form ammines without precipitation of any tungsten hydroxide. The following new coinpounds are generally sparingly soluble in water; their most concentrated aqueous solutions have an intense green colour becoming yellower on dilution. At lower temperatures the solutions are fairly stable more so in presence of hydrochloric acid.The figures in brackets indicate solubility a t 20" per 100 C.C. of solution. [Cr(NH,),]W,Cl,,2H20 dark green thin microscopic rectangular prisms ; [ Co(NH,) ,]W,Cl,,GH,O (0-96) bright green microscrystalline powder. [Ag(NH,),],W2C1 is very unstable towards water and air losing ammonia and deposit- ing metallic silver. Cu(NH,),KW,CI,,H,O (1.85) forms a finely crystalline powder. Cu(NH,) NH4W2Cb,H20 (2.4) a green crystal- line powder. Cd(NH,),NH,&,CI (2.17). Cd(NH,)4KW2C1 (1.9). The pyridine compound (C,H,N),W,CI (4.7) forms brownish- green metallic tabular crystals ; the hexumethylenetctrumine com- pound (C,H,,N,),W,Cl,,H,O (0-2) is a yellowish-green crystalline powder ; tetramethylammonium compound (XMe,),W,Cl (1 .IS) yellowish-brown microscopic crystals ; (NEt,),W,Cl (relatively high solubility) ; trimethylamine compound (NHMe,)3W,CI dark green thin pyramidal prisms ; dimethylamine compound (NH,Me,),W,Cl (8.25) dark green rhombohedra ; aniline compound (NH3Ph),W2Cl (0.37) greenish-yellow leaflets; phenyltrimethyl- ammonium compound (Nl\le,Ph),W2C19 (0-21) a voluminous greenish-yellow crystalline powder ; p-tolyltrimethylammonium com- pound (C,H4Me*NiUe3),W,C1 (0-48) yellowish-green striated prisms ; trimethylsulphine compound (SMe3),FV2Cl9 (0-24) a bright green crystalline powder. A solution of the free acid H,W,Cl was obtained by interaction of the thallium salt and hydriodic acid but the acid could not be isolated.The solubility of the potassium salt K,W,Cl at 20" is 15.4 g.per 100 C.C. of solution. E. H. R. Solubility of Titanic Acid in Alkali Hydroxides and in Alkali Carbonates. Crystalline Titanium Oxychloride. V. AUGER (Compt. rend. 1923 177 1302-1304).-The two com- pounds Na,Ti0,,4H20 and K,Ti0,,4H20 described by Demoly in 1849 are shown iiot to exist. The approximate solubility ofINORGANIC CHEMISTRY. ii. 53 t'itanic oxide in alkali hydroxides etc. has been sbudied using either the hydrated oxide or titanic chloride. The results are as follow (figures refer to mg. of TiO dissolved in 100 C.C. of solution) Sodium hydroxide loyo 2-2.5 ; 36% 6-10. Potassium hydr- oxide lo% 3 0 4 5 ; 40% 70-90. Sodium carbonate (saturated) does not dissolve titanic oxide. Sodium hydrogen carbonate (10 yo) 35.Potassium carbonate 30% 2 ; saturated solution 30. (All the titanic oxide present in the last three solutions is precipitated on diluting and boiling.) Potassium hydrogen carbona4te saturated sohtion 700. When 1 part of titanic oxide is fused with 40 parts of sodium hydroxide and the cooled melt extracted with water the only crystalline material obtained is a hydrate of sodium hydroxide. A little titanic oxide remains in solution the majority being prc- cipitated even from concentrated solutions. Fusion of titanic oxide with potassium hydroxide etc. affords a metastable eolu- tion of a titanate (containing up to 1,800 mg. of oxide per 100 c.c.) but this deposits most of its titanium (leaving about 100 mg. in solution) in a few hours. Fusion of titanic oxide with sodium carbonate also gives metastable solutions containing 25-10 mg. of oxide per 100 c.c.all of this being precipitated on keeping. When titanic chloride is added t o a mixture of potassium hydrogen carbonate and its aqueous solution as much as 2,000 mg. per 100 C.C. of titanic oxide remain in solution 1,300 mg. however being precipitated in a few hours. A double carbonate is probably present in the more concentrated solutions. If a solution of titanic chloride in concentrated hydrochloric acid is evaporated in the cold over sulphuric acid an oxychloride Ti02,HC1,3H20 or Ti( OH),C1,2H20 is deposited as large colourless rhombohedra1 plates decomposed in moist air. Reduction of Thorium Zirconimn and Titanium Dioxides. 0. RUFF and H. BRINTZIRGER (Z.anorg. Chem. 1923 129 267-275) .-The reduction of these oxides by means of metallic calcium and sodium a t high temperatures was studied. At 900- 950° sodium alone will not reduce the oxides to any great extent although calcium gives yields of from OO-l00./,. The bcst results were given by a mixture of calcium and sodium containing 30% of the latter. H. H. T. L. WALKER (Nature 1023 112 831).-A suggestion that Sorby's " jargonium " (1869) may have priority over either hafnium or celtium. G . HEVESY and V. T. JANTZEN (Chem. News 1923 127 353-355).-Detailed accounts are given of the preparation of ammonium zirconium fluoride and ammonium hafnium fluoride from alvite and of the separation of hafnium from this mineral by the double fluoride method (A. 1923 ii 570) employing the ammonium double fluorides in place of the potassium double fluorides as previously described. J.S. G. T. E. E. T. Hainiwn or Jargonium. A. A. E. Separation of Hafnium froin Zirconium.ii. 54 ABSTRACTS OF CHEMICAL PAPERS. Iso- and Hetero-poly-acids. XVIII. Vanadioiodates Vanadioperiodates and a few Vanadiophosphates. The Alkalimetric Determination of Vanadic Acid. A. ROSENHEIM and K. H. YANG (2. anorg. Chem. 1923 129 181-195; cf. A. 1922 ii 47).-By introducing vanadium pentoxide into a boiling aqueous solution of iodic acid the acids V205,1205,4H20 and V205,21205,10H20 were obtained according to the amount of iodic acid used. The potassium ammonium and guanidinium salts of these acids are described. Similarly by using alkali periodates and vanadates the sodium potassium and ammonium salts of the type 3R20,2V,05,120,,xH20 were obtained.By using phosphates and vanadates if care be taken that the phosphates are sufficiently dilute (2-3 normal) it is possible to obtain salts of the types 2R20,V205,P205,xH20 and R,0,2V205,P205,xH20. Conductivity measurements were made to ascertain the structures of the valrious anions. Vanadic acid is best determined in solution by the addition of excess of sodium hydroxide followed by back titration with sulphuric acid at loo" using a-naphtholphthalein as indicator. Iodic acid is also estimated by this method so that a mixture of the two may be analysed by adopting the above procedure and then reducing iodate to iodide and determining this with silver. The Gravimetric Ratio of Antimony to Antimony Tetroxide. J.KNOP (2. anal. Chem. 1923,63 181-188).-Pure antimony was treated with nitric acid and subsequently converted into the tetroxide by ignition at 800-900". The purity of the product was determined by the iodine-thiosulphate method. The results agree with a mean value of 122.04 for the atomic weight of antimony. A. G. P. Gold-Chromium Alloys. R. VOGEL and E. TRILLING (2. anorg. Chem. 1923,129 276-292) .-The temperature-composition diagram for gold-chromium alloys is given in full. Three kinds of mixed crystals are distinguished one rich in chromium and two rich in gold. No compounds of definite composition are formed. Chemistry of the Platinum Metals. IV. Alkali-Ruthenium Double Sulphites. 11. H. REMY and C. BREIMEYER (2. anorg. Chem. 1923 129 215-242; cf. A. 1922 ii 857).-The prepar- ation of the following new double sulphites of ruthenium and the alkali metals is described potassium trisulphitoruthenate dark green needles ; sodium undemsulphitodiruthenute yellowish-white crystals ; sodium ruthenoruthenisulphite 2RuS03,Ru2(S03),,4Na,S0 dark blue amorphous powder. In addition a method of analysis of these salts involving the determination of the ruthenium as tetroxide and the sulphur as barium sulphate is described. H. H. H. H. K,IIRu(SO3)31 Ru2(S03)3,8Na2S03,3H20 H. H.ANALYTICAL CHEMISTRY. Miner a1 o g i c a1 C h 8 mist r y. ii. 55 Bitumen of Judaea. The Sensitivity of Bitumen to Light as a Function of its Degree of Dispersity. J. ERRERA (Bull. SOC. chim. 1923 33 [iv] 1409-1414).-Bitumen which is sensitive to light appears to contain three distinct substances a- p- and y-bitumen of which only the last is sensitive. The author regards bitumen as a " polydispersoid," the sensitive portion being that which is in the form of a disperse colloid. It is the portion with the greatest sulphur content and this appears to be correlated with polymerisation molecular and colloidal bitumen being the extrema between which are found -intermediates of various degrees of asso- ciation. Isolation of any one of these probably has a coagulating action. The conclusions are confirmed by evidence from measure- ments of viscosity and of molecular weight dialysis and sensitive- ness to light. Uka-filtration is suggested as a method of separating the light-sensitive colloidal bitumen from the molecular portion. H. J. E.

ISSN:0368-1769    

DOI:10.1039/CA9242605034

出版商:RSC    

年代:1924

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. An a1 y t i c 8 1 C h 8 mist r y. ii. 55 Application of the Quinhydrone Electrode to Electrometric Acid-base Titrations in the Presence of Air and the Factors Limiting its Use in Alkaline Solution. V. K. LA MER and T. R. PARSONS ( J . Biol. Chem. 1923 57 613-631).-Measurements of the pE of solutions of hydrochloric acetic and boric acids and of acid potassium phosphate have been made with the quinhydrone electrode and the results have been compared with those obtained with the hydrogen electrode. In buffered solutions more acid than pH 8.0 the quinhydrone electrode gives trustworthy results pro- vided that no rapid oxidising or reducing agents are present. With more alkaline solutions the results are untrustworthy. This is mainly due to the autoxidation of quinol and t'o its weak acidic properties.E. S. New Methods of Determining Chlorine Bromine and Iodine in Organic Compounds. I. Hydrogenation Method. H. TER MEULEN and J. HESLINGA (Rec. trav. chim. 1923 42 1093-1096) .-The halogen derivative to be analysed (20-50 mg.) is placed in a small platinum boat near the left-hand end of a quartz tube 80 cm. long the other end of the tube being plugged loosely with cotton wool. A mixture of ammonia and hydrogen is passed through t'he tube from left to right and the tube to the right of the boat heated to redness over a distance of about 20 cm. Heating is then commenced to the left of the boat which during the courseii. 56 ABSTRACTS OF CHEMICAL PAPERS. of about twenty minutes is progressively heated until no further decomposition occurs The whole of the halogen element present even in the case of iodine is converted into ammonium halide which condenses in the right-hand end of the tube.The latter is washed out with water the solution acidified with acetic acid any hydrogen cyanide removed by boiling and the halogen estimated by Volhard’s method. Explosive substances are mixed with six times their weight of oxalic acid before being analysecl whilst volatile liquids are intro- duced in small tubes such as are used in ordinarv combustions. With a tube partly packed with platinised quartz ;cry low results are obtained. E. E. T. Determination of Dissolved Oxygen in the Presence of Iron Salts. A. M. BUSWELL and W. -U. GALLAHER (Ind. Eny. Chem. 1923,15 118G-l188).-The Winkler method for the deter- mination of dissolved oxygen in water depends on the oxidation of bivalent manganese in alkaline solution and the liberation of iodine from potassium iodide in acid solution by the oxidised manga- nese.If iron is present however it will be in the ferric state in consequence of the preliminary use of potassium permanganate to oxidise nitrites etc. and will itself liberate iodine from potassium iodide. Hence too high a value for the dissolved oxygen present is obtained in this case and as the action of ferric iron on the iodide solution is incomplete and depends on the concentration temper- ature and other conditions no correction can be applied. An investigation of the effect of the presence of iron salts on the Levy- Mohr method in which the dissolved oxygen is allowed to oxidise ferrous iron in alkaline solution showed that in this case no error was introduced.c. I. Determination of Sulphite and Thiosulphate by Oxidation with Nascent Bromine. C. MAYR and J. PEYFUSS (2. anorg. Chem. 1923 127 123-136).-Nasceiit bromine liberated from an acid bromide-bromate mixture oxidises sulphurous acid according t o the equation SO + Br + H,O =S03+2HBr; and thiosul- pliuric acid according to the equations S,O2+€I,O+Br,=2HBr+ S03+S and S+4H,0+3Br,=6HBr+H2S0,. Thus Na2SO,=.2Br and Na,S20,=8Br. By using an excess of standard bromide- bromate solution sulphites may be estimated in the absence of air and excess of bromine used to liberate iodine which may be deter- mined with standard thiosulphate. Advantage may be taken of the fact that iodine osidises thio- sulphates t o dithionates whilst bromine oxidises them to sulphates to determine sulphites and thiosulphates in one and the same solu- tion using the equivalents Na2S0,_2I and Na,S,O,=H together with those given above and calculating the amounts of sulphite and thiosulphate from the simultaneous equations so obtained.BROTHERTON & Co. LTD. (Chemistry and Industry l923,42,1131).-1n an iodometric method proposed for the determination of sodium hyposulphite the reaction H. H. Determination of Hyposulphite.ANALYTICAL CEEMISTRY. ii. 57 proceeds according to the equation 3Na,S,0,+4KI03+2KI= 31,+3Na,SO,~3K,SO,. Six g . of potassium iodate and 10 g. of potassium iodide are dissolved in about 500 C.C. of water in a litre flask 300 C.C.of N/lO-sodium thiosulphate solution is added the mixture is diluted to about 950 c.c. and 3 g . of the sample of hyposulphite is added from a weighing bot,tle. The whole mixture is then diluted to 1,000 c.c. shaken until the hyposulphite is dis- solved and the excess of thiosulphate titrated in an aliquot portion (100 c.c.) with N/lO-iodine solution. The method cannot be applied to sodium hyposulphite which contains decomposition products or sodium carbonate. w. P. s. Determination of Ammoniacal Nitrogen in certain Nitro- genous Materials and particularly in Proteins and Products of Proteolysis. J. FEOIDEVAUX (Compt. rend. 1923 177 1043- 1046).-The method previously described (A. 1922 ii 454) has been improved. The material is distilled in presence of aqueous lithium carbonate keeping the volume of liquid in the distilling flask con- stant by continued addition of water.The distillate is collected in a series of graduated flasks containing known quantities of standard acid. The distilling flask is heated in a calcium chloride bath kept at 110". The results are calculated as before and me satisfactory with proteins uric acid amino-acids and carbamide ; special procedure is necessary in the case of some compounds (diphenylamine oxamide etc .). Determination of Nitrate Nitrogen in the Presence of Calcium Cyanamide and some of its Derivatives. K. D. JACOB (Ind. Eng. Chem. 1923,15,1175-1177).-The determination of nitrogen present as nitrate in soil extracts by reduction with Devarda's alloy is interfered with by the presence of cyanamide derivatives. These however can be eliminated :-urea by decom- position with urease and calcium cyanamide dicyanodiamide and guanylurea by precipitation with silver aulphate when an accurate J .MTNICFI (Biochenz. Z. 1923 142 26&273).-The residual nitrogen of various types of mammalian blood has been determined by Pregl's method after removing the proteins by precipitation with trichloroacetic phosphomolybdic phosphotungstic and meta- phosphoric acids and with uranium acetate. The most consistent results were obtained with the first-mentioned acid whilst rneta- phosphoric acid gave the least trustworthy figures and the other reagents were intermediate between these extremes. No propor- tionality was observed between the quantity of precipitant used and the residual nitrogen found.Variations in the latter are not solely due t o differences in degree of precipitation. Detection of Small Quantities of Nitric Acid in Poisoning Cases. C. GHIGLIOTTO (Ann. Chim. Annlyt. 1923 5 325).- Tissues that have been in contact with nitric acid are stained blue by treatment with a sulphuric acid solution of diphenylamine. E. E. T. estimation becomes possible. [Cf. B. Jan.] c. I. Determination of the Residual Nitrogen in the Blood. J. P.2. 58 ABSTRACTS OF CHEMICAL PAPERS. The lining of the stomach responds to the test if it has been in contact with acid of a greater strength than 0.1 yo. Determination of Organic Phosphorus. E. J. BAUMANN (Proc. SOC. Exp. Biol. Med. 1922 20 171-173).-The loss by volatilisation of phosphorus experienced with Bloor’s or Bell and Doisy’s method is avoided by using 0-2 C.C.of 30% hydrogen peroxide and eight drops of sulphuric acid solution. After removal of most of the water by evaporation on a water-bath Bell and Doisy’s colorimetric method is used for the determination. Determination of Phosphorus in Organic Materials. ( ~MLLE) J. GAROLA (Ann. Chim. Analyt. 1923 5 326-328).-The loss of phosphorus during the incineration of organic materials containing it may be avoided by mixing 5 g. of the substance with 0.2 g. of light calcined magnesia and a little water drying the mixture on a sand-bath and heating it to dull redness until the residue is free from carbon. It is then dissolved in hydrochloric acid the solution filtered and the phosphorus precipitated as magnesium ammonium phosphate by the addition of an ammoniacal solution of ammonium citrate.This process is considerably quicker than the usual Kjeldahl method. A R. P. Determination of Phosphoric Acid by Means of Uranyl Acetate Solution. G. JANDER and K. REEH (2. anorg. Chem. 1823 129 302-305) .-The phosphate is precipitated as uranyl ammonium salt by the addition of a slight excess of uranyl acetate. The precipitate is filtered washed and redissolved in sulphuric acid (about 25%). The solution is heated to incipient ebullition and then reduced with aluminium as previously described (this vol. ii 65). The quadrivalentl uranium is then reoxidised to the sexavalent condition by means of potassium permanganate of known strength every atom of available oxygen used being equiva- lent to 1 mol.of uranyl ammonium phosphate. Modification of the Bell-Doisy-Briggs Method for Colori- metric Determination of Phosphoric Acid. B. SJOLLEMA and H. GIETELING (Chem. Weekblad 1923 20 658-659).-The method (cf. A. 1920 ii 769; 1922 ii 718) is now applied to cases such as foodstuffs urine etc. in which a preliminary destruction with sulphuric acid is necessary. Comparison is made with a standard phosphoric acid solution to which the reagents used in the destruc- tion (sulphuric acid potassium and copper sulphates) are added in the same proportions. Since the depth of colour is not proportional to the phosphoric acid present a correction graph is employed. A. R. P. CHEMICAL ABSTRACTS. H. H. s. I. L. Separation of Phosphates from Fluorides.E. M~~LLER and W. WAGNER (2. anorg. C‘hem. 1923 129 306-308).-The usual method is to precipitate the neutral phosphate as silver salt remove excess of silver with sodium chloride and then precipitate calcium fluoride. The authors criticise trhe method of neutralising theANALYTICIAL OHEMISTRY. ii. 59 solution before adding the silver nitrate. With Methyl-orange as indicator neutrality is obtained at NaH,PO ; with phenolphtha- lein at Na,HP04. As the silver salt is Ag,PO free hydrogen-ions are liberated during the precipitation causing solution of the silver phosphate to the extent of 37%. If the solution is neutralised to Methyl-orange after addition of the silver solution some silver oxide is included in the precipitate.The authors therefore recom- mend neutralisation with alkali hydroxide followed by acidificat,ion with a very small quantity of nitric acid. Determination of Arsenic in Organic Compounds. A. KIRCHER and F. VON RUPPERT (Ber. Deut. pharm. Ges. 1923 33 185-186).-1t has been suggested by StolIB and Fechtig (A. 1923 ii 335) that the authors' method for determining arsenic in neosalvarsan (A. 1921 ii 130) is liable to errors due to the passage of iodine-fixing organic substances into the absorption tube and the loss of arsenic on boiling to remove sulphur dioxide. The con- cordance of results obtained by the authors' method and that of StollB and Pechtig proves the above contention to be groundless. W. T. K. B. A. PIUTTI (Rend. Accud. Sci. Pis. Mat. Napoli 1922 [iii] 28 91-96).-The author has investigated the ability to absorb carbon monoxide exhibited by a number of different mixtures the best results being obtained with cuprous chloride mixed with fine charcoal granules of pumice and powdered soda-lime.This mixture is stable in the air and absorbs per 100 g. 3,960 C.C. of carbon monoxide. A. KARL and S. LOMBARD (Compt. rend. 1923 177 1036-1037).- The difliculty of obtaining a solution containing the constituents of minerals of the titano-niobate type has led to the following method The ground mineral is treated with hydrofluoric acid the product being evaporated to dryness and fused with potassium hydrogen sulphate until sulphuric anhydride vapours cease to be evolved. The cooled fused mass is mixed with sodium sulphate or even with lithium sulphate as well to depress the melting point to the minimum obtainable the whole is raised to a red heat cooled broken into pieces and so transferred to a Pyrex glass tube.By heating at 500-600" the product becomes completely liquid and the radium content may be determined in the usual way the emanation being displaced using a current of air and freed before measurement from acid fumes by being passed over soda-lime heated at 150". Gravimetric and Volumetric Determination of Potassium. W. STREKHER and A. JUNGCK (2. anal. Chern. 1923 63 161- 180).-Comparison is made of a number of methods of determining potassium. Precipitation as potassium cobaltinitrite does not lead to concordant results. The precipitate produced by the addition of sodium cobaltinitrite to potassium salts contains varying pro- portions of sodium presumably as the salt K,NaCo(NO,),. It is H.H. Mixtures Absorbing Carbon Monoxide. T. H. P. Determination of Radium in Natural Titano-niobates. E. E. T.ii. 60 ABSTRACTS OF CHEMICAL PAPERS. shown however that potassium can be precipitated completely from solution by this means and can be determined in the pre- cipitate by the perchlorate method. Satisfactory results are obtained by reduction of the perchlorate by (1) titanous sulphate (2) fusion with potassium nitrate and sodium hydroxide and (3) fusion with hydrazine sulphate and sodium hydroxide and titra- tion of the chloride produced with silver nitrate. Sodium and potassium can be determined together by determining the mixed chlorides volumetrically and subsequently precipitating the potassium as perchlorate which is reduced to chloride and titrated with silver nitrate.Concordant results can be obtained by pre- cipitation of potassium as the hydrogen tartrate and titration with sodium hydroxide. The picric acid method is not of sufficient accuracy owing to the solubility of potassium picrate in the solutions used. A. G . P. MARJAN G~RSKI (Prxemysl Cheznicxny 1922 6 311-312 ; from Chem. Zentr. 1923 iv 488).-Directions are given for the determination of potassium in potassium salk by the perchloric acid method. Determination of Potassium in Potassium Salts. G. W. R. A New Qualitative Test for Sodium. I. M. KOLTHOFF (Pharm. WeeEBlnd 1923 60 1251-1255).-The pyroantimonate test for sodium is not very sensitive and is trustworthy only in the absence of heavy metals and salts of ammonium and the alkaline earths. Magnesium uranyl acetate which has long been employed for the micro-chemical detection of sodium may be employed in ordinary qualitative analysis and in 50% alcohol solution will detect as little as 50 mg.of sodium per litre. The reagent is very suitable when potassium salts are present and will indicate 0.5% of sodium in a potassium salt ; salts of ammonium lead zinc aluminium magnesium and the alkaline earths do not interfere and the reagent may be used directly to detect sodium in them. s. I. L. Determination of Caesium as Perchlorate. E. MURMANN (Oesterr. Chem. Ztg. 1923 26 164).-About 0-5 g. of c3esium nitrate is dissolved in 50 C.C.of water an escess of 10% yerchloric acid is added and the mixture is evaporated. The residue of cEsium perchlorate when cold is treated with a small quantity of water containing perchloric acid collected on a weighed filter washed successively with 50 yo alcohol (containing a drop of perchloric acid) 95% alcohol and ether then dried a t loo" and weighed. Sulphates and potassium rubidium barium and ammonium salts New Method of Titrating Silver and Halogen-Ions with Organic Dyes as Indicators. I<. [FAJANS and 0. HASSEL (2. Elektrochem. $923 29 495-500).-Very dilute solutions of the alkali salts of fluorescein and its halogen substitution products show characteristic colour changes in the presence of ,silver halide sols when the solutions contain an excess of silver-ions.The must not be present. w. P. s.ANALYTICAL OHEMISTRY. ii. 61 colour changc is attributed to the association of the dye anion with the excess silver-ions which are adsorbed by the silver halide. By this association the electron sheaths of the dye anions undergo a similar change to that brought about in the formation of their silver and other salts. The colour change brought about in the presence of an cxcess of silver-ions can in some cases be reversed by an excess of halogen-ions. The halogen-ions in such cases displace the dye anions from the silver halido surface. The ease with which this occurs depends on the one hand on the adsorb- ability of the halogen-ion and on the other on the adsorbability of the dye anion. In the case of the halogen-ions the adsorbahility increases in the order I’ Br‘ Cl’ and in the case of the dye anions in the order fluorescein dibromofluorescein eosin di-iodofluorescein and erythrosin.On account of this behaviour these substances can be used as indicators in the titration of halogen-ions with silver-ions. In the case of chlorides fluorescein alone may be used the concentration of indicator should be about 1 /3OOOOOAV and the titration carried to a red colour. In the case of bromine and iodine dibromofluorescein and eosin may be used the concentration of the indicator (eosin) being 1/3OOOOM the titration being carried to il; violet colour. I n a mixture of chloride and iodide the iodide alone can be titratecl with eosin as indicator and the sum of the two halogen-ions with fluorescein as indicator.Determination of Calcium by the Qpacimetric [Nephelo- metric] Method. C. CHBNEVEAU and R. Boussu (Compt. rend. 1923 177 1296-1298).-A continuation of previous work (A. 1920 ii 327). It is shown that suspended calcium oxalate pre- cipitates obey within certain limits the general optical laws for turbid liquids and that the determination of calcium by the nephelometric method is always possible but necessitates careful preliminary experiments. E. E. T. Lead. VIII. The Microchemical Detection of Lead. L. T. FAIRHALL ( J . Biot. Chern. 1923 57 456461).-Behrens and Kley’s ‘‘ triple nitrite test,” which depends on the formation and recognition of the crystalline hexanitrite of potassium copper and lead [K,CuPb(NO,),] is employed. The conditions for carry- ing out this test on the ash from biological material containing traces of lead have been standardised.Amounts as small as l p g . may be detected. Electro-analytical Determination of Thallium by Means of the Anodic Deposition of Thallic Oxide. W. DIETERLE (Z. Elektrochem. 1923 29 493405) .-Using the method previously described by Gutbier and Dieterle (A. 1923 ii 880) the author has investigated the determination of thallium by anodic deposition of thallic oxide. The followiiig method is recommended a solution containing 0 - 1 4 - 5 g. of thallous nitrate and 0.1 g . of free nitric acid is placed in a roughened platinum dish diluted to 100 C.C. with water and either 10 C.C. of absolute alcohol or 5-10 C.C. of rectified acetone added. The dish is made the anode in the J.F. S. E. S.if. 62 ABSTRACTS OF CHEMICAL PAPERS. electrolysis and the cathode is a disk of platinum of 12 cmm2 which is rotated at 300 revolutions per minute. The electrolysis is carried out at 60-62" directly from a single lead accumulator. After ten hours the voltage is raised to 2-5-3-0 and a current of 0.05 ampere passed for a short time. The deposit which is firm is washed with water and dried at 160-170" preferably in an electrically heated oven but in any case reducing gases must not come into contact with the deposit. When dry the dish is cooled in a desiccator and weighed rapidly since the deposit is somewhat hygroscopic. The method is good the results being associated with an error of &0.2%. J. F. S. The Quantitative Separation from a Complex Mixture of Very Small Quantities of Copper Zinc Nickel and Cobalt.G. BERTRAND and M. MOKRAGNATZ (Bull. Xoc. chim. 1923 [iv] 33 1539-1547).-A method of separating traces of copper zinc nickel and cobalt from mixtures is described in detail. It is based on the precipitation of the hydroxides of the metals by ammonia in the presence of calcium hydroxide. In the case of zinc a crystal- line compound of the formula (OH*Zn*O),Ca,n,H,O is obtained but the precipitate given by each of the other metals may be a mixture of the hydroxide of that metal with a calcium compound. Experimental results for comparison of the method with standard procedure are given; these &ow good agreement. [Cf. B. Jan.] H. J. E. The Solubility of Mercuric Sulphide in Ammonia and Its Influence on the Tests for Mercury and Arsenic.C. GHIGLIOTTO (Ann. Chim. Anulyt. 1923 5 326).-In toxicological analysis the organic matter is destroyed by heating with sulphuric acid ; this solution after treatment with hydrogen sulphide for the precipitation of arsenic and mercury yields a mixture of sulphur and organic sulphur compounds. If the precipitate is extracted with ammonia to dissolve any arsenic all the mercury will also dissolve owing to the presence of the sulphur and organic sulphides and on subsequent treatment for arsenic by the Marsh test no mirror will be obtained if mercury is present. Thus neither arsenic nor mercury may be detected. The solution should be again evaporated with sulphuric acid and the heating continued for some time; subsequent treatment according to the usual methods will then give satisfactory separations.Determination of Aluminium and its Separation from other Metals. G. JANDER and B. WEBER (2. ungew. Chem. 1923 36 586-590).-The method of determining aluminium in alloys which is based on the sublimation of the chloride in a current of dry hydrogen chloride gas (Jander and Wendehorst A. 1922 ii 529) suffers from the disadvantage that traces of -magnesium and manganese sublime together with the aluminium chloride. A complete separation of these metals is effected by a series of re- sublimations carried out under carefully controlled conditions in a A. R. P.ANALYTICAL CHEMISTRY. ii. 63 slightly modified apparatus a diagram of which is given. The slight trace of manganese subliming in the first sublimation is easily separated but the somewhat large quantity of magnesium is only separated after four or five resublimations which are carried out by driving the sublimate on to successive portions of a glass tube lying inside the sublimation tube proper on which the aluminium chloride is ultimately allowed to deposit.The subliming operation takes about three hours. The improved method affords an accurate means of determining aluminium directly in alloys and of separ- ating it from the other metals present in much smaller proportions so that the determination of these metals can be effected with much greater accuracy. The method also allows of the determin- ation of oxides such as silica and alumina which occur in alloys and cause important variations in their properties. The aluminium chloride can eventually be obtained with less than 0-007% of manganese and 0.025% of magnesium.Details are given of the behaviour of the other metals present on heating in a current of dry hydrogen chloride gas. Any elementary silicon present sublimes as hydrides or silico-chloroform and is subsequently separated from the aluminium chloride by evaporation with acids and filtration. The silicon in “ Silumin ” can be accurately deter- mined by dissolving the alloy in dilute hydrochloric acid filtering off the silicon and weighing. Only 0.05y0 of silicon was found to escape in this process in the form of volatile compounds. Speci- men analyses of various alloys are given. Titrimetric Determination of Aluminium in Aluminium Salts in particular in ” Liquor Aluminii Acetici.” A. WBHLK (Ber. Deut. p h r m . Ges. 1923 33 195-204).-0wing to various objections to the titrimetric method proposed by Valentin (Apoth.- Ztg. 1912 590) notably the uncertainty of the composition of the precipitated basic aluminium arsenate and of the accuracy of iodimetric titrations of arsenic acid in strongly acid solution the following method which gives accura,te results is preferred. To a known quantity (about 10 c.c.) of “ Liquor aluminii acetici” is added 10 C.C. of a solution (12 g. of sulphuric acid and 6-5 g. of potassium sulphate made up to 100 C.C. with water) and the potassium alum formed is completely precipitated by addition of 90 yo ethyl alcohol (100 c .c .). The precipitate is collected repeatedly washed with 20 C.C.of 70% alcohol and finally dissolved in boiling water. The subsequent procedure depends on the reactions AlJS0,),+3BaC1,=3BaS0,+2AlC13 and AlC13+3NaOH=A1(OH) +3NaC1. To the alum solution is added 20 C.C. of a barium chloride solution (containing 4 g.) and five drops of 1% phenol- phthalein and N / l -sodium hydroxide is run in without removing the barium sulphate until a red colour is obtained. The solution is diluted to 200 c.c. and the hydrolysis completed by heating to boiling. The titration with sodium hydroxide is then carried to the true end-point. The application of this method to aluminium salts in the presence of ammonium and iron salts is being investi- gated. W. T. K. B. H. C. R.ii. 64 ABSTRACTS OF CHEMICAL PAPERS.The Simultaneous Electrometric Determination cf Iron and Manganese. E. MULLER and 0. WAHLE (2. anorg. Chem. 1923 130 63-68).-When the titration of a ferrous salt with potassium permanganate is continued after the normal end-point has been reached in presence of hydrofluoric acid a second reaction takes place namely the oxidation of the manganous salt according to the equation MnO,' +4Mn"+ SH'= 5Mn"'+4H20. The second reac- tion requires one-quarter as much permanganate as the first. Both end-points are sharply marked on the electrometric titration curve but if the first reaction takes place in presence of hydrofluoric acid the first end-point is reached too soon because ferrous salts in presencc of fluoride-ions are very susceptible to atmospheric oxidation.Obviously the method of titration can be applied to the determin- ation of manganese already present with the ferrous salt. It is recommended to carry out the &st titration colorimetrically in presence of sulphuric acid in a platinum dish at 18" then to add 7 g. of potassium fluoride and 5 C.C. of 2N-sulphuric acid per 100 C.C. of solution aiid titrate the manganese electrometrically at 80". E. H. E. Interference of Cobalt in the Bismuthate Method for Manganese. G. E. F. LUNDELL (J. Amer. Chem. Soc. 1923 45 2600-2603) .-The proper conditions for the determination of manganese by Blum's bismuthate method (A. 1912 ii 1214) have been investigated and it is shown that in addition to the conditions laid down by Blum the following must also be observed. The solution should not contain more than 0.05 g.of manganese; moderate amounts of sulphuric acid are not harmful as for example 5 C.C. of sulphuric acid and 10 C.C. of nitric acid in 50 C.C. of solution ; ehlorides must be absent; the temperature of the solution may be varied from 5" to 25" ; half a minute is a sufficient time for agitating the solution but a longer agitation will do no harm ; the bismuthate should always be tested for its oxidising power before use the asbestos used in the filtration must be very carefully purified all hydrochloric acid and chlorides must be removed from it; the ferrous sulphate solution should not be kept more than ten minutes before titration and the permanganate solution which may be 0.03N or O-lON is best standardbed against sodium oxalate as described by McBride (A.1912 ii 494). When thcse precau- tions are taken the accuracy of the method for amounts up to 0.06 g. is within 1 part in 500 parts. The process is singularly free from interference by other elements the only elements which have been recognised as troublesome being chromium and cerium. The interference caused by these and other elements is discussed. Cobalt is oxidised by the bismuthate and the oxidised compound reacts with both ferrous sulphate and permanganate. The latter reaction does not commence until some permanganate has been decomposed and then proceeds so rapidly that it causes low results for manganese. In the presence of cobalt Bord's method is to be preferred for accurate analyses and the persulphate arsenite method for routine work.J. F. S.ANALYTICAL CHEMISTRY. ii. 65 Determination of Small Quantities cf Mo3ybdenum. Application to Ammonium Phosphomolybdate for the Indirect Titration of Phosphorus. A. VILA (Compt. rend. 1923 177 1219-1321) .-If ammonium molybdate or phosphomolybdafe is reduced in hydrogen a t 700" (silica tube) it is quantitatively reduced to molybdenum. A solution of molybdic acid (3 g.) in 60% phosphoric acid (10 c.c.) is decolorised with permanganate and diluted to 50 C.C. The molybdenum is dissolved in this solution. After diluting and boiling molybdenum-blue Mo0,,4Mu03 is formed quantitatively and may be titrated against permanganate (cf. Font& and Thivolle A. 1923 ii 264). The method is used for determining small quantities of phosphorus.Determination of Rare Metals and their Separation from Other Metals. 111. The Separation of Uranium from Titanium Iron and Aluminium. L. MOSER (Nonutsh. 1923 44 91-96).-The separation by hydrogen sulphide from an ammoniacal sulphosalicylic acid solution occurs readily but the uranium sulphide is precipitated in a colloidal condition so that filtration is extremely diflicult) and the precipitate carries down other salts from the solution. The separation by means of the soluble complex carbonate (NH4)4'cTog(cj0& formed by addition of ammonium carbonate which throws down the common metals is quantitative only in presence of titanium if very small amounts of uranium compounds are present. Titanium may be separated as the hydroxide Ti(OH),; the two oxides are precipitated together by ammonia and after ignition and weighing are dissolved by fusion with potassium sodium carbonate and treatment with hydrochloric acid..Addition of potassium bromate and sulphate precipitates the titanium hydr- oxide which is filtered ofl dried and weighed; uranium may be separated from the bromate-free filtrate by precipitation with ammonia but if aluminium is present ammonium carbonate in excess is added to the neutralised solution to remove this as hydr- oxide ; the precipitation must be repeated to get a good separation. Iron is also separated by the complex carbonate method the E. E. T. precipitation being repeated for quantitative work. s. I. L. Determination of Uranyl Compounds. G. JANDER and K. REEH (2. anorg. Chem. 1923,129,293-301).-Sexavalent uranium is reduced to the quadrivalent state in sulphuric acid solution and may then be reoxidised by means of standard permanganate according to the equation 2MnO,'+5U""+2H,O=2Mh"+ 5U02"+4H'.In view of the fact that statements are to be found that acid reduction of F proceeds to a point below UIV tests were carried out using zinc zinc amalgam and aluminium for the reduction of a standard uranyl solution. Both zinc and zinc amalgam were found to be most unsuitable but aluminium in sulphuric acid reduces UVI quantitatively to F. A correction must be applied for any iron present in the aluminium nsed. H. H. The end-point is quite sharp. VOL. CXXVI. ii. 3ii. 66 ABSTRACTS OF CHEMICAL PAPERS Determination of Titanium by Reduction with Zinc and Titration with Permanganate.G. E. F. LUNDELL and H. B. KNOWLES ( J . Amer. Chem. SOC.. 1923 45 2620-2623).-Titanium may be determined volumetrically as follows. A solution of titanic sulphate in 5 vol.% sulphuric acid is run through a Jones's reductor 19 mm. bore containing a column of zinc 43 cm. in length into a bottle containing three times as much ferric sulphate solution as is necessary to oxidise the tervalent titanium back to the titanic state of oxidation. The solution is then titrated with a 0-1N solution of permanganate. The results are extremely accurate in the absence of substances which interfere with the reaction. All substances with such interfering action except niobium can be readily removed by well-known methods. Substances which interfere are some organic compounds tin arsenic antimony molybdenum (ous) iron (ow) chromium (ous) vanadium (ous) tungsten uranium and niobium. The above method for the determination of titanium is superior to the method in which the reduced material is run into standard permanganate and to methods in which the titanous solution is collected and prepared in atmospheres of hydrogen or nitrogen.Titanous solutions required for standard solutions can be prepared by means of a Jones's reductor which passes through the cork of a bottle through which a current of hydrogen is being circulated. 5. F. S. Electrometric Determination of Vanadium and Uranium Separately in the Presence of One Another and in the Presence of Iron. E. XULLER and A. FLATH (2. Elektrochem. 1923 29 500-508) .-The authors have repeated the electrometric titrations of Gustavson and Knudson (A.1923 ii 185) of vanadium uranium and iron separately and in the presence of one another. It is shown that vanadium when titrated electrometrically with potassium permanganate at 80" shows three sharply marked breaks in the titration curve. The volume of permanganate used between the first and second break corresponds with the oxidation from tervalent vanadium to quadrivalent vanadium and that between the second and third break to the oxidation from quadrivalent vanadium to quinquevalent vanadium. These breaks are very sharp very much sharper than those obtained in a titration at 18". In the presence of iron at SO" the three vanadium breaks are found in the curve but the break for the oxidation FeU+FeIII is not clear; at the ordinary temperature the iron break is sharp and the VI=+VIv disappears.Iron and vanadium can be estimated in mixtures by reducing in a Jones's reductor then titrating at 80" to the second break which leaves the vanadium in the VIV stage then in cold solution to the third break where the iron is all oxidised and finally at 80" to the fourth break where the vanadium is in the stage VV. The amount of iron can then be calculated from that of permanganate used for the cold titration between the second and third breaks and the vanadium from the amount used between the first and second or the third and fourth breaks. Uranium solutions reduced by zinc to the stage UIV are oxidisedANALYTICAL CHEMISTRY. ii. 67 by permanganate in the presence of sulphuric acid to the stage UVI and at this point a definite break is shown in the titration curve for SO".In the case of mixtures of uranium and iron the titration with permanganate after reduction is carried to the first break in the titration curve at SO" which indicates the completion of the oxidation Urn to UVI and then to the second break at 18" which indicates the completion of the oxidation FeII +Fern. Mixtures of vanadium and uranium are titrated a t 80" with permanganate the permanganate used between the first and second breaks effects the oxidations VIII+VIV and UIV+UVI and that between the second and third breaks Vm-+vV. Mixtures of uranium vanadium and iron are reduced with zinc and titrated at 80" to the second break in the titration curve with permanganate ; at this point the oxidations F1+V and Um-+VI are com- plete then the titration is continued a t 18" to the third break where the oxidation FeII-Fem is complete and then a t 80" to the fourth break where the oxidation Vm+-VP is complete.J. F. S. Volumetric Determination of Vanadium in Steel. A. T. ETHERIDGE (Analyst 1923 48 588-590).-!L'wo g. of steel is dissolved in 5 C.C. of dilute sulphuric acid in a 500 C.C. flask. Two to three C.C. of nitric acid (d. 1.42) is added and any residual carbide dissipated if necessary by digestion with a little more nitric acid. The solution is evaporated until fumes of sulphur trioxide appear. Nitric acid destroys the diphenylcarbazide subsequently used as an indicator and must be removed. The sulphatjes are dissolved in 400 C.C.of water and the solution is boiled porous platme being added to prevent bumping after which a saturated solution of potassium perrnanganate is added drop by drop until a permanent precipitate is formed and boiling is continued for fifteen minutes. A large excess of manganese dioxide must be avoided or chromium and vanadium may be associated with the precipitate. The solutioii is cooled filtered through asbestos and the precipitate washed with cold water the filtrate being received in a large Erlenmeyer flask. Fifty C.C. of syrupy phosphoric acid is added and after cooling a slight excess of ferrous ammonium sulphate to reduce chromate and vanadate. This excess is titrated with 0-IN permanganate to a permanent pink. Fifty C.C.of concentrated sulphuric acid is now added and the solution cooled after which sufficient standard ferrous ammonium sulphate solution is added to reduce all the vanadium and also to leave a small excess the approximate amount of vana- dium present being found by preliminary tests either by this process or colorimetrically with hydrogen peroxide. After thorough shaking standard 0-1N dichromate solution is added until within a few C.C. of the end this end-point being approximately known from the preliminary test. The indicator is prepared as follows 0.05 g. of diphenylcarbazide is dissolved in a few C.C. of glacial acetic acid and diluted to 500 C.C. Five C.C. of this solution is acidified with three drops of dilute sulphuric (1 3) and one drop of 0.1N dichromate solution added. About half of this solution is added to the liquid 3-2ii.68 ABSTRACTS OF CHEMICAL PAPERS. in the flask and dichromate solution continually added unt,il the purple colour has faded away. The remainder of the indicator is now added and the titration continued until the purple colour is discharged and the solution becomes apple-green. The ferrous ammonium sulphate is standardised under the same conditions of acidity and volume as in the test. The difference between the two tit'rations represents vanadium in terms of 0-1N dichromate solution. The process was tested on electrolytic iron to which known amounts of vanadium and chromium had been added. Up to 2% of vanadium results correct to wit'hin 0-020/ are obtained but beyond 2% of chromium the green chromic sulphate obscures the end-point and for 4% chromium steel it is recommended that work be carried out on a 1 g.sample. The presence of cobalt interferes with the permanganate end-point. Colorimetric Determination of Small Quantities of Bis- muth. c. E. LAPORTE ( J . Phurm. Chim. 1923 [vii] 28,304-305 ; cf. A. 1923 ii 792).-The method is based on the precipitation of b'smuth as quinine iodobismuthate followed by solution in acetone. clear yellow to orange-yellow proportionally to its bismuth content ; 0.0001 g. of bismuth can be determined with an error not exceeding 2-3%. To determine bismuth in urine the ash is taken up in 10% nitric acid in sufficient excess to prevent the formation of the basic salt and is treated with Leger's reagent as modified by Aubry (A.1922 ii 165) containing 1% quinine sulphate and 27k potassium iodide. It is better to make up the solutions of quinine sulphate and potassium iodide separately and mix the two as required. The precipitation of bismuth is quantitative and the orange-yellow precipitate that is formed is dissolved in acetone and its intensity compared with a standard solution prepared similarly. An Improved Method €or the Separation of Gas Mixtures. M. SHEPHERD and F. PORTER (Ind. Eng. Chem. 1923 15 1143- 1146) .-The apparatus described was designed for the separation of the hydrocarbons in natural gas by fractional distillation for the purpose of analysis and for the preparation of constituents in a state of purity with greater expedition than was possible with older types.The whole apparatus including distillation bulbs pump reservoirs and measuring burette is constructed in one unit. Three distillation bulbs are provided permitting of a rapid distillation from one and condensation of the vapour in another (by varying the pressure on the liquid air jackets surrounding them). I n the case of natural gas the nitrogen and helium which remain uncondensed at - 190" are a t once removed and measured. The methane fraction is twice distilled and condensed in successive distillation bulbs and is then removed and measured and the higher homologues are similarly separated one by one the temperatures of the bulbs being appropriately controlled throughout. Tests with an artificially prepared gas mixture have demonstrated the accuracy of this procedure.For the preparation of pure gases suitable for the determination of physical constants repeated distillations are H. C. R. T In e intensity of the coloration of the acetone solution varies from D. R. N.ANBLYTICAL CHEMISTRY. ii. 69 necessary. Analyses performed by the above method differ from those obtained by the combustion method but this is attributable to the impossibility of obtaining a correct percentage composition of a mixture of more than two hydrocarbons by the latter method and to the daculty of obtaining complete combustion. Determination of Methyl Alcohol. A. €3. LYOKS ( J . Amer. Pharm. Amoc. 1922 11 682-686; cf. ibid. 12).-Dried egg- albumin is used in preference to milk or peptone and Chapin's method of oxidation using permanganate is employed.A very dilute solution of methyl alcohol containing about 1% of ethyl alcohol is oxidised and 1 C.C. is mixed with 1 C.C. of water containing 0~005-0.010 g. of egg-albumin and 2 C.C. of sulphuric acid contain- ing a trace of ferric chloride. The purple colour which reaches a maximum intensity in ten minutes is compared with a standard. CHEMICAL ABSTRACTS. C. I. Detection of Methyl Alcohol in Ethyl Alcohol. C. H. LA W~LL (Amer. J. Phurrn. 1923 95 812-820).-The literature of the subject is reviewed. It is considered that the test depending on the oxidation of the alcohols with permanganate and the testing of the solution of aldehydes for formaldehyde with the magenta- sulphuric acid test solution described in the U.S. Pharmacopoeia tenth revision is satisfactory.The cooling of the solution after the addition of the sulphuric acid can be obviated by adding acid previously diluted (1 3) and cooled. The test is sensitive to 1 part of methyl alcohol in 500 parts of ethyl alcohol and if smaller pro- portions are present or suspected a preliminary fractioiiation may be carried out and the test applied to the 1 C.C. fraction coming over first from a 10 C.C. sample. In this way positive reactions were obtained with 1 part of methyl alcohol in 10,000 parts of ethyl alcohol. H. C. R. Ether Anssthesia. I. The Estimation of Ethyl Ether in Air and in Blood and its Distribution Ratio between Blood and Air. P. A. SHAFFER and E. RONZONI ( J . Biol. Chem. 1923,57 741-760).-A modification of the Nicloux method for the estimation of ether in air water or blood is described.The solution is grated and the air passed through a series of three tubes containing 500/ sulphuric acid and dichromate in excess of that required for the oxidation. When absorption is complete the solutions are heated to boiling to complete the oxidation. After cooling t>he contents of the tubes are washed into a flask diluted wit'h water potassium iodide is added and the iodine liberated titrated with thiosulphate. The difference between this result and that obtained with a blank experiment gives the amount of dichromate used in oxidising the ether to acetic acid. No carbon dioxide is produced if the tempera- ture and concentration of acid are properly controlled. If desired the ether may be absorbed in one tube of concentrated acid.This is then diluted to 40 or 50% and a measured quantity of dichromate added; the remainder of the procedure is as above. Using this method the distribution of ether between air and water and airii. 70 ABS!L'RACTS OF CHEMICAL PAPERS. and blood has been determined for a series of temperatures. The ratios obtained below 35" are somewhat higher than those obtained by Haggard (A. 1923 ii 343) ; between 35" and 40° the results agee. Determination of @-Naphthol in a-Naphthol and a-Naphthol in p-Naphthol. J. PROCHAZKA (Ind. Eng. Chem. 1923 15 944-945).-To determine @-naphthol in a-naphthol use is made of the fact that the latter couples in acid solution with p-nitro- diazobenzene whilst the former does not or only very slowly. a-Naphthol (0.36 g.) is dissolved in 3040 C.C.of alcohol cooled to ti" and titrated with p-nitrodiazobenzene solution (100 C.C. = 1 Q . of nitrite) containing about 30-50~0 excess of hydrochloric acid above the theoretical amount for diazotisation. Rather less than the calculated quantity of diazo-solution is run in fairly quickly and the solution left for about thirty minutes. The p-nitrobenzene- azo-a-naphthol separates and the disapperaance of the diazo- compound is determined by spotting on filter-paper with dilute sodium hydroxide solution. Addition of diazo-solution is then continued. When all the a-naphthol has combined the spot test after further addition of diazo-solution shows the red colour of p-nitrobenzeneazo- p-naphthol. The volume of diazo-solution used is a measure of the purity of the a-naphthol; the @-naphthol is obtained by difference. The method of determining a-naphthol in P-naphthol consists in adding to an alcoholic solution of the naphthol rather more than sufficient p-nitrodiazobenzene to com- bine with arll the a-naphthol present.After half an hour the solution is diluted with boiling water the precipitate of impure p-nitrobenzeneazo-wnaphthol collected on a filter washed with hot water and then boiled with 0.5% sodium hydroxide solution. The blue solution is filtered and compared colorimetrically with standard solutions of pure p-nitrobenzeneazo-cx-naphthol or since the colour is fugitive with a secondary standard for instance the colour from tetrazotised benzidine coupled with H-acid (Diamine Blue 2B).E. M. R. The Detection of Pentose Formaldehyde and Methyl Alcohol. J. B. SUMNER ( J . Arner. Chem. Soc. 1923 45 2378- 2380).-Bial's reagent for pentoses will keep if the six g. of orcinol and forty drops of 10% ferric chloride solution are dissolved together in 200 C.C. of ethyl alcohol without the addition of hydrochloric acid. Fifteen drops of this solution 5 C.C. of the sugar solution and an equal volume of fuming hydrochloric acid are heated at 100". A clear blue colour develops if 1 mg. of arabinose or xylose is present; with less pentose the colour is green with more a preci- pitate is formed. With formaldehyde a white precipitate appears but only on heating if the concentration is small. With a very small quantity of formaldehyde the precipitate is not formed but a yellow coloration is developed.When the material is heated at 100" for fifteen minutes the precipitate turns brown; it now dissolves in an excess of alkali to give a pink solution or with much precipitate pink E. s.ANALYTICAL CHEMISTRY. ii. 71 flocks are produced. With such a small quantity of formaldehyde that there i8 no precipitate after heating for fifteen to twenty minutes the addition of sodium hydroxide produces a pink or salmon-coloured solution with a green fluorescence which is so intense that this test will readily show one part of formaldehyde in ten million parts of water. One part of formaldehyde in one million parts of water may be detected by the use of an alcoholic solution of orcinol and two drops of ZOyo sodium hydroxide solution.The solution becomes pink owing to oxidation by atmospheric oxygen. The test is only of use in the absence of certain interfering substances Acetaldehyde gives a similar precipitate with orcinol ferric chloride and hydrochloric acid but only in concentrated solution; this precipitate does not darken on heating and dissolves in alkali to give a yellow solution which however does not show any fluorescence. The formation of the white precipitate may be used as a test for methyl alcohol after its oxidation to formaldehyde. The most suitable oxidising agent is potassium dichromate and sulphuric acid since this forms very little formaldehyde from ethyl alcohol. One C.C. of the suspected alcohol e.g. from the distillation of an alcoholic beverage 2 C.C. of 6.7 yo potassium dichromate solution and 2 C.C.of 62% sulphuric acid are allowed to remain. If the reduction to blue chromic sulphate takes much longer than forty seconds too much water is present. Fifteen C.C. of water is added and the mixture heated a t 100" for ten minutes. Five mg. of orcinol in one C.C. of water is added and the heating continued. If the alcohol contains 5% or more of methyl alcohol a precipitate is formed after about five minutes. With only lo/ fifteen minutes are required. The test will show methyl alcohol down to o*5y0 but it may tlhen be necessary to heat for thirty minutes and then cool. Even smaller quantities may be detected by removing the chromium by heating with sodium hydroxide. The filtered solution has a green fluorescence if traces of methyl alcohol are present.Formic acid amyl alcohol acetone and furfuraldehyde do not interfere with the reaction. Glycerol is eliminated during the distillation of the alcohol but gives a positive test if even as little as 5 mg. is added to the distillate w. s. N. Determination of Pentoses and Pentosans. 11. Determin- ation of Furfuraldehyde. N. C. PERVIER and R. A. GORTNER ( I d . Eng. Chem,. 1923 15 1255-1262).-Several new volumetric methods for determining furfuraldehyde in dilute aqueous solution were test'ed. Iodine in alkaline solution did not give dependable results and acid permanganate was unsuccessful owing to the catalytic reduction of the permanganate by furfuraldehyde. The use of potassium bromate in acidified furfuraldehyde solutions containing potassium bromide was eminentjly successful. Specific directions are given for obtaining theoretical yields of furfuraldehyde from pentose materials and for the volumetric determination of this substance in the resulting distillates.Representative results of determinations on pure pentoses and pure furfuraldehyde areii. 72 ABSTRACTS OF CHEMICAL PAPERS. recorded and the factors to be used for the conversion of potassiuin bromate used to furfuraldehyde pentose pentosan or the corre- sponding methyl derivatives are given. The acidity of the solution to be titrated should not exceed 4-5y0 as further oxidation of the primary product of the interaction of bromine and furfuraldehyde results in the presence of high concentrations of acid. The velocity of this secondary reaction appears to be so small as to be without appreciable effect on the titration if the conditions proposed are adhered to.Either hydrochloric or sulphuric acid may be used and a potassium bromide solut>ion of approximately 1 :/o concentra- tion is satisfactory. The potassium bromate solution must be added slowly and the presence of any considerable excess a t all times avoided. The amount of furfuraldehyde present does not influence the accuracy of the method. In titrating dilute solutions with potassium bromate the end-point can be readily located by the use of a simplified electrometric apparatus consisting of two platinum wires a galvanometer and a key. The time factor of the reaction involved is made the basis of the foregoing method for finding the end-point.Hydroxymethylfurfuraldehyde a product of the acid distillation of hexose materials apparently interferes slightly with the use of the proposed method but the effect is small enough to be disregarded. Lzevulic acid a further decomposition product of hexoses is without any effect whatever. Methyl pentoses or pentosans will interfere in that methylfurfuraldehyde is formed and this will react with the bromate solution. A bibliography of the subject is appended. J. B. SUMXER and V. A. GRAHAM (Proc. SOC. Exp. Biol. &led. 1922 20 96; cf. A. 1921 ii 564).-Blood (1 c.c.) is laked with 2 C.C. of water 4 C.C. of a 2.94% solution of neutral sodium dinitrosalicylate and 2 C.C. of 0-4N-sulphuric acid are added and the mixture is filtered ; 3 C.C. of the filtrate is heated for three minutes in a Folin sugar tube in a boiling water-bath 1 C.C.of 3% sodium hydroxide solution is added and the heating is continued for ten minutes. The solution is then cooled and diluted to a volume suitable for colorimetric comparison with a standard prepared by heating 2 C.C. of a o.01570 solution of dextrose with 1 C.C. of a 1.780,; solution of neutral sodium dinitrosalicylate for three minutes adding 1 C.C. of the alkali and heating for ten minutes. Determination of Lactose by the Polarimetric and the Gravimetric Methods. A. L. BACHARACH (Analyst 1923 48 521-528).-Careful redetermination of the polarimetric constants of lactose gave the following results [a]k=+62.40+(t-20) x 0.072 ; [a]~e54s=+61.94+(t-20) ~ 0 . 0 5 5 . The latter formula is applicable when the green band of the mercury vapour arc is the source of illumination.For the gravimetric determination of lactose the modified Fehling method of Quisumbing and Thomas (A. 1922 ii 92) was found satisfactory in the respects claimed by them. The copper was however determined after ignition by H. C. R. Dinitrosalicylic Acid as a Reagent for Blood-sugar. CHEMICAL ABSTRACTS.ANALYTICAL CHEMISTRY. ii. 73 weighing as cupric oxide. The ratio of cupric oxide to lactose was constant and equal to 1.565. A New Titrimetric Method for Determining Formic Acid. 0. RIESSER (Biochem. Z. 1923,142,280-281).-The author points out that the method described by Utkin-Ljubovzov (A. 1923 ii 588) for the determination of formic acid had already been published by him (2.physiol. Chem. 1916,97,355) and used by other workers. It is unnecessary to filter the precipitated mercurous chloride and the determination may be carried out in neutral solutions. Application of the Method of Diffusion to the Detection and Separation of Fatty Acids. A. HEIDUSCHKA and J. RIPPER (2. EZektrochem. 1923 29 552-555).-Details are given of the application of the method of diffusion to the separation of the so-called heptadecoic acid into its constituent fatty acids palmitic acid and stearic acid. An alcoholic solution of heptadecoic acid is allowed to diffuse through a collodion membrane and it is shown that the respective rates of diffusion of the constituents decrease as the molecular weights increase. The rate of diffusion is not always proportional to the concentration.A mixture containing an excess of palmitic acid may yield a diff usate containing an excess of stearic acid. The results were found to be applicable to a mixture of lauric and stearic acids. Determination of Tartaric Acid by Oxidation with Potassium Iodate and Sulphuric Acid. R. STREBINGER and J. WOLFRAM (Oesterr. Chem. Ztg. 1923 26 156-157).-The oxidation of the tartaric acid proceeds according to the equation C,H +2KIO + H,SO = K,SO + I + 4C0 + 4H,O. A weighed quantity of about 0.3 g. of the tartaric acid is added to a flask containing 1 g. of potassium iodate a few drops of water and 30 C.C. of concentrated sulphuric acid and the mixture is heated on a sand-bath for thirty minutes until the greater part of the liberated iodine has been expelled.After cooling the mixture is diluted with water the solution boiled to expel remaining traces of iodine again cooled and diluted to a definite volume. The excess of iodate is then determined by treating an aliquoit portion with potassium iodide and titrating the iodine with thiosulphate solution. If desired the tartaric acid may be precipitated as lead tartrate by means of lead acetate in acetic acid solution ; the lead tartrate is collected washed with hot water and then oxidised as described. Titration of Amino- and Carboxyl-groups in Amino-acids etc. 1-111. In Aqueous Solution. L. 3. HARRIS (Proc. Roy. Soc. 1923 [B] 95 440484).-From a consideration of the %itration curves of amino-acids it is deduced that the amino- and carboxyl-groups can be estimated by titration.At a pH of 0.7-0.1 the mono-amino-mono-carboxylic acids are completely dissociated as acid salts of the amino-group so that the amino-group can be estimated by titration with acid to this p,. Similarly their carboxyl groups are completely dissociated a t a pa of 11.75 and can be determined by titration with alkali to this degree of alkalinity. H. C. R. J. P. J. S. G. T. w. P. s.ii. 74 ABSTRACTS OF CHEMICAL PAPERS. I n practice the titration is carried to the mid-point i.e. the point zt which 50% of the amino- (or carboxyl-) group is neutralised. This point is determined from the titration curve of the acid under investigation. Mixtures of amino-acids may be determined by means of a series of titrations to different pH values.The original paper should be consulted for the theoretical basis of the work and the necessary corrections involved in the special cases of the various amino-acids. C. R. H. Action of Carbonyl Chloride on Ricinolein. A. PIUTTO and A. CURZIO (Rend. Accad. Sci. Fis. Bat. Napoli 1921 [iii] 27 40- 47).-The action of carbonyl chloride on castor oil or on ricinolein results in the formation of a compound which contains the per- centage of chlorine corresponding with glyceryl A-chlorocarbonato- ricinoleate (CH,*[ CH,],*CH[ OCOCl]=CH,*CH:CH*[CH,] ,*CO,),C,H ; with ricinoleic acid the chlorocarbonato-acid itself appears to be formed. On the other hand olive almond arachis and sesame oils take up only 0.08-0.18% of chlorine when treated with carbonyl chloride. Adulteration of castor oil with other oils is therefore detectable in this way.The name chlorine index is proposed for the percentage of chlorine thus absorbed the value for the samples of castor oil examined being 9.03. Melting Point and Iodine Value of Refined Natural &Camphor. MAURICE s. SALAMON (Analyst 1923 48,536-539). -The camphor was purified by sublimation only the middle fraction being used. No difficulty was experienced in obtaining samples by this means which had a melting point of 179" the melting point remaining constant after repeated sublimation. Iodine value determination on such samples by Wijs's method gave values not exceeding 0.1. It is extremely diflicult to remove the last traces of oil and it is probable that this small residual iodine value is due to a minute trace of oil still present in the camphor.To determine the iodine value of camphor oil samples of oil were expressed from both Chinese and Japanese crude camphor and the dissolved camphor was removed as completely as possible by repeated freezing. The iodine value of the oil finally obtained varied between 86.0 and 91.7. It is considered that this oil contained not more than 10% of camphor and in calculating the percentage of camphor in samples from the iodine value it is recommended t o take the iodine value of the oil as 100. L. KOFLER and 0. DAFERT (Ber. Deut. pharm. Ges. 1923 33 215-229).-Previous methods of determining the saponin content of the root (e.g. with baryta. magnesia lead acetate) are shown either to give too low results or to involve alteration of the substance.I n order to extract the saponin quantitatively and unchanged the powdered root is extracted exhaust'ively with boiling water the ext'ract; evaporated to a syrup and the saponin fractionally precipitated first with alcohol and then with ether. Each of the two precipitates represents about 10% of the starting material with an ash conteiif T. H. I?. H. C. R. Saponin from Gypsophila puniculatu.ANALYTICAL CHEMISTRY. ii. 75 of 10-19;& and 4-6:4 and a hamolytic index of 1 100,000 and 1 500,000 for the alcohol and ether fractions respectively. By means of Pauli's electrodialysis apparatus the ash in the saponin is reduced to o.0770. Elementary analysis of the alcohol and ether fractions gives respectively C = 47-88% H = 7-60% and C=48*40~0 H=7.21%.The saponin is considered to have a mo1. wt. of 3000 or more. Microchemical Detection of Hydrocyanic Acid. F. VON NEUREITER (Deut. 2. yes. gerichtl. Med. 1923 2 313-317; from Chem. Zentr. 1923 iv 230-231).-The material in which the presence of cyanides is suspected is mixed with concentrated oxalic acid solution in a glass vessel which is covered by a slide carrying a hanging drop of 1% silver nitrate solution coloured blue with Methylene-blue. In the presence of hydrocyanic acid a turbidity is produced which is seen under the microscope to consist of fine blue needles of silver cyanide the identity of which can ba established by ordinary reactions. The Colorimetric Determination of Hydrocyanic Acid as Thiocyanate. I. M. KOLTROFF (2.anal. Chem. 1923,63,188-190). -To 5-10 C.C. of a cyanide solution are added 1 C.C. of 1% sodium tetrrtthionate solution and 5 drops of 10% ammonia solution. The mixture is warmed on a water-bath for five minutes at 60-56" cooled and treated with 2 C.C. of 4Y-nitric acid and 3 drops of S-ferric chloride solution. The colour is matched against a standard. Working with 10 C.C. of test solution 1 mg. of hydrocyanic acid per litre is easily detected. The sensitiveness of the reaction is 0.3 mg. per litre. Determination of Uric Acid in Blood-serum and Tissue Extracts. K. HARPUDER (2. ges. Exp. Med. 1923 32 378-386; from Chern. Zentr. 1933 iv 443444).-The method for which detailed directions arz given consists in the case of sera of removal of proteins followed by precipitation of the uric acid as zinc mate.The precipitate after centrifuging is taken up with sodium chloride solution and the uric acid determined colorimetrically by means of phosphotungstic acid. In the case of tissues a modified method is described in which the material is first extracted with 3% sulphuric acid in a refiux apparatus. Determination of Uric Acid and Purines in Blood-serum and Urine by the Copper Urate Method. H. CHABANIER M. LEBERT and C. LOBO-ONELL (Bull. Xoc. Chim. biol. 1923 5 731-738).-The purines are precipitated in the form of their insoluble copper compounds and the nitrogen in the precipitate is determined by Kjeldahl's method. By this method uric acid added to urine or to serum can be determined to within about 6%. A Quantitative Colour Reaction given by Adrenaline and Urine.H. FRIEND ( J . Biol. Chem. 1923 57 497-505).- Adrenaline niay be determined coloriinetrically by means of the [Cf. B. Jan.] W. T. K. B. G. W. R. The above conditions must be closely adhered to. A. G. P. G. W. R. C. R. H.ii. 76 ABSTRACTS OF CHEMICAL PAPERS. red coloration which is produced when it is treated successively with sulphanilic acid nitrous acid and ammonia. For the deter- mination of adrenaline in urine the latter is precipitated with lead acetate and the excess of lead removed by means of ammonium sulphate. The determination is then carried out on two portions of the filtrate one of which is first treated with ferric chloride at 50" to destroy the adrenaline. The difference between the results gives the adrenaline content of the urine.According to this method normal urine contains 0.2-0.4 mg. of adrenaline Fer 100 c.c.; larger variations occur in pathological urines. Determination of Bilirubin in1 Urine. K. HOESCH (blunch. Xed. Woch. 1923,70 534; from Chem. Zenir. 1923 iv 444).-The method depends on coupling with diazoacetophenone. After treating the urine with a solution of diazoacetophenone potassium hydroxide and ethyl alcohol are added. The green precipitate is dissolved in hydrochloric acid and the solution extracted with chloroform. The blue chloroform solution is repeatedly extracted with water until the colour changes to a clear red. It is then evaporated. The residue consists of azobilirubin which can be determined colorimetrically by comparison with a standard solution of azo- bilirubin. G. W. R. E. S. The Refractometric Determination of Haemoglobin. J. L. STODDARD and G. S. ADAIX ( J . Biol. Chenz. 1923 57 437454).- When determined on hzemoglobin (from human blood) which has been dried a t 110" the refractive constant a of hzemoglobin has a value of 0.001942. The difference between this value and that obtained by Howard (A.' 1920 i 451) k probably clue to water of crystallisation in the latter's specimen. Two refractometric methods for the estimation of hzemoglobin in blood have been elaborated. In the first the red corpuscles from a measured volume of blocd are washed hzmolysed with water and saponin treated with salt to precipitate the stromata made up t o volume centrifuged and the refractive index of the solution determined before and after coagul- ation of the hzmoglobin by heat. The hzemoglobin content of the blood can be calculated from these readings by means of the constant a. Equal volumes of salt solution (0.8%) and salt solution containing sufficient saponin to haemolyse the blood are added respectively to separate portions of equal volume of the blood. After centrifuging the clear solutions are read in the refractometer and the hzemoglobin content is calculated as above. A correction must be made for the refraction due to the saponin. Determinations by these methods combined with determinations of the oxygen capacity of the blood indicate that the latter is determined more accurately by T'an Slyke's than The second method is shorter. by Haldane's method. E. s.

