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INORGANIC CHEMISTRY. 79 Inorganic Chemistry. Determination of the Density of Chlorine. FI~EDERICK P. TREADWELL and 147. A. K. CHRISTIE (Zed. ccngew. Chem. 1905 18 1934-1935).-A series of careful experiments gives for chlorine as a mean the density 2.488 a t 20" and 730 mm. pressure and 2.489 at 10" and 725 mm. pressure. One gram-molecule of chlorine a t 0" and 760 mm. occupies a volume of 22,043 C.C. L. DE K. The System Perchloric Acid and Water. H. J. VAN WIJK (Zeit. ccnory. Chem. 1905 48 1-52. Compare Abstr. 1902 ii 649 ; Roscoe Annuleu 186 1 121 %G).-From the freezing-point curve of mixtures of perchloric acid and water and from analysis of the crystals separating from the solutions on cooling it has been shown that bix well-defined hydrates exist the respective formuh and melting points of which are follows HClO,,H,O m.p. 50'; HC10,,2H20 m. p. - 17.5" ; HC1C),,2+H20 m. p. - 29.8" ; two hydrates of the formuh HC10,,3H,O melting at - 37" and - 43.2" respectively and HC104,3iH20 melting a t - 41.4'. The pure acid melts a t about - 112". It has further been found that between certain limits of conceiitratiori and temprature two series of niixecl crystals separate the curves of which show niaxinia a t about 78 and 55 mol. per cent. of water respectively. The eutectic mixture of the acid and water contains 88.7 mol. per cent. of the latter and solidifies at - 57.5". 6-280 ABSTRACTS OF CHEMICAL PAPERS. The boiling-point curve of the system shows a maximum at 203' and 72.4 per cent. by weight of water. The boiling point and composition of the vapour given off from mixtures containing more water t ban the constant boiling mixture were determined under atmospheric pressure ; up t o 60 per cent.of perchloric acid less than 1 per cent. of the latter is found in the vapour. Owing t o decomposition a t the ordinary pressure the boiling points of mixtures containing less water than the constant boiling mixture had to be determined under reduced pressure. The pure acid boils at 16' under 18 mm. pressure with slight decomposition ; the evolved vnpour contains small amounts of the compounds ClpO and ClO and a certain quant'ity of the monohydrate remains behind in the distilling flibsk (compare Roscoe Zoc. cit.). The density and viscosity curves of the system have been determined at 50" and partly at 20" ; both curves show distinct maxima.I n the former case the maximum corresponds approximately with the composi- tion of the hydrate HCIO,,H,O ; in the viscosity curve i t lies hetween the mono- and the di-hydrate. The following values were obtained for the density of the pure acid sp. p. 1.7676 at 20"/4'; 1.7098 a t 50'/4'. G. S. Bromine Fluoride BrF,. PAUL LEBEAU (Compt. rewd. 1905,141 1018-1020. Compare Prideaux ]'roc. 1905 21 240).-Fluorine combines with bromine at 0' with incandescence forming b~ontine t$?uoride Br F a colourless liquid solidifying in solid carbon diaxide t o a crystalline mass melting a t 4-5" reacting violently with water liberating oxygen and forming hypobromous hydrofluoric and traces of bromic acids; A similar reaction occurs with solutions of the alkali carbonates The solid compound reacts with incandescence with iodine below - 10' to form iodine pentafluoride and bromine (compare Moissan Abstr. 1903 ii 17) with sulphur t o form fluorine and sulphur bromide also with red phosphorus arsenic a u timony boron or silicon ; i t reacts with carbon on gentle heating attacks most of the metals and many of their compounds and behaves like fluorine towards organic compounds.M. A. W. Occurrence of Fluorine in Mineral Waters of the Pyrenees and in Geysers of the Yellowstone Park. Josk CASARES (Zeit. anal. Chent. 1905,44,729- 735) .-The author has previously recorded the detection of fluorine in certain Galician mineral waters (Abstr. 1896 ii 42) and now gives the quantities of this element found in mineral waters from the Pyrenees.Ten samples of water mere examined and yielded amounts of sodium fluoride varying from 0*0095 to 0 0301 gram per litre. Four samples of water from the Portuguese border contained from 0.0024 to 0.0212. Fluorine mas also detected iu the water from geysers in the Yellomstone Park District of North America. w. P. s. Ozone. ~ ~ O E E I ~ T LUTIIEIL (Zed. h'lektroclm,?. 190.5 11 838-835). -Ozone dissolves in 0.1 N sulphuric acid in sccordame with llenry's l i i w ; the ratio of the concentration in the liquid to that in the gas is 0.23 at 20° and 0.44 at 0".INORGANIC CH EM ISTRP. 81 The 2Z.Jf.F. of an iridium electrode immersed in a solution of ozone increases by 0.027 volt when the concentration of the ozone solution is increased tenfold.Luther arid Inglis (hbstr. 1903 ii 406) found the corresponding increase a t a platinum electrode to be 0.054 volt. The reason of the difference is unknown. T. E. Electrolytic F o r m a t i o n of Thiosulphates. MARIO G. LEVI and 39. VOGHERA ( A t t i R. Accad. Liiicei 1905 [v] 14 ii 433-443).- The authors have studied the formation of sodium thiosulphate by the electrolysis of a solution containing sodium sulphide and sodium sulphite the electrodes being of smooth platinum. I n some cases the cathodic sulphide solution was separated from the sulphite solution by means of a Puckall porous diaphragm whilst in others a diaphragm was not employed. The results shorn that notwithstanding the vigorous anodic oxidation which occurs the velocity of the reaction S03+S+20=S203 is such as to allow of the formation of thio- sulphate in appreciable quantity.The anodic current density does not appear to have a great influence on the yield of thiosulphate which is however diminished by raising or lowering the temperature excessively. The best yield was obtained with a diaphragm at 2 5 O although in the absence of a diaphragm the yield is in general increased. T. H. P. + - - _ _ _ - Action of Dextrose on Selenious Acid. WILLIAN OECHSNER DE CONINCK and CHAUVENET (Conapt. rend. 1905 141 1234-1235).- When selenious acid is reduced by dextrose in aqueous solution a colloidal form of seleniuni is obtained which cannot be separated by filtration. The solution which appears green by transmitted and reddish-brown by reflected light slowly deposits a red amorphous variety of selenium insoluble in carbon disnlphide and not affected by light; but if the solution is boiled the selenium is partially transformed into the black microcrystalline variety (Gutbier Abstr.1902 ii 652). Atomic Weight of Tellurium. 11. ALEXANDER GUTBIER (A~,ncden 1905 342 266-282. Compare Abstr. 1904 ii 254).- [With \VALTEE WAGENKNECHT.1-A new determination of the atomic weight of tellurium has been made using a material which has been purified by a special method. From the crude (95 per cent.) tellurium the metal was separated by sulphur dioxide and dried a t a low temperature. It was then distilled under reduced pressure in a combuition tube. The further purification was then carried out by two methods by conversion into telluric acid or by conversion into the basic tellurium nitrate.The tellurium W R S oxidised to telluric acid by chromic acid and the product crybtallised ten times from water in platinum vessels. It was then converted into the dioxide which dissolved in hydrochloric acid without evolution of chlorine. Finally the material purified by either method mas precipitated from hydrochloric acid by hydro- gen sulphide as a sulphide TeS or a mixture in the proportion Te S,; from this carbon disulphide extracted the major part of M. A. W.82 ARSTRACTS OF CHEMICAL PAPERS. the sulphur. The material still eontaining 1-18 to 1.2 per cent. of sulphur was now distilled under reduced pressure fourteen times. I n the first twelve distillations a small white residue was ohserved in the tube.Its chemical nature could not he discovered. The final product did not contain a detectable trace of sulphur or other impurity. The tellurium dioxide was prepared for analysis by converting the metal into the basic nitrate which was then carefully heated. In one series of analyses the dioxide mixed with silver and powdered quartz was reduced in a current of hydrogen. I n five experiments the value for the atomic weight lay between the limits 127.55-127.68 (0= 16). I n a second series of experiments the dioxide was reduced by hydrazine hydrochloride a t the ordinary temperature the reduction being finally completed a t a higher temperature. The tellurium mas collected in a platinum crucible and dried in hydrogen. Three experiments gave the numbers 127.62 127.67 and 127.55.The mean of all the determinations gives the value 127.6 ; the new methods of purification have therefore not poduced any change in the value of the atomic weight. Action of Nitrous Acid on Hydrazine. E. FRANCKE (Bey. 1 905 38 4102).-The decomposition of hydrazine by nitrous acid proceeds quantitatively according to the equation N,H + HNO = N,O + NH + H,O. The equation N,H H &30 + 2NaN0 = N + Na,804 + 2NOH + 2H,0 given by Girard and Saporta (Abstr. 1904 ii 678) could not be confirmed. Metallic Nitroso-compounds and Nitric Oxide. SIEGFRIXD ZIMMERMANN (AWonatslb. 1905 26 1277-1 294. Compare Chesneau Abstr. 1899 ii 661 ; Kohlschutter and Kutscheroff Abstr. 1904 ii 734).-Conductivity measurements were made with ferrous sulphate solutions before and after the passage of a current of nitric oxide for six hours With an N/16 ferrous sulphate solution the specific con- ductivity fell from 645.6 to 625.5 but with 1IT/32 N/64 and N/l2S solutions the specific conductivities rose from 377.0 2 17.9 and 129.S to 382.4 2294 and 152.3 respectively. Conductivity water through which a current of nitric oxide is passed for 3 44 49 5 6 15 16 and 24 hours has the specific conductivities XNO x lo5= 16.85 28.73 29.45 29.96 36.24 44.14 44.61 and 67.34 respectively.Tn aqueous solution with v = 497.375 994.665 and 1990.000 nitric oxide has the specific conductivities 2x0 x 105= 17.18 12.0'7 and 10.13 and the molecular conductivities p ~ o = 85-4 120.39 and 201.7 ; i t behaves therefore neither as a strong nor a weak acid.On deducting the specific conductivity xNO x lo5 = 36.2 from the conductivities of the iV/26 ,V/33 N/64 and N/128 ferrous sulphate solutions after the passage of nitric oxide for six hours the specific conductivities are found to fall from x x lo5= 645-6 377.0 217.9 and 129.8 to 589.3 346.2 193.2 and 116.1 the molecular conductivities from p= 103.30 120.64 139.46 and 166.14 to 94.2'3 110*'78 123-65 and 148.61 respectively. The complex ferrous-nit ric oxide ion has therefore a smaller velocity than the ferrous ion. K. J. P. 0. T. M. L. G. Y.INORGANIC CHEMISTRY. 53 Dissociation of Nitric Acid. PETRU BOGDAN (&it. EZektrocAew . 1905 11 824- 826).-From determinations of the coeflicient s of partition of nitric acid between ether and water it is possible to draw conclusions as to the concentration of the undishociated molecules of nitric acid in the aqueous solution since determinations of the boiling points of ethereal solutions of nitric acid show that the molecular weight of nitric acid dissolved in ether is normal.The results are calculated in the way described by Rothmund and Drucker (Abstr. 1904 ii 231) and the conclusion is drawn that nitric acid follows Ostwald's law of dissociation the dissociation constant lying between 3.0 and 3.5. T. E. Action of Gaseous Ammonia on Phosphorus Tribromide or Tri-iodide. CHARLES HUGOT (Conzpt. rend. 1905 141 1235-1 237. Compare Abstr. 1904 ii 559).-By the action of ammonia on phosphorus tribromide at - 70" in a special apparatus described previously (compare Abstr.1901 ii 1 S) phosphommide P(NH,) is obtained toget her with ammonio-ammonium bromide NH4Br,3NH (Troost Abstr. 1881 972). Phosphoramide is an unstable yellow solid insoluble in ammonio-ammonium bromide; i t begins to de- compose at - 2 5 O into phosphorimide P2(NH) and ammonia and the change is complete in twenty-four hours a t 0'. Phosphorimide is a brown solid decomposing on heating into ammonia nitrogen and phosphorus. When phosphorus tri-iodide replaces the tribromide in the above experiment a similar reaction occurs a t - 65O but the phosphoramide is soluble in the ammonio-ammonium iodide. M. A. W. Electrolytic Reduction of Carbonic Acid. RICHARD EHREKFELD (Bey. 1905 38 4138-4143. Compare Coehn and Jahn Abstr. 1904 ii 61 4).-Solutions of ammonium carbonate obtained by dissolving commercial ammonium carbonate jn one part of ammonium hydroxide of sp. gr.0.910 and four parts of water have been electrolysed in an apparatus in which the cathode and anode cells were separated by a porous diaphragm. Each experiment lasted twelve hours and was con- ducted at the ordinary temperature the anode consisting of platirlnm foil. Ammonium formate was produced a t the cathode when this consisted of amalgamated zinc and when a difference of potential of 5-10 volts and a current density of 0*01-0.08 ampere were employed. No formate could be detected (a) when iron platinum copper lead or nickel cathodes were used ( b ) when the current density was less than 0.01 ampere nor ( c ) when the solution was too dilute for example one-fifth the above concentration. Solutions of sodium carbonate or of carbonate and hydroxide do not yield formates under similar conditions The formation is not due to the presence of carbamate in the commercial carbonate but is attributed to the presence of NH,CO anions in the concentrated solution.J. J. S. Constitution of Silicides. 11. Double Aluminium Silicides. WILHELM MANCHOT and A. KIESER (Annalen 1905 342 356-363. Compare Abstr. 1905 ii 165).-The empirical constitution of the84 ABSTRACTS OF CHEMICAL PAPERS. silicides of metals rarely throws :my light on their constitution but the amount of hydrogen evolved when they are decomposed with acids generally hydrofluoric acid occasionally affords a clue to the character of the linking in the silicide molecule.Aluminium chromium silicicle which was previously described (Zoc. cit.) readily dissolves in hydro- fluoric acid with evolution of hydrogen. For each unit of valency of the metallic atoms in the silicide two atoms of hydrogen should be produced in this reaction. The aluminium chromium silicide Cr,AlSi should yield fourteen atomic proportions of hydrogen since here tile chromium is bivalent as the solution of the silicide in hydrofluoric acid is blue. It is found however that nineteen atomic proportions of hydrogen are evolved. Since a molecule of the compound must yield an even number of atoms of hydrogen the molecular formula of the silicide must be at least 2(Cr,AlSi,). The constitutional formula Si -A1 Al--Si is suggested. I \cr*Ai:ii*cr’ I ,Cr *Si:Si *Cr 1 1 \ The silicide Cr2A1Si yields twenty-two atomic proportions of hydrogen the increase of one atomic proportion of silicon increasing the hydrogen by three atomic proportions only.It is thought that the molecule must contain silicon atoms linked only with other atoms of silicon a linking which is not broken by hydrofluoric acid. If the residue after treatment with hydrofluoric acid is subjected to the action of potassium hydroxide which will break the linking of silicon with silicon the proportion of hydrogen is increased to twenty-three atoms. The formula must be doubled in order to give an even number of hydrogen atoms The following constitutional formula is suggested .Cr-Si* Si.-Cr. Simmonds’ observations (Trans 1903 83 1449 ; 1904 85 681) on the reduction products of lead silicate are not confirmed.K. J. P. 0. Preparation and Purification of the Hydrogel of Silicic Acid. EDUARD JOHDIS (Zeit. Elektrochern. 1905 11 835-836. Compare Abstr. 1905 ii 317).-By soaking the hydrogel of silicic acid in cold distilled water the alkali chloride absorbed in it graduallyLdiff uses out ; the washings leave less and less solid residue when they are evaporated until finally neither the washings nor the hydrogel gives the reactions of chlorine or alkali metal. If the hydrogel be now extracted with hot water the washings give a strong reaction for both alkali metal and chlorine. The residue left on evaporating the washings does not diminish regularly but rises and falls periodically. Much silica goes into solution so that it appears as if a compound were dissolving as such.T. E.INORGANIC CHEMISTRY. 85 Two Lithium Mercuric Iodides. ANDR~ G. DUBOIN (Compt. rend. l!)O5 141 1015-1018).-The saturated solution of mercuric and lithium iodides having a sp. gr. 3.2s at 25.6" and n=1-78S (Abstr. 1905 ii 637) slowly deposits the litltium memuric iodide 2LiI,Hg12,6H,0 in the form of long flattened deliquescent needles having a sp. gr. 3.26 at 0" readily soluble in methyl ethyl propyl iso- propyl isobutyl amyl or ally1 alcohol glycerol acetaldehyde acetone formic or acetic acid ethyl acetate or oxalate or ether less soluble in nitrobenzene ethylene bromide or chloroform insoluble in benzene or methyl iodide and decomposed by water. The mother liquor from which the crystals have been removed yields a t 8" a second lithium rnercuyic iodide 2LiI,Hg12,8H20 in the form of large soft prismatic crystals melting in the hand having a sp.gr. 2.95 a t 0" closelpresembling the first compound in solubility but insoluble in ethylene bromide and almost so in nitrobenzene. Decomposition of Mixtures of an Alkali Carbonate and an Alkaline Earth Carbonate under the Action of Heat in a Vacuum. PAUL LEBEAU (Ann. Chim. Phys. 1905 [viii] 6 433-441). -In addition to the decomposition of mixtures of calcium carbonate with an alkali carbonate already described (Abstr. 1905 ii 561 616) the effect of high temperatures on mixtures of lithium carbonate with strontium or barium carbonate has been examined ; such mixtures are completely decomposed a t 1150" t o 1250° the residue consisting of pure crystalline strontia or baryta respectively.Separation of Silver f r o m Silver Sulphide in the Presence of Mercury. F'. WILLY HINRICHSEN and TOSIO WATANABE (Chem. Centr. 1905 ii 1642- 1644 ; from Peestschr. '70 Geburtstag Adolf TYiilEner 214-216).-The conditions of equilibrium of systems consisting of silver sulphide mercury sodium chloride and water and the effect of replacing mercury by other metals and sodium chloride by sulphuric acid or potassium cyanide have been investigated with a view to elucidating the part played by mercury in the separation of silver from ores in the Patio and Kriihnke amalgamation processes. The results of experiments in which mercury and silver sulphide were agitated together by means of a shaking thermostat showed that noticeable quantities of silver were removed from the sulphide when the proportion of mercury to silver sulphide was 11.5 to 1.The yield of silver iccreased with the duration of the experiment but variation of the temperature from 15-4O"appeared to have but little effect. When zinc amalgam was employed iustead of mercury a t 40° the com- ponents mixed completely and the product formed a tough mass. When a saturated solution of sodium chloride is shaken with mercury no appreciable quantity of mercurous chloride is formed a t the ordinary temperature or on boiling. The decomposition of silver sulphide by a solution of sodium chloride can only take place to a very limited extent on account of the very slight solubility of silver chloride. The conductivity of a solution of sodium chloride containing 64 grams per litre is not affected by the addition of silver sulphide but when silver sulphide is added to a 20 per cent. solution of sodium chloride the filtrate gives a precipitate of silver sulphide on addition of M.A. W. M. A. W.86 ARSTRACTS OF CHEMICAL PAPERS. ammonium sulphide. Tlie action of nierciiry on silver su1l)hide is not so great at the ordinary temperature or a t 40' when water is piaesent :is in its absence but rise of teiriperature materially increases the yield of silver in the former case. When zinc amalgam is used instead of mercury silver amalgam is not formed. Experiments on the quaternary system silver sulphide mercury or zinc amalgam sodium chloride and water a t 14" and 40' show that the decomposition is aided by rise of temperature or increase of the quantity of sodium chloride in solution.When a piece of silver foil which has been coated with silver sulphide by immersing it in a warm solution of ammonium sulphide and a rod of zinc are placed in a solu- tion of sodium chloride and connected silver is deposited on the latter and zinc sulphide is formed. Zinc amalgam together with mercury gives better yields than mercury alone but at 40' the increase of the yield is only apparent in the case of more concentrated solutions of sodium chloride. Zinc amalgam does not attack silver sulphide to a n appreciable extent in water but decomposes forming zinc hydroxide. The E.M.F. of a zinc-silver sulphide couple in a 20 per cent. solution of sodium chloride is 0.965 volt at the ordinary temperature whilst that of a n iron-silver sulphide couple under similar conditions is 0.36-0.44 volt hence iron cannot liberate silver from silver sulphide in a solution of sodium chloride.The decomposition of silver sulphide by mercury in the presence of sulphuric acid or potassium cyanide is considerably increased by the addition of a piece of iron the effect being largely due t o change of mechanical conditions as glass produces a similar effect. When mercury is shaken with a solution of sodium chloride small globules are formed whilst with potassium cyanide the metal retains a continuous smooth surface. The decrease in the adhesion of mercury caused by water or R solution of salt probably accounts for the retarding influence of the water on the decomposition of silver sulphide by mercury.When zinc amalgam acts on silver sulphide in a solution of sodium chloride the yield is improved by increasing the quantity of zinc whilst the tendency of the amalgam to form globules becomes less ; increase of the quantity of mercury pro- duced a similar effect by enlarging the surface of contact. When iron acts on silver sulphide in a solution of potassium cyanide the yield of silver is proportional to the concentration of the cyanide. F,. w. w. Calcium Brornoborates. L ~ O N OUVRARD (Conzpt. rend. 7 905 141 1022-1024. Compare Abstr. 1905 ii 635).-The salt 3Ca0,CaBr,,5B,03 obtained in a similar manner t o the corresponding chlorine compound by fusing a mixture of boric anhydride (I mol.) with calcium bromide ( 2 mols.) with or without the addition of lime (not more than 0.5 mol.) forms needles o r prisms showing longitudinal extinction,almost insoluble in dilute acetic acid but soluble in mineral acids ; when the quantity of lime is increased to 1 mol.the compound :iCa0,CaRrp,3B,0 is formed as transparent octahedra or arborescent crystalline masses feebly active towards polarised light w r y sparingly soluble in water but readily so in dilute acetic acid ; if however the proportion of limeINORGANTC CHEMISTRY 87 is increased to 3 mols. or to 3 mols. crystals of calcium borate 2CaO,B,O or 3Cn0,B203 are obtained respectively. Attempts to prepare corresponding compounds containing iodine in place of chlorine or bromine mere not successful (cornpare Ditte Abstr.1883 784). By fusing mixtures of boric anhydride (1 mol.) with calcium iodide (2 mols.) and varying proportions of lime the borates Ca0,B203 2Cn0,6,03 or 3Ca0 B,O were obtained the last in the form of beautiful crystals when the proportion of lime reached 3 mols. 11. A. IlT. ANTOINE GUNTZ (Comyt. rend. 1905 141 1240-1241. Compare Abstr. 1902 ii 138).-Pure barium containing 99-56 per cent. of the metal can be obtained in small quantities by heating barium hyclride (Abstr. 1901 ii 385) in tt vacuum in an iron tube enclosed in a porcelain tube. The hydride begins to dissociate a t 900° and at 1200' the barium volatilises and is condensed in a polished steel tube cooled by cold water in the form of a silver-white crystalline metal having a sp. gr. 3.78 that of the hydride being 4.21.Pyrophoaphates of Barium Strontium and Lead. C. N. PAHL (Arkiv Kenz. A4in~ Geot. 1905 2 i No. 6 1-S).-The author has prepared and analysed the following salts of pyrophosphoric acid Ba2P20,,2H,0 ; BaBH2(P2O7),,9H,O ; Ba,H2(P,07),,5H20 ; New Method of Preparing Barium. M. A. W. Ba5H2(p207)3t5H20 ; Ba,,H8(P207),,121120. Sr9H2(P207)5 12H20 ; SrBH,(P,07)5,8H,0 ; Sr9H2(P207),,3H,0. of these salts melts a t a red heat. None of these melts a t a red heat;. Sr2P,07,2; HzO ; S ~ C J H ~ ( P ~ O ~ ) ~ ~ H ~ O ; ~ ~ ~ c J H ~ ( P ~ O ~ ) ~ O * 20H,O ; Sr,gH2(P207)10,18H20 ; None PbzP,07 ; NafjPb7(P207)5 ; K,Pb,,(P207)7 ; K,Pb,3(P207)7 ; Na,Pb,,(P,07)7 ; Pb(OH),,3Pb2P2O,,H2O all of which me1 t readily and re-solidify in the crystalline form. Constitution of certain Plumbates.ITALO BELLUCCI and NICOLA PARRAVANO (Gazxetta 1905 35 ii 500-509).-1n the salt described as potassium metaplumbate to which the formula K2Pb0,,3H,0 is assigned the water is present as water of constitution so that the formula Pb(OH),K must be ascribed to this salt (compare Abstr. 1905 ii 395). The three metals platinum tin and lead all form salts of the t'hree types R(OH),X R(OX) and RO(OX) which may be regarded as derived either from the orcho-hydrate R(OH) or from the meta- hydrate RO(OH) T. H. P. R(OH) + 2XOH = R(OH),X,. R(OH) + 2XOH = R(OX) + 2H,O. RO(OH) + 2XOH = RO(OX) + 3H20. T. H. P. New Analogies between Thallium and Aluminium. VALENTINO FORTINI (Gazxetta 1905 35 ii 450-460).-The position of thallium in the third group of the periodic system of the elements is88 ABSTRACTS OF CHEMICAL PAPERS.perfectly justified by its very intimate relations with aluminium evidenced by the following facts (1) thallium sesyuioxide can replace alumina in the alums ; (2) like indium thallium and probably also aluminiuza form with the sulphates of the alkali metals double sulphates crystallising with eight molecules of water. T. H. P. Chemistry of the Rare Earths. GREGOIRE N. WYROUBOFF and AUGUSTE VERNEUIL (Ann. chi?^ Pl~gs. 1905 [viii] 6 441-507).-A re‘sum5 of work already published (Abstr. 1898 ii 222 339 ; 1899 ii 105 224 423 598; also Wyrouboff Abstr. 1901 i 7 5179; ii 149 604; 1902 ii 565 609). M. A. W. Samarium Sulphates. CAMILLE MATIGNON (Compt. wm3. 1905 141 1230-1 232).-Samarium hydrogen sulphate Sm(HS04)3 or Sms(S0,),,3H2S04 obtained by evaporating a t 200’ a sulphuric acid solution of the normal sulphate 01- by allowing the boiling solution to cool forms thin needles less soluble than the corresponding salts of praseodymium or neodymium (compare lAbstr.1902 ii 325). The basic samarzum sulphate (SmO),SO or Sm,O,SO prepared by heating the normal sulphate a t lOOO’ is a pale yellow amorphous powder insoluble in water or in cold dilute sulphuric acid. The atomic weight of samarium determined by the conversion of the normal into the basic sulphate is 150.6 (0 = 16) (compare Urbain and Lacombe Abstr. 1904 ii 486). M. A. W. Alloys of Aluminium and Antimony. GUSTAV TAMMANN (Zeit. anorg. Chem. 1905 48 53 -60. Compare Campbell and Matthews Abstr. 1902 ii 399).-It was shown by Gautier and by Campbell and Matthewa (Zoc.cit.) that the melting-point curve of alloys of aluminiutu and antimony has two maxima a t about 18 and 6s per cent. by weight of the former metal respectively the first of which corresponds with the formula AlSb whereas the second does cot correspond with any simple formula ; microscopic examination showed only the presence of the compound AlSb and its components. I n the present paper i t is pointed out that if two metals enter into combination very slowly the melting point curve may show a maximum a t a point where no chemical com- pound exists and its position will depend on how long the alloy has been heated. I n agreement with this it is found that the compound AlSb is formed very &lowly from its components.On heating the metals in equivalent proportion at 715’ for one hundred minutes only 1/10 and in thirty minutes a t 1 1 0 0 O only 3/4 has entered into Combination. If the above theory is true there ought to be no second maximum if the alloy is kept at a high temperature sufficiently long for complete com- bination to take place but this could not be tested in the present instance owing to the action of the fused alloy on the porcelain tubes used in the experiments. G. S. “Temper” Carbon and Graphite in Iron. F. WUST and C. GEIGER (Chem. Centr. 1905 ii 1642 ; from Stcchl w. Eisen 25 1134-1 139).-Experiikrents on two kinds of white iron have shownINORGANIC CHEMISTRY. 89 that small quantities of '' temper " carbon are formed even at com- paratively low temperatures the time required varying inversely with the temperature.The greater portion of this form of carbon is formed suddenly at a certain temperature which varies with the quality of the iron. Up to temperatures near the melting point the quantity formed in this may is greater the higher the temperature but by prolonged heating a t the same temperature the quantity is only slightly increased a state of equilibrium being attained. The speed of cooling has but little effect on the quantity of temper carbon. When once formed in cast iron the quantity may be increased by reheating the increase being greater the nearer the temperature to a certain fixed temperature. Temper carbon does not disappear when the iron is quenched. This form of carbon cannot be assumed to be present i u the form of iron carbide Fe,C.I t is not removed in a gaseous state by the action of pure dry hydrogen or nitrogen and the process of tempering can only be effected by substances which can give up oxygen. Graphite may be eliminated in a gaseous form by carbon dioxide hydrogen or iron oxide. E. W. W. Physical and Chemical Properties of Iron Carbonyl. Sir JAMES DEWAR and HUMPHREY 0. JONES (Proc. Roy. SOC. 1905,76 A 558-577. Compare Abstr. 1903 ii 485).-The yellow colour of iron carbonyl is characteristic of the pure substance and is not due to impurities The best method of decomposing the substance consists in treating it with alcoholic potash in a sealed tube a t looo. The formula Fe(CU) has been coofirmed by repeated analyses and the following physical data have been determined sp.gr. 1.4937 a t Oo/4O 1.4565 at 2 1 * l o / 4 O 1.4330 a t 40-0°,/40 1.3825 a t 60"/4"; mean co- efficient of expansion 0.00138; boiling point 102.5" under 760 mm. pressure ; melting point - 19.5' to - 20" ; molecular volume a t boiling point 149.6 a t freezing point 128 ; refractive index for sodium light 1 *519 for thallium light 1-528 at 22" ; Vapour presslire a t - 7 " 0" 16.1" 18.4" 35" 57" 78" 14.0 16.0 25.9 28.2 52.0 133-0 311.2 mm; critical temperature 285-28S0 which agrees closely with the relation- ship T= O-66Tc ; critical density 0.49 ; critical pressure 29.6 atmospheres ; latent heat of vaporisation 39.45 cal. i n agreement with the Trouton constant. Cryoscopic measurements of the molecular weight in benzene solution gave 197 and 194 (theory 198).I n vapour form the substance dissociates a t higher temperatures. The dissociation i-; of the order of 1 per cent. at 13 )O and is practically complete a t 216"; it increases with diminution of pressure and is much smaller in an atmosphere of carbon monoxide than in an inert gas. Compared with nickel carbonyl the iron compound is much more stable and dissociation takes place slowly. I n carbon tetrachloride solution the halogens react with iron carbonyl to form carbon monoxide and the corresponding ferrons salts. In the case of chlorine ferric chloride is formed almost completely when :L large excess of the halogen is employed. The velocity of the change90 ABSTRACTS OF CHEMICAL PAPERS. diminishes very considerably from chlorine to iodine.Iodine mono- chloride and iodine trichloride in chloroform solution form carbon monoxide and ferrous chloride. Cyanogen gas has no action on pure iron carbonyl and in alcoholic solution the reactiou is very slow. Cysnogen iodide in chlorofornz solution forms ferrous cyanide and a little ferrous iodide. Gaseous hydrogen chloride and bromide are inactive but hydrogen iodide decomposes the compound with the formation OF ferrous iodide carbon monoxide and hydrogen. I n chloroform solution hydrogen chloride and bromide react slowly in a similar manner. These reactions are similar to those of nickel cctrbonyl but take place much less rapidly. I n contrast with this iron carbonyl does not react with nitric oxide or with sulphur dissolved in carbon disulphide or xylene.Gaseous hydrogen sulphide has no action but an alcoholic solution reacts slowly forming ferrous sulphide carbon motloxide and hydrogen. Concentrated sulphuric acid and nitric acid dissolved in carbon tetrachloride or ether react rapidly carbon monoxide and hydrogen being evolved. When heated with benzene and aluminium chloride in a sealed tube at loo" benzaldehyde and anthracene are formed; in the cold anthracene is not produced. When exposed to sunlight iron pentacarbonyl decomposes according to the equation 2Fe(CO) = Fe,(CO) + CO. The electric arc only iiiduces the change slowly and a strong acetylene flame is almost without action. Difer~.onorLcicccrbony I consists of lustrous orange hexagonal plates which remain unchanged in dry air.To obtain it in a pure condition the pentacarbonyl is dissolved in dry ether or light petroleum the solution exposed t o sunlight and the crystals which separate dried over sulphuric acid and solid paraffin. Itl is practically insoluble in ether light petroleum or benzene slightly soluble in methylal ethyl alcohol and acetone and much more so in pyridine. It has a sp. gr. 2.085 a t 18". On heating it decomposes a t about looo according to the equation 2Fe,(CO) = 3Fe(CO) + Fe + 3C0 forming a green liquid. When heated with ether light petroleum or toluene the change takes place at about 50" and the liquid becomes intensely green. These green solutions on exposure to light again deposit the solid car bony1 and become colourless. The decomposition of the pentacarbonyl in sunlight is not influenced by increasing the pressure to 123 atmospheres.On the other hand if heated a t 60-100' during the exposure no decomposition takes place. VS7hen dissolved in ether light petroleurn or amylene and exposed to sunlight at the temperature of liquid air slow decomposition takes place. The reaction induced by light is slowly reversed in the dark tubas containing pentacarbonyl which had been exposed to light becoming clear when left in the dark for several weeks. Blue light is most active in effecting the above chiinge then follow greeu and yellow light with red last. I t takes place much more readily in ether light petrolemi or alcoliol than in benzene. When dissolved in nickel carbonyl the decomposition by light is very slow and a 10 per cent.solution does not deposit solid or evolve gas even after several weeks' exposure to bright suulight. To accouiib for this i t is suggested that combination takes place resulting in the fo,mationIXOILGAXJC CHEhlIS'l'HT. 91 of a compound FeNi(CO)? which is not acted on by light. This view is in harmony with the fact that these solutions are much paler in colour than corresporiding solutions of the pentacarbonyl in other solvents. H. M. D. Oxidation of Ferrous Chloride by Water with Evolution of Hydrogen. HEINRICH PRECHT (Zeit. ccngew. Chern. 1905 18 1935-1936).-Further evidence to prove that explosive gases met with in the Stassfurt potash deposits consist of hydrogen formed by the oxidation of ferrous chloride by water. I n solutions very rich in magnesium chloride ferrous chloride is not oxidised.Should magne- sium hydroxide however be present ferrous hydroxide will be pre- cipitated and this will be oxidisec! gradually by water with liberation of hydrogen. L. DE K. The Silicate Na,Fe,Si,O,,. Z . WEYUERG (Centr. J&. 1905 717-71 9).-Eollowing on his experiments with the alumino-silicates containing the group Na2A1,Si,0s characteristic of the sodalite series (Abstr. 1905 ii 89 98) the aut,hor has attempted to prepare the corresponding iron compounds but without success there resulting usually spinels haematite or indefinite products. I n one case how- ever a definite crystallised product with the composition Na,Fe,Si,O and the form of small yellow prisms was obtained ; this was formed when a mixture of silicic acid ferric hydroxide and sodium carbonate in the proportions 2Si0 Fe,O Na,O was fused with a large amount of sodium chloride.L. J. S. Cobalt and Nickel. H. COPAUX ( A m C'him. Ykys. 1905 [viii] 6 508-574).-1n addition to a detailed account of work already published (compare Abstr. 1902 i 586; 1903 i 309 ii 451; 1905 ii 254) a description of cobaltic selenccte Co2(SeO,),,18H,O is given ; the salt which is unstable is prepared by electrolysing a solution of cobaltous selenate at - 10". 31. A. W. Preparation of a Double Salt of Ammonio-nickel Chloride HANS A. FRASCH (D.R.-I?. 161119. Compare Abstr. 1902 ii 128)- When an excess of an alkali chloride is added to an ammoniacal solution of nickel hydroxide an insoluble salt Xi( NH3),C1,,4 IS H3,2NH4Cl is precipitated. The formation of the ammonium chloride may be represeu ted in the following way Ni( OH) + GNH + zNaCl = Ni(NH3),Cl2,4NH3 + 2Na0H + (x - 2)NaCl ; Ni(NH3),C1,,4NH + 2H20 = Ni(OH) + 2NH,CI + 4NH,.In presence of an excess of alkdi salt the insoluble salt is ptecipitated. It resembles the salt formerly described and may be usetl to heprate nickel f i m i other inel& forming hydrosides soluble in ni~inonin. c. 1'1. Y. Nickelonickelic Oxide. HENRI BAUBIGKY (Cornpt. rend. 1905 141 1232-1 233).-Yolernical in reply to Bellacci mcl Clavari (Abstr. 1905 i 823). M. A. W.92 ABSTRACTS OP CHEMICAL PAPERS. Triammine Chromium Tetroxide. ERNST H. RIESENFELD [with WILLIAM A. KUTSCH and HERMAN OHL] (Ber. 1905 38 4068-40’74. Compare Riesenfeld Wohlers and Kutsch Abstr. 1905 ii 461 824 825).-Contrary toHofmann and Hiendlmaier’s statement (Abstr. 1905 ii 716) the action of hydrogen peroxide on ammonium chromate whether containing 2.5 per cent.of free ammonia or saturated with ammonia leads to the formation of ammonium perchroinnte (NH,),CrOs unless insufficient peroxide is used or the temperature is allowed to rise above Oo when a mixture of ammonium perchromate and Weide’s triaminine chromium tetroxide. Cr0,,3NH3 (Abstr. 1898 ii as) or the latter alone is obtained. When treated with 10 per cent. ammonia ammonium perchromate changes immediately at 40° but only slowly a t the laboratory temperature into Weide’s compound which separates in needles and rectangular and rhombic plates. The three forms have the sp. gr.1.964 at 1 5-S0 and when examined crys- tallographically appear probably to be identical and do not constitute two isomeric substances as stated by Hofmann and Hiendlmaier (Zoc. c i t . ) . The action of dilute sulphuric acid on Weide’s cornponnd leads t o the formation of chromium sulphate and hydrogen peroxide but not of chromic acid ; the amount of oxygen evolved varies from 3.54 equivalents with 1 per cent. to 2.24 equivalents with 20 per cent. acid. G. Y. Atomic Weight of Bismuth. ALEXANDER GUTBIER (Zeit. Elektyo- chern. 1905 11 831).-[With LOTHAR BIRCKENBACH.]-T~~ oxidation of the metal t o the oxide is the only trustworthy method of deter- mining the atomic weight. Twelve experiments by this method gave Bi = 208.02 the extreme values being 207.Sl and 208.22.Bismuth oxide in presence of metallic silver and quartz sand is reduced to the metal by ammonia a t 250’. The mean of the experi- ments by this method is Bi = 208.03 the extreme values being 207.92 and 208.17. [With HANS ME~r,~~.l-Eight analyses of bismuth bromide in which the bromine mas determined by means of silver gave Bi=208.05 the extreme values being 207.89 and 208.24. T. E. Distillation of Gold. Gold-copper and Gold-tin Alloys. A New Preparation of the Purple of Cassius. HENRI MOISSAN (Compt. rend. 1905 141 977-983).-Gold can be readily distilled when heated in the electric furnace and with a current of 500 amperes and 110 volts 13.3 per cent. of a 150 gram ingot of gold was volatilised in 64 minutes (compare Moissan Abstr. 1893 ii 507 ; Schuller Abstr.1904 ii 109). The surface of the residual gold presents a blistered appearance and is covered in patches with a thin film of crystalline graphite which was dissolved in the molten metal and expelled at the moment of solidification. The volatilised gold condenses on a copper cooler placed inside the furnace in the form of deep yellow leafy yystsls with a piirple reflex or in filaments (coinpal-c Margottet Auw. EcoZe ~ V o ~ m d 1879 [ ii] 8 347 ; Liversidge Abstr. 1893 ii 354; Ditte Abstr. 1900 ii 549). or in brilliant yellow cubical crystals which contain small quantities of lime and graphite.INORGANIC CHEMISTRY. 93 The boiling point of gold under atmospheric pressure calculated froiii its boiling point in the vacuum of the cathode light according to Krafft and Bergfeld (Abstr.1905 ii 244) is 2530° and is higher than that of copper or tin ; when therefore gold-copper or gold-tin alloys (compare Roberts-Austen Abstr. 1901 ii 25 ; Heycock and Neville Trans. 1891 59 936 ; Maey Abstr. 1901 ii 655) are distilled in the electric furnace the residual ingot is richer in gold than the original. When the metallic vapours from a gold-tin alloy are allowed to escape into the air the tin burns and a substance is obtained having the properties of the purple of C'assius and containing tin dioxide calcium oxide and gold in varying proportions; and since similar purple colours are obtained by condensing the vapours evolved on distilling mixtures of gold with lime alumina magnesia zirconia or silica Debray's view of the constitution of the purple of Cassius is probably correct (compare this Journ.1873 604; Abstr. 1885 875). M. A. W. Sublimation of Platinum below its Melting Point ANTOINE GUNTZ and HENRY EASSETT jun. (Bull. Soc. clhina. 1905 [iii] 33 1306-1308).-The authors have observed that there is slowly formed on the magnesia '' brasque " of electric furnaces in the neighbourhood of the platinum electrodes a deposit of pure platinum. This occurs in crystals which may be either cubical or octahedral or acombination of these two forms. T. A. H. MARCEL DEL~PINE (Coinpt. rend. 1905 141 1013-1015. Compare this vol. ii 24).- The solubility of platinum in pure sulphuric acid and in mixtures of sulphuric acid and potassium sulphate measured by the loss in weight per hour of one square decimetre of platinum foil 10 to 20 p thick is 0.008 to 0.012 gram at 33S3 the boiling point of sulphuric acid in a flask ; 0.04 to 0.05 gram a t 350-35507 the boiling point of a mixture of 50 grams of sulphuric acid and 10 grams of potassium sulphate; 0.12 to 0.13 gram a t 365-370" the boiling point of a mixture of 50 grams of sulphuric acid and 20 grams of potassium sulphate. The solubility of platinum in sulphuric acid is not to be attributed to the catalytic action of traces of nitrous compounds as stated by Scheurer- Kestner (Abstr.1876 i 345 ; ii 674 ; 1878,650 ; 1880 706) because platinum is dissolved to exactly the same extent in sulphuric acid containing less than 1/10,000,000 of nitric acid as in acid containing 1/50,000,1/250,000,1/10,000,or 1jlOOOnitric acid.Owing to the greater surface exposed platinum sponge is more readily dissolved than platinum foil by sulphuric acid; the acid assumes a yellow colour due to the presence of platinic sulphate Pt(SO,j which is precipitated as potassium platinichloride on the addition of potassium chloride to the diluted solution. Owing t o the reducing action of ainmonium snlphate platinum foil does not apprecialdy lose in weight when boiled in sulphuric acid containing ammonium compounds (compare this vol. ii 24 and Scheurer-Kestncr Zoc. cit.). The contrary result obtained by Conrog (Abstr. 1903 ii 433) was probably clue to the facts that his experiments were conducted a t a lower temperature 250° and were of shorter duration. M. A. W. Solution of Platinum in Sulphuric Acid.VOL. XC. ii. 794 ABSTRACTS OF CHEMICAL PAPERS. Oxidation of Palladium. LOTIIAR WOHLER (Zed. E'leLtroclbem. 1905 11 836-844).-Palladium monoxide decomposes when heated in accordance with the equation P d O z P d + 0 ; the reaction is reversible. The dissociation tension of palladium monoxide is measured on a sample of oxide prepared by hydroiytic dissociation of the nitrate and dried in oxygen a t 75O-SOO'. A definite dissocia- tion pressure cutve is obtained by heating the oxide until equilibrium is attained a t a series of temperatures gradually rising. A t the higher temperatures both the oxide and the metal sinter; and if the temperature is lowered and then raised again a new higher dissocia- tion tension i.; observed. A sample of palladium monoxide pre- pared by heating palladium sponge i n oxygen at 700-530' giLve a curve which up t o about 750' agreed with the firstl curve but a t higher temperatures gave higher pressures. The author is in- clined to ascribe this behaviour not to a mere retardation of the velocity of oxidation of palladium due to its diminished surface but rather to a change in the energy of the oxide and metal alike due to diminished surface. A change in the heat developed by the reaction changes the equilibrium constant (according to van't Hoff's equation) and in this case the heat development is very small. From the curve of dissociation tension the author calculates the molecular heat of the reaction PdO = Pd + 0 to be about - 23.5 Cals. The diseocia- tion pressure of palladium monoxide reaches 760 mm. a t 877". It is difficult to oxidise palladium completely by heating it in presence of oxygen owing t o the sintering of the metal and consequent slow attack ; palladium sponge is the best material ; i t should be heated in pure oxygen a t temperatures rising slowly from 700' to 840'. Palladium dioxide in presence of oxygen at atmospheric pressure is incapable of existence above 200'; it decoinposes thus PdO = PdO + 0. The reverse reaction takes place too slowly to be observed. T. E.

ISSN:0368-1769    

DOI:10.1039/CA9069005079

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

94 ABSTRACTS OF CHEMICAL PAPERS. Physiological Chemistry. Chemical Methods by which the Eggs of the Mollusc Lottia Gigantea can be caused to become Mature. JACQUES LOEB (Univ. Calif. Publ. Physiology 1905 3 1-8).-It is found that the eggs of the limpet Lot& gigccntecc which could not be fertilised by sperm in normal or acidified sea-water could be fertilised easily in alkaline sea-water. This is not due to an influence on the sperm but on the egg-cell. The maturating effect is due to chemical not physical action ; this conclusion is reached from experiments on the influence of temperature a n increase in which accelerates the velocity of chemical reactioiis more rapidly than it modifies any physical quality. Oxygen is also necessary for inaturation. The methods that cause artificial parthenogenesis must also incidentally cause thePHYSIOLOGICAL CHEhlISTRY.95 maturation of the eggs. such as benzene also causes maturation. Treatment of the eggs with a fat solverit W. I). H. Resistance t o Lack of Oxygen and a Method of' Increasing it. WALES H. PACKARD (Anzev. J. Physiol. 1905 15 30-41).-By increasing the alkalinity of the blood of Tundulus by the injection of sodium hydrogen carbonate its resistance to lack of oxygen is increased. Decreasing the alkalinity by the injection of acetic acid lessens the power of resistance. Increase of the amount of lxvulose in the blood has no such effect. W. D. H. Influence of Temperature on Vital Processes. KICILWD ABEGG (Zeit. E'ZektrocJbsnz. 1905 11 823).-The rate of production of carbon dioxide by frogs is approximately doubled by an increase of temperature of 10' between 14" and 25".The same is true of rabbits bet6een 38.6" and 40.6" (compare Herzog this vol. ii 115). T. E. Assimilation of Carbon Dioxide by Chrysalides of Lepidop- tera. MARIA (GELFIN) VON LINDEN (Conzpt. rend. 1905 141 1258-1260. Compare Abstr. 1903 ii 677 ; and Engelman ibid. 1883 611).-When chrysalides are kept in pure air the production of carbon dioxide is greater at night than in the day-time the relations between oxygen absorbed and carbon dioxide exhaled CO,/O being respectively 0.76 and 0,664. I n minter production of carbon dioxide may cease altogether. I n an atmosphere containing carbon dioxide there is often an absorption of carbon dioxide and elimination of oxygen.I n 113 experiments in winter carbon dioxide was absorbed 37 times and oxygen exhaled 4 times. I n the spring (116 experiments) the numbers were 60 and 6 3 respectively. Assimilation occurred more frequently in the day-time than a t night Respiration is more vigorous in the night. N. H. J. 11. Formation of Hsemoglobin in the Embryo. LOUIS HUGOUNENQ and ALBEBT MOREL (Con@. rend. 1905 141 848-849).-The hzmatogen of the egg belongs to the class of paranacleiiis ; on cleavage like hzemoglobin it yields a proteid and a pigment containing iron. It is believed to play a greater part in nutrition than that of an oxygen carrier containing as it does a reserve of sulphur phosphorus calcium and magnesium. W. D. H. Classification of Blood-corpuscles. G. H. SCOTT (J. Path.Bact. 1906 11 64-83).-The colourless corpuscles are classified as folloms (2) The coarsely granular eosinophile leucocyte. (3) The basophile leucocyte. (4) The hyaline leucocyte. (5) The lymphocyte. The first four originate from immature forms termed myelocytes in the red marrow. Tho coloured corpuscles are classified into (1) The finely granular eosinophile or neutrophile leucocyte. The lymphocyte is the lymph cell of adenoid tissue. 7-296 ABSTRACTS OF CHEMICAL PAPERS. 1. The megalocytes or embryonic red corpuscles ; these are nucleated and originate from immature forms termed megaloblasts in the marrow. The free nuclei of these cells are sometimes found in the blood. 2. The normal red corpuscles which originate in the marrow from immature nucleated normoblasts.The nucleus of the normoblast is not discharged but is absorbed within the cell hence the biconcave form of the red disc. Neither myelocytes nor nucleated immature red corpuscles undergo further development into mature forms when once they have made their way into the circulating blood. They are foreign elements ar0 filtered out by the spleen and are the cause of the splenic tumour in leuczmia. Leucocytes do not grow larger as they become mature but shrink in size. Lymphocytes do grow larger and may thus be distinguished into immature and mature; they do not grow into the other varieties of colourless corpuscles. W. D. H. Hamolytic Receptors of the Red Corpuscles. ROBERT MUIE and ALEXANDER R. FERGUSON (J. Patlh. Bccct. 1906 11 84-94).- The receptors are shown to be comparatively stable substances ; they are not destroyed when the blood is laked but remain attached to the stromata of the corpuscles.They do not pass through a porcelain filter when the lysis is produced by serum; but when the laking is performed with water (a more disruptive agent) a small fraction passes through. W. D. H. Action of Ricin on Lecithin. 0. PASCUCCI (Beit?.. them. PTqsioZ. PatlL. 1905 7 457)-Ricin has an agglutinating action on blood- corpuscles. The present preliminary statement relates to its action on three constituents of the stroma of the corpuscles namely lecithin cholesterol and cerebrin. If a lecithin emulsion is prepared with as little alcohol as possible and a large amount of physiological saline solution and a few drops of ricin dissolved in the same salt solution are added the lecithin is precipitated in flocculent form and can be filtered off.The filtrate produces haemolysis in an emulsion of blood- corpuscles ; the stromata can then be filtered off and the hsmoglobin passes into the filtrate. The original purely agglutinating action of the ricin has thus been transformed into a haemolytic action. This opens a possibility of studying the quantitative relations of aggluti- nation by haemolysis. Cholesterol and cerebrin have no such action. If excess of' ricin is added to the lecithin emulsion the precipitate dis- appears and the lecithin is again in suspension W. D. H. Iodine-s taining Granules of Leucocytes. S. H. HABERSHON (J. Putk. Nact. 1906 11 95-123).-The microscopic and other observations recorded lead to the conclusion that glycogen or an iodine- staining substance of similar nature has a inore definite relation to the colourless blood-corpuscles than has hitherto been recognised and that whether derived from the liver or not (a point which the experimentsPHYSIOLOGICAL CHEMISTRY.97 leave open) it is taken up by these cells and conveyed by them to the tissues where it is utilisecl for the purposes of nutrition. IV. D. I€. Physicochemical Investigation on the Action of Carbon Dioxide on Blood. A. VON KORBNYI and J. RENCE (PJuger’s Arc% 1905 110 513-532).-The following conclusions have been arrived at 1. For a solution of blood serum the value Q(R - 1.3228) is con- stant (Q= volume of solution containing 1 unit vol. of pigs’ blvod serum and B z the refractive index of the solution). RS + R,(& - S) Q 2.R = ? where R,= refractive index of a mixture containing S C.C. of serum and Q - S C.C. of sodium chloride solution R = original refraction of the serum solution and R,= the refraction of the chloride solution. 3. Alterations in the electrical conductivity of serum solutions caused by slight alterations in concentration are mainly due to alterations in the concentration of the albumin and only to a slight extent to other fact ors . 4. The refractive index of a serum is at a minimum when the blood is rich in oxygen and poor in carbon dioxide. 5. An increase in the amount of carbon dioxide present causes a rapid increase in the refraction but a t the same time a diminution of the electrical conductivity of the blood.6 . The conductivity on the other hand is not appreciably affected by tbe amount of gas present in the blood. 7. The viscosity of blood is at a maximum when richest in carbon dioxide. As the carbon dioxide is replaced by oxygen the viscosity diminishes reaches a minimurn and then increases again with the amount of oxygen. 8. The viscosity increases with the number of blood corpuscles present and the larger the individual corpuscles the greater is their influence on the viscosity. 9. The addition of acid to blood produces the same effects on the refractive index as the presence of carbon dioxide and the addition of alkali hydroxide solutions effects similar to those produced by the replacement of carbon dioxide by oxygen. The amount of alkali required to produce a minimum refraction increases with the amount of carbon dioxide present.10. The difference between the original value of the refractive index of the serum-common salt mixture and the minimum value obtained by the addition of alkali hydroxide increases with the amount oE carbon dioxide present in the blood and also with the number of corpuscles present. J. J. S. Hamolysis in Vitro and in Vivo. OSKAR R. VON WUNSCHHEIM (Arch. Hygiene 1905 54 3 85-296).-The hsemolysis produced by various toxins has been mainly studied in vitro; in the present research a comparative study of what occurs in the living body is also made. Among the many facts detailed the following are some of98 ABSTRACTS OF CHEMICAL PAPERS. the most iniportant. Iu chronic Stcc;rh&occus infection with multiple abscesses even althoiigh iiiany bacteria :we present in the blood there is no hamoljsis during life or in the blood after death but in the acute stage of infection whether the injection is made intravenously or intraperitoneally hmnolg sis occurs during life as evidenced by hzemoglcbinzemia and in the shed blood this continues. In Streptococcus infection the serum of freshly-drawn blood is free from hzemoglobin but if some time elapses after death before the blood is collected the serum is stained with htemoglobin.After death from infection with Bucillus anthacis there is always hzmolysis and intense hEmoglobin- zmia but the change in the red corpuscles mainly occurs in the last few hours of life. A large number of other pathogenic organisms were investigated with somewhat similar results all of which point to the danger of drawing conclusions from experiments in test-tubes without making parallel investigations during life.W. D. H. Action of Precipitins. FRIEDRICH OBERMAYER and ERNST P. PICK (Beitr. chewz. Physiol. Path. 1905 7 455-456).-By means of the authors’ refraction method an estimate of the amount of proteid matter in the’ precipitate produced by the mixture of a normal and an immune serum can be formed. The amount is very small; this con- firms previous estimations by weighing. W. D. H. Anti-immune Substances and Complementoids. The Action of Complement as Agglutinin. ROBERT Mum and C. H. BROWNING (J. Hygiene 1906 6 1-19 20-22).-Complementoid is the term applied to the material into which complement is changed by the tem- perature necessary to destroy the toxic action of the complement.When a large amount is present i t interferes with the combination of complement. Anti-immune substances or anti-amboceptors are obtained in serum in immunity experiments. They were first described by J3ordet. The present research deals with details of their action. Agglutination is usually produced by a single substance agglutinin possesced of combining and agglutinating groups but it cbn also result from the co-operation of two substances in a manner analogous to what is seen in hzemolysis and bacteriolysis. W. D. H. Agglutination of Bacteria. GEORGES DREYER and A. J. JEX- BLAKE (J. Path. Bact. 1906 11 1-47).-1n this research the nature of the changes produced in the agglutinating serum and in the bacteria is studied and the action of acids alkalis and other chemical and physical agents on agglutination is.described in full. W. D. H. Identity of Pepsin and Chymosin (Rennin). W. SAWJA- LOFF (Zeit. plqsiol. Chenz. 1905 46 307-331).-Pawloff’s conten- tion that gastric juice contains only one ferment which has both a proteolytic and a milk-curdling action is confirmed mainly on the ground of experiments on reaction-velocity. The occurrence of a milk- ciirdling ferment in the gastric juice of animals such as fishes whichPHYSIOLOGICAL CHEMISTRY. 99 never take milk and also in the vegetable kingdom is therefore capable of an easy explanatiou. Although the forination of plasteins may be regarded as due to the reversed action of pepsin the foymation of casein froiii caseinogen does not come under that head.The latter is regarded merely as a inasked stage in proteid digestion. W. D. H. Behaviour of Different Polypeptides towards Pancreas and Stomachic Juices. EMIL F~SCHER and EMIL ABDERHALDEN (Zeit. p h p i o l . Chent. 1905 46 5 2 - 4 2 . Compare Abstr. 1903 i 694 800 ; 1904 i 867 890 917; 1905 i 131 122 ; ii 333).-The list given in Abstr. 1905 ii 333 has been extended by an examination of the following polypeptides Hydro1 ysed Alanylglycine. Alany lalanine. Alanyl-leucine A. Leucylisoserine A. A lanylgl ycyl gl ycine. Leucy lglycy I gl yci ne. G1 ycyl-leucylalanin e. Not hydrolysed. Glycylalanine. Alan yl-leucine B. Leucylalanine. Leucylgly cine.Leucyl-leucine. Am inobutyrylglycine. Aminobutyrylamino- Aminoisovalery lgl y cine. Dileuc y lgl ycy lgl ycine. butyric acids A and B. The following points are discussed ( I ) Influence of structure. (2) Influence of the different amino-acids. (3) Influence of configuration. (4) The effect of the number of aminoacyl groups present. (5) Con- dition of the ferment. With respect to the last factor it is shown that fresh pancreas juice obtained from a Pawloff fistula has not always the same action as commercial trypsin or pancreatin. Glycyl-Z- tyrosine dialanylcystin e leucylalanine leucylglycine and leucyl-leucine are not fermented by the juices of the stomach. J. J. S. Pancreatic Juice rendered active by Calcium Salts. C . DELEZENNE (Compt. rend. 1905 141 781-784).-When sinall amounts of a calcium salt (chloride iodide nitrate or acetate) are added to pancreatic juice the latter acquires the power of digesting albumins. The soluble calcium salts may be removed by dialysis in preserice of sodium chloride without loss of activity and addition of an excess of sodium fluoride to the dialysed juice has no effect. All preparations are not rendered equally active by the same amount of calcium salt owing to the varying amounts of alkali salts especially sodium carbonate. Most of the calcium salt added is precipitated as carbonate or phosphate. When pancreatic juice is filtered through collodion it is no longer rendered active by calcium salts. It is suggested with all reserve that the substance retained by collodion may be a mother-substance aC100 ABSTRACTS OF CHEMICAL PAPERS.kinase and that calcium salts transform it into a ferment in a manner more or less analogous to the production of the fibrin ferment. K. H. J. hl. Activation of Pancreatic Juice by Salts. Specificity of Calcium. C. DELEZENNE (Conzpt. Tend. 1905 141 914-916)- Quite small quantities of calcium chloride increase the activity of pancreatic juice. The salt neutralises the carbonates and phosphates of the juice and what is left over is the activating agent. Chlorides of strontium barium and magnesium are not capable of acting in the same way or their action is extremely small. W. D. H. Changes of Refractive Properties of Glucosides and Pro- teids produced by Ferments Acids and Bacteria. FRIEDRICH OBERMAYER and ERNST P.PICK (b’eitr. che1,z. PhysioZ. I’ath,. 1905 7 331-380).-The action of emnlsin on amygdalin or salicin of ptyalin on dextrin and of acids on phloridzin produces no change in the re- fraction as measured by Pulfrich’s refractoineter. The sum of the action of the cleavage products is therefore equal to that of the intact molecules. The same is true for the peptic digestion of various pro- teids. After tryptic digestion there is an increase of the refraction of from 5 to 7 in the fourth decimal place. From this the conclusion is drawn that pepsin produces only a loosening of various complexes whereas the action of trypsin is to cause a deeper ‘( constitntional ” change. The action of acids on proteids if it goes beyond the acid albumin stage resembles that of try p i n .Bacterial decomposition in the Influence of Salts intimately united with Albuminous Material and with Enzymes on Proteolysis. G. MALFITANO (Conzpt. Tend. 1905 141 912-914).-The protease of anthrax rapidly liquefies gelatin but has no effect on coagulated white of egg. If however the latter is previously boiled in physiological salt solution it is rapidly dissolved by the protease. Boiling with a solution of calcium chloride of equivalent strength renders the egg-white refractory not only to the protease but also to activated pancreatic juice. Mixtures of kinase and pancreatic juice poor in the latter constituent behave exactly like the anthrax protease. 31. X. SULLIVAN (Arizer. J. Fhysiol. 1905 15 42-45).-These fishes (dogfish sharks kc.) swallow without mastication; there are no glands in t h e mouth region.Extracts of the mucous membrane of mouth and gullet have no digestive action. The cardiac sac of the stomach secretes pepsin- hydrochloric acid. The pyloric tube has no digestive act>ion. The same is true for the middle intestine spiral valve and rectal gland. The action of the pancreatic juice varies a good deal; the juice is activated by bile and by splenic extracts but not by intestiud extracts. Although the gastric juice in virtue of its relatively high percentage of acid dissolves out the calcareous salts from the carapace of crabs and lobsters swallowed there is no true digestion of chitin; the chitinous mass i s triturated and finally excreted by the anal orifice. cases investigated lowers the refraction.w. n. 13. W. D. H. Digestion in Elasmobranch Fishes. W. D. H.PHYSIOLOGICAL CIIEMISTRY. 101 Diastatic Hydrolysis of Xylan. GASTON SEILLI~RE (Compt. rend. 1905 141 104S-l050).-Many non-carnivorous molluscs and some insect larvre contain a diastase (xylanase) which converts xylan into xylose (compare Bicclermctnn and DIoritz PJiiger’s A d & 1 89S 73 236). N. 1%. J. 11. Morphogenetic Reaction of the Alimentary Canal of the Frog’s Larva on Muscle Proteids of different classes of Animals. EDWARD BAB~K (Beit?.. clbena. I’hysiol. PatJL. 1905 7 323-330).-1f tadpoles are fed on vegetable food the length of their alimentary canal becomes much greater than when fed on meat. The kind of flesh makes however a considerable difference. The following numbers giving the relative lengths of the canal are averages obtained from hundreds of measurements fed on frog’s flesh 6.6 ; on fish 6.6 ; on horseflesh 6.6 ; on mnssels 5.9 ; on crab meat 7.6 ; on vegetable proteid S.3.There are chemical differences between the muscle proteids of vertebrate animals but these seem to be insufficient to provoke a inorphogenetic reaction. The greater difficulty in digestion of Vegetable proteid calls forth greater digestive activity and so a growth in the secreting surface; crab meat seems to be nearly as difficult to digest ;but mussels much easier. The amount of fteces varies with the difficnlty of digestion. M7. D. H. Absorption of Lecithin in the Intestine. B. SLOWTZOFF (Beitr. chem. Physiol. Path. 1906 7 508--513).-A part of the lecithin in food is discoverable in the lymph.The greater part is saponified by the steapsin of pancreatic juice. A further decomposition of choline does not occur with fresh lecithin preparations. Lecith-albumins are affected by pepsin-hydrochloric acid. I n the acid albumin which is first formed lecithin appears to be still united with albumin and is absorbed as such when administered by the rectum. W. D. H. Influence of High Altitudes on General Nutrition. H. GUILLEMARD and R. MOOG (Cofiyt. rend. 1905 141 843-846),- From the examination oi the urine the conclusion is drawn that residence at great altitudes diminishes oxidation and diuresis and causes retention of fixed elements. This is most marked from the fourth to the eighth day after the beginning of the experiment; following that a return to the normal slowly sets in.W. D. H. Influence of Diet on Growth and Nutrition. CHALMERS WATSON and ANDREW HUNTER (Proc. PhysioZ. SOC. 1905 xiii ; J. PlqsioZ. 33).-The experiments were made on r a t s ; in these animals a meat diet is injurious and causes loss of weight stunting of growth and early death. Although there is great similarity chemically between porridge and bread and milk the former is injurious. I n the case of animals deprived of their ovaries the minimum proteid requirement is less than in normal females. W. D. H. The Effect of Abundant Proteid Food on Metabolism. MAX SCEIREUER (Pfliiyer’s Archiu 1905 110 227-253).-The relationships102 ABSTRACTS OF CHEMICAL PAPERS. between respiratory exchanges and the proteid in the nutriment are compared in experiments on dogs The increased consumption of oxygen and con.~ec1uent increase of cell activity which occurs is not a lasting effect. W.11. H. Considerations on Proteid Diet with reference to the Various Forms of Nitrogen it contains. LEWELLYS P. BARKER and B. A. COHOE (J. BioZ. Chem. 2Vew York 1906 1,229-238).-It is well known that certain articles of diet will ‘‘ agree ” and others ‘* disagree ” with people. On the slipposition that this may be due to the distribution of the nitrogen deteriuinations of amide nitrogen melanoiclin nitrogen diamino-nitrogen and monoamino-nitrogen were made in various foods (veal cutlets pork chops sirloin chicken fish C ~ C . h.) and the results given in tables. The differences are very striking but their ultimate valuation is for the future.W. D. H. Nuclein-metabolism and the Ferments concerned in Man and Animals. ALFRISD SCHITTENHELM (Zeit. plqsioZ. Chem. 1905 46 354-370).-From experiments on autolysis of the spleen i t is shown that differences exist in various animals. I n the spleen of the ox and horse uric acid is formed but not in t,hat of man dog or pig. There are also small quantitative differences in thc amount of amino- purines changed into oxypurines. TYV. D. H Feeding with Artificial Nutriment. W. FALTA and C. T. NOEGGERATH (Beit?.. chem. PIvpioE. Path. 1905 7 3 13-322).-Rats were fed on various purified proteids starch and sugar and fat with the addition of salts water and in some cases of lecithin. cholesterol and sodium nucleate all obtained as pure as possible. In all cases weight was rapidly lost and death ensued usually after about 60 or 70 days.W. D. H. Pituitary Feeding. WILLIAM H. THOMPSON and H. 11. JOHNSTON (J. PhysioZ. 1905 33 189-197). -Pituitary substance (whole gland dried a t 45-50°) stimulates metabolism in the dog as shown by the output of total nitrogen urea and phosphates (to a less degree) in the urine. The body-weight declines. The effects do not subside im- mediately when the pituitary feeding ceases. They are more pronounced when gland substance from a young animal is given. W. D. H. Metabolism in Cretins. W. SCHOLZ (Chenz. Centr. 1905 ii 1546 ; from Zed. exper. Path. Ther. 2 271-384).-1n cretins not treated by thyroid feeding the secretion of urine is small and there is re- tention of proteids and salts. The excretion of uric acid creatinine phosphate and sodium chloride is especially sniall.The amounts of urea xanthine bases ammonia and sulphates are normal. The excre- tion of alkaline earths in young cretins is increased. This is similar t o what occurs in mpxcedema. By feeding on thyroid diuresis is produced and the nitrogen output increased. The body-weight sinks mainly on account of increased metabolism in non-nitrogenous material. The urea output is but little affected ; in older cretins the uric acidPHYSIQLOGTCAL CHEMISTRY. 103 excreted rises; in young cretins this is preceded by a fall. The excretion of alkaline earths (especially calcium) is lessened but the amount of phosphates in the urine is not much altered.There is a great rise in the acidity of the urine especially in young cretins. The influence of the thyroid treatment is compared with that of other glands with an internal secretion such as the ovaries. There is no agreement in the actions. W. D. H. Revival of the Excised Mammalian Heart by Perfusion with Oil. TORALD SoLLhIliN (Amer. J. Phgsiol. 1906 15 121-126).-The excised mammalian heart can be made t o beat for a short time by perfusion with indifferent liquids such as mercury or oil ; with mercury vitality is soon lost; with oil the beats cease after about half an hour. The conclusion drawn is that the mammalian heart- beat is theconsequence of a stimulus initiated by the distension of the coronary vessels under pressure ; it is however admitted that such an explanation will not hold for the hearts of cold-blooded animals which have no coronary vessels and beat in solutions without pressure.If the explanation given for the mammal’s heart is correct the stimula- tion can be conceived more readily as originating in nervous than in muscular structures and so the experiments favour the neurogenic theory of the origin of the mammalian cardiac contraction. W. D. H. Survival of the Excised Mammalian Heart. FRANK S. LOCKE and OTTO ROSENIIEIM (Zentr. Physiol. 1905 19 737-739).-A remarkable instance of prolonged survivaI of the excised heart of an adult rabbit is recorded. The perfusion fluid employed was Locke’s (that is Ringer’s solution containing dextrose and saturated with oxygen at atmospheric pressure). During the nights and over Sunday perfusion was stopped and the heart remained quiescent.But when- ever during the course of fonr days perfusion was recommenced the heart resuiiiecl regular rhythmic contractions. W. D. H. Action of Saline Solutions on the Vitality of Blood-vessels. ROBERT A. HATCHER (Amer. J. Physiol. 1906 15 144-147).- Experiments on the excised dog’s kidney enclosed within an on- cometer and perfused with various saline solutions show that after perfusion with a 0.9 per cent. solution of pure sodium chloride the vessels show no reaction to adrenaline after three hours’ perfusion and after ten to twenty-four hours’ perfusion only a slight reaction occurs when a solution of oxyhmnoglobin is substituted for the saline solution. If Ringer’s solution is used instead of the pure saline these times are lengthened.If Locke’s solution is employed (that is Ringer’s solution containing 1 per cent. of dextrose) the times are greatly lengthened ; for instance a reaction to adrenaline is obtained twenty t o twenty-seven hours after the beginning of the perf usion. W. D. H. The Secretory Function of the Parotid in Man. EDUARD VON ZEBROWSKI (P’iigey’s Archiu 1905 110 105-173).-Changes in the104 ABSTRACTS OF CHEMTCAI PAPERS. parotid secretion are due to changes in the stimulation of the buccal mucous membrane. The quantity of the stimulating material influences mainly the rapidity of secretion. The rise in rapidity is nearly proportional to the sqnare root of the amount of stimulating substance. The intensity of tho stimulus inlluences the rapidity and also the composition of the secretion. Chewing has an important effect.One- sided chewing influences mainly the gland on the same side. The alkalinity of the saliva is proportional to the amount of ash. The ash increases with rapidity of secretion. The digestive power of and amount of oxydase in the saliva are proportional to the amount of organic mnterial it contains. The alkalinity of the saliva favours the digestion of starch. W. D. H. Action of Alkaloids on the Iris. HTrGIr K. ANDERSON (J. PhysioZ. 1905 33 414-438. Compare Abstr. 1905 ii 546).-After section of the third nerve pilocarpine constricts the paralysed pupil more than the control but physostigmine constricts it less. Both however constrict it for a longer time.After degenerative section of the short ciliary nerves physostigmine has no effect but pilocarpine constricts the pupil markedly. The former drug acts therefore on the nerve- ending but pilocarpine on the muscle itself. After imperfect regeneration of the third nerve physostigmine restores the light reflex biit pilocarpine does not. The impulses imperfectly transmitted by the regenerating fibres are blocked chiefly in the ciliary nerve-endings. Some months after removal of the ciliary ganglion the denervated sphincter begins to respond again to physostigmine but the exact nature of the regeneration to which this is due is uncertain ; a second section of the ciliary nerves causes it to disappear again. W. D. H. Action of Dilute Solutions on Living Cells. THOMAS BOKORNY (P$iiger's Arc/& 1905 110 174-226).-Further research on the action of dilute solutions of metallic and other poisons on the lines of the author's previous work (compare abstr.1905 ii 476 752) is given in detail. A tabular summary gives the main conclusions. W. D.H. Physiology of Cell Division. I. RALPII S. LILLIE (Amer. J. PhysioZ. 1905 15 46-54).-The arrangement of colloid aggregates in the cel1,especially t h e chromosomes during mitosis indicates that mutual electrostatic attractions and repulsions play an important part in determining their positions and movements. By the use of floating magnetised needles many of the mitotic figures can be simulated. W. D. H. Validity of Pfluger's Law for Paramoecium. FRANK W. BANCROFT (Univ. Calif. Publ. Ph@ology 1905 2,193-215).-Certain physiologists including Verworn have stated that Pfliiger's law as formulated for vertebrate muscle and nerve does not hold for certain invertebrate structures such as Paramoxium and that excitation occurs mainly a t the anode when a constant current.is passed through the auimal The present paper shows liow this misbake arose and drawsPHYSIOLOGICAL CHEMISTRY. 105 the following conclusions the cilia in the unstimulated Yaranta?cizcna are either a t rest or striking backwards thus producing amovement of the animal forwards. When stimulated the principal feature is a reversal of the stroke and of the movement of the animal. Adopting the reversal of the cilia as the criterion for stimulation Pfliiger’s law holds for the stimulation of the cilia for on making and during the flow of the current the cathodal and only the cathodal cilia reverse and on breaking the current the anodal cilia reverse.?V. D. H. Reactions of Infusoria to Chemical and Osmotic Stimuli. T. BRAILSFORD ROBERWON (J. BioZ. Cl~em. LVew York 1906 1 185-202).-Experiments with Pccranmciu are described in which various solutions of electrolytes and non-electrolytes were employed and the movements of the animals noted. W. D. H. Action of Anaesthetics and Narcotics. O~LVILLE H. BROWN (Amer. J. Physiol. 1905 15 S5-97).-Anzsthetics and narcotics a t certain concentrations cause liquefaction of starfish eggs in proportion to their narcotic power. Anmthesia is possibly the result of an inhibition by the compounds formed on the enzyme actions of the cells.Mathews’ idea that they produce their results by their influence on the respiratory elements (the bivalent carbon compounds) of the cell is considered tenable. W. D. H. Diffusion in Jellies. KURT MEYER (Beitr. chena. Pl~ysiol. Path,. 1905 7 393-410).-Gelatin was dissolved in water and the solution allowed to gelatinise in test-tubes; a solution of sodium chloride was placed on the surface of the jelly and the depth t o which it penetrated the cylinder of jelly determined at the end of a given time. It was found that the rate of diffusion diminished with the concentration of the gelatin. The bearing of this on physiological phenomena is pointed out. I n cells there are colloid materials of different concentrations and in substances like cartilage the concentration is high.The presence of cell membranes denser than the cell contents must also influence the rate of diffusion. Experiments with other sodium salts led to corresponding results. W. D. H. Formation of Acetone [in the Body]. GIUSEPPE SATTA (Ueitr. Compare Abstr. 1904 ii 829).- chenx. Yhysiol. Pccth. 1905 7 458. Polemical against Waldvogel (Abstr. 1905 ii 735). W. D. H. Oxidation of Amino-acids with the Production of Substances of Biological Importance. HENRY D. DAKIN (J. Hiol. Chem. New York 1906 1 171-176).-The formation of a carbo- hydrate from an amino-acid takes place during life but the chemistry of the change is difficult to explain. Enzymes are present in the liver which remove ammonia from amino-acids (Lang) ; it is also probable that carbon dioxide is readily removed from their carbouyl group by enzyme activity as in the transformation of oriiithine into tetramethylenediamine.If ammonia and carbon dioxide are removed from an amino-acid an alkyl group rich in carbon is left106 ABSTRAC’I’S OF CHEMICAL PAPERS. which might be further transformed into carbohydrate or into carbon dioxide and water. Accordingly a method was selected which closely approximates to biochemical reactions namely Fenton’s method of oxidation by means of hydrogen peroxide and a trace of R catalyst such as ferrous sulphate. A t present experiments have been made with glycine alanine and leucine. All of these may be represented by the formula NH,-CHK*CO,H where Ii is either a hydrogen atom (as in glycine) or a methyl or isobutyl group (as in alanine and leucine respectively). On oxidation all are readily resolved a t the ordinary temperature into carbon dioxide aiiimonia and an aldehyde.I n the case of glycine formaldehyde is produced the substance no doubt which is produced photosynthetically in plant life and is the forerunner of carbohydrate. The conversion of this substance into reducing sugars has already been accomplished in the laboratory by Butleroff and Fischer. Glycine given to animals without a pancreas increases the sugar output (Embden and Salomon). I n the oxidation of glycine formic and glyoxylic acids are formed a t the same time and this accounts for the small yield of aldehyde as compared with the yield from alanine and leucine. The formation of glyoxylic acid is not without interest as this acid occurs in unripe fruit and on ripen- ing is converted into sugar.I n similar fashion alanine yields acetaldehyde ancl acetic acid (but not pyruvic acid the product correspmding with glyosylic acid) whilst leucine yields isovaleraldehyde and isovaleric acid The oxidation of glycine is peculiar in that small quantities of osimincacetic acid and formaldoxime are formed. Their formation will explain the production of hydrogen cyanide from glycine by oxidation with nitric acid which was observed by Plimmer. W. D. H. The Distribution of Salicylic Acid in Normal and Infected Animals. SAMUEL RONDI and MARTIN JACOBY (Beitr. chem. PhysioE. Path. 1905,7,514-526).-lf salicylic acid or one of its salts is admiuis- tered to animals the greater part of i t is subsequently found in the blood ; the skeletal tissues in contradistinction to the muscles are also rich in it.Animals iufected with Stap?~ylococczcs excrete i t more slowly than normal animals. I u the blood the drug appears to be mainly held by the red corpuscles. W. I>. H. Organ-proteid. JULIUS POHL (Be&. chem. l’hysiol. Pccth. 1905 7 381-3392).-1n order t o study immunity phenomena in organs and tissues on the lines on which they have already been worked out in relation to the blood it is necessary to have some knowledge of the characters of the proteids in organs. The present investigation relates to the liver ancl t o the globulin which is the main proteid obtainable from that organ. It is not identical with fibrinogen or with myosin.Some attention is paid to its low coagulation temperat-tire ; admixture with blood-serum raises the coagulation point and the presence of blood in the tissues is believed to prevent coagulation which might otherwise occur at body temperature. W. 0. H.PHYSIOLOGICAL CHEMISTRX’. 107 Oxidation of Organic Substances by Ferrous Sulphate in the Presence of Animal Extracts. FR. BATTELLI and MLLH. L. STERN (Conzpt. ?-end. 1905 141 916-SlS).-Ferrous sulphate behavos like anticatalase in relation t o catalase. It is well known that this salt in presence of hydrogen peroxide exerts an energetic oxidising action. I n addition to what is already known lactic acetic and formic acids are in the list of substances thus decomposable with the formation of carbon dioxide. Without hydrogen peroxide ferrous sulphate has no appreciable action.Some observers have advanced the view that oxidation in animal tissues depends on the formation of peroxides but the hypothesis has received no expeiiniental proof. If? however they are present they should be activated by ferrous sulphate. The present experiments with muscle extracts show that this is so but the quantity of carbon dioxide liberated is variable. The variation appears to depend inainly on the freshness of the muscles. Twelve hours after death the experiments are negative ; the substance which ferrous sulphate activates is either rapidly destroyed or else other post mortevt products hinder the action. The action goes best when a stream of air is passed through the mixture.Without oxygen the action does not occur. These facts fit in with the hypothesis that peroxides exist in the muscles and are being continually reconstituted by absorption of oxygen. I n the living organisni the ferrous sulphate is represented by anticatalase which would thus play the part of a peroxydase. W. D. H. Moderating Action of Catalase on Oxidations produced by Extracts of Animal Tiesues. FR. BaTTELLI and MLLE. L. STERN (Con~pt. rend. 1905 141 1044-1046).-Catalase diminishes the oxidations produced by ferrous sulphate in presence of an emulsion of animal tissues. This lends support to the view that hydrogen peroxide is formed in animal tissues and it is suggested that the r8Ze of catalase may be to prevent excessive oxidation of organic substances. N. H.J. M. Cutaneous Excretion of Nitrogenous Substances. FRANCIS G KENEUICT (J. Biol. Chem. New Yo& 1906 1 263-270).-l’he amount of nitrogen-containing material excreted through the skin is markedly increased by muscular labour ; at rest it averages in man 0.071 gram per diem; during work it rises to 0.2 gram per hour. The more severe t,he work the greater is the increase. I n accurate metabolism work it will be necessary t o recognise this almost unconsidered channel of nitrogen excretion. W. 33. H. Ureter Pressure. V. E. HENDERSON ( J . Ph~siol. 1905 33 175-188).-The ureter pressure depends on and varies with the blood pressure and is not a secretion pressure properly so-called. The minimum difference between ureter pressure and blood pressure will vary first with the rate of urinary production and secondly with the proteid constitutiou of the plasma ; hence the explanation given by Starling of the dimensions of this minimal difference and of the108 ABSTRACTS OF CHEMICAL PAPERS.absence of urinary flow with low blood pressure is probably correct. Reabsorption of water and of slightly diffusible substances may take place in the renal tubules. W. D. H. Amino-acids in Normal Urine. GUSTAV EhiBDEN and HEINRICH REESE (Beitr. chem. Physiol. Patlh. 1905 7 41 1-424).-Sy means of P-naphthalenesulphonic chloride it is possible to obtain certain compounds of amino-acids from normal urine provided i t is kept alkaline. The glycine compound is obtainable even although the urine has been previously freed from hippuric acid ; small quantities of the alanine compound were also obtained.Whether these acids are free in the urine or in the form of a peptide is unsettled. W. D. H. Excretion of Greatinine. WALDEMAR KOCH (Avze~. J. I’lqsiol. 1905 15 1-14. Compare Abstr. 1905 ii 182).-Creatinine is excreted with remarkable constancy by the dog as well as by man. The excretion per kilo. of body-weight per diem is nearly the same in both (26-26 mg. for the dog 26-30 mg. for man). Under ordinary conditions of diet the methyl group of the lecithin and kephalin ingested can all be accounted for by the creatinine excreted. With excess of lecithin and kephalin this is not the case although the creatinine excreted is increased. Creatine is present not only in striated muscle but also in heart muscle and testis.W. D. H. Uniformity of Homogentisic Acid Excretion in Alcapton- uria. AECHIBALD E. GARROD and T. SHIRLEY HELE (J. PlLysioZ. 1905 33 198-205).-The average excretion of homogentisic acid in all observed cases of alcaptonuria (except one-Zimper’s) is fairly uniform. I t s relationship to nitrogen excretion varies between very narrow limiks in spite of the fact t h a t no simple standard diet has been adopted. It is more than probable that only one degree of alcaptonuria exists namely that the metabolic error is complete and the homogentisic acid represents the whole of the tyrosine and phenylalanine of the proteids broken down. Wr. I). H. Relation between Scatole and the p-Dimethylaminobenz- aldehyde Reaction of Urine. CHRISTIAN A. HERTER (J. Biol. Clhem.New York 1906 1 251-256).-1n an intense form the red colour given to urine by the addition of Ehrlich’s reagent mentioned in the title is pathological. The administration of large quantities of blood to a dog does not affect this urinary reaction ; the administration of 0.1 gram of indole has also negative results. Small quantities of scatole however given by the mouth markedly increase the reaction. Tryptophan has the same effect. It is probable that scatole or scatole derivatives originating in intestinal putrefaction may be the usual cause of the increased reaction in human wine. ’CV. D. H. Acetonuria following Chloroform and Ether Anmsthesia. HELEN BALDWIN (J. Bid. Clhena. New Yodc 1906 1 239-250).-The urine after anclesthesia has a high specific gravity a strongly acidPHYSIOLOGICAL CHEMISTRY.109 reaction and in 70 per cent. of the cases examined (40 in number) there was a marked acetone reaction due to a disturbance of metabolism probably in the liver cells. W. D. H. Epidemic Diarrhoea. J. E. SANDILANDS (J. Hygiene 1906 6 77-92).-Co~vs’ milk may have a high bacterial content and yet not cause diarrhea. Some preserved milks although containing comparatively few bacteria are a frequent cause of the ailment. The infection which leads to diarrhea usually originates in the district in which the food is prepared and is usually derived from t,he excrements of people suffering from diarrhma. House flies are regarded as the most important carriers of the infection from the f;eces to the food. W. I>. H. Uric Acid Metabolism.MARCO ALMAGIA (Beitr. chenz. Physiol. Path 1905 7 459-462). \‘VILIw:Lnr PFEIFFER (ibicl. 463 -465). hfaaco ALMAGIA (ibid. 466-472). The Occurrence of Glyoxylic Acid in Urine. RYOKICHI INADA (ibid. 4$3-478).-The first paper of the series confirms the statements of Wiener and Schittenhelm that iuany of the mammalian tissues have the pomer of destroying uric acid and gives details as to the extent of this action. The second deals more fully with tlie kidneys where the power is very great but greater in man and herbivorh than i n the dog. The third shows that cartilage has the property of being able to absorb solutions of urates and th-n deposit them in crystalline form ; this is of importance in view of gouty deposits. The last shows that glyoxylic acid one of the decomposition products of uric acid occurs iu the urine. I n herbivora fed on hay the acid is also present and is derived from the aromatic substances in the food.W. D. H. Excretion of Amino-acids in G x t and Leucemia. A . L I P s m r v (Be&. chem. Physiol. Yutlb. 1905 7 527-530).-1n gout and myelogenic leuczmia the amount of amino-acids in the urine varies within norm t1 limits. W. D. H. Solubility of Uric Acid in Blood Serum. ALONZO E. TAYLOR (J. Bid. Chm. Xew Yo& 1906 1 177-185).-From experiments with blood serum the conclusion is drawn t h a t the solvent power of blood for uric acid is about forty times that of water. This includes the aiuount held in solution by tlie water of the serum that held by adsorption by the colloids atld that held in some complex combination.The second qumtity is not inconsiderable since a solution of neutral globulin in water will hold about five times the amount soluble in the same volume of water. But the largest quantity of the three is the last ; in the complex combination referred to the uric acid figures in all probability in the molecule. Some of the bearings of these observations 011 the patliology of gout are pointed out. W. 1). H. Lipzmia and Diabetes. 1%. G. Tn.lmr- ant1 L~ox-.iitn S. DUD~EOX (J. I’ccth. L’mt. 1906 11 50-5S>.-S case of diabetes associated with I i p m i a is de,cribecl in full together with the autopsy. The lipzmia was first recognised during life by the ophthalmoscopic VOL. XC. ii. 8110 ABSTRACTS OF CHEMICAL PAPELLS. examination of the retinal blood-vessels.There was however no interference with vision. Oamic acid staining of the fat granules was unsatisfactory possibly because their envelopes hinder its action. Good results were obtained by the use of Scharlach R. and Sudan 111. W. D. H. Typhoid and Paratyphoid Bacteria and Sera. A. E. BOYCOTT (J. Hygiene 1906 6 33 -73). -Bacillus puratyphosus produces a typhoid-like illness. The diagnosis may usually be made from the agglutinative reactions of the serum. A fluid medium containing dulcitol is of great assistance in the isolation of the organism. W. D. H. Concentration of Antitoxin for Therapeutic Use. ROBERT B. GIBSON (J. B i d Clbem. New York 1906 1 161-17O).-The method is based on the fact that a saturated solution of sodium chloride will dissolve out from the mixed globulins (precipitated from serum by half-saturation with ammonium sulphate) the globulin which is anti- toxic.The material so obtained is very potent and is used in the .New Pork hospitals with excellent results including a comparative freedom from serum rashes. W. D. H. Action of Chloral Hydrate on the Heart. ERWIN ROHDE (Clhent. Centv. 1905 ii 1544 ; from Centr. Plhysiol. 19 503-504).-The experiments were performed with the ventricle apex of the frog's heart treated with a 0.75 per cent. solution of chloral hydrate. The refrac- tory period became shorter and disappeared ; the '' all or nothing " lam no longer held the amount of contraction being proportional to the strength of the stimulus and rhythmic replies to continuous stimula- tion mere no longer obtained.These appearances were also obtained with an atropinised heart and inhibitory phenomena were thereby excluded. By the use of poisons it is therefore possible to abolish the main characteristics of heart muscle and make it behave like an ordinary muscle W. D. H. Behaviour of Amino-acid administered to Animals. MAX PLAUT and HEINRCCH REESE (Beitr. clhenz. PlqsioZ. Path. 1905 7 425-432).-After feeding dogs and men on alanine it is possible to obtain much more of t h a t amino-acid from the urine than can be obtained by Embden and Reese's method (see this vol. ii 108) under normzl conditions. W. D. H. Behaviour of Toluidines in the Animal Organism. HERMANN HILDEBRANDT (Heit?.. chena. Ylqsiol. ruth. 1905 7 433-437. Compare Abstr. 1903 ii gas).- When dimethyl-p-toluidine is given to animals the same products are found in the urine as mhoii p-dimethylamino- benzaldehyde is used (Jaffh Abstr.1905 ii 1S6). The introduction of methyl groups into the amino-radicle of p-amino- benzoic acid considerably lessens the poisonous nature of the acid and so similarly with p-toluidine. The least active compound appears t o bePHYSIOLOGICAL CHEhIISTRY. 111 the trimethyl compound (p-benzobetaine C,H,<$?>O Abstr. 1904 i 235). J. J. S. Decomposition of Acids of the Propionic Series by Physio- logical Methods. KICCARDO LUZZATTO (Beitr. chenz. I’lqsiol. Puth. 1905 7 456-457).-When sodium hydracrylate (P-hydroxypro- pionate) is administered t o dogs no acids soluble in ether are formed. With sodium P-iodopropionate the iodine is eliminated as iodide.Doses of 1 gram of sodium acrylate have toxic effects and kynuric acid is found in the urine. J. J. S. Action of Atropine and other Alkaloids on the Spontaneous Movements of Plain Muscle. G. BECK (Chem. Centy. 1905 ii 1545 ; from Ceiztr. Yhysiol. 19 497-503).-The spontaneous move- ments observed in a ring of frog’s stomach do not always disappear after treatment with atropine; after removal of the poison by Ringer’s solution spontaneous movements often appear. Strong solutions of atropine however act injuriously on the muscle. One per cent. solutions of cocaine abolish the movements. ccpoC Jdeine and codeine act similarly. After treatment with a 1 per cent. solution of morphine the movements may rappear after a loiig time.W. D. H. Behaviour of Strychnine in Birds. HANS MOLITORIS (Zeit. ungew. Clbem. 1905 18 1977-1978).-Strychnine was administered t o different kinds of birds either by the mouth or subcutaneously. By microchemical examination of the tissues it is possible to recognise 0.00008 mg. Otto’s colour reaction being used. The quantity absorbed necessary t o cause death is extraordiunrily small. Absorption is slow from the digestive canal. Hens however as mas previously known possess a high degree of immunity to the poison not only on account of the slow rate of absorption but because these animals possess the power of destroying what is absorbed. W. D. H. Reaction of Cells and Nerve-endings to certain Poisons. JOHN N. LANGLEY (J. PIqsioZ. 1905 33 374-414).-Nicotine causes prolonged contraction in certain muscles of the fowl even after section of their nerves or after paralysis is produced by curare.The nicotine contraction is lessened by a sufficient dose of curare ; the two poisons are antagonistic but nicotine is the more powerful. At the height of nicotine contraction a galvanic current causes partial inhibition. Degeneration of the motor nerves leaves these effects unaltered but there is increased responsiveness t o nicotine and the action of curare is less marked. As the axon endings are destroyed the drugs must act on the muscle itself ; but as tjhe muscle responds to direct stimula- tion the poisons cannot act directly on the contractile substance but on other substances in t h e muscle which insy be termed receptive substances.This deduction may be applied t o other calls and the majority of poisons ordinarily supposed to act on nerve-endings act on the receptive substances of the cells. As adrenaline acts on receptivc s-2112 Al3S'l'RAC'l'S OF CHEMICAI PAPERS. substances i t is probable that secretin iodothyrin and other internal secretions also act on receptive substances although the cells may not be connected with nerve fibres. It may therefore be supposed that in all cells two constituents a t least are present (1) a chief substance concerned with cell function and (2) receptive substances which may be acted on by chemical materials or in certain cases by nervous stimuli. The receptive substance affects or can affect the metabolism of the chief substance.A cell may make motor or inhibiting receptive substances or both and the effect of a nerve impulse depends on the proportion of the two kinds of receptive substmce which is affected by the impulse. There are many other speculations arising out of the general idea pro- pounded. w. D. H. Toxicity of Sea-water for Fresh-water Animals. C. W. WOLFGANG OSTWALD (Uuiv. Gal$ PubE. Physiology 1905 2 163-191. Compare Abstr. 1905 ii 372).-Curves of the toxicity of sea-water of various concentrations up to 52 per cent. were constructed for the fresh-water Gccmmcwus. The females are less resistant than the males. The effects were then investigated for the individual salts alone and in combinations with the others. Sodium chloride in the concentration in which i t is contained in sea-water is much more toxic than sea-water.The toxicity of this salt is lowered more by potassium chloride than by any other salt. Calcium chloride acts similarly but less strongly Magnesium sulphate acts still more feebly and has further a specific influence making the decline of the curves more gradual for all solutions which contain it. Magnesium chloride increases the toxicity in all combinations of salts. The toxic effects do not fit in with any physical or osmotic theory but are specific chemical effects probably of the nature of coagulation. Certain unknown acids are also produced by the animals with increasing concentraf'ion of salts ; these possibly are toxic also. W. D. H. Toxicity of Semen and Genital Products. GUSTAVE LOISEL (Compt. ?-end. 1905 141 910-912).-The substances rejected by both ovaries and testis contain toxic materials ; feeding invalids with eggs should therefore be undertaken cautiously.Extracts of sperm modify growth and exaggerate normal oscillations ; injected into the veins death may be the result. The symptoms vary with the species of animal the sex and the stage of incubation. W. D. H. Poisoning as the Result of eating the Seeds of Phaseolus Lunatus. A. ROBERTSON and A. J. WYNNE (Zeit. anal. Chem. 1905 44 735-741).-Four persons out of seven who had made a meal of cooked PImseoZus Eunatus (Kratok) beans died the cause of death being hydrocyaoic acid. I n each case hydrocyanic acid was present in the intestines and urine but could not be detected in the stomach the acidity of the latter hindering the decomposition of the glucoside. Experiments with the beans themselves showed that free hydrocyanic acid was only produced in the presence of alkali. The quantity of hydrocyanic acid obtained from various samples of the beans variedVEGETABLE PHYSIOLOGY AND AGRICULTURE. 113 from nothing in the white variety t o 0.2 per cent. in certain dark- coloured beans examined. Although theFe beans may be used for food it will be seen that their use is attended by great danger (compare Diinstan and Henry Rbstr. 1904 ii '71). w. P. s. Precipitins of Snake Antivenoms and Antisera. ANDREW HUNTER (2 Ph~siol. 1905 33 239-250. Compare Abstr. 1905 ii 539).-Specific precipitins are produced by the injection of snake venom. Snake sera also lead t o the appearance of specific precipitins which however also precipitate the corresponding venoms. There is no constant relation between the precipitating power and antitoxic value of an antivenom. Similarly the amount of toxic substance in a venom bears no proportion to its content in precipitable substances. Consequently the precipitin- producing substances are not the toxins or at any rate not the whole of the toxins; they are probably merely the coagulable proteids of the venom. W. D H. These have no action on snake sera.

