摘要:

MINERALOGICAL CHEMISTRY. Mineralogical Chemistry ii. 119 Mineral Oils from Potash-Salt Deposits. EDMUND GRAEFE (C‘entr. Min. 1911 1-4).-Two oils differing nidely in their characters are compared I is from the potash-salt works “Desdemona” a t Alfeld on the Leine and I[ from the salt works “Gliickauf ” at Sander shausen. I. 11. Yellow transparent ; Dark brown ; ..................... Colour &c. { thin liquid. v1scous. Sp. gr. ....................... 0.802 0.935 Ignition point ............... 16” over 100“ 0‘95% Sulphur ........................ 0‘034% Iodine number ............... 1.54 11-47 Paraffin ........................ 9’36% 4‘30% M. 13. of paraffin ............ 54.4” 56 ‘2” Heat of combustion ......... 10,883 10,534 Boiling point ................. 115” 300” Distillate up to 300” - .........54 % ........................ 35.5% Asphalt 0% Suggestions are offered to explain as to how oils with these different charactors may have originated. Composition of Fahlerz. A. KRETSCHMER (Zeilsch. Evyst. Min. 1910 48 484-513).-A historical review is given of the different formulz that have at various times been proposed for fahlerz (tetra- hedrite and tennantite) and one hundred and sixty-two published analyses are tabulated. Fifteen new analysis are given. Details of the method of analysis are given; the material was decomposed in bromine vapour in a current of carbon dioxide. The material analysed in some cases was massive and not of ideal purity (and in others the fact that the fracture was uneven rather than conchoidal indicates that the material was not homogeneous).I. Crystals from Horhausen Rhenish Prussia. 11. Massive from Hornachuelos Cordoba Spain. 111. Massive from Huanchaca Bolivia IV. Crystals from Schemnitz Hungary. V. Crystals from Aurora mine Dillenburg Nassau. VI. Crystals from Kapnik Hungary. VII. Crystals from Botch Transylvania. VIII. Massive from Schwaben mine Musen Westphalia. IX. Massive from Kotterbach Zips Hungary. X. Crystals from Gross-Kogel Brixlegg Tyrol. XI. Massive from Mouzain Algeria. XII. Crystals from San Lorenzo mine Santiago Chile. XIII. Crystals from Guanajuato Mexico. XIV. Crystallised (“ julianite ”) from Friederike Juliane mine Kupferberg Silesia. XV. Crystals (tennantite) mixed with erubescite from C~okls Kitchen mine Bedruth Cornwall. L. J. S.ii.120 ABSTRACTS OF CHEMICAL PAPERS. I. 11. 111. I v. T. TI. VII. TIII. I S . s. s I. SJI. XIII. s IT. x v. CU. 37-75 38.95 29.99 37.93 38.52 38.59 36.10 33-30 4057 40.91 42’35 42.05 42.15 48-50 53.24 Ag. Zn. Fe. 0’11 6-51 1’10 0.02 2.21 4-77 12‘74 2.49 3-29 0.45 7‘57 0.60 0-08 7.05 0.94 0‘68 6.16 1.05 1’51 6-44 0.78 1-70 5-32 2.66 0‘03 1.61 4.53 0‘23 4-85 2.57 0.09 1.48 4.31 0‘04 6-09 1-48 1-31 2’62 5‘44 0.23 - 2.77 I 0 23 1-58 Pb. Sb. 0.71 28.66 - 27’00 0‘25 26.42 - 26’12 - 25.26 - 24.98 2.72 24-0C O*S3 23-44 - 20.60 - 15-77 - 14-51 - 10.87 - 4‘66 I 2-44 - - As. 1.40 0 -58 I -84 2’69 2’25 2 *75 4 *48 5.07 9.03 10.24 12’57 16-68 18.82 18-29 - S. 24’61 25-66 23‘71 25’21 25‘22 25-35 24-99 23.83 25-21 26.34 26.38 27’12 27’61 27.04 26.54 Total. 99.98§$ 100’01 99.47 99.72 99.76 99*20* 100.13-l 99.06s 99.892 100.5011 99‘36 100.22 100-47 100*24** 100.11-tJ- Sp. gr.5.079 4’680 4‘769 4.780 4.736 4.794 4.870 4.779 4.651 4’738 4-740 4‘597 4 - 3 6 4.692 4.746 3s Including Ri 0.53. * Including SiO 0-14. J. Including Mn 0.26 ; SiO 0’32. § * Iiicluding Ni 2’49 ; Hg 0.75 ; 8i02 0.26 the nickel ia present in an admixed nickel mineral. 2 Including Hg 1’52 ; BaS04 0 75. II Including Hg 0-80. ** Including insoluble 0’44. tJ. Including insoluble 0’23. The formula deduced from these analyses is (&’,R”)3R’’’S3+2//2 where R = Cu Ag ; R” = Zn Fe etc.; R”’ = Sb As BI ; x + y = 3. This is identical with the formula proposed by Prior and Spencer 3R,’S,R2”’S + x(GR”S,R,S,) (Abstr. 1900 ii 21). In the latter formula R,’S and R,”S are regarded as isomorpbously replace- able whilst the present author regards RdR3”’ and Rgl’R2’’’ as equivalent L. J.S. Braunite from Minas Geraes Brazil. B. JE~EK (Zeitsch. Ilryst. >fin. 1910 48 543-544; from Rozpravy bohm. Akad. 1908 13 11. KI. No. 7).-A crystallographic description is given of small brilliant crystals. The finely granular matrix of these crystals proved on analysis to be also braunite MnO. 0. Fe,O,. BaO. SiO,. H,O. Total. Sp. gr. 83.76 8-20 1-18 0.98 3’93 0.50 93-55 4.69-4‘72 L. J. S. Chromite from the Marjalahti Meteorite Analcite ‘ from Brodtorp. LEONARD H. BORGSTROM (Zeitsch. Kryst. Nin. 1910 48 540-541 ; from Geol. i%r. Stockholm B’orh. 1908 30 331-337)- On the olivine and in contact with the nickel-iron of the Marjalahti meteorite (Abstr. 1905 ii 537) are small crystals of chromite some of which are rich in faces.Analysis gave Cr,O,. AI20,. FeO. MgO. N O . Total. Sp. gr. 65’63 3.78 25’84 4‘27 0.73 100.25 4.93 Analcite occurs as crystals in cavities in granulite at Brodtorp. Analysis gave SiO,. A1,0,. Fe,O,. Na,O. K,O. H20. Rp. gr. 5-1 22 trace 12 trace 8 2 241-2.246 L. J. S.MINEKA1,OGICAL ClIEMlSTRY. ii. 121 Calcium Carbonate. J ~ Z E F NOROZEWICZ (Zeiisch. Kryst. Min.. 1910 48 522-523 ; from Kosrnos Leinberg 1907 32 487-495).- The name Zublinite is applied to a variety of calcium carbonate occurring as felt-like masses in crevices in chalk-marl a t Wysokie govt. Lublin Russian Poland. Analysis gave CaO 55.13 ; CO 43.06 ; insol. 1-04 ; loss on ignition 0-95. Under the microscope the fibres are strongly birefringent with oblique extinction ; they are therefore crystals of calcite greatly elongated in the direction of an edge of the primary rhombohedron.Small crystals of aragonite prepared artificially by precipitation with ammonium carbonate were heated for several hours at a low red- heat ; they thereby became transformed into calcite. When heated to bright redness the crystals were converted into lime although still preserving their external form. These isotropic crystal skeletons when moistened with ammonium carbonate solution are converted into calcite. The carbon dioxide can thus be removed and again replaced without destroying the external form of the crystals. L. J. S. Natramblygonite a New Mineral. WALDEMAR T. SCITALLER (Amer. J. Xci. 1911 [iv] 31 48-50).-This mas found in association with tourmaline lepidolite and albite in a pegmatite mass near Canon City Colorado. It is a massive cleavable greyish-white mineral resembling amblygonite in appearance from which it differs in contain- ing sodium in place of lithium being in fact a soda-amblygonite.The formula (Na,Li) AI(OH,F)PO is analogous to that of amblygonite. Analysis gave Total. P,O,. .A1,OJ. Li,O. Na,O. K,O. H,O. F. (1essOforF). Sp. gr. 44.35 33.59 3-21 11.23 0'14 4'78 5.63 100.56 3'04 L. J. S. Terminology of Alumosilicates. J ~ Z E F MOROZEWICZ (Zeit. Krygt. Min. 1910 48 523-524; from Kosmos Lemberg 1907 32 496-499).-The decomposition of alumosilicates gives rise to alumo- silicic acids there being a greater affinity between silicon and aluminium than between aluminium and the metals of the alkalis and alkaline earths.Lembsrg and Thugutt have obtained the well-crystallised compound 4(Na2AI2Si,0,),5H2O by acting on kaolin (H A!,Si,O,,H,O) with a 15% solution of sodium hydroxide. Kaolin is thus a n alumo- silicic acid of the foilowing series with the general formula H,Al,Si,O alumodisilicic acid kaolin (without water of crystallisa- H A1,Si,Ol alurnotrisilicic acid cimolite (without water of crystal- H Al2Si4Ol2 alumotetrasilicic acid pyrophyllite ; leucite is the H2AI,Si,01 alumopentasilicic acid in harmotone. H2A1,Si,0! alumohexasilicic acid in albite which is thus sodium H y q s m n + 4 . tion) ; in sodalite nosean etc. lisation) ; in natrolite. potassium salt K2A1,Si,01,. alumohexasilicate Na,A1,Si601,.L. J. S.ii. 122 ABSTRACTS OF CHEMICAL PAPERS. Solid Solution in Minerals with Special Reference to Nephelite. HARRY W. FOOTE and W. M. BRADLEY (Amer. J. Sci. 191 1 [iv] 31 25-32).-Even allowing for the presence of mechanically admixed impurities and isomorphous replacements there are certain minerals for which a satisfactory and simple formula cannot be deduced. It is suggested that in such cases some other constituent may be present i n the state of solid solution in the mineral in much the same way as salt is dissolved in water or as homogeneous crystals of ammonium chloride may contain ferric chloride (Roozeboom 1892). Here we have homogeneous mixtures of different compounds (not of the same type as in isomorphous mixtures) which cannot be separated by mechanical means and between certain limits the composition of such mixtures may vary continuously.This principle is held to apply in the case of nephelite the formula of which approximates to but never in the natural mineral quite agrees with the simple formula NaAlSiO,. This formula corresponds with those of the isomorphous minerals eucryptite Li AlSiO and kalio- philite KAlSiO ; and the artificial nephelites prepared by Doelter in 1 S84,varyfrom NaAlSiO to compounds containing potash and an excess of silica. The following is the mean of four analyses made of carefully purified nephelite from Eikaholmen Norway ; the material contained a trace of intimately admixed albite (insoluble in hydrochloric acid) but under the microscope it appeared to be homogeneous.SiO,. Al,O,. Fe,O,. K,O. Na@. H,O. Total. Sp. gr. 44'46 33-11 0 96 5'61 16-32 0.38 100.84 2.635. The molecular ratios are SiO,:Al,O etc. Na,O etc. = 2.23 1.00 0.98. I n the nephelite analyses by Morozewicz (Abstr. 1908 ii 201) AI,O Na,O also = 1 1 whilst the ratio of SiO A1,0 varies from 2 11 to 2.21 and the same relations hold wibh other published analyses. It is therefore assumed that the excess of silica over that required by the formula NaAlSiO is present in solid solution in the sodium aluminium silicate. The (' saturation ratio " of the silica is 2.21 since when more silica is present this has separated as albite (NaAlSi,O,) which occurs intimately intermixed with the nephelite. L. J. S. Chemical Distinction betwaen Orthoclase and Microcline.WLADIMIR I. VERNADSKY and Mlle. E. REVOUTSKY (Compt. rend. 1910 151 1372-1374. Compare Barbier Abstr. 1908 ii 704).- Barbier has indicated as a general chemical distinction between orthoclase and microcline the existence of traces of lithium and rubidium in the former and their absence from the latter. This being contrary to observations of one of the authors (Bull. Acad. Xci. St. Petersburg 1909 114 822) five new specimens of microcline from Russia Colorado Norway and Finland have been examined spectroscopically with the result that either lithium or rubidium or both were found to be present in each specimen. w. 0. w.PHYSIOLOGICAL CHEMISTRY. ii. 183 Remarkable Garnet from Fluminimaggiore [Sardinia]. AURELIO SEBRA (Rend. Accatd. Sci. Fig. Mat. Napoli 1910 [iii) 10 222-224).-The garnet mas found in association with galena.It has the following composition SiO,. A1,0,. FP,O~ FeO. MnO. CaO. Total. 34.53 6'05 25.10 0'84 trace 33.67 100.19 which indicates that it is andradite in which the silicate Ca,Fe,(SiO,) is associated with Ca,Al,(SiO,),. The colour of the mineral is honey- yellow and in this and other respects it is similar to a garnet from @ah in Isvezia (also found in association with galena) which was analysed by Bredberg. R. V. S. Chemical Composition of the Gases Evolved from the Thermal Spring at Uriage (Is6re). GUSTAVE MASSOL (Comnpt. rend. 1910 151 1124-1126. Compare Abstr. 1908 ii 1004; Besson ibid. ii 1005).-The spring at Uriage evolves a mixture of gases composed of nitrogen 03*98% carbou dioxide 4.1 50/ rare gases 1.87% with traces of oxygen.The rare gases were passed over wood charcoal a t the temperature of liquid oxygen when about half the volume consisting of argon krypton and xenon was absorbed. The remaining gas contained neon and helium the latter constituting 0.932% of the original mixture. The spring probably emits not less than twenty litres of helium daily and is one of the most considerable sources of t h i s element hitherto discovered. w. 0. w. Ratio of the C1- SO,- and ao-Values of a Series of Sea- water Samples Examined in the Hydrographical Laboratories of Heleingfors Kiel Christiania Monaco and Nancy. EHNST RUPPIN (Zeitsch. anorg. Chem. 1911 69 232-246).-Analyses of sea- waters collected at different depths show that there is a fairly definite connexion between density salt content and percentages of SO and C1 although this has been disputed. A recalculation of Dittmar's results (Reports of Voyage oj H.Z.S. Challenger 1873-76 ; Physics and Chemistry Val I) shows that the salt content of the sea-waters examined can be determined from a knowledge of the chlorine content. T. S. P.