ISSN:0368-1769    

DOI:10.1039/CA9242605055

出版商:RSC    

年代:1924

数据来源: RSC

摘要:

ii. 77 General and Phgsiesl Chemistry. The Quantum Theory of Line Spectra. N. BOHR (Danske Vid. Xelsk. Skrzfter nut. mat. Afd. 1922 4 [Sl 101-118; from Chem. Zentr. 1923 iii 1337; cf. A. 1922 ii 801).-The distinction between arc and spark spectra depending on the ratio of the number of electrons- to the nuclear charge is discussed. A cor- relation exists between the arc and spark spectra of elements of difEerent series of the periodic system. The probability of trans- ition between Merent stationary states of an atomic system is also considered with reference to the author’s theories. The series spectra of helium lithium beryllium and the Stark and Zeeman effects are discussed. G. W. R. The Spectrum of Iodine and the Band Spectrum of Mercury. W. GERLACH (Physikal. Z. l923,24,467469).-The nature of the spectrum of iodine is briefly referred to and reasons are advanced for regarding the band 3460 A.as the electron-afhity continuous band spectrum associated with the iodine atom whilst the band 4800 A. is attributable to the electro-negative iodine molecule. Brief reference is made to the resemblance between the R. FRERICHS (27. Physik 1923 20 170-187).-Particulars are given of the determination of the respective wave-lengths and intensities of R and P series of lines in the bands AX 4006 4063 4280 4328 4380 4650 and 4690 A. in the spectrum of copper excited by the introduction of finely powdered copper into an oxy-hydrogen blowpipe flame. The determination of combination relations amongst lines of the respective series indicates that the bands may be classified as follows bands characterised by the same initial energy level of the emitting molecule (n,=O) 4280 4650; (nl=l) 4006 4328 4690; (n1=2) 4063 4380; bands characterised by the same ha1 energy level of the emitting molecules (na=O) 4280 4006; (na=l) 4650 4328 and 4063; (n2=2) 4690 and 4380.The frequencies yo of the respective zero lines associated wifh &he various bands can be very accuratelr calculated by the formula v0 = 23,311.15 + (1658.81n1 - 44-71n1 )-(1903.48n2 - 37-18n$) in whch n and n2 are quantum numbers characterising the respective initial and final energy levels of the emitting molecules. An empirical formula of the Deslandres type permitting the fre- quencies of the heads of the bands to be very accurately calculated and involving half-quantum numbers and five constants is deduced.Two of the constants are shown to be related to the quantum level-numbers n and n2. The origin of the bands is discussed briefly. The calculated value of the moment of inertia of the emitting moleoule is 0.35 x 10-3 gr. cm.2. This result indicates the presence of hydrogen in the emitting system a result which is partly confirmed experimentally. spectra of iodine and mercury vapour. J . S. G. T. The Band Spectrum of Copper. J. S. G. T. VOL. CXXVI. ii. 4ii. 78 ABSTRACTS OF CHEMICAL PAPERS. Combination Relations in the Band Spectra of the Copper Flame. E. BENGTSSON (2. Physik 1923 20 229-236).- Particulars are given of the determination of the respective wave- numbers and intensities of lines in the bands AX 4689 4649 4280 4005 and 3777 8.in the flame spectrum of copper The lines in the various bands except for seven lines in the band 4328 and five in the band 4062 can be arranged in two series and the deduc- tion of combination relations between the respective series in the manner employed by Hulthitn (A 1923 ii 670) indicates that the bands 4280 4005 and 3777 correspond with the same final con- dition of the molecule whilst the bands 4280 and 4649 correspond with the same initial condition of the molecule and similarly in regard to the pair 4005 and 4689. The frequencies yo of the respective zero lines associated with the various bands can be calculated by the formula v0=23552*4+1743-4n-44.15n2- [1977*5n'-37*2n'2] in which n and n' are whole numbers ranging from 0 to 3 and represent quantum numbers associated respec- tively with the initial and final energy levels of the molecule.J. S. G. T. Spark Spectra of Higher Order associated with Mercury. L. BLOCH and E. BLOCH ( J . Phys. Raditzcm 1923 4 333- 348).-Particulars are given of measurements of the respective wave-lengths and intensities of about 600 classified lines in the spectra of Hgn Hgm and Hgm between wave-lengths 6149.37 and 2224.87 A. excited in an electrodeless discharge in mercury vapour by gradual increase of the exciting voltage. Classification of the lines into the respective orders is effected by reference to the variation of the lengths of the lines as the exciting voltage i s increased. J. S. G. T. The System of Quartets in the Scandium Spectrum and the Periodic System. M.A. CATALAN (Anal. Fb. Quim. 1923 21 464480; cf. A. 1923 ii 104).-The author discusses the application of Kossel and Sommerfeld's alternation law (" Wechsel- satz ") to the spectra of the neutral atoms of potassium calcium scandium titanium vanadium chromium manganese and iron. It is concluded that every element gives variws systems of series but either all odd or all even; one element never gives both odd and even series. A table is given showing the relation to the periodic classification of the various systems of series obtained. Whilst potassium gives doublets only calcium gives simplets and t.ripl& and scandium doublets and quarteta Larger numbers of systems are shown for element6 in the later groups for which however some systems still remain undiscovered. For example in the iron spectrum triplets and quintets are known whilst shplefs septets and nonets remain to be discovered G.W. R. The IiSeries of the Spectrum of Molybdenum. S. TANAKA and J. TSUTSUMI (Mem. CoZZ. Sci Kyoto 1923 7 1-5).- In continuation of previous work (A. 1922 ii 805) the authors have determined the wave-lengths of the four lines in theGENERAL AND PHYSICAL CHEWSTBY. ii. 79 R-series of the spectrum of molybdenum by observations of the second third fourth and fifth order spectra produced by a reflector of mica. The results are in close agreement with the values determined by h i d e and others. The Optical Spectrum of Hafnium. H. M. HANSEN and S. WERNER (Nature 1923 112 90O-W1).-A list is given of the strongest lines in the hafnium spectrum in the region between 7300 and 3500 A.the intensity for both arc and spark spectra being also noted. The authors find in the region of the spectrum for which Ewer and Haschek’s zirconium measurements are sufficiently exhaustive nearly all the strong hafnium lines here given among Exner and Hascheks zirconium spark lines as weak lines of intensity 1 or 2. The lines 6386 4093 and 3505 are for the time being regarded as the most persistent hafnium lines in this part of the spectrum. Ultra-red Natural Frequencies of Salts containing Sulphur. V. J. SIHVONEN (2. Physik 1923 20 272-279).-Employing the method used by Schaefer and Schubert (A. 1916 ii 506) the authors have determined the natural frequencies of the anions of various salts containing sulphur by observing the reflection of radiation included between Ah 5p and 2Op from the polished face of compressed pastilles of the respective salts.Reflection maxima indicating corresponding anionic natural frequencies were observed a t the following respective wave-lengths (measured in p) sodium sulphite 10.6 19.5; barium sulphite 10.9 19.7; sodium ethyl sulphonate 8-7 9.7 135 19.2 ; potassium ethanesulphonate 8.7 9.7 13.6 19-2; sodium thiosulphate 9.1 10.2 15.1 18.5 19.7; potassium thiosulphate 9.1 10.2 15.2 18.5 19.5; barium thio- sulphate 9.3 10.4 15.0 18.2; sodium dithionate 8.2 10-1 17.3 19.4 ; potassium dithionate 8-2 10.2 17-6 19.3 ; barium dithionate 8.2 10.2 18.0; potassium trithionate 8-3 10.0 15.1 16.5 19.3; potassium tetrathionate 8.6 10.1 16.3 19.4.Salts other than the sulphites and sulphates included in these results show two reflection maxima in the region 8p to 11p. The shorter of these wave- lengths is connected with the presence of the sulphate-ion the longer with the presence of the sulphite-ion. The occurrence of a reflection maximum at 8-7p (the sulphate maximum) in the case of the ethanesulphonates investigated is interpreted as indicating the presence of a sulphuryl group. It is suggested that the sulphonic group is in a state of labile equilibrium possessing alternately the frequencies associated respectively with the SO and SO configurations. J S. G. T. The Electrical Absorption and Dispersion Spectra of Methyl and Ethyl Alcohol in the Region M 30 to 90 Cm. G. POTAPENKO (2 Physik 1923 20 21-35).-The author has determined the respective values of the dielectric constants and absorption coofficients of methyl and ethyl alcohols for electric oscillations of wave-lengths ranging from 29.4 cm. to 89.7 cm.In the cam of methyl alcohol the value of the absorption coefficient increases 4 - 2 J. S. G. T. A. A. E,ii. 80 ABSTRACTS OF CHEXICAL PAPERS. rapidly as the wave-length employed decreases below about 60 cm. For short wave-lengths the value of the absorption coefficient of ethyl alcohol similarly increases rapidly and attains in the case of the shortest wave-lengths employed a very high value 0.843 which approximates to that characterising a metallic reflector. Under similar conditions the value of the dielectric constant of ethyl alcohol decreases rapidly a result which is interpreted as affording evidence of anomalous dispersion.No evidence of the existence of maxima of absorption characterising certain definite wave-lengths such as was deduced by Romanov from his observ- ations (A 1913 ii 182) was obtained. Values of the respective refractive indices calculated from the results are in close agreement with those determined by Drude von Bayer Wildermuth and Romanor. J. S. G. T. Ultra-violet Absorption Spectra of Unsaturated Com- pounds. Spectra of Vapours of Acraldehyde Crotonaldehyde and Glyoxal. A. LUTHY (2. physikal. Chem. 1923,107,285-304). -The absorption spectra of solutions of p-methyl-As-butylene ally1 alcohol acrylic acid acraldehyde crotonaldehyde and glyoxal have been measured in hexane and of the three last-named sub- stances also in ethyl alcohol. The absorption spectra of the last three substances have also been obtained with the vapours of these substances.p-Methyl-As-butylene shows two bands a flat one with a maximum at 2340-2350 8. and a second much stronger band which has its maximum beyond 1935 A . . Ally1 alcohol has a weak flat band in the region of 2340 8. possibly the maximum lies more towards the ultra-violet; the maximum of the second stronger band lies outside the region measured namely beyond 1935 8. Acrylic acid has a flat band with maximum a t 2409- 2415 8. and a second strong band with maximum a t 2050 A. Acraldehyde in hexane solution has a flat broad band with a maximum a t 3350 B.; further towards the red two small bands a t 3663 A.and 3514 A. are measured; it has a very strong band in the ultra-violet beyond 2080 8. In alcohol and water solution the maximum of the flat band iA displaced toward the violet whilst in ether solution the maximum is in the same position as in hexane solution. Crotonaldehyde has a flat band with maximum at 3290 A. in hexane which is displaced to 3205 8. in ethyl alcohol solution that is slightly more than the displacement of the corre- sponding band of acraldehyde. A second very intense band of crotonaldehyde lies in the extreme ultra-violet Glyoxal has no bands in the visible and long wave-length ultra-violet but the author has measured seventeen bands in the ultra-violet a t 4613 4483 4330 4199 4095 4013 3935 3863 3768 3670 3542 3487 3359 3301 3187 3154 and 3119 A.A very strong band occurs in the extreme ultra-violet at about 1960 A. and between this band and the last small band there is a flat broad band the maximum of which has not been measured The bands obtained with acraldehyde vapour agree very well with the bands of the hexane solution the bands of the vapour being slightly displaced towardsQENERAL AND PHYSICAL CHEMISTRY. ii. 81 the red. The heads of the vapour bands have an analogous structure the difEerence between the frequencies of the most intense lines being 1260. Crotonaldehyde has an entirely dserent spectrum from that of acraldehyde in the vapour condition In this case the bands are weak and not sharp but five regions which are much stronger than the remainder can be identified.The mean values are recorded. With glyoxal below 30 mm. pressure a group of very sharp absorption bands occurs in the visible region. At higher pressures a new absorption zone is found in the visible region. The second absorption region has the sisisisisisisisisisisisisisisisae position as that of acraldehyde. Glyoxal in the same way 88 acraldehyde shows strong absorption groups which coincide with the small bands in hexane solution. J. PICCARD and E. THOMAS (Heh. China. Ach 1923 6 1040-1043).-A.n attempt is made to correlate the colours of salts with the colour-producing properties of their const'ituent ions. Ions may be divided into three groups (1) coloured ions; compounds containing them are always coloured ; (2) ions possessing latent colour ; molecules formed from these tend to be coloured; (3) ions which have no colour latent or otherwise.Ions of the first group give a deeper colour with those of the second than with those of the third. The following classification is made. Group (1) MnOf Mn0411 CrOdI Cr20,11 PtCI,II AuCI,I CrII and Crm+aq Cu+aq Au Pt Fe Mn ; Group (2) S" 011 11 BrI ClI OH1 (phenols and derivatives certain enols) PeUI Gun C+ Bim Sb" Asrn HgI Hgn Pbn Cw AgI Tin Cdn; Group (3) FI SO4= ClO,= CH,*CO,I ZnI CsI RbI KI NaI LiI Can A P HI. Cadmium iodide is described as colourless but as both its 'ions have latent colour it might be expected to be coloured. Examination shows that a layer of the concentrated solution 10 cm. thick is distinctly yellow. Mercuric bromide and mercurous chloride also form distinctly yellow soh- tions. E.H. R. The Luminescence of Titanium Oxide. E. L. NICHOLS (Physica.2 Rev. 1923 [ii] 22 4 2 0 4 2 4 ; cf. Nichols and Wilber A. 1922 ii 105).-Cathode rays but not ultra-violet light from an iron spark excite a very faint orange-red fluorescence in titanium oxide or after fusion of the surface layer a fine blue fluorescence with rapid fatigue. A thin layer of the oxide when heated gave a very feeble greyish-blue fluorescence up to 425" strong red from 425" to 677" and strong yellow from 677" to 1,000". When the oxide is heated directly with an oxygen-hydrogen flame two distinct phases are observed according as the oxygen or the hydrogen is in excess. Velocity of Photochemical Reactions under the Action of Light the Intensity of which is Periodic.P. LASAREV (Cmpt. rend. 1923,177,1436-1438).-Talbot's Law is shown to be readily deducible from a consideration of photochemical kinetics [cf. J . Russ. Phys. Chem. Xoc. (physical sect.) 1915 47 9581. J. 3'. S. Coloured Ions and the Colours of Salts. A. A. E. E. E. T.ii. 82 ABSTRACTS OF CHEMICAL PAPERS The Photolysis of Carbonic Acid E. BAUR and P. BUCHI (Hdv. Chim. Acta 1923 6 959-965).-Attempts were made to repetit the experiments of Baly Heilbron and Barker (T. 1921 119 1025-1035) who observed the reduction of carbon dioxide to formaldehyde through the action of light in presence of a sensi- tising dye such as Malachite-green. Formaldehyde was indeed found in the solutions after illumination but just as much or more when carbon dioxide was absent as when it was present.The production of formaldehyde was increased in presence of barium hydroxide which precluded the possibility of the presence of carbon dioxide in solution. It is concluded that the form- aldehyde is formed from the dye especially when this is present as- a colloidal solution of the leuco-base [ ? colour base] as it is in the barium hydroxide solutions Solutions of dyes (Rhodamine and Phosphine) in xylene containing lecithin or spermaceti were exposed to light ; also dyeings of Eosin Rhodamine Phosphine and Malachite-green on cotton and silk and resinates of the same dyes were illuminated under water both pure and saturated with carbon dioxide. In no case could formation of formaldehyde oxalic acid or formic acid be detected.Validity of the Photochemical Law of Equivalence in the Case of Emulsions of Silver Halides. J. EGGERT (Phgsikal. Z. 1923 24 488-490).-The experimental method described in a previous paper (ibid. 1921 22 673) has been considerably improved and the result definitely established that provided the time of exposure of the emulsion to the radiation is not excessive photochemical absorption of radiation by emulsions of silver chloride or silver bromide obeys the photochemical law of equiv- alence viz. one silver atom is affected per quantum of energy absorbed. For longer exposures the ratio of the number of silver atoms affected to the number deduced from quantum considerations diminishes as the time of exposure increases. The author considers that the latent image is constituted of metallic silver.J. S. G. T. The Photo-electric Effect of Caesium Vapour. J. KUNZ and E. H. WILLIAMS (Physical Rev. 1923 [ii] 22,456460).-Previous work (A. 1922 ii 809) has been repeated with greater precision by the use of a quartz tube with plane parallel end plates. The critical wave-length for photo-electric emission from caxium vapour was found to be 3180 8. (average) in agreement with the con- vergence wave-length 3184.28 k which is related to the ionisation potential Vi according to the equation Vi=hc/eXi. It follows that the separation of an electron from a cmium atom requires the same amount of work whether produced by an impinging electron or by absorption of light. A. A. E. Spectro-photo-electrical Effects in Argentite. P. H. GEIGER (Physical Rev.1923 [ii] 22 461469).-When argentite is con- nected in a closed circuit with n galvanometer and one surface of contact is illuminated an E.M.F. is produced which increases with the intensity up to about 0.013 volt for 600 candle-metres and over. E. H. R.CIENEBAL AXD PHYSICAL CHEMZ3TBY. ii. 83 Continued exposure results in marked fatigue. The effect which is not thermo-electric is shown also with proustite (Ag3AsS3) ppargyrite (Ag,SbS,) bournonite [3(Cu2,PbS)Sb,S,] molybdenite (MoS,) stephanite (Ag,SbS,) and acanthite (Ag,S) although to a less extent than with argentite (Ag,S); cuprite gave indefinite results whilst the effect was no€ observed in the case of galenite stibnite and polybasite. The electrical resistance of argentite was found to be only half as great for 20 as for 4 volts and is about 0-8 as great in the light as in the dark Slow recovery followed a condition of insensitiveness to light attained after some time.A. A. E. Rontgenographic Chemical Investigations. I. Rontgen Spectra and the Periodic System. H. STINTZING (2. physikul. Chem. 1923 107 154-162).-A theoretical paper in which it is shown that up to the presevt the study of Rontgen spectra has only led indirectly to the possibility of determining structure according to Bohr’s theory. The author puts forward a number of numerical relationships in the periodic system which may serve as an indication of the lines on which the direct investigation of the structure of atoms and atomic nuclei may be pursued. Itl is suggested that such an investigation could be carried out by means of y-rays.It is also pointed out that positive ray analysis may explain atomic structure and other chemical problems particularly the definite fixing of whole number atomic weights. Rontgenographic Chemical Investigations. 11. Technique of Rontgenology. H. STINTZINQ (2. physikal. Chem. 1923,107 163-180 ; cf. preceding abstract).-A description of the most suitable forms of apparatus and the most favourable conditions for the investigation of Rontgen spectra. A new arrangement of the electrodes is described for Rontgen analytical purposes. It is shown that if the discharge is divided between the discharge tube and a spark gap in parallel then the maintenance of a definite tube voltage as measured by the spark potential has little influence on the production and the intensity of a suitable Rijntgen radiation.Constitution of the X-Ray Spectra belonging to the LSeries of the Elements. H. HIRATA (Proc. Roy. Soc. 1924 [ A ] 105 40- 60).-Experimental data due to Siegbahn (A. 1919 ii 488) and to Siegbahn and Friman (A. 1916 ii 167 277 361) are used to calculate the respective values of the ratio of the wave number V t o Rydberg’s constant N in the L-series of the X-ray spectra of forty-eight elements included between zinc (atomic number 30) and uranium (atomic number 92). Values so determined are shown to confirm approximately certain deductions made by Sommerfeld from the extension of the theory of “ wasserstoffahn- lich ” spectra to the K and L series of X-ray spectra (Ann. Physik 1916 [ivl 51 133).The slight discrepancy is attributable to the number of electrons in the K - and L-orbits being so large that their effects on the motion of an electron in the same or an inner orbit J. F. S. J. 3’. S.ii. 84 ABSTRACTS OF UEEItfICAL PAPEBS. are appreciable. Moreover the radius of the innermost ( K ) orbit cannot be' considered negligible compared with the radii of the outer orbits. Sommerfeld's theory is extended by taking account of these correcting factors. A mathematical discussion involving quantum considerations of the initial and h a 1 stationary orbits corresponding with X-ray radiation the planes of the stationary orbits and the intensities of X-ray radiation leads to the conclusion that an electron moves from a certain outer orbit to the neighbouring inner one without changing its spatial quantum number but if there are intermediate orbits between the initial and h a 1 orbits the spatial quantum number changes every time the electron passes through one of the intermediate orbits.Reflection of the Characteristic Rontgen Radiation associated with the Chemical Elements composing a Crystal by the Elements. B. WALTER (Z. Phpik 1923,20,257-271).- Employing an ionisation chamber for the measurement of the respective intensities of radiation of various wave-lengths reflected by crystals of bromides iodides or containing caesium on which Rontgen radiation excited by means of a tungsten anticathode was incident Clark and Duane found that the intensity of reflected radiation characteristic of bromine iodine etc.was of the same order of magnitude as and even greater than the intensity of reflection of the incident radiation characteristic of the material of the anti- cathode (A. 1923 ii 468). Employing a photographic method of comparing the intensities of the reflected radiation of difTerent wave-lengths and using Rontgen radiation excited by means of a molybdenum anticathode the author has been unable to confirm this result. The intensity of the reflected radiation characteristic of the crystal element was in all cases immeasurably small. No satisfactory explanation of the apparent discrepancy shown by the results obtained by the respective methods is at present avail- able. It is pointed out that the results obtained by Clark and Duane indicate a very rapid decrease of intensity of the reflected radiation on the long wave-length side of the head of the absorption band characterking the crystal elements in question.This result is contrary to what would be anticipated from a knowledge of the distribution of intensity throughout the continuous spectrum afforded by a Rontgen tube. Particles of Long Range Emitted by the Active Deposits of Radium Thorium and Actinium. L. F. BATES and J. S . ROGERS (Proc. Roy. Soc. 1924 [A] 105,97-116).-The emission of long-range particles by the active deposits of radium thorium and actinium has been investigated by means of the scintillation method (A. 1921 ii 671). In the case of radium active deposit in addition to particles of range 9.3 cm. previously found by Rutherford particles of respective ranges 11-2 and 13.3 cm.were found. For every lo7 a-rays emitted by radium-(? the respective numbers of these particles present are 380 125 and 65. Thorium active deposit emits particles of ranges 16.0 and 18-4 cm. in addition to particles of ranges 8.6 and 11-5 cm. (A. 1916 ii 282). The J. S. G. T. J. S. G. T.relative numbers of these particles emitted were found to be 47 55 106 and 220 respectively. Actinium active deposit was found to emit particles of range 6.49 cm. previously recorded by Marsden and Perkins (A. 1914 ii 410) to the extent of 0.322% of the total number of a-rays emitted by actinium-C. Indications of the presence of particles of range greater than 6.5 cm. were obtained. Evidence as to whether these long-range particles were a-rays or H-particles is inconclusive.Schemes hitherto proposed for the modes of transformation of the C products of the radio- active substances must be considered incomplete. More especially for the atoms of radium4 and thorium-C explanation must be found for the presence of four particles of different ranges. J. S. G. T. The Absolute Energies of the Groups in Magnetic p-Ray Spectra. C. D. ELLIS and H. W. B. SKINNER (Proc. Roy. Xoc. 1924 [ A ] 105 6049).-Absolute determinations correct to 1 part in 500 have been made of the respective energies of the electrons associated with six of the principal homogeneous groups of @-rays emitted from radium-B. The values expressed in volt deduced from determinations of the curvature of the respective rays in a magnetic field are 0.3725 0.4983 1.529 2.067 2.638 and 3.379.J. S. G. T. Discoloration and Luminescence due to Becquerel Rays. I<. PRZIBRAM (2. Physik 1923 20 196-208).-Iiiterature dealing with the discoloration and luminescence accompanying the incidence of Becquerel rays on substances e.g. rock salt is reviewed more especially with reference to conclusions concerning the ,phenomena reached by Meyer and the author in a previous paper (A. 1922 ii 339). The mechanism of the phenomena is discussed from the point of view of the quantum theory. Ionisation Hydrogen and Oxygen. H. D. SMYTH (Proc. Roy. Soc. 1933 [ A ] 105 116-128).-1n continuation of previcus work (A. 1923 ii SOZ) the author has investigated the ionisation of hydrogen and oxygen by electron impact. The results obtained show that ionisation in hydrogen at about 16.5 volts is not accom- panied by dissociation as has been generally supposed.Atomic hydrogen-ions are first produced at a potential 4*25&0-06 volts above that a t which molecular ions first appear and the proportion of atomic ions remains very small up to 720 volts. I n hydrogen at sufficiently high pressure atomic ions predominate over mole- cular ions and appear a t approximately the same voltage. They originate owing to dissociation due to collisions of ionised molecules with other molecules. In oxygen molecular ions are produced a t about 15.5 volts whilst doubly and singly charged atomic ions appear a t about 7 and 7*5&0.2 volts higher. Results in the cme of oxygen can be interpreted by thermochemical equations similar to those previously employed in the case of nitrogen. W.&I. LATIMER ( J . Arner. Chew. $m.. 1923 45 2803-2808).-The heats of ionisation of the J. S. G. T. J. S. G. T. Ionisation of Salt Vapours. 4*ii. 86 ABSTRACTS OX CHEMICAL PBPEBS. hydrogen and alkali metal chlorides bromides and iodides hare been tabulated for the gaseous condition. The ionisation constant of sodium chloride a t its boiling point has been found to be 4 x From a consideration of the fields of force about the ions and the molecular diameters it seems that the heats of ionisation cannot be calculated by any method which treafs the ions as rigid structures of electrons about a positive nucleus. Radioactivity of the Alkalis. G. HOFFXANN (Physikd. Z . 1923 24 475476).-The radioactive character of salts of sodium potassium rubidium and caesium and the relative magnitudes of the small activities associated with these elements have been determined in two djfferent ways.The results are in satisfactory agreement with values of the activities given by Hahn and Rothenbach (A 1919 ii 312). Thermionic and Photo-electrical Properties of the Electro- positive Metals. A. F. A. YOUNG (Proc. Roy. Soc. 1923 [ A ] 104 61 1-639).-The fhermionic and photo-electrical properties of sodium and potassium have been investigated. It is found that sodium does not give a measurable thermionic emission that is greater than amperes for temperatures up to 390'. Potassium is found to give currents measurable in some cases by an electroscope a t temperatures down to the ordinary.The currents are held to be thermionic in origin and not due to chemical action. The values of b for potassium in the emission formula i=AlcT1/2e-b/T are found to be lower than those obtained with other metals and the values of A are also low. The change of the potassium from solid to liquid makes no dserence in the magnitude of the thermionic current or in the value of b. Deter- minations of the photo-electric work function t& from photo-electric measurements made a t the same time as the thermionic measure- ments and a t nearly the same temperature show that & is always greater than the thermionic work function Q calculated from the value of b. J. F. S. Dielectric Constants of Organic Liquids at the Boiling Point. F. V. GRIMM and W.A. PATRICK ( J . Amer. Chem. Soc. 1923 45 2794-2802) .-The dielectric constant of thirty-five organic liquids has been determined a t the boiling point. The following values are recorded benzene 2-17 ; toluene 2.17 ; m-xylene 2.15 ; chloroform 4.23 ; carbon tetrachloride 2.10 ; carbon disulphide 2-58 ; ethyl ether 4-11 ; these values are accurate to 0.01 unit ; p-cymene 2.27 ; ethyl bromide 8.81 ; ethylene bromide 4-09 ; isoamyl bromide 4.70 ; n-butyl iodide 4.62 ; methyl iodide 6.48 ; ethyl acetate 5-30 ; chlorobenzene 4.20 ; aniline 4-54 ; o-toluidine 4.00 ; butaldehyde 10.78 ; paracetaldehyde 6-29 ; anisaldehyde 10.38 ; acetone 17.68 ; methyl ethyl ketone 14.46 ; acetophenone 8.64 ; ethyl alcohol 17.30 ; n-propyl alcohol 11.83 ; n-butyl alcohol 8-19 ; isoamyl alcohol 5-82 ; o-nitrotoluene 11-82 ; pyridine 9-38 ; quinoline 5.05 ; these values are accurate to 0.02 unit ; acetonitrile 26.2 ; phenylacetonitrile 8-5 ; ethylene chlorohydrin 13.2 ; and J.F. 8. J. 8. G. T.GEl,NERAL AND PHYSICAL CHEMISTRY. ii. 87 nitromethane 27.75; these values are accurate to 0.1 unit. A method has been suggested for evaluating the volume occupied by the molecules in the liquid state. The above idea has been applied to Bakker’s equation for the latent heat of vaporisation. [Relation between] Cathode Drop of Potential Ionisation Potential and Atomic Weight. A. GUNTHER-SCHULZE (2. Physik 1923 20 153-158).-The author shows that the average normal cathode drop of potential V in the case of a discharge through any elementary gas of atomic weight.M is approximately related to the ionisation potential Vi of the gas by the equation Vn=(O*245211+4)V~or in which cc is a constant having the value unity for all monatomic gases whilst the appropriate value of a in the case of diatomic gases is to determined from consideration of the loss of energy due to electronic impacts and the efficiency of such impacts. It follows that the efficiency of the process of ionisation of the gas due to kations is to a first approximation inversely proportional to the square of the atomic weight of the gas. J. S. G. T. Influence of Neutral Salts on the Potential of the Hydrogen Electrode. J. PRZEBOROWSKI [with M. FLEISSNER and A. SABRODINA] (2. physikul. Chem. 1923 107,270-278).-The action of 0-1N and 0.01N solutions of potassium nitrate chloride and bromide sodium nitrate chloride and bromide and lithium chloride and bromide in hydrobromic acid solution on the potential of the hydrogen electrode has been investigated.It is found that the potential of the hydrogen electrode in 0-1N and 0.01N hydrobromic acid solutions increases in all cases. A shght increase of the potential is found for solutions containing the potassium salts at concentrations less than 1N. The influence of the neutral salts increases with increase in their concentrations. The influence of these salts increases with their solubility hygroscopic properties and power of forming crystal hydrates. The influence of the salts is in the following order KNO KCl KBr NaC1 NaBr LiCl LiBr lithium bromide having the greatest influence.Bromides have a greater influence than chlorides the kation being the same in both cases. With a constant concentration of neutral salt and a variable concentration of hydrobromic acid the fall in the E.M.F. is almost independent of the hydrobromic acid concentration for salts which form crystal hydrates. The corresponding difference of E.M.F. for salts which do not form crystal hydrates varies very much with the difEerent salts and still more the greater the con- centration of hydrobromjc acid. The action of neutral salts can be explained by the assumption that only non-hydrated hydrogen- ions have an influence on the potential; the ions formed from neutral salts dehydrate the hydrogen-ions and so increase the concentration of non-hydrated ions and in consequence the potential.The electrolytic solution tension of the hydrogen changes with the concentration of the neutral salt. In addition to the ions of neutral salts the undissociated molecules also exercise a dehydrating action on the hydrogen-ions. J. F. S. J. F. S. 4*-2ii. 88 ABSWCTS OX CHElKICAL PAPERS. Hydrogen Electrode in Alkalm ' e Solutions. A. H. W. ATEX (Trans. Amr. Electrochem. Soc. 1923 43 89-98).-The potential of the hydrogen electrode has been determined in solutions of sodium hydroxide and in solutions of sodium hydroxide containing sodium chloride. It is shown that when a hydrogen electrode saturated with hydrogen is in equilibrium with 0.1N hydrochloric acid it is in the same state of equilibrium with 1.ON hydrochloric acid and vice versa.This however is not the case when a solution of an alkali hydroxide is used. When a hydrogen electrode hi equilibrium with 1*ON sodium hydroxide is placed in 0-1N sodium hydroxide a very considerable time elapses before it reaches a new equilibrium. The same phenomenon is observed in a more marked degree when the electrode is changed from 0*1N sodium hydroxide to 0.1N hydrochloric acid or the reverse. The explan- ation given is that the electrode must absorb sodium-ions or give them out as the case may be in order to reach an equilibrium with the final solution. J. F. S. M. KNOBEL P. CAPLAK and M. EISEMAN (I'rans. Amer. Electrochem. Xoc. 1923 43 55-74).-The value of the hydrogen overvoltage has been determined with cathodes composed of twenty-two different materials that of chlorine bromine and iodine at three different anodes and that of oxygen a t nine difTerent anodes.The deter- minations have been carried out at various current densities from 1-0 milliampere to 1.5 amperes per sq. cm. All measurements were made a t 25.0"&0.2". An investigation of the method of measuring overvoltage has led to the conclusion that the use of a small glass tip less than 1 mm. diam. pressed against the active electrode surface while the current is passing will give correct results . J. F. S. S. J. BIRCHER and W. D. HARKINS ( J . Amer. Chem. Xoc. 1923 46 2890-2898).-The effect of pressure on the potential of the hydrogen electrode and on the potential and overvoltage of a mercury cathode has been ascer- tained a t 0" for pressures from 757 mm.to 9 rnm. The results show that the effect of pressure on the potential of .a cathode a t which hydrogen is being liberated is in general very small at pres- sures between 760 mm. and 11 mm. The slight changes which occur are due to bubble expansion and consequent shielding of the cathode and to increased stirring caused by more rapid bubble liberation at low pressure. Overvoltage defined with reference to a reversible hydrogen electrode increases as the pressure is decreased. This increase is paralleled entirely by a decrease in potent.ia1 of the hydrogen electrode. Between 760 mm. and 11 mm. the range of variation of the overvoltage is about 50 millivolts. The present data are of importance in connexion with the theory of overvoltage due to MacInnes and Adler (A.1919 ii 131). Here the over- voltage E is given by E=(3RT/2p) y where p is the pressure in the bubbles r their radius and y the surface tension of the liquid. Since the bubble radius. is practically constant with variation of Effect of Current Density on Overvoltage. Effect of Pressure on Overvoltage.GENERAL AXD PHYSICAL CEEBIISTRY. ii. 89 pressure the overvoltage should vary inversely as the pressure and thus increase very rapidly as low pressures are approached. The present work indicates that the overvoltage increases with decrease of pressure only to the extent that the hydrogen electrode potential decreases that is a8 the logarithm of the pressure. On the other hand the overvoltage of a number of inactive metals is found to have the same temperature coefficient and to decrease 2 millivolts per degree in 0.1N sulphuric acid.This seems to point to the surface tension of the liquid as an important factor in overvoltage. This fact indicates that MacInnes and Adler's hypothesis is a partial rather than a complete hypothesis of over- voltage. In the experiments care was taken to avoid stirring the liquid round the cathode so the smallness of the increase of over- voltage with decrease of pressure cannot be due to the effect of stirring. The overvoltage a t a mercury meniscus in dilute sulphuric acid is found to increase as the large bubble a t the top of the meniscus becomes larger and to decrease suddenly when the bubble escapes. J. F. S. Free Energy of Dilution and the Activity of the Ions of Hydrogen Iodide in Aqueous Solution.J. N. PEARCE and A. R. FORTSCH ( J . Arner. Chem. Soc. 1923,45,2852-2857).-The E.9i.F. of cells of the type H,IH(c),AgIIAg has been measured at 25" 30" and 35" for concentrations of hydriodic acid between 0.24661 and 0-005M. The decrease of free energy and heat content attend- ing the cell reaction has been calculated for 25". The decrease of free energy accompanying the transfer of one gram-molecule of hydrogen iodide from the various concentrations to a concentration exactly 0.00561 has been calculated. From these values the geo- metric mean activity coefficients of the ions of hydrogen iodide have been calculated and it is found that for concentrations up to 0.00561 these coefficienfs are practically equal to the corresponding coefficients for hydrogen chloride at the same concentrations.Ob- viously therefore the activities of the iodide- and chloride-ions are equal when in equivalent concentrations of their salts. Activities of Zinc Cadmium Tin Lead and Bismuth in their Binary Liquid Mixtures. N. W. TAYLOR (J. Arner. Chem. Xoc. 1923 45 2865-2890).-Accurate determinatious of the activities of liquid zinc cadmium tin lead and bismuth in the binary alloy systems zinc-tin zinc-cadmium cadmium-bismuth cadmium-lead and cadmium-tin have been made at temperatures from 400" to 600" from E.M.F. measurements of cells of the type MIelectrolyteIAlloy. The electrolyte wm the entectic mixture of lithium and potassium chloride with a small amount of zinc or cadmium chloride and potassium hydroxide.With the single exception of the system cadmiurn-bismuth which gave. a very complicated type of activity curve all the alloy systems investigated showed escaping tendencies or activities greater than that required by Raoult's law. I n regard to divergencies from this ideal solution law and also in regard to the heats of mixing the results cjf the J. F. S.ii. 90 ABSTRACTS OF CHEMICAL PAPERS. present work furnish strong evidence for the validity of the internal- pressure theory as applied to liquid metal systems. Velocity of Hydrogen-ions in Gels under the Influence of a Current. N. ISGARISCHEV and A. POB~RANZEV (2. Elektrochem. 1923 29 581-586) .-The migration velocity of the hydrogen-ion in gelatin gels has been measured in the presence of difEerent electro- lytes including the chlorides of ammonium potassium sodium barium calcium magnesium lithium manganese and cadmium and the sulphates of most of the above-named metals and also of zinc and rubidium under various experimental condit.ions.A chamcteristic slowness of the hydrogen-ion is observed on passing from one potential to another which is explained by the fact that the gel has a semi-rigid structure in which the ions are included and have thereby lost to some extent their free condition and power of progressive movement. The influence of the various kations in the gel on the movement of the hydrogen-ions is in direct relationship with the atomic volumes of the kations. Mzgnetic Properties of some Paramagnetic Double Sulphates at Low Temperatures.L. C. JACKSON and H. KAMERLINGH ONNES (Proc. Roy. Soc. 1923 [A] 104 671-676; cf. A 1923 ii 609).-1n7 continuation of previous work on the magnetic properties of compounds of iron nickel and cobalt the magnetic susceptibility of cobalt potassium sulphate cobalt rubidium sulphate and manganese ammonium sulphate has been determined a t temperatures from 14.54" Abs. to 291.0" Abs. The results show together with those given in the previous paper (Zoc. cit.) that all the cobalt compounds obey Weiss's law x'm(T+A)=C down to about 70" Abs. where x'm is the molecular susceptibility but deviate from the law below 70" Abs. in such a manner that the susceptibility at the lowest temperature is greater than the value calculated by Weiss's law. The magneton numbers of the cobalt compounds are not equal but increase as the molecular weight of the com- pound increases Manganese ammonium sulphate follows the simple Curie law xT=C over the whole range of temperature investigated.Comparing this result with those obtained for hydrated and anhydrous manganese sulphate it is found that tfhe manganese compounds shorn a simple behaviour as regards the dependence of the susceptibility on temperature the greater the magnetic dilution of the substance. The complications found with cobalt nickel and iron compounds do not occur The Crystallisation of certain Salts in the Magnetic Field. G. ROASIO (Rev. gdol. 1923 4 297).-Experiments with salts of iron nickel and cobalt show that the magnetic field exercises an influeiice on (1) the orientation of the crystals the angles between axes and lines of force varying with the substance but being con- stant for a given compound; and (2) the growth of the crystals which become elongated in a definite direction the angles remaining constant but again varying with the substance.J. F. S. J. F. S. J. F. S. CHEMICAL ABSTRACTS.GENERAL AND PHYSICAL CHEMISTBY. ii. 91 Specific Heat and Heat of Mixing in the Neighbourhood of the State of Critical Miscibility. N. PERRAEIS (Compt. rend. 1924 178 83-86; cf. A. 1923 ii 836).-The specific heats and heats of mixing of the following pairs have been measured (1) di- phenyl ether and .ethyl alcohol ; (2) benzene and ethyl alcohol ; (3) benzene and n-butyl alcohol ; and (4) o-cresol and ethyl alcohol. It is shown that the found specific heat of a mixture is greater than that calculated from the simple law of mixtures this fact necessit- ating a correction in the calculation of the heats of mixing.Curves representing the above constants are approximately rectilinear for a longer or shorter portion of their course according as the mixture under examination is near to or remote from a state of non- miscibility. Thus the length of the rectilinear portions of the curves decreases in the order (l) (Z) (3) (4) this being also the order of increasing miscibility. Thermodynamics of the Ionisation of Monatomic Gases R. BECKER (Physikal. Z. 1923 24 485486).-Cu and C the respective concentrations of the atoms and electrons in a thermally-ionised monatomic gas at temperature To are related by the equation C$/Cu=e-Q~I~'T(KT)3~ 2 .( 2 ~ p ) ~ / 2 / p ~ h ~ in which Q0 denotes the heat of ionisation p the mass of the electron p is a stmatbistical factor and the other symbols have the customary significance. It follows on the basis of the quantum theory that if ccU(v) denote the power of absorption of the gas for radiation of frequency Y = ( & + E ) / ~ where e is the kinetic energy associated with an electron in a a-orbit then Q ( E ) / ~ C ~ ( Y ) = ( E + & ~ ~ ~ ~ ~ / C ~ C ~ qrT( E ) denoting the statistically calculated electron-absorbmg cross sectional area of the ion available for trapping an electron E in a a-orbit!. This equation applied to absorption measurements relating to the principal series of absorption bands should afford quantit,ati.c-e information relating to the trapping of free electrons by an ion.E. E. T. J. S. G. T. Calorimetric Determinations. V. The History of the Thermochemical Standard Substances. P. E. VERKADE (Chern. Weekblad 1024 21 13-20).-The considerations leading up t o the adoption of benzoic acid as a standard by the Inter- national Union at its third conference a t Lyons in 1922 are described in some detail and the desirability of deciding on some other The Heat of Formation of Bleaching Powder and the Thermochemical Explanation of its Decomposition and Formation. SHUICHIRO OCHI ( J . Chem. Ind. Jupan 1923 26 961-978; cf. ibid. 1923 26 1 ; A. 1923 ii 564 573).-Assuming that the formula of bleaching powder is OCl*CaCl,I3,0 the author has made a determination of the heat of formation and then tried to solve thermochemically the problem of the decomposition and the formation of the compound by applying the value obtained.As the reaction OC1*CaC1+H,O2=CaCl2+ 02+H20 proceeds material as a second standard is pointed out. s. I. L.quantitatively and is not affected by the impurities contained in bleaching powder the heat of formation was measured with a simple calorimeter using hydrogen peroxide OCI*CaCl=CaCI,+ O+lS,W cal. and [Ca,O,Cl&=177,260 cal. The method em- ploying the bomb calorimeter and that of decomposing with hydro- chloric acid did not give accurate results. The averages were 176.1 Cal. from the former and 179-7 Cal. from the latter. The heat of decomposition of OCl-CaCl was calculated as follows OCl*CaCl=CaC1,+0+ 13,040 cal. OCl*CaC1,H,O=CaC~,H20+O+ 14,440 cal.=CaCl,+H,O(liquid)+O+10,740 cal. =CaC&+H,O (vapour)+O+l50 cal. OCl*CaCl,aq. =CaCl,,aq. +0+20,620 cal. OCl-CaCl=CaO +C&-25,360 cal. OCl*CaCl,H,O =Ca( OH) +C12 - 12,120 cal. and OCl*CaCl,aq. =Ca(OH),+aq.+C4-20,650 cal. All oxygen-forming decompositions are exothermic reactions whiIst the chlorine-forming ones are endothermic. At the ordinary temperature chlorine may not therefore be evolved as indicated above but is produced by the decomposition of C1,0 which may be easily formed from moist bleaching powder. The chlorate which occurs without exception is considered to be the product of the oxidation of the other molecule of OCl*CaCl or Ca(OCl) caused by the eliminated oxygen in the presence of water. The partial pressure of decomposing oxygen from OCl*CaCl is calculated to be 2-86 x 1013 atm.by Nernst's heat theorem. The heat of reaction between calcium hydroxide and chlorine is represented its follows Ca( OH),+Cl,= OCl*CaCZ,H,O + 12,120 cal. and Ca( OH),+ aq. + C12=OCkCaCl,aq. +20,650 cal. The partial pressure of chlorine reacting on calcium hydroxide is calculated by Nernst's heat theorem 0.004 atm. a t O" 0.016 a t 15" 0.49 a t 30° 0.138 a t 45" 0.355 a t 60° 1.000 a t 78" 3.1 at loo" and 26-7 a t 150". The author has explained the preparation of bleaching powder from the thermochemical point of view. K. K. B. IUIN (2. physikizl. Chem. 1923 107 145-153).-A theoretical paper in which an equation in the form of that of a unimolecular reaction is derived for the kinetics of sorption; this equation is given the form dc fdt=kcM .e-kt where c is the sorption capacity and in general is a function of the concentration p or the temperature T and E is a constant which is a function of the temperature. An equation for the sorption isothermal in the form c 1 -e-yp) is deduced in which o is a constant. It is shown that under certaJn conditions the sorption capacity as placed in the above equation is not always constant and the correction in the kinetic equation introduced on this account increases the agreement between theory and experi- ment. In consequence the number of sorption processes expressed by the equation c=c (l-e-*t) is increased. The dependence of the sorption capacity on the temperature is given by the equation c ==coe-*dT where 6 is a constant.This equation agrees well with the experimental data. The influence of temperature on the initial sorption velocity wi has been determined and it is shown that wi can increase with the temperature whereas cK always decreases General Theory of the Phenomenon of Sorption.GENERAL AXD PHYSICAL C!HEMISTRY. ii. 93 with increase in temperature. This explains the crossing of the isotherms of the sorption kinetics for different temperatures. J. F. S. Investigations on the Adsorption of Iodine by Various Substances. A. LOTTERMOSER (Rolloid Z. 1923 33 271-274). -The adsorption of iodine from solutions in potassium iodide and carbon tetrachloride by starch basic lanthanum acetate lecithin-albumin calcium hydroxide cholic acid and calcium oxide has been investigated It is shown in the case of basic lanthanum acetate that when the basic acetate is prepared a t 18" iodine is adsorbed to form a brown precipitate but when the precipitate is kept for twelve hours or warmed at 40-50° it then adsorbs iodine to form a blue precipitate.Heating a t 70" gives a precipitate which adsorbs iodine with the formation of a dirty green precipitate whilst if the precipitate is boiled it then adsorbs iodine to form a yellow adsorption compound. The adsorption curves in the various cases are entirely different. The longer the basic acetate is kept the less iodine is adsorbed. This is due to the fact that the structure of the basic acetate changes on keeping and in four weeks it becomes crystalline and then ceases to adsorb iodine.Calcium hydroxide adsorbs iodine from a solution in carbon tetrachlolTide with the formation of a brown colour ; in this case it is held that the iodine is chemically combined with the calcium hydroxide. Calcium oxide adsorbs iodine from solutions in carbon tetrachloride according to an adsorption isotherm and calcium carbonate does not adsorb iodine a t all. Cholic acid adsorbs iodine from solutions in potassium iodide when it crystallises from such solutions but crystalline cholic acid when placed in a solution of iodine in potassium iodide does not adsorb iodine. J. F. S. Adsorption Compounds. IV. R. HALLER (Kolloid Z. 1923 33 306-309; cf. A. 1919 ii 198; 1921 ii 21).-!Che dyeing of cotton and wool by indigotin Alizarin VI Indanthren-blue-RS and Para-red sol both alone and in the presence of sodium hydrogen sulphate haa been investigated and both the dye solution and the dyed fibres have been examined microscopically.In the case of indigotin with cotton a greyish-blue colour is produced which is not changed much by sodium hydrogen sulphate and practically the whole of the dye can be removed by washing with water. The indigotin particles are very loosely held by the fibres. With wool the case is Merent ; here the fibres become dyed more rapidly and more intensely and very little of the colour is lost on prolonged mashing. The presence of sodium hydrogen sulphate gives a deeper colour and the dye is homogeneously disseminated through the fibre. With Alizarin VI suspensions cotton on boiling with the solution forms a weak adsorption compound which breaks down on washing repeatedly with water.In the presence of sodium hydrogen sul- phate there is a strong adsorption and the cotton is dyed brownish- yellow ; the adsorption compound thus formed is more stable towards water a d on repeated washing the cotton remains pale yellow. With wool the adsorption is much stronger than with cotton theii. 94 ABSTRACTS OP CHEMICA4L PAPERS. fibres becoming violet coloured but in the presence of sodium hydrogen sulphate chrome-yellow. Both withstand wmhing with water and microscopic examination shows that the fibres are homo- geneoilsly coloured. The results obtained with Indanthren-blue- RX are similar to those obtained with alizarin. The experiments show that wool is a more powerful adsorbent than cotton.Wool forms stable derivatives with chemically inactive substances which can only be termed adsorption compounds. The results raise a doubt as to the correctness of the generally held view that the dyeing of wool is a chemical process. H. G. DEMING and B. C. HENDRICKS ( J . Amer. Chem. SOC. 1923 45 2857-2864).- An apparatus is described which enables the diffusion of gases through metals to be measured a t temperatures up to 1,000" under perfectly definite conditions. The specific rate of diffusion of hydrogen t'hrough several common metals has been measured and the following values expressed in mg. per hour per sq. cm. area per mm. thickness have been obtained aluminium no diffusion detectable a t 555" ; zinc 0.0012 at 375" ; lead 0.001 a t 265" ; copper 0.011 a t 500" ; copper 0-028 a t 770" ; nickel 0.012 at 500" and 0-100 at 750".In addition the specific rate of diffusion of hydrogen has been measured for copper and nickel over a considerable range of temperature. The following results are recorded copper 500" 0.027; 550" 0-032; 645" 0.042; 687" 0-056; 770° 0.072. These values are C.C. of hydrogen per hour diffusing through 1 cm.2 of copper 0-391 mm. thick. Nickel 403" 0.004; 450" 0.007; 527" 0.020; 580" 0.029; 625" 0.056; 695" 0.114; 745" 0.153. In this case the nickel plate was 0-653 rnm thick. Solubility. IX. Metallic Solutions. J. H. HILDEBRAND T. H. HOGNESS and N. W. TAYLOR ( J . Amer. Chem. SOC. 1923 45,2828-2836 ; cf. A. 1923 ii 315).-A theoretical paper in which the authors discuss the various methods of estimating the relative internal pressures of metals. Tables are given of the values of this quantity deduced from expansion and compressibility surface tension and heat of vaporisation.Data are given showing the correlation between these tables and the behaviour of binary metallic solutions. J. F. S. Individual Thermodynamic Properties of Ions. J. N. BRONSTED ( J . Amer. Chem. AYOC. 1923 45 2898-2910).-The principle of the specific interaction of ions is presented in the form of a simple equation and a diagram. The individualities of the fhermodynamic properties of salts vary linearly with their concen- tration when the total concentration is kept constant. On the basis of this law several of the results obtained by means of the principle of the specific interaction may be derived.Thermodynamic and experimental evidence to prove the invalidity of the principle of the independent activity coefficients has been adduced. Solubility measurements embracing a series of cobaltic ammine salts in solutions of sodium sulphate and chloride have been carried out a t Z O O and J. F. 5. Diffusion of Hydrogen through Metals. J. F. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 95 the results are found to be in full agreement with the principle of specific int,eraction. J. 3'. S. Dependence of the Mobility of Univalent Ions on the Temperature. P. WALDEN and HERM. ULICH (2. physikal. Chem. 1923,107,219-234).-A theoretical paper in which i t is shown that the mobility of some ions changes proportionally with the fluidity of the solution and also follows Stokes's law.The deviations of the other ions from Stokes's law are represented by simple empirical relationships. The regularities found are in opposition to the deductions from Born's hydration hypothesis. It is shown to be probable that the meaning of the regularities found may be obtained from Cunningham's formula (Proc. Roy. Xoc. 1910 [ A ] 83 357). Many facts are shown to be best explained by the existence of a firmly held water sheath on the ions. The Crystal Structure of Metals Mixed Crystals and Metallic Compounds. K. BECKER (2. Metullk. 1923 15 303- 305).-A review of the present knowledge of. the crystal structure of metals is given together with a table showing the systems in which thirty-nine metals crystallise as shown by the Debye-Schemer method of X-ray analysis.Fifteen of these metals crystallise in a face-centred cubic lattice nine in a space-centred cubic lattice nine in the hexagonal two in the tetragonal two in the rhombohedral and two in a diamond lattice In addition five elements have a second crystalline modi6cation. Values for the density of the elements calculated from the dimensions and arrangement of the lattice are always about 2% higher than those actually found by experiment. Metallic mixed crystals with a static arrangement of the atoms give X-ray photographs in which the lattice constants if both metals crystallise in the same system are an approximate linear function of those of the constituents. If the lattices are clissimilar t.he atoms of the metal present in the smaller amount arrange themselves in the lattice of the other metal.No relation appears to exist between the symmetry of crystals of intermetallic compounds and that of their components ; thus Cu,Zn and A13Mg4 have a regular face-centred lattice whereas zinc and magnesium crystallise in the hexagonal system; &,A1 and CUM are tetragonal or hexagonal and NiAl has a simple cubic lattice whilst copper nickel and aluminium all have a cubic face-centred lattice (cf. A. 1923 ii 519). H. =GI (Kolloid Z. 1923 33 284-286).-h an earlier paper a description of the production of rhythmic crystals of the racemic form of the menthyl ester of benzyl- acetoacetic acid was given (A. 1920 i 748) ; further details for the production of rh-ythmic crystal figures are now given.It is shown that t'he ester employed must melt a t 48-52' and that it is best. purified by distillation in steam since crystallisation from acetic acid and alcohol produces a separation of the isomerides. Further a freshly prepared benzene solution should be used for when kept a iuutarotation occurs as shown by the following values of the rotation J. F. S. A. R. P. Rhythmic Crystallisation.ii. 96 ABSTRACTS OF CHEMICAL PAPEBS. measured at intervals of eight days - gelo -gago -l0-lo. The solution having the last-named value gives no ring-formed crystal structure. J. F. S. Explanation of the Colloidal Appearance of the Proteins. J. LOEB (Rev. Gen. Cdlokh 1923,1 3-17).-Portion of a lecture delivered a t the Institute of Medicine in Chicago November 24th 1922 in honour of Pasteur. The lecture deals with the pro- perties of the proteins and shows that the chemistry of these sub- stances is not Merent from that of crystalloid substances and that they can combine stoicheiometrically with acids and bases to form protein salts which in solution dissociate electrolytically.The very large ions and molecules of the proteins are unable to diffuse freely across gels and membranes which are easily permeable to the smaller crystalloid ions. These facts lead to an unequal partition of diffus- able crystalloid ions between a solution of a protein and an external aqueous solution or between a protein gel and an aqueous solution. In this partition the total concentration of crysta.lloid ions is alu7ays greater in the protein solution or gel than in the surrounding aqueous solution.This is the cause of the colloidal appearance of solutions and gels of proteins. Measurement of the membrane potential shows that the excess concentration of crystalloid ions in the solution of protein over that outside this solution can be determined by means of Donnan's theory of membrane equilibria and that all the effects of electrol_ytes on osmotic pressure swelling and viscosity of proteins can be calculated with satisfactory exactitude by Donnan's equili- brium equation. Colloidal chemistry therefore appears to be only an imperfectly observed condition of equilibrium of the classical chemistry a t least so far as it deals with the proteins. The mistake is due to two causes first the omission of colloid chemists to measure the hydrogen-ion concentration of their solutions which is the chief variable factor in these cases and second the failure to measure and take into consideration the membrane potential of the solutions and protein gels which furnishes the proof that the theory of membrane equilibria must be used to explain the colloidal appearance of proteins.J. F. S. Variable and Invariable Properties of Dispersion. TV. OSTWALD (Kolloid Z. 1923 33 300-306).-A theoretical paper in which it is shown that the independence of for example the osmotic pressure and the mean kinetic energy of a particle on its degree of dispersion is rather an intuitively derived fact than a rigidly derived consequence of the molecular kinetic theory. On the other hand the thermodynamic or the capillary physical theory of disperse systems gives a strict explanation of this remarkable independence.The osmotic pressure mean kinetic energy density refractive power and cataphoretic velocity belong to the group of properties which are proportional to the absolute surface of the particlea and also to the square of the specific surface. If the measure of these properties is given by W then W=R920(o/v)* or oln . (o/v)a=K where o is the surface v the volume n the number of monobperse particles and K a very general topographical con-QENEBAL AND PHYSICAL CHEMISTBY. ii. 97 stant which depends entirely on the shape of the particles ; for cubes K = 216 and for spheres K = 113. This constant in prticular is independent of the degree of dispersion.The experimentally observed independence of the above-named properties of the degree of dispersion is due therefore to the fact that these properties depend in a double sense on the degree of dispersion. These two functions are opposed to one another and in the h a 1 result eliminate each other. When one or other of the two functions varies so that the above-named condition is not fumed exceptions to .the secondary independence appear. The properties which are most strongly dependent on the degree of dispersion are those which are governed by only one of the functions Determination of Size and Distribution of Size of Particles by Centrifugal Methods. T. SVEDBERG and J. B. NICHOLS ( J . Amer. Chem. Soc. 1923 45 2910-2917).-Stokesys law has been modified to give an exact formula for determining the radius of a particle sedimenting under centrifugal force.This formula has the form r = d9qloge (x+a)/a!d2(4-dl)w21 where T is the radius a the distance from the axis of rotation to the meniscus of the sol in a centrifuge tube x the distance which the boundary has moved in time t,. r] the viscosity of the liquid and dp and dl are respectively the densities of the particle and the dispersion medium. A special type of centrifuge is described which permits a sol to be observed or photographed while it is being precipitated. This method depends on the projection of a uniform beam of light up through a tube con- taining the material each time the tube passes over a certain point. The rate of movement of the particles in the tube may then be observed.To illustrate the method for a fairly uniformly sized colloid results for two different gold sols clay barium sulphate and arsenious sulphide are given. Another method is discussed for determining the distribution of size of particles depending on the variation of concentration with distance from the axis ot rotation in a disperse system subjected to centrifugal force'. P. FINKLE H. D. DRAPER and J. H. HILDEBRAND ( J . Amer. Chem. Soc. 1923 45 2780-2788). -A paper in which the present position of the theory of emulsification is outlined. The types and relative stabilities of emulsions formed by the aid of various soaps have been explained by the aid of the theory of orientation of the soap molecules in the interface. The curvature of the film of soap adsorbed at the interface is more convex towards water yielding more stable emulsions of the oil-enclosed type the larger the metal atom in the. soap.As the number of hydrocarbon chains attached to a single metallic atom increases the curvature is reversed becoming strongly convex towards the oil phase with soaps of the tervalent metals aluminium and iron which yield the most stable emulsions of water in oil. Experimental data on the type and relative stabili- ties of emulsions of various liquids with water show that the transi- tion from the most stable oil-enclosed to the most stable water- J. F. S. ~ ~ _ _ _ ~- J. F. S. Theory of Emulsification.ii. 95 ABSTRACTS OF CHEMICA& PAPERS. enclosed emulsion for both stearates and oleates follows the order caesium potassium sodium calcium silver magnesium zinc aluminium iron This order is in accordance with the valencies and atomic diameters of the metals as interpreted by the orientation hypothesis.It is suggested that the type of emulsion produced by a solid powder is determined by the angle of contact of the inter- face with the solid. In order for the powder to remain in the inter- face the angle must be finite and unless the angle is go" the interface will be on one side or the other of the points of contact of the particles and its tension will cause the film to be concave on t,hat side. J. F. S. Preliminary Attempt to Measure Gravimetrically the Distance Effect of Chemical Affinity. T. W. RICHARDS and W. T. RICHARDS (Proc. Nut. Acad.Xci. 1923 9 379-383).- After a brief discussion of attempts which have been made to ascer- tain the law connecting the force of cohesion and distance a number of experiments designed to measure the force of chemical affinity a t short distances are described. The experiments consisted in suspending horizontally a plate of aluminium 6 cm. sq. to one arm of a delicate balance and after counterpoising it bringing materials which have considerable affinity for it underneath it and measur- ing the pull by the change of apparent weight,. The materials used were oxides of silver copper iron zinc and magnesium sulphur iodine and bromine the two last-named substances being covered with mica. I n the case of the oxides and sulphur the distance between the aluminium and the oxide was about 0.001 m.with iodine 0.01 mm. and with bromine 0.02 mm. The experiments shorn that in no case is there an attractive force amounting to 0.1 mg. Hence it is concluded that the force of chemical afkity must decrease very rapidly as the distance between the attracting atoms increases. J. F. S. Extremely Dry Liquids. G. N. LEWIS ( J . Amer. Che,m. Soc. 1923 45 2836-2840).-A theoretical pa er in which it is shown tive desiccation of liquids which seems to be consistent with thermo- dynamics rests on the assumption that water is a catalyst for pro- cesses between various molecular states and that its removal merely inhibits such processes. If this explanation is correct the process of drying only " freezes " an existing equilibrium and (at constant temperature) cannot alter the static properties of a liquid.This leads among other things to the prediction that liquids will be found which exhibit abnormally low as well as abnormally high boiling points. J. F. S. that the only plausible explanation of the e B ects produced by exhaus- Theory of Chemical Reactivity. F. 0. RICE ( J . arner. Chem. Sm. 1923 45 2808-2820).-A theoretical paper in which an ex- planation for the high temperature coefficient of chemical reactions is offered; it is assumed that the law of mass action in its classical form is true and that its apparent failure is due t o usingC ENERAL AXD PIiYSICdL CEENISTRY. ii. 99 stoicheiometric equations which do not represent even approxi- mately the reactions taking place in solutions. When the ordinary stoicheiometric equations are replaced by equations representing more nearly what occurs it has been shown that certain molecules are connected with an equilibrium constant in such a way that their concentrations vary with the temperature.These are referred to as active molecules and it is due to these that “ slow ” reactions have a high temperature coefficient. The hypothesis predicts that chemical reactions will fall into comparatively few classes each class having a characteristic temperature coefficient. In this hypo- thesis the assumption is made that the non-hydrated hydrogen- and hydroxyl-ions are the catalytically active particles and this leads to the conclusion that stoicheiometrically neutral water is distinctly alkaline catalytically and it is not until the hydrogen-ion concentration has a pE value about 5 that the concentrations of the non-hydrated ions become equal and the catalytic activity is a t a minimum.J. F. S An Extension of the Equation for the Velocity Constant of a Unimolecular Reaction. H. J. PRINS (Chem. WeehNud 1923 20 686-689).-Starting from the assumption that in the ideal gas the relation between the atomic energy and the combining energy is the same for the greater proportion of the individual molecules but in a few individuals may vary from the average value and combining the mathematjical probability of any given configuration so deduced with the relation between the stability and entropy of the system it is possible to arrive a t Boltzmann’s equation X=klog W+A where X is the entropy and W the probability of the given configura- ation at a given instant; then from the assumption that the small proportion of activated molecules take up radiant energy from the medium as expressed in the photochemical law of Einstein it is possible to form a conception to account for the relation v=vN for the velocity of dissociation of simple molecules in the gaseous The Rate of Hydrolysis of Methyl Acetoacetate.G. LJUNGGREN (Ber. 1923 56 [B] 2469-2471).-The hydrolysis of methyl acetoacetate by sodium hydroxide has been re-examined since the velocity constants observed by Goldschmidt and Oslan (A. 1900 i 132,373) and Goldschmidt and Scholz (A. 1907 ii 244) diminish rapidly for a reason which these authors have not been able to explain. A source of error in Goldschmidt’s experiments is caused by the ketonic hydrolysis of methyl acetoacetate which pro- ceeds fairly rapidly in acid solution and hence commences rapidly when the alkaline solution is introduced into an excess of acid in order to stop alkaline hydrolysis.The main cause of error how- ever lies in the unsuitability of phenolphthalein for the titration in the presence of the markedly acidic methyl acetoacetate. The previously observed irregularities disappear when phenolphthalein is replaced by Bromothymol-blue. The velocity constant is 0.01211 this value being lower than that observed by Goldschmidt. phase. s. I. L. H. W.ii. 100 ABST&AC!FS OF CHEIk5CA.L PAPERS. The Formation of Aniline Black a BimolecuIar Reaction. J. PICCARD and F. DE MONTMOUIN (Helv.Chirn. Act% 1923 6 1021-1029).-The oxidation of aniline by potassium dichromate and sulphuric acid to Aniline-black has been found to be a reaction of the second order (bimolecular). The experimental method used was the comparison of the rates of reaction a t different concentrations of aniline these being measured by the time taken for the solution to attain a given degree of opacity. It might be supposed that there may be a rapid unimolecular reaction a t first as suggested by Gold- schmidt (A. 1920 i 226) followed by a measurable bimolecular reaction but this suggestion is disproved by the recovery of un- changed aniline from solutions in which oxidation has been cut short. The reaction velocity increases with increasing acidity but the order of the reaction is not affected.The question is complicated by the discovery that the oxidation of aniline to Aniline-black is autocatalytic. If the velocity at any moment is proportional to the concentration of aniline present and to the amount already oxidised which is also proportional to the initial amount of aniline then the observed reaction velocity is a t least proportional to the square of the aniline concentration. The reaction is then unimolecular in Goldschmidt’s sense but bimolecular from the point of view of reaction velocity. It is impossible to draw conclusions regarding the intermediati products fiom the reaction velocity. E. H. R. Second Report of the Committee on Contact Catalysis. W. D. BANCROFT ( J . Physical Chem. 1023,27 Sol).-A review of the experimental work done during the last two years.Catalytic Metals. J. PICCARD and E. THOMAS (Helv. Chim. Acta 1923 6 1044-1045) .-The precipitate obtained by reducing copper sulphate with a chromous salt contains when freshly pre- pared 98.9% of copper. It is therefore essent4ially metallic copper not cuprous oxide as stated in Abegg’s handbook. A very active form of silver is obtained by reducing a solution of silver perchlorate with a solution of chromous acetate in perchloric acid. It forms a white powder d 1.7 containing 99.6% Ag and is twice as active as “ molecular ’’ silver prepared by the action of zinc on silver chloride. The activities were compared in the catalysis of the decomposition of chromous chloride by the reaction 2CrC12+2HC1 = 2CrCl,+ H,. A catalytically active colloidal palladium solution is obtained by dissolving palladium hydroxide in glacial acetic acid and reducing with hydrogen It is valuable for promoting reduc- tions with hydrogen.Hydrogenation of Fats. I. Influence of Various Sub- stances on the Nickel Catalyst. G. KITA and T. MAZUME (Mem. CoZZ. Sci. Kyoto 1923 3 81-94).-The influence of the addition of aluminium oxide magnesium phosphate magnesium oxide calcium borate calcium phosphate sodium carbonate stearic and palmitic acids and moisture respectively to the nickel cakalyst was studied as regards the volume of hydrogen absorbed and the E. H. R.GENERAL AHD PHYSICAL CHEMISTRY ii. 101 rate a t which this absorption took place. The effect of these addi- tions was found to depend on the conditions under which the mixing was carried out.In most cases optimal proportions of the mixture exist which give the maximum rate of absorption of hydrogen this optimum mixture depending on the conditions under which the mixing was effected. In most cases a much greater improvement in the activity of the catalyst was obtained if the exciting substance was added to the nickel oxide before its reduc- tion this being especially the case with aluminium and magnesium oxides and calcium borate. In the case of calcium phosphate an exceedingly active catalyst was obtained by adding 12% of calcium phosphate to nickel carbonate and reducing the mixture. The addition of stearic and palmitic acids to the oil to be hydrogenated was found to have a beneficial effect on the rate of hydrogenation especially the former acid in quantities up to 10% of the oil.Sodium carbonate was found to have a retarding effect on the catalyst in all the proportions studied. The oil used in all the above experiments was soja-bean oil Tehed with sodium hydroxide and hydrogenation was carried out at atmospheric pressure and a t 170". The presence of moisture in the catalyst whilst not specially affecting the activity of a powerful catalyst was found to have a serious disturbing influence on a weak catalyst. This feature and the existence of optimum quantities of exciting substances suggests an analogy with the action of enzymes. H. C. R. Heterogeneous Catalysis. L. GURWITSCH (2. physikd. C'henz. 1923 107 235-248).-The author describes a number of cases of heterogeneous catalysis from which he draws the conclusion that such catalysis is best explained by adsorption and the formation of adsorption compounds.There is no need to assume the formation of definite intermediate compounds. Among the examples quoted are the polymerisation of pinene in the presence of partly dehydrated floridin (Florida earth). In this reaction a considerable amount of beat is evolved and the products consist of camphenes and polyter- penes. The amount of polyterpenes produced is less the lower the temperature a t which the reaction take place. The amount of pinene changed is greater the smaller the water content of the floridin down to 6.19y0 of water a t which point 99% of the pinene is changed and of this 4.9% is converted into polyterpenes.The greater the water content of the floridin up to 30% the greater is the percentage of the changed pinene converted into polyterpenes. The mechanism of the reaction is therefore the formation of poly- terpenes as primary product due to the adsorption of pinene by the floridin; the polyterpenes are then broken down by the heat of the primary reaction with the formation of isomeric monoterpenes. The water of hydration of the floridin takes a part in the reaction and the active force which brings about the polymerisation is the force of attraction between the pinene and the strongly dehydrated floridin. Pa,rtly dehydrated " grown " alumina prepared according to Wislicenus's metthod catalyses the reaction between carbon disulphide and water giving hydrogen sulphide and carbon dioxide,ii.102 .ABSTRACTS OF CHEMICbl; PAPERS. and in the same way ethyl chloride and water give ethyl alcohol and aluminium chloride. Precipitated alumina whether moist or partly dehydrated or moist "grown " alumina have no such action. The reaction is explained by the adsorption of the carbon disulphide or ethyl chloride by the alumina which is thereby brought into intimate contact with the water and so into reaction. The practice of coating glass vessels with paraffin wax to reduce the decomposi- tion of hydrogen peroxide is quoted and in this connexion it is deduced theoretically that since high molecular paraffins have a greater power of adsorption than lower molecular paraffins the former will catalyse the decomposition of hydrogen peroxide more than the latter and also organic compounds containing oxygen having a greater physico-chemical energy have a greater adsorptive power than the paraffins consequently they catalyse the decomposition of hydrogen peroxide more than the paraffins.It follows therefore that adsorptive power and catalytic power run parallel. These conclusions are confirmed experimentally for it is shown that the catalytic power with respect to the decomposition of hydrogen peroxide increases in the order paraffin m p. 52" palmitic acid paraffin m. p. 88" cerotic acid. Other cases which also show the importance of adsorption in heterogeneous catalysis are quoted. J. F. S. Possible Reconciliation of the Octet and Positive-Negative Theories of Chemical Combination. W. A. NOYES (J. Amer. Chem. Soc. 1923 45 2959-2961).-A discussion of what happens to the electrons on the separation of two atoms from one another. The two alternative views namely that one electron remains attached to each atom in which case both atoms would be electro- neutral and that both electrons remain with one atom making it electro-negative whilst the other is electro-positive are considered. It is shown that an atom does not always separate from a compound in the same electrical condition as it enters it. H. G. GRIMM and K. F. HERZFELD (Physikul. Z. 1923 24 486-488).- The authors discuss the question of how loosely a valency electron mist be associated with the nucleus in order that it may become detached in a chemical reaction. The heat of formation of a metallic compound is regarded as numerically equivalent to the algebraic sum of the heat of sublimation of the metal the heat of ionisation of the vapour and the heat of dissociation of the kation together with the energy due to electronic affinities and that associated with the ionic lattice. The respective heats of formation of the fluorides of the elements in the third period of the periodic classiiication are deduced in this manner and attention is directed to an analogy be- tween the values so calculated and the respective heats of ionisation of the corresponding elements. Deductions are then made as to the possibility or otherwise of the production of the respective fluorides in which one two three or four fluorine atoms are associated with a single positive atom as the result of chemical reaction. J. F. S. Chemical Valency from the Point of View of Energy. J. S. G. T.INORGANIC CHEMISTRY. ii. 103 The Construction of Simple Micro-balances. H. 6. DENHAM ( J . T a t . Inst. 1924 15 T. 10-13).-A short-beam quartz fibre micro-balance is described; it is intended for use with a graticuled reading telescope and a graduated scale or by it mirror galvanometer method and has a sensitivity of 2 x lo4 mg. with maximum load about 1 mg. A short review is given of the subject of micro- balances generally. J. C. W.