ISSN:0368-1769    

DOI:10.1039/CA9069005094

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. 113 Chemistry of Vegetable Physiology and Agriculture. The Behaviour of Aerobic Organisms towards Complete With- drawal of Oxygen. WALTHER WILLIMSKY (Arch. Hygiene 1905,54 375-385).-Aerobic organisms live with minimal traces of oxygen and flourish better the more slowly the oxygen is withdrawn. If the oxygen is entirely removed they however die and the more suddenly the oxygen is removed the more rapid is the death. W. D. H. Liquefaction of Gelatin by Bacillus Cloaca. A. MACCONKEY (J. Hygiene 1906 6 23-32).-Bacillus cloacce liquefies gelatin very slowly sometimes taking a month or more to do so. By appropriate methods it is shown that the time may be shortened to a week and so delay and inconvenience can be avoided W. D. H. Oxidation of Hydrogen and Methane by Micro-organisms.HERMANN KASERER (Centr. Bnkt. Par. 1905 ii 15 573-5i6 ; from Zeit. Lccwi5.u. Versuchswes. Oesterr. 1905 8 789).-Bacteria are present in soils which in absence of light assimilate carbon dioxide and at the same time in presence of oxygen oxidise hydrogen. Methane is utilised by soil organisms as a source of carbon. This explains why there is no accumulation of methane in the atmcsphere (compare Sohngen this vol ii 42). The presence of hydrogen and methane hinders the production of nitrites from ammonium salts. With abundant aeration oxidation of hydrogen and nitrification may go on simultaneously but with deficient aeration nitrification only commences when the hydrogen is oxidised (compare van Tterson Centr. Bakt. Par.1904 ii 11 693). N. H. J M.114 ABSTRACTS OF CHEMICAL PAPERS. Utilisation of Atmospheric Nitrogen by Micro-organisms. ft. TIIIELE (La?Ldw. Versuchs-Stat. 1905 63 161-238).-Whilst there is no doubt that the Aaotobccctey has the power of fixing elementary nitrogen it is questionable whether this property is specifically inherent and it is possible that i t may even be lost under normal conditions. I n any case i t must be assumed that fixation is less in soils where the optimum temperature is only occasionally reached. It will however be impossible to ascertain how the organism behaves under natural soil conditions until more exact methods are devised for determining very small variations in the amounts of nitrogen in soils. N. H. J. M. Intensive Nitrification.ACHILLE MCNTZ and E. LA IN^ (Compt. rend. 1905 141 861-867).-The object of the experiments was t o obtain a process for the production of nitrates sufficiently rapid for the needs of the country in time of war. As a medium for nitrifying organisms it was found that animal charcoal is far better than cinders and that ten square decimeters gave with a solution of 0.75 per cent. of ammonium sulpbate 8.1 grams of sodium nitrate per day. With stronger solutions nitrification is less active. The difficulty is the evaporation of the large amounts of water but this may be diminished by adding fresh ammonium salts to the nitrified solution until the nitrate begins to interfere with the process. Experiments with soil to which 0.2 per cent. of ammonium sulphate was added produced nitrates a t the rate of 350 grams per cubic metre per day corresponding with 1750 kilos. of sodium nitrate per hectare in a bed 0.5 metre thick.Another soil consisting of leaves farmyard manure and soil yielded nearly twice as much nitrate. The limits to which nitrates may accumulate vary with different soils. Some light soils became sticky like clay ; in others nitrification continued until the chalk was exhausted. The highest amounts reached a t present were 2.7 and 3.3 per cent. of sodium nitrate in the soil whilst the water in the soil contained from 55 to 157 grams per litre. N. H. J. M. Probable Existence of Emulsin in Yeast. THOMAS A. HENRY and SAMUEL J. M. AULD (Yroc. Roy. Soc. 1905 ’76 B 568-580).- When ordinary pressed yeast is added t o a n aqueous solution of amygdalin and the mixture kept for some time a t 40° the glucoside undergoes hydrolysis into hydrogen cyanide benzaldehyde and dextrose the latter immediately undergoing alcoholic fermentation under the influence of zymase.I n most of the experiments the action ceases when about 70 per cent’. of the amygdalin has been hydrolysed. Yeast juice (Buchner’s zymase) and “ zymin ” bring about the same result; the latter is much less active than ordinary yeast. The hydrolytic action of yeast juice is not much affected by hydrogen cyanide and diminishes only very slowly on keeping in both of which respects it differs from the behaviour of zymase. The action in question is not due to invertin since it has been found in agree- ment with Fischer (compare Abstr.1895 i 6 553) that the latterVEGETABLE PHYSIOLOGY AND AGRICULTURE. 115 eneyme only partially h ydrolyses amygdalin to rnandeloni trile-glucoside and dextrose. The authors consider that the results obtained are due to the presence of emulsin in yeast and adduce in support of their conclusion the facts that yeast induces the hydrolysis of salicin and arbutin but not of sinnlbin or digitalin ; its activity is not affected by antiseptics but is dostroycd by small amounts of acids or alkalis; it is most actire at 40° and loses its activity on heating to 70° in all of which respects as well as in its action on amygdalin it behaves exactly like emulsin. G. S. Influence of Temperature on the Rate of Development of Organisms. REGINALD 0. HERZOG (Zed. Elektrochem.1905 11 820-822).-The rule that a rise of temperature of 10' increases 1 he velocity of a chemical reaction to two or three times its original value is shown t o hold for the rate of formation of the ascospores of yeast for the time required to double the number of yeast cells for the time of germination of the seeds of several plants and for the time of development of the eggs of fish. The rule only holds within compara- tively narrow limits of temperature (compare Abegg this vol. ii 95). 1'. E. Influence of Electrodes on Germinating Seeds. H. MICHEELS and P. DE Hem (BUZZ. Acad. roy. Belg. 1905 394-399).-Wheat grain was germinated in a series of vessels containing the same nutritive solution and subjected t o the same electric current (from twelve Daniel1 elements) but with different electrodes.The action of polarity is distinct from that resulting from the nature of the electrode. When aluminium and gold are employed together as electrodes the greatest length of root is obtained on the aluminium side; when aluminium forms the cathode the average weight of the neighbouring germinations is much greater thau that of the germinations near the gold anode whilst when the electrodes are reversed the weights produced are about the same. As regards aluminium therefore t h e nature of the electroda is of more influence than its polarity. Further experiments in which the effect of the latter was eliminated showed that it is towards the cathode that the development of roots is moat marked. N. H. J. M. Comparison of the Actions of Aluminium Zinc and Carbon Electrodes on Germination. H.MICHEELS and P. DE HEEN (Bull. Acad. roy. Relg. 1905 400-402).-The greatest effect was produced with aluminium electrodes but zinc although less favourable than aluminium has a distinct action on germination. N. H. J. M. Action of Colloidal Solutions of Tin on Germinating Seeds. H. MICREELS a n d . P. DE HEEN (BUZZ. Acad. rop. Belg. 1905 310-31 8).-Colloidal solutions of tin stimulate the germination of wheat and oats &c. and considerably increase the growth of roots. Similar solutions which have been twice filtered and contain only 0.0075 gram of solid matter per litre have much the same effect.116 ABSTRACTS O F CHEMICAL PAPERS. The action is diminished by an electric current or by ntldition of some snbstance which causes flocculation.The stimu1,zting effect is attributed to the uniform liberation of eneygy in all directions by the suspendetl particles resulting from the absence of ionic equilibrium. According to the nature of the suspended substance its influence will be favourable or unfavourable to the organism. N. H. J. &I. Development of Amylase during Germination. JEAN EFFRONT (Corn@. nm.cl. 1905 141 626-62S).-The saccharifying power of seeds increases irregularly as germination proceeds until a maximum is reached after which i t diminishes. The liquefying power increases more slowly but more regularly and after the maximum is reached remains the Fame for some time. Malt which has been prepared in clarliness and then exposed to sunlight retains its liquefying power a long time but loses its saccharifying power.Phosphates and 0.05 per cent. copper sulphate are favourable to germination. Ammoninm chloride increases the liquefying power and xylene ( I C.C. per litre) increases both the liquefying and saccharifying power. Bleaching powder in presence of alkali is favourable to germination. but hinders the formation of diastase; in absence of alkali it increases both the power of germination and the amylase. N. H. J. M. Development of Green Plants grown without Carbon Dioxide in Artificial Soil containing Amides. JULES LEFBVRE (Conzpt. rend. 1905 141 664-665 1035-1036).-Three pots ( A 3 and C) containing sand and mineral food two of them ( A and C) with an amide as well were exposed to the air for some weeks and watered with ordinary water.Basil was sown in two pots ( A and B) and when the plants were 4 em. high the three pots were placed under bell-jars with baryta. There was :I slight liberation of carbon dioxide from pots A and E which was without effect on the plants in B. I n pot A which contained an amide the plants developed rapidly. The results also show that the carbon dioxide of the soil. is not absorbed by the roots or if SO absorbed is not utilised. The second paper describes experiments with Lepidium sutivuiiz . I n absence of light and carbon dioxide the plants failed completely in artificial soil containing nmides. In presence of light the plants under otherwise similar conditions doubled their weight in seven day$. N. H. J. M. Increase in the Dry Weight of Green Plants grown in Light without Carbon Dioxide in Artificial Soil containing Amides.JULES LEFBVRE (Compt. rend. 1905 141 834-836).-Experiments with cress and basil showed that the dry matter of the plants rapidly increased in presence of an amide but without carbon dioxide. The growth is normal and not; a mere watery shoot (compare preceding abstract) N. H. J. M. 0VEGETABLE PHYSIOLOGY AND AGRICULTURE. 117 Structure of Plants developed in Presence of Light without Carbon Dioxide and with Organic Substances. MormAan (Compt. rend. 1906 142 49-5S).-Ylants grown in it confirled space without carbon dioxide but with organic iintrient acquire a stmct,ure similar to that of undei.grounc1 organs. Sometimes tissues are formed with multinucleate cells as in the case of certain galls.N. H. J. 11. Influence of Light of Various Kinds on the Migration of the Proteids in Wheat Grain. J. DI'Jrom (Cowpt. rend. 1905 141 086-688).-The wheat was enclosed in boxes with sides arid top of co!our.ed glass. Accumulation of nitrogen in the grain was greatest under the influence of brown ((' bistre fonci ") light then green blue and red. The most favourahle kind of light is therefore that which interferes least with the fnnctions of the chlorophyll. S. H. J. M. Insoluble Alkaline Compounds in Living Vegetable Tissues. MAECELLIN BERTHELOT (Coinpt. rend. 1905 141 793-802).-The insoluble organic matter of Festucn contains small amounts of potass- ium as well as calcium aluminium phosphoric acid and silica &c. When digested with solutions of potassium acetate the insoluble organic matter fixes a certain amount of potassium and at the same time liberates calcium ; with solutions of calcium acetate there is fixation of calcium and liberation of potassium.Chlorides of potass- ium and calcium have scarcely any effect. Wood charcoal contairs potassium compounds insoluble even in dilute hydrochloric acid. It has the power of fixing potassium or calcium when digested with potashiurn or calcium acetate. 'l'he results indicate that some analogy exists between the insoluble and polymerised acids of fresh plants of humic substances and of their mineral products. N. H. J. M. Insoluble Potassium Compounds in Humic Matters. MAR- CELLIN BERTHELOT (Compt. ?*end. 1905 141 1182-1 187).-Wood charcoal (60 grams) treated with 1 per cent.hydrochloric acid (600 c.c.) a t 100' and washed with 10-12 litres of water retained 5-6 per cent. of its total potassium and 5 per cent. of its calcium which are present as organic compounds the amounts of silica iron and alumina present being too small to account for their retention. When the charcoal treated as described was digested with dilute solutions of potassiuni acetate the amounts of potassium and calcium remained the same; whilst with calcium acetate the calcium remained the same and the potassium slightly diminished. N. H. J. M. Distribution of Manganese in the Different Parts of Lupinus Albus. NAPOLEONE PASSERINI (Bol. 1st. A g i w . Scarcdicci 1905 [ii] 6 3-14).-The soil in which the plants were grown contained when dried at IOO' 0.068 per cent.of manganese. The different parts of the plants dried a t loo' contained the following amounts of crude118 ABSTRACTS OF CHEMICAIi PAPERS. ash. the ash. The results relating to manganese are given as percentages in Legiuiies. 7 ~ c a w s . ( 1 7 ( 2 . Stciiis. ~:laiic~ics. Scccls. 1:oots. Nodules. Ash ...... 8.267 3.726 8.280 2'256 2.021 2.102 3.910 10'400 Mn,O ... 12.436 S*OSO 5.927 4.580 4'231 2.100 1.536 0.3T7 The legumes from the middle (1) of the plant were separated from those a t the ends (Z) and the upper portions of the stems were included with the branches. Pot experiments are described in which lupins were grown in sand containing 0.0002 per cent. of manganese both without further addition of manganese and with addition of manganese carbonate.The yield of fresh produce was about the same in both cases. The dry matter of the plants without manganese carbonate contained 0.0095 per cent. of Mn those with manganese 0.0636 per cent. N. H. J. M. Juglone [Hydroxynaphthaquinone]. BRISSEMORET and R. COMBES (Compt. rend. 1905 141 838-840).-Most plants of the order Juglandacectz cou tain hydroxynaphthaquinone to which the physiological properties of walnuts are in part due (compare Bernthsen and Sernper Abatr. 1885 546 and Mylius ibid. 803). N. H. J. M. Formation and Quantitative Variations of the Cyanogenetic Principle of Sambucus Nigra. L. GUIGNARD (Compt. rend. 1905 141 1193-1201. Compare Abstr. 1905 ii 604).-The amount of cyanogenetic glucosicle in the leaves of Sumbucus nigrcl diminishes only slightly with the age. A t the end of the vegetative period the gluco- side does not migrate to the stems but remains in the leaves until they fall off.N. H. J. M. Brown Pigment of Phaophyceze and Diatoms. HANS MOLISCH (Chem. Centr. 1905 ii 1607; from .Rot. Zeit. 1905 i 132-144).- The assumption that the brown colour of living chromatophores depends in the case of the brown algse (phseophyceze) on the presence of the brown pigment phycophaein which inasks the green colour of the chlorophyll is incorrect. The phycopbzein which may be isolated by boiling the algae is not contained in the living cell but is only formed from a chromogen after the death of the organism. A " brown chlorophyll " or phseophyll is contained in the living chromatophore and the rapid change to green which takes place when the algae are exposed t o hot air or placed in hot water alcohol or other liquids is caused by the conver- sion of this subsLance into ordinary chlorophyll. The diatoms behave in a similar manner and the living chromoplasts of the orchid Neottia nidus avis also contain a brown pigment which is rapidly converted into chloro- phyll on the death of the plant.The solution of crude chlorophyll prepared by extracting the phzeophyceze or diatoms with absolute alcohol not only contains chlorophyll and carotin but a new compound Zeucocyanin which when treated with very dilute hydrochloric acid yields a bluish-green pigment phzeocyanin. E. W. W.VEGETARTAE PHYSIOLOGY -4ND AGRICULTURE. 119 Emulsin; General Existence of the Ferment in Orchids.L ~ O N GUIGNAI~U (Conzpt. r e d . 1905 141 637-644).-Emulsin mas found in the roots of every variety of orchid examined both indigenous and exotic; it W ~ K not always detected in the tubers stems and leaves and when present was in much smaller quantity than in the roots. The amounts of hydrogen cyanide produced by 30 grams of substance and 0.2 gram of amygdalin in the case of (1) Goodyera repens and ( 2 ) Epipctis kt<folia were as follows Roots (1) 0.0064 (2) 0.0045 ; steins (1) 0.0021 (2) 0.0010 ; and leaves (1) I n the case of exotic orchids the roots (30 grams) of eight varieties yielded amounts of hydrogen cyanide varying from 0.001 gram (Stanhopecb tigrina) to 0.009 gram (Cypripediuna hirsutissimum). 0*0011 (2) 0*0031. N.H. J. M. Composition of the Dried Grapes used in the Preparation of Tokay Wine. LUDWIG KRAMSKY ( X e d . Nahr. Genussm. 1905 10 671-656).-The following results were obtained by the analysis of samples of the dried grapes from vines grown on the Hegyalya hills and employed in the preparation of Tokay water 39-42 ; total sugar (as invert sugar) 30.25 ; dextrose 19.47 ; lzvulose 7.42 ; total acid (as tartaric) 1.66; total tartaric acid 1.46; free tartaric acid none; potassium hydrogen tartrate 1.53 ; malic acid 0.78 ; tannin 0.02 ; total nitrogen (organic) 0.13 ; ash 1.12 ; phosphoric oxide 0.10 per cent. These dried grapes differ from raisins and similar fruits in several particulars They contain about 2.5 times as much dextrose as laevulose whilst in raisins the greater ha.lf of the total sugars is I~vulose.RaisiDs contain only traces of malic acid and to the presence of an appreciable amount of this acid in the Tokay grapes is attributed the characteristic bouquet of Tokay wine. The Tokay grapes are not dried so much as are raisins sultanas &c. w. P. s. Bacteriological and Chemical Studies of Soils from the Experimental Fields. FERDINAND WOHLTMANN H. FISCHER and PH. SCHNEIDER (Bied. Centr. 1905 34 805-807; from J. Landw. 1904 52 97).-The power of decomposing nitrogenous substances is increased in soils by manuring with lime and still more by complete mineral manure whilst ammonium sulphate has the opposite effect. Under natural conditions the decomposition will vary according to temperature Ssc. and in practice is not merely a question of decomposing nitrogen compounds the nature of the decomposition being of importance.Nitrification is favoured by lime and magnesia ; it mas least active on the plots receiving phosphoric acid,.potassium and ammonium sulphate. Denitrification is also assisted by lime. N. H. J. M. Effect of Plant Growth and of Manures on the Retention of Bases by the Soil. ALFRED D. HALL and NORMAR H. J. MILLER (Proc. Roy. Xoc. 1905 B 7'7 1-32).-The Rothamsted soils generally contain about 3 per cent. o calcium carbonate nearly all of which is120 ABSTRACTS O F CHEMICAL PAPERS. d ue to former applications of chalk. Determinations made in numerous samples from different plots of Broadbalk Agdell a i d Hoos Fields taken a t different dates from 1856 to the present time show that the soils of the unmanurecl 1)lots lose in drainage on the average about 1000 lbs.of calcium carbonate per acre per annnm This agrees closely with results derived from analyses of field drainage by Creydt von Seelhorst and Wilms (Abstr. 1902 ii 45 ; compare Voelcker this Journal 1871 24 276; and Miller PYOC. 1902 18 89). The loss of calcium carbonate is increased when ammonium salts am employed by an amoiiiit equivalent to the acid of the manure. Sodium nitrate and farmyard nianure diminish the loss. Analyses of wheat plants grown in water-culture and of the solu- tions themselves showed that the plants take up an excess of acid from the salts supplied leaving behind a corresponding excess of base. This explains how it is that despite losses by nitrification soils which contain only minute amounts of calcium carbonate (examples of such soils are given) are able to maintain a neutral condition (compare Lawes and Gilbert Jour.Rop. Agric. LYOC. Eng. 1894 55 640 ; Warington Abstr. 1900 ii 570). The experiments also furnished evidence that the roots of the plants did not excrete any organic acid or other organic matter (compare Czapek Jcikrb. 7T7iss. Bot. 29 321 ; Kossowitsch Abstr. 1903 ii 234). Finally i t is shown that calcium oxalate and other organic salts are converted into carbonate by soil organisms (Smopger Abstr. 1879 737). N. H. J. M. Behaviour of "Soluble" Phosphoric Acid and its Move- ments in the Soil. WILHELM HOFFMEISTER (Bied. Centr. 1905 34 817-820. Compare Abstr. 1898 ii 538).-The diminution in the soluble phosphoric acid of soils seems to be only due to nssimihtion by plants and not to conversion into insoluble forms.Notwithstanding the withdrawal of phosphoric acid from the sub- soil the relative amount of soluble phosphoric acid increases down- wards indicating a downward movement of phosphoric acid in the soil. Different varieties of peat which in their natural condition did not contain determinable amounts of phosphoric acid soluble in ammonium liuiiiate yielded 0.006 to 0.061 per cent when heated a t 160". N. H. J. M. Manurial Questions. PAUL VC'AGNER (Bietl. Centr. 1905 34 809-81 3 ; from Dungungsfrugen 1904 Heft. 6. Compare Abstr. 1904 ii 768).-.€Cxpei~iments with barley oats rye and potatoes showed that the average gain with sodium nitrate was twice that pro- duced by ammonium salts.This is attributed to loss of ammonia as carbonate. The most suitable soils for ammonium salts are loams containing moderate amounts of calcium carbonate and it may perhaps be desirable to plough the manure in. Vines should be manured with sodium iiitrate in addition to farm- yard manure. Potassium and phosphoric acid are only effective when plenty of nitrogen is a t the disposal of the vines. N. H. J. M.ANALYTlCAL CHEMISTRY. 121 Nitrates and Nitrites as Manures. TH~OPHILE SCHLWING jun. (Compt. rend. 1905 141 745-746).-Pot experiments with maize grown in soil showed that calcium and sodium nitrites produced the same results as sodium nitrate and calcium nitrate prepared by Birkeland and Eyde's process.N. H. J. 31. Factors which affect the Manurial Value of the Phosphoric Acid of Bone Meal. HENRIH G. SODERBACM (Lccndw. Versuch- Stat. 1905 83 247-262. Coinpare Abstr. 1904 ii 79).- Ammonium salts and organic nitrogen compunds are more favbur- able than sodium nitrate as regards the utilisation of bone meal. I n some years according to the season the total yield mas doubled and the yield of grain (which is more influenced than the straw) trebled. Ammonium salts as compared with sodium nitrate have a similar effect when employed in conjunction with Algeria phosphate and with precipitated tricalcium phosphate but not with superphosphate basic slag and precipitated dicalcium phosphate. When no considerable amounts of calciuix were present bone meal (with ammoniuiri salts) was equal to superphosphate. N. H. J . 11. Favourable Employment of Manganese as Manure. GABRIEL BERTRXND (Conzpt. rend. 1'303 141 1255-1257).-The soil on which the experiments were made was clayey and contained 0.057 per cent. of manganese soluble in hydrochloric acid and 0.024 per cent. soluble in boiling acetic acid. Oats were grown on two plots of 20 ares both of which bad the usual manures and one pure nian- ganese sulphate a t the rate of 50 kilos. per hectare. The application of manganese sulphate resulted in a gain of 17.4 per cent. of grain and of 36.0 per cent. of straw. The grain produced under the influence of manganese weighed 46.5 kilos. per hectolitre as compared with 44 kilos. without manganese. The gvain from both plots contained the same amount of manganese (0.000004 per cent.) (compare Passerini this vol. it 117). N. H . J . M.

ISSN:0368-1769    

DOI:10.1039/CA9069005113

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

ANALYTlCAL CHEM1Sl'lt.Y. 121 Analytical C hernis t r y . Methods of Refractometry. F. L ~ W E (Zed. EZekti*ochem. 1905 11 899-831).--The applications of the rehactometer in quantitative analysis aizd the advantages of different types of instrument are discussed. T. E. Gas Analysis Apparatus. JOHN S. HALDANE (J. IIyyieite 1906 6 74 -76).-A simplification of the author's earlier form of apparatus is described and figured. W. D. H.122 ABSTRACTS OF CHEMICAL PAPELiS. Estimation of Acids in Waste Gases. F. HENZ (Zeit. mzgew. Chem. 1905 18 2002).-The apparatus which somewhat resembles a German tobacco-pipe is half filled with glass beads and 25 C.C. of normal alkali are introduced. By means of a large earthenware aspirator 100 litres of the gas are drawn through the apparatus. The solution is now transferred to a beaker and titrated with seminornial acid the liquid is put back into the pipe re-emptied into the beaker a i d again titrated; this operation may be repeated a third time.The difference between the titration and the check represents the acidity of the gas. L. DE K. Estimation of Hydrogen Peroxide in Milk and the Pre- servation of Milk by t h i s Substance. SAMUEL AMBERG (J. Uiol. Chem. N e w Yon? 1'306 1 219-228).-Hydrogen peroxide is described as an '' apparently harmless " preservative for milk. It inhibits the growth of many bacteria without destroying them. The colorimetric method with titanium peroxide for its estimation is recommended W. 11. H. Analysis of Electrolytic Chlorine. FREDERICK I?. ~'READIVELL and W.A. K. CHRISTIE (Zed. ungew. Clietn. 1'305 18 193@-1934).- The joint amount of chlorine and carbon dioxide is found by absorp- tion with a ti per cent. solution of sodium hydroxide and the hypo- chlorite formed is estimated by titrating with 21'/10 arsenious acid (Treadwell's process) Owing however to a slight formation of chlorate the results are about 0.7 per cent. too low. The authors have therefore modified this method and absorb the chlorine in a standardised solution of potassium dihydrogeu arsenite thus avoiding formation of chlorate. The carbon dioxide is then absorbed by aqueous potassium hydroxide. The excess of arsenious acid is titrated by means of standard iodine. For minute details and illustrations of the apparatus the original paper should be consulted.L. DE K. Estimation of Iodine in Aristols [Iodised Thymols]. H. CORMIMBCEUF (Ann. Chinz. anal. 1905 10 453-454).-0.5 gram of the sample is intimately mixed with 3 grams of dry sodium carbonate and heated in a nickel crucible until the organic matter has burnt off; the heat is then raised until the mass begins to melt. When cold the residue is dissolved in water and to the filtrate is added half its bulk of ammonia. The iodine is now precipitated by cautious addition of silver nitrate and weighed as silver iodide. The filtrate may still contain chlorine as tbis often occurs in considerable quantity in commercial aristols; this may be precipitated by acidifying the filtrate with nitric acid aud adding more silver nitrate. The silver chloride is then collected and weighed.L. DE K. Estimation of Oxygen in Copper. LICONARI) A ~K!II~IU'IT (d?zcclyst 1905 30,3t35-390).-Hesults of inniiy estimations are given showing that tlie osygen iresent i n copper is completely removed by heating the sainple in a current of hydi-ogen (Abstr. 1'300 ii T G G ) :m(l tliat the thickness of the pieces of copper taken for the estimation hasANALYTICAL CHEMISTRY. 123 little if any influence on the results obtained if the heating is pro- longed sufficiently. Fine turnings and sawings yield the same amount of oxygen as 0.25 inch cubes of the same sample. I n some of the experiments the copper was heated to a red heat and in others to 8s high a temperature as could be obtained but the author does not consider that the actual temperature makes much difference.A number of microphotographs OF- deoxidised copper are also given. \JT. P. s. Estimation of Ozone. FREDERICK P. TREADWELL and E. ANNELER (Zeit. anorg. Chem. 1905 48 86-97. Compare Ladenburg and Quasig Abstr. 1901 ii 420; Ladenburg Abstr. 1903 ii 237).- The authors confirm the accuracy of Ladenburg’s method of estimating ozone (Zoc. cit.-absorption in neutral potassium iodide solutiou acidification and titration of iodine set free with sodium thiosulphate) but find that still better results are obtained if the ozone instead of being bubbled through the iodide solution is collected in a glass bulb into which the iodide solution is subsequently introduced. The excess of iodine set free when acid solution of potassium iodide is used is due to the formation of hydrogen peroxide since the latter substance can be detected by the titanic acid test.Potassium bromide cannot be used instead of the iodide as the results both in acid and neutral solution are too low; the arsenious acid method is inconvenient and does not give accurate results when the proportion of ozone is small. The sodium hydrogen sulphite method (Ladenburg loc. cit.) is a,lso inconvenient and gives rather too high results. G. S. Estimation of Sulphur in Petroleum and Bituminous Minerals. FREDERIC C. GARRETT and E. L. LOMAX ( J . Xoc. Chem Jnd. 1905 24 1212-1213).-F~r.om O a 7 to 1.5 gram of the substance is placed in a small platinum crucible intimately mixed with 3 or 4 grams of a mixture of four parts of calcium oxide with one part of sodium carbonate and the crucible then completely filled with latter mixture.A larger platinum crucible is now placed over the smaller one (mouth downwards) the whole inverted and the space between the two crucibles filled with the lime-sodium carbonate mixture. After closing the mouth of the crucible with a thick piece of asbestos board the ampparatus is placed in a muffle furnace heated t o bright redness. Distillation commences in about two minutes and as soon as a flame appears the asbestos may be removed. The heating is continued for two hours at the end of which time the mixture is brought into water the sulphides &c. are oxidised by the addition of bromine and the solution then acidified filtered and precipitated with barium chloride as usual. Experimental proof is given that the 111 e t h od is tr ns t woi- t h y .w. P. s. Estimations of Sulphate and Sulphur. OTTO FOLTX ( J . Biol. GhenL. Hew York 1906 1 13l-l6O>..-A discussion of the method of estimating sulphates as barium sulphate in view of the recent discovery of chlorine in barium sulphate precipitates (Hulett and Duschak,124 ABSTRACT8 OF CHEMICAL PAPERS. Abstr. 1904 ii 616) leads to suggesting means of overcoming this and other difficulties with special reference to the determination of sulphates in the urine. Previous work appears to be untrustworthy. A method for estimating total sulphur in urine by means of sodium peroxide is also given with full details. W. D. H. Estimation of Sulphurous Acid in Foods and Sulphur in Coal- gas. TH. SCHUMACHER and E.FEDER (Zeit. Xalw. Genussm. 1905 10 649-659).-Whilst the method previously described by the authors (Abstr. 1905 ii 856) gives sufficiently accurnte results in the case of pure sulphite solutions such is not the case when organic matter is present and the method is consequently not applicable to the estima- tion of sulphurous acid in meats dried fruits Ssc. A modification of the process is now described which gives trustworthy results. It con- sists in distilling the article of food after acidifying with phosphoric acid in a current of carbon dioxide aiicl collecting the distillate in a receiver containing a known volume of s tandardised potassium iodate solution. The iodine liberated by the sulphurous acid is expelled from the receiver by boiling the contents of the latter and the remaining iodate is titrated with X/10 thiosulphate solution after the addition of potassium iodide and sulphuric acid.For the estimation of sulphur in coal-gas 2 cubic feet or more of the gas are burnt and the products of combustion drawn by means of a current of air through a known volume of iodate solution. The iodate remaining unreduced is then titrated. W. P. s. Estimation of Sulphuric Acid by means of Barium Chloride in the Presence of Interfering Substances. GEORG LUNGE and R. STIERLIN (Zeit. unyew. Chem. 1905 18 1921-193O).-The con- clusions arrived a t by the authors are as follows. When estimating sulphur in pyrites by Lunge’s ammonia method the presence of copper causes no error. Sm:ill quantities of zinc are also harmles but if large quantities of this metal are present unsatisfactory results are obtained.It is recommended that the barium chloride solution should be added all a t once ; slight errors due to solubility of barium or to incomplete precipitation are then fully co npensatecl by occlusion of barium chloride. L. DE K. Estimation of Tellurous and Telluric Acids. ARMAND B E ~ G (Bull. Soc. chim. 1905 [iii] 33 1310-1312).-The method is based on the production of tellurium chloride by the aciion of hydrogen chloride on tellurous and telluric acids or their salts. A weighed quantity of the substance is placed in a hard glass combustion tube into which a t one end a current of dry hydrogen chloride can be passed. The other end of the tube is drawn out bent a t right angles and con- nected to the first of two U-tubes each containing 5 C.C.of water. The porcelain boat is heated a steady current of hydrogen chloride being i n a h tained meanwhile. The chloride formed is driven forwitrd ancl collectecl for the most part in the narrow drawn-out end of the com- bustion tube whence when the operation is finished i t is washed out by ‘‘ sucking back ” in succession the quantities of water contained inANALYTICAL CHERI ISTRY. 125 the t w o U-tubes. The solution is placed in a tared porcelain crucible and after the addition of some nitric acid evaporated to dryness on :t sand-bath and the residue heated so as to produce tellurous anhydride which is weighed. I n the case of tellurites and tellurates the chlorides left in the porcelain boat may be weighed.The method cannot be used with compounds containing mercury chromium or other sub- stances which yield volatile chlorides. T. A. H. Estimation of Nitrous and Nitric Acids. JAKOB MEISENHEIMEI~ and FRIEDRICH HEIM (Ber. 1905 38 4136).-A reply to Raschig (this vol. ii 50). The method previously described (ibid. 49) is for the estimation of the two acids in presence of one another. J. J. S. Analysis of Chili Salpetre. R. BENSEMANN (Zeit. nngew. Chem 1905 18 1072-1974).-A recapitulation of the oxalic acid process (Abstr. 1905 ii 481,555) illustrated with practical examples. L. DE K. Estimation of Nitric Acid in Soils. BUEILERT and FICKENDET (Landw. Versuchs-Xtut. 1905 63 239-246).-The fresh soil (2 kilos.) is shaken for a quarter of a minute at intervals of five minutes during half an hour with 2-3 litres of water.It is then allowed to settle and filtered. A portion of the filtrate (400-500 c.c.) is evaporated down with a few drops of sodium hydroxide and analysed by Schlcesing’s method. I n the case of soils which will not filter 2 per cent. of sodium chloride is added and the desired amount of extract obtained with a pipette. Prolonged extraction is to be avoided as it may result ji veyy considerable losses of nitrate. N. H. J . AT. Action of Acetylene on Iodine Pentoxide. GEORGE F. JAUBERT (Compt. r e d . 1905 141 1233-1234).-The author states that Levy and Pckoul’s method for estimating carbon monoxide in air (Abstr. 1905 ii 203) would give false indications in the case of air containing acetylene as this reduces iodine pentoxide according to the equation I,O + C,H = I + ZCO + H,O.Estimation of Carbon Monoxide in Air by means of Iodine Pentoxide. ARMAND GAUTIER (Compt. reizd. 1906 142 3 5).-A reply t o Jaubert (preceding abstract). The author has alieatly described the reducing action of acetylene on iodine pentoxide aid the correction t o be applied in estimating carbon monoxide by means of iodine pentoxide in air containing acetylene (compare Abstr. 1901 ii 232). M. A. W. M. A. W. Estimation of Silicon in Presence of Silica. M. PrIrLIrs (Zeit. angew. Chem. 1905 18 1969-1 972).-l’he usual separation by treating the ignj ted mixture with hydrofluoric acid is untrustworthy as silicon is somewhat oxidised on ignition and is moreover strongly attacked by hydrofluoric acid.Good results may however be obtained by heating the mixed silica and silicon with a 30 per cent. VOL. XC. ii. 9126 ABSTRACTS OF CHEMICAL PAPERS. solution of potassium hydroxide and collecting the hydrogen evolved in a gas burette Two mols. of hydrogen are liberated for each atom of silicon. L. DE K. Determination of Rare Gases in Natural Gaseous Mixtures. CHARLES MOUREU (Compt. rend. 1906 142 44-46).-The paper contains a diagram of the apparatus and a description of the method employed by the author for estimating and examining rare gases from natural sources. The gas (about 300 c.c.) is first circulated through a series of tubes containing soda lime phosphoric oxide heated lime and magnesium and heated copper oxide to remove carbon dioxide moisture oxygen and nitrogen or hydrogen and combustible material respectively.The purity of the gas is then tested by passing a sample through a second series of tubes which are practically the first series in miniature into a Plucker tube in which the spectrum is examined. Just before entering the last tube the gas passes through a tube containing selenium to remove mercurial vapour. When the spectrum of the gas contains only lines and bands of rare gases the Plucker tube is sealed off and the volume of the residual gas measured over mercury. M. A. W. General Method for the Separation of Metals without using Hydrogen Sulphide. ERICH EBLER (Zeit. anorg. Chem. 1905 48 6 1-85).-With the object of avoiding the inconveniences attending the use of hydrogen sdphide in qualitative analysis the author has devised a method of separation for all the common metals based on the very different behaviour of metallic hydroxides towards ammonia.Whereas some are quite insoluble in it others form stable complex compounds soluble in excess of the reagent. Tin antimony and arsenic compounds as well as phosphoric acid halogens and complex cyanides interfere with the working of the method and have to be removed; convenient,methods of effecting this are described. The chief group reagents with the metals belonging to each group are as follows Group reagent. Metals precipitated. ..................... Hydrochloric acid Age HC1 dilute and NH,*CNS ............ NH,*OH,HCl and NH,*OH ......... NH,*OH and NH,*SH ............... Mn Zn Cd Ni Co. Fe Pb Bi Al Cr Hg.cu. The salts of the alkalis and alkaline earths which remain in solution can be separated by the ordinary methods. Hydroxylamine hydrochloride is used in the second group to secure complete pre- cipitation of iron and to prevent partial precipitation of manganese by oxidation. For full details the original paper must be consulted. G. S. Separation of Barium from Strontium and Calcium by Precipitation as Chromate. ANTON SKRABAL and L. NEUSTADTL (Zeit. anal. Chem. 1905 44 742-755).-The following procedureANALYTICAL CHEMISTRY. 127 is recommended for the separation of barium from calcium and strontium by the chromate method. An excess of neutral ammonium acetate is added to the neutral or feebly acid solution of the mixed salts. The mixture is then boiled and stirred while a 10 per cent.ammonium dichromate solution is added drop by drop. When cold the clear supernatant liquid is decanted on t o a filter and the precipitate washed by decantation with dilute ammonium acetate solution until a colourless filtrate is obtained. The small quantity of precipitate on the filter is now dissolved in a little warm dilute nitric acid and the solution added to the beaker containing the bnlk of the precipitate. Sufficient nitric acid is added to dissolve the latter the solution is rendered neutral by the addition of ammonia boiled and ammonium acetate solution added drop by drop. The mixture is then cooled slowly and the precipitate collected on a filter and washed with cold dilute ammonium acetate solution. After drying the precipitate is detached as far as possible from the filter and ignited carefully in a platinum crucible the filter being ignited separately and the ash added to the crucible.The strontium and calcium present may be estimated in the filtrate i n the usual manner. w. P. s. Estimation of Cadmium by means of the Rotating Cathode. CHARLES P. FLORA (Amer. J. Sci. 1905 [iv)] 20 454-455. Compare Abstr. 1905 ii 855 ; this vol. ii 52).-Cadmium nitrate is ill-fitted for electrolytic estimation except in presence of potassium cyanide ; from a solution containing 1 per cent. or more of free nitric acid the cadmium is not deposited by the current. A summary of the CHARLES P. FLORA (Amer. J. Sci. 1905 [iv] 20 456-458).-The estimation of cadmium as oxide obtained by ignition of the carbonate gives unsatisfactory results when the precipitate is collected on an ordinary filter.The author however states that by using an asbestos filter placed in a Gooch crucible and then heating to constant weight a t a red heat very accurate and concordant results may be obtained. The use of potassium hydroxide as a precipitant for cadmium cannot be previous experiments is given. L. DE K. Estimation of Cadmium as Oxide. recommended. L. DE K. Analysis of Aluminium and its Chief Alloys. CARLO FORMENTI (Chenz. Centr. 1905 ii 1739-1740 ; from Boll. China. Farm. 44 661-675).-The original paper contains a description of the method of sampling commercial aluminium the determination OF its sp. gr. and the estimation of aluminium silicon iron copper sodium carbon lead nitrogen sulphur phosphorus arsenic &c.The analyses and sp. gr. of ten samples are quoted in the abstract ; the sp. gr. varied from 2.69 t o 2.73 whilst the percentage of aluminium was from 98.33 to 99.581 of silicon from 0.103 to 1.1'7 and of iron from 0.22 to 0.624. The distribution of the silicon is of importance in reference t o the use of the metal for culinary purposes since its accumulation a t different points considerably decreases the durability of the vessel. 9-2128 ABSTRACTS OF CHEMICAL PAPERS. Gold bronze from the Neuhausen factory was found to contain 3-5 per cent. of aluminium ; steel bronze 8.5 of aluminium and 1 of silicon “P.B.” bronze 8.5 of aluminium and 2 of silicon ; acid bronze ‘( C ” 10 of aluminium and diamond bronze ‘‘ D ” 10 of aluminium and 2 of silicon.“ Laschenm,etalZ ” is prepared from 88-92-5 parts of aluminium bronze containing 5 per cent. of aluminium 7-5-10 of tin and 62 parts of zinc whilst Hercules metal No. 2 consists of 50 parts of aluminium bronze containing 2.5 per cent. of aluminium and 30 of zinc. For analysis 3-4 grams of turnings are dissolved in dilute nitric acid and the silicon determined i n the residue after evaporating the solution acidifying with sulphuric acid and diluting with water. The copper is estimated by an electrolytic method and the aluminium by precipitation with ammonia or by difference. Aluminium brass is ordinary brass to which aluminium has been added. It is analysed by treating with dilute nitric acid and estimating the tin in the insoluble residue.The copper is determined electrolytically and the zinc by precipitation with ammonium sulphide whilst the iron and alumina are estimated in the filtrate in the usual way. ‘‘ Aluman ’’ is an aluminium brass. ‘‘ Argentan ” contains 7 per cent. of aluminium 70 of copper and 23 of nickel. Commercial magnalium always contains silicon iron and copper. For analysis 1 gram of shavings is treated with Otis-Handy’s acid mixture (compare Berg.-Hiittennz. Zeit. 1897,54)and thesilicon estimated in the residue. The iron is estimated volumetrically in a portion of the filtrate and the iron and aluminium precipitated together in another portion by means of ammonium acetate after oxidation with bromine water. The magnesium is precipitated by sodium phosphate. The copper is precipitated by hydrogen sulphide.E. W. W. Use of Potassium Periodate in the Detection of Manganese Cobalt. and Zinc. STANLEY R. BENEDICT (Amer. Chem. J. 1905 34 581-585).-When a few drops of N / l O solution of potassium periodate are added to a solution of it manganous salt a red precipitate is formed or i f only a very small amount of manganese is present a red coloration is produced. I n a neutral solution the precipitate retains its colour but in presence of ammonia it rapidly becomes brown or black. The red coloration is produced even in a &/lO,OOO solution of manganous chloride. Solutions of zinc salts yield a white precipitate with the reagent. I n presence of ammonium chloride and ammonium hydroxide precipit- ation does not take place in the cold unless the solution contains a large quantity of zinc in which case a portion of i t is precipitated. On boiling however the whole of the zinc is precipitated.The following method is recommended for the detection and separa- tion of manganese and zinc. The solution is treated with ammonium chloride and ammonium hydroxide and a drop of N/10 potassium periodate is added to a small portion of the solution when the production of a pink or red coloration indicates the presence of manganese. If manganese is found t o be present it is completely precipitated by tren ting thc solution with sodium phosphate. TheANALYTICAL CHEMISTRY. 120 solution is filtered and the filtrate is tested for zinc with potassium periodate potassium ferrocyanide or hydrogen sulphide.Periodates can be detected in presence of iodates by the addition of manganous chloride to the solution which has been previously treated with ammonium chloride and ammonium hydroxide iodates give neither a precipitate nor a coloration under these conditions. When pure nickel solutions are treated with the rea,pent a light green precipitate is formed which on boiling becomes faintly grey in colour. Cobalt solutions under similar conditions yield a dark brown precipitate which on further addition of the reagent becomes green in colour and when heated dissolves to form a greenish-black solution. The detection of cobalt in solutions of nickel salts can be accomplished a s follows. To about 2-3 C.C. of the solution of N/2-2N strength 1 C.C. of N/10 potassium periodate is added.If the precipitate produced is light green cobalt is not present t o the extent of more than 1 per cent. The solution is now heated to boiling; if cobalt is absent the colour of the precipitate changes very slightly but if present the precipitate becomes olive-green the depth of colour depending on the amount of cobalt. If more than 1 per cent. of cobalt is present the precipitate shows a brown or olive-green tint in the cold. This test is very trustworthy and is capable of detecting 0.1 per cent. of cobalt in solutions of nickel salts. Absolute Desiccation of Vegetable Substances. L ~ O N MAQUENNE (Cornpt. rend. 1905 141,609-612).-The constant weight of vegetable substances and probably of many mineral and organic compounds after being heated for some time in an oven in ordinary air cannot be considered as a criterion of perfect dryness.Ordinary ovens should be absolutely proscribed in the case of such substances as starch flours and entire grain. These can be completely dried by heating for one hour a t 120" and two hours at 100' in a current of dry air N. H. J. M. Chemical and Physical Methods for the Analysis of Pure Dilute Aqueous Solutions of Glycerol. HUGO HENKEL and A. W. ROTH (Zeit. angeuy. Chem. 1905 18 1936-1941).-A review of the more important chemical and physical processes for the estimation of glycerol in its dilute aqueous solutions. I n the absence of foreign matter the process to be recommended is the one proposed by Plancher (Abstr. 1888 1345) namely oxidation with sulpliuric acid and solid potassium permanganate and absorption of the dried carbon dioxide generated in a weighed soda-lime tube.E. G. L. DE K. Inhibition of Nylander's Sugar Reaction by the Presence of Mercury and Chloroform in the Urine. HEINRICH BECHHOLD (Zeit. physiol. Chern. 1905 46 371-375).- Small quantities of mercury salts added to the urine or present there as a result of the administration of mercury as a drug prevent or lessen the intensity of the Nylander sugar reaction. Albumin albumosea and chloroform act in a similar way. W. D. H.130 ABSTRACTS OF CHEMICAL PAPERS. Apparatus and Methods for the Investigation of Raw Sugar Fuels and Beet Seeds. 0. SCHREFELD (Zeit. Vei.. deut. Zuckerind. 1905 1005-1048).-Tbe aut?hor describes in detail the apparatus and methods used in the “ Institut fur Zucker-Industrie ” of Berlin for the following determinations.(1) Polarisation invert sugar water and ash of raw sugars. (2) Calorific value of fuels. (3) Foreign matter water and germinative power of beet seeds. T. H. P. Estimation of Sugar in Sugar-beets. AXEL TH. HOGLUND (Zeit. Ver. deut. Zuckerind. 1905 1048-1058).-The author finds that on filtering alcoholic solutions containing sugar the first portions of the filtrate give lower polariinetric readings than those obtained later. This is shown to be due to the action of the filter paper the loss in polarisation being nearly proportional to the amount of filter paper employed no matter whether this has been specially dried or not. After a certain amount of the sugar solution has passed through the filter the polarisation attains a constant value which is however less than it should be where large quantities of filter paper have been used.Wood cellulose exhibits a behaviour similar to that of cotton cellulose. Loss of sugar also takes place when the sugar-content of beets is estimated by the digestion process the sugar being here absorbed by the cellulose of the beets. Although such loss does not occur in every case and to an appreciable extent the author’s observations indicate that in the digestion of beets which are poor in juice or otherwise abnormal the loss of sugar amounts to about 0.2 per cent. T. H. P. Estimation of Homogentisic Acid in Urine. ARCHIBALD E. GARROD and WILLIAM H. HURTLEY (J. Physiol. 1905 33 206-210). -In estimating homogentisic acid in urine by Wolkoff and Baumann’s method the ammonia used should be in 8 per cent.solution. With 3 per cent. ammonia the reduction is not complete in five minutes. Care should be taken to avoid the addition of too much hydrochloric acid as excess masks the end-reaction. The correction for uric acid suggested by C. T. Mijrner is as adequate as any general correction can be for so uncertain a quantity. W. D. H. The “Aldehyde ” Value of Milk. R. STEINEaGER (Zeit. Nuhr. Genussm. 1905 10 659-671).-The natural acidity of milk is at once increased by the addition of formaldehyde the increase reaching a maximum with the addition of 1.8 per cent. of formaldehyde or about 5 per cent. of the ordinary formalin (40 per cent.) solution. The difference between the original acidity of the milk and the acidity after the addition of 5 or 6 per cent.of formaldehyde solution is termed by the author the ‘‘ aldehyde ” value of the milk the acidity of the formaldehyde solution itself being allowed for. For normal milks this value (expressed in Soxhlet-Henkel degrees) varies from 5.8 to 8.5. For colostrum the value may be as high as 17.3 but decreases as the milk becomes normal. The phenomenon is not due to the action of an oxidising ferment as the increase is equallyANALYTICAL CHEMISTRY. 131 marked in the case of boiled milk but as the aldehyde value varies with the amount of proteids contained in the milk is undoubtedly caused by chemical reaction between the formaldehyde and the pro- teids. It is proposed to employ the aldehyde value as a means of detecting added water in milk the value being lowered as the proteids decrease in percentage.The value is not however affected by abstraction of fat from the milk. w. P. 8 Sichler's Sinacid Butyrometer. LOTTERHOS (Zeit. Ndbr. Genussm. 1905 10 596-599).-The author considers this process to be as rapid and trustworthy as Gerber's process and shows that results which agree may be obtained in estimations of fat in full milk skim milk and cream. The details of the modification of the process used are 10 C.C. of the salt solution (containing 15 per cent. of trisodium phosphate and 1 per cent. of trisodium citrate) 10 C.C. of milk and 1 C.C. of isobutyl alcohol are placed in the butyrometer tube and well mixed. The tube and its contents are then heated t o a temperature of 75" to go" again shaken and subjected to centrifugal action for one minute.The reading is taken a t a temperature of 70'. w. P. s. Sinacid Butyrometer and its use for Sheep's Goats' and Cows' Milk. CARL BEGER (Milchw. Zentr. 1905 1 547-551).- The results of a number of estimations of fat in sheep's goats' and cows' milk are given showing that by this process differences of from 0 to 20.45 in the percentage of fat may be obtained. The author considers that even where trustworthy results are obtainable the method offers no advantages over other centrifugal methods. w. P. 8. Dika Fat. JULIUS LEWKOWITSCH (Analyst 1905 30 394-395)- This fat is obtained from the seed kernels of various kinds of Irvingia trees indigenous to the West Coast of Africa from Sierra Leone to Gaboon.A sample of the fat extracted by the author himself from the seeds gave the following analytical figures sp. gr. 0.9140 at 4Oo/4O0 ; melting point 38.9" ; saponification number 2445 ; iodine number 5.2 ; Reichert-Wollny number 0.42 ; unsaponifiable matter 0.73 per cent. Stearic acid was not present and as Oudemans has shown that palmitic acid is also absent the fat may be taken as con- sisting of myristin and laurin with a small quantity of olein. w. P. s. Foreign Fats and Oils. AUGUST SCHROEDER (Arch. Pharm. 1905 243 628-640).-The results of the examination of several fats and oils are tabulated below ; the columns of the table contain in succes- sion ( a ) saponification number ( b ) iodine number ( c ) Reichert- Meissl number (cl) Hehner number ( e ) acid number (when two numbers are given the first refers to the oil when newly extracted the second after i t has been kept for a time) (f) acetyl number (9) per- centage of glycerol (h) percentage of non-saponifiable matter.132 ABSTRACTS OF CBEMICAL PAPERS.e. f Ac 9 per h per CL . b. c. cl. No. cent. cent. I. 268.2 2'28 1.47 76.1 3.35 8.82 - 13.03 1'44 8-67 16-93 111. 198'2 127'8 117.5 - 95.1 57.4 27'9 9'49 0.71 IV. 193.8 81.9 78'4 6.43 85.8 37.9 44.5 8'3 12'78 11. 159% 64.2 1.71 94.9 27.4 69.2 - I. Fat from the seeds of Lepidadenia Wightiuna from Java (Litsma sebifera Cylicodaphne sebifera Tet~anthercc calophyllo) known as Tangkala fat. This melted a t 46O and had sp. gr. 0.8734 at 4 1 O ; it appeared to contain laurin 96.0 per cent.; olein 2.6. 11. Oil from the seeds of Xtyychnos nux vomicu (compare Harvey and 'Wilkes .I SOC. Chem. Ind. 1905 24 '718). The oil had the sp. gr. 0.8826 a t 20'; it appeared t o contain olein 74.5 per cent. solid glycerides 8.6 (arachate and palmitate with perhaps a little butyrate and decoate). 111. Oil from the seeds of the caoutchouc tree Hevea braxiliensis from Para. The oil had the sp. gr. 0.9293 at 20'; it appeared to contain palmitin with a little stearin and glycerides of unsaturated acids which could not be identified I V . Oil from the root of Polygala Senegu. The oil had the sp. gr. 0.9616 at 18'; it appeared to contain olein 79.3 per cent. palmitin (with a little valerin) 7.9. C. F. B. Detection of Formaldehyde. CARL GOLDSCHMIDT (J.p r . Chem. 1905 [ii] 72 536. Compare Abstr. 1905 ii 867).-A risurnS of some methods which have been proposed for the detection of formal- dehyde (Abstr. 1898 i 450; Trillat Abstr. 1893 ii 439 ; Lebbin Abstr. 1897 ii 606 ; Clowes and Tollens Abstr. 1900 ii 56 ; Pil- hashy ibid. 453). Pyridine and quinoline bases are readily soluble in 30-40 per cent. but are insoluble in 25 per cent. formaldehyde solu- tion. G. Y. Indirect Estimation of Aldehydes in Oil of Lemons. ENRICO BERT^ (Gazxettu 1905 35 ii 437-450).-This method is based on the change in the rotation of the oil of lemons produced by removal from it of the aldehydes by means of potassium hydrogen sulphite solution and is carried out as follows. To 10 C.C. of the oil contained in an Erlenmeyer flask of about 250 C.C.capacity are added 50 C.C. of saturated potassium hydrogen sulphite solution the flask being then closed by a stopper through which passes a glass tube 40-45 cm. in length. The mixture is shaken so as to form an emulsion and is then heated on a water-bath for ten minutes the flask being frequently shaken and care being taken not to heat it excessively. It is next allowed to cool completely and is then subjected to further heating with continuous agitation for five minutes. After cooling the contents of the flask are introduced into a 100 C.C. tapped separating funnel the yellow lower layer of oil being then separated washed twice with a little distilled water filtered in presence of a small quantity of anhydrous sodium sulphate and when quite clear read in the polari- meter.If the reading thus obtained is A and the initial reading of the oil before treatment with the sulphite solution a the per-ANALYTICAL CHEMISTRY. 133 centage C of aldehydes originally present in the oil is given by C = 100 ( A - a ) / d . The inet,hod is fouud to give good results. T. H. Y. Estimation of Vanillin. JOSEF HANUS (Zeit. Nahr. Genussna. 1905 10 585-591).-Aqueous solutions of vanillin are precipitated quantitatively by m-nitrobenzoylhydrazide the presence of acetanilide benzoic acid sugar and salicylic acid having no influence on the estimation. For the estimation of vanillin in vanilla 3 grams of the latter in powder are extracted for three hours with ether. The ethereal solution is evaporated the residue is redissolved in a small quantity of ether the solution filtered again evaporated and the residue heated for some time with 50 C.C.of water a t a temperature of 60'. The emulsion thus obtained is then precipitated by the addition of 0.2 gram of nz-nitrobenzoylhydrazide dissolved in 10 C.C. of water. The mixture is kept on the water-bath for thirty minutes and then set aside for twenty-four hours. The whole is now extracted three times with light petroleum the extracts being poured through a Gooch's filter and finally the precipitate is also brought on to the filter. The precipitate is washed with water then with light petroleum dried a t loo" and weighed. By multiplying the weight of precipitate obtained ALFRED WOHLK (Zeit. anal. Chem. 1905 44 765-766).-Unless ammonium salts are present hexamethylenetetramine gives no coloration with Nessler's reagent either in the cold or when heated.The presence of paraformaldehyde can be detected similarly since :c trace of the latter Detection of Choline by the Polarisation Microscope. JULIUS DONATH (J. PhpioZ. 1905 33 21 1-219).-The double refraction and chromatic polarisation exhibited by crystals of choline platinichloride may be used as a delicate test for distinguishing this cornpound from potassium and ammonium platinichlorides and for detecting small quantities of choline in liquids such as the cerebrospinal fluid. The results confirm those obtained previously by other methods. by 0.4829 the quantity of vanillin is found. w. P. s. Tests for the Purity of Hexamethylenetetramine. reduces Nessler's reagent on warming.w. P. s. W. D. H. Detection of Choline in Physiological Fluids. OTTO ROSENHEIM (J. Physiol. 1905 33 220-224).-The importance of the presence of choline in cerebrospinal fluid and blood in cases of degenera- tive nervous diseases as shown by Halliburton and Mott Donath and others renders necessary some simple test which can be applied to the small quantities which are alone available as a rule. The best test appears to be to prepare the platinichloride and add to it a solution of iodine in potassium iodide ; the crystals rapidly dissolve and crystals of choline periodide take their place ; as the iodine evaporates the latter disintegrate into oily droplets. Crystals of other platinichlorides liable to be mistaken for the choline cornpound are unaffected by the iodine solution.Other tests are (1) the addition of alloxan gives a rose-violet colour which is changed t o bluish-violet by sodium or potassium134 ABSTRACTS OF CHEMICAL PAPERS. hydroxide and discharged by mineral acids; and (2) the addition of potassium bisniuthoiodicle produces R brick-red amorphous precipitate. w. D. H. Estimation of Indole. CHRISTIAN A. HERTER and M. LOUISE FOSTER (J. Riol. Chem. New York 1906 1 257-262).-The method is based on the colour reaction which follows the condensation of indole with sodium P-naphthaquinonesulphonate. There is a rough pnrallel- ism between the intensity of the indican reaction of the urine and the quantity of indole in the faeces. W. D. H. Estimation of Tannin in Wine. LUDWIG KR~MSKY (Zeit.and. Chem. 1905 44 756-765).-From 50 to 100 C.C. of the wine are rendered alkaline with ammonia and precipitated with a solution of zinc hydroxide. The latter reagent is prepared by dissolving 25 grams of zinc sulphate in water adding sufficient ammonia to redissolve the pre- ctipitate formed then 300 C.C. of ammonia and finally water to make the volume up to 1 litre. The precipitate of zinc tannate is stirred until it coagulates and settles. Three hundred C.C. of hot water are added and the precipitate collected on a weighed filter? washed with dilute ammcnia dried at loo" and weighed. The filter and precipitate are now- ignited and the weight of zinc oxide obtained is subtracted from the total weight the difference giving the amount of tannin. Gallic acid is not precipitated by the above reagent and the ordinary constituents of wine have no influence on the estimation.w. P. s. Estimation of Tannin by means of Strychnine. SAMUEL R. TROTMAN and JOHN E. HACKFORD (J. SOC. Chem. Ind. 1905 24 1096-1 100).-Abopt 8.5 grams of material (sumach for instance) are extracted in a Soxhlet tube with alcohol. The solution is concen- trated to 50 c.c. then diluted with water to 100 c.c. and the resins hc. which are precipitated filtered off. Twenty-five C.C. of the filtrate are evaporated to obtain the total water-soluble matters and another 25 C.C. are treated as follows after introduction into a 250 C.C. flask and adding some water a solution is added prepared by dissolving 0.25 gram of strychnine in 50 C.C. of alcohol and diluting with 50 C.C.of water. After diluting to the mark the whole is well shaken and the precipitate collected a t the suction-pump on a weighed asbestos filter. The strychnine tannate is finally dried a t 60' in a vacuum. One hundred parts =49.1 parts of tannin. L. DE K. Value of the Spectrum of Hamochromogen. ANGELO DE DOMINICIS (Chenz. Centr. 1905 ii 1195 ; from Bed. klin. TVOCIL. 42 1219-1220).-A particle of the dried blood is rubbed with a drop of pyridine and a drop of ammonium sulphide added. I n this manner there is obtained the purplish-red colour reaction of haemochromogen hzemochromogen crystals and the spectrum of haemochromogen. N. H. J. M. Detection of Bile Pigments in Urine. L ~ O N GRTMBEI~T (J. Pharm. Chim. 1905 [vi] 22 487-498).-The author suggests theANALYTICAL CHEMISTRY. 135 following modification of the methods of Hammarsten (compare Abstr.1900 ii 637) and of Salkowski (compare J. Phann. Clzirn. 1894 [v] 30 125) for hhe detection of bile pigments in urine. A mixture of 10 C.C. of the urine and 5 C.C. of a 10 per cent. solution of barium chloride is centrifugalised the precipitate of the barium sulphate phosphate and possibly bilirubin compound taken up with 4 C.C. of alcohol containing 5 per cent of its voluine of hydrochloric acid is boiled on the water-bath for a minute and the precipitate allowed to settle. If the supernatant liquid is colourless the urine is free from bile pigments ; if it is coloured bluish-green or deep green bile pigments are present ; if however it has a brown colour two drops of hydrogen peroxide (10 vols.) are added and the heating repeated.This will oxidise t o biliverdin any bilirubin which may have escaped oxidation by the alcoholic hydrogen chloride and the characteristic green colour will appear. M. A. W. Valuation of Barley C. BLEISCH and P. REGENSBURGER (Chem. Centr. 1905 ii 1195-1196 ; from Zeit. yes. Brauw. 28 625-631).-The examination of about eighty barleys (mostly Bavarian) showed that with the increase in proteid the amount of extract diminishes (from 78.5 to 74.8 per cent.). The malt extract curve is not completely parallel to the barley extract curve ; between 10.0 and 10.5 per cent. of proteid in a large number of malts there is a rise. The maximum in both cases is with about 9 per cent. of proteid. The amount of spelt seems to have a certain importance in Bavarian (although perhaps not for Silesian) varieties.The loss of proteid in malting is greater in barleys rich in proteid than in those with less proteid. N. H. J. M. Relation of the Amount of Nitrogen to the Character of Barley. EUGEN PRIOR (Chem. Centr. 1905 ii 1390; from Allgem. Zeit. Bierbyau. Malxfabr. 1905 and Zeit. ges. Brauw. 28 684-685). -The determination of the apparent steeliness of barley by soften- ing and then drying (Gronlund) is preferable to the estimation in the original barley of the amounts of starchy steely and intermediate grains. (" Auflosungsgrad ") in which M is the number of starchy grains in 100 of the original barley arid M the number in 100 of softened and afterwards dried barley. Whilst single results showed no relation to the amount of nitrogen average results showed that this relation diminished as the nitrogen increased.The uncertainty of the indica- tions is attributed to differences in the character of the nitrogen com- pounds. N. H. J. M. The results are expressed by the formula (M1+M)100/(100-M)+2M Relations between the Amounts of Nitrogen and the Character of Austrian Barley8 to the Yield of Extract and to the Friability of the Malt. EUGEN PRIOR (Chem. Centr. 1905 ii 1390-1391 ; from Allgem. Zeit. Bierbrau. Malzfabr. 1905).-The amount of proteid in the barley agreed with that of the malt only in136 ABSTRACTS OF CHEMICAL PAPERS. twenty-three out of forty-eight cases owing to the varying amounts of water-soluble nitrogenous compounds in the barley and differences in the manner and duration of softening.Barleys with 10-11 per cent. of proteid gave results similar to those with 9-10 per cent. It would seem therefore that only those with more than 11 per cent. yield inferior malt. Evidence was obtained that an intimate relation exists between the ‘‘ Auflosungsgrad ” (preceding abstract) of tho barley the friability of the malt and the yield of extract. The rule applied by Haase to Silesian barley that the extract diminishes with an increase in the proteids does not hold good in the case of Austrian barley. N. H. J. M. Estimation of Lecithins. WALDEIJAR KOCH and HERBERT S. WOODS (J. Bio~?. Chenz. New I’ork 1906 1 203-212).-Some modifications of Koch’s former methods for the separation and esti- mation of lecithins and kephalins are proposed and the amounts of these two classes of substances in most of the body tissues and some foods (such as bread eggs and milk) are given in tabular form.The numbers are usually under 1 per cent and frequently the kephalins are more abundant than the lecithins. W. Y. H. Some Methods of forming Hydrazines and their Influence on Biochemical Analysis. NAZARENO TARUGI (Chem. Cenlr. 1905 ii 1638-1639 ; from Boll. Cl~im. Farm. 44 589-595. Compare Scheatakoff Abstr. 1905 i 332).-A sample of fresh urine was found to be incapable of reducing Pehling’s solution and did not acquire this property until i t was at least two hours old. After repeatedly filtering however i t gave a blue coloration with tincture of guaiacum although i t was completely free from both albumin and pus; after heating a t 50’ for five seconds it ceased to give the reaction but the coloration was again formed when hydrogen peroxide mas added. The filtered urine after boiling did not give the blue coloration either directly or when hydrogen peroxide was added. The abnormal be- haviour of the urine is probably due t o the presence of an oxydase (compare Abstr. 1903 ii 460; 1904 ii 220) which attacks the carbamide forming carbon dioxide and hydrazone. I n support of this hypothesis experiments have shown that by the action of oxidising agents (hypochlorites persulphates) and vegetable and animal extracts containing oxydase on Haga’s and Sachsse and Knapp’s solutions reducing actions also take place which are probably caused by the hydrazine that has been formed by oxidation of carbamide. The possibility of the occurrence of hydrazine is of importance in reference to bicchemical analysis. E. W. W.