ISSN:0368-1769    

DOI:10.1039/CA9110005119

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Ph y sio 1 o gical C h e mi s tr y. ii. 183 Action of Asphyxia on the Spinal Animal. G. C. MATHISON (J. Physiol. 1910 41 416-449).-Lack of oxygen is tbe main factor in asphyxia in the spinal animal b u t the spinal vaso-motor centres are much less sensitive to various agencies than the medullary centres. Excess of carbon dioxide and injection of acids act on the spinal cord much in the same way as lack of oxygen. *W. D. H.ii. 124 ABSTRACTS OF CHEMICAL PAPERS. Physiological Climatology. I. Relation of Loss of Water from the Skin a n d L u n g s to t h e External Temperature in Actual Climatic Conditions. WILLIAM A. OSBORNE (J. Pliysiol. 1910 41 345-354).-The usual statement that heat loss by radia- tion and conduction makes up the greaterportion of the total heat loss is only true under certain conditions; an air temperature equal to that of the body would reduce this loss to zero.If the metabolism of the body is constant during rest and the heat production fairly constant i t follows that if the air temperature is raised and loss by radiation and conduction lessened the heat loss due to evaporation must make up the balance otherwise heat accumulation mould occur. It would be expected therefore that the water loss would be a linear function of the air temperature. The linear relationship is however more perturbed; the cause is not clothing but is more complex ; one factor is the varying humidity and velocity of the air. If the air is dry and in movement it will tend to desiccate the skin but if body temperature and skin imbibition are to be kept constant then the metabolism must be augmented.What apparently occurs is a compromise; the skin loses some of its water of imbibition and the metabolism undergoes a moderate rise. Hence the unpopularity of the East wind in N.W. Europe. The lung ventilation is increased when the air temperature is high; this is a familiar fact with the lower animals. How the respiratory centre is affected by a high air temperature is a puzzle for the body temperature does not rise; possibly the carotid blood may become heated in its passage up the neck. It is also found that the carbon dioxide excreted varies directly not inversely as the external temperature ; the increase in pulmonary ventilation will in part explain this ; more carbon dioxide is produced from the additional work of the respiratory muscles and more “washed out” from the tissues.There is some indication that the respiratory quotient rises with rising shade temperature. Harvey Sutton found that this quotient approached unity when the wet bulb-temperature rose in a room which he could artificially make warm and moist and made some suggestions regarding the relation of this reaction to the preponderance of carbohydrates in the diets of tropical aboriginals. W. D. H. Influence of Lactic Acid on the Dissociation Curve of Blood. JOSEPH BABCROFT and L. ORBELI (J. Physiol. 1910 41 355-367).-Lactic acid is a valuable accessory to carbon dioxide in tissue respiration ; both tend to turn out the oxygen from the blood. The method of determining the tensions of the bloodgases is by a new tonometer which is figured and described in detail ; for this and for the discussion of certain difficulties which arise the original paper must be consulted.W. D. H. The Action of Choline on Blood-pressure. LEO POPIELSKI (Zeitsch. physiol. Chem. 1910 70 250-253).-The author reiterates the view expressed previously by Modrakowski and himself thatPHYSIOLOGICAL CR EMISTRY. ii. 135 choline produces a rise of arterial pressure and that the opposite result obtained by others is due to their having used impure-material. W. D. H. The Effect of Potassium Salts on the Circulation with Special Reference to the Production of Heart-Block. G. C. MATHISON (PTOC. physiol. Soc. 1910 xix-xx ; J. Physiol. 41).- Potassium salts cause vaso-constriction when both brain and spinal cord are destroyed; they therefore act directly on the vessel walls.On the heart large doses produce diastolic stoppage but in some cases smaller doses produce heart-block from which recovery occurs. W. D. H. The Influence of the Blood-corpuscle Lipoids on the Blood Formation. L. KEPINOW (Biochem. Zeitsch 1910 30 160-172).- The author shows that by the injection of blood-lipoids from ox-blood into rabbits rendered antemic by bleeding the rate of formation of new blood corpuscles is increased. The regeneration took about half the time to that required by control animals which had received no lipoid injection. The same result was not achieved by ovolecithin. S. B. S. Blood Sugar. VIII. The Sugar Content of the Corpuscles.PETER RONA and DENGO TAKAHASKI (Biochem. ZeitscA. 1910 30 99-106).-The authors confirm the observations of others as to the probable presence of dextrose in the corpusdes. The proteins mere precipitated by the Micbaelis-Rona dialysed iron method sodium dihydrogen phosphate being the salt employed for precipitating the colloid and the reducing power and polarisation were estimated in the filtrate before and after fermentation by yeast. I n the latter case the reducing power almost completely disappeared. The authors give a large number of estimations of the sugar in blood and serum especially in the case of dogs after bleeding where there is an increase of blood sugar and call attention to the possible clinical importance of differentiating between the blood of the corpuscles and the serum. s.B. s. The Behaviour oA the Red-blood Corpuscles in Chronic Oleic Acid Poisoning. ALEXANDER SCHMINCKE and FERDINAND FLURY (Arch. exp. Path. Phmm,. 1910 64 126-140).-1f the red corpuscles contain the normal amount of iron they show an increased specific resistance towards the hzmolytic action of oleic acid in cases of chronic poisoning by that substance i n dogs; this is attributed specially to an increase of the lipoid materials in the corpuscles ; these consist of a mixture of saturated and unsaturated fatty acids united to cholesterol. W. D. H. Cocaine Hmmolysis. ERNST P~IBRAM (PJliiger’s Archiv 19 11 137 350-358).-Koppe’s hypothesis that the hmolysis produced by cocaine is due to acid decomposing the alkaloid cannot be correct for it occura in neutral and increases in alkaline solutions and the sameii.126 ABSTRACTS OF CHEMICAL PAPERS. is true for the hzmolysis produced by other members af the cocaine group eucaine and novocaine ; these produce an elevation of the surface tension of the solvent in an alkaline medium. The non-toxic members of the group (ecgonine etc.) produce little or no such change. The physical and biological properties of the a1 kaloids run parallel with their pharmacodynamic properties and probably there is a causal relationship between them ; the anaesthetic and toxic properties rise with the changes they produce in surface tension and hsmolysis. Gros moreover has shown that their anaesthetic preperties:are increased when in an alkaline medium W.D. H. Vegetable Agglutinins. FRITZ RSSMANN (PJiiger’s A r c h 191 1 137 489-5 lo).-Previous work on vegetable agglutinins is referred to in relation to such toxic proteins as ricin and abrin. Previous writers manifest a good deal of difference of opinion on the mode of action of such poisons. A number of plants (beans vetches etc.) yield similar relatively non-toxic substances for which the term phasin (from Phaseolus) is adopted. Details are given of the agg!utinating action on various kinds of blood of both the toxic and non-toxic members of the group. The non-toxic compounds are believed to contain the same agglutinating component as is present in such toxic compounds as ricin but to be destitute of the toxic elem en t. W. D. H. Calcium Metabolism. I. A New Method for the Quanti- tative Estimation of Small Variations of the Calcium Content of the Blood.N. VOORHOEVE (Biochem. Zeitsch. 1910 30 195-206).-The method depends on the determination of the amount of calcium necessary to add to the blood to produce clotting after the natural content has been removed by the addition of ammonium oxalate. A syringe of 5 C.C. capacity is so constructed that it can be automatically half-filled with physiological saline containing 229 mg. of ammonium oxalate in 100 C.C. The blood is then sucked into the syringe directly from the veins; and immediately mixed with the oxalate solution. After several hours small measured portions are taken and mixed with varying quantities of calcium chloride isotonic with the saline and diluted with it to a definite bulk.I n this may the amount of calcium necessary to precipitate the excess of oxalate and thus produce clotting can be determined from which the original calcium content of the blood can be calculated. Control experiments where determinations were made by mixing the calcium solution with ascitic fluid etc. show that the results obtained are independent of the amount of proferment present. S. B. S. The Behaviour of Chlorine in the Serum. PETER RONA (Biochem. Zeitsch. 1 9 10 30 332).’-An adaission that the ‘‘ com- pensation-dialysis ” method for estimating the chlorine in serum (this vol. ii 50) was employed previously by Zunz and Loewy. S. B. S. Trypsin Action. The Tryptic Digestion of Caaein. MAX SIEGFRIED (Pfliiger’s Arckiv 1910 136 185-203).-According to thePHYSlOLOCfICAL CHEMISTRY.ii. 127 old theory of Kuhne on hemi- and anti-products of digestion casein (a hemi-protein) should not yield a peptone on tryptic digestion; it was however proved by the use of the iron method for isolating peptones that a peptone can be isolated from a tryptic digest of casein. This is regarded as a chemical unit and a few incomplete details are given of its cleavage products ; the large quantity of ammonia and the small amount of nitrogenous substances which are precipi table by phosphotungstic acid are noteworthy points. The Formation of Carbohydrates from Fat in the Animal Organism. PETER JUNKERSDORF (Pjiiyer’s Avchiu 19 10 137 269-328).-1n dogs during inanition during fat feeding and when under the influence of phloridzin and free from glycogen there is a genetic relationship between the excretion of nitrogen and sugar.I n yhloridzinised animals the’ whole of the sugar however cannot originate from protein because of the high sugar nitrogen quotient and the conclusion is drawn that part of i t comes from fat. I n dogs fed on fat there is at death abundance of body-fat present and the nitrogen and sugar excretion sink The highest excretion both of nitrogen and sugar is shown by those phloridzinised dogs which receive abundant protein and carbohydrate food. The Influence of Muscular Work on the Decomposition of Subcutaneously - administered Sugar. HERMANN HOHLWEQ (Zeitsch. Biol. 1911 55 396-408. Compare Abstr. 1909 ii 162).- I n continuation of previous work it is shown that after the sub- cutaneous injection of sugar the amount which passes into the urine is diminished during muscular work in the dog.This amount (about 20%) is accounted for on the hypothesis that it is utilised as a source of energy by the muscles. Sugars also which the cells are un- accustomed to are similarly utilised and details of experiments show the fact to be so for galactose sucrose and maltose. Lactose however passes quantitatively into the urine both during rest and muscular activity. W. D. H. The Chemistry of Honey Formation. M. KUSTENMACHER (Biochem. Zeitsch. 1910 30 237-254).-The author gives a detailed account of the morphology of the alimentary tract of the bee. In conversion into honey the nectar undergoes the following changes part of the water is evaporated the sucrose undergoes almost complete inversion the starch is converted into dextrin the tannins are oxidised and partly deposited on the walls of the honey cells the oxnlic acid disappears and is resorbed by the body of the bee and the odorous substances undergo a like fate; the mineral substances are partly resorbed and partly reappear in the honey.The invertase is derived not from the bee itself but from the spermatoplasma of the pollen. Diastase however could not be detected in the pollen but arises probably from the saliva or gastric secretion of the animal. W. D. H. W D. H S. B. 8. Protein Metabolism. FRANZ FRANK and ALFRED SCHITTENHELM (Zeitsch. physiol. Chem. 1910 70 98-1 ZS).-Experiments on dogs confirm hlichaud’s discovery that the kind of protein given influencesii. 125 ABSTRACTS OF CHEMICAL PAPERS.the minimum amount capable of maintaining nitrogenous equilibrium after inanition. Much more is necessary of a foreign protein than if the protein of dog’s muscle is given. H. DE WAELE and ALBERT J. J. VANDEVELDE (Biochem. Zeitsch. 1910 30 227-236).-The experiments mere carried out on rabbits with a known diet. The excretion of nitrogen and the protein in the urine were estimated and the changes in the excretion noted after injection of various protein substances. When small quantities of Witte’s peptone were injected there was a small addition of nitrogen to the body substances and in the case of larger iojectioas the animals kept approximately in nitrogen equilibrium. After injection of egg-white a large amount of protein was excreted in the urine which was greater than the amount injected and came therefore partly from the animal’s own body as it underwent loss of weight. After a second injection the loss of weight is smaller.Part OF the increased nitrogen output is in the form of urea. From the results obtained by themselves as well as those of other observers the authors dram the conclusion that the animals gradually acquire the capacity of peptonising tho injected Chemical and Microscopical Investigation on Fat Transport through the Intestinal Wall during Absorption. ALFRED NOLL (PJlugev’s Archiv 1910 136 208-247).-0n the grounds mainly of microscopical and microchemical examination (with osmic acid) the conclusions are reached that the fat which is seen in the epithelial cells has the same composition as that in the chyle that the fat in the epithelium cells is absorbed as fat and not as its cleavage products and that the.fat the course of which can be followed in this way microscopically only accounts for a part of that which is actually absorbed. W. D. H. The Carbamino-Reaction. WALTER SULZE (Pfliiger’s Amhiv 1910 136 712-723).-1f carbon dioxide is passed through a cooled solution of an amino-acid in lime water or baryta water the amino- acid takes up carbon dioxide and R carbamate of calcium or barium is formed. Other organic amino-compounds and hydroxyl compounds react in a corresponding way. This reaction which has been particu- larly studied by Siegfried is described at length for many such com- pounds and is believed t o have a physiological interest.Researches with serum peptone and crysballised serum albumin have shown that substances are present in the blood and lymph which give the reaction. The carbamates formed are readily decomposed and possibly come into action in such physiological occurrences as the production of carbon dioxide in muscles or in the liberation of hydrochloric acid in the gastric juice. W. D. H Physiology of Cell-Division. 111. Action of Calcium Salts in Preventing the Initiation of Clell-Division in Unfertilised Eggs through Isotonic Solutions of Sodium Salts. KALPH 8. LILLIE (Amer. J. Physiol. 1911 27 289-307. Compare Abstr. 1910 ii 522).-The addition of small quantities of calcium chloride to W. D. H. The Fate of Injected Foreign Proteins and Peptones.proteins. s. B. s.PHYSIOLOGICAL CHEMISTRY. ii. 129 isotonic solutions of sodium salts (1) prevents the rapid increase in permeability produced in the unfertilised eggs of dsterias and Aq-bucia by the puro solution; (2) lessens the toxicity of the solution and (3) prevents the membrane formation and initiation of cell-division \v hich are induced by the pure solution. The toxic action of the pure salt solution and i t s action in initiating cell-division are due primarily t o a condition of increased surface permeability. This increase is how- ever temporary in normal fnvourable parthenogenetic fertilisation. Treatment with hypertonic sea-water after the formation of fertilisa- tion membranes by salt solution leads to an increase in the proportion of successfully developing eggs. W.D. H. The Dextrose of the Egg and its Biological Significance. VINCENZO DIAMARE (Rend. Accad. Sci. -Fig. ,%!at. Nctpoli 1910 [iii] 16 242-244. Compare Abstr. 19 10 ii 320)-From experiments with eggs of the domestic fowl and of Testudo graeca it appears that those nearing maturity (in the ovary) contain dextrose of which about equal amounts are removed by dialysis and hydrolysis respectively. I n the younger eggs the proportion of dialysable sugar is less and in the very smallest no reducing sugar is present. R. V. S. Lipoid Nature of an Active Substance Secreted by the Corpus Luteum of Mammals. P. BOUIN and P. ANCEL (Compt. rend. 1910 151 1391-1393),-When the corpus luteum of a sow is extracted with physiological salt solution a turbid extract is obtained.After centrifugation the.clear liquid is found t o show no characteristic physiological properties the substance in suspension however when injected into rabbits produces sneezing nystagmus convulsions and finally death from respiratory arrest. The active substance does not occur in any other part of the ovary. Its behaviour towards solvents acids and alkalis and its stability to heat when dry suggest that the substance is of a lipoid nature. w. 0. w. The Alkaline Odour. MAX VON FREY (PJEiiger's Arcliizq 1910 136 275-281).-The so-called alkaline taste is really due to the sense of smell; it depends on the development of volatile bases (methylamines) which are decomposition products of epithelial cells. Freshly secreted saliva does not contain these bases.W. D. H. Sulphur Compounds of the Nervous System. 11. A Sulphatide from Nerve Substance. WALDEMAH. KOCH (Zeitsch. physiol. Chem. 1910 '70 94-97).-The sulphatide was prepared from human brain ; the analytical figures given of various preparations do not appear very concordant; the S N ratio i3 given as 1 ; 3.03. The preparation regarded as the purest contained 3.1% of potassium. The sulphur is considered to act as a link in connecting phosphatidcs and cerebrosides. W. D. €I. Chemical Investigations of Healthy and Rachitic Bones. TH. GASSMANN (Zeitsch. plkysiol. Chem. 1910 70 161-170).-Normal VOL. c. ii. 9ii. 130 ABSTRACTS OF CHEMICAL PAPERS. bones contain about 1% more water than those in rickets; calcium phosphoric acid and carbon dioxide are less in rachitic than in normal bones.The rela- and the complex in which they are contained is suggested to be (I). Other details given refer to magnesium (increased in rickets) potassium sodium chlorine etc. W. D. H. tionship Ca:PO,:CO is the same in both ; (1.1 Action of Tervalent Ions on the Heart and on Certain Colloidal Systems. GEORGE R. MINES (Proc. physiol. SOC. 1910 xvii-xviii ; J. Physiol. 41).-Eight simple tervalent positive ions which were examined agree in producing diastolic arrest of the frog’s heart when perfused at a concentration of 0.00001M. They also all confer a positive charge on gelatin and on agar-agar and precipitate in very low concentration a variety of colloidal solutions with negative particles. The complex tervalent positive ion Co(NH,) scarcely affects the heart in concentrations one hundred times greater but it precipitates negative colloidal solutions and confers a positive charge on agar-agar.It differs from the simple ions in its inability to precipitate unboiled diluted egg-white or dialysed haemoglobin or to confer a positive charge on gelatin or frog’s red corpuscles. The tervalent negative ions of the citrate and phosphate arrest the heart in diastole in concentration 0.01 M. They powerfully antagonise the effects of acid or of tervalent positive ions on the heart. These actions are not shared by the tervalent negative ion of the ferricyanide ; the latter also differs from the other two by being inactive in conferring a negative charge on a gelatin membrane.I n the action of tervalent ions on certain colloidal systems there exists an unexplored factor qualifying the familiar valency law of precipitation and Perrin’s law. This factor is also of physiological importance. W. D. H. The Relationship of Kidney Function and the Glycogen of the Liver. HERMANN FRIEDRICH GRUNWALD ( A ~ c h . exp. Path. Pharm. 1910 64 147-160).-Any severe bilateral kidney injury (extirpa- tion ligature of renal arteries or veins or ureters) leads to a disappear- ance of the hepatic glycogen in spite of feeding on dextrose. The action is attributed to the lack of a chemical stimulus from kidney to liver ; extirpation of the right kidney produces no such effect ; but extirpa- tion of the left kidney (except when it has previously been denervated) and injuries which involve the left kidney nerves lead to a great diminution of the glycogen in the liver.There is therefore in addition to the hormone a nervous stimulus which without passing through the central nervous system runs in the path of the nerves on the left side. The experiments were performed on rabbits. M7. D. H. Formation of Sugar in the Liver. M. LOEWIT (PfEiiger’s ArchZ‘v 1910 136 572-594).-Numorous researches have shown that the liver can produce sugar from substances which are not carbohydrate and in the present research it is shown that the liver free fromPHYSIOLOGICAL CHEMISTRY. ii. 131 glycogen will produce sugar after death. What the parent substance or substances of the sugar are is a question discussed at length but left still open.Tissues other than the liver yield under similar conditions either no sugar after death or only mere traces. W. D. H. The Isolation of a Uricoolastic Ferment. GINO GALEOTTI (Biochem. Zeitsch. 191 1 30 374-383).-Solutions containing this ferment in an active condition were obtained from the livers of the dog and the dog-fish in the following manner The organ was ground with sand and the juice expressed at 300 atmospheres. The juice mas diluted with water the fat separated and an equal volume of acetone added. The precipitate was then filtered off as rapidly as possible and the last traces of acetone removed by spreading on filter paper. The ferment was extracted from the precipitate by means of a very dilute solution of sodium chloride. W. J. Y Chemical Factors of Fatigue.W. BURRIDGE (J. Physiol. 1910 41 285-507).-1n a muscle nerve preparation very small quantities of sarcolactic acid produce fatigue phenomena by acting specially on the end-plates. If more than the merest trace is present free fatigue occurs ; therefore in muscle the lactic acid formed even in rest must be neutralised and creatine is credited with a power to perform this neutralisation. Another chemical factor in fatigue is believed to be the liberation of potassium salts from the active muscles; these also affect primarily the nerve-endings. The Replacement of Calcium in so-called Physiological Fluids. (Experiments on the Excitability of Striated Muscles of Warm-blooded Animals and the Variations oP Tonus of t h e Atrium in Emys europea.) GIUSEPPE BUGLIA (Zeilsch.Uiol. 191 1,55 343-359. Compare Abstr. 1910 ii 630).-Tho excitability direct and indirect of striated muscles soon disappears in Ringer’s solutiou if the calcium in it is omitted and is restored on the restor- ation of that element. The place of calcium cannot here be taken by czsium. In the variations of tonus in the atrium of the tortoise c;xsium also has not the same action and cannot replace calcium. I n both varieties o€ striped muscle the action of cmium is different from what occurs in smooth muscle. Tv’4. D. H. W. D. H. Investigations on Smooth Muscle IV. The Replacement of Calcium in so-called Physiological Fluids. (Experiments on Smooth Muscle ; Dog’s Oesophagus.) GIUSEPPE BUQLIA (Zeilsch. Biol. 1911 55 360-376. Compare Abstr.1910 ii 630).-ln maintaining the rhythmical contractions of the smooth muscle of the dog’s msophagus i t has been previously shown that casium chloride can replace calcium chloride in Ringer’s solution. Czsium nitrate or iodide can also be used; the sulphate is not so efficacious the anion appearing to have a harmful effect. A large number of other metallic salts were employed with negative results ; the only one found to act like caesium chloride was rubidium chloride. W. D H. 9-2ii 132 ABSTRACTS OF CHEMICAL PAPERS. Some Changes in Normal Tissues Produced by Radium. ALBERT S. GRUNBAUM and HELEN G. GJ~UNBAUM (PYOC. plqsiol. Soc. 1910 xviii ; J. Physiol. 4l).-Radium destroys liver cells but only t o a short distance ; in the gall bladder no obvious changes occur ; in the stomach an atrophic fibrosis of the mucous membrane and destruc- tion of the submncosa take place.The effect on incubating eggs is like that of X-rays to destroy the embryo. I n the skin the inflamma- tion produced is characterised by a relative absence of polynuclear leucocytes and the presence of many plasma cells. W. D. H. A Microchemical Method for Demonstrating the Presence of Guanine in Tissues. ANATORE DE GIACOMO (Zeitsch. wiss. dlikroscop. 1910 27 257-258).-A method was required for demonstrating the presence of guanine in the renal system of birds. The animal tissue (after the usual preparation) is treated with a solution of diazobenzenesulphonic acid (which has been previously tested and found sensitive t o guanine); after about ten minutes sodium hydroxide is carefully added when the presence of guanine is shown by a red coloration; in its absence the tissues remain pale ye1 low I?.M. G. M. The Oxidation of Succinic Acid by Animal Tissues. FR. BATTELLI and LINA STERN (Biochem. Zeitrrch. 1910 30 172-194).- All tissues of higher animals possess the capacity of oxidising succinic acid. This oxidation does not cause a n increased output of carbon dioxide as inactive malic acid is the product produced. The most active tissues are the heart muscle and liver with the exception of rabbit's muscles. The oxidative power of the blood is not very marked. The substance causing the oxidation cannot be extracted from the tissues by water and the tissues also lose their oxidative capacity after extraction with alcohol or acetone.The reaction takes place best in neutral or slightly alkaline media at the optimum temperature of 40'. The reaction rate is greater in pure oxygen than in air. Hydrocyanic acid acts toxically on the reaction but other substances such as arsenious acid and sodium fluoride have but a relatively small effect. 5. B. S' The Biological Significance of Inositolphosphorio Acid (Phytin). EMIL STARKENSTEIN (Biochem. Zeitsch. 19 10 30 5 6-98). -It was found that inositolphosphoric acid gives a precipitate with uranium magnesium and lead salts but not with ammonium molybdate in nitric acid solution. For this reason only the latter reagent is available for estimation of free phosphoric acid in the presence of phytin. The commercial preparation of the latter substance contains free inositol and phosphoric acid.To prepare pure phytin from the commercial product the latter is dissolved in dilute acetic acid and lead acetate is added; only the inositolphosphoric acid lead salt is precipitated. This after washing and decomposition is decomposed by hydrogen sulphide and the filtrate is treated with glacial acetic acid and calcium acetate until a precipitate is formed. The pure phytin (inositolphosphoric acid) is then obtained in the form of a nPHYSIOLOGICAL CHEMISTRY. ii. 133 insoluble calcium salt. The conclusion is drawn from the'analysis of the salts that phytin is a complex derivative of pyrophosphoric acid (for which a formula is suggested). The author gives an exhaustive review of the literature from which is drawn various conclusions the chief being that the free inositol in the body has no particular physiological significance.I n view of the fact that inoqitolphosphoric acid is also precipitated by various reagents for phosphates he draws attention to various possible errors in phosphate estimation in YOSFIISUMI TAHARA (Biochem. Zeitsclh. 19 10,30 255-275).-The toxin was extracted from the ovaries of the fish and from the aqueous extract the proteins were separated by heating the solution after acidification with acetic acid. Prom the solution thus obtained the phosphates etc. were precipitated by lead acetate. From the filtrate on addition of ammonia (not more than 0.34%) the toxin is precipitated with lead acetate. This is then decomposed with hydrogen sulphide.On evaporating under low pressure to a syrup and adding alcohol a precipitate is formed whilst the greater part of the toxin remains in solution and can be precipitated therefrom by the addition of ether. From the precipitate by redissolving in water and treating as before with alcohol and with ether a further amount of toxin can be obtained. The tetrodotoxin obtained in this way is not pure but contains a sugar tetrodopentose which is deposited in stout colourless prisms on keeping the solution and a crystalline base which does not melt even at 280° has the formula C,,H,,O,N and can be precipitated as an auri- chloride from a solution of the crude tetrodotoxin. The tetrodotoxin freed as completely as possible from these two substances has the approximate formula CI,,H~,O,,N. It is very soluble in water but is insoluble in most organic solvents although soluble in aqueous alcohol.It reduces Fehling's solution and its toxic dose mas found to be 0.0041 mg. per gram of body-weight for mice and 2.5 t o 4 mg. per kilo. for rabbits. The toxicity is readily destroyed by mineral acids alkalis and strong ammonia. Tetrodotoxin is neither acid nor base and yields on hydrolysis a base and a crystalline substance. The author considers that tetrodotoxin is not a protamine. Occurrence of HEematoporphyrin in the Meconium. V. BORR~EN (J. Yharm. C?~ivz 191 1 [vii] 3;59-63).-H=matoporphyrin bas been detected spectroscopically in a purified acetone extract of the meoonium The author suggests therefore that the passago from blood pigment to biliary pigment takes place in the following stages haemoglo bin -+ hsmatoporphyrin -+ bilirubin. FRANZ SPINDLER (Biochern.Zeitsch. 1911 30 384-412).-The activity of the catalase was compared in a number of samples of milk from healthy and diseased cows and also i n pre- parations from cow's milk and in milk from other animals. A. measure of the activity was obtained by determining the total volume of oxygen liberated at 37" by 15 C.C. of milk from 5 C.C. of 1% hydrogen peroxide by means of :Lobeck's 6' catalase glass," urine e t a s. €3. s. Tetrodon Poison. S. B. S . T. A. H. The Gatalase of Milk.ii. 134 ABSTRACTS OF CHEMICAL PAPERS. It was found that the activity was greater in sour than in fresh milk and increased with the age of the milk. This was however partly due to the growth of moulds in the milk.Sour milk products like Bulgarian &‘ Yoghurt ” and ‘‘ Kephir,” also contained more active catalases than fresh milk. Diseases of the udder and other complaints were accompanied by a markedly increased activity in this ferment and this activity decreased to the average for normal milk as the animal regained its health. The method is suggested as a means of detecting disease in cows. W. J. Y. The Excretion of Subcutaneous Injections of Sodium Chloride and their Effect on Nitrogen Metabolism. G. THOSIANZ (Zeitsch. Biol. 1910 55 241-266).-Dogs were kept on a constant diet containing known quantities of sodium chloride phos- phoric acid and nitrogen and the daily excretion of these three substances determined in the urine and fzeces.I n each case after a period of from two to four days solution of sodium chloride was injected and the effect produced on these excretions observed The effect was tried of varying the concentration of the salt (1) when the diet employed was rich in sodium chloride; (2) when the food contained only small quantities of this salt and (3) during starvation. The injections varied from 116 C.C. of 0.3% NaCl to 20 C.C. of 10% NaCI. Similar experiments were also carried out in which 100 C.C. of a solution of urea (5 or lo%) containing in some cases 1% NaC1 were injected into the animals. It was found that when equal amounts of sodium chloride mere injected the time required for the whole to reappear in the excretions was less the more concentrated the solutions employed.With a diet rich in sodium chloride injections of hypo- and iso-tonic solutions of sodium chloride caused no perceptible increase in the nitrogen output hypertonic solutions produced a slight increase? whilst urea was almost quantitatively recovered in the excretions and had no effect on the nitrogen metabolism. With food poor in sodium chloride even hypotonic solutions of salt produced a marked increase in the nitrogen excreted. The effect was still further marked in the case of starving animals both salt and urea causing an increased nitrogen metabolism. Practically no changes were observed in the phosphoric acid excreted. W. J. Y. The Excretion of Phosphates Ingested per os Especially of Calcium Phosphate. RAGNAR BERG (Biochem.Zeitsch. 191 0 30 107-142).-The author carried out a series of experiments on his own person taking over long periods of time diets with small cdlcium content in which the caloric value and the protein fat carbohydrate calcium magnesium and phosphoric acid contents were known. This was done with the object of diminishing the calcium store in the body. During the period of this diet he rapidly lost weight. At certain intervals during tbe experiment he added to his diet the following sources of calcium and phosphorus :-Calcium phosphate (neutral) and calcium hydrogen phosphate calcium hypophosphite lecithin lecithin and calcium lactate and calcium lactate alone. The phosphate,PHYSIOLOGICAL CHEMISTRY. ii. 135 magnesium and calcium were estimated both in the urine and fzeces.He draws the conclusion from a long series of experiments that these substances are of little therapeutic value in increasing the calcium and phosphate stores in the body. Tricalcium phosphate is excreted mostly in the feces and the acid calcium phosphate is positively harmful in that it is also excreted in the feces as neutral salt and actually draws on the phosphoric acid store in the body. The effect of these preparations on diuresis and acidosis is also discussed. S. B. S. The Influence of the Fat of the Food on the Excretion of the Acetone Substances. GUNNAR FORSSNER (Xkand. A&. Physiol. 1910 23 305-325).-The experiments mere made with the object of determining the influence of the amount of fat ingested on the excretion of P-hydroxybutyric acid and acetone and were performed on the person of the author. The constant diet taken contained only ft small amount of carbohydrate and relatively large amounts of fat.To eliminate the influence of stored glycogen a definite amount of hard exercise was taken each evenicg and during the investigation the conditions of living were kept as constant as possible. On certain days definite additional amounts of fat (olive oil) were ingested after the period of exercise and before retiring to rest and the influence of this added fat was determined by estimating the amount of acetone substances excreted in the urine in different periods during the course of the investigation. From the results the author draws the conclusion amongst other things that the addition of f a t to t h e food causes an increased output in the acetone substances which is approximately proportional to the amount of added fat.S. B. 5. Studies on Water Drinking. 111. Uric Acid Elimination following Copious Water Drinking between Meals. S. A. RULON and PHILIP B. HAWK (J. Amer. Chem. SOC. 1910 32 1686-1691. Compare Abstr. 1910 ii 625)-It has been stated by some authors that the ingestion of large quantities of water has the effect of decreasing the amount of uric acid excreted whilst others have stated that it has the opposite effect. Experiments have now been made to ascertain the influence of copious water drinking between meals on the elimination of uric acid. The subjects were two men aged twenty-four and twenty-nine and a uniform diet was maintained throughout the experiments.In one case the data showed that the amount of uric acid excreted was not affected whilst in the other case they indicated that there was a marked decrease in the quantity. It is considered however that the latter result was probably due to the fact that the Folin-Shaffer method of estimation which was employed does not give a sufficiently high result with urines of very low sp. gr. The urines in the other case were of such a character as to admit of accurate estimation and it is therefore considered probable that the ingestion of large quantities of water does not have any influence on the amount of uric acid excreted. E. G.ii. 136 ABSTRACTS OF CHEMICAL PAPERS. The Relation of the Precursors of the Normal Yellow Figment of Urine to the Diazo-reaction and a Colorimetric Estimation of Urochrome and Urochromogen. MORIZ WEISZ (Biochem.Zeitsch. 191 1 30 333-356).-The protoic acid fraction of urine which is precipitated by baryta and alcohol yields a precipitate with basic lead acetate containing the normal yellow pigment (the urochrome of Thudichum and Garrod) and the urochrome obtained by Dornbrowski by means of copper acetate. These two pigments are not identical and may be separated from each other by means of the greater solubility of the lead salt of the normal yellow urochrome in dilute acetic acid. The substance in pathological urine which brings about Ehrlich’s diazo-reaction (red coloration with a mixture of aniline-p-sulphonic and nitrous acids) is precipitated from the proteic acid fraction by mercury acetate.The nature of this substance is not known but it is termed urochromogen on account of its properties. Another uro- chromogen is found in urine; this does not give the diazo-reaction but on digesting the urine for some time it changes into a urochromogen which does give the reaction; it is therefore termed urochrornogen-a and the other urochromogen-P. Both these substances yield on oxidation a urochrome identical with the normal yellow pigment of urine. Urochrome and its precursors are probably produced from the protein of the cell and the presence of urochromogens in pathological urine points to a change in the metabolisms of the organism brought about by toxic substances. Estimations of t h e urochrome in different urines were made by precipitating the other pigments with ammonium sulphate and com- paring the filtrate in a Dubosq colorimeter with a standard solution of a yellow dye the quantity of urochrome being expressed in terms of the standard.The urochromes were estimated in the same manner after oxidation to urochrome. W. J. P. Narcotics and Local Anesthetics. OSCAR GROS and 0. HARTUNG (Arch. exp. Path. Pharm. 1910 64 67-71. Compare Abstr. 1910 ii 793).-Details are given OF the limits of concentration which produce narcosis in tadpoles etc. of cocaine eucaine novocaine and alypine. W. D. H. The Signiflcance of the Active Constituent of the Suprarenal Capsules in Conjunction with Local Anaesthetics. I?. ESCH (Arch. exp. Path. Pharm. 1910 64 84-104).-The addition of adrenaline to novocaine alypine and especially cocaine intensifies their local narcotic action.This is a specific influence on nerves. The addition of adrenaline to tropococaine does not increase its action. W. D. H. The Influence of the Presence and Position of the various Radicles of Adrenaline on its Physiological Activity. C. H. H. HAROLD MAXIMILIAN NIERENSTEIN and HEREERT E. ROAF (J. Physiol. 1910,41 308-317).-The activity of adrenaline is largely dependent on the presence of an amine (or substituted amine)PHYSIOLOGICAL CHEMISTRY. ii. 131 group separated from the benzene nucleus by some other group. Two hydroxyls attached to the benzene ring in the 3:4-position increase the action and when these are present the placing of a secondary alcohol group between the benzene ring and the amine-containing group intensifies the activity.I n the latter case i t is the laxorotatory com- pound that is mainly responsible for the ‘‘ sympathomimetic action.” W. D. H. The Production of Glycosuria by Adrenaline in Thyroid- ectomised Dogs. FRANK P. UNDERRILL (dmer. J. Physiol. 1911 27 331-339).-Renewed investigation concerning the eaciency of adrenaline in provoking glycosuria in thyroidectomised dogs confirms the author’s previous conclusion that doses of I mg. per kilo. of body- weight causes glycosuria in dogs deprived of both thyroids but retain- ing at least two parathyroids ; these dogs thus resemble normal dogs. Fa1 ta and Rudinger’s criticisms in no way invalidate this conclusion. W. D. H. The Fate of Cineol (Eucalyptol) in the Organism.JUHO HAMALAINEN (Skand. Arch. PhysioE. 1910 24 l-l2).-After oxidation of the metabolism product (a glycuronate) with perman- ganate the author succeeded in isolating cineolic acid from which he draws the conclusion that the cineol before conjugation is oxidised yielding one of two possible products of which he gives the formulae. It was also noticed that the toxic action of the cineol was greatly diminighed in animals which had been immunised with emulsin and the urine of such animals after cineol ingestion is much more strongly Izevorotatory than in non-immunised animals. The author gives reasons for deducing from these facts that the glycuronate formed after cioeol ingestion has the P-glucoside structure. S. B. S. Physiological Action of Organic Bases. A.BRISSEMORET and A. JOANIN (Conapt. rend. 1910 151 1151-1 1.53)-The physiological effect of an organic base is regarded as the resultant of the effects of the hydrocarbon residue and the basic nitrogen-containing group. It has been found by experiments on dogs that in the case of coniceine the secondary narcotic effects are similar to those induced by n-octane. I n the same way the narcosis produced by morphine can be imitated by intraperitonenl injection of hexahydrophenanthrene the parent hydrocarbon of the alkaloid. w. 0. w. Physiological Action of - Iminoazolylethylamine [4 - p - aminoethylglyoxaline]. HENRY H. DALE and PATRICK P. LAIDLAW (J. Physiol. 1910 41 318-344).-This amine is produced when carbon dioxide is split off from histidine. It is identical with one of the ergot bases (compare Barger and Dale Trans.1910 97 2592). It has a direct stimulating effect on plain muscle especially of the uterus and the bronchioles; cardiac muscle is mildly stimulated anti skeletal muscle not affected. I n rodents it produces a rise of blood pressure unless this is masked by embarrassed respiration ; in carnivora the direct action on plain muscle in the systemic arteriolesii. 138 ABSTRACTS OF CHEMICAL PAPERS. is overcome by an antagonistic peripheral action the mechanism of which is not clear. The result is general vaso-dilatation (in which the kidney vessels do not participate) and a fall of arterial pressure ; the pulmonary pressure rises. The drug also produces narcosis and is a mild direct stimulant to the salivary glands and pancreas The general effect is not unlike that of the injection of Witte’s peptone and of certain agar extracts and of Popielski’s ‘‘ vasodilatin.” The base has in fact been separated from intestinal extract.It has no effect on blood coagulability. It is further pointed out that the general effect is not unlike that seen in anaphylaxis. W. D. H. Pharmacology of the Rue (Peganum harmala). FERDINAND FLURY (Arch. exp. Path. Phnrrn. 1910 64 105-125).-The physio- logical action of some of the derivatives was investigated namely harmine (Cl,H1,0N2) harmaline ( C,,H1,ON,) dihydroharrnaline (C,,H160N2) and apoharmine (C,HsN2). The first three have a paraly sing action on frogs whilst apoharmine causes increased reflex irritability and tetanus. Harmine and harmaline paralyse the skeletal and cardiac muscle of the frog.Harmaline has an anthelmintic action probably by paralysing the musculature of the parasites. I n warm- blooded animals harmine and harmaline cause convulsions increase of saliva interference with respiration and depression of temperature. I n the East the seeds are used as a substitute for hashish and in dogs it is evident that psychic disturbances occur. The drugs are partly destroyed in the body (blood liver and nervous system) and partly excreted by the kidneys and intestine. W. D. H Comparative Effects of Yohimbine Protoveratrine and Veratrine on Isolated Muscle and Nerve. AUGUSTUS D. WALLER (Proc. physiol. Soc. 1910 xi-xiv ; J. Physiol. 41).-The results described confirm the author’s previous conclusion that veratrine especially affects muscle and protoveratrine nerve.The character- istic effect on nerve produced by protoveratrine is not produced by yohimbine although Tait regards the two drugs as pharmacologically identical. W. D. H. The Toxic Action of the Free Fatty Acids in Animal and Vegetable Fats and Oils J. HERTKORN (Chem. Zeit. 1911 35 29-30).-The decompositions taking place when a fat or oil becomes rancid result in the formation of lower and higher fatty acids and aldehydic substances etc. It may happen that higher aldehydes are formed and these together with the acids (crotonic acrylic etc.) into which they are readily converted may cause the injurious effects noted when rancid fats and oils are consumed. w. P. s. The Sensitising Action of Eamatoporphyrin. WALTHER HAUSSMANN (Biochem. Zeitsch. 1910 30 276-31 6).-If paramaxia are exposed to light in solutions containing small quantities of hzematoporphyrin which in the dark is harmless they rapidly die. This is a case of photosensitisation as if they are treated withVEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 139 the same solution in the dark after the solution has been exposed to light the paramscia remain alive. The toxic action is not due therefore to a decomposition product of the hsmatoporphyrin after exposure to light. The most active rays as determined by light filters are those of about ~5OOpp. Hsmatoporphyrin solutions under the same conditions can also act h~molyticnlly. Furthermore if hcematoporphyrin is injected into mice and the animals are exposed t o light toxic effects are produced which can ultimately end in death. Control animals kept in the dark remain healthy. According to the degree of light t o which the animals are exposed or the time which has elapsed since injection various stages of intoxication can be distinguished namely acute sub-acute or chronic. The various symptoms characterising these stages are described in detail by the author. The injury to the peripheral vessels seems to be the primary effect of the toxins. When toxic action took place no hamatoporphyrin could be found in the blood (tested by the haemolysis method). White mice are much more sensitive to the hEmatoporphyrin action than grey or black mice. I n the case of the latter no lethal effects were ever experienced. S. B. S.