ISSN:0368-1769    

DOI:10.1039/CA9242605077

出版商:RSC    

年代:1924

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. Inorganic Chemistry. ii. 103 Composition of Chlorine Hydrate. A. BOUZAT and L. AZINI~ES (Compt. rend. l923,177,1444--1446).-Chlorine hydrate prepared in presence of liquid chlorine not water as the liquid phase has the formula C12,6H,0. A. L. MARSHALL and H. S. TAYLOR (Nature 1923,112,937-938).-In an attempt to test the validity of Nernst’s theory (A 1919 ii 208) of the wide deviation of the hydrogen-chlorine combination from Einstein’s photochemical equivalence law atomic hydrogen has been led into a mixture of hydrogen with chlorine and bromine respectively. The amount of hydrogen chloride formed appeared greatly to exceed that due to the atomic hydrogen present a result which would be anticipated from the theory. Electroisomerism The Constitutional Formula of Hypo- sulphurous ’’ [Thiosulphuric] Acid and the True Thiosul- phuric Acid.J. PICCARD and E. THOMAS (Helv. Chirn. Acta 1923 6,1032-1036) .-The conception of the acid H,S,O as thiosulphuric acid OH*SO,*SH implies that it is a mixed anhydride of sulphuric acid and hydrogen sulphide just as chlorosulphonic acid is a mixed anhydride of sulphuric and hydrochloric acids. Its properties do not agree with this conception for it decomposes not into sulphuric acid and hydrogen sulphide but into sulphurous acid and sulphur in aqueous solution. It is shown that a t the temperature of liquid air in carbon dioxide solution sulphur trioxide and hydrogen sulphide combine to give what is presumed to be the true thiosulphuric acid. In this compound the sulphur takes the place of negative bivalent oxygen in sulphuric acid.Ordinary ‘‘ hyposulphurous acid ” (thio- sulphuric acid) must be an electronic isomeride of the true thio- sulphuric acid the additional sulphur atom being neutral. In the true thiosulphuric acid the central sulphur atom is sexavalent ; in the isomeride it is quadrivalent. The difference can only be expressed by co-ordinative formulae thus E. E. T. Mechanism of the Hydrogen Chlorine Combination. . A. A. E. I i so+srr -011 - jH’ H’ [;zsv?ll 1; -orxJ L-On -o= ‘‘ Hyposulphurous acid.” Thiosulphuric acid. E. H. R.ii. 104 ABSTRACTS OF CHEIKICAL PAPERS. The Existence of Free Thiosulphrrm'c Acid in the Presence .of Fuming Hydrochloric Acid and the Preparation of Alcoholic Solutions of Thiosulphuric Acid.J. CASARES GIL and J. BEATO (Ber. 1923 56 [B] 2451-2453).-1f a concentrated solution of sodium thiosulphate ( 3 - 4 drops) is added to fuming hydrochloric acid ( 3 4 c.c.) sodium chloride is precipitated after which the clear solution can be preserved without change for about an hour a t 15" ; it gives the reactions typical of thiosulphuric acid. An alcoholic solution of thiosulphuric acid is obtained by the action of dry hydrogen sulphide on lead thiosulphate (dried at 105") suspended in alcohol. The precipitated lead sulphide is filtered and excess of hydrogen sulphide removed from the filtrate by a current of air. The acid decomposes in the course of a few days at about 28" into sulphur and apparently pentathionic acid. A. GUTBIER [with A. FIECHTL] (KoEloid. Z.1923 33 334-337).-Relatively stable sols of selenium may be prepared by evaporating on the water-bath to a syrupy consistency an aqueous solution containing equimolecular quantities of selenium dioxide and dextrose and then adding one drop at a time of con- centrated ammonia taking care that the solution remains syrupy. After cooling and mixing with water reddish-brown sols are obtained which after a short time are stable and contain about 0.016 g. of selenium per 100 C.C. The stability of the sol is increased by the presence of a slight excess of dextrose. The sols are stable on boiling but on freezing they are completely and irreversibly coagulated if there is no excess of dextrose. The sols are sensitive to electrolytes. Glycerol sols can be prepared in the same way as the hydrosol and have similar properties.Ammonia Equilibrium. A. T. LARSON and R. L. DODGE ( J . Amer. Chem. Xoc. 1923 45 2918-2930).-The equilibrium values for the reaction N2+3H 2NH have been determined at 10 30 50 and 100 atmospheres pressure for the temperature range 325" to 500". The following values observed for the percentage of ammonia at equilibrium are recorded a t 10 atms. pressure 360° 7-35; 400" 3.85; 450" 2.04; 500" 1.20; 30 atms. pressure 350" 17.80 ; 400" 10.09 ; 450" 5-80 ; 500" 3-48 ; 50 atms. pressure 3N" 25.11 ; 400" 15.11 ; 450" 9.17 ; 500" 5.58 ; 100 atms. pressure N O " 24.91 ; 450" 16.35 ; 500" 10-40. Equilibrium constants have been calculated for each of the pressure-temperature conditions inves- tigated. These constants are found to increase with increase of pressure.By means of empirical formulze the percentage of ammonia at equilibrium has been calculated for a temperature range 200-1,000" and a pressure range 10-100 atms. The Reduction of Azoimide. J. PICCARD and E. THOMAS (Helv. Chim. Actu l923,6,1039-1040).-The reduction of azoimide by chromous chloride in acid solution takes place according to the equation HN3+H,=NH,+N (cf. Briner and Winkler A. 1923 ii 485). E. H. R. H. W. Colloidal Selenium. J. F. S. J. F. S.INORGANIC CHEMISTRY. ii. 105 Vapoxlr Pressure of Nitric Oxide. H. GOLDSCHMIDT (2. Physik 1923 20 159-165).-Particulars are given of the deter- mination of the vapour pressure of nitric oxide at temperatures between -148" and -181". The results indicate that at To (Abs.) the vapour pressure of the liquid phase (measured in mm.of mercury) is given by the equation log p=6.92669-0~010801T+1*75 log T- '778*13/T'. The corresponding equation for the solid phase is log p = 6*m69-O-005895T+ 1-75 log T-837-42/T. The occurrence of considerable association amongst the molecules of liquid nitric oxide is established. From the results the following values of physical constants relating to nitric oxide are calculated b. p. -151-13" ; triple point -163.21" ; vapour pressure a t the triple point 170.2 mm. ; latent heat of evaporation a t respective temper- atures -151-13" 3199 cal.; -155" 3230; -160" 3289; -163.21' (liquid) 3324; -163-21" (solid) 3863; -165" 3872 ; -168" 3885; -173" 3902; -177" 3912; -183" 3923; latent heat of fusion a t the triple point 539 cals.& 1%. Hydrofluosilicic Acid. 11. .C. A. JACOBSON ( J . Physical Chem. 1923 27 761-770 ; cf. A. 1923 ii 561).-Experiments are described which show that silicon tetrafluoride and water vapour do not react at temperatures between 30" and 125". Four types of experiment have been carried out with the object of ascertaining the condition of hydrofluosilicic acid in the vapour phase. In the first case air was passed through dilute solutions of the acid a t various temperatures and the resulting products passed through water for absorption. In the second and third cases strong solu- tions of the acid were distilled fist a t the ordihary temperature and then by boiling with various desiccating agents introduced in the stream of vapour. In every ,experiment where the water was removed from the vapour mixture no trace of hydrofluosilicic acid was obtained in the receivers. In the fourth case an attempt was made to liberate the acid from its sodium salt by means of concen- trated sulphuric acid and to condense the acid in a receiver cooled by ice and salt.No liquid condensed because the sulphuric acid removed the water from the gas mixture leaving the apparatus filled with silicon tetrafluoride. The vapour density measurements made by Baur and Glaessner (A. 1904 ii 119) on the gas obtained by treating barium silicofluoride with sulphuric acid indicate the complete decomposition of hydrofluosilicic acid into hydrogen fluoride and silicon tetrafluoride. All the above results indicate that hydrofluosilicic acid is a non-volatile acid like carbonic acid and sulphurous acid and cannot exist under ordinary conditions in the vapour state.A. RUTTI and E. BOGGIO-LERA (Hem. A c d . Lincei 1923 [v] 14 1257132).-The explanation advanced by Lo Surdo (A. 1921 ii 331) of the divergence of the results of Ramsay Collie Patterson and Masson (A 1914 ii 727,847) from those uf Merton (A. 1914 ii 726) S t r u t t (A. 1914 ii 201) and Piutti and C a b s o (A 19-20 ii 311) is not valid (cf. Baly Ann. Reports 1913 37; 1914 411 J. S. G. T. J. F. S. Diffusibility of Helium through Thuringian Glass.ii. 106 ABSTRACTS OF CHEMICAL PAPERS. fiince the amount of helium able to penetrate from the air into a discharge tube even one of large surface kept for many hours at 260" is about 1% of the quantity recognisable spectroscopically by the methods used by the above investigators.The velocity of d8usion of helium through Thuringian glass is proportional to the pressure and increases very rapidly with rise of temperatiire being apparently an exponential function of the latter. The Free Electron Characteristics of Sodium-Potassium Alloys. C. V. KENT (Physical Rev. 1923 [ii] 22 479485).- The free electron parameters of the sodium-potassium alloys have been calculated from optical data obtained by Morgan (ibid. 1922 20 204). The number of free electrons per atom is about 1.5 for all the alloys but with an indication of a minimal value of 1.2 for the one-third sodium alloy. The frequency of impact of a free electron with molecules (1 to 3 x 1014) increases linearly with increa.se of either constituent to a maximum for the compound NaK sup- posed to exist in the liquid alloys.Calculated resistivities agree with those experimentally determined. Displacement of Metals from Solutions of their Salts by Less Electropositive Elements. I. Replacement of Sodium and Potassium by Magnesium and Aluminium. F. W. BERGSTROM ( J . Amer. Chem. Soc. 1923 45 2788-2794).-AmaI- gamated aluminium reacts with sodamide in liquid ammonia solu- tion to form a definite crystalline compound sodium ammono- aluminate to which any of the following formulae may be given A1(NH2),*NHNa,NH3 ; Al(NH,),,NaNH ; Na[AI(NH,),]. This compound loses one molecule of ammonia when heated in a vacuum above 90". The equations for the reaction are shown to be Al+3Na(NH2) Z A1(NH2)+3Na ; Al(NH,),+NaNH,= Al(NH,),*NHNa,NH ; 3Na+ 3NH3=3/2H2+3NaNH,. The actions of potassamide on amalgamated aluminium and on magnesium are analogous in character.An explanation is given which depends on the fact that dilute solutions of the alkali metals in ammonia are salt-like in character. The initial stages may be regarded as metatheses although actually involving equilibria which suffer continual displacement because of secondary reactions. A solution of sodium in liquid ammonia reacts with amalgamated aluminium to form the same sodium ammono-aluminate mentioned above. Sodamide is probably first formed and this then reacts in accord- ance with the equations above The mercury of the amalgam does not play an essential part in the reaction. 111.System Water and the Chlorides and Carbonates of Sodium and Potassium at 2 5 O . N. System Water and the Sulphates and Carbonates of Sodium and Potassium at 25". W. C. BLASDALE ( J . Amer. Chem. Suc. 1923,45,2935-2946; cf. A. 1918 ii 231 ; 1920 ii 237).-Certain optical and crystallographic proper- ties of the hydrates of sodium carbonate and of the hydrate of the double sodium potassium carbonate have been determined which T. H. P. A. A. E. J. P. S. Equilibria in Solutions containing Mixtures of Salts.INORGANIC CHEMISTRY. ii. 107 can be used in identifying these compounds by means of the micro- scope. The solubility data necessary for the preparation of com- plete phase rule diagrams for the systems H,O-Na,CO,-KCl and H20-Na&03-K,S04 a t 25" have been determined. Triple Salts.F. E P H R A ~ (Helv. Chim. Acta 1923 6 920- 930) .-The important part played by space considerations in deter- mining the possibility of formation of complex compounds is well illustrated by the series of triple nitrites of which the best known member is the salt K,P~[CU(NO,)~]. The extent to which each of the constituent metals can be replaced by related metals is deter- mined by the atomic volumes of the metals. The copper (at. volume 7.1) can be replaced by nickel (6.6) cobalt (6-Q and iron (7*1) but not by any metal with greater atomic volume such as manganese (7.4) or zinc (9.2). The potassium (45.3) can only be replaced by rubidium (56.2) caesium (70.4) and ammonium not by sodium (22.9) or thallium (17.2). The lead (18.2) can be replaced only by calcium (25.2) strontium (32-6) and barium (36-3) save under exceptional conditions.When nickel with the amdl atomic volume 6-6 replaces copper it is possible to introduce cadmium (13.0) and mercury (14-1) in place of the bigger lead atom. Most of the known triple salts are derived from weak acids but one triple chloride 6KCl,CuC1,,3HgC1,,2H20 has been described (von BonsdorfT Ann Phys. Chem. 1834 33 81). The existence of this salt could not be confirmed but a new triple potassium copper mercuric chlmide 8KC1,CuCl2,4HgC4 was dis- covered. It separates from a hot aqueous solution of its components in yellowish-brown needles. It is not stable in the cold in contact with the mother-liquor Attempts to prepare similar salts contain- ing nickel or magnesium instead of copper or bromine instead of chlorine were unsuccessful.A triple chloride of another type KCuCI,,2KPbC13 was discovered however. It can only be obtained from a solution of its constituents in concentrated hydrochloric acid and forms microscopic brownish-yellow prisms. Another type of salt which was prepared containing three merent metals has the composition K,[CU(NO,)~,H,O] + BK..JHgCI,,H,O]. It crystallises in thick black prisms and is probably to be regarded as a mixture of its constituents possibly as a solid solution. The known potassium copper nitrite is found to have the formula K,[Cu(NO,),,H,O] instead of K,[Cu(NO,),]. The following new triple nitrites are described cclesium barium nickel nitrite Cs,Ba[Ni(NO,),] forms an orange-brown powder very sparingly soluble in water ; cmium lead wpper nitrite Cs,Pb[Cu(NO,),] sparingly soluble black microscopic crystals.A new ammonzum rnanganwe carbonate (NH4)&03,MnC03,4H20 microscopic prisms was also obtained The Fusibility of the Ternary System Sodium Fluoride- Calcium Fluorid+Aluminium Fluoride. P. P. FEDOT~EEV and W. P. ILJINSKY (2. anorg. Chem. 1923,129,93-107).-The examin- ation of the system AlF,-NaF (A. 1913 ii 324) has been completed and the investigation extended to the ternary system with calcium J. F. S. E. H. R.ii. 108 ABSTRACTS OF CHEMICAL PAPERS. fluoride the concentration triangle being fully worked out. The system NaF-CaF shows st simple eutectic a t 810" 6'7.5 mol.O/b NaF. Fusions of calcium fluoride with aluminium fluoride are only realis- able between the. limits 30 mol.% and 60 mol.% AlF ; the eutectic is at 820" 37-5 mol.yo AlF and there is a marked tendency to supercooling with formation of solid solutions of the components. The system NaF-AlF has two maxima one corresponding with cryolite 25 mo1.X NaF m. p. 1,000" which melts without decom- position the other with a compound with 40 mol.yo NaF which melts with decomposition a t 725"; the minima are a t 885" 86 mol.% NaF and 685" 53.4 mol.% NaF. The temperatures of invariant equilibrium for the ternary system are 780" 705" and 675" the minimum point for the space pyramid lying between the compositions NaF CaF AlF = 58.7 5.9 354 and : 56.5 8-3 35.2 rnol.% respectively; the diagram shows Crystal Structure of Sodium Chlorate.N. H. KOLEMEIJER J. M. BIJVOET and A. KARSSEN (2. PhysiE 1923,20,82).-Referring to the work of Kiby on the crystal structure of sodium chlorate (Ae 1923 ii 687) the authors point out that the calculation of the parameters relating to light atoms from the observed intensities of the higher orders of X-ray reflections making the approximate assumption that the reflecting power is proportional to the elec- tronic number and independent of the angle of deviation of the rays is unjustifiable. Vappur Pressures of Lithium Chloride Solutions at 20". B. F. LOVELACE W. H. BAHLKE and J. C. W. FRAZER ( J . Amer. Chem. Soc. 1923 45 2930-2934).-The lowering of the vapour pressure of water due to dissolved lithium chloride has been measured at 20" and in the concentration range of 0.1N to 1.ON.An improved method for removing air from the solutions before measuring is described. This consists in introducing the solution as nearly air-free as possible into the bulb which had previously been pumped air-free and rapidly distilling a small portion of the solvent a t the pressure of its vapour into a bulb containing phosphoric oxide. The observed lowering of the vapour pressure has been compared with the values calculated from freezing-point measurements and a difference of -0.015 to +0.014 mm. between the two sets of values found J. F. S. An Explanation of the Explosive Decomposition of Bleaching Powder and the Mode of its Decomposition at Higher Tern- peratures. s. OCHI ( J . Chern. Ind. Japan 1923 26 978-983).- When bleaching powder is heated above loo" the chlorine-forming oxygen-forming and chlorate-forming decompositions occur together.If it contains a comparatively large amount (e.g. 18-01 %) of water it is very rapidly decomposed a t temperatures above 100" and the chlorine-forming and the chlorate-forming decompositions predominate. In this case explosive decomposition may not occur but suoh a powder is unsuitable for storage. By decreasing the thirteen regions. s. I. L. J. S. G. T.INORGANIC CHEMISTRY. ii. 109 water content of the powder the mode of decomposition is changed to the oxygen-forming one which proceeds mildly a t first but advances suddenly when the temperature is raised a little higher than 150"; explosion then occurs. The decomposition may be expressed as follows OC1*CaCl,H,0=CaC12,H20+ 0+14,440 cal.The explosive decomposition may be brought about by external heating or by the accumulatioii of heat produced by auto-decom- position. K. K. The Reaction of Carbon Dioxide with Bleaching Powder. 8. OCHI (J. Chem. I n d . Japan 1923 26 1154-1161).-The action of carbon dioxide on bleaching powder is accelerated not only by the rise of the reacting temperature and the increase of the water content of the powder but also by the imperfection of crystallisatioii of the powder. The gas produced by the decomposition of bleaching powder is composed of chlorine only. On passing moist carbon dioxide or air containing carbon dioxide into bleaching powder at about 60" chlorine is produced; it is free from carbon dioxide when the velocity of the gas is well regulated.Chlorine containing a certain amount of carbon dioxide is purified in the same way. In making the powder with chlorine containing carbon dioxide it is concluded that the water content of the raw materials must be increased and the temperature of the bleaching chamber must be raised. K. K. W. L. BRAGG (Proc. Roy. SOC. 1924 [ A ] 105 16-39).-By X-ray analysis it is shown that the crystal structure of aragonite is based on the simple orthorhombic lattice. The cell the sides of which are of lengths 4.94 A. 7.94 d. and 5-72 8. contains four molecules of CaC03 and the symmetry is that characterising the space group &l6tL. The structure is built of calcium atoms and CO groups having a form almost identical with the CO groups in calcite. Calcium atoms are arranged on a distorted hexagonal close-packed point system intimately related in its dimensions to the distorted cubic close-packed point system associated with the calcium atoms in calcite.In aragonite the CO groups are arranged differently from the corresponding groups in calcite each oxygen atom being surrounded by three calcium atoms in the former crystal and by two only in the latter. Con- sidered as a whole the CO group lies between two groups of three calcium atoins in both crystals. A comparison of t'he observed int'ensities of reflection of the rays and calculated amplitude factors for aragonite shows that in accordance with the empirical law discovered by Sir W. H. Bragg in the case of calcite the intensity is proportional to the amplitude-factor and not to the square of the latter as suggested by theory.Twinning of aragonite crystals about the plane (1 10) is simply explained by the suggested structure. Hydration of Anhydrite. 11. G. WEISSENBERGER and B. SOINI (KoEZoid Z. 1923 33 290-296; cf. A 1923 ii 241).-The hydration of anhydrite has been investigated by measuring the VOL. CXXVT. ii. 5 The Structure of Aragonite. J. S. G . T.ii. 110 ABSTRACTS OF CHEMICAL PAPERS viscosity of suspensions of anhydrite in water a t 18" 30" 40" 50" and 62". It is shown that the addition of water to anhydrite proceed9 to a definite c!id value. The quantity of added water is dependent on the concentration and on the temperature but is independent of the size of the particles. The greater the concentra- tion and the lower the temperature the smaller is the amount of water added.The intensity of the combination with water achieved technically is approximately parallel with the internal friction of dilute suspensions measured viscosimetrically but not with the amount of water taken up. J. F. S. The Constitutional Formula of Barium Peroxide. J. PICCARD (Helv. Chim. d c t a 1923 6 1036-1038).-The strain t'heory renders it improbable that barium peroxide has the formula Ba<? whereas the double formula containing a six-membered ring Ba<Exg>Ba shoulcl represent a stable system. The ready formation of hariuin peroxide from barium oxide and mole- cular oxygen can be simply represcntecl without rupture of the oxygen molecule if the double formula be assumed thus Ba/'o--oNBa + Ba< O-O>Ba.The fact that sodiuiii per- oxide cannot be formed from sodium oxide and oxygen but only from sodium and osygen points t!o a similar oxidation mechanisin in this case Na+O~O+Na-+Na-O-O--Na. The mode of formation of many organic peroxides gives additional support to the theory. Crystal Structure of Magnesium Stannide. L. PAULING ( J . Amer. Chem. SOC. 1923,45 2777-2780).-Crystals of the inter- metallic compound magnesium stannide Rlg,Sn have been prepared and investigated by means of Laue and X-ray spectrum phot,o- graphs with the aid of the theory of space groups. This compound is found to have the calcium fluoride structure with d1,,=6-78&0.02~. The structure places eight magnesium atoms round each tin atom a t the corners of a cube and four tin atoms round each magnesium atom a t the corners of a tetrahedron.The closest approach of tin and magnesium atoms is 2.94*0-01 A. E. A. OWEN and G. D. PRESTON (Proc. Phpical SOC. 1923,36,49-65).-Particulars are given of an investigation by means of X-ray analysis of the respective structures of alloys constituting the a p p' 7 and E phases of the zinc-copper alloys. J. PICCARD and E. THOMAS (HeEv. Chim. Acta 1923 6 1046).-The solubility of cad- mium sulphide in dilute sulphurie acid is apparently greatly increased a t the boiling point that is the equilibrium in the equation CdSO4+H,S~CdS+H,SO4 moves to the left. It is now shown however that complete solution of the sulphide can be accomplished 0 7 0-0 0=0 E. H. R. J. F. S. X-Ray Analysis of Zinc-Copper Alloys.J. S. G. T. The Solubility of Cadmium Sulphide.INORGANIC CHEMISTRY. ii. 111 by passing a current of carbon dioxide through a suspension of the sulphide in cold dilute acid. The reaction is therefore subject to the usual mass-action laws. E. H. R. T. .W. RICHARDS and P. PUTZEYS ( J . Amer. Chem. Soc. 1923 45 2954- 2958).-The atomic weight of a sample of radioactive lead obtained from a mixture of minerals found in radium ore from the Belgian Congo was determined as 206.20 as compared wit,h a control sample of ordinary lead which gave a value of 207.18. Evidently therefore the lead in these minerals consists chiefly of uranium lead; and the minerals must have been formed long after the original deposit of the uraninite. J. F. S.Hardness of Lead-Thallium and Cadmium-Thallium Alloys. C. DI CAPUA (Atti R. Accad. Lincei 1923 [v] 32 ii 343-346).-The thermal diagram obtained by the author for the miscibility gap of the system lead-thallium confirms that given by Lewkonja (A. 1907 ii 261) and by Kurnakov and Pushin (A. 1907 ii 262) the gap extending over the region 6-23% of lead. The hardness diagram resembles the pressure of flow curve for these alloys (cf. Kurnakov and Schemtschuschny A. 1909 ii 855). Thallium increases the hardness of lead to a maximum a t 60-60~o T1 a minimum .being reached at about SOYO which is the saturation point; from 80 to 94% the course of the hardness curve does not correspond with the diagram of state. The hardness of thallium is increased by addition of lead to a maximum corresponding with the formation of saturated mixed crystals of lead in thallium.The hardness diagram for cadmium-thallium alloys agrees well with the fusion diagram and indicates a slight solubility of cadmium in thallium in the solid state. T. H. P. E. ,4. OWEN and G . D. PRESTON (Proc. Physical SOC. 1923,36,14-30).-By X-ray analysis it is established that a distortion of the respective lattices character- ising the atomic structures of solid solutions of copper-aluminium aluminium-magnesium and copper-nickel is produced when a solute atom replaces an atom in the lattice of the solvent. The eutectic alloy of aluminium and copper is shown to consist of CuAl and another substance. CuA1 possesses a simple tetragonal lattice of side 4-28 A. and axial ratio 0.562 whilst the atomic structure of CuAl resembles that of a salid solution of aluminium in copper but the distortion is considerably greater. Instability of Cupric Hydroxide.G. FOWLEY (Chem. News 1924 128 2-5).-The hypothesis of Weiser (A. 1923 ii 566) to account for the stabilising effect of dilute solutions of certain salts such as manganous sulphate on suspensions of gelatinous cupric hydroxide is held to be untenable because other solvents which exert a slight solvent action on cupric hydroxide such as sodium hydroxide accelerate its decomposition. The amounts of added salts were not trifling when their action is considered and varying molecular quantities were required to produce the same effect. Atomic Weight of Lead from the Belgian Congo. X-Ray Analysis of Solid Solutions.J. S. G . T. 5 - 2ii. 112 ABSTRACTS OF CHEMICAL PAPERS. The author adduces experimental evidence to prove that no such continuous solvent action as Weiser imagines can possibly take place. Crystalline varieties of cupric hydroxide on being kept at the ordinary temperature gradually become discoloured the change being first noticeable after about two years. One sample at least twelve years old eventually went quite black. The crystalline hydroxide appears to pass very slowly through those changes which are so rapid in the gelatinous variety that the intermediate stages are not seen. In each case the changes are accelerated by soluble hydroxides. The crystalline variety must therefore be regarded as a highly stable intermediate form in a state of suspended transformation.It is considered that the gelatinous copper hydroxide used by Weiser contained adsorbed or combined sodium hydroxide which was effectively removed by the hot salt solutions added as insoluble basic salts. The stabilisation described therefore consisted in removing a catalyst and in allowing the unstable gelatinous substance safely to pass into the more stable crystalline form. In every case in which stabilisation was successful a substance was added which wculd very thoroughly remove a soluble base. Sodium sulphate and suspensions of colloidal metallic oxides however showed no stabilising power. Chemical Constant of Mercury. F. SIMON (2. physikal. Chem. 1923,107,279-284).-The atomic heat of mercury has been measured a t temperatures betweeen 9' and 14" Abs.and the following values have been obtained 9-78" 1.107; 10.17" 1-151 ; 10.89' 1.244 ; 11-09' 1.284 ; 12-35' 1.443 ; 12-55' 1.482 and 13-35" 1.570. These values are expressed by the equation Cp=$ Debye function (l20)+ Einstein function (25)+21.10-5!PT.:''3. The chemical constant of mercury has been calculated to + 1.950 with a maximum error of O-OSY,. H. C. R. This value is 0.084 larger than the theoretical value. J. F. S. Ebullioscopy of Double Salts of Mercuric Chloride with Alkali Chlorides. P. BOURION and E. ROUYER (Compt. rend. 1924 178 86-88).-The proof (A. 1923 ii 568) that mercuric chloride exists in solution partly as treble molecules is taken into account in connexion with the ebullioscopic determination of the molecular weights of sodium potassium and ammonium mercuri- chlorides (cf.A. 1923 ii 534) which are shown to be of the type MCl,HgCl or M[HgCl,]. If the association of mercuric chloride is ignored the results lead to the formula BMCl,HgCl,. E. E. T. Complex Sulphates of Quadrivalent Cerium and the Position of this Element in the Periodic Classification. V. CUTTICA (Gazzetta 1923 53 761-768).-The formuh of the two cerous-ceric sulphates show that these compounds may be regarded as derivatives of a hypothetical ceri-sulphuric acid H,Ce(SO,) originating from ceric hydroxide by replacement of the four oxygen atoms by four SO radicals. The assumption that this complex acid is present in sulphuric acid solutions of ceric sulphate finds support in the compositions of the double compounds formed by ceric sulphate with sodium and thallous sulphates.No tendencyIN'ORGANIC CHEMISTRY. ii. 113 to unite with ceric sulphate is however observed with lithium sulphate and the double silver compound 10Ce(S0,),,6Ag,S04 is totally different from those given by sodium and thallium. A solution containing bismuth sulphate which is isomorphous with the sulphates of the rare earths deposits according to the conditions one of the three compounds (1) Ce~(S0,),(Ce1=,Bi)H,12H,0 (2) Ce( SO,),,Bi( OH)SO,,SH,O and (3) Ce( S04),,2Bi,( SO,) 15H,O. Compound (1) contains always little bismuth the presence of which is due to the solubility in the solid state of bismuth sulphate in cerous sulphate ; it forms orange bipyramidal prisms belonging to the hexagonal system and similar in every way to those of the acid sulphate Ce1V(S04)4,CeIIIH 12H,O.Compound (2) crystal- lises in long cedar-yellow needles and compound (3) in long yolk-yellow prisms. The question of the position to be assigned to cerium in the periodic system is discussed and it is considered that the weight of the evidence favours the view that this metal belongs to the first sub-group of group IV. That cerium should be placed in the same column as thorium is indicated by the fact that cerium and t'horium sulphates form mixed crystals. As a general rule it is indeed found that isomorphism exists between the salts of the lowest oxide of the heavy metal occupying the lowest position in each group and those of the element of the first sub-group of the preceding group.With organic bases as with silver and bismuth the hypothetical acid H4Ce(S0,) forms double or complex salts with constitutions varying according to the nature of the base. Only with strong bases does normal salification occur. [With L. BONAMICI.]-I~ addition to those described above the following salts have been prepared Ce(S0,),,2Na2SO orange-yellow prismatic crystals ; Ce(S04),,2T1,S0 deep orange-red prismatic crystals ; with guanidine sulphate 2Ce(SO,),NH:C(NH,),,O*5H,SO 10H,O elongated yellow prisms ; Ce2(S04),,5CO(NH,),,H,S0 amher- yellow crystals . T. H. P. Double Sulphites of Cerium Lanthanum and Didymium with the Alkali Elements. V. CUTTICA (Gametta 1923 53 769-772).-According to Grossmann (A 1905 ij 326) the sul- phites of cerium lanthanum and didymium exhibit no tendency to form molecular compounds with sulphites of the alkali metals but the author finds that such double sulphites are readily obtainable under suitable conditions.If excess of an alkali metal sulphite is added to a solution of the hydrogen sulphite of the rare earth metal and the liquid subsequently heated on a water-bath in a flask connected with a water pump so that air is largely excluded the double sulphite separates as a microscopic powder which is highly stable in the air but undergoes gradual oxidation to sulphate if suspended in water. In this way were prepared cerium potassium sulphite Ce2(S0,)3,K,S0,,4H20 ; cerium ammonium sulphite 2Ce,(S0,),,3(NH4)2SO ; 6"ii. 114 ABSTRACTS OF CHEMICAL PAPERS. cerium sodium sulphite Ce( S0,),,Na2S03,2H20 ; lanthanum potassium sulphite 2La2( SO3),,3K2SO,,~H2O ; lanthanum ammonium sulphite La,(SO,) (NH,),S03 ; didymtum potassium sulphite If in the above method of preparation a deficit of sodium sulphite is employed the cerium sodium sulphite 3Ce2(S0,)3,2Na2S0,,2H20 is obtained.T. H. P. Di2( SO,) K2S 0,,4H20. Ternary Alloys of Aluminium Copper and Magnesium. BUNTARO OHTANI ( J . Chem. Ind. Japan 1923 26 427448).- The author has studied that part of the ternary system containing alloys of which the copper content extends up to 13o;d and magnes- ium content to 147;. The liquidus of these alloys is depressed with increasing copper and magnesium content and the liquidus surface of the system slopes downwards from the aluminium corner. The solubility of magnesium and of copper in aluminium decreases according to the increasing content of copper and magnesium respectively.For example in the presence of Syo of magnesium the maximum solubility of copper is reduced from 6% to 374. The alloys of composition within the limit above described form a homogeneous solid solution ( a ) but the alloys of a composition beyond this limit have two arrest-points on these cooling curves and show a duplex structure consisting of a and an eutectic (a+p) on the cooling curve ingot. This eutectic surface slopes downwards from the Al-Cu binary eutectic line to the A1-Mg alloy side. Tensile tests and measurements of Brinell’s hardness and specific gravities on chill and sand castings were applied. The hardness increases slowly with copper content and rapidly with magnesium content within the limit of l:/o magnesium then slowly increases.The specific gravity increases linearly with copper content and decreases linearly with magnesium content. If the ratio of magnesium and copper is 5 6 the specific gravity remains constant. K. K. Manganese Dioxide in the Catalytic Oxidation of Carbon Monoxide. W. A. WHITESELL and J. C. W. FRAZER ( J . Amer. Chem. Xoc. 1923 45 2841-2851).-Manganese dioxide which has a great catalytic activity in the oxidation of carbon monoxide at temperatures as low as -9O” may be prepared (a) by the decom- position of potassium permanganate with concentrated nitric acid ( b ) by treating Prbmy’s oxide with concentrated nitric acid diluting and washing (c) by the oxidation of manganous sulphate with potassium permanganate in nitric acid solution and ( d ) by thc oxidation of precipitated manganous hydroxide.Analytical results show that the amount of impurities such as adsorbed alkali plays an important part in the activity of these catalysts. Experiments show a considerable temperature interval between the points required to oxidise hydrogen and carbon nionoside by these samples of active manganese dioxide. Carbon monoxide adsorbed by nian- ganese dioxide is desorbed as carbon dioxide. It is suggested that the mechanism of the oxidation of carbon monoxide consists in the adsorption and simultaneous Oxidation hy thc manganeseINORGANIC CHEMISTRY. ii. 116 dioxide followed by desorption of the carbon dioxide and re- oxidation of the catalyst.Mechanism of the Reduction of Permanganate and its Physico-chemical Basis. VII. The Reduction of Manganate by Formaldehyde. J. HOLLUTA (2. .;l~ysikuZ. Chem. 1923 107 249-269; cf. A. 1923 ii 864).-A continuation of previous work in which it is shown that the reduction of inanganate by formalde- hyde takes place with the intermediate formation of forinate-ions and consequently is a reaction which takes place in two stages. The order of the reaction has been determined by two methods and the influence of the concentration of the participating species on the velocity of the reaction has been investigated. I n keeping with the theory of successive reactions it ir found that tJhe velocity coefficient of the second order calciilated on the basis of the equation 2Mn0,”+H*CHO=2MnO2+CO,”+2OH’ exhibits a tendency to decrease whilst that calculated on the basis of the equation MnOql’+ H*CHO=MnO,+HCO,’+OH‘ shows a tendency to increase.In consequence of the great difference of velocity of the reduction by formaldehydc and by formates the velocity coefficient calcu- lated on the second equation given above comes very close to the true coefficient. The connexion between the alkalinity of the solution and the velocity coefficient has also been studied and it is found that the latter as a first approximation is inversely propor- tional to the square root of the hydroxyl-ion concentration and also directly proportional to the eighth root of the partial pressure of the oxygen liberated by the manganate. Small divergences from these relationships are explained.The influence of the hydroxyl-ion on the molecular condition of the formaldehyde in its connexion with the reduction of the inanganate is discussed. The mechanism of the reduction is represented by the scheme 2[Mn04”+3H20= Mn(OH),+20H’+ 01 O+H*CHO + OH’=HCO,’+H,O (rapid re- action measured) ; 0 +HCO,’ + OH’ ==CO,” +K,O. Slow Coagulation of Concentrated Ferric Oxide Sols to Reversible Jellies. E. SCHALEK and A. SZEGVARI (KoZZoid Z . 1923 33 326-334).-Concentrated ferric oxide sols set on the addition of definite concentrations of electrolytes to coherent jellies which on shaking become again liquid and then again set; this process may be repeated indefinitely. On changing the con- centration of electrolyte the sol and gel undergo the usual floccu- lation.The time necessary for the re-solidification of the jelly is a reproducible quantity. The velocity of solidification increases rapidly with the temperature and its logarithm is proportional to the temperature ; it also increases rapidly with the concentration of the added electrolyte; the logarithm of the velocity is also pro- portional to the concentration. Consequently the process is to be regarded as a slow coagulation. The solidification process is sensi- tised by alcohol. In comparison with the sol the liquefied gel shows an increased displacement elasticity. Ultramicroscopic examination of the resolidification shows that the particles do not come closer together and there is no formation of secondary particles. Similar J. F.S . J. 3’. S. 5”-2ii. 116 ABSTRACTS OF CHEMICAL PAPERS. results have been obtained with zirconium scandirim and aluminium hydroxide sols and with stannic oxide sols. Pharmacological Investigations on Iron. I. Colloidal Ferrous Sulphide prepared in Presence of Gelatin. L. SABBATANI (Atti R. Accnd. Lincei 1923 [v] 32 ii 326-330).- Colloidal ferrous sulphide solutions prepared from ferrous sulphate and sodium sulphide in presence of gelatin are highly stable and serve well for pharmacological experiments the gelatin and sodium sulphate they contain being without disturbing effect. The most stable and most highly disperse solutions are those containing 0.05 g.-mol. of ferrous sulphide per litre and 5% of gelatin. Such solutions set hard and must be liquefied in warm water and used when tepid; they readily undergo oxidation which may be pre- vented by covering the surface with a layer of vaselin oil or better paraffin wax.If great care is taken they withstand sterilisation in steam and they may be diluted with water which has been thoroughly boiled and then cooled. Oxidation which is facilitated by heating or diluting the solutions proceeds in accordance with the equation 2FeS + 3 0 =Fe,O3+S2. T. H. P. Double Halides of Cobalt Bases. F. EPHRAIM and P. MOSIMANN (Helv. Chim. Acta 1923 6 1112-1132).-The halides of cobaltammine bases do not form double salts with other halides with such readiness as was expected. As far as could be ascertained double salts were only formed with salts of zinc cadmium mercury and lead and in the case of luteo-salts with antimony and bismuth trichlorides.In the case of both luteo- and roseo-salts zinc forms a double chloride cadmium a chloride and bromide and mercury a chloride bromide and iodide; there is thus a diminishing tendency to form double salts as the atomic weight of the halogen increases. Flavo-salts and croceo-salts do riot form double salts with zinc but both do so with mercury and thc flavo-salts form a double chloride and bromide but not an iodide with cadmium salts The complexity of the salts increases with the atomic weight of the heavy metal; thus the luteo-chloride combines with lZnCl 2CdC12 3HgCl or 4PbC1,. The following new compounds are described Luteo-salts.-Two hc~arnmi?zecobalti-cadmium chlorides were obtained both microcrystalline powders [Co (NH,) 6]c137 2CdC1,,31-120 and [ Co (NH3)6]C'j,,CdC1,,H20 ; the double bromide [Co(NH3),]Br,,3CdBr2,3H20 forms very thin flat rectangular tablets.Hexamminecobalti-zinc chloride [Co(NH,),]C1,,ZnC12,H,? forms lustrous apparently hexagonal prisms. Two hexamm%necobalti-mercuric bromides were obtained [Co (NH,) 6]Br3,3HgRr microscopic needles and glistening rectangular leaflets. The iodide corresponding with the second bromidc has been previously described; there was also obtained [ Co (NH,) 6]13. 3Hg12 6H20 in well-f ormed microscopic crystals. J. F. S. [Co(~'H,),]Br,,HgBr A cklorocyanvde of the composition 2[Co(NH3) JC13 5Hg (CN)z,H,O,INORGANIC CREMISTRY. ii. 117 forming glistening six-sided leaflets was also obtained. Two hexamminecobalti-lead chlorides were obtained ; forms long hairy needles and [CO(NH,)~]C~~,~P~C~ extremely thin six-sided leaflets showing all colours.Three bromides are described [Co(NH,),]Br,,4PbBr2,2H2O forms glistening four-sided leaflets ; ~ [ C O ( N H ) ~ ] B ~ ~ P ~ B ~ ~ forms long glistening orange- brown needles and [Co(NH,),]Br,,PbBr needles. Ilexammine- cobalti-antimony chloride [CO(NH,)~]C~~,S~C~,,H,O forms a pale yellow precipitate ; the bismuth compound is similar but anhydrous. Roseo-salts.-The composition of aquopentamminecobalti-zinc chloride is doubtful but approximates to [CO(NH,)~H,O]C~,,Z~C~~. The cadmium salt aggregates of red microscopic prisms has the composition [Co( NH,)~5H,0]C1,,2CdC1 3H20. The double bromide forms dark red glistenlng plates ~[CO(NH,)~H,O]B~,,~C~E~,.Two aquopentamminecobalti-mercuric bromides were obfamed bright red microscopic star-shaped aggregates of needles and [Co(NH3),HzO]Br3,3HgBr fine needles or a dull rose crystalline powder. The corresponding iodide appears to contain Co Hg= 1 1. Flavo- and croceo-salts.-trans-Dinitrotetrammine( croceo)cobalti- mercuric chloride forms yellow microscopic four-sided plates or needles [CO(NH,),(NO~)~]C~,~H~C~~,~H,O. Two mercuric chlorides of the flavo-(cis)series were obtained [Co(NH,),(N02),]C1,2HgC1 long yellowish- brown needles and 2[ Co ( NHp)4(N02)2]Cl,HgCl similar crystals. Similarly one double bromide of the trans- series was obtained 2[Co(NH3),( N0,),]Br,3HgBr2 microscopic rectangular leaflets and two of the cis-series felted microscopic yellow needles and the second containing potassium bromide ~[CO(NH~)~(NO~),]B~,H~B~~,KB~ needles.The double iodide of the croceo-series forms dask yellow six-sided tablets Co Hg=3 2 and of the flavo-series bright yellow needles of the same composition. cis-Dinitrotetrammine(flaz.o)cobalti- cadmium chloride [CO(NH,),(NO,)]C~,C~C~~ forms fine bundles of needles and the corresponding bromide Co Cd=2 1 long brown needles. Corresponding croceo-cadmium salts were not obtained. [Co(NH3)61C13,PbC1~ [Co(NH3)5HzOIBr3 HgBr [Co(NH,),(NO,),IBr,2HgBr E. H. R. Molybdovanado-arsenates and Tungstovanado-arsenates (Hetero-tri-arsenates). G. CANNERI (Gazxetta 1923 53 773- 778).-The compounds here described have been prepared by the following methods the solutions in all cases being kept acid (1) By means of solutions containing a small proportion of an arsenate together with vanadic and molybdic (or tungstic) acids ; (2) by addition of vanadic anhydride to solutions of molybdo- arsenates or tungsto-arsenates; (3) by addition of arsenic acid to solutions containing molybdates (or tungstates) and vanadates.The composition of the complex compound varies with the con- centration and acidity of the solution.li. 118 ARSTRSCTS OF CHEMICAL PAPERS. The variety of the ratios in which combination occurs between the constituent oxides in these compounds would appear to indicate that many of the compounds are mere isomorphous mixtures of far simpler true compounds. On the other hand however from the very small and but slightly variable proportions of arsenic present it may be assumed that the miscibility is effected between groupings of which the arsenic constitutes the central nucleus.The typical heterotri-arsenates may thus be represented by the annexed scheme in which R' represents R ' P S ( ~ ~ ~ ? ~ ~ ) ' ]nH20 six (three) atoms of an alkali (alkaline- (R 207)Y earth) metal R" vanadium and R"' molybdenum or tungsten. Only in certain cases do the salts now described approximate to this hypothetical scheme. Analysis of these compounds presents difficulties means for over- coming which are described (cf. Friedheim Decker and Diem X. 1905 ii 764). Three ammonium arsenomolybdo~anadates have been prepared 6(NH,),0,As20,,l 1Mo0,,5V205,50H,0 an orange-yellow micro- crystalline precipitate ; 5 (NH,),O As,O ,,20Mo 0 3V,O ,,50H,O a yellow microcrystalline precipitate ; 11 (NH,)20,~As,05,25M003,4V205,96H,0 a red powder.Two barzum arsenomolybdocanadates 15Ba0,As,0,,26M00,,3V~05,62H,0 and 7Ba0,As205,33M003,4V,0,,34H,0 a yellow precipitate. Thall- ium arsenomolybdoranadate 3T1,0,As20,,32M00,,5V205,45H,0 forms a yellow precipitate ; ammonium arsenotungstocanadate 1 8(NH,),0,As,05,2 1 W 0,,4V205 13H,O red prismatic crystals ; thallium arsenot ungstocanadate 6T1,O,As2O5,2 1 W O,,5V,O5 1 3H,O a red powder ; and barium arsenotungstocanadate 6Ba0,As,05 17WO,,Ci~V,O,,40HZ0 small blood-red octahedra. T. H. P. Molybdovanadates. G. CANKERI (G'axxetta 1923 53 779- 794) .-The composition of the molybdovanadahes varies with the conditions under which they are formed particularly with the acidity of the medium and with the temperature of crystallisation.The author finds that the electrical conductivity a t 30" of solutions of sodium metavanadate acidified with increasing proportions of acetic acid varies continuously the condensation of the molecules of vanadic acid being thus a continuous function of the concentra- tion of the acetic acid; a t tlhe same time the colour changes gradually from yellow to orange-red. In view of the fact that dissolution of molybdic anhydride in solutions of metavanadates constitutes a met'hod of preparing the molybdovanadates the author has commenced an investigation into the systems NH4V0 MOO KVO MOO and NaVO MOO at different temperatures. The results a t present available show that within the limits imposed by the value of the solubility of molybdic anhydride in solutions of the metavanadates compounds of two types differing sharply in their physical properties are formed. These crystalhe respectively in large orange-red prisms,INORGANIC CHEMISTRY.ii. 119 and in yellow silky needles or sometimes in pulverulent form. One and the same solution may give both red and yellow crystals either together or successively in either order. The value of the ratio V,O MOO varies gradually in the red crystals from 3 1 to values corresponding with the maximum percentage of vanadium this approaching the proportion occurring in polyvanadates. The ratio changes suddenly in value for the yellow crystals which are poorer in vanadium. The various red crystals appear to consist of isomorphous mix- tures but the isomorphogenous terms cannot yet be defined neither can their chemical natures be established ; it is however possible that they consist of polyvanadates and polymolybdates.Along with these isomorphous mixtures there exist certain well-defined compounds which are obtained under definite conditions. With these com- pounds difliculty is encountered in distinguishing between combined water and water of crystallisation but the author regards them as heteropolyaquates and ascribes to them formulae based on the hypothesis of Rosenheim (A. 1911 i 109 265 ; ii 116 612 ; 1913 ii 59) and of Miolati and Pizzighelli (A. 1908 ii 595) to which preference is to be accorded over Prandtl's views (A. 1913 ii 61). according to the latter the molybdovanadates are double salts and should hence be completely dissociated in solution ; in sufficiently dilute solution therefore fractional precipitation of the dif€erent constituents should be possible but this is not found to be the case.w i t h R. RAGIONIERI.]-T~~ red crystals formed by the system NH,,VO MOO have the same colour and crystalline habit in all cases. The pale yellow silky crystals consist of the compound 4(NH,)20,5M00,,3V20,,10H20. The guanidine compound pre- pared from the latter has the composition 3 (CH6N,),0,4M00,,4V,0 10H20. w i t h G. WINSPEARE.]-T~~ pale yellow crystals formed by the system KVO,:MoO at 30" vary in composition according to the concentration of the solution; compounds of the formulz 4K,0,4M00,,3V205 7H,O and 3K,O 6Mo O SV,O 7H20 were separated.[With c. DELLA PERcoLA.']-In the system NaVO Moo the compound 4Na20,8M00,,3V205 10H20 occurs in equilibrium with the red mixed crystals until the molybdenum is increased to make the ratio V,O MoO,=l 2 and separates as a single pure phase when the molybdenum is still further increased in amount. The red salt 2Na20,Mo0,,3V,05,9H,0 yields the barium compound 3Ba0,Mo03,4V205 12H20 and the red salt 3Na20,2M00,,3V,05 1 2H20 the guanidine compound 3(CH6N,),O,N1oO3,V,O5. T. H. P. Electrolytic Preparation of Antimony-Copper and Antimony-Bismuth Alloys. A. MAZZUCCHELLI and L. TONINI (Atti R. Accad. Lincei 1923 [v] 32 ji 290-292).-Electrolysis of a hydrochloric acid solution of a mixture of antimony and copper the latter constituting 20-50% of the total dissolvedii.120 ABSTRACTS OF CHEMICAL PAPERS. metal results in a homogeneous brittle violet deposit containing a small proportion of antimony trichloride (cf. Mazzucchelli A. 1915 ii 19) and copper and antimony approximately in the propor- tions corresponding with the compound Cu,Sb. When the dissolved metal contains about 90% of copper the deposit formed is graphite- grey and highly brittle and contains a little antimony trichloride together with rather more copper and rather less antimony than the formula C'u,S b requires. Similar experiments with hydrochloric acid solutioiis of antimony and bismuth yield extremely brittle deposits containing the two metals in proportions varying in the same sense as the compositions of the original solutions.H. FREUNDLICH and 13. BAERW~ND (Kolloid Z . 1923 33,275-279).-The properties of the sol produced by shaking hydrated osmium dioxide with water have been investigated. It! is shown that the colloidal particles are negatively charged and migrate to the anode. The sol in its behaviour to electrolytes shows the behaviour typical of negatively charged sols that is the kation of the precipitating electrolyte is determinative of the action of the electrolyte. The precipitation values are in keeping with the valency rule. Observation of the sol by means of an ultramicroscope shows that the particles are not spherical. The addition of gelatin to osmium dioxide sols at first brings about coagulation which is followed by a protective action. In keeping with this it is found that on the addition of electrolytes gelatin exercises both a sensitising and a protective actian. The so1 is not coagulated at any concentrations by tannin and saponin. The migration velocity of osmium dioxide sols on the addition of gelatin increases almost up to the coagulating concentration ; it then falls and finally increases but there is no reversal of the charge of the sol. The osmium dioxide sol as such has no decomposing action on formic acid a t loo" but it is reduced to the metal sol and this brings about a rapid decomposition of the acid. 5. F. S. T. H. P. Some Properties of Osmium Dioxide Sol. Mineralogical Chemistry. Chalcophyllite from Chile. E. V. SHANNON (,4mer. J . Sci. 1924 [v] 7 31-36).-Emerald-green crusts of minute platy crystals from the Teniente copper mine near Rancagua gave CuO. Also,. As,O,. P,O,. SO,. SiO,. H,O(at 110'). H,O(over 110"). Total. 46.54 3.49 13.23 0.67 6.67 1-33 14.40 14-04 100.37 corresponding with 4Cu0 ~Al,O,,~As,O SO,,lOH,O. The refrac- tive indices of fresh material are ~=1*552 w = 1 . 6 1 8 ; these change when the material is exposed to air owing to loss of water ; and for material dried a t 110" they arc E-1.618 0=1.680. L. J . s.

ISSN:0368-1769    

DOI:10.1039/CA9242605103

出版商:RSC    

年代:1924

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry . i. 111 The Consumption of Oxygen in Sea Organisms when exposed to the Atmospheric Air. IVAN GJAJA (GZus. Amd. Xci. Belgrade 105 35-41).-Experiments with the sea-gastropod Trochus and the sea-urchin Echinocidccris show that both organisms are able to live a certain time when exposed to atmospheric air. The results were compared with the consumption of oxygen in some land-organisms (Helix nemoralis Rana esculenta). The amount of oxygen consumed was found to be respectively Trochus and Helix nemoralis 1.3 c.c. Echinocidaris 3.1 c.c. Rana esculenta 0.66-1.32 C.C. of oxygen per hour and per g. of dry organic substance. The experiments were made at approximately the same temperature. S. S. M. Physiology of Muscular Exercise. V.Oxygen Relation- ships in the Arterial Blood. H. E. HIMWICII and D. P. BARR ( J . Biol. C'hem. 1923 57 363-378).-During and after short periods of vigorous leg exercise (cf. A. 1923 i 623 624) there is a rise in the oxygen content oxygen capacity and oxygen saturation of arterial blood. The factors which cause this change are dis- cussed in detail and the conclusion is drawn that the increased diffusion of oxygen through the lungs is mainly responsible. With longer periods of exercise it is probable that there is it decrease in the oxygen content of arterial blood owing to the continued rise in the circulation rate. E. S. The Transport of Carbon Dioxide in the Blood of Marine Invertebrates. T. R. PARSONS and W. PARSONS (J. Gen. Physiol. 1923 6 153-1 66).-The blood of the lower marine invertebrates can take up no more carbon dioxide than can sea-water ; that of the higher forms can take up twice or three times as much. The form of the carbon dioxide dissociation curves obtained indicates that the haemocyanin in the blood of these animals plays a similar part in the carrying of carbon dioxide to that played by haemoglobin in the blood of vertebrates. Ether Anesthesia.11. Ansesthetic Concentration of Ether for Dogs. E. ROKZONI ( J . Biol. Chem. 1923 57 761-788).- Using the method of Shaffer and Ronzoni (this vol. ii 69) for the ether estimations it has been found that during ether anzsthesia the concentration of ether in arterial blood varies directly with thatt in alveolar air a,nd depends on the distribution coefficient between air and blood at body temperature.During the induction of anaesthesia and with a continued administration of a constant amount of ether the concentration in arterial is greater than in venous blood. This is probably due to the great solubility of ether in the depot fat. For the same reason the concentration is higher in venous blood during the elimination of the ether. An ether tension in alveolar air of 3 3 4 1 mm. produces respiratorg failure C. R. H.i. 112 ABSTRACTS OF CHEMICAL PAPERS. in dogs when anaesthesia is induced rapidly; after several hours a tension of 27-34 mm. is sufficient. T. F. ZUCKER and M. GUTMAN (Proc. SOC. Exp. Biol. Med. 1922 20 133-136).- Estimations made on the fresh protein-free filtrate of human blood by Tisdall’s method gave 2-66 mg.of inorganic phosphorus in a total phosphorus content of 19.43 mg. Boiling for two hours caused the hydrolysis of 9.73 mg. of the remaining phosphorus in organic combination. CHEMICAL ABSTRACTS. The Inorganic Phosphorus and Calcium in Maternal and Foetal Blood. A. F. HESS and M. MATZNER (Proc. SOC. Exp. Biol. Med. 1922 20 75-76).-Tests were made on the maternal blood before and forty-eight hours after parturition and on the cord blood of infants. The calcium did not vary significantly from the normal. The average inorganic phosphorus content for twenty- one infants was 3-71 mg.%; the mothers’ blood contained 2-89 mg.% when taken from one to two days after parturition. The maternal blood during pregnancy averaged 2-77 mg. o/o of inorganic phosphorus for twelve individuals. The normal inorganic phosphorus content of the blood of young infants is 4.5 mg.%.The estimations were made on the whole blood by Bell and Doisy’s method. E. S. Distribution of Phosphorus in the Blood. CHEMICAL ABSTRACTS. Rickets in Relation to the Inorganic Phosphate and Calcium in Maternal and Foetal Blood. AL. H. HESS and M. J. M~TZNER (Amer. J . Diseases Children 1923 26 285-289).-The inorganic phosphorus of the new-born is generally lower than that of infants of one month of age or older. However even when the percentage was within rachitic range rickets was not evident. No relationship was found between the percentage of inorganic phosphorus in the blood of the new-born and the occurrence of rickets during the first year of life.CHEMICAL ABSTRACTS. Calcium and Phosphorus in the Blood Plasma in Rickets and Tetany. J. H. HESS J. K. CALVIN C. C. WANG and A. FELCHER (Amer. J . Diseases Children 1923 26 271-279).- In moderate rickets the phosphorus or calcium or both may be moderately lowered ; in severe rickets the phosphorus is markedly reduced whilst the calcium may or may not be lowered. I n rickets complicated by tetany the calcium is reduced whilst the phosphorus may or may not be reduced. Changes in the Lipoid Content of the Blood and Lymph during Fat Absorption in the Dog. H. C. ECKSTEIN (Proc. SOC. Exp. Biol. Med. 1922 20 74-75).- The thoracic lymph of an eighteen-hour fasting dog was collected before and after the introduction of olive oil into the duodenum. The total fatty acids increased rapidly during fat absorption; the phosphatides remained unchanged.Phosphatides were not lsynthesised during the passage of the fat components through the intestinal wall. CHEMICAL ABSTRACTS. CHEMICAL ABSTRACTS. Fat Transport in the Body.PHYSIOLOCIICAL CHEMISTRY. i. 113 Insulin and Glycolysis. G. S. EADIE J. J. R. R~ACLEOD and E. C. NOBLE (Amer. J. Yhpiol. 1923 65 462-476).-1nsulin added to defibrinated blood (dog and rabbit) in vitro or injected into the animals previously to drawing the blood does not accelerate the rate of glycolysis in the blood samples. In mixtures of blood muscle juice and phosphates insulin decidedly retarded glycolysis whereas Cohnheim’s extract of pancreas had no influence. The action of insulin is thought to be an extravascular or intracellular process.CHEMICAL ABSTRACTS. Changes in the Permeability of Red Blood-corpuscles in Non-electrolytic Solutions. R. HOBER and A. MENMESHEIMER (PJEiiger’s Archiv 1923 198 564-570; from Chem. Zentr. 1923 iii 686).-Red blood-corpuscles washed with an isotonic solution show decreased absorption of “ vital colouring ” (“ vital farbender ”) basic dyes in comparison with corpuscles washed with isotonic sodium chloride solution of the same reaction. The difference is not observed with “ non-vital colouring ” acid dyes. Glycine has the same inhibitory effect on dye absorption as sugar. G. W. R. The Distribution of Chlorine in the Blood. L. CsriKr (Biochem. Z. 1923 142 360-369) .-The average chloride content of red blood-corpuscles is 60% of that of the plasma the extreme values found including both normal and pathological cases being 43% and 780/,.A similar difference is shown by defibrinated and hirudin blood. The chloride content of both native and hirudin serum after spontaneous coagulation is the same as that of the corresponding plasma but a marked alteration in the distribution of the chlorine occurs after defibrination on passing carbon dioxide and on previously administering large doses of sodium hydrogen carbonate. Corpuscles from defibrinated blood in contact with isotonic sodium sulphate or dextrose solutions lose chloride and after some hours the external solution contains more than the corpuscles (cf. also A 1922 i 1086). Does Dextrose in Blood Undergo Modification by other Blood Constituents before Oxidation in the Tissues? T.BUDINGEN (2. Klin. Med. 1923 97 147-168; from Chem. Zentr. 1923 iii 634).-The combustion of dextrose is facilitated by pre- liminary moistening with blood. It is supposed that by reaction of destrose with mineral salts in blood “ dextrates ” are formed which are more readily combustible than the sugar itself. It is suggested that such dextrates occur in blood. Proteins and certain amino-acids such as tyrosine leucine glycine and aspartic acid also increase tlhe combustibility of dextrose. Iron compounds containing hydroxyl groups show a similar effect but iron and iron oxides are without effect. The rate of oxidation of sugar in blood is increased by the addition of certain salts whilst under pathological conditions the rate of oxidation may be diminished.The increase in the respiratory quotient after injection of dextrose is held to be due to the blood-sugar becoming more readily oxidised through reaction with the kations present. J. P. G W. R,i. 114 ABSTRACTS OF CHEMICAL PAPERS. The Potassium Content of Human Serum. L. WILKINS and B. KRAMER (Arch. Intern. Ned. 1923 31 916-932).-Normal human serum contains 18-22 mg. of potassium per 100 C.C. Increases were observed only in nephritis (25-26 mg.) and in tetany (23-29 mg.). There was no apparent relation between an increased potassium and a decreased calcium content. The ingestion of 1.3 g. of potassium iodide three times daily for a long time did not increase the potassium content of the serum but after the ingestion of 2 10 and 15 g.of potassium chloride the potassium content of the serum was increased to 25,30 and 35 mg. respectively in about two hours with subsequent return to normal. CHEMICAL ABSTRACTS. Mode of Occurrence of Proteins in Plasma and Serum. I. Are Serum Proteins combined with Alkalis’? R. MOND (PJEiiger’s Archiv 1923 199 187-193 ; from Chem. Zentr. 1923 iii 570).-In normally reacting blood only a very small proportion of the sodium present in the serum is combined with proteins which are principally present in forms other than salts. A minimal buffer effect occurs between the neutral point and the isoelectric point for globulins. The buffering ( ‘1 titration) curve is markedly sigmoid. G . W. R. The Organic Constituents of the Saliva. H. B. LEWIS and H. UPDEGRAFF (Proc.SOC. Exp. Biol. Med. 1922 20 168-169).- Human saliva contained approximately 30% as much uric acid as the blood; the values ranged from 0.6 to 2.9 mg. per 100 C.C. Benedict’s method applied to a filtrate obtained by a modified Folin and Wu precipitation method was used. The salivary glands were not readily permeable to dextrose. Cholesterol in Duodenal Contents. J. J. HERTZ and M. KAHN (Proc. Xoc. Exp. Biol. Med. 1922 20 167-168).-1n the fasting state the cholesterol in the duodenal contents of different individuals varied from 25 to 105 mg. in 10 C.C. Concentrated magnesium sulphate solution introduced into the duodenum caused a rapid increase in the cholesterol content indicating an outpouring of concentrated bile. Fat and Protein Absorption after Comprehensive Resec- tion of the Intestine.0. SCHTJMM and A. PAPENDIECK (2. p?hysiol. Chem. 1923 131 54-59).-After resection of 3.7 m. of the intestine about four-fifths of the fat consumed was excreted in the faxes which also contained about two-thirds of the nitrogen in the food. W. 0. K. Investigations on Iodine Metabolism. I. Experiments with Physiological Quantities of Iodine on Adults. T. VON FELLENBERG (Biochem. Z . 1923 142 246-262) .-Iodine taken in physiological quantities is excreted chiefly by the kidney but also in variable amounts in the fzces nasal excrement and in the sweat. Potassium bromide sodium fluoride and chloride and copious water drinking do not affect the excretion of iodine. A Turkish bath CHEMICAL ABSTRACTS. CHEMICAL ABSTRACTS.PHY SIOLOOICAL CHEMISTRY.i. 115 increases the iodine excretion by the skin but the total is not increased. Physical exercise and fevers increase the total excretion whilst during fasting and sleeping it diminishes. Iodine equilibrium is attained on a daily intake of about 14 micrograms (cf. Biochem. %. 1923 139 371). If the intake is increased a readily mobilised " actual'' reserve is built up which is distinguished from the potential reserve of the thyroids. The course of iodine metabolism is dependent to a certain extent on the nature of the iodine compound administered thus iodine fats are more readily absorbed than iodides. J. P. I. GJAJA and BRANDIMIR MALEB (Glus. Acad. Sci. Belgrade 105,l-34).-The ener- getic metabolism in mouse and rat was measured by the consumption of oxygen.The first series of experiments with mice a t constant temperatures showed that in the whole interval from 1.5" to 40" (the lethal temperature) the amount of oxygen consumed was almost constant from the beginning of the experiment. In a second series of experiments with mice and rats the temperature during the experiment was changed in order to examine the influence of various temperatures on the consumption of oxygen. The consumption of oxygen increases with decreasing temperature owing to the pro- duction of complementary heat in the organism to compensate loss by radiation. A third series of experiments on mice has shown that the temperature a t which the animal produces a complementary heat does not depend on the size of the animal but depends rather on its greater or lesser protection by fur the beginning of the pro- duction of a complementary heat being a t a higher temperature in the case of a badly protected animal.J. L. GAMBLE G . S. Ross and F. F. TISDALL (J. Biol. Chem. 1923,57,633-695).- The discussion which is developed in this paper is based on the con- ception that since the osmotic pressure and pH of the body-fluids are to a large extent dependent on the concentration in them of total fixed base the maintenance of an approximately constant value of the latter is the chief result of the processes of acid-base metabolism. During starvation the following causes contribute to an increased excretion of acidic radicles destruction of tissue protoplasm with the production of sulphuric and phosphoric acids reduction in the total volume of the body-fluids and the production of ketonic acids owing to the incomplete oxidation of fat.The first two processes also liberate fixed base which is available for the excretion of acidic radicles; in addition a certain quantity of calcium is derived from the calcium deposits of the body. The total amount of base available is however insufficient for the excretion of the acids produced by the above causes and two regulatory mechanisms come into play to adjust this and so maintain the concentration of total fixed base in the plasma and consequently in the other body- fluids. These are the excretion of urine of an acidity greater than that of the plasma and the production of ammonia in the kidney. Calculations made from estimations of the inorganic constituents Energetic Metabolism in Mouse and Rat.S. S. M. Metabolism of Fixed Base during Fasting.i. 116 ABSTRACCS OF CHEMICAL PAPERS. of the plasma and urine of four epileptic children undergoing periods of fast approximately confirm these views which are discussed in great detail in the original. Estimation of the Alkali Retention in Growth. A. T. SHOHL (Proc. Soc. Exp. Biol. Med. 1922 20 139-140).-The acids and bases in the food urine and faeces were estimated in terms of N solutions. The alkali retention expressed in C.C. of 0.1N solution per kg. of body-weight amounted to 11 C.C. in infants. Of the alkali retained 2 C.C. was required for protein increase 4 C.C. for the alkaline reserve and about 57 C.C. for the formation of bone.E. S. CHEMICAL ABSTRACTS. The Physiology of Sleep. I. The Effects of Prolonged Sleeplessness on Man. N. KLEITMAN (Amer. J . Physiol. 1923 66 67-92).-Experimental insomnia in man (forty to one hundred and fifteen hours) produced no change in the blood-sugar alkaline reserve of the blood and plasma haemoglobin content or certain other factors. Increased excretion of phosphates and acids is apparently due to’ sleep. There is a greater excretion of chlorine in the day time ; the same is true in insomnia but there is a tendency to reversal in a subject who sleeps during the day. The excretion of total nitrogen and of creatinine shows little diurnal variation and is unaffected by either insomnia or reversed routine. CHEMICAL ABSTRACTS. Composition of Herring Ova.111. Researches on Ova Using Micro-methods. H. STEUDEL and S. OSATO (2. physiol. Chem. 1923 131 60-64).-Micro-estimations show that there are in 100 herring ova 1.546 mg. of total N 0.0054 mg. of ammonia N 0.1054 mg. of urea N 0.0024 mg. of creatinine and an amount of a reducing substance corresponding with 0.2 mg. of dextrose. The total nitrogen is 13.59% of the weight of the dried eggs and this corresponds with the value 13.23% obtained by using micro- methods on larger quantities of eggs. The Composition of Herring Ova. IV. H. STEUDEL and E. TAKAHASHI (2. physiol. Chem. 1923 131 99-106).-1n the aqueous extract of herring ova the following substances have been isolated and identified guanidine adenine histidine arginine lysine and cystine. Colour reactions indicate the presence of small quantities of tyrosine tryptophan and of creatinine.The Composition of Herring Ova. V. The Monoamino- acids of the Skins of the Ova. S. OSATO (2. physiol. Chem. 1923 131 151-158).-The monoamino-acids of the skin of 38.7 g. of herring ova have been investigated using Fisclier’s ester method and the following constituents have been isolated alanine 0.1 g. ; valine 1.1 g. ; leucine 4-3 g. ; glutamic acid 0.16 g. ; proline 0.6 g. ; tyrosine 6.27% ; cystine 0.71 % tryptophan 2.02%. The last three have been estimated by the method of Folin and Looney (A. 1922 ii 539). W. 0. K. W. 0. K. W. 0. K.PHYSIOLOGICAL CHEMISTRY. i. 117 The Concentration of Various Anions and Kations in Cerebrospinal Fluid and Serum. J. B. PINCUS and B. KRAMER ( J .Biol. Chem. 1923 57 463-470).-Analyses have been made of the serum and cerebrospinal fluid of normal and pathological subjects. The results show that in the cerebrospinal fluid of a normal individual the concentration of inorganic phosphorus is considerably and of potassium somewhat smaller than in the serum ; chlorides on the other hand have a much higher concentration than in the serum whilst that of sodium and of hydrogen carbonate is the same in both fluids ; the concentration of calcium is 40-50% of that of the serum. The Donnan membrane equilibrium appears to be important in determining the relation between the concentration of the various constituents in the two body-fluids. P. V. PREWITT (Amer. J . Physiol. 1923,65 287-295).-The isolated dog liver perfused with defibrinated dog blood may increase or decrease in lipolytic activity under various conditions.The lipolytic activity of the liver was determined by extraction with water and testing the hydrolysing power of the extract on ethyl butyrate. The lipase content of the unperfiised liver is very much greater than that of the perfused organ the marked decrease in liver-tissue following the initial perfusion not being accounted for by the slight increase in the lipase of the perfusion fluid. The addition of secretin to the perfusion fluid results in an increased lipase content of the liver-tissue. Although hepatic lipase does not seem to be increased by the action of pilo- carpine interchange of lipase between liver and blood is apparently facilitated under its influence. The lipolytic activity of the liver is not altered immediately by asphyxia but changes are induced which are favourable to increased activity during subsequent perfusion.CHEMICAL ABSTRACTS. E. S. Lipase Production by the Liver. The Physiology of the Polyamyloses. 11. Glycogen Form- ation and Animal Combustion. H. VON HOESSLIN and H. PRINGSHEIM (2. physiol. Chem. 1923 131 168-176).-Perfusion of the surviving liver of the guinea-pig with a solution of maltose or of tetra-amylose does not result in the formation of glycogen. No excretion of tetra-amylose takes place after administration of tetra-amylose to the living animal neither is there any increase of glycogen in the liver. A similar result is obtained with hexa-amylose. No increase of dextrose appeared in the urines of two diabetic patients after administration of 50 g.of tetra-amylose. W. 0. K. Chemical Study of Several Marine Molluscs of the Pacific Coast. The Liver. P. G. ALBRECHT (J. Biol. Chem. 1923 57 789-794) .-Analyses are presented of the liver of certain marine molluscs (abalone Pismo clam Cryptochiton Ischnochiton owl limpet). All had a relatively high iron content ; creatine creatinine and uric acid were absent ; urea was present in all except the abalone ; and all contained those enzymes which are known to be present in the alimentary canal. The last result supports the view that thei. 118 ABSTRACK'3 OF CHEMICAL PAPERS. enzymes have their origin in the liver. An active uricase was found in the abalone and €'ism0 clam. The Effect of Quinine on the Iodine Content of the Thyroid Gland.H. SVCIATA (Arner. J . Physiol. 1923 65 282-286).- Quinine sulphate administered to dogs (fasting or fed) in daily doses of 0.2 to 0.3 g. per kg. caused a considerable increase in the iodine content and concentration of the thyroid. High external temperature (35") also causes an increase in iodine whilst a decrease is produced by starvation. It is believed that endogenous protein metabolism is fundamentally responsible for the distribution of iodine in the body. CHEMICAL ABSTRACTS. 0. MEYERHOF (PJliiger's Archiw 1923 199 531-566).-Experiments similar to those of Hopkins and Dixon (cf. A. 1923 i 167) were performed to investigate the oxygen uptake of systems consisting of a sulph- hydryl compound and muscle treated in various ways.The sulph-hydryl compounds employed were thioglycollic acid and cysteine. It was found that with a system of thioglycollic acid and the dried muscle powder prepared according to Hopkins and Dixon the uptake of oxygen might be twelve times the amount necessary to convert the sulph-hydryl compound to the corresponding disulphide. It was then found that after prolonged extraction with alcohol and ether the muscle powder lost its power of taking up oxygen this power being retained in a substance precipitated by acetone from the concentrated ethereal extracts. Next it was shown that a mixture of lecithin and thioglycollic acid reacted in the same way as the muscle powder and finally that of the constituents of lecithin linolenic acid alone possessed this property.It is therefore probable that linolenic acid is the heat stable substance of unspecified nature described by Hopkins and Dixon. All the above reactions proceed best in an acid solution (pH about 3) and may be entirely inhibited in neutral or alkaline solution; moreover the uptake of Qxygen ceases when the reaction for the -SH group disappears. The amount of oxygen taken up is about 5 C.C. per g. of dried muscle or in the case of linolenic acid two moIecules of oxygen to each molecule of acid; estimation of the iodine value before and after oxidation shows that only two of the double bonds have disappeared; these must therefore have been oxidised to a peroxide linking E. S. A New Autoxidisable System of the Cell. as is known to occur in the spontaneous oxidation of linolenic acid.A close analogy is drawn between the oxidation of lecithin in these experiments and that which takes place in the presence of iron. A consideration of the kinetics of the reaction and of the other experimental facts enumerated leads the author to suggest that the course of physiological oxidation by the agency of such substances as glutathione is not as generally accepted ZR-SH+O=PHYSIOLOaICAL CHEMISTRY. i. 119 RS*SR +H20 and RS-SR +H20 +M=BR*SH +MO (M being an R*SH-? oxidisable constituent of the muscle) but 2R*SH +O - I I 2- R*SH-0 +2M=2R*SH +2MO. R.SH.0 and According to this theory it is only the reduced form of such a substance as glutathione which actually takes part in this process of tissue oxidation. C. R. H. The Antagonism between Magnesium- and Calcium-ions.W. BAUMECKER (Biochem. Z. 1923 142 142-158).-Magnesium and calcium chlorides inhibit the imbibition of water by fibrin to the same extent whereas on muscle pulp the former in certain low concentrations causes an increased the latter a diminished imbibi- tion whilst mixtures of the two salts show a balanced antagonistic action. On the living isolated frog-muscle the narcotic action of magnesium is unaccompanied by imbibition until the narcosis has become irreversible. Calcium salts cause a marked loss of water. Unlike sodium salts calcium does not remove the reversible paralysis caused by magnesium. The antagonism between magnesium and calcium on the living muscle is therefore not brought about by their action in causing imbibition or loss of water but is effected through the myoneural junction.The narcotic action of magnesium on the end-plate is only observed in Ringer solutions containing calcium. It is conc$ded that magnesium replaces the calcium which is necessary for the proper functioning of the end-plates. Behaviour of Calcium Phosphate and Calcium Carbonate (Bone Salts) precipitated in various Media with Applications to Bone Formation. J. C. WATT (Biol. Bull. Marine Biol. Lab. 1923 4-4 280-308) .-Calcium phosphate when precipitated in water or in colloidal solutions is constantly granular and amorphous in character and is apparently uninfluenced by the nature of the solution. On the other hand calcium carbonate when precipitated in water shows a great diversity of crystalline form; in colloidal solutions it exhibits two main forms irregular crystalline and spherical respectively.Mixtures obtained by simultaneous preci- pitation of both salts in the same solution admit of identification of each salt separately. The character of the spherules and crystals is influenced by the presence of normal or pathological constituents of blood especially lecithin and acetone and by the hydrogen-ion concentration of the colloidal solution. Large spherules after persisting for months may undergo structural change finally dissolving ; the substance is then deposited in the crystalline form. The mechanism of the formation of bone in animals is discussed. CHEMICAL ABSTRACTS. J. P. A Method of Micro-incineration Applicable to Histochemical Researches.A. POLICARD (Bull. SOC. chim. 1923 33 [iv] 1551-1558).-The author has devised a method of studying the distribution of mineral salts in histological sections. The sectioni. 120 ABSTRACTS OF CHEMICAL PAPERS. is placed on a platinum slide carefully dried then raised to a dull red heat for twelve to fifteen minutes. A very slow current of air facilitates the burning off of the organic matter and is stated to be preferable to oxygen for that purpose. Glass is inadmissible for the slide material as it softens a t the temperature required for the operation. Unglazed porcelain may be used. The ash result- ing from the incineration forms a " mineral plan '' of the section dealt with. This is examined microscopically by reflected light and it is stated that this examination clearly shows the djstri- bution and relative quant,ities of mineral matter.The presence and distribution of iron in particular is readily studied by the intensity of coloration of the ash by the ferric oxide resulting from the combustion. H. J. E. Asteriasterol-a New Sterol from the Starfish and the Sterols of certain other Marine Echinoderms. I. H. PAGE ( J . Biol. Chem. 1923 57 471476).-A sterol m. p. about 70° to which the name asteriasterol is given has been isolated from Asterim forbesi. It forms an acetate m. p. 97" and a benzoate m. p. 125". The colour reactions which it gives with various sterol reagents a,re described. The sterols present in Echinarachnius parmu and Arbacia punctula.ta are identical and those in Cumingia tellinoides Choetopterus pergamentaceous and Arenicola cristatu probably identical with cholesterol. Oxycholesterol gives an immediate deep violet coloration with arsenious chloride which changes to bright blue on gently heating and to bright green on vigorously boiling E.FORRAI (Bio- chem. Z. 1923 142 282-290).-The possibility has been investig- ated of the presence of glycerophosphatase in various dried human organs examined soon after death. The observations of Grosser and Husler (A. 1912 ii 367) were confirmed and in addition the enzyme was found in the adrenals thyroids testes and in carcinomas. Amyloid kidneys contained less and in a case of eclampsia muscle contained more than the normal organs. None of the organs in which the enzyme was found is of mesodermal origin.It is supposed that the enzyme originates in the epithelial layers. J. P. The Distribution of Calcium and Inorganic Phosphorus in Milk. P. GYORGY (Biochem. Z . 1923 142 l-lo).-That portion of the calcium and inorganic phosphate of human milk and of cow's milk which is indsusible (50-60% in the former and 3 0 4 0 % in the latter) diminishes with increasing hydrogen- ion concentration and at the isoelectric point of casein all the calcium and phosphate of the milk is dialysable. During the tryptic digestion of milk a t constant pE the diffusible calcium and phosphate increases and similar results were obtained on a casein solution to which calcium chloride and a phosphate mixture had been added. It is concluded that the non-diffusible calcium phosphate of milk is combined with the casein in the form of a E.S. Glycerophosphatase in Humw Organs.PHYSIOLOGICAL CHEMISTRY. i. 121 complex double compound and not simply adsorbed by the pro- tein (cf. Van Slyke and Bosworth J. Biol. Chem. 1914 14; 1915 Copper as a Constituent in Woman’s and Cow’s Milk. Its Absorption and Excretion by the Infant. A. F. HESS G. C. SUPPLEE and B. BELLIS (J. Biol. Chem. 1923 57 725-729). -Raw cow’s milk contains 0.55 mg. of copper per litre and com- mercially pasteurised milk 0-6-0.7 mg. per litre. Analyses of two specimens of human milk gave values of 0.4 and 0.61 mg. per litre respectively. The constant presence of copper in the urine of both infants and adults indicates that it is absorbed from the alimentary canal. E. S. Urinary Acidity. 11.The Increased Acidity produced by Eating Prunes and Cranberries. N. R. BLATHERWICK and M. L. LONG ( J . Biol. Chem. 1923 57 815418).-The increased acidity of the urine which is produced by eating prunes or cran- berries (A. 1914 i 627) is due to the excretion of hippuric acid. The benzoic acid present in the fruit appears to be insufficient to account for all the hippuric acid excreted which must therefore be derived from some other source. VI. The Influence of the Protein of the Diet on the Synthesis and Rate of Elimination of Hippuric Acid after the Administra- tion of Benzoates. W. H. GRIFFITIE and H. B. LEWIS ( J . Biol. Chem. 1923 57 697-707; cf. A. 1923 i 1261).-The rate of synthesis of hippuric acid by rabbits following the administration of sodium benzoate is increased when the hydrolytic products of proteins containing glycine are administered simultaneously with the benzoate but not when the proteins do not contain this amino- acid.It is therefore improbable that any readily available pre- cursors of glycine are produced during the ordinary metabolism of proteins. E. S. Allantoin. I. The Influence of Amino-acids on the Excre- tion of Allantoin by the Rabbit. A. A. CHRISTMAN and H. B . LEWIS ( J . Biol. Chem. 1923 57 379-395).-The excretion of allantoin by rabbits was decreased markedly by the administration of amino-acids (glycine alanine glutamic acid) or urea and to a smaller degree by gelatin. J. M. LOONEY H. BERGLUND and R. C. GRAVES ( J . Biol. Chem. 1923 57 515-531).-Using recent methods of estimation the authors have examined several cases of cystinuris and have confirmed older work.The total amount of cystine excreted is composed of two fractions a small and constant amount derived from endogenous metabolism and a larger fraction which is proportional to the protein intake. An increased excretion of cystine is not accompanied by an increased elimination of other amino-acids. In the absence of the admini- stration of sodium hydrogen carbonate or of atophan practically 20; 1916 24). J. P. E. S. Synthesis of Hippuric Acid in the Animal Organism. E. S. Several Cases of Cystinuria.1. 122 ABSTRACTS OF CHEMICAL PAPERS. the whole of the neutral sulphur in the urine is due to cystine; the administration of sodium hydrogen carbonate however de- creases the excretion of cystine and disturbs the distribution of the neutral sulphur.E. S. The Proteic Acids of the Urine. 111. Oxyproteic Acid. S. EDLBACHER (2. physiol. Chem. 1923 131 177-178; cf. 2. physiol. Chem. 1922 120 71 ; 127 186).-The so-called " oxy- proteic acid" of urine appears to consist essentially of urea con- taminated with some impurities as it is decomposed by urease with the formation of ammonia and gives the characteristic crystalline compound with Naphthol Yellow-S (dinitronaphthol- sulphonic acid). These results agree with those of Freund and Sittenberger-Kraft (A. 1923 i 511). Fat Metabolism in Avitaminosis. 11. The Total Fat Neutral Fat Cholesterol and Cholesterol Ester in the Blood of Normal Starving Avitaminosed and Phosphorus Poisoned Rats. K. ASADA (Biochem.Z . 1923 142 44-52).- The total and neutral fat cholesterol and cholesterol ester have been determined in the blood of normal starving and avitaminosed rats with and without simultaneous phosphorus poisoning. The blood-fat is highest in the avitaminosed rat and least in the starved rat. After phosphorus poisoning the total blood-fat in the normally fed animal is unchanged in starvation it is increased to approxim- ately the normal level and in avitaminosis associated with phos- phorus administrat'ion it is markedly increased but later sinks to sub-normal values. The variations in the amounts of cholesterol and of the ester are parallel to the changes in total fat under the three conditions of experiment. After poisoning with phosphorus the ester especially is increased this being most marked in the early stages of avitaminosis.Fat Metabolism in Avitaminosis. 111. The Fat and Chole- sterol Content of the Liver after Phosphorus Poisoning in Normal Starved and Avitaminosed Rats. K. ASADA (Bio- chem. Z . 1923 142 165--180).-1n avitaminosed rats the total and neutral fat of the liver diminishes but after prolonged vitamin- free feeding it again rises still keeping within sub-normal limits. The liver cholesterol progressively decreases and does not run parallel to the altered fat content. In the starved animals the diminution of liver fat is marked whilst the cholesterol is increased. After phosphorus poisoning which greatly lowers the liver-fat and cholesterol of the starved animal the liver of the avitaminosed animal is but slightly less rich in fat and cholesterol than that of the normally fed but poisoned rat but both show a much greater fat content than do the similarly treated but non-poisoned animals.I n advanced avitaminosis the phosphorus poisoned liver which is practically free from glycogen contains more fat than the normal poisoned liver. Starved and avitaminosed rats are much more susceptible to death from phosphorus poisoning than are normally fed animals. The water content of avitaminosed livers first in- W. 0. K. J. P.i. 123 PHPQOLO(X1CAL CHEMISTRY. creases then diminishes in relation to normal conditions. After phosphorus poisoning it is increased in the starved rat lessened in avitaminosis and unchanged in the normal rat. The Content of Copper and Zinc in Normal and Car- cinomatous Tissues.H. J. TAVERNE (Nederl. Tijdschr. Genees- hnde 1923 67 i 2810-2812; from Chem. Zentr. iii 946).-In a mammary carcinoma normal tissue contained 0.94 mg. of copper and 3-74 mg. zinc per kg. whilst the cancerous matmerial contained 0.54 mg. of copper and 3.65 mg. of zinc per kg. Effect of Treatment with Insulin on the Hydrogen-ion Concentration and Alkali Reserve of the Blood in Diabetic Acidosis. G. E. CULLEN and L. JONAS ( J . Biol. Chem.? 1923 57 541-552) .-The treatment of diabetic patient's with insulin causes the alkali reserve and the pH of the plasma both of which are lowered to return concurrently to the normal. [Physiological] Action of Acetylene. 111. The Gases of the Blood of Rabbits during the Administration of Acetylene. R.SCHOEN and G. SLIWKA (2. physiol. Chem. 1923 131 131- 145; cf. A. 1923 i 727).-During inhalation of a constant mixture of acetylene and oxygen the acetylene content of the arterial and venous blood of rabbits gradually increases and saturation is reached after seventeen minutes 88 yo saturation being reached after five minutes. The presence of acetylene in the air breathed does not influence the oxygen content of the arterial blood but the carbon dioxide content constantly decreases. After ceasing the administration of the acetylene increased breathing occurs and acetylene is rapidly expired. W. 0. K. [Physiological] Action of Acetylene. IV. Critical Remarks on the Action of Acetylene. H. WIELAND (2. physiol. Chem. 1923 131 146-150).-The author has suggested (A. 1922 i 497) that ethylene and nitrous oxide differ from other inhalation anaes- thetics such as chloroform and ether as they have no effect on anoxybiotic processes and now replies to criticisms of this vjew by Bart (Verh. Deutsch. pha.rrnako1. Ges. 1922 2 7) and by Meyer and Hopff (A. 1923 i 632). W. 0. K. K. k4KOVI6 (Glm. Acad. Sci. Belgrade 105 4244).-Injections of a solution of guanidine in the frog causes the same symptoms of tetany its was observed by Paton and Findlay with rabbits mice and rats. J. P. G. W. R. E. S. The Influence of Guanidine on the Frog. S. S. M. Behaviour of Quinoline in the Animal Organism. B. SCHEUNEMANX (Arch. expt. Path. Pharm. 1923 100 51-60).- The three quinoline derivatives observed by Fuhner (A. 1906 ii 692) to occur in the urine after administration of quinoline have been studied in the urine of the rabbit after oral administration of 20 g. of quinoline tartrate. Two of them have been identified as 8-hydroxyquinoline and 6-hydroxyquinoline ; the third one is probably 6-hydroxy-4quinolone. C. R. H.