ISSN:0368-1769    

DOI:10.1039/CA9069005121

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

129 Organic Chemistry. New Isomeride of Heptane s-Tetramethylpropane [pa- Dimethylpentane ]. MICHAKL I K ONOWALOFF (J. Russ. Phys. Chem. Soc. 1905,37 910-91 l).-For pa-dimethylpeutane (compare Chonin Abstr. 1905 i 729) the author gives the following canstants boiling point 83-84' under 749 mm. pessure; sp. gr. 0.7022 at Uo/Oo and 0.6879 a t 22'/Oo; n 1.38477 a t 22'. T. H. P. New Method of Preparing Olefines. ALPHONSE MAILHE (Chem. Zeit. 1906 30 37).-When the monohalogen substituted para- ffins are passed through a glass tube containing reduced nickel cobalt or copper heated at 250' or more they are decomposed into the corre- sponding halogen acid and an olefine; these two substances are prc- vented from recombining by passing through potassium hydroxide solution. The chloro-derivatives are decomposed below 250° whilst the bromo- and iodo-derivatives require increasingly higher tempera- tures ; ethyl iodide for example is only decomposed at a temperature of 360'.The dried chlorides of the bivalent metals nickel cobalt cadmium iron lead barium &c. also act catalytically in the same way at about 300° barium chloride being most efficieut. In the case of the bromo- derivatives a slightly higher temperature about 320° is necessary and owing to the greater tendency of the decomposition products to reunite the yield of hydrocarbon is not so good. The anhydrous brom;dcs of lead cadmium nickel or barium and the iodides of lead or cadmium have been found to act in a similar manner a t 320". Since the halogen derivatives of univalent metals are not able to effect this decomposition it is assumed that the reaction entails the intermediate formation of an organo-metallic compound as follows MCI + C,Hp+,Cl= HCI + ClM*C,HpCl; ClM*C,,H,,Cl= CnHZtL + MCI,.S. A. POGOR~ELSKY (J. Russ. Phys. Chem. Xoc. 1905 37 814-818. Compare Abstr. 1905 i 165 315).-The action of isobutylene on iodine in potassium iodide solution yields mainly trimethylcnrbinol and isobutylene a-oxide together with a small quantity of tert.-butyl alcohol. The author regards the reaction as expressed by either (1) CXe2:CH2+I,= C,Me,I*CH,I ; CMe21*CH,1+ H20 = OH*CMe2*CH,I -_ c + HI ; P. H. Reaction of Iodine with isoButylene. or (2) I + H,O = HI + HI0 ; CXe,:CH2 + HI0 = OH.CJZP~*C~I,T ; T. H. P. OH*CMe,CE€,I = y'">.o + HI. (2 H2 Combustion of Aoetylene i n Oxygen.PAUL MAURICHEAU- BEAUPRB (Compt. rend. 1906 142 165-166).-Tn addition to carboii - VOL. XC. i. Z130 ABSTRACTS OF CHEMICAL PAPERS. dioxide and water vapour the gaseous products of the oxyacetylene blowpipe flame contain oxides of nit.rogen and ozone (compare Berthelot Abstr. 1900 ii 475 538); after removing the oxides of nitrogen by means of ferrous sulphate crystals moistened with con- centrated potassium carbonate solution (compare Grtutier Abstr. 1898 ii 537) the amount of carbon monoxide in the residual gaseous mixture was determined by the method of Albert-LBvy and Pecoul (Abstr. 1905 ii 203) and found to be less than 1 in 100,000. M. A. W. The Simplest Hydrocarbon with Two Conjugated Systems of Double Bonds. aye-Hexatriene.PIETER VAN ROMBURGH and W VAN DORSSEN (Proc. K. Akad. Wetensch. Anzsterdam 1905 8 565-568. Compare this vol. i 14l).-When slowly heated at 165O and then gradually to 200° the diformate of s-divinyl glycol or a mixture of the diformate with the glycol evolves carbon dioxide and a small amount of carbon monoxide and yields a distillate coneist- ing of two layers of which the upper layer is uychexatriene CH,:CH*CH:CH*CH:CH,. This is a colourless strongly refracting liquid which boiIs at '78.5 -80" {corr.) under 766 mm. pressure and has the sp. gr. 0.7565 at loo and i)zD = 1.49856 at 10' ; it is reduced by sodium and boiling absolute alcohol and is oxidised slowly when exposed to the air. It forms a dibromide melting at 89-90' and a teti-abromide melting at 1 1 5 O .G. Y. Conditions under which the Metal-ammonium Compounds reduce Halogen Derivatives of the Fatty Hydrocarbons. Preparation of Olefines atid Paraffins. E. CHABLAY (Compt. rend. 1906 142 93-95. Compare A.bstr. 1905 i 502; Lebeau Abstr. 1905 i 401 512).-Ethylene dichloride reacts with sodammonium to form ethylene sodium chloride and ammonia according to the equation C,H,CI + ZNaNH == 2NaC1+ C2H + ZNH and similar results were obtained when the dibromides of propylene pseudobutylene isobutylene or trimothyleue replaced the ethylene dichloride in the above reaction. The dichloride of methylene ethylidene or propylidene or /3P-dichloro- propane yields t>he corresponding paraffin (methane ethane or propane) by the action of sodammonium. M. A. W. Pyrogenic Behaviour of Tetrachloroethylene Acetyl Ghlor- ide Trichloroacetic Acid and Bromoform.MATTH~AS JOIST and WALTHER LOB (Zeit. EZektrochem. 1905 11 938-944).-Experi- ments made in the way described previously (Abstr. 1902 i 3) show that tetrachloroethylene yields hexachlorobenzeue and hexachloro- ethane. The decomposition of acetyl chloride is represented by the equation ZCH,*COCl= 2HC1+ 2CO + C,H,. Bromoform yields tetra- bromoethylene and bromine whilst in presence of water formic acid is also produced. The reactions are explained as before by the inter- mediate formation of CCI CBr and similar unsaturated substances. Tricl~loroacetic acid is entirely broken up thus 2CCl,*CO,H + H,O = 3CO + CO + 4HC1+ C1,. T E.ORGANIC CHEMISTRY. 131 Diisobutenyl Tetrabromide [ap$-Tetrabromo-Pe-dimethyl- hexane].S. A. POGOR~ELSKY (J. Russ. Phys. Chem. Xoc. 1905 37 809-8 14).-Diisobutenyl tetrabromide CH,Br*CBrMe*C H,*CH,*CBrMe*CH,Br separates from ether in monoclinic crystals [a b c = 1,2413 1 1.2318 ; /I= 118'56*5'] melting a t 100". T. H. P. Etherates of Haloid Compounds of Magnesium. 11. Action of Anhydrous Alcohols on Etherates of Magnesium Bromide ; Crystalline Alcoholates of Magnesium Bromide. BORIS N. MENSCHUTKIN (Reprint from Bull. St. Petersburg Polgteclinic Inst. 1905 3 29 pp. Compare Abstr. 1904 i 215).-The etherates of magnesium bromide and iodide react readily with organic compounds of various kinds such as alcohols acids aldehydes ketones and ethers. On dissolving MgBr,,Et20 in a slight excess of an alcohol heat is developed and the ether is replaced by the alcohol forming a compound of the type MgBr2,6R-OH.These compounds are colourless hygro- scopic and slightly soluble in water. Each of them can be crystallised from the alcohol it contains the readiness of crystallisation falling off continuously as the molecular weight increases. The melting points of the compounds formed with methyl ethyl propyl isobutyl and iso- nmyl alcohols are given below together with those of the corresponding alcohols MeOH ......... - 94O MgEr2,6MeOH ......... 190' PPOH ......... - 127 MgBr2,6PrOH ......... 52 C,H,*OH ...... - 108 MgBr,,6C4H,.O 11 80 C,H,,.OH ...... - 117.2 L\lgBr2,6C5H11*OH 46 EtOH ........ - 112 Mg Br2 6 Et OH ......... 1 08.5 ...... ...... The solubilities of the separate compounds i n the corresponding alcohols a t different temperatures are given in the form both of tables and curves.T. H. P. Etherates of Haloid Compounds of Magnesium. 111. Action of Anhydrous Alcohols on Etherates of Magnesium Iodide ; Crystalline Alcoholates of Magnesium Iodide. BORIS N. MENSCHUTKIN (Reprint from Bull. St. Petembwg Polytechnic Inst. 1905,3 12 pp. Compare preceding abstract).-Crystalline alcoholates of magnesium iodide can be prepared by a method analogous to that employed for the corresponding magnesium bromide compounds (Zoc. c i t . ) . The ethylate of magnesium iodide crystallises in six-sided plates 8-9 mm. in length and rapidly turns yellow in the air. The melting points of the compounds prepared by the author are as follows MgI,,GMeOH above 210' ; MgI,,GEtOH 146.5' ; Mg11,6PrOH could not be obtained in a crystalline form.The solubilities of the methylate i n methyl alcohol and that of the ethylate in ethyl alcohol have been determined at various temperatures. 65-70' ; Mg12,6C4H,*OH SO) 95-100' ; MgI,,GC,H,,*OEt SO) T. H. P. 1 2132 ABSTRACTS OF CHEMICAL PAPERS. Etheratos of Haloid Gompounds of Magnesium. IV. Action of Water on the Etherates ; Solubility of Hydrates of Magnesium Bromide and Iodide in Water. BORIS N. MENSCHUTKIN (Reprint from Bull. Xt. Petersburg Polytechnic Inst. 1905 4 26 pp. Compare preceding abstracts).-The action of small qtiantities of water on etherates of magnesium bromide and iodide at moderately high temperatures (35-40') yields etherates of hydroxyhaloid compounds of magnesium.With larger quantities of water acting at the ordinary temperature the hexahydrate of magnesium bromide and the octahydrate of magnesium iodide are obtained. The etherate of magnesium hydroxybromide MgBr*OH,MgBr2,2Et,O has already been prepared by Holioyd (Proc. 1904 20 38). The etherate of magnesium hydroxyiodide MgI*OH,SEt,O is obtained as a hygroscopic unstable white powder. Magnesium bromide hexahydrate melts at 164' and its solubility in water has been determined from -5' t o 164'. The solubility of magnesium iodide octahydrste melting a t 43*5' has been measured from 0' to 43' a t which temperature i t is converted into the hexa- hydrate decomposing a t above 200'; the solubility curve for the bexahydrate is given for the range of temperature 43-2OUO.The solubility curves ol hexahydrated magnesium bromide and iodide in water and of the crystalline methyl and ethyl alcoholates of magnesium bromide and iodide in methyl and ethyl alcohols are in general of the same type. The curve for MgEr2,6MeOH in methyl alcohol however although similar to the other curves does not lie between that for XgBr,,6H20 in water and that for MgBr,,GEtOH in ethyl alcohol; this depends on the divergence in character of methyl alcohol from its homologues. T. H. P. Etherates of Haloid Compounds of Magnesium. V. Action of Esters Compounds of Magnesium Iodide and Bromide with Esters. BORIS N. MENSCHUTKIN (Reprint from Bull. St. I'etersbury Yolylechnic Inst 1905 4 37 pp. Compare preceding abstracts and Abstr. 1904 i 2 15).-With manyestere,magnesium iodide and bromide form compounds which in many cases crystallise well.The compounds of magnesium iodide with acetic esters which are well-crystallised substances melt a t the following temperatures MgT,,GMe*CO,Me 121'. MgI,,6Me*C02Et 78.5'. MgI 6 Me*CO,Pra 6 5'. MgI,,GMe* CO,*C,H (iso) 87 5'. MgI,,6Me*C0,*C,H1 (iso) 60'. The alternate fall and rise of the melting point here exhibited finds a very close parallel in the behaviour of the melting points of the corresponding esters of furandicarboxylic acid (see Yoder and Tollens Abstr. 1902 i 49. Compare also Arbusoff hbstr. 1905 i 316). Solubility curves and tables are given for each of the above magnesium iodide compounds in the particular ester it contains. These compounds are all very hygroscopic and are decomposed by water with liberation of the esters from which they are prepared.ORGASIC CHEMISTRY 133 The following compounds have also been prepared Mg12,6HC0,Et which melts at 70.5" and the solubility of which in ethyl formate has been determined from 0" to 70.5" ; MgBr2,2C,H,*C0,Et~ melting a t about 1 I 0' ; MgBr,,2C,H5-CO2C4H9 melting a t about 130' ; Mg12,3UGH,*C0,Me melting a t 115-117'; MgI2,3C6H;CO,Et melting a t 105'; melting at 135' ; Mg12,4CH,(C0,Et)2 melting a t 115' and decompos- ing and resolidifying at 1 20-125O. blg3rp2C H,( CO,E Q2 T.H. P. The IC(0H) Group of Tertiary Alcohols. LOUIS HENRY (Compt. rend. 1906 142 129-136).-A theoretical paper in which the author discusses the effect on the IC(OH) group of a tertiary alcohol of introducing negative elements or groups such as C1 CN or CO as subst,ituents into the molecule in respect of its behaviour towards such reagents as hydrochloric acid and acetyl chloride.M. A. W. Application of Grignard's Reaction to Ethyl Chloroacetate. E. S~SSKIND (Be?*. 1906 39 ~25-226).-C~~Zoromet?~~Zdiet~~yZcarbinol CH,Cl*CEt,*OH obtained from magnesium ethyl bromide and ethyl chloroacctate boils at 166-167" under the ordinary pressure and at 70-72" under 18 mm. By interaction with secondary amines the following compounds have been obtained climethyZaminomet?~~Lyldieth?/Z- carbinol boiling at 172" under the ordinary pressure and a t 62.5-63.5' under 12.5 mm. diethylaminomethyldiethylcarbinol boiling at 89-90' under 20 mm. pressure and Piperidiizornetl~~l~et?~~Zcarb~noE boiling a t EEE-Trichloro-a-me thoxypentane-6-01 and 2-Trichloromethyl- tetrahydrofuran. JULES HAMONET (Compt.rend. 1906 142 210-211. Compare Abstr. 1904 i 467 705; this vol. i 5s)- c~~-Trichloro-a-methoxypen tane-8-01 OMe* CH2*CH2*CH,*CH(OH) *CCl obtained by the action of chloral on the magnesium derivative of a-iodo-y-methoxypropane is a colourless solid melt.ing at 5 9' and boiling at 142-143' under 17 mm. pressure ; it has an odour similar to that of camphor and a bitter taste is insoluble in water but readily soluble in alcohol chloroform o r ether crystallising from the last solvent in monoclinic plates [a 6 c = 1 008 1 1.75 ; /3= lOS'25'l. I t does not reduce an alcoholic solution of silver nitrate in the presence of ammonia but readily reduces Fehling's solution or silver oxide precipitated by a n alkali An attempt to prepare the corresponding pentene derivative by distilling ccr-trichloro-a-methoxypropane-8-01 with phosphoric oxide (compare Vitoria Abstr.1905 i 110) was not successful the product of the reaction being 2-trichZoromethyZtetrcchydroficra,rt 11 2" under 15 mm. pressure. c. s. CCl,* CH< ,0-$33,. CH,*CH2 ' it is a colourless mobile liquid wihh a strong odour similar to that of camphor has a bitter and burning taste and a sp. gr. 1.42 a t 18"; it134 ABSTRACTS OF CHEMICAL PAPERS. boils at 90-91' under 17 mm. or 203-204' under 758 mm. pressure ; it is insoluble in water but soluble in alcohol or ether. It has no reducing action on alcoholic silver nitrate or on Fehling's solution and is not readily attacked by alcoholic sodium hydroxide.M. A. W. Asymmetric Derivative8 of Hexane-at-diol ; Diethyl Ether and Di-iodo-derivative of Heptane-av-diol. R. DIONNEAU (Conipt . rend. 1906 142 91-32).-~-Bromo-a-ethoxyhexane OEt*[CH216*Br prepared by the action of hydrobromic acid on a(-diethoxyhexane has not yet been obtained quite pure but forms the chief constituent of the fraction boiling between 121" and 123' under 35 mm. pressure. By boiling with sodium iodide in alcoholic solution it is converted into (-iodo-a-ethoxyhexane OEt*[CH,],*I a colourless liquid boiling at 138-139' under 35 mm. pressure and having a sp. gr. 1.379 at 11'/4'. This forms a magnesium derivative OEt*[CH,],*MgI which reacts with iodoethoxymethane to form arpdiethoxyheptcne OEt*[CH,],*OEt (compare Hamonet Abstr. 1904 i 467; 1905 i 403) a colourless liquid with a fruity odour boiling at 129' under 35 mm.pressure and having a sp. gr. 0.853 at 1 1°/4'. ar)-Bi-iodoheptane i;,H1412 prepared by the action of hydriodic acid ia sealed tubes at 100' on the preceding compound is a stable liquid which boils a t 178' under 20 mm. pres- sure has a sp. gr. 1.943 at SO/SO and solidses to form colourless crystals melting at about 0'. M. A. W. a B~-Trichloroethyl Ether. GIUSEPPE ODDO and EFISIO MAMELI (Atti R. Accad. Lincei 1905 [v] 14 ii 587-4595. Compare Abstr. 1904 i 280).-The action of 50 per cent. potassium hydroxide solution on aPP-trichloroethyl ether proceeds much more rapidly than that of water but yields the same products; the same is the case with the action of an aqueous solution of ethylamine and with that of saturated sodium hydrogen sulphite solution.The action of dry ammonia on the ether yields dichloroacetal in quantities varying with the conditions together with liquids boiling below and above 181-184' and complex resinous substances con- taining nitrogen. When heated with magnesium the ether is only slightly attacked giving small quantities of substances boiling below and above 170-1 75". Also when solvents are present the magnesium effects but little action yielding when benzene is employed dichloroacetal. Zinc dust acts more readily on the ether than does magnesium giving hydrogen chloride dichloroacetaldehyde and a voluminous resinous mass. I n presence of ethyl ether an energetic reaction takes place on heating but 110 organo-zinc compound analogous with the organo-magnesium compounds prepared by Grignard is obtained. On treating with water the product of the reaction between zinc and the trichloro-ether in presence of ethyl ether,it yields dichloroacetal together with small quantities of dichloroacetaldehyde hydrate of the additive product of dichloroacetaldehyde (1 mol.) with ethoxide (2 mols.) boiling at 110-111' and of products boiling at above 184'.Attempts have been made to prepare PP-dichloroethyl ether byORGANIC CHEMISTRY. 135 reducing the trichloro-ether with zinc or magnesium under various conditions but without success. DichZoromonotr"LioacetaZ CHCI,*CH(OEt)*SEt prepared by the inter- action of ethyl mercaptan and aPP-trichloroethyl ether was obtained as a yellowish-red liquid boiling a t 110-125° under 20-30 mm.pressure. Phen?lZetlLyZdichloroncetaZ CHC1 CH (OEt )* OP h prepared by the action of anhydrous sodium phenoxide on aPP- trichloroethyl ether in benzene solution is a reddish-brown unstable liquid which boils a t 165-170O under 40 mm. pressure dissolves in alcohol decolorises potassium permangnnate and combines with bromine giving a white solid substance. The interaction of molecular proportions of up@-trichloroethyl ether and pyridine in ethereal solution yields an oily red precipitate which forms (1) a platinichloridp (CHCl,*CHC1*OEt,C,H,N),,PtC14 crystal- lising from dilute hydrochloric acid in mamillary masses of slender orange-yellow needles melting and decomposing a t 208-209O ; (2) an auricMoride (CHC1,*CHCl*OEt,C,HI,N),AuCl3 as a heavy yellow precipitate melting at 92-93O.T. 13. P. Liberation of Carbon Monoxide [from Organic Compounds]. AUGUSTIN BISTRZYCKI and B. VON SIEMIRADZKI (Ber. 1906 39 5 1-66).-The following compounds yield carbon monoxide when heated alone or with sulphuric acid sulphur chloride phosphorus pentachloride &c. Quantitative experiments were made on all substances the formulse of which are given I. Formic acid and its methyl and ethyl esters. 11. a-Hydroxy-acids and their derivatives namely diphenylene- glycollic acid C1,H,oO ; lactic acid C3HB03 ; a-niethoxyphenylacetic acid. OIMe*CHPh*CO,H ; mandelic acid C,H,O ; o-methoxyphenoxy- acetic acid OMe*C,H,*O-CH,*CO,H ; phenylchloroacetic acid and a-alanine C3H702N.111. Oxalic acid and its derivatives ethyl oxalate and oxamide IV. a-Dicarbonyl compounds pyruvic acid C3H403 and benzoyl- formic acid CSHG03. V. Tertiary acids sulphocamphylic acid C,,H,,O ; m-chloro-p- hydroxytriphenylacetic acid C,,Hl,O,Cl ; camphoronic acid dimethylmalonic acid C5H804 ; methyl diphenyl-p-tolylacetate p-tolyldiphenylacetolactone C,,H1G03; 3 &(or 2 4-)dihydroxytritano- lactone H O * C 6 H 3 < ~ ~ ~ > C 0 . C,H,O,N,. C02H*CMe,*CMe(C0,H) CH2*C0,H ; C,,~,OO ; TI. Secondary and primary acids p-hydroxydiphenylacetic acid diphenylacetic acid C,,H!,O ; and (in small amounts) phenylacetic acid C,H,02 ; palmitic acid C,6H,202. VII. Ketones and aldehydes benzaldehyde (small amounts) ; camphor at 360' ; potassium lsvulate (by electrolysis) ; ptolylpenta- decyl ketone.c14H1203 ;136 ABSTRACTS OF CHEMICAL PAPERS. m-Chlonq-hydroxytriphenplacelic acid C02H*CPb2*C,H,C1*OH prepared by condensing benzilic acid with o-chlorophenol by means of stannic chloride crystallises from a mixture of benzene and light petroleum in colourless microscopic tablets and melts at 189’. Methyl di~hen~l-p-tolylacetate (compare Bistrzycki and Wehrbein Abstr. 1901 i 712) crystallises from methyl alcohol in long colour- less microscopic tablets and melts a t 135’. The Capacity of Methoxyl and Ethoxyl Groups for Replace- ment by [Alkyl] Radicles. Synthesis of Polybasic Acids. SERGIUS N. REFORMATSKY (J. Buss. Plq/s. Chern. Xoc. 1905 37 881-889).-In the replacement of alkoxyl groups by alkyl radicles by the action of for instance an organo-zinc compound on an ester it is generally assumed that the carbonyl group reacts in the first stage of the change and the alkoxyl group in the second thus (1) R*CO*OEt + ZnI1’1= IZn*O*CRR’*OEt ; (2) IZn*O*CRK‘*OEt + ZnR’I = CRR’,*OZnI + ZnI-OEt.It has not however been shown that the OEt group is not directly repiaced by the alkyl radicle forming R*CO*R’ which would then react with ZnR’I giving T. M. L. CRR,*OZnI. The author’s attempts t o isolate intermediate products formed in reactions similar to the above have as yet yielded no definite results (see this vol. i 138). Double Acetates of Gold. Crystallised Barium Auryl Oxide. F. WEIGAND (Zeit. angew. Chew. 1906 19 139-140).- The double acetates of gold with calcium barium strontium mag- nesium or lead were prepared by adding the hydroxides of these metals to a solution of auric chloride and dissolving the moist pre- cipitates so obtained in boiling glacial acetic acid; the solutions deposited monoclinic crystals of compounds of the following formulze.T. I€. P. Ba(C,Ha0,)2,29u(C,H30~)3 ; sr(C2H,02),,2Au(C,H302)3,2H20 ; Ca(C‘,H302),,2Bu(C2H3o2)3,2H2o ; BTg( C,H 302),2AU( C2H302)3,4H20 ; Pb( c2H302)?,2Au( C2H302)3,2H20. These substances are all soluble in water to give neutral solutions which slowly decompose; when heated on platinum foil the gold is partially volatilised in the form of red fumes. The filtrate from the precipitate obtained by adding barium hydroxide to the auric chloride solution deposited after some time small yellowish-green rhombic crystals having the composition B~(O*AUO)~,~H,O ; these dissolve with difficulty in water to give an alkaline solution.HENRY R. PROCTER and W. E. HOLMES (J. SOC. Chem. Ind. 1905 24 1287-1290).-The results of numerous experiments are giren in tabular form with the object of elucidating the chemical changes which take place when oils are oxidised by blowing air through them while in a heated condition. Without exception the sp. gr. and refractive index increased as oxygen was absorbed and the iodine number diminished but complete saturation was never reached. I n some instances the iodine number remained unaltered during the first three or four hours’ blowing although oxygen mas being absorbed indicating that the oxygen was not P. H. The Oxidation of Oils.ORGANIC CHEMISTRY. 137 attached to the unsaturated linkings measured by the iodine number.When however the iodine number commenced to decrease it did so rapidly. The oils experimented with comprised liver oils fish oils linseed oil rape oil cotton-seed oil olive oil castor oil lard oil &c. w. P. s. Pyruvic Acid. WILLIAM OECHSNER DE CONINCK (Bull. Acad. roy. BeZg. 1905 524-525).-When pyruvic acid is dissolved in sulphuric acid and the solution gently heated it blackens and carbon monoxide mixed with a little carbon dioxide is evolved. Concentrated nitric acid converts it into oxalic acid but with dilute nitric acid carbon dioxide and a little formic acid are formed. Pyruvic acid reduces chromic acid auric chloride and selenic acid when warmed with their aqueous solutions.At temperatures slightly higher it reduces mercuric chloride to mercurous chloride and mercurous nitrate to metallic mercury. When warmed with mercuric or silver oxide some acetic acid is produced. Pyruvic acid reduces uranic sulphate uranium nitrate and potassium dichrornate. With the last-named carbon dioxide and some acetic acid are produced. T. A. H. Glycidic Condensation of Aldehydes with Ethyl a-Chloro- propionate. GEORGES DARZENS (Conzpt. Tend. 1906 142,214-215. Compare this vol. i 62)-Acetaldehyde propaldehyde or isovaler- aldehyde condense with ethyl a-chioropropionate to form up-disubsti- tuted glycidates of the type O< c''e*CozEt I but the yield is poor 20 CHR t o 30 per cent. of the theoretical. The aromatic aldehydes readily condense with ethyl a-chloropropionate and the substituted glycidic acids thus prepared yield ketones of the type R*CH,=COMe on distilla- tion ; ethyl /3-phenyl-a-nzetlLylglycidate boils a t 153-1 54' under 1s mm.pressure and the corresponding acid yields carbon dioxide and benzyl- methyl ketone on distillation. Ethyl P-anisyl-a-met7LyTgZ~cid~~e boils at 189-190' under 20 mm. pressure and the aqueous solution of the corre- sponding sodium salt is decomposed by boiling into sodium hydrogen carbonate and anisyl ketone Ethyl P-~~ipero~ayZ-a-metl7L~Zglycidnte boils at 205-210' under 25 mm. pressure and piperonylacetone is obtainad by boiling an aqueous solution of the corresponding sodium salt'. Elkyl /3-furyl-a-methyl glycidate is a colourless liquid boiling a t 150-15 1' under 30 mm.pressure and on boiling with sodium carbonate yields fui-ylacetone ~ ~ ~ ~ > C * C H 2 * C O * C H ; this is a colourless liquid with an odour of horse-radish and boils at 179-180'; its semicarbaxone melts at 173-174' and its oxime boils a t 135-140° under .25 mm. pressure. M. A. W. Dialkylmalonic Acids HANS MEYER (Ber. 1906 39 198-200. Compare E. Fischer and Dilthey Abstr. 1902 i 269).-The dimethyl ester of dimethylmalonic acid is transformed into the amide CMe,(CO*NH,) when kept a t the ordinary temperature with concentrated ammonia for138 ABSTRACTS OF CHEMICAL PAPERS. twenty-four hours and occasionally shaken. The corresponding diethyl ester is not trankformed under similar conditions even after several weeks. Bimsthyl methylethylmalonate CMeEt(CO,Me) is a colourless oil distilling at 189-19 1' (uncorr.) and dimethyl diethylmnlonate distils a t 204-205'.Dimethyl methylethylmalonate reacts with ammonia yielding methylethylmalonunaide CMeEt (CO-NH,) which forms glistening crystals melting st 182-183' and methyl rnethylethyl- rnalonamate CO,Me*CMeEt*CO*NH which sublimes in glistening needles melting at 106-1 08'. Dimethyl- and diethyl-malonyl chlorides readily react with concentrated ammonium hydroxide yield- ing the corresponding diamides whereas methylethylmaIony1 chloride yields methylethylacetamide (Scheuble and Loebl Abstr. 1904 i 466). Fischer and Dilthey's views regarding the formation of the amides from the esters are adversely criticised. Action of Ammonia on Itaconic and Pyrocinchonic Anhydrides.LUCIANO Rossr (Rend. Accad. Sci. Pis. Mat. Napoli 1905 [iii] 11 254-258. Compare Foil Abstr. 1904 i 230)-The action of alcoholic ammonia on pyrocinchonic anhydride a t different temperatures always yields pyrocinchonimide which however melts at 113' if obtained at low temperatures or at 118' if at high temperatures. The action of liquid ammonia on pyrocinchonic anhydride yields pyrocinchoaimide at the ordinary temperature whilst at higher tempera- tures (70-1 00') a yellowish-brown syrup is obtained. These results demonstrate firstly the great resistance exerted by the double linking of pyrocinchonic anhydride against the introduction of an amino-group and secondly the great stability of the anhydride. I n the cold or at 70-80' itsconic anhydride gives with liquid ammonia a yellowish-brown acid syrup which contains nitrogen dissolves Peligot's copper oxide giving a green solution and is pro- bably a mono-amide.In the reaction at loo' the yellowish-brown syrup obtained probably contains a small amount of amino-acid. J. J S. T. H. P. Action of Zinc on a Mixture of Ethyl Orthoformate and Ethyl Bromopropionate. Synthesis of s-Trimethylisobutane- tricarboxylic Acid. 5. SOKOLOWSKY (.I Buss. Phys. Chem. Soc. 1905 37 889-896).-Zinc acts on a. mixture of ethyl orthoformate (1 mol.) and ethyl a-bromopropionate (3 mols.) according to the equations (1) CHMeBr*CO,Et + Zn = BrZn*CHMe*CO,Et ; (2) 3BrZn*CHMe* C0,Et + CH(OEt) = CH(CHMe*CO,Et) + 3ZnBr.OEt. Triethyl s-trirnethylisobutanetricarboxykcte [y-ethylpentane-psc'-tri- carboxylate] C,6H2806 thus obtained is a colourless mobile liquid boil- ing at 200-201°.On hydrolysis it yields the monoethyl ester CO,Et*CHMe*CH(CHMe*CO,H) which crystallises from water in shining white needles and from benzene in long shining plates melting a t 109' and is readily soluble in ether or chloroform. The caZcium Ca(C,,H,80,),4H,0 barium and sodium salts of the monoethyl ester were prepared and analysed. T. H. P.ORGANIC CHEMISTRY. 139 Formation of Ethyl Sodiodicarboxyglutaconate from Ethyl Malonate Sodium Ethoxide and Chloroform. CARL COUTELLE (J. pr. C'hem. 1906 [ii] 73 49-100. Compare Conrad and Guthzeit Abstr. 1883 31 l).-Recrystallised ethyl sodiocarboxygluta- conate is obtained by Conrad and Guthzeit's reaction (Zoc. cit.) in a yield of 41.36 per cent.of the theoretical if the absolute alcoholic solution of 4 mols. of sodium ethoxide is cooled to the laboratory temperature 2 mols. of ethyl malonate and 1% mols. of chloroform added and the mixture quickly boiled in a reflux apparatus. Smaller yields are obtained by varying the proportions of the reacting substances or the temperature or order of mixing. Only 0.55 gram of the sodio- ester was obtained by the action of sodium and chloroform on 16 grams of ethyl malonate in benzene solution (compare Oppenheim and Precht this Journal 1876 ii 69). The formation of et,hyl sodiodi- carboxyglutaconate is not due to the action of primarily formed ethyl o-formate on ethyl malonats as when boiled with ethyl o-formate and sodium in alcoholic solution in a reflux apparatus 32 grams of ethyl malonate yielded only 1.1 grams of the sodio-ester (compare Claisen Abstr.1897 i 592). The sodio-ester remains unchanged when boiled with chloroform in alcoholic solution. The formation of carbon monoxide which must result from the decomposition of ethyl o-formate primarily formed is shown by passing a current of hydrogen successively through the reacting mixture and a solution of cuprous chloride (Hullemann Abstr. 1890 582). The salts which separate from the reaction mixture are sodium chloride ethyl sodiomalonate and sodium formate. The reddish-brown residue obtained from the mother liquor on distillation of the alcohol in a vacuum was extracted successively with light petroleum A and with acetone B. A. The light petroleum extract contains et h y 1 malonate and ethyl is0 but anehexacar box y late CH[CH(CO,Et),],; this is a viscid yellow oil which boils at 235' under 1S mm.pressure has an odour of onions dissolves in alcoholic sodium ethoxide to form a dark red solution decolorises immediately dilute potassium permanganate solution in presence of sodium carbonate interacts with bromine in carbon disulphide evolving hydrogen bromide and when boiled with 10 per cent. hydrochloric acid is hydrolysed with formation of carbon dioxide and isobutane- tricarboxylic acid. This is obtained as a brownish-red resin ; it forms a bsrizcm salt C,,HI,01,Ba,,4H,0 and the trimethpl ester CH(CH,*CO,Me) which is a colourlees liquid boiling a t 180-185O under 23 mm. pressure. Hydrolysis of the ethyl hexacarboxylate with alcoholic potassium hydroxide leads to the formation of a red oil which deposits needles melting at 129O or with baryta water to the formation of barium formate and malonate (compare Bottomley and Perkin Trans.1900 77 294 ; Guthzeit and Engelmann Abstr. 1902 i 742). When heated with aniline at 15OU the ethyl hexacarboxylate forms malon- anilide and the penta-anilide CO,Et*CH(CO*NHPh) *CH[CH(CO*NHPh),] which crystallises from much alcohol and melts a t 245".140 ABSTRACTS OF CHEMICAL PAPERS. B. The acetone solution contains the last traces of ethyl sodiodi- carboxyglutaconate sodium malonate and sodium formate. On treat- ment with sulphuric acid and ether sodium formate yields an ethereal solution which when shaken with water and mercuric oxide filtered and heated in the water-bath gives a grey precipitate of metallic mercury.When treated in the same way sodium malonate forms a yellow precipitate whilst glutaconic acid and ethyl sodiodicnrboxy- glutaconate do not form precipitates. I n a mixture of formates and malonates the formic acid is detected by this reaction the malonic acid by the formation of its sparingly soluble barium salt. On evaporation of the acetone solution treatment of the residue with chloroform and evaporation of the extract a red resinous mass is obtained ; this contains probably a sodio-derivative of ethyl iso- butane h exacarboxylate. In the quantitative examination of the products of the reaction the formic acid is estimated by Lieben's method (see Scala Abstr 1891 248) after precipitation of the malonic acid by means of barium chloride and alcohol or after liberation of the formic acid by means of phosphorib acid and distillation in a current of steam in which malonic acid is not volatile.As ethyl dicarboxyglutaconate is slightly volatile in a current of steam the distillate is filtered after some hours whereby a saturated solution of the ester is obtained; with mercuric chloride 100 C.C. of this form 0.0551 gram of a precipitate which weight is deducted from that of the mercuric chloride formed in the estimation of formic acid. As the barium derivative of ethyl dicarb- oxyglutaconate is only sparingly soluble in alcohol it is precipitated partially together with the barium malonate ; the amount of the latter which when dried at looo has the composition C3H,O,Ba,5/6H,O (compare Guthzeit and Bolam Abstr.1898 i 12) is determined by indirect analysis. Ethyl sodiodicarboxyglutaconate and ethyl o-formate could not be estimated directly. Under the conditions most favourable to the formation of ethyl sodiocarboxyglutaconate 100 grams of ethyl malonate 29 grams of sodium as sodium ethoxide and 38 grams of chloroform interact to form 50.3 grams of ethyl sodiodicarboxyglutaconate 32.6 grams of sodium malonate 10.06 grams of ethyl sodioisobutnnehexadar boxylate 3.99 grams of the free ethyl hexacarboxylate 3-27 grams of sodium formate 0.18 gram of carbon monoxide and 0.66 gramof ethylo-formate more than 13 grams of the ethyl malonate remaining unchanged. G. Y. Formaldehyds and Formate Formation.HANS EULER and ASTRID EULER (Ber. 1906 39 36-39. Compare Abstr. 1905 i 633). -More exact measurements have given for the dissociation-constant of formaldehyde acting as a weak acid the value 1-4 x a t Oo in close agreement with the approximate value 1 x 10-l' previously obtained with formaldehyde containing methyl alcohol. HANS EULER (Bey. 1906 39 344-350. Compare Euler and Euler Abstr. 1905 i 633)-Acetaldehyde has the dissociation constant K=0*8 x 10-14 a t Oo as determined by the T. M. L. Aldehydes as Acids.ORGANIC CHEMISTRY. 141 depression of the freezing point of the solution of its sodium salt (Goldschmidt and Roder Abstr. 1895 i 657) or X=O.5 x at lo as determined by the conductivity of its sodium salt solution; the mean constant is K=0*7 x 10-14 a t 0'.As ammonia forms complex compounds which are not electrolytically dissociated and not salts with acetaldehyde the conductivity of aqueous ammonia is diminished on addition of the aldehyde. a t 1S0 as determined by the change in the conductivity of dilute ammonia which takes place on the addition of the aldehyde or K= 0.8 x 10-14 at 18" as calculated from the comparison of the conductivity of dilute solutions of its ammonium salt with the conductivities of similar solutions of the ammonium salts of boric acid and phenol. The salts of acetone with alkalis or with hydrogen chloride are dissociated bydrolytically t o too great an extent to permit of the determination of the acid dissociation constant by either the con- ductivity or the cryoscopic method. Furfuraldehyde has only feeble salt-forming properties ; its dissociation constant as an acid is l / l O O of that of acetaldehyde.at Oo as determined with the sodium salt; by the cryoscopic method agrees with that calculated by Madsen (Abstr. 1901 ii 228) from the rate of hydrolysis of the ester. As in dextrose and Izvulose solutions containing the equivalent amount of sodium hydroxide the'hexose is present chiefly in the form of the ion the rotation of an alkaline hexose solution is due principally to that of the sodium salt. With sodium light at Oo N-dextrose solution when mixed with equal volumes of water N-sodium bydroxide 'ZN-sodium hydroxide 2N-potass- ium hydroxide and N/2 sodium hydroxide has the rotations 10.4' 8.1" 7 8" 7.8" and 9.9' respectively whilst N/2 dextrose solution with equal volumes of water _V/2 sodium hydroxide and 2iV-sodium hydroxide has the rotations 5 * 3 O 4.2" and 4.2' respectively.The Reduction of Acraldehyde and some Derivatives of s-Divinyl Glycol (y&Dihydroxy-ae-hexadiene). PIETER VAN ROMBURUH and W. VAN DORSSEN (Proc. I[. Akad. Wetensch. Amsterdam 1905 8 541-544. Compare Griner Abstr. 1893 i 237).-When reduced with zinc dust and glacial acetic acid acraldehyde yields ally1 and propyl alcohols and the substance O-YH'CH CH CH E%-CH°CH CH,' which is formed also by heating propaldehyde with s-divinyl glycol a t 90Ofor six days. It is a neutral liquid which boils a t 59-5-60" under 15 mm. pressure is not decomposed by potassium hydroxide sodium or phosphorus pentachloride and does not form a benzoyl derivative when treated with benzoyl chlnride and pyridine; i t yields an odour of aldehyde and forms a brownish-black resinous mass when treated with dilute acids and forms an additive conipound with bromine in carbon tetrachloride solution.The Jifornzate formed by heating s-divinpl glycol with formic acid Chloral hydrate has the dissociation constant K= 1 x The acid dissociation constant of dextrose I{= 1.8 x G. Y.142 ABSTgACTS OF CHEMICAL PAPERS. is a colourless liquid which boils at 109' under 20 mm. pressure and has the sp. gr. 1.0747 a t 11'. G. Y. P-Chloroethyl Ketones and Alkyl Vinyl Ketones. EDMOND E. BLAISE and M. MAIRE (Compt. rend. 1906 1142 215-217).- P-Chloroethyl alkyl ketones of the type CH,Cl*CH,*CO*R readily obtained by the action of P-chloropropionyl chloride on the corre- sponding zinc alkyl are liquids with a faint odour ; their semicarbazones are unstable and readily converted into the carbamide of a pyrazole according to the equation Ethyl Jhhloroethyl ketone boils at 6s' under 20 mm.pressure. P-Chloroethyl popyl ketone boils at 73' under 10 mm. pressure. P-Cfdoroethyl isobutyl ketone boils at 80' under 12 mm. pressure. When the alkyl P-chloroethyl ketones are boiled with diethyl- aniline they yield the corresponding alkyl vinyl ketones in the form of mobile liquids with an intensely penetrating odour; ethyl vinyl ketone boils a t 31' under 47 mm. pressure; propyl vinyl ketone boils a t 24' under 10 mm. pressure; and isobutyl vinyl ketone boils at 32' under 10 mm. pressure. These compounds polymerise rapidly under the action of heat or of alkalis and yield semicarbazo- semicarbazones with semicarbazide hydroxglamino-oximes with hydroxylamine pyrazoles with hydrazine or phenylpyrazoles with phenylhydrazine ; the last compounds give an intense violet-red colour with a trace of nitric acid.The pyrazoles are basic liquids forming salts platinichlorides picrates and phenylcarbamides and with secondary bases yielding additive compounds of the type NEt,*CH,*CH,*CO*R which are also basic and form picrates and platinichlorides. Ethyl P-diethylaminoethyl ketone boils a t 80' under 10 mm. pressure and ethyl P-piperidinoethyl ketone boils at 107' under 11 mm. pressure. HANS EULER and ASTRID EULER (Ber. 1906 39 39-45).-The action of alkalis on formaldehyde leads both to the formation of formates and the formation of sugars but the latter process is not directly dependent on and does not run parallel with the former; addition of formate does not affect the rate at which sugar is formed.Curves are given to show the rate at which sodium carbonate is neutralised by formalde- hyde previously to the formation of sugar. The concentration of formaldehyde at which sugar-formation sets in is dependent on the initial concentrations of the sodium carbonate and of the aldehyde and sugar-formation never appears to occur until a part of the aldehyde has been converted into formate and alcohol ; the most suitable concentra- tion is nearly half an equivalent of soda for each equivalent of alde- hyde. Experiments were also made with calcium carbonate as a con- densing agent the increased time required being compensated for by the increased stability of the sugar and the more constant composition OF the solutions; it was noticed that sugar formation proceeds very CH2C1 CH2* C0.R -+ CH, CH* CO *R 1511.A. W. Formation of Sugar from Formaldehyde.ORGANIC CHEMISTRY. 143 slowly a t first but after boiling for several hours proceeds very rapidly t o a limit ; this is explained by the formation of intermediate com- pounds and the preseice of glicollaldehyde was actually proved. T. M. L. Formation of i-Arabinoketose from Formaldehyde. HANS EULER and ASTRID EULER (Ber. 1906 39 45-51).-When formalde- hyde is condensed by means of calcium carbonate the chief product is a pentose which was identified by means of its osazone and phenylmethyl- osazone and by oxidation with bromine and with nitric acid as i-arabino- ketose.If the action of the alkali is stopped before half the formaldehyde has disappeared glycollaldehyde is one of the chief products but glyceraldehyde could not be detected. A small amount of a hexose is also produced. T. M. L. Apiose. EDUARD VONGERICHTEN and FR. MULLER (Ber. 1906 39 235-240. Compare Abstr. 1901 i 40 646 ; 1902 i 425).-Apiose obtained from the leaves of parsley is identical with t h a t obtained from the seeds. Apiose phep~yZbenxyZh?/drc~~o~~e C,,H,,O,N separates from benzene solution in colourless crystalline flocks which melt a t 135". By the action of formaldehyde apiose is recovered as a colourless syrup which in aqueous solution has [ aID + 3.8" a t 20' and is in all respects identical with the apiose from which the hydrazone was prepared. At 50' the oxidation of calcium apionate by three times its weight of nitric acid of sp.gr. 1.2 results in the formation of an acid isomeric with trihydroxyglutaric acid the calcium salt of which has [a] + 6.58' a t 20'. The oxidation of the acid by silver oxide produces glycollic acid. Neutralised with brucine the acid yields two salts ; the one insoluble in acetone corresDonds with the formula L CHz>C( OH) CO,H C,,H2,0,N O- CO*CH( OH) I has [.ID - 23.7' at SdO and the lactonic acid obtained from it is con- verted on boiling with baryta water into the dibasic hydroxy-acid. The other brucine salt is soluble in acetone melts a t 148-150° and has [a] - 27.2" a t 20" ; the analytical data agree with the formula CH,(OH)*y(OH)*CH (OH)*CO,H,C,,H,,O,Nz C02H*C,,H260,N2 Of the known trihydroxyglutaric acids only the inact,ive ri botri- hydroxyglataric acid is capable of lactone-formation ; it is quite different from the hydroxymethyltartaric acid described above.c. s. Action of Oxygen on Aliphatic Amines in Presence of Copper. WILHELM TRAUBE and ALBERT SCHONEWALD (Be?.. 1906,39 178-184).-When an aqueous solution of ethylamine is shaken for several dajs with copper powder in the presence of oxygen at the ordinary temperature a copious absorption of oxygen is observed (some 7 litres for 10 grams of ethylamine) the copper is oxidised to the hydroxide and the ethylamine to acetaldehyde and ammonia.Nitrogen and nitrous acid do not appear to be formed.144 ABSTRACTS OF CHEMICAL PAPERS. When a 5 per cent. solution of aldehyde-ammonia is shaken with copper and oxygen very little oxidation occurs. It is thus possible that the primary oxidation product in the earlier experiments was aldehyde-ammonia and not free aldehyde and free ammonia since the latter would tend t o become oxidised to nitrous acid. Methylamine reacts in much the same manner as ethylamine yield- ing formaldehyde and ammonia. Sodium -glycine copper and oxygen yield considerable quantities of nitrous acid and probably glyoxylic acid. J. J. S. Electro-synthesis in the Oximo-ether Group. CELSO ULPIANI and G. A. RODANO (Atti R. Accad. Lincei 1905 [v] 14 ii 601-607. Compare Abstr. 1905 i 260).-Using platinum electrodes and a current intensity of 0*2-0*25 ampere the authors have electrolysed the sodium or potassium derivative of ethyl oximinomalonate ethyl a-oximinopropionate and ethyl a-oximinobutyrtrte.These compounds which have the general formula CRR’XONa are decomposed into metal which evolves hydrogen a t the negative pole and the anion CKR’:NO* ; of the last two groups combine a t tbe positive pole. I n this way t,he sodium hydrogen derivative of ethyl oximinomalonate OH-N C( CO E t),,ORTa*N C( C@,E t) yields the compound NO*C(CO Et),*C(CO Et),*NO as an oil which is insoluble in alkali and yields Liebermann’s reaction characteristic of true nitroso-compounds. The potassium derivative of ethyl a-oximinopropionate OK*N:CMe*CO,Et yields the compound NO*CMe(CO,Et)*CMe(CO,Et)*NO as an oil which is insoluble in alkali and gives Liebermann’s reaction.The potassium derivative of ethyl a-oximinobutyrate yields the compound CH,Me*C(NO)(CO,Et)*C(NO)(CO,Et)-CH,Me which is an oil ii soluble in alkali and giving Liebermann’s reaction. T. H. P. Isolation of Amino-acids. MAX SIEGFRIED (Ber.. 1906 39. 397-401. Compare Abstr. 1905 i 5 9 ; ii 332).LGlycine is readily precipitated as bccriuin carbaminoacetate f! H2*co2>Ba when NH,*CO carbon dioxide is led into a solution of the amin’o-aci”d in baryta water at 0’ until phenolphthalein is decolorised aiid the mixture then kept for some time a t 09 Better yields~ are obtained when more bnryta water is added after the carbon dioxide has been led in and when the precipitate is washed with dilute barium hydroxide solution instead of with water.Pure glycine is obtained when the barium salt is decomposed with ammoilium carbonate solution filtered and the solution evaporated. Glycylglgcine yields a similar barium salt C,H,O,N,Bn which is much more readily soluble in water. It is most readily obtained by the addition of alcohol and when decomposed with ammonium carbonate yields pure gl ycylglycine. Lysine and albumoses give similar barium salts. Glyeine andORGANIC CHEMISTRY. 145 alanine can be separated with great readiness by this method as the barium salt from alanine is readily soluble in water. J. J. S. Synthesis of Polypeptides. XIV. BMIL FISCHER (Ber. 1905 30 45 3-47 4). -a- Bronaoi sohexoyldiglycylgl yc y l c l d o d e C4H9*CHBr*CO* [NH*CH,*C0I2*NH*CH,* COCl prepared by the action of acetyl chloride and phosphorus pentachloride on bromoisohesoyldiglycylglycine freshly crystallised from alcohol is obtained as a colourless powder easily decomposed by water.It reacts with glycine ethyl ester in chloroform solution to form a-bomoiso- hexoyltriglycylglycine ethyl ester crystallising in coIourless microscopic needles which become brown a t 235' (corr.) and melt and evolve gas a t 241' (corr.) a- ~ r o ~ a o i s o ~ e x o y Z ~ r i g l ~ c ~ Z g Zycine C,H,*CHBr*CO* [NH* CH,*CO],*NH* CH,*CO,H prepared by the interaction of the above chloride with glycino crystal- lises in microscopic colourless plates which become brown a t 212' (corr.) and melt and decampose a t 218' (corr.). a-Hromoisohe.xoyltetrcc- glpylylgcine C4H9*CH Br*CO.[ NH* CH,* CO] ;NH CH,* CO,H formed by the interaction of the chloride with glycine anhydride is obtained as a crystalline powder which turns brown a t 330' (corr.) aid melts a t 237' (corr.). Leuc yltetragl ycylgl ycine C,H,-CH( N H2) CO.[NH CH,*CO] ;NH*CH,*CO,H prepared by the action of aqneous ammonia on the foregoing forms a colourless crystalline powder which on heating becomes coloured a t 225' (corr.) and partially melts and decomposes at 240' (corr.). It shows a marked biuret coloration. a-Brol?aoisohexoyl~entuglycylglycine formed by the interaction of diglycylglycine with bromoisohexoyldiglycylglycine chloride crystal- lises in coloiirless aggregates of no definite crystalline form which become coloured a t 220' (corr.) and melt at 250' (corr.).Leucyl~entaglyc?/lgZycine C,H,*CH( N H,)*CO*[ NH*CH',*CO],*NH* CH,*CO,H prepared by the action of aqueous ammonia on the foregoing also has no definite crystalline structure becomes yellow at 220° and decom- poses at 270'. A method for the preparation of d-alanine from silk is described a t length. This crystallises from water in well-formed centimetre long rhombic crystals [ a b c = 0.9784 1 0.49261. d- and I-Alauine have the same taste. The hydrochloride has [a] + 10.3' a t 20'; the racemate can only be removed from the active substance by crystal- lisation OF the free amino-acid. d-AZanyl-d-ulanine crystallises in centimetre long thin prisms has [.ID - 31.6' a t ZOO and melts and decomposes at about 298' (corr.) some 20' higher than the racemic alanylalanine. I n hydrochloric acid solution it has [a] about - 36.5' at 20'; on heating with 10 per cent.acid it is converted into alanine about 73 per cent being changed after five hours and 87 per cent. after seven and a half hours' heating. d-Alunine anhydride (cis-dimethylliketopipera.zine) crystallises in VOL. xc. i. ?n It gives a strong biuret coloration.146 ABSTRACTS OF CHEMICAL PAPERS. silvery glistening leaflets which melt a t 297' (corr.) and have [a] - 28.8' at 20' ; the inactive compound melts at 282'. NH2-CH,*CO*NH*CH,*CO*NH*CH2*C02Me prepared by the action of methyl alcohol and hydrogen chloride on the tripeptide crystallises in long needles grouped in stellar aggregates which melt indefinitely about 111' (corr.) ; the hydrochloride crystal- lises in glistening small plates sinters at' 200° and melts and decom- poses at 204' (corr.). NH,*CH,*CO*[ NH*CH,*C0],*NH*CH2*C02Me prepared by heating the powdered diglycylglycine methyl ester at 100'.when it condenses with elimination of methyl alcohol when separated from hot water forms a fine precipitate having no definite crystalline form and decomposing between 200" and 300'. Pentaglycylglycine prepared by the action of sodium hydroxide on the foregoing is obtained as a colourless powder very sparingly soluble in water which begins to decompose above 256" (corr.) and gives the biuret coloration ; the nitrate crystallises in microscopic needles melting and decomposing at about 240' (corr.) Along with the above what is probably a still higher condensation product is obtained on heating diglycylglycine methyl ester this gives a strong biuret reaction. Uiglycylglycine methyl ester Pentaglycylglycine methyl eater E.F. A. Amino- and Diazo-malonic Esters. OSCAR PILOTY and J. NERESHEIMER (Ber. 1906 39 5 14 -5 17).-Ethyl aminomalonate hydrochloride NH,*CH(CO,Et),,HCI is obtained by passing dry hydrogen chloride into absolute alcohol containing sodium amino- malonate in suspension or by reducing ethyl isonitrosomalonate with aluminium amalgam. It crystallises from acetone in small colourless needles and melts and decomposes at 162'. The hydrochloride of the corresponding methyl ester is easily soluble in water and is precipi- tated from methyl-alcoholic solution by the addition of ether in small coluurless rhombic crystals frequently twinned which melt and decompose a t 159'.Each of the preceding ester hydrochlorides on treat- ment with ammonia yields aminomalonamide the melting point of which is 1 9 2 O 10' higher than the value found by Conrad and Guthzeit (Abstr. 1882 947). When a cold concentrated aqueous solution of ethyl aminomalonate hydrochloride is treated with nitrous acid and the product extracted with ether an intensely yellow ethereal solution is obtained ; after evaporation of the ether a viscous yellow oil remains which is probably ethyl diaxomalonate since it has an odour resembling that of ethyl diazoacetate explodes on heating and is decomposed by mineral acids with violent evolution of nitrogen. c. s. Cyanuric Acid as a Pseudo-acid.ARTHUR HANTZSCH (Ber. 1906 39 139-153. Compare Ponomareff Abstr. 1886 216).- Cyanuric acid is a tricarbimide and as a complete pseudo-acid should be termed pseudocyanuric acid. The three pseudo-groups CO-NH can be transformed into the groups C(OH):N which can then formORG..4NIC CHEMISTRY. 147 salts The transformation proceeds in three distinct stages ; the first stage proceeds most readily and the last least readily. The first group is partially transformed by water alone as the aqueous solution of cyanuric acid behaves as a feeble monobasic acid (at 2 5 O K= O*OOOOlS). Preparations of the acid from different sources all give the same result. The temperature-coefficient of the conductivity increases rapidly with the temperature as is also the case with other pseudo-acids.The transformation of the first CO-NH group is complete in the presence of one equivalent of alkali as the primary metallic cyanurntes C,N,O,H,X are neutral to phenolphthalein Thus when titrated with N / 10 sodium hydroxide in the presence of phenolphthalein cyanuric acid acts as a monobasic acid. These primary cyanurates have the same properties whether pre- pared from concentrated or dilute from hot or cold solutions. The following are described Ammonium salt C,N,O,H,N H,,H,O ; this readily loses ammonia on exposure to the air and at 130' leaves a residue of pure cyanuric acid. Calcium salt (C3N,0,H2),Ca,8H20 slender needles only sparingly soluble i n hot water ; it retains part of its water even a t ZOO". iVc6gnesium salt (C,N,0,H2)2Mg,14H,0 needles readily soluble in hot water ; when heated it decomposes before it is completely dehydrated.The same salt is obtained when the secondary sodium salt is treated with magnesia mixture. The second CO*NH group is only partially transformed into C(0X):N when treated with two equivalents of alkali in aqueous solution solu- tions of the composition C3N,0,H3,2NaOH are strongly hydrolysed. The transformation is however complete at the ordinary temperature when the secondary salt is insoluble for example calcium barium and silver salts. The following secondary salts are described Sodium salt C,N30,HNa2,H,0 which is precipitated even when a large excess of alkali is present. It crystallises in needles and may be dehydrated a t 130° ; its aqueous solution is strongly alkaline and hydrolysed to an appreciable extent even more strongly than disodium hydrogen phosphate as is shown by conductivity determinations.Calcium salt C3N,O,HCa,3H,O is precipitated at Oo or a t the ordinary tempera- ture and may be dehydrated at 165". At looo it becomes converted into the monohydrate C,N,O,HCa,H,O which is also formed when the salt is precipitated from boiling solutions or from the trisodium salt a t 0". It also may be dehydrated a t 165O. Theconversion of the monohydrate into the trihydrate has not been accomplished. Barium salts C,N30,HBa,3H,0 and C3N,0,H13a,H20. The trihydrate cannot be transformed into the monohydrate by heating in a thermostat. Silver salt C,N,0,HAg2,H20 is precipitated from both the mono- and di-sodium salts. The anhydrous salt may be obtained by heating the monohydrate or by precipitating the salt at 100".The third CO*NH group is not transformed a t the ordinary tem- perature when a large excess of alkali is present even when the tertiary salts are insoluble. A t the ordinary temperature cyanuric acid is a dibasic acid only. The secondary salts are all pseudo-acids either N<C(oX).B>C-OX CO-NH or N H < ~ [ ~ ~ ~ ~ ~ > C O . The third CO*NH group is transformed at loo" and tertiary salts can then be obtained. *m 2148 ABSTRACTS OF CHEMICAL PAPERS. The tertiary sodium salt C,N,O,Na,,H?O is precipitated in slender needles when a cold solution of the acid in excess of 20 per cent. sodium hydroxide is heated to 100'. It cannot be recrystallised on account of the readiness with which it is hydrolysed and decomposed by carbon dioxide; it appears to be stable in presence of its mother liquor.It may also be precipitated by the addition of alcohol to a solution of the acid in sodium hydroxide (three equivalents). Two equivalents of alkali in its solution may be titrated by standard acid using phenolphthalein as indicator. The conductivity of its aqueous solution has a high value due to considerable hydrolysis and in this respect is identical with the solution oE the acid in sodium hydroxide (three equivalents). The tertiary calcium barium and silver salts are ail anhydrous and are only precipitated at 100" ; a t the ordinary te~nperature secondary salts are usually obtained. I n the preparation of the tertiary salts pure sodium hydroxide must be employed and the solutions must be protected from atmospheric carbon dioxide. When the silver salt is treated with sodium hydroxide solution the secondary silver salt and silver oxide are formed.The tertiary mercuric salt may be obtained a t 0' or at the ordinary temperature. When cyanuric acid is evaporated with mercuric chloride solution the double compound 2C3N,O,H,,HgC1,,4H,O is obtained in the form of lustrous plates which effloresce on exposure to the air. Aluminium salts could not be prepared. Acetylenic Arnidea and Nitriles. CHARLES MOUREU and I. LAZENNEC (Compt. rend. 1906 142 21 1-214).-Acetylenic amides of the type R*CiC*CO*NH are readily prepared by the action of ammonia on the corresponding ester. CH,* [ CH,],*CI C* COON H2 (compare Abstr.1903 i 31 a) melts at 9 1' ; hexylpropiokamide CH,*[CHJ C i C*CO*NH melts a t 9 a' and phenylpropiolamide melts a t 106' (compare Stockhauser and Gattermann Abstr. 1893 i 163) ; they crystallise in colourless plates are readily soluble in alcohol methyl alcohol or chloroform less soluble in ether alzd sparingly so in water ; phenylpropiolamide is converted into benzoyl- acetamide by the action of sulphuric acid and water (compare ObrBgia Abstr. 1892 324). The acetylenic nitriles R*CiC*CN are obtained by the action of phosphoric oxide on the corresponding amide. AmyZpropioZonitriZe CH,*[CH,],*CiC-CN boils a t 194-196' (corr.) under 760 mm. or 80-81" under 13 mm. pressure has a sp. gr. 0.8508 at 13"/4' and nD 1.4553 at 13" ; hexylpropiolonitde CH,*[CH,],*CiC-CN boils a t 212-213" (corr.) under normal or 95-96' under 13 mm.pressure has a sp. gr. 0.8493 a t 14*4'/4' and n 1.45637 at 14.4'; phenyl- propiolonitrile CPhlC.CN melts a t 41" boils at 228-229" (corr.) under normal or a t 105-106" under 13 mm. pressure has a sp. gr. 1.0046 a t 41-5'/4' and n 1,58535 at 41.5' (compare Bull. Xoc. chim. 1902 [iii] 26 9 9 ; Claisen Abstr. 1904 i 14). By the action of alcoholic potassium hydroxide the acetylenic nitriles yield the corresponding acid and compounds of the type R*C(OEt):CH*CN J. J. S. Amylpropiolamide,ORGANIC CHEMISTRY. 149 and by the action of sulphuric acid the nitriles of the aliphatic series yield the corresponding acid whilst phenylpropiolonitrile yields benzoylacetamide. M. A. W. Action of Potassium Cyanide on Sodium Tetrathionate and Dithionate. AUGUST GUTMANN (Bsr.1906 39 509-513).-The reaction between sodium tetrathionate and potassium cyanide in the presence of alkali was quantitatively examined and shown to follow a course represented by the equation Na,S,O + 2CNK + 2NaOH = SCNSK + Na2S0 + Na,SO + H20. Potassium cyanate and potassium sulphite do not react either at the ordinary temperature or on warming. Sodium dithionate is stable towards potassium cyanide even at 100'. c. s. Detection and Precipitation of the Ferrous Iron in Aqueous S o h tions of Potassium Ferrocyanide. FRITZ HABER (Zeit. Elektroclzem. 1905 11 846-849).-Berthelot (Abstr. 1901 i 20) showed that alkali snlphides produce a precipitate of ferrous sulphide in solutions of potassium ferrocyanide.The author finds that this only occurs in the light. Air passed through a solution of potassium ferrocyanide exposed to light precipitates ferric hydroxide. T. E. Potassium Mercuric Ferrocyanide. GUSTAVE FERNEKES (J. Amer. Chem. Soc. 1906 28 87-90).-A detailed account is given of the preparation of potassium mercuric ferrocyanide K2HgFe( CN) by the interactioq of mercuric chloride and potassium ferrocyanide. The salt is obtained as a fine faintly blue powder is insoluble in water and is decomposed by hydrochloric acid with formation of Prnssian blue mercuric chloride and hydroferrocyanic acid ; when treated with sodium hydroxide ferric hydroxide mercuric oxide and potassium ferrocyanide are produced. E. G. Compounds of Hydroferrocyanic Hydroferricyanic and Hydrocobalticyanic Acids with Furfuraldehyde and with Nitrogen Derivatives.FI~IEDRICH WAGENER and BERNHARD TOLLEKB (Ber. 1906 39 410-423. Compare Baeyer and Villiger Abstr. 1901 i 658; 1902 i 112 355).-Furan and furfuraldrhyde yield unstable additive compounds with hydroferrocyanic and hydroferri- cyanic acids. The compoiition of the cornpounds has not been settled as they readily lose the basic constituent and yield the pure acid. Trimethylumine cobalticyanide 2NMe3 H,CoC,N,H,O forms a thick white crystalline precipitate readily soluble in water but is thrown down by alcohol ; the ferricyunide forms small yellow crystals and begins to decompose at 175" ; the fewocyanide crystallises in pale yellow octahedral crystals and begins to decompose at 140O.Tetra- methylammonium hydroxide and hydrocobalticyanic acid yield the compound 4NMe,*OH,H,CoC,N6 which crystallises from hot water in colourless plates. It begins to decompose a t 203'. The corre- sponding ferricyanide forms orange-yellow plates and begins t o decom- pose at about 175'. The ferrocycinide forms small pale yellow crystals.150 ABSTRACTS OF CHEMICAL PAPERS. Rexamethylenetetramine cobalticyanide 2CIHl,N4,HH,CoC6N6,3~H20 forms colourless crystals and decomposes at about 1 60° ; hexn- methylenetetramine ferricyanide 2C,H12~?,H3FeC6N,,2SH20 is a red- dish-brown precipitate and the fwrocyanzde is greenish-white. Pyridine cobabticyanide SC5NH5,H3CoC6N,!2H20 forms white prisms and decomposes at 175' the corresponding ferricyanide forms yellowish-brown prisms and decomposes at 125' and the ferrocyunide forms yellow prisms decomposing a t 135'.Piperidine cobalticyanide 2C,NH,,,H,CoC6N6,2H20 crystallises in colourless needles and de- composes at 160' ; the ferricyanide forms monohydrated yellow crystals decomposing a t 125O and the ferrocyanide (with 1$H20) colour less octahedral crystals decomposing at 125'. Quinoline cobaltz- cpanide 3C,NH7,H,CoC6N6,4H20 forms colourless crystals decom- posing at 190' ; the ferricyanide (with H20) sulphur-yellow crystals decomposing a t 155O and theferrocyanide 2C,NH7,H,FeC,N yellow- ish-brown plates. Betaine cobulticyanide 2C,H,,0,N,H,CoC,N,,2H20 forms long colourless needles decomposing at 130' ; theferricyanide (with 4H20) yellow needles decomposing a t 130° and the ferrocyanide (with 4H2O) greenish-white needles decomposing a t 140'.Phenylhydracxine ferrocyanide 4C,H,N2,H,FeC6N forms colourless minute plates. J. J. S. c6 H,2N,,H4FeC,N,,7~H20 Secondary Arsines. WILLIAM M. DEHN and BURTON B. WILCOX (A'mer. Chem. J. 1906 35 1-54).-A method is described for pre- paring dimethylarsine by the reduction of cacodyl oxide. Dimethyl- arsine boils a t 35.6' under 747 mm. and at 55' under 1-74 atmo- spheres pressure and has a sp. gr. 1.213 a t 29". When dimethylarsine is heated in a sealed tube for an hour a t 335' in presence of not more than traces of air the inner surface of the tube becomes coated with a lustrous black substance which appears t o be the black polymeride of methylarsine described by Auger (Abstr. 1904 i 724) ; a gas which is either methane or a mixture of ethane and hydrogen is produced simultaneously.On allowing dimethylarsine to oxidise slowly in the air the eryth- arsine (AsCH,),,As,O described by Bunsen (Anncden 1842 42 41) is formed. When the arsine is treated with pure oxygen ethane is produced together with a black solid which consists of a mixture of the polymeride of methylarsine and metallic arsenic. The oxidation is always accompanied by the formation of cacodyl oxide and cacodylic acid. By the action of bromine on dimethylarsine hydrogen bromide hydrogen and cacodyl bromide are produced together with bromo- cucodyl Iqdrobyomide AsMe2Br,HBr which forms white tabular crystals is soluble in hot chloroform insoluble in ether and is decom- posed by water into cacodyl bromide and hydrogen bromide.Chlorine reacts with the arsine with formation of methylarsine dichloride. When dimethylarsine is treated with iodine in a sealed tube iodo- cacodyl hydriodide AsMe,I,HI is obtained which crystallises in large,ORGANIC CHEMISTRY. 151 pale yellow needles softens and darkens a t 160° melts a t 1 7 5 O is soluble in alcohol and is easily decomposed by water. By the action of aqueous iodine on the arsine cacodylic acid and hydrogen iodide are produced. Dimethylc2iisobzctyZarsonilun~ iodide AsMe2(C,HJ21 obtained by heating dimethylarsioe with isobutyl iodide in a sesled tube at l l O o for five hours is a white crystalline substance which melts a t 155O and is soluble in alcohol or chloroform but insoluble in ether. Dimethyldicetylursonizcm iodide AsMe,( CI6H3J21 forms white crystals and melts a t 53 -54".AsMe,Prfi,I c is a white crystalline solid which does not melt below 230O. Di- nzetl~yldiullylarsonium iodide forms light yellow crystals Dimethyl- allylarsine AsMe,*C,H obtained by the action of ally1 iodide (1 mol.) on dimethylarsine (1 mol.) is a pale yellow liquid which boils at about 160° is irritating to the eyes and skin and has a strong disagreeable odour; when heated with methyl iodide it is converted into trimethylallylarsonium iodide. Dirnethylallylarsine reacts violently with bromine in ethereal solution with formation of the dibronzide C,H,*As;Me,Br2 as a yellow flocculent precipitate. When dimethyl- arsine is treated with dry hydrogen bromide a t - loo a hydrobromide seems to be formed which readily undergoes decomposition a t the ordinary temperature with formation of cacodyl bromide and hydro- gen.Dry hydrogen iodide unites with dimethylarsine to form a white crystalline compound which decomposes into cacodyl iodide and hydrogen. By the action of concentrated sulphuric acid on the arsine the sulphate 2AsHMe,,H,SO is produced together with cacodyl sulphide and cacodylic acid. Nitrous oxide has no action on dimethylarsine but nitric oxide nitric peroxide nitrous acid and nitric acid react with the base with forma- tion of nitrous oxide or nitrogen the arsine being converted into various oxidation products of which cacodylic acid is the most abundant. Chromic acid rapidly oxidises the arsine to dicacodyl or cacodylic acid. An aqueous solution of potassium dichromate is instantly reduced by the arsine.When dimethylarsine is treated with molybdic acid in presence of water molybdenum dioxide and cacodylic acid are slowly formed. Lead peroxide reacts with the arsine with formation of dicacodyl lead cacodylate and lead. Ferric chloride is immediately reduced by the arsine with production of ferrous chloride and cacodyl chloride If molecixlar quantities of dimethyl- arsine and cacodyl chloride are heated together in a sealed tube f o r two or three hours at looo dicacodyl and hydrogen chloride are pro- duced. A study was made of the action of platinic chloride on dimethyl- arsine but no definite conclusions could be drawn as to the composition of the products obtained. The compound obtained by Bunsen (Jahyb.Chem. 21,500) by the action of platinic chloride on cacodyl chloride to which he assigned the formula AsMe,Cl,PtO,H,O is unstable and varies in composition according to the method of preparation. Auric chloride reacts with dimethylarsine with formation of dicacodyl cacodyl chloride cacodylic acid and a precipitate of indefinite com- Di~~tl~yldiiso~ropylarso.lzizcm iodide The secondary arsines possess basic propertieq.152 ABSTRACTS OF CHEMICAL PAPERS. position. Dimethylarsine rapidly reduces silver nitrate and mercuric chloride to the metal. By the action of potassium ferricyanide on the nrsine potassium ferrocyanide dicacodyl and potassium cacodylate are produced. Sulphur reacts readily with the arsine with formation of cacodyl sulphide or disulphide according to the quantity of sulphur used.By the action of liquid sulphur dioxide on the arsine cacodyl disulphide methylarsine sulphide trimethylarsine sulphide and caco- dylic acid are formed When dimethylarsine is treated with sulphur dichloride cacod y1 chloride sulphur and hydrogen sulphide are pro- duced. Stannic chloride reacts with the arsine with formation of hydrogen chloride and the ehlorostannide AsMe,SnCl which forms large colourless needles. By the action of phosphorus trichloride on the arsine hydrogen chloride cacodyl chloride and a compound which is probably (CH,P) or (CH,),P are produced. Arsenic trichloride reacts with dimethylarsine with formation of cacodyl chloride hydrogen chloride and the compound (CH,As),. When the arsine is heated with antimony trichloride antimony hydride hydrogen chloride antimony and cacodyl chloride are produced.By the action of the arsine on dibromosuccinic acid cacodyl bromide and succinic acid are formed. An improved method is described for the preparation of diphenyl- arsinic acid. Diphenylarsine obtained by the reduction of diphenyl- arsinic acid is a clear colourless oil which boils at 174" under 25 mm. and at 155' under 37 mm. pressure; it is rapidly oxidised in the air with formation oE diphenylarsinic acid and phenylcacodyl oxide. The tribromide AsPh,Br obtained by the action of bromine on the arsine crystallises in golden-yellow plates softens a t 120" melts at 1 2 9 O and is decomposed by water with formation of phenylcacodyl bromide. Diphenylarsine iodide AsPh,I was obtained as an oil.Basic diisoamylarsine chZwide,6As( C5H11)2Cl,[As(C5H11),1,0 obtained by the interaction of isoamyl chloride (2 mols.) and arsenic trichloride (1 mol.) in presence of sodium is a colourless oil which boils at 263' under 750 mm. and at 148O under 33 mm. pressure has a peculiar odour and is soluble in the ordinary organic solvents but insoluble in water ; on distilling this compound a small quantity of a white soapy solid substance is formed which is probably isocgmylcacodyl oxide [ As(C5Hll)&0. By the action of bromine on diisoamylarsine chloride the chZorodi6ronaide As(C5H1J2C1Br2 is obtained which forms white crystals is soluble in ether or chloroform and is slowly dissolved by water with formation of isoamylarsinic acid. When diisoamylarsine chloride is treated with hydrogen sulphide in presence of water the suZphide [As(C,Hll),],S is produced which crystallises in white needles melts at 29-30' is easily soluble in ether or carbon disulphide sparingly so in alcohol and insoluble in water.isoAmyL arsinic acid (C,Hll),As0*OH,2H,0 forms large flaky crystals melts at 153-154' and is easily soluble in alcohol slightly so in water and insoluble in ether. Diisonmylarsine AsH(C5HlJ2 obtained by the reduction of diisoamylarsinic acid boils a t 150" under 99 mm. pressure and is oxidised by the air with formation of diisoamylarsinic acid and an oil which is probably diisoamylcacodyl oxide. E. G.ORGANIC CHEMISTRY. 