ISSN:0368-1769    

DOI:10.1039/CA9110005123

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 139 Chemistry of Vegetable Physiology and Agriculture. The Oxidation of Phenol by Gertain Bacteria in Pure Cultures. GILBERT J. FOWLER,. EDWARD ARDERN and WILLIAM T. LOCKETT (Proc. Roy. Sac. 1910 83 B 149-156).-1t was noticed that phenol was oxidised on bacterial sewage filters from which three or four different organisms could be afterwards isolated. The chief were Bcccillus liquefaciens cfzuorescens a liquefying organism and another organism which Sidebotham has identified with B. Helvolus (Zimmermann). The experiments made with eultures on various media show that the oxidation of phenol is due to the latter organism which can grow on media in which the phenol is the only source of carbon. S. B. S. Production of Acid and Alkali by Diphtheria Bacilli.K. A. JAC~BSEN (Centr. Bakt. Par. 1910 i 16-27).-The results both of Madsen (Zeitsch. Hyg. 26) and of Lubenau (Arch. Hyg. 66) are confirmed their divergence being due to different experimental conditions. N. H. J. M. ERICH PELZ (Celzt;. Bakt. Pa7*. 1910 i 59 1-16).-1n addition to cholera vibrios a number of bacteria have the power of reducing nitrates to nitrites. These are divided into three groups according to the vigour with which they act on nitrates. The most active are the cholera vibrios Paratgphus B. Production of Nitrite by Bacteria.ii. 140 ARSTRACTS OF CHEMICAL PAPERS. mouse typhus Aerogenes Vibrio Nordhafeen Yibrio Metschnikof swine cholera and some varieties of type Flexner. The following bacteria show lees activity in producing nitrites Typhus Paratyphus A.Enteritis Gartner Bacterium coli Yersin and Proteus Dysentedae. The production of nitrites by this group never exceeded 18-20 mg. in 50 C.C. It is however possible that some of the nitrite produced underwent further decomposition with liberation of free nitrogen. No ammonia could be detected except in a culture of Xtaphylococcws aurelzs which produced nearly 5 mg. in four days. Dysentery bacteria of type Kruse and streptococci produce only small amounts of nitrite. N. H. J. 31. The Chemical Reactions of Kumiss and Kephir Fer- mentation. I. The Kumiss of the Steppes. ALEXANDER GINZBERG (Biochem. Zeitsch. 1910 30 1-24).-The course of the reactions occurring during the souring and fermenting of mare’s milk to form kumiss was followed by mixing fresh mare’s milk with an equal volume of kumiss incubating a t 25O and determining the lactic acid sugar and alcohol present a t intervals during the <‘ripening ” of the mixture.The results show that the lactic and alcoholic fermentations proceed concurrently beginning slowly and gradually increasing in intensity. A t the same time the casein and albumin of the milk are acted on by the ferments the former losing its mineral constituents and both being partly hydrolyeed. W. J. Y. The Chemical Reactions of Kumiss and Kephir Fer- mentation. 11. Artificial Kurpiss and Kephir. ALEXANDER GINZBERG (Biochern. Zeitsch. 19 10 30 25-38).-Kepbir is produced from cow’s milk by lactic and alcoholic fermentations of the sugar which take place side by side in a manner similar to that observed during the preparation of knmiss (preceding abstract).The fermentations are not however carried so far as in the case of kumiss; thus kephir contains only 1% alcohol kumiss 2 to 376 whilst the proteins are not hydrolysed to the same extent in kephir. Artificial kephir and kumiss may be prepared from cow’s and mare’s milk respectively by means of a mixture of Bacillus bulgaricus and beer yeast. In these cases also the course of the reactions is similar to that described above. A number of photomicrographs are given of the micro-organisms found in these fermentations. W. J. Y. Action of the Bulgarian Ferment on Proteins. GABRIEL BERTMND (Compt. rend. 1910 151 1161-1162 ; Bull. Xoc. chim. [iv] 9 103-104)-The observations of Effront (this vol.ii 61) are not in agreement with results published by the present author (Abstr. 1907 ii 120 ; 1909 i 633 ; Margaillan Abstr. 1910 ii 163). The production of lactic acid in milk by the action of the Bulgarian ferment is mainly due in the author’s opinion t o transformation ol the lactose,VEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 141 and not to degradation of casein. presence of foreign bacteria in the Bulgarian ferment employed. Effront’s results may be due t o the w. 0. w. The Influence of Alkalis and Acids on the Autolysis of Yeast. E. NAVASSART (Zeitsch. phpsiol. Chem. 1910 70 189-197). -Alkali lessens the autolysis of yeast as i t does that of animal tissues; the action is proportional to the alkali added that is the more alkali the less is the autolysis noted.The action of acid (hydro- chloric) does not increase autolysis as it does in animal tissues but it diminishes it. Nuclease is more affected by change in reaction than proteolytic enzymes. W. I>. H. The Action of Rubber on Mercurial Antiseptic Solutions. A. T. GLENNY and GEORGE S. WALPOLE (J. Efpgiene 1910 10 586-5SS).-Nercurial solutions in which rubber articles (tubing catheters stoppers etc.) are placed lose merciiric salt and the rubber is attacked especially on prolonged immersion. The knowledge of this fact is important in view of the extensive use of mercurial solutions for sterilisation and sterile storage. The loss of mercury means that the solution is no longer of the same antiseptic strength. W. D. H. Conservation of Salts during the Course of Vegetation of an Annual Plant.GUSTAVE ANDRE (Compt. rend. 1910 151 1378-2382).-The view has been held that loss of mineral matter may occur from osmosis through the roots and dead leaves of plants. This is not supported by the observations described in the present communication which contains a n account of experim,ents on beans lupins and pinks. No appreciable loss of salts was detected up to complete development of the plants even when some of the leaves had partly withered and were only acting imperfectly as organs of assimilation and elaboration. \v. 0 w. The Action of Salts on the Respiration of Plants. A. REINHARD (Ber. Beut. Rot. Ges. 1910 28 451-455).-The author confirms a result he has previously obtained that phosphates increase the evolution of carbon dioxide from powdered seeds whilst other salts do not.H e now works with more dilute solutions and finds as before that nitrates tend t o depress respiration and phosphates increase it E. J. R. Induced Maturation of Urains. Antigerminative Action of Acetaldehyde. PIERRE MAZE (Conzpt. rend. 1910 151 1383-1386).-Seeds of maize or peas collected from the plant when they contain 50-60% of water do not germinate when placed in a sterile atmosphere. I f previously dried however in a vacuum in the air or in a current of carbon dioxide germination is enabled to take place. This appears t o be due t o the removal in the latter case of volatile substances which inhibit germination. Acetaldehyde is effective in this way and has been shown to occur in the freshlyii.142 ABSTRACTS OP CHEMICAL PAPERS. collected seeds. It may be removed by desiccation or by the destructive action of moulds such as Aspergillus Mucor etc. which have been shown to act in this way. The juice of the young plant also contains aldehyde and this may play an important part in regulating maturation. The oxygen absorbed by the juice of the living plant is partly employed in oxidising this to alcohol. w. 0. w. Tolerance of Maize to Boron. HENRI AGULHON (Compt. rend. 1910 151,1382-1383).-Plants which bave been grown in a medium containing somewhat less than the fatal amount of boric acid produce seeds the plants from which have acquired a certain measure of immunity against the poison. They benefit by the administpition of small doses to a greater extent than the parent crop and support a toxic dose more easily.w. 0. w. Occurrence of d-Galactose. EDWUND 0. VON LTPPMANK (Ber. 1910 43 3611-3612).-Following a sudden frost the first after a late dry warm autumn the berries of an ivy were observed to be covered with a colourless crystalline effloresence resembling hoar frost which proved to be galactose. No other carbohydrate was found accompanying it and the berries themselves did not contain galactose or any substance yielding mucic acid on oxidation. E. F. A. Microchemical Examination of Tannins and Natural Colour- ing Matters. LUIGI ERMANNO CAVAZZA (Zeitsch. wiss. Mikroscop. 1910 27 34-40).-An account of experiments on the natural colouring matters contained in plants which the author tabulates in a list containing fifteen groups.The colour reactions given with these by various reagents are also appended. F. M. G . M. Intravital Caffeine Reactions. THOMAS BOKORNY (PJliiger’s Archiv. 1911 137 470-488).-Caffeine is a reagent for active albumin first introduced by 0. Loew and the author. Details are given in the present paper of the reactions (mainly microchemical) produced by caffeine in various vegetable structures ; the most characteristic of them is the formation of proteosomes and evidence is adduced that these are not a simple precipitate of tannic acid compounds of caffeine or of protein. W. D. H. Relative Proportions of Arsenic Present in Marine Alga and their Preparations. EUG&NE TASSILLY and J. LEROIDE (Bull. Soc. chirn. 1911 [iv] 9 63-66. Compare Gautier Abstr.1903 ii 92).-The estimation of the arsenic was made by Gautier’s method as modified by Bertrand (Abstr. 1904 ii 85). The following quantities expressed in mg. per 100 grams of seaweed were found. Chondrus crispus (“ Irish moss ”) 0.07 ; Fucus vesiculosus (“ Bladder wrack ”) 0.01 ; “ Corsican moss,” 0.025 ; Laminaria digitata 0.05 ; L. saccharina 0.01 and LJZexicaulis 0.01. ‘‘ Norgin I’ prepared from Laminaria spp. contained 0.03 and ‘‘ gelose,” prepared from Japanese seaweed gave 0.20 to 0.25. The amounts in Irish moss norgin and gelose may be due in part to the use of impure chemicals in preparing them for theVEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 143 market. '' Kelp " made from L. digitccta contained the whole of the arsenic naturally present in the seaweed.Alkaloids of Datura Mete1 Seed. ERNST SCHMIDT (Arch. Pharm. 1910 248 641-643).-de Plato has stated recently (Abstr. 1910 ii 742) that Datura getel seed contains allantoin but neither alkaloids nor cyanogenetic glucosides. The author has therefore repeated Kircher's work on this seed (Abstr. 1905 i 717) and confirmed his observation that the chief alkaloid present is scopolamine (hyoscine). Small quantities of hyoscyarnine and of a third alkaloid giving an nurichloride m. p. 140° crystallising in dark yellow needles are also present. T. A. H. Constituents of Iris versicolor Rhizome. FREDERICK B. POWER and ARTHUR H. SALWAY (Amer. J. Pharm. 1911 83 1-14).- Authenticated rhizomes and rootlets of Iris versicolor (" blue flag root ") furnished the following constituents on extraction with alcohol and separation of the alcoholic extract into ( a ) matter volatile in steam ( b ) matter soluble in water and ( c ) matter insoluble in water.Fraction ( a ) consisted of volatile oil Di 0.9410 possessing a yellow colour and a strong rather unpleasant odour. From portion (b) k o - phthalic acid a trace of salicylic acid tannin and a reducing sugar which gave d-phenylglucosazone were isolated. The first of these substances has not been recorded from a natural product previously. Fraction (c) was composed chiefly of a dark-coloured soft resin forming 8.7% by weight of the crude drug. This resin contained apart from amorphous matter (1) a phytosterol C27H,,0,H20 m. p. 133" (148' when anhydrous) [aID - 35.6" in chloroform which crys- tallised in colourless needles from alcohol ; (2) myricyl alcohol ; (3) ipuranol (compare Abstr.1910 ii 338); (4) heptncosane; (5) a mixture of lauric palmitic stearic cerotic oleic and linolic acids ; and (6) possibly some ceryl alcohol. Physiological tests made with the crude alcoholic extract an aqueous extract of the drug and fractions ( b ) and (c) referred to above proved that these were all inactive. Since the physiological activity of fresh '' blue flag root " is apparently well established it would seem that the drug may lose its activity entirely on keeping. T. A. H. The Cyanogen Compounds of Tobacco Smoke. JULIUS T ~ T H (Chem. Zeit. 1910 34 1357. Compare Abstr. 1910 ii 443).-!I!he amount of cyanide compounds (calculated as C,N2) in tobacco smoke is not influenced by the amount of nicotine present in the samples.The cyanide found in tobacco smoke is not due t o a reaction between dicyanogen and the ammonia which is always present in the smoke for a direct experiment showed that contrary to Wohler's idea no hydrogen cyanide or other cyanides are formed when these products The Glucoside of Pear Leaves [Arbutin] and its Function in Producing Autumn Tints. EMILE BOUXQUELOT and [Mlle.] A. FICHTEKHOLZ (J. Pharm. Chim. 1911 [vii] 3 5-13. Compare Abstr. 1910 ii 742).-The authors have examined leaves from n T. A. H. interact. L. DE K.ii. 144 ABSTRACTS OF CHEMICAL PAPERS number of trees that were formerly classified as Pyrus but are now regarded by most botanists as distinct. They find that Pyms comnzunis alone contains arbutin while none of the other trees d o ; none could be detected in Cydonia vulgaris Maltis comnzunis Sorbus aucupcwia or S.towninalis all of which were a t one time classed with Pyrus. There are therefore recognisable chemical characters correlated with the botanical characters and the modern classification is justified on biochemical as well as on morphological grounds. The leaves of certain varieties of P y ~ u s turn black when they fall ; in other cases a golden-yellow tint first appears but then gives place to black. The authors support Wewers' hypothesis that the black colour is due to the oxidation of quinol by an oxyilnse but as the quinol arises from arbutin this latter substance must first undergo hydrolysis by the emulsin in the leaf before the blackening can appear.Methylarbutin does not at once produce a black oxidation product but a yellow one and evidence is adduced that those leaves that first turn yellow contain methylarbutin [compare H. E. and E. F. Armstrong Proc. 1910 26 3341. E J. R. The Behaviour of Penicillium in the Presence of Acetic Acid and its Salts. JOHANNES REICHEL (Biochem. Zeitsch. 19 10 30 152).-Free acetic acid was found to have an inhibitory action on the growth of Penicillium glaucum. Tho presence in an otherwise favourable medium of a very small concentration of acetic acid (0.01 23 to 0-04201) considerably delayed the production of spores whilst greater concentrations (0.0940 and 0.2996lV) completely prevented growth. This action was not due to the hydrogen ions of the acid since the mould grew quite well on the same medium in the presence of either sulphuric hydrochloric tartaric o r oxalic acid of much greater normality.It was also not caused by the acetyl ionP since acetates did not exhibit this property which was therefore ascribed to the undissociated acetic acid. When Penicillium was grown in the presence of acetates i t was observed that the acidity of the medium was decreased. It is suggested that the mould regulates the acidity of the medium by utilising the acetate as a ' source of carbon thereby preventing the liberation of sufficient acetic acid to inhibit its growth. The Alkaloids in Strychnos Nux Vomica During Germina- tion. 0. TUNMANN (Arch. Pharrn. 1910 248 644-657. Compare Feldhaus Abstr.1905 ii 648; Kerboscb Abstr. 1910 ii 1101). -The author has investigated the distribution of alkaloids in nux vomica seeds before and after germination and finds that there is no justification for Heckel's view that the a1 kaloids are wholly transformed into more assircilable substances as one result of germination. A portion of the alkaloids is passed into the soil another is thrown off in the seed shell whilst a small part is used in forming a protective layer for the embryonic leaves. The following are the chief conclusions arrived at. The two alkaloids brucine and strychnine occur only in the oil-plasma of the endosperm cell contents. The embryo of the resting seed contains brucine only. The alkaloids ol the endosperm W. J. Y.VEGETABLE AND AGRICULTURAL CHEMISTRY.ii. 145 are not absorbed by the embryo on germination. Nearly one-third of the total alkaloids is excreted into the surrounding soil and remains there in a form insoluble in water and probably forms a protecting layer for the rootlets. About one-fifth together with the residue of unabsorbed endosperm is thrown off with the seed shell. Brucine is to some extent converted into strychnine during germination but there is no evidence of the formation of nitrates from the alkaloids. Brucine is formed first in all parts of the embryo during germination and both alkaloids are formed before the formation of chlorophyll takes place in the leaves. The following quantities in grams of total alkaloids were found in the various parts of one seed whole seed 0.0556 ; seed shell thrown off in germination 0.0156; young em- bryonic root 0.018 ; older embryonic root 0.021 ; hypocotyl axis 0.003 ; young embryonic leaf 0*0078 ; older embryonic lesf 0.0078 T.A. H. Non-pratein Nitrogenoys Substances in t h e Sugar-Beet. K. SMOLENSKI (Zeitsch. Yer. deut. Zuckerind 1910 1215-1261).-The diffusion liquors of a Russian sugar factory were found to contain the following non-protein nitrogenous substances vernine allantoin asparagine glutamine (1) and betaine. Tyrosine and choline were abaent. A summary of the literature available as to the rotatory power of these compounds shows that glutamine will have but little effect on the polarisation of beet juice ; asparagine will slightly increase the polarisation in aqueous solution. I n alcoholic solution with lead acetate the foreign substances have no influence on the polarisation.Polarisation after inversion in presence of glutamine or asparagine will indicate an excess of dextrorotatory csrbohydrate. E. F. A. Manurial Experinients with Sugar-Beet. E. SAILLARD (Bied. Zentr. 1910 39 859-860; from J. Agric. p a t . 1910 i 267)- Sodium nitrate and cyanamide produced about the same amounts of roots and sugar whilst calcium nitrate gave rather higher results. Kaioite produced more roots and more sugar than the same amount of potassium as chloride. This is attributed to the magnesium present in tho kainite. N. H. J. M. Relationship between the Fertility of the Soil and the Contained Phosphoric Acid Soluble in Water. ISIDORE POUGET and D. CEIOUCHAK (Rev. gen.Chim. pure AppZ. 1910 13 157-178 219-222).-A detailed account of numerous experiments on the relationship between the fertility of soils and the contained phosphoric acid soluble in water or in 1% citric acid solution. The methods of culture are described with photographs showing the relative growths of the plants experimented on ; the mechanical mineralogical and chemical conditions of the soils are noted and the amount and composition of the produce tabulated. The second Eaper contains the results of varying the concentration of the solution of phosphoric acid supplied ; when the concentration was greater than 1 mg. of P,O per litre tbe quantity absorbed was in direct proportion to the concentration; at a lower concentration the VOL. C. ii. 10ii. 146 ABSTRACTS OF CHEMICAL PAPERS.absorption decreased more rapidly than the concentration and at 0.1 mg. per litre assimilation practically ceased. G. H. FAILYER (U.X. Dept. Agric. Bur. Soils Bull. 72 1910).-Barium occurs in most soils in the United States the greatest amounts being found in soils derived from the neighbour- hood of barite deposits and in soils derived from the rocks of the Rocky Mountains. Analyses of about a hundred Colorado and Kansas soils and subsoils showed that they contained from 0.01 to 0.11% of barium. Other soils were examined spectroscopically. Barium was also found in various plants collected in different parts of Nebraska Colorado and Kansas (compare Bureau oj’ Plants Ind. Bull. 129). Studies in Soil Oxidation. OSWALD SCHREINER MICHAEL X.SULLIVAN and F. R. REID (U.8. Dept. Agric. Bur. Xoils Bull. 73 1910).-Oxidation in soils is in part due to the action of roots and partly to processes mainly non-enzymatic in the soil itself Oxidation in soils is increased by the presence of salts of manganese; iron aluminium calcium and magnesium especially in conjunction with bydroxy-acids (citric tartaric malic and glycollic acids) and their salts the greatest effect being obtained with manganese and the stimulating effect of manganese is attributed to this increased oxidation rather than to any direct action on the plant. Manurial salts increase the oxidising power of roots whilst their action on the oxidising processes in the soil itself is variable Excessive oxidation is injurious to vegetation. Pentosans in Soils.EDMUND C. SHOREY and ELBERT C. LATHROP (J. Anzer. Chem. Xoc. 1910 32 1680-16S3).-Estimations of the pentosans in ten soils of widely different character have been made by boiling the soils with hydrochloric acid and weighing tho furfur- aldehyde produced in the form of its phloroglucinol compcund. The results show that the amounts of pentosans in these soils ranged from 0.027 to 2.750% whilst the proportion of carbon in the form of pentosans to the total carbon in the soils varied between 1.30 and 28.53%. The soil which contained the largest quantity of pentosan (2.75%) was a Marshall loam taken from a field in North Dakota on which flax had been grown for several years. From this soil a crude pentosan was obtained which when hcated with hydrochloric acid yielded f urf uraldehyde and on digestion with sulphuric acid furnished a pentose which was identified as xylose.Tests for other pentoses gave negative results. It is pointed out that the metkod employed for estimating pentosans is merely an estimation of the furfuraldehyde which may originate from a pentoean a pentose or a pentose-yielding material other than a pentotan. The Fentosans or pentoee-yielding material in soils must be regarded either as plant residues such as a portion of the ligno- cellulose which has resisted decomposition or as products of the decomposition of complex CompoundP such as nucleoproteins. E’. M. G. M. Barium in Soils. N. H. J. M. N. H. J. 31. E. G,ANALY'I'ICA I; CHEMIS'I'RY. ii. 147 Some Acid Constituents of Soil Humus.OSWALD SCRREINER iknd EDMU~D C. SIIOHEY (J. Amer. Chem. SOC. 1910 32 1674-1680). -The authors have already isolated certain acid substances from t h e soil namely dihydroxystearic 2-picoline-4-carboxylic and agroceric w i d s (Abstr. 1908 ii 421 889 1067 ; Bull. 53 Bureau of h'oili~ b+.h'. Uept. Agric. 1909). The study of the acid constituents of soil humus has been continued and a-hyd roxystearic paraffinic and lignoceric acids have now been isolated. CH,*[CH,],*C'II(OH)*[CH,],*CO,H 111. p. 84-85° and the dihydroxystearic acid described previously a r e prohably produced in the soil by the action of micro-organisms on organic matter of vegetable or animal origin. The paraffinic acid C2 H4802 i h identical with that obtained by Pouchet (hbstr. 1875,50) by the actiou of fuming nitric acid on paraan.The manner i n which t h i s substance is formed in the soil is not clear but i t is probably produced by t h e oxidation of solid hydrocarbons such as a r e known t o occur in plant tissues. Lignoceric acid Cz4H,,O2 (Hell and Herrnanns h b s t r . 1881 249) occurs as a glyceride in ground-nut oil and may possibly be a constituent of other vegetable oils ; i t s production in the soil may be due to the decomposition of such glycerides. This acid i s also obtained by the distillation of wood and it is therefore possible that its occurrerice in t h e soil may be the result of the decomposition The so-called a-hy droxy st earic acid of woody tissues by the agency of micro-organisms. E. G. Chemical Nature of Soil Organic Matter. OSWALD SCHREINER and EDnruNu C. SHOREY (U.S. Ddpt. A g ~ i c . Bur. *!hi& Bull. 74,1910). -In addition to the four substances previously obtained from soils (dihydroxystearic acid picolinecarboxylic acid agroceric acid and agrosterol) the following compounds have now been isolated hentri- montane a-hydroxystearic acid paraffinic acid lignoceric acid phytosterol pentosan histidine arginine cytosine xanthine hypo- xnnthine fatty glycerides and several resin acids. N. H. J. M. Manurial Value of Manganese Sulphate. A. CARLIER (Bied. Zentr. 1910 39 859 ; from Ann,. Gemliloux 1910 423).-Manganese sulphate applied t o grass at the rate of 50 and 100 kilos. per hectare itxreased the yield of hay 0.9 and 9.5% respectively. The same amounts of manganese sulphate reduced t h e yield of potatoes by 9 and 0.6%. The yield of mangolds (roots) was reduced by 2.5 and 1% and the leaf of mangolds by 25 and 20%. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9110005139