ISSN:0368-1769    

DOI:10.1039/CA9242600111

出版商:RSC    

年代:1924

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. Analytical Chemistry. ii. 121 Application of X-Rays to Quantitative Chemical Analysis. R. GLOCKER (Portschr. Geb. Rontgenstr. 1923 31 90-92; from Chem. Zentr. 1923 iv 763).-The author proposes as a measure of the amount of an element present in a substance the intensity ratio of the discontinuity of the K-absorption (Absorptionssprung) when the substance is submitted to a continuous X-ray pencil. For the K-discontinuity f photometrically measured the relation- ship f = e p c is given where p is the amount of the element present and c is a constant which is characteristic for the element and apparently an exponential function of the atomic number. The method has hitherto only been used for the K-absorption. G. W. R. Benzidine as a Reagent and as an Indicator for Specific Oxidation-potential.I. M. KOLTHOFF (Chem. Weekblad 1924 21 24).-The work of Feigl and others (A. 1920 ji 709; 1921 ii 278; 1922 ii 865; 2. anal. Chem. 1923,62,369) and of Olszewski (Chem. Ztg. 1923 47 273) on the detection of metals and phosphates has been examined and confirmed but the sensitiveness in most cases is not found so high as has been stated. An examin- ation of the behaviour of oxidising agents towards benzidine shows that the colour reaction is not dependent on the concentration of the former but on the oxidation-potential. Thus ferric salts give a coloration after one hour in a concentration as low as 1 mg. per litre ferrous salts not a t all; mixtures of ferrous and ferric salts give the same result independently of concentration the effect depending on the proportion of ferrous to ferric compound; no coloration is obtained with a mixture of 1 part of ferric and 9 parts of ferrous salt even in concentration of 10 g.per litre. Similarly iodates give a definite coloration but the result is negative in presence of iodides. If the potential is above the specific point the benzidine is oxidised; if below it remains unaltered but at the specific point the appropriate coloration is developed. Qualitative Reaction of Halogens in Organic Compounds. J. PICCARD and F. DE MONTMOLLIN (Helv. Chim. Acta 1923 6 1020).-The usual copper wire test for halogen in organic compounds sometimes fails because the substance volatilises before it decom- poses. It is recommended to hold a copper gauze in the flame about 1 cm.above the heated substance ; the copper gauze is then attacked by the halogen in the flame giving the green colour. If the substance gives a luminous flame two flames may be used a small one to heat the substance and a larger one above in which the copper gauze is held. To detect halogen in a volatile liquid a piece of filter-paper saturated with the liquid is placed a t the top of a vertical glass tube. The vapours fall down the tube at the lower end of which is attached a bent tube A flame containing copper gauze S. I. L.ii. 122 ABSTRACTS OF CHEMICAL PAPERS. is applied to the cnd of the latter tube and an intense green coloration is obtained. Determination of Chloride in Bleaching Powder. MATSUWO NAKAMURA ( J . Chem. I92d. Japan 1923,26,984-985).-The sodium arsenite-silver nitrate method for the determination of chloride gives no distinct end-point and the manipulation is too complex.In the method proposed the hypochlorite is converted into chloride with hydrogen peroxide solution and titrated with silver nitrate. Fifty C.C. of bleaching powder solution (4.0-6.0 g. per litre) is treated with 3-5 C.C. of 3:4 hydrogen peroxide and then boiled for several minutes for decomposition of the excess of the peroxide. The solution is neutralised with dilute nitric acid and titrated with an 0.1N silver nitrate solution using potassium chromate solution as indicator. The percent,age of the chloride is obtained by sub- tracting that of the available chlorhe from the total. -4 small amount of hydrogen peroxide remaining in the solution is not objectionable in the titration.K. K. S. OCHI ( J . Chem. Ind. Japan 1923 26 1152-1154).-The water in bleaching powder is determined by the combustion method by heating the tube quickly a t 200-250" (cf. ibid. 1923 26 349) but the amor- phous form of bleaching powder produces much chlorine according to the equation Ca(OG1)C1,€I,O=Ca(O€€),+Cl2. By absorption of the chlorine thus produced in a washing bottle containing potass- ium iodide solution next t o the absorption tube the amount of water fixed in the residue can be determined and thus the total water content. K. K. Determination of Bromine in Organic Compounds. TETSUO MAZUME and KIICHIRO KIKO ( J . Chem. Ind. Japan 1923 26 1133-1 139).-The authors have experimentally compared the method of Baubigny and Chavanne (A.1904 ii 203) and that of Stepanow (A 1905 i 335; 1907 ii 50) and Bacon (A. 1909 ii 179) for the determination of bromine in organic compounds finding that the former gives lower results than the theoretical whilst the latter is accurate and simple in manipulation. In the former case nitrous acid is formed and part of the alkali bromide is decom- posed the bromine being lost. In the latter method the titration with ammonium thiocyanate is conducted safely after coagulating the silver bromide without filtering it. Determination of Fluorine in Organic Compounds. J. PICCARD and C. BUFFAT (Nelv. Chim. dcta 1923 6 1047-1048). -The method consists in converting the fluorine into potassium fluoride by heating the compound with potassium a t 400".The compound (fluorobenzene 0.1-0-2 g.) is weighed in a thin-walled sealed glass tube which is introduced into a bomb-tube containing 20 C.C. of absolute ether. About 0.5 g. of potassium is added and the tube is drawn out exhausted and sealed. The ampoule is broken and the tube heated at first gently then a t 400". The E. H. R. Determination of Water in Bleaching Powder. I<. K.ANALYTICAL CHEMISTRY ii. 133 tube is then opened and the potassium fluoride determined by conductometric titration with calcium chloride. E. H. R. Volumetric Determination of [Sulphur in] Sodium Sulphide. V. HASSREIDTER (Chem. Ztg. 1923 47 891-892).- The iodometric method of determining sodium sulphide in solution (A. 1923 ii 790) suffers from the disadvantage that sulphites and thiosulphates which may be present in commercial sodium sulphide will also decolorise the iodine solution. These salts do not affect the determination of sodium sulphide if the latter is carried out by allowing the solution to run into a standard ammoniacal zinc solution until a drop of the latter just stains lead acetate paper.Alternatively the standard zinc solut im may be run into a known volume of sodiuni sulphide solution until the latter just fails to stain the test-paper. Somewhat more accurate results are obtained by allowing a known volume of the sulphide solution to flow into excess of alkaline copper sulphate solution separating qnd washing the copper sulphide dissolving it in nitric acid and depositing the copper electrolytically.One mg. Cu=1.227 mg. Na,S. The copper solution is prepared in a similar way to Fehling’s solution and should contain about 50 g. of copper sulphate crystals per 1. Microchemical Detection of Sulphuric Acid as Silver Sulphate. L. ROSEXTHALER (Mikrochemie 1923 1 47).- Characteristic crystals (rhombic pyramids) are obtained when a sulphate solution is treated with silver nitrate in nitric acid solution ; the crystals of silver sulphate may be obtained from a drop of 1% sodium sulphate solution; oxalates and chromntes do not interfere with the reaction. but chlorides must be removed me- H. C. R. viously by adding the requisite amount of silver nitrate. I w. P. s. Micro-volumetric Determination of Arsenic Anthony and Iron. A. BRUKL (Mikrochemie 1923 1 54-57).-The iodometric method is recommended for the determination of small quantities (less than 1 mg.) of arsenic or antimony N/500 iodine solution is used for the titration with starch solution as the indicator.In the case of ferrous salts the titration is made with titanium trichloride solution; a small combined container and burette for the latter is described means being provided for filling the apparatus New Light Filter. [Detection of Potassium.] LER. W. MCCAY ( J . Amer. Chem. SOC. 1923 45 2958).-A solution of 31 g. of crystallised chrome alum in 100 C.C. of water forms an excellent light filter for use in the detection of potassium. When this filter is used potassium may be detected by the flame test in the presence of sodium lithium strontium barium and calcium. The rays from rubidium and cesium however are not cut off.A Volumetric Micro-method for the Estimation of Sodium. HANS MULLER (Helv. Chim. Acta 1923 6 1152-1161).-The method described has been worked out especially for the deter- with an atmosphere of dry carbon dioxide. w. P. s. J. F. S.ii. 124 ABSTRACTS OF CHEMICAL PAPERS. mination of sodium in serum. It can be used for ordinary or micro- estimations For the latter 0.1 C.C. of serum is diluted to 1 C.C. with water in a cehtrifuging tube and there are added 1 C.C. of potassium pyroantinionate solution (2 g. per litre) and drop by drop 0.4 C.C. of 95% alcohol. After two hours the tube is centrifuged the supernatant solution removed and the precipitate washed three times with 30:/ alcohol. The precipitate of sodium pyro- antimonate is then treated with 1 C.C.of 2% potassium iodide solution 1 C.C. of concentrated hydrochloric acid solution and 2 C.C. of water and after ten minutes the free iodine is titrated with 0.01N thiosulphate. The method depends on the reduction of the antimonic acid in the sodium pyroantimonate Na,H,Sb,O 7 according to the equation Sb,0,+4HI=Sb20,+2H,0-t-21,. To obtain a sharp end-point in the titration the concentration of hydrochloric acid must not exceed the limits 7-9% and not more than four times the necessary potassium iodide should be used. Magnesium calcium and phosphate in amounts exceeding those likely to be present in serum do not affect the titration. E. H. R. Determination of Silver in Molecular Solution in Presence of Colloidal Silver. K.VON NEERGAARD (Arch. expt. Path. Pharm. 1923 100 162-189).-The silver-ions are determined in presence of colloidal silver by means of electrometric titration. Among the results are given the concentration of silver-ions found in a number of therapeutic preparations. Use of Picrolonic Acid €or the Micro- and Histological Detection of Calcium. J. KISSER (Mikrochemie 1923,1,25-31). -Characteristic crystals are obtained when a dilute solution of a calcium salt is treated with picrolonic acid solution ; the reaction may be obtained with 0.01 mg. of calcium. The reaction may be used to detect the presence of calcium in tissues but in this case the form of the crystals obtained is more varied. Calcium oxalate Determination of Calcium in Organic Material by de Waard’s Method. G.HECHT (Biochem. Z . 1923 143 342- 346).-With quantities as low as 0.1 mg. de Waard’s micro- method for determining calcium (A. 1920 ii 53) gives results accurate within 5%. The determination is not affected within these limits by the presence of phosphates magnesium or iron. C. R. H. does not react with picrolonic acid. w. P. s. T D Diphenylcarbazide as a Qualitative Reagent €or Metals. I. M. KOLTHOFF (Chem. W-eekblad 1924 21 20-22).-The form- ation of intensely coloured compounds between diphenylcarbazide and metals (Cazeneuve A. 1900 ii 627) is not satisfactory for general identification since the solutions must always be neutral but the conditions may be so chosen as to make the reaction specific for particular metals. The bluish-violet colour given with mercury salts in dilutions down to 0.1 mg.of metal per litre is very sensitive to the presence of halogen-ions but cupric salts give a colorationANALYTICAL CHEMISTRY. ii. 125 (reddish-violet 0.1 mg. per litre of copper) not affected by halogen- ions so that copper may readily be detected in presence of mercury (5 mg. in presence of 2,000 mg. of mercury per litre). Cadmium may also be detected in presence of mercury and copper if the latter be reduced and halides are added. Magnesium salts give no coloration but the hydroxide gives an intense red by which the metal may be identified in presence of the alkaline-earth metals. Reaction of Potassium Permanganate with Cuprous Oxide in Dilute Sulphuric Acid and the Determination of Metallic Copper and Cuprous and Cupric Oxides in their Mixtures.DENGORO NISHIDA and KEN-ICHI HIRABAYASHI ( J . Chem. Ind. Japan 1923 26 1123-1133).-Powdered pure metallic copper is practically insoluble in 3-6N sulphuric acid at room temperature by contact for twenty minutes; the addition of potassium per- manganate solution to the acid has no influence on the solubility. Cupric oxide is however completely dissolved in 6N sulphuric acid at room temperature; potassium permanganate in the acid has also no influence on the solubility. When cuprous oxide is stirred in 3-6N sulphuric acid a t room temperature it is com- pletely dissolved and potassium permanganate if added into the acid is consumed according to the equation 2KMn0,+4H2S04= 2KHSO4+2MnSO,+3H2O+50 and 5Cu2O +50 + 10H2S0 = lOCuSO,+ 10H20.One C.C. of 0.1N potassium permanganate solution corresponds with 0.007157 g. of the oxide. For analysis 0.5 g. of a mixture of metallic copper cuprous and cupric oxides is dissolved in nitric acid and the total copper content is determined by iodometry. Another weighed sample is stirred with 100 C.C. of 6N sulphuric acid and 1 C.C. of 0-1N potassium permanganate solution to which permanganate solution is gradually added until the pink colour of the solution no longer disappears; the percentage of the cuprous oxide is thus determined. After titration the residue is dissolved in nitric acid and the metallic copper is determined; the cupric oxide can then be calculated. s. I. L. K. K. Experiments Relative to the Determination of Uranium by means of Cupferron.J. A. HOLLADAY and T. R. CUNNING- HAM (Tram. Amer. Electrochem. SOC. 1923 43 329-339).-A number of experiments are described dealing with the estimation of uranium by means of cupferron which show that quadrivalent uranium or uranium in a lower state of oxidation can be pre- cipitated completely by means of a freshly prepared solution of cupferron from solutions containing 2-8 C.C. of sulphuric acid (d 1-84) in 100 C.C. On ignition the precipitate is converted quantitatively into U,O,. If the amount of sulphuric acid is less than 4 .c.c. per 100 c.c. aluminium and possibly phosphorus will be carried down with the precipitate whilst if the acidity is greater than 8 C.C. per 100 c.c. tlhe uranium Will not be completely precipitated. If the acidity is kept between 4 and 8”/ preferably at 6% a sharp separation of uranium from aluminium zmc calcium,ii.126 ABSTRACTS OF CHEMICAL PAPERS. magnesium and phosphorus can b3 obtained by a single precipit- ation. Uranium and vanadium can be separated and estimated with a sufficient degree of accuracy in tlhe presence of widely vary- ing quantities of iron aluminium. calcium magnesium and phos- phorus by the following method. The iron and vanadium are precipitated by cupferron from a 12yo sulphuric acid solution in which the uranium vanadium and iron are present respectively in the sexavalent quinquevalent and tervalent condition. Uranium aluminium calcium magnesium and phosphorus pass quantitatively into the filtrate. The vanadium in the precipitate is then estimated by any of the usual methods.The filtrate is evaporated with nitric acid to destroy Che cupferron and the solution then passed through a Jones's reductor to reduce tlhe uranium. The solution is then diluted t o 60,; sulphuric acid content and the uranium precipitated with cupferron filtered washed and ignited to u,o,. J. F. S. Determination of Iridium in Platinum by the Method of Fusion with Lead. R. Gir.cHItIs'r ( J . Amer. Chem. Xoc. 1923 45 2820-2828).-The analytical details of the Deville and Stas method for the estimation of iridium in platinum alloys containing 0-1-200,& of iridium have been investigated. It is Eound that the concentration of nitric acid t,he concentration of aqua regia the proportion of lead and the time and temperature of the lead fusion can be varied over a wide range without any efiect on the determination.The observations of Ueville and Stas to the effect that palladium and rhodium have no effect on thc determination and that ruthenium separates quantitatively with the iridium are confirmed. Gold is also found not to interfere with the determin- ation. Iron separates almost quantitatively with the iridium as observed by Deville and Stas. Iron can be separated satisfactorily from iridium by the following method. The alloy is fused with zinc and the excess of zinc removed by treatment with hydrochloric acid. The resulting alloy is then fused with potassium pyrosulphate. The fusion after cooling is extracted with dilute sulphuric acid. The iron all dissolves and the insoluble residue contains the iridium and silica.The loss in weight of crystalline iridium during the ignition periods is insignificant and thc weight of the crystalline iridium is not affected by heating and cooling in an atmosphere of hydrogen. Spectrographic examination of samples of iridium from the analyses showed that neither lead nor platinum is present in quantities sufficient to afiect the determination. The iridium results tend to be low by a small but variable amount. One factor in this error is a slight dissolution of iridium by aqua regia. A modified method is presented which combines the optimum of speed and accuracy. The modified method is as follows The alloy is fused with ten times its weight of granular lead for one hour a t about 1,000" in a graphite crucible and then allowed to cool.The button is removed and brushed to free it from carbon placed in a beaker containing 1 volume of nitric acid (d 1-42) to 4 volumes of water using 1 C.C. of acid per Q . of lead. The beaker is keptANALYTICAL CHEMISTRY. ii. 127 a t 85" for two hours when the alloy will be disintegrated. The solution is diluted to twice its volume and decanted through a double filter-paper. The residue is washed with hot water and the washings passed through the filters. The filter-papers are returned to the beaker without ignition. To the beaker is now added 15 C.C. of water 6 C.C. of hydrochloric acid (d 1.18) and 0.8 C.C. of nitric acid (d 1-42) for each gram of sample taken and the mixture heated a t 85'; in about one and a half hours the lead platinum alloy will be dissolved.The solution is diluted with twice its weight of water and filtered through a double filter-paper in which the iridium collects in fine crystals. The precipitate and filter-paper are washed with hot water and finally with hot dilute hydrochloric acid (1 100). The iridium and filter-papers are placed in a Rose crucible and dried the filter-paper is then destroyed and the residue heated with the full heat of a Tirrill burner. The ignited metal is then heated in hydrogen for five minutes and allowed to cool in the gas. The Colorimetric Determination of Cholesterol in Blood- serum. s. KRASTELEVSKY (Biochem. Z. 1923 143,403407),- Of the colour reactions of cholesterol the Salkowski reaction is found to be best suited for determining the substance in blood by colorimetric methods.The colour tone is not affected by the presence of other plasma constituents if water is excluded. One C.C. of the serum from 5-10 C.C. of blood is added to 5 C.C. of absolute alcohol shaken and kept in a thermostat a t 55-66' for twelve to twenty-four hours. To the dried powdered residue is added 5 C.C. of chloroform and after fifteen to twenty minutes 5 C.C. of pure sulphuric acid (d 143388). After shaking the mixture is left in an ice-chest for six to twelve hours and the chloroform layer is removed and compared with the standard colours of various known concentrations of pure cholesterol. Solutions of Bayer's Benzobrown and Benzoazurin in aqueous alcohol may be used as standards. The normal cholesterol content of blood-serum is 0~0005-0~0012 g.per C.C. J. P. Determination of Dextrose by Oxidation with Iodine. F. AUERBACH and E. BODLANDER (2. angew. Chern. 1923 36 602-607) .-Under the conditions described by Willstatter and Schudel (A. 1918 ii 337) the oxidation of dextrose by iodine proceeds beyond the gluconic acid stage and laevulose and sucrose are also to some extent attacked. By adjusting the alkalinity of the reaction medium however and the time of reaction a quantitative oxidation of dextrose is effected without any appreci- able reaction taking place with lzvulose and sucrose. To the sugar solution which should preferably contain not more than 200 mg. of dextrose in about 25 c.c. a quantity of an N/10 solution of iodine in potassium iodide is added such that a t least one-third to one-half of the iodine remains unchanged.To the solution is then added 100 C.C. of a mixture of equal volumes of one-fifth-molar solutions of sodium carbonate and sodium hydrogen carbonate (having pH 10.1-10.2) and this reaction mixture is kept in the J. F". S.ii. 128 ABSTRACTS OF CHEMICAL PAPERS. dark for one and a half to two hours. It is then acidified with 25y0 sulphuric acid (12 c.c.) and the unchanged iodine is titrated back with N/10 thiosulphate and starch. The quantity of thio- sulphate required is subtracted from that required in a blank experiment carried out simultaneously and of the difference 1 C.C. of the N/10 solution is equivalent t~ 9.005 mg. of dextrose. Under these conditions lactose also is quantitatively oxidised 1 mol. requiring two equivalents of iodine and the same applies a t any rate approximately to maltose.The method may be used to distinguish between natural and artificial honey and to detect adulteration of honey with artificial invert-sugar or dextrose. [Cf. R. 107.1 W. T. K. R. Comparison of the Action of Chlorine and Chlorine Dioxide on Wood. E. HEUSER and 0. MERLAU (Cellulosechem. 1923 4 101-109) .-An investigation of the method proposed by Schmidt and Graumann (A. 1921 ii 912) for the removal of incrustive substances from plants for example lignin from wood by means of chlorine dioxide. It is shown that the method is serviceable as a means for the rapid separation of raw+ellulose so-called " skeleton-substance " from wood and that under certain con- ditions it is a useful alternative method for the quantitative analysis of wood.When wood is treated by the Schmidt and Graumann method hexosans remain in the " skeleton-substance " whereas pentosans are found in both the cellulose and the lignin portions. For instance spruce wood freed from ash and resin and containing 10+30~0 of pentosans and 6.38% of mannose yielded 62.71 yo of " skeleton-substance," which contained 4.4% of pentosans 5.4374 of mannose and 52.84% of pure cellulose. By dialysis and subsequent evaporation of the lignin extract obtained by Creatment of wood with chlorine dioxide and aqueous sodium sulphite 70% of the lignin originally present in wood was obtained in a dry state and this contained 8-16y0 of pentosans. Hence in the determination of pure cellulose and lignin in wood by means of the method of Schmidt and Granmann allowance must be made for the presence of mannose and pentosans in thc " skeleton-substance " and the lignin extract.The pure cellulose- content of wood as determined by the methods of Schmidt and Graumann and of Cross and Bevan was 52.2% and 52.8% re- spectively and the lignin content as determined by the former method and by Willstatter and Zechmeister was 30.3% and 2S.01~0 respectively. Chlorine dioxide has an appreciable action on xylan but not on pure cellulose and cotton. Pentosans present in wood are partly removed by treatment with hot water* and hot dilute solutions of sodium sulphite (cf. Euler following abstract) but this solubility is not dependent on simultaneous processes of oxidatioii or hydrolysis.Methods for carrying out the analysis of wood by the method of Schmidt and Graumann are fully described and also ail improved form of Gooch crucible for use with these methods. A. J. H.ANALYTICAL CHEMISTRY. ii. 129 Determination of Lignin in Wood by the Method of Schmidt and Graumann. A. C. \TON EULER (CeZZuZosechem. 1923 4 109-1 13).-In view of the considerable difTerence (9.37 %) between the lignin-content of pine wood as determined by Willstatter and Zechmeister and by the method of Schmidt and Graumann (A. 1921 ii 912) the latter method has been critically examined. Since albumin is not affected by treatment with an aqueous solution of chlorine dioxide it is probable that about O4y0 of wood-gum containing xylose mannose and dextrose will remain in the so- called carbohydrate " akeleton-substance " ; the latter also retains about 0.2% of mineral substances so that an error of l"/b is possible in the determination of the carbohydrate content.A more serious error arises from the fact that when wood after successive extrac- tion with benzene and alcohol whereby fats resins and turpentine are removed is subjected to the various processes of washing by means of hot and cold water and aqueous solutions of sodium sulphide as described in the Schmidt and Graumann method it suffers a considerable loss of weight due to the solubility under such conditions of wood-gum and lignin. For instance one sample of pine wood freed from fats resins and turpentine was subjected to thirteen successive treatments comprising steeping in water for twenty-four hours washing with hot and cold water extraction with a 2% aqueous solution of neutral sodium sulphite and subsequent washing with water and the respective losses in weight were 6.5 2.8 0;7 1-5 1.5 0.9 0.7 1.2 1.7 1-2 0.6 0.4 and 0.7% (total=20.4%).The Schmidt and Graumann method is therefore likely to give a low carbohydrate-content and a corre- spondingly high lignin-content. Attention is directed to the apparent solubility of lignin in a neutral aqueous 2% solution of sodium sulphite but this solubility may be due to the formation of a small amount of sodium hydrogen sulphite during hydrolysis of the wood complex. A. J. H. Detection and Determination of Tartaric Acid. M. FRAN~OIS and C. LORMAND ( J . Pharrn. Chirn. 1923 [vii] 28 433-442).-In Kling's method for determining tartaric acid in wine (cf.A. 1910 ii 359) which depends on tJhe precipitation of the very insoluble calcium racemate by addition of Z-tartaric acid in excess and calcium acetate incorrect results are liable to be obtained on account of the sparing solubility of calcium Z-tartrate. The present authors find the solubility of the calcium tartrates in water a t 20" to be calcium d-tartrate and calcium Z-tartrate both C,H40,Ca,4H,0 0.232 and 0.249 g. per l. respectively ; calcium racemate 0.0493 g. per 1. The solubility of the d-tartrate in alcohol of 32 vol. yo strength is however sufficientlysmall (0-038 g. per l. a t 20') to allow of the direct determination of tartaric acid by precipitation of this salt. The sample for analysis should contain about 0.4-0-6 g.of tartaric acid and is made up to 100 c:c. with water. To this solution is added 20 C.C. of a solution of calcium acetate (32 g. of pure calcium carbonate and 120 C.C. of glacial acetic acid made up to 1 1. with water) and then after stirring,ii. 130 ABSTRACTS OF CHEMICAL PAPERS. 30 C.C. of alcohol of 95 vol. ?h strength. After keeping the mixture for twenty-four hours a further 30 C.C. of the alcohol is added. After a further twenty-four hours the crystals of calcium d-tartrate are collected preferably in a Gooch crucible dried in the air a t room temperature and weighed. The results are accurate to about 1%. The characteristic appearance of the crystals of calcium d-tartrate may be used for the detection of the acid.W. T. K. B. Determination of Malic Acid in Fruit Syrups and other Fruit Products. F. AUERBACH and D. KRUGER (2. Unters. Nahr. Genussm. 1923 46 177-217).-A 25 C.C. sample of the material is acidified with h7/2-hydrochloric acid allowing an excess of 0.5 C.C. over the ash-alkalinity. The latter is determined by titration to Methyl-orange. In the case of ( a ) natural juices lemonade etc. (with small sugar content) 100 C.C. of 96% alcohol is added and ( b ) syrups marmalade etc. (containing much sugar) 400 C.C. of alcohol is needed. The solution is filtered through a dry filter and if the volume of the precipitate is considerable a correction is made for its volume. Ten C.C. of the filtrate is titrated with NjlO sodium hydroxide solution (litmus) and the amount of barium carbonate required to neutralise is calculated.Three hundred and fifty C.C. of filtrate ( b ) or 75 C.C. of filtrate ( a ) to which 250 C.C. of alcohol is added is neutralised with the requisite amount of barium carbonate. Two C.C. of 50% barium acetate solution is added and the liquid heated on a water-bath until precipitation is complete. The precipitate is filtered after twenty-four hours and washed with 95y0 alcohol and dried in a steam oven. Pre- cipitate and paper are placed in a 50 C.C. graduated flask 0.1 g. of barium citrate and 0.05 g. of barium tartrate are added and the whole is diluted with water nearly to 50 C.C. After several hours' shaking the volume of liquid is made ul) to the mark with a saturat'ed solution of limium citratc and tartrate. The liquid is filtered and if necessary decolorised with animal charcoal.The malate in the solution is determined polarimetrically . For this 20 C.C. of solution is sliakcn for four hours with 3.5 g. of uranyl acetate and 2.5 C.C. of dljl0 dkodiuni citrate solution and diluted to 25 c.c.; or 10 C.C. of solution is mixed with 2 C.C. of glacial acetic acid and 10 C . C . of satnmted aqueous ainmonium inolybdatc solution decolorised if necessary with animal charcoal and diluted to 25 e.c. The necessary corrections are described and the effect of various sugars amino-acids p r e s ( ~ v r ~ t i v ~ s chtc. on the accuracy of the method detailed. A. G. P. Determination of Hydpoxyl Values [of Oils and Fats] by Normann's Method. W. MEIGEN and 0. RAMGE (Cheni.Umschau 1024 31 3-4).-Norinann's method of determining the hydroxyl values of oils and fats was tested on specially purified samples of mono- and di-hydroxystearic acids and on mixtures of known proportions of these acids with cacao butter and olive oil. In all cases the values obtained were somewhat higher thanANALYTICAL CHEMISTRY. ii. 131 the theoretical the discrepancies ranging froni 1% to 4%. The fact that high values were obtained by this method was confirmed by parallel determinations of the hydroxyl values of castor and rape oils and of the methyl esters of the mixed fatty acids prepared from these oils. In each case the value obtained for the oils themselves was higher than that calculated from the hydroxyl value of the methyl esters of the mixed fatty acids.According to Griin (Uel & Fett. Ind. 1919 Nos. 13 14) the theoretical value is obtained by applying Normann's method to the methyl esters. When however the hydroxyl value is not too large the error introduced falls within the experimental error and in such cases Normann's method may be considered applicable in view of its convenience. H. C. R. A. EIBNER and K. SCHMIDINGER (Chem. Umschau 1923 30 293-302).-The linseed oil examined was of Dutch origin and was of iodine value 173.6 and acid valuc 2-3. Its composition was as follows or-linolenic acid 20.1% ; isolinolenic acid 2.7% ; a-linoleic acid 17.0% ; p-linoleic acid 41.8% ; oleic acid 4.5% ; hydroxy-acids 0.5% ; glycerol 4.1% ; saturated acids 8.3% ; phytosterol 1.0%. By treating the oil with nitrous acid 0.6% of an elaidin was obtained which was identified as di-elaidopalmitin.Bromination of the oil in alcoholic solution gave 54.2% of crude solid bromide which on purification was identified as brominated di-a-linolenic-a-linoleic glyceride. The oil contained about 25% of this mixed glyceride. The form in which the remaining unsaturated acids were combined was not determined. [Cf. B. Feb.] H. C. R. G. WALKER (J. Xoc. Chem. Ind. 1923 42 497-498~).-1t is suggested that the percentage of cineole in essential oils may be determined from the freezing point and density of a mixture of the oil with a-naphthol. To make such determinations possible measurements have been made of freezing points and densities a t 20"/4" of mixtures of 3.6 g. of a-naphthol and 3.85 g.of artificial eucalyptus oil con- taining from 65 to 95% of cineole. These oils were prepared by adding pure cineole to various eucalyptus oils free from cineole. Curves are given showing the change of density with the percentage of cineole for each variety of oil used namely pinene Eucalyptus mdiata E. nora angelica E. citriodora E. dityes and E. cineritolia residues. E. H. R. Quantitative Analysis of Linseed Oil. The Determination of Cineole in Essential Oils. Microchemical Identification of a-Monoamino-Acids. 0. WERNER (Mikrochemie 1923,1 3346).-A microchemical method for the separation and identification of the more important a-mono- amino-acids is described and also outlined in tabular form; it consists essentially in the sublimation of certain of the substances in a special apparatus.The operation is carried out under reduced pressure and means are provided for cooling the receiver. The character of the crystalline sublimates (in those cases where the substance sublimes) and of the crystals etc. obtained when theii. 132 ABSTRACTS OF CHEMICAL PAPERS. sublimates and residues are treated with cunric livdroxide reagent or phosphotungstic acid affords a means of ;dentaying the amino- acids. w. P. s. Amylolytic Enzymes. R. FABRE and H. P ~ N A U ( J . Phamz. Chim. 1923 [vii] 28 280-304 341-348).-The causes of thc variations observed in determining the amyloclastic activity of pancreatin and diastase preparations with commercial potato starches are critically examined and they are shown to be principally influenced by the character of the water employed in the manufacture of the starch (cf.A. 1923 ii 512). Water with,a pH on the alkaline side activates the pancreatic diastase and inhibits malt diastase whilst the reverse is the case with water having a pII on the acid side. I n order therefore to obtain comparable results it is recommended to prepare the starch employed for such determinations under standard conditions of maceration to avoid influences which tend to produce an extensive demineralisation of the starch granules and that the water employed in its preparation should be absolutely neutral and to adopt as analytical method either that of Bertrand or that of Grimbert’s modification of Lehmann’s method (A. 1913 ii 254) both of which are more exact than the method of direct reduction. Twenty-five to 30% of the sugar produced during the saccharification under the conditions required by the pharmacopoeia is soluble in absolute alcohol. With malt diastase maltose is the only sugar produced whilst in the case of pancreatic dimtase which contains maltase small quantities of dextrose are also formed [Cf. B. 27.1 D. R. N. The Inorganic Elements of Blood Plasma. A. P. BRIGGS ( J . Biol. Chem. 1923 57 351-357).-A system of analysis of the inorganic constituents of b,looci has been developed by means of which determinations may be made of the sodium potassium calcium magnesium chloride and phosphate content of blood using one small sample. The important point is the choice of an anti-coagulant which will not interfere with the subsequent deter- minations. Lithium citrate lias been selected as the most suitable for this purpose. Nine to 15 C.C. of plasma obtained from blood treated with this anti-coagulant is sufficient for the complete analysis. Proteins are precipitated with 20% trichloroacetic acid and the potassium is determined in a portion of the filtrate by a colorimetric method based on its precipitation as cobaltinitrite and the determination of the latter by Griess’s nitrite method. Separate portions of the filtrate are used for determining the remaining constituents slight modifications of existing methods being used for this purpose. The method has been applied to a number of pathological bloods. E. S.

ISSN:0368-1769    

DOI:10.1039/CA9242605121

出版商:RSC    

年代:1924

数据来源: RSC

摘要:

i. 124 ABS'FRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agrieulture The r6le of Bacteria in the " Lactic Acid Fermentation of Dextrose by Peptone." I11 and N. 0. ACKLIN (Biochem. Z . 1923,142 117-141 351-359).-111. A further study has been made of the action of bacteria-bearing peptones in producing the fermentation observed by Schlatter (A 1922 i 1096) in dextrose- peptone-bicarbonate mixtures. The supposed autocatalytic fer- mentation (J.S.C.I. 1923 993A 1145~) can be fully reproduced in sterile peptones inoculated with bacteria from preparations showing the fermentation The incubation period and the quanti- tative course of the process is dependent solely on the extent of active bacterial infection. Schlatter ascribed variations in the activities of different peptones to their variable phosphate content and postulated the existence of an active organic combination between the peptone and phosphoric acid.The author finds that in peptones poor in phosphates (Witte) added phosphate increases the extent of bacterial fermentation up to a limit determined by the hydrogen-ion concentration. On the other hand peptones rich in phosphorus (Siegfried) showed no increased fermentation on the addition of phosphates. A careful study has been made of the effect of phosphate and acetate buffers on the pH of the fermentation mixtures and on the general course of the action of the bacteria. The optimum pH lies between 6.8 and 7.2 being rather nearer the former value than the latter. If sodium acetate is substituted for sodium hydrogen carbonate the fermentation is still observed but in less degree as measured by acid or gas formation which diminish with increasing acetate concentration. During the fermentation in the presence of sodium acetate the p becomes more acid than is the case when bicarbonate is present.IV. The course of the fermentation in inoculated peptone is not appreciably influenced by the sterilisation methods employed. The peptone may be sterilised by ultra-filtration through a De Haen filter of 0.78p. Lactic Acid Fermentation of Dextrose by Peptone. E. BAUR (2. physiol. Chem. 1923 131 65).-The author agrees with Barthel and von Euler (A. 1923 i 985) that the formation of lactic acid from dextrose in presence of peptone described by Schlatter (A. 1922 i 1096) is due to bacterial contamination.Tnhihition of Bacterial Growth by Amino-acids. G. A. WYON and J. W. MCLEOD ( J . Hyg. 1923 21 376-384).-Amino- acids in appropriate concentrations aid bacterial growth but in relatively low concentrations they may be inhibitory. Inhibition occurred with ten out of eleven acids studied and with several mixtures rich in amino-acids. The inhibitory concentration varies from 11 to 130 millimols. per litre. The cyclic compounds were inhibitory in the lowest concentrations. Histidine tyrosine J. P. W. 0. K.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 125 tryptophan and phenylalanine were tested. Of the chain com- pounds tested cystine was most inhibitory. Staphylococcus uureus was able to split glycine in a high but sub-inhibitory concentration.A polypeptide medium may prove valuable for bacterial growth. CHEMICAL ABSTRACTS. Catalase in Bacteria and its relation to Ana6robiosis. A. B. CALLOW ( J . Path. Bact. 1923 26 320-325).-Comparative estimations were made of the catalase content of nine anerobes and twelve aerobes. None of the former and only streptococci among the latter produced gas when treated with hydrogen per- oxide. Hydrogen peroxide was not detected when anGrobes were grown anGrobically and then subjected to the action of the air. It could not be shown conclusively that anaerobes can grow Grobic- ally in the presence of catalase. Catalase Production and Sensitiveness to Hydrogen Per- oxide among Bacteria a Scheme of Classification based on these Properties. J. W. MCLEOD and J. GORDON ( J .Path. Bact. 1923 26 326-331).-When the characteristics of sensi- tiveness to hydrogen peroxide power of producing catalase and power of producing hydrogen peroxide are taken into account bacteria can be roughly divided into four groups (1) those ex- tremely sensitive to hydrogen peroxide and devoid of catalase (the anaerobes) potential peroxide producers ; (2) those moder- ately sensitive to hydrogen peroxide and devoid of catalase (the peroxide producers) ; (3) those moderately sensitive to hydrogen peroxide and devoid of catalase but not peroxide producers; and (4) those sensitive to hydrogen peroxide in varying degrees and producers of catalase (the majority of facultative anaerobes). CHEMICAL ABSTRACTS. CHEMICAL ABSTRACTS. Reduction of Sulphites by certain Bacteria in Media con- taining a Fermentable Carbohydrate and Metallic Salts.W. J. WILSON ( J . Hyg. 1923 21 392-398).-1n media containing sodium sulphite dextrose and iron salts reduction of sulphite to sulphide is effected by Bacillus typhsus B. enteritidis B. para- typhosus B and other members of the Salmonella group but not by B. paratyphosus A and the dysenteriae bacilli. CHEMICAL ABSTRACTS. Toluenated Yeast is not Dead. IGOR ASHESHOV and I. GJAJA (Glas. A d . Xci. Belgrade 105 50-57).-In a previous paper (Compt. rend. SOC. Biol. 1922 86 703) it was shown that toluen- ated yeast consumes considerable quantities of oxygen. In order to determine whether this consumption is due to an oxidation of the dead substance or to the vital functions of the yeast yeast was toluenated by addition of 2% of toluene.When the toluene was removed by animal charcoal the yeast regained its activity after incubation for a certain time if transferred to a new substrate. The length of incubation required varied according to the duration of the action of the toluene. If the toluene was absorbed immedi- ately after the toluenisation eighteen hours’ incubation caused thei. 126 ABSTRACTS OF CHEMICAL PAPERS. yeast to regain its activity. After seventy-two hours’ contact with toluene incubation for sixty hours was required. S. AKAMATSU (Biochem. Z. 1923 142 188-190).-Yeast actively growing in sugar solutions reduces inactive 1 -methylcyclohexan- %one to dextrorotatory 1 -methylcyclohexan-2-01. Growth of Yeast on a Medium of Wholly Synthetic Origin.E. I. FULMER V. E. NELSON and A. WHITE ( J . Biol. Chem. 1923 57 397-399).-Yeast has been subcultured on a wholly synthetic medium. The carbohydrate employed was Loew’s methose which was synthesised from formaldehyde. Relationships between Hydrogen-ion Hydroxyl-ion and Salt Concentrations and the Growth of Seven Moulds. H W. JOHNSON (Iowa State Coll. Research Bull. 1923 No. 76 307-344). -The known extremes of soil reaction pH 3-62-9.68 have little or no inhibiting effect on soil moulds. Seven moulds studied show that the degree of acidity necessary to inhibit growth vanes from pE 1.6 to 3.4 and the degree of alkalinity from p 9.0 to 11.2. Salts in order of increasing toxicity are (1) molecule for molecule. Magnesium sulphate potassium chloride magnesium chloride sodium chloride calcium chloride sodium sulphate sodium carbon- ate potassium carbonate ; (2) g..per litre. Magnesium sulphate sodium sulphate potassium chloride magnesium chloride calcium chloride sodium chloride potassium carbonate sodium carbonate. All moulds change the reaction of media in which they grow. S. S. M. Phytochemical Reduction in the cycloHexane Series. J. P. E. S. CHEMICAL ABSTRACTS. Citric Acid Fermentation. W. BUTKEWITSCH (Biochem. Z. 1923 142 195-211) .-Cultures of Aspergillus nigel and Citromyces glaber growing in the presence of quinic acid do not produce citric acid. If calcium carbonate is present considerable formation of oxalic acid occurs. Sucrose the hexoses and glycerol form the best substrates for citric acid fermentation by these fungi whilst arabinose and mannitol undergo the fermentation to a less extent.Saccharic and gluconic acids do not give rise to citric acid and are therefore not to be regarded as intermediate stages in the ferment- ation. Evidence is adduced in favour of the view that the form- ation of citric acid from the hexoses takes place with intermediate formation of an acid allied to parasaccharinic acid rather than Euler’s view that acetaldehyde is an intermediate. The inter- mediate acid product is precipitated from the fermentation mixtures by the addition of lead acetate and ammonia. J. P. A. K. ANDERSON and J. J. WELAMAN (Proc. SOC. Exp. Biol. Bed. 1922 20 108-110).-Fusarium lini when grown on dextrose media produces ethyl alcohol and carbon dioxide as the main by-products of metabolism.Succinic acid was not produced in appreciable amount. In the absence of dextrose this organism can utilise ethyl alcohol preferably a t a concentration of 2%. The Fermentation of Dextrose by Rusarium lini. CHENICAL ABSTRACTS.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 127 Chemical Composition of the Walls of certain Algae. M. E. WURDACK (Ohio J. A%. 1923 23 181-191).-The cell-walls of representatives of Vaucheria Cladophora. Oedogonium Spirogyra Zygnema and Braparnaldia are composed of an inner layer of cellulose and an outer layer of pectose or chitin; when the last- named is present pectose forms a middle layer. In some forms ( Vaucheria Drapurnaldia) the pectose is difficultly permeable to an ammoniacal solution of cupric oxide and a solution of iodine in potassium iodide ; in others (Cladophora glomeratra OerEogonium irregulare) a third layer of chitin is present and in Cedogonium crassurn amplum there is a layer of an unidentified substance. Mucilaginous sheaths of the algae studied are of pectic compounds of which pectic acid predominates with pectose in some cases.CHEMICAL ABSTRACTS. Is Gaseous Nitrogen a Product of Seedling Metabolism? J. DAVIDSON (Bot. Gaz. 1923 76 95-101).-Wheat seedlings and cow pea seedlings were grown in Kjeldahl flasks under sterile and non-sterile conditions. The results indicate that no nitrogen in the gaseous form is lost in the process of germination and in the early life of the seedlings as an inherent function of the metabolic processes.D. R. HOAGLAND (Soil Xci. 1923 16 225-246).-The results of a comprehensive series of studies on the absorption of ions by barley plants from different solutions are reported. Diflerent ions were absorbed at different rates and the absorption of any one ion was found to be affected by other ions. Thus kations are affected both by kations and anions and vice versa. For example potassium is absorbed most rapidly from potassium nitrate less rapidly from potassium chloride and least rapidly from potassium sulphate solutions. The proportion of ions absorbed from a solution decreases as their concentration in the solution falls. Ions may be absorbed either more rapidly or less rapidly than water. Thus whilst potassium- nitrate- and phosphate-ions may be taken up more rapidly than water calcium- magnesium- and sulphate-ions may be taken up at the same time at a slower rate than water.Attention is directed to the fact that energy exchanges are involved in the process of absorption and that permeability relations alone are inadequat,e to explain the phenomena of absorption by plants. G. W. R. W. SEIFRIZ (Amer. J. Physiol. 1923,66 124-139 ; cf. Science 1923 57 694).- The effects of various electrolytes (sodium hydroxide sodium chloride barium hydroxide barium chloride and calcium chloride) in causing phase reversal in emulsions of (1) oil in water and (2) water in oil prepared with various emulsifying agents were studied. Olive oil emulsions with casein gliadin cholesterol or cephalin in the aqueous phase form water in oil systems which are reversible -with sodium hydroxide.Oil emulsions in which saponin (senegin smilacin) gelatose gum arabic albumin lecithin or plant extract CHEMICAL ABSTRACTS. The Absorption of Ions by Plants. Phase Reversal in Emulsions and Protoplasm.i. 128 ABSTRACTS OF CHEMICAL PAPERS. is t,he emulsifier form oil in water systems which are not reversible with barium chloride. The hypothesis of Clowes (A. 1916 i 583) on the mechanism of permeability changes in the plasma membrane of organisms is based on the behaviour of only one type of emulsion in the presence of certain ions and must be regarded a,s a purely speculative hypothesis which rests on very uncertain evidence. CHEMICAL ABSTRACTS. Amylase in Plants. 111. I<. SJOBERG (Biochem. Z . 1923 142 274--279).-Following the earlier work of the author on the activity of plant amylases (A 1923 i 275) it is shown that an amylase is present in tulip plants which do not form starch in the dark and very little when exposed to light.It occurs in leaves sepals stem and juice and is more prominent in the young than in the old plants. Amylase is also present in the roots and more especially in the stem and buds of young specimens of Pisum sativum. From the fact that the enzyme is most prominent in actively growing plant-tissues it is assumed to have a synthetic function possibly in forming cellobiose. J. P. Analysis of the Jerusalem Artichoke. A. T. SHOHL ( J . Amer. Chem. Xoc. l923,45,2754-2756).-The juice of the Jerusalem artichoke has pH 5.0. It contains only traces of water-soluble-B vitamin.Analysis of the pared tuber (69 yo of total weight) gives moisture 79-oy0 ; total nitrogen 3.10/ (of which 71.5% is water- soluble and 27.5% present as amino-acids); fat 0.2%; carbo- hydrate (inulin) 15*50/ ; fibre 0.8% ; ash 1*1% in close agreement with the results of Strauss (Berlin. Klin. Woch. 1912 49 1213) and of Langworthy (U.X. Dept. Agric. Bull. 1917 468). The metabolism of inulin is discussed and a reinvestigation recommended of the use of the Jerusalem artichoke in the treatment of diabetes. W. S. N. Saponins [of Chestnut Seeds]. A. W. VAN DER HAAR (Rec. trav. chim. 1923 42 1080-1083).-1t is shown that the saponin from chestnut seeds if obtained free from accompanying sucrose does not give rise on hydrolysis to lmulose as stated by Blau (Diss. Univ. Zurich 1911) and Bosshard (Diss. Tech. Hochschule Zurich 1916). The saponin in question contains 9*Sy0 of water 1% of ash and on hydrolysis affords sapogenins 46.2% ; dextrose 23% ; pentose 4.8% ; methylpentose 4.2% ; &galactose 2.24% ; d-glycuronic acid 10% (identified as d-glycuronolactone) ; and acetic acid WY0. Xylose d-mannose fucose and galacturonic acid are not products of the hydrolysis. Influence of Hexamethylenetetramie and Formaldehyde on the Haricot Bean. E. NICOLAS and G. NICOLAS (Compt. rend. 1923,177 1062-1064).-A continuation and confirmation of previous work (A. 1923 i 427) using different varieties of haricot beans. E. E. T. E. E. T.

ISSN:0368-1769    

DOI:10.1039/CA9242600124

出版商:RSC    

年代:1924

数据来源: RSC

摘要:

i 129 Organic Chemistry. The Lubricant and Asphaltic Hydrocarbons in Petroleum. C. P. ~ B E R Y (Ind Eng. Chem. 1923 15 1233-1238).-Most crude petroleums begin to show evidence of decomposition a t a temperature of 300" even at 20 mm. pressure. In an investigation of the hydrocarbons boiling above this point applied to samples of crude petroleum of varying origin separation was therefore effected by means of fractional solution in a mixture of ether and ethyl alcohol. The fractions so obtained were examined as to density mol. weight (as determined by solution in stearic acid a t m") and composition by analysis. In all cases these heavy hydro- carbons fall into one of two classes ( D ) hydrocarbons lubricants throughout and ( H ) hydrocarbons of which the heavier are asphaltic. The latter are usually poorer in hydrogen the series identzed through the whole range of samples varying from C,H to C,H,,-m.The halogens react normally with these hydro- carbons. The nitro-derivatives of the (0) hydrocarbons separate as finely divided crystals those of ( H ) hydrocarbons as oils when poured into water. These derivatives have much lower mol. weights than the original oils and are nitro-carboxylic acids. All samples of fractions from American petroleum were found t o contain carb- oxylic acids or esters in proportions ranging from traces up to 2%. This probably accounts for irregular variations in the density of succeeding fractions. Iodine number determinations show that only the ring type of unsaturation exists in lubricant hydrocarbons.The Processes of Dehydrogenation in the Presence of Catalysts. J. K. PFAFF and R. BRUNCK (Ber. 1923 56 [ B ] 2463-2464).-The catalyst is prepared by mixing solutions of sodium aluminate and nickel nitrate and rendering the precipita- tion complete by passing carbon dioxide to saturation The paste is mixed with pure ignited aluminium oxide filtered and washed as free as possible from alkali. It is subsequently dried and reduced by hydrogen a t 320". In the presence of this material benzene is smoothly hydrogenated a t 180-200° to hexahydrobenzene but unexpectedly the latter substance is not reconverted into benzene to more than a minimal extent a t any temperature below about 500'. Purified lignite tar oil b. p. 80-150' is similarly readily saturated with hydrogen a t 180-200' but under the conditions used in the attempted dehydrogenation of hexahydrobenzene the product is converted quantitatively into methahe.Under similar conditions a purely aliphatic fraction of American petroleum yields almost entirely methane and leaves a small carbonised deposit on the catalyst; the reaction commences a t about 240" and is almost quantitative at 260'. [a. B. Feb.] c. I. VOL. CXXTV. i. fi. 130 ABSTRACTS OF CHEMICAL PAPERS. By means of the nickel catalyst the aliphatic components can readily be removed as methane from a mixture of aliphatic hydro- carbons and naphthenes. H. W. Addition of Nitrogen Trichloride to Unsaturated Hydro- carbons. I. G. H. COLEMAN and H. P. HOWELLS ( J . Amer. Chem. Soc. 1923 45 3084-3089; cf A. 1922 i 133).-Nitrogen trichloride was added slowly to a solution of Ap-butene in carbon tetrachloride a t -lo' and after washing and removal of water the p-chloro-y-dichloroaminobutane formed NCb*CHMe*CHMeCI was reduced by concentrated hydrochloric acid to p-chloro-y-amino- butane NH,=CHMe*CHMeCI ; the benzoyl derivative colourless needles m.p. 105-106' was isolated. Similar reactions with Aa-butene rzsulted in the isolation of r-a-chloro-p-benzamido- butane slender silky needles m. p. 91-92' which was reduced to r-p-benzamidobutane m. p. 84-85'. The latter subsfance was also prepared from methyl ethyl ketoxime and it had the same melting point (Pope and Gibson T. 1912 101 1702). @-p-Nitrobenzamidobutane obtained from Aa-butene and from methylethylketoxime melted a t 114.5-115.5".. Nitrogen tri- chloride reacted rapidly with p-methyl-As-butene ; no amine was produced but amylene dichloride and chloroamylene chloride were formed. F. B. Acetylene Condensations. 11. The Theory of the Form- ation of Cuprene. H. P. KAUFMANN and W. MOHNHAUFT (Ber. €923 56 [B] 2533-.2536).-The conversion of acetylene into cuprene in the presence of copper or copper compounds at 230- 300' does not take place in the complete absence of oxygen. The product is not homogeneous the composition varying between (CllHlo)z and (Cl,H,o),. In addition small amounfa of oily compounds are produced. The colour of the product ranges from pale yellow to dark brown. The authors consider that its formation is due to the production of an intermediate additive compound of acetylene with cuprous or cupric oxide which immediately undergoes pyrogenic decomposition.Possibly the variafion in temperature due to the rapid stream of gas plays a distinct part. Since the oxide which is regenerated by decomposition of the acetylide again takes part in the reaction the proportion of oxygen present (in the case of copper) need not be great. The formation and decomposition of the acetylide explains the peculiar observation that the copper catalyst which originally lies a t the bottom of the vessel ultimately becomes distributed throughout the whole reaction chamber. The superiority of copper over other metals as a catalyst is ascribed to the possibility of the simultaneous production of oxide and acetylide. The liberated acetylene must be endowed with particular reactivity as a consequence of which the reactions whidh occur are much more profound than those involved in the pyrogenic decomposition of acetylene alone and lead through the most stable forms of combination to the in- active cuprene the purely aromatic nature of which is thus readily explained (cf.Kaufmann and Schneider A. 1922 i 245). H. W.ORGANIC CHEMISTRY. i. 131 Process for Converting Halogen Substitution Products of Hydrocarbons into Hydrocarbons or other Halogen Substitution Products of Hydrocarbons containing a Higher Number of Carbon Atoms. FARBWERKE VORM. MEISTER Locms & BRUNING (Brit. Pat. 196272).-The process consists in passing halogen substitution products of hydrocarbons or mixtures of them in the presence of water over a catalyst com- prising metals (e.g. platinum) or their compounds (e.g.thorium oxide zirconium chloride bismuth oxide sfannic chloride zinc chloride) or non-metals (e.g. charcoal) carried on porous materials {particularly active charcoal) at an elevated temperature not exceeding 400”. Details are given for the production of ethyl chloride and ethylene from methyl chloride and of ethylidene chloride from a mixture of methyl chloride and methylene chloride. iCY. B. Feb.]. E. DEISS (2. Elektro- chrn. 1923 29 586-587).-!L’he ignition temperature of ethyl chloride lies below -18*5” the lower limit of explosion for mixtures of air and ethyl chloride is found with the mixtures containing 3.6% of ethyl chloride the upper limit being the mixture containing 11.2% and the maximum explosion occurs with 6.5% of ethyI chloride.J. F. S. Auto-oxidation of Chloroform. A. M. CLOVER (J. Amer. Chem. Sm. 1923 45 3133-3138).-When chloroform was exposed to diffused light it developed acidity and oxidising power. The latter reached a maximum and then decreased whilst the acidity continued to increase. On dilution with water the oxidising substance reacted to form hydrogen peroxide. The oxidising substance is probably dichlorocarbon peroxide CO,CI,. The addition of petroleum alcohol phenol and many other substances inhibits the decomposition of chloroform but the mechanism of their action remains obscure. Bromoform and methylene chloride also develop oxidising substances on standing. The Synthesis of Higher Members of the Aliphatic Series from Carbon Monoxide F.F’ISCHEE and H. TROPSCH (Fy; 1923 56 [B] 2428-2443).-An examination of the pos- sibhty of the conversion of water gaa into motor spirit. In the presence of a suitable catalyst carban monoxide is reduced by hydrogen to a mixture of alcohols ketones aldehydes etc. which is designated “synthol.” It is converted when heated under pressure into a mixture of hydrocarbons to which the name “ synthin ” is assigned. In a somewhat similar manner the direct production of hydrocarbons from mixtures of carbon monoxide and hydrogen has been patented by the Badische Aniljn- & Soda- Fabrik (D.R.-P. 293787 295203 and 295202) ; the dif3erent course of the reaction is possibly due to the fact that technical water gas containing carbon dioxide and an excess of hydrogen over carbon monoxide is used in the experiments now described whereaa in the work of the Badische Anilin- & Soda-Fabrik the carbon mon- oxide W~EI invariabIy in excess.W. T. K. B. Some Constants of Ethyl Chloride. F. B. f 2i. 132 ABS'JJRACTS OF CHEMICAL PAPERS. [With W KEtiiNxa.J-Technica1 water gas is freed as far as possible from compounds of sulphur compressed at 150 atmospheres and heated at 400-450" in the presence of iron covered with potassium carbonate; the product of the reaction separates into an aqueous and an oily layer in the volume proportion 2 1. A marked difference in the components of the two phases is not observed. Each consists of fatty acids aliphatic aldehydes ketones and alcohols; in addition the oily layer contains esters and hydrocarbons in small amounts.The presence of formic acetic propionic and isobutyric acids is established. Higher fatty acids are also present which have not been identified individually; as judged by equivalent and boiling point acids of the formula C,H,,O are produced. The presence of propaldehyde probably n-butaldehyde and isobutaldehyde is established whereas form- aldehyde could not be detected. The ketones comprise acetone methyl ethyl ketone diethyl ketone and methyl n-propyl ketone. Methyl ethyl and n-propyl alcohols are identified in addition to higher homologues. The esters have not been identified. Hydro. oarbons are present only in minor amount (about 2%). The conversion of synthol b. p. 99-225" into synthin is effected under pressure a t 400450" in an autoclave in an atmo- sphere of nitrogen.The liberated gas consists of carbon dioxide (14*5%) hydrocarbons soluble in fuming sulphuric acid (2207%)~ oxygen (o.7y0) carbon monoxide (14.6%) hydrogen (9.6%) paraffin hydrocarbons (21*8y0) and nitrogen (16-1y0). The liquid product consisfs mainly of hydrocarbons which boil over a wider range than the initial material. They are stable towards con- centrated sulphuric acid and therefore saturated. The atomic ratio C H increases from the fractions of lowest to those of highest boiling point. Whereas in the former this ratio is nearly 1 2 as is required for the simpler naphthenes in the latter its value indicates that only saturated hydrocarbons with several condensed ring systems can be present. Possibly the process consists in the initial conversion of the alcohols by loss of water into olefines which become further subdivided into small portions which unite to form naphthenes.The theory of the experiments is discussed in detail. It is pointed out that the presence of a hydrogen carrier such as iron nickel cobalt or possibly manganese is essential in addition to a base or the salt of a base with a weak acid. Apparently the production of oil is favoured by the strength of the base which however by ifself (e.g. potassium hydroxide in the presence of pumice) is not sufficient. It appears most probable that the initial product is formaldehyde which in the absence of bases passes into methane; in the presence of the latter however it becomes converted into methyl alcohol as is established by the production of large amounts of the latter from paraformaldehyde and hydrogen a t 400" under 100 atmospheres in the presence of pumice loaded with potassium carbonate.Methyl alcohol is converted by carbon monoxide either directly or through methyl formate into acetic acid the stepwise reduction of which givesOMANIC CHEMISTRY. i. 133 acetaldehyde and ethyl alcohol whilst its catalytic decomposition gives acetone. An extension of this operation yields propionic acid propaldehyde n-propyl alcohol and diethyl ketone. The non-production of members containing more than seven or eight carbon atoms is due to their instability under the experimental conditions. The production of higher alcohols is probably due to loss of water from the simpler members of the series.H. W. Alcohols and Hydrocarbons from Beeswax. GASCARD and G. DAMOY (Compt. rend. 1923 177 1442-1443; cf. this vol. i 8).-The following alcohols (2 and 4 in largest quantity) have been obtained from beeswax after alkaline hydrolysh (1) Neowyl C25H520 m. p. 75.5"; (2) ceryl C2,H5,0 m. p. 80'; (3) rno&tw& C,H,,O m. p. 84". and (4) myricyl aleoh&* Cs m. p. 87". After cryst&llising the alcohols the following gl carbons were obtained from the mother-liquors Pentacosane C25H52 m. p. 54-5445" ; heptacosane C27H56 m. p. 59.2-59.5' ; nonacosane C29H60 m. p. 63.5" and hentriacontane C,,H m. p. 68-449". All the acids alcohols and hydrocarbons obtamed from beeswax crystallise in hexagonal plates. Aa-Pentene-y-ol [Ethyl Ally1 Alcohol].J. BAU DRE NGJTIE x (Bull. Xoc. chim. Belg. 1923 32 337-339; cf. A. 1922 i 710; also Delaby A. 1923 i 741).-The following physical constants are given b. p. 114.2-114-4"/753 mm. dJ" 0.8373 n$ 1.4254. Dry hydrogen chloride is absorbed by the alcohol yielding a mixture of products one of which believed to be CH2:CH*CHEtC1 has b. p. 93-94"/759.8 mm. dy 043978 ng 1.4254. This sub- stance reacts with potassium acetate with formation of a mixture of isomerides. Hydrogen bromide gives with the alcohol a product b. p. 124-131" which is very unstable. Molecular Conductivity of Potassium Iodide in Epichloro- hydrin. N. A. YAJNIK and B. R. SOBTI ( J . Amer. Chem. SOC. 1923 45 3138-3139).-The molecular conductivity of potassium iodide in epichlorohydrin was determined by the Kohlrausch method. The results are mol.volume (litres) 60 120 240 480; specific conductivity 10 mhos 2-3 1.3 0.8 0-53 ; mol. conductivity (mhos) 13-8 15.6 19.2 25.4 respectively. Carbohydrates and Polysaccharides. V. Use of Acetylene for the Synthesis of Cyclic Acetals. H. S. HILL and H. HIBBERT ( J . Amer. Chem. Soc. 1923 45 3108-3116; cf. A 1923 i 439 753).-The following cyclic acetals were prepared by passing acetylene into a mixture of a polyhydroxy-compound and a small amount of mercuric sulphate with 93% sulphuric acid. Ethylidene trimethylene ether b. p. 108-1 ll" ethylidene a@- propylene ether b. p. 92"; ethylidene glycerol bromohydrin b. p. 170-182" ; ethylidene glycerol b. p. 189-196" ; ethylidene u8-tetramethylene ether a colourless hquid b.p. 124-127" ; ethyl- idene p h c o l b. p. 133-134" ; P-methyl~ntane- p8-diol ethylidene ether b. p. 139-140" ; monoethylidene a-methyl glucoside silky E. E. T. H. J. E. F. B.j. 134 ABSTRACTS OF CHEMICAL PAPERS. colourless crystals m. p. 77" and ethylidene glucose. The mechanism of the reaction is discussed. Carbohydrates and Polysaccharides. VI. Relative Eass of Formation of Five- and Six-membered Heterocyclic Carbon-Oxygen Configurations. H. S. HILL and H. HIBBERT ( J . Amer. Chem. Soc. 1923,45 3117-3124; cf. preceding abstract). -When one equivalent of acetylene was passed into a mixture of one equivalent of ethylene glycol and one equivalent of tri- rnethylene glycol the proportion of ethylidene ethylene ether (five-membered ring) to ethylidene trimethylene ether (six- membered ring) was 1 2. A similar result was obtained in the case of a mixture of propylene ap-glycol and trimethylene glycol whilst with a mixture of ethylene glycol and p-methylpentane- p6-diol the ratio was 1 5 .Using a mixture of trimethylene glycol and p-methylpcntane-p6-diol the ratio of the two six-membered ring derivatives was 1 2. Thus the six-membered ring compound was formed in preference to the five-membered ring compound and the presence of methyl groups attached to the glycol carbon atoms favours ring formation. Similar partition experiments with F. B. mixtilres of glyceG1 and ethylene glycol-led to the Gonclusion that ethylidenc glycerol consists of a mixture of CHMe\ /O*YH*CH2*OH O*CH - and CHMC<~:~~~>C!H*OH the latter predominating.&F. €3. Carbohydrates and Polysaccharides. VII. The Ease of Formation and Nature of certain Six- Seven- and Larger Carbon-Oxygen Cyclic Structures. H. S. HIr,L and H. HIBBERT (J. A?ner. Chena. Xoc. 1023 45 3124-3132; cf. pre- ceding abstract).-Thc partition of one equivalent of acetylene between one equivalent each of ethylene glycol and tetramethylene giycol shows that the five-membered cyclic acetal is formed three times as readily as the seven-membered compound. Attempts to prepare the cyclic ethylidene derivatives of octa- and deca-methylene glycols resulted in syrupy odourless acetals with very high and indefinite boiling points. The tendency of atomic chains to assume spiral ring formation is discussed. Preparation of Chloroethylsulphuryl Chloride.CKEMISCFE F-~BRIK VORM. WEILER-TER MEER (D.R.-P. 374141 ; from Chem. Zentr. 1923 iv 'i20).-Ethylenc chloride is treated with fuming sulphuric acid with or without a catalyst and the resulting chloro- ethy?suZphuryZ chloride a colourless heavy oil with an odour like that of formaldehyde b. p. 130-122"/80 mxn. is obtained by first separating through addition of ice-water and then distilling in a vacuum. Dichlorodiethyl szrlphate b. p. 1SO-lS2"/60 mm. is also obtained. G. W. R. Noteworthy Behaviour of Organic Sulphur Compounds towards Sodium Arsenite. A. GUTMANN (Ber. 1923 56 [ B ] 2365-2367) .-The mode of Combination of sulphur in certain organic (and inorganic) compounds can be distinguished by their 3'. B.ORGANIC CHEMISTRY. i. 136 behaviour towards sodium arsenite.Those which convert the arsenite into sodium thioarsenate Na,AsSO contain sulphur in the polysulphide form ; these also convert cyanide into thiocyanate ; those compounds which through- the intermediary action of water oxidise the arsenite to arsenate contain sulphur in the persulphide form corresponding with the peroxide form of oxygen. Di- xanthogen disulphide diacetyl disulphide and cupric sulphide all belong to the first class ; tin disulphide and ultramarine however contain sulphur only in the bivalent form and are not reactive. Diamyl disulphi de diphen yl disulphide dit hio -N- dimethylaniline and phenyl ethyl disulphide all oxidise arsenite to arsenate and are reduced to mercaptans; they contain one atom of persulphide sulphur. Methyl trisulphide with sodium arsenite gives both arsenate and thioarsenate and is reduced to methyl mercaptan; it therefore contains one atom each of polysulphide- and persulphide- sulphur.The free thiocyanogen of Soderbacks (A. 1920 i 219) and the phenylthiolthiocyanate of Lecher and Wittwer (A. 1922 i 641) both contain 1 atom of persulphide sulphur whilsf the disulphur dithiocyanate of tlhe same authors contains 2 atoms of polysulphide and 1 atom of persulphide sulphur. When cupric thiocyanate is heated with sodium arsenite a green precipitate is first formed which on boiling changes into red cuprous oxide arsenate being formed. In acid solution white cuprous thio- cyanate and arsenate are formed. In this reaction the formation of cuprous salt is not due to the redycing action of the arsenite; this is oxidised to arsenate by the thiocyanic acid formed when the cupric salt is heated.The Stereoisomerism of Brassidic and Erucic Acids D. HOLDE (Ber. 1923 56 [B] 2405).-A claim of priority in this field zgainst von Auwers (cf. A. 1923 i 294). A New Unsaturated Fatty Acid in Sperm and Dolphin Oils. M. TSUJIMOTO ( J . Chem. Ind. Japan 1923 26 608-620).-By the bromo-ester method of Griin and Janko (2. deut. Oel-Fett Ind. 1921 553 572) and the lead salt-light petroleum method a new tetrndecenoic acid C14H2602 has been isolated from sperm and dolphin oils the amount being about 3% of the material The acid was found to be chiefly responsible for the iodine absorption of the lower fractions of the methyl esters. It is a colourless liquid b. p.172"/5 mm. d:F 0.9079 1.4566 iodine value 106.8 (methgl ester b. p. 140"/5 mm. barium salt a white powder) and gives myristic acid C,4H2802 by reduction with hydrogen in the presence of platinum black and dihydroxymyristic acid C,,H,,( OH),02 m. p. 118-119" by oxidation by Hazura's method. By oxidising with potassium dichromate and sulphuric acid the acid gave nonoic acid. On treating the acid with ozone in a chloroform solution an ozonide peroxide C!,H2,O2 was obtained as a viscid colourless liquid the decomposition of which with water gave nonaldehyde nonoic acid glutaric acid semialdehyde ( ?) and glultaric acid. From these facts it is concluded that the formula is CH,*[CH,],*CH:CH*[CH2]3*C0,H. K. K. E. H. R. E. H. R.i. 136 ABSTRACTS OF CHEMICAL PAPERS.Preparation of the Highly Unsaturated Acids of Fish Oils. M. TSUJIMOTO and KANESUKE KIMURA (J. Chern. In&. Japan 1923,26,891-893).-The lithium salt-acetone method of Tsujimoto (A. 1921 i 78) for the separation of highly unsaturated acids is applicable to the quantitative analysis of the acids but unsuitable for the preparation of the acids owing to the need of large amounts of acetone and lithium hydroxide; a modification of the method is therefore proposed for the latter purpose. The fatty acids from fish oil (10 g). are dissolved in acetone (95 c.c.) neutralised with ammonia and mixed with an aqueous solution of the equivalent amount of lithium acetate or chloride the sulphate not being suitable for the purpose owing t o its smaller solubilify in water.The amount of water is kept such that the resulting acetone solution is of 95% strength. It is well shaken for thirty minutes and then cooled in ice-water for one hour. Highly unsaturated acids are dissolved chiefly as ammonium soaps and the lithium salt acts as the precipitant for less unsaturated acids. The solution is filtered through a dry filter-paper in a cold funnel. After evapor- ation of the solvent the residue is treated with a dilute mineral acid and thus highly unsaturated acids are isolated. The yield of the acids by this method is less than that by the peroxide method but the properties of the products are almost the same. K. K. The Decarboxylation of Dimethylpyruvic Acid and its Preparation. H. K. SEN (Biochem. Z. 1923 143 195-200).- Dimethylpyruvic acid (a-ketoisovaleric acid) was obtained by the following process used in preference to the method described by Rassow and Bauer (A.1909 i 632). Ethyl isopropylacetoacetate was treated with dry ethyl nitrite gas in the presence of sodium ethoxide and from the resulting sodium derivative the oxime of ethyl dimethylpyruvate was obtained and purified by distill- ation in a vacuum. From the oxime dissolved in 85% formic acid and treated with nitrosyl sulphuric aeid ethyl dimethylpyruvate together with the free acid was obtained. Hydrolysis of the ester with 5% aqueous potassium hydroxide yielded dimethylpyruvic acid boiling a t 76-78"/11 mm. The semicarbazone (prismatic needles) had m. p. 102-103". Dimethylpyruvic acid in the presence of phosphate buffer mixt,ures is fermented by preparations of dried yeast to give isobutaldehyde in 50% peld A 75% yield of the aldehyde is obtained when the fermentation IS carried out in the presence of acetate and sodium sulphite.isoButyl alcohol is not formed in detectable amount. Keto-enolic Tautomerism. 11. The Combined Applic- ation of Chemical Methods to the Estimation of -01s. H. P. KAUFMANN and G. WOLFF (Ber. 1923 56 [B] 2521-2526; cf. A. 1922 i 985 ; 1923 i go).-Fission of the dienolic form of ethyl diacetylsuccinate by ozone a t a low temperature gives rise to acetic and oxalic acids alcohol and ethyl diketobutyrate. The course of the reaction is explained by assuming that ozonisation occurs a t only one double bond and that the product then suffers fission The reaction is studied quantitatively by estimating the J.P.ORGANIC CHENISTRY. i. 137 oxalic acid produced in the form of calcium oxalate. Fission of the semi-enol by means of ozone occurs in a similar manner and gives rise to the same products. On the basis of these observations it is possible to investigate the equilibrium of ethyl diacetylsuccinate dissolved in hexane carbon tetrachloride or ether. The proportion of a$-ester is determined by the bromine titration method; the colormetric estimation with ferric chloride gives the sum of a-ester and a,p-ester whereas the fission by ozone gives the sum of all the enols (each of which gives a molecular proportion of oxalic acid). The examples which are cited show that chemical methods in t-hese instances lead to results which cannot be obtained by physical means.The relative proportions of the three enols can be estimated with sufficient exactitude but there is no process available for est,imating directly the proportion of the ketonic form. Starting from the @-ester numerous investigations of the equilibria of diacetylsuccinic ester in various solvents have been made. The main difficulty in establishing an exact relationship between the velocity of transformation and the proportion of the enol consists in obtaining absolutely pure solvents free from catalytically active substances. It is however certain that equilibrium is established most rapidly and that the keto-forms predominate in liquids of high dissociating power. Thus in the presence of water the (3-variety is remarkably favoured and all the isomerides are converted into it on contact with water.In nitromethane (e=39.4) a small proportion of the a,p-ester (4.0%) but no other enol is present. In the series of the alcohols the a,@-ester is capable of existence; in addition the a,@-compound is present to a considerable extent (42% in ethyl alcohol). In solvents of smaller dissociating power such as hexane the relationships are displaced greatly towards the other side. The p-ester is not present in appreciable amount and the small percentage of ketonic form exists as the ).-ester. The proportion of a,p-ester recedes whereas that of the a,p-compound attains 50% and the dienolic form is capable of existence. The slight dissociating power of hexane carbon tetrachloride and ether influences markedly the rate of transformation of the isomerides. Loss of the enolic hydrogen atom which takes place instantaneously from the dienol rapidly from the semi-enols in the presence of solvents of higher dielectric constant becomes so retarded thaf even the very strongly acidic dienolic variety is preserved.The primary formation of the a,@-ester in the establishment of all equilibria is very distinct. Equilibrium in the System Calcium Oxalate-Dilute Hydro- chloric Acid. E. CARRIARE and M. AUMBRAS (Compt. rend. 1923 177 1288-1290).-The equilibrium in the system calcium oxalate4ilute hydrochloric acid has been studied by observing the disappearance of the calcium oxalate precipitate a t a certain concentration of acid. Four influences are studied (1) that of concentration of oxalic acid produced ; by plotting concentrations of hydrochloric acid against those of oxalic acid an almost straight line is obtained; (2) that of temperature the concentration of H.W f*i. 138 ABSTRACTS OF CHEMICAL PAPERS. hydrochloric acid is roughly proportional to the solubility product of calcium ortalate a t different temperatures; (3) that of excess of calcium chloride the concentrations of hydrochloric acid are approximately proportional to the square root of the concentra- tions of calcium chloride; (4) that of excess of oxalic acid the concentrations of hydrochloric acid are roughly proportional to the square root of tlhe concentrations of oxalic acid. The Catalytic Bromination of Aliphatic Acid Chlorides. W. F. GOEBEL ( J .Amer. Chem. Soc. 1923 45 2770-2771).- a-Bromoanhydrocamphoronyl chloride (Bredt A. 1895 i 242) is prepared as follows. Anhydrocamphoronic acid is warmed with phosphorus pentachloride until the reaction ceases a small quantity of iron powder is then added and while the mixture is heated on the water-bath bromine is slowly added; the heating is then con- tinued for forty-five minutes and t,he mixture allowed to cool. The crude product (yield 75%) is purified by washing with dry The Supposed Autoxidation of Cysteine. 0. WARBURG and S. SAHUMA (Ppiiqer’s Archiv 1923 200 203-206; from Chem. Zentr. 1023 iii 1290; cf. A 1923 i ll).-The autoxidation of cysteine described by Abderhalden and Wertheimer consists in reality of the oxidation and reduction of a metallic cysteine corn- pound.G. W. R. The Oxidation of Hydrocarbons with Special Reference to the Production of Formaldehyde. V. The Slow Oxid- ation of the Higher Liquid Saturated Hydrocarbons. T. S. WHEELER and E. W. BLAIR ( J . Soc. Chem. I d . 1923 42 491- 497~).-Experiments on the oxidation of hexane were made using a method previously described (A. 1923 i 1175) in which the hydrocarbon mixed with oxygen is passed through a hot tube. The temperatures used were 480° 520° 540° and 590° the time of heating being 2 sec. The products obtained included higher aldehydes unsaturated hydrocarbons formaldehyde acids in small quantity carbon monoxide carbon dioxide hydrogen- a t higher temperatures and water. In presence of excess of oxygen much of the hexane consumed appears as higher aldehydes just as with other hydrocarbons except methane (cf.T. 1923 123 2079). The amount of carbon dioxide formed also increases when more oxygen is used and as the rate of oxidation of the hexane does not increase as fast as would be expected from the law of mass action it is clear that surface action is predominant. As the temperature increases less of thB higher aldehyde appears in the product but more formaldehyde unsaturated hydrocarbon carbon monoxide and carbon dioxide. The unsaturated hydrocarbon at all temperatures is mainly ethylene and the higher aldehydes tend towards acetaldehyde with increasing temperature. No saturated hydrocarbons appear in the products showing that thermal decom- position of the liexane does not occur appreciably otherwise methane would appear in quantity.The results are discussed in connexion E. E. T. ether and then recrystallking from benzene. w. s. N.ORGANIC CHEMISTRY. i. 139 with those obtained by other workers and the probable course of the slow oxidation of hydrocarbons generally is shown diagmm- matically. E. H. R. Condensation cf Aldehydes to Esters by Aluminium Ethoxide. W. C. CHILD and H. ADKINS ( J . Amer. Chern. Xoc. 1923 45 3013-3023).-During an investigation on the con- densation of acetaldehyde t o ethyl acetate using aluminium ethoxide as catalyst it was found that the latter existed in two forms. When prepared by the method of Wislicenus the a-form only was produced and this solidified at a little above the ordinary temperature; it was partly converted into the P-form in.p. 140" on distillatlion. The P- was completely converted into the or-form by heating in a sealed tube at 275" for fifteen hours. Both forms had the same catalytic activity being more active than Henle's ethoxide (A. 19.20 ii 446). The presence of water in the catalyst or in the aldehyde was detrimental. The effect of the addition of a third substance on the rate of reaction was studied and the results show that alcohols containing fewer than six carbon atoms are inhibitors methyl alcohol being the most effective whilst tlic chlorides of aluminium mercury calcium and zinc are promoters. The addition of increasing amounts of aluminium chloride was accompanied by increasing yield of ethyl acetate to a certain value ; further increase in the amount of promoter caused a decreased pro- duction of ester and an increase in the rate of paracetaldehyde formation. The reaction apparently takes place in a homogeneous system and the exclusion of light has no effect.The temperature coefficient of the reaction in xylene solution is approximately I 630 for a rise of 10" in the vicinity of the ordinary temperature. F. B. The Activation of Hydrogen in Organic Compounds. E. H. USHERWOOD (Chemistry and Industry 1923 42 1246- 1251).-The presence of activated hydrogen in an organic com- pound may be recognised by a number of properties among which may be mentioned cliad or triad tautomerism ability to form i?ietallic derivatives and capacity for alkylation. The ability of a compound to take part in an ddol reaction a Michael reaction / / [HI-C- +>C=C< + [H]-&-t]-Cy or a T h o r p reaction \ I I ./ / [HI-CK + [H]-N=C-C ivay also he taken as I cviclence of the presence of an activated hydrogen atom indicated above in square brackets. The phenomenon of tautomerism may be regarded as due to the migration of an activated hydrogen atom within the mo!ecule thus >C[H]-&O >&=CO[H]. There is a strong formal resemblance between this reaction and the aldol reaction >C[H]X + >C:O >CX-&O[H] and this resemblance is intcmsified by a recent demonstration that the aldol reaction is reversible. Keto-enol tautomerism may therefore be I p 2i. 140 ABSTRACTS OF CHEMICAL PAPERS. regarded as an intramolecular aldol reaction. There is a similar analogy between three-carbon tautomerism and the Michael reaction. The structural conditions necessary for the activation of a hydrogen atom to give rise to the above phenomena may be provisionally embraced in two formulae (1) The hydrogen atom represented by fH] in the group [HIC-X is activated no matter whether X is C or N; (2) The hydrogen atom in the group [H]C-X=Y or [HIGC-XY is activated no matter whether X is C or N provided Y is either the electronegative 0 N or S or is C which itself is iiivolved in the group =C-X=Y or =C-X-Y.The benzene nucleus considered as a Kekule individual forms a special case of the second rule and it enters into a number of reactions which show that it possesses an activated hydrogen atom. A number of such reactions are discussed including the addition of benzene to cinnamic acid the conversion of p-imino-y-cyano-or-phenylpropane into 1 3-naphthalenediamine and Skraup’s quinoline synthesis.E. H. R. Production of Acetone by the Action of Potassium Acetate on Acetic Anhydride. E. LUCE (Compt. rend. 1923 177 1306-1 309) .-When an equimolecular mixture of potassium acetate acetic acid and acetic anhydride is heated under reflux for thirty hours in a Path kept at 170-180” some acetone and carbon dioxide are formed. Equimolecular mixtures of potassium acetate and acetic acid or of acetic anhydride and acetic acid when similarly treated give practically no acetone. An equimolecular mixture of potassium acetate (100 8.) and acetic anhydride how- ever gives 12-32 g. of carbon dioxide corresponding with a con- siderable production of acetone most of which is lost by polymeris- ation or evaporation.If the acetone is allowed to distil as fast as it is formed about 24% of the theoretical quantity (see below) is obtained. This type of rearction was observed first by Perkin (T. 1886 49 317) whose explanation has now been confirmed. Thus when a mixture of potassium butyrate and acetic anhydride interacts acetone and methyl propyi ketone are formed as would be expected from the decomposition of the intermediate compound OK*CPP (OAc) whereas if the reaction were due simply to the decomposition of the acid anhydride acetone alone would result whilst interaction (with elimination of potassium carbonate) of 2 mols. of alkali salt would only lead to the formation of dipropyl ketone.Keten and Methyl- keten. C. D. HURD ( J . Amer. Chem. Xoc. 1923 45 3095-3101; cf. A. 1911 i 30’7).-Acetone vapour was decomposed by contact with a hot platinum wire filament but the yield of keten was not so good as in the method previously described (A. 1923 i 1060). Both methyl ethyl ketone and diethyl ketone gave a mixture of methylketen and keten. The presence of keten in the product from diethyl ketone must be due to the decomposition of methyl- keten. F. B. E. E. T. Ketenic Decomposition of Ketones.ORGAXIC CHEMISTRY. i. 141 Oxidation of Carbohydrates. J. STIEGLITZ (Proc. Inst. Ned. Chicccgo 1916-1917 1 41-50).-1n the oxidation of dextrose an intra-atomic phenomenon involving the loss of electrons by the carbon atoms and essentially like that of an element the productioii of an electric current has been observed.The presence of alkalis causes great acceleration and of acids retardation ; the former condition yields decomposition products more readily oxidised than dextrose itself. There is evidently some fundamental specific factor probably the oxidising enzymes having a paramount influence on the physiological processes of oxidation of carbo- hydrates. CHENICAL ABSTRACTS. Sources of the Rare Sugars XI. Preparation of Man- nose. XII. Preparation of Inulin. T SWANN HARDING (Sugur 1923 583-585 636-638) .-Mannose.-A modification of the method of Hudson and Sawyer (A. 1917 i 321) is described Ivory sawdust is mixed with its own weight of sulphuric acid (76y0) hydrolysed as directed by Hudson and Sawyer (Zoc. cit.) and barium carbonate added until the reaction is neutral to Congo- red paper.After adding sufficient phosphoric acid to impart a slight acidity using the same indicator and also some decolorising carbon the liquid is filtered. Basic lead acetate is added to the filtrate which is concentrated to a thin syrup in a vacuum and treated with twice its volume of alcohol. After further concen- tration and the addition of a little glacial acetic acid crystallisation is readily effected the mass obtained being diluted with alcohol containing 1% of nitric acid and the sugar filtered and washed with the acid-alcohol on a Buchner funnel. Lastly it is dried in a vacuum at the ordinary temperature ground finely and the drying continued for twenty-four hours while gradually raising the temperature to 46" mannose free from acetic acid thus being obtained. Indin.-A mixture of 1,OOO g.of finely ground chicory root and 5 litres of water is boiled for one hour filtered and the residue washed with hot water. The filtrate and washings are treated at 40" with basic lead acetate using a slight excess over that required for the precipitation of the impurities decolorising carbon is added the excess of lead thrown down with hydrogen sulphide and the liquid filtered After concentrating the filtrate to about 500 c.c. and adding twice its volume of SOYo alcohol the mixture is allowed t o remain over-night when 10-15 per cent. of inulin will deposit. This is dissolved in 1,000 C.C. of 40% alcohol treated with decoloris- ing carbon and filtered.Two volumes of SOYo alcohol containing 1% of nitric acid are added the liquid is left over-night at a low temperature and the inulin obtained dried in a vacuum at about 35" and reprecipitated. G . R ~ ~ ~ ~ W I T A N O and M. CATOIRE (Cmpt. rend. 1923,177,1309-1311).-A 1% aqueous solution of potato starch was obtained (heating not above 80°) the cooled product consisting of two layers then being diluted to one-tenth of its original concentration and the clear portion J. P. 0. Solubility and Insolubility of Starch.i. 142 ABS!l'RAOFS OF CHEMICAL PAPERS. evaporated. The gelatinous stapch separating did not give a clear solution with boiling water and on being dried merely swelled when so treated. After washing with water and then with alcohol the product (containing like the original material combined phosphorus calcium magnesium and silicon) resembled cotton dissolving in water only when heated at 150" with the latter and being reprecipitated on cooling.On treatment with acids etc. it gave a product resembling soluble starch. It is concluded that the solubility of starch depends on the inorganic matter present starch itself b e g amylaceous matter combined with phosphates and silicates (of calcium and magnesium) Starch Paste. I. Relation between the Viscosity of Wheat Starch Paste and the Concentration and Temperature. MORIZO YOSHINO ( J . Chem. Ind. Japan 1923 26 870-873).- The viscosity was measured by Ostwald's capillary viscosimeter at 20° 30° 40° and 50" for the range of concentration of 0.5- 2.5%. The relation between viscosity and concentration is expressed with sufficient accuracy by Arrhenius's formula log q/qo= 8C where C=lOOp/[lOO-(n+l)p] p being the number of grams of starch in 100 grams of paste and n the hydration factor.The amount of water absorbed decreases according to the elevation of temperature. The values of 8 and n were observed to be as follows 0.412 and 12.6 at 20" 0.407 and 10.0 at 30" 0.407 and 7-6 at 40° and 0.408 and 5.7 a t 50". When the values of p become 7.4 at ZOO 9.1 at 30° 11-6 at 40" and 14.9 at 50" the viscosity becomes infinite ; that is the solution changes into a solid. K. K. Cellulose. VIII. K. HESS W. WELTZIEN and E. MESSMER (Annalen 1923 435 1-144).-( A ) Cuprammonium-cellulose solutions E. MESSMER [and in part (FRL.) ELLY J A G u ] .- I t has already been shown (A. 1921 i 401) that the copper is present in cellulose-cuprammonium solutions as an optically active com- plex anion and as (kation) an ammine. The solutions have now been examined further from a mass-action point of view and the molecular complexity of the dissolved cellulose has been deter- mined. In order to make such a determination trustworthy the following points had to be proved (1) Cellulose (in cuprammonium solutions) undergoes no hydrolytic decomposition. This is clearly the case since the maximum rotation for a particular concentration is reached immediately dissolution of cellulose is effected. (2) The rotation is due to a single complex copper compound of high rotatory power. This is shown by the form of the rotation curves (concentration of components of solution against rotation etc.).Moreover a maximum rotation is observed when the solution con- tains 1 atom of copper to 1 mol. C,H,,O,. (3) The copper complex is in equilibrium with very weakly rotating cellulose (the latter functioning in dissolving as a base). This is shown by other curves connecting rotation and concentration of copper. A slight excess (1 mol.) of copper is necessary to drive back the dissociation of the complex. When excess of copper is present addition of E. E. T.ORGANIC CHEMISTRY. i. 143 cellulose within limits causes a rectilinear rotation-increase curve. (4) The (reacting) copper is used entirely to give the strongly rotating complex. This is shown by studying the effect of sodium hydroxide which does not increase the rotatory power of the solution (see equation 2 below).( 5 ) The copper dissolves unimolecularly. This is shown by a parallel investigation of dextrosemonoacetone (below). The above relations are expressed by the equation mCu+ n(C6H1005) Cellulose-copper Complex and since it has been shown ( 2 above) that an atom of copper corresponds with C6H1005 in the given solution m=nz. The formation of a cellulose+mprammonium solution is expressed by the following equations (1) In absence of alkali cellulose is dissolved by cuprammonium hydroxide (a) (C6Hlo05),(solid) + the complex of high rotatory power) [C6H905],[Cu(NH,),]+ (2) In presence of alkali (which takes the place of cuprammonium hydroxide) Na[ C6Hs05] + [Cu( NH3),]( OH) =+= [ C ,H ,05Cu]Na + 4NH3+2H,O.The equations (1) and (2) may be summarised thus [C,Hs05]'+ [Cu ( NH3),]'*+ 20H' =$= [ C6H ,O 5Cu]'+ 4NH3+ 2H,O. (3) In presence of excess of alkali [C,H905]Na+ [C,H,O,Cu]Na + c6 9 5cu Na (the last formula relating to the copper-sodium-cellulose complex precipitated in presence of excess of alkali). Since in equation (1) above the copper has two functions the investigation of this solution will throw little light on the question at issue. In presence of alkali (2) however the copper has only one function. If a=rotatory powet of the copper complex a and b are respectively the total number of copper atoms and C6f-I,005 units present in volume v and x is the number of C6HlOO5 umts m the combined cellulose then for the interaction of m atoms of copper and n molecules of cellulose K the reaction constant is given by K=(a/v-m .a . k)m(b/xv-nak)"/a. k. Various values (1 to 4) were taken for m 72 and x and k and K determined whence knowing a and b a could be calculated. Approximate agreement between a (found) and a (calc.) was only obtained f o r (1) n=m=x=l (2) n=m=l x=2 (3) n=2 m=3 x=1 and (4) n=3 m=4 z=1. Of these possibilities (2) (3) and (4) are excluded on other (experimental) grounds as is also the possibility of expressing (1) as n=m=x=2 (i.e. 2Cu Cl$€mO1o -i.e. cellobiose) or as n=m=x=3 and so on. From the above it follows that in cuprammonium solutions of cellulose (say one containing 28 mols. of cellulose 15 mols. of copper and 25 mob. of sodium hydroxide) cellulose reacts as if it possessed the molecular formula C6HlOO5.The correctness of this conclusion was established in other ways. Thus solutions containing z mob. of cupric hydroxide and y mols. of celluloee gave the same rotation as solutions containing y mols. of cupric hydroxide and z mols. of cellulose. [Cu(NH3),I(OH) * 2H,0+ [C6H905],[Cu(NH,)*] ; ( b ) (giving 2[Cu(NH3),] (OH )z * [c6H,05cu],[ cu(NH3)4] + 8NH3 + 4H@- rf?:7:5 1i. 144 ABSTRACTS OF ClHEB6ICAL PAPERS. Experiments were also carried out (cf. A. 1921 i 401) with cuprammonium solutions of other carbohydrates or their deriv- atives. Cellobiose had [a]435.8 +50*6O +50*6" and +160*Oo in aqueous in ammoniacal sodium hydroxide and in sodium hydr- oxidwuprammonium solutions respectively. The investigation of the solutions is rendered difficult because of mutarotation oxidation etc.a-Methylglucoside in the above three solvents had [a]p35.8 +324" +340" and +460". The tendency of the glucoside to form copper complexes is very strong. Although for this reason the equilibrium relationship could not be experi- mentally investigated clear evidence was obtained that the in- creased rotation of the cuprammonium solutions was due to a complex 1 glucoside 1 copper p-Methylglucoside in the above three solvents had [ Q ] ~ ~ ~ . ~ -57.4" -53-3" and +38.1" re- spectively. The quantitative study of the cuprammonium solutions of the last three compounds is complicated by the rotation possessed by these compounds. In the case of dextrose monoisopropylidene ether which had in the above three solvents -24.8" -31.6" and -212.5" respectively the equilibrium was amenable to experi- ment and the existence of the complex containing 1Cu C,H,,O definitely established. Moreover the molecular weight of the dissolved dextrose monoisopropylidene ether was determined as in the case of cellulose and also by direct cryoscopic measurement in aqueous solution when a normal result was obtained.Dextrose monopropylidene ether was found to have m. p. 1606-161" [XI -12.12" (cf. Fischer and Rund A. 1916 i 363). Laevoglucosan gives no complex in cuprammonium solutions the rotation in the latter being the same as that of an aqueous solution. (B) The acetylation of cellulose (W. WELTZIEN [and in part R. SINGER H. JENSEK and A. R~~]).-whilst dried cotton cellu- lose does not react with pure dry acetyl chloride cotton cellulose containing 6 5 % of moisture when shaken for four days with eleven times its weight of acetyl chloride a t 17-20' is converted (92% yield) into crude cellulose triacetate A .I€ the cooled solution obtained is allowed slowly to lose the hydrogen chloride present evaporated in a vacuum the residue treated with chloroform and the latter evaporated a solution of the second residue in glacial acetic acid then being precipitated with ether pure cellulose triacetate A is obtained as a pale yellow or colourless powder (607h yield). If in the original acetylation the conditions are varied by-pro- ducts (formed in the above preparation in small quantities) viz. cdMextrin acetate and acetochlorocellobiose are obtained in larger quantities although they are readily separable from cellulose triacetate A .The acetylated celluloses described by Skraup (A. 1906 i 67) and by Zechmeister (A. 1923 i 306) are mixtures (In connexion with the analysis of cellulose acetates a modification of the Ost and Katayama and the Wenzel method is described steam vacuum distillation being used. A diagram of the apparatus used is given.)ORGANIC CHEMISTBY. i. 143 Cellulose triacetate A has m. p. 270-275" (decomp. with brown coloration and frothing) is soluble in chloroform and acetic acid and insoluble in alcohol or ether Dissolution is preceded by swelling. Cellulose triacetate A has [.ID -16.7" in chloroform and + 4 4 " in glacial acetic acid. Its solutions in the latter solvent throw little light on its molecular weight a consfant depression being obtained for all solutions containing between 0.03 and 0.3% of the acetate whilst irregular results are obtained with higher concentrations. The constant depression obtained with low con- centrations may be due to the presence of water (cf.Patern6 and Salimei A. 1913 ii 849). In phenol cellulose triacetate A gives a mol. weight value of 2,380-3,350 (with a specimen obtained in a slightly different manner 2,030-2,270). Ost's cellulose acetate (in phenol) had a variable mol. weight (2,037-10,133). On treat- ment with a mixture of acetic and sulphuric acids Ost's cellulose acetate became more like cellulose triacetate A . Thus whilst originally its product of alkaline hydrolysis was practically in- soluble in alkali after the acetic-sulphuric acid treatment the hydrolysis product was soluble in alkali.Cellulose triacetate A on treatment with cold N-methyl-alcoholic sodium hydroxide affords cellulose A readily soluble in 2N-sodium hydroxide the solution affording cellulose A on acidification. Cellulose A is a white powder with [.ID (in 2N-NaOH) -12.4". It is shown by X-ray analysis to be crystalline whilst its rotatory power in cuprammonium solutions establishes clearly its structural identity with the original cotton cellulose used An alkaline solution of cellulose slowly undergoes hydrolysis reducing properties developing. In the methyl-alcoholic alkaline hydrolysis (above) a little of the reducing substances is formed and is removed by treating the alkaline solution with ammonia when pure cellulose A is precipitated. In this connexion it is found that the Schwalbe copper number does not always give trustworthy comparisons of reducing power.A method based on the precipitation of the cellulose to be tested as the sodium-copper derivative (above) is described. Pure cellulose A a'nd hydrocellulose (as prepared by Knoevenagel and Busch A. 1922 i 636) show no reduction with the improved method the crude products showing feeble reduction. Ost's cellulose acetate after acid treatment (as above) was feebly reducing whilst cellodextrin acetate and the acetyl derivative obtained by treating cellulose with acetyl chloride at 24-27' were strongly reducing. By effecting the acetylation of cellulose with acetyl chloride in presence of acetic anhydride which decreases the concentration of hydrogen chloride (Ac,O+HCl t Ac-Cl+Ac*OH) a cellulose acetate was obtained which on hydrolysis gave a cellulose less soluble in alkali than cellulose A .Cellodextrin acetate is a white amorphous powder m. p. 260" (softening at 250°) [a]? -11.0 (&2.0)" [a]:" -12.0 (-+1*5)" in chloroform. It is more soluble in solvents than is cellulose triacetate A . It gives a molecular weight in acetic acid of 318- 1,366 in phenol of 1,260-1,480 in urethane of 1,500-1,540 andi. 146 ABSTRACTS OF CBEWCAL PAPERS. in naphthalene of 1,350-1,470. On hydrolysis with methyl- alcoholic sodium hydroxide it gives dextrin as a white powder which darkens without melting reduces Fehling's solution under proper conditions (above) and is converted by acetyl bromide containing hydrogen bromide into acetobromoeellobiose whilst acetic anhydride (and a trace of sulphuric acid) converts the dextrin into octa-acetylcellobiose (m.p. 228"). (c) Jfethykztion of Cdlulose A [w. Wn~~zr~,u.]-The methylation of cellulose as effected in presence of alkali (Irvine T. 1923 123 518) gives results of doubtful value owing to the definite action of alkali on cellulose a t the temperature of methylation. Cellulose A on warming with dilute alkali is so altered that it reduces Fehling's solution and is no longer precipitated on acidification. Hydrated barium hydroxide has no effect on cellulose A and methylation carried out using this hydroxide and methyl sulphate (at 90-95") may be assumed to proceed without effecting structural changes.The product obtained in this way was a yellow glass (OMe=30-40%) insoluble in and unaffected by alkali and on further methylation with sodium hydroxide and methyl sulphate (at 80-90") for three hours gave a product (OMe=4243y0) corre- sponding with trimethyl cellulose A . Further methylation (using silver oxide and methyl iodide or piperidine and methyl sulphate) was impossible. Trimethyl cellulose A is a white powder m. p. 230-245" (softening a t 217") dissolving in cold water and separ- ating on heating this solution owing to hydrate formation etc. It has [a]$ -18" in water and is inactive in chloroform solution. The freezing-point depression of an aqueous solution slowly decreased on keeping a result in accordance with the structural similarity of trimethyl cellulose A to cellulose A .It is concluded that the results obtained by Heuser and von Neuenstein (A. 1923 i 17) indicate that these authors mere dealing with a partly hydrolysed cellulose complex. ( D ) Action of Hydrogen Bromide on Cellulose triacetate A [K. HESS W. WELTZIEN and F. KuN~u.]-~e~u~ose triacetate A when treated in glacial acetic acid solution with hydrogen bromide gave acetobromocellobiose (yield 10-30 yo). No hexa-acetylbromo- cellobiose but EL little hepta-acetylbromocellobiose was also formed. Cellulose triacetate A is unaffected by acetyl bromide but ki presence of hydrogen bromide a 50 yo conversion into acetobromo- cellobiose results. There is also formed a new a.cetobromodwtrose (white amorphous powder m. p. 60-70" [indef.] [.ID +so") which does not yield penta-acetyldextrose when treated mth silver. acetate.The new compound does not depress the freezing point of bromoform has a normal molecular weight in acetic acid and in phenol and is (twice) associated in benzene solution. It affords acetobromocellobiose when treated with acetyl bromide containing hydrogen bromide. The acetobromodextrose is readily deacetylated by the method of Fischer and Bergmann (A. 1919 i 278) whereas acid hydrolysis caused the elimination of bromine with formation in very variable yield of a new substance ceUo- glucosan C,H,,O,,H,O plates m. p. 107-log" [.ID +89-31" inORQANIC? CHEMISTBY. i. 147 aqueous solution. The molecule of water is firmly attached and the suhtance (which is accompanied in its formation by a bromine- free amorphous substance) is not hygroscopic like some glucosans (below).TribenzoyZcehgZwoogEucosan. has m. p. 126-128". Cello- glucosan is unaffected by boiling alkali but affords reducing com- pounds on acid hydrolysis. It is quantitatively converted by methyl alcohol containing a trace of hydrogen chloride into a-methyl- glucoside a fact which is difficult to reconcile with Karrer's sug- gestion that cellulose is derived from p-glucose (A. 1920 i 370). Celloglucosan in many respects resembles glucosan (Pictet and Castan A. 1920 i 594) but unlike the latter substance does not reduce Fehling's solution. The rotation of an aqueous solution of celloglucosan is higher than that of a similar solution of glucosan but falls to the rotation of the latter if a little hydrochloric acid is added.The formation of the new acetobromodextrose which cannot like its previously known isomeride be obtained from cellobiose proves that cellulose may be converted into derivat>ives of dextrose without the intermediate formation of cellobiose. It is concluded (in a comprehensive survey of the whole of the work) that natural (cotton) cellulose is built up from glucose anhydride units which are associated not condensed or polymerised . The X-ray diagrams of natural cellulose and of the cellulose (shown to be a chemical individual) obtained by precipitating cupram- monium solutions suggest but do not prove the identity of these two products. Cellulose and cellulose A give identical values for k and K when examined by the above (cuprammonium) method whilst the hydrolysis product of Ost's cellulose acetate is also shown to be identical from the same point of view with cellulose.If 2 3 6-trimethylglucose is produced (Irvine Zoc. cit.) without structural change cellulose will be I- 0 . OHCH,CH.CH-CH( OH ).CH ( OH ~ C H . At variance with this formula however are the results of the action of hydrogen bromide on cellulose triacetate A . The authors prefer t o write cellulose as I in the scheme below when its dis- solution in cuprammonium solution (which effects satumtion of the partial valencies involved in the association of the sinzple cellulose units) is expressed thus +pu(NH3)4]"+30H' -f Lo o:~C6H7(O-)}~>Cu]'+3H,0 \ etc. Such a formula for cellulose explains its amphoteric character and its behaviour towards neutral salts such as zinc chloride.An interesting but probably misleading fact is the identity of the heats of combustion of cellulose and of laevoglucosan.i. 148 ABSTRACTS OF CHEMICAL PAPERS. Natural cellulose may contain as its crystal unit (cf. X-ray analysis) four C,H,,05 residues associated together. An important result also emerges cellobiose need no longer be regarded as a degradation product of cellulose the converse being nearer the truth. Comparative Investigations of Cellulose and Lignin. F. FISCHER and H. TROPSCH (Ber. 1923 56 [B] 2418-2428).- ,4 restatement and extension of the work carried out in the authors' laboratory during recent years The hydrogenation of cellulose and lignin by hydriodic acid uiider pressure does not appear to be suitable to the elucidation of the genetic relationships between the substances since the come of the change is not obvious and has led to very conflicting results in the hands of various workers.Cellulose is far more stable than lignin towards aqueous alkali hydroxide under pressure and at elevated temperatures. It is completely dissolved at 300" with production of much carbon dioxide. Lignin on the other hand is decomposed by 9.5N- potassium hydroxide solution at 300" with production of phenols or phenolcarboxylic acids and adipic acid and by 10N sodium hydroxide solution at 250" with formation of succinic and oxalic acids. Lignin easily becomes autoxidised in the presence of sodium hydroxide yielding humic acids non-volatile acids such as succinic.oxalic and ( ? ) isophthalic in addition to acetic formic and carbonic acids ; cellulose is comparatively little attacked. Similar differences are observed in the oxidation of the substances under pressure ; it is significant that whereas cellulose yields aliphatic acids aromatic acids are in addition obtained from lignin. The ready nitration of lignin by 5N nitric acid is in harmony with a phenolic structure. The comparative behaviour of cellulose and lignin when subjected t o distillation under diminished pressure is described in detail. The yields of coke and tar are widely different with the two com- pounds The most significant result however appears to be the absence of optically active compounds in the aqueous extracts of lignin tar whereas under like conditions laevoglucosan is obtained from cellulose.It appears therefore improbable that the ligniii molecule is composed of polysaccharide components Lignin-content of Spruce Wood. P. &ASON (Cellulose- chemie 1923 4 81-84).-The sulphuric acid method for the determination of lignin is recommended; easy filtration is secured by using a weaker acid than the 72% concentration prescribed by Ost and Wilkening; the washed lignin retains sulphuric acid but not in the form of a combination. About 1 g. of finely rasped wood is suspended in 50 C.C. of 64% sulphuric acid and allowed to remain over-night. The liquid is diluted and the residue collected on a tared filter then washed with cold or warm water. The resin and fat are extracted by washing with 50 C.C.of hot alcohol and the lignin is then neutralised with water containing 5 C.C. of .iV/lO-potassium hydroxide washed and dried a t 105'. E. E. T. H. W.ORGAMC CHE116ISTRY. i. 149 The correction for ash includes any sulphuric acid not removed in the washing. Calculated on dry substance the values for an eighty-year old spruce stem were l i p i n corrected for sulphate 29.4%; sulphuric acid 3.6%; resin and fat 101%. The lignin showed on analysis C 63.97%; H 5.32%; pentosans 1.7%. Another stem from the same forest but of one hundred years’ growth yielded only 26.6% of lignin. Deposits of “red wood” in the branches contained locally up to 37.1% of lignin. For the direct extraction of fat and resin from wood ether appears to be the best solvent free from drawbacks which accompany the use of benzene or alcohol. The benzene extracts always show reactions of lignin and the alcohol extract which is indefinite in quantity increasing with the time of extraction contains very substantial quantities of lignin and carbohydrates in about equal proportions. AS a rapid and approximate method for the determination of resin and fat the washing of the lignin residue after treatment with sulphuric acid may be considered to be satisfactory.Chloro-bismuthates. A. GUTBIER and MANFRED MUUER (2. anorg. Chem. 1923 128 137-152).-By treatment of one molecular proportion of bismuth trichloride with three molecular proportions of the hydrochlorides of organic bases in presence of hydrochloric acid three new series of compounds have been pre- pared viz.,.~-dichloro-octachloro-di~ismuthates [NHR3],[BiCI,]? of which the dimethylanilinium and diethylanilinium salts are descnbed p-irichloro-hexachloro-dibismuthates [NH3Rl3[B&Cl9] of which the methylammonium tetramethylammonium triethylammonium tetraethylammonium n-propylammonium tripropylammonium n-butylammonium isobutylammonium and isoamylammonium salts are described and hexachloro-bismuthates [RNH,],[BiCl,] of which the dimethyl- trimethyl- ethyl- diethyl- isopropyl- diim propyl- and allyl-ammonium salts the methyl- ethyl- and isoamyl- anilinium salts and the guanidinium pyridinium a-picolinium I?-picolinium lutidinium collidinium quinolinium and isoquino- h i u m salts are described. The first and second series may be regarded as hexa-co-ordination compounds by assuming the formulze given the two bismuth atoms being linked through two and three chlorine atoms respectively.All the compounds are extremely sensitive to changes in environ- ment and decompose at once in contact with water or moist air. The Derivatives of Hexachloro-antimonic Acid. A. GUT- BIER and W. H~USMANN (2. anorg. Chem. 1923 128 153-168).- By combination of antimony pentachloride with alkyl- and aryl- amines in hydrochloric acid solution a large number of com- pounds of the general formuh [R-NH3][SbC1,] [R$?Hz~[Sbc1,] [R,NH][SbCl,] and [R4N][SbC16] as well as pyridine and piperidhe derivatives have been prepared. They are moderately stable crystallking unchanged from hydrochloric acid in colourless well- formed crystals; they dissolve in water to colourless solutions which slowly become cloudy and deposit white precipitates but J.F. B. s. I. L.i. 1% ABSTRACTS OF CLEMICAL PAPERS. from alcohol solution they may be recovered for the most part unchanged. The moho- di- tri- and tetra-methylammonium salts the mono- di- tri- and tetra-ethylammonium salts the mono- di- and tri- propylammonium isopropyl- bhtyl- i.sobutyl- and diisobutyl- ammonium salts the allyl- isoamyl- and benzyl-ammonium salts the dibenzylethylammonium ethylenediammonium salts and the a-picolinium collidinium and piperidinium salts are described. s. I. L. Derivatives of Hexachloro-stannic Acid. A. GUTBIER G. KUNZE and E. GUHRING (2. anorg. Chem. 1923 128 169-178).- A series of alkylammonium arylammonium and pyridine and quinoline derivatives of the general formula X2[SnCI,] has been prepared.They are generally colourless and crystallise readily from hydrochloric acid solution. They dissolve readily in water hydrolysing slowly in the cold; the freshly prepared alcoholic solutions are neutral. Tripropylammonium hexachlorostannate [NHPr,],[SnCl,] crystallises in two forms one bright rose- coloured tablets the other deep reddish-brown leaflets. The following compounds are described the methyl- dimethyl- trimethy I- te tramethyl e thy1 - die t h yl- triet h yl- tetrae t h y 1 - normal and isopropyl- dipropyl- tripropyl- normal and isobutyl- diisobutyl- triisobutyl- allyl and isoamyl-ammonium salttj the ethylene- and propylene-diammonium salts and the anilinium Raneenographic Determination of the Structural Formula of Hexamethylenetetramine.H. W. GONELL and H. MARK (2. phpikal. Chem. 1923 107 181-218).-The crystal structure of hexamethylenetetramine has been investigated by means of X-ray spect>ra and Laue figures. It is shown that hexamethylene- tetramine does not belong to the hexakisoct'ahedral class Oh as has been assumed from macroscopic examination but more pro- bably it belongs to the hexakistetrahedral class Td or possibly to the tetrahedral pentagonal dodecahedra1 class T. The elementary cube has an edge 7-02 A. long and contains 2 mols. of hexamethylene- tetramine. Each nitrogen atom lies between the three nearest carbon atoms in close spherical packing. The shortest distances between neighbouring atoms in the molecule are N-C=1.48 A.and C-C=2.58 A. The lattice is a molecular lattice. The structure thus deduced confirms that found by Duden and Schadf (A. 1896 i 122) from purely chemical investigation according to which the molecule is built up of trimethylenetriamine rings. The present work furnishes an example where Rontgenographic investigation enables a decision between possible structural formulae to be reached when such has not been possible by purely chemical treatment. J. F. S. The Reactivity cjf Different Amino-acids in the Presence of Blood Charcoal and cf Hydrogen Peroxide. E. NEGELEIN (Biochem. Z. 1923 142 493-506).-Measurements pyridinium collidinium and quinolinium salts. -s. I. L.OIWKNIC CHEMISTBY. i. 151 have been made of the rate of oxidation in an atmosphere of oxygen and of the adsorption constants of various amino-acids in the presence of blood charcoal.The considerable variations found in &he former when equimolecular solutions of the vlllrious acids are brought into equilibrium with the adsorbent are ascribed to Werences in the extent of adsorption. In general primary and secondary amino-acids are much more reactive to oxygen in the presence of charcoal tha.n are the tertiary acids. Closely parallel results are obtained when the rates of oxidation of the amino-acids by activated oxygen (hydrogen peroxide) a t pH 9.2 are memured the tertiary acids being again much less reactive than the others. The similarity of the two types of oxidation lends support to the views of Warburg in which the oxidation of amino-acids in the presence of charcoal is ascribed to activated oxygen.The Configuration of Amino-acids. 11. P. KARRER (Helv. Chim. Acta 1923 6 957-959).-The conversion of d-serine into I - py-diaminopropionic acid shows that these must have the same configuration.. d-Serine was converted into its methyl ester which by the action of phosphorus pentachloride was converted into d- 7-chloro-p-aminopropionic acid as described by Fischer and Raske (A. 1907 i 900) for the corresponding I-compounds. The d-chloroaminopropionic acid was converted into I-diaminopropionic acid by heating with liquid ammonia. The product contained some racemate its rotation being [a] -18-1" instead of -24.9". It follows that I-serine must have the same configuration as d-di- aminopropionic acid which has been shown to correspond with I-asparagine and Z-aspartic acid (A.1923 i 660). It therefore follows that the following constituents of natural albumin all have the same configuration d-alanine I-serine I-cystine I-asparagine and E-aspartic acid. It would appear to be a general rule that naturally occurring amino-acids have the same configuration. Aliphatic Dialkylaminoalkyl Compounds. PARBWERKE VORM. MEISTER LUCIUS & BRUNING (U.S. Pat. 1429922; from Chem. Zentr. 1923 iv 591).-Additional data are given for com- pounds already mentioned (A 1922 i 529). Ethyl or-diethyl- aminoethylacetoacetate has b. p. 132-135"/10 mm. ethyl or-di- rnethylaminoethylacetoacetate b. p. I24"/12 mm. ethyl diethyl- aminobutylacetoacetate b. p. 138"/10 mm. J. P. E.H. R. G. W. R. The Electro-chemical Preparation of Cyanuric Acid and Allophanic Esters from Formamide. K. SCHATJM [with H. SCHNEIDER] (Bey. 1923 56 [B] 2460-2462) .-isoCyanuric acid is obtained when formamide is elect,rolysed between plattinurn elec- trodes a t a temperature not exceeding 45" with a pressure of 70 volts. A yellow substance the nature of which has not been elucidated is obtained as by-product; it is obtained in greater quantity if higher temperatures and current densities are employed. The electrolysis of mixtures of formamide and an alcohol leads to the formation of allophanic esters of which the methyl ethyl isopropyl and isobutyl compounds have been'prepared in goodi. 152 ABSTRACTS OF CHEMICBL PAPERS. yield. Apparently cyanic acid is formed intermediately either by discharge of a formamide-ion or by anodic oxidation of formamide ; the former process appears to predominate when small quantities of water are present the latter when the quantities are more con- siderable.The electrolysis of molten acetamide does not give well-defined products. H. W. Crotononitriles. A. BUELENS (Bull. Soc. chim. Bdg. 1923 32,334-337) .-Crotononitrile prepared by three different methods dehydration of a-hydroxybutyronitrile and of P-hydroxybutyro- iiitrile and catalytic transformation of ethyl crotonate by Mailhe's method (A. 1920 i 476) is obtained in each case as a mixture of tlhe two stereoisomerides that of higher b. p. predominating. In the tlhird case the author shows that isomerisation occurs during catalysis as the mixture is formed in the same proportions by submitting the isomeride of higher b.p. to the conditions under which catalysis is effected. H. J. E. The Vapour Pressure of Hydrocyanic Acid.. RYGSABUR~ HARA and HEIMA SHINOZAKI ( J . Chem. Ind. Japan 1923 26 884-890).-The vapour-pressure curve of hydrocyanic acid has been determined by Smith and Menzies's static isoteniscope method (A. 1910 ii 1036) within the range of 0 4 6 " . It is believed that the observed values are correct to &0.2%. The equation log Pmm- 1836-63/T1'U5 +7.5030 shows satisfactory agreement with the observations. For obtaining the pressure at any desired temperatures between O".and 47.5" the following two values observed were used for the above formula 519.4 mm. at 15.88" and 1128-4 mm.at 36.68". The boiling point of the acid was found to be 25.7" instead of 26.5" as generally accepted. Considering the acid as an ideal gas the heat of vaporisation of the acid was calculated from the Clausius-Clapeyron formula to be 246.4 cal. a t 0" 245.5 cal. a t 20" and 244.5 cal. a t 45". The results are tqabulated. K. K. Cacodyl Derivatives. F. A. LEE C. THING and W. M. DEHN ( J . Amer. Chem. Soc. 1923 45 2996-2998).-Cacodyl prepared by Bunsen's method is converted into the chloride b. p. log" which gives the bromide b. p. 130" the iodide b. p. 155-160" and the cyanide b. p. 138" when heated with the molecular pro- portion of potassium bromide iodide and cyanide respectively. Oxidation of the chloride with moist air gives hydrated cacodyl oxychloride m.p. 85". Cacodyl chloride reacts with mercurous and mercuric chlorides cuprous and cupric chlorides to form additive compounds which are described. Aliphatic Arseno-compounds. I. Arsenoacetic Acid and Tetra-arsenoacetic Acid. C. S. PALMER ( J . Amer. Chem. SOL 1923 45 3023-3029) .-The barium salt of arsinoacetic acid (AsO,Ba*CH,*CO,),Ba was quantitatively produced from chloro- acetic acid by reaction with excess of sodium arsenite; the reaction mixture was acidified with acetic acid the precipitated arsenic trioxide filtered off and the filtrate added to a solution of barium F. B.ORBANIO CEEMISTRY. i. 1.53 chloride. The barium salt was converted into the sodium salt and treatment of the latter with sulphuric acid and sodium hypophos- phite gave arsenatcetic acid C0,H*CH,*AsfAsCH,*C02H yellow crystals decomp.above 200". Simultaneous reduction of one molecular equivalent of arsenic trioxide and two of arsinoacetic acid in the cold gave tetra-arsenoacetic acid CO,H*CH,As:As*As:As*CH,*CO,H a vermilion red crystalline powder decomp. at 180". Preparation of Arsinic Acid Derivatives of Aliphatic Carboxylic Acids. FARBENFABRIKEN VORM. F ~ I E DR. BAPER & CO. (Austr. Pat. 93325 and Swiss Pat. 97977; from Chem. Zentr. 1923 iv 721).-Aliphatic halogen carboxylic acids or their derivatives such as amides or esters are treated with arsenious acid its derivatives or its salts in the presence of alkaline reagents. For example from chloroacetic acid and arsenious oxide arsino- acetic mid is obtained as colourless crystals m. p.152". Sodium arsenite and ethyl acetate give ethyl arsinuucetute light yellow leaflets m. p. about 95". Arsinolactic acid is a viscous yellow syrup obtained from p-chlorolactic acid and arsenious acid. Di- arsinuudipic acid from dibromoadipic acid forms colourless crystals m. p. 165" (decomp.). Phenylarsine oxide and chloroacetic acid give ursinophenyhcetic acid m. p. 145" (decomp.). Oxidation of Magnesyl [Magnesium Alkyl] Derivatives by Means of Hydrogen Peroxide. B. ODDO and R. BINAGHr (Atti R. Accad. Lincei 1923 [v] 32 ii 349-353; cf. A. 1922 i 314).-When oxidised by means of hydrogen peroxide magnesium sec. - and tert. -alkyl bromides yield the corresponding alcohols. Similarly phenols are obtained from magnesium aryl bromides with the exception of magnesium phenyl bromide and substituted hydroxylamines and per-acids from the products formed by replacing the active hydrogen of primary amines and of the carboxyl group by the grouping 1ClgBr. Treatment of magnesium phenyl bromide with hydrogen peroxide may give rise to the initial formation of phenol but the products recognised are phenyl ether p-hydroxyphenyl ether benzene diphenyl and possibly phenyl peroxide.With the other organomagnesium compounds however the oxidation proceeds normally and especially with compounds of t,he types R,:CH*MgBr and R3X*MgBr with such regularity in respect to time as to furnish fresh support to the view that only one of the oxygen atoms of hydrogen peroxide is quadrivalent and to strengthen the analogy in behaviour and constitution between the peroxide and formaldehyde (Zoc.cit.). Thus with hydrogen peroxide CHR,*MgBr + CHR,*O(:H,)-O-MgBr + CHR,*[OH,]*OH -+ CHR,*OH and CR,*MgBr --+ CR,*O(:H,)*O*MgBr + CR3*[OH,]*OH + CR,*OH and with formaldehyde CHR,*MgBr - CHR,*CH,*O*MgBr + CHR,*CH,*OH and CR,*iMgBr + CR,*CH,*O*RlgBr - CwCH,*OH. Ethyl hydroperoxide may be regarded as having the aldehydic structure O:OEt*H 60 that like the aldehydes it should yield F. B. G. W. R.i. 154 ABSTILWTS 0s CIHEXXCAL PAPERS. alcohols of the tliree series when treated with the three types of magnesium alkyl derivatives. Ethyl peroxide on the other hand having the ketonic constitution O:OEt should yield always secondary and tertiary alcohols. An outline is given of the experimental results which are to be published elsewhere.T. H. P. Behaviour of Mercuric Salts of Organic Acids towards Heat. M. S. KHARASCH and F. W. STAVELEY ( J . Amer. Chem. Soc. 1923 45 2961-2972); cf. A. 1922 i 189).-The behaviour of mercuric salts of substituted acetic acids on heating depends on the character of the substituting group. Thus mercuric ua-di- methylpropionate was not decomposed when heated in a vacuum at 240" for twenty minutes or when melted in air whilst the mercury salfs of phenylacetic diphenylacetic and triphenylacetic acid gave various products but none in which the mercury replaces a hydrogen atom attached to the u-carbon atom. The ease with which the salt loses carbon dioxide is an important factor. When mercuric ua-diethylacetoacetate m. p. 103" is heated in a vacuum at 85" carbon dioxide is evolved and mercury his-u-acetyl-a-ethyl- propyZ m.p. log" is formed. Treatment of this compound with mercuric chloride gives cc-acetyl-u-ethylpropylmercuric chloride CEt,Ac*HgCl m. p. 77". On heating mercuric dimethyl- acetoacetate in a vacuum a t go" mercury bis-u-atcetyl-a-iso~opyl m. p. 120" is produced. This gives a mercuric chloride compound m. p. 124.5". Mercuric aa-dimethylpropionate m. p. 235" did not give off carbon dioxide when heated a t 240" in a vacuum. When benzoylacetic acid and mercuric oxide are heated in alcohol solution mercury diphenacyl Hg(CH,*COPh) m. p. 159.5" is formed and this on treatment with mercuric chloride gives phenacylmercuric chloride m. p. 146" which is identical with the substance of known constitution prepared by direct mercuration of acetophenone (A 1902 i 849). When benzoylacetic acid and mercuric oxide are heated in chloroform solution the product is anhydro-u-hydroxy- co mercuribenzoylacetic acid COPh*CH< >0 decomp.290". On adding a solution of mercuric acetate to a solution of pht,halide- Hg carbogylic acid mercuric phthalidecarboxylate a ( CO<!~~CH*C02)2~g is obtained. This' reacts with sodium hydroxide to give phthalonic acid and phthalidecarboxylic acid and has m. p. 195" (decomp.) forming dihydrophthalide m. p. 250". Benzoyl- formic acid in alcohol solution reacted with mercuric oxide to form the mercurous salt which is decomposed by sodium carbonate. The mercuric salt m. p. 164" is obtained by adding a solution of mercuric acetate to a solution of benzoylformic acid.Fixation of Unsaturated ,Molecules by Metals produced from their Organometallic Derivatives. A. JOB and R. REICH (Cornpt. rend. 1923 177 1439-1441).