153 Preparation of Trialkyl-stibines -arsines and -phospbines by the Grignard Reaction.HAROLD HIBBERT (Bey. 1905 39 160-162. Compare Pfeiffer Abstr. 1905 i 164; Auger and Billy ibid. 1904 i 983).-Good yields (60-70 per cent.) of trimethylstibine may be obtained by the action of magnesium methyl iodide (3 mols.) on an ethereal solution of antimony trichloride cooled in ice and salt. When the product is distilled the greater part of the stibine passes over with the ether but the distillation is continued until the tempera- ture of the oil-bath is 170". Trimethylstibine is immediately thrown down in the form of the crystalline dibromide SbMe,Br on the addition of bromine. The ethereal solution of trimethylarsine when mixed with excess of bromine yields the perbromide AsMe,Br,. Triethylphosphine may be prepared by using a large excess of magnesium ethyl bromide.When the product is distilled only 6 per cent. of the phosphine distils over with the ether the larger portion distils over slowly when the oil-bath is at 160-200". [Grignard's Reaction with Dihaloids.] EDMOND E. BLAISE (Bull. Soc. china. 1906 [iii] 35 90-94).-l'he author claims that some of the observations given as new by Ahrens and Stapler (Abstr. 1905 i 423 868) have previously been recorded by himself and others (Abstr. 1901 i 317; 1905 i 111. Coinpare Zelinsky Abstr. 1903 i SO2 and archibald and IllcIntosh Trans. 1904 85 919). He also questious the probability of some of the conclusions drawn by the authors from these and other results contained in their memoirs on this subject. T. A. H. Remarkable Difference in the Behaviour of Homolo- gous Cyclic Molecules towards Animonio-nickel Cyanide.KARL A. HOFMANN and H. ARNOLDI (Ber. 1906 39 339-344. Compare Hofmann and Hochtlen Abstr. 1903 i 469).-Whilst benzene aniline and phenol interact with ammonio-nickel cyanide as previously described (Zoc. cit.) the following substances are in- different to the reagent toluene xylene cumene +cumene cymene meaitylene hexamethylbenzene triphenylmethane naphthalene anthracene phenanthrene fluorene diphenyl triphenylmethane tri- phenylcarbinol styrene amylene ethylaniline dimethylaniline phenylhydrazine 0- and p-toluidine anisole o-cresol nitrobenzene fluorobenzene chlorobenzene bromobenzene iodobenzene 2-methyl- pyridiue and quinoline. Ammonio-nickel cyanide may be used to test for benzene in petroleum; Russian and American petroleums alone give no precipitate with the reagent but do so on addition of benzene. When shaken with the reagent piperidine forms a bluish-white precipitate Ni( CN),,C,H,N which evolves pyridine but not ammonia when boiled with aqueous potassium hydroxide.Pyrrole forms a colourless crystalline powder Ni(CN),,NH,,C,H,N which becomes brown on exposure to air and gives the pinewood reaction. Thiophen forms a violet-white crystalline precipitate 3Ni( CN) 3 N H C,H4S. Furan forms a light violet-w hit e delicate crys talliue precipitate N i( CiY)2,NH3 C,H,O. J. J. S.154 ABSTRACTS OF CHEMICAL PAPERS. A similar difference is shown by benzene and its homologues in their behaviour towards pibric mid ; this forms additive compounds with benzene and its higher homologues which are solid a t or slightly below the ordinary temperature but not with toluene m-xylene cumene $-cumene fluorobenzene or chlorobenzene.The benzene-picric acid compound decomposes completely in a few minutes in a vacuum at the ordinary temperature whereas the benzene ammonio-nickel cyanide remains unchanged during four weeks in a vacuum at the ordinary temperature. The interaction with ammonio-nickel cyanide appears to depend on the molecular volume of the compound those which are precipitated having small molecular volumes at 15" benzene 88.6 ; aniline 90.5 ; phenol 88.8 ; pyridine 80 ; pyrrole 69.3 ; thiophen 78.5 ; and furan 72; whilst those which are not precipitated have large molecular volumes toluene 105.6 ; nitrobenzene 103.6 ; iodobenzene 110 ; bromobenzene 105 ; chlorobenzene 102 ; tiuorobenzene 93.8 ; o-tolu- idine 107 ; o-cresol 102 ; anisole 109 ; phonylhydrazine 97.6 ; a-methylpyridine 97.6 ; quinoline 117.8 ; and naphthalene 11 1.G . Y. Chlorobenxenes as Solvents for Resins. L. E. ANDES (Chem. Rev. Fett. Harx. h d . 1906 13 32-33).-Chlorobenzene readily dissolves galipot (the resin obtained from Pinus maritimo) colophony mastic asphalt dammar and metallic resinates. These substances with the exception of dammar are also soluble in dichlorobenzene whilst the following are insoluble in either solvent shellac sandarac copals benzoin and amber. The inflammability of both solvents is very slight they are miscible in all proportions with drying oils turpentine &c. and evaporate quickly.A good matt varoish is obtained by dissolving any resin in a mixture of alcohol and chloro- benzene. w. I?. s. Bromination of Toluene. ARNOLD F. HOLLEMAN and F. H. VAN DER LAAN (Pvoc. K. Akad. Wetensch. Amsterdam 1905,8,512-518).- The authors have investigated quantitatively the influence of tempera- ture of light and of bromine carriers on the action of bromine on an excess of toluene. The 0- and p-bromotoluenes and the benzyl bromide formed by the reaction are estimated by the following method. After removal of hydrogen bromide and unchanged bromine by means of a current of air and by treatment with potassium iodide solution and of the excess of toluene by distillation the benzyl bromide is estimated in a portion of the product by means of alcoholic silver nitrate with which benzyl bromide interacts to form silver bromide quantitatively.The remainder of the product is shaken with dimethylaniline washed with dilute nitric acid dried and distilled in a vacuum. The solidify- ing point of the distillate being determined the amounts of 0- and p-bromotoluene present are found to within 1 per cent. by reference to a solidifying point curve constructed from the results of determina- tions with mixtures of known composition. Toluene is broininated in the dark a t 25" only slowly the reaction becoming more rapid as the temperature rises. The product obtainedORGANIC CHEMISTRY. 155 at 25" contains 35.5 53.9 and 10.6 at 50° 23.5 32*S and 43.7 and at 75O 6.2 7.5 and 86.3 per cent. of o- and p-bromotoluenes and benzyl bromide respectively ; the product formed a t 100' consists wholly of benzyl bromide.I n diffuse daylight the bromination proceeds rapidly a t 25' the reaction being completed in about ten minutes. If an excess of toluene is used the product obtained a t 25' contains 99.0 a t 100" 99.5 per cent. of benzyl bromide but if equivalent amounts of toluene and bromine are heated together at the boiling point of toluene the product contains fractions which boil a t higher temperatures. The experiments with bromine carriers were carried out at 50' and in complete absence of light. The amounts of the carrier added are given in molecular proportion to each mol. of bromine used in the reaction. With 0.0017 0.0084 and 0.034 mol. of antimony tribromide the product contains 22.4 24.0 and 28.0 per cent.of o-bromotoluene 33.4 37.8 and 44.1 per cent. of p-bromotoluene and 44.2 38.2 and 27-9 per cent. of benzyl bromide respectively. With 0.002 0.004 0.006 and 0.017 mol. of aluminium tlrichloride the product contains 43.1 0*5(2) 0 and 0 per cent. of benzyl bromide the mixture of bromotoluenes consisting of 43.9 44.6 44.3 and 49.2 per cent. of the ortho- and 56.1 55-4 55.7 and 50.1 per cent. of the para-i someride respectively. With 0.0007 0.001 and 0.002 mol. of ferric bromide the product contains 40.8 7.8 and 0 per cent. of benzyl bromide whilst with 0.0007 0.002 0.006 and 0.01 mol. of this carrier the mixture of bromotoluenes contains 36.9 36.0 37.9 and 37.0 per cent. of the ortho- and 63.1 64.0 62.1 and 63.0 per cent. of the para-isomeride respectively.On the other hand with 0.02 mol. of phosphorus tribromide the product contains 54.7 per cent. benzyl bromide the mixture of bromo- toluenes consisting of 41 *4 and 58.6 per cent. of the or tho- and para- isomerides respectively. G. Y. Ortho-substituted Iodo-compounds with Uni- and Multi- valent Iodine. CONRAD WILLGERODT and MAX SInioNIs (Ber. 1906 30 269-228).-m-Nitro-p-toZyZ iododichloride NO,*C,H,Me*ICl pre- pared by passing dry chlorine into a well-cooled chloroform solution of p-iodo-m-nitrotoluene crystallises in large yellow lustrous plates and decomposes a t 71"; by aqueous sodium hydroxide it is converted into p-iodoso-m-nityotoluene NO,*C,H,Me * 10 which is a stable intensely red powder exploding at 129'; the acelate NO,*C,H31LIe*1(OAc) forms bright yellow slender needles and when dry explodes a t 200' ; the hasic sulphcbte C14H~4010N212S forms crystalline crusts and decomposes at 91' ; the basic nitrate C7H70,N21 melts and decomposes at 132' ; the basic iodide C7H70,Nl begins to decompose a t 80'; the basic chromate explodes at 94" and the formate C9H,0,NI a t 72".p-Iocloxy-m-?ziti*otoZuene NO,*C,H,Me*IO prepared by decomposing the iodochloride with a solution of sodium hydroxide and sodium hypochlorite crystallises from water or glacial acetic acid in long slender colourless needles and detonates at 196.5'.156 ABSTRACTS OF CHEMICAL PAPERS. Di-m-nitro-p-tolyZ.iodin~zlm hydroxide is obtained in solution by the action of moist silver oxide on a mixture of p-iodoxy- and p-iodoso-m- nitrotoluene ; the iodide I ( C,,H,Me*NO,),T crystallises from water in slender colourless needles and decomposes a t 51'.Phenyl m-nitro-p-tolyZiodinium hydroxide is prepared from iodoxy- benzene and p-iodoso-m-nitrotoluene in a similar manner. p- Iodo-m-toluidine prepared by heating p-iodo-m-nitro toluene with freshly precipitated ferrous hydroxide and alcohol crystallises from dilute alcohol melts at 48' and is nearly colourless. The hydrochloride forms pale yellow needles the nitrccte red needles the sulphate is colourless ; the oxalate 2C,H,NI,H,C,O melts at 11 3'. p-lodo-m- acetotoluidide crystallises from acetic acid in slender colourless needles and melts a t 145-1 46' ; p-iodo-m-formotoluidide is similar and melts a t 129'. On Chlorinating p-iodo-rn-toluidiue in chloroform solution a definite product cannot be isolated but on similarly chlorinating p-iodo-na- acetotoluidide 6-cl~loro-4-iodo-m-ccetotoluidide is obtained ; it crystal- lises from benzene or glacial acetic acid in fan-like aggregates of small colourless needles melts at 196*5' and combines with chlorine to form the iododichloride NHAc*C,H,MeCl*ICl which on warming loses chlorine and regenerates 6-chloro-4-iodo-m-acetotoluidide.On hydrolysis the acetyl derivative gives 6-chloro-4-iodo-m-toluidine which crystallises from dilute alcohol in thin colourless plates melts a t 65" and gives an oxaEate C16H1604C12N212 crystallisiog in large plates and melting at 165'. On replacing the amino-group by chlorine oxidising the 3 6-dichloro-4-iodotoluene so formed and decomposing the dichloroiodobenzoic acid 1 4-dichloro-2-iodobenzene melting at ZOO is obtained. 3 4-Di-iodotoluene *prepared from 4-iodo-m-toluidiue through the diazo-reaction crystallises from alcohol in flat colourless needles and melts a t 117.5". C,H,MeI*ICl is obtained a di-iododichloride not being formed ; attempts to convert this chloride into the corresponding iodoso- and iodoxy-compounds were without successful issue.On chlorination only the monoiododidZoride W. A. D. Certain Derivatives of Benzenesulphonylaminoacetonitrile. TREAT B. JOHNSON and ELMER V. MCCOLLUM (Amer. Chem. J. 1906 35 5 4- 6 7). -Benzenesul phonylaminoacetonitrile (Knoevenagel and Lebacb Abstr. 1904 i 994) may be prepared by treating amino- acetonitrile with benzenesulphonic chloride ; it melts at 809 By the action of methyl iodide on the silver derivative of this com- pound benxenesu~honylmtl~~Za~inoacetonitrile S0,Ph-NMe.CH,.CN is obtained which crystnllises from water in plates melts at 97' and is readily hydrolgsed by hydrochloric acid. Ben~enesuZp~on~Z~~et?~yl- aminoacet ic acid SO,Ph*NMe *CH,* CO,H crystallises from hot water in prisms and melts at 179' ; its ethyE ester boils a t 215-216' under 15 mm.pressure. When this acid is boiled with hydrochloric acid for fifteen hours sarcoaine benzenesulphonate is obtained. BenzenesuZpholzyZethyZa~inoucetonitriZe S0,Ph.NEt CH,*CN boils and suffers partial decomposition at 225-2435' under 21 nun. pressure jORGANIC CHEMISTRY. 157 the corresponding acid crystallises from water in colourless plates and melts at 116'.Benzenesulphonyl-n-propylaminoacetonitrile was obtained a3 an oil which on hydrolysis yielded the corresponding acid which crystallises in stout prisms and melts at 99-101'. Benxenesu ZphonyZcarbethoxyaminoacetonitrile S0,Ph*N(C0,Et)*CH2*CN obtained by the action of ethyl chloroformate on the potassium deriv- ative of beiizenesulphonylaminoacetonitrile crystallises from alcohol in needles melts at 83-S5' and when heated with solution of sodium hydroxide and afterwards acidified with hydrochloric or sulphuric acid is reconverted into benzenesulphonylaminoacetonitrile. BenxenesulphonylbenzyZaminoacetonitriZe forms colourless prisms and melts a t 68-70'; the corresponding acid crystallises in needles and melts a t 123-125'. Benxenesul~i~onyZ-p-nitrobenx?jlan~inoacetonitrile cry stallises in prisms and melts at 123-125'; the acid forms hair-like needles and melts and decomposes a t 2 10-2 12'.Ethyl benxenesulpiLonylc?/anometiL ylaminoacet a te SO,Ph*N(CH,* CN)* CH,*CO,Et obtained by the action of ethyl chloroacetate on benzenesulphonyl- aminoacetonitrile crystallises in radiating needles and me1 ts at 68-70'. When this ester is warmed with solution of sodium hydroxide until it hss completely dissolved and is subsequently acidi- fied with hydrochloric or sulphuric acid 2 6-diketo-4-benxeneuZphonyl- pipeyaxine N R < ~ ~ ~ ~ ~ > N * S O P h is produced which crystallises in prisms melts and decomposes at 198-199' and when heated with strong hydrochloric acid in a sealed tube for two hours a t 140-150' is converted into iminodiacetic acid which melts and decomposes a t 2 3 5-2 3 6'.2-Et~~o~y-4-benxenesuZ~Aony1-6 -ketopiperaxine (oEt)*CH2>N.s~,Ph N % O C H obtained by the action of ethyl iodide on the silver derivative of 2 6- diketo-4-benzenesulphonylpiperazine crystallises in pyramids and melts at 130-132'. Benzenesu~honnyEbenzo~~~minoacetonitriZe SO,Ph*NBz* CH,* CN forms radiating needles melts a t 110-112' and when boiled with concen- trated hydrochloric acid is converted into a mixture of benzoic and benzenesulphon ylnminoacetic acids. Phosphorus pen tachloride reacts with benzenesulphonylaminoacetic acid with formation of benzenesul- phony lari il ine. CarbetiLox~aminoaceto?iitriEe C0,Et *NH-(3H,.CN obtained by t.he action of ethyl chloroformate on the sulphate of aminoacetonitrile in presence of sodium hydroxide boils at 275' under 35 mm.pressure crystallises in radiating prisms and melts at 48-50'. An attempt was made to effect the condensation of benzenesul- phonylaminoacetic acid with catechol but without success. E. G. Molecular Compounds of Nitro-compounds with Amines. EMILIO NOELTING and E. 0. SOMMERHOFF (Ber. 1906 39 76-79. Compare Hepp Abstr. 1883 315 ; van Romburgh Abstr. 1895 i,158 ABSTRACTS OF CHEMICAL PAPERS. 652 ; Sudborough Trans. 1901 79 522 ; Sschs and Steinert Abstr. 1904 i 506).-The authors have prepared a number of additive compounds from 1 mol. of trinitrobenzene with 1 mol. of each of the amines mentioned below. The colours and crystalline forms are those of the additive compounds; the temperatures given are the melting points. o-Toluidine light red ueedles 125-127' ; m-toluidine light red needles 93' ; p-toluidine dark red needles easily decomposed ; o-3-xylidine red needles 125-128O ; m-Cxylidine brownish-red needles 96-98'; m-2-xylidine light red needles 118-120' ; p-xylidine red needles 1OO-10lo ; mesidine brownish-red needles 120-122' ; q-mesidine dark brownish-red needles 108-1 10' ; 5-tert.-butyl-m-2-xylidine brown needles 120-1 22' ; benzidine black needles ; tolidine black needles 1 78' ; dimethyl-p-toluidine black needles 124' ; o-phenylenediamine brown needles 175' ; m-phenylenediamine brown needles ; p-phenylenediamine blackish- brown needles ; m-tolylenediamine brown needles ; m-xylylene-4 6- diamine blackish-brown needles ; 4-amino-1-toluquinoline black needles ; tetrahydroquinoline dark red needles.Aromatic diamines do not form additive compounds with 2 mols. of trinitrobenzene. A dditive compounds are not formed by trinitro- benzene with p-bromoaniline bromo-m-xylidine azobenzene or the nitro-o-toluidines. The following amines form additiwe compounds with 2 mols. of trinitrobenzene Diphenylamine glistening black plates 109-1 10' ; 7-ditolylamine glistening black plates ; quinoline white needles readily decomposed ; 1 2-xyloquinoline long white needles 113'. The additive compounds of 1 mol. of trinitrotoluene with 1 mol. of the following amines are formed less readily and are less stable than the additive compounds of trinitrobenzene o-Toluidine light red needles 53-55'; m-toluidine light red needles 62-63' ; m-4-xylidine red needles 43-45' ; +-cui-nidine stable brown needles ; dimethyl-p-toluidme bluish-black needles.When mixed in molecular proportions in alcoholic solution at the laboratory temperature trinitrobenzoic acid and +-cumidine form a colourless saEt which when warmed loses carbon dioxide and yields the red additive compound of trinitrobenzene and q-cumidine. But when heated together in methyl-alcoholic solution on the water-bath trinitrobenzoic acid and t,b-cumidine form a brown additive compound which melts at 140-143' and dissolves in warm hydrochloric acid to form a red solution. The basic component of this compound can be titrated with sodium nitrite solution. With freshly distilled colourless aniline nitrobenzene p-nitro- toluene and m-dinitrobenzene give intense red colorations which disappear on adding alcohol.G. Y. Formation of Anilides. HEINRICH GOLDSCHMIDT and ROBERT BBAUER (Ber. 1906 39 97-108. Compare Goldschmidt and Wachs Abstr. 1898 ii 67).-Experiments with aniline or o-toluidine and n-butyric or isobutyric acid at 100' show that the formation of the anilide is a reaction of the second order whereas on addition of picricORGANIC CHEMISTRY. 159 acid it becomes unimolecular. The rate of formation of the anilides and o-toluidides with or without the addition of picric acid diminishes for the four acids investigated in the order acetic propionic n-butyric and isobutyric acid. As the reaction between formic acid and aniline a t 100' is com- pleted in a few minutes the experiments with this acid and aniline or o-toluidine were carried out a t 45-55'.As with the above-mentioned aliphatic acids the reaction is bimolecular but on addition of picric acid an increase in the velocity of the reaction is observed only if the concentration of the catalyst is not less than that of the formic acid. It may be that in the formation of anilides in presence of a catalytic agent the two reactions of the first and second orders respectively take place together in which case the velocity of the whole reaction is dx represented by the equation dt = k(a - x)c + k'(a - x)~ in which k and k' are products of the velocity constants with the constants of equilibrium which determine the different states in which the aliphatic acid exists in the basic solvent.The reaction between formic acid and aniline in presence of picric acid does not stop at the formation of the anilide but proceeds to that of diphenylformamidine. G. Y. Kinetics of the Fission of Carbon Dioxide from Trichloro- acetic Acid in Aniline Solution. HEINRICH GOLDSCHMIDT and ROBERT BRAUER (Rer. 1906 39 109-1 12. Compare preceding abstract ; Silberstein Abstr. 1885 160 ; Balcom Inaug. Diss. Heidelberg 1905).-Contrary to the behaviour of acetic acid and its homologues with aniline the interaction of trichloroacetic acid and aniline a t 25-45' is unimolecular and leads to the formation of carbon dioxide and chloroform. The velocity of the reaction is influenced to only a slight extent by the addition of strong acids; thus the value of k for the reaction in presence of picric acid at 25" is slightly greater than tho value obtained without addition of picric acid whilst a t 45' the two values of k are identical.G. Y. Action of Hydrogen Peroxide on Sulphuric Acid Solutions of Diphenylamine. A. USCHAKOFF (J. Russ. Phys. Chem. Xoc. 1905 37 913-915).-The action of a solution of hydrogen peroxide on a concentrated sulphuric acid solution of diphenylamine yields (1) the compound C,,H,,O,N which is soluble in 5 per cent. potassium hydroxide solution and also in concentrated sulphuric acid t o which it imparts a blue colour; on reduction with zinc dust and acetic acid or with sodium and alcohol diphenylamine is not formed but the violet colour of the solution changes to pale yellow which in presence of air or water again becomes violet ; (2) the compound C60H,,0,N which is an amorphous violet powder melting at above 100" ; with sulphuric acid it behaves like compound (l) and when heated with zinc dust it yields a small proportion of diphenylamine certain oily products and from 10 to 20 per cent.of a compound crystallising from ethyl acetate in silvery hexagonal plates which melt at 240'. T. H. P.160 ABSTRACTS OF CHEMICAL PAPERS. Diphenylamine Nitrates. A. USCHAKOFF (J. Buss. Phys. Chem. Soc. 1905 37 911-912).-The saZt 3NHPh2,2HNO forms well- developed crystals melting at 102-103' and dissolves in alcohol ether aniline or acetic acid ; it is decomposed by boiling water and turns blue in the air. The salt 4NHPh,,HNO has the melting point 54O the same as diphenylamine itself indicating that it decomposes before melting.T. H. P. Terpenes and Ethereal Oils. LXXV. Conversion of Ketones and Aldehydes into Bases. OTTO WALLACH [with KARL HUTTNER and JOHANNES 1iLTENBURG-j (Annalen 1905 343 64-74).-The conversion of ketones and aldehydes into bases by treat - ment with ammonium formate is represented as follows COR + NH = OH*CR,*NH ; OH*CR,*NH + HC0,H = CHR,*NH + CO + H20 the free formic acid acting as a reducing agent. This view of the reaction accounts for the fact that secondary and tertiary bases are formed with the primary base ; the primary base reacts with the aldehyde or ketone in the place of the ammonia. Since the reaction depends on the base being free axid uncombined with acids the presence of acids affects the course of the reaction.Generally under the conditions a t which these reactions occur the salts of the primary bases are less dissociated than ammonium salts and hence the reaction between ammonia and the aldehyde or ketone predominates but Emall amounts of secondary (or tertiary) bases are then produced. It has been found (i) that the addition of anhydrous formic or acetic acid to the mixture of the ammonium formate and aldehyde or ketone leads t o a single product the primary amine; (ii) that tlie reaction will take place at a low temperature and accordingly the formation of formyl derivatives is avoided ; aromatic bases form such derivatives at any temperature a t which the reaction will take place. (iii) The reaction can be used with all ketones and aldehydes and all classes of bases and can thus be used in the preparation of mixed secondary and tertiary bases.Diethylmethylamine [y-aminopentane] CHEt,*NH was prepared from diethyl ketone and ammonium formate the two substances being boiled together in the presence of a little acetic acid. J'o~*myZ-u- phnp!ethylnmide CHMePh*XfOCH was prepared from acetophenone and ammonium formate at lbB0 and is an oil boiling a t S O O O under 14 mm. pressure ; in the presence of acetic acid a-phenylethylamine is obtained. cycZoHexanone and ammonium formate in the presence of acetic acid yield mainly dicyclohexylamine NH(C,H,,) which is a liquid boiling at 251-252' and has a sp. gr. 0.925 and nD 1.4861 at 18' ; the nitrate oxalate and thiocyanate are sparingly soluble ; the Izitrosoarnine N(C,H,,),*NO is characteristic and melts a t 105-1 06'.Benzylcyclohexylanaane C6Hll *NH*CH ,Ph prepared by boiling for four hours cyclohexanone benzylamine and formic acid is a colourless liquid boiling at 281-282' ; its formyl derivative is produced at the same time. 1 -MethylcycZohexane-3-one and ammonium formate in the presence of acetic or formic acid yield the secondary base di-1 -methyEcyclohexyl- 3-anaine NH(C6H.loMe)2 which boils at 134-1 35O under 12-14 mm.ORGANIC CHEMISTRY. 161 and a t 273' in an atmosphere of hydrogen under the ordinary pressure ; it has a sp. gr. 0.88'78 and n 1.4756 a t 21'; the base appears to be a mixture of stereoisomeric compounds. The same mixture can be obtained by heating together the methylcyclohexanone and methyl- hexylamine formate and formic acid.Amylamine and the methylcyctohexanone in the presence of formic acid give 1 -nzetii y Icy clohexylum ylarnine C H,,*N H* C,H,,Me which boils a t 234". 1-Methylcyclohexanone-3 and benzylamine yield benxyl-1 -me~hylcyclohexyZ-3-~mine C,H,,Me*NH*CH,Ph which boils at 165-170" under 12 mm. pressure and has a sp. gr. 0.946 and nD 1.5182 at 22'. Triisoamylamine is formed from valeraldehyde ammonium formate and formic acid and tri benzylamine from benzaldehyde and ammonium formate and formic acid Valeraldehyde and aniline formate give formanilide and diamylaniline NPh(C,H,J2 which boils a t 264-265". Methylsmylaniline is obtained from valeraldehyde and methylaniline for mate. At low temperatures benzaldehyde and aniline formate yield benzyl- aniline CH,Ph*NHPh which melts a t 32" and yields a nitrosoumine melting at 57'.~orntylbenzylccnilide which is mainly produced a t higher temperatures melts a t 48". Methylcyclohexylamine f ormate and benzaldehyde in the presence of formic acid yield at 1 60" the same benzylmethylcycZohexylamine which is formed in the interaction of methylhexanone and cyclohexyl- amine. Benzaldehyde and ethylamine formate give benzylethylamine and with piperidine formate benzylpiperidine boiling at 248". K. J. P. 0. Asymmetric Nitrogen. XXII. Optically Active Ammonium Salts. EDGAR WEDEKIND (Ber. 1906 39,474-480. Compare this vol. i 1 4).-Z-Phenylbenzylmethylpropylammoni um iodide and l-phenyl- benzylmethylisobutylitmmonium icdide respectively were examined crystallographically and no hemihedrism was detected in either case.I-Phenylbenzylmethylpropylammonium bromide prepared by the addi - tion of potassium bromide to a solution of Z-phenylbensylinethylpropyl- ammonium d-bromocamphorsulphonate when crgstallised either from water or from alcohol also shows no tendency to hemihedrism; the specimen which was crystallised from water was isomorphous with the iodide described whilst the specimen crystallised from alcohol had a different crystalline form. The tendency to autoracernisation exhibited by various opt.ically active ammonium salts investigated by the author in chloroform solu- tion is characteristic with the chlorides bromides and iodides ; the nitrates however are optically stable. d-Pl~enylbenx?llntetlyZ~o~yZ- amnzonium nitrate prepared by the addition of silver nitrate to a n alcoholic sol ur ion of the d-iodide forms colourless crystal- and decom- poses at 170'; it has [a] + 114' in chloroform solution a value wtiich exhibited practically no variation when the solution remained at the laboratory temperature for two days.Solutions of the corresponding chloride bromide and iodide respectively all exhibited autoracemisa- tion the phenomenon being more marked with the iodide than with VOL. xc i. 12162 ABSTRACTS OF CHEMICAL PAPERS. the bromide. The fluoride does not appear to undergo any marked autoracemisation. The free base I-phenylbenzylmethyli8obutylam- monium hydroxide undergoes autoracemisation in chloroform solution more slowly than does its iodide. Asymmetric Nitrogen.XXIII. Isomerism with Asymmetric Ammonium Salts. EDGAR WEDEKIND (Bw. 1906 39 481-488. Compare preceding abstract). -W h ils t o-met hoxypheh yl benzylmet hyl- allylammonium iodide may be prepared from benzyl iodide and methyl- allyl-o-anisidine or from allyl iodide and benzylmethyl-o-anisidine the product obtained from methyl iodide and benzylallyl-o-anisidine consists of anisyltrimethylammonium iodide. This observation taken in con- junction with the results obtained by Jones (Trans. 1905 87 1721) led the author to re-examine the case of isomerism which he thought he had discovered with phenyl benzylmet hylallylammonium iodide ; the so-called &‘/I-iodide” is now shown to be phenylbenzyldimethylammonium iodide which decomposes at 164-1 65’. The analyses formerly made by the author with the “/I-iodide,” were made with a mixture of phenylbenzyldimethylammonium iodide and the normal phenylbenzyl- methylallylammonium iodide.Optically inactive isomerides of phenyl- benzylmethylallylammonium iodide accordingly do not exist. [With EMANUEL FROHLICH.] -Met?bylallyl-o-anisidine prepared from allyl iodide and methyl-o-anisidine is a yellow oil which boils a t 167’ under 85 mm. pressure ; its picrate melts a t 139’. Benzylmethyl-o-ccnisidine prepared from benzyl bromide and methyl- o-anisidine is a viscid yellow oil which boils at 217-220’ under 65 mm. pressure ; its pic?*ccte melts a t 129’. BenzyZ-o-anisidine prepared from benzyl chloride and o-anisidine or from benzyl chloride o-anisidine and potassium hydroxide is a viscid yellow oil which boils at 217-220’ under 25 mm.pressure ; its picrate melts at 137’. BenxylaZZyZ-o-anisidine prepared from allyl iodide benzyl-o-anisidine and potassium hydroxide boils a t 205-206’ under 50 mm. pressure. o-Methoxyuhenylbelzxylmet~yZaZZyZamm~~~m iodide prepared from benzyl iodide and methylallyl-o-auisidine is identical with the com- pound obtained from allyl iodide and benzylmethyl-o-anisidine and decomposes a t 120’. 9nivyltrimethylarnmoniun~ iodide obtained from methyl iodide and benzylallyl-o-anisidine decomposes and sublimes at about 2 10-220’. A. McK. A. McK. Certain Nitrogen Compounds. ANGELO ANGELI and VINCENZO CASTELLANA ( A t t i R. Accad. Lincei 1905 [v] 14 ii 657-660).- Angeli and his collabora%ors have shown (Abstr.1905 i 873) that in the form of salts nitrosophenylhydroxylamine NO*NPh*OH and phenylnitroamine (phenylnitroamic acid) NHPhONO have the struc- tures O:NPh:N*OH and NPh:NO*OH respectively. These differ as regards the position which the oxygen atom takes tip in the diazo- benzene hydroxide NPh:N*OH from which they are derived. Since some authorities ascribe the structure O< NPh I to phenylnitroamic N*OHORGANIC CHEMISTRY. 163 acid it is seen that this substance stands in very close relationship to the aromatic azoxy-compounds which contain the ring *N-N* \/ 0 united to two radicles generally identical. Asymmetric or mixed azoxy-compounds R( N,O)R' which are very difficult to prepare should exist in only one modification if they contain the N,O ring whilst if their constitution is analogous with that of nitrosophenylhydroxyl- amine two isomerides should be possible.By condensing nitrobenzene and aniline the authors have obtained besides azoxybenzene a brownish-red oil . which does not reduce Fehling's solution is decomposed by hydrochloric acid into nitrobenzene and aniline and is probably a condensation product of the formula O:NPh(OH)*NHPh. Nitrobenzene reacts in a similar way with p-toluidine. To the condensation products of aldehydes with substituted hydroxyl- aminee Bamberger attributes a structure O< I analogous with that of the azoxg-compounds. The authors find that the product obtained from benzaldehyde and phenyl hydroxylamine forms an additive compound melting a t 170° with 1 mol. of phenylcarbimide a fact which is best explained if the compound has the structure CHPh :N*C,H,*OH since this does not require intramolecular change t o be effected by the phenylcarbimide.Confirmation of this conclu$ion is obtained in the behaviour of phenylhydroxylamine which combines with 1 mol. of phenylcarbimide to give a compound melting at 1 2 6 O soluble in alkali and capable of reducing Fehling's solution the reduction being accompanied by the odour of nitrosobenzene. Phenylcarbimide does not therefore determine the transposition of phenylhydroxylamine into p-aminophenol since if this mere effected two molecules of the carbimide should participate in the reaction and no odour of nitroso- compound should be observed. CHR NR T. H. P. Action of Carbamide on Compounds of Cyanoacetic Acid.GUSTAV FRERICHS and L. HARTWIG (J. pr. Chem. 1906 [ii] 73 21-48. Compare this vol. i 74).-When heated with aniline over a naked flame the ethyl ester C,H,O,N melting a t 162' (Zoc. cit.) yields s-diphenylcarbamide a small quantity of s-diphenylbiuret and n dibasic m i d C3,H,,0,N6 which forms white leaflets melts at 195" and gives an intense red coloration with alcoholic ferric chloride. The action of aniline on the methyl ester C,H,03N melting at 128' (Zoc. cit.) leads to the formation of the same products. The sodium potassium aud siluer salts of the dibasic acid were analysed ; i t s diethyl ester C,oH,,03N6Et2 formed by the action of ethyl iodide and alcoholic potassium hydroxide on the acid crystallises in white needles and melts at 158' ; the dibenzyl ester C,0H2,0,N,(C1H2Ph)2 crystallises in white needles and melts and decomposes at 215'.When hydrolysed with concentrated hydrochloric acid or with 10 per cent. aqueous 1L 2164 ABSTRACTS OF CHEMICAL PAPERS. potassium hydroxide the dibasic acid yields ammonia and aniline ; no other organic substance could be detected amongst the products of the hydrolysis. When heated with p-toluidine the ethyl ester C6H,03N2 forms p- tolylcarbamide s-di-p-tolylcarbamide and a dibasic acid C?,H,,O,N which crystallises in white leaflets melts at 221° and gives a red colorat ion with alcoholic ferric chloride. With nz-toluidine the ethyl ester C6Hs0,N2 yields m-tolylcarbamide s-di-nz-tolylcarbamide and a dibasic aczd C33H3003N6 which crystal- lises in glistening colourless leaflets melts a t 1 8 6 O and gives a red coloration with alcoholic ferric chloride.The dibasic acid C30H,103N6C13 formed by heating the ethyl ester C6H,0,N2 with m-chloroanihne is obtained as a crystalline powder melting at 2 17'. When treated with benzyl chloride and alcoholic potass- ium hydroxide it yields the dibenxyl ester C,0H,90,N6C1,( CH,Ph) which crystallises in needles melts at 186-188° and is insoluble in aqueous ammonia or dilute alkali hydroxides. When heated with m-bromoaniline the ethyl ester C,H,O,N yields a mixture of m-bromophenylcarbamide and s-di-m-bromophenylcarb- amide and the dibasic acid C,,~,lO,N,Br which is obtained on acidi- fication of its ammoniacsl solution as a white crystalline powder and when heated with benzyl chloride and alcoholic potassium hydroxide on the water-bath forms the dibenxyl ester C,oH,90,N,Br,(CH2Ph)2 ; this crystallises in white needles and melts a t 185-187O.When heated with an excess of methylaniline the ethyl ester CGHS03N2 yields (1) its ammonium salt ; this must be due to partial decomposi- tion of the acid yielding cyanic acid which interacts with methyl- aniline to form s-diphenyldimethylcarbamide and ammonia ; and (2) a dibasic m i d C,,H,OO,N which forms thick yellow rhombic crystals melts at l'i5' and gives a red coloration with alcoholic ferric chloride. The same products are obtained by the action of methylaniline on the methyl ester C,HGO3N2. The ethyl ester C,H,O,N interacts with an excess of warm benzyl alcohol to form ( 1 ) the bermyl ester - CO<GE>C* CH2*C0,*CH,Ph which crystallises from dilute alcohol in colourless octahedra or broad flat denticulate aggregates and melts and decomposes at 14S0 and (2) a substccnce Cl7HI3O5N which crystallises in flat white needles melts at 267O and with ferric chloride in aqueous solution forms a reddish- violet precipitate which dissolves in alcohol forming a dark red solution which gradually deposits dark violet prisms.When heated a t lSOo the ethyl ester C6H,03N2 melts and evolves at first alkaline but later acid vapours having an odour OF ethyl cyanoacetate ; the distillate gives the iodoform reaction. The vesidue consists of a white crystalline powder CsH70,N (?) which decom- poses at high temperatures becoming yellow and finally black ; it is soluble in aqueous ammonia from its solution in which it is reprecipi- tated by addition of hydrochloric acid; it does not give the murexide reaction and does not give the reaction products of cyanic acid whenORGANIC CHEMISTRY.165 heated with aniline but yields bromoform and ammonium bromide when treated with bromine water When heated with carbamide cyanoacetic acid forms cyanoacetyl- carbamide or on prolonged heating uric acid (compare Formhek Abstr. 1892,149). A number of experiments intended to throw light on the mechanism of this reaction yielded only negative results. G . Y. Hexahydrothiophenol (cycloHexy1 Mercaptan). WALTHER BORSCHE and W. LANGE (Bep. 1906 39 392-397. Compare Abstr. 1905 i 766).-The yield of cyclohexyl hydrosulphide obtained by reducing cyclohexanesulphonic chloride with tin and hydrochloric acid is some 40-50 per cent. of the theoretical.Only a small amount of the mercaptan is formed when cyclohexyl bromide is heated with an alcoholic solution of potassium hydrogen sulphide the chief product being cyclohexene cycloHexyZ xanthute C,HI,S-CS*OEt is obtained as a yellow oil dis- tilling at 150-153' under 16 mm. pressure when cyclohexyl bromide is warmed with an alcoholic solution of potassium xanthate. A small amount of cyclohexyl tritliiocai*bonate CS(S*C,H,,) is also formed. It crystallises from alcohol in yellow needles and melts at 75-76" Ammonia converts cyclohexyl xanthate into cyclohexyl mercsptan and xanthamide The mercaptan is a colourless oil distilling at 158-160" and is lighter than water.The mercuric compound C,H,,S*HgCl is obtained as a white precipitate on the addition of an alcoholic solution of mercuric chloride t o the mercaptan dissolved in alcohol. cycloHexyl rnetlhpl sulphide C,H,,*SMe is a colourless oil distilling a t 179-180". cyclo- Hex~Zclimetl~ylsulp?~on~um iodide C,H,,SMe,I forms small crystals melting a t 102'. It is deliquescent and dissolves readily in methyl o r ethyl alcohol but only sparingly in ether. The corresponding Iqdroxide C6HJ,*SMe,*OH meltts a t about SO' the chloride a t about go" and the ylatznichloride (C,H,,SMe,),,PtCl a t 136O. The last cornpound crystallises from water in brick-red needles. [4-Nitro-2-amino-6-acetylaminophenol.] LEOPOLD CASSELLA ck Go. (U.R.-P. 161341).-Acetic anhydride reacts with sodium picramate a t 60' to form sodium acetylpicramate which is reduced by sodium sulphide at SO' and acids then precipitate 4-nitro-2-umi~zo-6-ucet~l- anainop?benol sparingly soluble in alcohol more readily in ether or acetic acid.Acids hydrolyae it to 4-nitro-2 6-diaminophenol. The diazonium compound forms sparingly soluble yellow crystals and may be used for the preparation of azo-dyes. Nitration of Benzoyl- and Dibenzoyl-p-aminophenol. FREDERIC REVERDIN and ERNE~T DELETRA (Be?. 1906 39 125-129. Compare Reverdin and Dresel Abstr. 1905 i 51,430).-2 6-Binitro-4-6enxoyF ccnainophenol NHBz*C6H,(NO2),* OH is formed by the action on p-benzoylaminophenol of ft mixture of concentrated sulphuric acid and nitric acid of sp. gr. 1.4 at 7-12' or of nitric acid of sp.gr. 1.5 a t - 10-O' or of nitric acid of sp. gr. 1.34 a t 20-26'. It crystallises from acetone in golden leaflets melts at 263' and when heated with C,HIIS*CS*OEt + NH3 =. NH,*CS*OEt + C,H,,*SH. J. J. S. C H. C166 ABSTRACTS OF CHEMICAL PAPERS concentrated sulphuric acid on the water-bath is hydrolysed with formation of isopicramic acid. The acetyl derivative crystallises in yellowish-brown needles or brown prisms and melts at 1 80°. When reduced with zinc and hydrochloric acid 2 6-dinitro-4-benzoylamino- phenol yields p-triaminophenol and benzoic acid. The action of nitric acid of sp. gr. 1-4 on dibmzoyl-p-aminophenol (a) in concentrated sulphuric acid at 7-14' leads to the formation of 2 6-dinitro-4-benzoy1aminopheno1 melting at 263' ; (b) in a mix- ture of concentrated sulphuric acid and acetic anhydride at 6-11' leads to the formation of dinitro-p-nitrobenzoylaminophenyl nitro- benzoate melting a t 229'; or ( c ) in a mixture of concentrated sulphuric acid and glacial acetic acid to the formation of 3-nitro-4- benzoylaminophenyl benzoate melting at 147'.G. Y. Tetrabromo-p-cresol $-Bromide. XV. THEODOR ZINCICE and K. BGTTCRER (Annalen 1905 343 100-129. Compare t h i s vol. i 172).-This communication is an extension of the research on the same subject previously published (Abstr. 1902 i 284). The results are in agreement with the views expressed by Auwers (Abstr. 1902 i 217) and in consequence the formuh previously suggested are now somewhat modified. Octubrorno-p-diphenolmethme CH,(C6Br4*OH)2 prepared by dissolving tetrabromo-p-cresol $-bromide in 5 per cent. sodium hydroxide or by heating tetrnbromo-p-hydroxybenzyl alcohol at 200° cryst allises in needles or leaflets melting a t 280-281' ; its ucetyl derivative crystal- lises in needles melting at 278-279'.Tetru brorno-p-hydrox ybenzylaceto ne OH C,Br,* CH,. C H,* COMe pre - pared from the $-bromide by the action of alkali hydroxide in acetone solution crystallises in colourless needles melting at 175-176' ; its sodium salt forms scales and its ucetyl derivative needles melting at 1 8 1-1 8 2 O. Ethyl tetru b porno- p-hydrox3 berzx y Zcicetoaceta te OH*c6Br,*cH2*CHAc* CO,Et prepared by boiling a mixture of ethyl sodioacetoacetate and tetrabromo- p-cresol +-bromide in benzene solution crystallisos in needles melting at 117-11So and is converted into the acetone derivative just described by boiling with a solution of barium hydroxide.Tetra bromo- p-hydroxybenxy Zan ilin e prepared from the t e trabromo- @-bromide and aniline (2 molecules) crystallises in needles melting at 120-1 22'. The corresponding tetrubronzo-p-hydroxyphenylacetonitrile prepared from the tetrabromo-$-bromide and potassium cyanide crystallises in needles melting a t 214-216' ; by dilute sulphuric acid it is hydrolysed to the corresponding acid and by nitric acid it is oxidised to a $-quinol and oxslic acid. I t s acetyl derivative forms crystals melting at 183-184O. v The qzcinol CO<CBr:CB>C(OH)*CH,*CN CRr'CR prepared from the nitrile crystallises in yellow needles or prisms melting at 209-211O. ~etrubronzo-p-1TLydroxyphenylu~etic acid OH* C6Br,*CH2*C02H prepared from the nitrile crystallises in needles melting and decomposing at 265'; its ncetyl derivative forms crystals melting at 250-255'; its wethy8 ester crystallises in needles melting a t 220-221° and forms aORGANIC CHEMISTRY. 16'7 sparingly soluble sodium derivative and an acetyl derivative which crystallises in needles melting at 159'.OH*C,Br,*CH;CO*NH formed as an intermediate product in the preparation of the acid crystallises in prisms. Tetrabromo-p-hydroxybenzyl nitrite OH*C,Br;CH,*ONO prepared from the tetrabromo-$-bromide and potassium nitrite crystallises in needles from benzene melting and decomposing a t 143' and when boiled with a methyl-alcoholic solution of sodium hydroxide is con- verted into tetrabromo-p-hydroxybenzyl methyl ether.Its acetyl derivative crystallises in leaflets melting a t 172-1 73'. Tetrabromo-p-hydroxybenzyl mercaptan OH.C,Br,*CH,*SH prepared by treating the $-bromide with alcoholic solution of sodium hydrogen sulphide crystallises in prisms or needles melting at 152' and is reconverted into the $-bromide by heating with bromine. Its diclcetyl derivative forms crystals melting a t 132 -133'. Tetrabromo-p-hydroxy- benxyl suZpli,ide (OH*C,Br,*CH2),S is formed a t the same time as the mercaptan and is a crystalline powder decomposing at 255'. The oxide CO<CBr:CRr >C<gH2 is obtained from pentabromo- tolu-$-quinol (Zoc. cit.) by regulated treatment of its alcoholic solutionwith aqueous sodium carbonate ; aniline converts the tolu-p-quinol into the The amide CBr:CBr .- CBr C(NHPh' which crystallises in C B r = z CBr>C<bH ' cornpound CO< yellow leaflets melting and decomposing *at 209'. When the oxide is heated with a saturated solution of hydrogen bromide in acetic acid it yields the compound OH*C<cBr:CBr CBr*CBr>C*O*CH2Br which crystallises in white needles melting a t 150-160'; its acetyl deriv- ative prepared either directly from the compound or by treating the oxide with acetyl bromide and a little concentrated sulphuric acid crystallises in leaflets melting a t 144-145'. When heated with sulphuric acid in acetic acid solution tetrabromoquinone and tetra- bromoquinol are formed. CBr:CBr Tetrabromomethylenequinone Co<CBr:CIr>C:CH' (Or a poly- meride) is obtained by eliminating hydrogen bromide from the tetra- bromo-p-cresol $-bromide by shaking its benzene solution wit,h anhydrous sodium acetate and is an amorphous white powder which is oxidised t o tetrabromobenzoquinone by nitric acid and is reconverted into the +-bromide by hydrogen bromide ; by alkalis in acetone solution i t is changed to tetrabromo-p-hydroxybenzyl alcohol and tetrabromo- p-hydroxybenzylacetone.It yields tetrabromo-p-hydroxybenzyl methyl ether with methyl alcohol and with acetic anhydride tetrabromo- p-acetoxybenzyl acetate With aniline i t yields two anilides one identical with that obtained by the action of aniline on the +bromide and a second probably C O < ~ ~ ~ i ~ ~ ~ > C H * C H Z . N H ~ h ? which crys- tallises in yellow needles melting at 203-205'.Yetrabromo-p-cresol rCI-chloride C7H30ClBr prepared from tetra-168 ABSTRACTS OF CHEMICAL PAPERS. bromo-p-hydroxybenzyl alcohol and hydrogen chloride crystallises in needles melting at 1 7 4 O and resembles the $-bromide; its metyl derivative crystallises in needles melting at 18O-18lo and when boiled with acetic anhydride is converted into tetrabromo-p-acetoxy- benzyl acetate. An isomeride of the acetyl derivative is obtained when the +-chloride is boiled with sodium acetate and acetic acid; it melts at 159-160'. W-CJdoro-2 ; 3 ; 5 ; 6-tet~*abromotolu-~-quinol prepared by heating the +-chloride with nitric acid crystallises in yellow needles melting at 175-1 7 6 O ; its ncetyl derivative crystallises in needles melting a t 154-155'; both are converted into the oxide above described by treatment with alkalis.Aniline converts the tolu-+-quinol into an unibide CO<Csr~~!!Ph)>C(OH)*CHzCl CBr-- CBr or C(NHPh) CBr C O < C J ~ ~ - - - ~ ~ ~ > C ( O H ) . C ~ ~ which crystallises in yellowish- red needles melting a t 180-181'. K. J. P. 0. Derivatives of the Volatile Nitroresorcinol. HUGO KAUFFMANN and ERWIN DE PAY (Bey. 1906 39 323-328. Compare Abstr. 1 904 i 157).-The hydrochloride of 2-aminoresorcinol C,H,O,N,HCl is prepared by reducing 2-nitroresorcinol with tin and hydrochloric acid at 85" saturating the cooled reaction-product with hydrogen chloride and recrystallising the precipitate from concentrated hydrochloric acid; it is obtained in white well-formed crystals. The free base is unstable and cannot be isolated; i t reduces ammoniacal silver and Fehling's solutions and may be used as a photographic developer.The action of sodium nitrite on the cooled solution of the hydro- chloride leads to the formation of a nitroso-derivative of resorcinol diazonium anhydride C H,O,N which crystallises from acetone in greyish-green needles begins to decompose a t 1 7 6 O and explodes at 195' ; it dissolves in aqueous alkali hydroxides to form red solutions from which it is reprecipitated unchanged on acidification. Dibenzoyl-2-nitroresorcinol formed from 2-nitroresorcinol by the action of benzoy 1 chloride and sodium carbonate crystallises from alcohol i n yellowish-white needles and melts at 140' (compare Pechmann and Obermiller Abstr. 1901 i 336).When reduced with iron powder and glacial acet,ic acid it yields 2-benxoylaniinoresorcinol C,H3(0H),*NHBz which crystallises from alcohol in nacreous leaflets melts at 1 8 7 O and is soluble in aqueous alkali hydroxides and 3-beiaxoxy- 1 -phenylbenxoxaxole OBz*C,H,<N>CPh 0 which crystallises from light petroleum in white leaflets melts at 140' and is insoluble in aqueous alkali hydroxides. When treated with sodium nitrite and dilute hydrochloric acid 2-benzoylaminoresorcinol yields a niti*oso-derivative C,,H,,O,N which crystallises in red needles melts a t 208' and dissolves without decomposing in aqueous alkali hydroxides,ORGANIC CHEMISTRY. 169 2-Nitroresorcinol couples with 1 mol. nf benzenediazonium chloride in alkaline solution to form the mono-uzo-dye C12H904N3 which crystallises from glacial acetic acid in dark red needles melts at 171° and is soluble in aqueous alkali hydroxides forming orange-red solutions.The am-dye ClsH1304N5 formed by coupling 2-nitroresorcinol with 2 mols. of benzenediazoniurn chloride crystallises in dark red needles and commences to decompose at 260'; it dissolves in dilute alkali hydroxides to form violet-red solutions. The nitro-azo-dyes were compared spectroscopically with the corresponding resorcinol dyes in sulphuric acid and in acetone solution containing 4/3 x niol. per litre. All the solutions exhibit absorption at the vioIet end of the spectrum only; with the nitro-dyes in long layers (20 cm.) the absorption extends further into the yellow than with the resorcinol derivatives; the difference is greatest with the mono-azo-dyes in acetone solution.The introduction of a nitro-group into a resorcinol azo-dye is accompanied by a slight increase in the depth of colour. 2-Nitroresorcinol interacts with benzenediazonium chloride in acid- alcoholic solution to form a substance C,,H,O,N which crystallises from glacial acetic acid in light red needles and melts at 175 -176'. G. Y. Action of Hydroxylamine on Dimethyldihydroresorcin. W. GITTEL (Cliem. Centr. 1906 i 33-35 ; from Z e d . fur AVuturwiss 77 145-1 73).-Dimethylditiydroresorcin yields a crystalline and an amorphous oxime both of which have the same molecular weight. Since the amorphous form which is stable in the presence of acids cannot be converted into a dioxirne. it would amear t o have the ' A constitution of a hydroxamic acid CMe2<CH:.C(NH.0H) CH co>CH.On the other hand however the fact that bYOt1; forms have faintly acid properties renders it more probable that they are stereoisomerides. The anilino-derivative of dimethyldihydroresorcin only exists in one form which resembles that of the amorphous oxime ; it neither yields a dianilino-derivative nor a dioxime. the action of b ydroxylamine hydrochlohde on dimeth yldihydroresorcin separates from ether i u the form of a brittle mass which is soluble in alcohol chloroform or benzene somewhat soluble in a large quantity of a solution of sodium carbonate and very readily so in potassium hydroxide acetic acid or dilute hydrocbloric acid ; it gives a reddish- brown coloration with ferric chloride and reduces Fehling's solution on warming.It neither forms an oxirne nor yields crystalline compounds with acetic anhydride in preseince of hydrogen chloride or concentrated sulphuric acid. The hydrochZoride of the crystalline mime C,,H,,O,NCl obtained by allowing the oxime t o remain with concentrated hydrochloric acid for six days forms large crystals melts about 152" and is readily soluble in alcohol or water but insoluble in170 ABSTRACTS OF CHEMICAL PAPERS. ether. It is not readily attacked by concentrated hydrochloric acid ; its aqueous solution gives a yellow precipitate with formaldehyde which melts at 78-80°. The crystalline oxime forms a white mass which melts at 115O 'and is soluble in hot wate; alkali hydroxides hydrochloric acid or acetic acid ; it reduces alkaline solutions of copper or ammoniacal solutions of silver on warming and gives a reddish- brown coloration with ferric chloride but is not attacked by warm acetic anhydride.By the action of semicarbazide in alkaline solution an amorphous brick-red substance is formed which is soluble in hydrochloric acid and potassium hydroxide forming yellow and red solutions respec- tively. The dioxime CMe2<E2:$:EE;>CH2 (compare Vorlander Abstr. 1897 i 273),. prepared from the crystalline oxime or from dimethyldihydroresorcin is soluble in alkali hydroxides hydrochloric acid or acetic acid but is insoluble in a solution of sodium carbonate ; it reduces an alkaline solution of copper and with ferric chloride gives a faint brown coloration which gradually becomes darker.Benzoyl chloride and acetic anhydride yield amorphous products. The ethyl derivative prepared by the action of ethyl iodide and sodium on the dioxime separates as a resin which is soluble in hydrochloric or acetic acid less so in solutions of alkali hydroxides and insoluble in sodium carbonate. The hydrochloride C,H,,O,N,Cl forms highly refractive colourless crystals which are probably monoclinic and are readily soluble in alcohol ; it becomes darker at 175O and decomposes at 185' without melting. The phenglhgdraxone CMe,<CH2. CH,-- c(N,Hfh(CH2 is a hygroscopic bright yellow powder which on exposure to air becomes flesh-coloured to orange-red and melts and decomposes a t 158". It is soluble in alcohol or acetone sparingly so in chloroform and insoluble in ethyl acetate ether carbon disulphide light petroleum benzene hydrochloric acid or potassium hydroxide and gives a slight brown coloration with ferric chloride.The alcoholic solution forms a deep blue coloration with dilute nitric acid and becomes green when warmed with dilute sulphuric acid. When concentrated hydrochloric acid is poured over the phenylhydrazone a white substance is obtained which becomes dark a t 170" and melts at 181'. When treated with dry hydrogen chloride the phenylhydrazone becomes emerald-green but by the action of the gas on the powder suspended in chloroform or ethyl acetate the liquid changes to bluish-green bright blue and finally to greyish-blue or violet and a cmpound C,,H,,NSC1 (I) is formed the phenylhydrazone being partially decomposed and dimethyldihgdro- resorcin regenerated; the compound forms a white powder which on exposure to the atmosphere! partially becomes blue.By the action of concentrated alkaline solutions orange-red flakes are formed which rapidly become scarlet and dissolve in alcohol forming an orange-red solution. When the solution is treated with hydrochloric acid it becomes green then blue and finally olive-green and an amorphous flocculent precipitate is formed ; ammonia restores the orange-redORGANIC CHEMISTRY. 171 colour of the solution By the action of dilute nitric acid a blackish- brown dye is formed and when treated with a small quantity of concentrated sulphuric acid a product is obtained which is possibly a sulphonic acid.Anilinodimetl~~ldii~~droresorcin CH - co separates from its alcoholic solution in white crystals melts at 18l0 is readily soluble in alcohol chloroform or glacial acetic acid less so in hydrochloric acid sparingly soluble in acetone ether or light petroleum asd insoluble in potassium hydroxide; it gives a wine-red coloration with ferric chloride and a blackish-brown dye is formed by the action of nitrous acid. The h?/drochZoride C,,H,,ONCI prepared by passing hydrogen chloride into a solution of the anilino-derivative in chloroform is a white substance which crystallises from alcohol sinters at 205' and melts at 2 14-21 7'. The acetoxy-derivative separates from ethyl acetate i n the form of a yellow crystalline mass which sinters a t 67' and melts a t 62'; it is readily soluble in alcohol ether chloroform or light petroleum less so in hydrochloric acid in presence of alcohol and only sparingly so in potassium hydroxide.It does not give a reaction with ferric chloride but is decomposed by concentrated bydrochloric acid at the ordinary temperature. The o-toluidino-derivative C,,H,,ON crystallises from aqueous alcohol in slender needles melts a t 135O and gives a reddish-brown coloration with ferric chloride. The hydrochloride C,,H,,ONCl separates from the alcoholic solution in white crystals sinters a t 204' and melts a t 208'; when treated with water it becomes yellow and is apparently decomposed. The p-toluidino-derivative crystallises from alcohol and melts a t 202'; the hydrochloride forms strongly etched crystals is soluble in alcohol sinters at 197' and becomes dark and melts at 206-210°.The a-naphthylamino-derivative separates from the alcoholic solution in a greyish-white crystalline form melts at 1 7 5 O and gives a blood-red coloration with ferric chloride ; the hydro- chlol.ide forms rectangular crystals melts a t 226 -230° is soluble in alcohol or chloroform insoluble in ether and gives a reddish-brown coloration with ferric chloride. It is probable tbat phenyldihydroresorcin also forms two isomeric oximes. The greasy yellow substance which is obtained together with a resinous product by the action of hydroxylamine hydrochloride on phenyldihydroreaorcin melts at 95-103' is soluble in alcohol (com- pare Vorlander Zoc. cit.) and reduces Fehling's solution on warming ; its solution in hydrochloric acid is yellow and in alkali red.The main product of the reaction however forms a white resinous mass which on exposure to the atmosphere becomes successively yellow orange and brown. With glacial acetic acid it yields a small quantity of a substance which melts a t 185-187' and is readily soluble in potassium hydroxide but only sparingly so in hydrochloric acid or a solution of sodium carbonate ; by the action of acetic anhydride and dry hydrogen chloride a portion probably is converted into the crystal- line oxime which melts a t 79-82". CW2<C&C(NHpq>cH ' E. W. W.172 ABSTRACTS OF CHEMICAL PAPERS. Action of BromineandCh1orineonPhenoI.s. Substitution Pro- ducts. +-Bromides and $-Chlorides. XIV. Action of Bromine on p-Diphenoldimethylmethane.$-Bromides and Quinones of p-isoPropylpheno1. THEODOR ZINCKE arid MAX GR~TERS ( AnnaZen 1905 343 75-99. Compare Abstr. 1904 i 41 401 1005 ; 1905 i 55 342).-The $-bromide of isopropylphenol is obtained from diphenoldimethylmethane which readily decomposes into phenol and isopro pylphenol. p-~phenoldimethylrnethane CMe,( C,H,*OH) is prepared by warming a mixture of phenol acetone and concentrated hydrochloric acid for three days and then treating the mixture with 40 per cent. acetic acid ; it crystallises in colourless needles or prisms melting at 152-183". 3 5 3' 5'-Tetrabromo-p-dip?~enoldimet?~~hethcne CMe,( C,H,Br,*OH) prepared by the action of bromine in acetic acid on the compound last mentioned crystallises in prisms or spikes melting at 162-163' and is soluble in alkali hydroxides without decomposition ; the acetyl derivative crystallises in needles melting at 169-170".When a solution of the tetrabromide in acetic acid is treated with solid sodium nitrite at the ordinary temperature two atoms of bromine are replaced by nitro-groups a 3 3'-dibromo-5 5'-diniti*o-p-diphenoZdi- methylmethane C,,H1,O,N,Br being formed ; it crystallises in yellow needles melting a t 176" and yields red ammonium and alkali salts ; its acetgl derivative crystallises in yellow needles melting at 196-1 9 7 O . I)-p- Tribromoisopropgltetrabro moplienot (+!~-I~eptabromo-p-isopropyZ- phenol) CO<cB:?gE>C CB H*CBrMe*CHBr is formed together with tribromophenol when the tetrabromide described above is heated- with bromine at 100' ; it crystallises in prisms melting and decompos- ing at 182-183O and when treated with acetone is immediately converted into hexabromoquinone; with acetic anhydride at theordinary temperature a heptabromoacetyl derivative is produced and at a higher temperature the pentabromoacetyl derivative.AcetyZ?beptabromo-p-iso- propylphenol C,,H70,Br crystallises in colourless needles melting a t 166O and by alcoholic potash is converted into hexabromoisopropenyl- phenol. p-D ibrornois opro 1 y lidenetetra bromoquinons (hexabromoisopropg Zidene- quinone) CO< C 3r:CB>C:CMe*CHB~2 3r:CBr is prepared by slowly adding water to a1 acetone solution of the heptabromide and crystal- lises in yellow needles or prisms melting a t 185'. When treated with acetic anhydride in the presence of sulphuric acid at the ordinary temperature it is converted into pa-dibromo.-/3-acetoxyisopropyZtetra- bromophenyl acetate OAc*C6Br,*CMe(OAc)*CHBr2 which crystallises in prisms melting a t 144-145"; when hydrolysed it yields not the corresponding phenol but hexabromoisopropenylphenol. The cor- responding phenolalcohol is formed in small qunnti ty when the qriinone is treated with sulphuric acid in acetic acid solution and crystallises in needles melting at 114-1 17".It readily loses water forming theORGANIC CHEMISTRY. 173 propenyl derivative. p-Dibmoisopropenyltetrabromophenol (hxabromo- pisopropylenephenol) OH*C6Br4-CMe:CBr2 formed by hydrolysing the heptabromo-acetate in alcoholic solution or by reduction of the quinone with an alkaline solution of stannous chloride crystallises in colourless needles melting at 134-135' ; it yields a sparingly soluble sodium salt and is again converted into the $,-heptabromide by hydro- bromic acid in acetic acid solution.The acetyl derivative crystallises in monoclinic prisms melting a t 11 4-115". p-Bromoisopropenyltetra- bromophenol (pentubromo-p-isopropylenepl~enol) OH-C,Br,*CRle:CHBr prepared from the hexabromoisopropy lidenequinone by keeping its acetone solution or by reducing the hexabromoquinone with stannous chloride in acetic acid solution crystallises in needles melting a t 88-89'; it yields a crystalline sodium salt is converted by bromine into the heptabromo-+-bromide and with nitric acid yields a crystalline product. Its acetyl derivative crystallises in monoclinic prisms melting a t 126-127' and is forrued when the heptabromo-+bromide or hexabromoquinone is boiled with acetic anhydride. The Isomeric Nitroso-orcinols.ARTHUR HANTZSCH and C. H. SLUITER (Bey. 1906 39 162-166. Compare Henrich Abstr. 1900 i 163 436; 1901 i 464; Hantzsch and Voegelen 1902 i 260).- Henrich's yellow,modification of nitroso-orcinol crystallises from alcohol in yellowish-brown needles decomposes at 1 6 3 O and has K = 0.037. Its aqueous solution has an orange-yellow colour. The red modification crystallises from boiling benzene and has a transition temperature 124-125" and K=0.051. Its aqueous solutions are orange-red in colour and are perfectly stable when the compounds are pure other- wise there is a tendency to the formation of an equilibrium mixture of the two; the point of equilibrium is not reached however even a t the end of several weeks.The addition of alcohol immediately causes the equilibrium to be attained solutions of both substances then have the same conductivity. Raising the temperature to 50' does not produco the change of the one form into the other. Both modifications yield the same potassium or ammonium salt. These facts are in harmony with Henrich's constitutional formule K. J. P. 0. Red. Yellow. J. J. S. Replaoement of the Acetyl Group by Methoxyl under the Action of Diazomethane. JOSEF HERZIG and J. TICHATSCHEK (Ber. 1906 39 268).-When triacetylpyrogallol is exposed to the action of diazomethane at the ordinary temperature for forty-eight hours the product is found to contain 10.4 per cent.of methoxyl. The acetyl derivative of phloroglucinol diethyl ether is under similar conditions converted almost completely into phloroglucinol methyl diethyl ether. W. A. D. Peculiar Behaviour of Hexabrornodiresorcinol in Alkaline Solution. HEINHICH BECHHOLD (Zed. Elektrochem. 1905 11 845-846).-When dissolved in less than 2.5 molecules of alkali174 ABSTRACTS OF CHEMICAL PAPERS. hexabromodiresorcinol oxidises in presence of the atmosphere to a blue colouring matter when more alkali is used the solution remains unchanged. The different ionisation in the two cases is suggested as the cause of the difference T. E. a- and P-Campholytic Alcohols. GUSTAVE BLANC (Compt. r e d . 1906 142 283-285. Compare Abstr. 1900 i 581 ; 1905 i ll).- Dihydro-/?-camphoZyZ dcohol C,Hl,*CH,*OH obtained by reducing ethyl P-campholytate or the corresponding amide with alcohol and sodium is a colourless viscous liquid which boils at 198' has a sp.gr. 0.9056 at 21 *5'/4O and 12 1,4641 at 21.5'. -Thepyruvate C8H,,*CH2*O*CO*COMe is a mobile liquid boiling a t 140-142O under 17 mm. pressure and has an agreeable penetrating odour ; the semicarbaxone crystallises from alcohol and melts at 158"; the chloride CsH,,-CH,Cl boils at 175'. 2>CH*CH,-OH obtained by reduc- ing the ethyl ester or the amide of a-campholytic acid with alcohol and sodium is a viscous liquid boiling at 200' and having a sp. gr. 0.9273 a t 23O/4' and n 1.4762 a t 23' ; the pyruvate C8H,,*CH,*O*CO*COMe boils a t 143-144O under 17 mm. pressure ; the semicarbaxone melts at 131".M. A. W. gMe*CMe CH-CH a- Campholy l alcohol Gholesterol. V. ADOLF WINDAUS (Ber. 1906 39 518-523. Compare Abstr. 1904 i 49 667 1010; 1905 i 128; Diels and Abderhalden Abstr. 1904 i 880).-Chromic acid and acetic acid at 70° or sulphuric acid and potassium perrnnnganate in the cold oxidise dibromocholesterol to dibromocholest,enone which is reduced to cholestenone by zinc dust and acetic acid. Cholestenone gives a rose-red coloration with concentrated nitric acid ; when heated on the water-bath with a mixture of equal volumes of acetic acid and nitric acid of sp. gr. 1.4 it yields a nitro-derivative probably C,7H,,0,N which crystallises from acetone in glassy leaflets melting at 194-195'. Cholestenone is stable towards a 3 per cent.alcoholic solution of hydrogen chloride a 10 per cent. alcoholic solution of potassium hydroxide or towards diethylamine ; when heated at 210-220' with piperidine it yields a substance C,,H,,N or C,,H,,N which forms large crystals melting at 159'. Cholestenone is probably not an up-unsaturated ketone since its reduction by sodium amalgam in 95 per cent. alcoholic solution gives an unsaturated pinacone C,,H,,O or C5*Hg0O2 cry stallising in needles which sinter and melt a t 281' (compare Harries Abstr. 1904 i 427). With acetic anhydride the pinacone yields a hydrocarbon C,,H8 or C,,H (compare Lieben Abstr. 1905 i 167). The same hydrocarbon seems to be produced by the reduction of cholestenone with zinc dust and alcoholic hydrogen chloride and in the reduction of dibromo- cholestenone.c. s. Ergosterol. D. OTTOLENGHI (Atti R. Accad. Lincei 1905 [v] 14 ii 697-705. See this vol ii 202).ORGANIC CHEMISTRY. 175 Action of Ethylene Dibromide on Ethyl Sodiocyanoacetate. LBONCE BARTHE (Bull. #oc. chim. 1906 [iii] 35 40-47. Compare Abstr. 1894 i 492).-The author has repeated the work of Carpenter and Perkin (Trans. 1899 75 924) and generally confirmed their observations. Ethyl cyanotrimethylenecarboxylate yH2>C(CN)*C0,Et boils at 137' under 80 mm. pressure and is hydrolysed by hydrogen chloride in presence of alcohol to ethyl trimethylenedicarboxylate CH2 FH">C( CO,Et) CH which is a colourless oily liquid and boils a t 130' under 70 mm. pressure. The author cannot confirm Carpenter\ and Perkin's state- ment that ethyl cyanotrimethylenecarboxylate is hydrolysed by potassium hydroxide in alcohol to the corresponding cyano-acid but a small yield of the latter was obtained by adding metallic sodium to a solution of the ester in alcohol.The magnesium salt crystsllises with H,O. The crystalline accessory substance melting at 119' obtained by Carpenter and Perkin (Zoc. cit.) and which since it yielded adipic acid on hydrolysis they regarded as ethyl a&dicyanovalerate furnished malonic acid when hydrolysed with hydrochloric acid. Hydrolysis carried out with other agents gave the present author inconclusive results. T. A. H. Terpenes and Ethereal Oils. LXXIV. cycZoHexanone. OTTO WALLACH (Annalen 1905 343 40-53).-This paper contains in part an account of work previously published together with cor- rections and amdifications. yH,*CH,*CH CH;CH,-CO cy cZoHexanoneisooxime >NH yields on hydrolysis r-aminohexoic acid NH,*CH,:[ CHl],*CO,H which is oxidised by alkaline permanganate to normal adipic acid.Suberoneisooxime similarly yields c-aminoheptoic acid which is oxidised to pimelic acid. On reducing the hexanoneisooxime with sodium in amyl alcohol solution unsaturated fatty acids are mainly formed together with cyclohexylamine (not as was expected hexamethyleneimine Abstr. 1905 i 826) C,H,,*NH2 which is an oil boiling at 135-138' and having a sp. gr. 0.863 and n 1,4575 at 24'. The hydrochloride melts at 203-204' the benzoyl derivative at 149' the cnrbamide a t 195-196' and the niethiodide at 260'. The amine is probably formed from the hexamethyleneimine by fission into an intermediary acyclic compound which by renewed ring formation passes into cyclo- hexylamine.Some hexamsthyleneimine seems to be present in the more volatile fractions. When eaminohexoic acid is oxidised with nitric acid c-hydroxy- hexoic acid is formed. The latter loses water forming a mixture of As- and Av-hexenoic acids. Tetrahydrobenzene forms a nitrosochloride when a solution of the17'6 ABSTRACTS OF CHEMICAL PAPERS. hydrocarbon in acetic acid is treated successively with ethyl nitrite and concentrated hydrochloric acid. The nitrosochloride is an un- usually stable substance. 1-Methylcyclohexane-2-one is prepared from Al-tetrahydrotoluene which can now be easily obtained by Grignard's method from methyl iodide and cyclohexanone ; this reaction first yields 1-methylcyclo- hexane-1-01. The latter is then dehydrated.[With EDUARU I s ~ ~ c . ] - x t h y l cyciohexanolacetate CH2<",~~:~~~>C(OH)*CH2*C02Et Z L is prepared from cyclohexanone and ethyl bromoacetate by the agency of magnesium. It passes readily by loss of water into ethyl cyclo- hexeneacetate which on hydrolysis yields cyclohexeneacetic acid C H 2 < g ~ ~ ~ > C * C H 2 * C 0 2 H or ,H,<g.,~:~~>C:CH=CO,H melting at 37-38" and boiling at 140' under 12 mm. pressure. It takes up bromine in ethereal solution,. giving dibromocyclohexaneacetic acid C,H,,0,Br2,. which crystallises in prisms melting a t 119-120' and is converted into an oil on treatment with alkali carbonates. When cyclohexeneacetic acid is oxidised at 0' by permanganate a cyclohexanone is not formed but a compound with seven carbon atoms which is not an aldehyde.K. J. P. 0. 5-Bromo-2-aminobenzoic Acid and Certain Derivatives. MARSTON T. BOGERT and WILLIAM F. HAND (J. Amer. Chem. Soc. 1905 27 1476-1 484).