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

ANALY'I'ICA I; CHEMIS'I'RY. Analytical Chemistry. ii. 147 Preparation of a Sensitive and Stable Litmus Solution. A. PUSCHEL (Oesterr. Chem. Zeit. 1910 [ii] 13 185-186).-The sensitive violet-coloured constituent of litmus can be separated from the other colouriag matters and gums present in the commercial 11ii. 148 ABSTRACTS OF CHEMICAL PAPERS. product by heating with dilute sulphuric acid (about a%) when it is precipitated presumably in tlie form of a sulphonic acid; this after collection and mahhing is redissolved in hot water and neutralised with sodium hydroxide when an exceedingly sensitive violet solution is obtained. P. M. G. M. T h e Colouring Matter of Red Radishes. JULIUS F. SACHER (Chem. Zeit. 1910 34 1333)-Further particulars as to the colouring matter of red radishes and its applications in titrations (Abstr.1910 ji 1106). I n dilute alcoholic solutions however the case is different. If for instance to 1 C.C. of the alcoholic solution of the indicator is added a small crystal of sodium carbonate and then water drop by drop a solu- tion is a t first obtained which in incident light is of an emerald-green and in transmitted light of a red colour. On shaking tbe liquid looks bluish-green. On adding more water the liquid turns violet then blue and after about half an hour the colour changes to green and finally to yellow. It has been remai ked that the indicator is too unstable t o be of use in practice but the author states that it keeps unchanged in alcoholic solution ; I n aqueous solutions alkali carbonates behave like hydroxides.With gas light it is wine-red in any direction. moreover it may be prepared fresh in a few minutes. L. DE K. Use of Sulphur Dioxide in Checking S t r e n g t h s of Volumetic S o l u t i o n s of Iodine Alkali and Silver. ELIAS ELVOVE (Arne?.. J. Pitarm. 1913 83 19-23).-A scheme is outlined for basing the determination of the strengths of volumetric solutions on pure silver as a standard. The solutions mould be prepared in the following order each serving as a standard for the succeeding one ammonium thiocyanate (standardised against pure silver) silver nitrate hydro- chloric acid sodium hydroxide oxalic acid potassium permanganate sodium thiosulphate iodine. To control the standardisation 25 C.C. of the standard iodine solution should be just decolorised by freshly prepared sulphur dioxide solution and the acid formed titrated with the standard sodium hydroxide solution.The total iodide in this neutralised solution could then be determined by adding excess of silver nitrate and titrating the excess of silver with standard ammonium thiocyanate allowance being made for tbe pure potassium iodide used in preparing the iodine solution. T. A. H. Rapid Estimations and Separations by means of a Mercury Cathode and Stationary Anode. RAYMOND C. BENNER and M. L. HARTMANN (J. Anier. Chem. Xoc. 1910 32 1628-1636).- It has been shown (Stoddard Abstr. 1909 ii 347; Benner Abstr. 1910 ii 999) that electro-analysis can be carried out with a mercury cathode and stationary platinum gauze anode su6cient agitation being produced by the evolution of gas to enable the metal to be deposited in an adherent form.Comparisons have now been made of the rates of precipitation under similar conditions which show that although the rate is greater with the rotaticg anode than with the stationary anode it is not sufficientlyAXALYTICAL CHE MISTH Y. ii. 149 so t o justify the use of the much more complicated apparatus. The results obtained with the stationary anode are as accurate as those obtained by other marcury cathode methods and it has been found that the estimation and separation of various metals can be effected under the same conditions as are employed with the rotating anode. E. Q. A New Apparatus for Effecting Slow and Certain Incinera- tion. EDMOND J. APS (Chem. Zeit. 1910 34 1374).-The vessel in which the ignition is carried out is supported on three prongs attached to a vertical axis which i u slowly rotated by means of a motor.By this means i t is claimed that uniform heating is obtained and spurting prevented. F. B. Gas-Volumetric Estimation of Hydrogen. OTTO BRUNCK (Chem. Zeit. 1910 34 1313-1314 ; 1331-1332).-After a short reference to the various methods for estimating hydrogen the remainder of the paper is occupied by a description of Paal and Hart- mann’s method which makes use of colloidal palladium (compare Abbtr. 1910 ii 237). T. S. P. Gas Analysis by Toepler’s Pressure Balance. ERNST MOHK (J. pr. Chem. 1910 [ii] 540-546. Compare Toepler Abstr. 1896 ii 235).-An apparatus is described for the measurement of the small amount of hydrogen in technical electrolytic oxygen.Two similar vertical glass tubea of the same height and. open a t the upper ends are connected by their lower ends to a bent tube containing a thread of petroleum the two limbs of which are very slightly inclined to the horizontal plane. One tube is filled with the gas under examination the other with pure dry oxygen; in consequence of the small difference in density of the two gases the thread of petroleum is shifted from its null positioa the amount of the displacement being read by an optical micrometer. An equation is given by wbich the desired percentage of hydrogen can be calculated. The constant of the apparatus is determined by using gaseous mixtures of known composition. About 0.02% of hydrogen can be estimated rapidly and with suficient accuracy. c.s. Estimation of the Acidity of Hydrogen Peroxide. LOTHAR WOHLER and W. FREY (Zeitsch. cmgew. Chem. 1910,23,2353-2354).- The acidity of hydrogen peroxide can be accurately determined by direct titration with N/lO-alkali. Methyl-orange should be used as indicator when the acid present allows uf it since its indica- tions are quite sharp even with a 30% solution of hydrogen peroxide. When the acid present necessitates the use of phenolphthalein as indicator i t is beht to destroy the hydrogen peroxide with pldtinutn- black or by wtlrxuiug with excess of alkali before the acidity is determined taking great care to exclude carbon dioxide. Endemann’s results (Abstr. 1909 ii 432) are due to the fact that carbon dioxide was not excluded so that correct results could not be obtained with phenolph thaleiri as indicator.T. s. P 11-2ii. 150 ABSTRACTS OF CHEMICAL PAPERS. Estimation of Chlorides in Blood. BERTHOLD OPPLER (Zeitsch physiol. Chem. 1910 70 198-204).-The removal of protein by phosphotungstic acid gives good results in the estimation of sugar but not of chlorides in such fluids as blood Metaphosphoric acid is for chlorides the best substance to use for getting rid of the protein. The chlorine may be estimated gravimetrically as silver chloride or electrolytically. W. D. H. Estimation of Iodine in Alcoholic Solutions. G. FAVREL (Anit. China. anal. 1911 16 12-13).-The author has tried the gravimetric process recommended by Desvignes (weighing as silver iodide after conversion into potassium iodide) and the volumetric process recom- mended by Lebeau for aqueous solutions (titralion with silver nitrate after treat,meut with zinc powder) and finds both processes to give the same result as the titration with thiosulphate.When applying Lebeau’s process to tinctures it is advisable t o iieutralise any free acid present by means OF a little zinc carbonate. Both processes have the advantage over the thiosulphate method that they are applicable to alcoholic solutions which have been kept for a long time and in which hydriodic acid may be present. Estimation of Sulphur in Brass and B r O n Z e . - ~ U S T A V TIIURNAUER (J. f n d . Enyin. Chem. 1910 2 293).-The author recornniends the following process adapted from organic analytical procedure for estimating sulphur iu brass and bronze ; i t gives excellent ieesults and avoids the tedious operations of oxidising with aqua regia and subsequently removing metals.One gram of bronze filings is thorougly mixed with six grams of a mixture consisting of potassium clrlorate (2 parts) and sodium carbonate (1 part) transferred to a wrought-iron crucible (lined with a layer of sodium carbonate) and (*overed with a further quantity of the mixturc.. The crucible is gradually heated until the mass is completely fused ; after cooling the fusion is digested with hot water aud the metallic oxides are removed by filtration the bolution acidified with hydro- chloric acid and the sulphqr estitnated in the usual manner as barium sulphate. If great accuracy is required a silver crucible should be employed but the amount of sulphur abstracted from the iron does not usually introduce a n error exceeding 0.01 per cent.L. DE K. F. M. G. M. Red Coloration given by Esbach’s Reagent [with CJrine]. c. OAZZETTI and c. SARTI (Arch.furvt. sperim. fici. 1910 9,319-385). -A pathological urine was fouud t o give a rubj,-red colorittion with Esbdch’s r e a p n t . The colour was due to picramic acid formed from t h e picric acid by ammonia and ammonium sulphide present in the urine. It was also produced on addition of picric acid alone and in fact is destroyed by excess of citric acid. Siuce the amount of ammonium sulphide present was scarcely t o be detected with lead test-papers it appears t h a t this reaction is very delicate. A New Apparatus for the Quantitative Estimation of Sulphur Trioxide in Sulphuric Acid.GEORGE FINCH (Zeitsch Schiess und. Sprengstoflmsen 1910 5 167-168.)-The apparatuw It. V. S.ANALYTICAL CHEMISTRY. ii. 151 consists of a flask t o the lower bulb portion of which is attached a narrow tube bent a t a convenient angle through which the liquid to be nnalysed is introduced by suction ; this can be closed by an accurately fitting capsule. The neck of the flask may be closed with a stopper or by a dropping funnel which is connected below its tap with a U-tube the other arm of which is open to the atmosphere. The required amount of fuming acid is drawn into the tared flask aiid weighed the neck stopper is then replaced by the dropping funnel and the U-tube at its side half filled with water; the acid is then diluted with distilled water by means of the dropping funnel (the btem of which is drawn out into a capillary) made up to a convenient volume and titrated with sodium hydroxide.I!’. M. G. 81. Gravimetric Estimation of Tellurium and Alkalimetric Estimation of Telluric Acid. ARTHUR ROSENHEIM and M. WEIN- IIEBEH. (Zeitsch. ccnorg. Chem. 191 1 GQ 266-269).-When the estirnu- tion of tellurium by reduction with hydrazine in weakly alkaline solutions is carried out according to Gutbier’s instructions (Abstr. 1901 ii 687) tho results are not trustworthy some tellurium often remaining unprecipitated or else some of it is oxidised in the drying. The authors recommend that the tellurium solution be reduced with :t 10% hydrazine sulphate solution while contained in a covered beaker in an autoclave heated to 130’ under 3-4 atmospheres’ pressure.The tellurium is then deposited completely in half-an-hour and in such a form that it does not oxidise during the subsequent treatment. Telluric acid when mixed wihh glycerol in aqueous solution behaves as a nion3basic acid towards phenolphthalein but the results :ire somewhat variable. Better volumetric results are obtained as follows To the solution of telluric acid is added a large excess OF iV/lO-barium hydroxide or of N/lO-sodium hydroxide containing bniiurn chloride. I n consequence of the excess of barium ions t h e precipitation t f the telluric acid as barium tellurate BaTeO is complete. The excess of hydroxide can then be determined by titration with oxslic acid using phenolphthalein as indicator without i t being necessary t o first collect the precipitate.I n this process telluric acid ncts as a dibasic acid. T. S. P. E s t i m a t i o n of Free Ammonia and Ammonium C a r b o n a t e by Titration. JOHN C. THOMLINSOX (C’hewz. & e m 1911 103 13).- The author htates that this may be effected as foliows The liquid is titrated iir to Y-sulphuric acid using phenolphthalein as indicator until the liquid assumes a transient pink colour through its entire bulk; this gives the normal ammonium carbonate. Methyl orange is then added and the titration is continued ; this gives the totnl ammonia. L. DE K. Detection and Estimation of N i t r i c Acid in Milk by means of the Diphenylamine-Sulphuric Acid Test.J. TIT,LnIANS (Zeitsch. 1vahr. Gerhussm. 19 10 20 676-707).--The results of an investigation of this test are given the chief object being to ascertain the conditions Under which the test is capable of detecting very small amounts ofii. 152 ARSTRACTS OF CHEMICAL PAPERS. nitric acid in milk as the presence of nitric acid indicates that wrtter containing nitrates has been added t o the milk. The milk is first treated with calcium chloride and the serum thus obtained is shaken with ether and calcium hydroxide in order t o remove certain proteins and lactoFe. A portion 0.5 c c of the clear solution obtained is then mixed with 2 c c. of the reagent cooled and placed aside for a hour; the blue coloration prodnced if nitric acid is present reaches its full intensity after this lapse of time. The reagent is prepared by mixing 0.085 gram of diphenylarnine with 190 C.C.of dilute sulphuric acid (1 :3) and adding a quantity of concentrated sulphuric acid; t h e mixture becomes heated and the diphenylamine di-solves. Con- centrated sulphnric acid is now added to make the volume of the whole neaily 500 c.c. the mixture is cooled and finally made up t o a volume of 500 C.C. by the addition of concentrated acid. I t is essential t h a t chlorides be present in the solution t o be tested ; water containing a large amount of nitrates but free from chloridep does not yield a coloration with the reagent. Water containing 0.1 mg. of nitric acid (N,O,) per litre and milk serum with 0.25 mg. per litre yield distinct colorations. In the absence of nitric acid milk serum gives a yellow or pink coloration.By comparing the coloration obtained with those yielded under similar conditions by portions of milk ser urn containing known quantities of nitric acid ib is possible to estim.rte the amount of nitric acid i n the milk from which the serum was prepared. Nitrous acid also yields a blue coloration with the reagent; in this case the presence of chlorides is not essential and the coloration develops almost at once Milk containing a n abnormal quantity of dirt may give a reaction for nitric acid but the small amounts of foreign matters usually present in milk do not cause the production of a coloration. w. P. s. Estimation of Phosphoric Acid in Soils and Crops. HERMANN KASERER and IGNAZ K. GREISENEGGER (Zeitsch.Zundw. Vers.-we8en Oesterr. 1910 13 795).-The methods advocated for the analysis of organic material by Neumann ( Hoppe-Seyler’s Hastdbuch der Physio- Zogischen und puthologisch-chemischen AlzaZyse) are discussed and some modifications suggested. For the estimation of phosphoric acid the author advises that a measured portion of the liquid from the “Kjeldahl” flask be treated with excess of ammonium nitrate ammonium molybdate added the mixture thoroughly agitated and rapidly cooled. The precipitate is collected in a n asbestos-lined Gooch crucible washed with water and alcohol and the whole transferred into a beaker and titrated with N/4-sodium hydroxide (employing phenol- phthalein aq indicator) until the pi ecipitate is completely dissolved 2(NH4),P04,24M~0,,4HN0 + 56NaOH = 2Na,HPO + 24Ka2M00 + 4NaN0 + 38H,O + 6NHr The red liquid is then boiled until all ammonia is evolved (more sodium hydroxide being added as required) excess oE standard sulphuric acid added and any carhon dioxide removed by boiling and the hot solution then finally titrated back with alkali A table of comparative results with those obtained by Neumann’s method is given in the p~ per.F. M G. M.ANALYTICAL CEEMISTRY. ii. 153 Easy Detection of Arsenic; Rapid Separation of Arsenic and Some Otber Metals from Liquids. ERNST SALKOWSKI (Zeitsch. physioE. Chem. 1910 70 186-188. Compare Cnlson Abstr. 1910 ii 998).-Attention is drawn to the fact that i t has been known for a long time that the afldition of ether or chloroform to an aqueous colloidal solution produces a precipitation of the colloid. Arsenious sulphide is not diGsolved by either ether or chloroform but the use of ether for precipitating is preferable as the separation of the sulphide can be effected more readily than when chloroform is used.J. J. S. Convenient Potash Bulb. C. E. WATERS (J. A m e ~ . Chem Soc. 1910 32 1691-1693).-The apparatus consists of an inner tube terminating in either a brilb or disc pierced by a number of small holes to break the gas up into small bubbles and an outer larger tube or bulb which is sealed to the inner tube at the top. From the shoulder of the large bulb pass two tubes one for the exit of the gas and the other for the admission of the potassium hydroxide solution ; the latter is furnished with a ground glass stopper.Between the inner and outer tubes are a number of annular glass discs which fit so loosely that they can move freely up and down between projections blown on the wall of the inner tube. The gas after passing through theinner tube rises in the outer tube and is trapped successively by the discs which alternately rise and fall thereby wetting the wall of the outer tube with fresh solution. The free spaces between the discs and the malls of the tubes should not be less than 1 mm. wide The volume of solution in the bulb is usually sufficient if it just reaches the second disc. This apparatus is less fragile and much lighter than Geissler’s bulb and by means of the special stoppered tube for filling all danger of contact between the solution and the rubber connexions is obviated.E. G. Detection and Estimation of Potassium Perchlorate in Potassium Chlorate. K. SCHERINGA (Pharrn. Weekblud 191 1 48 15).-The new method is based on the fact that potassium perchlorate is not reduced by sulphur dioxide. One gram of a sample of potass- ium chlorate is dissolved in 130 C.C. of water in an Erlenmeyer flask plugged with cotton wool. A current of sulphur dioxide generated by heating a solution of 15 grams of sodium sulphite with 3 C.C. of sulphuric acid is passed just above the solution; the sulphur dioxide is rapidly absorbed and causes reduction of the chlorate to chloride. After boiling for some time a solution of 1.5 gram of silver nitrate is added and the silver chloride is collected and weighed as usual. The filtrate which contains the perchlorate is made alkaline with sodium carbonate and after filtering off from the silver oxide it is evaporated to a very small bulk introduced into a test-tube boiled until solidification sets in and then dried completely in an air-batb.After plugging the tube with asbestos the mass is heated to redness for some time and the asbestos layer is then also heated for a while.ii. 154 ABSTRACTS OF CHEMICAL PAPERS. The chlorine in the mass which represents the perchlorate is then estimated as usual. Potassium perchlorate free from chlorate does not rediice indigo solution. L. DE K. Character of Silver Deposit8 from Various Electrolytes. JOSIAR SIMPSON HUGHES and JAMES R. WITHROW (L Arner. Chenz,. Soc. 1910 32 1571-1556).-Experiments ale described which include the repetition of some of the earlier work on the electrolytic estima- tion of silver and a series of trials with electrolytes which have not been used previously.I n the case of the nitric acid electrolyte it was found that dense deposits could not be obtained if the E.M.F. \VilS high hiit that with a low E.M.F. good crystalline deposits were produced ; t,his is in accord with the statement of Kuster and von Steinmehr (Abstr. 1839 i i 125). With an electrolyte of ammonium sulphate and ammonium hydroxide bright deposits were often obtained a t first but became more velvet-like as their weight increaFed and darkened when the E.M.P. was over 1.4 volts; in all cases the weights of tho deposits were too high unless the E.M.F. was kept below 1.4 volts. When ammoniuni sulphate was used in the absence of ammonium hydroxide a heavy black graphite-like deposit was formed on the anode but disappeared on the addition of a few drops of ammonium hydroxide.With electrolytes consisting of ammoniacal solutions of ammonium phosphate and pyrophosphate crystalline deposits were produced but were spongy if the E.M.3’. was too high. Potassium cyanide gave good white deposits especially at a temperuture of 60-70’. The other electrolytes studied were sulphuric acid sulphuric acid and glycerol ammonium thiocyanate sodium hydroxide and ammonium hydroxide ammonium perchlorate potassium fluoride and hydro- fluosilicic acid. The deposits from sulphuric acid and glycerol were coarsely crystalline and non-adherent. Hydrofluosilicic acid gave satisfactory results.I n the case of each of these eiectrolytes except potassium cyanide there is a point at about 1.4 volts above which spongy deposits are produced ; with potassium cyanide the point is much higher. E. G. Estimation of Minimum Quantities of‘ Calcium in Presence of a Large Excess of Magnesium. CH. LTESSE ( A m . Chim. anal. 1911 16 7-8).-The sample is dissolved in twenty-five parts of hydrochloric acid one hundred parts of water are added and the solu- t i o n is neutralised with ammonia using phenolphtbalein as indicator. The precipitate (silica alumina iron oxide) is removed by filtration and water is added up to 1500 C.C. for each gram of sample. Four grams (or more) of solid ammonium oxalate are introduced and the solution is acidified with acetic acid.After waiting for two hours with occasional stirring the calcium oxalate is collected and treated as usual. Owing t o the large dilution i t is free from magnesium oxalate. L. DE K.ANALYTICAL CEEMISTRY. ii. 155 New Test Paper for the Volumetric Estimation of Zinc [with Sodium Sulphide]. R. KOPENHAGUE (Ann. C'him. anal. 1911 16 10-12).-As external indicator i s used a strip of filter- paper impregnated with a 10% solution of cadmium nitrate and dried at S0-90°. A small drop of the solution deposited on the paper will in a fern seconds turn yellow if sufficient sodium sulphide has been added. L. DE K. Rapid Estimation of Lead in Ores by Electrolysis with Stationary Electrodes. R. C. BENNER (J. I n d Engin. Chem. 1910 2 348-349).-The work of Sand was repeated and his results con- firmed showing that it is possible to deposit all the lead which can occur in a 0.5 gram sample of ore in five to ten minutes; for the electrolysis 75 C.C.of the solution in the presence of 20 C.C. of nitric acid (D 1.4) are used with a current of 4% amperes arid 2.5 volts; the electrolyte is warmed during the deposition s3 as t o maintain the cell just below boiling point. About 0.5-1 gram of pulverised ore was freed from sulphide by boiling with hydrochloric acid but not concentrated to the point where lead chloride would crystnllise out; the hydrochloric acid was then expelled with concentrated nitric acid and the volume of the solution reduced to about 10 c.c. diluted to 75 c.c. and electrolysed as above.I n ores where this method was impossible aqua regia was employed and the solution evaporated until fumes of sulphur trioxide became apparent water added and the basic iron sulphates dissolved by t)oiling; the lead sulphate was then collected and converted into lead carbonate by treatment with hot ammonium carbonate ; this was collected washed redissolved in nitric acid and the lead finally deposited by electrolysis. F. 51. G. 31. Quantitative Analysis of German Silver and Similar Alloys. REINHOLD KORTE (Zeitsch. angew. Ghern. 1910 23 2354-2356). - The author recommends the following methods of analysis To determine the copper nickel and zinc about 0.8 grain of the alloy is dissolved in aqua regia the solution evaporated t o dryness and the residue taken up with hydrochloric acid and water.The copper is precipitated with hydrogen sulphide the copper sulphide collected dissolved in nitric acid and tho copper determined electro- lytically. The filtrate from the copper sulphide is concentrated to about 50 c.c. a hot solution of 2 gratns of dicyanodinmidine sulphate in 20 C.C. of water added cooled and then made alkaline with ammonia. A 30% solution of potassium hydroxide is then added until the blue colour changes to yellow ; on remaining overnight the nickel dicyano- diamidine sulphate has completely precipitated. It is mashed by decantation with ammonia water dissolved in dilute sulphuric acid and t h e nickel determined electrolytically after the addition of ammonium sulphate and ammonium hydroxide ; or the precipitate may be collected in a Gooch crucible dried a t 115" and weighed directly but in this case it is necessary t o add a little tartaric acid to the solution before precipitating in order to retain the iron iu solution.ii. 156 ABSTRACTS OF CHEMICAL PAPERS.The filtrate from the nickel precipitate is acidified with hydrochloric acid made up to 500 c.c. and the zinc in 100 C.C. determined by direct ti tration with potassium ferrocyanide using ammonium moly bdate as i nd ica tor. To determine iron and manganese the latter is precipitated as peroxide from a nitric acid solution of 3 grams of the alloy by heating with potassium chlorate. The collected and mashed manganese peroxide is dissolved in hot concentrated hydrochloric acid the diluted solution made ammoniacal and the manganese again precipitated as peroxide by boiling with ammonium persulphate; it is weighed as Mn,04.The iron in the filtrate is precipitated by ammonium hydroxide after the addition of solid ammonium chloride the ferric hydroxide collected and dissolved in hydrochloric acid. After the addition of 150 c,c. of warm water and a few drops of a 5% solution of copper chloride in hydrochloric acid together with 15-20 C.C. of a 10% solution of solium salicylate the deep violet solution is titrated with a standard solution of sodium thiosulphate until colourless ; this gives the percentage of iron. The author recommends this method for estimating iron as being quite as trustworthy as titration with permanganate; it is only necessary to exclude nitric acid or a large excess of hydrochloric acid.T. s. P. TCHARVIANI and WUNDER (Ann. Clhim. anal. 1911 16 1-'7).-Separation of Iron and Cltromiuna.-About 0.5 gram of the mixed oxides is fused in a platinum crucible with 6 grams of sodium carbonate over a Thclu burner for tbree hours with free access of air. The fused mass is boiled with water and the residual iron oxide subjected to a second fusion to remove the last traces of chromium. As iron oxide always retains alkali i t must be purified by solution i n hot dilute hydrochloric acid and reprecipitation with ammonia. Tbe chromium is recovered as oxide from the alkali chromate solution in the usual manner ; it should be purified by solution in hydrochloric acid and reprecipitation with ammonia. Sepurution of Chromiunz and Aluminium.-The fusion should be continued for about six hours.The aqueous solution is then heated with excess of ammonium nitrate until the free ammonia has been expelled. The filtrate is acidified with nitric acid reduced by addition of alcohol and the chromic oxide is pracipitated with ammonia. Separation of Iron and Aluminium.-A double fusion is required and both iron and alumiuium are then estimated as just directed. Sepnmtion of Iron Chromium and A Zuminium-A seven hours' fusion is required ; although this suffices for a complete disintegration a second fusion is perhaps advisable. The fused mass is then treated F. WILLY HINRICHSEN and TH. DIECKMANN (Mitt. K. Muterialpru fungsumt Gross-Lichterfelde West. i910,28,229-246. CompareAbstr. 1908 ii,900).-Acomparative S e p a r a t i o n of Iron Chromium and Aluminium.The alumina is thus obtained in a pure condition. as previously directed. L. DP! K. Analysis of Chromium Tungsten-Steel.ANALYTICAL CHEMISTRY. ii. 157 discussion on the different methods employed by the author and others for the estimation of chromium tungsten and phosphoric acid in ateelp. Knorre’s method of precipitating hngsten with benzidine (Abstr. 1905 ii 286; 1908 ii 231 779) is considered fairly satisfactory the employment of tartaric and tannic acids and hydroxylamine is likewise discussed. F. M. G. M. Estimation of Chromium in Chrome-Tungsten Steel. HENRIK ~VDOWJSZEWSKI [with P. BOGOLUBOFF] (Chenb. Zeit. 1910 34 1365).-A modification of von Knorre’s method (Abstr. 1908 ii 779). One to two grams of steel borings are placed into a 500 C.C.Erlenmeyer flask 10-15 C.C. of 15% solution of sodium hydrogen phosphate are added and then 8-16 C.C. of sulphuric acid (D 1.65) and 5 C.C. of water. The metal dissolves with the aid of a gentle heat in about fifteen minutes and after heating a little more strongly 2 C.C. of nitric acid (D 1.4) are added which converts the tungsten into soluble yhosphotungstic acid. The clear liquid is then diluted with 300-500 C.C. of hot water 3-5 grams of ammonium persulphate are added t o oxidise the chromium to chromic acid and the excess of the reagent is then destroyed by boiling. After adding a few more C.C. of sulphuric acid the chromic acid is titrated with standard ferrous ammonium sulphate the excess of which is titrated with standard permanganate. L.DE K. The Analysis of Ferro-Uranium. WOLDEMAR TRAUTMANN (Zeitsch. angew. Chem. 191 1 24 61-62).-The powdered alloy (0.4 t o 0.6 gram) is dissolved in warm aqua regin three hours’ warm- ing being sulficient even when much carbon and silicon are present. After diluting with water and cooling an excess of solid ammonium carbonate is added and the solution is repeatedly stirred. After twenty-four hours the precipitate containing the whole of the iron and aluminium and the silica is collected. The filtrate is boiled precipi- tating most of the uranium. The addition of a few drops of ammonia precipitates the remainder and the precipitate is then collected washed with ammonium nitrate and weighed as U,O,. Carbon is estimated by direct combustion in oxygen and silicon by the usual method.Aluminium may be estimated by fusion with sodium peroxide precipitation of alumina and silica by ammonia and separation by means of hydrofluoric acid o r bp fusion with potassium hydrogen su 1 p hate. C. €3. D. The Analysis of Ferro-Zirconium. WOLDEMAR TRAUTMANN (Zeitsch. angew. Chem. 191 1 24 62).-The alloys which contain lees than 20% of zirconium may be roasted in a platinum crucible fused with sodium carbonate and a little nitrate dissolved in water with the aid of n little hydrochloric acid and repeatedly evaporated t o dryness with hydrochloric acid. The silica is estimated in the usual way and is then tested for purity by fusion with potassium hydrogen sulphute. I t retains from 1.2 to 2.9% of the zirconium present.The zirconium is best estimated by boiling the approximately neutral filtrate with sodium thiosulphate fusing the ignited precipitate with potassiumii. 158 ABSTRACTS OF CHEMICAL PAPERS. hydrogen sulphato and repeating the precipitation. If aluminium is present in the alloy i t passes into the zirconia and must be removed by fusion with sodium peroxide. The alloy may also be dissolved after roasting in hydrofluoric acid the zirconium being estimated by any of the usual methods. Carbon is estimated by combustion in oxygen. A New Reagent for Nickel and Cobalt and its Use for Distinguishing between these Metals. H. WEIL (Bull. SOC. chim. 1911 Liv] 9 20-23).-The procoss depends essentially on the difference in solubility of the basic chromates of the two metals in water.Potassium chromate gives with cold neutral aqueous solutions of cobalt salts containing not less than 2 grams per litre a reddish- brown precipitate of the basic chromate CoCrO,,CoO,xaq. With very dilute solutions the precipitate only appears on boiling and in this way 0.000038 gram of cobalt may be detected. The precipitate is soluble in acids or ammonia and is decomposed by alkali hydroxides. Nickel gives under the same conditions a chocolate-brown precipitate NiCr0,.2NiO which forms very slowly in the cold even in concentrated solutions but rapidly on boiling. A precipitate is formed with 0.000028 gram of nickel. For use in distinguishing between the two metals when present in nearly equal quantities the cobalt is precipitated in the cold and the nickel on boiling the filtrate both being recognised by the colour of the respective precipitates.If nickel is present in small amount relatively to cobalt the precipitate obtained on boiling the filtrate which may contain some cobalt is washed dissolved in dilute ammonia solution and the liquid freed from ammonia by evaporation when chocolate- brown basic nickel chromate is precipitated whilst cobalt under these conditions gives a green precipitate. If nickel is present in great excess cobalt is no longer precipitated in the cold and the deposit obtained on boiling must then be treated with ammonia as described when tbe formation of a green precipitate indicates the presence of cobalt. 'l' A. H. Analysis of Tin Alloys. FRANZ KIETREIBER (Oesterr. Ciienz.Zeit. 1910 [ii] 13 185-186).-Alloys containing tin antimony lead and copper (wch as Britannia metal and type metal) can be conveniently analysed as follows. About 1 gram of the alloy after heating with moderately concentrated nitric acid (1 0-15 c.c.) until all action bas ceased is tranferred t o a basin and evaporated down with about 25 grams of pure crystalline sodium sulphide (Na,S,SH,O) and the temperature subsequently raised until the melt begins t o harden; it is then digested with hot water whereby t h e tin and antimony are dissolved and the lead and copper remain insoluble; the former are then separated as described by Panafojow (Abstr. 1909 ii 523). C. H. D. F. M. G. M. A New Method of Analysing White Metal. E SCHURMANN (Matt. K. Materialprufungsart Gross-Lichterfelds West.19 10 28 349 -350).-A lloys containing possibly tin antimony copper arsenic,ANALYTICAL CHEMISTRY. ii. 159 lead and niercury and can be conveniently tmalysed by convet t i n g t h e metals into their bromides. The alloy is carefully treated with ii solution of bromine in chloroform or carbon tetrachloride and on warming a violent reaction takes place; when this is ended t h e mixture is thoroughly shaken with a n aqueous solution of oxnlic acid separated and the insoluble bromides and statlnic acid collected. The antimony i s precipitated from the solution with hydrogen sulphide and the remaining tin subsequently by electrolysis. F. M. 0. 37. Estimation of Glycerol. W. STEINFELS (LCeJjcensieder Zeit. 1910 37 793-795). -The author discusses the vdrious methods advocated for the estimation of glycerol and haggest.; some modifications t o the one introduced by l3ehner.The alkaline liquid containing glycerol (not more than 2 grams) is acidified with hulphuric acid rendered feebly nllialine w i t h sodium hydroxide and treated with 20 C.C. of 10% zinc sulphate solution ; i t is then filtered and made up to 250 C.C. ; 35 C.C. of this are oxidised by heating on the water-bath for two hours with 25 C.C. of Hehner's potassium dichromate solution and 5 0 C.C. of dilute sulphiiric acid (1 4). After coolinp i t is diluted t o 500 C.C. with cold water. Twenty-five C.C. are run into a $-litre flask containing 2 grams of potassium iodide dissolved in the least possible amount of water and 10 c c. of hydrochloric acid (1 2) diluted to 1 litre and titrnted with sodium thiosulphate. F.M. G. M. Colorimetric Estimation of Dextrose in Urine. i%'ILHELbi AUTENRKETH arid THEODOR TESDORPF (Jliinch. med. JVoch. 1910 37 No. 34 Reprint 13 pp.)-The authors find that the end-point in the titration of urinary dextroPe by Bang's method (hbstr. 1907 ii 136) is not sharp and moreover is dependent 011 various factors such as temperature concentration and rapidity of working. Better results may be obtained by employing a n excess of Bang's copper solution and estimating t h e unaltered copper with the help of the colorirneter previously described (But enrieth itrid Koclnigsberger Abstr. 19 10 ii 910). The copper solution changes slightly when kept or when boiled b u t the accuracy of the results is not affected if t h e same duration of ebullition (three minutes) is always employed.A ciirve is prepared hhowing the amounts of dextrose corresponding with the scale divisions of the colorirneter. The agitation with blood-charcoal suggested by Bang and Bohmans- son (Abstr. 1910 ii 163) for the removal from urine of reducing substances other than dextrose is not to be recommended because t h e charcoal absorbs dextrose as well Loss of dextrose also occurs when the agitation wlth charcoal is effected in presence of hydrochloric acid. R. V. S. The Micro-Chemistry of Inulin. 0. TUNMANN (Ber. Deut. pharrn. Gea. 1910 20 577-585).-l!he so-called amorphous inulixi granules in cellular tissues are not of a uniform nature ; inulin crystals occur in them and these crystals are bound together by other substances.The ~rnost useful reactions for detecting inulin are given by pyrogallol andii. 160 ABSTRACTS OF CHEMICAL PAPERS. resorcinol-hydrochloric acid (0.1 gram of resorcinol dissolved in 5 C.C. of alcohol and 5 C.C. of hydrochloric acid) ; the former yields a violet-red coloration on warming for a short time and the latter a red coloration. Before applying the test the preparation should be immersed for eight days in alcohol containing tartaric acid to remove alkaloids then for eight weeks in alcohol to harden the inulin and finally be washed with water to remove sugars. The membrane of the cells and starch do not give a coloration with the reagents. w. P. s. A New Mode of Estimating Pentosans by the Copper Reduction Method. J.TR. Fr,oam (Chern. Weekbkad 1910 7 1057-1063).-The amount of Furfuraldehyde generated by boiling pentosans with dilute hydrochloric acid can be estimated by its reducing action on Fehling’s solution the cuprous oxide being weighed or the excess of cupric salt ascertained by iodometry. Tbe procedure is to prepare 400 C.C. of the furfuraldehyde distillate and to add sodium hydroxide (1 3) to 50 C.C. of the cooled distillate until the reaction is slightly alkaline. To the mixture are added 10 C.C. of a solution containing 69.28 grams of crystallised copper sulphate per litre and 10 C.C. of one containing 346 grams of Rochelle halt aid 100 grams of sodium hydroxide per litre. After diluting t h e solution t o 100 C.C. with distilled water it is boiled in a reflux apparatus for thirty-five minutes pieces of ice being placed in the open end of the condenser t o ensure complete condensation of the furfuraldehyde.When the operation is finished the liquid is cooled quickly and the extent of the oxidation is ascertained by the gravimetric or volumetric method. Each C.C. of N/lO-sodium thioaulpliate corresponds with 0.0024 gram of furfuraldehyde and each mg. of copper with 0*00@3775 gram. The percentage of pentosan can be calculated by means of Tollens’s formula. The amount of reduction of the Pehling’s solution in the absence OF furfuraldehyde must be ascertained by the aid of a blank experiment carried out with similar conditions and deducted from the analytical results before calculating the percentage of furfuraldehyde.A. J. W. Estimation of Lactic Acid. ELIAS ELVOVE (Amer. J. Pharm. 1911 83 14-19).-The United States Pharmacopeia specifies a lactic acid containing 75% of true lactic acid and having D25 1,206. An acid of this specific gravity shouId contain about 85% oE true lactic acid and this anomalous specification is due to the inaccuracy of the pharmacopeial method of estimation which involves direct titration of the boiling acid. The author recommends instead the addition of 50 C.C. of normal sodium hydroxide solution t o 2 grams of the acid and titration of the excess of alkali with normal sulphuric acid after the mixture has remained for thirty minutes in the cold. Phenol- phthalein should be used as indicator. T. A. H. The Anhydride of Lactic Acid. A. A.BESSON (Chem. Zeit. 1911 35 26).-Attention is drawn to the fact that specimens of lactic acid frequently contain quantities of the anhydride and that the latter is not estimated when the acidity of a sample is determinedAKALY'I'ICAL CHEMlSTRY. ii. 161 by direct titration. The total amount of acid is found by treating the neutralised solution with a n excess of alkali leaving the mixture for ten minutes then adding an excess of acid boiling the solution and neutralising. The quantity of alkali used in these operations is a measure of the total lactic acid present (that is acid plus anhy- dride) in the sample. In cases where dextrin has been removed from the sample by treatment with alcohol and the alcoholic solution of the acid evaporated before the titration it is necessary to collect the distillate and titrate its acidity as a small quantity of the acid distils over with the alcohol.w. P. s. Influence of Potassium Dichromate on Certain Anaiytical Constants of Milk. LEON GARNIER (J. Pharm. Chim. 191 1 [vii] 3 55-59).-Samples of milk collected oficially in France in connexion with the food adulteration law of 1905 are ordered to be preserved by the addition of 1 gram of potassium dichromate per litre. The author points out that in analysing milk so treated allowance must be made for the increase in specific gravity acidity refraction '' dry extract," and ash due to the addition. He also finds that inilk preserved by means of dichromate when kept increases steadily in acidity and refraction and decreases in optical activity these changes being no doubt in part due to conversion of lactose into lactic acid.The changes induced are' irregular in amount but the variations are usually within limits narrow enough to permit of corrections being made in analytical reaults. T. A. H. Simple Method for the Estimation of Formaldehyde. FELIX HERRMANN (Chen2. Zeit. 191 1 35 25-26).-The .formaldehyde solu- tion is mixed with ammonium chloride and treated with a definite volume of standard sodium hydroxide solution ; the ammonia liberated combines with the formaldehyde to form hexawethylenetetramine and the excess of alkali is then titrated. The difference between the quantity of alkali added and that found by titration iepresents the amount of ammonia which has combined with the formaldehyde and is a measure of the qaantity of the latter present. A corre2tion must be made for the amount of free acid which is always present in commercial for ma1 deh y d e solutions.w. P. s. Estimation of Cyrtnogen Compounds in Coke Oven Gases. EMLIE LECOCQ (Bull. Xoc. chim. Belg. 1910 24 439-445).-Fifty t o 100 litres of the gas are passed through abIorption tubes containing 2-5 grams of lead acetate dissolved in 200 cc. of n 10% potassium hydroxide solution. The precipitated lead sulphide is removed by filtration and the filtrate transferred t o a 500 C.C. flask; the lead is then precipitated by addition of dilute sulphuric acid the solution being cooled during the process to prevent the ebcape of hydrogen cyanide. After making up t o the mark 400 C.C. of the clear solution are removed for the estimation of cyanide and thiocyanate. For this purpose 10 C.C.of a solution containing 10% of a mixture of equal parts of ferrous and ferric sulphates are added folloned by potasbium hydroxide solution sufficient to precipitate a considerableii. 162 ABSTRACTS OF CHEMICAL PAPERS. proportion of the iron in solution. After about an hour the contents of the flask are acidified b y addition of sulphuric acid heated on the water-bath for a quarter of a n hour and left for some hours. The reddish-coloured solution is then decanted off and the Prussian-blue hepal ated by filtration through a small fine-grained filter-paper The proportion of cyanide in the precipitate is now estimated by Feld’s method which conHists in converting the complex cyanide into mercuric .c*yanide by heating with a n alkaline solution of rnagnesium and rriercuric chlorides.For the estimation of the thiocganate the decanted solution and the wash liquois are combined made up t o a definite volume and the colour of the solution compared with t h a t of a similar solution containing a known quantity of thiocyanate. Actual experimental results are recorded according t o which the average amount of cyanogen is 0.093 gram and t h a t of thiocyanogen 0.189 gram per cubic metre of gas. Estimation of Cyanamide Dicyanodiamide and Carbamide in Calciuni Cyanamide (Kalkstickstoff). NIKODEM CAEO [with B. ~ C I I U C K ] ( ~ e h s c h . fcizyrw. Chem. 19 10 23 2407-241 l).-see this vol. i 119. Tests for Cocaine and Certain other Anesthetics.ERNEST H. HANKIN (Ancclyst 19 11 35 2-fi).-The permanganate test for cocaine is extremely sensitive if the cocaine is dissolved in alum solution and the permanganate is used in the form of a dried film ; the test readily distinguishes between cocaine and certain cocaine sub- stitutes. Of these. bubsti tutes alypine tropacocaine and scopolanJirie form crystalline per manganates which can easily bo distinguished from each other and from cocaine permanganate. P-EucEtine stovaine novocaine hoiocaine and nirvsne do not form crystalline per- manganates but bromine- water furnishes a means of distinguishing them. With bromine-water cocairie scopolamine stovaine arld novo- caine give a yellow precipitate which dissolves on heating ; p-eucaiue yields a precipitate which dissolves on warming but is re-precipitated OIL boiling the solution. Nirvane also gives a yellow precipitate soluble on heating the solution; the liquid acquires a red colour.Holocaine yields a yellow precipitate with bromine-water ; when the mixture is boiled the precipitate dissolves and a pinkish-white opalescence is GEORGES DENIC~S (Conzpt. rend. 1910 151 1354-1355. Compare this vol. ii 79).-Ten C.C. of a solution of tt cupreine salt (about 0.2%) is mixed with 1 C.C. of ammonia and 1 C.C. of 1 vol. hydrogeu peroxide. After shaking 0.1 C.C. of copper sulphate solution containing 3-4% of the crystalline salt is added and the mixture again shaken. The liquid becomes green and shows greenish-blue pat tides in suspension ; a n absorption band is visible in the infra-red.On the addition of a n equal volume of alcohol t o the solution it changes t o deep emerald-green. The reaction is visible in solutions considerably more dilute than the one mentioned. w. 0. w. 11. M. 1). produced in the liquid. w. P. s. New Reaction of Cupreine.ANALYTICAL CHEMISTRY. ii. 163 Estimation of Morphine. RUDOLF GOTTLIEB and 0. STEPPUHN (Arch. exp. Path. Pharrn. 1910 04 54-66. Compare Abstr. 1910 ii 558).-Rubsamen’s method is defended and details given of the method and of the sources of error and how to avoid them. W. D. H. Estimation of Nicotine in Concentrated Tobacco Juice. JOHANNES SCHRODER (Chenz. Zeit. 191 1 35 30).-Very varying results are obtained by the processes which have been proposed by different workers (Kissling Heut Keller Bid Schloesing T6th etc.) for the estimation of nicotine in tobacco although fairly concordant figures are yielded by each particular method.The discrepancy is particularly marked in the case of products containing considerable quantities of nicotine such for instance as the concentrated tobacco extracts which are used as insecticides. The method described by T6th has been recommended as being trustworthy for technical purposes but the author points out that the results obtained for one sample may vary by as much as 20% of the quantity of nicotine actually present. He considers that the subject needs further Volumetric Estimation of Phenolphthalein. V. ZOTIER (Bull. Soc. chim. 1910 [iv] 7 993-995).-A weighed quantity of the material containingphenolphthalein is triturated with sodium hydroxide free from carbonate and mixed with a few C.C.of water and the solution made up to 50 C.C. and filtered. To 25 C.C. of the filtrate dilute hydro- chloric acid is added until phenolphthalein begins to be precipitated any precipitate formed being then just redissolved by a drop or two of N/lO-sodium hydroxide. h’/lO-Siilphuric acid is then added until the red colour disappears the liquid being vigorously shaken after each addition of acid. If n be the quantity in C.C. of N/lO-acid added and V the volume of the liquid after titration the quantity in centigrams of phenolphthalein in the material used is given by the formula 2[1*59n + ( V - n)O*OO92]. It is convenient to use the second 25 C.C. of filtrate as a control.investigation. w. P. s. T. A. H. Estimation of the Tannin in Tanning Liquids by m e a n s of the Zeiss Immersion Refractometer. P~ETRO FALCIOLA and M. CORRIDI (Gaxxetta 1910 40 ii 229-236).-The change of refractive index caused by removal of the tanning substance from the solutions is compared with the weight of tanning substance precipitated and in this way the amount of the latter corresponding with one-scale division of the refractomcter is ascertained. The results agree fairly closely with those of Zwick (Cheni. Zeit. 1908 32 405) and Sager (Collegium 1909 146) and indicate that the refractometric equivalents for tanning substances of different origins do not *differ more than those for different samples of the same origin so that it would not seem possible to identify the Eource of a given extract by this means as was suggested by Zwick.R. V. S. Estimation of the Amide Nitrogen in Proteins. W. DENIS (J. Biol. Chem. 1910 8> 427-435).-.Folin’s method for the estima-ii. 164 ABSTRACTS OF CHEMICAL PAPERS. tion of ammonia in urine can also be used with good results for the estimation of ammonia in the cleavage products of proteins ; amino- acids are not affected. W. D. H. Method for the E s t i m a t i o n of the Aliphatic Amino-group. Application t o the Chemistry of the Proteins Urine and Enzymes. DONALD D. VAN SLYKE (Ber. 1910 43 3170-3181).- The apparatus described in which the principle of Sachs and Kormann is adopted allows of the determination of aliphatic amino-groups within a few minutes with an accuracy of & 1/20 mg.of nitrogen. A flask containing 35-37 C.C. is nearly filled with a mixture of sodium nitrite and acetic acid and closed with a cork through which pass capillary tubes closed by stopcocks connecting with a gas burette a tube Containing the amino-acid solution and a tube containing water. The air is entirely displaced from the flask by nitric oxide and about 20 C.C. of soIution are driven back into the tube containing water by the pressure of the gas formed. The flask is then connected to the burette and the amino-acid run in. Nitrogen is evolved and passes together with much nitric oxide into the burette. After about five minutes all the gas is expelled from the flask by running in water and the mixture of gases collected is passed into an absorption pipette oontaining alkaline potassium permanganate. The residual nitrogen is measured. A few drops of amyl alcohol are introduced Then protein solutions which are inclined t o froth are analysed. Arginine histi- dine and tryptophan give LIP one molecule of nitrogen. I n leucyl- leucine the peptide amino-group does not react; this group is partly active in glycylglycine. Cytosine and guanine react only slowly with the primary amino-groups Proline and oxyproline do not react. By determining the total and amine nitrogen in an impure proline fraction the amount of this present is accurately obtained ; thus casein contains 6.7% proline. It is possible almost completely to analyse a protein even when only small amounts are available by hydrolysis and determination of the nitrogen as ammonia melanine nitrogen total and total amino- nitrogen and also of the total and amino-nitrogen in the phospho- tungstic acid precipitate and filtrate. The method is applicable to urine after removal of the carbamide and ammonia ; 1.5 to 2.5% of the total nitrogen is urine in amino-nitrogen. By taking proofs from time to time it is possible to follow the course of protein hydrolysis by trypsin or by sodium hydroxide. The amino- acid nitrogen increases as hydrolysis proceeds. E. F. A. The simple amino-acids give up all their nitrogen.