-0n keeping a solution of F. B.ferrous ethyl iodide (cf. A. 1922 i 645) metallic iron is deposited as a mirror ethylene and ethane also being formed. These changes are explained by the following scheme 2FeEtI + FeEtz+Fe& - 2C2H4+FeH,+Fe12 + C$€4+C2Hs+Fe+Fe12 where ferrous hydride reduces ethylene to ethane. This explains why Wanklyn obtained ethylene and ethane from zinc ethyl and ferrous iodide. The iron deposit which contains traces of ferrous ethyl iodide is pyrophoric and decomposes water to give hydrogen. Nickel cobalt chromium and manganese are also produced in active forms from a halide salt and magnesium ethyl bromide part of the metal being precipitated the rest remaining in (colloidal) solution.Thus when an ether-benzene solution of magnesium phenyl bromide is treated in absence of air with nickelous chloride a solution is obtained which (1) rapidly absorbs carbon monoxide in amount corresponding with the formation of nickel carbonyl Ni(CO),; (2) slowly absorbs per atom of nickel 2 mols. of nitric oxide (giving a bluish-green solution) ; (3) absorbs ethylene (2 mols. for each atom of nickel) to give a reddish-brown solution; (4) absorbs acetylene (Ni 3C2H,) ; and (5) rapidly absorbs hydrogen (2H Ni) nickel hydride being precipitated as a black very reactive powder (cf. Schlenk and Weichselfelder Ber. 1923 56 [B] 2230). Organometallic Compounds.111. Compounds formed between Tin Alkyl Halides and Ammonia and the Amioes. C. A. KRAUS and W. N. GREER ( J . Amer. Chem. Soc. 1923 45 3078-3083).-Tin trimethyl chloride forms a compound with 1 mol. of aniline and with 1 mol. of pyridine (m. p. 37"). Tin trimethyl iodide combines with two equivalents of ammonia one of which is loosely held two equivalents of aniline and one equivalenb of pyridine. The compound with pyridine solidifies homogeneously at -17". Tin dimethyl dichloride combines with two equivalents of pyridine. Mercury ethyl chloride and mercury amyl chloride each combine with one equivalent of ammonia. Solutions of the metal alkyl halides in amines are fair conductors of electricity whilst the solutions in neutral solvents are virtually non-conductors. It is E.E. T. suggested that these compounds are &f the ammonium type C,H,.N<Sn(CH,),* P. B. I Organometallic Compounds. IV. Conductivity of Tin Trimethyl Chloride in Mixed Solvents. C. A. KRAUS and W. N. GREER ( J . Amer. Chern. Soc. 1923 45 2946-2954; cf. this vol. i 25).-The electrical conductivity of tin trimethyl chloride in nitrobenzene and acetone solutions on the addition of small amounts of pyridine has been measured. A marked increase in conductivity takes place on the addition of pyridine and this effect is greater the smaller the amount of pyridine already presenf; The conductivity of solutions of tin trimethyl chloride in mixtures of 0-100% of acetone and alcohol nitrobenzene and pyridine respectively has been measured a t 25".The initial conductivity in nitrobenzene is extremely low indicating that tin trimethyli. 156 ABSTRACTS OF CliEXICXL PAPERS. chloride is not much ionised in this solvent. The initial conductivity in acetone is markedly higher than in nitrobenzene. Whilst the conductivity in acetone is increased on the addition of alcohol this increase is much less marked than it is on the addition of pyridine. The results are in keeping with the view that tin trimethyl chloride itself is not a true electrolyte and that its electrolytic pro- perties in solution are due to the formation of compounds of the oxonium and ammonium type the tin trimethyl group transferring from chlorine to quadrivalent oxygen or quinquevalent nitrogen respectively . J. F. S. The Conditions of Equilibrium and Motion of Molecules in Space.J. BOESEKEN (Ber. 1923 56 [B] E2411-2414).- A discussion of the structures of cyclohexane and cycloheptane ring systems in which a theory previously put forward (Derx A. 1922 i 651) is restated. The proof by Schrauth and G6rig (A. 1923 i 1084) that dicyclohexane can exist in three forms'is important in this connexion. E. H. R. J. H. WALTOW and J. D. JENKINS ( J . Amer. Chem. Xoc. 1923 45 2555-2559).- The equilibrium curves for the system toluene-acetone-water have been determined experimentally a t O" 20" and 30". It is shown that temperature has very little effect on the mutual solubility of the three components. J. I?. S. Catalytic Condensation of Acetylene with Benzene and its Homologues. J. S. REICHERT and J. A. NIEUWLAND ( J .Amer. Chem. ~ o c . 1923 45 3090-3091; cf. A. 1923 i 753).-Diphenyl- ethane ditolylethane and dixylylethane were prepared by passing acetylene into benzene toluene and xylene respectively at 10- 20" in the presence of concentrated sulphuric acid and a mercuric sdt. Similarly dimesitylethane was prepared from mesitylene and ethylidinebisethylbenzene from ethylbenzene. The Disulphonation of Naphthalene. H. E. FIERZ-DAVID and A. W. HASLER (Helv. Chim. Acta l923,6,1133-1146).-Anextended account of work already published in brief (Fierz-David A. 1921 i 409 ; 1923 i 1190). 1 5-Naphthalenedisulphonic acid crystallises in well-formed monoclinic tablets containing 4H20 losing 2H20 in a vacuum at 55" and the remainder a t 125"; m. p. 240-245" (decomp.). It is soluble in 0.98 part of water a t 20° and is not deliquescent.Its salts with their solubilities in parts of water per part of anhydrous salt are as follows Li2+2H,0 monoclinic; Na,+2H20 monoclinic 9 ; K,+2H20 monoclinic 15 ; Rb Cs2 TI and (NH4)2 all anhydrous monoclinic ; Ca+2H20 triclinic 40; Sr+H,O monoclinic ( a) 96; Ba+H,O rhombic 470; 250 a t 100"; Pb+3H20 monoclinic 82; Mg (22) Zn (as) Co (46) Ni (73) Cu (21) all with 6H,O form an isomorphous monoclinic series. The sulpharnide forms small needles m. p. above 310" and the sulphaniZide has m. p. 248-249". Naphthalene- 1 6-disulphonic acid crystallises in large mono- clinic striated prisms wi6h 4H,O; it loses water gradually when Ternary System Toluene-Acetone-Water. 3'. B.ORGANIC CHEXlS!L'RY. i. 157 heated and melts a t 125" (decomp.). It is deliquescent in damp air.The sulphonamide has m. p. 297-298". The salts and their solubilities are as follows Na2+7H,0 3 ; K 5; (NH4),+2H,0 2 ; Ca+4H20 10; Sr+5H20 10; Ba+3iH20 16; Pb+4H20 12; all the foregoing are rhombic; Mg Zn (3) Co (5) Ni (5) all with 6H,O isomorphous rhombic Cu+4H20 2. Naphthalene- p-sulphonamide can be separated almost quanti- tatively from the a-compound or from disulphonamide by dissolving the mixed amides in 20% sodium hydroxide solution and cooling in ice when the sodium salt of the'p-sulphonamide crystallises out. The calcium salt of the 2 6-disulphonic acid can be precipitated quantitatively in the anhydrous form by heating its aqueous solu- tion alone or mixed with other calcium salts in a closed vessel a t 130".. E. H. R. The Diphensuccindene Series. V. Colourless and Coloured 9 12-Dialkyl-A~~~~-diphensuccindadienes. K. BRAND and F. SCHJAGER (Ber. 1923,56 [B] 2541-2545 ; cf. A.,'1912 i 960 ; 1920 i 486 487).-An extension of previous work to compounds containing alkyl instead of aryl groups in the 9 12-positions. Diphensuccindan-9 12-dione is converted by magnesium methyl iodide into 9 12-dimethyldiphensucindun-9 12-diol (annexed formula) colourless needles m. p. 170". It is converted by boiling formic and glacial &\-CHAh/4\ acetic acids into 9 12-dimethyl-AgJl-di- CMe*OH HO.CMe I \> phensuccindadiene $Mez~'C,H dark red fy\,i"CH- I l 1 I C,H,*C=CMe or yellowish-brown needles m. p. 212" which is hydrogenated in alcoholic solution in the presence of palladised charcoal to 9 12-dimethyZdiphensucindune colourless needles m.p. 94". 9 12-Diethyldiphensucindun-9 12-diol forms coarse colourless crystals m. p. 102". It is transformed by a boiling mixture of formic and glacial acetic acids into 9 12-diethylidene- diphensuccindune slender colourless needles m. p. 199.5" (which is oxidised by chromic acid to acetaldehyde and diphensuccin- dandione) and 9 12-diethyl-A9J1-diphensuccinda&iene red or red- dish-brown leaflets m. p. 154" (indefinite). 9 12-Dibenxyldiphen- succindan-9 12-dioZ small colourless needles m. p. 206" is con- verted by acetic and formic acids into a mixture of coloured 9 12-di- benzyl-A9Jf-diphensuccindadiene (which could not be isolated in the homogeneous condition) and 9 12-dibenxyZidenediphc- cindune colourless needles m.p. 255"; the latter substance is oxidised by chromic acid to benzoic acid and diphensuccindan- 9 12-dione m. p. 202". The Diphensuccindene Series. VI. 9 12-DinaphthyI Derivatives of the Diphensuccindene Series. K. BRAND and K. TREBINC (Ber. 1923,56 [B] 2545-2547 ; cf. preceding abstract). -Diphensuccindadione is transformed by magnesium a-naphthyl bromide in the presence of ether and benzene into 9 12-di-a- naphthyldiphensuccindan-9 12-did colourless needles m. p. 244" which is converted by a boiling mixture of acetic and formic acids H. W.i. 158 ABSTadCTS Or CEElKICAL PAPEBS. info naphthalene and diphensuccindan-9 1Edione. 9 12-Di-s- nqhthyldiph.mmmindi.vn-9 12-diol colourle~~ needles m. p.286- 287" is transformed under similar conditions into 9 12-di-p- nap~~yyl-Ag.ll-~iphensuccindadiene reddish-brown leaflets m. p. 266'. The hydrocarbon is oxidked by chromic acid to o-p-naphthoyl- benzoic acid m. p. 168" (cf. Pickles and Weizmann P. 1905 20 201) which is converted by concentrated sulphuric acid into 1 2-naphthanthraquinone m. p. 168"; it is hydrogenated in the presence of alcohol and palladised charcoal to 9 12-di-p-naphthyZ- diphemccindtzne slender colourless needles m. p. 225". Magnesium 2-methoxy-a-naphthyl iodide appears to react normally with diphensuccindandione but the action of water on the product gives naphthyl methyl ether and diphensuccindandione. Some Colouring Matters Derived from Bidiphenylen- ethylene. F. KEHRMANN and C. BUFFAT (Hdv.Chim. Acta 1923 6 955-956) .-The red hydrocarbon bidiphenylen- ethylene (A. 1896 i 565) is readily sulphonated by concentrated sulphuric acid forming a soluble sulphonic acid having an intense orange colour which dyes wool and silk in the same way as other acid dyes. The hydrocarbon can be nitrated in glacial acetic acid; fwo dinitro-derivatives were obtained one forming deep red granules sparingly soluble in alcohol m. p. 171" the other crystallising in orange-red prisms more soluble in alcohol m. p. 170". The nitro- compounds can be reduced to amino-derivatives which form orange- coloured hydrochlorides. E. H. R. W. A. DEMOXBREUN and R. E. KREMERS ( J . Amer. Pharm. ASSOC. 1923 12 296-300).- For the nitration of cymene 67 g. is added to an equal weight of sulphuric acid cooled with ice and the mixture is stirred until 0" is reached. A cooled mixture of 105 g.of sulphuric acid agd 50 g. of nitric acid is then added drop by drop with constant stirring? common salt being occasionally mixed with the ice. About six hours are required for the reaction. After being stirred for a further thirty minutes the mixture is poured into an equal volume of cold water. The oily layer is washed with water and fractionally dis- tilled the heavier fraction having b. p. 130-135"/14 mm. P 1.0355 nz 1.5290. Reduction by tin or iron and hydrochloric acid gave 2-aminocymene gB 0.9448 ng 16395 (hydrochloride m. p. 206-207"; acetyl derivative m. p. 70-71"). H. W. 2-Nitro- and 2-Amino-cymene. CHEMICAL ABSTRACTS. p-Naphthylamine-5 7- and -6 8-disulphonic Acids.H. E. FIERZ-DAVID and M. BRAUNSCHWEI~ (Helu. Chim. Acta 1923 6 1146-1151).-A number of salts of these two acids were prepared in the hope of discovering some method of separating the two acids superior to that previously described (Fierz &' Farbenchemie," 2nd ed. p. 43). Although a separation can be effected through the magnesium salts it offers no advantages. (3-Naphthylamine-5 7-disulphonic acid crystallises with 5H,OORGANIC C r n S T R Y . i. 159 in well-formed rhombic needles (from hydrochloric acid) or glisten- ing leaflets (from water). It loses its water completely at 150". The following salts are described with solubilities at 20" in g. per 100 g. of saturated solution Na2+6H20 felted needles which melt in the hand 72.2; NaH+4H20 rhombic needles 7.91; K,+2H20 rosettes of rhombic needlw 63.9; KH+4H2O short rhombic prisms 2-58 ; (NH4),+3H20 rhombic prisms 68.1 ; Ca+4H20 monoclinic prisms 40.2 ; Sr+4H20 29.48 Ba+3H20 22.7; the following all crystallise in well-formed rhombic needles or prisms Mg+8H20 21-09 ; Zn+8H20 39.4 ; Co+8H20 29.4 ; Pb+6H20 48-1; Ni+6H20 35.5.The solubility of the free acid is 22.97. @-Naphthylamine-6 8-disulphonic acid crystallises with 4H20 in small monoclinic needles solubility 9.24 g. per 100 g. of saturated solution a t 20". The following salts are described Na,+3H20 well-formed prisms 59.04 ; NaH+4H20 long thin needles 7-46 ; K2+2H,0 lustrous prisms 51.6 ; KH+2H20 long rhombic prisms 2.47 ; (NH4),+2H,0 monoclinic 70.35 ; the alkaline-earth metal salts are isomorphous monoclinic with 3H20,Ca 29.1 Sr 20.8 Ba 12.0; Mg+8H20 8.7 Zn+8H20 34-5; Co+8H20 27-96; Ni+6H20 monoclinic prisms 33.2 ; Pb+H20 44.5 aggregates of small needles. The preparation of the two acids from p-naphthylamine is described in detail Chloroamidines.PAUL ROBIN (Compt. rend. 1923 177 1304-1306) .-Alkali hypochlorites convert amidine hydrochlorides in aqueous solution into chloroamidines (cf. Bougault and Robin A. 1920 i 568). Thus benzamidine affords benzochloroamidine NH,*CPh:NCl or NHCl-CPh:NH colourless odourless needles not affected by heating up to 100". It may be crystallised from alcohol but when heated with this solvent a t loo" in a closed tube affords benzamidine and a volatile chloro-compound. With boiling dilute acids benzochloroamidine gives chlorine whilst with aqueous potassium iodide solution one mol.of the amidine gives 2 atoms of iodine. When heated with water at 100" in a closed tube the chloroamidine affords a mixture of cyaphenin (PhaCN) benzo- nitrile benzoic acid ammonia and benzamidine. Benzochloro- amidine does not react with antipyrine but is converted by acetic anhydride in boiling benzene solution into an acetyl derivative m. p. 122" in which the chlorine is still reactive towards potassium iodide. p-Tolylchloroamidine and benzylchloroamidine CH2Ph-CN2H2CI melt respectively a t 96" and 72". Preparation of Amidines. CHEMISCHE FABRIKEN VOW. WEILER TER MEER (D.R.-P. 372842 from Chem. Zentr. 1923 [iv} 661).-Acetanilide its derivatives homologues or analogous com- pounds with the exception of arylglycine anilides are treated with carbonyl chloride in the presence or absence of condensing reagents.The following reaction is typical 2NHPh*COMe+COCI,=HCl+ CO,+ COMe*Cl+ NHPh*CMe:NPh. The reaction proceeds amoothly E. H. R. E. E. T.i. 160 ABSTRAOTS OF CHEMICAL PAPERS. without the formation of by-products. Acetanilide and carbonyl chloride give &s above diphenylacetamidine hydrochloride. p-Acetotoluidide and carbonyl chloride yield pp'-ditoZ&cetamiidhe m. p. 122". 00'-Ditolylacetamidine forms flat needles m. p. 65". Acetyl compounds of the amines of alkoxylated or halogenatd hydrocarbons or of polynuclear or condensed hydrocarbons may also be used. a-Dinaphthylacetamidine is crystalline and has in. p. 137". Basic Derivatives of p-Aminophenyl Ethyl Ether.SOCIETY FOR CHEMICAL INDUSTRY IN BASLE (Swiss Pats. 96389 96606 and 96607 ; from Chem. Zentr. 1923 iv 662-663).-p-Acetarnino- phenol halogenethyl ethers NHAc*C,H+*O.CH,*CH,X or their derivatives alkylated in the nucleus obtamed by acting on alkali acetamidophenoxides with ethylene dihalogenides are allowed to react with secondary aliphatic amines. p-Acetamidophenyl /I-brmethyl ether crystals m. p. 130" gives with diethylamine p-acetamidophenyl p-diethylaminoethyl ether; the hydrochbride forms small needles m. p. above 200". p-Acetamidophenyl p-bromoethyl ether gives with piperidine p-acetamidophenyl 2-piperidylethyl ether ,- the hydrochloride forms crystals m. p. 252". From 4-acetamido-2-allylphenyl p-chloroethyl ether crystals m. p.W" and diet hy lamine 4 -a cetnmido- 2 - a1 1 ylphen yl p -dieth ylaminoeth y 1 ether m. p. 70° is obtained; its hydrochloride is crystalline and has m. p. 149". G. W. R. Methyl Sulphites of Secondary Aromatic Aliphatic Amines. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (Austr. Pat. 93319; from Chem. Zentr. 1923 iv 802; cf. Bockmiihl and Windisch A 1923 i 29).-The compounds obtained by earlier patents may also be prepared by N-alkylation of the methyl sulphites obtained from primary aromatic amines and a hydrogen sulphite compound of formaldehyde. Examples are given of the pre- paration of sodium 1 -phenyl-2 3-dimethylpyrazole-5-one-4-ethyl- aminomethyl sulphite and sodium N-ethylphenetidine methyl sulphite. G. W. R. [Alkali Metal as a Reagent for Weakened Valencies in Organic Compounds.] K.ZIEGLER and F. THIELMANN (Ber. 1923 56 [B] 2453).-In their communication on this subject (A. 1923 i 921) the authors have overlooked the fact that a portion of the work has been described previously by Marcus (Diss. Jena 1914). H. W. G . W. R. The Preparation of pp'-Dinaphthyl Ether. V. M. RODIONOV and S. J. MANZOV ( J . SOC. Chem. Id. 1923 42 509-510~).- During the distillation of crude naphthol on the technical scale the formation of a large proportion of pp'-dinaphthyl ether was observed. The cause of this was traced to the presence of inorganic salts particularly acid salts during the distillation. When p-naphthol is heated at 200-210" for about ten hours it is converted entirely into pg'-dinaphthyl ether. E. H. R .ORGawIcl OHBXXST&Y.i 161 Substitution Products of Diphenylene Oxide. II. W. BORSCHE and B. SCHACKE (Ber. 1923 56 [B] 2498-2508; of. Borsche and Bothe A. 1908 i 528).-An extension of previous work. In oonsequence of the communication of Mayer andKrieger (A. 1922 i 746) the compound described previously (loc. cit.) as 3-nitro- diphenylene oxide is now considered to be the 2-nitro-derivative. The nitration of diphenylene oxide in glacial acetic acid solution gives a mixture of 2-nitrodiphenylene oxide and 3( ?)-nitrodiphenylene oxide small yellow-needles m. p. about 110". The former compound is reduced by sodium and methyl alcohol to 2 Z'-azoxydiphenyZene oxide pale yellow matted needles m. p. 259-260° and by sodium and boiling amyl alcohol to 2 2'-azodiphenyZene oxide m.p. 282". It is converted by concentrated sulphuric acid into 2-nitrodiphenyl- eneoxidesulphonic acid N0,~C12H,0*S0,€€ which is isolated in the form of its sodium salt pale yellow needles. The salt is converted by phosphorus pentachloride into Z - n i t r o d i p h e n y l e n e o x ~ d ~ ~ ~ ~ y Z chloride m. p. about 200" (decomp.) which is transformed by ammonia into the correspohding umide an amorphous white powder m. p. (indefinite) 265" (decomp.). The action of tin and concentrated hydrochloric acid on sodium 2-nitrodiphenyleneoxide- sulphonate yields 2-aminodiphenylelzwxidesulphonic acid the barium salt of which colourless leaflets is described. 2-Aminodiphenylene oxide is converted by ethyl bromomalonate into et h y 1 dip hen y leneoxid e- 2 - arninorndltmute C,,H ,O*RTH *CH (C0,E t)2 pale yellow needles m.p. 100"; it is transformed when heated at 240" into ethyl diphenyleneoxideindoxylate C l 2 H 6 0 < ~ ~ ~ * c O 2 E t m. p. 191" which when fused with alkali 0 co-c= hydroxide yields '' bisdiphenylenm"d-in- digo," a bluish-black powder which remains [I I I I ' unchanged below 350" ; the annexed formula J 2 is assigned to it but the possibility of the formation of the new ring in the 2 3-position is not excluded. 2-Diphenyleneoxide-2'-aminobenzoic acid C B O*NH*C,H,*CO,H pale yellow needles m. p. 227" is obtaineb2 b$ heating 0-chloro- benzoic acid 2-aminodiphenylene oxide hydrochloride potassium carbonate and copper bronze in the presence of amyl alcohol at 14-0-150". It passes when heated with zinc chloride at 240" into 2-anilinodiphenylene oxide C1,H,O*NHPh oolourless laslfl& m.p. 132" ; the acid is transformed by the successive action of phm- phorus pentachloride and aluminium chloride into phenylene oxideacridone C1,H,,O,N green- f) ish-yellow leaflets m. p. above 350" (annexed ()NH 2-Diacetamidodiphenylene oxide is converted by nitric acid in glacial acetic acid solution fu".f I into 3( 1 ) - n i t r o - 2 - d i a c ~ m i d o d i p ~ ~ ~ l € n e oxide \/-\/ 3;~.llow leaflets m. p. 19&197" which is hydrolysed by dcohol and fuming hydrochloric acid into 3(?)% /\/\/\-NH \/-/ o:/\/ formula). VOL. CXXVI. i. 9i. 162 ABSTRACT8 OF 0'HWOAI.i PAPERS. nitro-2-amid+phn&ne oxide orangemd needles m. p. 222"- 2 3( ?)-Diamidiphylene oxide forms colourless crystals m.p. 166" (hydr&l.i&e colourless leaflets); it is charaeterised M an OFthodiamine by its ability to condense with benzil to give the - quinoxaline derivative c12H6o<gyg greenish-yellow needles . i m. p. 179" and with phenanthraqinone to give the compound C 1 2 H 6 0 < ~ ~ 8 6 2 yellow needles m. p. 297". The action of aluminium chloride on diphenylene oxide and metyl chloride in the presence of carbon disulphide leads to the formation of 3-acetyldiphenylene oxide and 3 6( '2)-diacetyldi- phenylene oxide colourless needles m. p. 140". Nitro-3-acetyldi- phenylene oxide a brown crystalline powder m. p. 105" 3-ethyl- diphenyzene oxide a colourless liquid b. p. 3lO"/atmospheric pres- sure and nitro-3-ethyZdiphenylene oxide yellow needles m.p. 96" b p. 2L8-226"/15 m. are described. Diacetyldiphenylene oxide yields a dioxime Cr,HF403N2 a colourless sandy powder m. p. 250" (decomp.) whch is isomerised by phosphorus pentachloride in the presence of ether into dia;cetyZuminod$phenyZene oxide colour- less leaflets m. p. 258" from which diaminodiphenylene oride slender colourless needles m. p. 213" is obtained. Diethyldiphenylene oxide a colourlw odourless liquid b. p. 197-199"/20 mm. 334"/750 mm. is prepred by the action of amalgamated zinc and hydrochloric acid on diacetyldiphenylene oxide. Diphenylene oxide is converted by phthalic anhydride in the presence of nitrobenzene and aluminium chloride into diphenylene- oxidephthalonic acid m. p. 203-204" which passes under the influence of anhydrous zinc chloride at 260" into phthuloyldiphenylene de,'C,H,O greenish-yellow needles m.p. 258". The latter substance is reduced by zinc dust and aqueous ammonia to a mixture of phenylenwxidedih ydroanthranol C,,H 1402 a pale yellow powder m. p. 169" and a compound C,,,Hl,O yellow leaflets with a green fluorescence m. p. 311" the constitution of which has not been elucidated. Diphthaloyldphenylene oxide C2,H1,0 crystallises in slender greenish-yellow needles m. p. 295". J. BOESEEEN (Ber. 1923 56 [BJ 2409-2411).-Methods previously described (cf. Derx A. 1922 i 651) have been applied to the determination of the configuration of isomerides of 1-methyl- 1 -phenyl- and 1 -cycle- hexyl-cyclohexane-1 2-diols. The 1 -methylcyclohexane-1 2-diol m. p. 67" obtained by oxidation of 1-methyl-A1-cyclohexene is the ck-compound (not tram see Nametikin and Janev A.1923 i 1081). With potassium hydroxide &Dd boric acid it forms a crysfahe salt C6H&e:0,:BOK,4H@. The isomeric oompound m. p. 84" has therefore the trans-configuration. cis-1-Phanykyclo- hexme-1 2-diol is the product m. p. 95" obtained by oxidation of 1 -phenyl-Al-cycbhexene with permanganatz. It is also the principal product of hydrolysis of 1-phenylcycZohexene 1 2-oxide but trans- I-pknylcyclohexane-1 2-diol is also formed in the reaction product ; 6 4 H. W. The Configuration of Cyclic 1 2-Diols.it forms short prisms m. p. 98-5". It is probably the primary product but under the experimental conditions homerises into the cis-form (cf. Nametkin and Ivanov A. 1923 i 1097).cis-l-cyclo- Hczylcyclohexune-1 2-diol m. p. 122-123" is obtained by oxid- ation of the corresponding cyclohexene and the trans-ismeride m. p. 142O by hydration of 1-cyclohexylcyclohexene 1 2-oxide. E. H. R. Action of Nitric Acid and Nitrogen Peroxide on Tetra- chloro- and Tetrabromo-pyrocatechol and the Corresponding Quinones. T. ZINCEE (Annalen 1923 435 145-173).- Tetrachloro-o-benzoquinone when treated with nitric acid (d 14- 1-51) gives according to the concentration of the acid one of two cornpunds A C,H40,C14 or B C,H,0,N2C14 which are also produced under similar conditions from tetrachloropyrocatechol. The former (A) colourless needles m. p. 95-96" is a t r i h y b t e of a tri-keto-compound ; when heated it is converted into trichloro- hydroxy-p-benzoquinone and on reduction gives trichloro- hydroxyquinol (cf.[Frl. J Weishaupt Dissert. Marburg 1923). Compound B forms white needles decomposing at the m. p. (114-115") to give water carbon dioxide oxides of nitrogen and the compound C,,O,Cl described previously (A 1909 i 591; 1912 i 964). The last compound is formed intermedialzly on boiling an aqueous solution of B then decomposing to give per- chlmoindone. Similarly on heating a solution of B in alcohol acetone or acetic or concentrated sulphuric acids the compound C,,O,Cl is formed. Compound B when treated with alkali affords a number of decomposition products depending on the concentration of alkali etc. Producfs identified include ammonia nitrogen mrbon dioxide and oxalic and nitrous acids. Mainly from this decom- position and from the fact that compound B is also produced (here not accompanied by A) by treating tetrachloropyrocatechol at 0" with liquid nitrogen peroxide the constitution I1 is assigned to B the formation of this substance from tetrachloropyrocatecho€ proceeding through the corresponding quinone and its nitrogen peroxide additive compound I co (One N02-group is probably nitro- the other nitrite *ONO).A low value is obtained for the molecular weight of B when determined cryoscopicafly in acetic acid owing to the dissociation of the hydrate (11). Whilst tetrachloro-o-benzoquinone does not d o r d compound (I) (but only tarry products) when treated with nitrogen peroxide 9 2i. I64 ABSmCTS OF CHEMICbL PAPERS. the constitution (11) assigned to B fa& into line with the abore decomposition in presence of alkali.In this process chloro-groups and a nitrite group are replaced by hydroxyl oxalic acid and the compound OH*CH:C( OH)*C( OH),-CH( OH) resulting. Further decomposition affords s-dihydroxyethylene or the isomeric glycoll- aldehyde and glyoxylic acid whence carbon dioxide and more oxalic acid are produced. When substance B is treated with aniline or phenylhydrazine red or dark-coloured substances result respectively. Tetrabromo-o-benzoquinone behaves unlike the chloroquinone towards nitric acid white insoluble poducb being formed Tetra- bromoppcatechol is however converted by nitric acid into a compound C6H405Br4 (type A4) which decomposes partly to give a substance C502Br4 m. p. 142-143". Bromo-compounds corresponding with B result when tetrabromopyrocatechol is treated with nitrogen peroxide no compound of type A being produced in this case.- The homo-compound C6H20,N2Br,,H,0 (type B) which forms colourless needles m. p. 113-114" (decornp.) on drying undergoes partial decomposition (the m. p. rising to 126-127"). On keeping or on warming in solution in glacial acetic sulphuric or formic acids the bromo-compound affords the substance CIoO,Br8 ; on boiling in aqueous solution it gives perbromoindone ; whilst with alkalis the bmmo-compound decomposes in a manner similar to that observed with the corresponding chloro-compound (B). When halogenated pyrocatechols are treated with mixed acid (HNO 88.9% H,S04 9-9:/ H20 1-2%) type A is produced to a greater extent than when nitric acid alone is used owing to increased oxidation. The corresponding quinones when treated with mixed acid give in the case of the chloro-compound tarry products and in that of the bromo-compound decomposition products of the intermediately-formed substance C,H,O,Br,.3 4 6-Trichloro-5-methyl- and 3 4 5-trichloro-6-methyl-pyro- oatechol are converted into compounds of type B (but not of type A ) C6H40,N2Cl,Me when treated with nitric acid (d 1.45-1.48) or with nitrogen peroxide indifferent results being obtained using mixed acid. The compound C,H4Me0,N2CI obtained from the 3 4 6- derivative forms white needles m. p. 116-117" (decornp.) (one specimen m. p. 110-111") crystallised from dilute hydrochloric acid. After careful drying the m.p. rises to 126-127" this m. p. being obtained when the substance is crystallised from nitric acid. The compound on melting or better on being heated in glacial acetic or sulphuric acid solution is converted into the substance C,,O CI6Me2 (m. p. 182") described previously (A. 1897 i 507). J%om the decomposition in presence of alkali of the compound C,H,lhfeO,N,CI the latter is given the constitution NO,.CHCI -CCI (NO,)CMe:CCl*C( OH),*CO,H. NO,*CRClCCl( NO,)*CClXMe*C( OH),-CO,H obtained from 3 4 5-trichloro-6-methy1pyrocatecho1 forms The isomeric compound,needles melting at 115-116" (or after drying 125-126") to give the substance C,oO,CI,Me which is more readily obtained by heating the h t compound in aqueous acetic or sulphuric acid solution and is identical with a compound (m.p. 175") previously described (A. 1897 i 509). The substance Cl,0,C18 mentioned above which is also obtained from the nitric acid decomposition product (C&O,"C14&) of tetrachloro-o-cresol by warming with concentrated sulphunc acid has been re-investigated. It was previously stated that it wa8 converted by boiling methyl alcohol into the compound C,C16(OH)*OMe (m. p. j38") which is now written as C,02C~*OMe (m. P. 136-137"). ' TGe constitution of the compound Clo0,Br8 (cf. A. 1907 i 322; 1912 i 964) is still unsettled but the possibility of it being a derivative of tetrahydmmphthalene is excluded. The compound on melting a t 207-208";m heating with glacial acetic acid and sodium acetate or on hakikg in nitrobenzene solution affords perbromoindone (m.p. 195-1969) the latter being converted by warm aniline into the anilide C,OBr,*NHPh scarlet leaflets m. p. 224" (decomp.). E. E. T. The Constitution of Weselsky and Benedict 's Dinitro- @no1 Methyl Ether. F. KEHRMANN and G. JEQUIER (Hdu. Chim. Ada 1923 6 949-951).-The comtitution of this ether given by Reverdin and de Luc (A. 1911 i 965) who concluded that it is 3 5-&nitro-4-hydroxyanisole has been confirmed by the preparation of the isomeric ether. The silver salt of 3 Ei-dinitro- quinol 1-acetate reacts with methyl iodide to give 2 6-dinitro- 4-acetoxyanisuZe small yellow crystals m p. 63" which when hydrolysed gives 2 6-dinitro-4-hydroxganzsole yellow crystals m. p. 149". The dinitroquinol monoacetate used for the prepar- ation was obtained by nitration of quinol diacetate (see following abstract).E. H. R. The Action of Nitric Acid on Quinol Diacetate. F. KEXR- BIANN and W. KLOPFENSTEIN (Helq. Chim. Actu 1923 6 952- 954).-Nitration of quinol diacetate with fuming nitric acid below 10" gives not 3 5-dinitroquinol diacetate as stated by Nietzki and Preusser (A. 1887 574) but 3 5-dinitroquid 1-monatcetate yellow tablets m. p. 94". Acetylation of this with acetic anhydride gives 3 5-dinitroquinol diacetate colourless needles m. p. 134". More careful nitration of quinol diacetate at 0" gives 3-nitro- quinol 1-acetate lemon-yellow needles m. p. 84". This can be acetylated to 3-nitroquinol diacetate colourless needles m. p. 80". It is evident that nitration of quinol diacetate cannot proceed without elimination of one acetyl group.Some Condensation Products of Hydroxyquinol Trimethyl Ether. T. SZ~EICI (Ber. 1923 56 [ B ] 2464-%68).-Hydroxy- quinol trimethyl ether condenses wi$h acetone in glacial acetic acid solution in the presence of concentrated sulphuric acid to give E. H. R.i. 166 ABSTRACTS OF OKEMIOAL PAPERS 2 4 5 2' ; 4' 5'-kamethoxydiphenylisophorone [l 5 5-tri- methyl-3 3-bis-2' 4' 5'-trimethoxyphn~l- A1-cyclohxene] (annexed formula) colour- HCH\CH less needles m. p. 207" which is converted by bromine in glacial acetic acid solution into the bromo-derivative C,,H,,O,Br colourless lustrous crystah m. p. 1190; as by-product of the condensation 2 4 5-trimethoxybenzeneiulphonic acid colourless needles m. p. 115" is obtained the sodium salt of which is described. The action of hydrogen chloride on it solution of 2 4 5-tri- methoxybenzene and alloxan in alcohol leads to the production of 2 4 5-trimethoxyp~nyldi~uric acid co <zg::E>c( oH)*c6H2( OMe) small colourless needles m.p. 248-249" (decomp.). It is con- verted by acetic anhydride and sulphuric acid monohydrate into the corresponding acetate decomp. 270-292" and is decomposed by boiling N / 5 sodium hydroxide solution into ammonia carbon dioxide and 2 4 5-trimethoxyphenyltartronimide colourless microscopic leaflets m. p. 220-221". 2 4 52%- methoxyphenacyldialuric acid slender colourless crystals m. p . 245" (decomp.) after darkening a t 220" is prepared from 2 4 5- trimethoxyacetophenone and alloxan. Benzhydrol is converted by 2 4 5-trimethoxybenzene in alcoholic solution in the presence of hydrogen chloride into 2 4 5-trimethoxytriphenylmethane C,H,( OMe),*CHPh colourless needles m.p. 117". In a similar manner 2 4 5 4'-tetra- methoxydiphenylcarbinol and 2 4 5-trimethoxybenzene yield 2 4 5 2' 4' 5' 4"-heptamethox~7.i~he~~~lmethane slender colourless needles m. p. 162" whereas 2 4 5-trimethoxyphenyl- a-naphthylcarbinol and 2 4 5-trimethoxybenzene give 2 4 5 2' 4' 5'-hexamethoxydiphenyl-~-nnphthylmet7~ane slender colourless needles m. p. 198". c6H2( ()&)3.C\/CMe I CH2 NH<C-j co\ /C(OH)=C,H*(OMe) H. W. Action of Sulphur on p-Toluidine in the Presence of Litharge. Thio-p-toluidine its Constitution and some of its Derivatives. M. T. BOGERT and &I.R. MNDELBAUM ( J . Amer. Chem. Soc. 1923 45 3045-3055).-The formation of thio- p-toluidine by heating p-toluidine with sulphur a t 140" in the presence of litha,rge takes place through the mercaptan (annexed formula) which reacts with a nuclear hydrogen atom of unchanged p-toluidine. A small proportion of SH the mercaptan was oxidised to dithio-p-toluidine m. p. 88*5" acetyl derivative m. p. 213". The sul- phide produced by de-amination of thio-p-toluidine was identical with di-m-tolyl sulphide synthesised from m-iodofoluene and sodium m-tolyl sulphide. The respective sulphones and a mixture of them melted at 94'. In the absence of litharge and 8 \/ NHzomma -mY. i. 167 at 180-220" the intermediate mercaptan reacted with the methyl group of unchanged p-toluidine to give dehydrothio-p-toluidine.The authors failed to convert thio-p-toluidine into dehydrothiu- p-toluidine. The former gave a diucetyl derivative m. p. 165" (con.) which was oxidised to bis-2-acetamido-5-carboxt~phenylszrlphone m. p. above 360". The latter was de-acetylated and the resulting bis-2-amino-5-carboxyphenyZsulphone melted above 360" (decomp. j ; the methyl ester forms thin square colourless tablets m. p. 234" (COIT.) the ethyl ester forms yellow transparent prisms m. p. 206" (corn.). F. B. Formation of Liquid Crystals of Mixtures of Cholesterol and Cetyl Alcohol. A. M~ODZIEJOWSKI (2. Physik 1923 20 317-342) .-The conditions necessary for the production of liquid crystals of mixtures of cholesterol and cetyl alcohol and the approximate character of the equilibrium diagram relating to the phases of mixtures of these substances have been determined.Cholesterol exists in two solid enantiomorphic modifications the transformation temperature associated with which is about 43". Liquid cetyl alcohol on cooling deposits needle-shaped crystals at about 50". Crystalhation is accompanied by the separation of an amorphous solid phase characterised by the presence of lenticular masses. The transformation from liquid to solid is reversible. Liquid crystals of mixtures of cholesterol and cetyl a.lcoho1 may be either homogeneous or may exhibit a spherolitic or myelin structure characterised by the presence of rod-like biscuit- or worm-shaped masses in a state of agitation. Of these two varieties of liquid crystals the homogeneous variety is the more stable.Cetyl alcohol is practically insoluble in this modific- ation. The liquid crystals are probably composed of equal mole- cular proportions of the two components and on heating are reversibly converted into solid crystals provided the concentrations of the components are within certain limits. They form an eutectic mixture with cetyl alcohol. Preparation of Nucleus-substituted Hydroxyl Derivatives of p -Amino-a-hy droxy- a-arylet hanes and p -Amino- a-bisaryl- ethanes. 0. HINSBERQ (D.R.-P. 373286; from Chern. Zentr. 1923 iv 662; cf. A. 1923 i 923).-Phenols naphthols or their substitution products are allowed to react with aminoacetal or its N-mono- or di-alkylated derivatives in the presence of hydro- chloric acid under pressure.For example with equimolecular proportions of phenol and aminoacetal in the presence of hydro- chloric acid under pressure a t loo" the following reaction takes place PhOH+NH,*CH,*CH( OEt) + HCl+H,O = OHC,H,*CH( OH)-CH,*NH,,HCl+ 2EtOH. a-p-Hydroxyphenyl- p-aminoethanol thereby obtained has m. p. above 250"; the hydrochloride has m. p. 172" (decomp.). Phenol (2 mols.) and aminoacetal (1 mol.) give p-amiizo-a-bis(p-hydroxy- phenyZ)ethane which has m. p. 105". Pyrocatechol and methyl- aminoacetal yield o-dihydroxyphenylethanolmethylamine (adren- a'line). p-Cresol and aminoacetal give p-amino-a-hydroxy-a- 1 - J. S. G. T.hyd?wxy-4-ntethzJphenyZethne an unstable compound which gives =a h y W & with m. p. 120' (decomp.). Naphthenic Acid. III. Naphthenic Acids from Kubiki g e r O ~ e ~ e Distillate.Y. TANAEA and 8. NAGAI (J:Chem. Znd. Japan 1923 26 1115-1123; cf. ibid. 1923 26 309; A. 1933 i &).-A crude mixture of acid substances was obtained by acidify- h g a waste lye obtained in the refking of kerosene distillate from crude oil produced at Kubiki. Crude naphthenic acids (d? 0.9647 rig 1.4790 and acid value 202.8) were then obtained by three methods. About 86% of the crude acids distilled at 140- 210"/8-9-9 mm. The lower distillates contained some phenolic compounds and the fractions above 200" showed lower specific gravities than the preceding ones. The acid was converted into methyl esters d:" 0.9368 n; 1-4663 about 83% of which distilled at 120-180"/8.9-9 mm. and the fractions above 170" gave decreasing specific gravities.A mixture of pure naphthenic acids (di6 0.9587 n 1.4707 and acid value 244.5) was obtained by saponifying the mixed esters about 90% of which distilled a t 150-210"~8~9-9 mm. The higher fractions above 200" showed again lower specific gravities than the preceding ones. The mixed naphthenic acids and their distillates of Kubiki origin have much smaller spec& gravities than those of Kurokawa origin which indicates the presence of isomeridea having low specific gravities in the former. K. K. Normal Ammonium Salts of some Organic Acids and their Substitution Derivatives. VIII. L. MCMASTER and P. K. PRATTE ( J . Amer. Chem. Soc. 1923 45 2999-3001).-A descrip- tion of normal ammonium salts of organic acids prepared by the method previously described (A. 1918 i 263).The solubilities of the normal ammonium salts of the following acids are expressed in g. of salt per hundred g. of water methyl alcohol and ethyl alcahol in the order named. Phenoxyacetic acid 13-03 3.97 0.44 p-nitroghenylacetic acid 7-41 15.14 1-82 o-iodobenzoic acid 67.1 1 184-10 63-37 o-methoxybenzoic acid 38.25 17.85 4.82 2 4-di- nitrobenzoic acid 62.70 21-39 3.85 5-nitrosalicylic acid 4-43 4.41 7-96 naphthalene-l-sulphonic acid 45.91 34.45 9-22 na hthal- acid 11.30 20.15 2-59 6-chloro-3-nitrobenzenesulphonic acid 4.72 2.76 0.96. F. B. R. C. BROWN and R. E. KREMERS ( J . Amer. Pharm. ASSOC. 1922 11 607-608).-3 5-Di- nitrobenzoic esters of phenol (m. p. 145-146") o-cresol (133- 134") m-cresol (160-162") p-cresol (180-.-182") guaiacol (138- 139") carvacrol (76-7?") and thymol (102-103") mere prepared as a means of identification of the phenols.G. W. R. ene-2-sulphonic acid lP71,8-33,2.53,2 5-dichlorobenzenesu f phonic 3 5aDinitrobenzoates of Phenols. CHEMICAL ABSTRACTS Prdeinogenous Aminc-alcohols aqd Cholines. IfI. P. KARRER E. HORLACHER F. LOCHER and M. GI~LEB (Helv. Chim. Ada 1m3 6 905-919; ef. A. 1922 i 813).-N-~ethyl-leucinolORQBNIO 4lEEXIsTBY. i. 169 [~-d;lleth~a~ninoi~ohexyldcohol] (cf. A. 1921 i 228) condenses with p-nitrobenzoyl chloride in chloroform solution to give p-nitro- benzoyl-N-dimethyl-leucinol. This can be reduced to p-amino- benzoyl-N-dimethyl-leucinol which in the form of its hydrochloride is a very powerful local anssthetic. The corresponding N-diethyl LV-dipropyl and N-pentamethylene Cpiperidino] compounds are likewise powerful local anaesthetics.Of the four .the N-&ethyl compound is the most powerful being eight times as ackive as novocaine and a t the same time less poisonous than cocaine. p-2\.'itrobenzo~l-N-dirnethyl-leucinol hydrochloride CHMe,*CH,.CH(NMe,,HCl)*CH,O*CO*C,H .NO forms yellow needles m. p. 149.5". It is reduce4 by hydrogen in the presence of platinum black to p-aminobenzoyl-N-dimethyl- Zewinol hydrochloride bright yellow needles m. p. 196". N-Di- ethyl-Zeucine ethyl ester is prepared by condensing racemic a-bromo- isohexoic acid with diethylamine and esterifying; it forms a pale yellow oil b. p. 204-208"/720 mm. It is reduccd by sodium and alcohol to N-diethyl-leucinol a colourless oil b. p.208-211". p-Nitrobenzoyl-N-diethyl-leucinol hydrochloride forms pale yellow needles m. p. about 163" (depending on the rate of heating). p-Aminobenzoyl-N-diethyl-leucinol hydrochloride forms white leaflets m. p. 191". N-Pentarnethyleneleucine ethyl ester [ethyl a-p-'peridino- isohezoate] from a-bromoisohexoic acid and piperidine forms an oil b. p. 248-255"/726 mm.; by reduction it gives N-penta- naeth@!eneleucind [ibpiperidinoisohexyZ dcohol] b. p. 250-252". The p-nitrobenzoate hydrochloride crystallisss in nodular aggregates of thin prisms m. p. 156" and the p-anaindenzoa,te hpirochide crystalhes similarly. The synthesis of 3 4-methylenedihydroxyphenylaIaninecholine iodide m m accomplished as follows. Piperonyl bromide was obtained by the action of hydrogen bromide on piperonyl alcohol; it crystal- lises in needles and does not form a compound with magnesium in ether solution.It condenses with ethyl malonate by means of sodium in alcoholic solution forming ethyl piperonylmdonate CH,:0,:C,H3*CH,*CH(C02Et) a yellow vkcous oil b. p. 200- 220"/15 mm. which when hydrolysed gives piperonylmalonic acid m. p . 156". This was brominated to bromopiperonylmahnic acid CH,:0,.C6~CH,*CB(CO,Et) m. p. 147-148" (decornp.) which when heated at 120-130" loses carbon dioxide forming a-bromo- piperonylacetic acid. The latter waa not isolated but was heated directly with dimethylamine a t 100" ; the N-dimethyl-3 4-meth.ytene- dioxyphenylakcnine formed waa not isolated but treated with alcohol and hydrochloric acid forming the ethyl ester a Viscous yellow oil b.p. 200"/14 mm. This waa reduced with sodium and alcohol forming N-dimethyl-3 4-methylenediox~phenylalanin~ CH, 0,:C ,H,-CH,=CH (me,) -CH2*OH b. p. 180"/14 mm.; the hydruchlon'de crystallises in white leaflets m. p . 165". When the alaninol is treated with excess of methyl iodide in alcohol solution 3 4-methylenedioxyphengl&nine- chdine iodide [P-dimethylamino-y-piperonylpropyl alwhd meth- idide] m. p. 184" is formed. The following palmitic and skaric 9"i. 170 ABSTBAOT8 OB ( l m C A L PAPERS. acid esters of proteinogenous cholines are described p-methoxy- phnylalanine rnethiodide stearate bunches of needles sintern from 98" m p. 195"; the corresponding pdmitate similar crystals m. p. 138-141"; alanine methiodide stewate s a y leaflets m.p. 210-212" ; palmitate white needles m. p. 203-210" ; &nine inethochlm.de stearate hygroscopic needles m p. 202-205" and pahiitate m. p. 202-205". Effect of Silver Nitrate and Alkali Nitrates on Aromatic Anhydrides. C. V. GHEORGHIU (Ann. Xci. Univ. Jassy 1923 ii 308-309; from Clzem. Zentr. 1923 iii 1155).-Benzoic an- hydride when heated with silver nitrate explodes with evolution of gas development of the odour of nitrobenzene and formation of silver Phthalic anhydride and coumarin behave in a similar way. The alkali nitrates can also act like silver nitrate. The author supposes that benzoyl peroxide or perbenzoic acid the salts of which are explosive may be formed e.g. 4Bz,0+2NaN03= 2BzONa+3Bz20,+N2. Por the per-acids the formulze CO,H*C,H,*CO*O*OH and O~~C,H,*CH:CH*CO~O~OH respectively are given.Nitrobenzene is probably formed by nitration of benzoyl peroxide. o-Nitrophenylpropionic Acid. A. JAENISCH (Ber. 1923 56 [B] 2448-245O).-An improved method is described for the conversion of o-nitrobenzylmalonic ester into p-o-nitrophenyl- propionic acid m. p. 115"; the silver lead copper mercury barium calcium (+2H20) and zinc (+2H20) salts are described. The methyl ester is a liquid b. p. 171-172"/12 mm. p-o-Nitrophenyl- propionyl chloride needles m. p. 43" (prepared from the acid and phosphorus pentachloride) is transformed by ammonia into the corresponding amide colourless plates and needles m. p. 121- 122" which is converted by Hofmann's method into the bromo- amide C,H,O,N,Br yellow needles m. p. 136-137" and thence into p-o-nitrophenylethylamine NO,*C,H,=CH,*CH,*NH a liquid b.p. 147"/13 mm. (hydrochloride plates m. p. 174.5"; picrate m. p. 148.5"). Benzo- p-o-nitrophenylethylamide NO,*C,H,*CH,*CH,=NHBz crystallises in stellar aggregates m. p. 98"; it is reduced by phosphorus and hydriodic acid to benm- /3-o-aminophenylethylamide leaflets m. p. 135" (the hydriodide is described). p-o-Nitrophenyl- ethylphtharlimide NO,~C,H,*CH,*CH,*N:C,H,O needles m. p. 120-121 " p-o-aminophenylethylphthcclimide needles m. p. 163" p-o-nitrophenylethylsuccinimide needles m. p. 116" and p-o-amino- phnylethylsuccinimide needles m. p. 141 " are described. Reduc- tion of p-o-nitrophenylethylamine by phosphorus and hydriodic acid yields p-o-aminophenylethylamine [di-hydroiodide yellow needles and leaflets m.p. (indehite) 260" ; dihydrochloride softening a t 184"; picrate m. p. 142-143"; benxoyl derivative m. p. 139-140"]. o-o-Nitrobenzylmetophelzone stellar aggregates m. p. 68-69" prepared from o-nitrobenzylacetyl chloride benzene and aluminium chloride is reduced by phosphorus and hydriodic acid to 2-phenyl- E. H. R. G. W. R.quinoline 112. p. 81 ". u-Keto-y-o-nitrophenyl-u-an~~ylpropne pale yellow rodlets m. p. 59" and 2-anisylquinoline leaflets m. p. 123.5" are described. Similarly the reduction of ethyl 0-nitro- benzylmethylacetmcetate a liquid yields 2 3-dimethylquinoline m. p. 64*5" and not a dihydro-derivative. P-o-NitrophenylpropzsonitriEe prepared from the amidc and thionyl chloride m. p. 4 1 4 2 " is reduced by stannous chloride and hydrochloric acid to 2-aminoquinoline hydrochloride.a-Bromo-p-o-nitrophenylpropionic acid rhombohedra m. p. 115- 116" is prepared by the action of bromine and phosphorus on the parent acid or by heating bromo-o-nitrobenxylmdonic acid prisms m. p. 143" (decomp.). .a-Hydroxy-P-o-nitrophenylpropionic m i d rectangular plates m. p. 103" is prepared from the bromo-acid and silver nitrate solution; it is decomposed by sodium hydroxide solution with production of o-nitrotoluene. H. W. asp-Triphenylpropionic Acid and some of its Derivatives. [MME] P. RAMART (Compt. rend. 1924 178 93-96).-Benzyl diphenylacetate (needles m. p. 35" b. p. 205-207"/2 mm.) from diphenylacetyl chloride and benzyl alcohol when treated successively with sodamide and benzyl chloride affords benxyl uup-triphenyl- propionate (prisms m.p. S5" b. p. 270-276"/2 mm.). The latter on hydrolysis affords ucwp-triphenylpropionic acid (prisms m. p. 132"; amide needles m. p. 111"). The nitrile (m. p. 126") 1s formed from benzyl chloride and sodio-diphenylacetonitrile or from phosphoric oxide and the amide (above). Neure (A. 1889 597) obtained the nitrile but was mistaken with regard to the constitution of his acid of m. I>. 162" (cf. Bistrzycki and Mauron A. 1910 i 845). E. E. T. Higher Terpene Compounds. XVI. The Carbon Frame- work of Abietic Acid and Dehydrogenating Disruption in the Abietic Acid Series. L. RUZICKA E. SCHINZ and *J. MEYER (Helv. Chim. Acta 1923 6 1077-1096).-The annexed constitu- tional formula for abietic acid (pinabietic acid) put forward by Virtanen (A.1921 i 669) does not conform with the principle which has been foundgeneral for the sesquiterpenes that the carbon framework must be divisible into H,F/'\$.co,H isoprene residues. This formula was based partly on the observation that the hydrocarbon abietin C,,H, when oxidised with manganese dioxide "7 YH2 and sulphuric acid gives trimellitic acid. Hence CH2 it is argued that abietin must contain a benzene /\ / ring and that the corresponding ring in abietic H2$! YH acid must contain the double bond and the bridge- H,C ring (or as is now known to be the case the two double bonds) as well as the carboxyl group. A study of the oxidation of abietin abietene methyl- abietin and abietic acid leads to the conclusion that Virtanen's reasoning is incorrect.Rlethylabietin which according to Virtanen should also contain a benzene ring is com- CPrS HC</C\ MeC CHMe \/ CH2 9" 2i. 172 ABSTRACTS OF CHEMXCAL PAPERS. pletely oxidised by cold aqueous permanganate to acids and by oxidation with manganese dioxide and sulphuric acid it gives tri- mellitic acid as also does abietic acid. It is.concluded therefore that the carboxyl group cannot be in the same ring as the isopropyl group and as the 9 and 10 &\A positions are excluded (see annexed diagram and 1;; A. 1922 i 829) the only remaining positioiis qv\,/i are 2 3 and 4. The remaining methyl group ’ may be in position 11 or possibly in 12 but only Oxidation of abietic acid and its related compounds with man- ganese dioxide and 57% sulphuric acid leads to a mixture of benzene polycarboxylic acids some of which are formed normally from the carbon framework of the oxidised substance some indirectly.Trimellitic acid and mellophanic acid (which is confirmed to be the I 2 3 4tetracarboxylic acid cf. Bamford and Simon T. 1910 97 1904) are probably formed normally and are obtained from abietene (mixed with abietin) abietic acid and methylabietin. Pyromellitic acid and benzenepentacarboxylic acid are obtained from abietic acid their formation being possibly due to polymeris- ation of the abietic acid a t a double bond. A number of methods in which this may occur are discussed. Retenequinone and methyl- retenequinone are oxidised to mellitic acid whilst the former also gives pyromellitic acid. Dihydroabietene is oxidised to mellophanic acid without formation of any trimellitic acid and the same is the case when niethylabietin is oxidised first with cold permanganate and then boiled with manganese dioxide and sulphuric acid.The mechanism of the oxidation of the above compounds with manganese dioxide and sulphuric acid consists first in dehydro- genation of the individual hydroaromatic rings followed by dis- ruption to benzenecarboxylic acids. The process is referred to as “ dehydrogenating disruption.’’ The different benzenepolycarb- oxylic acids are best separated by fractional distillation of their methyl esters which crystallise readily. The reduction of ethyl abietate by Bouveault’s method to abietenol which still contains one unsaturated bond indicates that there is no double bond in the ring containing the carboxyl group (A.1922 i 829). The exact position of the double bonds in abietic acid remains uncertain. I kT\ if the carboxyl is in 2. E. H. R. Higher Terpene Compounds. XVII. The Gentle Action of Potassium Permanganate on Abietic Acid. L. RUZICKA and J. MEYER (Helv. Chim. Acta 1923,6,1097-1108).-To obtain a crystalline product by the oxidation of abietic acid with potassium permanganate great care is required. The oxidation is carried out in potassium hydroxide solution using 2 to 3 atoms of available oxygen per mol. and a t a high dilution. After fifteen hours the manganese dioxide is filtered off and unoxidised abietic acid precipitated by a current of carbon dioxide. When part of the oxidation product has started to precipitate the solution is filtered and the main product precipitated with acetic acid.The precipi-ORGAWrO CHEMISTRY. i. 173 tate is filtered dried and digested with a little methyl alcohol which leaves a crystalline residue about 3 4 3 % of the weight of .the abietic acid taken m. p. 106". This is separable by fractional precipitation into an unknown substance C,,H,,O m. p. 154" and a dihydroxyubietic acid CmHm02(OH)2 m. p. 152" which gives a diacetyZ derivative m. p. 163" (decomp.) and it possibly stereo- isomeric diacetyl compound m. p. 240". On separate occasions the oxidation took different courses giving products of m. p. 135" and 360". E. H. R. The Resolution of &I-Tyrosine into its Two Optically Active Components. E. ABDERHALDEN and H. SICEEL (2.physiol. Chem. 1923,131 277-280) .-Formyl-dl-tyrosine obtained from tyrosine by boiling with formic acid for three hours has been separated into its components by recrystallisation from hot water containing four equivalents of brucine. The brucine salt of formyl- d-tyrosine which crystallises out forms four- or six-sided leaflets which decompose a t 145". Formyl-d-tyrosine is obtained from this salt on decomposing it with alkali. Hydrolysis of formyl-d- tyrosine with 10% hydrochloric acid yields d-tyrosine [a]? +8-7". The corresponding h a l t waB not obtained pure from the mother- liquors. The best preparation gave [a] -6.2O. W. 0. K. Dichlorotyrosine [ a - A m i n O - p 3 54lichloro4hydroxy- phenylpropionic Acid]. CHEMISCHE FABRIK RORA (swiss Pat. 99453 ; from Chem.Zentr. 1923 iv 828).-A suspension of tyrosine in acet,ic acid is treated with chlorine. Dichlorotyrosiize hydro- chloride separates out from which the free bme may be obtained in crystalline form. It is optically active. G. W. R. Preparation of Dibromotyrosine [a-Amino-p-3 5-dibromo- 4-hydroxyphenylpropionic Acid]. CHEMISCHE FABRIK FLORA (Swiss Pat. 95300 ; from Chem. Zentr. 1923 iv 663).-A suspen- sion of tyrosine in acetic acid is treated with bromine; from the products of reaction a-amino-p-3 5-dibrmno-4-hydroxyphenylpo- pioiiic acid is obtained. It is crystalline and optically active. G. W. R. Derivatives of a-Naphtho1-2carboxylic Acid. SOCIETY FOR CHEMICAL INDUSTRY IN BASLE (D.R.-P. 373736; from Chem. Zeittr. 1923 iv 593).-Additional to Brit. Pat. 195513.4 4'-Di- hydroxydinaphthylketone-3 3'-dimrboxyZic acid is a powder decom- posing a t 259". u-Xuphthol-2 4-dicarboxylic acid decomposes at about 286". G. W. R. a-Naphthol-4-carboxylanilide. SOCIETY FOR CHEMICAL IKDUSTRY IN BASLE (Swiss Pat. 99280; from Chem. Zentr. 1923 ir 829).-h ester of u-naphthol-4-carboqlic acid for example methyl a-naphthol-4-carboxylate is heated with aniline. a-Naphthol- 4-carrbo.zylanilide thus obtained is crystalline and has m. p 203" G. W. R.i. 174 ABSW@rS OF CHEIkfICbL PAPERS. The Constitution of Sparassol. E. WEDEKIND and K . FLEISCKER (Ber. 1923 56 [B] 2556-2663; cf. Falck ibid 2555).-The substance is shown to be methyl 4-hydroxy-2-methoxy I 0-toluate . Sparassol C1JiIl2O4 crystallises from methyl or ethyl alcohc ! in needles m.p. 67-68". It contains two methoxyl groups i I saturated and does not possess a ketonic or a reactive methylen group. Its aromatic nature is established by the isolation 0 ' methyl 3 ( ? 5)-nitro-4-hydroxy-2 -methoxy-o-toluate yellow needles m. p. 168-169" and methyl 3 5-dinitro-4-hydroxy-2-methoxy o-toluate small pale yellow needles m. p. 150". The presence o a phenolic hydroxyl group in sparassol is established by its solubilitj in alkali hydroxide but not in alkali carbonate and by the form ation of methyl 4-acetoxy-2-methoxy-o-toluate small hexagona plates m. p. 63-64' and of methyl 2 4-dimethoxy-o-toluate rhombic plates m. p. 4243.5' ; the isolation of 4-hydroxy-2-methoxy o-toluic acid m. p. 165-166" (decomp.) after slight previous soften- ing as by-product of the action of methyl sulphate and potassium hydroxide on sparassol indicates the presence of the.carbomethoxy- group. When treated with fuming hydrochloric acid under pressure sparassol yields orcinol. A comparison of the properties .of sparassol and the corresponding carboxylic acid with those of the known orcinolcarboxylic acids and their methylated derivatives excludes the poasibility that the constitution of sparassol is other than methyl 4-hydroxy-2-methoxy-o-toluate. It is established that the amount of benzenoid compounds in the culture medium is insufficient to account for the production of sparassol; an example is therefore afforded of the conversion of an aliphatic compound (sugar) into an aromatic substance by a biochemical method. H. W.Preparation of Aryl Hydroxynaphthyl Ketones. SOCIETY FOR CHEMICAL INDUSTRY IN BASLE (D.R.-P. 378908 378909 and Swiss Pat. 98559; from Chem. Zentr. 1923 iv 593-594).- @-Naphthol or negatively substituted derivatives of a- or @-naphthol are treated with aryl trichlorides with or without addition of diluents or condensing reagents in the absence of alkali hydroxides. The carboxylic acids and sulphonic acids of 4-hydroxynaphthalene- 1-arylketem are heated at high temperatures preferably in suspen- sion or in the presence of diluents. 1 -Hydroxynaphthalene-2-carb- oxylic. acid when heated with benzotrichloride a t 100-120" until eyolution of hydrogen chloride has ceased or a t 15" in the presence of strong sulphuric acid gives 4-hydroxy-1- benzoy~nccfhthalene-3-carb- oxylic acid small needles m.p. 205". On heating the latter com- pound under pressure with strong sulphuric acid phenyl4-hydroxy- a-naphthyl ketone is obtained m. p. 164-165". 4-Hydroxy- 1 -o-chlqrobenzoylnaphthulene-3-cccrboxylic acid from 1 -hydroxy- naphthalene-2-carboxylic acid and o-chlorobenzotrichloride has m. p. 2 13". 1 -Chloro-4'-hydroxy-2 1 '-dinaphthyl- ketone-3'-cccrboxylic & ~&R.I I-hydroxynaphthalene-2-carboxylic acid and 1-chloro- Z-naph+hofrichloride has m. p. 210-211". The following corn-0IUxmc CHEMISTRY. i. 175 pounds are also mentioned phenyl 2-hydroxy-a-mphthyl ketone rn. p. 175"' from @-naphthol and benzotrichloride ; 2-izydroxy-l- benzoylmphthulene-3-cccrboxyli~ acid from 2-hydroxynaphthalene- 3-carboxylic acid and benzotrichloride ; p7henyl 5-chloro-4-hydroxy- u-mphthyl ketone m.p. 121" from 8-chloro-l-hydroxynaphthalene and benzotrichloride ; 4hydrox y- 1 -benxoylnuphthulene-3 -sulphonic acid a white powder giving phenyl 4-hydroxy-a-naphthyl ketone by elimination of the sulphonic acid group from l-hydroxynaphthal- ene-2-sulphonic acid and benzotrichloride ; 4-hydroxy-l- benzoyl- -naphthalene-5-su~ph~i~ acid ; 1 -hydroxy-2-benxoylnap7~thalene-4-sul- phonic acid ; 1 -izydroxy-:!-benxoylnaphthalene-5-sulphonic acid. By heating the above-mentioned carboxylic acids or sulphonic acids with 5% sulphuric acid under pressure a t 180-190" or in the presence of dimethylaniline at 150" the carboxylic acid or sulphonic acid groups are eliminated. Examples are given of the preparation by fhis reaction of phenyl 4-hydroxy-a-nuphthyl ketone i-chloro-4'- hydroxy-2 1'-dinaphthyl ketone crystals m.p. 213") and 4 4'-di- hydroxy-1 1'-dimphthyl ketone. 3-Methoxynaphthalene-2-ketocarboxylic Acid. W. DIL- THEY and G. LIPPS (Ber. 1923 56 [B] 2443-2445).-3-Acetyl- 2-methoxynaphthalene condenses with benzaldehyde in the presence of alcoholic sodium ethoxide to give 2-cinnamoyl-3-met~ox~pht~~- deep yellow leaflets. m. p. 87" ene7 C6H4<H 6*CO -CH :CHP h ' G. W. R. H:C*OMe which is oxidised by potassium permanganate in the presence of pyridine to 3-rnethoxy-2-mphthoylformic acid c6H4< CH F*OMe CH:C*CO*CO,H ' pale greenish-yellow crystals m p. 162-163' (decornp.). $he presence of the carbonyl group m the latter acid could not be established in the usual manner but it is shown that the gas evolved when it is melted consists of approximately equal volumes of uarbon monoxide and carbon dioxide.Attempts to oxidise it to 3-methoxy- naphthalene-2-carboxylic acid were unsuccessful the substance being either unchanged or transformed into a-naphthyl methyl ether. During the preparation of the acid a second acid; colour- less rhombohedra1 crystals m. p. 142-143" is also obtained the constitution of which has not been elucidated. The follo- wpbstances are also described l-tin-8- 4 - & h ; y n a r p h yellow needles or almost colourless l~affelx.j xn. p. 85" ; 2-meth1xycinna~l-3-~nethoxynaphthalene yellow needles m. p. 99-100" ; l-metbxycinmmoyZ-4-ethoxyna/phthalene greenish-yellow needles m. p. 110-1 11 " ; 2-o-chlorocinnramoyZ- 3-ooadli-o~yrurphthaZene~ pale yellow needles m.p. 121"; l-o-c&o- c i n ~ m o y 1 - 4 - e t ~ ~ p h t h a l e n e 7 pale yellow needles m. p. 97-98". Substituted Salicylic Acids. 111. The React.ion of 7-DG carboxyl Chlorides with Sodium Salicylate. H. P. KAWP- MANN and H. VOSS (Ber. 1923 56 [B] 2508-2514; cf. A. 1922 i 252 ; 1923 i 795).-The condensation of s-o-phthaloyl chloride with sodium or disodium salicylate with the production of salicylic H. W.i. 176 ABSTRBOTIJ OR CHEMICAL PAPERS. phthalidylidene ether ester (annexed formula) has caused the authors to examine the action with other 7-dicarb- oxyl chlorides. The problem is intimately con- n?>O nected with the transformation of symmetrical into \//\ unsymmetrical acid chlorides and the production of 0 9 unsymmetrically constituted derivatives from the I 70 former.s-Tetrachlorophthaloyl chloride reacts with di- '-\ sodium salicylate in the presence of benzene to give '-' salicylic tetrachlorophthalidylidene ether ester colour- less crystals m. p. 199" which is stable towards cold sodium carbonate solution but is hydrolysed when warmed. as-Tetra- chlorophthaloyl chloride prepared by the action of aluminium chloride on the symmetrical chloride a t 150" (cf. Ott A. 1912 i 828) long lustrous needles m. p. 137" is more stable than as-phthaloyl chloride and is only partly transformed into the symmetrical variety when distilled. s-Az.s-Dihydrophthaloyl chloride a pale yellow liquid b. p. 122O/ 13 mm. gives with sodium salicylate in the presence of ether salicglic Az.6-dihydrophthalidylidene ether ester colourless crystals m.p. 165" ; as-A2:6-dihydrophthuloyZ chloride forms pale yellow crystals m. p. 131". s-A2-Tetrahydrophthaloyl chloride a pale yellow liquid b. p. 129"/ 14 mm. is readily converted into salicylic Az-tetrahydrophthulidyl- idene ether ester a colourless substance m. p. (indefinite) 105" (decomp.). The conversion of the symmetrical into the unsym- metrical chloride could not be effected. Pyridine-2 3-dicarboxyl chloride and sodium salicylate in the presence of boiling benzene give salicylic pyridine - phthalylidylidene ether ester (annexed formula) m. p. /f\is!h 168". \/,\ Succinyl chloride and sodium salicylate yield sali- cylic succinidylidene ether ester which exists in two c,H,.co isomeric forms colourless needles m.p. 176" when rapidly heated and m. p. 192" ; the former compound passes into the latter when it is boiled with glacial acetic acid. The isomerism probably depends on keto-enolic desmotropy. Salicylic maleinidylidene ether ester m. p. 204" ia prepared with the aid of fumaroyl chloride. It dissolves in cold sodium carbonate solution from which it is precipitated unchanged by acetic acid. The unusual solubility is attributed to the wandering of a hydrogen atom although the mobility of hydrogen attached to a doubly bound carbon atom is surprising. [With w. DBHN~~~.]-ap-Dibromomaleinyl chloride reacts with sodium salicylate in the presence of ether to give salicylic ap-di- brmomaleinidylidene ether ester needles m. p. 10" which does not dissolve in cold sodium carbonate solution.N 9 9 IF. W. The Diphenic Acid and the Fluorenone Serieq. I. H. W. UNDERWOOD jun. and E. L. KOCRMANN ( J . Amer. Chem. SOC. 1923,4-5,3071-3077).-Diphenic anhydride and phenol react in theOIKIANIC ClHEMISTRY. i. IT7 presence of fuming stannic chloride and from the product phenoldi- phenein colourless rhombic crystals m. p. 250-251" and an amor- phous powder were isolated. The former dissolved in sodium hydr- oxide to a yellow solution whilst the latter gave a deep red colour. The reaction between resorcinol and the anhydride in the presence of zinc chloride gave resorcinol-diphenein colourless crystals m. p. 178-179" soluble in sodium hydroxide without fluorescence and an amorphous powder which gave strong fluorescence when dis- solved in dilute sodium hydroxide (T.1923,123,225). No definite substance was isolated from the product of reaction between diphenic anhydride and pyrogallol in the presence of stannic chloride. Diphenic anhydride was converted into its isomeride diphenylene- ketone-4-carboxylic acid on heating with stannous chloride or zinc chloride and the reverse change was accomplished by heating the ketone acid with acetic anhydride and glacial acetic acid. The ketone acid reacted with phenol and resorcinol to give amorphous substances identical with those obtained in the reactions described above. Fluorenone reacted with phenol and resorcinol to give similar products. None of these products appear to possess quinoid structure . F. B. Certain Cyclic and Fatty-aromatic Bases from Di-o-nitro- benzyl-acetoacetic and -malonic Esters.S. GABRIEL and REINHOLD WOLTER (Ber. 1923 56 [B] 2445-2448).-Ethyl di-o-nitrobemylacetoacetate is reduced by stannous chloride in the presence of glacial acetic and y6H4*CH2\ CH2ev6H fuming hydrochloric acids to the sub- K--cMe/ ''~0 -N H stance (annexed formula) colourless needles m. p. 184" after softening a t 178",- which is transformedb by boiling 0 hydriodic acid into non-homogeneous 3-o-aminobenzyl-2 -methylquinoline (see below). Ethyl di-o-nitrobenzylmalonate is conveniently transformed into di-o-nitrobenzylacetic acid m. p. 149" by treatment with some- what diluted sulphuric acid a t 180-185". Di-o-nitrobenzylacetyl chloride prepared from the acid and phosphorus pentachloride m. p. 91-92" is converted by ethyl sodiomalonate in the presence of benzene into ethyl di-o-nitrobenzylacetylmte ( NO2*C,H4*CH2),CH*CO*CH( CO,Et) .colourless rhombic leaflets m. p. 80" after softening a t 77" from which di-o-nitrobenzylucetone (NO,*C6H,~CH),CH0COMe prisms m. p. 89-89-5" is prepared by the action of boiling hydrochloric acid. The ketone.is reduced by phosphorus and hydriodic acid to 3-o-aminobenzyl-2-methylquinoi?ine (see above) flat needles or oblong plates m. p. 166-167" which yields a crystalline diibydro- iodide and dikydrochloride. The base is converted by phthalic anhydride into the substance C2,H1,0& m. p. 127-128" and by benzaldehyde into the benzylidene derivative m. p. 17O-171". Di-o-nitrobenzylacetylchloride is converted by benzene and aluminium chloride into di-o-nitrobenzylacethenone (N0,*CBH,*CH2),CH.COPh .I - \/i.178 ABSTRACTS OF CHJEMICAL PAPERS. m. p. 108-108-5" which is transformed by hydriodic acid and phosphorus into 2-phenyl-3-o-aminobenxyZquinoline m. p. 177- 178"; the base yields the cmpound C30H2002N2 m. p. 185" when treated with phthalic anhydride. Di-o-nitrobenxylacetmide colourless leaflets m. p. 162" pre- pared by the action of ammonia on a concentrated solution of the corresponding chloride in benzene could not be transformed into the amine by potassium hypobromite. It is converted how- ever by the action of sodium and bromine in the presence of alcohol into the compound (N0,*C6H,*CH,),CH*NH*C02Me needles m. p. 139" which is hydrolysed and decomposed by sulphuric acid a t 120" into di-o-r,itrobenxylmethylamine (NO C 6H4*CH2) ,CH*NH colourless hexagonal plates m.p. 82-83" (the sulphcite is described). Treatment with red phosphorus and hydriodic acid converts t'he base into di-o-aminobenxylmethylamine a glassy solid which yields a trihydroiodide decornp. above 230' and a trihydrochloride which softens above 260". H. W. The Action of Potassium ferricyanide on Quinizarin in Alkaline Solution. R. SCHOLL P. DAHLL and F. HANSGIRG (Ber. 1923,56 [B] 2548-2555).-The oxidation of 1 4-dihydroxyanthra- quinone by potassium ferricyanide in 0 alkaline solution occurs in a similar manner to that of alizarin (Scholl and Zinke A. 1919 i 25 406) and ' ('*c0*cH'cH*co2H leads to the formation of p-2-hydroxy- 1 4-naphthaquinonyl - 3 - acrylic acid (annexed formula).[With P. HASENCLEVER and F. FLEISCHMANN.]-A solution of 1 4-dihydroxyanthraquinone in aqueous potassium hydroxide is rapidly oxidised by six molecular proportions of potassium ferri- cyanide to @-2-hydroxy-1 4-naphthaquinonoyZ-3-ctcrylic acid yellow needles; the acid decomposes rapidly at about 190" and more slowly a t a lower temperature even in solution. The ammonium Salt the potassium salt C,,H,O,K and the silver salt C$&?,& are described. The silver salt is converted by methyl iodide a t the atmospheric temperature in the absence of light into methyl p-2-h ydrox y- 1 4-mphthuquinon yl-3-acr ylate OHC ,H40,*CO*CH:CH*C0,Me pnbh-yellow crystakine needles m. p. 158O the sodium salt of which if3 described. The acid is converted by saturated methyl- almhdio hpogen chloride into @-2-methoxy-1 4-mphthapinonyl- 3-awgZic d m.p. 165' which is transformed by aqueous sodium acetab info the orange-yellow sodium salt; the silver salt a y d b q amorphous substance is also described. The esterification of the naphtholic hydroxyl p u p by alcoholic hydrogen chloride has been observed meviouslv but it is verv remarkable that the \I' .OH \/ / 0 carboxyl group remths unaffvected ; the poss:bility that t,he product is it lactone,ORGAXXO CHEMISTRY. i. 179 disregarded. The phenolic ester m. p. 158" is isomerised by treat- ment with methyl-alcoholic hydrogen chloride to the methosy- acid m. p. 165". Methyl 8-2-methoxy-1 4-mphthaquinonyl-3- wrylate OMe*C1~02*CO*CH:CH*C02Me,MeOH pale yellow needles m. p.130-131" (decomp.) is prepared by the action of a large excess of boiling methyl iodide on the di-silver salt of the hydroxy-acid; the firmness with which the molecule of methyl alcohol is retained suggests that it is attached to a carbonyl group in the form of a semi-acetal. The hydroxy- and methoxy-acids are only very slowly acted on by bromine dissolved in chloroform whereas the phenolic ester m. p. 158" absorbs two atomic pro- portions of the halogen one of which is subsequently lost in the form of hydrogen bromide. The hydroxy-acid and the phenolic ester give reddish-brown or orange-yellow solutions in hot sodium hydroxide solution which rapidly become dark blue and from which a dark violet acid is precipitated by dilute sulphuric acid; this acid has not been obtained in the homogeneous crystalline form but there can be little doubt that it is a chromanone deriv- ative C,H,< Co*?-o*?HeCo2H.The phenolic ester unlike the CO*C*CO* CH hydroxy- or methoxy-acia is converted rapidly at the atmo- spheric temperature by ammonia into a bluish-black compound to which the constitution C,H,< Co*fi*NH*~H*Co2Me is assigned. CO*C*CO-CH Reduction of di-potassium p-2-hydroxy-1 4-naphthaquinonyl- 3-acrylate by sodium hyposulphite in aqueous solution leads to the production of p-1 2 4-trihydroxy-3-mphthoylacryZic acid yellow needles m. p. 208". Bile Acids. .X. M. SCHENCK (2. physiol. Chem. 1923 131 269-276).-( 1) Deoxycholic acid when heated with alcoholic ammonia in a sealed tube at about 220" yields the amide C,H,,O,N m. p.186" which crystallises from a mixture of alcohol and water in needles containing 3H,O. (2) Biloidanic acid obtained from bilianic acid purified by means of a new method through the dioxime has the formula C,H,,O,,. From Gobilianic acid when oxidised by 32-35% nitric acid there is obtained in small yield a triketo- tricurboxylic acid C,H,,O fine six-sided rectilinear plates which froth and turn brown at 230-235". W. 0. K. H. W. Preparation of Deoxycholic Acid. J. D. RIEDEL AKT.-GES (D.R.-P. 374367 ; from Chem. Zentr. 1923 iv 726).-Dihydroxy- cholenic acid is hydrogenated in the presence of catalysts. Deoxy- chdk acid. ia &hind from the products by way of the crystalline acetic acid-deoxycholic acid compound m. p. 141". G . W. R. Preparation of an Unsaturated Bile Acid.J. D. RIEDEL AKT.-GES. (D.R.-P.. 374366; from Chm. Zentr. 1923 iii 726; ef. A. 1922 i 1160).-1n variation of an earlier patent dihydroxy- cholenic acid m. p. 260" is treated with bromine and alkalinei. 180 ABSTRB(ITS OB CEETUICAL PAPEBS. reagents. For example dihydroxycholenic acid is treated with bromine in methyl-alcoholic solution. From the products after boiling with an alkali hydroxide a substance apparently dihydroxy- choladienic acid is obtained m. p. 245-247". G. W. R. Preparation of Benzaldehyde. THE BARRETT Co. (Brit. Pat. 189091).-The catalytic action of the oxides of various metals on toluene in the vapour phase and in the presence of a gas containing oxygen (e.g. air oxygen ozone) is found to differ considerably. Thus vanadium oxide gives benzoic acid benzaldehyde maleic acid and a measurable amount of the products of complete combustion ; the oxides of molybdenum tantalum tungsten and zirconium give relatively high yielh of benzaldehyde and a relatively low degree of combustion ; the oxides of uranium manganese copper nickel chromium and thorium give relatively high yields of benzaldehyde together with relatively high degrees of combustion ; the oxides of cobalt and cerium give relatively low yields of benz- aldehyde and relatively high degrees of combustion whilst the oxides of titanium bismuth and tin give relatively low yields of benzaldehyde and relatively low degrees of combustion.Greatly increased yields of benzaldehyde accompanied by low degrees of combustion are obtained by using as cstalyst mixtures of the above oxides provided that at least one of these oxides is that of a metal of the fifth or sixth periodic group.Particularly efficient is a mixture of oxides of uranium and molybdenum (approximately in the proportion of from three to thirteen of the former to one of the latter) or of oxides of molybdenum uranium and copper. In preparing these oxides the best results are obtained by starting from a solution of the metals in organic acids. * The temperature of the catalyst should be between about 300" and 700". Organomagnesiurn Derivatives. 111. A. GARC~A BAN~S and L. MEDRANO (Anal. Pis. Quim. 1923,21 436-463 ; cf. Garcia BanGs and Vila A. 1922 i 734).-A study of the reaction between benzaldehyde and magnesium benzyl halides. On adding benz- aldehyde (1 mol.) to magnesium benzyl iodide (1 mol.) in ethereal solution the react ion proceeds normally yielding phenyl-o- t ol y 1 - carbinol whilst when magnesium benzyl bromide is used phenyl- benzylcarbinol crystals m.p. 62-65" is formed. In the inverse reaction where magnesium benzyl bromide is added to benzaldehyde in ethereal solution stilbene phenylbenzylcarbinol and diphenyl- isochroman m. p. 90-95" are formed. Using an excess of benz- aldehyde with magnesium benzyl chloride phenylbenzylcarbinol is formed by reaction in the cold. When the reaction is carried out with boiling in a reflux apparatus the reaction proceeds differently. From the products of the reaction dibenzoylphenylmethane m. p. 144-146" stilbene deoxybenzoin benzylidenedeoxybenzoin m.p. lOl-l02" and isobenzylidenedeoxybenzoin m. p. 86" are obtained but no diphenylisochroman. Magnesium bemy1 iodide gives with an excess of benzaldehyde amongst other products dibenzoyl- phenylmethane and a small quantity of diphenylisochroman. The W. T. K. B.ammo cJHEBm3TRY. i. 181 formation of. diphenylisochroman is held to be conditioned by the CHph' presence of excess of benzaldehyde. When heated with hydrochloric and acetic acids diphenyl- /\/\O isochroman @yes diphenylindene. From this and I ICHPh from the fact that a hydroxyl group was shown to \/\/ be absent the annexed formula is suggested for CH2 diphenylisochroman. From t,he formation of diphenylisochroman from benzaldehyde and magnesium benzyl bromide the presence of a conjugated double bond in the latter compound is indicated. G.W. R. Quinonemethides [Methyleneqyinones] and Pseudophenol- halogenides. 11. H. LIXDEMANN and H. FORTH (Annakn 1923 435 219-232).-An attempt has been made to prepare o-quinonemethides (cf. A. 1923 i 686). 3 5-Dibromosalicyl- aldehyde is converted by thionyl Br chloride into a colourless anhydro- Br/\/'H-O\/\ compound (m. p. 243") (annexed I I I IBr formula). The tri- andmono-acetates \/\O-bH/\/ of the aldehyde have m. p. 99-100" and 71" respectively (Simonis and Wenzel A. 1900 i 496 give 103" and No respectively). 3 5- Dibromo-2-methoxybenzaldehyde with phosphorus pentachloride gives the corresponding benzylidene chloride (needles m. p. 76") from which a quinonemethide cannot be obtained. 3 5-Di- brm-2-hydroxybenxylidene ChEoride from phosphorus pentachloride and the corresponding aldehyde (in presence of benzene) forms needles m.p. 97". It is rapidly reconverted into the aldehyde when treated with warm alcohol or acetic acid a cold solution in these solvents when treated with water becoming Erst orange (possibly owing to formation of quinonechloromethide) and then yellow (aldehyde). In the preparation of the last-named chloride a pZymeridz of 3 5-dibromo-1 2-benzoquinone-l-chloromethide m. p. 220-225" is also formed. 3 5-Dibromosalicylaldehyde with phosphorus pentabromide gives together with some anhydro-compound (m. p. 243' above) the corresponding bromide (needles m. p. 99") the latter (or the corresponding chloride) giving an m t y l derivative (m. p. 113-114") and an a d red needles m.p. 105" and imine. 2-Hydroxy-4 6-dimethylbenzaldehyde on bromination in presence of sodium acetate and acetic acid affords the 3 S-dibromo- derivative yellow needles m. p. 190-191" (the a d red needles has m. p. 180-181"). The dibromo-aldehyde which is unaffected by thionyl chloride is converted by phosphorus penfachloride (in presence of phosphorus oxychloride) into the anhydro-derivative (m. p. above 300") or (in presence of benzene) into the corresponding benzylidene chhide (needles m. p. 114-115") the latter with aqueous alkali giving first a transient orange colour (quinone- methide?) and then the yellow colour of the aldehyde. 