-5-Bromo-2-acetylaminobenzoic acid (5-bromo- acetylanthranilic acid) (Jackson Abstr. 1 S81 735) was prepared by the direct bromination of acetylanthranilic acid by the oxidation of 5-bromo-o-acetgltoluidine and by the hvdrolysis of 5-bromoacetyl- ant hranil; it crystallises in transparent six-sided microscopic prisms and melts a t 222-223' (corr.). The barium salt was prepared. 5-Bromo-2- aminobenzoic acid melts a t 219-220' (corr.) and not a t 21 1*5-212'as stated by Alt (Abstr. 1889,987) ; its hydrocldovide and barium salt are described.5 - Brontoacetylant?~rcnil crystallises in colourless scales and melts a t 131' (corr. j. 5-Bromo-~-cccetylu~inob~nzonitrile obtained by the action of bromine on acetylaminobenzonitrile forms six-sided prisms melts at 158' (corr.) and is easily soluble in alcohol acetone ethyl acetate hot benzene or chloroform and sparingly so in water. E. G. Stereoisomeric Cinnamic Acids. EMIL EBLENMEYER jun. (Ber. 1906 39 385-292. Compare Abstr. 1905 i 892 ; this vol. i 2 l).-Synthetically prepared cinnamic acid gives with brucine in alcoholic solution three different brucine salts of the same composition melting at 135' 113' and 107' respectively. Cinnamic acid from storax gives only the brucine salt melting at 135' which in 1 per cent.alcoholic solution is optically inactive. The salt melting at 1 13" in 1 per cent alcoholic solution has La]D - 12.5'. Cirinamic acid from storax has a solubility in absolute alcohol of 12-72 grams per 100 c.c. whilst synthetical cinnamic acid has a somewhat greater solubility namely 13.88 grams per 100 c.c.; the two acids show a strikinglyORGANIC CHEMISTRY. 177 different behaviour when recrystallised from alcohol. Cinnamic acid from storax is converted into synthetical cinnamic acid when heated for ten hours with concentrated sodium hydroxide. All three of the brucine salts separated from alcohol give on crystallisation from benzene the same product C,H,0,,C,,H,,0,Na,C,H6 melting at 92-93' ; but on volatilising the benzene of crystallisation a t 70-80° the differences between the salts reappear.On combining synthetical cinnamic acid with Z-isodiphenyloxyethyl- amiue and crystallising from alcohol two different salts containing alcohol of crystallisation are obtained ; the more soluble sult melts when the alcohol has been expelled a t 128' and in 1 per cent. alcoholic solution gives [ u ] ~ - 46.5' ; the less soluble salt melts a t 136-137' and has [a]= - 63.5'. From d-isodiphenyloxyethylamine and synthet- ical cinnamic acid two analogous salts are obtained melting at 136' and 128' with nearly corresponding dextro-rotations. With storax cinnamic acid I-isodiphenyloxyethylamine gives only a salt containing 2EtOH which when dried in the air melts at 75-80G and when dried a t 80"melts a t 128"; in 1 per cent alcoholic solution it has [ alD - 44.4'.With the same acid cl-isodiphenyloxyethylamine gives a salt melting a t 130-138" when dried in the air and at 136' when dried a t 80' ; in 1 per cent. alcoholic solution it has [a] + 64'. Storax cinnamic acid thus seems to be a component of synthetical cinnamic acid. The cases which the author has dealt with seem to point to the existence of a new class of stereoisomerism ; its nature is briefly discussed. W. A.D. Action of Pyridine on Salicyl Chlorides. RICHARD B. EARLE and H. LOUIS JACKSON (J. Amer. Chem. Soc. 1906 28 104-114)- When pyridine is added to a solution of 3 5-dichlorosalicyl chloride dichlorosalicylide (C7H20,C12) corresponding with the salicylide described by Anechutz (Abstr. 1893 i 165) is produced which is insoluble in the usual solvents but is soluble in hot anisole or hot nitrobenzene separates from the latter solvent in short prismatic crystals melts and decomposes at about 330° and is very stable; it is very slowly attacked by aqueous potassium hydroxide but is readily hydrolysed by alcoholic potassium hydroxide.The molecular weight was determined in boiling anisole ; the constant K for this eolvent was found to be 4502 (calculated K= 4595). 3 5-Uibromosalicyl chloride obtained by the action of phosphorus pentachloride on 3 5-dibromosalicylic acid crystallises from light petroleum and melts a t 83-85'. When pyridine is added to a solution of the chloride in light petroleum cooled to - 6O a precipitate is pro- duced which is probably a mixture of substances.On adding pyridine to a solution of the chloride in acetone cooled t o - 16O a precipitate is obtained which has no definite melting point and is easily soluble in chloroform o r benzene ; a cryoscopic determination of the molecular weight in benzene solution indicated that the substance was a heptasalz'cylide but it is possible that its complexity changes on solu- tion. The lack of a definite melting point suggested that changes take place in the mclecular weight of the substance and its behaviour on heating was therefore studied by means of a dilatometer; it was VOL. xc. i. 0178 ABSTRACTS OF CHEMICAL PAPERS. found that the substance behaves normally from 75' to 1 loo contracts slowly at a constant rate from 110' to 1 70° and expands at a rapidly increasing rate from 170" to 200".It was observed that during the action of pyridine on each chloride the solution a t first became bright yellow but rapidly faded the dura- tion of the colour varying with different solvents ; a table is given recording the number of seconds during which the colour lasted in varioue solvents. The colour remained longest in a xylene solution lasting in this case for about a minute. On adding organic bases to the coloured solution colourless precipi- tates are produced which are at present under investigation. E. G. Action of Zinc on a Mixture of Cinnamaldehyde and Ethyl a-Bromopropionate. L. BAIDAKOWSKY (J. Russ. Phys. Chem. Xoc. 1905 37 896-902).-The action of a freshly-prepared zinc-copper couple on a mixture of cinnamaldehyde and ethyl a-bromopropionate in an atmosphere of carbon dioxide proceeds according to the equations (1) CHRleBr*CO,Et + Zn = BrZn*CHMe-C0,Et ; (2) CHPh:CH*CHO + BrZn*CHMe*CO,Et = CHPh:CH*CH(OZnBr)*CHMe*CO,Et which is decomposed by water giving Zn Br(0H) + EtOH + CHPh:CH*CH(OH)*CHMe*CO,Et.This ester could not be distilled unchanged and on hydrolysis with 10 per cent. potassium hydroxide or sulphuric acid solution it yields cinnamenylcrotonic acid CRPh:CH*CH:CMe*CO,H. If however the ester is hydrolysed with cold 5 per cent. barium hydroxide solu- tion the barium salt Ba(C,,E€,,O3),,2~H,O is obtained as silvery leaflets and yields the acid Cl2Hl4O3 in a syrupy form; on boiling the latter with 10 per cent. sulphuric acid solution it yields a lactone cinnamenylcrotonic acid and the unsaturated hydrocarbon CHPh:CH*CH:CHMe isolated by Markownikoff (Abstr.1886 1015) from Caucasian naphtha. Cinnamenylcrotonic acid combines with bromine (4 atoms) giving a comnpotmd which melts and decomposes at about 130' and is readily soluble in alcohol ether or benzene and slightly so in light petroleum. T. H. P. Action of Zinc on a Mixture of Salicylaldehyde and Ethyl a-Bromopropionate. Synthesis of a-Methylcoumarin. L. BAIDAKOWSKY (J. Russ. Phys. Chern. Xoc. 1905 37 902-905).- The action of zinc or of a zinc-copper couple on a mixture of salicyl- aldehyde and ethyl a-bromopropionate should give the ester OH*C,H,*CHMe*CO,H but the ester obtained could not be purified as it decomposed on distil- lation giving salicylaldehyde and a-methylcoumarin. T. H.P. Preparation and Properties of p-Cumenyl-a-ethylhydr- acrylic Acid. A. RALISCHEFF (J. Russ. Phys. Chem. Xoc. 1905 37 905-910).-The action of zinc on a mixture of cuminaldehyde and ethyl u-bromobutyrate yields ethyl p-cumenyl-a-ethylhydracrylate which on hydrolysis with sodium hydroxide and decomposition of theORGANIC CHEMISTRY. 179 sodium salt with dilute mineral acid yields p-c.rinaenyl-a-etl~ylhydr- acrylic acid C,H7*C6H4*CH(OH)*CHEt*CO2H in two modificutions one soluble and the other insoluble in light petroleum. The latter separates from benzene or aqueous alcohol in small crystals melting a t 124*5-125*5° ; its sod&mh bai*ium (4H20) ccdcium (4H,O) and silver salts were prepared and analysed. On distillation with dilute sulphuric acid this acid loses water and carbon dioxide yielding isopropyl- butenylbenzene C,H7-C,H,*CH:CHEt. T.H. P. Carboxylation of Phenols by means of Carbon Dioxide. 11. P-Naphthol-1-carboxylic Acid. SIJBE TIJMSTRA jun. and B. G. EGGINK (Ber. 1906 39 14-16. Compare Abstr. 1905 i 439).-A modified method is described of preparing pure sodium P-naphthoxide. When heated with an excess of carbon dioxide a t 1 10-120° it is converted into /3-sodoxynaphthoic acid ONa*C,,,H;CO,H which differs from sodium P-hydroxynaphthoate OH*C,oH,*C@2Na in that it is capable of absorbing nearly one equivalent of dry ammonia. 2-Hydroxynaphthoic acid [P-naphthol-1 -carboxylic acid] melts when quickly heated at 156' liberating gas and decomposes into naphthol and carbon dioxide when boiled with water ; the acid contains a small quantity of water as represented by the formula 4C,,H80,,H,0. T.M. L. Isomerism and Tautomerism. ARTHUR MICHAEL (Bey. 1906 39 203-211).--.A discussion of the constitutions of ethyl formyl- phenylacetate oxalacetic acid and its esters and of dibenzoylacetyl- methane. When carbon dioxide is passed into a solution of the sodium derivative of ethyl formylphenylacetate an oil is precipitated which quickly changes to a solid melting a t about 50'. Using sulphuric acid of sp. gr. of a t least 1-36 as the precipitant a solid is at once obtained which melts at 98-100'. The use of a weaker solution of sulphuric acid causes the separation of an oil which changes somewhat slowly to a solid which melts between 60" and 90" and appears to be a mixture of the forms melting respectively a t 50' and 100'.The modification melting at 60" is more soluble and is more easily trans- formed into the liquid tautomeride than is the form which melts at 100". The use of phenylcarbimide (Wislicenus Abstr. 1896 i 552) to differentiate bet.ween the enolic and ketonic forms is inadmissible since all the modifications of ethyl formylphenylacetate unite with this reagent to form the ethereal carbanilide which melts a t 116'. Normal tertiary fatty amines which unite only with enolic derivatives are suitable reagents for the purpose in question and according to this criterion all the forms of the ester are enolic. [With ARTHUR MURPHY jun.1-When a 10 per cent. solution of sulphuric acid is slowly added at 0" to rz solution of the sodium derivative of methyl oxalacetate (Wislicenus and Grossman Abstr.1894 i 116) LL modification of the ester is obtained which melts a t 85-87' and is extraordinarily sensitive to heat changing above 50' 0 2180 ABSTRACTS OF CHEMICAL PAPERS. into the ordinary form. Towards ferric chloride and other reagents both modifications behave alike and both are hydrolysed by hydro- chloric acid into the oxalacetic acid which melts at 152'. If to the mixture of the enolic and ketonic forms of dibenzoyl- acety lmethane obtained by crystallising the ketonic form which melts at 107-110' from 50 per cent. alcohol a trace of acetic acid is added and Claisen's directions are then followed (Anndea 1896 291 78) a new modification of the ketonic tautomeride is obtaimd which melts at 147-149' ; the same substance can be prepared in a similar way from the ketonic form melting a t 110' or from the enolic form by the action of acetyl chloride.Prom ethylene dibromide both the new and the old ketonic modifications of dibenzoylacetylmethane crystallise unchanged below 25'; from methyl or ethyl alcohol chloroform or carbon tetrachloride either form separates as a mixture of both modifications which melts a t 126-136' whilst the enolic tautomeride remains in solution. The new isomeride is at once enolised by benzene ; so also is the old keto-derivative contrary to Claisen's statement (Zoc. cit.). Of the two ketonic forms the one with the higher melting point is the more stable and the less reactive. Triisobutylamine in a solution of benzene and ether converts the less fusible form into an enol-keto-mixture; in the presence of light petroleum the Bromo- a n d Bromonitro-derivatives of o-Bensoylbensoic Acid.FRANZ KUNCKELL and G. KNIGGE (Ber. 1906 39 194-196). -Bromo-o-benxoylbanxoic acid C6H4Br*CO*C6H4*C02H is obtained when o-benzoylbenzoic acid (Pechmann Abstr. 1882 96) is heated with water and bromine (2 mols.) for five hours at 120'. It crys- tallises from alcohol melts a t 156O and dissolves readily in most organic solvents. When heated for 10-20 minutes with 5-10 times its weight of fuming nitric acid it yields bromotetrunitro-o-benzoylbenzoic acid CI4HdOl1N4Br which crystallises from alcohol in pale yellow plates melting a t 178'. When o-benzoylbenzoic acid is heated with water and bromine (3 mols.) at 180° a mixture of mono- and dibromo- benzoylbenzoic acids and tetrabromobenzoic acid is obtained.The dibromo-o-benxoylbenxoic acid Cl,H803BrT crystalliees from benzene in colourless needles melts a t 194O and is readily soluble in acetic acid ether or alcohol. The tetrabromobenxoic acid is sparingly soluble in alcohol crystallises in yellow plates and melts a t 295O. ketonic form melting a t 110' is obtained. c. 8. J. J. S. Formation of Indigotin from Quinoline. HERMAN DECKER and C. KOPP (Ber. 1906 39 72).-If the additive product of qninol- ine with ethyl chloroacetate is oxidised with potassium permanganate the filtrate rendered alkaline evaporated and heated at 200' it is converted into indigotin. Formylphenylglycine-o-carboxylic acid CO E€*C,H,*N( CHO) *CH,*CO,H is probably an intermediate pro- duct of the oxidation.Influence of Alkyloxy-groups on the Reactivity of a-Brom- ine Atoms in Aromatic Compounds. ALFRED WERNER [with P. SCHORNDORFF and CH. CHOROWER] (Ber. 1906 3B 27-36).- The presence of 0- or p-alkyloxy-groups greatly facilitates the replace- T. M L.ORGANIC CHEMISTRY. 181 ment of a-halogen atoms by alkyloxy- or phenoxy-gronps a reaction which has been frequently observed by Zincke in derivatives of p - hydroxybenzyl bromide OH*C,€€,gCH,Br -f OH*C6H,*CH2*OR but not in benzyl bromide itself. Thus o-methylcoumaric dibromide O~~e*C,H;CHBr*CHBr*CO,H when boiled with methyl alcohol yields the a-methozy-ester OMe*C,H,* CH( OMe)*C HBr*CO,Rle which separates from light petroleum in colourless crystals and melts a t 64" ; the a-methoxy-cccid CllH1304Br separates from light petrol- eum in colourless crystals and melts at 118"; the potassium salt forms large clear square crystals with a blue fluorescence. The di- bromide of cinnamic acid C,H,*C€€Br*CHBr~CO,H does not behave in this way but is merely esterified.OMe*C,H,-CH(OEt)*CHBr.CO H separates from light petroleum in large asymmetric crystals and melts a t 103'. The a-isopropyloxy-acid OMe*CGH4*CH(OPr@) *CHBr*CO,H separates from light petroleum in colourless prisms and melts a t 125'. The action of phenol on methylcoumaric acid dibromide is more com- plex than that of alcohols; methyl bromide is apparently formed and a- p-hydroxgpheny lcoumccran O<22>CH*C6H4*OH is the chief product ; i t crystallises from much hot water in minute glistening Bakes and melts at 150-154".The ucetyl derivative CI6HI4O3 crystallises from concentrated alcoholic solution in thin glistening scales or broad needles melts at 102" and has a normal molecular weight when dissolved in acetic acid. The methyl ether crystallises from alcohol in thin scales and melts at 94-95". Anisylideneacetophenone di bromide OMe-C,H,*C HB c*C HBr*COPh is acted on in a similar manner by methyl alcohol the a-bromine atom being replaced by methoxyl. OMw C,H,*CH(ORle)*CHBr*COPh separates from methyl alcohol in colourless needles and melts at 101". The ethoxp-ketone OMe*C,H,* CH(0Et) CH Br* COPh crys talli ses from alcohol in long colourless needles and melts a t 70'. The hyd~oxy-ketone OM.e*G,H,*CH(OH).CHBr*COPh prepared by boiling with aqueous acetone crystallises from light petroleum in long colourless needles and melts a t 78".The a-ethoxy-acid The a-metlzozy-ketone T. M. L. 2-Aminoisophthdic Acid. EMILIO NOELTING and 'CK. GACEIOT (Ber. 1906 39 73-76).-When boiled with nitric acid of sp. gr. 1.4 2-nitro-nz-xylene yields u-dinitro-rn-xylene a substance NO,*C,H,Me*CH,*NO (I) which changes readily into an aldehyde and 2-nitro-ni-toZuic cccid C,H70,N melting at 21'7.5-218". When oxidised with potassium permanganate in alkaline solution this yields 2-nit~oisopZ~thuZic cicid C,H,O,N which is formed directly from 2-nitro-m-xylene by oxidation with potassium permanganate in presence of magnesium sulphate. It crystallises in white needles commences to become brown a t 287" and is not completely melted at 300".The barium salt was analyked; the dimethyl ester C,,H,O,N crystallises in glistening white scales melts at 1 29-130° and undergoes partial hydrolysis when recrystal-182 ABSTRACTS OF CHEMICAL PAPERS. lised from boiling water. The hydrochlorids of 2-tbminoieophthalic acid obtained by reduction of the nitro-acid with zinc and concentrated hydrochloric acid crystallises in white needles and on exposure to the air readily loses hydrogen chloride forming the free amino-acid C8H704N ; this crystallises from alcohol in yellow leaflets melts above 260° and is easily soluble in alcohol or ether. The copper salt C8Hb04NUu is obtained as a green precipitate which after drying a t 1 19" has the composition 2C,I&04NCu,Cu0. 2-Acetylaminoisoplithalic acid NHAc*C,H,(CO,H) is prepared by oxidising aceto-m-2-xylidide with potassium permanganate in presence of magnesium sulphate ; it crystallises in long slender white needles and on prolonged boiling with concentrated hydrochloric acid yields the hydrochloride of 2-aminoisophthalic acid.When titrated with methyl-orange as indicator the acid neutralises only 1 mol. of sodium hydroxide ; the copper salt NHAC*C~H,(CO,)~CU was analysed. When cooled and diazotised with sodium nitrite and bydrocbloric acid or with nitrosyl sulphate and concentrated sulphuric acid and ' I coupled " with phenol in alkaline solution 2-aruinoisophthalic acid forms the am-derivat ive C6H,( C0,H),*N2*CGH,* OH which is obtained in glistening yellow anhydrous scales or in red spear-like needles containing 2/3H,O which is lost at 115O.When dissolved in boiling water and allowed to cool slowly the yellow modification is converted into the red; if this is heated with concentrated hydrochloric acid it yields a yellow product which is insoluble in most solvents and cannot be reconverted into the red azo-compound. With p-cresol diazotised 2-aminoisophthalic acid forms an nxo-derivative C,,H1,O,N which is obtained in two anhydrous modifications red and yellow respectively. G. Y. Preparation of Cbloro- and Bromo-phthalimides. BADISCHE ANILIN- & SODA-FABBIK (D.R.-P. 161340)-The action of alkali hypochlorites on an aqueous suspension of phthalimide is very slow whilst if the alkali salts of phthalimide are employed partial hydrolysie to pbthalamates occurs.If the phthalimide is suspended in acetic acid and sodium hypochlorite or hypobromite is added chloro- or bromo- phthalimide is precipitated in a pure form. 0. H. D. Synthesis of a- Amino-acids by means of Bromo-fatty Acids. EMIL FISCHER and WILHELM SCHMITZ (Ber. 1906 39 351-356. Compare Fischer Abstr. 1904 i 890).-a-BromoisobutylmaZonic acid CPH1104Br prepared by brominating isobutylmalonic acid (Guthzeit Abstr. 1882 3Y) crystallises from benzene melts at 139-141' (corr.) is readily soluble in water alcohol or ether and when heated a t its melting point under 12 mm. pressure evolves carbon dioxide and forms a-bromoisohexoic acid CHMe,*CH,*C.E€Br*CO,H which boils at 126-128*5O under 9 mm. pressure. With this is partially or wholly identical the bromoisohexoic acid formed by the action of bromine and phosphorus on isohexoic acid prepared from isoamyl cyanide.Ethyl y-p~nyletliylmalortate CH,Ph*CH,*CH(CO,Et) formed by boiling ethyl sodiomalonate with o-chloroethylbenzene in alcoholicORGANIC CHEMISTRY. 183 solution in a reflux apparatus boils at 185-187O under 24 mm. pressure and on hydrolysis with concentrated potassium hydroxide yields y-phenylethylmalonic acid CH,Ph*CH,*CH(CO,H),. This crystal- lises from toluene in glistening colourless leaflets melts and evolves carbon dioxide a t 142-144' (corr.) and is readily soluble in hot water alcohol or ether. a-Bronzo-y-pl~enyZell~~ZrnnZonic acid CH,Ph*CH:,*CBr(CO,H) formed by brorninating y-phenylethylmalonic acid crystitilises from benzene in small nodular aggregates or from water in microscopic needles or thin prisms and melts and decomposes at 116-118' (corr.).a-Bronzo-y- phenylbutyric acid CH,Ph*CH,*CHBr*CO,H crystallises from water i n thin leaflets or from benzene in small rectangular thin plates melts at 188-190' (corr.) and may be distilled i f rapidly heated under 10 mm. pressure. When treated with 25 per cent. aqueous ammonia a t 100' for one and a half hours or at the laboratory temperature for some days i t forms a-amino- y-phenylbutyric acid CH,Ph*CH,*CH(NH,)*CO,H ; this crystallises from boiling water i n glistening needles or stellate aggregates of small plates containing H,O which is lost a t SO' in a vacuum. When quickly heated the dry amino-acid becomes yellow at 247' and melts and decomposes a t about 252' (corr.); it has an unpleasant bitter taste and is moderately soluble in boiling alcohol.The hydrochEoride crystallises from hot hydrochloric acid in glistening leaflets ; the boiling aqueous solution of the base dissolves copper oxide forming a blue solution from which the copper salt crystallises on cooling in small light blue needles or long slender prisms. G. Y. Butadiene Compounds. XIV. Nitrophenyldimethylfulgenic HANS STOBBE (Ber. 1906 39 Compare this V O ~ . i 91 92 lOl).-[With KARL 1,EUNER.I Acids and their Yellow Fulgides. 292-298. -8-0 -Nit r ophenyl- aa-dim e t l y l f u lgenic .acid CMe, C( C0,H) C( C0,H) CH. C6H4=NO2 prepared from o-nitrobenzaldehyde and ethyl teraconate crystallises from dilute alcohol or 80 per cent. acetic acid; it is white with a yellow lustre and gives a yellowish-white barium salt C1,H,lO,NBa H,O.The corresponding ficlgide C14Hl105N prepared by means of acetyl chloride crystallises from benzene with 4C6H in bright yellow lustrous leaflets and melts and decomposes at 155'. 8-m-Nitrophenyl-aa-dimethylfulgcrzk acid prepared in similar manner from m-nitrobenzaldehyde crystallises from ether acetic acid or dilute alcohol and is bright yellow in colour with a green tinge; i t melts at 228' and gives a wbite barium salt C,,H,,O,NBa,K,O. The,fuZgide C,,H,,O,N crystallises from benzene either with C,H in large well- formed intensely yellow prisms or in smaller yellow prisms not con- taining the solvent ; both forms melt at 120.5'. 6-p-Nitrophenyl-aa-dimethylfulgenic acid prepared by means I of p-nitrobenzaldehyde crystallises from ether or dilute alcohol has a feebly yellow colour with a brown lustre and melts and decomposes at 234' ; the barium salt C,,Hi,0,NBa,H20 has a greenish-yellow184 ABSTRACTS OF CHEMICAL PAPERS.colour which becomes yellow at 180O. The fulgide separates from benzene in orange-red crystals with C,H which rapidly effloresce giving a bright orange-coloured powder similar in shade to lead iodide ; from chloroform long yellow needles are obtained. The fulgide melts a t 175-177'. A table is given showing the relationships of colour presented by aa-dimethylfulgenic acid its 0- m- and p-nitrophenyl derivatives and their fulgides and analogous derivatives of aa8-triphenylf ulgenic acid The relation between colour and constitution is discussed in these cases.W. A. D. Sulphonic Derivatives of Naphthalic Anhydride. GUIDO BARGELLINI (Atti R. Accad. Lincei 1905 [v] 14 ii 688-696. Compare Francesconi :md Bargellini Abstr. 1903 i 34).-The blue fluorescence exhibited by a solution of naphtbalic anhydride in con- centrated or fuming sulphuric acid is not due to the formation of any compound in the solution. If the liquid is kept for several months the fluorescence diminishes continuously and sulphonaphthalic acid is formed. This change proceeds more rapidly on heating and at tempera- tures above 100' disulphonaphthalic acid is also formed. Neither of these compounds exhibits fluorescence. When fused with potassium hydroxide sulphonaphthalic acid (Anselm and Zuckmayer Abstr. 1900 i 175) yields the hydroxy- naphthalic anhydride melting at 287'.Since this anhydride has also been obtained from a 3-nitronaphthalic anhydride (Anselm and Zuck- mayer Zoc. cit.) and since also 4-hydroxynaphthalic anhydride melts at 257" (Graebe Abstr. 1903 i 408) sulphonaphthalic acid must have the sulphonic group in the 3-position the two carboxyl groups being at positions 1 and 8. DisuZphonaphthaZic acid C,,H,( CO,H),(SO,H) [( CO,H) (SO,H) = 1 8 2 61 melts at about 220' and is readily soluble in water. The barium salt crystallises from water with 4H,O and is precipitated by addition of alcohol t o its aqueous solution as the dihydrate. The anilide C2,H,,0,N,S2 crystallises from alcohol in colourless plates decomposing at above 290' and is readily soluble in methyl alcohol and slightly so in ether benzene or carbon disulphide. 4 5-Dibrom 0-3 -su@honaphthalic acid C ,,H,Br,( C0,H) ,-SO,H pre - pared by the action of bromine on a fuming sulphuric acid solution of naphthalic anhydride crystallises from a mixture of sthyl acetate and ether in white needles melting at 204-205O and dissolves in water nitric acid acetic acid methyl ethyl or amyl alcohol or dilute solu- tions of the alkali hydroxides or carbonates and to a slight extent in benzene or carbon disulphide ; it dissolves also in ammonia solution giving a yellow liquid which deposits yellow silky needles on cool- ing.Not one of these solutions or that in concentrated sulphuric acid is fluorescent. The barium salt C2,H,0,,Br,S,Ba3,SH20,. crystal- lises from water in white needles.The solution of the barium salt gives with copper acetate a greenish-blue gelatinous precipitate with lead acetate a white flocculent precipitate and with silver nitrate a white precipitate which blackens in the air. T. H. P.ORGANIC CHEMISTRY. 185 New Coumarins and some of their Derivatives. PH. CHUIT and FR. BOLSING (Bull. Xoc. ckirn. 1906 [iii] 35 76-90).-These coumarins and their derivatives were prepared by condensing hydroxyaldehydes with the appropriate ketonic acid or ester in presence of an amine usually aniline or piperidine a reaction first employed by Knoevenagel (Abstr. 1899 i 116). prepared by condensing 3-methylsalicylaldehyde with malonic acid in presence of aniline hydrochloride crystallises from benzene in colourless needles melts at 142-143" is readily soluble in hot benzene or acetic acid soluble in alcohol (2.28 grams in 100 C.C.a t 14') and boiling water. slightly so in hot petroleum. The ethyl ester obtained by using ethyl malonttte in the condensation forms colourless crystals is inodorous and melts at 81'. 8-MethyZcoumarin obtained by heating the acid separates from alcohol in long colourless needles melts at 109-1 loo boils a t 178' under 20 mm. pressure and has a feeble odour of coumarin. When ethyl acetoacetate is used in place of ethyl malonate CHI y-CO,H 8-Methylcozcmurincarboxylic acid C6H3Me<O-C0 in the condensation 3-acetyl-8-methylcoumarin; CH:YAc C6H3'1e<0 -(-lo 9 is formed this crystallises in brilliant flattened faintly yellow needles is inodorous and melts at 125*8-126.2'.The phenylhydrazone forms short *yellow tinted needles and melts at 168-169"; the oxime yellowish-white needles melting and decomposing a t 212-21 3O and the semicarbaxone small yellow crystals which melt and decompose a t When the Tiemann-Schotten reaction is applied to m-cresol in addi- tion to the p-aldehyde 4-methylsalicylaldehyde (m. p. 59') a.nd 6-methylsalicylaldehyde (m. p. 3 1.5') are produced. From the former 7-methylcoumarincarboxylic acid was prepared this crystallises in colourlt?ss leaflets melts at 198*8-199.8" is soluble in boiling acetic acid slightly so in alcohol (0.45 gram in 100 C.C. at 14') and in boiling water. The ethyl ester forms colourless nacreous spangles from dilute alcohol melts at 101*5-102~5' and is readily soluble in warm alcohol slightly so in light petroleum.7-MethyZcoumurin obtained by heating the acid a t 250-300° crystallises from a mixture of alcohol and water in colourless leaflets melts at 125*8-126.4' boils a t 171.5' under 11 mm. pressure and possesses a strong odour of coumarin (compare Schmidt Inaug. Diss. Rostock). 3-Acetyl-7-methylcoumarin prepared by con- densing the aldehyde with ethyl acetoacetate in presence of piperi- dine crystallises from alcohol in brilliant colourless needles melts a t 156-157' and is inodorous ; the oxime separates from alcohol in yellow needles and melts and decomposes at 224'. 5-Methylcozcmurinca~boxylic ucid similarly prepared from 6-methyl- salicylaldehyde crystallises from alcohol in colourless leaflets and melts at 162.5-163"; its solubility in alcohol is 1 gram in 100 C.C.at 14'. The ethyl ester crystallises from dilute alcohol in brilliant colourless needles and me1 ts at 122-1 22.5". 5-Methylcoumarin produced by heating the acid at 260° crystallises from water in long needles 224-225".186 ABSTRACTS OF CHEMICAL PAPERS. possesses a faint coumarin odour and melts at 65-65~8~. 3-Acetyl-5- methylcoumarin forms yellow needles melts at 115' and is easily soluble in warm alcohol. The o x i m crystallises in white needles and melts and decomposes at 214'. 6-~ethylcozcmari~arboxyl~c acid prepared similarly from 5-methyl- salicylaldehyde crystallises from alcohol in yellowish-white needles melts at 166-8' and is soluble in acetic acid less so in alcohol (1.22 grams in 100 C.C.at 14'). The ethyl ester separates from alcohol in large colourless tables is inodorous melts a t 103-104' and is readily soluble in benzene soluble in alcohol and slightly so in water or light petroleum. 6-Methylcoumarin forms colourless needles from alcohol melts at 74-6-75" and boils at 303' under 725 mm. and at 174' under 14 mm. pressure. Its odour is slightly different from and more per- sistent than that of coumarin. 3-Acetyl-6-methyZcoumarin separates on cooling a solution in warm alcohol in yellowish-white nacreous leaflets and melts at 128-128.4'. The phenylhydrazone melts a t 193-194' the oxime with decomposition at 219' and the senzicarbaxons at 211° also with decomposition. T. A H. Action of Aqueous Solutions of Mercuric Acetate on Olefinic Compounds.LUIGI BALBIANO [with VINCENZO PAOLINI A. NARDACCI U. TONAZZI ENRICO LUZZI F. BERNARDINI D. CIRELLI G. MAMMOLA and GION VESPIGNANI] (Hem. R. Accad. Lincei 1905 [v] 5,515-578). -The greater part of this work has been already published (see Abstr. 1902 i 808; ii 109; 1904 i 72 and 261) the new matter being as follows. [With D. CIRELLI.]-T~~ action of mercuric acetate on asarone which contains the propenyl group should yield the glycol C,H,( OMe),*CH( OH) CHMe* OH ; if this compound is formed it loses water giving the aldehyde C,H2(OMe),*CH2*CH2*CH0 which boils a t 184' under 14 mm. pres- sure and solidifies in lamellated aggregates melting at 47-48' The semicarbazone C,,H,,04N2 crystallises f rom alcohol in shining plates melting at 157-158'. [With VINCENZO PAOLINI.]-on dehydrating the glycol OMe-C,H,*C,H,(OH) prepared by the action of mercuric acetate on anethole (Abstr.1902 i 808) by means of zinc chloride it is converted into P-p-methoxy- phsnyZpropaldehyde OMe.C,H,*CH,*CH,*CHO which is a pale yellow liquid with a faint aromatic odour is soluble in alcohol or ether and boils at 132-135' under 10 mm. pressure. The semicarbazone C,,H,,O,N crystallises from alcohol in superposed laminae melts at 174' and is soluble in all organic solvents. The semicarhazone of the isomeric aldehyde obtained by Bougault by the action of iodine and yeflow mercuric oxide on anethole (Abstr. 1902 i 452) erystallises from alcohol in feathery aggregates of white opaque needles melting at 134O and is soluble in all the organic solvents. On treating P-p-methoxyphenylpropaldehyde in strongly alkaline alcoholic solution with benzenesulphohydroxamic acid (compare Rimini Abstr.1901 i 450) and afterwards neutralising the cold solution with acetic acid andORGANIC CHEMISTRY. 187 NO treating with copper acetate the compound OMe*C,I14*C,H4<-O>Cu is obtained as a green powder slightly soluble in alcohol. On oxidation with moist silver oxide in presence of sodium hydroxide P-p-methoxyphenylpropaldehyde yields a large proportion of resinous matter and a small quantity of anisic acid whilst p-methoxyhydra- tropaldehyde (Bougault Zoc. cit.) gives an almost quantitative yield of p-methoxyhydratropic acid. When the glycol CH,O,:C,H,*CH(OH)*CHMe*OH obtained by the action of mercuric acetate on isosafrole (Abstr.1903 i 80s) is dehydrated by means of zinc chloride i t yields the aldehyde CH,O,:C,H,*CH,*CH,* CHO which is a pale yellow liquid with a penetrating aromatic odour and boils at 145-150' under 22 mm. pressure. The ozinze C!oH1lO:IN crystallises from aqueous alcohol in faintly yellow prismatic needles melting at 89'. The sernicaybaxone C11H1103N3 crystallises from aqueous alcohol in white lamins melting at 158'. On treatment with benzenesulphohydroxamic acid and subsequent neutralisation with acetic acid it gives on addition of copper acetate (vide supra) the compound CH,02:C,H3*C2H,*C<-O->Cln /NO in the form of a bluish- green powder. When oxidised with silver oxide in presence of sodium hydroxide solution the aldehyde is mainly resinified but yields a small quantity of piperonylic acid ; the isomeric 3 4-methylenedioxyhydra- tropaldehyde (Bougault Abstr.1901 i 721) yields 3 4-methylene- dioxy hydratropic acid. On dehydrating the glycol C,H,(OMe),*C,H,(OH) obtained by the action of mercuric acetate on methyl isoeugenole (Abstr. 1904 i 72) by means of zinc chloride it is converted into the aldehyde C,H,(OMe),*CH,*CH,*CHO which is a pale yellow oily liquid with a faint aromatic odour is soluble in alcohol or ether and boils a t 146-147' under 6 mm. pressure. The semkarbazone CI,H,703N crystallises from alcohol in silky white needles melting at 176-1 77' ; the oxime C H,,O,N crystal- lises from alcohol in radiating lamins melting at 62-5-63' and is soluble in ether C,H3(0Me),* CH,*CH,*C<$?>Cu has been prepared.On oxidation with silver oxide in presence of sodium hydroxide the aldehyde mostly resinifies but gives a small quantity of veratric acid whilst the isomeric aldehyde C,H,(OMe),*CHMe-CHO The copper compound (Bougault Abstr. 1902,"i 452) yrelds-3 4-dimethoxyhydratropic acid. T. H. P. Oxidation of Aromatic Aldoximes with Amy1 Nitrite. GAETANO MINUNXI and KOBERTO CIUSA (Atti R. Accad. Lincei 1905 [v] 14 ii 518-525).-0xidation of benzaldoxime by meam of amyl nitrite in ethereal solution yields (1) azobenzenyl peroxide (benzald- oxime peroxide) CHPh:N*O*O*N :CHPh which was obtained by Beck- mann by oxidising benzaldoxime with potassium ferricyanide (Abstr.,188 ABSTRACTS OF CHEMICAL PAPERS. 1889 980) and melts and decomposes at 96O not at l0S0 as Beck- $?Ph:N maan stated ; (2) dibenzenylazoxime cph>O which has the melting point 102.5-104° and not 108O as stated in the literature; ?Ph:N*Q * (4) a small quantity of a corn- CPh N 00 ' (3) benzildioxime peroxide pound crystallising from alcohol in colourless needles melting at m-Nitrobenzaldoxime on oxidation in ethereal solution with amyl 152-1 53".nitrite yields (1) m-nitrobenxaldoxime peroxide which crystallises from a mixture of chloroform and alcohol in shining plates melting and decomposing at 105' ; (2) di-m-nitrobenzenyl- azoxime which was described by Stieglitz (Abstr. 1890 254) and melts at 168" the melting point 1 3 8 O given by Kriimmel (Abstr. 1895 i E61) being erroneous ; the compound described by Bamberger and Scheutz (Abstr. 1901 i 548) as di-m-nitrobenzenylaxoxime has some other structure.T. H. P. NO,*C6 H4* CH N*O 0.N CH* C,H,*NO Ohlorodinitrobenzophenone and its Conversion into Dinitro- phenylacridine Derivatives. FRITZ ULLMANN and J. BROIDO (Ber. 1906 39 356-370. Compare Ullmann and Ernst this vol. i 205).-2-Cldoro-3 5-dinitrobenzophenone C,?H705N,C1 formed by the action of 2-chloro-3 5-dinitrobenzoyl chloride on benzene in presence af aluminium chloride crystallises from glacial acetic acid in long slightly yellow needles and melts at 149O. On treatment with sodium hydroxide in boiling alcoholic solution it yields the sodium derivative of 3 5-dinitro-2-hydroxybenzophenone which crystallises in orange- yellow needles decomposes at about 318O and has a bitter taste ; the bydroxy-compound C1,H,0,N2 crystallises in small yellow needles melts a t 116" is soluble in benzene ether glacial acetic acid or boiling alcohol and gives a light yellow coloration with concentrated sulphuric acid and an intense yellow with dilute sodium hydroxide. 3 5-Dinitro-2-meth.oxybenxophenone OMe*C6H,(N02),*COPh formed in a poor yield by the action of sodium methoxide on the chloro-corn- pound crystallises in a colourless mass and melts at 8 3 O .The action of anhydrous ammonia on 2-chloro-3 5-dinitrobenzo- phenone in boiling amyl-alcoholic solution leads to the formation of 3 5-dinitro-2-aminobenxophenone NH,*C6H2(N0,),*COPh which crys- tallises in yellowish-brown needles melts at 166O and when treated with sodium nitrite in concentrated sulphuric acid solution at the ordinary temperature and finally at 80-85O yields 2 4-dinitro- Ruorenone CO< I ti This crystallises from boiling glacial acetic acid in stellate aggregates of yellow needles melts at 197" and dissolves readily in benzene or chloroform forming a yellow solution.3 5-Dinitro-2-ethylaminobenzophenone C15H1305N3 formed by the action of ethylamine on 2-chloro-3 5-dinitrobenzophenone in alcoholic solution cry stallises in glistening lemon-yellow leaflets melts at 104O and is readily soluble in benzene chloroform or hot alcohol ether 'GH4ORGANIC CHEbl ISTRY. 189 or glacial acetic acid. When heated with copper powder and nitro- benzene a t ZOO" 2-chloro-3 5dinitrobenzene forms 1 1'-dibenxoyl- 3 3' 5 5'-tetranitrodiphenyZ COPh*C,H,(N02)2*C,H2(N0,)2*COPh which melts at 186".3 5-Dinitro-2-anilinobenzophenone NHPh*C,H,(NO,),*COPh is formed by fusing 2-chloro-3 5-dinitrobenzophenone with aniline and dissolving the product in alcohol ; it crystallises in small,. glisten- ing orange-red needles melts at 206" and on prolonged heating with aniline yields 1 3-dinitro-5-pheizyZcccridine C,H,<~~>C,H,(NO,),. which crystallises in lemon-yellow needles melts a t 240' and dissolves in concentrated sulphuric or hydrochloric acid to form a yellow solu- tion from which the base separates in a yellow flocculent precipitate on dilution. When reduced with stannous chloride and hydrochloric acid it forms 1 3-diacmino-5-phe?zyZacridi?ze which is isolated as the nitrate C19-F15N3,HN03 ; this crystallises from dilute acetic .acid and dissolves in boiling alcohol to form a yellowish-brown solution having a slight green fluorescence The base forms orange-yellow to brown crystals melts a t 159" and dissolves in alcohol forming an orange-yellow solution with slight green fluorescence or in concentrated sulphuric acid forming a yellow solution with brilliant green fluorescence ; the orange solution in concentrated hydrochloric acid becomes red when diluted with water.1 3-Diacetylarnino-5- plmaykacridine cry stallises in yellowish- bro wn needles me1 t s a t 232-2333' and dissolves in concentrated sulphuric acid to form a yellow solution with green fluorescence. 3 5-Dinitro-2-a-nc~ph~lz~lc~mir~obenxo;uhenone COPh-C,H,( N0,),-NH*C,,H7 crystallises from glacial acetic acid in glistening orange-red needles melts a t 190° and when heated with concentrated sulphuric acid at 90-1 00" forms 9 11 -dinitro-?-p?~ei.Z-Z l-iu?~enonap?~thacridine - - C Ph C oH,<~>C6H,(N0,)2 which separates in yellow crystals me1 ts at 3 1 5 O is soluble in hot benzene or chloroform and dissolves in con- centrated sulphuric acid to form an orange-red solution; this on dilution deposits the base as a yellow flocculent precipitate.3 5-Dinitro-2-P-nuphthylaminob~n~o~~eno~~e C,,HI,0,N3 crystallise s in orange-red needles melts at 20S0 and is moderately soluble in chloroform or glacial acetic acid forming yellow solutions. 9 11-Bi- nitro-7-phenyZ- 1 2-phenonaphthacridine C23H1304N3 forms yellow crystals and melts a t 320O. 3 ; 5-Dinitro-2-p-uminoanibinobenxopher~one NH,*C,H,*NH* C,H2( NO,),*COPh formed by the action of an excess of p-phenylenediamine on 2-chloro- 3 5-dinitrobenzophenone crystallises from toluene in glistening reddish-brown needles and melts at 22 lo.1 3-Uinitro-7-amino-5- phenykccridine NH2*C6H,<~~C6H,(N0,) crystallises from aniline in reddish-violet needles and melts above 360". C Ph190 ABSTRACTS OF CHEMICAL PAPERS. 3' 5' 3" 5"-Tetran&tro-l' l"-di~n~oyldienyZ-l 4phylmei€hmine C,H,[N~.C~H2(NO,),*COPh] is formed together with 3 5-dinitro- 2-p-~minoanilinobenzophenone by the interaction of 2-chloro-3 5- dinitrobenzophenone and p-phenylenediamine in molecular propor- tions; it crystallises in glistening scarlet leaflets melts a t 318q and dissolves in concentrated sulphuric acid forming a reddish-brown solution.When heated a t 100' with concentrated sulphuric acid and glacial acetic acid i t forms tetranitrodip~enyl~~~n~~idine 06H2(N02)2<g3cf3H2< N- ph>C6H2(N02)2 which is precipitated from its solution in boiling aniline by alcohol as a brown powder and dissolves sparingly in boiling toluene or glacial acetic acid. 3 5-Dinitro-2-04 ydroxyanilinobenzophenone OH*C,H,*NH*C6H2(N02)2*COPh crysta,llises in glistening yellow leaflets melts a t 233O and dissolves in aqueous sodium hydroxide forming a reddish-brown or in concen- trated sulphuric acid forming a wine-red solution. 1 3-Dinitro-9- hydroxp-5 -phen y lacridine OH C6H,<k->C6H ( N 02)2 forms a reddish-brown powder melts a t 233O is readily soluble in chloroform and dissolves in concentrated sulphuric acid forming a red or in aqueous sodium hydroxide forming a reddish-brown solution.The action of aqueous sodium hydroxide on 3 5-dinitro-2-o-hydroxy- anilinobenzophenone in boiling alcoholic solution leads to the forma- CPh - tion of 3-nitro-5-benxoylphenoxaxine which crystallises from amyl alcohol or toluene in red needles melts at 217" and is readily soluble in boiling benzene or chloroform but onIy sparingly so in boiling alcohol or ether. It dissolves in alcohol containing a few drops of concentrated aqueous sodium hydroxide t o form a blue solution from which it is precipitated unchanged on dilution with water; in concentrated sulphuric acid it dissolves to form a red solution which becomes blue when warmed. 1-Methyl-P-naphthol and its Quinonoid Derivatives.K. FRIES and EDUARD HUBNER (Ber. 1906 39 435-453. Compare Zincke Abstr. 1903 i 756).-Di-P-naphthylmethane is most readily prepared by the condensing action of sodium acetate on an alcoholic solution of /3-naphthol and formaldehyde and is converted by nitrous acid into the diquinonitrole CH2[ C(N02)e$.2i>CH]2 which crystal- lises in pale yellow plates melting- and decomposing at 115'. It dis- solves readily in acetone chloroform or ether sparingly in benzene or alcohol and is insoluble in alkalis. It is decomposed when boiled with a mixture of ether and glacial acetic acid and when reduced with zinc and hydrochloric acid yields dinaphthylmethane. When warmed with an acetic acid solution of hydrogen chloride a t 60° the hydro- carbon yields a brown crystalline compound whichis transformed into di- naphthaxanthen when dissolved in acetone and precipitated with water.Dinaphthylme thane is readily decomposed by sodium hydroxide G. Y.ORGANIC CHEMISTRY. 191 solution and zinc dust yielding P-naphthol and I-methyE-P-?zap~LtiLol CloH6Me-OH ; the amount of the methylnaphthol may be increased by adding formaldehyde and again heating with zinc dust and repeat- ing the operations several times. It may be separated from di- naphthylmethane by means of its solubility in hot water. It crystal- lises in colourless needles melts a t l l O o dissolves readily in most organic solvents and is volatile in steam. It does not couple with clinzoniuru salts and is oxidised by nitric acid to phthalic acid. The met$ derivative C,,H,,O crystallises from light petroleum in long flat prisms melting at 66". The methpl ether crystallises in colourless plates melting a t 39' and the ethyl ether also in plates melting at 50".6-Bromo-l-methyl-/3-naphthol C,,H,MeBr*OH crystallises from benzene in colourless needles melting at 129' and when oxidised yields 4-bromophthalic acid. The ethyl ether C,,H5MeBr*OEt melts at 66' and the acetyl derivative C,oH,MeBr*OAc at 88". 3 6-Dibronzo- l-mtlql-P-naphtlzol CloH,MeBr2-OH forms colourless needles melts a t 180" and dissolves readily in cold ether acetone or chloroform ; it also dissolves in aqueous sodium hydroxide but is precipitated on the addition of much water. When oxidised it yields 4-bromophthalic acid. l-i~eth~l-/3-napht~~Zu~~ne obtained by the action of calcium chloride ammonia on the naphthol a t 270' crystallises from light petroleum in colourless needles melting a t 5 1'.I t dissolves readily in most organic solvents yields a sparingly soluble sulphute and an acetyl derivative C,,H,Me*NHAc melting a t 189'. Nitrous acid converts methyl-&naphthol into 1 %methylnaphtha- quinonitvole C,H,< CMe(Noz)*~o which crystallises from benzene in colourless flat needles melting at 60". When rapidly heated it decomposes a t 140' evolving nitric oxide; it is readily soluble in the ordinary organic solvents and when reduced yields methyl-P-naphthol. When its solution in a mixture of glacial acetic acid and ether is heated at 70" for some time 1 2-nzethylnaphtha-$-quinol The acetyl derivative CloH,MeBr2*OAc melts at 154'.C H G C I I ' CMe(OH)*~O CGH4<CH===C* ' is obtained. It crystallises from water in glistening colourless plates melting at 8 9 O and is readily soluble in most organic solvents. The acetyl derivative melts at 1 30". 1 2-Nap frthanzetl~ylenequinone is obtained when (P-naphthaquinone 1 -methide) C6H4< sodium nitrite is added slowly to a glacial acetic acid solution of methyl- naphthol the mixture kept for eight hours and then ponred into cold water. It crystallises from light petroleum in compact yellow needles melts at 132") and is insoluble in alkalis. When boiled for some time with alcohol water or acetone it is converted into products which dissolve in alkalis. C(CH,) 70 CH-CH' CMe( NO,)*C;O CH' 6 - Bromo - 1 2 - methylnaphthapinonitrole C,H,BI-<~~ - crystallises in flat compact needles melts and decomposes a t 99" and when reduced yields bromomethylnaphthol.6-Bromo- 1 2-methyl-192 ABSTRACTS OF CHEMICAL PAPERS. naphtha-+-quinol C ,H,O,Br crystallises in yellow plates melts at 84O and is readily soluble in most organic solvents but dissolves only slowly in- alkalis. The ncetyl derivative C1,Hl,O,Br melts at 101'. 6 -Brorno-3-nitro- 1 ; 2-methylnaphtha- $-quinol CMe(OH)*FO C6H3Br<CH-C. NO 3 obtained by the action of nitric acid on the bromoquinonitrole or on bromomethglnaphthol crystallises in golden-yellow plates melts a t 155O and is only moderately soluble in ether alcohol benzene or acetic acid. It dissolves in alkali hydroxides a t the ordinary temperature. When reduced with sulphurous acid in acetic acid solution it yields 6-bromo- 3-nit~~o-l-met?~y~-~-nap?~t~ol C6H3Br<CH UMe:F*oH CNO which crystallises in orange-red needles melting at 1633.This dissolves in hot sodium carbonate solution yielding a violet-black coloured liquid from which the unaltered naphthol crystallises on cooling. The sodium salt forms long blackish-violet needles but is hydrolysed by water. The alkali saltslof methylnaphthol and of its bromo-derivative and also the alkali salts of bromoaminomethylnaphthol are not hydrolysed in the same manner and it is suggested that the nitro-compound may have the ketonic constitution C,H,Br< CHMe* yo 6-Bromo-3-amino-l-meth~l- P-nuphthol obtained by reducing the nitrobromoquinonitrole with zinc and hydrochloric acid cryst,allises from benzene in slender colourless needles melting at 163".It dissolves readily in ether acetone or alkali hydroxides. The rnonoacet3Z derivative C,3H!202NBr crgstal- lises in colourless needles melting at 183" and the dzacetyl derivative in needles melting a t 240". With nitrous acid the aminophenol yields a yellow diazophenol anhvdride. CH = C-NO,' '6-Bron10- 1 ~2-naphtha&ethylenequinone (6- bromo-~-nap?~t?~aquinone- crystallises from light petroleum in C(CH2) 70 CH==CH' 1 -methide) UGH,&< yellow plates melting at 144". It forms an udditive compound with acetyl chloride C,3H,,0,C1Br which forms compact needles melting at 158". 3 6-Bibronao- 1 2-~et/~ylnaphthaqzlinonilrole crystallises in colourless flat needles melting at 130" and is the most stable of the o-q uinonitroles. With acetic acid.it is slowlv transformed 6Me(OH) S O CH- CBr' into 3 6-dibromo-I 2met?~yZnaphtl~u-~-quiiiol C6H3Br< which crys t allises in colourless needles me1 ting at 10 1". The cccetyl derivative melts a t 152O. J. J. S. Constitution of Alizarin Monomethyl Ethers. HERMAN DECKER and ED. LAUBE (Ber. 1906 39 112-1 16 526).-1-ChZoro-2- hydroxyunthraquinone C6H,<CO>C6H2C1*OH co is formed by boiling 2-hydroxyanthraquinone which melts at 306' (cow.) with sodium hypochlorite in aqueous sodium hydroxide solution (Wedekind D.R.-P.ORGANIC CHEMISTRY. 193 152172) ; it crystallises in small yellow needles or on slow evapora- tion of its solutions in rosettes of needles melts at 226" (corr.) and dissolves in aqueous alkali hydroxides or carbonates to form red solutions; the potussium derivative is insoluble in cold water but dissolves in alcohol forming a violet solution.When fused with sodium ethoxide i t forms alizarin and when heated with ammonia under pressure yields an amino-compound melting a t 240-245' (corr.). 1 -ChZoro-2-acetoxyanthmpuinone C,,H,03ClAc formed by boiling the hydroxy-compound with acetic anhydride containing one to two drops of concentrated sulphuric acid crystallises from alcohol in yellow flocculent aggregates melts a t 163*5O is hydrolysed only slowly by boiling aqueous alkali hydroxides and dissolves in con- centrated sulphuric acid forming a red solution. pared by heating the sodium derivative of 1 -chloro-2-hydroxyanthra- quinone with methyl sulphate a t 140O ; after recrystallisation from alcohol or benzene it melts a t 223-221O (corr.).It is easily soluble in hot amyl alcohol or in concentrated sulphuric acid forming an orange-red solution and when heated with aqueous sodium hydroxide under pressure yields chiefly alizarin. When heated with sodium methoxide in methyl-alcoholic solution in a sealed tube a t 100' for twelve hours it yields alizarin monomethyl ether [ l-hydroxy-2- methoxyanthraquinone] melting at 232-233O (Schunck and March- lewski Trans. 1894 65 185). When heated with sodium ethoxide and ethyl alcohol l-chloro-2- methoxyanthraquinone yields a mixture of 1 -hydroxy-2-methoxy- and 1 -ethoxy-2-methoxy-an thraquinono ; these are separated by treatment with benzene and aqueous sodium hydroxide.The monomethyl ether melting a t 232-233" is obtained on acidification of the alkaline solution whilst 1-ethoxy-2-methoxyanthraquinone crystallises from the benzene solution and melts at 169-170O. G. Y. Reduction Products of Hydroxyanthraquinones. MAURICE PRUD'HOMME (Bull. Xoc. chim. 1906 [ iii] 35 71-76).-When freshly precipitated alizarin anthrapurpurin 01- flavopurpurin is suspended in dilute acid and zinc dust is added a brown or olive-green reduction product is formed depending on the conditions of the experiment. Each of these reduction products is convertible into the same yellow substance by the action of acids All three substances dissolve in alkalis to form solutions which are redder but less intense than that given by alizuin; they dye with the usual mordants in neutral solution giving tints similar t o those produced by alizarin but in presence of acetic acid owing apparently to the reduction of the mordant by the dyes they give feeble tints or none at all with chromium and iron mordants.or C( NH) # C(0H) 7 0 H CO-C*CHICH C6H4<C(NH)*C*CH -CH ' Alixarinimide C,H,< CO--E*C(OH):Y*OH VOL. xc. i. P194 ABSTRACTS OF CHEMICAL PAPERS is prepared by heating alizarin with ammonia solution under pressure (Farbenfabriken vorm. Fr. Bayer & Co.). It crystallises from pyridine and when warmed with alkalis or acids is resolved into its generators. With aniline or phenylhydrazine the imino-group is replaced by :NPh or :N*NHPh. Alizarinimide is also produced when the precipitate obtained by acidifying the brown solution produced by the reduction of alizarin with hot ammonia solution and zinc dust is washed redissolved in ammonia and oxidised by exposure to air.If however the brown solution itself is exposed to air it also re-oxidises forming the isomeride of alixarinimide represented by the alternative formula. It js con- sidered therefore that the brown solution contains one form of the anthranol corresponding with alizarin and the precipitate obtained by acidifying the brown solution consists of the other form the possible formulie being C6H4<& C W ) >C,H2(OH) and The isomeride of alizarinirnide’ is also formed when the brown olive- green or yellow reduction-products of alizarin referred to in the first paragraph are dissolved in ammonia solution and exposed to air.Two anthrapurpurinimides were obtained from anthrapurpurin these resembled the alizarinimides. Flavopurpurin also yields a similar substance when its corresponding anthranol is treated with ammonia solution. T. A. H. Preparation of Camphor from Borneo1 orisoBorneo1. CHEMISCHE FABRIK AUF AKTIEN VORM. E. SCHERING (D.R.-P. 161306. Compare Abstr. 1905 i 709 ; this vol. i 28).-When borneol or isoborneol is dissolved in 95 per cent acetic acid or light petroleum water added and a current of ozone passed through the solution at the ordinary temperature camphor is formed readily. Camphene under similar conditions yields only camphenilone and formaldehyde. C. H. D. Terpenes and Ethereal Oills. LXXIII. OTTO WALLACH (Alnnden 1905,343 28-40. Compare Abstr.1903 i 103,105,567 ; 1904 i 74 104 424 752 753 754,987,1035 ; 1905 i 147,450 709).-A special name is suggested for the methylene group CH which is found in semicyclic linking in many hydroaromatic and analogous compounds and in the methylenequinone and other substances studied by Auwers and Zincke. Such a methylene group has charbcteristic reactions which distinguish it from the same group in cyclic or acyclic molecules. Semmler has suggested the name +terpenes ’’ for terpenes possessing this semicyclic methylene group. But such hydrocarbons do not bear to the terpenes the relation which $-compounds in general bear to their isomerides. It is consequently suggested that the acyclic methylene group found in limonene carvone citronellal and isopulegone should be called L L methene.” Thus for example the expressionORGANIC CIIEMISTRP.195 represents methenecyclopentane (methenecyclopentamethylene) the expression 2>CI:CH2 methenecycloheptane ; P-phel- yH,*CH,*CH CH;CH,*CH ' C H - C H landrene CHPr~<CII&C~>C:CH2 is called A2-1 -methene-4-iso- propylcyclohexene or I-methene-4-isopropyltetrahydrobenzene. Experiments have been made in order to determine whether the tetrahydrocuminaldehyde obtained by oxidat ion by /3-phellandrene (Abstr. 1905 i 709) is present in the source of the phellandrene (oil of Phellandriunt apuuticum) or whether it is formed in the oxidation of the phellandrene in the process of preparation. Phellandrene was shaken with an equal quantity of water in a large flask with oxygen at the ordinary temperature and exposed to sunlight.Oxygen is rapidly absorbed ; when the absorption has ceased after three days a heavy viscous oil remains which is distilled in steam; at first unchanged phellandrene distils over mixed with a small amount of a substance which yields a semicarbazone. The non-volatile product does not contain a glycol. The semicarbuxone C,H,,:N*NH*CO*NH melts at 183-184' and is converted by oxalic or suIphuric acid into an unsaturated kefone C,H,,O which boils at 103-106' under 15 mm or a t 220-224' under the ordinary pressure; it has a sp. gr. 0.9387 and rzD 1.4788 a t 26a. The ketone combines easily with sodium hydrogen sulphite but is unchanged when treated with sodium hypobromite and yields with hydrogen sulphide in amnioniacal solu- tion a sulphur compound which melts at 121-122'.When reduced with sodium in moist ether an alcohol is formed in small quantity with an odour resembling that of terpineol ; it is oxidised in acetic acid solu- tion to a saturated ketone C,H,,O the semicarhone of which meltsat 188'. The ketone is oxidised by chromic acid in sulphuric acid solution to P-isopropyladipic acid. Hence it follows that the product of oxids- tion of P-phellandrene with free oxygen has the constitution and is therefore 1 -isopropyl-A2-cyczohexene-4-one. Further the tetra- hydrocuminaldehyde is an original constituent of the ethereal oils in which i t is found and not formed from the phellandrene. The conclusion may also be drawn from the experiments that the oxidation of a n un- saturated compound by permangannte follows a different course from the oxidation of that compound by oxygen in the presence of water.The oxidation of the ethylene linking by oxygen is brought about by the addition of oxygen and the conversion of the double into the single linking whilst the oxidation by permanganate brings about the addition of two hydroxyl groups at the ethylene linking. The reaction with oxygen is identical with that with ozone. Attention is called to the fact that the odour of cyclic ketones depends on the relative positions of the carbonyl and the isopropyl group; thus when they occupy o-positions relative to one another the ketone has the odour of menthone in the m-position relative t o one another the odour of carvone and in the v-position a cumin-like odour.196 ABSTRACTS OF CHEMICAL PAPERS. oxidised by chromic acid in sulphuric acid solution 148opropyI hexene-4- one is formed.The glycol is converted into dihydrocuminalcohol C H P r ~ < ~ ~ & ~ ~ > C * C H * O H together with tetrahydrocuminaldehyde on boiling with dilute sulphuric acid When the aldoxime (m. p. 8'7") of the tetrahydrocuminaldehyde just mentioned is reduced in alcoholic solution with sodium a base is obtained the carbamide of which melts at 160--161" and is identical with the base formed together with the carbamide of cuminylamine from nitro-P-phellandrene ; the base therefore is probably a derivative of tetrahvdrocuminvlamine. These facts are in favoiir of the constitu- tion of dnitro-P-ph*ellandrene previously suggested (Ahstr.1905 i 709). By the reactions above described the question as to the occurrence of P-phellandrene together with the a-isomeride in the ethereal oil from Eucalyptus amygdalina has been decided ; but a very small quantity of P-phellandrene is present ALBERT VERLEY (D.R.-P. 160834. Compare Abstr. 1904 i 880).-Certain cyclic citral derivatives combine with magnesium alkyl iodides and the resulting compounds are decomposed by water to form tertiary alcohols. Thus methyl cyclocitrylideneacetate combines with magnesium methyl iodide in ethereal solution to form the compound yH,*CMe2*g*CH :CH*CMe,*O*MgI CH,-CH,-CMe which is converted by water into cyclocitrylidene-tert.-butyl alcohol C,,H,,O which boils at 131" under 16 mm. pressure has a sp. gr. 0.9003 at 15O and has a fresh odour of violets.The same alcohol is obtained from ionone and magnesium methyl iodide. The corresponding alcohol C,,H2,0 from ethyl cyclocitrylideneacetate and magnesium ethyl iodide boils a t 162" under 16 mm. pressure and has a sp. gr. 0.94229 at 15'. The alcohol C,,H,,O from ionone and magnesium ethyl iodide boils at 153' under 15 mm. pressure. The same series of tertiary alcohols may be obtained by combining the open chain esters of citrylideneacetic acid with magnesium alkyl iodides and converting the products into their cyclic isomerides by means of dilute acids. Thus methyl citrylideneacetate and magnesium methyl iodide yield the alcohol CMe2:CH*CH2*CH,*CMe:CH*CH:CH*CXe2*OH which boils at 154" under 18 mm. pressure and has a sp. gr. 0.890 at 154 C.H. D. K. J. P. 0. Tertiary Alcohols of the cycloCitrylidene Series. 9 Action of Atmospheric Oxygen on Para Caoutchouc. EDGAR HERBST (Ber. 1906 39 523-525).-When a current of purified air is passed for 140 hours through a hot solution of Para caoutchouc in benzene two substances are obtained a transparent reddish- brown syrup soluble in light petroleum having the composition C,,H,,O and an amorphous friable yellow solid of the composition C,,H,,O insoluble in light petroleum. The latter is sparingly soluble in a mixture of benzene and light petroleum; from thisORGANIC CHEMISTRY. 197 solvent a modification separates as a hard glassy mass with sub- stantially different physical properties. c. s. Occurrence of P-Amyrin Acetate in some Varieties of Gutta- percha.PIETER VAN ROMBURGH and N. H. COHEN (Proc. K. Akad. TVetensch. Awasterdanz 1905 8 544-546. Compare Romburgh Abstr. 1904 i 905; this vol. i 20).-The acetic ester obtained from the gutta-percha of Puyena Leerii and from djelutung is identical with P-amyrin acetate (Vesterberg Abstr. 1891 165); it melts a t 240-241' (corr.) and has [a] + S1.l0 in chloroform solution. The P-amyrin obtained on hydrolysis of the acetate crystallises in long thin needles melts at 197-191*5° (corr.) and has [ a ] +SS0 in chloroform or + 98' in benzene solution; when treated with benzoic chloride in pyridine solution it forms the benzoate which crystallises in small rectangular plates and melts at 234-235' (corr.). The substance melting a t 239-240' obtained by Marek from the milky juice of Asclepiccs syriaca (Abstr.1904 ii 141) and a-balalban obtained from balata by Tschirch and Schereschewski (Abstr. 1905 i 713) also are identical with P-amyrin acetate G. Y. Heerabol Myrrh. ALEXANDER TSCHIRCH and W. BERGMANN (Arch. Pharrn. 1906 243 641-654).-The material examined was a corn- mercial sample of Myrrha electa ; it consisted of reddish-brown pieces with a waxy fracture and the following solvents dissolved the percentages of it indicated alcohol 36 ; ether 29; chloroform 31; light petroleum 9 ; methyl alcohol 38 ; water 60 ; ethyl and methyl alcohols 36; toluene 30. From an ethereal extract of the drug ammonium carbonate and sodium carbonate alike dissolved nothing. One per cent. aqueous potassium hydroxide however dissolved the following two amorphous grey ifh-yellow neutral substances which were separated in alcoholic solution by means of lead acetate with which the first of them forms an insoluble precipitate but not the second a-hee~abo-rnyrrl~oZ C17H2,05 melting at 158-165' and P-heerabo-rnyrrhol C1,H,,O melting at 116-124'.From the residue insoluble in ether alcohol extracted two brown amorphous substances soluble in dilute aqueous potassium hydroxide a-~~eerabo-myrr~olol C,,H,,O7 or C,,H,,O, melting a t 207-220° and P-lLeerabo-myrrhoZoZ C,,H,,O, melting at 205 -213' ; of these the first is precipitated from the solution by lead acetate the second is not. From the ethereal solution after the extraction with alkali the ether was driven off and the residue distilled with steam; an essential oil passed over. More of this oil was obtained by repeated distillation of the residue with very dilute aqueous potassium hydroxide; at the same time a substance dissolved gradually in the alkali which melted at l8S-19'i0 and had the composition and reactions of a-heerabo- myrrhol.The heeruboresen finally remaining C29H4004 melted at 98-104'. The essential oiE mas yellow rather syrupy and had the sp. gr. 1,046 ; it resinified readily.198 ABSTRACTS OF CHEMICAL PAPERS. The unusually high percentage of oxygen in these substances is noteworthy . From the residue remaining after extraction with ether and alcohol water extracted a mixture of a gum with an enzyme having the character of an oxydase. This mixture could not be separated into its constituents; it yielded 5.15 per cent of ash containing calcium and magnesium and gave pyrrole when heated with dry potassium hydroxide furfuraldehyde when distilled with 12 per cent.hydrochloric acid mucic acid when treated with nitric acid and arabinose when hydrolysed with 5 per cent. sulphuric acid. The bitter principle was not isolated in a state of purity. The sample contained in 100 parts approximately heerabo- myrrhol a 4 (and secondary 2) P 2 ; heerabo-myrrholol a 3 P 2 ; heeraboresen 6 ; essential oil 6-7 (and secondary 1.5) ; gum and enzyme 61 ; impurities 3-4; water 5. Two small specimens collected from unknown species of Commiphora in German East Africa were also examined cursorily. d-Glucosephloroglucinol and P-Glucosan. EDUARD VONGERICH- TEN and FR. M~TLLER (Ber. 1906 39 241-245).-When d-glucose- apigenin is boiled for five hours with a 25 per cent.solution of sodium hydroxide it yields d-glucosephloroglucinol which is in its turn partially converted into phloroglucinol and P-glucosan. From an aqueous solution containing d-glucosephloroglucinol and P-glucosan the former is precipitated by the addition of lead acetate. d-Glucosephloyo- glucinol is a white amorphous hygroscopic powder dissolving readily in alcohol. h aqueous solution it has [ a] - 24*20° a t Z O O in alcoholic solution [a] -24.95O at 20'. It is unaffected by yeast or emulsin and reduces Fehling's solution only after having been boiled with mineral acids. It reacts with diazonium salts t o form disazo-corn- pounds d-glucosephloroglucinoldisc~xocT~~orobenx~ne C2,H2,O8N,Cl2 is a reddish-brown flocculent precipitate obtained from p-chlorophenyl- diazonium chloride ; d-glucosephloroglucinold~saxobenxene C24H,,0,y4 obtained from diazobenzene chloride forms a reddish-brown crystalline mass soluble in alkalis.P-Glucosan obtained as described above forms large rhombic plates melting at 177-178O and is identical with Tanret's lsevoglucosan (Abstr. 1894 i 564). The tribenzoyl derivative in contradistinction to the triacetyl com- pound is scarcely hydrolysed by hydrochloric acid. A boiling solution of baryta-water changes P-glucosan into a hydrate which melts at 108' and in a vacuum loses water re-forming P-glucosan. /I-Glucosan is almost unaffected by bromine or potassium permanganate in neutral solution but is converted into dextrose by hydrochloric acid.Brazilin and Hamatoxylin. JOSEF HERZTG and JACQUES POLLAK (Ber. 1906 39 265-267. Compare Abstr. 1003 i 270 713; 1904 i 81; 1905 i 605).-On warming on the water-bath ft solution of tetramethylhaematoxylone in glacial acetic acid with phenylhydrazine a compound C,,H,,ON,(Oh~e) is obtained analogous with the sub- stance prepared in a similar manner from trimethylbrdzilone ; it crystallises from ethyl acetate in yellow needles melts at 234-237O C. F. B. C. S.ORGANIC CHEMISTRY. 199 and is not affected by acetic anhydride or an excess of phenyl- h ydrazine. The phenylhydrazine derivative of trimethylbrazilone (Loc. cit.) cannot be directly acetylated but when heated with acetic anhydride sodium acetate and zinc dust a reduced nzonocccetyl derivative is obtained; this crystallises from alcohol melts at 214-2117' and when hydrolysed gives a product which is oxidised by ferric chloride to the original phenylhydrazine derivative melting at 240-243'.The bearhg of these facts on the structure of brazilin is discussed. W. A. D. C,2H1,ON,(OMe),*OAc Grignard Syntheses in the Furan Group. WILLIA&f J. HALE IV. D. MONALLY and C. J. PATER (Amer Chern- J. 1906,235 68-78). -DiphenyZ-2-ficryZcarbinoZ I I >CPh,*OH obtained by treating e thy1 pyromucate with magnesium phenyl bromide and decomposing the product with water crystallises in colourless rhombic prisms melts a t 92.4" (corr.) is soluble in ether alcohol chloroform benzene ethyl acetate or warm light petroleum and gradually changes into a dark red gummy mass; its methyl ether is a colourless oil which boils a t 206-207" under 26 mm.pressure and has a sp. gr. 1.1195 at 20'. CH*CH CH-0 - - 2-FuryldietJ~ylcarbinol ~H'cH>CEt*OH was obtained as a pale CH-0 yellow liquid which had a pleasant ethereal odour and gradually changed into a dark brown crystalline mass; it could not be purified bv distillation as it readily suffers decomvosition with formation of which crystallises in coloudesi needles or prisms melts at 249' (corr,) is soluble in chloroform benzene carbon disulphide ether or light petroleum is insoluble in water and decolorises a solution of bromine in carbon disulphide. By the action of magnesium methyl iodide on ethyl pyromucate an unstable red liquid is produced. DibenxyZ-2-firyZcarbinoZ C,OH,*C( C,H,),*OH crystallises in silky needles melts at 82.7" (corr.) is soluble in the usual organic solvents and insoluble in water and is much more stable than the corresponding diphenyl derivative ; its methyl et7~er crystallises in long colourless needles and melts at 61-21' (corr.).Eicrylene-2 5-6isdiphenylcarbinoZ C,OH,(CPh,*OH) obtained by the action of magnesium phenyl bromide on ethyl dehydromucate forms small colourless rhombic crystals melts at 165.5" (corr.) is soluble in alcohol ether acetone benzene or chloroform and is more stable than diphenyl-2-furylcarbinol ; its methyl etJLer crystallises in groups of white needles and melts a t 88-2' (corr.); the ethyl ether forms rhombic prisms and melts a t 171" (con-.). J?uwJene-2 ~-bisdibe,zc!/Zcc~rbilzol C,0H,[C(C,H7)2.0H] is a fairly stable substance of a light straw colour; it boils and partially decom- poses at 193-195' under 30 mm.pressure has an agreeable odour a200 ABSTRACTS OF CHEMICAL PAPERS. sp. gr. 1.126 at 27' and is soluble in all the usual solvents except light petroleum and water. E. G. 1- and 2-Aminocoumaran (Coumaranamine). RICHARD STOERMER and W. KONIG (Ber. 1906 39 492-499. Compare Stoermer and Calov Abstr. 1901 i 336).