ISSN:0368-1769    

DOI:10.1039/CA9110005147

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

ii. 165 General and Physical Chemistry. Character of the Double Refraction of Liquid Crystals. DANIEL VORL~NDER and M. E. HUTH (Zeitsch. physikal. Chem. 1911 75 641-650. Compare Abstr. 1908 ii 88).-Purther evidence has been obtained of the rule already enunciated that all liquid crystals are optically uniaxial. Pleochroism surface colours and iridescence of liquid crystals are only observed with substances showing circular polarisation but crystals showing no pleochroism or play of colours may be optically active. All liquid crystals showing pleochroism and iridescence show negative double refraction ; all other crystals shorn positive double refraction. The latter rule also applies to crystals which exist in more than one liquid-crystalline phase. I n such a case the region of the phases showing pleochroism and iridescence occurs regularly between those of the amorphous liquid and of the colourless crystalline liquid.G. S. The Variation of the Refractive Index with the Tempera- ture in the Ultra-red Region for Rock Salt Sylvine and Fluorite. ERIK ZIEBREICH (Ber. Deut. physikal. Ges. 1911 13 1-18).-Measurements of the variation of the refractive index with the temperature have been made for wave-lengths extending t o X = 6-5p in the case of fluorite and to X = 9p and 2 1 p for rock salt and sylvine. The temperature-coefficients are negative a result which is identical with that obtained for rays of the visible spectrum. I n con- trast with the behaviour of visible rays the temperature-coefficient for the ultra-red rays diminishes as the wave-length increases.This difference is attributed to a shift of the region of absorption in the direction of greater wave-lengths as the temperature is raised. H. M. D. Structure of Liquids with Conical Focal Lines. GEORGES FRIEDEL and F. GRANDJEAN (Compt. rend. 1911 152 322-335. Compare Abstr. 1910 ii 809 1018).-Contrary to the view upheld in a previous paper the author now agrees with Mauguin (Compt. rend. 1910 51 1141) that liquids such as azoxyphenetole are doubly refrac- tive throughout their whole mass and optically homogeneous. This is not evident from the appearance of a film of the substance in polarised light unless the utmost precautions are taken to ensure the purity of the compound the cleanliness of the glass plates between which it is viewed and their freedom from relative movement.The geometri- cal nature of the phenomena observed when these precautions are taken is discussed. I-. 0. w. Optical Dispersion An Analysis of its Actual Dependence on Physical Conditions. T. H. HAVELOCK (Proc. Boy. Soc. 1911 8,84 492-523).-The effect of the physical state of a medium on its optical dispersion can be represented by means of two variables one of which is the density (p) and the other a factor ((r) which expresses VOL. C . ii. 12ii. 166 ABSTRACTS OF CHEMICAL PAPERS. the effect of surrounding molecules. For two different states of aggregation of the same substance it is found that the difference ~ ~ / ( n ~ - 1) - p,/(n,2 - 1) = fluz - p2u2 is independent of the wave-length of the rays passing through the substance and is a function only of physical conditions such as pressure temperature and density.Experimental data for gases and liquids are shown to be in satisfactory agreement with this deduction. By assigning a zero value t o u in the case of a gas a t 0" and 760 mm. numerical values can be obtained which express the effect of the molecular aggregation in different states. Anomalies in the refractivity are to be ascribed in part to variations in the magnitude of the factor U. The Doppler Spectrum of the Hydrogen Canal Rays. E. GEHRCKE and 0. REICHENHEIM (Ber. Beut. physikcd. Ges 1911 13 111-118.)-The Doppler effect exhibited by the line Hp in the canal- ray spectrum of hydrogen has been investigated. For a given fall of the cathode potential the distribution of intensity in the Doppler spectrum is dependent on the size of the cathode.With a cathode of 1'5 mm. diameter the intensity of the two Doppler lines is approxi- mately the same when the cathode fall amounts to 730-800 volts. The sharpness of the Doppler lines increases as the pressure of the hydrogen in the discharge tube diminishes. From the observations at higher pressures it is found that the wave-lengths of the Doppler lines do not correspond with velocities of particles in the ratio of ,@ 1 and this is considered to be irreconcilable with the hypothesis that the lines are due to hydrogen atoms and hydrogen molecules respectively under the influence of the same driving force. H. M. D. Normals from the Arc Spectrum of Ion in the International System.HEINRICH KAYSER (Zeitsch. wiss. Photochem. 191 1 9 173-185),-To supplement the determinations of the normal lines of the second order measurements have been made of further lines in the arc spectrum of iron of wave-lengths digering by 5-10 A. These normal lines of the third order were obtained by means of a concave grating having 20,000 lines to the inch and a radius of curvature of 6.5 metres The measurements extend from X = 4120 to h = 6495. The recorded wave-lengths were obtained by an interpolation method in which the data for several pairs of adjacent secondary normal lines were made use of and the several interpolated values were then combined to give a mean value. On comparison of the differences bet ween the corresponding wave- length numbers in Rowland's and the international system it is found these increase from about 0.16 a t X=4100 to about 0.21 a t X = 6500. Absorption Spectra of Certain Salts of Cobalt Erbium Neodymium and Uranium as Affected by Temperature and by Chemical Reagents.HARRY C. JONES and W. W. STRONG (Amer. Chcm. J. 1911 45 1-36 113--159).-The work of Jones and Anderson (Abstr. 1909 ii 359) on the absorption spectra of cobalt erbium and neodymium salts has been continued. I. Solutions of cobalt chloride and bromide in glycerol do not give H. RI. D. H. M. D. I. and 11.GENERAL AND PHYSICAL CHEMISTRY. ii. 167 any of the fine red cobalt bands. A rise of temperature of the more concentrated solutions causes the yellow absorption band a t X 5100 to widen so as finally t o absorb all the red and thus cause the solution to appear blue. Concentrated aqueous solutions of cobalt chloride show an enormous increase in the absorption with rise of temperature ; this increase takes place a t lower temperatures as the concentration is increased.I n the case of the more dilute solutions the widening of the absorption with rise of temperature is quite symmetrical. The effect of a rise of temperature on the absorption of cobalt nitrate or sulphate is very small as compared with its effect on the chloride. The presence of calcium or aluminium chloride in aqueous solutions of cobalt chloride increases the effect of temperature on the absorption and causes the red absorption to take place in more dilute solutions. The temperature a t which the absorption in the red increases so greatly is termed the '( critical colour temperature," and seems to depend on the existence of some solvate or peculiar condition of the cobalt molecule; it is much higher in water and glycerol than in other solvents.A review is given of Becquerel's investigations of the effect of low temperatures and magnetic fields on the absorption spectra of erbium and neodymium. The absorption in solutions of erbium chloride in glycerol is very similar to that i n aqueous solutions but the bands in general are shifted towards the red and most of them are of greater wave-length than those of aqueous solutions. A rise of temperature from 15" to 200' produces no appreciable change in wave-length but at the higher temperature the bands are much less distinct1and considerahly weaker.An examination of the spectra of aqueous solutions of erbium nitrate has shown that the NO group does not exert a hypsochromous effect such as has been found for the uranyl bands. It has been found that Beer's law holds for solutions of neodymium salts in glycerol except in the case of the more dilute solutions which show greater general absorption in the ultra-violet. A rise of tempora- ture of a solution of neodymium chloride in glycerol effects scarcely any noticeable shift in the bands. The presence of calcium chloride causes the temperature shift of the bands to be increased but the effect is not so great as in aqueous solutions. The absorption spectra of neodymium chloride in 4 cerol are very similar to those of aqueous solutions. The " glycero? 'bands closely resemble the '' water " bands but are all of slightly greater wave-length.The presence of free nitric acid in aqueous solutions of the nitrate causes the bands to become much broader and more diffuse than those of the neutral salt. A study has been made of the effect of nitric acid hydrobromic acid and hydrochloric acid on neodymium acetate solutions and of hydro- chloric acid on neodymium citrate solutions. The spectra indicate that in some of these reactions there probably exist several systems or compounds between the acetate and the salt of the acid added. An investigation of concentrated solutions of erbiurn and neodymium salts and of the salts themselves has shown that the spectra are entireIy different for the diEerent salts. It has also been found that the absorption of different salts in the same solvent is very similar 12-2ii.168 ABSTRACTS OF CHEMICAL PAPERS. which indicates that the solvent plays an important part in the absorption of light. 11. It is unusual for the absorption spectra of solutions of salts to shorn much if any influence of the acid radicle but an exception exists in the case of aqueous solutions of uranium salts the uranyl nitrate bands being all of shorter wave-length than those of other uranyl salts. The absorption spectra of the uranyl salts have been photographed over a wide range of concentration and the results show that the wave- lengths of the bands do not depend on the concentration. Experiments have been made on the influence of nitric acid on the absorption spectra of uranyl nitrate of sulphuric acid on those of the sulphate of acetic acid on those of the acetate and of hydrochloric acid calcium chloride or aluminium chloride on those of the chloride.I n general the presence of these reagents causes the uranyl bands to become more intense and in some cases narrower. The action of all the reagents except nitric acid is to cause the uranyl bands to be shifted towards the red. Nitric acid however causes a considerable s h i f t towards the violet. Similar effects are produced on the bands of the corresponding uranous salts These effects are probably due to the formation of aggregates. A study has also been made of the effect of gradually adding sulphuric or hydrochloric acid to uranyl nitrate and it has been found t h a t the spectra change gradually as one salt is transformed into the other (compare Abstr.1910 ii 247). It bas been shown previously (Abstr. 1909 ii 360) that the spectrum of any one salt often varies greatly with different solvents. Uranous salts have been found to show very characteristic bands in water methyl and ethyl alcohols acetone and glycerol. I n mixtures of two solvents both sets of solvent bands appear the intensity of any solvent band being a function of the relative amounts of the solvents present. A rise of temperature causes the general absorption of an aqueous solution of any salt to increase and also causes the bands to become wider and more intense. The uranyl chloride bands are shifted towards the red as the temperature increases but those of uranyl nitrate do not appear to shift.Uranyl nitrate dissolved in concentrated nitric acid however shows a considerable shift. The bands of uranyl acetate and sulphate are only slightly shifted. It is pointed out t h a t the results of this investigation furnish additional evidence that ions and certain molecules combine to some extent with the solvent. These so-called solvates have very different compositions and absorption spectra depending on the solvent employed for the solution of a particular salt. The paper concludes with a discussion of the bearing of the solvate hypothesis on the theory of electrolytic dissociation (compare Abstr. 1909 ii 221 ; and Zeitsch. physikal. Chenz. 1910 74 325). A biblio- graphy of the work of Jones and others on this subject is appended. E.G. Selective Oxidation. XXXIII. HARRY C. JONES and W. W. STRONQ (Arne?.. C'hern. J. 19 11 45 36-38).-The absorption spectrumGENERAL AND PHYSICAL CHEMISTRY. ii. 169 of a solution of uranous bromide in a mixture of methyl alcohol and water shows two well-defined sets of bands the ‘‘ methyl alcohol bands” and the “water bands.” On adding a small quantity of potassium perchlorate to such a solution the uranous ‘‘ water bands ” disappear whilst the “ methyl alcohol bands ” remain thus showing that the portion of the uranous salt combined with themater has been oxidised whilst that combined with the methyl alcohol has not under- gone any change. Calcium nitrate produces the same effect but hydrogen peroxide oxidises both the “ hydrated ” and ‘‘ alcoholated ” uranous bromide to the uraoyl state.Similar results are obtained with uranous chloride. E. G. The Destruction of the Fluorescence of Iodine and Bromine Vapour by other Gases. ROBERT W. WOOD (Ber. Beut. physikul. Ges. 1911,13 72-77 *).-The intensity of the fluorescent light which is emitted by iodine vapour when subjected t o sunlight decreases when foreign gases are admixed with the vapnur. From a series of comparative measurements it has been found that the flnoresceuce is diminished in the ratio 5.3 to 1 by ethyl ether carbon dioxide air and hydrogen when the pressures of the admixed gases are respectively 3 7 11.5 and 24 mm. The influence of the foreign gas increases with its molecular weight but there is no simple connexion between the two quantities.I n the absence of traces of foreign gases the intensity of t h e fluorescence of iodine increases in a linear manner with the tempcra- ture between - 20’ and + 20’. At 30° the intensity is the same as a t 20° but diminishes with further rise of temperature. I t is probable that at the higher temperatures the increase in the fluorescence is more than counterbalanced by the increased absorption. Some experiments with bromine vapour show that this can be made t o fluoresce if the tube containing i t is cooled by means of solid carbon dioxide. This indicates that the density of the vapour must be reduced below a certain value before the molecules of the vaFour show fluorescent effects. H. &I. D. The Influence on the Fluorescence of Iodine and Mercury Vapour of Gases with Different Affinities for Elec rons.J. FRANCK and ROBERT W. WOOD (Ber. Deut. physikccl. Ges 1911 13 78-83 +).-The effect of varying quantities of helium argon nitrogen oxygen and chlorine on the intensity of the fluorescence of iodine vapour has been examined. On compming the results with those obtained in presence of hydrogen air carbon dioxide and ethyl ether (see preceding abstract) i t is found that the reduction in the intensity of the fluorescence for a given pressure of the admixed gas increases as the electro-negative character becomes more pro- nounced. The inert gases are least active whilst chlorine is the most effective. Preliminary experiments with mercury vapour in presence of helium and oxygen have given similnr iesults.I n presence of oxygen at a pressure of 3 mm. mercury cannot be made to fluoresce * and Phil. Mag. 1911 [vi] 21 309-313. .I. and Phil. Mag. 1911 [vi] 21 314-318.ii. 170 ABSTRACTS OF CHEMICAL PAPERS. whereas helium at a pressure of one atmosphere is apparently without influence. These observations are connected with the fact that the pressures at which fluorescence can be excited in the case of mercury iodine rind bromine are very different. The optimum pressure for mercury amounts to several atmospheres; for iodine it is 0.2 mm. and for bromine it is very small. The fall in pressure with increase in the electro-negative character of the vapour is supposed to be due to the increasing influence of the vibrating molecules on one another. H. M. D. The Transformation of the Resonance Spectrum of Fluorescing Iodine into a Banded Spectrum by Addition of Helium.ROBERT W. WOOD and J. FRANCK (Ber. Deut.physikaZ. Ges. 1911 13 84-87; also Phil. Mag. 1911 [vi] 21 865-268. Compare preceding abstracts).-Spectroscopic examination of the fluorescent light emitted by iodine vapour exposed to the green mercury line has shown that the presence of helium at a pressure of 2 mm. of mercury causes a marked change in the spectrum. The series of lines which are observed in pure iodine vapour are greatly diminished in intensity and this change is accompanied by the appearance of a banded spectrum. This spectrum appears to be identical with that which is obtained when the iodine vapour (without helium) is excited by means of white light.When the pressure of the helium is raised to 10 mm. the series of resonance lines can no longer be observed. When the helium is replaced by chlorine there is 110 trace of this banded spectrum. I n explanation of these observations it is supposed that impacts of iodine molecules with molecules of helium set up vibrations in all the contained systems of electrons the energy of the original vibrating systems being thereby diminished. The change in the colour of the fluorescence from green to red when increasing quantities of helium are admixed with the iodine vapour is consistent with this hypothesis. The absence of the banded spectrum in presence of chlorine is due t o the damping effect of the strongly electr-o-negative molecules. H M . D . Photolysis of Acids with a Complex Grouping by Ultra- violet Light.Action of Uranium Salts as Luminous Catalysts DANIEL BERTHELOT and HENRY GAUDECHON (Compt. rend. 1911 152 262-265. Compare Abstr. 1910 i 349 543; ii 564 606 813 814).-Dibasic acids in the solid state or in aqueous solution lose carbon dioxide on exposure to ultra-violet light and form monobasic acids which on prolonged exposure undergo further decom- position as previously indicated. Maleic and fumaric acids give a mixture of carbon monoxide and dioxide. Pyruvic acid is decomposed in the same way as by heat but laevulic acid behaves differently yielding carbon dioxide carbon monoxide and gaseous hydrocarbons. Lactic acid forms mainly carbon dioxide with carbon monoxide hydrogen and methane. The action of the rays on the foregoing substaaces is accelerated by the presence of uranium salts which act its catalysts.Other fluorescentGENERAL AND PHYSICAL CHEMISTRY. ii. 171 substances such as thorium sulphate or eosin are without action. The presence of fluorescent substances diminishes the decomposition of The Re-combination of Ions Produoed in Gases by a-Rays. RI. MOULIN (I;e Radium 1910 '7 350-354).-Curves are given showing the relation between the ionisation current and voltage for carbon dioxide air and hydrogen ionised by the a-rays of polonium when the electric field acts in the direction of at right angles to and at 45" to the path of the rays through the gas It is possible to pre- dict the form of saturation ourve for different inclinations of the electric field to the trajectories of the rays by supposing that only the component of the field perpendicular to the trajectories acts.This would not be the case if the phenomenon of lack of saturation with a-ray ionisation were due to initial re-combination of ions produced from the same molecule but is well explained on the view that the ions are formed in columns along the trajectory of the rays and are not uniformly distributed throughout the volume of the gas. eimple compounds such as alcohol or acetaldehyde. w. 0. w. F. 8. The Different Influences of a- p- and 7-Rays on the Colours of Solid Substances. CORNELIO DOELTER and HEINRICH SIRK (Monatsh. 1910 31 1057-1066).-Rock salt quartz fluorspar and barytes were exposed for four months to the a-rays of polonium deposited on a platinium foil.Only the first-named showed coloration which was brownish and extended only some hundredths of a millimetre into the material. A glass vessel in which a radium pre- paration had been kept showed in addition to the brown coloration throughout due to 6-rays an intense surface coloration due to a-rays. Glass cubes exposed to the 6- and y-rays of radium showed an intense dark brown coloration diminishing with depth due to P-rays and a much lighter uniform yellowish-brown coloration beyond due to the y-rap. A cylinder of salmon-red gold-ruby-glass covered on all sides but one with 5 mm. thickness of tin foil and exposed t o two radium pre- parations consisting of 1 *O and 0.5 gram of radium chloride one acting directly and the other through the foil showed after twenty-three days a uniform orange-brown colour showing that the /3-rays were without action in this case.A clear rock-crystal after exposure to the rays showed a remarkable dibtribution of colour reminiscent of what is often seen in natural amethysts consisting of lighter and darker shades of colour parallel to the hexagonal contour. From the centre extended three rhomb- shaped streaks parallel to the crystal axes. The darker streaks mere all dichroic. There was no alteration of the rotatory power or of the interference figure of the crystal. Coloured zircons are coloured more deeply and those rendered colourless by heating are re-coloured by the rays. Solutions of barium and calcium chloride were not coloured by thirty days' exposure to the rays from 0.5 gram of radium chloride but those of mercuric chloride potassium chloride and sodium sulphate showed respectively faint yellowish milky-blue and yellow coloration as is the case for the solid salts.F. s.ii. 172 ABSTRACTS OF CHEMICAL PAPERS. Scattering During Radioactive Recoil. WALTER MAKOWER and SYDNEY Kuss (Afem. Munchester PhiE. Sot# 1910,55 No. 2 1-4). -In experiments on the recoil in a vacuum of radium-B from a wire coated with radium-A surfaces out of the direct line-of-fire also received some active deposit. Under Conditions where the surface could only receive active deposit by reflexion from an opposite surface the decay curve showed that more than one-half of the active matter deposited mas radium-C and not radium-B. The lather is probably due t o reflexion and the former to recoil from radium-B deposited on the reflector.The large proportion of r a d i u m 4 under these conditions is surprising as in ordinary circumstances only one-thousand t h of the atoms of radium-C formed recoil from radium-B. It is probable t h a t the absence of films on the surface in this experiment is the cause of the greater proportion of the radium4 recoiling. The Chemical Reactions of Radioactive Elements. BBLA SZILARD (Le Radium 1910 7 366-372).-The views that the fixation of radioactive elements by precipitates formed in their solutions is due to chemical similarity between the precipitant and the substance fixed or t o the great insolubility of the radioactive substance the precipitant acting as a nucleus or t o the electro-positive character of the elements like barium most used as precipitants or t o isomorphism or t o the lowering of the solubility of the radio-element by addition of another electrolyte are dismissed as untenable.The view is advanced t h a t the precipitates are charged particles in suspension which attract the charged ions of the dissolved radio- element forming complexes less highly charged. Precipitates like barium sulphate and ferric hydroxide formed in non-radioactive solutions and afterwards mixed with them still fix the radioactive substance. The precipitates most useful as barium sulphate carbon &c. are extremely insoluble substances capable of existing un- dissolved in the state of fine suspensions. Whether radioactive substances act differently in neutralising the charge on these fine particles from ordinary electrolytes cannot at the present time be decided.F. S. Some Probable Chemical PropertierJ of Radium and its Compounds. ROBERT DE FORCRAND (Compt. rend. 1911 152 66-69).-The heats of solution and of formation respectively augment or diminish regularly for the halogen salts and the oxides of the alkali and alkaline earth metals in the order calcium lithium strontium barium sodium potassium rubidium cesium. So far as is known the same is true for the sulphates and selenates and for the bydrides and carbides. The affinity of the oxides for oxygen water or carbon dioxide and the solubility of the fluorides oxides and with some irregularities the carbonates augment progressively in the order given.Similar considerations apply to the solubility in alcohol or in hydrochloric acid of most of the halides and carbonates and to the formation from the fluorides of more and more stable compounds with hydrofluoric acid. I n this scheme radium by analogy is t o be placed betwean barium and sodium and by taking the mean of the values for these elements the heat of formation of the F. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 173 halogen salts and oxide in solution can be approximately calculated for radium (&Ra) as follow chloride 98.5 ; bt omide 91.0 ; iodide 79.0 ; fluoride 112.0 ; oxide 79.6 Gal. The solubilities at 15' per 100 parts of water calculated in the same way are chloride 35 t o 36; bromide 100; iodide 180 ; fluoride 1 to 2 ; oxide 10 t o 20. The calculated heat of reaction between radium (GRa) and excess of water is 45 Cal.The hydroxide should be more stable than that of barium and less stable than sodium hydroxide. The oxide should be peroxidised easily a t a red heat with development of 19 Cal. and the carbonate should be formed from the oxide with 70 Cal. and should be with difficulty decomposed at a red heat. The heat of formation of the hydride (4Ra) should be 17.7 Cal. and it should decompose a t about 900". It is to be expected that the metal should be formed by the action of calcium or lithium on the fluoride or by calcium or aluminium on the oxide. F. S. The Density of Niton (Radium Emanation) and the Dis- integration Theory. R. WHYTLAW GRAY and Sir WILLIAM RallrsAY (Proc. Roy. SOC 1911 A 84 536-550).-13y means of a modified form of the micro-balance described by Steele arid Grant (Abstr.1909 ii 876) the authors have succeeded in determining the density of niton from experiments with about 0.1 cubic mm. of the gas weighing approximately 1/1400 mg. The balance employed was sensitive to about 2.10-6 mg. and its zero was found to remain constant for days together. As in Steele and Grant's balance a small silica tube containing air was used as counterpoise its capacity being about 20 cubic mm. Instead of weighing by displacement from the zero position a null method was adopted the pressure in the balance being altered until the spot of light reflected from a platinised silica mirror and deflected by movement of the beam was brought back to its initial position.The volume of niton at disposal representing the equilibrium amount yielded by the available radium was known from previous experiments and the proportion of this actually present in the weighing tube was ascertained by measurements of the y-ray activity. I n five independent experiments the values obtained for the density of niton corresponded with molecular weight values of 227 226 225 220 and 218 mean = 223. After the lapse of sufficient time for the decay of the niton and the conversion of its quick-change products A B C into radium-B t h e density tube mas opened and the loss of weight corresponding with the helium produced was determined. After correction this diminution in weight was found to correspond with the loss of three atoms of helium from each atom of niton.Since four atoms of helium are emitted by an atom of radium during its conversion into radium-D and the atomic weight of radium is 226.4 it follows that the true atomic weight of niton is 222.4. H. M. D. The Half Period of Actinium-C. ALOES F. KovAfirrc (Physikul. Zeitsch 191 1 12 83).-The period of decay of actinium-C obtained by recoil methods has been frequently measured. Prom 150 curvesii. 174 ABSTRACTS OF CHEMICAL PAPERS. the mean value of the half-period 4.71 minutes was found no single value being SO great as five minutes. Hahn and Meitner found by several methods the value 5-1 minutes (compare Abstr. 1908 ii 920). F. S. Radioactive Equlibrium in Vesuvian Cotunnite. PAOLO ROSSI ( A t t i R. Accad. Lincei 1910 [v] 19 ii 578-583. Compare Abatr. 1908 ii 9 ; and Zambonini Abstr.1907 ii 663).-From theoretical considerations the author deduces what measurements are necessary for ascertaining whether a given specimen of cotunnite (containing radium-D radium-E and radium-F) has reached radio- active equilibrium. The question may be settled either by examining the radioactivity of the specimen a t intervals of a few month@ or by comparing its activity with that of a sample known t o be in equilibrium. For the latter purpose the author has employed a cotunriite dating from 1872 and has found that the sample of the mineral of 1907 examined by Zambonini (Zoc. cit.) was by no means in equilibrium and contained in fact at that time very little radium-F. It had attained to an equilibrium condition by July 1910.I n this con- nexion interest attaches to the observation of Piutti (Rend. Acad. Xci. Js. mat. NupoZi 1910 [iii] 16 30j who found no helium in t.he mineral and suggested that possibly this disintegration product of radium-P had not had time to accumulate. The Radioactivity of Rocks. ALBERT GOCEEL (Juhr6. Radiouktiv. EZektronik 1910 7 487-527).-The a-radioactivity and in some cases the P-activity also of a great variety of rocks and minerals from all parts of the world has been examined. The radioactivity was found t o vary witbin far wider limits tbanwhen determined by means of the emar ation method. Igneous rocks may he divided into three classes. The first is strongly radioactive and comprises granite porphyry syenite and pegmatite the activity being due t o zircon rutile titanite and rare earths.The second class comprising diabase andesite and gabbro are alniost inactive. The third class com- prising the remainder are of intermediate activity. The activity of the first class varies over a range of 1 to 280 due to variation in the amount of active constituent minerals. Among sedimentary rocks quartz sand rock salt gypsum anhydrite and chalk are inactive the activity of the others averaging only one-tenth of that of the first group of igneous rocks. Many rocks send out P-rays in considerable intensity and of penetrating power varying with t h e nature of the rock. Potassium accounts for this in some cases but in others the rays are much mare penetrating and may be due to mesothorium-2 or t o unrecognised radioactive substances.Radiation from Quinine Sulphate Ionisation and Luminescence. MAURICE DE BROGLIE and L. BRIZARU (Compt. rend. 191 1 152 136-1 38).-The ionisation produced in a gas when quinine or cinchonine sulphate is heated or allowed to cool after heating appears to be connected with the production of small electrical dis- charges due to disruption of the crystals. Thus on heating cinchonide sulphate a t 120° for half an hovr and allowing it to cool in the air R. V. S. F. S.GENERAL AND PHYSICAL CHEMISTRY. ii. 175 brilliant scintillations are visible under a lens recalling those seen in a spinthariscope. The scintillations increase under diminished pressure. The luminous and electrical phenomena are more marked in hydrogen than in air. w. 0. w. The Isolation of an Ion a n d the Exact Measurement of its Charge; Correction to the Law of Stokes.R. A. MILLIKAN (Le Radium 1910 '7 345-350).-8 cloud of droplets of oil mercury or other non-volatile liquid is' produced by spraying in dust-free air above a condenser with horizontal plates. A few droplets are allowed t o fall through a small hole in the upper plate which is then closed and one droplet illuminated by a horizontal beam from an arc lamp passed through a long column of water is kept under observation in a cathetometer. By alternately applying a suitable electric field t o the plates of the condensor and discharging them the same drop may be watched for many hours at a time falling under gravity and ascending against it under the field in the same vertical line.I n absence of the field during the fall of the drop the air is always ionised to a certain extent naturally and this ionisation may be increased at will by the presence of radioactive preparations. The speed of fall is throughout independent of the charge on the drop if precautions are taken against air currents but as during the fall one or more ions of either sign may join themselves to the drop altering by definite increments the value of its charge the speed of ascent which is a simple function of the charge on the drop varies step-wise in successive measurements. I n one case the speed of fall and ascent were observed for a single negatively-charged drop for four and a quarter hours during which the number of atomic charges on the drop varied from 4 to 17.The value of the charge can be altered at will by holding the drop with a suitable field near to either plate with the air uniformly ionised by radium. Near the plate the concentration of the ion of opposite sign to the plate is the greater so that to increase the charge on a positively charged drop it is kept near the negative plate when more positive than negative ions attach them- selves t o it. The spontaneous alteration of the charge during descent must be due to the kinetic energy of the ion assisted or opposed by the electrostatic attraction or repulsion according to the sign project- ing the ion against the drop. Since the spontaneous accretion of negative ions by a drop already charged negatively with 126 to 150 but never more units has been observed it follows that the kinetic energy of the ion must be greater than 4.6 to 5.47 ( x 10-14 ergs).This agrees with the accepted value (5.756 x 10-14 ergs) for the kinetic energy of a molecule at ordinary temperatures as deduced from the kinetic theory and furnishes a direct experimental proof of the existence of this kinetic energy. The results of forty-seven days consecutive observations comprising 33 drops ranging in radius from 313 to 6581 ( x lop7 cm.) as determined from the velocity of fall under gravity gives a mean value for e the atomic charge 4.9016 x .E.8.U. with a probable error of 1 in 1000 although the value involves that of the coefficient of viscosity of the air taken a8 0.0001785 at 15" which may be wrong to 5 in 1000. By assumingii. 176 ABSTRACTS OF CHEMICAL PAPERS.always a multiple of this charge and measuring the departures from i t for drops comparable in diameter with the mean free path of the molecule it is deduced that Stokes’ Law gives velocities of fall for such drops which must be multiplied by 1 + AZ/a where I is the mean free path of the molecule a the radius of the drop and A a constant found equal t o 0.815. This is in agreement with the theory of The Ions and Neutral Particles Present in Certain Gases when Recently Prepared. L ~ O N BLOCH (Le Radium 1910 7 354-368).