3 5-Dibromo-2-hydroxy-4-methoxybenzaldehyde (pale yellow needles m. p. 97-98'; triacetute m. p. 98" monoacetate rn.p. 78") Eri. 182 ABSTBbarS OF UEEMIOAL P-. gives an unil (yellow needles m. p. 105") and an k i n e (m. p. 206") $he corresponding benzylidene chloride having m. p. 99". 3 5-Dibromo-4-hyd~oq-2-methoxybenzuldehyde has m. p. 170- 171" (triacetate a. p. 124"; anil m. p. 185') the corresponding benzylidene bromide having m. p. 111". The latter with aqueous alkali or ammonia gives successively a yellow blue and yellow colour whilst with sodium acetate solution 3 5-dibrm-2-methoxy- 1 4-benzoqzcirwne-l-bromomethide is formed (yellow needles m. p. 78-79'). The latter when treated with water gives the origifial aldehyde. The corresponding benzylidene chloride has m. p. 81" and affords the chloromethide m. p. 98-100". 2-Hydroxy- 1 -naphthaldehyde could not be converted into any derivatives of the type under discussion. E.E. T. Compound of Cinnamaldehyde with Arnylene. NEVERKA ALUJEVICH (Atti A. Accad. Lincei 1923 [v] 32 ii 292-294).- Exposure to the action of light in a glass tube of a mixture of cinnamaldehyde with excess of amylene results in the formation of an oily additive compound C,,H,,O which has the normal molecular weight in freezing benzene or acetic acid but was not found capable of purification. The compound unites with bromine yielding a brown dibromide and gives benzoic acid when oxidised by means of permanganate. Reduction of the compound by means of hydriodic acid yields a small proportion of a product not yet identified and treatment with phosphoric oxide gives a crystalline compound m. p. X25" also unidentified.W. BORSCHE (Ber. 1923,56 [B] 2357-2;359).-1t was shown previously (A. 1912 i 180) that both methyl groups of 4 6-dinitro-m-xylene react with benzaldehyde to give 4 6-dinitro-1 3-distyrylbenzene. It is now found that the 4 6-dinitro-m-xylene does not react with nitrous acid to form the expected dialdoxime but does react with p-nitrosodimethylaniline in alcoholic solution in presence of sodium carbonate t>o give 4 6-dinitroisophthalaldehyde-bis-p-dimethylami~ani1 a black crystalline powder m. p. 208". This is readily hydrolysed by nitric acid in benzene suspension to 4 6-dinitroisophthalaZdehyde CgH&CHO),(N02) pale yellow needles m. p. 132". This gives a dzoxzme bright yellow needles m. p. 184" and a bisphenylhydraxone black needles m.p. 251". From benzene solution in sunlight the aldehyde is gradually precipitated in the form of yellow needles m. p. 185;-186" apparently of 4 6-dinitrosoisophthalic m i d . 4 6-Dinit;ro-m-xylene also reacts with mercuric chloride in presence of sodium efhoxide to form 4 6-dinitroisophthalybidenetetramercuri- dioxide C8H406N,Hg4 a heavy yellow powder. Electrolytic Oxidation of isoEugenol. A. LOWRY and C. M. MOORE (Trans. Amer. Electrochem. Xoc. 1922 42 273-284).-The authors have investigated a process for the production of vanillin by the electrolytic oxidation of isoeugenol described in the German patent (D.R.-P. 92007). Experiments carried out with sodium T. H. P. 4 6-Dinitroisophthalaldehyde. CGH2 ( CH:N'C,H4'~e2)2(Nq,) E. H. R.OWANIO CHEBfISTRY. i. 183 hydroxide or sulphuric acid as electrolyte gave in every case negative results. Vanillin itself is found to be readily oxidised electro- lytically and even if formed by the electrolytic oxidation it would be immediately converted into other products.Hence it is concluded that if vanillin is produced by t4he electrolytic oxidation a totally different condition must prevail from that described in the patent. J. F. S. Acetyl Derivative of Deoxybenzoin (Tautomeric Form). C. V. GHEORGIU (Ann. Scient. Univ. Jassy 1923 11 307-308; from Chem. Zentr. 1923 iii 1159).-By treatment of deoxybenzoin with acetic acid and zinc chloride a crystalline precipitate m. p. 102-106" held to be the ncetyl derivative in the enol form is obtained. On hydrolysis however it does not give the corres- ponding alcohol but deoxybenzoin.Electrolytic Reduction of Oximes. I. Benzoinoxime. NASAYOSHI ISMBASHI (Mern. Coll. Xci. Kyoto 1923 7 39-44).- Benzoinoxime is only partly reduced electrolyticalIy in acid solution. A part is hydrolysed before electrolytic reduction occurs and the benzoin resulting from the hydrolysis is reduced to form hydro- benzoin benzoinpinacone and deoxybenzoinpinacone. Optimal conditioiis for the preparation of the amine require that the electrolysis be conducted a t 19" to 20" with a current density of about 0-3 amp. per sq. cm. and that a cathode of tin or lead be employed. The concentration of sulphuric acid in the catholyte should not exceed 5%. In alkaline or neutral solution na appreciable electrolytic reduction or hydrolysis of benzoinoxime is observed.3'. ANGELICO and F RIONFORTE (Gaxsetta 1923 53 800-807; cf. A. 1909 i 318; 1910 i 402 576).-The failure of the action of sodium hypobromite on picrotin ketone to yield bromoform and that of the action of iodine and potassium hydroxide to give iodoform render doubtful Horrmann and Bischof's suggestion that the molecule of this ketone contains the grouping -CH,*CO*CH (A. 1922 i 161). Fusion with potassium hydroxide of picrotinic acid for which formula (I) or (11) may be assumed yields besides products of profound decomposition a CHPh:CPh*OAc G. W. R. J. S. G. T. Picrotin Ketone and Picrotinic Acid. hie CH,*CH,*CH,*CO,H /\CH,*CH,-CH,*CO,H o<CO-/)Me o < q ) (I*) CMe2.?/ (11.) dicarboxylic acid C12H,,0 m. p. 132" of constitution (111) or (IV).On the other hand gradual oxidation of picrotinic acid yields a (111.) /-'CH2*CH2*CH2*C0,H /-\CH2*CH,*CH,*C0,H UV.) series of acids of the formulze C,,H,,O C,,Hl,O and C,,H,,O all HO,C Me C0,H \-/ \-/ Mei. 184 ABS!L'RACTS OW cBtE116ICAX PAPERS. of which give acetone when fused with potassium hydroxide aiid hence confain the phthalide grouping intact (A. 1910 i 404). From ifs formula the acid C,,H,,06 known as picrotinphthaldi- carboxylic acid evidently contains a carboxyl group in place of the methyl group of picrotiiiic acid so that its possible constitutions follow from formulae (I) and (11). Since when fused with potassium hydroxide picrotinic acid loses only acetone and gives a ciibasic acid picrotinphthaldicarboxylic acid should under similar conditions yield a tribasic acid.A crystalline acid m. p. about 153" is indeed obtained in this way but in quantity insufficient for analvsis since. however. it condenses with resorcinol in mesence of s;lph&ic acid to yieid a fluorescent compound it is ;robable HO,C C0,H that its formula is 7-\~H2*CH,*CH2*C02H and that picro- tinic acid is represented by formula (I). Horrmann (A. 1916 i 828) suggests that picrotin ketone and picrotinic acid may be derived from a @-ketonic acid CH,R*CO*CH,*C02H which cannot be isolated possibly owing to the readiness with which it loses carbon dioxide. Neither picrotin nor picrotoxinin has however yet yielded an oxime and the authors find that the action of amyl nitrite on picrotin in preseiice of sodium ethoxide gives principally two nitrogen-free acids. Oximimpicrotin ketone Cl,R,50,N m.p. 215" (decomp.) is readily convertible into the dzoxzme C,4H1404N2 which crystallises in minute needles m. p. 232" (decomp.). The acid C1,H1,05 or c&606 obtained by treating picrotin with amyl nitrite and sodium ethoxide forms minute crystals m. p. 330° and sublimes a t the melting point giving vapours which irritate the mucus. When heated with fused potassium hydroxide it yields acetone and with siilphuric acid and resorcinol it forms a fluorescein. It is accompanied by another acid which cont.aias C 54.29% and H 7.587/ and forms silky white needles m. p. 95". \-/ m n l 3 1. u. L. Anomalous Splitting of Ketimides. F. KROLLPFEIFFER (Ber. 1923 56 [B] 23&2365).-The ketimides obtained by con- densing anthranol methyl ether with nitriles are not as was to be expected hydrolysed by dilute acids to the corresponding ketones but are decomposed into anthrone.Thus 10-methoxy-9-anthryl- methyl-ketimide decomposes with formation of methyl alcohol acetic acid and anthrone. The ketone lO-methoxy-9-a~thryl methyl ketone is only obtained in small yield by boiling an aqueous solution of the hydrochloride of the ketimide; the ketone itself is readily hydrolysed to anthrone. The phenyl derivative 10-methoxy- 9-anthryl-phenyl-ketimide is much more stable than the methyl compound; it is only hydrolysed by boiling concentrated hydro- chloric acid giving anthrone and benzoic acid. The N-methyl derivative of this ketimide is likewise hydrolysed by boiling concen- trated hydrochloric acid forming ant hrone methylamine andORGANIC (3HEMISTRY.i. 185 benzoic acid. The readiness with which the acyl residue is removed in the zanthryl ketones appears to be influenced by the p-methoxy group for p-anthryl phenyl ketone is not hydrolysed by hot hydro- chloric acid in acetic mid solution althoagh with warm concentrated sulphuric acid it gives anthribcenesulphonic acid and benzoic acid. . I IO-Hethoxy-9-anth yLmethyl-kdirnide (annexed formula) is obtained by mixing anthranol methyl ether and acetonitrile with aluminium chloride and passing a current of dry hydrochloric acid through the cooled mixture; it forms a pale yellow crystalline powder m- p. 145-146". 10- Methox y -9 -ant hry Z methyl ketone forms \./\/\/' I pale yeIlow glistening square leaflets m.p. 18% ('J&:NH 183". l0-MetZboxy-g-anthryZ-~hen yl-ketimide forms stout yellowish-green crystals m. p. 147-148O ; its hydrocldoride forms an orange crystalline precipitate. 10-bfehq-9- anthryl-~henyZ-N-methyl-ketimide is obtained by methylating the ketimide with methyl sulphate; it forms gale yellow needles m. p. 127". E. H. R. 2 3-Diaminoanthraquino. SOCIETY FOR CHEMICAL INDUSTRY IN BASLE (Swiss Pat. 98312; from Chem. Zentr. 1923 iv 829).-3-Bromo-2-aminoanthraquinone is treated with aqueous or ethyl-alcoholic ammonia in the presence or absence of catlalysts at 170-190" under pressure. 2 3-Diaminmnthrquinone thus obtained is crystalline. OMe G. W. R. Derivatives of p-Methylanthraquinone. 111. The Synthesis of Prungula Emodin.R. EDER and C. WIDMER (Helv. Chim. A& 1923 6 966-981).-1t is known that emodin is a trihydroxy- P-methylanthraquinone and it is highly probable that two of the hydroxyl groups are in the 1 8-positions and the methyl group in the 3-position as in chrysophanic acid. It is also probable that the third hydroxyl is in a P-position and not adjacent to an or-hydroxyl group. These probabilities have now been confirmed by synthesis and the constitution of emodin esfablished as 1 6 8-trihydroxy- 3-methylanthraquinone. The synthesis was accomplished in a manner similar to that of chrysophanic acid (A. 1923 i SSS) starting from 3 5-dinitrophthalic acid and m-cresol. 3 5-Dinitro- p7ithalic anhydride is formed by boiling the acid with acetic anhydride ; it crystallises in white stout hygroscopic needles m.p. 163-164". It condenses with m-cresol in presence of aluminium chloride to give 3 5-dinitro-o-3'-hydroxy-p-toluoylhenzoic acid greenish-yellow leaflets m p. 2364237". This compound is very sensitive to alkalis forming a compound C,H,O,N white needles m. p. 251-252O (decomp.). It corresponds in composition with a nitrohydroxytoluoylbenzoic acid but could not be identifietl as such a compound. It can be reduced to an amino-compound yellow needles m. p. 305-306" (decomp.). 3 5-Dinitro-o- 3'-hydroxy-p-toluoylbenzoic acid is reduced by ferrous sulphate and ammonia to 3 5-diamino-o-3'-hydroxy-p-toZuoylbenz~c mid palei. 186 ABSTRACTS 03' CHEMICAL PAPERS. yellow needles m. p. 233-234". When heated in concentrated sulphuric acid at 160-170" this is converted into 6 8-diamino- ~ - h y d ~ o ~ - 3 - m e ~ ~ ~ n t h r a q u i n e stout red needles m.p. 306-307". This compound is soluble in alkalis separating as a salt on cooling; in concentrated sulphuric acid it dissolves with a yellow colour. It can be tetrazotised in concentrated sulphuric acid solution and when the solution is heated on the water-bath it decomposes forming 1 6 8-trihydroxy-3-methylanthr~u~none orange needles m. p. 256" identical with emodin. It was not possible to condense 3 5-dinit4ro-o-3'-hydroxy-p-toluoylbenzoic acid to an anthra- quinone derivative. E. H. R.. 1 8-Dihydroxy-3-methylanthraquinone. R. EDER (Swiss Pats. 95614 and 95947; from Chem. Zentr. 1923 iv 664).- 1 8-Dihydroxy-3-methylanthraquinone may be prepared from a-nitrophthalic acid (Eder and Widmer A.1922 i 260) and also by condensation of or-aminoacetylphthalic acid with m-cresol in the presence of aluminium chloride t o 3-amino-o-2'-hydroxy-p-toluoyl- benzoic acid from which 1 8-dihydroxy-3-methylanthraquinone is obtained by way of the diazo-compound or by heating k t h strong sulphuric acid a t 1 50 O where by 8 -amino - 1 - hydroxy- 3 -met h y Z - unthruyuime reddish-brown needles m. p. 237-238" is obt,ained. The latter by diazotisation and boiling yields the 1 8-dihydroxy- compound. G. W. R. Intramolecular Displacements of Atoms. I. Addition of Alcohols to Camphene. H. MEERWEIN and L. G~RARD ( A nnnlen. i923 435 174-189).-Semmler (A. 1901 i 90) by treating camphene with alcohols in presence of sulphuric acid obtained as he supposed isobornyl ethers which are similarly obtainable from isoborneol.A precise proof of the constitution of the ethers is now given for the f$mt time. isoBornyl methyl ether is formed by the interaction of camphene methyl alcohol and sulphuric acid or by that of methyl iodide and sodium bornyloxide and is quite distinct from the methyl ether of camphene hydrate obtained from the potassium derivative of camphene hydrate and methyl iodide. The results recorded previously (A. 1920 i 855) in connexion with the action of alcohols on camphene hydrochloride have an interesting sequel If a solution of camphene hydrochloride in an alcohol is kept at 20" the concentration of free hydrogen chloride (cf. A. 1922 ii 751) initially high slowly falls to a minimum (after several days) and then slowly rises to 100% of that present originally. These phenomena are due fo the following processes (1) Reversible interaction of camphene hydrochloride (I) and alcohol fo give hydrogen chloride and an ether (11).This inter- conversion is entirely analogous to that of triphenylchloromethane and triphenylcarbinyl ethers (a little of I1 decomposes into camphene and alcohol). (2) Isomerisation of unchanged camphene hydro- chloride into isobornyl chloride (111). As a result of this the .change I1 +I is promoted until no more ether remains.ORUAXIC UEFAMISTRY. i. 187 (3) Interaction of isobornyl chloride with alcohol to give isobornyl ethers (IV) ' CH,-CH-CMe CH,-CH-CMe I IR'OH --+ 1 CH,/ (1.) I (11.1 HC1+ I CH,/ CH 1 CMe*OR CH 1 CMeCl \CH/' \CH/ W.) (111.) .CH-OR CHCI This scheme was suggested by the results of a determination (against time) of the relative proportions of free hydrogen chloride isobornyl chloride a,nd camphene hydrochloride in such a system starting with camphene hydrochloride and an alcohol. With methyl alcohol a maximum content of isobornyl chloride is present a t the time corresponding with the above minimum concentration of hydrogen chloride. Proof of the explanation given is afforded in the following If an ethereal solution of camphene hydrochloride is slowly added to a methyl-alcoholic suspension of anhydrous potassium carbonate so that the solution never becomes acidic camphene hydrate methyl ether is obtained (in 50% yield) identical with the product from the action of methyl iodide on the potassium derivative of camphene hydrate (this preparation being effected in xylene suspension unchanged camphene being finally removed by means of ozone).Camphene hydrate methyl ether has m. p. 12-14' b. p. 201.5" or 88.5-89"/17 mm. df' 0.947749481 and n 1.47153 (mean constants of the two samples obtained). Active camphene [a] +50.75" when converted through the hydrochloride into the ether gives the latter with [cx~~-12*7lo. When shaken with a solution containing potassium ferrocyanide and hydro- chloric acid the methyl ether aff or& an additive compound 3C ,OMe,H,Fe (CN) 6. Whdst camphene hydrate ethyl ether could not be obtained from camphene hydrate it is readily obtained (although in small yield because of its sensitivity to acids) from camphene hydrochloride potassium carbonate and ethyl alcohol and forms a colourlem oil (b.p. 93"/17 mm. $2' 0.9350) decomposing a t 200" into camphene and alcohol. If camphene hydrochloride is allowed to remain in methyl- alcoholic solution for about fourteen days at 30" or until the con- centration of free hydrogen chloride no longer increases isobornyl methyl ether results; if the above active camphene is used the resulting ether has [a]' -23.4". Semmler's method using active camphene gives the ether with [a]$ -14.82' a rotation decreasedi . 188 ABSTRACTS OR' CEEMICAZ PAPERS. by prolonging the action of the methyl-alcoholic sulphuric acid. (This preparation depends on the initial formation of camphene hydrate sulphuric ester which changes into the isobornyl ester this with alcohol giving the ether.The rate of conversion of camphene hydrate esters into isobornyl ethers is greater with sulphuric and aromatic sulphonic esters than with halogen esters.) Similarly the ether mas obtained from sodium bornoxide and methyl iodide the mean physical constants of the various products being b. p. 191-191.5" 78"/17 mm. or 80°/19 mm. &io 0.9250- 0.9277 n$ 1.46252-1-46282. The unstable additive compounds described by Bertram and Walbaum (A. 1894 i 204) could not be obtained. It was found that isobornyl methyl ether was readily converted by hydrogen bromide into isobornyl bromide hydrogen chloride acting similarly but more slowly. When treated with hydrochloric acid and potassium ferrocyanide the ether gives an additive compound 3C,J3,,0Me,H4Fe(CN) 6 decomposing a t 170" whilst on heating with anhydrous zinc chloride it gives camphene and methyl alcohol stannic chloride effecting the same change more slowly whilst other metallic chlorides are without action.isoBornyl methyl ether is also formed by warming camphene hydrate methyl ether with methyl-alcoholic hydrogen chloride or by treating isobornyl chloride with methyl alcohol. Camphene hydrate methyl ether is rapidly decomposed whereas isobornyl methyl ether is unaffected by glacial acetic acid a t 80". The camphene produced (through the first-formed camphene hydrate acetate) is readily estimated by titration with perbenzoic acid so that mixtures of the two ethers may readily be analysed.Camphene hydrate ethyl ether affords camphene even when shaken 'for a few hours with 1% sulphuric acid the methyl ether being practically unaffected by the latter. The methyl ether is rapidly converted by traces of zinc stannic aluminium ferric and mercuric chlorides or antimony pentachloride into camphene and methyl alcohol (cf. isobornyl methyl ether) whilst hydrogen chloride and bromide decompose both hydrate ethers to give camphene hydrochloride (hydrobromide) this passing rapidly into isobornyl chloride (bromide). E. E. T. Camphor dichloride. [2 2-Dichlorocamphane]. H. MEERWEIN and R. WORTNANN (AnnaZen 1923 435 190-206).-The conversion CMe,-CHNe*OAcyl CMe,( OAcyl)*CHMe may be regarded as a result of ionisation followed by intra-ionic rearrangement (CMe,*CHMe)O*Acyl (CMe,*CHMe,)O-Acyl free radicals not being involved.The ordinary pinacone-pinacolin change may similarly be written (CMe,*CMe,*OAcyl) O*Acyl-+ ( CMe3*CMe*OAcyl)0*Acyl the reverse change not occurring owing to the instability of pin- acolin esters other than those with halogen acids. Pinacolin dichloride [n-dichloro- P P-dimethylbutane] and pinacone dichloride [Intramolecular Displacements of Atoms. J ,II. f - + - + - + -ORQANIO OHEndIgTaY. i. 189 [&diohloro- &dimethylbutane] cannot be interoonverted but if the vapours af the first substance be passed over barium chloride heated a t 400-.450" a little py-dimethylbuhdiene results probably owing to the intermediate formation of pinacone dichloride. Greater powers of isomerisation would be expected from 2 2 4 - chlorocarnphane which possesses a similar structure to pinacolin dichloride.The substance described as dichlorocamphane by previous authors (e.g. Bredt A. 1901 i 217; Marsh and Gardner T. 1897 71 290; Marsh and Hartridge T. 1898 73 852) is now shown to be a mixture of substances. If however a mixture of camphor (200 g.)? hosphorus trichloride (170 g.)? and pure phos- phorus pentachloriz (294 g.) is left a t 0" for a month pure a-cam#wr dichlom.de (2 2-dichZorocccmpkne) (I) is obtained m. p. 146-148" (decomp.). Occasional preparations fail and it is always necessary to test the product by studying its interaction with sodium ethoxide (boiling alcoholic solution) or with methyl alcohol (at 60") which proceeds in a characterbtic manner. When heated with a mixture of phenol and potassium acetate 2 2-dichlorocamphane affords a-chlormmphene (111) (colourless setting point about 20" b.p. 193-197") this on reduction with sodium and alcohol affording camphene (setting point 44.5" b. p. 156.5-158") and on ozonolysis giving a-chlorocamphenilone. The latter compound (in which CO replaces the hemi-cyclic CH group in 111) has setting point 14.5" b. p. 116-118"/18 mm. gives a semicarbaxone m. p. 206-207" (mixed with a little p-chlorocamphen- done semicarbazone 1 ) and an oxime m. p. 210-211". Phacolin dichloride with phenol and potassium acetate gives P-chloro-ry-dimethyZ-Aa-butene no intramolecular change occurring. The conversion of 2 2-dichlorocamphene into a-chlorocamphene occurs according to the scheme 3 CrCH (111.) the intermediate a-chloroeamphene hydrochloride (11) being obtain- able by combining a-chlorocamphene and hydrogen chloride.Thk hydrochloride is leess easily decomposed than camphene hydro- chloride but is completely decomposed by methyl alcohol at 50" in half an hour. This shows that the dichlorocamphane of previous authors contained at most traces of a-chlorocamphene hydro- chloride. The bomerism between pinacolin dichloride and pinacone dichloride is now seen to be similar to that between dichloro- oamphane and a-chlorocamphene hydrochloride CMe,*CMeC1 + CMe,Cl*CMe,Cl so that the present work affords a first confirmation of the authors' views with regard to the pinacoh change (above). Moreover 2 2-dichlorocamphane may undergo the retrogradechange.If in ifs preparation the temperature is^ allowed to rise or if impure phosphorus pentachloride is used an isomeride p-cumpk dichloride (colourless crystals m. p. 178-179*) is the main product. This substance is easily distinguished from its a-isomeride by its much smaller rate of reaction with 0.2N sodium ethoxide (or methyl alcohol) and is best prepared by treating a-camphor dichloride in toluene solution with stannic chloride until the product no longer reacts rapidly with sodium ethoxide (or methyl alcohol). On reduction p-camphor dichloride affords camphane and on warming with phenol and potassium acetate gives a mixture of 8-chtopocamphene (V) and chlorotricyclene (VI) as waa proved by the fact that this mixture on reduction with sodium and alcohol afforded tricyclene and camphene.The latter but not tricyclene is oxidised by ozone and the mixture can thus be identified. Again the mixture of p-chlorocamphene and chlorotricyclene on treating with ozone gave a mixture of chlorotricyclene (m. p. 13&135" b. p. 194-196") and p-chlorommphenilone needles m. p. 162-163" (semicarbazone m. p. 244-245'). p-Camphor dichloride is there- fore trans-2 6-dichlorocamphane (IV) the above reactions being expressed H. .. C l 2 CH2-yH-CH2 'v') CH-~!!!?~~(J I t CCH CMe-Cl \ p-CUormmphene hydrochloride (VI) may be obtained from p-chlorocamphene and hydrogen chloride. The conversion of a- into p-camphor dichloride is effected under conditions causing the change of camphene hydrochloride into ieobornyl chloride. The conversion is rapid in phenol solution but very slow in most solvents unless stannic chloride or antimony pentaohloride is resent.The dielectric constant of the solvent is of far gre&x d e n c e than the nature of the catalyst the change being very S~OW in light petroleum more rapid in benzene and still more rapid in the ionising solvents chlorobenzene and nitrobenzene. The case is evidently one of the intra-ionic isomerisation of esters no tricyclene compounds being necessarily involved. Into the same clasr~ of change may be put the relationships (hitherto unex- plained) between fenchyl alcohol a-fenchene hydrate isofenchyl alcohol and p-fenchene hydrate (these relationships being shown schematically in the paper). E. E. T.ORGIANIO CHEMlSTRY. i. 191 [Intramolecular Displacements of Atoms.] 111. Racemis- ation Phenomena in the Camphor Series. H. MEERWEIN and F. MONTBORT (Annden 1923 435 207-218).-0ptically active isobornyl esters undergo racemisation under conditions specially favouring the rapid conversion of camphene hydrate esters into isobornyl esters (A. 1922 ii 751). isoBorny1 chloride undergoes complete racemisation in three hours'in cresol solution a t 20". In most solvents racemisation is too slow to follow and the use of catalysts is to be avoided owing to their tendency to form additive compounds with the solvent with resulting decay of activity. To overcome this difficulty the velocity of racemisation has been measured in cresol and in mixtures of this solvent with nitromethane nitrobenzene bromobenzene chlorobenzene ethyl bromide benzene light petroleum benzonitrile anisole aceto- nitrile and ether.It is found that except in the cases of aceto- nitrile benzonitrile and anisole which form additive compounds with cresol the order of solvents from the point of view of decreas- ing racemisation velocities is the same as that of the velocity of conversion of camphene hydrochloride into isobornyl chloride (loc. cit.) which in turn is (approximately) the order of decreasing dielectric constants. In the three cases where additive compounds are formed the velocity constant tends to decrease. If however the solvent-mixture is left for some time before use a good constant is obtained somewhat smaller than that otherwise observed. The parallelism between the two above types of change suggests that the racemisation change like that of camphene hydrochloride into isobornyl chloride is due fo ionisation ; two alternative schemes are suggested for the actual mechanism of the former change (1) By analogy to the behaviour of a-camphor dichloride (this vol. i 188) the chlorine atom in &-isobornyl chloride (I) may be assumed to wander from position 2 to position 6 when I-isobornyl chloride (11) results (2) The second suggested scheme is self-explanatoq (I to V being respectively d-isobornyl chloride the isoborn Lion (plane formula) I-isobornyl chloride and d- and I-bornyl ohyorides) :i.192 ABSTRAOTg (up C?HEl¶IW PAPER% This wonld account for the observed formation af b0rny-l chloride during the Facemidion of iaobornyl chloride (loc.eat.). E. E. T. The Rotation-dispersion of some Homologo~s Methylene- camphor Derivatives. H. RUPE and C. COURVOISIER (Hdv. China. A& 1923 6 1049-1071).-The method described by Rupe and Burckhardt for the synthesis of p-camphorylidenepro- pionic acid from chloromethylenecamphor and ethyl sodioaceto- acetate (A. 1917 i 141) is a general one and has now been used for the synthesis of a number of homologous acids from chloro- methylenecamphor and ethyl alkylacetoacetates. Since the acids readily lose carbon dioxide when heated giving alkylmethylene- camphors a general method is provided for the synthesis of these compounds. It was found that the optical rotations of these alkylidenecamphors changed when the substances were repeatedly distilled. This phenomenon is to be attributed to cis-tram-iso- merism and in the case of ethylmethylenecamphor it is probable tlpt at least one isomeride was obtained in the pure form.This isomeric change during distillation accounts for the difTerent values €or the optical rotation of methylmethylenecamphor recorded by Gff erent observers. The rotations of the compounds described were measured for four Werent wave-lengths and all showed normal rotation-dispersion. ~ 8 ~ 1 4 < X $ ~ ~ c H ~ e - c o 2 ~ t ~ obtained from c~loromethylenecamphor and ethyl methylaceto- acetahe by the action of sodium ethoxide distils a t 164-167"/ 12 mm. It is hydrolysed by boiling in a mixture of glacial acetic acid and fuming hydrochloric acid. The free P-mmphorylidene- a-methylpropionic acid is purified through its calcium salt and by distillation.It forms an oil which crystallises slowly in bunches of needles m. p. 109-110". It decomposes at 160' giving a quantitative yield of ethylmethylenemmphor (n-propylidenemm&oam23hor) b. p. 113-llS" [a] +l4943lo d 0.9497 (prepared from non-crystal- line acid) or [a]; +73.26' dzo 0.9533 (from the crystalline acid). The latter product partly crystalliqed in white needles m. p. 41- 43' giving in benzene [a] +22.67" [a]F/[ct]c 2-16'. The crystalline product is probably a pure isomeride but whether cis or tram it is impossible to say. Ethyl P-cam~horyl~dene-a-ethyZ~rop~o~te from ethyl ethylacetoacetate and chloromethylenecamphor is a pale yellow bitter liquid b. p. 169'112 mm. The free acid forms silky white needles rn.p. 118" ; the calcium salt forms bunches of short white needles. The free acid begins to decompose at 125" giving a quantitative yield of n-butpZidenemmphor b. p. 130-131'/12 mm. [a] +94-58" di0 0.9389 [alp/[ aIc 2.36. Ethyl p-camphurylidene- a-propyEpropionate from ethyl n-propylacetoacetate and chloro- methylene camphor has h. p. 176-179'/9-5 mm.; the free acid has m. p. 95-96'. n-Valerylidenecamphor has b. p. 139-141'J 12 mm. [a]; +ll648" di0 0.9333 [alF![aIc 2.36. The condensation of ethyl sodioisopropylacetoacetate with chloromethylenecamphor Et&yl Q-ca~phorylidene-a-ntethylpropionate,ommc CHEMISTBY. i. 193 was unsatisfactory but ethyl sodiobutylacetoacetab condensed normally forming ethyl P-camphorylidene-#-n-butyl~opionc~ yellow oil b. p. 191-193"/11 mm.; the free acid can be crystallised with difficulty in white needles m. p. 76". The acid decomposes at 170" giving n-hexylidenecump7wr b. p. 147-149"/13 mm. [ a x + 141*13" $? 0.9252 [aIP/[alo 2-37. Ethyl p-cctmphorylidene- a-isobutylprqionate is a viscous pale yellow oil b. p. 183-185"/ 10 mm. ; the free acid forms white needles m. p. 97-98'; it has [a]; + 108.74" in benzene. CsH14'~~H*[CH212*CHMe ' is a viscous oil b. p. 144-146"/12 mm. [a] +133-84" dp 0.9202 [ a]p/[a]0 2.35. p-Camphorylidene-a-allylpro23ionic acid (annexed formula) has m. p. 95"; its ethyl ester is a mobile oil b. p. 183- 185"/11 mm. The acid loses carbon dioxide normally when heated giving CsH14<&CH*~€€*C02H a-camphorylidene-Aa-pentene a pale CH,.CH:CH~ yellow mobile oil having an odour of camphor and garlic b.p. 136-137°f 11 mm. [a]' +144.23" i-ZF 0-9475 [aIp/[alC 2-37. p-Camphorylidene- a-benzylpropionic mid forms white silky crystals m. p. 127"; the ethyl ester is a pale yellow viscous oil b. p. 226-228"/12 mm.; the sodium salt is very sparingly soluble. Distillation of the acid gives phenylpropylidenemmpamphor a pale yellow viscous oil b. p. 204-206" [ a ] g +126.92" &J" 1.0104 [alP/[aJc 2-36 Camphorylidene- methylsuccinic acid c,H,,< co I (?H2*Co2H crystttllises in bunches of small white needles m. p. 158" ; the ethyl ester is a yellow viscous oil b. p. 214-222'112 mm. Distillation of the dicarboxylic acid a t 190-215"/12 mm. gives y-camphorylidenebutyric acid a viscow yellow oil b. p. 210-213"/10 mm. [a] +32.31" in benzene d? 0.9078. In the course of the work a number of by-products were obtained.In several cases the cis-form of dicamphoethandiene (A. 1919 i 335) was isolated from the reaction product. Another qlw of by-product resulkd from the fact that the p-camphorylidepepro- pionic acid and its derivatives form sodium derivatives which can react with a second molecule of chloromethylenecamphor forming dicamphorylidene derivatives. The following compoundb of t b type were identified. Ethyl di (mmphorylidenemeth yl) -pl'opioncce (C,Hl~<~~H)2:CMeoC02Et m. p. '118" ; ethyl di(mmphqZ&ne- methyl)-n-butyrate m. p. 161" ; ethyl di(carnphory1idenemethyZ)- n-valerate m. p. 175" ; ethyl di(campamphorylidenemethyl)allylcccetate m. p. 148" and ethyl di(camphurylidenemthyl)succinute m.p. 105'. Action of Ferric Chloride on Hydroxymethylenecamphm. If. RUPE and M. SCH~~RER (Helv. Cliim. Acta 1923,6,1072-l076).- When hydroxymethylenecamphor is boiled for some hours in alooholic solution with ferric chloride z-chlorocamphor is formed ; isoAmylmethylenecarnphor co C:CH*CH*CO,H E. H. R. VOL. CXXVI. i. 73i. 194 ABS!FBA65 OB UEEMIaAL PAPEES. in the same manner ferric bromide gives a-bromocamphor. To explain the reaction it may be assumed that hydrochloric acid combines with the hydroxymethylenecamphor forming hydroxy- methylchlorocamphor which reacts with water forming chloro- cttmphar and formic acid. Prolonged action of ferric chloride on hydroxymethylenecamphor results in the formation of camphoric anhydride probably with camphorquinone as an intermediate stage.E. H. R. Preparation of Menthyl Diethylaminoethylcarbarnate. from Chem. Zentr. 1923 iv 829).-Menthyl halogen formates are treated with at least the molecular quantity of diethylethylene- diamine NH,*CH,-CH,*NEt,. Menthyl diethylaminoethylcurbamte thus prepaxed from an ethereal solution of menthyl chloroformate and an aqueous solution of diethylethylenediamie with agitation and cooling is an oil having b. p. 142"/0.015 mm. The Action of Phenylhydrazine on Pinene Nitrosochloride. R. E. KREBEERS ( J . Amer. Pharm. ASSOC. 1922 11 604-606).- Phenylhydrazine and pinene nitrosochloride when allowed to react ih 95 yo ethyl alcohol yielded phenylhydrazine hydrochloride an unidentified substance yellow crystals m. p. 147-148" and a substance C,,H,lN faintly yellow hard prisms m.p. 148-150". Stick-hc. A. TSCHIRCH and F. LUDY jun. (Hdv. Chim. Acta 1923 6 994-1008; cf. Tschirch and Farner A 1899 i 446).- A systematic investigation has been made of Indian stick-lac the resin formed by a species of louse Tachardia h c a parasitic on certain trees in the East. The aqueous extract contains one of the dyes! present in the stick-lac; this is precipitated by lead acetate as d violet lake. The filtrate contains dextrose and laevulose besides albumin ; the ash from the evaporated filtrate contains nitrogen sulphur potassium and calcium. The lac appears to contain invert-sugar probably formed enzymatically by the insect from the sucrose of the tree. The red dye laccaic acid is obtained from the lead acetate precipitate by extraction with alcohol con- tkining hydrochloric acid; it crystallises in stout red prisms.Dimroth and Goldschmidt (A. 1913 i 981) failed to prove that the dye is an anthraquinone derivative; this has now been done by distillation with zinc dust. In dilute alcohol laccaic acid shows absorption bands at X 0-545-0*520 p and 0-510-0*488 p. Since the dye-is formed in the Tachardia by a yeast-like organism it is interwting to find that its absorption bands are very similar to thme ehown by the colouring matters from red yeasts and bacteria. In concentrated sulphuric acid laccaic acid dissolves with a carmine- red colour showing the bands A 04XkO.560 p 0*540-0.520 p and 8*MM-o-490 p and in sodium hydroxide solution its colour is reddish4olet ~ t h the three bands A 0-6104.575 p 0.555-0-533 p and 0*510-0*490 t. The dye is a good indicator the change from yellow (acid) to violet (alkali) being sharp.Alkaline solutions of the dye are unstable. Dyeings on silk and wool from an acid bath SOCIETY FOR CHEMICAL INDUSTRY IN BASLE (swiss Pat. 99625; G. W. R. CHEMICAL ABSTRACTS.ORQANIO CHEMISTRY. i. 195 are very fast to light. The constitution of the dye is as yet unknown. Although it is probably a glucoside no sugar could be obtained from it by hydrolysis. Extraction of the residue from the aqueous extraction of the stick-lac with cold alcohol removes the resin the perfume and a second dye erythrolaccin. The alcoholic extract is poured into dilute hydrochloric acid and the precipitate filtered off dried and extracted with ether.The ethereal extract is evaporated and from the residual resinous oil the erythrolaccin crystallises in yellow leaflets. The crystals can be freed from resin by means of chloroform. The dye can be sublimed forming red felted crystals. Its yellow solution in an ether-alcohol mixture has a band at X 0.510-0.485 p ; with sodium hydroxide there are two bands at X0-6154.59Op and 0-572-0-548p. The bluish- violet solution in concent,rated sulphuric acid shows four bands at X 0.680-4.640 p 0.6104.590 p 0.560-0.540 p and 0625- 0.300 p. It forms a tetra-acetyl derivative green oblique tablets and is probably a tetrahydroxymthylunthraquinme. From an alkaline solution of the resins after separation of the erythrolacoin ether extracts the perfume which crystallises in tablets having the characteristic shellac odour.The portion of the resins soluble in ether contains besides aleuritic acid shown by Harries and Nagel to #be a trihydroxypalmitic acid (A. 1922 i 522) a monohydroxy- palmitic acid m. p. 76.5-77" and probably other fatty acids. These are probably present as lactides. The resin insoluble in ether is soluble in hot alcohol and can also be hydrolysed giving aleuritic acid. Ethyl aleurate crystallises in long needles m. .p. 57-58". The residue from the stick-lac when extracted mth boiling alcohol gives a wax crystallising in colourless leaflets m. p. 82" from which by hydrolysis an alcohol tuchrdiucerol C,H,O m. p. 81-82' and an acid m. p. 74-76" were obtained. The remainder of the wax was extracted by boiling benzene; this fraction has been examined by Gascard (A.1914 i 1045). After these extractions the residue of the stick-lac consists only of the skeleton of the Tnchardia with a little adsorbed laccaic acid. E. H. R. Scission of Potassium Atractylate. F. ANGELICO and F. MONFORTE (Gazzetta 1923 53 808-812; cf. A. 1907 ii 122; 1910 i 403).-Potassium atractylate the glucoside of AtradyZis gummif era or either of its decomposition products atrwtyliretin and atractyligenin serves aa an excellent colour reagent for aromatio hydroxy-aldehydes in general. The reagent is treated first with a little concentrated sulphuric acid and after a few minutes with a drop of an aqueous solution of the hydroxy-aldehyde; a red color- ation similar to that of rosolic acid is obtained the exact tint varying somewhat with the aldehyde employed.Estimation of the sulphur and potassium present in and of the raleric acid and dextrose formed on hydrolysis of it sample of potassium atractylate gives results in agreement with the fckula C&,,O,,S&,. Atractyligenin c14H&4 obtained by hydro- lysing the glucoside and aiterwards acidifying the liquid forms h 2white crystals m. p. 168" and does not reduce Fehling's suh&ion. Atractyliretin prepared by prolonged boiling of the glucoaide with normal sulphuric acid is obtained as a white compound which hardens when it is triturated with water and then forms a white powder m. p. about 190" (decomp.) ; like the isomeric atractyligenin it exhibits acid properties and does not react with hydroxylamine or phenylhydrazine. T.H. P. M. BRIDEL (Bull. SOC. Chim. biol. 2923 5 801-805).-The work of Rosenthaler recently has shown that the glucoside loganin originally described by Dunstan and Short (A. 1885 395) is a mixture of meliatin (A 1910 i 692) and another substance not identified. The name loganin has therefore no longer any significance. The Saponins of the Sarsaparilla Root. H. P. KAUFMANN and C. Fums (Ber. 1923 56 [B] 2527-2533).-A.n investigation of the saponins of sarsaparilla root imported from Honduras in 1918 ; the date of harvesting is uncertain. The ash contains the following substances expressed as per- centages of the dried root SiO 1.25; A1,0 0.79; CaO 0.57; MgO 0.50; G O 1.51 ; C1 0.46. The finely divided root is extracted successively with chloroform light petroleum benzene ether anhydrous alcohol and aqueous alcohol (50%).The light petroleum extract contains cetyl alcohol. The saponins are isolated as a form soluble in absolute alcohol (saponin A) and an insoluble form (saponin B). Saponin A is purified by dialysis against running water whereby it is obtained as a fawn-coloured powder which cannot be caused to crystallise. The presence of considerable amounts of dextrose in the sarsaparilla root considered in conjunction with the ready hydrolysis of the saponins by acids justifies the conclusion that the primary crystalline glucosides are partly changed by fermentative fission to amorphous secondary glucosides ; the contradictory results of previous investi- gations are probably due to the use of fresh or stored material. Saponin B is similarly purified by dialysis which however does not remove a considerable content of aluminium magnesium and calcium which are probably present in combination with galac- turonic acid.These can be eliminated by solution of saponin B in alkali and precipitation with acid. The purified material then closely resembles saponin A. The composition of the products vmies somewhat in d8erent preparations ; it appears that a loosely combined saccharide component is removed during the protracted extract ion. The saponins are hydrolysed by sulphuric acid (3-5y0) whereby possibly galacturonic acid glucose pentoses and methylpentoses are obtained. The presence of galactose arabinose or rhamnose could not be established. The sapogenin is freed from dark coloured impurities by solution in alcohol and precipitation with sodium ethoxide whereby ultimately sarsapogenin CB6H4203,HT0 slender colourless needles m.p. 183" (corr.) [a]a -58.68" m absolute methyl alcohol is isolated; the substance is identical with that Loganin or Meliatin? C. R. H.ORGANIC CHEMISTRY. i 197 obfahed by Power and Solway (T. 1914,105 201) from Jamaica sarsaparilla. The substance contains one hydroxyl group since it yields a monoacetate colourless needles m. p. 127" [a] - 57.1" when dissolved in chloroform (Power and Solway loc. cit. give m. p. 137"). The acetyl compound is hydrolysed by barium hydroxide to a substance C,6H4203,H20 m. p. 122"; possibly racemisation or intramolecular transformation takes place. The monobenxoyl derivative forms colourless crystals m.p. 124". The presence of a carboxyl carbonyl alkyloxy- or lactonic group could not be established in the usual manner.. The remaining two oxygen atoms must therefore be present in the molecule as a stable bridge. Distillation with zinc dust and treatment of the Willate with steam gives a diterpene C,&, b. p. 204-206"/748 mm. The Influence of Oxalic Acid on the Formation of Aniline- black. J. PICCARD (Elelv. Chim. Acta 1923 6 1029-1032).-The oxidation of a solution of aniline hydrochloride by sodium dichromate is accelerated about forty times by the addition of a small quantity of oxalic acid to the solution. The mechanism of the accelerating action has not been elucidated. The printing of Aniline-black on cotton or silk is facilitated by impregnating the material with aniline oxalate.[Cf. B. 91.1;' E. H. R. Platinum Oxide as a Catalyst in the Reduction of Organic Compounds. IV. Reduction of Furfuraldehyde and its Derivatives. W. E. KAUFMANN and R. ADAMS ( J . Amer. Chem. When furfuraldehyde in alcoholic solution was reduced with hydrogen under 1-2 atm. pressure in the presence of platinum black the first molecular equivalent of hydrogen absorbed gave a quantitative yield of furfuryl alcohol. The latter then reacted with hydrogen in four different ways to produce tetrahydrofurfuryl alcohol n-amyl alcohol pentane-a€-diol and pentane-a@-diol. The last-named substance CH,Me*CH,*CH(OH).CH,.OH; boiled a t 210-5-21 1*5"/ 751 mm. n'," 1.4412 ~$2 0.9802. Its diucetate boiled a t 219-220"/ '748 mm.ng 1.4202 di! 1.0148. The catalyst made from spectro- scopically pure chloroplatinic acid was very inefficient and the addition of ferrous chloride increased the rate of reduction to a maximum beyond which the rate decreased rapidly. This decrease in the case of the reduction of the aldehyde group was much less than that of the subsequent reduction of the ethylene double bonds. After the absorption of each molecular equivalent of hydrogen the catalyst was reactivated by shaking with air or oxygen. Pyromucic acid gave fetrahydropyromucic acid m. p. 21" and ethyl pyro- mucate gave ethyl tetrahydropyromucate b. p. 82"/11 mm. p-furylacrylic acid gave @-tetrahydrofurylpropionic acid b. p. 135-1 37 "/4 mm. f uroin gave a@ -dihydroxy- ap-ditetrahydrofuryl- ethane C,H,O*CH( OH)*CH( OH)*C,H,O furfurylideneacetone gave 01 -tetrahydrofurylbutan - y - one and a - tetrahydrofurylbutan - y - 01 b.p. 93-94"/2 mm. furfurylideneacetophenone gave y-phenyl- (slight decomp.). 33.- W. SOC. 1923,45,3029-3044 ; cf. A. 1922 ii 558 ; 1923 ii 310,773).-i. 198 ABSTRACTS OF CHEMICAL PAPERS. tetrahydrofurylpropan-7-one b. p. 153-154"/2 mm. and y-phenyl- tetrahydrofurylpropan-7-01 b. p. 167-168"/2 mm. F. B. Hydroxymethylfurfuraldehyde from Cellulose and its Derivatives. E. HEUSER and W. SCHOTT (Cellulosechemie 1923 4 85-89) .-The h ydroxymethylfurfuraldehyde which is formed on heating cellulose with 5% oxalic acid solution in an autoclai-e at 180" for half an hour has been shown to be identical with the isomeric modification described by Kiermayer.The following derivatives were prepared for this identification Semicarbazone m. p. 235-236"; phenylhydrazone m. p. 140"; anhydride m. p. 112"; anti-aldoxime m. p. 76"; syn-aldoxime m. p. 106". The normal modification prepared by Erdmann from bromomethyl- furfuraldehyde (from lmulose) gave a semicarbazone melting a t 216". This modification is converted into the isomeride by heating with 0.3% oxalic acid in it sealed tube. The hydroxymethyl- furfuraldehyde is extracted from the filtered digestion liquor by shaking with ethyl acetate. The quantity of the aldehyde increases with the degree of hydrolysis of the cellulose; thus normal cotton yielded 15.36% of dextrose and only 0.82% of the aldehyde viscose cellulose gave 63.21% of dextrose and 5.16% of the aldehyde whilst hydrocellulose prepared from viscose according to the prescription of Knoevenagel and Busch yielded 68.47% of dextrose and 10*840/ of hydroxymethylfurfuraldehyde.The presence of the aldehyde does not interfere with the estimation of the dextrose by the ferment- ation method. J. P. B. Preparation of Chromans. L. CLAISEN (D.R.-P. 374142 ; from Chem. Zentr. 1923 iv 725; cf. Claisen and Tietze A. 1921 i 263-264).-Phenols are treated with butadienes in the presence of acid condensing reagents. Phenol and isoprene gim 2 2-dimethylchroman. p-Cresol and isoprene give 2 2 6-tri- methylchroman a colourless oil with a strong odour b. p. 244- 244.5" ; ell, 0.9920. p-Cresol and py-dimethylbutadiene gire 2 2 3 6-tetramethylchroman an oil b. p.257-258" ; 4 0.9813. m-Xylenol and py-dimethylbutadiene give a pentamethglchrornan b. p. 263-265". G. W. R. The Reduction of Chrysin. J. PICCARD and E. OPPENHEIM (HeZw. Chim. Acta 1923 6 1009-1011).-Chrysin is reduced by magnesium in glacial acetic acid solution forming a compound which is probably the hydro1 of chrysin CI6Hl2O4. It forms an amorphous red powder m. p. 210-226" soluble in concentrated sulphuric acid and in alkalis with a yellow colour. It does not appear to be analogous to the violet substance obtained by Baeyer and Piccard by the reduction of dimethylpyrone (A 1911 i 901). E. H. R. Dipyrylenes. F. ARNDT and P. NACHTWEY (Ber. 1923 56 [B] 2406-2409).-When ethyl acetonedioxalate or ethyl chelidonate is boiled in benzene solution with phosphorus pentasulphide a com-ORGANIC CHEMISTRY.i. 199 pound is formed probably having the constitution ethyl 4 4'-di- pyrylene-2 6 ; 2' 6'-tetracarboxylcte O<C(CO2Et) :CH/ c:c<,:C( C0,Et) It forms slender cinnamon to carmine-red needles m. p. 203- 204". In concentrated sulphuric acid it dissolves with a deep red colour changing slowly to deep green but the ester is recovered from the green solution unchanged. 4 4'-Dipyrylene-2 ; G 2' 6'- tetracarboqkic acid forms a brownish-red infusible powder ; the sodium salt Cl,H,010Na,,3H,0 is brownish-red. The formation of the above tetracarboxvlate IS meceded bv that of an intermediate C( C0,Et) :CH\ CH :C( C02Et)> 0 .I I CH:C( CO,Et)> compound ethyl thiochelidonate S:C<CH:C(CO,Et) 0 bluish- green needles m.p. 51" which on heating dec6mposes into the et,hyl dipyrylenetetracarboxylate and free sulphur. The thio- chelidonate is conveniently isolated in the form of an additive compound with mercuric chloride a deep yellow precipitate m. p. 135-137". E. H. R. A Molecular Compound of Caffeine and Salicylic Acid. A. REGENBOGEN and N. SCHOORL (Phrm. Weekbkad 1924 61 34-36).-The melting-point curve for mixtures of the two sub- stances shows the existence of an equimolecular compound- with melting point about 135". By fusing together equal molecular proportions of the components and recrystallising from water the compound is obtained as fine needles m. p. 137" ; it is unaltered by recrystallisation from chloroform but decomposes in alcoholic solution. Its existence explains the solubility of caffeine in aqueous Strychnos Alkaloids.XXXXI. Various Observations on Derivatives of Brucine. H. LEUCHS W. GLADKORN and E. HELLRIEGEL (Ber. 1923 56 [B] 2472-2477).-Dihydrobmcinonic acid is decomposed by prolonged treatment with methyl-alcoholic ammonia at 100" into isobrucinolone an amorphous substance and aminodihydrobrucinolone. The conversion of isobrucinolone by 5N nitric acid into the red quinone C,,H,,O,N decomp. about 300" is described in detail; the substance is reduced by sulphur dioxide to the corresponding qtiinok C19H1805N2 needles or prisms m. p. 325-328" (decomp.) after darkening a t 320". The oxidation of acetylisobrucinolone dissolved in acetone by pofassium permanganate does not take place smoothly and gives dihydroxyucetyldihydroisobrucindone C,,H,,O,N slender needles m.p. 245" as sole crystalline product in yield which does not exceed 12%. The acidic products of the oxidation are amorphous but show the expected properties such as the red coloration with ferric chloride the loss of carbon dioxide when heated the decomposition by acidic hydrolysis into a hydrochloride (probably curbine hydro- chloride in place of the expected isocurbine salt) and a nitrogen-free acid apparently malonic acid. It therefore appears probable that iso- solutions of sodium salicylate. s. I. L.i 200 ABSTRACTS OF GHEMICAL PAPER& brucinolone conhins the same oxidisable group NCO*CH,*CH:C:C as brucinolone-b and yields a substance which is a semi-amide of malonic acid and a ketone. The study of the oxidation of benzoyl- isobrucinolone C2,H2,O6N2 very slender needles m.p. 250" after darkening at 240" when rapidly heated [a]! +99" in glacial acetic acid solution did not lead to more favourable results. Brucinolic acid is converted by methyl-alcoholic ammonia at 100" into brucinolone glycollic acid and aminodihydrobrucinolone. Brucinolone-b is converted by benzoic anhydride and sodium benzoate at 100" into benxoylbrucinolone-b c2sH2606N2 prismatic aggregates m. p. 235-236" [a] -148" in glacial acetic acid solution and by phosphorus pentachloride in the presence of chloro- form at -20" and treatment of the product with ethyl alcohol into brucinolone diethyl phosphate PO(OEt),*O~C21H2,04N large colour- less leaflets m. p. 232-235". Brucinolone hydrate I and phenylcarbimide yield the com- pound C,,H,,O,N,,H,O coarse domatic prkms m.p. 191-192" (decomp.). Dihydroxydihydroacetylbrucinolone is converted by acetic anhydride and anhydrous sodium acetate a t 100" into diacetyldi- h~~ro~~~ihydrobrucinolone-b C2,Hls0,N2 colourless crystals m. p. about 280" (decomp.) after darkening and softening at 240P [a] -149.2" in glacial acetic acid solution. The oximation of ON-diacetylcurbin by a boiling alcoholic solu- tion of hydroxylamine causes the loss of the 0-acetyl group and formation of N-acetylcurbinoxime C20H2306N2 lustrous rectangular prisms m. p. 185-187". The attempted isomerisation of the oxime by acetyl chloride at 100" leads to the production of triacetylcurbin- oxime C,H2,0,N3 double pyramids m. p. 275" (decomp.) after becoming yellow a t 250".The Behaviour of Eucupine and Uric Acid Gels during Dialysis. The Distribution of Ions. P. RONA and W. B. MEYER (Biochem. Z . 1923 143 161-178).-In dialysing eucupine dihydrochloride ( C~H3,02N2,2HC1 +2H,O) considerable membrane adsorption occurs. This is greater with collodion membranes than when Schleicher-Schull shells are used but diminishes with increasing acidity and disappears a t pH 4. The adsorption may be overcome by previously saturating the membrane with eucupine. Eucupine dihydrochloride forms a true solution. Eucupine acetate gel and lithium urate gel are partly colloidal (60 %) and partly true solutions. In dialysing the urate gel lithium and uric acid pass into the external fluid in equimolecular concentrations. The transition between super- saturated uric acid solution in lithium hydroxide and lithium urate gel is sharp the former behaving as a true solution.On dialysing mte against potassium chloride the potassium diffuses inwards and the lithium outwards in proportional amounts whilst the external uric acid concentration diminishes with increasing amounts of potassium chloride. The system illustrates the unequal dis- tribution of electrolytes on the two sides of a membrane with a non-diffusible colloidal ion on one side. H. W. J. P.ORGANIC CHEMISTBY. i. 201 Some New NSubstituted Pyrrole-aldehydes ; and Oxindole-aldehyde. HANS FISCHER and K. SMEYKAL (Ber. 1923 56 [B] 2368-2378) .-The Gattermann aldehyde synthesis (cf. Pischer and Zerweck A. 1922 i 758) has been applied to the synthesis of a number of N-substituted pyrrole-aldehydes. Ethyl 1-phenyl-2 5-dimethyl-4-aklehyd~pyrrole-3-mrboxylate CMe:c*CO,Et NPh<CMe:&CHO ' from ethyl 1-phenyl-2 5-dimethylpyrrole-3-carboxylate forms colourless crystals m.p. 82"; the free acid has m. p. 240". The ethyl ester forms a phenylhydmzone colourless crystals m. p. 156-160" and an oxime m. p. 150". Ethyl 1-p-tolyl-2 5-dimetltyl- pgrrole-3-carboxylate from p-toluidine chloroacetone and ethyl acetoacetate forms colourless crystals m. p. 55"; the free acid forms large crystals m. p. 240". By Gattermann's synthesis with hydrocyanic acid the ester gives ethyl 1-p-tolyl-2 5 - d i d y l - 4-akEehydopyrrole-3-mrboxylate white glistening crystals m. . p. 133" ; the phenylhydrazone forms colourless strongly refractmg crystals m.p. 92-96"; the oxime forms glistening leaflets m. p. 138" and the free acid forms colourless needles m. p. 212O. The semicurbaxone forms colourless needles m. p. 240". Ethyl 1 2 5- trimeth yl-4-aldeh ycZupyrrole- 3 - curbox y lat e forms long white needles m. p. 97" ; the phenylhydrazone forms fine needles m. p. 159-161". It has been suggested by Alessandri (A. 1915 i 452) that a number of a-pyrrole-aldehydes have a hydroxymethylene structure since they do not react with dihydroxyammonia whilst the corre- sponding N-substituted a-pyrrole-aldehydes do so react. It is now found that neither ethyl 2 5-dimethyl-4-aldehydopyrrole-3-carb- ox ylat e ethyl 2 4-dime t h yl- 3 -aldeh ydopyrrole - 5 -car boxylate nor the new N-substituted pyrrole-aldehydes reacts with benzenesulpho- hydroxamic acid.Probably all are true aldehydes although not giving all the typical aldehyde reactiom. There may be an equili- brium between the two forms. The N-substituted pyrrole-aldehydes react with nitroacetic acid with loss of carbon dioxide forming nitrovinylpyrroles and with ethyl cyanoacetate to give substituted vinylpyrroles. Ethyl 1-phenyl-2 5-dimethyl-4-nitrovinylpyrrole-3-carboxyktte forms yellow crystals m. p. 130-132" ; the corresponding 1-p-tolyl compound forms glistening yellow leaflets m. p. 125-133". Ethyl 2 6-di- methyl - 4 - [W - cyano - w -carbethoxyvinylJpyrroZe - 3 - mrboxyhte forms white needles m. p. 139". The 1-phenyl derivative forms colourless needles m. p. 110" and the 1-p-tolyl derivative white needles Oxindole-3-aldehyde condenses with hippuric acid to form an axlactone which forms an acetyl derivative stout prisms m.p. 185". It may have the annexed formula. -CH=$!-N> Cph Hydrolysis experiments failed to give an unsaturated acid but merely re- moved the acetyl group which may therefore be attached to the nitrogen. The hydrolysed product had m. p. 260". N-Methyloxindole- In. p. 121". / /OAc CO.0 (1 NH ' h'lci. 202 ABSTRACTS OB CHEMICAL PAPERS. 3-aldehyde slso formed an acetyEcszlactone glistening red needles m. p. 205" which when hydrolped gave the axlactone red needles 113. p. 287". The acetyl group cannot in this case be attached to nitrogen but it is still doubtful what positions are occupied in the molecule by the acetyl and benzoyl groups.Oxindole-3-aldehyde gives by Perkin's reaction a compound C,,H7O2N yellow tablets m. p. 247" probably having the (\m/NYH annexed coumarin formula. It forms a crystal- co line molecular compound with 1 mol. of aniline \/"/H\o/ m. p. 160". Oxindole-3-aldehyde forms an ucetyl derivative m. p. 185" and a benmyl derivative m. p. 196" ; N-methyloxindole-3-aldehyde gives an acetyl derivative yellow needles m. p. 135" and a benzoyl derivative greenish-yellow needles m. p. 147". W. KUSTER and H. MAURER (Ber. 1923 56 [B] 2478-2481).-A new synthesis of haernatic acid starting from ethyl 4-aldehydo-3 5-dimethylpyrrole- 2-carboxylate (cf. Fischer Weiss and Schubert A 1923 i 703) is recorded. The preliminary work is carried out with the more accessible ethyl 2-aldehydo-3 5-dimethylpyrrole-4-carboxylate.Ethyl 2-aldehydo-3 5-dimethylpyrrole-4-carboxylate is con- densed with ethyl malonate in the presence of acetic anhydride at a temperature not exceeding 150" t o ethyl 4-mrbethoxy-3 5-dimthyl- p yrrok-2-uinyZ- o w -d icarboxy lat e small yellow needles m . p . 86" which is reduced and partly hydrolysed by sodium amalgam to 4-carbethoxy-3 5-d~rnethylpyrrole-2-ethyl-~~-dicarboxylic acid C13H1,06N a colourlesa powder m. p. 218". The acid loses carbon dioxide when heated and passes into 4-carbethoxy-3 5-dimethyZ- pyrrole-2-pqionic acid slender colourless needles or rectangular prisms m. p. 120"; the iron and copper salts are described. Et hy 1 4-a ldehy do - 3 5-dime thylp yrrole-2 -carboxylat e and e thy1 maJonat e yield ethyl 2 -carbethoxy-3 5-dimeth ylp ywole-4-vinyl- ww -d i- curboxylate Co2Et*y :c"e>C*CH:C(C0,Et)2 colourless needles m.p. 99-100" which is transformed by sodium amaIgam into 2-arb- ethoxy- 3. 5-dimethylp yrrole-4- ethyl - ww-dicurboxp?ic acid CH E. H. R. A New Synthesis of Haematic Acid. HN*CMe Co2Et*(? 'cMe,>C*CH2*CH(C02H)2 HNCMe colourless leaflets or thick needles m. p. 184-185" (decomp.); the ferric and calcium salts are described. The acid passes when heaced above its melting point into 2-carbethoxy-3A 5-dimethyl- pyrrole-4-propionic acid co2E 'C'*e>CCH2*CH2*C02H colour- H N*CMe less leaflets m. p. 152" the silver and ferric salts of which are described. Oxidat ion of 2 - carbethoxy- 3 5-dime thylp yrrole -4-pro - pionic acid by chromic acid in glacial acetic acid solution gives the imide of hEmatic a,cid I o*cRI">C*CH2*CH2*C02H which is NH-CO characterised by hydrolysis by means of barium hydroxide t o the anhydride m.p. 97". H. W.ORGANIC OHEMISTBY. i. 203 Pyrroles. F. AKGELICO and F. MONFORTE (Gazzetta 1923 53 795-800).-1t has been shown (A. 1905 i 938; 1909 i 122; 19lO,-i 444; 1911 i 1032) that when boiled with dilute aulphuric acid diazotriphenylpyrrole yields szinetriphenylpyrrole. Further experiments show that diazotriphenylpyrrole is a highly stable compound and is not altered by iodine sodium thioaulphate alcohol or organic acids. With mineral acids it yields salts and with nitric acid also nitro-derivatives. Energetic oxidising agents cause pro- found decomposition of the molecule.Reducing agents mcb as zinc dust and acetic acid zinc dust and ammonium chloride am- monium sulphide or hydroxylamine convert it into the amino- compound whilst by the action of hydrogen in presence of palladium black it is converted into ammonia and triphenylpyrroline ; the latter reduction resembles that of diphenyldiazomethane which yields principally diphenylmethane and nitrogen (cf. Staudinger Gaule and Siegwart A. 1921 i 323) but it has not been found possible to convert diazotriphenylpyrrole by reduction into the corresponding hydrazine although this is possible with certain of the aliphatic diazo-compounds. Like both the corresponding indole derivative and various aromatic diazo-compounds diazotriphenyl- pyrrole is extremely sensitive to the action of light this causing it to darken and to undergo transformation into a compound which has a lower melting point and a diminished proportion of nitrogen but has not yet been identified.2 5-Diphenylpyrrole-3-carboxylic acid readily yields the corre- sponding oximino-compound but in the passage to the amine the csrboxyl group is eliminated in the cold. Hence to prepare the diazo-compound it is not necesszry to convert the carboxylic acid into 2 3-diphenylpyrrole itself. The compound C,,Hl,O,NS obtained by the action of concen- trated nitric acid in the cold on diazotriphenylpyrrole forms crystals iu. p. 185". If a mixture of nitric and sulphuric acids is employed the product forms crystals m. p. 110" and contains rather more nitrogen than is represented by the above formula.Oximino - 2 5 - diphenylpyrrole - 3 - mrboxylic m i d C,,H,,O,N crystallises in golden-yellow scales m. p. 212" (decomp.) and yields aminodiplienylpyrrole m. p. 186" when reduced in alcoholic solu- tion by means of ammonium sulphide. T. H. P. A Complex Silver Fluoride. A. BURADA (Ann Sci. Uniu. JCWUJ 1923 12 33-34; from Chem. Zentr. 1923 iii 1225).-By addition to a solution of silver fluoride of the theoretical quantity of pyridine and evaporation in a vacuum over sulphuric acid with exclusion of light a compound is obtained of the composition AgF,2C,H,N,5H20 ; it forms colourless t,ransparent crystals unstable m air and light. When heated it is decomposed completely leaving a residue of metallic silver. G. W. R. Preparation of Amino-substitution Products of pSridine and Quinoline Series.A. E. TSCHITSCHIBABIN (D.R.-P. 374291 ; from Chem. Zentr. 1923 iv 726; cf. A. 1923 i 112l).-]eyridine h* 2i. 204 ABS!CBACTS OB CHEMICAL PAPERS. quinoline their homologues or derivatives or other bases containing the pyridhe ring or natural organic bases such as alkaloids are treated in the absence or presence of indifEerent solvents with sodamide or compounds of the general formula R-NHNa where R=aryl alkyl or a heterocyclic basic residue such as pyridyl or q d y l or mixtures of sodium with primary amines. After tredjzwrit of the products of reaction with water the amino- unds obtained are separated by distillation or other suitable ze%. The reactions are shown by the following equations (i) C5R N+NH2Na=C5H4NNHNa+H2 (ii) C5H,N*NHNa+H,0i C5H4NkH2+NaOH (ni) C5H4N*NHNa+C5H,N=(C5H4N)2Nha +H (iv) (C5H4N),NNa+H20= (C5H4N),NH+NaOH.The amino- group goes into the ortho-position relatively to the pyridine nitrogen. 2-Aminopyridhe has m. p. 56". Other compounds mentioned are 6-arnino-2-methylpyridine a deliquescent substance m. p. 36.5" b. p. 208-209" ; 2-aminoquinoline leaflets m. p. 129" ; 2 6-diamino- pyridine obtained by heating pyridine and sodamide in the presence of vaseline oil at 125" and then a t MOO leaflets m. p. 121.5"; 2-anilinopyridine from pyridine and sodium anilide crystals m. p. 108"; 2 2-dipyridylamine small needles m. p. 95" (stable form) m. p. 86-87" (labile form) ; aminonicotine crystals m. p. 125-126" ; 6-amino-2-hydroxypyridine ; 2 6-diaminopyridine couples with aromatic diazo-compounds with formation of colouring matters. Nitration of 2-aminopyridine yields 5-nitro-2-aminolry7idine yellow leaflets m.p. 188" and 3-nitro-2-aminopyridine yellow needles m. p. 164". From 5-nitro-Z-aminopyridine 2 5-diaminopyridine UI obtained by reduction. The Synthesis of Ricinine. E. SPATH and G. KOLLER (Ber. 1923 56 [B] 24&2460).-The constitution assigned previously to ricinine (Spath and Koller A. 1923 i 594) is confirmed by its synthesis from 4-chloroquinoline. Ricinidine is converted by a molecular proportion of bromine in aqueous solution into a mixture of bromo-compounh which is transformed by boiling potassium carbonate solution into a product m. p. 287"; it is not identical with ricinic acid. 4-Hydroxy-l-methylpyrid-%one reacts with a molecular proportion of bromine in aqueous solution to give a homogeneous bromo-derivative m.p. 219-219.5" ; attempts to replace- the halogen atom of this compound by the cyano-group were unsuccessful . 4-Chloroquinoline is oxidised by potassium permanganate in boiling aqueous solution in the presence of carbon dioxide to 4-chloropyridine-2 3-dicarboxylic acid coarse pale yellow crystals m. p. 173" (decomp.) when rapidly heated. The acid is fairly smoothly converted by acetic anhydride into the corresponding anhydride colourless needles m. p. 200-202" (slight decomp.) in an evacuated tube which is converted by ammonia in the presence of benzene into 4-cMoro-2-carbamidopyn'dine-3-carboxylic acid lustrous needles m. p. 148-150' (decomp.) when rapidly heated.The latter acid is converted by bromine and potassium hydroxide into G. W. R.ORQANICJ OHEMISTRY. i. 205 4-chloro-2-aminopyridirrae-3-earboxyl~c acid slender colourless crystals decomp. 173" which is conveniently purified through the ammonium salt; it is transformed by nitrous acid in sulphuric acid solution info 4-chloro-2-hydraxy~~dine-3-~rboxyl~c mid colourless needles m. p. 220" (decomp.). The constitution of the hydroxy- acid is established by its conversion by hydrogen in the presence of palladised barium sulphate into the previously described 2-hydroxy- pyridine-3-carboxylic acid and thence into 2-hydroxypyridhe. Attempts to effect the complete methylation of 4-chloro-2-hydroxy- pyridine-3-carboxylic acid with diazomethane or by the action of methyl iodide on the di-silver salt mere not successful.The acid is therefore converted by the successive action of phosphoryl chloride and phosphoms pentachloride and of ammonia into 2 4-dz'chloro~rz'dine-3-carboxylamide colourless crystals m. p. 181-182" (decomp.) which is transformed by phosphoryl chloride into 2 4-dichloro-3-cyanopyridine m. p. 112-113". When t+reated with boiling methyl-alcoholic sodium methoxide solution both chlorine atoms are replaced by methoxy-groups with the production of 3-cyano-2 4-dimethoxypyridine coarse colourless crystals m. p. 145-146" and a substance m. p. 221-222" which has not been examined completely. The conversion of 3-cyano-2 4-dimethoxy- pyridine into ricinine m. p. 197" could not be effected by heating it at 300" but occurs readily when it is treated with methyl iodide in an evacuated tube a t 120-130". H.W. Keto-mils. V. The Formation of Quinolines from Ketones and Aromatic Amines. E. KNOEVENAGEL [with E. WAGNER and H. BAHR] (Ber. 1923 56 [B] 2414-2418).-The production of derivat,ives of quinoline from aniline and ketones or aldehydes has been ascribed to the intermediate formation of alkylidene ketones and aldols respectively. Evidence is now brought forward however in favour of the view that in the formation of 2-methyl- or 2 4-dimethyl-quinolines an alkylidene- or a ketylidene-amine derivative is essential which passes into a dimeride and thence into a quinoline compound. It is quite possible that the formation of aldols from aldehydes ketones or mixtures occurs under the condensing influence of hydrogen chloride but compounds of this type are decomposed hy aromatic amines with formation of alkylidene- or ketylidene-amines and liberation of the equivalent quantity of aldehyde or ketone.The preparation of methylisopropenylaniline (cf. Bahr A. 1922 i 750) from acetoneanil and methyl sulphate is described. It is converted by cyanoacetic or chloroacetic acid (but not by the dichloro- or trichloro-acid) into dimeric methylisopropenylaniline in. p. 148" which is identical with the by-product isolated by Biihr (Zoc. cit.) during the preparation of methylisopropenylaniline by means of methyl iodide. The dimeride is transformed by dry hydrogen chloride a t 180-200" into 2 4-dimethylquinoline. The action of mesityl oxide on aniline in the presence of a little iodine leads to the formation of acetoneanil and acetone.The condensation of mesityl oxide with aniline hydrochloride at 180"i. 206 ABSTRACTS OR' m C A L PAPERS. takes place with liberation of methane and not of methyl chloride as stated by Beyer. In the presence of iodine phorone and mesityl oxide yield acetone unchanged phorone and acetoneanil. In the absence of iodine condensation does not appear to occur. Under the in3uence of iodine and water phorone does not appear to yield acetone. H. W. Amino-alcohols of the Quinoline Series. SOCIETY FOR CHEMICAL INDUSTRY IN BASLE (Swiss Pats. 98482 98712 and 98713 ; from Chem. Zentr. 1923 iv 829-830; cf. A. 1923 i 148 149).- 6-Ethoxy-2-phenyl-4-quinolyl methyl ketone is halogenated in the methyl group and the resultant halogen derivative allowed to react with dimethylamine diethylamine or piperidhe. The N-sub- stituted 6-ethoxy-2-phenyl-4-quinolylamino-ethanone thereby obtained is then reduced to the corresponding aminoalcohol.6-E~7wxy-2-phenyl-4-quinolyt methyl ketone forms yellow crystals m. p. 107"; the hydrochloride yellow crystals has m. p. about 220" (decomp.). It is obtained by condensation of ethyl 6-ethoxy- 2-phenylquinoline-4-carboxylate with ethyl acetate and elimination of carbon dioxide from the ethyl 6-ethoxy-2-phenylquinoline-4-aetafe m. p. 98-99' thereby formed or from 4-cyano-6-ethoxy-2-phenyl- quinoline by the Grignard reaction. By acting on the above- mentioned ketone with bromine in hydrobromic acid solution 6-ethoxy-2-p~nyl-4-qui~lyl brornomethyl ketoze hydrochloride yellow qystals m.p. 207" (decomp.) is obtained; the free ketone forms yellow crystals m. p. 129". By acting on the bromomethyl ketone with dimethylamine G- ethoxy-2 -phenyZ-4-quinolyl dimethyl - aminomethyl ketone OEt*CgNH4Ph*CO*CH2*NMe2 is obtained as the hydrobromide yellow crystals m. p. 230" (decomp.). The latter by reduction with hydrogen in the presence of a catalyst gives 6-ethoxy- 2-phenylquinolyl-4-dimethylamin&hanol OEf. CgNH,Ph*CH (OH)*CH,*NMe which forms colourless rosette-like needles m. p. 95' ; the dihydro- chloride forms light yellow crystals m. p. about 210" (decomp.). 6-Ethoxy-2-phenyl-4-quinolyl diethylaminomethyl ketone monohydro- bromide yellow crystals m. p. about 210" (decomp.) G-eth0.q- 2-phenyl-4-quinolyl piperidinomethyl ketone a yellow powder m.p. 82" (indef.) the hydrochloride m. p. about 260" (decomp.) and the hydrobromide m. p. 235-240" (decomp.) of the latter are similarly obtained. The corresponding amino-alcohols are obtained by reduction. 6- Ethoxy-2-phenyl-4-quinolyldiethylaminoethanol forms crystals m. p. 89" after softening ; the dihydrochloride yellow cr tals has m. p. 205". 6-Ethoxy-2-phenyl-4-quinolylpiperidi?m- G. W. R. yellow crystals has m. p. 218". Preparation of a 2-Phenylquinolinedicarboxylic Acid. NEUMANN & Co. and J. ZELTNER (D.R.-P. 373285; from Chem. Zentr. 1923 iv 664-665) .-Acetophenone-o-carboxylic acid prepared for example from phthalic anhydride acetic anhydride and potassium acetate is condensed with isatin by heating in the presence of potassium hydroxide solution at 100'.On acidifying ef E noZ forms colourless crystals m. p. 110"; the dihydrochloride,ORUNI(3 CHEMISTRY. i. 207 2-phenylgrcinoline-4 7-dicarboxylic acid is obtained; it is a yellow crystalline powder m. p. 200". Preparation of Tetrahydrocarbazoles. CHEMSCHE FABBIKEN VORM. WEILER-TER MEER (D.R.-P. 374098 ; from Chem. Zenlr. 1923 ivy 724).-2-HalogencycZohexanones are condensed with primary or secondary aromatic amines unsubstituted in the ortho-position to the amino-group. The reaction takes place in the presence of such basic substances as potassium carbonate or anhydrous potassium acetate and is represented by CH,/\CO CH,(,!CHX + /-NHR- - H O + H S T 2 CHZ CH,NR The following compounds are mentioned tetrahydrocarbazole from aniline and chlorocyclohexanone ; 3-methyltetruhy&rocarbazole m.p. 142" from o-toluidine and chlorocyclohexanone ; 1-mthgltetrahydro- carbuzole m. p. 98" from p-toluidine and chlorocyclohexanone ; N-ethyltetrahydrocarbaxole a viscous oil b. p. 220"/40 mm. from ethylaniline and 1 2-chlorocycZohexanone. G. W. R. R. Sii DERQUIST (Suensk Kern. Tidskr. 1922 34 189-192; from Chem. Zentr. 1923 iii 1082-1083) .-Aromatic a-ketonic acids are prepared by condensation of aldehydes with 4-oxo-2-thio-3-phenyloxazolidine. After oxidation and fission of the substituted oxazolidine ring aromatic a-ketonic acids are obtained together with phenyl thio- carbimide. The condensation proceeds readily in acetic anhydride solution in the presence of anhydrous sodium acetate.Fission of the aryldihydroxyoxazoles obtained by oxidation takes place a t the ordinary temperature on treatment with sodium ethoxide. The compounds may be separated by fractiomtion or by way of their hydrogen sulphite compounds. Anhydro-acids are also obtained from the elimination of a molecule of water from two ketonic acid molecules. 4-0xo-2-thio-3-phenyZ-5-benz~Zi~e~coxa~~ol- idine from benzaldehyde and 4-oso-2-thio-3-phenyloxazolidine has m. p. 185-185*5O. On oxidation if yields 2 4-dihgdroxy- 3 - p hen y 1 - 5 - b enz ylideneoxaxolidine m . p . 23 8-2 3 9 " whilst among the products of reaction with sodium ethoxide is phenylpyruvic acid. 0 ther compounds mentioned are 4-0~0-2-thio-3-ph.en yl-5-o-chloro- benxylideneoxazolidine fine thread-like or prismatic crystals m.p. 14 1.5" ; 2 4-d ih ydrox y -3 -phen yl-5-0 -chloro benz ylideneoxaxolidin e m. p. 152"; o-chlorophenylpyruuic acid colowless leaflets rn. p. 145" (m. p. 152-152-5" when heated quickly) ; semicurbaxone of the latter m. p. 167-5" ; phenylhydraxone m. p. 141" ; 4-oxo-2-fhio- 3-phenyl-5-m-chlorobenzylideneozaxolidine light yellow prisms m. p. 192" ; m-chlorophen ylpyruvic mid prisms ; semicarbazone of the latter m. p. 176" ; phenylhydraxone m. p. 141" ; 4-0x0-2-thio- 3-phen yl-5-p-chlorobenxylideneoxazolidine m. p. 237-237.5" ; p-chlorophenylpyvic acid platelets ; semicurbaxone of the latter G. W. R. CHZ CH CH2/\-A CH1!?\? 3 Preparation of Aromatic a-Ketonic Acids.i. 208 ABSTRACTS OR' CHEXKIOffi PAPERS. m. p. 184" ; phenylhydrazone m.p. 164" ; 4-oxo-2-thio-3-p&enyL 543' 4')mthylenedioxybenzylideneoxazolidine m. p. 240" ; 2 4-~thylenedioxyphenylpymvic acid colourless leaflets ; semi- curbaxone of the latter m. p. 197"; phenylhydrazme m. p. 144"; 4- 0x0-2 -t&io- 3 -phen y 1 - 5 - m - nit ro benx y lidenwxazolidine m . p . 20 7 " ; 4-oxo-2-thio-3-phenyl-5-o-acetoxybenx ylideneoxazolidine yellow prisms m. p. 1624%-163". Action of Hydroxylamine and of Hydrazine on the Aryl Monothioamides of Carbethoxyethylmalonate. D. E. WORRALL (J. Amer. Chem. Soc. 1923 a 3092-3095; cf. A. 1022 i 874).-isoOxazoles and pyrazoles were obtained by the action of hydroxylamine and hydrazine respectively on carbethoxy- ethylmalonate monothioamides. Thus carbethoxyethylmalonate monothioanilide gave ethyl 3-anilino-5-oxo-isooxazole-4-carboxylate srnaaU needles m.p. 166" and the corresponding pyraxole ester fluey white needles m. p. 194-195". Ethyl 3-o-toluidino-5-iso- oxazole-4-carboxykcte flat needles m. p. 165-167" (decomp.) and the corresponding pyraxole ester white needles m. p. 215" (decomp.) ; e th y 1 3 - p- toluid ino- 5 - oxoisooxuxol e - 4 - curbox y Zat e needles and plates m. p. 172-173" (decomp.) and the corresponding pyrazole ester feathery needles decomp. above 200" ; ethyl 3-p-brommnilino- 5-o~o~sooxaxoZe-4-carboxyZute slender needles,. m. p. 163-170" (decomp.) and the corresponding pyrazole ester needles m. p. 217" were obtained. F. B. 4'-Amino-l-phenyl-5-methylbenzthiazole and its Bromin- ation in Glacial Acetic Acid. The Dibromo-product of Gatterman.The Fluorescence of some Benzthiazoles. R. F. HUNTER (Chem. News 1923 127 385-386).-An alcoholic solution of dehydrothiotoluidine (4'-amino-l-phenyl-5-rnethylbenz- thiazole) exhibits a green fluorescence in the light of a mercury lamp; its dibromide shows a blue fluorescence in glacial acetic acid solution and the acetyl derivative is also strongly fluorescent. The dibromide is decomposed by nitrous acid and consequently cannot be diazotised. Absorption Colours of the Second Order. J. PICCARD and F. DE MONTMOLLIN (Helu. Chim. Acta 1923,6,1011-1019).