-Hydrocoumarilic acid (coumaranilic acid) prepared by the reduction of coumarilic acid in alkaline solution by sodium amalgam melts a t 116.5" ; its ethyl ester boils at 273' and melts at 23'. Couinaranilic hydraxide prepared from ethyl coumaranilate and hydrazine hydrate separates from alcohol in snow-white needles and melts a t 148'.Dicoumaranilic hgdraxide C,H70.CO*NH*NH*CO*C,H70 crystallises in needles. Cournaranilic cczoinzide N,*CO*C,H,O prepared by dissolving coumar - anilic hydrazide in water and gradually adding sodium nitrite (2 mols.) and dilute acetic acid is a snow-white solid and melts at 32'. It is probably formed as an intermediate product in the preparation of dicoumaranilic hydrazide from coumaranilic hydrazide ; thus G,H70*CO*NH*NH + N,*CO*C,H70 = N2H,(C0.C,H70) + HN represents the formation of dicoumaranilic hydrazide. When coumaranilic azoimide is heated with absolute alcohol 1 -carboxyethyl- aminocoumaran (1-urethylcoumaran) C,H70*NH*C!0,Et melting at 105' is formed. PiLenyZztrethylcoumaran prepared from coumaranilic azoimide and phenol forms glistening leaflets and melts a t 151'.Bicournaranyl caybarnide CO(NH*C,H~O) prepared by boiling the azoimide with water separates from dilute alcohol as a crystalline powder and melts a t 205'. CournaraniZic anilide prepared by the action of aniline on the azoimide separates from dilute alcohol in glistening scales and melts at 104'. Coumarone was formed as one of the products of the action of cold concentrated hydrochloric acid on coumaranylurethane. Coumaranone was prepared by the dehydration of phenoxyacetic acid with phosphoric oxide (compare Stoermer and Bartsch Abstr. 1901 i 94). Its oxime when reduced by sodium amalgam and glacial acetic acid yielded 2-aminocoumaran as a yellow oil which boils at 122' &der 18 mm. pressure. It has the sp. gr. 1.1303 at 17" and n 1.5645 at 19".Its hydrochloride melts and decomposes at 226'; its plati&hZoride decomposes at 220'; its clztrichloride melts and decomposes a t 161'. 2-Carboxyethyla~ninocouma~un (2 -uret?iyZcoumuran) C,H& H(N:.=CHz * prepared from 2-aminocoumaran and ethyl chlorocarbonate separates from dilute alcohol in needles and melts at 101.5'. Cournaranylphenylcarbarnide C H 4 < G o G > C H 2 prepared from 2-aminocoumaran and phenylcarbimide separates from dilute alcohol in needles and melts a t 2 0 4 O . Coilmarone and ammonium chloride are formed when %amino- coumaran hydrochloride is heated.ORGANIC CHEMISTRY. 201 2-Coumaranol nitrite CcH,<CHroqN:.G>CH2 prepared from 2-aminocoumarone hydrochloride and potassium nitrite separates from dilute alcohol in glistening leaflets and melts at 65'.When heated i t decomposes into coumarone and nitrous acid. A. McK. 7-Hydroxy-2-o-n~p-trimethoxyphenyl-4-methylene-l 4-benzo- pyran and its Derivatives. CARL BULOW and CARL SCHNID (Ber. 1906 39 214-225. Compare Abstr. 1901 i 400 559; 1904 i 362 ; 1905 i 15O).-The copper derivative of 2 3 4-tri- rnethoxybenzoylacetone (Blumberg and Kostanecki Abstr. 1903 i 644) separates from dilute alcohol in clusters of needles and melts at 150-152'. Resorcinol condenses with 2 3 4-trimethoxybenzoylacetone in the presence of dry hydrogen chloride t o form 7-hydrox~-~-o-rn-p-tr~nze~~~- ox~l-'henyl-4-metiLytene- 1 4- benxopyran hydrochloride Ho* c6H,<c( CH,). CH J O(HCI)-fl* C,H,(OMe) which is obtained in clusters of dark yellow needles soluble in water or alcohol.A concentrated aqueous solution is orange-yellow in colour turning red on dilution owing to hydrolytic dissociation. The sutphate forms tufts of silky needles which melt at 203' to a steel- blue liquid. The picrate C25H21012N3 forms minute yellow needles which darken at looo become black a t ZOO' and melt and decompose at 212'. The free base obtained from an aqueous solution of the hydrochloride by adding a slight excess of ammonium hydroxide and then neutralising with acetic acid separates in light red microcrystal- line flocks sinters at 95' becomes dark and molts at 105-110'. The acetyt derivative C,,H2,,0 melts at 245-247'. By reduction with zinc dust and acetic acid i n the presence of acetic anhydride the base yields a dihydro-derivative C,,H,,O which forms a greenish-yellow amorphous powder and melts a t 230-235'.By brominating the hydrochloride in acetic acid a dibromo-derivative is obtained the hydrob~omide of which C,,H,,O,Br,,HBr forms red prismatic crystals which blacken on heating bnt do not melt below 270'. The base C,,EI,,O,Br forms small greenish-brown needles which melt and decompose at 215'. Bromination of the hydrochloride in the presence of anhydrous sodium acetate leads to the formation of a tetrabyorno-derivative C19H1805Br4 which crystallises in dark red prisms and does not melt below 300'. 7-Lly~~~ox~-2-a-m-p-triiiydroxy~he1~ y 2-4-meth ylene- 1 4-6enxopyran hydro- chloride C,6H1,0,,HCl is obtained by heating the corresponding tri- methoxy-compound a t 150-180' with hydrochloric acid.It crystal- Iises in small red leaflets with blue reflex and in solution is more stable than the hydrochloride of the trimet.hy1 ether. The base c,,H,,O crystallises in minute brown needles which partially decom- pose on exposure t o air. Concentrated sulphuric acid dissolves it form- Synthesis of 6 2' 4'-Trihydroxyflavonol. E. BONJFAZI STANISLAUS VON KOSTANECKI and JOSEF TAMBOR (Ber. 1906 39 86-9 1).-2 4-Dimethoxybenzaldehyde and quinacetophenone mono- ing an orange-red non-fluorescent solution. c. s.202 ABSTRACTS OF CHEMICAL PAPERS. methyl ether (Abstr. 1904 i 440) condense in warm alcoholic sodium hydroxide solution forming 2'-hydroxy-5' 2 4-trimathoxychaZkone OH* C,H,( OMe) *CO*CH:CH* C,H,(OMe) which crystallises in slender orange needles melts a t 11S0 and gives a red coloration with concen- trated sulphuric acid.When heated with acetic anhydride and sodium acetate it yields 2'-acetoxy-5' 2 4-ti*imethoxychaZkone C,,W80,(OMe)3*OAc which crystallises in yellow needles and melts at 87" and 6 2' 4'-trinaethoxz/Ruvanone V ' 0-CH*C,H,(OMe) OMe C6H3<C0. b ~ 9 which is formed also by boiling 2'-hydioxy-5' 2 4-trimethoxychalkone with alcoholic hydrochloric acid in a reflux apparatus. It crystallises i n yellow prisms melts a t 160° and gives a red coloration with con- centrated sulphuric acid. The isonitroso-derivative formed by the action of amyl nitrite and hydrochloric acid on the pre- ceding compound in alcoholic solution crystallises in small yellow needles melts and decomposes a t 173-175' dissolves in aqueous sodium hydroxide to form a yellow solution and dyes with cobalt mordants orange uranium cadmium and lead mordants yellow and copper mordants brown.0-C*C H (OMe) 6 2' 4'-Trimethoxy~uvonol OMe*C,H,<CO,JCI.o& 9 pre- pared by boiling the isonitroso-compound with sulphuric acid in glacial acetic acid solution crystallises in yellow spears melts at 193c when warmed with dilute sodium hydroxide forms a sparingly solublo yellow sodium derivative dyes with alumina mordants a light yellow and dissolves in concentrated sulphuric acid to form a greenish- yellow solution which becomes almost colourless and shows a green fluorescence. The acetyl derivative crystallises from dilute alcohol in prismatic needles and melts at 162'.formed 0-8' C,*,(OH) 2 CO* C*OH 6 2' 4'-Frihydroxy$avonol OH*C,H,< by boiling the trimethoxy-compound with concentrated hydriodic acid crystallises in light yellow needles containing H,O which is lost a t 130° melts a t 285O and dissolves in dilute sodium hydroxide to form a greenish-yellow sollition with strong green fluorescence in concen- trated sulphuric acid to form a yellow solution with slight green fluorescence. It dyes fibres mordanted with alumina yellow with iron salts olive-brown to almost black. When boiled with acetic anhydride and sodium acetate it forms the tetra-acetyl derivative C,,H,O,(OAc) which crystallises from dilute alcohol in white needles an& melts a t 163'. G. Y. Dyeing Properties of 7 2' 4'-Trihydroxyflavonol. STANISLAUS VON KOSTANECKI VICTOR LAMPE and S.TRIULZI (Bey. 1906 39 9 2-9 6).-2'-EI$roxy-4' 2 4-trimethoxycha Zko ze OH* C,H,( OMe) *CO*CH C'H*C,H,( OMe) is obtained in the form of its yellow sodium derivative by the con-ORGANIC CHEMISTRY. 203 densation of 2 4-dimethoxybenzaldeliyde with resacetophenone mono- methyl ether (pzonol) in hot alcoholic sodium hydroxide solution ; when liberated by means of hydrochloric acid and recrystallised from alcohol the chalkone forms yellow needles melts at 1 5 7 O and gives a red coloration with concentrated sulphuric acid. 2’-Acetoxy-4’ 2 4-tri- metlioxychalkone C,,H,O,( OAle),*OAc crystallises from dilute alcohol in yellow nodular aggregates and melts at 110-1 12’. When boiled with alcoholic hydrochloric acid in a rcflux apparatus for twenty-four hours the chalkone is partially converted into 7 2’ Q’-trimethox~- o - ~ H ~ ~ H ( o M ~ ) Jzavanone OMe*C,H,< which is extracted from CO*CH the mixture by much boiling wker ; it crystallises from dilute alcohol in whita needles melts at 139O and dissolves in alcoholic sodium hydroxide to a yellow,in concentrated sulphuric acid to a red solution.The isonit~oso-derivative OMe*C,H,<CO,C:N.OH 0- FH*C,H,( OMe) forms small yellow crystals melts and decomposes at 1 7 2 O dissolves in dilute sodium hydroxide to form a yellow solution and dyes with cobalt mordants yellow. O-~*C,H,(OMe) CO*C*OH 7 2’ 4‘-Trimethoxyjavonol 0Me.C H < crys- tallises from alcohol in yellow spears melts a t 2054 and dyes with aluminium mordants a light yellow ; when warmed with aqueous sodium hydroxide it forms a sparingly soluble yellow sodium derivative and dissolves in concentrated sulphuric acid to form a yellow solution with an intense bluish-green fluorescence.crystallises from dilute alcohol in short prisms and melts at 189-191’. 7 2’ 4’-Trihydrox~uvonol (resomorin) formed by boiling 7 2‘ 4’-trimethoxyflavonol with concentrated hydriodic acid separates from dilute alcohol as a gelatinous mass ; its behaviour towards metallic mordants is the same as that of 6 2’ 4’-trihydroxyflavonol (see pre- ceding abstract) and of morin. The character of the last-named sub- stance as a dye must depend therefore on the presence of the group -CO*C(OH)- and not on the presence of a hydroxyl in the peri- position to the carbonyl group.When boiled with acetic anhydride and sodium acetate resomorin forms the tetra-acetyl derivative The ucstyl derivative C,,H,,O,(OMe),*OAc OAc* w%<CO. O - p 6 3 0 A c ) 2 c. OAc which crystallises in rosettes of small stout needles and melts at 129-130°. G. Y Cotarnine Ferrichloride. ARNOLD VOSWINKEL (D.R.-P. 161400). -On mixing solutions of ferric chloride and cotarnine hydrochloride in absolute alcohol cotarnine ferrichloride C,,H,,O3N,HFeC1 is precipi- tated in orange leaflets slowly agglomerating t o form ruby-red crystals. The same compound is obtained on heating anhydrous ferric chloride with cotarnine hydroshloride in a vacuum. The salt dissolves in water or dilute alcohol and is decomposed on boiling. It finds therapeutic application as a styptic.C. H. D.204 ABSTRACTS OF CHEMICAL PAPERS. Transformation of a-Methylmorphimethine into the P-Gorn- pound by Heat. Grystallographic Behaviour of the Two Isomerides. ROBERT PSCHORR HEINRICH ROTH and F. TANNHAUSER (Ber. 1906 39 19-26).-Whan a-methylmarphimethine is heated in a vacuum it changes to a violet liquid which then assumes a clear yellow colour ; if the temperature is then suddenly raised a yellow oil distils at 220 -240' under 12 mm. pressure consisting of the P-isomeride pre- viously prepared by the action of alcoholic potash (Knorr and Smiles Abstr. 1908 i 817); its identity mas confirmed by preparing the benzoate and the methiodide. a-Methylmorphimethine separates from dilute alcohol in crystals belonging to the sphenoidal-rhombic system [a 6 c = 0.7265 1 0.51421 which exhibit rotatory polarisation in the solid state as well as in solu- tion.The P-isomeride crystallises in the same system [a b c = 0.5832 1 0.95601. a-Ethylthiocodide also crystallises in the same system [u b c = 0.7481 1 0.76591. T. M. L. Resolution of Thebaine by Benzoyl Chloride. ROBERT PSCHORR and W. HAAS (Ber. 1906 39 16-1 9) .-BenxoyZthebnoZ C23H1804 prepared by the action of benzoyl chloride on thebaine at 0' crystallises from acetic acid in thin colourless needles and melts a t 160-161'. The dibromo-derivative C,,Hl,04J3r2 crystallises from acetic acid in long needles and melts a t 229". BenxoyZtZLebaoZquinone C13H,606 prepared by oxidation with chromic acid separates from acetic acid in yellow crystals and melts at 216' ; it is hgdrolysed by sodium ethoxide to Freund's thebaolquinone.The basic product of the action of benzcyl chloride was identified by means of its aurichloride C,HloONAuC1 as ethoxymethylamine. The decomposition is thus essentially similar to that brought about by C H (OMe) NMe H 0 ' ~ 2 ~ ~ ~ ~ ~ > C 2 H 2 + NHMe*CH,*CH,*OH and involves the resolution of a furan ring and of a nitrogen riug and the separation of a carbon to carbon linking. acetic anhydride O< I ' >C2KCH2>CH2 -+ C,H,(OMe) T. M. L. Hordenine a New Alkaloid obtained from Malt Germs. EUGBNE LBGER (Compt. rend. 1906 142 108-1 lO).-Hordenine C,,H,,ON a new alkaloid extracted by Stas' method from malt germs forms colourless voluminous strongly doubly refracting orthorhombic prisms [a b c = 0.5257 1 0.3551 (Wyrouboff)]. It melts at 117%' (corr.) sublimes like camphor at 140-150' dissolves readily in alcohol chloroform or ether forming optically inactive solutions is sparingly soluble in benzene and is almost insoluble in toluene xylene or light petroleum.Hordenine is alkaline towards litmus or phenolphthalein liberates ammonia from its salts and is not attacked by concentrated sulphuric acid or by potassium hydroxide either fused or in aqueous solution. It reduces acid soIutions of potassium permanganate ammoniacal soh-ORGANIC CHEMISTRY. 205 tions of silver nitrate or iodic acid and forms soluble salts with acids ; the suZphccte ( CloHl,0N),,H,S0,,H20 crystallises in brilliant prismatic needles readily soluble in water sparingly so in alcohol; the hydro- chloride C,,H,,ON,HCl crystailises from alcohol in thin needles ; the hydrobromzde CloHl,ON H Br forms brilliant long prismatic needles readily soluble in water less so in alcohol ; the hydriodide crystallises in long prisms slightly less soluble than the preceding salt.CloH150X,MeI which crystallises from water in colourless prisms; it contains R phenolic hydroxyl group and reacts with acetic anhydride to form R syrupy acetyl derivative which is basic and forms ucetylhordeni.rte hydriodide CloH,,ONAc,HI crystallising from alcohol or water in yellowish-white tabular crystals. c OH] ,ON H I Hordenine is a tertiary base and yields a ?netli,iodide M. A. 'CV. New Synthesis of Phenylacridine Derivatives. FRITZ ULLMANN and HANS W. ERNST (Ber.1906 36 298-310).-5-ATitro- 2-aniZinobenxop?benone NHPh*C,H,(NO,)*COPh prepared by heating aniline with 2-chloro-5-nitrobenzophenone and potassium carbonate for three hours at lSOo crystsllises from alcohol nielts a t 155" and by heating with glacial acetic acid containing a little concentrated sulphuric acid is converted into 3-nitro-5-phenyZacridine c,H,<~~>c,H,.No,. This can also be prepared directly from 2-chloro-5-nitrobenzophenone by heating the latter with aniline and sodium acetate at 1 5 0 O ; it crystallises from alcohol in intensely yellow needles and melts at 209O. On reduction 3-amino-5-phenylacridine is obtained ; Hess and Bernthsen (Abstr. 1885 800) describe this substance and its salts as resinous in character but bythe authors' method the base is obtained on crystallising from alcohol in the form of slender yellow needles which melt a t 200° ; the hydrochloride crystallises in large needles with a bronze-like lustre and in alcoholic solution shows a green fluorescence.3-Acetylamino- B-phenyZacridine crystallises from benzene melts at 256O and also shows a green fluorescence in alcoholic solution. 9-Nitro-7-phenp?- 1 2 -~henorbapl~thcccridine prepared by heating together 2-ehloro-5-nitrobenzophenone and P-naphthylamine in nitrobenzene solution at 205O crystallises from glacial acetic acid in straw-coloured needles melts a t 274" and on reduction gives 9-amino-7 -pheny? - 1 ; 2 -ph enonccphthacrid ine ; this crystallises from alcohol in dark yellow prisms melts at 282") and gives a Ii,ytZrochZoi*ide crystallising in red needles which become yellow when heated with water.9-~Vitro-7-phenpZ-2 ; I-phenona;uht?~c~cridine prepared by heating 2- chloro-5-nitrobenzophenone with alcoholic a-naphthylamine for five hours a t 150-170" crystallises from glacial acetic acid in yellow needles and melts at 264".206 ABSTRACTS OF CHEMICAL PAPERS. 9-Arnino-7-p?tenyZ-2 1 -phefionaphthacridim crystallises from alcohol in stellate aggregates of brown needles melts at 224O and gives ared hydrochloride. 3-NitTo- 7-amino-5-phen~lacridine prepared by heating 2-chloro-5-nitrobenzophenone with p-phenylene- diamine for three-quarters of an hour at 200° crystallises from benzene i n garnet-coloured needles and melts at about 181' ; the hydrochloride forms yellowish-brown needles.On reduction 3 7-diamino-5-pT~enyl- ncridine is obtained which crystallises from benzene in lemon-yellow needles ; the picrate C,,H,,N,,g6H3o7N3 forms purplish-red needles. N02*C6.H,C1*CO* C,If,*OMe prepared from 2-chloro-4-nitrobenzoyl chloride and anisole by the Friedel-Crafts reaction crystallises from benzene on adding light petroleum in colourless needles and melts at 105'. On heating it with aniline and powdered potassium carbonate a t 1 SO' 5-nitro-2-anilino-4'- methoxy benxophenone NHPh* C,H,( NO,)*CO*C,H,*O~!e is obtained ; it crystallises from alcohol in yellow needles or plates melts at 144-155' and when heated with glacial acetic acid containing sulphuric acid is converted into 3-nitro-5-p-methoxypher~ylacrid-e 2-Chloro-5-nitro-4'-methoxybenxophenone C,H4<y N [c,H,(oM~I> C6H,*N0 which crystallises from alcohol and melts at 178".2-0- Methoxya~dino-5-nitrobenzophenone OMe*C,H,*NH*C,H,(NO,)*COPh prepared by heating 2-chloro-5-nitrobenzophenone with o-anisidine and potassium carbonate a t 215' crystallises from alcohol either 'in bright yellow needles sparingly soluble in the solvent or more soluble greenish- yellow leaflets ; the two forms melt at 139' and are interconvertible. 3-Nitro-%methoxy-5-phenylncridine prepared by heating together the .same substances in the absence of potassium carbonate or by heating 5-nitro-2-o-methoxyanilinobenzophenone with concentrated sulphuric acid crystallises from alcohol in orange-yellow needles and melts a t 285'. W. A. D. Nature of Oxazine and Thiazine Dyes.ARTHUR HANTZSCH (Bey. 1906 39 153-159. Compare Abstr. 1905 i 605).-Largely polemical in reply to Kehrmann (ibid. i 670). The ammonium quinonoid constitutional formulz are regarded as being more in harmony with known facts than are Kehrmann's oxonium or thiazonium formule Bernthsen's methylene-azure (0. Fischer Ber. 1905 38 3435) has been examined and in solution its salts behave as neutral salts and are comparable with the aromatic quaternary ammonium salts. The azure-blue colour of the solution persists for a long time after the addition of sodium acetate or carbonate. This would not be probable if the compound contained t h s group >SO*Cl. J. J. S.ORGANIC CHEMISTRY. 207 Arylhydantoins. GUSTAV FRERICHS and M. HOLLMANN (Arch. Compare Abstr. 1899 i 806 ; 1903 i Pharnz. 1905 243 684-710.1 6).-Substit,uted aminopropion ylcarbamides NH,*CO.NH.CO*CHMe.NH*C,H*R [R = H or Me] were prepared by heating a-bromopropionylcarbamide NH;CO*NH*CO.CHMeBr (H. Frerichs Arcli Phnrm. 1903 241 195)) with an arylamine NH,*C,H,R in alcoholic solution. By heating the same mixture without the addition of alcohol to a higher temperature or by heating the products just mentioned above their melting points substituted a-methyl-/I-arylhydantoins were prepared and by heating these with alkyl iodides RII and alcoholic potassium hydroxide a-methy 1-P-aryl-y-alkylhydantoins N(C,H,R) *?HMO CO<NR'- co ' were obtained (the ally1 derivatives united with hydrogen bromide or bromine in acetic acid solution forming bromo- and dibromo-propyl derivatives).Similar condensations took place with chloroacetic acid and with chloroacetamide ; with ethylene bromide 2 molecules of the hydantoins condensed. a-Methyl-P-phenylhydantoin was prepared not only by the method given above but also by heating with alcoholic potassium hydroxide a-bromopropionylphenylcarbamide melting a t 158' which was obtained by mixing a-bromopropionyl bromide with phenylcarbamide in ethereal solution The other new substances described are enumerated below ; the numbers indicate melting points. Propionylcarbamides. a-Anilino- 143' ; a-toluidino- o 160° m 156' p 160'. a-Methylhydantoins. P-Phenyl- 146' ; P-tolyl- o 167' m 137" p 173'. Derivatives of these in this order y-methyl 128' 114") 89") 96' ; y-ethyl 114O liquid 76' 86' ; y-nllyl S8O liquid 58' 96" ; y- bron.eopropy1 89' liquid 92") 85" ; y-dibromopropJ 137' (nzonobronio- substitution derivative of this 148"; obtained by the action of bromine in acetic acid solution) 104" 85" 101'; y-acetic acid 163(' 182" 148' 179' (barium salts crystnllise with 3 3 2 2H,O) ; y-acet- amicle 2 2 5 O 166' 159') 205' ; y-ethylene (di-) ZOO" liquid liquid 173".C . F. B. Constitution of the Cyanine Dyes. W. KONIG (J. pr. Chenz. 1906 [iil 73,100-108. Compare Miethe and Book Abstr. 1904 i 622 776; Book thisvol. i 42).-As no case is known where a methyl group in the 2- or 3-position in pyridine or quinoline retains its property of condensing with aldehydes and ketones when the ring is reduced wholly or partially it is probable that the cyanine dyes con- tain 2 atoms of hydrogen less than shown in Miethe and Book's formula (Zoc.cit.) ethyl-red having the structure CH-CH - - - and the blue diethylcyanine ?H-CH>C:CH*C<C ~ .iSEtI These formulz are used t o explain the similarity of the cyanine dyes 6 4 NE t C,H,208 ABSTRACTS OF CHEMICAL PAPERS. and the pyridine dyes obtained from furfuraldehyde (Konig this vol. i 109). Contrary to the view of Miethe and Book (Eoc cit.) the additive compounds with iodine are considered to be periodides as they are not lighter in colour than the parent dyes as would be the case if the addition took place to an ethylene linking. G . Y. Preparation of 6-Bromo-4-ketodihydroquinazolines from 6-Bromo-2-aminobenzoic Acid and certain of its Derivatives. MARSTON T. BOGERT and WILLIAM F. HAND (J.Amer. Chem. Xoc. 1906 28 94-104. Compare Abstr. 1904 i 108).-Quinazolines have been prepared by the following methods. I. From 5-bromo-2-amino- benzoic acid (1) by heating the acid with an acid anhydride or a nitrile in a sealed tube a t 230-250" ; this method gives a poor yield and an impure product; (2) by heating the acid or its ammonium salt with a&d amides a method which gives excellent results with formamide but less satisfactory results with acetamide and is not applicable to the higher amides; (3) by heating the acid with excess of glacial formic acid or an acid anhydride and afterwards adding excess of ammonium carbonate and continuing the heating ; good yields are generally obtained in this way and the products can be easily purified. 11. By heating ammonium 5-bromo-2-acetylaminobenzoate when a nearly quantitative yield is obtained.111. From 5-bromo-2-acetyl- aminobenzonitrile (1) by warmingit with solutionof alkali dioxide; this method gives a quantitative yield of the pure substance ; (2) by boiling it with concentrated hydrochloric acid. IV. By the action of primary amines on 5-bromo-2-acetylanthranil. The following quinazolines are described. RH-CH:C;-N f! H CBr*CH:C*C(OH):N ' crystallises in transparent six-sided prisms melts a t 272-273' (corr.) and is soluble in alcohol acetone or aniline ; its platinicldoride forms short thick prisms. H-CH:$?-N 7 Me CBr*CH:C.CO*NH ' 6 - Brorno- 4- keto - 2 -methyldi?~ydroq~iItaxoline crystallises in colourless needles decomposes when slowly heated but melts a t 298-300O (corr.) if rapidly heated is easily soluble in hot; acetone or hot aniline and moderately so in hot alcohol; its hydro- chloride is instantly dissociated by water.6-Bromo-4-keto-2-ethyldihydroquinuzoline forms slender prismatic needles softens at 2639 melts a t 267-268-5' (corr.) and behaves towards solvents like the methyl homologue. 6-Brorno-4-keto-2-isopropyZdihdih?/droquinaxoline crystallises in colourless prismatic needles and when rapidly heated melts at 259-260.5' (corr.). 6- Bronto-4-keto-2-isobutyldihydroquinuxolilte forms small prismatic needles softens a t 250° and melts and decomposes slightly at 253-254" (corr . ). 6-B~~omo-4-keto-S-isoamyZdihydroquinccxoZine crystallises in prismaticORGANIC CHEMISTRY. 209 needles melts at 235-236' (corr.) is easily soluble in hot aniline and moderately so in hot alcohol.6-Bromo-4-keto-3-pIenyl- 2 methyldi~~ydroquinaxoline crystal lises from alcohol in colourless six-sided prisms and melts a t 185-186' (corr.). 6-Bi~omo-4-keto-3-o-tolyl-2-methy~di~~~droqui~a~oli~ae forms colourless crystals and melts a t 137-138' (corr.). Attention is drawn to the fact that with the exception of the methyl derivative the melting. points of these quinazolines fall regularly as the molecu1;tr weight increases and that those of the iso-coapounds are higher than those of the corresponding n-compounds. E. G. Quinazoline Alkyl Haloids. SIEQMUND GABRIEL and JAMES COLMAN (D.R.-P. 16 140 l).-Quinazoline-3-methylium hydroxide (Abstr. 1904 i 1060) dissolves in concentrated hydrochloric acid t o form the chloride melting a t i71-172°.The bromide dissolves in water and melts a t 150-152'. The hydroxide prepared from quin- azoline ethiodide is insoluble in cold water but dissolves in hot water and melts at 145-146' ; the chloride melts at 150-151'. The salts find therapeutic application. C. H. D. Hydroxyquinacridine and Phloroquinyl. STEFAN VON NIEMENTOWSKI (Ber. 1906 39 385-392. Compare Abstr. 1896 i 261 ; Eliaiberg and FriedIGnder Abstr. l892,1106).-When heated to 115-120° a mixture of 2 mols. of o-aminobenzaldehyde and 1 mol. of phloroglucinol develops heat and forms hydroxy-P-quinacridine together with small amounts of dihydroxyacridine and of phloro- quinyl which is formed as the chief product of the interaction of 3 mols. of o-aminobenzaldehyde with 1 mol.of phloroglucinol. crystallises from glacial acetic acid in glistening black needles containing 3C,H,O which is lost at 125'; i t melts a t 360' is readily soluble in boiling glacial acetic acid but only sparingly so in water chloroform carbon tetrachloride or benzene forming brownish- yellow or in alcohol ether or acetone emeraldpeen solutions ; the solution in nitrobenzene is brownish-yellow and becomes emerald- green when heated. It is only very sparingly soluble in aqueous ammonia alkali hydroxides or dilute acids but dissolves in concen- trated sulphuric acid to form a green solution having a slight fluor- escence. 4-Acetoxy-P-quinaci*idine C,,H,,ON,Ac crystallises from nitrobenzene in slender glistening almost black needles with steel- blue lustre and melts a t 300".When oxidised with sodium dichromate in boiling glacial acetic acid solution 4-hyciroxy-/3-quinacridine yields 3 4-diketo-3 ; 4-clil~ydro-P-quinacricline N-fi*CO*CO*C*CH CGH4 qJ K. c-c 1 ' .N I >C,H which crystallises in long golden-yellow leaflets becomes black and melts about 410° and dissolves in concentrated sulphuric acid to form a golden-yellow solution or in boiling methyl alcohol containing VOL. xc. i. 9210 ABSTRACTS OF CHEMICAL PAPERS. a drop of concentrated aqueous potassium hydroxide solution forming a dark-coloured solutipa; this does not change in colour when shaken with air (compare Bamherger Abstr. 1885 807). When heated with o-phenylenediamine in glacial acetic acid solu- tion diketoquinacridine yields ~-quinucrid-S 4-asine I I which crystallises from nitrobenzene in yellow needles melts becomes black and forms a crystalline sublimate at 420° and is only sparingly soluble in the ordinary solvents but dissolves in concentrated sulph- uric or hydrochloricacid to form a yellow solution ; it forms a crystal- line hydrochloride platinichloride and aurichloride.p*C,H,*X N=Q*C-C*$XCH C_N>C,H crystallises CH:C- Phloroquinyl C,H4< from nitrobenzene in yellow or light brown needles melts at 4 0 3 O is moderately soluble in boiling nitrobenzene but is only sparingly so or is insoluble in other organic solvents and is insoluble in dilute alkali hydr- oxides or acids but dissolves in concentrated sulphuric acid forming a yellow solution. It remains unchanged when heated with concentrated hydrochloric acid in a sealed tube at 200° or when distilled over zinc dust or when treated with sodium amalgam.It forms a red nitro- derivative when boiled with concentrated nitric acid ndditive and substitution products when acted on by bromine with or in the absence of a solvent and an unstable udditiue-compound with methyl sulphate which yields the phloroqixinyl when boiled with aqueous potassium hydroxide. G. Y. Oxidation Products of o-Aminophenols. FRIEDRICH KEHRMANN (Bey. 1906 39 134-138).-[With M. MATTISSON.]-A~~ is passed through a hot aqueous solution of o-aminophenol until the amount of precipitate no longer increases and the product removed dried and extracted with boiling benzene in the presence of animal charcoal. The benzene solution yields a mixture of two azine derivatives which may be separated by acetylation and crystallisation of the acetyl derivatives from glacial acetic acid.The acetylaminophenoxazone which is present in larger quantity forms large brownish-red plates and melts at 275O ; the isomeric compound is less soluble forms brick- red needles and melts a t 285O. Both acetyl derivatives are decom- posed by 50 per cent. sulphuric acid yielding on the addition of water brownish-blood-red solutions. The solution from the compoundmelting at 285' reacts with nitrous acid with a brisk evolution of gas but no indication of a precipitate. The isomeric compound under similar treatment yields no gas but forms an orange-red precipitate C12H70sN3 which crybtallises from a mixture of alcohol and benzene in y ellowish-red needles decomposing at 175".[With w. uRECH.]-when o-amino-o-cresol is oxidised in a similar manner it yields orange-red glistening crystals C,,H,,O,N whichORGANIC CHEMISTRY. 211 separate from a mixture of alcohol and benzene as red prisms with a violet metallic lnst8re. The hychochloride forms brownish-black needles. With nitrous acid an orange-coloured precipitate is obtained. [With E. ~u~~ER.]-o-Amino-m-creso~ yields orange-red crystals C,H,ON with a blue fluorescence; they melt at 176' and dissolve sparingly in water but readily in organic solvents. The compound is decidedly basic ; the hydrochloride (C,H,ON),,HCl forms brown crystals ; tho platinichloride is insolnble in water and forms brownish- red crystals ; the dichronzate C,,H,,O,N,Cr,O forms red crystals ; the nitrate C,,H,,O,N,NO forms red needles which dissolve readily in water.The base cannot be reduced readily. J. J. S. Chemical and Thermochemical Researches on the Consti- tution of the Rosanilines. JULES SCHMIDLIN (Ann. Chinz. Phys. 1906 [viii] 7 195-279).-A r5sunz5 of work already published in Abstr. 1903 i 687; ii 530 633; 1904 i 698 785 943 944 945 1061 ; 1905 i 75 and ii 11 and 12. T. A. H. Indamines and Thiaaines. ROBERT GNEHM and W. SCHROTER (J. py. Chem. 1906 [ii] 73 1-20. Compare Gnehm Bot and Weber Abstr. 1902 i 831 ; Gnehm and Bot Abstr. 1904 i 451 ; Gnehm and Weber ibid. 532 ; Gnehm and Kaufler ibid. 687 935).- p-Amino-derivatives of methyl- and ethyl-anilines and of methyl- and ethyl-o-toluidines are prepared by formation of the nitrosoamines con- version of these into the p-nitroso-derivatives by means of alcoholic hydrochloric acid and ether in the case of the aniline derivatives o r of concentrated aqueous hydrochloric acid with the derivatives of o-toluidine and reduction of the nitroso-compounds with zinc and hydrochloric acid.p-Aminomethyl-o-tohidine NH,*C,H,Me*NHMe is obtained as a colourless viscid oil which does not solidify at - Z O O boils a t 276-276.5' (corr.) and becomes brown owing to oxidation when exposed t o the air. The sulphccte (C,H12N2)2,H2S0 crystallises from dilute alcohol in slender white needles. s-Bi-p-metl~ylnnzinodiphenylamine NH(C,H,*NHMe) is formed by oxidation with aqueous sodium hypochlorite of a mixture of methyl- aniline and p-phenylenemethyldiamine and reduction of the resulting solution with zinc dust.It crystallises in glistening colourless leaflets or needles melts a t 115' (corr.) is easily soluble ip chloro- form or acetone but less so in ether alcohol benzene toluene or hot light petroleum and when moist is oxidised rapidly by the air becoming yellow t o brownish-blue. The hydroclJovide C,,H17N,,2HC1 forms brown leaflets froths a t 220° and melts a t 225-227" (corr.). The triucetyl derivative C14H1,N3Ac3 melts a t 245' (corr.). Di-p-ethylaminodiphenyZamane NH(CGH,*NHEt) formed from ethylaniline and p-phenylene-ethyldiamine melts at 95O (corr.) and is more readily soluble than the s-dimethyl compound The h y d w chloride CI,H2,N,,2HC1 melts a t 21 7-218' (corr.). The tyiucetyl derivative Cl6HIUNsAcP melts a t 207' (corr,).As they undergo oxidation with great ease the s-dialkyl-leucind- nmines formed from ethyl-o-toluidine and ethyl-p-tolylenediamine and 4 2212 ABSTRACTS OF CHEMICAL PAPERS. from me thyl-o-toluidine and methyl-p-tolylenediamine cannot be isolated except in the form of salts or derivatives. B i- p-e t h y laminod it oly lamine hy driodide NH( C6H3Me*NHEt),,3 HI,2H20 crystallises in glistening orange leaflets and melts a t 120-122O (corr.). The tribenzoyl derivative CI8H,JY3Bz3 formed by the action of benzoyl chloride and sodium hydroxide on the hydriodide is obtained as a white glutinous powder which becomes soft at 60Oand melts above 90". Di-p-)nethyZa,minoditolylumine hydriodide NH( C,H,&Te*NHMe),. 2 HI crystallises in sheaves of slender white needles and melts at 242". The tribenxoyl derivative CI6HlSN3Bz3 resembles that of the s-diethyl compound. Trinitrophenyl- p-pltenylenemetlqldiamine NHMe*C,H,*NH C,H,( N o,) is formed by boiling p-phenylenemethyldiamine with picryl chloride and potassium acetate in alcoholic solution in a reflux apparatus ; it crystallises in dark brownish-red glistening leaflets melts at 188" (corr.) and when condensed with sulphur chloride in presence of potassium acetate yields a mixture of products from which no one could be isolated.Binilrop~enyl-p-pheizyllenemet7yldiulmine N HMe C,H,*N H C,R,(NO,) formed from p-phenylenemethyldisrnine and 1-chloro-2 4-dinitro- benzene melts at 153". The action of sulphur chloride on di-p-ethyldiaminodiphenglamine in benzene solution leads to the formation of a labile additive com- pound which is obtained as a green precipitate becoming greyish- green on drying.~'olylenemeth?jldiaminethiosulp7~0nic acid NH,*C,H,Me( NHMe) *S,O,H [Me NHMe S,03H NH = 1 2 4 51 is formed by adding acetic acid and potassium dichromate to a mixture of p-methylamino-o- toluidine sulphate aluminium sulphate and sodium thiosulphate in aqueous solution. It forms green crystals melts a t 212-213" and when oxidised with sodium hypochlorite in dilute aqueous sodium carbonate solution yields a product which may be the thiazine CMe-CHI ?*N:Q *C(ONa):QH C(NHRIIe)* C H C-S-C CH-CNH' AminoJeucornethylene-blue C1,H,,N,S is formed by reduction of methylene-green (nitromethylene-blue) with zinc dust and acetic acid.It crystallises in sheaves of slightly green needles melts at 143-145" and is very easily oxidised so that it can be obtained only with complete exclusion of air. G. Y. Phenylcarbamidodiphanylmethenylamidine and its easy Decomposition with Formation of Phenylcarbimide. REINHOLD VON WALTHER (J. p?.. Chem. 1906 [ii] 73 108-112).-PhenyZ- car banzid odiphen y lmethen ylumidine i s formed when diphenylmethenylamidine is heated with phenylcarbimide on the water-bath It crystallises from light petroleum in small stout transparent prisms melts a t 104" and is readily soluble in the I i N HP h CO *NPh* CH NPh,ORGANIC CHEMISTRY. 213 ordinary solvents when warm. s-Diphenylcarbamide melts a t % 3 5 O and diphenyllnethylcarbamide a t 104".A table is giveti to show that the introduction of aliphatic groups into phenyl- or s-dipheuyl- carbamide depresses the melting point the ethyl group effecting the fusibility to a greater extent than the methyl group and that the melting point rises amgain slowly as successive methyl groups am introduced. Phenylcarbamidodiphenylmethenylamidine decomposes slowly a t the laboratory temperature with formation of s-diphenylcarbamide o r quickly when boiled with alcohol with formation of diphenylmethenyl- amidine and ethyl phenylcarbamate ; i t interacts with aniline with development of heat and formation of s-diphenylcarbamide or with p-chloroaniline to form p-chloro-s-diphenylcarbamide. p - C ~ ~ l o ~ ~ o ~ J ~ e n y ~ c a r b a ~ ~ d o d ~ ~ ~ e n y Z m e t ~ ~ e n y l c ~ m ~ ~ ~ n e C,H,Cl* NH CO*NPh*CH X P h formed from diphenylmethenylamidine and p-chlorophenylcarbimide crystallises from light petroleum in white prismatic needles melts a t 97-103" and interacts with aniline to form p-chloro-s-diphenyl- carbamide or with p-chloroaniline to form s-di-p-chlorophenyl- carbamide.Diphenylmethylcarbamide and complex carbamides such as l-phenyl- carbamido-2-methylindole do not interact with aniline a t the laboratory tempera t ur e. Derivatives of Triazole. WILHELM MANCHOT and R. NOLL (Annalen 1905 343 1-27).-The constitution for diazotriazo!e7 G. Y. NH*C-N carboxylic acid I $" >O,H,O suggested by Thiele and Manchot &= c *GO/ (Abstr. 1S99 i 167) represents the compound as an internal anhydride. Since however the ester of sminotriazolecarboxylic acid yields an analogous diazo-compound which is obviously unable to form such an anhydride it is more probable that the acid above N -CO,H C(NH .NO) N mentioned is represented by the formula NH< Diazotriazolecarboxylic acid is best prepared by addini to sodinm aminotriazolecarboxylate first concentrated hydrochloric acid and then at - 4' a solution of sodium nitrite.The ethyl ester is prepared in a similar manner by diazotising ethyl aminotriazolecarboxylnte ; it is very explosive. It is to be noted that chlorotriazoIe (Zoc. cit.) does not lose chloiine when treated either with nascent hydrogen or nitric acid. Bromo- trinxole NH< N=(? H is prepared by pouring fuming hydrobroniic acid over the diazo-acid rubbed up with a little water ; it crystallises in prisms melting a t 188-189" and by sodium amalgam is converted into triazole. With silver nitrate i t gives a white and with copper acetate a pale blue precipitate. Diazotriazolecarboxylic acid reacts with aqueons potassium iodide iodine being set free and triazole and iodotriaxole formed.The latter cry stallises in needles melting and CBr:N214 ABSTRACTS OF CHEMICAL PAPERS. decomposing at 208O iodine being liberated; with silver nitrate and copper acetate it gives precipitates ,similar to those formed from the bromotriazole and by sodium amalgam it is reduced to triazole. Hydroxytriazolecarboxylic acid (Abstr. 1899 i 84) can be obtained from the diazo-acid and acetic acid; at first orange-red needles of the anhydrous acid are formed which gradually pass into the crystals of the hydrated acid.When reduced a t a low temperature with stannous chloride and hydrochloric acid diazotriazolecarboxylic acid is con- YH the hydrochloride of N= C(N,H,) :N verted into triaxylhydraxirze NH< which crystallises in needles melting aAd *decomposing a t 224'. The picrate crystallises in pale yellow needles melting at 165'. Benxylidene- triaxylhydraxone crystallises in needles melting at 225-5-226' ; the corresponding salicyl derivative melts and decomposes at 259O ; the acetophenone derivative forms small plates melting at 276' and the acetone derivative melts a t 216'. N===CH C( N,) N I prepared from the hydrazine Triazylaxoimide NH< hydrochloride and sodium nitrize forms crystals melting at 121-1 22" and vields an exdosive silver salt. .I A N-__Q *OH C(NO,\ N prepared when hydroxy- Nitrohydi.oxytriaxoZe NH< af triazole is treated with fuming nitric acid forms crystals decomposing at 254O ; its siEver salt is a pale yellow crystalline precipitate exploding when heated When nitrohydroxytriazole is reduced with tin and hydrochloric acid the corresponding aminohyds.oxytriasoZe is produced.Its hydrochloride is crystalline and melts a t 196' and the picrate crystallises in pale yellow needles melting at 204'; the silver salt is red and gives a silver mirror when heated. Preparation of 4 5-Diamino-2 6-dihydroxypyrimidine and its Derivatives. EMANUEL MERCK (D.R.-P. 161493).-5-isoNitroso- 4-amino-2 6-dihydroxy-3-methylpyrimidine (Traube Abstr. 1900 i 416 ; 1901 i 54) may be reduced to 4 5-diamino-2 6-dihydroxy-3- methylpyrimidine in sulphuric acid solution by means of iron or zinc dust.Ammonia precipitates the base in bright yellow needles from a hot solution of the sulphate. 4 5-Diamino-2 6-dihydroxypyrimidine and its 1 3-dimethyl derivative may be prepared in similar manner. C. H D. K. J. P. 0. Action of Aldehydes on o-Diamines of the Pyrimidine Series. WILHELM TRAUBE and WALTHER NITHACK (Ber. 1906 39 227-235. Compare Abstr. 1900 i 416 ; 1901 i 54; 1904 i 632 ; Gabriel and Cplman Abstr. 1901 i 427).-Benzaldehyde (1 mol.) when added to an aqueous solution of 4 5-diamino-2 6-dioxy-1 3-dimethylpyrimidine (1 mol.) causes the separation of the 6enxyZidene compound O*C(N:CHPh) 7 *NH NMe-CO-NMe ' which is easily hydrolysed by acids into its constituents On heating this compound with a second molecular proportion of benzaldehyde S-phenyl- 7- benzyl- 1 3-dimethylxanthine is obtained Oxidation ofORGANIC CHEMISTRY. 215 the benzylidene compound with ferric chloride produces 8-phenyl- theopliglline. 4-Amino-5-benxylideneumino-2 6-dioxy-3-methyZpyrimidine c1'2H!202N49 crystallises from hot alcohol in delicate needles which melt and decom- pose a t 274".It is insoluble in water or cold alcohol and is hydrolysed into its constituents by mineral acids. Ammoniacal solutions of silver salts are vigorously reduced by it and on evaporation with nitric acid a reddish-purple residue is obtained. The corresponding hydq-oxy- benxylidene compound obtained from salicylaldehyde forms long yellow needles.8-Phen yl- 7- benxyl- 3 -methylxanthine C,,H,,O,N obtained by heating the benzylidene compound (1 mol.) described previously and benzalde- hyde (1 mol.) at lSO' separates from alcohol in yellow crystals which are unaffected by boiling acids and dissolve in alkalis to a yellow solution from which acids reprecipitate the substance unchanged. 3-Methylxanthine is prepared by warming a solution of 4 5-diamino- 2 6-dioxy,-3-methylpyrimidine in acetic acid adding a solution of formaldehyde and subsequently oxidising the condensation product formed by means of ferric chloride. I n all its properties and colour reactions the substance is identical with the 3-methylxanthine obtained by E. Fischer (Abstr. 1898 i 700) and by Traube (Zoc. cit.). 8-Hydroxyp?~enyl-3-methylxunthine C,,H,,O,N is obtained like the preceding compound employing salicylaldehyde in the place of form- aldehyde.It separates from alcohol in colourless needles which do not possess reducing properties and are not acted on by acids. By evapora- tion with nitric acid a yellow-coloured residue is formed. 3-MethyZ-S-isobutyZxanthine C,,H,,O,N obtained in similar manner from valeraldehyde separates from hot water in minute colourless needles. 4-Amino-5- benx ylide~zeamino-2 6-dioxy- 1 3-dimeth yl'yrimidine ~,3Hl,O,N separates f r o g alcohol in orange-yellow needles which melt and decom- pose a t 220". It is hydrolysed by mineral acids and reduces ammoniacal solutions of silver salts. by fusing the preceding compound with an equivalent quantity of benzaldehyde has a bright yellow colour melts and decomposes at 221° and is unaffected by mineral acids.8-P?~enyl-l 3-dimet?~ylxnnt~~iney C1,H1202K4 obtained from the benzylidene compound by oxidation with ferric chloride crystallises from acetic acid in colourless rhombic plates insoluble in water or alcohol and remains unchanged a t 300'. It does not possess reducing properties and is practically unaffected by acids. s-Hydroxyphenyl-7-hydroxybenzyZ- 1 3-dimethyExanthine C2,H1804N4 obtained from the pyrimidine base and 2 mols. of salicylaldehyde at 180" forms a yellow crystalline powder. The intermediate hydroxy- benzglidene compound (from 1 mol. of salicylaldehyde) crystallises in yellow needles which decompose at 242". 1 3-Di~ethyZ-8-isobutylxant~~ine Cl1Hl6O2N4 separates from hot aqueous solution in colourless needles melting at 227'.It is stable towards acids and does not possess reducing properties. 8- Pheny Z - 7- benxy I- 1 3-dimeth ylxanthine C,,H,,O,N obtained216 ABSTRACTS OF CHEMICAL PAPERS. 8-Phenyl-7-benzylgznim C,,H,,ON is obtained by heating at 1 80° 2 4 5-triamino-6-oxypyrimidine and benzaldehyde (2 mols.). It separates from hot alcohol in light yellow needles. The intermediate benzplidene compound (from 1 mol. of benzaldehyde) crystallises in yellow needles which melt and decompose a t 2'76' and is easily hydro- lysed by mineral acids. c. s. Action of Phosphorus Oxychloride on Bispyrazolone Deriv- atives of Aldehydes and Ketones. AUGUST MICHAELIS and ADALBERT ZILG (Ber. 1906 39 370-381.Compare Abstr. 1905 i 377 392). - 4 4'-Renxenyl-l 3 5-phenylmstAylpyrci~olone-l' 3'- pheny lmeth ylpyraxo Ze rPh* Co>C:CPh*C<Cye:N CH-yPh is formed when benzylidenebis- 1 3 5-phenylmethylpyrazolone (Lachowicz Abstr. 1897 i 119) is heated with phosphorus oxychloride a t 135-140' and the product poured into water and treated with dilute sodium hydroxide. It crystallises from alcohol or ethyl acetate in slender white needles melts at 196') has feeble basic properties is readily soluble in hot alcohol ethyl acetate chloroform ether or benzene and dissolves in concentrated hydrochloric acid from which it separates unchanged on addition of water. forms slender yellow needles and melts above 260'; the aurichboride C27H2,0N,,HAuC11 crystallises in yellow needles and melts a t 216' ; the methiodide 027H2,0N,,2MeI 3H,O crystallises from alcohol and forms a periodide C,7H,20N4,2 MeT,I,.C27&oON4Br Erp formed by the action of an excess of bromine on the base in glacial acetic acid solution crystallises in yellow needles and when treated with hot dilute sodium hydroxide loses bromine and yields the dibromide C,7H,qON4Br which crystallises in slender needles and melts at 219'. The nztro-derivative C27H2,0N4*N02 formed by the action of fuming nitric acid on the base crystallises from glacial acetic acid and melts at 235-243'. N-CMe The pkc6€inichloride C27x,2ON4,H2PtC1 The perbromide 4 4'-Benxenylbis-l 3 5-phenyZmethylpyrazoZone ~Ph-Co>C:CPh*CH<CMe:N CO-r Ph NXCMe is formed by the action of phosphorus pentachloride on benzenyl- phenylmethylpyrazolonephenylmetJhylpyrazole at 140' or by oxidation of this with potassium permanganate and sulphuric acid below 30'.It crystallises in yellow needles melts at 242' and dissolves in aqueous alkali hydroxides to form a dark red solution or in concentrated hydrochloric acid from its solution in which it is precipitated on dilution with water. The ammonium and barium derivatives are red ; the silver derivative C,,Y2,02N4Ag forms dark red nodular crystals. is formed by heating phenylmethylpyrazolone with p-chlorobenzalde- hyde ; it crystallises from alcohol in slender white needles melts and becomes red at 213') and is readily soluble in alcohol chloroform 4 4'-p-Chlorobenxenylbas- 1 3 5-phenylmethylpyraaolone C,7H,,O,N*C1,ORGANIC CHEMISTRY.217 dilute acids or aqueous alkali hydroxides. When heated with phomhorus oxychloride in a sealed tube a t 145' for ten hours it jields 4 4;-p-chlorobenxe~~~E-l ; 3 5-~J~e~tylmethylpyraxolone-1 3 plze n y lme th y lp yr axole $7Ph*CO >C:C(c6H4cl) *CH=C$E~$'~ which N=Cl\le crystallises in needles melts at 213' is insoluble in dilute aqueous alkali hydroxides and when treated with phosphorus pentachloride yields a product C,7H210,N,CI. This crystallises in yellowish-red needles sinters at 185" and melts a t 21 1'. Phenylmethylpyrazolone condenses with 0- and with m-nitrobenz- aldehyde to form the corresponding nitrobenxenylbisphenylmethyl- pyraxolones Cz7H2,0,N ; these form yellowish-green crystals ; the m-compound melts a t 230'; the 0-compound which is readily soluble in benzene melts at 226'.When heated with phosphorus oxychloride the bispyrazolones form the corresponding nitrobenzenylphenylmethyl- pyraxolo nephen ylnzeti ylp yraxoles NPh-CO CH-XPh &-CMe>C:C(C6H4*No2) .C<C&le 9 which are insoluble in aqueous alkali hydroxides. The m-compound forms colourless crystals and melts at 240'; the o compound forms green crystals and melts at 237". Wheu treated with phosphorus pentachloride these sii bstances yield oxidation products Cz7H2104N5 of which the m-derivative melts a t 183" and the o-compound at 207'. 2 4 6-Trinitrobenzaldehyde does not condense with phenylmethyl- pyrazolone but 2 5-dichloro-6-nitrobenzaldehyde interacts with the pyrazolone to form a mixture of 2 5-dichloro-6-nitro6enxyZ~dene- 1 3' 5-~1,en?/ln~ethylpyr~xoZone CloH,0N,:CH~C,H,C12*N02 which crystallises in yellowish-red needles and melts at 139' and 2 5-di- chloro-6-nitrobenxylidenebis-1 3 ; 5 -pheny lmetiqlpymxolone N0,*c6H,C1,*CH(Cl,HSON,) which forms dark yellow crystals melts a t 250' and when treated with phosphorus oxychloride yields a product insoluble in aqueous a1 kali hydroxides.Anhydrois o p o p y Zidenebis- 1 -phen9l- 3 -methplpyrn xo Zone R*NPh*s-O-E*NPh*E C Xe-C*CDle,*C- C Me' is formed by heating 4-isopropylenebis-1-phenylmethylpyrazolone (Knorr Sbstr. 1887 602) with phosphorus oxychloride in a sealed tube a t 125-130'; it forms colourless crystals melts a t 1 6 3 O boils with only slight decomposition at 400-405' and is insoluble i n aqueous alkali hydroxides but dissolves in concentrated sulphuric acid.The platinichloride C,,H,,0N4,H,PtC16 melts above 300' ; the yellow crystalline auwkhloride C,,H,,0N,,HAuCI4 melts a t 256O ; the methiodide C2,H,,0N4,MeI crystallises in slender needles and melts at 213" ; the dimethiodide C,,H,,0N4,2RIeI,2H20 crystallisos from hot water in needles and decomposes with formation of the monomethiodide a t 150-1 60'. With bromine in glacial acetic acid solution the anbydro-base forms a perbromide which crystallises in slender yellow needles and when treated with aqueous alkali hydroxides forms the dibronzo-derivative C23H:200N4Br2 crystallising218 ABSTRACTS OF CHEMICAL PAPERS. in slender glistening colourless needles and melting at 239'. The dinitro-derivative C,3H200N4(N0,)2 crystallisee in yellow needles and melts at 290O.When heated on the water-bath with phosphorus pentachloride the anhydro-base yields 4 5-dichloro-1-phenyl-3-methyl- pyrazole (Michaelis and Pasternack Abstr. 1899 i 941). Butylidenebis-l-phenyl-3-methyl-5-pyraxolone c24H,Go2N4 is formed by heating phenylmethylpyrazolone with methyl ethyl ketone ; it separates from alcohol in colourless crystals melts a t 248' is readily soluble in alcohol aqueous alkali hydroxides or acids and when heated with phosphorus oxychloride a t 125-1 30' yields the anhydro- K*NPh*fi-O-fi*NPh*E which separates from alcohol in CMe' base I C Me-C*CMeEt*C- colourless crystals melts at 1 8 2 O and is insoluble in aqueous alkali hydroxides. G. Y. Synthesis of Purine. OSKAR ISAY (Ber.1906,39 250-265).- 2 4-Bichloro-$-nitropyrimidine C C l < ~ ~ ~ ~ > C * N O prepared by heating 5-nitrouracil with phosphorus oxychloride containing a little hydrochloric acid for about twenty minutes at 185O crystallises from alcohol ether or light petroleum in lustrous leaflets melts at 29*3' and boils a t 153-165O under 58 mm. pressure. By cold alcoholic ammonia it is converted into 2-chloro-5-nitro-4-aminopyrimidine >C-N02 which crystallises from water in white silky four-sided prisms darkens at 205' decomposes at 217' and is reduced by hydriodic acid and phosphonium iodide to 4 s-diamino- >C*NH ; this crystallises from water in aggregates of slender needles melts at 202.5' boils a t 229' under 32 mm. pressure and gives the following crystalline salts the hydro- chloride hydrobromide aurichloride platinichloride 2C,X$N4,H2PtC16 ; the picrate decomposes at 264O.On heating 4 5-diaminopyrimidine with anhydrous formic acid the formyl derivative N==CH CCI% c(NH,y N==CH pyrimidine CH<N. C( j-j H2) CHGN*C( N = = C H > ~ o ~ ~ - ~ ~ ~ NH,) is obtained; it crystallises from alcohol in white leaflets melts at 198' and at a higher temperature loses water giving purine. The latter substance can be prepared directly from 4 5-diaminopyrimidine by heating it with anhydrous formic acid evaporating the excess of the latter and subliming the aroduct under reduced aressure. N:CH.C$H I 8-Methy@urine bH:N.z-N>CMe prepared by heating 4 5-di- aminop yrimidine with acetic anhydride at 210' and distilling the product solidifies in stellar aggregates of needles and melts at 265-266' ; the hydrochloride hydriodide and platinichloride CGH6N,,H2PtC16 are crystalline. On heating 4 5-diaminopyrimidine with carbamide a t 165" it is converted into 8-oxypurine (Fischer and Ach Abstr.1898 i 47). Substituting thiocarbamide for carbamide 8-thiopurine C,H,N4S isORGANIC CHEMISTRY. 219 obtained ; this crystallises from alcohol in lanceolate needles and begins to decompose at 268'. On melting 4 5-diaminopyrimidine with benzil a t 175' the axine r*CH *f? *N:yPh is formed ; it crys- CH:N*C*N :CPh' tallises from alcohol in small yellow plates and melts at 170.5". -- 5 -Nitro- 2 4 - d iaminop yrimidine NH C < ~ ~ ~ - ~ > C 'NO pre - irl pared by heating 2 4- dichloro-5-nitropyrimidine with alcoholic ammonia for two hours at looo crystallises from water in which i t is very slightly soluble in white rhombic prisms and does not melt a t 260' ; the hydrochloride plcctinichloride aurichloride and picrccte are crystalline; the szclphate melts a t 201' and the ititrccte a t 213".On reducing the base with stannous chloride and hydrochloric acid 2 4 5-triaminopyrimidine is obtained ; it forms slender needles may be distilled under reduced pressure sinters at 176O and melts at 179'; the hydrochloride platinichloride sulphate and nitrate are crystalline and the picrccte C,H7N,C,H,i-),Nq decomposes at 264". On heating 2 4 5-triaminopyrlmldlne with formic acid the formyl derivative N H 2 * C ~ ~ ~ ~ ~ > C * N H * C H 0 is produced ; it gives well-defined salts melts a t 224;' and a t a higher temperature is converted by loss of water into 2-aminopurine or isoadenine which appears to be identical with the substance described by Tafel and Ach (Abstr.1901 i 436). 2-&4minopurine does not give the adenine reaction of Kossel and Fischer. W. A. D. Conversion of Caffeine into Paraxanthine Theophylline EMIL FISCHER and FRIEDRICH ACH (Bey. 1906 39 Compare Abstr. 1896 i 13).-A 30 per cent. yield of and Xanthine. 423-435. 8-chlo ro - 3 - ch Zor ome thy Zparaxunt hine ( 3' 8 -dicTdorocafeine) >CCl NMe-CO-E.NMe I C O*X( CH2C1) *C-N is formed when caffeine or better 8-chlorocaffeine is heated for eleven hours with a mixture of phosphorus oxychloride and pentachloride a t 158-1629 A small amount of a trichlorocaffeine is formed a t the same time.An 18 per cent. yield of the dichloro-compound is obtained when chlorine is led into the fused and well-stirred 8-chloro-derivative first at 200' and then a t 170". It crystallises from a mixture of benzene and ether in nodular aggregates of needles melting a t 145-146" (com.)) is readily soluble in cold chloroform benzene acetone or ethyl acetate and in hot ether or alcohol and gives the murexide reaction with chlorine water. When boiled with water the dichloro-derivative is decomposed and formaldehyde hydrogen chloride and chloroparaxanthine (Abstr. 1899 i 173) are formed. Ni\le-CO-E*NICIe >CCI is C O*N( CH,*O1\IIe)*C-N 8 - Chloro- S'-methoxyca$eine I readily formed when the crude dichloro-comiound'is boiled with methyl alcohol.It crystallises in colourless glistening needles sin ters at 126" and melts at 130-131' (corr,) is very sparingly soluble in ether or220 ARSTRACTS OF CHEMICAL PAPERS. hot water and when heated with fuming hydrochloric acid at 100' yields chloroparaxan thine. 7' 8-DichZoroca$eine ~Me-Co-8*N(CH2c1)~CCl N is produced by C O*NMe*C- the action of chlorine on a nitrobenzene or phosphorus oxychloride solu- tion of chlorocaffeine at 90-100'. It crystallises from hot methyl alcohol in slender colourless needles melts a t 150.5-152.5" is readily soluble in glacial acetic acid or benzene only sparingly so in hot alcohol and dissolves in only 70 parts of boiling water. When boiled with ten times its weight of water i t yields 8-cblorotheophylline (Abstr.1896 i 263) and with an ethyl-alcoholic solution of sodium ethoxide 7' 8-di- ethoxyccfeine C12Hl,0,N,. This crystallises in colourless felted needles and melts at 125-126' (corr.). One gram dissolves in about 70 C.C. of warm ether 10 C.C. of hot alcohol 90 C.C. of boiling water or 1250 C.C. of water a t 23". 7' 8-dichlorocaff eine is heatid wfth'a phosphorus oxychloride solution of chlorine at 160-162". It crystdlises from ether melts at 129-1 30.5" (corr.) and dissolves readily in acetone acetic acid or benzene. When boiled with sodium methoxide in methyl-alcoholic solution it yields tetrccmethoxyca$eine Ci,H,,PGN which melts at 119-121O (corr.) and dissolves only Fparingly in cold ether or water. When boiled with dilute acetic acid the methoxy-derivative yields chloroxanthine and this when reduced with hydriodic acid and phosphonium iodide gives xanthine.J. 5. S. Condensation of Phenylhydraeine with Ethyl 4-Chloro-3- ALFRED WERNER and W. PETERS (Ber. 1906 39 nitrobenxoate. 1 85- 19 2).-EthyZ 2-nit~ohydruxobenxene-4-carboxyZate CO,Et*C,H,(NO,)*NH*NHPh is obtained together with phenylhydrazine hydrochloride when ethyl 4-chloro-3-nitrobenzoate is heated on the water-bath with pure colour- less phenylhydrazine (2 mols.). It crystallises from alcohol melts at 129O and dissolves readily in alcohol ether or acetone. When the alcoholic solution is oxidised with yellow mercuric oxide it yields ethyl p-6enxeneazo.m-nitrobenxoste which crystallises in brilliant red needles melting a t 139'. p-Benzene- .azo-m-nitrubenzoic acid is obtained when the ester is hydrolysed with alcoholic potash.It crystallises from alcohol in red needles melts at 215O and dissolves in &her alcohol or benzene. When ethyl 4-chloro-3-nitrobenzoate is heated at 90' with commercial phenylhydrazine the product is ethyl pheny~c~xnitrosobenxeneca~boxylate CO,Et*C,H,<k N->NPh which crystallises in long colourless needles melting at 105" and soluble in ether alcohol benzene or acetic acid. The corresponding acid CI3H9OaN3 crystallises from dilute alcohol in colourless glistening needles melting at 250' and is insoluble in C0,Et *C,H,( N02)*N,*Ph,ORGANlC CHE&IIS'l'EY. 221 water. The potassium salt C,,H,O,N,K crystallises from alcohol in slender needles. NH,*NH*CO*C,H, N,OPh obtained by the action of hydrnzine hydrate on the ester forms a gelatinous flocculent mass me1 ting at 220".N,*CO*C,H,-N,O-l?h obtained by the action of nitrous acid on the hydrazide crystallises from benzene in slender yellow needles melting at 140'. Phenylaxnitrosobenxeneurethane C02Et*NH*C6H3:N,0*P!1 obtained by boiling the azoimide with absolute alcohol for five to six hours crys- tallises in pale yellow needles and melts a t 215'. When boiled with alcoholic sodium hydroxide the urethane compound is hydrolysed t o aminop?Len ylaxnitroso benzene N H2*C,H N,O Ph which c ryst all ises from alcohol i n greenish-yellow needles melting at 180" and readily soluble in organic solvents and also in hot water. The hydrochloi-icle dissolves fairly readily in water. forms glistening needles and melts a t 233'.Ethyl phenylaximidobenzenecarboxylate CO,Et*C,H,:N,*Ph obtained by reducing ethyl phenylaznitrosobenzenecarboxylate with stannous chloride and hydrochloric acid crys tallises from alcohol in glistening needles melting at 84' and readily soluble in organic solvents. The corresponding acid CI3H9O2N3 sublimes in needles melts at 232' and dissolves readily in ether alcohol or acetic acid. Substitution of Negative Groups by the Hydroxyl Group in Ortho-substituted Diazonium Salts. EMILTO NOELTING and MARTIN BATTEGAY (Ber. 1906 39 79-86).-2 5 6-FrichZo~o- ccniline-3-sulphonic acid formed by nitration and reduction of 2 4 5-trichlorobenzene-3-sulphonic acid crystallises in white needles and is easily soluble in hot but only spnringly so in cold water.The sodium C,H30,NC13SNa,H,0 and barium salts were analy sed. The hydraxide of the acid The axoimide The acetyl derivative NHAc*C,H,:N,O*Yh J. J. S. 2 ; 5 6-Trzc?~lorobenxenediaxonium-3-sulphonic anhydride c 6 H c 1 3 < i 3 7 0 7 Erepared by treating the sodium salt of the above acid with hydro- chloric acid and sodium nitrite at 20-25" is obtained as a brown crystalline powder. It detonates when heated does not give a pre- cipitate with silver nitrate in aqueous solution dissolves in concen- trated sulphuric acid t o form a red solution and loses nitrogen when heated in aqueous or alcoholic solution. When ( ( coupled " with P-naph t hol it forms the sodium salt S0,Na*C6HCl,*N:N*C,oH,*OH which crystallises from glacial acetic acid in glistening orange needles dissolves in concentrated sulphuric acid t o form a carmine solution and dyes wool orange.When treated with cuprous_ chloride in hydro- chloric acid solution the diazonium compound yields 2 3 4 5-tetra- chlovohenxenesulphonic acid which crystallises in white needles and is readily soluble in water. The sodium salt C6H0,C1,SNa,H,0 crystal- lises in sheaves of white needles; the buriuna salt' (&H20) was analysed. The action of sodium hydrogen carbonate or acetate on trichloro-222 ABSTRACTS OF CHEMICAL PAPERS. benzenediazoniumsulphonic anhydride leads to the formation of sodium dichlorodiazophenollphonate which when treated with cuprous chloride in hydrochloric acid solution yields trichlorophenoZsuZphonic acid. This crystallises in slender white needles; the sodium salt C6H,0,C1,SNa,l~H20 forms white needles ; the 6arium salt is only sparingly soluble.When ‘( coupled ” with P-naphthol in alkaline solution sodium dichlorodiazophenolsulphonate forms a violet disodium salt which on treatment with dilute hydrochloric acid yields the monosodium salt OH* c6HC12( SO,Na)-N:N*C,,H,*OH ; this crystallises in glistening brown needles dissolves in water to form a violet solution gives a violet coloration with alkali hydroxides or concentrated sulphuric acid and on reduction yields 3 6-dichloro-2-aminophenol-4-sulphonic acid (Julius Chem. Zeit. 1903 27 846). The azo-compound dyes wool brownish-red becoming violet-brown when treated with an alkali hydroxide ; on treatmect with potassium dichromate and sulphuric acid there is obtained a violet colour fast to alkali hydroxides.When treated with copper sulphate the dyed wool becomes carmine-red. The axo-dye S0,Na*C6HBr3*N:N*C,,H6*OH obtained by “coupling ” diszotised 2 4 6- tribromoaniline-3-sulphonic acid with /3-naphthol in alkaline solution forms a carmine-red solution in concentrated sul- phuric acid dyes shades which are stable towards alkali hydroxides and when treated with sodium hydrogen carbonate yields a product in which a bromine atom is substituted by a hydroxyl group. When “ coupled ” with /3-naphthol this forms the axo-dye OH* C6HBr2( S0,Na) ON N*C which crystallises in glistening brown needles dissolves in water t o form a violet-red in aqueous alkali hydroxides to form a violet solution containing the disodium salt and gives a bluish-violet coloration with concentrated sulphuric acid.It dyes wool a red shade which changes t o dark violet and becomes fast to alkali hydroxides when treated with chromic acid. coupled ” with P-naphthol the diazonium anhydride obtained from 2 5-dichloroaniline-4-sulphonic acid (Noelting and Kopp Abstr. 1905 i 873) forms the axo-dye SO,Na*C,H,Cl,*N:N*C,,H,*OH which crystallises in red needles and in its properties resembles Orange 11. When treated with sodium hydrogen carbonate the diazonium anhydride is converted into the corresponding o-hydroxy- compound only to the extent of 40 per cent.; when coupled with P-naphthol the resulting mixture of diazo-compounds yields a red pToduct which has the properties of an o-bydroxyazo-compound. o-ClzlorocLniZi?ze-p-su~~onic acid is formed by heating o-chloroaniline hydrogen sulphate a t 160° under 20-30 mm.pressure. The sodium salt (4H,O) crystallises in needles and is only sparingly soluble in water. When treated with bromine it forms 2-cbloro-4 6-dibrom- aniline melting a t 103O (m. p. 93.5’; Fittig and Buchner Abstr. 1878 50). When diazotised and “ coupled ” with P-naphthol o-chloronniline-p-sulphonic acid yields an azo-dye resembling Orange 11. The action of sodium hydrogen carbonate on the diazonium anhydride leads to substitution of only 25 per cent. of the chlorine by hydroxyl ; on ( I coupling ” the resulting mixture a product is obtained which OH WhenORGANIC CHEMISTRY. 223 dyes dirty-yellow shades is only slightly altered by treatment with chromic acid and does not exhibit the properties of an o-amino- phenol derivative.The /I-naphthol dye SO3Na*C,H3(NO,)~N:N*Cl,H6-0H,H,O obtained from the diazonium anhydride of o-nitraniline-p-sulphonic acid (Nietzki and Lerch Abstr. 1889 144) crystallises in red needles dyes wool a redder tone than does Orange 11 and is stable towards alkali hydr- oxides. The diazoniurn anhydride dissolves in aqueous sodium hydrogen carbonate below 40' with evolution of carbon dioxide and formation of sodizc~jt c2iaxo~l~enolsulpl~onate. The solution '' couples " with P-naphthol in presence of sodium hydroxide to form the axo-dye OH*C6H3( SO,Na)*N:N*C,oHG 'OH which crystallises in glistening black needles and dissolves in concen- trated sulphuric acid to a bluish-violet solution. G. Y. Diazo-derivatives of Diamines (Phenylenediamines Benz- idine). LEO VIGNON (Compt. rend. 1906 142 159-161).-A solu- tion of diazobenzene chloride is decomposed by 0- or p-phenylene- diamine and with nz-phenylenediamine yields chrysoidine. Diazotised benzidine combines readily with amines and phenols to form stable derivatives. The author attributes this difference in the behaviour of the two types of diamines to the fact that in the former the two amino-groups are attached to the same benzene nucleus and either cannot be diazotised as in the case of the ortho-compound or yield very unstable diazo-compounds as in the case of the meta- and para-compounds ; whilst in the latter the two amino-groups being attached t o different benzene nuclei are diazotised as readily as the monoamines. M. A. W. The Combination of more than One Molecule of a Diazo- or Tetrazo-compound in the production of Aao-dyes. WILHELM VAUBEL and OTTO SCHEUER (Zeit. Fccrb.-Ind. 1906 5 1-2).-1n the preparation of benzidine-blue from tetrazodiphenyl and R-salt an excess of tetrazodiphenyl converts the dye into a substance insoluble in water and aqueous alkalis. The product seems to contain tetrazo- diphenyl and R-salt in the ratio 3C,,H,N,:OH*C,,H,(SO,") ; the original sulphonic groups appear to be present but diazo- or diazoxy- groups cannot be detected. W. A. D. Properties of Columbin an Albumin from the White of Pigeons' Eggs. ALEXEI 9. PANORMOFF (J. Buss. PJhys. Cltenz. Soc. 1905 37 915-923. Compare Abstr. 1900 i 709).-In addition to columbinin (loc. cit.) the author has separated from the white of pigeons' eggs another albumin colzcmbin which hss the composition C 52.47; H 7.16 ; N 14.82 per cent. These two albumins occur in equal proportions in the white of pigeons' eggs. Columbin is unstable and gives acid aqueous solutions from which it is precipitated by alcohol a solution of mercuric iodide in potassium iodide or ammoniacal lead acetate solution. Colzcnabin hydro- chloride has [.ID - 67*21° in aqueous solution or - 87-27" after being It has [.ID - 36.33" at 20".224 ABSTRACTS OF CHEMICAL PAPERS heated at 100" for some time; on analysis it gives the following numbers C 50.67 ; H 6-87 ; N 14.03 ; C1 2.85 ; S 1.34 per cent. The hydrobromide has [aID -87.39" after heating in solution at 100" ; its composition was determined. T. H. P. Properties of Albumins found in the White of Ducks' Eggs. ALEXEI A. PANORMOFF (J. Russ. Phys. Chem. Xoc. 1905,37,923-930). -The white of ducks' eggs contains only two albumins to which the names anatinin and anutin are given; these occur in the proportion of two parts of the former to one of the latter. Anatin is precipitable by dilute ammonium sulphate solution has [.ID - 81-95" at 20° and yields the following numbers on analysis C 50.32; H 6-84; N 14.64; S 2.96. The hydrochloride has [ a ] -77.2" at 20' in freshly-prepared solutions or -80.71" in solutions previously heated a t 100". Anatinin is precipitated by concentrated ammonium sulphate solution has [ u ] ~ -37.09" a t 20° and has the composition C 52.15 ; H 7.30; N 14.92; 8 2.01 per cent. Its hydrochloride has [a]. - 39.23' at 20". T. H. P. Albumin from the Blood-serum of the COW. STEPHAN MAXIMOWITSCH (J. Buss. Phjs. Clwn. Soc. 1905 3'7 931-940).-By fractional precipitation of serum from defibrinated cows' blood with ammonium sulphate the author has obtained an albumin which has the formula C,,~H,,,O,,,N,,S and [ u ] ~ - 48.36' at 20° and resembles the albumin separated from the serum of horses' blood (Abstr. 1902 i 66). The hydrocldoride Alb. 7HC1 has [.ID - 77%" at 20" in freshly-prepared solutions and - S4.05" after heating at 100". The phosphate Alb. 3H,PO has [u] - 71.3S0 a t 20' or - 82-52' after heating at 100". T. H. P. Precipitation of Serum-globulin from Blood-serum by means of Acetic Acid. WILLEM HUISKAMP (Zeit. p?~ysioZ. Chem. 1905 46 394-400).-'l'he proteid precipitated by the addition of dilute acetic acid to diluted serum appears to be the same substance as that obtained by Hammarsten as a precipitate when 0.3 per cent. of sodium chloride is added. The reactions and elementary composition of the two are identical. It is further identical with serum-globulin. It is precipitated almost entirely by one-third saturation with ammonium sulphate and therefore consists chiefly of euglobulin. Animal Gelatins. I V. WL. S. SADIKOFF (Zeit. physiol. Chent. 1905 46 387-393. Compare Abstr. 1904 i 462).-Gelatins or glutins differ in many of their solubilities from gluteins or cartilage- glutins. By means of saline solutions gelatin is divisible into (1) a part which is insoluble in salb solution (2) a part soluble in salt solution but precipitated by acid and (3) a part soluble in both salt solution and acids. W. D. H. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9069000129