-lt is probable t h a t ions produced by spraying bubbling and splashing are produced in the same way as those produced in chemical reactions. A liquid surface disengaging very fine bubbles of hydrogen by chemical action was made one plate of a condenser and it was found that the current was nearly proportional to the voltage no indication of saturation being obtained with fields exceeding 1100 volts.This is shown to be due to the projection from the surface of neutral particles which when a field is applied become charged electro- statically carrying away part of the surface charge. Tbe larger part of the ionisation due to chemical reactions is due to these “neutral particles,’’ which become charged electrostatically and which are to be sharply distinguished from true ions because their charges and mobilities are functions of the electric field where they origi~iate. They are to be distinguished from dust particles? etc. which attract ‘6 small ions” forming ‘(large ions,” for they do not form large ions” in this way.They are formed in liquids which give ions by bubbling whilst the ‘‘ neutral centres,” similar to those investigated by others which are produced by bubbling are only formed in liquids which do not give ions. They are too small to be visible in the ultramicroscope and may be present in large numbers in a gas optically void. Determination of their diffusion coefficients and mobility gave 2.5 units for the mean value of their charge but the particles are too small to obey Stokes’ Law and probably have a radius of the order of 10-7 cm. Their production is prevented by a layer of benzene petroleum and various oils also by alcohols and ethyl ether but acetone and aldehyde do not stop their formation. I n t h e first case the action cannot be explained by supposing that the surface liquid stops the formation of spray. Since a liquid does not lose its charge by evaporation there must exist somewhere between the dimensions of these new “ neutral particles ” and that of the molecule a critical diameter at which the particle loses its power of becoming electrified by contact.F. S. A Relationship between the Temperature-coefficient and the Specific Resistance of Certain Metals with Special Reference t o Copper. STEPHAN LINDESK (Ber. Deut. physikal. %es. 1911 13 65-71).-From a comparison of the data for a large number of bamples of copper it is found that the product of the specific resistance ( c ) and the temperature-coefficient (u) a t a given temperature is very nearly constant. At 15’ the mean value of the product is 6-78 x lo_”_ and the relationship holds good for samples of copper the specific resistances of which vary as much as 3 1.F o r Cunningham based on kinetic considerations. F. s.GENERAL AND PHYSICAL CHEMISTRY. ii. 177 copper containing a considerable proportion of arsenic the conductivity of which is only one-eleventh of that of pure copper the product cu has nearly the same value as that for the pure metal. Similar relationships have been found in the case of samples of commercial aluminium and iron. For aluminium the value of c150a150 is 11-6 x 10-5 and for iron 58.5 x 10-5. The relationship appears therefore t o be of a general nature. Experiments with Metallic Conductors of Very High Resistance and the Application of the Electron Theory.HILDA VON MARTIN (Pl~ysikal. Zeitsch. I91 1 12 41 -48).-The conduction of electricity through columbite and stibnite both of which have a specific resistance of the order of l o 7 ohms takes place accord- ing to Ohm’s law. From observations on the variation of the resistance with the temperature the heat of dissociation is calculated to be about 4400 for columbite and about 10,000 €or stibnite. Accordiug to this the latter occupies a position between those substances for which the conduction is electronic in character and those for which the conduction is due to ions. Various anom-tlous phenomena have been observed in the further investigation of the conducting properties of stibnite. On prolonged prssage of a curreiit through the substance in one direction the conductivity increases but this increase is accompznied by a diminu- tion of the conductivity when the current is passed in the opposite direction.The original direction of the flow of the current is without influence on this phenomena. After the lapse of a considerable time during which no current is passed through the stibnite i t returns to its original condition. This unipolar effect which is quantitatively reproducible cannot be attributed to polarisation. A further primary unipolar effect is also observable which cannot be reproduced in a quantitative mauuer and this is supposed to be due t o lack of homogeneity in the crystal under examination. H. 35. D. H. Bf. D. Regularities in the Changes of the Electrical Conductivity of Metals on Liquefaction.ERNSF WAGNER (Ann. Physik 1910 [iv] 33 1481-1492).-A comparison of the electric conductivities of solid and liquid metals a t the melting point shows that in many cases the conductivities are related to one another in a simple manner. For mercury the ratio of the conductivity of the solid t o that of the liquid is approximstely 4; for lead zinc tin cadmium thallium and tellurium 2; for sodium potassium rubidium and casium 1.5 and for bismuth and gallium 0.5. If the number of free electrons in unit volume is the same for the two states of aggregation the changes in the conductivity must be attributed to simply related changes in the mobilities of the electrons. The possibility that these changes are connected w i t h variation8 in the molecular complexity in the solid and liquid states is discussed. H.M. D. The Thomson Effect and its Variation with Temperature in Lead Mercury Tin Zinc Cadmium and Aluminium. PAUL CERMAK (Ann. YhysiL 1910 [iv] 33 1195-1215).-Mea~urementsii. 178 ABSTRACTS OF CHEMICAL PAPERS. of the Thomson effect in the above six metals have been made a t various temperatures reaching up to 350’. In general the magnitude of the effect increases as the temperature rises but this increase is not consistent with the assumption that the Thomson effect is propor- tional to the absolute temperature. At the melting point the curves which show the relationship between the Thomson effect and the temperature are apparently quite continuous in spite of the very considerable change in the conductivity. H. M.D. The Dielectric Constants of the Halogen Compounds of Lead. AUGUST LENERT (Ber. Deut. physikal. Ges. 1910 12 1051-1053).-The fact that the pure halogen compounds of lead have a very small electric conductivity has led the author t o measure their dielectric constants. The substances were examined in the form of powder or compressed plates by Nernst’s method and gave the following values lead chloride 4.20 ; bromide 4.89 ; iodide 2.35 and fluoride 3.62. A determination of the dielectric constant of the chloride by Drude’s method comfirmed these results. After the substances bad been melted and solidified much higher values were obtained and this is attributed to the loss of halogen and the formation of sub-halides. H. M. D. The Cathode Fall in Argon (Air Nitrogen Hydrogen) and the Periodic System of the Elements.KARL ROTTGARDT (Ann. Physik 1910 [iv] 33 1161-1194).-0bservations have been made relating to the distribution of potential in discharge tubes containing different gases and cathodes of different metals. A considerable difference of potential exists between the two ends of the negative glow region. This varies from 26 to 60 volts in argon from 26 to 56 volts in air from 26 to 49 volts in nitrogen and from 30 to 60 volts in hydrogen. By using different metals as cathodes i t is found that the potential fall in the glow light increases as the cathode fall increases. Although the fall of potential in the glow light is practically constant when the cathode fall is normal it appears to increase slightly with increasing current density and with diminution in the pressure.The normal cathode fall is defined as the minimum value of the potential difference between the earthed cathode and that part of the negative glow region which is in immediate contact with the cabhode dark space. For variations in pressure current strength and dimensions of the discharge tube the normal cathode fall defined in this may appears t o be constant within 5% when the tube contains argon and within 3% for the other gases investigated. I n argon the normal cathode fall has the same value for series of metals which have the same valency and diminishes as the valency increases. For copper silver and gold it is 131 volts; for magnesium zinc and cadmium 119 volts and for aluminium 100 volts. Tin and lead gave 123.5 and approximate therefore to the bivalent metals while antimony and bismuth gave 135.5.Similar relationships are found between the cathode falls in nitrogen. I n hydrogen the normal cathode potential increases in most cases with the passage of theGENERAL AND PHYSICAL CHEMISTRY. ii. 179 discharge and this is attributed to the conversion of the metal into a hydride. When small quantities of foreign gases are admixed with argon the normal cathode fall is altered to a considerable extent hydrogen having the smallest oxygen and water the greatest effect. With a zinc cathode the change brought about by 2% of moist oxygen is equal to that effected by 10% of nitrogen or 35% of hydrogen. H. M. D. Value of the Components of the Eleotromotive Force of the Voltaic Couple.GIOVANNI GUCJLIELMO (Atti R. Accad. L i n c e i 1910 [v] 19 ii 572--577).-If Y be the electromotive force of the couple V and V" the difference of potential between the metals and the electrolyte respectively C' and C" the respective heats of com- bustion (in Joules) of 1 gram-equivalent of the metals with the electronegative constituent of the solution and e the quantity of electricity which produces this amount of chemical action (for 1 gram- equivalent e will be 96540 coulombs) then Y= v' - V" = (C" - C")/e whence T"= C/o + K and v"= C"/e + R. If K be negligibly small V'= C'/e and V" = C / e . The value of K can be calculated however (1) by using Helmholtz's formula V'= C'/e + dV'/TdT from which i t follows that K=dV'/TdT=dV"/TdT; the value of K calculated by this means from the experimental results of previous workers is 0.22 volt ; (2) by applying the fact that of the total heat of combination C' of one of the metals only a fraction c' appears locally the rest mltni- festiag itself in the whole circuit hence V'= ((7'- c')/e and V" = (C" - c")/e and therefore K = c'/e = c"/e ; the value of R obtained by this method is also about 0.2 volt Mercurous Sulphate as Depolariser in Weston and Clark Normal Cells. P..J. H. VAN GINNEKEN (Zeitsch. physikul. Chem. 191 1 '75 687-709).-8 theoretical paper. Hulett (Abstr. 1904 ii 695) observed that the E.N.3'. of a cadmium element rose on sbaking t o a value higher than the normal but slowly recoveied the former value when kept. He gave an explanation of this based on the slow hydrolysis of mercurous sulphate and the consequent increase of the " mercury concentration " in the solution.It was further assumed that the hydrolysis is accelerated by the catalytic action of the mercury surface. It is not clear exactly what Hulett means by " mercury concentration " i n this case. The author accepts Hulett'a assumptions in the main but shows as the result of a detailtcl consideration of the equilibria in the system that the mercury ion concentration would be diminished and not increased by hydrolysis. The author's explanation of the observations is as follows. On remaining quiescent hydrolysis takes place fairly rapidly in the layer in contact with the mercury surface owing to the catalytic action of the latter but is very slow in the main bulk of material.The result is that the mercury ion concentration in the surface layer diminishes and the E.M.F. falls but on shaking the mercury concentration in the surface layer becomes practically the same as that in the main bulk of material and the E.M.3'. rises. I n normal circumstances therefore the E.M.3'. is depressed owing to hydrolysis. R. V. S. G. S.ii. 180 ABSTRACTS OF CHEMICAL PAPERS. Thermodynamics of Normal Cells. ERNST COHEN (Chem. FVeekblad 1911 8 1-4. Compare Abstr. 1910 ii 176).-The values obtained by the thermochernical method for the chemical energy of the normal cells of Clark and of Weston differ from those deiived from Gibbs and von Helmholtz's equation by the aid of electro-measurements. The author attributes the discrepancies t o errors in the temperature formulae employed.For neither cell can the relation of E.dfJ'. to temperdture be represented by a continuous curve. A. J. W. Determination of Specific Heats at Low Temperatures and Their Use in the Calculation of Electromotive Forces. F. POLL~TZER (Zeitsch. Elektroclwn. 19 11 17 5-1 4).-The method of measuring the rise of temperature produced by the additicn electrically of a known quantity of heat described by Nernst (Abstr. 1910 ii 263) is employed. The ppecific heats of zinc mercury heptahydrated zinc sulphate and of mercurous sulphate and chloride are determined a t temperatures between - 200' and -30". The results are calculated by means of t h e formula given by Magnus and Lindemann (Abstr. 1910 ii 580) the values of the constants being n.Bv. a. Hg (solid) ............... 1 80 21.0 x c1 236 - ........................ 1 Zn ........................ 1 173 5 4 x 10-5. The specific heat of mercurous chloride is cnlculated by adding the expressions for one atom of mercury and one of chlorine the value of a for the compound being 12 x With the more complicated substances zinc sulphate and mercurous sulphate empirical expressions were used instead of attempting to introduce a special value for the frequency of each kind of atom. The heat of fusion of mercury is found to be 554.5 csls. per gram- atom a t the melting point - 35.7". Using these data the followir?g &.M.F.'s are calculated by means of Nernst's theorem Zn I ZnSO,,fH,O I Hn2S0 I Hg ( - f " ) 1.4610 volt (calculated) 1.4556 volt (oh.).H g I HgCl I PbCI I Pb ( - 39") 0'4636 volt (calculated) 0-5216 volt (obs.). Hg I HgCl I AgCl 1 Ag ( - 39") 0'0341 volt (calculated) - 0.0270 volt (oh.). The differences between t h e observed and calculated values in the last two cases are possibly due to errors in the values of the heats of formation of the compounds. Calculation of Electromotive Force from Thermal Effects. ERNST COHEN (Chem. TYeekbZud 1911 8 51-52 ; Zeitsch. &Zektro- chew,. 191 1 17 143-145. Compare Pollitzer preceding abstract).- The great discrepancies between the values deduced by the aid of Nernst's theorem for the E.M.P. of galvanic combinations and those obtained by experiment are attributed by Pollitzer to errors in the thermochemical determinations involved.The author points out t h a t for a cell Eg-HgCl-PbCl,-Yb the difference is due to the use of an electrode of lead amalgam instead of pure lead. T. E. A. J. W.GENERAL AND PHYSICAL CHEMISTRY. ii. 181 Mathematical Theory of the Changes of Concentration at the Electrode brought about by Diffusion and by Chemical Reaction. T. R. ROSEBRUGH and W. LASE MILLER (J. PhysicaE. Chern. 1910 14 816-883).-A mathematical paper in which the changes in concentration a t the electrodes which take place as the result of electrolysis under different conditions have been deduced from a consideration of the effects of ionic migration and diffusion. H. M. D. The Behaviour of Copper Anodes in Uhloride Soh- tions. SAUL DUSHMAN (J. Physical Chem. 1910 14 885-908).- The behaviour of copper anodes in the electrolysis of solutions of hydrochloric acid in the absence of air has been investigated.I n an extensive series of experiments in which the concentration of the hydrochloric acid was varied from 0.00465 to 0.01615 mol. per litre the current from 0.013 to 0.051 ampere the anode area from 18 to 47 square cm. and the rate of circulation of the electrolyte from 0.242 to 2.361 C.C. per second it was found that the proportion of the copper which passed into solution as cuproion varied from 25 to 74%. By taking into account the change resulting from diffusion values have been obtained for the constant K = [Cu"]/'[Cu*]2 corresponding with the equilibrium Cu" + Cu '-f 2Cu'. The numbers so obtained vary from 0.5 to 3-5 x 10-4 whereas the value obtained by Bodlander and Storbeck from experiments in which finely divided copper and cuprous chloride were shaken with solutions of potassium chloride was The proportion of copper dissolved as cuprous salt at a rotatory anode in hydrochloric acid with different concentrations of acid current densities rates of rotation of the anode and rates of circula- tion of the electrolyte is found to be in accord with the assumption of the above equilibrium condition. 1.5 x 10-4.H. M. D. Velocity of Anodic Solution of Niokel in Normal Sulphuric Acid. C. Russo (Gaxzettcc 1910 40 ii 491-508).-The rate a t which nickel functioning as anode passes into solution in normal sulphuric acid is proportional to the strength of the current when this is not great. After a certain critical strength of current has been reached (usually about 0.1 ampere) the electrode is passive and the rate of solution decreases being a linear function of the current strength.A minimum is plainly observable when the current is 0.4 ampere and thereafter the velocity of solution increases again forming a linear function of the strength of the current. R. V. X. Gomparison between the Velocity of Solution and the Anodic Polarisation of Nickel in Normal Sulphuric Acid. C. Russo (Gaxzetta 1910 40 ii 508-518. Compare preceding abstract).-The results obtained by the author support the theory of Muthmann and Prauenberger thst the passivity of nickel is due to the formation of a solid solution of oxygen at the surface of the anode. In following the variation of anodic polarisation with increasing current no sudden change is observed which could correspond with VOL.C. ii. 13ii. 182 ABSTRACTS OF CHEMICAL PAPERS. the singular point (at 0.4 ampere) in the curve of velocity of anodic solution so that the existence of the latter must be due t o some cause which does not sensibly affect the polarisation. It is suggested that it may be connected with the discharge of the ion HSO,’. When a certain degree of polarisation has been exceeded the nickel anode no longer remains practically unattacked by the solution; in spite of the gaseous envelope of oxygen which surrounds it it is in a semi-active condition and this forms another argument in favour of the hypothesis that the passivity OF the metal is due to dissolved not to enveloping oxygen. R.V. S. Planck’s Formula for Diffusion Potentials. NIELS BJERRUM (Zeitsch. EZektyochem. 19 11 17 58-6 l).-Planck’s formula for the difference of potential between two solutions of electrolytes is obtained on the assumption that two solutions of constant concentration are separated by a layer the composition of which is also not changed by the diffusion going on through it. This condition is not fulfilled in general. The real state of affairs is better represented by a formula obtained by Henderson from Nernst’s theory (Abstr. 1907 ii 426 ; 1908 ii 655) in deducing which i t is supposed that the two solutions are separated by a fairly thick layer in which they have simply mixed together. It is shown that when such a layer is formed the potential difference changes with the time the change being inversely pro- portional to the thickness of layer. For 0.1 iV-potassium chloride and O*OlN-hydrochloric acid and a layer of separation 1 cm.thick the change is about 0.2 millivolt in a quarter of an hour ; usually i t is much smaller and s_uite negligible Electrometric Measurements [of Acidity] in Liquids con- taining Carbon Dioxide. K. A. HASSELBALCH (Biochem. Zeitech. 1910 30 317-331).-The measurements were made with the hydrogen electrode by a slight modification of the usual method. Hydrogen was passed for half an hour through the electrode vessel containing the electrode only until the latter was thoroughly saturated. The solution to be examined saturated with air or oxygen was then drawn in until its upper surface just touched the bottom of the electrode the electrode vessel was then shaken to establish equilibrium between the liquid and the gas space and the potential measurements made in the usual way.This method gives satisfactory results for solutions saturated with air or oxygen (the latter gas produces no depolarising effects on the electrode) but is not satisfactory for solutions contain- ing carbon dioxide as the latter escapes into the gas space and the measured H’ ion concentration is too low. This difficulty has been overcome by shaking one portion of the solution until equilibrium is established with the gas space; this portion is then replaced by a second portion and as the gas space already contains carbon dioxide none of the gas escapes from the liquid. A series of measurements with blood shows that the pret-ious methods of measurements (compare Michaelis and Rona Abstr.1909 ii 680) give rather too low values for the H’ ion concentration as would be anticipated from the source of error above referred to T. E. G. S.GENERAL AND PHYSICAL CHENISTRI'. ii. 183 Rationality of the Ratios of t h e Magnetic Moments of Atoms and a New Universal Constituent of Matter. PIERRE WEISS (Compt. rend. 1911,152 187-189. Compare this vol. ii 91).- Values have been calculated for the magnetic susceptibility at absdute specific saturation of a number of metals in the form of aqueous solutions of their salts. To explain the results which together with those of Pascal and others are shown in graphic form the author is led to assume the existence in all forms of matter of magneton a substance having a definite determinable magnetic moment.w. 0. w. New Method for Investigation of t h e Magnetic Permeability of Gases. W. P. Roop (Physikctl. Zeitsch. 1911 12 48-56).-8 method of determining the difference between the magnetic perme- abilities of two gases is described which depends on the deflevion of a jet of the one gas streaming tbrough the other under the influence of a magnetic field in which the lines of force are very unevenly distributed From experiments with carbon dioxide and air for the former of which the magnetic susceptibility is probably nil the susceptibility of air has been found to 0.0260 x The Magnetism of the Copper-Manganese-Tin Alloys under Varying Thermal Treatment. ALEXANDER D.Ross and ROBERT C. GRAY (Proc. Roy. Xoc. Edin. 1910 31 85-99. Compare Abstr. 1909 ii S59).-A series of ternary alloys has been prepared in which copper and manganese are presenb throughout in the ratio 7 3 whilst the alloys contain respectively 14 16 18 30 38 and 48% of tin. The alloys cast in the form of rods were tested magnetically as cast and also after normalising by heating and cooling fairly rapidly. Other specimens were tested after baking for several hours at 180' or 200° and after annealing a t higher temperatures. Baking diminishes the susceptibility and increases the coercive force and hysteresis. The three alloys containing the amallest quantity of t i n are much more magnetic at - 190' than at the ordinary temperature. Quenching from 350' or 580" produces complex changes the coercive force being always diminished and the effect cannot be reversed by again annealing. The quenched alloys are more improved in magnetic properties by cooling t o - 190" than those in the normal condition.C. H. D. The Magnetisation of Ferro-magnetic Substances above the Curie Point. PIERRE WErss and U. Fofx (Arch. Sci. Phys. Nat. 191 1 Liv] 31 5-19).-1n connexion with a n investigation of the variation of magnetisability with the temperature preliminary measurements of the coefficient of magnetisation of anhydrous cobnl t sulphate and the heptahydratod salt and of solutions of cobalt and nickel nitrate have been made with a specially designed form of apparatus. H. M. D. Use of the Magnetic Field ae a means of Determining Constitution in Organic Chemistry.VI. PAUL PASCAL (Bull. Xoc. chim. 1911 [iv] 9 79-84. Compare Abstr. 1910 ii 100 179 680 ; this vol. ii 91).-The method of calculating magnetic suscepti- H. M. D. 13-2ii. 184 ABSTRACTS OF CHEMICAL PAPERS. bilities of carbon compounds has been described previously and i t has been shown that although this property is additive a correction B must be made the value of which varies with the structure of the group of compounds under consideration The present communication deals with cycloid substances and it is shown that ring-formation invariably exalts the magnetic suscepti- bility. For purposes of calculation in these cases a definite value is assigned to each carbon atom apart from its intrinsic value as a carbon atom according as it occurs in one ring only (mononuclear carbon as in benzene) two rings (binuclear carbon as in naphthalene) or three rings (trinuclear carbon as in chrysene).The value.; of B for carbon atoms so linked are - 2.5 x lW7 - 32.0 x and - 42.0 x 10-7 respectively. The magnetic susceptibility of indene C,H calculated according to these rules and those already given (Zoc. cit.) is ( - 9 x 62.5 + - 8 x 30.8 + - 2 x 32.0 + - 6 x 2.5)10-7= - 885.5 x 10-7 which compares well with the experimental value - 883 x 10-7. The magnetic susceptibilities found experimentally are best explained by the Claus formulae for cycloid substances but they are not entirely in harmony with any formulz yet put forward. A long list of calculated and experimental values for compounds of various types is given showing as a rule good agreement between the two values.T. A. H. Electrical Double Refrrtdion (Kerr Effect) in Liquids and its Relation to Chemical Composition and Constitution. ALEXANDER LIPPMANN (Zeitsch. Elektrochem. 191 1 17 15-20).- The values of the electro-optical constants of some eighty-eight sub- stances dissolved in benzene are determined. It appears that this constant is influenced enormously by the constitution of the substances depending for example in the case of benzene derivatives on the nnmber nature and relative positions of the substituting groups. T. E. Experiments Relating to the ‘( Swarm” Theory of Aniso- tropic Liquids. EMIL BOSE (Physikal. Ztzitsch. 1911 12 60-62 Compare Abstr. 1909 ii 383).-Observations relating to the behaviour of anisotropic liquids in a magnetic field are described as evidence in support of the theory which the author has put forward previously. In a magnetic field the lines of force in which are parallel to the line of sight a clearing of the turbid liquid has been observed in the case of anisaldazine p-azoxyanisole T-azoxyanisolephenetole and a mixture of anisylidenepropionic acid wlth anisic acid.With cholesteryl benzoate which is much more viscous than the other substances examined no effect was obtained even when a strong magnetic field was employed. With a weak field the clearing takes an appreciable time but the clearing period diminishes rapidly with increase in the strength of the field. When the lines of force of the applied field were a t right angles t o t,he line of sight no clearing eflect was observed in any of the bu bs; ta IJ C8S exik UJ i 11 ed.H. M. D.GEEERAL AND PHYSICAL CHEMISTRY. ii. 185 Density Coefflcient of Expansion and V a r i a t i o n in Volume on Fusion of the Alkali Metals. LOUIS HACKSPILL (Cornpt. rend. 1911 152 259-262).-A description is given of the methods whereby the following results have been obtained Column A contains the coefficients of expansion of the solid metals B the same constants for the liquid metals a t temperature t and C the percentage increase in volume on fusion. D". D96.5. A . B. t. C. CS ............... 1'9029 - 0'000291 0*000341 23- 50" 2.32 Rb ............... 1.5248 - 0*00027 0 000339 40-140" 2.28 0'000348 50-123" - K ............... 0.859 {~~~)?$,} 0*000280 70-100" 2-42 0 000286 100-150" Na ..............0.9725 0.9385 { ~ ~ ~ ) ~ $ ) 0*000275 100-180" 1-50 Toluene and benzene are rapidly attacked by liquid cssium. The compouods formed are under investigation. w. 0. w. Anomalous Expansion of Nickel Steels. CHARLES EDOUARD GUILLAUME (Comgt. rend. 1911 152 189-191).-The coefficients of expansion of reversible alloys of iron and nickel have been determined and the results plotted in the form of a curve showing the variation of the coefficient as a function of the proportion of nickel. Owing to the small cohesion of the pure alloys specimens containing a small proportion of manganese (or chromium) silicon and carbon were employed. The curve shows a well-marked minimum corresponding with about 36% of nickel; as the percentage of the latter rises it gradually approaches and finally coincides with the line representing the expansion as calculated from the law of mixtures.The effect of the manganese and chromium i n the alloys has also been studied. The influence of theso metals on the expansion is some- what complex ; in general the addition of small amounts of manganese dimiriihhes the expansion in the neighbourhood of the minimum of the curve. w. 0. w. The Variation of the Thermal Conductivity of Solid Non- Metals with the Temperature. ARNOLD EUCKEN (Ann. Phpsik 19 11 [i~] 34 185-221).-Two forms of apparatus are described which have been used in the investigat,ion of the thermal conductivity of crystalline and amorphous substances. From experiments with crystals of sodium chloride potassium chloride fluorspar calcspar sodium chlorate and sucrose between - 190" and + looo it is found t h a t the thermal resistance increases in approximately the same ratio as the absolute temperature.This holds with greater exactness for quartz i n a direction perpendicular t o the axis than for any of the other substances examined. The magnitude of the thermal conduc- tivity does not depend on the system to which a particular crystal belongs. I n general it is found to increase with a diminution in t h e number of atoms in the molecule of the substance and with increase i n the melting point. Crystals containing two and three atoms in theii. 186 ABSTRACTS OF CHEMICAL PAPERS molecule have approximately the same thermal conductivity at their respective melting points. For substances in the form oE crydtalline aggregates the above relationship between thermal conductivity and temperature does not hold.This is attributed to the existence of thermal resistance between the individual small crystals and this effect becomes relatively more important as the conductivity of the substance increases. According to experiments with various kinds of glass the behnviour of amorphous substances is quite different from that of crystals for the thermal resistance of these diminishes a9 the temperature rises. A comparison of the conductivity of the same substance in the crystalline and amorphous form shows that the crystalline form always conducts better than the amorphouc. A t 0' crystalline quartz conducts 7.5 timee and at - 190' fifty-five times as well as fused quartz.A t the melting point the conductivities are probably equal. H. M. D. Connexion between the Elastic Properties and the Speciflc Heat of Solid Substances Gonsisting of Monatomic Mole- cules. ALBERT EINSTEIN (Ann. Physik. 1911 [iv] 34 170-176). -Reference is made to the calculation by Sutherland (Abstr. 1910 ii 946) of the wave-lengths which correspond with the fundamental mechanical vibrations of the atoms of the alkali metals and the halogens and it is pointed out that the frequencies corresponding with the molecular vibrations of monatomic substances can be calculated from the variation of the specific heat of these substances with the temperature. The wave-lengths which have been deduced from the elastic properties for ten different metals vary from A = 45 x for aluminium and nickel to A = 163 x 10-4 for bismuth.The value for silver is X = 73 x 10-4 whereas that calculated from the variation of the specific heat with the temperature is X = 90 x 10-4. For the other metals the specific heat a t low temperatures is not known accurately enough to permit of a comparison but the agreement in the case of silver affords strong evidence of the correctness of Sutherland's views relating to the nature of the ultra-red rays. H. M. D. Specific Heat of Carbon Tetrachloride and of its Saturated Vapour. JAMES E. MILLS and DUNCAN MACRAE (J. Physical Chem. 1911 15 54-66. Compare Abstr. 1910 ii 932).-The method previously described for benzene has bsen used to determine tbe specific heat of carbon tetrachloride with a maximum error of & 0.001.The purified tetrachloride of b. p. 76.64' to 76.69O a t 760 mm. has a specific heat which increases regularly from 0.2010 a t 0' to 0.2031 a t 70". This value is somewhat lower than that obtained by Hirn and by Winkelmann at the same temperatures. The specific heat of the saturated vapour is calculated from the sp. heat of the liquid and the latent heat. The values obtained are some- what lower if the latent heat is calculated by the thermodynamical equation than if by the equation given by Mills (Abstr. 1909 ii 861). The specific heat of the vapour falls from 0.140 at Oo to 0.115 at 70°GENERAL AND PHYSICAL CHEMISTRY. ii. 187 according to the latter method of calculation which is preferred by the authors.When the quantities of heat employed in doing external work in increasing the kinetic energy of the molecuies and in overcoming molecular attraction are subtracted from the specific heat there remains about 0.3 cal. in the case of benzene liquid or vapour and of 0 16 cal. in the case of carbon tetrachloride unaccounted For. Nearly as much energy is required to raise carbon and hydrogen combined as benzene from -273' to +20° as when they exist separately. R. J. C. The Specific Heat of Liquid Benzene and of its Saturated Vapour. JAMES E. MILLS and DUNCAN MACRAE (J. P?gsicaZ Chem. 19 10 14 797-815).-Measurernents have been made of the specific heat of liquid benzene a t temperatures ranging from the freezing point to 70° a Dewar vessel being employed as calorimeter and the heat supplied by an electrical current. The specific heat varies with the temperature in a linear manner the straight line representing the data giving the values 0.3970 and 0.4369 at 0' and 70" respectively.From the heats of vaporisation of benzene a t different temperatures the authors have also calculated the specific heat of the saturated vapour. It is shown that the heats of vaporisation obtained in different ways are not in satisfactory agreement and as a consequence the calculated specific heat values differ considerably according t o the vaporisation data which are utilised. The values adopted tentatively lie on a straight line corresponding with the specific heats 0,284 and 0.268 a t 0" and 70" respectively. H. M. D. The Latent Heat of Fusion of Antimony Trichloride and Tribromide Arsenic Trichloride and Stannic Bromide in Relation to the Molecular Depression of their Freezing Points.STANISLAW TO~;LOCZKO and M. MEYER (Chem. Zentr. 1910 ii 1024-1025 ; from Kosmos 1910,35; Radziszewski-Pestband 641-648). -The latent heats of fusion of antimony trichloride and tribromide arsenic trichloride and stannic bromide were determined from the measurement of the heats of solution of the substances in solid and liquid (supercooled) states in 20.5% hydrochloric acid solution and 25% hydrobromic acid solution and the results are given. The moiecular depression of the freezing points calculated from these latent heats of fusion agree with those obtained by cryoscopic methods At the same time it is shown that the latent heat of fusion given by Berthelot (T?hei*mochirnie 1897 2 156) for stannic bromide 7.07 cal was much too high.The specific heat of a 25% dilute hydrobromic acid solution is 0.715 cal. M. c. Use of a Dewar Flask in Measurements of Heats of Neutralisation. J. HOWARD MATHEWS and A. F. 0. GERMANN (J. Physical Chem. 1911 15 73-82).-By the use of a silvered Dewar flask as calorimeter in measurements of heats of neutralisation the radiation correction is much reduced and the error due to thermometric lag is minimised. The acid is placed in the Dewar flask and is stirredii. 188 ABSTRACTS OF CHEMICAL PAPERS. by an inner reciprocating tube containing the equivalent of alkali which in turn contains a rotating stirrer. The liquids are broughb into contact by tearing with the rotating stirrer the rubber disc which forms the bottom of the inner vessel.Only one thermometer is required. Parallel determinations of the heats of neutralisation of sodium hydroxide by hydrochloric nitric sulphuric and acetic acids in 2N N N/2 and iV/4 strengths were in very close agreement in every case and show that the method is susceptible of great accuracy. Stress is not laid on the actual values obtained in this investigation since the thermometer was not specially standardised. R. J. C. Thermochemical Analysis of Tautomeric Compounds. WOXIECH SVENTOSLAVSKY (Chern. Zentr. 