-1t was shown previously that meri-quinonoid salts of tetraphenylbenzidine have a yellow colour of the second order (A. 1913 i 895). It is now shown that Nietzki's rule also applies to such second order colours ; the second absorption band can be moved further into the visible spectrum by increasing the molecular weight changing the colour of the compound from yellow to red.This has been demons- trated by preparing a meri-quinonoid salt of diphenyldi-p-diphenylyl- benzidine C6~4~hoNPh~C,H4~C6H40~Ph*~6H4Ph. Diphenyl-p-di- phenyZyZumine C,H,Ph*NPh is formed by heating diphenylamine with p-iododiphenyl in nitrobenzene in presence of potassium carbonate and a little copper; it forms long nearly colourless crystals m. p. 114". It forms a yellowish-green compound with chloranil and gives a greenish-blue coloration with concentrated G. W. R. E. H. R.ORGANIC CHEMISTRY. i. 209 sulphuric acid. When oxidised in glacial acetic acid with sodium dichromate it gives a red colour changing to green; the green solution is reduced with zinc dust and from the diluted solution diphenyldidiphenylylbenx8dine can be extracted with chloroform in 20% yield.It forms a brown powder m. p. 135-140". The same substance can be obtained in an impure form by condensing s-diphenylbenzidine with p-iododiphenyl. All solutions of the compound show a strong violet fluorescence which is excited by ultra-violet light a t the limit of the visible spectrum. This benzidine derivative is oxidised by sodium dichromate in glacial acetic acid solution into a meri-quinonoid salt which can be precipitated by picric acid as meri-diphenyldi-p-diphenylyldiphenoquinonedi- immonium picrate a red powder. Further oxidation gives the green hob-quinonoid salt. E.H. R. H. P. KAUFMANN and J. LIEPE (Ber. 1923 56 [B] 2514-2520).-Attempts have been made to estimate enols by titration with solutions of thiocyanogen in t'he hope of thereby avoiding secondary disturbances such as may be caused by the liberated hydrogen bromide in Meyer's bromine titration method. It is found however that the reagent can be applied only under definite conditions ; in general applicability and rapidity of execution the method is not equal to Meyer's process. Quantitative experiments with solutions of thiocyanogen are rendered very difficult on account of the ease with which it becomes polymerised particularly on exposure to sunlight or to an elevated temperature . Thiocyanogen reacts with antipyrine in the presence of chloroform to give a mixture of antipyrine thiocyanate colourless lustrous needles m.p. 125' (which is also obtained from antipyrine sulphate and potassium thiocyanate) and 4-thiocyano-1-phenyl-2 3-dimethyl- pyrazoZ-5-one K(scN)*co >NPh colourless crystals m. p. 147- 148"; the constitution of the latter substance follows from its preparation from 4-bromoantipyrine and potassium thiocyanate in boiling aqueous solution. 4-Thiocyanoantipyrine thiocyanate has m. p. 84". 4-Thiocyanoantipyrine is very readily hydrolysed by alkali hydroxide t o potassium cyanide potassium cyanate and his- 1 -phen yl-2 ; 3 -dimethyl-5-p yrazolonyl4-disul'hide rph-c*>cs *sKme.bMe CO-NPh NMe*CMe rery pale yellow hexagonal plates m. p. 256"; the compound ca.n also be prepared by means of aqueous alcohol. 4-Thiocyanoanti- pyrine is reduced by zinc and hydrochloric acid in the presence of alcohol to the additive compound of zinc chloride and 4-thiolanti- pyrine C,,H,,ON,S,ZnC~ a white precipitate from which the thiol could not be isolated.[With 'M. !FHOMAS. J-Addition and substitution of free thio- cyanogen occur much more slowly than in the case of bromine. Thus ethyl hydrocollidinedicarboxylate reacts with seven atomic pro- portions of chlorine and four of bromine but not with iodine; with Additive Reactions of Thiocyanogen. CMe-NMei. 210 ABSTRACTS OF CHEMICAL PAP-. thiocyanogen it gives a di-thiocyano-derivative Cl6HI9O4N3Sz m. p. 115' (decomp.). Ethyl coWi&inedicarboxykcte thiocyanute crystallkes in colourleas monoclinic plates m. p. 133". [With M. THous.]-Reactions with free cyanogen depend greatly on the solvent used addition occurring particularly rapidly in the presence of nitromethane (as example of a solvent of high dissociating power).The action of sunlight and of certain catalysts notably iron is advantageous. Thus whereas salicylic acid is indifferent towards thiocyanogen under the usual conditions it is converted in nitromethane solution in the presence of iron powder into 2-hydroxy- 5-thiocyarwbenzoic acid monoclinic leaflets m. p. 167-168'. H. W. New Methods of Splitting Pyrimidines. 11. Decom- position of Pyrimidines by means of Ferrous Salts. M. H. PFALTZ and 0. BAUDISCH ( J . Amer. Chem. Soc. 1923 45 297%- 2980; cf. A. 1921 ii 337).-The splitting of pyrimidines under conditions closely resembling those in the metabolism of plants and animals was accomplished by the action of the syst'em ferrous sulphate-sodium hydrogen carbonate-air and the system sodium pentacyanoaquoferroate-oxygen or air (A.1900 i 591) on uracil and thymine. In each case the pyrimidine ring was partly hydrolysed with the formation of highly coloured intermediate substances which were completely hydrolysed by warm sodiuin hydrogen carbonate with the production of carbamide. The action mas retarded by hydrogefiation of the pyrimidine ring as in hydro- uracil and by the presence of a methyl group in the 5-position as in thymine and by the addition of any substance possessing a strong affinity for iron e.g. ammonia potassium cyanide. H. BILTZ and T. KOHLER (Ber. 1923 56 [B] 2482-2489).-1n continuation of the work on 5-acylbarbituric acid (cf.Biltz and Wittek A. 1921 i 4M) 5-benzoylbarbituric acid has been examined in detail. The position of the benzoyl group is placed beyond doubt by t.he observed ketonic properties of the compound by the existence of similar derivatives of 1 3-dimethyl- and 1 3-diethyl-barbituric acids and by the inability of alkalis to effect hydrolysis. pale yellow aggregates of prisms m. p. 275" (decornp.) is prepared by heating barbituric acid with benzoic anhydride a t 175" during five hours; it cannot be prepared from barbituric acid benzoyl chloride and sodium hydroxide or from barbituric and benzoic acids. The potassium salt rhombic leaflets decomp. about 315" is described. It is stable towards sodium hydroxide solution or concentrated hydrochloric acid.It is decomposed by hot fuming nitric acid into alloxan and benzoic or nitrobenzoic acids and by bromine in aqueous solution a t the atmospheric temperature into hnzoic and 5 5-dibromobarbituric acids. It gives a hydrazone C H ,,03N4 slender pale yellow needles decomp. 260° and a phenyZhydrazone C,,H,,O,N small pale yellow needles decomp. 218"; a semi- F. B. 5-Benzoylbarbituric Acids. 5-Benxoylbarbituric acid CO<m.CO>CHB~ NH*COORGAN10 CHElldISTRY i. 211 carbazone could not be obtained. It is decomposed by thiosemi- carbazide in boiling aqueous-alcoholic solution info barbituric acid and 2-amino-5-phenylthiodiazole (cf. Young and Eyre T. 1901 79 57); 5-acetylbarbituric acid yields in a similar manner barbituric acid and 5-amino-2-methylthiodiazole. The action of hydroxyl- amine on 5-benzoylharbituric acid in boiling alcoholic solution gives a substance colourless lustrous hexagonal platelets m.p. 261 " which is regarded as the oxime of 5-amino-5-benzoylbarbituric acid CO<m.Co>C(NH2)*CPh:NOH NH*CO ; it is converted by hot concen- trated nitric acid into alloxan by highly concentrated hydriodic acid into benzoylbarbituric acid and by bromine water into alloxan and benzaldehyde. 5-Benzoylbarbifuric acid is converted by sodium hydroxide and methyl sulphate into the methyl ether of the colourless lustrous prisms decomp. 105" ; the corresponding phenylhydrazone C,,H,,O,N decomp. 225" is described. The ethylation of 5-benzoylbarbituric acid could not be effected by ethyl sulphate or ethyl bromide magnesium oxide and carbon tetrachloride at 140".1-Methylbarbituric acid and benzoic anhydride react a t 130-140" to give 5-benzoyl-1 -meth?/Zbarbituric acid small pale brown prisms decomp. 225" (phenylhydrazone slender yellow needles decornp. 205"). 5-Benzoyl-1-ethyzbarbituric acid flattened prisms m. p. 205" (decornp.) and its phenylhydrazone slender needles decomp. 190" after darkening at 175" are described. 1 3-Dimethylbarbituric acid reacts with benzoic anhydride at 130" but the expected 5-benzoyl-1 3-dimethylbarbituric acid could not be isolated from the product of the reaction in the homogeneous condition; it is characterised as the phenylhydrazone CI9Hl8O3N4 colourless quadratic leaflets decornp. 218". 5-Benzoyl-1 3-diethylbarbituric acid could not be caused to crystallise ; the phenyzhydraxone C21H2,0,N4 forms long yellow leaflets decornp.164". Attempts to cause interaction between barbituric acid and oxalic acid oxalyl chloride oxalyl bromide or phthalic anhydride were not successful. Thiobarbituric acid does not react smoothly with acetic or benzoic anhydrides. The acetyl group of 5-acetyl- barbituric acids does not appear to be capable of condensing with aldehydes. H. W. Alkylisopropylbarbituric Acids. F. HOFFMANN LA ROCHE & Co. (Austr. Pat. 92386; from Chem. Zentr. 1923 iv 665).-In modification of an earlier patent (A. 1922 i 872) other alkyl halides are used in place of ally1 bromide. 5-MethyZ-Ei-iso- propylbarbituric acid from isopropylbarbituric acid and methyl iodide forms crystals m.p. 186-187". 5 5-Diiso2rropyZbarbitziric acid forms crystals m. p. above 230" (decomp.). Preparation of New Barbituric Acid Compounds. CHEMISCHE FABRIK AUF AETIEN VORM. E. SCHERINQ (Brit. Pat. 198379 ; addn. to 158558 ; cf. A. 1922 i 582).-New compounds enolic form of 5-benzoylbarbituric acid CO<NH.c(oMe)/ NH-co> CBz G. W. R.i. 212 ABSTRAflTS OF C7HEMICIu PAPEBS. similar in properties to that previously described (Zoc. cit.) are obtained by replacing the diethylbarbituric acid in the original process by dipropyl- diallyl- or phenylethyl-barbituric acid. The products of these three fusions melt respectively at 82-86' 85-88' and 106-120". P. I ~ R E R C. G-NACHER and A. SCHLOSSER (Helv. Chim. Acta 1923 6 1108-1112).- Benzyl chloride reacts with the silver salt of glycine anhydride to give 2 5-dihydroxydihydropjraxine dibenxyl ether crystallising in white leaflets m.p. 164". The reaction therefore follows a difEerent course from that of methyl iodide on the anhydride (A. 1922 i 235). The new compound is readily hydrolysed by- boiling dilute acids to benzyl alcohol and glycine and in this respect difEers markedly from its isomerides N N'-dibenzylglycine anhydride and dikefo-2 5-dibenzylpiperazine. New Syntheses in the Quinoneimide Dye Group. I. Syntheses with 1-Chloro-2 4-dinitronaphthalene. F. KEHRMANN (with A. VAN BAERLE) (Ber. 1923,56 [B] 2385-2390). -A number of known and some new quinoneimide dyes have been prepared by condensing 1-chloro-2 4-dinitronaphthalene with different bases. In many cases the toluene-p-sulphonic ester of Martius's yellow (2 4-dinitro-or-naphthol) can also be used.0-2 ; 4-Dinitronaphthylaminodiphenyla.mine is obtained by con- densing the dinitrochloronaphthalene with o-aminodiphenylamine in alcohol ; it forms large brownish-red prisms containing benzene from that solvent which lose benzene and turn black at 70" m. p. 140". With 5-chloro-2-aminodiphenylamine the corresponding 5-chloro-2- (2 4-dinitronaphthylamino)diphenylamine is obtained dark brown leaves m. p. 110". Both these compounds are reduced smoothly by stannous chloride to rosinduline and chlororosinduline respectively. The rosindones are obtained by fusing the dinitro- compound with benzoic acid. By condensing 2 4-dinitro-1 -naphthyltoluenesulphonate with o-aminophenol 0-2 4-dinitronaphthylaminophenol is obtained which by careful treatment with aqueous A sodium hydroxide is converted into 5-nitro-7 12- NH I I naphthaphenoxaxine (annexed formula) a violet A/\/\/ precipitate which decomposes when heated.An I I INO acetyl derivative could not be obtained but (/\/\/ instead the known phenonaphthoxazone was formed. With 00'-diaminodiphenyl disulphide 0 the above toluenesulphonate condenses to give 0-bis-2 4-dinitro- naphthylaminophenyl disulphide (annexed formula) orange-yellow leaflets m. p. 169". With o-aminothiophenol it gives ' I NO,\,NO I I 1 captan a lemon-yellow crystalline powder c \/ 12 m. p. 198" which by careful treatment with alkali gives 5-nitro-7 ; 12-naphthuphenthiaxine nearly black needles with a brassy reflex m.p. 156" (decornp). It is much W. T. K. B. Diketopiperazine Derivatives. E. H. R. r A 1 \/\/ 0-2 ; 4-dinitronaphthylaminophenyl rner- ' I IORGANIC CHEMISTRY. i. 213 more stable than the corresponding oxazine. A by-product of the last condensation yellow glistening crysta,ls m. p. 150° appeared to be 2 4-dinitronaphthyl-o-aminophenyl sulphide. E. H. R. New Syntheses in the Quinoneimide Dye Group. 11. Steric Influence in the Condensation of Hydroxyquinones with o-Diamines. E". KEHRMANN [with c. BUFFAT] (Ber. 1923 56 [B] 2390-2394).-1t has long been known that substituted quinones such as chloranilic acid and 3-chloro-4-hydroxy-1 2- naphthaquinone react with difiiculty or not at all with o-diamines but it is now found that these reactions proceed under suitable conditions.Thus when chloranilic acid is heated with o-phenylene- diamine hydrochloride and a large quantity of benzoic acid a t the boiling point 1 4-dichloro-2 3-dihydroxyphenaxine is formed dark brownish-red metallic crystals blackening a t 310". It gives a dichroic sulphuric acid solution brown in thick greenish-yellow in thin layers. With o-aminodiphenylamine chloranilic acid gives 1 4-dichlwo-2-hydroxyapafranone dark reddish-brown crystals with a weak brassy lustre decomposing a t 285". 3-ChIoro-4-hydr- oxy- 1 2-naphthaquinone with o-phenylenediamine gives 6-chloro- 5-hydroxy-a@-naphth~phenuzine (formula I) dark red brassy crystals decomposing a t about 280". It gives a dirty yellowish-green colour with concentrated sulphuric acid ponceau-red with hot alkali.With o - aminodiphenylamine 3 - chloro-2-hydroxy - 1 4 - naphthaquinone gives 6-chlorwosindone (formula 11) red needles with golden lustre m. p. 255" giving a dark yellowish-green colour in sulphuric acid. With 2-amino-5-chlorodiphenylamine 6 9-dichlmorosindone is formed red needles with strong gold reflex m. p. 242-243" giving a dirty violet-red colour in sulphuric acid. (1.1 (TI.) (111.) \/ When the above 5-hydroxy-6-chloronaphthaphenazhe is fused with o-phenylenediamine a new dihydrtmuphthudiphmzine (formula 111) is formed golden-yellow leaflets with brassy reflex m. p. 263". Its hydrochloride forms dark red metallic needles and it gives a pure green colour in concentrated sulphuric acid. E. H. R. New Syntheses in the Quinoneimide Dye Group. IIL Syntheses of Induline-3B and -6B.F. KEHRMANN [with w. COPFENSTEIN] (Ber. 1923 56 [B] 2394-2397).-The Con-i. 214 ABSTRACTS OE OEEMICcbL PAPERS. stitutional formulae assigned to Induline-3B and -6B have now been confirmed by synthesis of these dyes from. dianilino- o-quinone gf);:. When this is condensed with 2-amino- 5-chlorodiphenylamke hydrochloride in alcohol 3-cMmo-8-aniZin o- phenylaposafranine (annexed formula) is NHph/\// /\ formed crystallising in needles with a green I ) Icl reflex. The free base forms brownish-red NHPh(/\\N(\/ needles m. p. 258". The colour in con- Ph,/ c1 centrated sulphuric acid is violet-blue be- coming violet and then Bordeaux-red on dilution. When this is boiled with aniline and aniline hydrochloride the ring chlorine is replaced by the anilino-group forming 8-anilino- 3 7-di~henyl~~nosafranineY identical with Induline-3B.The free base forms nearly black leaflets with Induline-3B is converted lnto Indu- phenosafranine (annexed formula) by boiling with aniline and aniline hydro- chloride in presence of 1 mol. of mercuric oxide. The free base forms greenish-black metallic crystals m. p. 286-288" ; the hydro- chloride and hydrobromide both form crystals with a coppery lustre insoluble in water. N a weak green reflex m p. 242". line-6B 2 8-dianilino-3 7-diphenyl- E. H. R. New Syntheses in the Quinoneimide Dye Group. IV. The Colour of the Simple Quinoneimines. F. KEHRMANN [with B. CORDONE] (Ber. 1923,56 [B] 2398-2405).-1n a previous paper (A. 1922 ii 333) the rule was established that the effect of salt formation on the colour of basic nitrogen compounds is to intensify the colour if the unsaturated condition persists.This rule has IIOW been found to apply to compounds of the quinoneimine series of which several new members have been pre- 9 pared. Th~moquinonemonoimine (annexed formula) was /\prs prepared by oxidising p-aminothymol with silver oxide in ethereal solution; it crystallises in bright yellow silky leaflets m. p. 74-75'. It is stable for some time in the dark at low temperatures and is much less sensitive to light than p-benzoquinonemonoimine. Its salts are deeper yellow in colour than the compound itself; the hydro- chloride is obtained as a voluminous yellow precipitate from ether ; the p'crate which is stable for some time in water forms bright yellow sparingly soluble crystals.The monoimines of benzo- and tolu-quinone were prepared afresh to confirm their yellow colour. Benzoquinonechloroimine 0 /-\:NU is also yellow but benzo- quinonedi-imine is colourless whilst its dihydrochloride is yellow. Benzoquinonedichlorodi-imine CNr\:NC1 is colourless ; it Me{) NH .. \-/ \-/ORGANIU CHEMISTRY. i. 215 gives a salt only with concentrated sulphuric acid and this is yellow. Duroquinonedi-imine (annexed formula) wits obtained by oxidising diaminodurene with silver oxide in ether ; it forms colourless crystals not very sensitive to light m. p. 136135". It dissolves in dilute mineral B',l!''e acids giving bright yellow solutions which soon de- NH compose with deposition of duroquinone.The salts which can be obtained in crystalline form from ether are bright yellow. The results show that the carbonyl group is a stronger chromophore than the iminocarbonyl group *C:IW. This is also shown by the fact that whilst tetramethyldiaminobenzophenone is yellow auramine base is colourless. Determination of the Constitutional Form& of Colouring Matters from their Absorption Spectra. V. F. KEHRMANN and &It SANDOZ (Helv. Chim. Acta 1923 6 982-994).-The absorption spectra of the mono-acid and di-acid &\ salts of phenyl-ap-benzophenazonium (an- nexed formula) and of the mono- di- and t)\p\A$ tri-acid salts of nine of its monoamino-deriv- 1s 1 I atives have been measured. The mono-salt of v/?bx(xy/ the parent substance is yellow with orange fluorescence the di-salt violet; both have an ortho-quinonoid structure.The amino deriv- atives 1- 2- 3- and 4- form a group. Their mono-salts are bluish-green except that of the 3-amino-derivative which is brown ; their di- salts are yeilow similar to bhe mono-salt of the parent substance and their tri-salts deep red comparable with the di-salt of the parent. The 1-amino-compound does not form a tri-salt probably on account of steric hindrance. All these salts are given an ortho-quinonoid structure. The mono-salt of the 10-amino-derivative (violet) is probably also ortho-quinonoid. The 9- and 5-amino-compounds form another group; they behave similarly to aposafranine (A. 1920 ii 142). The mono-acid salt (scarlet) and the di-acid salt (green) are para-quinonoid whilst the tri-acid salt (violet) has the ortho-quinonoid structure.The fact that the di-acid salts can be diazotised indicates that the solutions contain a small amount of the yellow ortho-quinonoid di-acid salt in equilibrium with the para-quinonoid form. Two amino-derivatives the meta- and para- were prepared having the amino-group in the external benzene ring. Here the auxochromic effect of the amino-group is reduced to a minimum and there is little difEerence between the colours of the mono-acid salt and of the di-acid salt both being yellow in solution; the tri-acid salt is violet and all three are ortho-quinonoid. Curves are given showing the absorption spectra of all the salts examined. Spirans. XII. Heterocyclic Dispirans and the Nature of the Basic Properties of the Imino-group.D. RADULESCU (Bul. fw. ytiinfe Cluj 1922 1 356-360; from Chem. Zentr. 1923 iii 1081 ; cf. this vol. i 58).-Heterocyclic dispirans have NH E. H. R. I I 1 \/ ('\ E. H. R.i. 216 ABSTRACTS OF CHEMICAL PAPERS. been prepared by the author by the action of o-diamines on dichloro- bisdiketohydrindene (I). Piperazinebis-3-1 S-diketohydrindene- 2 2 3 2-diqiran CaH,,O4N2 (11) f o m yellow prisms m. p. 249" (corn.). The spiran (111) CHH140+N2 forms microcrystalline brown prisms m. p. 272" (corr.). Splran I11 is scarcely basic whilst the dispiran I1 is moderately basic. This is explained by Thiele's theory of partial valencies which is also applicable to the slight basicity of pyrrole and indole. Spirans with tertiary nitrogen are more basic.N N'-Dipiperidylbis-1 3-diketohydrindene (IV) forms orange prisms m. p. 174". The diethylamino-derivative of the latter forms yellow prisms 111. p. 129" and the dibenzylamino- derivative yellow needles m. p. 178". The author concludes that the hydroxy-derivatives corresponding with the amines must be strongly acid. The compound described by Gabriel and Leupold (A. 1898 i 481) as bisdiketohydrindene oxide (V) is really a spiran pinacone (VI). It is hydrolysed by weak acids and alkalis to diketohydrindene and its decomposition producfs and phthalonic acid. G. W. R. Reactions of certain Substituted Guanidines with Sulphur. G. BRUNI and T. G. LEM (Atti R. Accd. Lincei 1923 [v] 32 ii 313-316).-When heated together in a sealed tube a t 260- 270° s-diphenylguanidine and sulphur give a good yield of mer- captobenzthiazole.In aniline solution subjected to prolonged boiling in a reflux apparatus the reaction gives rise to little or no mercaptobenzthiazole but to anilinobenzthiazole (cf . Hofmann A. 1880 388; Jacobson and Frankenbacher A. 1891 1048; Hugershoff A. 1903 i 865; and Rassow and Diihle A. 1916 i 747) NIIPh:C(:NH)*NHPh+S=C,H,<~~C*~Ph+NH~ ; the wet$ derivative of anilinobenzthiazole has m. p. 162-163". Mercaptobenzthiazole k formed in good yield when phenyl- guanidine and in poor yield when s-triphenylguanidine is heatedORGAlUC CHEMISTRY. i. 217 in a sealed tube with sulphur a t 270" (cf. SebrelI and Bord this vol. i 89). T. H. P. Tetrapyrrlethanes. I. HANS FISCHER and M. SCHUBERT (Ber. 1923 56 [B] 2379-2384; cf.A 1923 i 707).-Glyoxal can be condensed with ethyl 2 4-dimethylpyrrole-3-carboxylate in alkaline or better in acid alcoholic solution to form tetra(3-curbethoxy- 2 4 -dimethyZ-5-pyrryZ)ethane (annexed formula) which crystallises in colourless leaflets m. p. EtO,C*fi-fiMe Mefi-fi*CO&t 282". It gives an intense MeC C-YH-C CMe green solution in acetic acid. Oxidation with ferric chloride gives 2 mols. of bis-2 4-di- " 1 2 methyl - 3 - carbethoxyppyl - methene whilst reduction with hydriodic acid in acetic acid solution gives a mixture of pyrroles containing 2 4-dimethyl- and 2 4 5-tri- methyl-pyrrole. Potassium methoxide converts the ethane com- pound into tetramethylpyrrole. It can also be hydrolysed to tetra(3-curboxy-2 4-dimethylpyrryl)ethaney small tetrahedral crystals m.p. 233" (decornp.) but this product is not identical with that obtained by condensing glyoxal with 2 4-dimethylpyrrole-3-carb- oxylic acid. The relationship of tetrapyrrylethane derivatives with blood- and bile-pigments is discussed the conclusion being that there is a closer relationship with the latter. This conclusion is supported by spectroscopic examination of copper and zinc salts of a number of dipyrrylmethene derivatives. E. H. R. ;.d Diallylxanthine. SOCIETY FOR CHE~CAI INDUSTRY IN BASLE (Swiss Pat. 97978; from Chem. Zentr. 1923 iv 830).-By heating 4 5-dianaino-2 6-dioxo-l 3-didlylpyrimidine obtained by con- densation of diallylcarbamide with cyanoacetic acid or ethyl cyanoacetate treatment with nitrous acid and reduction with formic acid 5 -form ylamino - 4 - amino-2 6 - dioxo- 1 3 - diallylpyr- imidine is obtained. This is heated with N sodium hydroxide solution at 100" and then acidified whereby 1 3-diallylxunthine m.p. 155-156" is obtained. The intermediate compound 4-amino- 6-0x0-5-oximino-1 3-diallylpyrimidine can also be obtained by direct condensation of s-diallylcarbamide with ethyl oximinocyano- acetate. G. W. R. 1 3 7-Triallylxanthine. SOCIETY FOR CHEMICAL INDUSTRY IN BASLE (Swiss Pat. 97979; from Chem. Zentr. 1923 iv 830; cf. preceding abstract).-1 3-Diallylxcanthine is alkylated for example by treatment with ally1 benzoate in the presence of ethyl- alcoholic potassium hydroxide a t 80". 1 3 7-TriaZlyZxanthine has m. p. 57-58'; b. p. 17G0/5 mm. G. W. R. Oxidation of Uric Acid with Ferrous Salts.I. M. H. PFALTZ (J. Amer. Chem. Soc. 1923 45 2980-2984; cf. this vol. i 210).-Cleavage of the uric acid molecule was accomplished by the systems ferrous sulphate-sodium hydrogen carbonate- air and sodium pentacyanoaquoferroate-air or oxygen but not m \/ I NHi. 218 ABSTRACTS OR' OHEMICAL PAPERS. by the system ferrous sulphate-oxygen. The action was similar to .that which occurred with pyrimidines. Action of Alkali on Substituted Uric Acids. I. 9-Phenyl- 1 3-dimethyluric Acid. E. S. GATEWOOD ( J . Amer. Chem. Soc. 1923 45 3056-3064; cf. A. 1923 i 253).-Thk substituted uric acid waa decomposed instantaneously a t 100" with 4N sodium hydroxide with the elimination of methylamine. On acidifying fhe solution carbon dioxide was evolved and crystals m. p.249-250"; of 3-phenylisohy~ntoin-5-~rboxyl-o-methy~mide separated. This was further decomposed by alkali into phenylcarbamide methylamine oxalic acid and formic acid whilst oxidation with hydrogen per- oxide in alkaline solution yielded 5- hydroxy- 3-phenylhydantoi n 5-mrboxyZ-o-methyZamide large thin rectangular plates m. p. 195-196:. This was further decomposed by alkali into methyl- lamine phenylcarbamide and meso-oxalic acid. 9-PhenyZ-1 7-di- methyluric acid was synthesised. It did not melt below 280" and was not affected by boiling with 4N sodium hydroxide for ten minutes. F. B. F. B. The Activation of Halogen and Methyl in Aromatic Com- pounds by the Azo-group *N:NR. W. BORSCHE and I. Exss (Ber. 1923 56 [S] 2353-2357).-Experiments with 4-chloro- 3-nitroazobenzene and 6-chloro-3-nitro-4'-methoxyazobenzene show that the azo-group in ortho- or para-posit,ion to the halogen imparts to it increased activity.These compounds react more readily with hydrazine ammonia aniline or sodium ethoxide than 0- or p-chloro- nitrobenzene although not so readily as chloro-2 4-dinitrobenzene. On the other hand benzeneazo-2-nitro-p-toluene does not react with benzaldehyde to form a stilbene derivative as does 2 4-dinitro- toluene. 4-ChZoro-3-nitroaxobenxene from 4-chloro-3-nitroaniline and nitrosobenzene forms brown needles m. p. 84". 6-Chloro-3-nitro- 4'-hydroxyazobenxene from diazotised 6-chloro-3-nitroaniline and phenol forms red needles m. p. 218"; it is methylated by methyl sulphate to 6-chloro-3-nitro-4'-methoxyuzobenzene deep yellow leaflets m.p. 103". Benzeneuxo-2-nitro-p-toZuene from 2-nitro-p-toluidine and nitrosobenzene forms brown needles m. p. 106". 3-Nitro-4-hydruzinmaxobenxene Ph*N,*C,H,(NO,)*NH*NH forms red needles m. p. 206" (decomp.); with acetophenone it forms the corresponding hydrazone Ph*~~*C,H,(NO,);~*~:CMePh red needles m. p. 195". 2-Nitro-4-benxeneo-4 -hydroxyazobenxene Ph*N,*C,H,(NO,)*N,*C,H,*OH obtained from the above hydrazine and p-benzoquinone forms brown needles m. p. 203" (decomp.); with quinoneoxime the hydrazine forms an oxilnehydrazone Ph.N,*C,~~(NO,).~=N:C,H,:N*OH a red crystalline powder m. p. 235" (decomp.). 3-Nitro-4-aminaczobenzene forms red needles m. p. 173-5". 3-Nitro-4-~.~eri&i~zobenxene7 by condensing 4-chloro-3-nitroazo- benzene with piperidhe forms orange-red tablets m.p. 64". 3-Nitro- 4-uniZinoaxobenzene Ph*N,*C,H,(NO,)*NHPh forms brown needles,ORGANIC CHEMISTRY. i. 219 m. p. .124". 3-Nilro-4-methoxyazobenxene crystallisea in orange-red needles m p. 107". 3 - N i t r o - 4 ' - m e t h - 6 - h ~ d ~ ~ z i n ~ z ~ e ~ e n e forms red needles m. p. 173" ; with panisaldehyde it gives the corresponding hydruzone red needles m. p. 208". 5-Nitro-2-amino-4'-methoxyazobenzene forms brownish-yellow needles m. p. 136". 3-Nitro-6 4'-dimethoxy- mobenzene form orange-yellow needles m. p. 123". Thiophenols. V. Salts and Additive Compounds of 00'-Azophenyl Methyl Sulphide and 00'-Azoxyphenyl Methyl Sulphide. K. BRAND and P. GROBEL (Ber. 1923,56 [B] 2563- 2567).-An extension of the work of Brand and Wirsing (A.1912 i 666; 1913 i 406) on the para-compounds to the ortho-series. SMe*C,H,*N:N*C,H,*SMe are described the perchlwute C14H14N2S2,HC104 bluish-violet needles which are very sensitive to moisture m. p. 154" ;. the sulphate C14HI N2S2,2H2S04 dark violet needles ; the very unstable hydro- chlori$e blue needles and its additive cornpotmds with stannic chloride C14H14N2S2,HCI,SnC1 blackish-violet needles with ferric chloride Ci~4H14N2S2,HCI,FeC1 dark violet almost black needles and mercuric chloride an unstable blue compound. 00'-Dimethylthiolazobenzene is transformed by methyl sulphate into the met hosu lphte N2(C 6H*4*SMe2*O*S O,*OMe) coarse crystals m. p. 189" (decomp.) which IS converted into the corresponding iodide Cl4H1,N2S2,2MeI long red needles m.p. 154" which readily loses methyl iodide when preserved the bromide m. p. 154" and the unstable thiocyanate decomp. 102-105". o-Nitrophenyl methyl sulphide ia reduced by sodium and methyl alcohol to 00'-dimethylthiohzoxybenzene crystals m. p. 72" from which the corresponding methsulphate C14H140N,S2,2Me2S04 yellow leaflets m. p. (indefinite) 167-169" (decomp.) after becoming red at 160-162" and the methiodide C,,H,,ON2S2,2MeI m. p. 103" (decomp.) are obtained. 00'-Dimethylthiolazobenzene and the azoxy-compound combine with iodine in chloroform solution to give the compounds m. p. 155" after evolving iodine at 140° and C14H,4.0N2S2,21 dark green needles m. p. 11 3-1 14" ; the corresponhg sulphonium methosulphates when treated in aqueous solution with iodine and potassium iodide yield the compounds C14H14N2S2,2MeI,212 m.p. 113-115" (decomp.) and C14H140N2S2,2~~eI,212 m. p. 193" (decomp.) after darkening a t 100". The following additive compounds are described the stibstance Cl4Hl4N2S2,AgNO3 from the components in boiling aqueous- alcoholic solution orange-coloured needles which is completely decomposed into its components by hot water ; the salt yellow needles ; oo'-diethylthiohzobenxene silver nitrate E. H. R. The f ollo wing s alfs of 00'- dimethyl t hiolazo benzene c14H 1dN2s2 2MeBr 14H 14N2s2,212 C14H 140N2s2Y AgNO CH 1 8N2S2,AgN03,i. 220 ABsTqAms or CKEMICBL PAPERS. orange-coloured leaflets ; o-nitrophenyl methyl sulphide silver nitrade N0,*C,H4-SMe,AgN0 yellow leaflets m p. 122'. H. W.The Influence of Sulphonic Groups on the Colour of ,Azo- dyes. W. M E ~ Y (Helw. Chim. Acta 1923 6 931-935).-To determine the influence of the num%er and position of sulphonic groups on the colour of azo-dyes spectroscopic comparison was made of a large number of secondary bisazo-dyes in which the first component was an aniline mono- or di-sulphonic or a naphthyl- amine mono- di- or tri-sulphonic acid the middle component was cresidine (3-amino-p-cresol ether) and the end component an a- or p-naphthol mono- di- or tri-sulphonic acid. In every case an additional sulphonic group in either the first or the end component deepens the colour but the effect diminishes as the number of sulphonic groups increases. In the naphtholsulphonic acids the effect of changing the position of the sulphonic group is smaller than the effect of an additional group. Similar results were obtained with a number of monoazo- and trisazo-dyes. As an example of the effect of additional sulphonic groups the dye from sulphanilic acid 3-amino-p-cresol ether and 1 4-naphtholsulphonic acid is red whilst the corresponding dye using 1 3 6 8-naphtholtrisulphonic acid is violet. An absorption band may be shifted 10 to 20 p~ by a single sulphonic group the influence being generally greater m the end component than in the first component. These results apply both to aqueous and to .alcoholic solutions; in sulphuric acid and formic acid solutions the absorption bands are shifted in the opposite direction by sulphonic @oups.[Cf. B. 86.1 E. H. R. Certain Double Salts of Diazo-compounds with Lead Tetrachloride.E. SAKELLARIOS (Ber. 1923 56 [B] 2536- 2541) .-A series of double salts of the general formula (ArN,Cl),PbCl has been prepared. They are generally yellow in colour and insoluble in water. They are decomposed when heated with water with production of phenols. Thermal decomposition in the presence of inert solvents such as carbon tetrachloride or benzene gives p-chloronitrobenzene from the p-nitrodiazonium compound and mixtures of chlorinated benzenes from the benzenediazonium salt. The p-tolyl- m-nitrophenyl- and p-chlorophenyl-diazonium compounds are remarkably stable towards heat. The double salts dissolve in concentrated sulphuric acid with separation of lead tetrachloride and production of the diazonium sulphate.They couple immediately with an alkaline solution of p-naphthol and retain this power after being preserved during many months in a desiccator ; an exception is however provided by the benzene- diazonium salt which undergoes rapid decomposition. Direct sunlight and increased temperature facilitate the decomposition in a remarkable degree. The lead tetrachloride solution is prepared by dissolving lead carbonate in concentrated hydrochloric acid and passing chlorine into the mixture a t 10" until the suspended lead chloride is dissolved ; exces8 of chlorine is removed in a current of air. The solution thusORGANIC CHEMISTRY. i. 221 prepared is added to the requisite diazonium solution a t -6' when the double salts separate. The following individual substances are described the salt (PhN,Cl),PbC14 straw-yellow leaflets and the similarly constituted compouotds from p-toluidine (a yellow crystalline powder) p-chloroaniline (yellow leaflets) p-nitroaniline (yellow leaflets) and m-nitroaniline Ethylamine hydrochloride and lead tetrachloride give the compound (EtNH,*HCl),PbCl yellow leaflets which is decomposed by water with formation of ethyldichloroamine b.p. 89'. H. W. Characterisation of Aminoazo-derivatives. G. CHARRIER and A. BERETTA (Gaxxettu 1923 53 729-760).-!l!he authors find that the reaction suggested by Nietzki and Ernst (A. 1890 11 14) for charactmising the primary aromatic amino-group (cf. Reitzenstein A. 1903 i 815; Meigen A. 1908 i 580; Kiichel Diss. Giessen 1N9) and based on the action of 1-chloro-2 44%- nitrobenzene in alcoholic solution and in presence of sodium acetate followed by reduction of the resulting 2 4-dinitrodiarylamino- derivative to nitroaminodiarylamino-compound by meam of sodium sulphide is general for all aminoazo-derivatives irrespective of the position of the amino-group to the azo-group.The yield of the condensation product is moderately good from the p- and m-arninoazo-compounds but less from the ortho-compounds especially those of the naphthalene series. However no resin is formed and the product is usually almost insoluble in alcohol so that purification is easy. [With A. NANI L. ALBANI A. DE LEONIBUS G. DRISALDI P. PAVESI and 0. ~~v~zz~~1.]-2'-Benxeneaxo-2 4-dinitrodiphenyl- amine ~h:N*C6H4*NH0C6H~(NO,) obtained by the action of 1-chloro-2 4-dinitrobenzene on 0-aminoazobenzene forms slender orange-yellow needles m.p. 206' dissolves in concentrated sulphuric acid with a green coloration and resists boiling acetic anhydride. When suspended in alcohol and treated with sodium sulphide it yields 2'- benxeneuxo-4-nitro-2-aminodiphenylumine NPh:N*C,H,*NH*C 6H3( NH,)*NO which crystallises in slender deep red needles m. p. El0 and gives a benmyZ derivative C,,H,,O,N crystallising in slender yellow needles m. p. 199". C ,H,Me*N:N*C ,H,Me*~*C,H,( NO,) prepared from o-tolueneazo-p-toluidine forms lustrous red needles m. p. 232" gives a green solution in concentrated sulphuric acid and on reduction with sodium sulphide yields 2'-p-toluenmxo- 4-nitro-2-amino-4'-methyldi~henylamineY CtH4Me*N:N*C,H3Me*NH*C6H3( NH,)*NO which crystallises in reddish-brown needles m.p. 166' and gives a benzoyl compound C2,H2303N5 separating in yellow needles m. p. 206'. m-Aminoazobenzene m y be obtained in satisfactory yield by benzoylating m-nitroaniline reducing the m-nitrobenzanilide to m-aminobenzanilide and converting the latter by means of nitroso- 2' -p-Tolueneam-2 ; 4-dinitro -4'-meth yldiphen ylumine,i. 222 ABSTRACTS OR' m C A L PAPEW. benzene into the benzoyl derivative of m-aminoazobenzene. The melting point of m-aminoazobenzene given by Mills (T. 1895 67 917) as 56-57" is found to be 62". NPh:N*C ,H,*NH*C sH3( NO,) 2 prepared from m-aminoazobenzene crystalllses in orange-yellow leaflets m. p. 162" and dissolves in ooncentrated sulphuric acid giving a red coloration.4'-Benzeneazo-2 4-dinitrodiphenylamine prepared from p-amino- azobenzene has m. p. 176" (cf. Walther and Lehmann A. 1904 i 352). 4' - Benzeneam - 4-nitro-2 -aminodiphen ylamine C *HI ,Q2N obtained by reducing the preceding compound forms minute deep red crystals m. p. 164"; its acetyl compound crystallises in slender yellow needles m. p. 153" and its benxoyl derivative in yellow needles m. p. 226". prepared from o-tolueneazo-o-toluidine forms deep red needles m. p. 186" dissolves in concentrated sulphuric acid to a reddish- violet solution and on reduction with sodium sulphide and alcohol yields 4'-Q -tolueneuxo-4-nitro-2-amino-2'-methyldiphen ylamine which separates in reddish-brown needles m. p. 159". 4'-p-Toluewxo- 2 4-dinitro-2'-methyldiphenylamine prepared from p-tolueneazo- o-toluidine crystallises in slender lustrous red needles m.p. 151" and dissolves in concentrated sulphuric acid giving a violet -red coloration. The actioa of I-chloro-2 4-dinitrobenzene on m-diaminoazo- benzenes results in the replacement by 2 4-dinitrophenyl of a hydrogen atom of the amino-group situate in the para-position to the azo-group. The amino-group in the ortho-position to the azo-group does not enter into the reaction even when the chloro- dinitrobenzene is taken in large excess; this appears to be due to the fact that the mono-condensation product is insoluble in alcohol and is hence removed from the sphere of reaction. The resulting diphenylamine derivatives have constitutions analogous to (I) and on oxidation yield the corresponding triazole compounds (11) 3'-Benxeneam-2 4-dinitrodiphenylamine 4' -0 - Tolueneazo -2 4-d initro-2' -methyldiphen ylamine C,H4Me*N:N*C,H3?le =NH*C,H3( NO,) 2 /-\-NH-/-\-N:Nph + (1.) L/ NO2 NH2 (11.1 N 0 2 ~ > - N H - r ~ ~ > N P h .\-/ N They readily yield monoacetyl and monobenzoyl derivatives the substituent groups entering the amino-group in the ortho-position to the azo-group. By sodium sulphide in alcoholic solution they are reduced to benzeneazonitrodiaminodiarylamines of the general formula NO2<:>-NH-<3-N:NPh. NO2 NHZ NHZOBGANICl cYHEMrsTBY. i. 223 4'- Benxeneaxo-2 4 -dinit TO- 3'-aminodiphenylami n e NPh:NS?*H3( NH2) *NH*C,H,( NO,) obtained by the action of 1-chloro-2 4-dinitrobenzene on 4-benzene- azo-1 3-diaminobenzene (chrysoidine) crystallises in bright red needles m.p. 187" and gives a violet solution in concentrated sulphuric acid ; its acetyl compound forms slender orange-red needles m. p. 218" and its benzoyl compound silky red needles m. p. 241 ". N-Phenyl-2' 4'-dinitrophenylamino(3)benztriaxole (formula 11 above) crystallises in slender yellow nedes m. p. 188" and dissolves in concentrated sulphuric acid giving a reddish- yellow coloration. c ,H4C1*N:N*C6H3( NH,)*NH*C,R,( NO,) prepared from 4-p-chlorobenzeneazo-1 3-diaminobenzene forms lustrous reddish-brown leaflets m. p. 220" and gives a blue solution in concentrated sulphuric acid. ( p-chlorochrysoidine) CGH4Cl*N:N*C61rT,(NH,) prepared by the interaction of p-chloro- phenyldiazonium chloride on m-phenylenediamine hydrochloride erystallises in lustrous yellow needles m.p. 140" and its hydro- chloride in slender red needles m. p. 225". 4-p-Brmbenzeneum- 1 3-diaminobenxene (p-brmchrysoidine) C,,H11N4Br similarly prepared forms lustrous golden-yellow needles m. p. 155" and its hydrochloride red needles m. p. 213". 4'-p-Bromobenzeneum- 2 4-dinitro-3'-aminodi~enylamine C18H.1304N6Br prepared from the preceding compound forms lustrous brick-red needles m. p. 218" and dissolves in concenkrated sulphuric acid giving a blue coloration. ~ h ~ * C 6 H ~ e ( N H 2 ) * ~ o C 6 H 3 ( N 0 2 ) forms deep red needles m. p. 273-274" and dissolves to an emerald-green solution in concentrated sulphuric acid ; its acetyl derivative forms orange-yellow needles m. p. 196" and its benzoyl derivative orange-red needles M.p. 252". 4'-Benxenmz0-4-nitro- 2 3'-diamino-6'-methyldiphenylamine C,,H180&Y6 formed on reduction of the preceding compound by means of sodium sulphide and alcohol crystallises in lustrous garnet-red prisms with metallic reflection m. p. 244". 4 - p - Chhobenxeneam - 1 3 - diamino-6-methylbenzene (p - chloro- meth ykhrysoidine) C ,H4ClaN:N*C ,H&e ( NH,) 2 prepared from p-chlorophenyldiazonium chloride and m-tolylenedismine hydro- chloride forms lustrous golden-yellow leaflets m. p. 169" and its hydrochloride lustrous red needles m. p. 235". 4'-p-chloro- benzeneam-2 4-dinitro-3'-amino-6'-~thy~iphenylamine prepared from the preceding compound crystallises in reddish- brown lustrous needles m. p. 286" and dissolves in concentrated sulphuric acid giving a green coloration ; its acetyl compound forms slender orange-yellow needles m.p. 248" and its benxoyl com- pound orange needles m. p. 285". On reduction with sodium sulphide in alcoholic solution it gives 4'-p-chlorobenxeneum-4-nitro- 4'-p-~~lorobenxeneaxo-2 4-dinitro-3'-amimdiphenylamine 4-p- Chlorobenxeneaxo- 1 ; 3-diaminobenzene 4'- Benzeneam -2 4 -din itr0-3'-amino- 6'-methyldiphen ylama'ne c19H1504N6c1,i. 224 ABSTRACTS OF c,xiElmCl& PISPEBS. 2 3'-diamim-6'-methyZdiphenylamine C,,H,,O~,,Cl whicth forms slender reddish-brown crystals m. p. 262". 4-p-Bromobenzeneaxo- 1 3 -& iamino- 6-mth ylbenxene ( p- b romometh yhhrysoidine) crystallises in lustrous golden-yellow leaflets m. p. 177" and its hydrmhhide in lustrous red needles m.p. 236". 4'-p-Bromo- benzeneurn-2 4-dinitro-3'-amino-6'-methyl&iphenykcmine prepared from the preceding compound crystallises in brownish- red leaflets m. p. 290" and yields a green solution in sulphuric acid ; its acetyl derivative forms orange needles m. p. 242" and its benmyl derivative orange-yellow needles m. p. 275". 4'-p-Bromo- benzeneam-4-nitro-2 ; 3'-diamir~-6'-methyldiphenylamine forms reddish-brown leaflets m. p. 265". CloH7*N:N-C,H$fe( PU'R,) prepared from a-naphthyldiazonium chloride on m,tolylenediamine hydrochloride crystallises in brown needles with green metallic reflection m. p. 148". 4'-u-Naphthaleneuxo-2 4-dinitro-3'-amino- 6'-meth yMiphen y kcmine C,H ,ON :N*C sH2Me (NH,)*NH-C 6H3( NO,) obtained from the preceding compound forms reddish-brown needles with violet metallic reflection m.p. 286"; its acetyl compound forms red needles m. p. 268" and its benxoyl compound yellow needles m. p. 246". 4'-a-NaphtbZeneam- 4-nitro-2 3'-diamino-i3'-methyldiphenylamine C,H,O3 forms reddish-brown needles m. p. 214". 4-p-Napht7uzkneaxo-1 3-di- amino- 6-meth ylbenzene ( (3 -mphth ylrneth ylchr ysoidine) c17H16N4 crystafises in yellow needles m. p. 242". 4 - p - N a p h M w z o - 2 4-dinitr0-3'-amino-6'-~thyMiphen~kcm~ne forms a reddish-brown crystalline powder chars without melting above 300" and gives a green solution in concentrated sulphuric acid ; its acetyl compound sepmtes in slender yellow needles m. p. 272" and its benxoyl compound in orange needles m. p. 267O. 4-p-Naphthaleneam-4- nitro-2 3'-diamino-6'-methyldiphenylamine C,H,Oa forms minute reddish-brown crystals m.p. 261" a - Benzeneax0 - p - nuphthyl - 2 ; 4 - dinitrophenylumine (annexed formula) prepared by the action of 1-chloro- 2 4-dinitrobenzene on a-benzeneazo- p- naphthylamine crystallises in slender red needles m. p. 285" and gives a greenish- / \-N:NPh \- &H.c,H,(NO,) blue solution in concentrated sulphuric acid. a- Benzeneam- -naphth yl-4-nitro-2- amimphenylumine Nph :N~ClooH,*NH*C,H,(NH,).N02 forms reddish-brown needles m. p. 147 . a-o-Tolueneam-~-~phthyl-2 4-dinitrophenylumine7 c&~704~5 obtained from a-o-tolueneazo-P-naphthylamine crystallmea m slender red needles m. p. 223" and dissolves in Concentrated sulphuric acid to a greenish-blue solution. a-m-ToZzcemm- ~-nuphi?hykcmine has m.p. 103-104°. a-m-Tolueneaxo- p-naphthyl- 2 r4-dinitrophenylamine forms slender red needles m. p. 845" C13H 13N4Br9 '1gHl 5°4N6Br 1f+H170$ 6Br 9 4- U- Naphthaleneaxo- 1 3-diamino-6-methylbenzene c>ORQAWIO OHEMZSTBY. i. 225 and 'VW a greenish-blue solution in concentrated sulphuric acid. a-m-!f&ueWzo- p - ~ ~ h t h y l - 4 - n i t ~ ~ - ~ - ~ ~ i ~ ~ h is obtained as a dark red microcrystalline powder m. p. 116'. a-p-Tolueneaxo-p-~phthyl-2 ; 4-dinitrodiphenylamine crystabes in slender red needles m. p. 280" and dissolves in concentrated sulphuric acid to a green solution. a-p-Tolueneazo- p-mphthyl- 4-nitro-2-aminophenylamine forms microscopic reddish-brown crystals m. p. 155". crystallises in slender bright red needles m.p. 278" and dissolves in Concentrated sulphuric acid to a deep blue solution. a-p-Brm- benxeneaxo- p-nuphthylamine C,H4Br*N:N*CloH,-~2 forms red crystals m. p. 135-136". a-p-Bromobenxeneazo-p-mphthyl-2 4-di- nitrophenylumine crystallises in slender red needles m. p. 263" and gives a deep blue solution in concentrated sulphuric acid. 4-Benzeneum- a-nuphth yl-2 4-dinitrophen ylumine obtained from 4-benzeneazo- a-naphthylamine forms long bright-red silky needles m. p. 200" and colours concentrated sulphuric acid bright blue. 4 - Benxeneaxo - a - nupht h y 1-4- nitro - 2 - amimphen ylurnine se ar at es in slender red needles m. p. 216". 4-0-Tolueneaxo-U-naphthyl-2 4-dinitrophenylamine C,H,Me*~:N*CloH,~NH*C,H,(NO )2 forms lustrous reddish-brown crystals m. p. 824' and dissolves in concentrated sulphuric acid to a deep blue solution.4-p-Tohem- am-a-nuphthyl-2 4-dinitrophenyhmine crystauses in lustrous bright red needles m. p. 207" and gives a blue solution in concentrated sulphuric acid. 4-p-Tolueneaxo-a-naphthyl-4-nitro-2- amimphenylumine separates in reddish-brown crystals m. 4-o-Nitrobenzeneam-a-nuphthyluntine N0,*C,H4*N:NClo s a M l [ e crystafises in slender metallic green needles m. p. 165". 4-a-"ttPo- benxeneuxo- a-mphthyl-2 4dinitrophenylumine forms a reddish-brown microcrystalline powder m. p. 212" and yields a blue solution in concentrated sulphuric acid. 4-p-Nitro- benxeneum-a-nuphthylumine crystallises in deep red needles with metallic reflection m. p. 252". 4-p-Nitrobenxeneaxo-a-~~AthyZ- 2 4-dinitrophenylamine separates in slender brownish-red needles m.p. 263" and dissolves in concentrated sulphuric acid giving a violet coloration. c23H190a5 a-p-Chlorobenxeneaxo-p-mphthyl-2 4-dinitrophenylamine C!22H1404N5C1 minute reddish-brown crystals m. p. 181" and its acety P compound I$* 2ooo* NO,*C,H4*N:N*Cl,H,'NH0C,H,(NO,) 4-p - Chlorobenzeneuxo - a - napht h y 1 - 2 4 -dinitrop henyhmine C22H1404N5c1 forms slender orange needles m. p. 258" and gives a peen solution in concentrated sulphuric acid. 4-p-Chlorobenxeneaxo-a-nccphth2/1- 4-nitro-2-aminophenyhmine separates in slender deep red crystals m. p. 228". crpfrtllises in slender brownish-red needles m. p. 203" and dia- 4- a-Naphthaleneuxo- a-mphthyl-2 4-dinitrophenyhmk 'w*. q. 1 C,H,*N:N*C~oH,.NH*C,H,(NO2) VOL. OXXVI.i. ii. 226 ABSTRA@IS OF CHEMICAL PAPERS. solves to a blue solution in concentrated sulphuric acid. 4-8- Na~hthaleneaxo-a-nalpht~yl-2 4dinitrophenylamine forms reddish- brown needles m. p. 241" and dissolves in concentrated sulphuric acid giving a blue solution. E. J. POTH and J. R. BAILEY (J. Amer. Chem. Xoc. 1923 45 3001-3008; cf. A. 1922 i 880).- Semicarbazones were reduced to $he corresponding semicarbazides under a pressure of 1+-23. atm. of hydrogen in the presence of colloidal platinum. The minimum proportion of platinum necessary for efficient reaction varied considerably and when the reduction produced a basic substance the yield was increased by the addition of acid ; the amount of acid required varied greatly. The following semicarbazides were prepared.~enchylsemicarbazide short needles m. p. 181". Benxoylfenchylsemicarbaxide a crystalline powder decomp. 226". a-Phenylcarbamylfenchylsemicarbazide thin plates m. p. 192". Car~ome~zthylsemica~~bazide thin plates m. p. 126" (decomp.) and its hydrochloride short needles decomp. 186". Benxoylcarvomenthylsenzicarbazide m. p. 235". a-Phen ylcarbanzyl- carvomenthylsemicarbaxide clusters of radiating needles m. p. 205". cycloHexylsenzicarbazide needles decomp. 185" and its hydro- chloride m. p. 176-178'. Benzoylcyclo7~exylsemicarbazide fine needles m. p. 267" (decomp.). a-Phenylcarbamylcyclohexykemi- curbazide microscopic short needles decomp. 236". Benzylsemi- carbazide. Benzoylnzenthylsemicarbazide a crystalline powder m. p. 2 16" (decomp.). u- Phenylcarbamylment hylsemicarbazide radiating needles decomp.184". In the preparation of isopropyl bornyl and menthyl semicarbazides the proportion of colloidal platinum may be considerably reduced with advantage. The following triazoles were obtained by boiling the corresponding acyl semicarbazide with caustic alkali. 3-Hydroxy-5-phenyZ-l-fenchyltriazole thick triangular plates m. p. 234". 3-Hydroxy-5-phenyl-l-carz;omenthyl- triazole thin plates m. p. 187". 3-Hydroxy-l-cyclohexyl-5-phenyl- triaxole slender prisms m. p. 232-234". T. H. P. Reduction of Semicarbazones. F. B. Behaviour of Semicarbazides at Elevated Temperatures. E. J. POTH and J. R. BAILEY ( J . Amer. Chem. Soc. 1923,45,3008- 3012 ; cf. preceding abstract).-cycloHexylsemicarbazide when heated a t 200" during twelve minutes yielded dicyclohexylcurbaxide (I) CO(NH*NH*C,H,,) plates m.p. 187" and unchanged semi- carbazide. When the semicarbazide was heated for one and a half hours at 180-185" the products were cyclohexyluraxok (11) ~H-co>N*c6H11 thin prismatic plates m. p. 271" and c 0.m prisms m. p. 197"; (I) was obtained in good yield when the semi- carbazide was mixed wit'h half its weight of urethane and heated at 160° (11) was prepared by heating the semicarbazide and carbamide in molecular proportions and (111) by decomposing the hydro- chloride of the corresponding semicarbazide. F. B.ORGANIC CHEMISTRY. i. 227 Arylazides. I. Conversion of p-Methylarylazides into Homologues of Quinol in Presence and Absence of Phenol. E. BAMBERGER and J. BRUN (Helw. Chim.Acta 1923,6,935-941).- Some further experiments on the conversion of arylazides into homologues of quinol (cf. A. 1921 i 716) are described. p-Tolyl- azide (5 g.) boiled with dilute sulphuric acid (1 3 by volume) gives about 1 g. of toluquinol with some p-toluidine a strong odour of cresol but no aminocresol. From 25 g. of m-4-xylylazide boiled for nine hours with dilute sulphuric acid there mere obtained 1.8 g. 1 3-dimethylquinol,O*2 g. as-m-xylenol 4.2 g. as-m-xylidine and a considerable quantity of amorphous acids bases and resin. When p-tolylazidc was boiled as before in dilute acid in presence of excess of phenol from 6 g. of azide 4.27 g. of p-hydroxyphenyl-p-tolyl- amine was obtained and about 0-32 g. of toluquinol. The theory of the reactions involved has been previously discussed (Em.cit.). E. H. R. Arylazides. 11. The Conversion of p-Methylarylazides into Imino-tpquinols and q-Quinols. E. BAMBERGER and J. BRTTN (HeZv. C'him. Acta 1923 6 942-951).-Practical details are given of experiment,s previously reported (A. 1921 i 716). E. H. R. Partial Decomposition of Proteins. E. ABDERHALDEN (2. physiol. Chem. 1923 131 284-295) .-A general description is given of the method of isolating the products of the partial hydrolysis of proteins. The protein is treated with 70% sulphuric acid at a low temperature e.g. a t the ordinary temperature or at blood heat and the course of hydrolysis is followed by estimating the amino-nitrogen and comparing it with the total nitrogen of which an estimation is made on the original protein.The sulphuric acid is removed as barium sulphate and the filtrate is concentrated in a vacuum. If the prdduct is a solid it is extracted directly with ether in a Soxhlet apparatus ; if it is a syrup it is mixed with sand to a thick consistency and t'hen extracted. It is afterwards extracted in turn with ethyl acetate acetone or methyl alcohol and if necessary with other solvents such as chloroform or butyl alcohol. It is usually possible after evaporation of the solvent to obtain the fractions in a crystalline form and they are purified according to their particular composition. In particular cases variations a t any stage may be advisable. In an attempt to obtain the maximum yield of d-alanylglycine anhydride from silk clippings the residue after hydrolysis removal of sulphuric acid and concentration was treated with alcohol and hydrogen chloride evaporated to dryness arid the residue dis- solved in alcohol.The ammonium chloride separating at once on saturation with ammonia was filtered off. On keeping a t 37" a series of crystalline fractions was obtained which were extracted in a Soxhlet apparatus with ethyl acetate. Eighty-five g. cf pure glycylalanine anhydride was obtained from 1 kg. of silk clippings. Small quantities of glycyl-Z-tyrosine anhydride and of d-alanyl anhydride (dimethylpiperzzine) were also obtained i2i 228 ABSTRACTS OF UHEMICAL PAPERS. One kg. of casein was hydrolysed with 10% sulphuric acid at 80° and the product extracted with ethyl acetate when 2.5 g. of crystals were obtained decomp.280° and this compound proved to be I-Ieucyl-d-valine anhydride. On extracting the residue from the ethyl acetate extraction with acetone crystals were obtained which on hydrolysis yielded leucine valine and glutamic acid but there was no guarantee that the compound was pure. On further extraction with methyl alcohol d-alanyl-Z-leucine was obtained along with a crystalline compound C,,H,O,N m. p. 192" [01] -183" which yielded proline I-leucine and d-alanine on hydrolysis. It is apparently an anhydride formed from these acids by the elimination of 3 mob. of water. The Formation of Carbon Dioxide during the Breakdown of Proteins in the Autoclave. V. S. SADIKOV (Biochem. Z. l923,143,492495).-The method used for the catalytic hydrolysis of proteins by dilute hydrochloric acid under pressure (A.1923 i 867) leads in the case of gelatin to a slight formation of carbon dioxide amounting to 2% of the protein. It is suggested that this arises by decarboxylation of the amino-acids under the conditions used. Increasing pressure favours carbon dioxide formation. Nitrogen is also present in the residual gas in the autoclave and oxygen is largely absorbed during the process. V. 8. SADIKOV (Biochem. Z. 1923 143 496-503).-Arising from the author's work on the catalytic hydrolysis of proteins under pressure (cf. preceding abstract) it is found that a retention of nitrogen results when this is carried out in an atmosphere of the gas. Dextrose gives negative results but a fixation is observed in the case of aspartic acid and to a less extent in the case of glycine.Similar treatment of fumaric and succinic acids in the autoclave leads to a notable retention of nitrogen which is ascribed to the unsaturated compounds arising from these acids. Separation of Proteins of White of Egg by the Acetone Method. M. PIETTRE (Compt. rend. 1924,178,91-93).-Details are given for the separation of the proteins of white of egg into a globulin ovalbumin (coagulating at 52-5-53" and having uD -41*25") and a glucoprotein. The latter (aD -62.47") reduces boiling Fehling's solution and a t a moderate temperature mercury and bismuth salts (in presence of alkali) and ammoniacal silver nitrate. E. E. T. A Furtber Method of Determining the Isoelectric Point of Proteins and its Application to the Serum-albumins of Various Animals.L. WCHAELIS and T. NAKASHIMA (Biochem. Z. 1923 143 484-491).-The optimum precipitation point of a mixture of mastic and gelatin in the presence of an acetate buffer approaches the isoelectric point of the latter as its relative amount is increased. This observation is made the basis of it method of determining the isoelectric points of various serum-albumins. To a series of tubes containing mastic sol and an acetate buffer at W. 0. K. J. P. Hydrolysis in an Autoclave containing Nitrogen. J. P.ORGANIC CHEMISTRY. i. 229 varying known m increasing amounts of the albumin are added and the p H of the zone of optimum precipitation is observed to rise to a constant value beyond which addition of the albumin produces no further shift. This maximum p~ corresponds with the koelectrio point.The following values for the albumins examined were found ox and guinea-pig 4.65 ; dog 4.66 ; puppy 4.67; turtle and man 4-68. J. P. Nature of the Reaction between Carbophosphide and Blood- serum. G. CTJNEO (Atti R. A d . fincei 1923 [v] 32 fi 294- 298; cf. this vol. i loo).-The interaction of carbophosphide and blood-serum yields a phospho-albumin which contains phosphorus in organic combination and either in the most highly oxidised state or as metaphosphoric acid. Since further nuclein bases occur among its products of hydrolysis this phospho-albumin probably owe8 its existence to a hydrolytic process coupled with atmospheric oxidation as a result of which the phosphorus of the carbophosphide enters the protein molecule as phosphoric oxide or as a hydrate of the latter.Nature of the Reaction between Carbophosphide and Blood- serurn. G . CUNEO (Atti R. A d . Lincei 1923 [v] 32 ii 353- 357; cf. this vol. i 100 and preceding abstract).-The author has now investigated the behaviour of blood-serum towards a number of d8erent compounds some free from and others con- taining phosphorus. Certain of these compounds do not denature the serum albumin molecule which remains phosphorus-free normally digestible by gastric juice and without hindering effect on putrefactive processes. On the other hand phosphorus di- iodide ethylphosphine and sodium hypochlorite effect denaturation of the protein molecule the reaction like that produced by carbo- phosphide being probably of the nature of an auto-oxidation. The reaction of the serum-albumin with hypochlorite is complex but the principal product is devoid of iron and phosphorus and exhibits the chemical and biological properties of the nucleic acids.Formation of Methaemoglobin. 11. W. HEUBNER and H. RHODE. 111. R. MEIER. IV. W. HEUBNER and R. MEIER. V. W. HEUBNEE R. MEIER and H. RHODE (Arch. mpt. Puth. Phrrn. 1923 100 117-127 128-136 137-148 14&161).- I. A comparison of various substances which convert oxyhaemo- globin into methsmoglobin shows that the actions of potassium ferricyanide and of p-benzoquinone are almost identical in this respect. Although the compound of haemoglobin with nitric oxide is resistant to the aotion of reducing agents it may be decomposed by means of indifferent gases and also by dialysis. IL Optical and gasometric observations show that by the use of ferricyanide or of p-benzoquinone in varying proportions it is possible to produoe a mixture of oxyhzemoglobin and me-1110- globin with bhe two conetituenfs in any desired propartiOnS.The T. H. P. T. H. P.i. 230 ABSmACTS OF CHEMICAL PAPERS. last traces of oxyhaemoglobin are converted into methaemoglobin more easily by ferricyanide than by p-benzoquinone. 111. In the presence of haemogfobin quinol p-aminophenol and hydrazobenzene are rapidly oxidised by atmospheric oxygen. Whereaa the oxidation products of the first two of these substances are active in forming methaemoglobin that of hydrazobenzene is not ; the formation of methzemoglobin by hydrazobenzene there- fore must be due to an activation of the atmospheric oxygen in the process of oxidation of this substance.Nitrosobenzene converts oxyhaemoglobin in part into methaemo- globin and in part into reduced haemoglobin. IV. Phenylhydroxylamine converts oxyhzemoglobin into methaemoglobin and is itself simultaneously converted into azoxybenzene ; excess of phenylhydroxylamine in this reaction reduces the methaemoglobin first formed t o haemoglobin. Reduced haemoglobin is unaltered optically by phenylhydroxylamine. m-Nitrophenylhydroxylamine reacts similarly to phenylhydroxyl- amine but not so strongly. The Natural Porphyrins. IV. Ooporphyrin. HANS FISCHER and F. KOGL (2. physiol. Chem. 1923 131 241-261).-Three hundred g. of gull's egg-shells were extracted with methyl alcohol containing hydrogen chloride the extract was concentrated made alkaline with sodium carbonate and the precipitate washed and dried a t 100".The material was extracted with chloroform which was then distilled off and the residue dissolved in a little chloroform precipitated by the addition of light petroleum collected on a filter and dried. It was then again dissolved in a little chloroform and boiling methyl alcohol was added. Oopor- phyrin dimethyl ester C,H,,O,N,( OMe) was obtained as leaflets grouped in rosettes m. p. 225-230'. The absorption bands of this compound are described at length. They resemble those of Kammerer's porphyrin. When ooporphyrin methyl ester from the shell of the gull or of the plover egg is treated with powdered iron in boiling acetic acid crystals are obtained which although similar are not identical crystallographically and spectroscopically.The absorption bands of solutions of ooporphyrin froin the egg-shells of various species of birds are described. The Precipitation of the Lactoproteins by Copper Salts. A. J. J. VANDEVELDE (Bull. SOC. chim. Belg. 1923 32 376-386). -The lactoproteins have been precipitated by the addition of various salts of copper (sulphate chloride nitrate and acetate) and the effect of washing the precipitates by water has been examined. With the sulphate chloride and nitrate the results obtained are practically identical. Apart from the case of the .acetate pre- cipitate washing by water appears to have no influence on the composition of the precipitate and its copper content. A second series of experiments was carried out to determine the composition of the solid and liquid phases forming the primitive complex The results obtained show that the quantity of copper in the pre- cipitates increases as the initial concentration of the copper increases C. R.H. W. 0. K.ORGANIC CHEMISTRY. i. 231 whilst the ratio of the quantity of copper precipitated to the total quantity of copper employed diminishes generally in proportion as the initial concentration of the copper increases. The anion present is shown to have a visibly marked effect on the precipitation of the metallic kation. Galeotti's conclusions (A 1904 i 355) as to the equilibrium between the proteins and sulphate of copper are not upheld. F. G. P. S. J. THANN- HAUSER (2. physiol.Chem. 1923 131 296-303; cf. Feulgen and Rosenbeck A. 1923 i 618 and Feulgen ibid. i 964; al80 Thann- hauser and Sachs A 1920 i 201).-The author has found that after hydrolysing triphosphonucleic acid by alkali the adenosine may be precipitated as picrate and has obtained almost the theo- retical yield of this picrate. He does not admit the validity of the criticism of Feulgen (Zoc. cit.) who doubts the existence of the acid but he considers that triphosphonucleic acid is with great probability a pure substance. The author also criticises the results of Feulgen (cf. loc. cit.) regarding thymic acid. Influence of Time on the Physico-chemical Properties of Gelatin Solutions. R. DE IZAGUIRRE (Kolloid 2.' 1923 33 337-347) .-The effect of time on the viscosity multi-rotation and the action of electrolytes on gelatin solutions has been examined.It is shown that in the presence of hydrochloric acid the influence of time on the viscosity of gelatin solutions passes through a minimum with increasing concentration of hydrochloric acid. This minimum corresponds with the initial viscosity of the solution. The same regularity is found with the time change of the osmotic pressure whereby the change with time is smaller the larger the osmotic pressure. Since the maximum of the viscosity and the osmotic pressilre is closely connected with the swelling it follows that the time change takes place in the opposite sense to the swelling that is the greater the degree of swelling the smaller the time change. Since the viscosity serves as a measure of the gelatinisation this must be regarded as an " unmixing " process and not as the form- ation of a hypothetical new modification of the gelatin.The optical rotation of gelatin solutions increases with time in such a way that a curve plotted between the logarithm of the angle of rotation and the logarithm of the time is a straight line. The multirotation is expressed by the formula [.ID =RP in which for a 1% solution of gelatin K=209 and n=0.082. 0. GERNGROSS and S. BACH (Biochem. Z. 1923 143 542-552).- The isoelectric points of various preparations of gelatin have been found t o range from p H 4.45 to 5.55 according to their source. [Cf. also B. Feb.] The Displacement of the Isoelectric Point of Gelatin by Formaldehyde. 0. GERNGROSS and S. BACH (Biochem.Z. 1023 143 533-542) .-The isoelectric points of two preparatians of Triphosphonucleic Acid and Thymic Acid. W. 0. K. J. F. S. The Isoelectric Point of Gelatin from Hide and Bone. J. P. i"i. 232 ABSTRAW OF (3HICMTOAL PAPERS. gelatin were lowered from p H 5-05 to 4.6 and from p~ 4.76; to 4.3 respeotively by the presence of formaldehyde. J. A. WZSON and E. J. KERN (J. Amer. Chem. Soc. 1923 45 3139- 3140; cf. A 1923 i 68).-The two points of minimum in the curve showing the degree of swelling of gelatin as a function of the p H value namely a t 4.7 and 7.7 were confirmed when using ash free gelatin. The points coincide with those at which minimum values for the wave-length of maximum absorption in the ultra-violet are observed. 3'. B. J. P. Points of Minimum Swelling of Ash-free Gelatin.Diffusion of Arsenic [Trioxide] in Gelatin. R. SCHAEFER (KoZZoid Z. 1923 33 286-289).-A clear transparent gel con- taining arsenious oxide and suitable for dental purposes may be prepared by adding a few C.C. of hot 30% gelatin aolution to a hot solution of arsenious oxide with vigorous stirring. The solution is evaporated slowly on a water-bath and every Bteen minutes a quarter of the evaporated water is replaced by gelatin solution. This process is continued until the concentration desired is reached and the whole allowed to cool to a clear gel. In this way a gel containing 12-15% of arsenious oxide and 20-30% of gelatin is obtained. The diffusion of arsenious oxide in gelatin has been investigated by laying small portions of the above described gel and a paste of the powdered oxide and water on a large piece of gelatin and after sufficient time has elapsed examining the gelatin by exposing it to hydrogen sulphide.In the case of the arsenic gel it is found that the amount of arsenic diffused falls off quite regularly as the distance travelled increases but with the paste there is no apparent diffusion beyond the surface of the gelatin although this has undoubtedly taken place. The author is of the opinion that in the paste simple molecules are present but in the gel more complicated molecules are present and these move more slowly but the total amount of arsenic diffused is greater in the latter case than in the former. J. F. S. Reaction of Alkaloids with Gelatin [Solutions] containing Iodine.H. HANDOVSEY and E. DU BOIS-REYMOND (KoZZoid Z. 1923,33,347-348).-Liesegang rings are produced when a solution of 1 1000 pilocarpine hydrochloride is placed on a gel containing 3% of gelatin 0.6% of potassium iodide and 0.4% of iodine. The rings are alternately reddish-yellow and dark brown and are about 1-2 mm. apart. Similar but differently coloured rings are produced with strychnine nitrate 1 1000 and papaverine hydro- chloride 1 100. J. F. S. The Composition of Spinning Silk. E. ABDERHALDBN (2. phzpiol. Chem. 1923 131 281-283).-From the product of the hydrolysis of spinning silk by 70% sulphuric acid a t 37" there has been isolated glycyl-Z-tyrosine anhydride m. p. 2$2" and glycyl- d-alanine anhydride m. p. 245". W. 0. K.ORGIANIC CHEMISTRY. i.233 The Influence of Temperature on the Action of Amylase. The Action on the Saccharifying Power of b y l a s e . T. CHRZ~ZCZ (Biochem. Z . 1923 142 417439).-The influence of temperature on the activity of the amylases of various cereals a t the optimum p H of 4-9 is not uniform. The optimum ranges found are for barley amylase 49-54" for rye and wheat amylases 49-55" for oats amylase 51-53" and for buckwheat amylase 50-55". In the cases of maize (56-57") millet (58-59') and African millet (62-64') the optima quoted in brackets lie above the temperatures a t which destruction of the enzyme begins. In aqueous solutions barley amylase is inactivated a t 61-62" rye and wheat amylases a t 63-64" and the other varieties a t 65- 66". In general plant amylases are completely destroyed in one hour when exposed to a temperature of 75".Amylases from the same genera but of different varieties show the same susceptibility to alteration of temperature a t the optimum p ~ . Aqueous malt extracts prepared by shaking for at least one hour give a precipitate when heated at 50° but if the shaking be of shorter duration (thirty minutes) precipitation does not commence below 55-60'. The precipitate does not affect the activity of the enzyme. Rye-malt extract is exceptional in giving at most a slight opalescence even at 80". J. P. H. HAEHN and H. SCIIWEIGART (Biochem. Z. 1923 143 516-526).-Potato amylase is activated by sodium chloride and fluoride and by potassium calcium barium and magnesium chlorides. It is inhibited by the salts of the heavy metals.Amino-acids have an activating effect (cf. Doby Biochem. Z. 1914 67 166). Potato amylase after being freed from most of its salts by dialysis or ultra-filtration loses much but not all of its activity but is reactivated by the addition of the salts of the alkali or alkaline-earth metals. A method of combined dialysis and ultra-filtration yields inactive salt -free preparations of the amylase which are reactivated by salts. It is concluded that potato amylase consists of an inactive organic constituent together with an indispensable activating mineral salt. The Hexose Monophosphatase of Takadiastase. J. NOGUCHI (Biochem. Z. 1923 143 190-194).-A phosphatase is present in takadiastase which hydrolyses barium and sodium hexose mono- phosphates a t 37". In the former case barium phosphate separates as a gel and in the latter the extent of the hydrolysis which may be practically quantitative is dependent on the concentration of the enzyme.J. P. C. NEWERG and 0. ROSENTHAL (Biochem. Z. 1923 143 399401).-Takadiastase contains a cellase which at 37" completely hydrolyses cellobiose to dextrose in five days. J. P. Potato Amylase. J. P. The Cellase of Takadiastase. Hemicellusose. IV. Cellobiase and Lichenase. H. PRING SHEIM and J. LEIBOWITZ (2. physiol. Chem. 1923,131,262-268).- Gohenin which is hydrolysed to dextrose by malt exbact has i* 2i. 234 ABSTRACTS OF CHEMICAL PAPERS. been acetylated and then hydrolysed to octoacetylcellobiose (Karrer and Joos A. 1923 i 541). It ought therefore to be possible to show that malt extract hydrolyses it first to cellobiose by means of a lichenase and then to glucose by cellobiase i.e.to show that both lichenase and cellobiase are present in malt extract. This is verified as cellobiose is hydrolysed to dextrose by malt extract a t 37" and pH 5 and on the other hand malt extract after being kept for three months hydrolyses lichenin only to cellobiose as the cellobiase apparently disappears on keeping. The presence of cellobiose was determined by the determination of the reducing power and of the rotation of the solution and also by the formation of the osazone. Synthetic Action of a-d-Mannosidase in Presence of some Monohydric Alcohols. H. HBRISSEY and J. CIIEYMOL (Compt. rend. 1924 178 123-125).-cc-d-Mannosidase effects a partial conversion of mannose in presence of ethyl propyl isopropyl and n-butyl alcohols into the corresponding d-mannosides (cf.A. 1923 i 497). The Separation of the Anti-neuritic Vitamin by Means of its Picrate. G. BERTRAND and A. SEIDELL (Bull. Xoc. Chim. biol. 1923 5 79&796).-The crude extract containing the active material is separated from inorganic substances as far as possible dissolved in 60% alcohol and treated with a solution of picric acid in methyl alcohol. The crude picrate thus obtained is active in amounts of 2 mg. per diem when added to a diet of polished rice and administered to pigeons. On recrystallisation of the picrate from water two separate substances are obtained ; one crystallises in needles m. p. 202" and is inactive ; the other forms a crystalline powder m. p. 160" and is active. C. R. H. M. MASRIERA (Anal. Fis. Quim. 1923 21 4 1 8 4 3 5 ; cf. Staudinger and Hauser A. 1922 i 68).-The constitution of the additive products formed from phosphineimines and alkyl or acyl chlorides is discussed. Triphenylphosphinephenylimine reacts with acetyl chloride' in ethereal solution giving a white compound to which the formula PPh,:NPhAcCl is assigned. It is unstable and gives on decom- position acetanilide and triphenylphosphine oxide. The additive cmpound of triphenylphosphinephenylimine with methyl iodide is a white substance having m. p. 235". Attempts to obtain addition of a second molecule of methyl iodide were unsuccessful. The additive cmpound of toluene-p-sulphonyl chloride with triphenyl- phosphineimine is a white crystalline substance which decomposes when heated forming resins. On keeping a mixture of triphenyl- phosphinephenylimine and toluene-p-sulphonyl chloride in ethyl- alcoholic solution for three months two substances are obtained name1 y trip hen y lp hosphin e - p - t oluenesulpbn y lp hen y lummonium h y d r - oxide PPh,:NPh(SO,*C,H,Me)*OH a white crystalline substance m. p. 191" and its ismeride for which the formula i s suggested ; it is crystalline and has m. p. 115". W. 0. K. E. E. T. Additive Products of the Phosphineimines. OH*PPh,*NPh*S0,*C,H4Me G. W. R.OBQANIO OHEMISTBY. 1. 235 The Syntheses of Arsenic Acids by Means of Diazanium Salts. Z. FOLDI (Ber. 1923 56 [B] 2489-2498).-Evidence is adduced in favour of the view that the diazonium arsenife is the primary product of Bart's arsinic acid synthesis (cf. Schmidt A. 1920 i 897). The transformation of the arsenious ion into the arsinic group is simply explained in accordance with Werner's theory if the constitution HHO-AsOH or H OAsOH is assigned to arsenious acid and it is regarded as functioning as a monobasic acid as is generally the case towards alkali kations including the diazonium-ion. I n arsenious acid the arsinic group exists there- fore preformed. The production of the arsinate can therefore be explained by assuming that the diazonium kation present in the second sphere of the central arsenic atom enters the first sphere thereby transforming the tervalent into quinquevalent arsenic atom and that the diazoarsinic acid decomposes with evolution of nitrogen. p-Toluidine is diazotised in hydrochloric acid solution by means of sodium nitrite; the cooled solution is saturated with hydrogen chloride filtered to remove the precipitated sodium chloride and treated with arsenic chloride whereby a paste of colourless granular crystals is produced without evolution of nitrogen. The product can be coupled with phenols or apines thus showing the diazonium group to be intact. The addition of alkali hydroxide to the aqueous solution causes immediate evolution of nitrogen and the development of the colours and odours characteristic of Bart's reaction. In the presence of sodium hydrogen carbonate the arsenious acid can be titrated with iodine the end-point being shown by the formation of a dark coloured diazonium periodide. According to experimental conditions the campounds C6H,Me*N2C1,AsC1 C6H,Me*N,C1,2AsC1 C,H,Me*N2C1,AsCl,*OH and CGH4Me*N2C1,AsC1,,AsC12*OH can be obtained. The first two of these are extremely labile and particula,rly sensitive to moisture ; they can only be obtained from solutions which are completely saturated with hydrogen chloride. The fourth substance has m. p. 9 A 9 8 " (decomp.) ; it readily loses hydrogen chloride and passes into the pentuchloro-salt C,H,Me*N2(As2C1,0) pale pink octahedra m. p. 111-112" (decomp.) whereas when its solution in absolute alcohol is treated with anhydrous ether it gives the compound C6H4~~e*N2C1,AsC1200H colourless crystals m. p. about 90" (decomp.). The saEt C,H,Me-N,(AsBr,*OH) m. p. 105" is de- scribed. The hydroxy-chloro-salts can also be prepared from solid p-toluenediazonium chloride and arsenic trichloride in concentrated absolute alcoholic solution. The diazonium chloroarsenites decompose vigorously in aqueous or alcoholic solution or in suspension in organic media with evolu- tion of nitrogen in the presence of Gattermann's copper powder or cuprous chloride. In alcoholic solution the reaction is very com- plex giving di-p-tolyl p-tolyl ethyl ether arsenic acid p-tolylarsinic acid ethyl p-tolylarsinate and p-tolylchloroarsine. [ : J OH]i. 236 ABSTRAC!I% OF wEb6ICAL PAP'BRS. A study of the action of p-toluenediazodum sulphate on bmium araenife in the presence of water shows that diazonium arsenites am capable of existence in aqueous solution in the presence of an excess of arsenious acid but attempts to obtain them in the solid state were not successful. Attempts to prepare solutions of diazonium arsenites in the absence of excess of arsenious acid are rendered difficult by the impossibility of preparing undecomposed diazonium hydroxide solutions. When however solutions of p-toluenediazonium sulphate barium hydroxide and arsenious acid in the molecular proportion 1 1 1 are mixed a pale yellow turbid alkaline solution is obtained which is alkaline towards litmus but gradually becomes acidic ; decomposition of the diazonium arsenite is shown to occur in accordance with the two schemes 2C6H4Me*N2*O*As( OH),= C,H,Me*AsO( OH)*O*N2*C6H4Me +N +As( OH) and 2C6H4Me*N,*O*As (OH) = CGH4Me*N2*AsO( O13)*O*N,*C6H4Me +As( OH) the second being the more important. H. W.

ISSN:0368-1769    

DOI:10.1039/CA9242600129

出版商:RSC    

年代:1924

数据来源: RSC