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

137 General and Physical Chemistry Periodic Relation between the Atomic Weights and the Index of Refraction. F. L. BISHOP ( A m e r . Chenz J. 1906 35 84-86).-A table is given of the elements arranged in order of increasing atomic weight together with their atomic weights and refractive indices A curve is constructed in which the atomic weighbs are plotted as abscissie and the refractive indices as ordinate.. In this way a periodic relation between the atomic weight and index of refraction is made apparent. The elements form certain well- defined groups in which the minima are Ns Cu Ag and Au. The periodicity is most evident in the series from C to C1 as in this series the refracbive indices of all the elements are available. E. G. Flame Spectrum of Mercury. CHARLES DE WATTEVILLE (Contpt.clqend. 1906 142 269-270).-When the spray from a solution of mercuric acetate cyanide or nitrate is injected into the gas to be burned the flame spectrum of the metal thus obtained consists of one well-marked line 2536.72 (compare Hartley and Ramage Abstr. 1902 ii 189 ; Gouy Abstr. 1877 ii 105) and in this respect mer- cury resembles the other metals (magnesium calcium zinc strontium cadmium and barium) of the second group in the periodic classification (compare Ramage Abstr. 1902 ii 545 ; Watteville Abstr. 1905 ii 2). The three points obtained for magnesium zinc and cadmium by plotting the atomic weights of the metals against the wave-lengths of the characteristic line of their spectra lie almost on a straight line the prolongation of which passes through a point which requires the wave-length 3650.31 for the characteristic ray of mercury the line which is very prominent in the arc spectrum of the metal. M.A. W. [Mutarotation of Sugars.] CHARLES TANRET (Zeit. physikal. Chem. 1905 53 692).-Jungius in his recent paper (Abstr. 1905 i 573) has overlooked the author’s latest work (ibid. i 327). J. C. P. Solarisation in Silver Bromide Filma HERMAN WEISZ (Zeit. physikal. Chem. 1906 54. 305-352).-The author after reviewing recent work bearing on the nature of the latent image in silver bromide and chloride (see for example Luther Abstr. 1900 ii 181 253 ; Abegg Abstr. 1900 ii 253; 1901 ii 217; Baur Abstr. 1904 ii 4) concludes that it consists of a solid solution of silver subhaloid and (possibly) silver in silver haloid. This solid solution contains but little silver subhaloid or silver and is very stable towards oxidising and reducing agents.It appears that every substance capable of forming a solid solution with silver can act as a nucleus for both chemical and physical development ; thus gold platinum rhodium iridium and silver sulphide can act as nuclei for development. VOL. xc. ii. 10138 ABSTRACTS OF CHEMICAL PAPERS. The latent image is developable probably because the solid solution referred to above is able to form solid solutions with silver and silver subhaloid. The silver haloid of the sensitive film is reduced by the developer to silver and to silver subhaloid. The phenomenon of solarisation has been observed in the case of silver bromide films deposited on glass without the aid of any binding medium such as gelatin.It is shown that solarisation is due neither to conversion of the silver bromide of the film into a modification which is reduced only with difficulty nor to tanning of the gelatin pre- venting diffusion of the developer. A method is described whereby the tanning of gelatin in different plates may be detected and compared. J. C. P. Cathodic Phosphorescence of Europium. GEORGES U~~BAIN (Compt. reszd. 1906 142 205-207. Compare Abstr. 1904 ii 340 ; 1905 ii 250 458 711 ; this vol. ii 28).-Pure europium oxide does not give a phosphorescent spectrum but when diluted with lime even in the proportion of lEu,O,. Y9CaO it gives a red phosphorescence and similar results are obtained with the mixtures of europium arld gadolinium oxides forming the intermediate fractions in the separation of the two elements. The fractions rich in europium give a red and those rich in gadolinium give a white phosphorescence the spectra of the consecutive fractions changing gradually just as if europium were a mixture of two phosphorescent earths already beginning to separate.This is however not necessarily the explanation for if a specimen of pure europium oxide be diluted with increasing quantities of pure gadolinium oxide the spectra of the mixtures show a similar series of changes and similar results are also obtained with mixtures of pure europium oxide and alumina or lime. M. A. W. Absorption of a-Rays. R. K. MCCLUNG (PhiZ. Mag. 1906 [vi] 11 131-142).-A uniform and homogeneous source of a-rays is obtained by exposing a thin wire in a vessel containing the emanation from radium; the deposit on the wire contains three products radium A B and C but the first disappears in a very short time and the second gives out no rays.A wire prepared in the foregoing mauner was placed at the bottom of a narrow hole in the middle of a brass black and the well-defined cone of rays thus obtained was directed towards wire gauze kept at a constant potential and placed opposite to a zinc plate which in its turn was connected to one pair of quadrants of an electrometer. From the rate of leak observed for different positions of the radiating material it was possible to study the extent to which the a-rays are absorbed by their passage through air. Allowance was duly made for the gradual decay of the activity.When the source of radiation is at first quiteclose to the gauze arid is then gradually moved away the ionisation produced gradually increases and at a distance of about 5.8 cm. reaches a maximum; it then diminishes very rapidly until at a distance of 6-S cm. it ceases altogether. The range in air over which the a-ray can produce ionisation is therefore about 6.8 cm. in good agreement with the value 6.7 cm. obtained by Bragg and Kleeman (Abstr. 1905,4 5). AlmostGENERAL AND PHPSICAL CIIEMISTET. 139 the same value too has been found by Eatherford (Abstr. 1905 ii 495) i n his investigation of the distance at which the photographic and phosphorescent actions of the a-rays cease. When thin aluminium foil is interposed between the source of a-radiation and the gauze the total effective range of the a-rays is shortened and the maximum ionisation occurs at a point nearer the gauze.From a comparison of the thickness of the aluminium foil and the extent to which the total range of the a-rays is shortened it is calculated that the thickness of air equivalent to one layer of the aluminium foil (0.00031 cm. thick) is 0.5 cm. Rutherford (Eoc. cit.) using the photographic and phosphorescent screen methods found that 0.00031 cm. of aluminium was equivalent in absorptive power to 0.54cm. of air. J. C. P. Some Properties of the a-Rays from Radium. ERNEST RUTHERFORD (Phil. Mag. 1906 [ vi] 11,166-176).-The author deals with the criticisms contained in a recent paper by Becquerel (Abstr.1905 ii 665; compare also 1903 ii 256 257 403 523; 1904 ii 6) who believes that the a-rays from radium are homogeneous that the a-particles all escape into the air with the same velocity that this Felocity is not altered by their passage through matter and that the mass of the a-particle somehow increases in its passage through air the last statement being the explanation of the decreasing curvature of the path of the rays in their passage through air. The author reviews the experimental evidence and the various interpretations suggested by Bragg and Kleemann (Abstr. 1905 ii 4 5 791) Becquerel (Zoc. cit.) and himself (Abstr. 1905 ii 495) and concludes that the rays from radium in radioactive equilibrium are complex that they consist of a-particles projected with different velocities and that these velocities decrease as the particles pass through air or aluminium.The two phenomena observed by Becquerel namely (1) the absence of increased deflection of the rays from a thick layer of radium after passing through aluminium (2) the decreasing curvature of the path of the rays in air are both necessary consequences of the complexity of the rays. There is evidence also of a distinct scattering of the rays from radium C in their passage through air. J. C. P. Character of a- and 7-Rays. OTTO WIGGER (Jcdwb. Rccdioci%t Zlektro~~ik. 1905 2 391-433).-1n order to obtain a-rays of homo- geneous character radiotellurium and polonium were used as source of the radiation instead of radium which gives rise to several types of a-rays.Evidence of the nature of the a-rays has been obtained by a study of their absorption. Whereas the total absorption co- efficient of a bundle of rays of light of different wave-lengths decreases with increasing thickness of the absorbing layer the opposite is the case with rays consisting of small material particles. I n con- sequence of collisions in the absorbing medium an initially homo- geneous bundle of rays becomes heterogeneous the mean energy (velocity) becomes smaller and since the absorption increases as the velocity diminishes the absorption-coefficient should increase with the 10-2140 ABSTRACTS OF CHEMICAL PAPERS thickness of the layer traversed. The experimental data indicate that the absorption-coefficient of the a-rays of radiotellurium and polonium increases with the thickness of the absorbing layer and the material nature of the rays is established.Experiments on the leakage between a radiotellurium or polonium rod and a copper cylinder both well insulated and contained in a highly exhausted vessel indicate that these substances emit negatively charged particles of low velocity as well as positively charged a-rays. The P-rays are deviated by a mag- netic field but Becquerel’s observation that the U-rays of polonium are deviated is not confirmed by the author’s experiments on radio- tellurium. Using the photographic method ng evidence of deviation of tho a-rays could be obtained and the conclusion is reached that these cannot be identical with the a-rays of radium In order to obtain information on the question as to whether tbe y-rays of radium are rapidly moving P-rays or Rontgen rays the author has examined by the ionisation method the absorption of these rays by plates of lead employing much thicker layers of the metals than mere used in the previous experiments of Rutherford and McClelland.The absorption-coefficient decreases a t first with increasing thickness of the lead plate but attains a constant value for a thickness of 1.6 cm. This can only be explained on the assumption that the y-rays consist of Rontgen rays. When the y-rays traverse any material they give rise to a secondary radiation which is also capable of ionising gases and thus interferes with the effect due to the y-rays. The amount of this secondary radiation depends on the material traversed by the rays and in the experiments on the absorption power of different metals the effect was eliminated by interposing the substance be tween the radium prepara- tion and a lead plate 2.8 em.thick. This plate served to absorb the secondary radiation and was placed at the entrance to the ionisation chsmber. The absorption-coefficient of the penetrating y-rays which enter the chamber in. these circumstances is found to be strictly proportional to the density of the interposed material. The following values were obtained K being the absorption-coefficient and d the density Mercury. Lead. Copper.. Iron. Zinc. Aluminium. Sulphur. K(cm-l) ...... 0.283 0.241 0.191 0.159 0.141 0.054 0.040 These values for K are much smaller than those given by Rutherford and McClelland.A definite significance can only be ascribed to such numbers when the thickness of the medium traversed is indicated and the effect of secondary radiation is eliminated. Ionisation produced in various Gases by the Secondary /3- and 7-Rays of Radium. GOTTLIEB KU~ERA (Ann. Physih 1905 [iv] 18 974-990).-The ionisation produced in a number of gases by secondary radiation from varidus solid substances is found to be the same for all the gases. The intensity of the secondary radiation from those of the solid substances which are elements falls 08 in general with increase of the atomic weight. Comparison of the author’s results with those of Strntt (Proc. Roy. Soc. 1903 72 208) shows that there Kid ......... 0‘0208 0.0213 0’0226 0’0211 0’0201 0*0200 0.0202 H.M. D.GENERAL AND PHYSICAL CHEMISTRY. 141 is complete agreement between the relative ionisation due to secondary radiation and that due to the p-rays of radium. Certain abnormal phenomena observed in the case of freshly-prepared gases are attributed to the presence of very sluggish ions which are only gradually elimin- ated. J. C. P. Heating Effects produced by Rontgen Rays in different Metals and their Relation to the Question of Change in the Atom. H. A. BUMSTEAD ( P M Mag. 1906 [vi] 11 292-317).- When metals and other substances are exposed to Rontgen rays a complex secondary radiation is produced which is to some extent a t least of different character from the primary radiation. The secondary radiation may arise from atomic disintegration produced by the Rontgen rays in which case the law of the conservation of energy will not apply or may be due to other causes when the law in question may be expected to hold.To test this point thin strips of lead and zinc covered on both sides with aluminium foil so as to have the same emissive power were exposed alternately to the rays and the radiation from the two compared by reading the deflections on a radiometer with aluminium vanes; since the secondary radiation is to a great extent absorbed by the metals the readings mill be a measure of the amounts of heat generated in the strips. When the conditions were such that the rays were equally absorbed in the two strips it was found that approximately twice as much energy was generated in the lead as in the zinc. The result is best accounted for on the view that Rontgen rays bring about atomic disintegration ; the energy thus liberated probably forms the greater part of the energy which appears when the rays are absorbed by matter.ELEUTH~RE MASCART (Compt. red. 1906 142 122-124. Compare Blondlot Abstr. 1904 ii 604; Bichat Abstr. 1904 ii 531 532 641 ; Becquerel Abstr. 1904 ii 602 641 642; Rothe Abstr. 1904 ii 603 ; Gutton Abstr. 1904 ii 603).-Detds are given of a series of measurements of the position of points of maximum intensity in the spectrum produced by passing the n-rays from a Nernst lamp through an aluminium prism For this purpose a phosphorescent screen was mounted on the carriage of a dividing engine and each of four independent observers (Blondlot Gutton Virtz and Mascart) either recorded the position of the screen at points of maximum intensity whilst the carriage proceeded in one direction or the carriage was arrested by the observer a t such points whilst proceeding both up and down the scale and the readings were taken by a second person. G.8. n-Rays. The results obtained by the latter method are appended -+375*6 370.4 363.4 356.2 371.4 364.2 356.1 367.4 361.3 356.6 -+ 374.9 369.8 364.6 357.6 ......... t - 3 7 5 . 3 370.3 363.4 356.2 i Blondlot Gut toil ............ J + - ............... t - 3 7 4 . 6 371.6 364.3 358.2 372 - 356 Mascart [ 2?3'i6.5 S70 - 356 Virtz ............ i t-374.8 M. A. W.142 ABSTRACTS OF CHEMICAL PAPERS. Photographic Experiments on the Action of n-Rays on an Oscillating Spark. C. GUTTON (Compt.rend. 1906,142 145-149). -Rlondlot observed that when the primary spark of a Hertzian oscillator is subjected t o the action of n-rays the brightness of the secondary spark is diminished (Rev. g h t . Sci. 1905 727). The author has obtained photographic confirmation of this observation by develop- ing a photographic plate one-half of which has been exposed €or one minute to the action of the secondary spark of a Hertzian oscillator and the other half similarly exposed while the primary spark is subjected to the action of n-rays from a Nernst lamp; thirty-seven such photographs show that the brightness of the secondary spark is diminished by the action of n-rays on the primary spark The original contains full details of the apparatus employed. M. A. W. Relation between the Radioactivity and the Composition of Uranium Compounds.HERBERT N. McCoy (PhiZ. Mag. 1906 [vi] 11 176-lS6. Compare Abstr. 1904 ii 528 ; 1905 ii 366).- The author’s previous work showed that the total activity of 1 gram of pure uranium is 791 times that of 1 sq. cm. of a layer of the pure oxide U,O,,. sufficiently thick to be of maximum activity. The proof that this oxide was free from appreciable quantities of radium has now been obtained by starting with a uranium ore and continuing the pro- cesses of purification until no further change of activity occurred. The oxide U3.0 obtained as a result of these processes had practically the same activity as the pure oxide used previously which was obtained by the ignition of uranium nitrate. The oxide U,O may be used in preparing a standard of activity capable of being reproduced with an accuracy of a few tenths of 1 per cent.Ordinary uranium salts are treated successively with ammonium carbonate ammonium sulphide and barium chloride. Ammonium urmate is precipitated and converted into the oxide U,O by ignition in a current of oxygen. About 1 gram of the oxide is re- duced to an impalpable powder by grinding in an agate mortar with some freshly-distilled chloroform. It is then stirred up with more chloroform and poured into a shallow metal dish about 7 cm. in dia- meter. Spontaneous evaporation of the chloroform then leaves a uni- form adherent black film of the oxide. The total activity of 1 gram of uranium is 791 times the observed or surface activity of each sq.cm. of such a film. The totalactivity of any uranium compound may be found also by comparing the activities of films of the compound of different thick- nesses with the activity of a standard film of the oxide U,O prepared as above,and then extrapolating to zero thicknes3. This method is shown t o give good results in the case of pure uranium compounds and has further been used to determine the total activity of samples of pitch- blende gummite and carnotite. It is found that for the foregoing minerals the ratio k / P where k is the total activity of unit-mass of the mineral and I-’ is the weight of urnninm in 1 gram of the mineral is nearly constant and equal to 3280. This means that for equal content of uranium the ores are 4.15 times as active as the pure uranium com-GENERAL AND PHYSICAL CHEMISTRY.143 pounds. It is further estimated that radium is 3.3 x 106 to 4.25 x lo6 times as active as uranium. Radioactivity of Uranyl Double Salts. WILLY MARCKWALD ( B e y . 1906 39 200-203. Compare Meyer and Wendel Abstr. 1904 ii 130 ; Rimbach ibid. ii 264).-The statement of Rimbach and Grewe that certain uranium compounds exhibit greater activity than uranium itself is inconsistent with Rutherford's theory. The author has there- fore examined the behaviour of uranyl potassium nitrate uranyl thallium nitrate uranyl ethylenediamine nitrate and sulphate and uranium nitrate and finds that the intensity of the a-rays measured by an electrometer is the same i n each case. I n order to compare the intensity of the p-rays flat thin-walled glass flasks containing the salts were placed on opaque paper enclosing a photographic plate and masked with patterns of glass lead and aluminium foil ; the behaviour of the five salts was almost the same.When the flasks are placed directly on the plate the latter exhibits marked blackening due to the emission of light from the salts particularly the uranyl potassium nitrate and the uranyl ethylenediamine nitrate which by their pronounced fluorescence also differ from the other three. Diminution of the Radioactivity of Polonium with Time. [Madame] MARIE CURIE (Compt. rend. 1906 142 273-276).-A specimen of poloniferous bismuth oxide (Abstr. 1900 ii S2) 250 times more active than uranium was placed in a shallow circular cavity in a metal disc and the radioactivity measured at stated intervals of time.The diminution in the intensity of the radiation is an exponential function of the time and is expressed by the equation I=I,e-at ; the activity falls to half the original value i n 140 days. The value of the constant a which is characteristic of polonium is 0.00495 when t is measured in days and is identical with the corresponding constant (0.00497) found by Marckwald for radiotellurium (Abstr. 1902 ii 508; 1905 ii 159 623) a fact which establishes its identity with polonium the first strongly radioactive element discovered by the author and Pierre Curie. The curve obtained by plotting the time against log1 in the above experiment is a straight line and parallel lines are obtained when plates of bismuth dipped in solutions of the chloride of radioactive bismuth are used instead of the poloniferous bismuth oxide (Marckwald Abstr.1902 ii 508) or when a similar plate is covered with a sheet of aluminium 0.01 mm. in thickness. J. C. P. C. s. M. A. W. Photoelectric Effect of Selenium. CAMILLO CARPINI ( A t t i R. Accad. Lincei 1905 [v] 14 ii 667-673).-At the temperature of liquid air the photoelectric effect of selenium is detectable but very slight. Bidwell's theory according to which the action of light determines the formation of conducting selenides is hence improbable. The author found that the photoelectric effects of two preparations of selenium were 0.32 and 0-247 respectively at about 8" and 0.07 a t 96" the temperature-coefficient being hence 0.003 and 0.002 in the two cases.The resistance-brightness curve for selenium varies according as the light-intensity is being raised or diminished T. H. P.144 ABSTRACTS OF CHEMICAL PAPERS. Decomposition of Carbon Dioxide by the Point Discharge. T NODA and EMIL WARBURG (Ann. Pl~ysiJi 1906 [iv 1 19 1-13. Compare Warburg Abstr. 1904 ii 24 ; Gray ibid. 25).-Brodie using a Siemen tube found (Phil. Trans. 1874 164 83) that carbon dioxide exposed to the action of the silent discharge was decomposed to the extent of 1.5-2.7 per cent. and that about 50 per cent. of the oxygen produced was ozonised. The authors using a point discharge find that the carbon dioxide is decomposed to the extent of 3 per cent. and that about 19 per cent. of the oxygen produced is ozonised. The number of coulombs required to decompose a gram-equivalent of carbon dioxide is only 2610 which shows that the decomposition of this gas by the silent discharge is not an electrolytic process.It is shown also that of the electrical energy supplied only 1.1 per cent. is converted into chemical energy. For a negative point discharge it appears that the amount of decomposition depends only on the total electricity not on the current strength. Further the number ( N ) of coulombs per molecule OE carbon dioxide decomposed increases as the density of the gas is diminished. It is found that N falls off as the temperature rises ; but this result requires further experimental support. J. C. P. Some Concentration Cells in Methyl and Ethyl Alcohols. J. HUNT WILSON (Amer. CIm72. J. 1906,35,78-84).-Determinations have been made of the E.M.F.of some cells of the type Ag-N/lO alcoholic silver nitrate-N/ 100 alcoholic silver nitrate-Ag a t 25’ and 0’. Solutions of silver nitrate of four digerent concentrations in methyl alcohol and of three different concentrations in ethyl alcohol were employed. The results are tabulated and compared with the values of the E.M.F. calculated from Nernst’s formula. The agree- ment between the observed and calculated values is good in the case of the ethyl alcohol cells but somewhat poor in that of the methyl alcohol cells. The results indicate that Nernst’s formula is applicable t o alcoholic as well as t o aqueous solutions but further experiments are required to confirm this conclusion. E. G. Electrical Conductivity of Solutions of Compounds of Dimethylpyrone with Trichloroacetic Acid in Chloroform and Benzene.WLAUIMIR A. PLOTNIKOFF (J. Russ. Phys. Chem. Soc. 1905 37,875-881. Compare Abstr. 1905 ii 433).-The author finds that the two double compounds formed from dimethylpyrone and trichloro- acetic acid have measurable conductivities and are hence dissociated in benzene or chloroform solution. These results are in disagreement with those of Kahlenberg and Lincoln (Abstr. 1899 ii 397) and of Patten (Abstr. 1903 ii 411)’ who state that chloroform has no appreciable ionising power. T. H. P. Relation between Electrolytic Dissociation and Dielectric Constant. EMIL BAUR (Zeit. Elektroclwm. 1905 11 936-938).-1n the partition of an electrolyte between two solvents it is not unlikely that the ratio of t,he concentrations of the ions in the two solvents might be equal to the ratio of the cubes of tho dielectric constants ofGENERAL AND PHYSICAL CHEMISTRY.145 the solvents. data without any conclusive result. The author attempts to test this by means of existing T. E. Cathodic Behaviour of Sulphur Selenium and Tellurium. ERICH MULLER acd ROMUALD NOWAKOWSKI (Zeit. Ehktrochem. 1905 11 931-936. Compare this vol. ii 18 and Le Blanc this vol. ii 67). -In 0.1N potassium hydroxide solution selenium dissolves at the cathode with the valency 0.67 to 0.75 sulphur with the valency 0.57 to 0.89 and tellurium with valency about 0.9. The potentials at which solution begins (measured against the O a l i l r calomel electrode) are sulphur 0.53 volt selenium 0.804 volt tellurium 1-07 volt.T. E. Oxidation and Reduction in the Electrolysis of Salts of Iron. Z. KARAOGLANOFF (Zeit. Elektrochem. 1906 12 5-16. Com- pare Abstr. 1905 ii 674).-The rate of reduction of a ferric salt by electrolysis depends on the rate at which ferric ions can be changed into ferrous ions at the electrode and on the rate a t which ferric ions can diffuse into the layer of solution in contact with the electrode. I n a solution which is not stirred convection also occurs; owing t o the changes of composition and density in the solution near the electrode convection currents are produced which tend to keep up the concentra- tion of the ferric ions a t the electrode. The same considerations hold good for the oxidation of a solution of a ferrous salt.By an application of Sand’s method (Abstr. 1901 ii 82) the author shows that the time t during which a current i must flow in order to diminish the concentration of the ferric or ferrous ions a t the electrode to such a small value that hydrogen (or oxygen) is evolved in a solu- tion of concentration c is given by the expression i Jc=k.c. The constant k is proportional to the square root of the diffusion co- efficient of the salt,. This formula is shown t o hold good for ferrous and ferric salts so long as the current is not too small. For very small currents convection a t the electrode suffices to maintain the con- centration of the ferrous or ferric ions above the limit at which gas is evolved. The potential of the electrode during the period in which the con- centration of the iron salt is diminishing is also measured and the curves obtained are found to have the geneial form required by the assumptions that the loss of ferric ions a t the electrode is being replaced by diffusion and that the relation between the potential of the electrode and the concentration of the solution is given by Peters’ formula (Abstr.1898 ii 419). T. E. Rate of Migration of Complex Ions. JAMES W. MCBAIN (Zeit. Elektrochem. 1905 11 961-963).-A rbsunzg of the methods which have been proposed for measuring the rate of migration of complex ions (Trans. 1904 85 1305 and Abstr. 1905 ii 371). T. E. Physico-chemical Side of Organic Electrochemistry. WALTHER LOB (Zeit. Elektrochem. 1906 12 2-B).-General remarks on the146 ABSTRACTS OF CHEMICAL PAPERS inter-connection of the physico-chemical and preparative aspects of organic chemistry.T. E. New Magneto-optical Properties of Colloidal Solutions of Ferric Hydroxide. A. COTTON and H. MOUTON (Compt. rend. 1906 142 203-205).-The authors have previously shown (Conzpt. rend. 1905 141 317 349) that the property shown by certain colloidal solutions of ferric hydroxide of becoming doubly refracting (positive or negative) when placed in a uniform magnetic field and illuminated by a ray of light perpendicular to the field appears to be associated with the size and not with the nature of the particles for the double refrac- tion is greatly increased by heating the solutions whereby the size of the particles is augmented. Similar results were obtained with a solution containing minute crystals of calcium carbonate in suspension.I n the present paper it is shown that the matter in suspension in these solutions has a negative magnetic rotation greater in extent and opposite in sign to that of water so that when such a concentrated solution is diluted the magnetic rotation initially negative becomes zero and finally positive. The magnetic rotation of these solutions does not vary directly with the strength of the magnetic field (law of Verdet) but increases rapidly at first and then more slowly. The effects produced by a magnetic field on certain colloida.1 solutions are probably due to the magnetism and orientation of the particles in suspension for if gelatin is added to one of these solutions contained in a hollow glass prism and it is allowed t o solidify while placed between the poles of an electro-magnet the double refraction persists for several days after the prism is removed from the magnetic field.M. A. W. Velocity of Ions produced by a Flame. GIUSEPPE GIANFRAN- CESCHI (Mem. R. Accad. Lincei 1905 [v] 5 594-619).-The author describes a modification of J. J. Thomson’s method for measuring the velocity of ions produced by a flame. Results obtained by the new method show that the variation of the potential in the region between a flame and two plates parallel with it is sensibly the same for the positive as for the negative flame The curves representing this variation exhibit however appreciable differences according as the potential difference between the plates is high or lorn.The curve has a true maximum corresponding with the top of the flame. The force is zero in the flame but outside of the latter rapidly increases to a value which is maintained nearly up to the plate where rapid increase again occurs Just outside of the flame the electrical density produced by the ions of either sign reaches a maximum afterwards falling to a minimum which is maintained constant over a certain space ; near the plate it increases. The space over which the density remains constant is the smaller the larger the P.D. between the plates. The formuke given by J. J. Thomson and by Child do not accurately express the velocity of the ions The results obtained are better in accordance with the expression rl = 4~i/(X.dX’/clx) where i represents the current and X the electric force and x is the direction given by the commonGENERAL AND PHYSICBL CHEMISTRY.147 normal to the two plates. All the elements in this formula are measured at one and the same point PO that the velocity obtained is the true specific velocity of the ions a t that point and not merely t'he mean value over a certain space. The specific velocity of the ions depends on ( I ) the intensity of the flame ; (2) the difference of potential between the plates and (3) the distance from the flame. The numbers obtained agree very well with those given by Mache (Phys. Zeit. 1903 717) but differ from those of Child (Phgs. Review 1899 12 65) and of McClelland (Phil. Mag. 1898 46 29). The value arrived at for &/kP is in complete accord with that given by Mache (loc.cit.) and is very near to that obtained by Zeleny (Phil. Mag. 1898 46 133). T. H. P. Specific Heat of Superheated Steam. LUDWIG HOLEORN and FRITZ HENNING (Ann. Physik 1905 [iv] 18 739-756).-The authors have determined the specific heat *of superheated steam relatively to that of air and find that the mean value (ce) of the specific heat of water vapour between Oo and 0" and a t the constant pressure of one atmosphere is given satisfactorily by the forniula ce= 0*4460(1+ 0*0000960). The increase of specific heat with temperature involved in this formula is not so rapid as that which has been deduced from explosion experiments. J. C. P. Fusion Boiling-point and Vapour Composition Curves (760 mm. pressure) in the Binary Systems Ortho- + Para- Ortho- + Meta- Para- + Meta-bromonitrobenz- ene; Fusion Curves for Mixtures of Diphenylamine and Phenanthrene.J. VON NARBUTT (Zeit. physikal. Chem. 1905 53 697-714).-The boiling-point curves in the case of the isomerides rise continuously from the boiling point of the more volatile con- stituent to that of the less volatile constituent. As the differences between the boiling points of the pure substances are small the vapour cornposition curves in all cases are nearly straight lines. The fusion curves in all cases are of the simplest type consisting of two branches which meet at a eutectic point. The two curves obtained when (1) 0- (2) p-bromonitrobenzene is added to m-lwomonitro- benzene are exactly coincident whilst the two similar pairs of curves obtained when the ortho- and the para-compounds are taken as solvents exhibit a divergence.Hence the author concludes in view of Jaeger's work on the tribromotoluenes (Abstr. 1905 ii 304) that the crystallo- graphic symmetry of 0- and p-bromonitrobenzene is close m- bromonitrobenzene belonging to a different category. The author makes a detailed comparison of the actual fusion curves obtained with the '( ideal " fusion curves calculated from Le Chatelier's formula (Abstr. 1894 ii 272). The agreement is generally good. J. C. P. Modification of Beckmann's Boiling-point Apparatus. ERWIN RUPP (Zeit. physikal. Chem. 1905 53 693-696).-1n order to permit the determination of the weight of the solvent as well as its volume the apparatus described by Beckmann (Abstr. 1902 ii 303 ;118 ABSTRACTS OF CHEMICAL PAPERS.1903 ii 533) has been slightly modified. Instead of the inner tube being fused into the outer tube the latter is provided with a ground neck into wbich the former fits. The various operations necessary for a molecular weight determination by this modified apparatus are described in detail. ERNST ERDMANN (Bey. 1906 39 192-194).-The method described by Wohl and Losanitsch (this vol. ii 72) has been already used by the author and also by Valentiner and Schmidt (Abstr. 1905 ii 704). The author's method consists in using a glass tube containing charcoal from cocoanut shells in conjunction with the apparatus already described (Abstr. 1904 ii 20). The need f o r an absolutely air-tight apparatns is insisted on. J. J. 8.[Distillations in High Vacua.] ALFRED WOHL (Bey. 1906 39 513-514).-A reply to E. Erdmann (preceding abstract). C. S. Heat of Neutralisation of Strong Acids and Bases as affected by Temperature and Concentration. A. WORMANN (Awz. Physik 1905 [ iv] 18 775-795).-The heat of neutralisation (s) has been determined for several strong acids and bases a t tempera- tures between 0' and 32'. The variation of s with temperature ( t ) over this interval is satisfactorily represented by the formula s = so At in which so is the heat of neutralisation a t Oo and A is a constant. It mill thus be seen that the temperature-coefficient of the heat of neutralisation increases as the temperature rises. The value of s for potassium salts is greater than for the corresponding sodium salts and the decrease of s with rising temperature is more marked for the sodium salts than for the potassium salts.There is no appreciable difference in the values of s for nitrate and chloride although the temperature-coefficient is rather greater in the first case. The heat of neutralisation is independent of the concentration in solutions between N/2 and N/lO strength. I n N-solutions the heat of neutralisation is greater wliilst trustworthy measurements could not be made in solu- tions of less than N/10 strength. Constant Temperature Bath for Low Temperatures. A. GIVEN (J. Amer. Chernh. Soc. 1905 2'7 1519-1524).-A bath is described which is designed to maintain the water in it at a constant tempera- ture of 15*6" and is particularly suitable for adjusting the temperature of pyknometers in sp.gr. determinations. The temperature is regulated by the use of a large ice-box immersed in the water andalso by means of a Bunsen burner connected with a gas-regulator. The pyknometers are supported on a shelf and kept immersed in the water in the bath. Modifications have been devised for giving a temperature of 20'. For details of the apparatus the description and diagrams in the original must be consulted. Direct Proportionality between the Freezing Point of a Mineral Water of the Acid Carbonate Class and the Composi- tion of the Water expressed in terms of the Anhydrous Salts and Normal Carbonates. LUCIEN GRAUX (Compt. rend. 1906 142 166-167).-The freezing point of a solution containing J. C. P. Distillations in High Vacua. J.C. P. E. G.GENE 11 A 11 AND PHYSIC A L CH E M 1 STRY . 149 1/10 gram-molecule of sodium carbonate per litre is - 0.455' whilst that of the corresponding solution of sodium hydrogen carbonate is - 0.389' or practically the same as that of a solution containing 1/20 gram-molecule of sodium carbonate per litre namely - 0.356". It follows therefore that the osmotic pressure of a solution of sodium hydrogen carbonate is determined by sodium carbonate molecules only the carbonic acid behaving from the cryoscopic point of view as if it were entirely free and the freezing point of R mineral water of the acid carbonate class is proportional to the number expressing the composi- tion of the water in anhydrous salts and normal carbonates. M. A. W. Osmotic Pressure of Dilute Aqueous Solutions.PERCIVAL S. BARLOW (Proc. Camb. Phil. Soc. 1905 13 (iv) 229-240. Compare Abstr. 1903 ii 507).-Details of experiments on the measurement of the osmotic pressure of dilute solutions are recorded. On account of the impurities absorbed by the outer water from the air and the slight solubility of the material of the pot the values obtained for the pressure of very dilute solutions are too small. When the first source of error is guarded against the experimental values approach more closely to the theoretical ones but still exhibit considerable deviations. H. M. D. Organic Solvent and Ionising Media. 11. PAUL WALDEN (Zed. physikccl. Chem. 1906 54 131-230. Compare Abstr. 1904 ii 227).-The author has studied the dissociating power of 49 solvents by taking one solute throughout namely tetraethylammonium iodide and determining the equivalent conductivity A for various dilutions a t the temperatures 0" and 25".The value of A wits obtained by calcula- tion and extrapolation and the degree of dissociation a was calculated for each solution by the usual formula a=A/Am. In the great majority of cases A increases with the dilution as in aqueous solutions ; the irregular variation of A for a few solvents (aldehyde and acetic acid for example) is attributed to interaction between solvent and svlute. The author's results are in harmony with the Nernst-Thomson rule and show clearly the close parallelism between the dielectric constant of the solvent and its dissociating power; the greater the dielectric constant of the solvent the greater for a given dilution is the degree of dissociation of the tetraethylammonium iodide. This will be seen from the following table in which the solvents which behave normally in regard to variation of A are arranged according to their dielectric constants the corresponding data for writer being added for the sake of comparison.The degrees of dissociation are recorded for Ar/lOO N/lOOO and N/ZOOO solution ; E is the dielectric constant a t 20". It will be observed that the dissociating power of solvents belonging to the same homologous series diminishes from the first member upwards (for example methyl alcohol and ethyl alcohol ; methyl thio- cyanate and ethyl thiocyanate ; benzonitrile and pheiylacetonitrile). Certain solvents (for example acetaldoxime and tetranitromethane) which do not appear in the following table supply in another way it150 ABSTRACTS OF CHEMICAL PAPERS.Solvent. Water ..................... Formamide ............... G lycollonitrile ............ Succiiionitrile ........... Citraconic anhydride ... Nitroniethane ............ Lactonitrile ............... Acetonitrile ............. Methyl thiocyanate ... Ethyleiie glycol ......... Nitrobenzene ............ Methyl cyanoacetate . Propionitrile ............ Ethyl thiocyaiiate . . . Ethyl cyanoacetate ...... Benzonitrile ............... Epichloroh ydrin ......... Ethyl alcohol ............ Acetone ................. Ethylthiocarbimide ...... Fur fu ral ci e h y de ......... Methyl alcohol.. . . . . . . . Acetylacetone ...........Acetic anhydride ........ Benzaldehy de ............ Phenylacetonitrile ...... Acetvl bromide ......... E. 81.7 84.0 67.9 57'3-6 1 ' 2 39.5 38 *2-40*4 36.5-39'4 37 +7 35.8-36.4 33 '3 - 35.9 34.5 33.4 - 37'4 32 -5-3 4 *a 28% 2 6 ' 5-27'2 26'5-31 *2 26.2-26.7 26'0 26.0 (2) 25 '1-26'0 2 1 *7-2 7 '4 20*7-21*9 19 $4-22 '0 17.9 15*0-16*7 16-2 145-1 6 '9 Anishdehyde ............ 15.5 Percentage dissociation. A A 3 a t 25". *=loo. 2;=1000. v=2000. 112 91 25 93 71.5 93 35.5 (60") 90 22.5 82 120 78 50 about 78 40 200 96 8 40 124 29.5 165 84.5 28 *2 56.5 66'8 79 60 225 106 76 42.5 36 114 16.5 Acetyl chioride ........... 15.5 about I f 2 Salicylaldehyde ........... 13 '9 25 Methyl sulphate ......... 46.5 43 Ethyl sulphate ............ about 30'0 as-Ethyl sulphite .........38.6 26.4 s-Ethyl sulphite ......... 16.0 76 43 - 74 77 78 71 73 69 65 63 65 61 60 54 50 58 51 46 47 46 34 - - - - - - - 98 98 98 95 93 92 91 89 90 a9 89 88 88 84 a4 83 83 80 81 83 78 74 66 79 73 74 73 76 72 55 91 84 94 50 99 98 99 96 91 93 93 91 92 91 90 90 87 87 86 87 84 85 87 a2 80 84 78 79 78 81 79 61 93 a6 95 61 - - confirmation of the Nernst-Thomson rule. These two substances con- trary to expectation exhibited practically no dissociating power and were found to have very low dielectric constants about 3.4 and 2.2 respectively. Compare also Dutoit and Friderich Abstr. 1S99 ii 350 ; Jones and Carroll Abstr. 1905 ii 73) conductivity is determined by the association or polymerisation of the solvent molecules but the author's results are quite opposed to this view showing as they do ( I ) that the value of A has nothing to do with the association factor of the solvent (2) that solutions of high conductivity are obtained even with non- associated solvents.There is remarkable variation in the values of A for the different solvents but there is no simple relationship between these values and the dielectric constants. It is shown however that for the great majority of the solvents the product of A and the temperature-coefficient of conductivity is approximately a constant and equal t o 1.30 on t,he average. Another empirical Ielstionship found to be widely applicable for differens solvents is the one expressed by the formula c vF= const. In According to Dutoit and Aston (Abstr. 1897 ii 546.GENERAL AND PHYSICAL CIIEMISTRP.151 this expression 6 is the dielectric constant of the solvent and u is the dilution at which in that solvent the degree of dissociation of the tetraethylammonium iodide has a given value. With acetonitrile and epichlorohydrin other solutes were used besides tetraethylammonium iodide and it was shown that in these two solvents Kohlrausch’a law of the independent migration of the ions is valid. J. C. P. Solubility of Mercuric Chloride in Ethyl Acetate and Acetone. A. H. W. ATEN (Zeit. physikal. Chem. 1905,54,121-123). -To test a theoretical point referred to in a recent paper (Roozeboom and Aten Abstr. 1905 ij 803) the author has redetermined part of the solubility curves fo_r mercuric chloride in ethyl acetate and acetone originally studied by Etard (Abstr.1894 ii 442). The chief point of interest is the evident formation of a compound of mercuric chloride and acetone. Below loo mercuric chloride is a t first readily dissolved by acetone but after a time the compound HgCl,,CORle is deposited from the clear solution. The two separate solubility curves obtained when mercuric chloride and the compound respectively are the solid phases intersect at 1 3 O and 27 molecular per cent. of mercuric chloride. The transition point is far removed from the composition of the compound and the latter must be largely dissociated in the solution. The solubility curves for mercuric chloride itself in both ethyl acetate and a2etone are nearly parallel to the temperature axis. The values obtained for the solubi!ity are for both solvents markedly less than the values recorded by Etard.J. C. P. Solid Solutions. FR~D~RIC WALLERANT (Compt. rend. 1906 142 100-101).-When fused ammonium nitrate containing 20 t o 7 per cent. of potassium nitrate is cooled two kinds of crystals separate simultaneously above 1 0 4 O one isomorphous with potassium nitrate and containing 80 per cent. of ammonium nitrate; the other belong- ing to the tetragonal system and containing 93 per cent. of the ammonium salt; a t 104O the mixture becomes opaque and mono- clinic crystals are gradually formed at the expense of the two first- formed varieties. The inverse phenomenon is observed in the case of mixtures of czesium and ammonium nitrates. On cooling a fused mixture of 2 parts of ammonium and 1 part of czsium nitrate cubic crys- tals are first formed which on further cooling pass into rhombohedral crystals isomorphous with czsium nitrate ; these are slomly transformed into a conglomerate of two kinds of mixed crystals one quadratic and isomorphous with that form of ammonium nitrate which is stable at 83-12P (compare Abstr.1904 ii 31) the other rhombohedral arid isomorphous with c2esium nitrate. These two results afford illustrations of the phenomena of diffusion and crystallisation occurring in isomorphous mixtures which according to van’t Hoff are t o be regarded as solid solutions. M. A. W. Mixed Crystals of Alkali Nitrates. FR~DERIC WALLERANT (Compt. rend. 1906 142 168-169. Compare Abstr. 1904 ii 31 ; 1905 ii 161 237 380 ; and preceding abstract),-Ammonium arid rubidium nitrates mix in all proportions to form mixed crystals,152 ABSTRACTS OF CHEMICAL PAPERY. belonging to three crystalline systems one rhombohedral and iso- morphous with rubidium nitrat.e ; a second isomorphous with ammonium nitrate ; whilst the third is orthorhombic and isomorplrous with thallium nitrate the two crystals having in fact identical physical properties.A t the ordinary temperatnre potassium and ammonium nitrates form a discontinuous series of mixed crystals belonging to three different systems the first being orthorhombic and isomorphous with potassium nitrate the second monosymmetric and isomorphous with that variety of ammonium nitrate which is stable between 38' and 82" and the third isomorphous with ammonium nitrate. M. A. W. Origin of the Conception of Solid Solutions.P. E. LECOQ DE BOISBAUDRAN (Compt. rend. 1906 142 195-196. Compare Wallerant preceding abstracts).-A claim for priority (Abstr. 1892 398). M. A. W. A Crystalline Modification Stable in Two Intervals of Temperature. F R ~ D ~ R I C WALLERANT (Compt. vend. 1906 142 217-219).-When the orthorhombic variety of ammonium nitrste which is stable a t 3 2 O is cooled i t breaks down a t - 16" into hemi- tropic plates which slowly change into quadratic crystals and not into rhombohedral crystals as stated originally (Abstr. 1904 ii 31). This quadratic variety of ammonium nitrate is stable between - 16' and - 40' and is identical with the quadratic variety which is stable between 82" and 32'. M. A. W. Influence of the Colouring Matter of the Mother Liquor on the Form of Crystals deposited in it (Phthalic Acid).P. GAUBERT (Compt. Fend. 1906 142 219-221).-When phthalic acid is crystal- lised from aqueous solutions coloured with organic dyes the normal form and size of the crystal are modified and the crystals absorb a small quantity of the colouring matter becoming coloured but not uniformly throughout their mass. The amount of colouring matter absorbed is very small (1/220 in the case of bismarck-brown) and has no influence on the density melting point or angular values of the crystal. The artificially coloured crystals exhibit pleochroism. The original contains a description of the dominant forms of the crystals of phthalic acid deposited from solutions containing methylene- blue magenta rosaniline bismarck-brown biebrich-scarlet malachite- green methyl-green methyl-violet or diphenylamine- blue.M. A. W. Laws of the Reciprocal Action of Solid Substances in Cryohydrate Mixtures and in Eutectic Alloys. FLAVIAN M. ELAWITZKY (J. Russ. Php. Chem. Soc. 1905 3'7 862-875).-The author deduces the following relations between the compositions and solidifying points of cryohydrate or eutectic mixtures and the solidi- fying points of their components. 1. Law of Equal kfo~ecu~cir Freezing-point ~e~ress~o~as.-Assurning that the molecular freezing-point depressions of each of two sub-GENERAL ANb PHYSICAL CHEMISTRY. 153 stancesin the other are equal as is often the case it is shown that the ratio between the amounts of the two present in the eutectic mixture is represented by the expression no= JMITl/ ,/m where To and T1 are the differences between the freezing point of the eutectic mixture and those of the two components having the molecular weights Mo and Ml and rzo the ratio between the percentage contents of the second and first of the two compounds present in the mixture.2. Law of Mukiple Molecular Depressions.-When however the two substances with molecular weights of Mo and 2cfl occur in the solid form in a polymerised or associated state the association factors being p and q the relation becomes no= Jml/ ,&To from which the association ratio p g can be calculated. 3. Law of the Equavcclence of Molecular Freezing-point Depressiom.- This law states that the degree of polymerisation is a characteristic constant for any substance and remains unchanged in binary mixtures.T. H. P. Chemical and Electrical Study of the Equilibria 6H’ + 51’ + 10,’ VIKTOR SAMMET (Zeit. physikal. Chem. 1905 53 641-691).-Full details are given of work already reported (see Luther and Sammet Abstr. 1905 ii 508). J. C. P. Acceleration of certain Oxidation Reactions by Hydrogen Cyanide ARTHUR S. LOEVENHART (Ber. 1906 39 130-133. Com- pare Kastle and Loevenhart Abstr. 1903 ii 53$).-Whilst some catalytic reactions are retarded by hydrogen cyanide it accelerates the catalytic decomposition of hydrogen peroxide by copper or iron or their salts and therefore accelerates also oxidations such as that of formic acid or of phenolphthalin by hydrogen peroxide in presence of copper sulphate (compare Weehuizen Abstr.1905 ii 489). This is explained on the assumption that the first stage in the catalytic decomposition as also in the oxidation is the formation of an additive compound of hydrogen peroxide and the catalyst. Those substances which decom- pose hydrogen peroxide catalytically must be capable of existence in two states of oxidation and the velocity of the oxidation by means of hydrogen peroxide must depend on the ease with which the catalyst changes from one state of oxidation to the other. Whilst cupric sulphate is reduced to cuprous sulphate only by strong reducing agents the hydrogen cyanide converts it partially into cupric cyanide which readily changes into the cuprous salt. 31 + 3H,O and 6H’ + 5Br’ + BrO,’ Z 3Br + 3H,O. G. Y. Velocity of Electrolytic Reduction of Azobenzene.P. FARUP (Zed. physikal. Chem. 1906 54 231-251. Compare Haber Abstr. 1900 ii 257; Haber and RUSS Abstr. 1904 ii 309)-A silver nitrate voltameter and a cell containing an alkaline solution of azo- benzene in aqueous alcohol mere placed in series and a suitable current passed. The volume of hydrogen evolved in the cathode compartment of the azobenzene cell was compared with the weight of silver deposited in the voltameter and the amount of azobenzene reduced could thus be calculated. The azobenzene cell was provided with a rotating cathode VOL. XC. ii. 11154 ABSTRACTS OF CHEMICAL PAPERS. and the author has studied the manner in which the velocity of reduction is influenced by the rate of revolution of the cathode by the concentration of the azobenzene and by the composition of the solvent.For a given concentration the velocity of reduction increases as the number of cathode revolutions increases but gradually approaches an upper limit when the speed of revolution is very great. The velocity of reduction being represented by the formula dxldt = &(a - %)?a it is found that for moderately concentrated solutions (0.07-0.025 normal) and a low speed of revolution n = 1 nearly ; for higher speeds of revolu- tion n gradually diminishes and becomes =2/3 when the number of revolutions is 300-1000 per minute and =fr when the speed has risen to 5000-6000 per minute. The velocity of reduction is little affected by altering the relative proportions of water and alcohol but falls off slightly as the concentration of sodium hydroxide increases. J. C. P. New Form of Water-pump ANTOINE VILLIERS ( A m . Chim. anal. 1906 11 9).-In this apparatus the water enters a bulb in which is a small hole fitting immediately above the narrow end of a conical tube. The bulb and tube are surrounded by a wider tube and bulb the latter being provided with a side-tube through which the air is drawn. The outer tube is constricted to fit the bottom of the inner conical tube. w. P. s. Delivery Funnel for introducing Liquids under Increased or Diminished Pressure. T. J. BRYAN (3. Amer. Chem. Xoc. 1906 28 80-84).-The apparatus described is a modification of the ordinary stoppered tap-funnel. From the top of the pear-shaped bulb a side- tube passes downwards and opens into a wide tube surrounding the long delivery tube of the tap-funnel. The upper end of this wide tube is sealed on to the delivery tube; it passes through the cork of the reaction flask into which it opens a little below the cork. The space above the liquid in the bulb of the tap-funnel is thus brought under the same pressure as that in the flask and on opening the tap the liquid runs in by its own weight. Modifications of the apparatus are described with the aid of diagrams. E. G. A New and Improved Chronograph. ROBERT L. MOND and MEYER WILDERMANN (Zeit. physikal. Chem. 1906 54 294-304).- For illustrations and details of construction the original must be con- sulted. J. C. P. Shaking Machine. ALFRED MANDL and FRANZ Russ (Chem. Zeit. 1906 30 19).-The apparatus consists of a metal box the temperature of which may be kept constant by means of a thermo- regulator ; inside the box is the shaking apparatus proper for details of which the original paper must be consulted. P. H.

ISSN:0368-1769    

DOI:10.1039/CA9069005137

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. 155 Inorganic Chemistry. Density of Ice. ANATOLE LEDUC (Conzpt. re?zd. 1906 142 149-151).-The author has redetermined the sp. gr. of ice by weighing the water which when frozen fills a flask of known volume (about 100 c.c.) up to a definite mark. I n order to expel completely all the dissolved air the water which had been boiled previously was frozen in a vacuum melted and frozen again and the operation repeated three or four times until on finally freezing the water very gradually under atmospheric pressure but protected from the atmosphere by a column of liquid vaseline the ice obtained was quite transparent. The value thus obtained for the sp. gr. of ice a t 0' is 0.91752 or correcting for the contraction of the glass vessel 0.9176 and differs by about 0.1 per cent.from the value obtained by Bunsen who used the same method but did not repeat the freezing operation. The author there- fore draws the conclusion that water cannot be completely deprived of dissolved air by prolonged boiling; it still contains about 1 C.C. of dissolved gases per litre. M. A. W. Action of Strong Hydrochloric Acid on Potassium Chlorate in Presence of Potassium Iodide or Bromide and the Esti- mation of Ghlorate. HUGO DITZ (Zeit. angew. Chenz. 1906 19 A. H. RICHARDS ( J . Xoc. Chem. Ind. 1906 25 4-5).-When liquid bromine is added in large excess to an almost saturated solution of silver nitrate bromous acid is formed probably according to the equations Br + AgNO + H,O = AgBr + HNO + HBrO ; HBrO + Br + 2AgN0 + H,O = 2AgBr + ZHNO + HBrO,. The presence of bromous acid in the filtered solution was proved as follows a portion of the solution from which the excess of bromine had been removed by a current of air was first made alkaline with sodium hydroxide and after the addition of potassium iodide rendered slightly acid with sulphuric acid.The iodine liberated by the oxygen from the bromous acid was then determined by titration with sodium thiosulphate. A second portion of the original mixture after filtration and extraction with carbon disulphide to remove free bromine was reduced with sulphurous acid the excess of this reagent being subsequently removed by means of potassium permanganate. After making the solution alkaline with sodium hydrogen carbonate the amount of bromide was determined by titration with N/lO silver nitrate.From the above experiments the ratio of oxygen to bromine was found to agree closely with that required by the formula HBrO,. A further portion of the filtered solution from which excess of bromine had been removed by a current of air mas made alkaline with sodium hydroxide treated with excess of sodium bromide and made acid with sulphwric acid ; the bromine thus liberated was estimated by 66).-Polemical. A reply to Kolb (this vol. ii 15). L. DE K. Existence of Bromous Acid. 11-2156 ABSTRACTS OF CHEMICAL PAPERS. blowing it into a solution of potassium iodide and titrating the iodine by means of sodium thiosulphate. The difference between this amount of bromine and the bromine existing in the solution as shown by the second experiment gave the amount of bromine liberated from the hvdrobromic acid it was found to be in agreement with the equatioi 3HBr + HBrO = 2Br2 + 2H,O.These results were confirmed by repeating the last experiment using the amount of sodium bromide required by the above equation instead of adding as before an excess and finding that at the conclusion of the experiment the solution contained only the faintest traces of bromide. P. H. Rapid Preparation of Hydriodic Acid Solutions. F. BOD- ROUX (Compt. rend. 1906 142 279-280).-A solution of hydriodic acid is obtained readily by mixing equivalent quantities of iodine and barium peroxide in hot water adding a second equivalent of iodine to the solution and passing a stream of sulphur dioxide through the solution until it becomes colourless ; the barium sulphate is separated by filtration and the filtrate which contains hydriodic acid and a trace of sulphuric acid is concentrated by distillation. By this method 140 grams of a solution of hydriodic acid boiling a t 127' and having a sp.gr. 1.67 can be prepared in three hours. M. A. W. Chemical and Geological History of the Atmosphere. IV. JOHN STEVENSON (PhiZ. Mug. 1906 [vi] 11 226-237. Compare Abstr. 1905 ii 239).-In a former paper it was pointed out that the proportion of carbon dioxide in the atmosphere must have varied within wide limits in geological history and that t h i s has been of great importance in bringing about changes in terrestrial climate; in the present paper the question as to whether the amount of this gas is a t present increas- ing or decreasing is considered.The available analytical data are not sufficient to decide this point as it is only recently that su5ciently ac- curate met4hods have been employed and local and temporary variations are ,pery difficult to allow for but it is suggested that some- thing may be learnt by comparison of the proportion of carbon dioxide in inland air with that above the sea as the latter is a great reservoir of the gas and owing to its great depth and volume it may be expected to lag behind the atmosphere with respect to variations and thus exert a regulating effect. From the results of Thorpe and others the conclusion is drawn that the proportion is smaller in the latter case so that the amount of carbon dioxide is probably slowly increasing.Among other factors the effect of increased coal consumption is discussed. It is considered probable that if the increase continues a t the same rate as in recent times the greater proportion of carbon dioxide arising from this cause will be appreciable in 20 years and in 100 years will be sufficient to bring about modifications in climate. The effect of changes in the amount of this gas on plant evolution is also considered. It is pointed out that the estimates of the age of the earth arrivedINORGANIC CHEMISTRY. 157 at from physical and geological data are subject to great uncertainty; in particular the estimate of Lord Kelvin deduced from the rate of cooling may have to be greatly moditied when the high absorptive power of carbon dioxide for radiant energy is taken into account. G.S. Amorphous Sulphur. 111. Nature of Amorphous Sulphur and the Influence of Foreign Substances on the Behaviour of Supercooled Fused Sulphur. ALEXANDER SNITH and W ILLIS B. HOLMES (Zeit. physikal. ’Chem. 1906 54 257-293).-Numerous experiments are described which have contributed t o the results already communicated (Abstr. 1903 ii 139 284 ; 1905 ii 382 580). J. C. P. The System Sulphur-Chlorine. A. H. W. ATEN (Zeit. physikal. Chem. 1905 54 55-97. Compare Ruff and Fischer Abstr. 1903 ii 204; Roozeboom and Aten Abstr. 1904 ii 3!34).-The vapour pressures of mixtures of sulphur chloride and chlorine have been determined a t various temperatures and the character of the variation of vapour pressure with composition shows that a t Oo the compound SC1 is present in the mixtures and is partly dissociated.The variation of boiling point with composition for mixtures of disulphur dichloride and chlorine confirms the existence of the compound SCl and indicates also the existence of the compound SC1,. It appears further from these boiling-point curves that disulphur dichloride is dissociated to a small extent at its boiling point. It has been possible to determine the boiling point of mixtures containing only the molecules S,C1 and Cl for freshly-prepared mixtures of these substances are yellow i u colour whilst mixtures which have stood for some time are red have a different boiling point and may be shown to contain at least one compound (SC1,). It thus appears that the forma- tion of the compound SCI from S,CI + C1 takes place more or less slowly.Dilatometer experiments which confirm the existence of the compound SCl indicate that its formation is a catalytically ac- celerated reaction and it is probable that the substance responsible for the acceleration is the compound SC14.. Fusion curves have been determined for mixtures of sulphur chloride and chlorine and of disulphur dichloride and sulphur. The phenomena observed in the former case correspond in the main with those of the ternary system S,Cl + SC1 + C1,. J. C. P. Conditions of Precipitation and of Solution of Metallic Sulphidea. GIUSEPPE BRUNI and MAURICE PADOA (Alti R. Accad. Lincei 1905 [v] 14 ii 525-528).-1n deriving a general theory of the formation of metallic sulphidea and similar precipitates on the basis of the law of mass action and the electrolytic dissociation hypothesis Ostwald (“ Wiss.Grund. anal. Chem.,” 1904) stated that the equilibrium H,S + ZnC1 2HC1+ ZnS can be displaced towards the right or towards the left that is the sulphide will be precipitated or dissolved according as the concentration of the hydrogen sulphide in the solution is increased or diminished,158 BBSTRACTS OF CHEMICAL PAPERS. To test this statement the authors have examined the action of hydrogen sulphide under pressures of about 14-16 atmospheres on solutions of certain metallic salts the reaction of the solution being such that no precipitate would be formed under the ordinary pressure. The hydrogen sulphide was liquefied in the bottom of a stout glass tube immersed in a mixture of solid carbon dioxide and ether in a Dewar’s vessel a small test-tube with a glass rod fused into the bottom to serve as a foot and containing the salt solution being subsequently added.The stout-walled tube was then sealed up in the blowpipe flame and allowed to assume gradually the ordinary temperature of the air at which the hydrogen sulphide exerts the pressure given above. Concentrated solutions of ferrous zinc and cadmium sulphates and of cobalt and nickel chlorides all containing acid yielded abundant precipitates of the corresponding sulphides but inanganous sulphate gave no precipitate under these conditions. After a few days the sealed tubes were again immersed in the freezing mixture when it was found that none of the precipitates underwent solution; the zinc sulphide dissolved on heating the liquid. The explanation of the fact that the sulphides do not dissolve when the pressure in the tube is lowered is not clear.No precipitation is produced by passing hydrogen sulphide tbrough an acid solution of cadmium sulphate if the surrounding space is kept a t a low pressure. Also cadmium sulphide after precipitation in the ordinary way redissolves completely if a current of air or hydrogen is passed subsequently through the solution. T. H. P. Electrolytic Oxidation of Ammonia and its Dependence on the Material of the Anode. ERICR MULLER and FRITZ SPITZER (Zed. Elektrochem. 1905 11 917-931).-A solution containing sodium hydroxide and ammonia is used and the cathode surrounded by a cell of porous earthenware.At a platinum anode a large quantity of gas is evolved (nitrogen with a little oxygen) and sodium nitrate and traces of nitrite formed in solution. The anodic polarisation of the platinum is greater in presence of ammonia than it is in a solution of sodium hydroxide probably owing to the formation of nitrate. With anodes of copper nickel iron and cobalt the products are nitrogen oxygen and sodium nitrite ; the proportions in which these are formed depend on the metal used ; with cobalt some nitrate is also formed. The anodic potential is in all cases lower than that observed with platinum. The anodic potential of platinum is much diminished by the addition of salts of copper nickel cobalt or silver to the electrolyte; the pro- ducts also become similar to those obtained with anodes of the metals in question.The platinum anode becomes coated in these cases with the oxide of the metal added. The same effect is obtained by using a platinum anode previously coated with the oxide of one of the metals mentioned . A copper anode soon becomes coated with copper oxide a d the oxidation of ammonia to nitrite then takes place almost quantita- tively. T. E.INORGANIC CHEMISTRY. 159 Production of Nitrites and Nitrates by the Electrolytic Oxidation of Ammonia in the Presence of Cupric Hydroxide. 11. WILHELM TRAUBE and ARTHUR BILTZ (Ber. 1906 39 166-178. Compare Abstr. 1904 ii 727; also Muller and Spitzer ibid. 1905 ii 242 and preceding abstract).-The nitrate in all the experi- ments was estimated by Busch’s method (Abstr.1905 ii 282). The following are the chief conclusions obtained from numerous ex- periments. Ammonia can be oxidised electrolytically a t the anode provided copper salts and an alkali hydroxide are present. A soluble alkaline earth may be substituted for the fixed alkali. When no free alkali is present the formation of nitrite ceases but if care is taken to keep the anode compartment permanently alkaline the pro- duction of nitrite continues until a very concentrated solution is ob- tained. I n addition to the nitrite formation a small amount of nitrate is also produced a t the expense of the nitrite. The amount of this is small at the beginning but tends to increase even when an excess of alkali is present as the ratio concentration of nitrite/con- centration of ammonia increases.The conversion of nitrite into nitrate in the strongly alkaline liquid is accelerated by the presence of small amounts of cupric hydroxide. This has been proved by parallel experiments with solu- tions the one containing the copper hydroxide and the other not but otherwise identical in all respects. If the amount of alkali hydroxide in the anode compartment becomes less and less and finally completely disappears so that a t the end only an ammoniacal solution is present it is found that a rapid oxidation of nitrite to nitrate occurs but even this is accelerated by the presence of the cupric hydroxide so long as free alkali is still present. The amount of copper used in the experiments was small never more than 0.38 gram per 100 C.C.of solution. When solutions containing ammonia and cupric hydroxide are electrolyged with platinum or iron electrodes the formation of a thin black deposit on the anode is observed. This deposit is apparently a peroxide of copper. J. J. S. New Hydroxylamine-sulphonic Acids. FRITZ RASCHIG (Ber. 1906 39 245-248. Compare Ahstr. 1887 549 635; Haga Trans. 1904 85 78 ; ibid. 1906 87 240).-Potassiurn hydroxylamineiso- didphonate S0,K.N H*O*SO,K separates in hard crystals from a slowly cooled solution of potassium hydroxylaminetrisulphonate in hot slightly acidified water. It differs from the ordinary disulphonate in forming anhydrous crystals and in not giving a coloration with lead peroxide in warm water; it is stable at looo whereas the tri- sulphonate which contains the same percentage of sulphur and potass- ium undergoes decomposition at this temperature.The imino- hydrogen atom is replaceable by metals. Excess of boiling dilute hydrochloric acid decomposes the isodisulphonate into sulphuric acid and hydroxylamine. The intermediate isomonosulphonic acid has not been isolated ; it differs from the known hydroxylamine-monosulphonic acid OH*HN*SO,H in possessing oxidising properties liberating160 ABSTRACTS OF CHEMICAL PAPERS. iodine from potassium iodide and is therefore regarded as the amide OTTO RUFF and HUGO GIGAF [and in part HELLER] (Ber. 1906 39 67-7l).-Arsenic pentafluoride prepared by the action of bromine and antimony pentafluoride on arsenic trifluoride is a colourless gas which condenses a t - 53" to a clear pale yellow liquid and solidifies at - SO" to a white mass.It dissolves in water and in alkalis with development of heat and fumes in the air like sulphur trioxide. I t does not attack dry glass when cold but a vigorous action results if a trace of moisture or of hydrogen fluoride is present; silicon lias no action when cold but on heating arsenic and silicon tetrafluoride are produced. Most metals act on the gas in a similar way liberating arsenic The gas has tho normal composition and vapour density for the formula AsF,. of Caro's acid H,N*O*SO,H. c. s. Arsenic Pentafluoride. T. M. L. a- and p-Silicic Acids. FRANZ MYLIUS and ERICH GXOSCHUFF (Ber. 1906 39 116-125).-A solution A containing 1 per cent. of silicon dioxide and 0.97 per cent. of sodium chloride is prepared by mixing the required amount of hydrochloric acid with an aqueous solution of the sodium silicate Na,Si,O (Kohlrausch Abstr.1893 ii 166). The a-silicic acid in this solution differs from colloidal or p-silicic acid in that it is not precipitated by egg-albumin at 0-18" by methylene-blue or by sodium hydroxide. A solution of a-silicic acid may be obtained also by neutralisation of a cooled aqueous solution of silicon chloride with sodium hydroxide. a-Silicic acid changes when heated or more slowly a t the laboratory temperature into colloidal silicic acid which is precipitated by egg-albumin even from solutions containing 0.02 per cent. of silicon dioxide. The conversion of the a- into the P-modific,ation is accelerated by t he presence of sodium silicate and therefore if the sodium silicate solution is neutralised fractionally the P-silicic acid only is obtained.The change from the a- into the P-modification is accompanied by a change in the conductivity of the solution from k x lo6 = 14,032 for the freshly-prepared solution A t o k x lo6 = 14,083 for a solution seven days old and by a change in the freezing point from -0.648" for the freshly-prepared solution to - 0.608O after three days a t Oo t o - 0*580° after two days at lS" and to - 0.530" after one and a half hours a t 100'. The molecular weight of a-silicic acid is calculated to be about 155 ; that of colloidal silicic acid has been shown by SabanBeff (Abstr. 1891 145) to be not less than 49,000. If the solution A is cooled to - 20" ice separates and there remains a watery liquid from which sodium chloride is precipitated on addition of alcohol; when evaporated the liquid deposits crystals of sodium chloride together with an amorphous mass of hydrated silicon dioxide. I f cooled to - 25" the liquid deposits a further quantity of ice and forms a cryohydrate which solidifies ; this when warmed again becomes liquid without depositing silicon dioxide.Whilst solutions of alkali silicates of the types R,SiO R.,SiO and R,Si,O which are strongly hy drolytically dissociated contain only a-silicic acid solutions of commercial water-glass contain alsoINORGANIC CHEMISTRY. 161 /%silicic acid as the solutions obtained on neutralisation immediately precipitate egg-a1 bumin. G. Y. Sodammonium and Potassammonium. ALEXANDRE JOANNIS (Ann.Chim. Phys. 1906 [viii] 7 5-118).-A detailed account of the work done by the author on sodammonium and potassammonium during the past seventeen years (compare Abstr. 1890 ii 209 319 560 643; 1891 ii 642; 1892 ii 275 773; 1893 ii 115 462 520; 1894 ii 280; 1895 ii 75; 1905 ii 450); a complete bibliography is appended. M. A. W. Volatility and Dissociation of Alkali Carbonates. PAUL LEBEAU (Bull. Xoc. chim. 1906 [iii] 35 5-S. Compare Abstr. 1903 ii 477 ; 1904 ii 181 ; and von Wittorf Abstr. 1904 ii 400),- A known weight of the alkali carbonate was placed in a platinum boat and heated in a porcelain tube through which a slow current of carbon dioxide was passed the tube being heated in an electric furnace. Under these conditions lithium carbonate proved to be non-volatile when heated a t temperatures from 780' to 1200° and the carbonates of sodium potassium and rubidium showed very small and negligiblo losses in weight.Ctesium carbonate lost 0.32 per cent. of its weight a t 1110'. One gram of cEsium carbonate contained in a platinum boat placed in a platinum tube which was rendered vacuous and heated to 720° gave off 1.5 C.C. of carbon dioxide in thirty-five minutes. The salt dissociates therefore a t a temperature much below that at which it begins to volatilise. T. A. H. Molecular Weight of Silver Vapour. H. VON WARTENBERG (Ber. 1906 39 381-385. Compare Nernst Abstr. 1903 ii 636).- The vapour density of silver at 2000" was determined by Nernst's inettiod (Zoc. cit.). The statement by that author that silver is not volatile a t 1950' was made in error.To protect the iridium bulb from the action of the silver vapour the inside WAS coated repeatedly with a solution of zirconium and yttrium nitrates and the bulb heated to a high temperature. The results are plotted in curves with the time in seconds as abscissE and the displacement TI of the mercury thread as ordinates. As the silver tends to condense in the cool upper portion of the apparatus before the displacement of the mercury has reached the maximum n observed is too small and the molecular weight therefore found is too large unless the mercury thread is drawn o u t almost to the calculated maximum before the silver is added to the bulb. The molecular weight of silver vapour a t 2000° as determined by t h i s method was 107 and 111.At t h i s temperature the molecule of silver vapour is monatomic. G. Y. Reduction of Silver and of Copper Chloride by Calcium. L. HACKSPILL (Compt. rend. 1906,142,89-9 1 . Compare Abstr. 1905 ii 585).-When an intimate mixture of silver chloride and calcium turnings is heated to dull redness in a vacuum in a porcelain tube,162 ABSTRACTS OF CHEMICAL PAPERS. the chloride is reduced and a silver-calcium alloy formed the composi- tion of which varies with the proportion of calcium and silver chloride in the original mixture. Homogeneous alloys containing 6.3 13.3 or 16 per cent. of calcium were obtained in the form of brittle grey solids having a crystalline fracture whilst one containing 44.9 per cent. of calcium formed a spongy mass.All the alloys are readily oxidised when heated in the air and are decomposed by cold water. A copper-calcium alloy similarly prepared contained 18.3 to 18.8 per cent. of calcium and 1.2 to 0.9 per cent. of silicon and formed an orange-yellow brittle solid closely resembling the silver-calcium alloys in properties (compare Setlick Chem. Zeit 1905 29 218). M. A. W. Action of Silv2r N i t r a t e on Disodium Orthophosphate in Dilute Solution. WILLIAM R. LANG and WILLIAM PEROT KAUFMANN (J. Amer. Chem. SOC. 1905 27 1515-1519).-1t is usually supposed that solutions of silver nitrate and disodium orthophosphate interact i n accordance with the equation Na2HP0 + 3AgN0 = Ag,PO + 2NaN03+HN03. From a study of the reaction under different conditions it appears that it takes place in several distinct stages and generally results in the formation of a silver phosphate containing about 76 per cent.of silver (Ag,PO reqiiires Ag = 77.32 per cent.). It is also found that free nitric acid remains in the solution together with some phosphoric acid which is not precipitated by the further addition qf silver nitrate. E. G. Preparation of Metallic Calcium by Electrolysis. SAMUEL A. TUCKER and J. B. WHITNEY (J. Amer. Chem. SOC. 1906 28 84-87). --Notes of experiments made with the object of improving the yield in the preparation of calcium by the electrolysis of the fused chloride. E. G. Properties of Electrolytic Calcium. L. DOERMER (.Bey. 1906 39 21 1-2 14).-The explosions which take place when electrolytic calcium either in the form of powder or shavings is struck on an anvil seem to be due to the presence of oxide of iron (compare Goodwin PTOC.Amer. Phil. Soc. 43 381). Calcium powder when heated evolves hydrogen which is reabsorbed on raising the tempera- ture to a low red-heat. When a pile of calcium powder is ignited it burns throughout at a white heat; occasionally however only a feeble combustion takes place and some unburnt calcium remains. Such calcium has a yellower colour and is more resistant .towards moist air than ordinary calcium ; it has a granular crystalline fracture and is less tenacious. c. s. Presence of a Gaseous Hydride of Calcium in Technical Acetylene. CAMILL HOFFMEISTER (Zeit. anorg. Chem. 1906 48 137-139).-1t was noticed that the acetylene prepared from some specimens of calcium carbide even after being filtered through cotton- wool and passed through water gave a deposit of calcium oxide in the conducting pipes a fact which seemed t o indicate the presence of aINORGANIC CHEMISTRY.163 volatile calcium compound in the gas. To investigate the matter further a large volume of the gas obtained from calcium carbide was passed through a number of wash-bottles containing acetone and then through an ammoniacal copper solution to remove the acetylene corn- pletely ; a colourless gaseous residue was thus obtained which burned in the air to calcium oxide and water and formed an exceedingly explosive mixture with oxygen. The gas has not yet been obtained quite free from air so that its quantitative composition could not be determined .G. S. Composition of Bleaching Powder. 11. WOLDEMAR VON TIESENHOLT (J. Buss. Phys. Chern. Soc. 1905 3’7 834-S62. Compare Abstr. 1902 ii 562)-In confirmation of the view that bleaching powder consists of a mixture of calcium chloride and hypochlorite the author finds that (1) chlorine is evolved from bleaching powder or from a mixture of calcium or lithium hypochlorite w ~ t h calcium chloride by the action of either moisture or carbon dioxide; (2) when pounded with carbon tetrachloride bleaching powder is separated into two powders which differ in their densities and contents of active chlorine. The evolution of chlorine from aqueous solutions of bleach- ing powder is preceded by the hydrolysis of the calcium hypochlorite with formation of hypochloric acid.The action of carbon dioxide in the evolution of chlorine also depends on the liberation of hypochloric acid and the neutralisation of the lime simultaneously formed. The fact that calcium chloride is the most suitable of the metallic chlorides to bring about the reaction Ca(OCl) + CaC1 + 2H20 Z 2Ca(OH) + 2C1 is ascribed to the peculiar properties of its compounds with water of crystallisation. T. H. P. Phosphates of Calcium. I. FRANK K. CAMERON and ATHERTON SEIDELL (J. Amer. Chenz. Xoc. 1905 2’7 1503-1512. Compare Abstr. 1905 ii 33).-The composition has been determined of the solutions and solids in contact with them in the system water lime and phosphoric acid under conditions of final equilibrium at 25’ and at different concentrations. The concentration of phosphoric acid (P205) varied up to nearly 540 grams per litre and that of the lime (CaO) to a maximum of 77 grams per litre.Solutions were made by adding (1) tricalcium phosphate and (2) dicalcium phosphate to phosphoric acid solutions of concentrations up to about 200 grams per litre and (3) monocalcium phosphate con- taining an excess of acid to water until a permanent solid residue was obtained. The solid phase in contact with the solution after equili- brium had been reached was identified as dicalcium phosphate CaHP0,,2H20 in each case. In two other series of experiments monocalcium phosphate and dicalcium phosphate respectively were added to solutions of phosphoric acid which were more concentrated than those wed in the previous experiments. I n each case the solid phase remaining consisted of monocalcium phosphate CaH,( PO,) H,O.The results of the experiments are tabulated and a chart is given representing the concentrations of the solutions in phosphoric acid (P205) and lime (CaO). It has been found that with concentrations of164 ABSTRACTS OF CHEMICAL PAPERS. phosphoric acid above 317 grams of P,O per litre the stable solid phase at 25' is monocalcium phosphate and below that concentration down t o 20 grams per litre the solid phase is dicalcium phosphate. It is shown that either tricalcium phosphate can exist under equilibrium conditions in contact with water over but a very narrow range of concentration or that it exists only as a metastable form which changes but slowly into the stable form. The results of the investigation show that the relative values of mono- and di-calcium phosphates as manures cnnnot be entirely accounted for by the difference in their solubilities.E. G. Phosphates of Calcium. 11. FRANK K. CAMERON and JAMES 1sI. BELL (J. Amer. Chenz. Xoc. 1905 2'7 1512-1514).-Experiments have been made with the object of determining the equilibrium condi- tions for lower concentrations of phosphoric acid and of lime than those used by Cameron and Seidell (compare preceding abstract). Solutions were prepared by adding lime-water or dicalcium phos- phate to solutions of phosphoric acid of concentrations varying from 20 grams to 0.012 gram of P,O per litre. I n the case of solutions prepared by adding dicalcium phosphate to solutions of phosphoric acid of concentrations from 19.96 t o 3.66 grams per litre the solid phase was found to be dicalcium phosphate.I n the case of solutions made by the addition of dicalcium phosphate to solutions of phosphoric acid of concentrations from 1.516 grams to 0.381 gram per b e and by adding lime-water t o phosphoric acid solutions containing @*19-0*015 gram per litre the ratio P,O :CaO varies from 1-17 to 0.85 and the solid phases over this range are evidently solid solutions (The ratio for tricalcinm phosphate is 0.84.) For very low concentra- tions of phosphoric acid there is a quantity of lime in solution and the solid phase is again a solid solution. The results of the experiments are tabulated and show that the ratio P,O CaO i n the limiting solid solution must be above 1-10 or below 1.27 and that the composition of the liquid solution at that point is between 0.40 and 0.54 gram CaO and between 1.11 and 1.52 grams P,O per litre.E. Q. Compounds of the Halides and Borates of Strontium or Barium. LEON OUVRARD (Compt. rend. 1906 142 281-283. Compare Abstr. 1905 ii 635 ; this vol. ii 86).-The salt 3Sr0,SrC12!5R203 obtained by fusing a mixture of boron trioxide and strontium chloride with or without the addition of strontia (not more than 1 mol. for each mol. of boron trioxide) forms long needles showing longitudinal extinction unaltered by cold water or dilute acetic acid. When the proportion of strontia is increased the borates SrO,B,O or 2SrO,B,O are formed as large crystalline plates or prisms respectively ; these compounds are however readily hydrated by the action of water and in order to isolate them the fused product is suspended in a tall vessel of water with a layer of glycerol a t the bottom; as the mass disintegrates the crystals fall to the bottom and are protected by the glycerol from the action of the water.The borate SrO,B,O forms the hydrate Sr0,B,03,2H,0 ; and the borate,INORGANIC CHEMISTRY. 165 2Sr0,B203 is decomposed by water forming strontium hydroxide and the crystalline hydrute Sr0,B,03,4H,0. When strontium bromide or barium chloride or bromide replace strontium chloride in the above reactions the following compounds are obtained respectively strontium bromoborate SSrO,SrBr,,5 B,OS ; barium cldoroborate 3E;t0,BaC1,,5B,03 ; bcwium bromoborate 3Ba0,BaBr2,5B203 ; and the barium boyutes Ba0.B20 and 2Ba0,B203 which yield the hydrates Ba0,B20,,2H20 and Ba0,B,0,,4H20 respectively. Attempts to prepare strontium or barium iodoborates were un- successful. 3%.a. w. Hydrates of Glucinum Sulphate. MARIO LEVI-MALVANO ( A t t i R. Accud. Lincei 1905 [ v] 14 ii 502-510).-Hexahydrated glu- cinum sulphate crystallises alone only from highly supersaturated solutions a mixture containing tetrahydrate being mostly obtained on adding hexahydrate to solutions of the tetrahydrate. When once pre- pared the hexahydrate does not readily change into the tetrahydrate but can be obtained by evaporation of even dilute solut,ions at various temperatures. The cryohydrate of the solution of hexahydrate which is obtained at about - 30' consists of fine crystals of hexahydrate a fact which seems to exclude the existence of a hydrate containing more than 6H,O.The hexahydrate is octahedral in habit and melts at 78.8". The solubility curve of the hexahydrate cuts that of the dihydrate at about 77.4" which is hence the transformation temperature at the ordinary pressure. The tetrahydrate forms octahedral crystals has the cryohydric point - 21" and is converted into the dihydrate at about 113.6". Its solubility curve lies roughly parallel with and close to that of the hexahydrate. The solubility curve of the dihydrate is given from 77.4' t o about 158O at which temperature it melts partially and becomes transformed into the monohydrate. T. H. P. S odium-aluminium S odium-magnesium and Sodium- zinc Alloys. C. H. MA$HEWSON (Zeit.anorg. Chem. 1906 48 191-200). -These alloys were investigated by Tammann's thermal method (see this vol. ii lo) and the conclusions confirmed by microscopic investiga- tions and in some cases by chemical analysis. Sodium and aluminium are not mutually soluble and do not form chemical compounds. Magnesium saturated with sodium contains about 2 per cent. by weight of the latter metal and the freezing point is lowered from 650' to 638O. On the other hand sodium dissolves about 1.6 per cent. of magnesium at 657'; the latter metal separates out completely in hexagonal crystals as the temperature falls so that the melting point of sodium is not altered. Sodium and zinc are also only partially miscible but form a chemical compound already described by Rieth acd Beilstein (AnnaEen 1862 123 245; 1863 126 248). All mixtures containing from 3.2 up t o at least 60 per cent.by weight of sodium show a break in166 ABSTRACTS OF CHEMICAL PAPERS. the cooling curve a t 557”. A t this point the temperature of the eutectic crystallisation there is a non-variant equilibrium the phases of which are the crystals of the compound a saturated solution of sodium in zinc practically pure melted sodium (zinc is almost insoluble in sodium) and the vapours of the two metals. The saturated solution of sodium in zinc contains about 3 per cent. by weight of the former metal. Thermal and direct analyses gave slightly different values for the composition of the compound the approximate formula of which is NaZn or NaZn,,. It is grey in colour harder and more brittle than zinc and only slowly acted on by water.G. S. Alloys of Thallium with Copper and Aluminium. FR. DOERINCKEL (Zeit. anorg. Chem. 1906 48 185-1 90).-The cooling curves of these alloys were determined and the conclusions arrived at by Tammann’s method of thermal analysis (Abstr. 1904 ii 113 ; 1905 ii 444 ; this vol. ii 10) confirmed by microscopic observations. Thallium and copper are only partially miscible ; at 959’ (the melting point of copper) the layer rich in copper contains 35.1 per cent by weight of thallium the layer rich in the latter metal only 1.8 per cent. of copper. The eutectic point of the alloy rich in thallium lies a t 3 0 2 O 9 O below the melting point of thallium. The solubility curves could not be determined by Tammann’s method as the thermal change on admixture is too small. The two metals do not form any chemical compound or mixed crystals.Thallium and aluminium are not mutually soluble to any appre- ciable extent; they do not enter into chemical combination or form mixed crystals. G . S. Influence of Small Quantities of Elements in Copper on its Reactions with Nitric Acid. JOHN H. STANSBIE (J. Xoc. Chem. Ind. 1906 25 45-50).-The author has measured the variation in volume and composition of the evolved gas caused by the introduction of small quantities of other elements into pure copper. The reaction was carried out in a small beaker fitted with a rubber cork through which passed a thermometer and two tubes A and B ; A was of narrow bore and was attached to a burette from which the acid was delivered into the beaker ; B was connected to a graduated tube C the lower end of which was connected by rubber tubing to a movable reservoir for altering the level of the water in the apparatus ; the burette beaker and tube C were surrounded by water-jackets.The experiments were carried out as follows 1 gram of the metal in the form of filings which had been sifted through brass gauze with 64 meshes t o the linear inch and had been treated with a magnet to remove any particles of iron from the file were placed in the dry beaker ; after filling the jackets around the burette and the beaker with hot water the acid was allowed t o run slowly into the beaker the temperature being noted. When the reaction was finished the gas was transferred to the graduated tube C by running in water through the burette ; after reading the volume a measured quantity of oxygen was added to the gas and after shak- ing the tube to remove the last traces of nitrogen peroxide the volume of residual gas was again rend off.I n this way the volume of nitricINORGANIC CHEMISTKT. 167 oxide originally present in the collected gas could be determined and this together with the volume of nitric oxide already removed by the oxygen of the air present in the apparatus a t the beginning of the experiment gave the total volume of nitric oxide liberated from the acid solution. The copper used in these experiments was obtained by fusing the electrically deposited metal under charcoal in a carbon crucible and allowing it to solidify under charcoal so as to prevent the absorption of oxygen during solidification. It as found that an increase in the temperature at which the reaction takes place causes a considerable increase in the volume of nitric oxide liberated and a slight decrease in the volume of gas other than nitric oxide ; accordingly 65' was fixed on as the temperature for carrying out these experiments the acid used being of sp.gr. 1.2. Alloys of copper with arsenic antimony and bismuth were prepared by adding weighed quantities of alloys rich in these metals to pure copper melted under charcoal in a carbon crucible. Owing to the tendency of the bismuth alloys to liquate and reject bismuth their composition was not so uniform as those of antimony and arsenic. The results of experiments with ten alloys each of copper with arsenic antimony or bismuth are expressed in the form of tables and curves showing in each case the total volume of the gas evolved and the volume of the nitric oxide.It is shown that the presence of impurities in copper even in very small proportions modifies the reaction of the metal with nitric acid the effect being altogether out of propor- tion to the quantity of impurity present. I n a pure copper arsenic alloy the arsenic is present as arsenide and it is the relation of the arsenide to the excess of copper which confers on the alloy its character- istic properties. The condition of most intimate relation of the arsenic with the whole of the copper would be furnished by a perfect solid solu- tion. Thus the minimum action would be given by the alloy contain- ing the percentage of the added metal which gave the most perfect solid solution.If this view is correct the point is reached for copper- arsenic when the arsenic equals 0.25 per cent. and for copper-antimony when the antimony equals 0.5 per cent The behaviour of the copper- bismuth alloys seems to indicate the absence of solid solutions from their compositions. P. H. Metallic Substitution. ALBERT J. J. VANDEVELDE and C. E. WASTEELS (Bull. Acccd. roy. Belg. 1906 461-513. Compare Abstr. 1903 ii 200 ; 1904 ii 549).-The authors have investigated the action of various substances on the replacement of copper in aqueous solutions of copper sulphate by metallic zinc. Influence of Non-eZectroZ9tes.-Sucrose and alcohol diminish the velocity of substitution and this effect becomes greater as the con- centration of sucrose or alcohol is increased.The retarding influence of sucrose is maintained throughout the reaction. I n the case of alcohol when small quantities are employed this retarding influence only exists in the initial stages ; later on the rate of substitution is accelerated. The retardation is due to the diminution of the con- ductivity and diffusibility of the solution as the result of the addition of alcohol or sucrose. The final acceleration by alcohol of the rate of substitution is probably due t o the formation and precipitation of168 ABSTRACTS OF CHEMICAL PAPERS. basic zinc sulphate (compare Abstr. 1904 ii 549 and Ericson-Aurh and Yalmaer Abstr. 1902 ii 64).Influence of Neutral Electrolytes.-All the salts used give an initial increase in the velocity of substitution. This increase is not proportional to the concentration of the salt but reaches a maximum for a certain optimum concentration of the salt (compare Ericson- Aurh and Palmaer loc. cit.). I n all cases the precipitate formed con- tains at first zinc hydroxide and towards the end of the reaction some basic zinc sulphate is also deposited (Abstr. 1904 ii 549). InJEwnce of Acid Electrolytes.-Sulphuric acid was the only acid electrolyte the action of which was investigated. The phenomena in this case are very complex. At very low concentrations the acid diminishes the velocity of the reaction but when the concentration is increased the velocity of reaction augments and increases wihh further concentration (compare Kajander Abstr.1881 344). The initial “period of induction” observed by Spring and van Aubel (Abstr. 1887 1074) in the action of sulphuric acid on zinc appears to be reduced to zero when copper sulphate is present. Detailed tables showing the results of the exDeriments made and ” illustrating the above conclusions are given in the original. T. A. H. Cuprous Silicide. J ~ ~ L E VIGOUROUX (Compt. rend. 1906 142 87-89. Compare Prods-verb. SOC. Sci. pl~ys. mat. Bordeaux 1901).- Cuprous silicide Cu,Ri is obtained free from iron when 17 parts of pure silicon and 90 parts of electrolytic copper are fused in a current of hydrogen and the uncombined silicon removed from the product by the action of 5 per cent. sodium carbonate solution.It has a metallic appearance and a silver-white colour rapidly darkening becoming first yellow and finally brick-red ; it is hard brittle and easily powdered has a sp. gr. 7.48 that of the fused substance being 7.58 ; i t is readily attacked by chlorine by warm dilute or concentrated nitric acid or by a mixture of nitric and hydrofluoric acids whilst hydrochloric sulphuric or hydrofluoric acid has hardly any action on the compound (compare Lebeau this vol. ii 29). nil. A. W. Cuprosilicon and a New Method of preparing Silicon Soluble in Hydrofluoric Acid PAUL LEBEAU (Compt. rend. 1906 142 154-157).-When a mixture of copper and silicon is fused and cooled rapidly the cuprosilicon obtained after the removal of free silicon by treatment with 10 per cent.sodium carbonate solution contains 12.64 to 12.93 per cent. of silicon whilst the compound ob- tained by the gradual cooling of the fused mixture contains 11 -31 t o 11.36 per cent. ; the difference between these values and t<hat required for the compound Cu,Si namely 10.04 per cent. (compare this vol. ii 29 and Vigouroux preceding abstract) is due to the presence of uncombined silicon in the form which is soluble in hydrofluoric acid (compare Moissan and Siemens Abstr. 1904 ii 560). The cooling curves for copper and silicon indicate the existence of only one definite compound Cu,Si melting a t 800’. M. A. W.INORGANIC CIrTERIISTRY. 169 ANew Typeof Compound in the Group of Rare Metals. CAMILLE MATIGNON and E. CAZES (Compt. rend. 1906 142 83-85).-Anhydrous samarium chloride SmC1 (compare Abstr. 1902 ii 263 505 ; 1905 ii 391) can be reduced a t a high temperature by dry hydrogen ammonia or aluminium powder to form sumccrium dichloride (samarous chloride) SmCl,. This forms a dark brown crystalline mass having a sp. gr. 3.687 at 2 2 O insoluble in carbon disulphide benzene toluene chloroform or pyricline or even in alcohol in which the anhydrous chlorides of the rare metals dissolve so readily (compare Abstr. 1901 ii 602 ; 1902 ii 263). It is decomposed by water liberating hydrogen and forming samarium oxide and samarium oxy- chloride. As praseodymium and neodymium chlorides are not similarly reduced by hydrogen or ammonia a t high temperatures this reaction affords a convenient method of separating samarium compounds from mixtures of compounds of these three rare metals.Sulphates of the Rare Metals. CAMILLE MATIGNON (Compt. rend. 1006 142,276-27S).-l'he heats of formation of the sulphates of lanthanum praseodymium neodymium and samarium from the acid and generating oxides calculated from the experimental values for the heats of solution of the oxides in dilute sulphuric acid and the heats of solution of the anhydrous sulphates in water are 1389 125.7 125.1 and 113.8 Cal. respectively. The basic function of the oxides diminishes from lanthanum to samarium that is as the atomic weight of the element increases. M. A. W. ALFRED THIEL (Zeit. nnorg. Chenz. 1906 48 201-202. Compare Meyer this vol. ii 30).-Polemical. A question of priority. Mixed Crystals of Manganese Sulphate and Zinc Sulphate between 0' and 3Q0.R. SAHMEN (Zeit. physikaZ. Chem. 1905 54 111-120).-The author works out in detail an illustration of Holl- xxann's theory on the decomposition of hydrated mixed crystals (Abstr. 1902 ii 446 ; 1905 ii 154). Solutions containing manganese and zinc sulpha tes in various proportions and slightly supersaturated were shaken at several temperatures between 0' and 39'. When sufficient time had elapsed for the attainment of equilibrium an analysis was made both of the separated crystals and of the solution from which they had separated. The complex results which do not lend themselves to abstraction are represented on a diagram indicat- ing the limits of stability of the various types of mixed crystals. The types of mixed crystals involved are ZnS0,,6H20 (monoclinic) ZnSO 7 H,O (rhom bic) MnSO 4 H ,O (rhombic) MnS04 5 H,O (t ri- clinic) MnS0,,7H20 (monoclinic).Effect of certain Elements on the Structure of Cast Iron. ARTHUR H. HIORNS (J. Xoc. Chem. Ind. 1906,25,50-54).-A detailed account of the influence of varying qnantities of silicon phosphorus manganese or sulphur on the formation of crystals of cementite ferrite or graphite in cast iron. The paper contains eleven illustra- tions of sections of the various samples. M. A. W. Volatility of Indium Oxide. G. S. J. C. P. P. H. VOL. XC. ii. 12170 ABSTRACTS OF CHEMICAL PAPERS. Formation of a New Salt of the Formula Fe”‘H(80,),,4H20 or Fe20,,4S0,,9H,0. V. KOMAR (Chem. Zeit. 1906 30 15-16).-0n evaporating a solution of ferric sulphate in sulphuric acid (containing 400 C.C.of monohydrated acid per litre) to a concentration of 50’ B. white crystals having the composition Fe,03,4S0,,9H,0 or Fe”’H(S0,),,4H,O separate; they decompose a t loo’ are soluble in water but are insoluble in sulphuric acid of 45-50’ B. P. H. Nickelo-nickelic Oxide. A Correction. HENRI BAUBIGNY Compare this vol. ii 91).-A further (Compt. rend. 1906 142 154. reply to Bellucci and Clavari (Abstr. 1905 ii 824). M. A. W. Chromium Salts. ALFRED WERNER and R. HUBER (Ber. 1906 39 329-338. Compare Werner and Gubser Abstr. 1901 ii 453; Werner Abstr.. 1902 i 686; Weinland and Koch Abstr. 1904 ii 488).-Recoura’s chromium chlorosulphate (Abstr. 1902 ii 562) which is considered to be chloropenta-aqaochromium sulphate [Cr(OH,),Cl]SO,,H,O is formed by dissolving violet chromium sulphate (Higley Abstr.1904 ii 565) in boiling fuming hydrochlolric acid ; if allowed to crystallise slowly it forms large green leaflets. On treatment with barium chloride it yields a chromium chloride which crystallises in green needles behaves towards silver nitrate as an impure dichlorotetra- aquochromium chloride [Cr(OH2),C12]C1,2H20 and when treated with sulphuric acid is reconverted into Recoura’s chlorosulphate. The product obtained on saturating a concentrated aqueous solutiou of green chromium chlorosulphate with hydrogen chloride under cooling with ice and salt is a mixture of dichlorotetra-aquochromium and hexa-aquochromium chlorides. The green chlorosulphate has therefore the constitution [Cr( OH2),]:(S0,)2:[Cr(OH2),C1,],2H20.I n agreement with this it can be prepared by the action of concentrated sulphuric acid on a mixture of 1 mol. of violet chromium sulphate and 2-6 mols. of green chromium chloride. DicliEorotetra-aquocl~ronzium ~~e~a-nquoduminiunz sulphccte CCr(OH,)*C12( OH,!,I w 4 ) 2 [A1(OH,) t i 1 9 is formed by the action of sulphuric acid on a mixture of aluminium sulphate and green chromium chloride; it is precipitated from its aqueous solution on adding sulphuric acid in small light green crystals. Dibromotetra-aquochrornium hexa- aquochrornium sulphate [ Cr(OH,),Br(OH2)J (SO&[ Cr( oH2)ti]7 prepared by heating violet chromium sulphate with hydrobromic acid of sp. gr. 1.49 separates from the ice-cooled solution in glistening dark green crystals or more slowly in large leaflets. G.Y. Chemistry and Crystallography of the Silicomolybdates. H. COPAUX (Ann. Chim. Phgs. 1906 [viii] 7 118-144)-Sodium ailicomolybdate is readily prepared by heating a mixture of sodium silicate and molybdic acid in the proportion 12MoOa SiO 2Na20,INORGANIC CHEMISTRY. 171 with a little water ih a sealed tube at 150° (compare Parmentier Abstr. 1881 880; 1882 702). The fme acid can be obtained from the sodium salt by acidifying its dilute aqueous solution and extracting with ether (compare Drechsel Abstr. 1887 703 and Asch Abstr. 1902 ii 83) or more directly and with a yield of 75 per cent. of the theoretical by mixing warm aqueous solutions of ammonium molybdate and sodium silicate in the proportion of 12Mo03 SiO adding excess of sulphuric acid and extracting the cooled liquid with ether.Silicomolybdic acid SiO 12M00,,2H20,31H,0 forms yellow efflorescent tetragonal crystals [a c = 1 1.0071. The potassium salt SiO 1 2NoO3,2K,0,18H~O is very soluble 1.076 gram of a solution saturated a t 14' containing 0.448 gram of the anhydrous salt; it crystallises in the hexagonal system [a c= 1 0*6809]. The acid potassium salt 2(SiO 1 2Mo0,) 3K2O,H,0,27H,O is monoclinic The sodium salt SiO 1 2M00,,2Na20 1 4H,O forms triclinic crystals [a b c = 1.633 1 0.544 ; u = 96'30' p = 89'23' y = 85'39'1 whilst the salt Si02,1 2M00,,2Na20,22H,0 forms triclinic crystals which are too efflorescent to admit of measurement; 1.527 grams of solution satu- rated at 14' contain 1.056 grams of the anhydrous salt The acid sodium salt 2( SiO 1 ZMoO,) 3Na,0,H20,32H,0 is monoclinic The lithium salt SiO,,l 2M00,,2Li20,29H,0 forms cubic crystals.The barium salt Si02,12M00,,2Ba0,29H,0 forms large octahedra belonging to the cubic system whilst the hydrate SiO,,l2 NoO3,2Ba0,22H,O forms rhombohedral crystals [a c = 1 2.5731 and the lower hydrate Si0,,12Mo03,2Ba0,1 6H,O forms monoclinic crystals [a b c = 1.811 1 1.554 ; p= 75'45'1. The strontium salt Si0,,12MoO3,2Sr0,26H~0 forms rhombohedral crystals [a c = 1 2.6391. The calcium salt SiO,,12M00~,2CaO,31H~0 forms cubic octahedra and the lower hydrate SiO 1 2M00,,2Ca0,26H20 is isomorphous with the corre- sponding strontium salt. Salts of the type SiO,,12MoO,,2~10,31H20 where 1Sf = Mg Zn Mn Ni or Co crystallise in octahedra belonging to the cubic system and have characteristic colours those of zinc and magnesium being yellow manganese orange copper and nickel green or greenish-blue and cobalt garnet-red.SiO 1 2M00,,2Cd0,22H20 forms triclinic crystals [a 6 c = 0.440 1 0,383 ; a = 88'43' /3 = 91'14' y = 84'42'1 ; the silicomolybdates of iron aluminium and chromium have the general formula 3(Sio2,12 MoO3),2M,0,,93H,O and are isornorphous with the magnesium series of salts. The silicomolybdates are usually isomorphous with the corresponding silicotungstates which they also closely resemble in degree of hydra- tion and solubility the mercurous thallium rubidium and ammonium salts of the two series being very sparingly soluble whilst the alkaloid silicomoly bdates are as insoluble as the corresponding silicotungstates.The potassium salts of silicomolybdic and of silicotungstic acid con- taining 1 SH,O form hexagonal crystals closely resembling those of quartz and they are dextrorotatory whilst their solutions are optically [a b C = 1.200 1 0.860 ; p= 77'39'1. [a 6 c = 1.341 1 0,999 ; /3 = 79'32'1. The cadmium salt 12-2172 ABSTRACTS OF CHEMlCAL PAPERS. inactive; lworotatory crystals of these salts can also be obtained from solutions containing traces of alkali impurity ; dextro-potassium silicomolybdate crystals have [ a]D + 17*0-17*4° and the lclevo-crystals [a] '- 17.1'. BX. A. W. Electrolytic Preparation of Spongy Tin. DONATO TONMASI (Compt. rend. 1!106 142 86).-Spongy tin can be prepared by electrolysing a solution consisting of 50 parts of water 10 parts of stannous chloride and 1 part of hydrochloric acid using two tin anodes situated on either side of a revolving cathode formed of a copper disc and so arranged that part only is immersed in the liquid the exposed part revolving between two mechanical brass scrapers which remove the spongy tin and depolarise the cathode.The spongy tin is collected drained and washed the washings con- centrated to the strength of the original solution and returned to the bath. With a cathode of 3 cm. diameter and a current of 40 amperes and 3 volts the yield of spongy tin per hour is 86-36 per cent. of the the ore t ical quantity . M. A. W. Auto-oxidation of Tervalent Titanium. WrLmmf MANCHOT and I?. RICHTER (Bey. 1906 39 320-323).-When titanium sesqui- oxide is shaken with aqueous potassium hydroxide and oxygen i t is found that a considerably larger volume of oxygen is absorbed than corresponds with one equivalent of oxygen.The hydrogen peroxide primarily formed is reduced partially by the titanium sesquioxide the remainder of the peroxide oxidising the titanium dioxide to pertitanic acid on acidification or possibly even in the alkaline solution. If a thick milk of lime or baryts water is used in place of the potassium hydroxide the hydrogen peroxide formed is not reduced by the titanium sesquioxide or dioxide and the whole of the oxygen absorbed is found in the form of hydrogen peroxide. If the solutionof tervalent titanium in sulphuric acid is boiled with potassium hydroxide it evolves a volume of hydrogen equal to that of the oxygen absorbed on shaking the alkaline solution with oxygen The acid solution also evolves hydrogen when boiled but only extremely slowly.When shaken with oxygen a solution of tervalent titanium in sulphuric acid containing ferrous ammonium sulphate absorbs a still larger excess of the gas and the solution contains ferric oxide whereas an acid solution of ferrous ammonium sulphate alone does not absorb a measurable volume of oxygen. G. Y. Oxidation of Tervalent Titanium. 11. WILHELM -MANCHOT aild P. RICHTER (Bey. 1906 39 488-492. Compare preceding abstract). -When titanium sesquioxide is added to a solution of chromic and hydriodic acids dissolved in the requisite amount of water the liberated iodine may be estimated by thiosulphnte.For the oxidation 3 atoms of oxygen were reqalired for 1 atom of titanium. The oxida- tion of titanium sesquioxide with permanganic acid in the presence of tartaric acid also led to a similar result. A . McK.INORGANIC CHEMISTRY. 173 Preparation of Titanium Tetrachloride and of Tin Tetra- chloride. CARL RENZ (Ber. 19c)6,39,249-250).-When the vapour of chloroform is passed over finely-divided titanium oxide heated in a hard glass tube the main reaction proceeds according to the equation TiO + 2CHC1 = TiCl + 2CO + 2HC1. The temperature determines the nature of the by-products among which carbon dioxide phosgene and hexachlorobenzene have been identified together with a colourless gas probably titanium hydride TiH,. I n a prolonged reaction reduction of the titanium oxide and titanium tetTachloride takes place with the formation of titanium titanium dichloride and titanium trichloride.Tin tetrachloride but not silicon tetrachloride may be obtained in a similar way. c. 8. Thorium-aluminium Alloy. OTTO HONIGSCHMID (Compt. Tend. 1906 142 280-281).-The compound ThAI prepared by the direct union of aluminium and thorium in a vacuum at a high temperature or by reducing potassium thorium fluoride or thorium oxide with alumirii.um in the electric fiirnace forms long prismatic needles having the colour and metallic aspect of aluminium. It burns in fluorine or chlorine is attacked by bromine or iodine without incandescence is stable in the air but burns when heated to redness. It is attacked by the mineral acids is unaltered by alkali solutions but oxidised with incandescence by the fused alkali hydroxides or carbonates. M.A. W. A Silicide of Thorium. OTTO H~NIGSCHNID (Compt. rend. 1906 142 157-159).-Thorium silicide ThSi is prepared by the inter- action of a mixture of the double fluoride of thorium and potassium potassium silicofluoride and aluminium at 1 200° and purified from free aluminium and silicon by treatment with potassium carbonate solution. It forms quadratic plates resembling graphite in colour has a sp. gr. 7.96 at 16O and when heated combines readily with the halogens oxygen sulphur selenium or hydrogen chloride but is not attacked by hydrogen at a red heat. It is soluble in aqueous solutions of the mineral acids is not attacked by solutions of the alkalis but is decomposed on fusion with sodium or potassium hydroxides.For analysis the compound was dissolved in aqua regis or in a mixture of hydrofluoric and nitric acids or decomposed by fusingwith moist sodium hydroxide. Thorium silicide can also be prepared by heating a mixture of thorium oxide and silicon in an electric furnace with a current of 700 amperes and 100 volts or by heating a mixture of aluminium silicon and thorium at 1000°. M. A. W. Mixtures of Antimony and Tellurium and of Antimony and Selenium. Cryoscopic Constant of Antimony. HENRI PI~LABON (Compt. rend. 1906 142 207-210).-When mixtures of antimony and tellurium are fused tbe telluride Sb,Te is formed which yields a homogeneous liquid with excess of either constituent and the cooling curve exhibits one maximum at the solidification temperature of the174 ABSTRACTS OF CHEMICAL PAPERS.compound Sb,Te and two minima one corresponding with the point of solidification of the mixture 5Sb 2Te and the other with the eutectic point of the mixture Sb 1OTe. Antimony selenide forms homogeneous liquids when fused with excess of either antimony or selenium but there is a discontinuity in the cooling curve of the mixtures in which the value of R (the ratio of the mass of selenium to the total mass) lies between 11 and 3 9 ; such mixtures have two solidifying points a t 566’ and 5180 respectively the cooling curve consisting of two straight lines parallel to the abscissa along which R is measured. The melting point 605O of the compound Sb,Ye is a maximum point and the melt- ing point of the mixture 2Sb 7Se is a point of inflexion on the cooling curve.The cryoscopic constant of antimony calculated from the depression of its freezing point caused by the addition of antimony telluride selenide or sulphide (compare Abstr. 1904 ii 267) is 1246 1233 or 1225 respectively. N. A. W. Antimony Sulphate and its Double Salts with Alkali Sulphates. SIGMUND METZL (Zeit. ccnorg. Chem. 1906,48,140-155). -When antimony oxide is dissolved in concentrated sulphuric acid and the solution cooled the normal sulphate Sb,(SO,) separates in long glistening needles which can be freed from adherent acid by drying on porous plates and finally log washing with xylene. The salt has the sp. gr. 3.624 and is very hygroscopic. With cold water it gives the basic sulphate Sb,O,,SO or (SbO),SO ; with excess of hot water i t forms a much more basic salt but cannot be changed completely into the oxide.With alcohol in the cold the basic salt Sb2O,,2SO is produced. The contradictory statements regarding this salt in the literature are due to the fact that adherent sulphuric acid cannot be completely removed by drying on porous plates. Double sulphates of antimony with potassium sodium and ammonium have been prepared by heating antimony oxide and the alkali sulphate with concentrated sulphuric acid and then cooling the clear solution. They have the general formula Sb,(SO,),,M,SO occur in long glistening needles and are decomposed by water and alcohol with formation of the same basic salts as in the caw of the sulphate itself (compare Gutmann Abstr.1899 ii 33). Metallic antimony’ and the sulphide are only slowly and in the latter case incompletely decomposed by concentrated sulphuric acid but in presence of an alkali sulphate the action goes smoothly and completely; this fact is of importance for the technical preparation of antimony compounds. G. S. Peroxides of Bismuth. I. ALEXANDER GUTBIER and R. BONZ (Zeit. anorg. Chem. 1906 48 162-1 84. Compare Pattison Muir Trans. 1881 39 22; 1887 51 7 7 ; Deichler Abstr. 1899 ii 428).- The peroxides were prepared by the usual method the freshly- precipit tted hydroxide was suspended in hot concentrated potassiuniINORGANIC CHEMISTRY. 175 hydroxide solution and chlorine gas passed in for some time; the precipitate was then washed and treated with concentrated nitric acid to separate the lower from the higher oxides the latter remaining undissolved.The results are greatly influenced by the nature and strength of the alkali used ; the most highly oxidised products were obtained with a large excess of concentrated potassium hydroxide solution of sp. gr. 1.4. It was found impossible to obtain a product of uniform composition and no definite chemical compound could be isolated. The scarlet powder obtained by the action of concentrated nitric acid of sp. gr. 1.4 on the most highly oxidised precipitates and regarded by Muir (Zoc. cit.) and others as “ bismuthic acid,” HBiO always contains considerably less oxygen than corresponds with this formula and is not a uniform substance; this is in agreement with Deichler’s results.On continued washing with the object of freeing i t from potassium nitrate it decomposes with evolution of oxygen and formation of an orange-yellow powder formerly regarded as hydrated bismuth tetroxide Bi20,,2H,0. Attempts to prepare the latter substance by Deichler’s method (Zoc. cit.) were unsuccessful as no compound of uniform composition could be obtained. The contention of Muir that (‘ bismuthic acid ” changes to the pentoxide at 120’ and to tbe tetroxide at a higher temperature is inaccurate since the scarlet powder begins to lose oxygen at 100’. Neither the scarlet nor the orange-yellow product shows any sign of salt formation on treatment with concentrated potassium hydroxide solution. G. S. Boiling of Osmium Ruthenium Platinum Palladium Iridium and Rhodium.HENRI MOISSAN (Compt. rend. 1906 142 189-195. Compare this vol. ii 92).-The author has examined the behaviour’of the metals of the platinum group at the temperature of the electric arc ; the metals were placed in a carbon crucible inside an electric furnace (Abstr. 1893 ii 167 314) through which passed a copper tube cooled by a current of cold water. With a current of 500 to 700 amperes and 110 volts all the metals rapidly fused and entered into ebullition. The metallic distillates consisted of spherules together with microscopic crystals or crystalline plates ; the residual ingots showed a crystalline structure i n the cases of osmium platinum iridium and rhodium ; they all contained graphite 3.89-3.97 per cent. in osmium ; 4.8 per cent. in ruthenium ; 2.8 per cent. in iridium and 2.19 per cent. in rhodium ; and palladium exhibited the phenomenon of spitting. Palladium is more readily fusible than platinum and osmium is the most difficult to distil the weight of distillate obtained from 150 grams of the metal when heated for five minutes with a current of 700 amperes and 11 0 volts being 29 grams whilst the same weight of the other metals heated for the same length OF time with a current of 500 amperes and 110 volts gave the following distillates ruthenium 10 grams ; platinnix 12 grams ; palla.dium 9.6 grams ; iridium 9 grams; and rhodium 10.2 grams. &I. A. W.176 ABSTRACTS OF CHEMICAL PAPERS. Oxides of Palladium. LOTHAR WOHLER and JAMES KONIG (Zeit. anorg. Chem. 1906 48 203-204).-Polemical. Reply t o Bellucci (this vol. ii 35). G. S. Nitrilobromo-osmonates. ALFRED WERNER and KARL DINKLAGE (Rer. 1906 39 499-503).--Pot~~ssium nitdotetrctbromo-osnionate [OsNBr4]K,3H,0 prepared from potassium osmiamate and hydro- bromic acid of sp. gr. 1.49 forms dark red monoclinic prisms; its aqueous solution is cherry-coloured. Ammonium nitrilopentabromo-osnzonate [OSNB~,](NH,)~,H,O~ pre- pared by the addition of ammonium bromide to the mother liquors resulting from the preparation of the preceding salt forms dark brown monoclinic prisms with a reddish-violet tint. Rubidium rzitrilopeiatabromo-osmonate [ OsNBr,] Rb prepared in an analogous manner forms a dark brown powder with a reddish-violet t i n t ; its aqueous solution is red. Hydrogeta coesium rzitrilopentabronao-osnzonate [ O S N B ~ ~ ] ~ C S ~ H is an amorphous brown powder with a green t i n t ; it is the least soluble in water of the salts described and its aqueous solution is bright red. A. McK.