19 10 ii 1022 ; from Kosmos 1 9 10 35 Radzisxewski-Feestband 469-477).-The analysis of the thermochemical data of organic compounds led the author to study the thermochemical characteristics of some atomic linkings.These characteristics make it possible to state the energy contents of tautomeric forms of the same compound The author explains the results for some examples of well known tautomeric compounds and shows that the mutual interconversion of tautomericforms of ethylaceto- acetate isatin and benzoquinoneoxime takes place either without any heat change or is accompanied by very slight thermal disturbance. I n the two tautomeric forms of methylisatin the energy content is decidedly different ; the mutual interconversion of the two forms would be accompanied by considerable heat effeot and therefore it does The Influence of Temperature on the Compressibility of Metals. EDUARD GRUNEISEN (Ann. Physik 1910 [iv] 33 1239-1 274).-An apparatus is described by means of which measurements of the compressibility of metals at different tem- peratures have been made Iron copper silver and platinum were investigated between - 190Oand + 1 6 5 O aluminium between - 1 90° and + 1 2 5 O and tin and lead between - 190' and + 16'.These data shorn that in some cases the compressibility increases with the temperature according to a linear equation whilst in others the increase is more rapid. At low temperatures the magnitude of the temperature- coefficient of the compressibility increases as the coefficient of thermal expansion increases. H. M. D. Thermal Molecular Pressure of Gases in Tubes MARTIN KNUDSEN (Ann. Physik 1910 [iv] 33 1435-1448).-A method of measuring small differences of pressure is described.This has been employed to determine the molecular pressures of hydrogen and oxygen contained in a tube different parts of which are a t different tem- peratures. If p and p denote the molecular pressures observed a t points tbe absolute temperatures of which are Tl and T2 these are found dines 2 to be connected by the equation p12 -p,2 = C( T12 - T 2 2 ) / 2 7 3 ( s ) where C is a constant which depends on the diameter of the tube on the viscosity of t h e gas and on its density. not take place. * N. c. 8. M. I>,GENERAL AXD PHYSICAL CHEMISTRY. ii. 189 Application of the Prinoiple of Archimedes to the Exact Determination of t h e Densitiels of Gases. ADRIEN JAQUEROD and M. TOURPATAN ( A ~ c h . Sci. Phys Nat. 1911 [iv] 31 20-35).- A method of measuring gas densities is described which depends on changes in the weight of a closed cylindrical glass tube when suspended in the different gases.This cylinder is suspended by a thin platinum wire from one arm of a balance and is surrounded by a wider tube immersed in a thermostat. The wider tube is provided a t its lower end with an inlet through which the gas to be examined is introduced. At its upper end the containing tube is drawn out to a capillary sufficiently wide to permit of the free movement of the platinum wire suspension. For experiments with chemically active gases an attachment is pro- vided above the hydrometer tube by means of which the gases can be removed from the neighbourhood of the balance. With this apparatus the density of oxygen at 0' and 760 mm.was found to be 0.0014890 and the coefficient of expansion between loo and 37" 0.003674 a t 730 mrn. pressure. I n the case of hydrogen the rapid diffusion of gas through the capillary was found to introduce an error into the density measure- ments This can be eliminated by making weighings when hydrogen is passing through the containing tube at different rates and extra- polating the results t o the stationary condition. It is shown that this method yields satisfactory results and that the density found f o r hydrogen agrees with Morley's value. Determination of Degree of Molecular Associakion in Liquids. ALEXIUS BATCHINSKI (Zeitsch. physikal. Chem. 191 1 '76 665-673. Compare Abstr. 1902 ii 444).-It is shown that the familiar Ramsay-Shields' formula y ( ~ M v ) ~ ! ~ = 2.1 2( T'k - T - 6) for deter- mining the molecular complexity of liquids from measurements of surface tension requires a correction which can be made by substi- tutirig for T'k the magnitude T the '( metacritical temperature " already defined by the author (loc.cit.). The metacriticnl temperature can be obtained from the results of viscosity measurements by means of the equation Tm[p&p3)2]1i7 = 16-31 where pk is the critical density and r] is tbe viscosity at the absolute temperature 2". When the critical density is not known the density a t Oo po may be used; the formula then becomes Tm[po/(r]T3)2]1/7 = 19.4. By means of these formulz the molecular complexities of methyl and ethyl alcohols acetic acid and water have been calculated.H. M. D. G. S. Surface Tension of Solutions of Salts in Alcohol. IVAR W. CEDERBERG (J. Chim. Phys. 1911 0 3-14).-The surface tension of purified alcohol and of alcoholic solutions of sodium bromide sodium iodide and potassium acetate was determined from the capillary rise in tubes of Jena glass. Care was taken to maintain the temperature constant and to compensate for evaporation of solvent during the determinations. The surface tension of alcohol is increased by each of the salts the bromide being most effective and the acetate least. The increase is relatively rapid with the first additions of salt but afterwards falls,ii. 190 ABSTRACTS OF CHEMICAL PAPERS. and becomes a linear function of the salt added when the concentration OF the latter is more than about 0.3 mol.per litre. The highest surface tension observed was 22.93 dynes with a solution of 0.9381 mol. of sodium iodide per litre. The increment 1.72 dyneq is the same as that produced in water by 0.94 mol. of sodium chloride per litre. Quincke found (18’77) that lithium chloride and calcium chloride increase the surface tension of alcohol in proportion to their concentration but his measurements were made before the sources of error in capillary rise determinations had been studied by Volkmann. R. J. C. Degree of Dispersity and Viscosity. H. W. WOUDSTRA (Zeitsch. Chern. I n d . Kolloide 1911 8 73-80).-The influence of the degree of dispersity of the disperse phase on the viscosity of colloidal solutions of ferric and chromic hydroxides has been investigated.On addition of successive small quantities of electrolytes the viscosity diminishes at first attains a minimum and afterwards increases. Small quantities of a non-electrolyte such as sucrose have no influence on the viscosity. When the colloidal solutions are kept at 4 5 O a gradual diminution in the viscosity is observed both in presence and absence of electrolytes. Continued Fihaking of the colloidal solutions has no measurable effect on the viscosity. Since addition of electrolytes rise of temperature and shaking reduce the degree of dispersity of the hydrosol it is supposed that the changes in viscosity are dependent on the changes in the character of the disperse phase. For small variations in the degree of dispersity the viscosity diminishes whereas the formation of much larger particles results in an increase of viscosity. H.M. D. Balling-together Phenomena. J. HERTKORN (Chem. Zeit. 191 1 35 89).-The various phenomena in connexion with the balling- together of precipitates (this vol. ii 9s) are readily explained by the convection currents set up by the difference in temperature between the liquid in which the precipitate is suspended and the surrounding atmosphere. T. S. P. Adsorption of Neutral Salts. HILARY LACHS and LEONOR MICHAELIS (Zeitsch. Elektrochem. 191 1 17 1-5).-1t is first shown that potassium and sodium chlorides are adsorbed (from aqueous solutions) by blood charcoal in a normal way (the quantity adsorbed per gram of charcoal is nearly proportional to the square root of the equilibrium concentration of the salt) and that the cation and anion are adsorbed in equivalent quantities.The adsorption is not affected by the addition of acetone amyl alcohol or phenol to the solution and conversely the adsorption of these substances is not affected by the presence of the salts. On the other hand the addition of a salt (sodium or potassium nitrate or sodium sulphate) to the solution diminishes the quantity of the chloride adsorbed in a very marked way. The addition of a basic substance (sodium or potassium hydroxide,GEISEKAL AND PHYSICAL CHEMISTRY. ii. 191 ammonia sodium carbonate trisodium phosphate) to the solution prevents the adsorption of chlorine ion altogether whilbt acids have the opposite effect. This effect of acids is not entirely dependent on the hydrion but depends also on the nature of the anion.Sulphuric and phosphoric acids were the most active of those tried nitric acid had but little effect and the halogen hydracids diminished the adsorption instead of increasing it. The authors draw the conclusion that whilst the adsorption of non- electrolytes is probably due to changes of surface tension that of electrolytes must be ascribed to some different cause probably of electrical origin. T. E. Adsorption Experiments. K. SCHERINGA (Chern. Weekblad 191 1 8 11-12) -The author describes experiments on the diminu- tion of the lead content of lead solutions by contact with parafin- wax and states that the amount of lead abstracted from the solutions is independent of the surface area of the wax. His inference is that the action is due to solution and not to surface condensation.A. J. W. Ostwald's Dilution Law. JAN ~ E B O R (Zeitsch. physikal. CAem. 191 1,75 685-686).-1t is shown mathematically that the dilution law is only valid when no reaction takes place between the electrolktes in the mixture. G. S. Relation of Osmotic Pressure to Temperature. I. Manu- facture of the Cells employed in the Measurements. HARMON N. MORSE WILLIAM W. HOLLAND JOSEPH C. W. FRAZER and B. MEARS (Amey. Chem. J. 1911 45 91-113. Compare Morse and Frazer Abstr. 1905 ii 575).-Morse and Holland (Abstr. 1909 ii 386) have given an account of measurements of t b e osmotic pressure of sucrose solutions at ZOO and have compared the results with those obtained a t Oo 5 O loo 15" and 25' (Abstr 1907 ii 744 ; 1908 ii 671 1019; 1909 ii 216).It has been found that mithin this range of 0-25O the temperature-coefficient of osmotic pressure in the case of sucrose solutions of concentration from 0*lN to N is practically identical with that of gas pressures. The method of investigation has now been further improved and the work at the six temperatures mentioned has been repeated. The results obtained confirm the conclusion arrived a t previously but a few preliminary experiments with concentrated solutions at 30° 40° and 50" indicate that at these higher temperatures the ratio of osmotic to gas pressure does not remain constant but tends to diminish beginning at come point between 26" and 30'. A detailed account of the work is t o bo published in a series of papers of which this is the first.A full description is given of the method of manufacturing the cells including the treatment of the clays the burning and glazing of the cells and the mode of attaching the manometer. The cells are glazed both inside and outside from the middle upwards. They have beon found satisfactory in all respects except that there is a chanceii. 192 ABSTRACTS OF CHEMICAL PAPERS. that dissolved matter may diffuse in between the two glazed surfaces and afterwards affect the pressure measurement by diffusing down- wards and distributing itself about the membrane. It is considered probable that the results of the experiments have not been vitiated in the slightest degree by this defect but efforts mill be made to obviate the ri6k by making a cell half porous and half porcelain. E.G. Theory of the Isoelectric Point. LEONOR MICHAELIS and HEINRICH DAVIDSOHN (Biochem. Zeitsclz. 19 10 3Q 143-1 50)-In previous papers (Abstr. 1910 ii 592 etc.) it has been shown by experiments with protein solutions that the so-called isoelectric point and the point of optimum coagulation coincide. The acidic and basic dissociation constants of these proteins are however not known and experiments have now been made with simpler compounds for which both dissociation constants are known. The rate of crystallisation from fairly concentrated solutions of these electrolytes in N/l-sodium hydroxide to which different proportions of acid had been added was observed ; the hydrogen concentration of the solution showing the maximum crystallisation velocity was determined by E.M.F.measure- ments and the H’ ion concentration J a t the isoelectric point thus obtained compared with that calculated by means of the formula J= JR,KwfKb where Ka and Kb are the acidic and basic dissociation constants of the electrolyte and Kw is the ionic product for water. With m- and p-aminobenzoic acids there is excellent agreement between the observed and calculated values of J with aspartic acid the agreement is moderate with theobromine unsatisfactory and W i t h a1 senious acid the velocities of crystallisation were so irregular t h a t no definite results were obtained. ~ G. S. Ideal Solutions. I;. GAY (J. Chim. Phys. 1911 9 103-104).- Criticism of a recent paper by Washburn (Abstr. 1910 Polemical. ii 1044).‘ R. J. C. Transference and Transformations of Energy with Applications to the Theory of Solutions. MADISON M. GARVER (J. Physicd Chem. 1911 15 20-44. Compare Abstr. 1910 ii 935).-The second law of thermodynamics may be enunciated thus ‘‘ I n an isolated system work or potential energy appears only during the spontaneous transfer of energy from points of higher t o points of lower intensity accompanied by an equilibrating of the various energy intensities.” All natural processes are equilibrating processes during which each type of energy independently tends to become uniformly distributed. Equilibrium may be established between a solution and the pure solvent by (1) raising the temperature of the solution until its vapour pressure equals that of the solvent or (2) raising the level of the solution so that the difference in vapour pressures is compensated by the higher barometric pressure of the vapour on the solvent or (3) increasing the pressure on the solution. If any two of these coaditioas are prevented the spontaneous transfer of solvent vapour toGENERAL AND PHYSICAL CHEMISTRY.ii. 193 the solution will establish the third. The solution is therefore in a state of less potential (free) energy than the pure solvent a t the same temperature although the energy per molezule is unchanged. If it is assumed that dissolution entails no chemical union but merely the distribution of the energy of the N-molecules of solvent among the ( N + n ) molecules of solution the abs. temperatures before and after dissolving the solute should be as (N+n) N.The fdll in temperature on dissolving 1 gram-mol. of sucrose in a litre of water a t 20" would be 5O instead of the actual 0.8'. The difference must be supplied by chemical union with a decrease in the number of reacting molecules and the liberation of a definite amount of energy. R. J. C. The Critical Phenomena of Dissolution of Mixtures with Normal Components Examined under Variable Pressure. JEAN TIMMERMANS (Proc. K. Aknd. Wetensch. Amsterdam 1910 13 507-526).-The influence of pressure on the critical solution temperature has been investigated for mixtures of cyclohexane and aniline (3 1 *05O) nitrobenzene and hexane (2 1.00') and nitrobenzene and isopentane (32.20'). For the first pair of liquids the critical solution temperature rises with increase of pressure the rise per atmosphere being about 0*0065O.For the other two pairs the temperature fells with increase of pressure the fall per atmosphere decreasing as the pressure becomes greater. I n the case of a mixture of nitrobenzene and hexane dt/dp is equal t o 0.0186" at low pressures and O*0122° at 220 atmospheres. For a mixture of nitrobenzene and isopentane dt/dp is equal to 0.0413' at low pressures and 0.0200' at 250 atmospheres. H. M. D. Crystallisation from Aqueous Solutions. V. Adsorption by Grys tals. ROBERT MARC (Zeitsch. physikal. Chem. 19 1 1 75 710-732. Compare Abstr. 1909 ii 798 983; 1910 ii 834).-In connexion with the observation that the presence of dyes retards the velocity of crystallisation the equilibrium between certain crystals and dyes in solution has now been systematically investigated. As dyes methylene-blue Bismarck-brown methyl-violet and ponceau- RR and as adsorbing surfaces [crystals of uric acid barium sulphate and barium and strontium carbonates were used.It is shown that the colouring of crystals is an adsorption pheno- menon and follows the well-known exponential law a = kllln where a is the amount adsorbed by a detinite surface I is the concentration of the dye in the solution and L and n are constants. With different substances the values of l/n vary between 1/3 and 1. Further for every crystalline substance with definite surface there is an upper limit of saturation beyond which a no longer increases as Z is increased. The bearing of the saturation limit on the phonomenl of crystallisa- tion from coloured solutions is discussed in detail The same crystal does not adsorb to the same extent on all its surfaces and in this connexion it is shown generally that the ratio in which the different dyes are adsorbed does not depend on the chemical rla ure of the adsorbent but on the crystallographic nature of the adsorbing surface Q.s.ii. 194 ABSTRACTS OF CHEMICAL PAPERS. Crystallisation thrmgh Membranes. Jams H. WALTON jun (J. Physical Chent. 1911 15 45-53. Compare Abstr. 1909 ii 649).-Supercooled phosphorus which crystallises a t a speed of 60,000 mm. per minute cannot transmit its crystallisation through gold- beater's skin or through 0.005 in. of rubber although salol witlk a crystallisation speed of only 4 mm.per minute is able to pass its solid phase through these membranes. Aqueous supersaturated solutions of sodium acetate potassium alum and lead acetate are unable to crystnllise through rubber membranes OsOO03 to 0.0004 in. thick. The necessary contact with the solid phase is not established unless the membrane is wetted by the solvent as in the case of aqueous solutions with parchment or collodion. I n order that an aqueous solution shall crystallise through either of these membranes a definite minimum degree of supersaturation is necessary depending on the particular salt and membrane. Potassium alum appears to pass through parchment less readily than through collodion and the rzverse holds for sodium acetate. The author suggests that thero is a concentration of the water in the pores of the membrane so that in order t o produce a saturated solution in the membrane a definite degree of supersaturation is necessary outside it.R. J. C. Solid Colloidal Solutions ALFRED LOTTERMOSER (Zeitsch. Chern. Ind. KolZoide 1911 8 95-96).-1n reference to the views of Benedicks on the natureof troostite (this vol. ii 25> the author calls attention to the similarity between the phenomena which are observed in the slow and rapid cooling of iron carbon alloys on the one hand and gold glasses on the other. H. M. D. Emulsion Colloids (Emuleoids) and Observations on the Methods of Counting Ultra-microscopic Particles. GEORG WIEGNER (Roll. Chem. BeihPfle 1911 2 213-242).-It has been found that independent estimations of the number of ultra-microscopic particles in a solution of colloidal gold carried out by different observers a t different times exhibit discrepancies such as can be entirely accounted for on the basis of the law of probability.Experiments are described which show that olive oil-water emulsions can be prepared by means of a Lava1 emulsifier which contain as many as 5.109 colloidal particles in 1 C.C. Emulsoids containing from 2 to 3.109 particles per C.C. are quite stable but those containing a larger or a smaller number of particles are comparatively unstable. The olive oil-water emulsoids exhi bit the characteristic properties of colloidal solutions. Coagulation takes place on addition of electrolytes. Corresponding with the fact that the emulsoid particles are negatively charged it is found that acids cause coagulation even in very dilute solution.In very small quantities (less than 2-5 millimols. per litre) hydroxides have no effect but above this limit the activity of hydroxides exceeds that of acids. This is attributed to the greater readiness with which the OH' ions are adsorbed as compared with the H' ions. In presence of egg-albumin coagulation takes place more readily andGENERAL AND PHYSICAL CHEMISTRY. ii. 195 this is supposed to be an effect of the same kind although opposite in sign as that which is involved in the action of protective colloids. H. M. D. Some General Properties of the Binary Equilibrium Diagram. KARL BORNEMANN (Metallurgie 1910 7 7'40-747)- Complete immiscibility of the components in two co-existing phases is impossible and every homogeneous field of the equilibrium diagram must therefore have a certain extension in the direction of the axis of concentration.As two co-existing saturated phases cannot have the same composition the heterogeneous field separating these two phases must also have a definite extension in the same direction. These rules apply t o all systems which are not in invariant equilibrium. Their effect on the diagram is illustrated by application to the nickel-sulphur system (Abstr. 1910 ii 1072). C. H. D. The A n a l y s i s of Binary Compounds by a Method Based on the Law of Mass Action. IWAN OSTROMISSLENSKY (Bey. 191 1 44 268-373).-It is shown that if two substances A and B unite to form an unstable compound and if varying amounts represented by a and b (in gram-mols.) of the two are mixed in solution so that a; + b is always constant then t h e maximum yield of the compound is formed when the two components are prosent in the proportions in which they combine with one another.The maximum yield of compound can be determined by some physical method such as change in colour. It is shown that in the case of aniline and nitrobenzene a definite compound of molecular proportions of the components is formed in the absence of a solvent. The coloration was determined with a Kriiss spectro- photometer using a n incandescent gas lamp and a thickness of liquid 10 mm. at 22-23". The formula a/s.(9M+ 3M')/R can be used €or calculating the relative amounts of product in the solution when a+b=12 and a/b=3.M and M' represent the mol. wts. of the two components X the sp. gr. of the mixture and R the proportionality factor. J. J. S. Equilibrium Diagram of Silver Iodide. GUSTAV TAMMANN (Zeitsch. physikal. Chem. 191 1 75 733-768).-1n a previous paper (Ann. Phys. Chem. 1899 [ill 68 643) evidence was obtained that three solid forms of silver iodide exist. A.s a result of t h e present investigation this conclusion is confirmed the three forms being silver iodide I the ordinary yellow modification ; 11 a red modification and 111 which is only stable when the pressure exceeds 3000 kilog./cm.2. The equilibrium curves 1-111 and 1-11 have been determined in detail and also the position of the triple point a t which the three forms are in equilibrium ; the latter point lies a t 100' and 2940 kilog.pressure. The change of volume when modification I changes to the denser form I11 is about 0.0265 C.C. per gram whereas the converse change from 111 to I is attended by a n expansion of only 0.0233 C.C. per gram. The cause of this discrepancy is so far undetermined. The average change of volume in changing I1 t o IIL is about 0.0115 cm. per grmi. The velocity of transfolmation of I to 111 and vice196 ABSTRACTS OF CHEMICAL PAPERS versh does not take place like a system of one component for example like the transformation ice I-ice 111. I n the range of temperature from 90' to 20' the transformation 1-111 takes place a t a definite pressure which only depends on the rate of change of volume; in the converse transition 111-1 the maximum velocity is reached at 2700 kilog.jcm.2 practically independent of the temperature.A t the end of the transformation 1-111 the pressure must exceed 3200 kilog. in order t o complete the change; similarly to complete the converse transformation the pressure must be Fery considerably lowered. As an explanation of these peculiarities it is suggested that both I and 111 form saturated mixed crystals the composition of which depends on the temperature and pressure. When 111 is cooled to - 80' and the pressure reduced the change 111-1 occurs at 1700 kilog. pressure but when the same form is cooled to - ]SO0 the transformation does not occur even at 1 kilog. pressure. I n the course of the investigation it was shown that the precipitated so-called amorphous silver iodide is identical with the crystalline modification.G. S. Mixed Crystals in Liquid-Grystalline'Syatems and the Phase Rule. ADA YRINS (Zeitsch. physikal. Chem. 1911 '75 681-684).- An answer to the criticisms of Lehmann (Abstr. 1910 ii 772) on the author's work (compare Abstr. 1909 ii 869). The importance of quantitative observations as opposed to purely qualitative microscopic observations is emphasised. G. S. JULIUS HIRNIAE (Zeitsch. physikal. Chenz. 1911 75 675-680. Compare Lotka Abstr. 1910 ii 401)-It is shown mathematically that under certain conditions a periodic chemical reaction may occur in the unimolecular reversible transformation of three isomerides. G. 5. Periodic Reaotions. Speed of Reaction in Heterogeneous Systems. J. BOSELLI (Compt. rend. 19 11 152 256-259).-The following conclusions derived from theoretical considerations to be published hereafter refer t o that particular type of reaction illustrated by the dissolution of magnesia in dilute hydrochloric acid a case in which the velocity of reaction depends on the rate of diffusion of the acid towards the solid. (1) The velocity of dissolution or vaporisation of a solid in a liquid is proportional other conditions being equal to a power slightly less than the 4/3 of the difference between the mean concentration of the dissolved solid a t an infinitely small distance from the undissolved sur- face and its average concentration in the solution.The velocity is also proportional to the 1/3 power of the coefficient of diffusion of the solute in the solvent. (2) The speed of dissolution is proportional to the square root of the coefficient of diffusion t o the square root of the velocity of the stream of liquid (moving uniformly in a straight line) and to the difference between the concentration at saturation and the average con- cen tratil jn.GENERAL AND PHYSICAL CHEMISTRY. ii.197 (3) The following expressions indicate the speed of total dissolution Q of a rectangular plate (dimensions I x y ) and of a circular plate radius R respectively each being parallel to the flow of liquid K is the coefficient of diffusion Vthe veIocity of the liquid and B the difference between concentration at saturation and mean con- centration. These expressions have an advantage over those of Nernst inasmuch Q = 2By ,J VKE/.rr ; Q = 2fR2 JVK/r.EfG(l - a2)f.da.as they contain no arbitrary constant. w. 0. w. Comparison of Reaction Velocity and the Fluidity of the Medium. ERNEST S. GRUMELL (J. C h h . Phys. 1911 0 143-159). -The rates of hydrolysis of sucrose aiid ethyl acetate by hydrogen chloride have been compared with the viscosities of the same solutions at various temperatures from 0' to 9s'. In neither case does the progress of the hydrolysis introduce any appreciable change in the viscosity of the solutions. No quantitative relation between viscosity and chemical activity coiild be traced and the introduction of solubility considerations in the case of sucrose led to no better result. The coefficients of increase of velocity and decrease of viscosity with temperature both show a diminution as temperature rises. The ratios of the temperature-coefficients of velocity and viscosity at any tem- perature were appreciably constant in both reactions.This is held to demonstrate a connexion between the phenomena. It is suggested that connexion is to be sought in Trautz' hypothesis (Abstr. 1909 ii 651) according to which the variations in the temperature-coefficient of reaction velocity are due to changes in the specific heat of the solution to which also the viscosity is closely connected. R J. C. The Velocity of the Ring Opening in Connexion with the Composition of the Unsaturated Ring Systems. JACOB BOESEKEN and A. SCHWEIZER (PTOC. K . Akad. Fetensch. Amsterdam 1910 13 534-536).-The rates of hydration of succinic and malic anhydrides hare been compared at 0' by means of measurements of the electrical conductivities of the aqueous solutions.The observed rate of change indicates that the reaction is unimolecular and that maleic anhydride takes up water 14.2 times as fast as succinic anhydride (compare Rivett and Sidgwick Trans. 1910 97 1677). Repeating Figures in the Atomic Weight Values. HEINRICH LOEWEN (Chern. Zeit. 1911 35 55).-A severe adverse criticism of Loring's suggestion (compare Abstr. 1910 ii 1053) that there is some significance in the occasional recurrence of the figure in the unit's place in the second place of decimals. H. M. D. G S Atomic Weight Relations. F. H. LORING (Physikal. Zeitsch. 1911 12 107-1 12).-The paper consists mainly of tables and curves illustrating relationships between the atomic weights some of which have already been given in previous papers (compare Abstr.1909 ii 392 562 715 ; 1910 ii 26). The inactive gases are supposed to be VOL. c. ii. 14ii. 198 ABSTRACTS OF CHEMICAL PAPERS. formed by the association of acid and basic principles and a number of methods of arriving at their atomic weights on this basls are indicated. The atomic weights of these elements are also derived hp a geometrical method. I n the course of the investigation the atomic weights of a number of elements so far unknown are deduced. G. S. Periodic System [of the Elements]. CUET SCHMIDT (Zeitsch. physikal. Chern. 19 11 75 651-664).-The author considers that the weaknesses of Mendelkeff’s classification of the elements can be avoided by dividing the elements into four groups which are genetically connected.The first group comprises hydrogen certain gases present in stars and ‘( proto-metals.” The second group consists bubstantially of the members of the even series of Mendelt5eff’s table which are characterised by pronounced chemical individuality and the division into metals and nou-metals separated by a neutral zone of inactive gases. The third group which consists mainly of the uneven series of I\lendeldeff’s table consists of metals only and the members form no definite chemical compounds among themselves but merely alloys. The fourth group comprises the metals of the rare earths. The advantages of this system of classification and the possible stages in the genesis of the elements are discussed in detail. Finally as regards tendencies now at work the development is towards the elimination of cheniical differences and therefore towards the dis- appearance of chemical affinity.This is brought about by the forma- tion of sybtems of elements the members of which become cherriically more alike and finally identical. Helix Chemica. Study of the Periodic Relations of the Elements and Their Graphic Representation. BENJAMIN K. EMERSON (Amel.. Chern. J. 1911 45 160-210).-The elements have been arranged in the form of a spiral based on the idea of Crookes’ spiral (Trans. 1888 53,503). The curve begins with “ der Urstofl ” or ether with valency and density of zero. From this an initial half-circle rises with coronium at its summit. The second curve is a half-octave circle passing from hydrogen through nebulium and ‘‘ protofluorine ” to helium (compare Jessup and Jessup Abstr.1908 i i 96). This is folIowed by two octave circles in which the elements sink through lithium to carbon rise through fluorine to neon and repeat the curve through sodium to silicon and on through chlJrine t o argon. The spiral is continued by four double-octave circles and terminates in a quadruple octave. The first double octave begins with potassium and ends with krypton ; the second begins with rubidium and ends with xenon; the third begins with cesium and ends with an unknown element ; the fourth begins with a u unknown element and ends with ‘6 radium emanation.’’ The quadruple octave contains radium ionium thorium and uranium. The position of the elements in the spiral are correlated with the atomic weights densities valencies refractivities specific volumes compressibilities electropotential relations crystallographic forms fu~bilities volatilities hardness ductility and other properties.G. S. The paper is illustrated with numerous diagrams. E. G.GENERAL AND PHYSICAL CHEMISTRY. ii. 199 The State of Aggregation of Matter. I.-111. SAMUEL €3. SCHRYVER (Proc. Rop. Xoc. 1910 B 83 96-123).-See this vol. i 245. EDMUND 0. VON LIPPMANN (Chem. Zeit. 191 1 35 41-43 62-64 70-72).-Historical. The History of the Name “Gas.” L. DE K. Congress of Chemists at Karlsruhe in 1860. ERNST VON MEYER (J. pi.. Chenz. 1911 [ ii] 83 182-189).-Historical. c. s. Gas Regulator for Thermostats. ARTHUR SLATOR (J. Xoc. Chem. Ind. 191 1 30 61-62).-The part of the regulator containing the merciiry is provided with a side-tube which is bent slightly down- wards close to the junction and then rises vertically By means of a glass rod fitted into the upper end of this side-tube the level of the mercury in the main tube may be regulated as desired the rod being moved up or down for this purpose. The rod passes through a rubber stopper fitted in a cup at the top of the tube and this cup is filled with New Form of Constant Temperature Drying Oven. RAYMOND L. SIAU (J. Xoc. Chem. I ~ z d . 1911 30 61).-The oven consists of a round or square cylinder mounted horizontally and surrounded by a jacket of similar shape. The jacket is united to the cylinder a t one end and this end of the oven is closed by means of a closely-fitting door. Steam or the vapour of any other liquid is admitted t o the jacket which is provided with a condenser and a current of air is drawn through the oven itself this air before enter- ing the oven having been passed through a spiral tube situated in the jacket and surrounding the cylinder form- i n g the oven. A tube leaving the oven a t the opposite end to the door is con- nected with a pump in order to draw the current of heated air through the spiral tubo and oven. a mixture of glycerol and water. w. P. s. w. P. s. Cheap Crucible Supports. VON HEY- GENDORFF (Chenz. Zeit. 19 11 35 139).- The disused fire-clay supports of inverted incaandescent mantles will be found snit- able for supporting red-hot crucibles either on the bench or in a desiccator. L. DE K. A Closing Contrivance for Gas- washing Bottles Wash-Bottles etc. FRANZ MICHEL (Chem. Zeit. 1911 35 72).-The arrangement (see Fig.) renders unnecessary the use of stopcocks or pinch- cocks and allows the current of the gas to be.regulated or to be shut off. A l l that is necessary is t o move the bulb-tube upwards or downwards in the cork SO as to partly or totally close the opening A . 14-2ii. 200 ABSTRACTS OF CHEMICAL PAPERS. The same principle may be applied to ordinary wash-bottles. L. UE K. A New Gas-generating Apparatus. FEANZ MICHEL (Chem. Zeit 19 11 35 52).-An Improved Kipp Apparatus.-An exit tube for tho gas generated is fused on to the neck of the lower vessel. Corresponding in position with this a groove is cut in the upper vessel where it is ground into the neck of the lower vessel so as to form a passage from the lower vessel to the exit tube. On rotating the upper vessel this passage is closed thus replacing the usual external stopcock on the exit tube. L. DE K.