ISSN:0368-1769    

DOI:10.1039/CA9069005155

出版商:RSC    

年代:1906

数据来源: RSC

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176 ABSTRACTS OF CHEMICAL PAPERS. Miraera 1 ogical Chemistry. Rleinite a Hexagonal Mercury Oxychloride from Texas. ARTHUR SACHS (Sitxungsbei-. K. Akacl. Wiss. Berlin 1905 1091-1094). -This is probably identical with the undetermined yellow mercury oxychloride mentioned by Moses (Abstr. 1904 ii 46) ; the small crystals are however not orthorhombic but hexagonal There is a perfect cleavage parallel to the basal plane and less distinct cleavages parallel to the faces of a prism. The purest crystals are sulphur- yellow and have an adamantine lustre but in the slightly altered crystals the colour is orange-yellow and the lustre is rather duller. The hardness is 3-4; sp. gr. 7,441. Analyses gave Hg S6.68-87.13 ; C1 7.63-8-25 per cent. corresponding with the formula Hg,C1,0, The other mercury oxychlorides recently described by Moses from this locality Terlingua in Texas are eglestonite (cubic Hg,CI,O,) and terlinguaite (monoclinic Hg,C10).L. J. S. Chemical Study of Sea Waters. THI~~PRILE SCHLOESING (Goinpt. rend. 1906 142 320-324).-Annlyses of the water of the Atlantic Ocean and of the Mediterranean show that the two waters differ only in degree of salinity the composition of the mineral con- stituents being almost identical in the two cases ; the analytical results are given in the folloKing table; 1 litre of water at 20" contains :MINERALOGICAL CHEMISTRY. I i 7 Mediterranean. Calcium carbonate ............... 0.127 gram Sulphuric acid ..................... 2.551 Chlorine.. ............................ 2 1.376 Bromine.. ............................ 0.0'72 Lime (not included above) ......0,599 Magnesia ........................... 2.36 1 Sodium oxide ...................... 16.017 Potassium oxide .................. 0.5 10 Atlantic. 0.099 2.120 17.830 0,060 0.519 1-993 13.410 0.41 3 Ratio. 0.78 0.831 0-834 0.833 0-866 0.844 0.837 0.810 - - 43.613 36.444 and bromine ..................... 4.824 4.024 Oxygen equivalent of chlorine Total salts per litre .............. 38,789 32.420 0.836 M. A. W. Formation of Oceanic Salt Deposits. XLV. Formation of Tincal and Octahedral Borax. JACOBUS H. VAN'T HOFF and WALTER C. BLASDALE (Sitxungsber. K. Akad. Kiss. Berlin 1905 1086-1 090).-Potassium borate does not separate from a solution con- taining this salt and sodium chloride but only potassium chloride and sodium borate.The saturations of solutions containing sodium borate and sodium chloride in the presence of potassium chloride sodium sul- phate and glaserite are given for temperatures of 25' and 83'. Below 35-51' sodium borate separates as tincd ( Na,B407,1 OH,O) but above this temperature it separates as '' octahedral " [that is rhombohedra11 borax (Na,B40,,5H20). The latter has been observed as a natural product in the lagoons of Tuscany. L. J. S. Analysis of the Ash which fell in Naples on the Night of October 2nd 1904. EZIO COMANDUCCI and L. PESCITELLI (Rend. Accad. Sci. Pis. Mat. ATapoZi 1905 [iii] 11 249-253).-The Vesuvian ash which fell in Naples at intervals during the night of October Znd 1904 is a heavy granular dark chocolate-coloured magnetic powder having the following percentage composition SiO 41.738 ; SO 1,518; C1 0,242; P,O 1.428; Fe203 25.338 ; A1,0 7.714 ; MgO 0.214; CaO 5.310 ; K,O 0.102 ; Na,O 1.91'7 ; NH traces; loss on ignition 3.72.T. H. P. Isomorphism and Thermal Properties of the Felspars. ARTHUR L. DAY and EUGESE T. ALLEN (.Zeit.plqsiknZ. CJ~e972 1905 54 1-54).- The authors have prepared a series of artificial felspars namely albite (Ab) anorthite (An) and the following combinations of these Ab,An AblAn Ab,An Ab,An Ab,An Ab4Anl. All these with the exception of albite were obtained in completely or partially crystalline form by crystallisation from the corresponding fused mass. With the help of a thermoelectric junction the temperature of fusion was deter- mined for the members of the foregoing series. As the albite end of the series was approached however the determination of the melting point became increasingly difficult owing to the very gradual transi-178 ABSTRACTS OF CHEMICAL PAPERS.tion from the solid to the liquid condition. obtained were as follows All. Ab,An,. Ab,An,. Ab,An,. Ab,An,. Ab,An,. 1532' 1500' 1463" 1419O 1367O 1340O The melting-point curve is continuous and the view adopted is that the triclinic felspars are solid solutions and together form an isomorphous series. It is noteworthy that the solid phase obtained in each case has the same composition as the liquid phase of glass from which i t separates. The view that the felspars form an isomorphous series is strongly supported by a study of the way in which the specific gravity (sc) of the crystals varies with the composition This is shown in the following table which shosvs also the specific gravity (sg) of the corre- sponding glasses The melting points An. Ah,An,. Ab,An,. Ab,An,. Ab,An,. Ab,An,. Ab. s 2.764 2.734 2.710 2.680 2.660 2.649 2.6 sg 2.700 2.648 2.590 2.533 2.486 2.458 2.382 The paper contains many detailed observations on the processes of fusion and crystallisation in these glasses. Thus amongst other things it was shown that microscopic crystals of a homogeneous compound might if slowly heated retain their form for 200' above the point a t which fusion began. J. C. P.

ISSN:0368-1769    

DOI:10.1039/CA9069005176

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

178 ABSTRACTS OF CHEMICAL PAPERS. Physiological Chemistry. Oxygen Tension in Submaxillary Glands and other Tissues. JOSEPH L. BARCROFT (Bio-chem. J. 1906 1 1-lo).-The experiments recorded confirm those of Pfluger and of Kiilz who showed that the oxygen tension in the saliva is greater than that in blood-plasma and that there is a definite oxygen tension in other secretions. Injection of thionin shows that the submaxillary gland does not reduce the dye sufficiently to prevent it from becoming blue throughout. The saliva and urine are also blue. The gland becomes bluer the muscles less blue on activity. In view of the great consumption of oxygen in the submaxillary gland the high oxygen tension in saliva is not easy to account for but the most probable explanation is that the capillary walls have the power of raising the tension of the gas as it passes through them.W. D. H. Survival Respiration of Muscle. GEORGE T. KEMP and E. R. HAYHURST (PTOC. Amer. Physiol. SOC. 1905 xxviii-xxix ; Amcr. J. Physiol. 15).-Isolated muscle at rest produces carbon dioxide espe- cially immediately after excision. I n frog’s muscle there are further increases at the third and sixth hours; then the yield becomes constantPHYSIOLOGICAL CHEMISTRY. 179 until there is a sudden increase when putrefaction sets in. In mam- malian mnscle there is regular steady fall. Work increases the output whether the muscle is directly or indirectly stimulated. Temperatures between 18’ and 30° or variations in the speed of the air current bathing the muscles have no effect. If no oxygen is supplied how- ever the yield of carbon dioxide is reduced. Curare has no influence on the output from unstimulated frogs’ muscles; if the nerves of such muscles are stimulated the results are inconstant.Curarised mam- malian muscle on nerve stimulation gives off mor0 carbon dioxide than when a t rest but this statement at present rests on only three experi- ments. W. D. H. Estimation of the Volume of Blood in Animals C. GORDON DOUGLAS (J. Physiol. 1906 33? 493-505).-The volume of the blood estimated in animals by Haldane and Lorrain Smith’s carbon monoxide method during life closely corresponds with that found by Welcker’s older method after death. W. D. H. Ion-proteid Compounds. I. Influence of Electrolytes on the Heart’s Frequency. T.BRAILSFORD ROBERTSON (PJliqw’s Amhiv 1905 110 610-624).-Experiments on the frog’s heart lead to the conclusion that the frequency of the beat is determined by ions in the fluid which bathes it and a mathematical formula is given to show what the rate will be if the relative velocities of anions and cations are known. The alternate formation of proteid compounds containing anion and cation is suggested. W. D. H. Vague Inhibition and Salts of the Blood. WILLIAM H. HOWELL (Amer. J. Physiol. 1906 15 280-294).-In a circulating fluid containing only the chlorides of sodium potassium and calcium an increase in the potassium salt augments the sensitiveness of the heart to vagus inhibition until it a t last itself causes inhibition. Com- plete lack of potassium is accompanied by a lessening or loss of vagus control.. A solution of pure sodium chloride (0.7 per cent.) causes loss of vagus control. An increase of calcium salt has no effect on vagus inhibition of the auricles but is followed by diminution and finally loss of vagus action on the ventricle (of the terrapin) owing probably to the development of an independent ventricular rhythm. The experiments indicate that inhibition of the heart depends on the presence of diffusible potassium compounds in the heart tissue and that vagus impulses act indirectly by increasing the amount of potass- ium compounds oE this character. W. D. 33. Centrifugalisation of Arbacia Eggs. ELIAS P. LYON (Yroc. Amer. Physiol. Xoc. 1905 xxi-xxii ; Amer. J. Physiol. 15).-Centri- fngalising unfertilised eggs effects a separation of the egg material into four layers.These are capable of subsequent fertilisation and develop into plutei normal in all respects except pigmentation. During centrifugalisation the pigment of the egg collects in the lowest layer. In the pliiteus larva it is distributed in every possible may. W D H,180 ABSTRACTS OF CHEMICAL PAPERS. Effect of Alkalis and Acids and of Alkaline and Acid Salts on Growth and Cell Division in the Fertilised Eggs of Echinus esculentus. BENJAMIN MOORE HERBERT E. ROAF and EDWARD WHITLEY (Proc. Roy. SOC. 1906 77B 102-136).-1n malignant disease the secretion of acid by the stomach is reduced owing to a change in the distribution of the salts of the blood which increases its alkalinity. I n flchinus eggs small amounts of alkali or alkaline salts stimulate growth and.cell division but the cells are irregular in size and shape and the cells beccme multinucleated. An increase of alkali stops the process. Where stimulation occurs non- typical mitosis like that seen in cancer cells is noticeable. Acid pro- duces no such results; the effect of acid is simply inhibitory. The cells are most sensitive to even slight changes in the concentration of hydrogen and hydroxyl ions. Effect of Acid and Alkali and certain Indicators in Arrest- ing or otherwise Influencing the Development of the Eggs of Pleuronectes platessa and Echinus esculentus. EDWARD WHITLEY (Proc. Roy. Soc. 1906 '774 137-149).-The amount of variation from the normal concentration of hydrogen and hydroxyl ions in sea-water which the eggs of Pteuronectea will tolerate is very small a disturbance towards the acid side being more fatal than the opposite.As the eggs grow they become more resistant. Phenol- phthalein is deadly to Echinus eggs but harmless t o those of Pteuro- nectes. Dimethylaniinoezobenzene quickly kills the latter but influences the former favourably. Influence of Chloroform on the Growth of Young Animals. A. SCHAPIRO (Proc. Physiol. Xoc. 1905 xxxi-xxxiii ; J. Physiol. 33). -Daily anaesthetisation with chloroform retards the growth of young kittens ; this is compensated by accelerated growth subsequent'ly. W. D. H. W. D. H. W. D. H. Physical Conditions of Colloids. V. The Electrical Charge of Proteids. WOLFGANG PAULI (Beitr. chem. Physiol. Path. 1906 7 531-547).-The experiments were made with serum freed as far as possible from electrolytes by dialysis or with the proteids separated from serum.Such serum shows no appreciable electrical conductivity. If acid is added the probeid assumes an electro-positive character and is carried to the cathode ; if alkali is added the reverse occurs ; sodium chloride and other neutral salts have no effect (compare Hardy this vol. i 121) ; acid or alkaline salts produce the same effect as acids and alkalis. Some conclusions are drawn from this as to the precipitation of proteids by various reagents and the question is mooted whether changes in the electrical charge of proteids in the body may explain certain physiological phenomena in connection with proteid chemistry and assimilation immunity and histological reactions.Mechanism of the Pylorus. WALTER B. CANNON. Movements of Stomach and Intestines. WALTFR B. CANNON and F. T. MURPHY (Proc. Amer. Physiol. SOC. 1905 xxv xxv-xxvi; Amer. J. Physiol. 15).-The theory that free acid in the stomach is the signal for the W. D. H.PHYSIOLOGICAL CHEMISTRT. 181 opening of the pylorus is confirmed by observations through a gastric fistula. After intestinal section and suture the pylorus remains closed against the peristaltic pressure of the stomach and food does not enter the injured gut until the intestinal wound is cemented. I n intestinal obstruction violent peristalsis occurs repeatedly in attempts to force the contents against the obstacle. I t is then moved backwards to the stomach. Anzsthesia or exposure of the intestines to the air has little or no effect but handling even gently inhibits movements for hours.The actual movements were studied as in previous work by observation with X-rays the food being mixed with bismuth sub- nitrate. W. D. H. Trypsinogen and Enterokinase. J. MOLYNEUX HAMILL ( J . Physiol. 1906 33 476-478).-Trypsinogen and enterokinase are not specific for each animal but are always the same definite chemical individuals although they occur in widely separated classes of the animal kingdom. Enterokinase from any animal is able to activate the trypsinogen of any animal so far as has yet been investigated. W. D. H. Absorption of Proteids from the Intestine. E. PROVAN CATHCART and JOHN B. LEATHES (J. Physiol. 1906 33 462-475).- No evidence of any absorption could be obtained in loops of intestine prepared with oxygenated defibririated blood.The muscular move- ments continue but the epithelium of the mucous membrane desquamates. By examining the blood of an animal at intervals during absorption of proteid cleavage products introduced into the intestine a small increase accounting for about 15 per cent. of the nitrogen absorbed wws found in the amount of nitrogenous material in the blood which is not precipitable by tannic acid; a similar increase occurs in the liver. A flow of urine set u p during the operation contains a considerable amount of nitrogen. No increase in the coagulable proteids of the blood was detected. The tendency of the experiments is not in favour of proteid synthesis by the intestinal epithelium although this is not absolutely excluded.The amount of amino-acid and similar substances found a t any moment in the blood should not be tisken as an index of the amount of nitrogen absorbed in this form any more than Kuhne was right in arguing from the amount of amino-acid in the intestine that the amount formed there is small; if formed they are formed for absorption not for accumulation in the intestine. So with amino-acids in the blood they are not absorbed for storage in the blood but are removed from the blood by the tissue cells and dealt with there being either assimilated with protoplasm or changed and a t last discharged as waste material by the kidneys. W. D. H. Enzymes of the Embryonic Alimentary Canal. LAFAYETTE B. MENDEL (Proc. Amr.Physiol. Soc. 1905 xiii-xiv ; Amer. J. Physiol. 15).-The intestines of embryo pigs were examined for inverting ferments. Blaltase is universally present lactase is present very early,182 ABSTRACTS OF CHEMICAL PAPERS. whilst sucrase is absent. They do not occur in other organs such as liver and kidney. I n adult animals sucrase is always present but no lactase. There are similar differences in the dog. Lactase was not found in the hen or chick but sucrase was present in both. Pepsin and rennin are absent from the embryonic stomach of the pig. I n the sucking-pig all three are present. W. D. H. Protective Mechanism of Intestinal Worms. J. MOLYNEUX HAMILL (J. Physiol. 1906 33 479-492).-Intestinal parasites resist digestion because they contain an anti-ferment. Dnstre and Stassano consider this is anti-kinasic ; this would confirm Delezenne’s view that enterokinase is not a ferment which acts on trypsinogen but that trypsin plays the part of an amboceptor to allow enterokinase t o attack the proteid molecule.The present experiments were made with an extract of intestinal worms added to solutions of enterokinase or of trypsin or of mixtures of the two. They prove that the anti- substance is antitryptic not antikinasic. W. D. H. Metabolism of the Nervous System. WALDEMAR KOCH (Proc. Amey. PhysioE. SOC. 1905 xv-xvi; Amer.J. F’hysiol. 15).-A hypothesis is advanced that in nervous metabolism compounds resembling poly- peptides are elaborated from proteid. Such compounds contain 4 per cent. of sulphur in a form which is easily split off as sulphate and is not present as cystine sulphur.h change in the state of oxidation of the sulphur gives a clue to the r6Ze played by oxygen in this metabolism. An excess of easily available oxygen is necessary for the vitality of nervous structures but the yield of carbon dioxide is very low. W. D. H. Influence of Normal Salts on the Staining and Fixation of Nervous Tissues. EMIL MAYR (Beitr. elhem. Physiol. Path. 1906 7 548- 574).-The longitudinal fibres of the spinal cord are rapidly swollen and disintegrated by the action of physiological salt solution or by a corresponding solution of sodium sulphate. Distilled water has a similar effect and even Ringer’s solution is not harmless. This occurs most readily in the posterior columns where after twenty-four hours’ exposure to the salt solution a neuroglia network is all that remains intact.The fibres of the spinal nerve roots are not affected. This is not due to putrefaction nor markedly to autolysis although the experiments do not entirely exclude ferment action. I n regard to temperature there is close correspondence a t certain critical temperatures between the action of the salt solution and the coagulation temperatures of the different nerve-proteids as described by Halliburton. The influence of alcohol and various fixatives on this phenomenon is discussed as also is their varying effect on the staining reactions of the Nissl granules in the light of our knowledge on the actions of ions. W. D. H. Distribution of Chlorides in Nerve Cells and Fibres.ARCHIBALD B. MACALLUM and Miss RI. L. MENTEN (Froc. Roy. SOC 1906 77B 165-192).-It has been shown previously that the well-PHYSIOLOGICAL CHEMISTR,Y. 183 known reduction staining with silver nitrate so much used in histology ilp due to the presence of chlorides. The transverse striae produced at the nodes of Ranvier in nerve-fibres and known as the lines of Frommann can be obtained a t any portion of the axis cylinder provided means are taken to allow the reagent to get a t it. These lines do not indicate however a pre-existent distribution of the chlorides in alternating layers. The same appearance can be reproduced in capillary tubes containing egg-white or gelatin impregnated with potassiiim dichromate (Bochm Liesegang). Ostmald explains this by supposing that when the critical concentration in the advancing solution is reached precipitation begins and continues until a stria is formed.This brings the solution back to the metastable condition then another development of the labile condition obtains and thus a new stria after an interstriate zone is formed. As the silver salt becomes more and more dilute critical concentration is attained later and later and so new striae are separated by interstriate zones of increasing width. Tho cytoplasm of the nerve cell shows the same appearances but less intensely; this may be due to difficulty of penetratios but it is held that probably the cell-body is poorer in chlorides than the axon. The nucleus is destitute of chlorides. The mixture of electrolytes and colloids in the nerve-fibre mould not permit the ions carrying the electrical charge to travel nnimpeded and the change of potential transmitted would travel with diminished velocity.This would bring into line the nerve impulse and the action current of nerve. Ib is freely admitted that caution must be exercised at present in drawing physiological conclusions from physical data but the following facts are very suggestive (1) the presence of electrolytes (chloride or chlorides) in a concentrated degree and uniform in distribution; (2) the maintenance ot this concentration through the impermeability of the sheaths of the fibres and (3) the high conductivity of the axon and the occurrence of electrical phenomena when it is injured. W. D. H. Chemistry of Nerve Degeneration.WALDEMAR KOCH and WILLIAM H. GOODSON (Amer. J. BhysioZ. 1906 15 272-279).-The grey matter of the prefrontal and motor areas ditfers very little in composition. The corpus cccZZomrn a mass of white matter contains less water less proteid and more cerebrins. The sciatic nerve contains more connective tissue and more nucleo-proteid. The substance spoken of as the sulphur compound is more abundant in nerve and white matter than in grey matter. In the degenerated tissues of general paralytics the water is more abundant the nucleo-proteids are increased but the proportion between the other constituents (lecithin kephalin cerebrin &c.) is but little altered although their absolute amounts are much reduced. I n Wallerian degeneration experimentally produced in a dog’s spinal cord the same condition was found.The paper is illustrated by tables of analyses. W. D. H. Phrenoaine and Gerebrone. HANS THIERFELUER (Zed. physioZ. Chrna. 1905 46 518-622).-Posner aud Gies (this vol. ii 54)184 ABSTRACTS OF CHEhIICAL PAPERS. consider that Thudichum’s phrenosine is identical with Thierfelder’s cerebrone and that the latter name ought to be dropped. The identity of the two substances is here disputed. Thudichum’s material appears to have been an impure product and so the name cerebrone should be retained. W. D. H. Composition of Nasal Mucous Membrane. BERT RUSSELL and WILLIAM J. GIES (Proc. Amer. Phpsiol. Xoc. 1905 xxiii-xxiv; Amer. J. Physiol. 15).-The nasal mucous membrane of the ox contains from 20 to 23 per cent. of solids about 1 per cent.being ash. Enzymes are absent. The organic material is mainly collagen and proteid including nucleo-proteid. No mucoid is found. The relation between composition and secretion has yet to be studied. W. D. H. Oxidation in Tissues in the Presence of Ferric Salts. FR. BATTELLI and Mlle. L. STERN (Compt. ?*end. 1906,142 175-177). -In extracts of muscle on the addition of a ferric salt lactic acid is oxidised vigorously with the formation of carbon dioxide. This is con- sidered to be due t o the combined action of the iron salt and hydrogen peroxide. In the body the iron sa,lt is represented by anticatalase. The same is true for extracts of other tissues. It is assumed that in the tissues a substance is present termed 4 4 peroxydogen,” which liberates hydrogen peroxide in the presence of oxygen.This substance disappears soon after death is destroyed by acid and preserved by alkali I n the body nitrogen is not completely burnt but the chief end-product is urea; the method employed does not oxidise urea and so a further analogy is drawn between oxidation so produced and that which occurs in the body. W. D. H. The Suprarenal Capsules in Cases of Nervous and other Diseases. By FREDERICK W. MOTT and WILLIAM D. HALLIBURTON (Proc. Physiol. Xoc. 1906 iii-iv ; J. I’lqsiol. 34).-At the autopsies performed on cases which died in the London County Asylums it was frequently noticed that the suprarenal capsules were atrophied or disintegrated. Knowing the close relationship between the nervous system and the suprarenal medulla from the embryological point of view it did not appear on apriorigrounds impossible that there might be a similar connection between nervous disease and suprarenal atrophy.The suprarenals in over seventy successive cases were examined ; a small portion of each was reserved for microscopic study ; Vulpian’s colour reaction with ferric chloride was applied to another portion and the intensity of the result noted. The remainder was rapidly dried in a vacuum and extracts of the dried powder mere examined physiologically for adrenaline. The glands were atrophied degenerated or disintegrated in about half of the specimens and in these adrenaline was either absent or present only in traces. But no connection could be traced between such a condition and the original nervous or mental disease for which the patient had been admitted to the asylum. Suprarenal atrophy appears however to be related to the secondary digeases from whichPHYSIOLOGICAL CHEMISTRY.185 the patient ultimately died. I n the majority of cases where it occurred the patients had suffered from chronic diseases. Such diseases as is well known affect injuriously the secreting mechanism of the whole body and the suprarenal apparently shares in this depression. Acute diseases on the other hand do not appear to produce these effects so markedly unless they are very intense. The observations suggest the possibility that the fatal termination of chronic diseases may be accelerated by the lack of suprarenal secretion and consequent circulatory depression.W. D. H. Coagulation of the Swimming Plate and Contractility. RALPH S. LILLIE (Proc. Amel.. Physiol. SOC. 1905 xii ; Amer. J. Physiol. 15).-The swimming plate of Eucharis Zobatcc beats normally 3 to 6 times per second. I n a solution of alkaline sodium chloride i t becomes much faster and ths colloids become opaque and coagulate movement ceasing within half a minute. This is explained by the hypothesis that partial coagulation accompanies the normal beat and repair during the relaxation. If the rate increases the time for recovery is lessened and so the colloids progressively coagulate. W. D. H. The Chromogen of so-called Scatole-red. LOUIS C. MAILLARD Compare Abstr. 1905 ii (Zeit. phpsiol. Chenz. 1905 46 515-517. 27 1)-Polemical. The author reaffirms the views stated previously.W. D. H. Galvanotropism-of Volvox. OLIVER P. TERRY (Amer. J Physiol. 1906 15 235-243).-The galvanotropism of Volvox depends on its state of chlorophyll metabolism ; normally YoZvox goes to the cathode. If kept in the dark for two or three days it goes to the anode. This is reversed on exposure to light. Bluelight has little or no effect. Red light stimulates assimilation and affects the organisms like sunlight. W. D. H. Gain and Loss of Fixed Alkali in the Body ; Estimation of Organic Acids in Urine with Reference to Diabetes. EDWARD S. EDIE and EDWARD WHITLEY (Bio-chem. J. 1906 1 11-2'7).- Methods are described for estimating in the urine the output of fixed alkali fixed acid and organic acid from the body. The total output of organic acid is important in diabetes.Administration of alkali decreases the amount of ammonia but increases that of organic acids Just as in acid poisoning the body protects itself by ammonia-formation from urea so in alkali poisoning there is a similar protection in the increased amount of organic acid formed from carbohydrate. W. D. H. Equilibrium in Solutions of Phosphates. LAWRENCE J. HENDERSON (Amer. J. Physiol. 1906 15 257-271).-The acidity of urine which can be estimated by titration varies with the temperature partly because of variations in the ionisation of water. Neglect of this factor may produce an error of 5 per cent. The hydrogen ionisation of serum corresponds to that of solutions in which the ratio of Na2HP0 VOL. XC ii 13186 ABSTRACTS OF CHEMICAL PAPERS.and NaH,PO varies between 6 4 and 1 0. Within this range varia- tion is harmless t o protoplasm ; this is a protective mechanism whereby large amounts of acid or alkali may be immediately neutralised and t h e hydrogen ionisation preserved within normal limits. The re- action Na2HP04 + H,CO = NaH,P04 + NaHCO is a balanced one and even in solutions less acid than monosodium phosphate sodium hydrogen carbonate cannot exist. Both the determinations of hydrogen ionisahion in urine and in phosphate solutions and their behaviour t o methyl-orange indicate that urine contains a mixture of mono- and di- hydrogen phosphates. W. D. H. Organic Phosphorus in Urine. DOUGLAS STMMERS (J. Puth. Bact. 1905 10 427-430. Compare Abstr. 1905 ii 102).-An increase in excretion of organic phosphorus occurred intermittently i n a case of typhoid fever.I n a case of extensive organic disease of the central nervous system the organic phosphorus excretion rose and fell intermittently but the output was not markedly increased. The data are admittedly too few yet for definite conclusions t o be drawn. W. D. H. Salt Glycosuria. FRANK P. UNDERIIILL and OLIVER E. CLOSSON (Proc. Amer. Physiol. Soc. 1905 xx-xxi ; Anrer. J. Physiol. 15).- When sodium chloride is injected intravenously in rabbits polyuria and glycosuria occiir probably as a result of increased permeability of the kidney. This may be decreased by adding calcium chloride. The blood contains less sugar than normal i n the former and more in the latter case. This points to a glycosuria of renal origin.Injection of sodium chloride into the cerebral circulation or of magnesium sulphate into the ear vein produces glycosuria but no polyuria. I n these cases the dyspncea produced explains the condition. \V. D. IT. Excretion of Creatinine in Man. C. J. C. VAN HOOGENHUYZE and H. VERPLOEGII (Zeit. physiol. Clhenz. 1905 46 415-471).-A more detailed account of experiments previously published (this vol. ii 40) showing that muscular work on ordinary diet leaves the creatinine excretion unaltered (see Folin Abstr. 1905 ii 183 268). W. D. H. Treatment of Diabetes by Extract of Duodenum. BENJAMIN MOORE EDWAED 8. BEDIE and JOHN H. ABRAM (Bio-chenz. J. 1906 1 28-38).-A neutralised acid extract of duodenum given by the mouth alleviates the diabetic condition in young patients.The extract is believed t o stimulate the pancreas t o form the internal secretion which normally regulates carbohydrate metabolism. At present the number. of cases is too small for positive conclusions t o be drawn. W. D. H. Pancreatic Diabetes. OSKAR MINKOWSKI (Pjiiger’s Archiv 1906 111,13-60). BDUARD PFL~~GER (lbid 61-93).-A distinctly polemical discussion on questions raised by Pfliiger’s recent work and criticisms. The points principally at issue are whether partial extirpation of thePHYSIOLOGICAL CHEMISTRY. 187 pamreas mill produce a diabetic condition whether the explanation of the diabetes is a nervous disturbance or due to interference with the internal secretion of the pancreas and whether the sugar originates from proteid or from fat.H. L~;'DI<E ( J . Path. Bact. 1905 10 32§-333).-A method of obtaining the toxin from the bacilli of dysentery is described. Some of the results brought forward differ from those of previous observers. Lactase and Sugar Excretion in Infants with Gastric Diseases. LEO LANGSTEIN and PRANZ STEINITZ (Beitr. c h u . Pl~ysiol. Path. 1906 7 575-5S9).-In suckling infants with severe gastric disturbance only a part of the lactose given is resolved by lactase into dextrose snd galactose. These products are either burnt i n the body or in the case of galactose especially if oxidative processes are not efficient excreted in the urine. A second part of the hctose administered is absorbed as such and leads to Inctosuria. The remain- ing and largest portion is never absorbed a t all but undergoes fer- W.I). H. The Changes in Blood-forming Organs in Typhus Fever. ANDREW LOVE (J. Path. Bact. 1905 10 405-417).-1n this disease the bone marrow is the seat of a well-marked neutrophile reaction and the chief seat of formation of polymorpho-nuclear neutrophile corpuscles. The spleen acts as a scarenger and its main function is phagocytosis. The lymphatic glands are normal. W. D. H. Physical and Chemical Properties of Solutions of Chloro- form and other Anaesthetics. Chemistry of Anesthesia. 11. BENJAMIN NOORE and HERBERT E. XOAF (PYOC. Boy. Soc. 1906 '77 B 86-102. Compare Abstr. '1904 ii 501).-Confirmation is given t o the theory that chloroform and other a n d h e t i c s form unstable com- pounds with proteids and prodnce their effects by thus interfering with the chemical activities of protoplasm.The solubility of the nnmthetics is greater in serum than in water; beyond a certain con- centration which is definite for each anmthetic precipitation of the compound with proteid occurs The vapour pressure is always higher in an aqueous solution than in solutions which contain proteid. Deter- minations of freezing points and electrical conductivity support the main contention of the paper. When the lipoids extracted from setwin or tissues by ether are made into an emulsion with normal saline soln- tion many of them tAke the form of bi-concave discs. Such emulsions are very permanent but separate on the aclclition of aimsthetics or neutral salts in similar fashion to colloidal solutions. W. D. H. R.J. HARvEY GIBSON (Uio-chen2. J. 1906 1 39-53).-An alkaloid is present in West Indian boxwood which is shown to be a cardiac poison by experiments on the excised cat's heart ; the effect is cumulative. I n workmen employing this mood the poison is evidently dissolved by the moisture on their perspiring hands and is absorbed leading t o serious cardiac symptoms. W. D. H. The Toxin of Dysentery. W. D. H. mentative changes in the intestine. Physiological Properties of West African Boxwood. W. D. H. 13-2188 ABSTRACTS OF CHEMICAL PAPERS. y-Ethoxyphenylcamphorylirnide (Camphenal) as an Anti- pyretic. ELIJAH M. HOUGHTON (Yroc. Amer. Pi~ysiol. Xoc. 1905 xxvi-xxvii ; Amer. J. Pi~ysiol. 15).-This substance differs from acetylphenetidine in that an acetyl is replaced by a camphoryl group.In animals i t has no action as an antipyretic. Hordenine its Degree of Toxicity Symptoms of Intoxi- cation. LUCIEN CAMUS (Compt. rend. 1906 142 110-1 13)-Hor- denine sulphate is only slightly toxic. It causes death by arresting respiration. Recovery from large doses is very rapid and the weight of the animal is not appreciably affected during the days following recovery. N. H. J. M. Toxicity of Strychnine Morphine and Quinine to Para- mcecium. ORVILLE H. BROWN (Proc. ' Amev. PlqsioZ. Xoc. 1905 xxiv ; Amer. J. PhysioZ. 15).-Various salts of the alkaloids named of m/100 concentration kill paramecia in times varying from a few seconds to two minutes. W. D. H. W. D. H. Pharmacology of a Colloidal Compound of Strychnine. ORVILLE H. BROWN (Proc. Amer. Physiol. Xoc. 1905 xxii-xxiii ; Amer. J. Physiol. 15).-Fresh egg-albumin hydrogen peroxide and a solution of a strychnine salt when mixed form a gel in the course of a. fetv days which no longer gives the strychnine tests but when injected into frogs i t produces typical strychnine tetanus which starts about five hours after the injection instead of in a fetv minutes. W. D. H. Antitoxic Action of Anions. RALPH 8. LILLIE (Proc. Anzer. Physiol. Soc. 1005 xiii ; Amer. J. Physiol. 15).-The destructive action of the chlorides of calcium barium and strontium on the ciliated cells of the mussel is due to the preponderant action of the cation and is retarded by salts with strongly acting anions. On the other hand toxicity due to a preponderance of the anion (as in sodium salts) is counteracted by cations. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9069005178

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

188 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Production of Methane in Biological Processes. v. ObfELIAN- SKY (Centr. Bcckt. Pav. 1906 ii 15 673-687).-Methane is produced by fermentation from cellulose gum arabic acetic acid egg-albumin glue gelatin wool pFptone and very many otlier substances. It is probable that all soils containing organic matter yield methane. Hence it is impossible to draw any conclusions as to the nature of the decomposing organic matter from the fact that methane is one of the products. N. H. J. M.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 189 Action of Living Microbes on a Solution of Azure-blue in Methyl Alcohol. F. MARINO (Ann. Inst. Pasteur 1905 19 81 6-820).-The preparation of a staining solution for microbes similar to Leishman’s is described.To an aqueous solution of methjlene-blue a little sodium carbonate is added and the mixtnre kept at 60-80° until it takes a purple tint’ an aqueous solution of eosin is then added the mixture left for some time the precipitate collected and dissolved in methyl alcohol. The best results are obtained when two parts by weight of the blue and one of eosin are employed. Reasons are given for supposing that the blue dye and the eosin are not in stable chemical combination in methyl-alcoholic solution. When a little of the staining solution is poured into a tube contain- ing a culture of certain bacilli in bouillon in such a way that it forms a layer above the latter a rose-coloured layer surmounted by a blue layer soon forms on the surface of the culture; this effect is due to the reduction of the blue dye by the bacilli so that the rose colour of the eosin alone appears.Experiments with anthrax and other bacilli show that the rapidity with which the effect described is produced does not depend on the virulence or” the different bacilli towards animals; it is the more rapid the greater the number of bacilli and is favoured by increase of temperature up to 35’. It is suggested that this method might be employed for the detection of microbes which cannot be observed microscopically but the results so far obtained are not conclusive. G. S. Bacteriological Examination of some Samples of Abnormal Milk. ROBERT BURRI and M. D~GGELI (centr. Bakt. Pccr. 1906 ii 15 709-7~4).--Four samples of milk were examined (1) had an odour of Limburger cheese ; (2) an odour of dogs ; (3) had a bitter taste ; and (4) a taste and odour of Glarner Schabzieger cheese.The ap- pearance and characters of the organisms which produced the peculiarities referred t o are described. I n the case of the milk having an odour of dogs i t mas found that whilst the organism produced the odour in peptone broth and some other solutions i t did not have this effect on other samples of milk. It is probable therefore that the original sample of milk (2) was abnormal from the commencement. The organisms responsible for the changes in samples (1) and (3) are very similar and morphologically identical or nearly so. The microbe of sample (4) is very much like Escherich’s Bacterium Zactis aerogenes.N. H. J. M. Fermentation of Guanine. CELSO ULPIANI and MANSANIELLO CINGOLANI ( A t t i R. Accud. Lincei 1905 [v] 14 ii 596-600).-The authors have isolated from the excrements of pigeons a micro- organism which grows readily in a solution containing a small propor- tion of inorganic salts together with guanine which is decomposed yielding urea guanidine and carbon dioxide according to the equation C,H,0N5 + 2H20 + 4 0 = 3C0 + CO(NH,) + NH:C(NH,),. The organism belongs to the class of coccus-bacteria forming most,ly rods which are about 2p in length with swollen and refractile190 ABSTRACTS OF CHEMICAL PAPERS. extremities and are distinctly capsuled. It also presents itself in the form of stout filaments 6-Sp in length and comprising three or four distinct segments furnished with a single capsule.As the culture increases in age these large filaments become more abundant and the phenomena of bacteriolysis are observed. The organism is stained by Gram’s method by magenta (Ziehl’s reagent) which exhibits clearly the capsule and by gentian.violet assuming a uniform colouring. T t is very motile the short rods being endowed with a very rapid move- ment and the larger filaments with a moderately rapid zig-zag motion. The characteristics of the cultures on solid and liquid media are described. T. H. P. Oligonitrophilous and Mesonitrophilous Bacteria in the Soil of the Roman Campagna. R. PEROTTI (Atti 22. Accad. Lincei 1905 [v] 14 ii 623-629).-From the soil about Rome the author has isolated two species of Axotobacter probably A .chroococcuvic and A . ugilis Clostridiurn Yusteuriunzcm and certain pseudomonnds. T. H. P. The Wax of Tubercle Bacilli in Relation to their Acid Resistance. W. T. RITCHIE (J. Path. Buct. 1905 10 334-340).- Fatty or waxy substance can be demonstrated by osmic acid scharlach roth and Sudan I11 in tubercle bacilli in two acid-proof bacilli and in certain bacteria such as Bacillus anthrcccis which are not acid-proof More occurs in the tubercle bacillus than in bacteria which are not acid-proof. The power of resisting acid but not alcohol was restored to a bacillus formerly acid-proof by cultivating i t in a fatty medium. The acid resistance is due to a substance soluble in ether. Tubercle bacilli are no longer acid-proof after treatment with boiling xylene toluene and other reagents.W. D. H. Bacillus Typhosus Simulans. J. G. MCNAUGHT (J. Path. Baet. 1905 10 380-3S2).-Two typhoid-like organisms are described as occurring in water not obviously polluted. Distinctions are described i n the mode of growth on media. W. D. H. Autodigestion of some Yeast Species (Top Fermentation Yeasts Distillery and Film Yeasts). M. SCHENK (Chem. Centr. 1905 ii 181 2-1813 ; from Zeit. $piritusind. 28 397-399 409-410 416. Compare Abstr. 1905 ii 547).-Top fermentation yeast gives rise to the following products on autodigestion succinic acid tyrosine leucine adenine hypoxanthine in truces glutamic and aspartic acids arginine guanidine lysine and tetrsmethylenediamine. Distillery and film yeasts yield besides most of these substances lactic acid uracil and choline and somewhat more hypoxanthine but only traces of glutamic acid.Arginine and guanidine are absent either because the arginine previously present has been converted into tetra- methylenediamine or owing to the action of arginase. The products from top fermentation and distillery yeasts give a marked tryptophan reaction the film yeast however shows no such reaction. E. F. A.VEGETABLE PHYSIOLOGY AND AGRICULTURE 191 Importance of Vegetable Organisms for the Oxygen Supply of Water. W. CRONHEIX (Bied. Centr. 1906 35 1-5; from PEiiner Forsclmngsber. 1904 276).-Attention is drawn to the importance of vegetable organisms in supplying the oxygen required by fishes and for the purification of rivers. Schimanski showed that water which in strong light contained 1.8 C.C.of oxygen per 100 C.C. contained only 0.53 C.C. immediately after dark and only 0.23 C.C. an hour later. Water free from organisms which contained only 0.23 C.C. of oxygen contained 1.45 C.C. after addition of Euglena viridis and two hours’ exposure to light,. N. H. J. 151. Formation of Oxalic. Acid by Aspergillus Niger. CARL WEIIMER (Centr. Bakt. Pur. 1906 ii 15 6SS-G90).-A reply to Charpentier (Abstr. 1905 ii 749. Compare Wehmer ibid. 1892 230). N. €1. J. IT. Action of Aluminium Salts on Germination. H. NICHEELS and P. DE HEEN (Bull. Acad. roy. Belg. 1905 520-523. Compare Abstr. 1905 ii 431).-Jamano has shown that the addition of small quantities of ammonium alum to soil leads to an increased develop- ment in plants grown therein (Bull.CoZZ. Agr. Ttjky6 1905 6 429). This observation has been extended by the authors to the germination oE seeds (wheat) in aqueous solutions. Under these conditions they find that the addition of soluble aluminium salts is injurious whereas the addition of alumina or kaolin is beneficial espe- cially if the solution in which the seeds are germinating is traversed by an electric current carried in by aluminium electrodes (compare this vol. ii 115). T. A. H. Influence of Aluminium Ions on Lupin Seedlinga H. D. HOUSE and WILLIAM J. GIES (L’YOC. Amer. Physiol. Soc. 1905 xix-xx ; Amel.. J. Physiol. 15).-Little or no effect on the growth of seedlings is produced by various aluminium salts a t a concentration of m/G5536. I n concentrations greater than this growth is usually inhibited ; in smaller concentrations down t o m/2097152 growth is usually accelerated.W. D. H. Action of Phosphoric Acid on Higher Plants and a New Nutritive Solution. C. VON DER CRONE (Bied. Centr. 1906 35 30-33 ; from I?zauy. Diss. Bonn 1904 and IVatzww. IL)undsch. 1905 264).-In water-culture experiments with different plants it was found that when phosphoric acid mas absent the root development was retarded and the roots were yeilow when iron (as sulpbate) was present but not in absence of iron. When n phosphate was added the iron was precipitated and its injurious action prevented; the plants then suffered from chlorosis. Good results were obtained when ferrous phosphate and tribasic calcium phosphate were added to the solution. With dibasic calcium phcsphate the plants were chlorotic and the root development more rcs t rict ed.The assumption that the constituents of nutritive liquids should all192 ABSTRACTS OF CHEMICAL PAPERS. be in solution is incorrect. The solution recommended contains per litre potassium nitrate (1 gram) calcium sulphate magnesium sul- phate (each 0.5 gram) ferrous phosphate and tertiary calcium phosphate (each 0.25 gram). N. H. J. M. Respiration of Flowers. MAIGE (Conapt. rend. 1906 142 101-106).-1n most plants the intensity of respiration in relation to the fresh weight and the carbon dioxide liberated decreases regularly from the coivmencement t o the end of flowering. I n a very fewcases however there is an increase during the development of the flower. N. H. J. M.Composition of' the Liquids which Circulate in Plants ; Variations of the Nitrogen in the Leaves. GUSTAVE ANDRE (Compt. rend. 1906 142 106-108).-Determinations of total nitrogen nitrogen as nitrates and phosphoric acid were made in the expressed sap of the leaves of a quickly growing annual (Papaver somniferum) from June 14 t o July 10 and of Pyrethrum balsarnita from May 3 t o June 30. The total nitrogen in the sap of the leaves of Pyrethrum diminished from 0,103 to 0.068 per cent. whilst the phosphoric acid increased. I n the case of Papaver there was a slight increase in the nitrogen whilst the phosphoric acid was highest a t the second date (June 28). The disappearance of the nitrogen as nitrates was much more rapid in the case of Papaver than in Pyrethrum.N. H. J. M. Migration in the Leaves of Acer Negundo. B. SCHULTZE (Bied. Centr. 1906 35 35-37 ; from Verhandl. Ges. deut. Nnturforsch. Aerxte '76 ii 175).-The increase in the weight of leaves under the influence of light is not exclusively due to starch production the amounts of proteids and other substances being also increased. Leaves are able to assimilate carbon to the end whilst the power of producing proteids gradually diminishes-so that finally the leaf becomes poor in the more readily soluble proteids. At the same time the tissues become thickened and fat accumulates owing to diminished oxidation. The leaf has now become useless and falls off. N. H. J. M. Examination of Aethusa Cynapium. FREDERICK B. POWER and FRANK TUTIN (J. Amer. Clzem. Xoc. 1905 27 1461-1476).-This investigation was made with entire fresh plants of Aethusa Cynupium (fools' parsley) collected near London during July and August.The material was found to contain an esseiztial oil which has a rather unpleasant odour is colourless when first distilled but rapidly becomes dark brown and is present to the extent of 0.015 per cent. of the weight of the fresh plant. A mixture of resinous substances mas extracted equivalent to 0.8 per cent. of the weight of the fresh plant from which were isolated a small quantity of pentatriacontane melt- ing at 74" and a crystalline alcohol which melts at 140-141° has [ ~ ] ~ - 3 5 - 7 ~ and is either an isomeride of phytosterol or a lower homologue. When the resin was fused with potassium hydroxide,VEGETABLE PHYSIOLOGY AND AGRICULTURE. 193 formic butyric and protocatechuic acids were produced.Other con- stituents of the plant are d-mannitol i-dextrose and amorphous colouring matter. A small quantity of a volatile alkaloid mas isolatecl which is present only to the extent of about 0.0003 per cent. The physical and chemical properties of this alkaloid and its physiological action indicate that it is probably either coniine or a mixture of bases such as that yielded by Coniurrb maculutunz. E. G. Carbohydrates from Lichens A. ULANDER and BERNHAHD TOLLENS (Be?.. 1906 39 401-409. Compare Muller Abstr. 1905 ii 648).-The lichens are divided into the two following groups I. Group of Iceland Mosses including Cetrariu islandica Evernict prunastra Usnea burbata Cornicularia aculeata and the mould Bulguria inquinans. Amorphous compounds of the type of lichenin everniin and a similar product from Usneu are obtained when these lichens are boiled with water and the extract precipitated with alcohol.When hydrolysed these products yield dextrose. The lichens when hydrolysed with 5-6 per cent. sulphuric acid after extraction with hot water yield large quantities of dextrose and com- paratively little d-mannose and d-galactose. 11. Group of Reindeer Mosses including Cludonia rangijirintc Stereocaulon puscale Yeltigercc aphtoscc. These yield no amorphous products of the type of lichenin and the residues left after extraction with hot water are less readily hydrolpsed. The chief products of hydrolysis are d-mannose and d-galactose together with small amounts of dextrose.The residue left after hydrolysis consists essentially of cellulose. J. J. S. Both groups contain pentosans and methylpentosans. Fruit Juice Statistics. HEINrtICH 'I,UHRIG ADOLF BEYTIXIEN L. WATERS ADOLF JUCKENACK F. MORSCHijCK and A. and M. DOMINIKIEWICZ (Zeit. Nuhr.. Genussm. 1905 10 7 13-744).- Tabulated results of the analyses of numerous samples of fruit juices made during the year 1905 are given. The samples include currant cherry bilberry raspberry blackberry and strawberry juices. w. P. s. Importance of Asparagine and Lactic Acid for the Feeding of Non-carnivorous Animals. OSCAR KELLNER (Bied. Centr. 1906 35 45-48 ; from Yei~l~uiadl. deut. Nutu2foorsch. Aerxte 76 ii 145).- The results of experiments with sheep indicated that lactic acid is simply oxidised and produces only heat which is not required. With a low proteid food asparagine indirectly economises a small amount of pro tei d. N. H. J. M. Manurial Experiments with Lime. M. HOFFMANN (Bied. Certtr. 1906 35 12-21; from Arb. deut. Landw.-ges. Heft. 106).-The results of five years' experiments in different places showed that as a rule application of lime is beneficial. As regards the effect of lime on leguminous plants most of the194 ABSTRACTS OF CHEMICAL PAPERS experiments failed owing to dry weather. I n some cases aowever very marked results were obtained even yellow lupins being benefited by lime in conjunction with kainite. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9069005188

出版商:RSC    

年代:1906

数据来源: RSC