ISSN:0368-1769    

DOI:10.1039/CA9110005165

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

i. 173 Organic Chemistry. Synthesis of us-Heptachloropropane from Tetrachloro- ethylene and Chloroform with the Co-operation of Aluminium Chloride. JACOB BOESEKEN and H. J. PRINS (Proc. I[. Akad. Wetensch. Anasterdam 191 1 13 685-6S7).-It has previously been shown (Abstr. 1910 i 153) that when dichloroacetyl chloride is decomposed by aluminium chloride one of the products is a crystalline substance m. p. 33O to which the composition C,CI was assigned. A larger quantity oE this substance has now been prepared and it is found to be identical with the as-heptachloropropme obtained by Fritsch from pentachloroacetone and phosphorus pentachloride (Abstr. 1898 i 63). The heptachloropropane may also be prepared by the direct addition of chloroform to tetrachloroethylene under the influence of aluminium chloride.This synthesis gives another proof that the theory of the formation of intermediate products as an explanation of Friedel and Crafts' reaction must be abandoned as there are no indications of the forma- tion of such products. It may be assumed that aluminium chloride renders the chloroform active so that the molecular parts CHCI and C1 attach themselves to the double linking of the ethylene perchloride also rendered active. It is also shown that pentachloroethane yields as-heptachloropropane with chloroform and aluminium chloride. N. c. Preparation of Bromides from Primary and Secondary Saturated Alcohols. FELIX TABOURY (Bull. Xoc. chim. 19 1 I [ iv] 9 124-125).-Fournier (Abstr. 1906 i 787) has shown that hydrogen bromide reacts with primary and secondary saturated alcohols a t the ordinary pressure giving good yields of alkyl bromides.The author states that it is unnecessary t o prepare the hydrogen bromide separately and gives details for carrying out the reaction in one large flask. Yields varying from 75 to 85% of methyl ethyl propyl and isopropyl bromides were obtained in this way. I n the case of isobutyl bromide the yield fell to SO% owing t o a secondary action of the bromine on the bromide produced. It was found in this case that on raising the temperature at the end of the experiment a liquid was obtained b. p. 149-150' ; this is dibromoisobutane CH,Br *CMe,Br. N. c. Acetylenic Pinacone [&-Dimethyl - Av - hexinene -PL- diol]. GEORGES DUPONT (Compt. rend. 191 1 152 197-199).-/3~-Dimethyl- Ay-hexinene-pr-diol OH-CMe,*C:C*CMe,*OH (Jotsitch J.Russ. Phys. Chem. Xoc. 1904 36 1545) is a colourless substance m p. 95" which unlike corresponding saturated compounds does not form a hydrate It resembles these subtances however in its behaviour towards the halogen acids but approaches more closely to Pa-dimethylpentane- VOL. C. i. 0i. 174 ABSTRACTS OF CHEMICAL PAPERS. PG-diol (Franke Abstr. 1905 I 111 ; 1907 i S16) in its reactions with dehydrating agents. The corresponding dibromide CMe2Br*CiC*CMe2Br m. p. 39' b. p. 219' is an exceedingly stable substance. I n its formation by the action of hydrogen bromide a n unstable intermediate compound was noticed m. p. about 50'. The corresponding dichloride has m. p. 29' b. p. 62-63'/15 mm. By the action of dilute sulphuric acid on the diol t h e two following substances are obtained in proportions varying with the concentration and duration of heating.(1) P-Methyl-c-methylene- AY-hexinene-P-ol CH,:CMe*CiC*CMe,*OH a pale yellow liquid with an agreeable odonr m p. -2' b. p. 159-160° D15 0.8772 n 1.4687. When treated with hydrogen in presence of spongy platinum it yields dimethyl- isoamylcarbinol (Konownloff Abstr. 1902 i 336). (2) +Dimethyl- ene- AY-hexkene CH,:CMe*CiC*CMe:CH is a colourless mobile liquid b. p. 123-124' DI5 0.7598 nD 1.4859 which rapidly becomes resinous on exposure t o air. It is best prepared by the action of potassium hydroxide on the foregoing dibromide. On reduction i t yields ARTHUR ST~HLER and ERIK SCHIRM (Ber. 191 1 44 319-323).-Well-cooled ethyl alcohol is treated slowly with thionyl chloride and the mixture is distilled under 19 mm.pressure after being kept overnight. The resulting ethyl chlorosulphinate Cl*SO,Et b. p. 29'/13 mm. is a faintly yellow liquid which decomposes at its b. p. 122' under ordinary pressure into sulphur dioxide and ethyl chloride as found by previous investigators. The methyl ester b. p. 19'/13 mm. or 102'/755 mm. (decomp.) is obtained and behaves in a similar manner. Neither of the esters however can be separated completely from the excess of the thionyl chloride on account of proximity of b. p. The propyl ester however has been obtained in a pure state as a colourless liquid b. p. 7 8 O / 7 5 mm. The chlorosulphinic esters are very unstable substances which are vigorously decomposed by water into sulphur dioxide hydrogen chloride and a n alcohol.JAIME FERRER HERNANDEZ and ANGEL DEL CAMPO Y CERDAN (Anal. Pis. Quim. 1911 9 17-26. Compare Delepine Abstr. 1910 i 295 545).-The authors have repeated Delepine's observations on the phosphorescence of dimethyl dithiocarbonate OMe*CS*SMe and find that ionisation of the air is produced during the phenomenon whilst the compound appears to possess feeble radioactivity. The potassium methyl salt OMe*CS*SK yields methyl tetrathionate when oxidised by potassium permanganate or sodiiim perborate in dilute acid solution. Separation of the Liquid Fatty Acids (Unsaturated) from the Solid Fatty Acids (Saturated) in Natural Mixtures of Fatty Acids and the Ammonium Salts of Some Fatty Acids.11. PIETRO FALCIOLA (Gaxxetta 1910 40 ii 425-435. Compare this vol. i &).-When applied to mixtures of natural origin PE-dimethyl hexane. w. 0. w. Existence of Chlorosulphinic Esters. The isobutyl ester has b. p. 48*5'/9 mm. c. s. Delepine's Phcsphorescent Esters. G. D. L.ORGANIC CHEMISTRY. i. 175 the method previously described does not effect a rigorously quantita- tive separation but nevertheless it may be employed with more or less success and yields more satisfactory results in the case of mixtures containing a preponderance of the solid acids. The ammonium salts of the solid fatty acids (such as the palmitate and stearate) are more soluble i n ammoniacal alcohol containing ammonium salts of liquid fatty acids (for example the oleate) than in that solvent alone.Moreover the solid fatty acids separated by the niethod always contain appreciable quantities of the liquid fatty acids. Ammonium linoleate C17H,,*C0,*NH is prepared by passing dry ammonia into a cold ethereal salution of the acid in an atmosphere of hydrogen. I n presence of ammonia and lime the pasty mass obtained becomes solid. It begins t o melt at 57-58' and is completely melted at 75O forming a red liquid. is similarly prepared and has m. p. 70-77". Ammonium laurate C,,H,,*CO,*NH is a white substance m. p. about 75". Ammonium myrastate C,,H,,*CO,*NH has m. p. about 75-90" Ammo?zium octoate C,H,,O,*NH has m. p. '70-85'. Ammonium hexoate may be prepared i n the same way. Ammonium crotonate C,H,*CO,*NH forms colourless crystals m. p. 105-1 15".Ammoniwn butyrate C,H7*C0,*NH has m. p. 70-85". Ammonium eiwcate C,,H,lO,*N H4 R. V. S. Linolenic Acid and Linseed Oil. ADOLF ROLLETT (Zeitsch. physiol. Chem. 191 1,70,404-407).-Polemical (compare Erdmann and Bedford Abstr. 1910 i 810; Rollet; Abstr. 1909 i 760). Pure linolenic acid has the iodine value 273.7. E. F. A. Action of the Chlorides of a-Alkyl?xy-acids on Organo- metallic Derivatives of Zinc. EDMOND E. BLAME and L. PICARD (Compt. rend. 191 1 152 268-269).-The chlorides of a-alkyloxy- acids are acted on abnormally by organozinc iodides giving rise under some conditions to ttn ether in addition t o the usual alkyloxy-ketone. This arises from the elimination of carbon monoxide from the acid chloride probably through catalytic influence of t h e zinc compound.The action is represented as R*O*CH,*COCl= R*O*CH,Cl+ CO ; R*O*CH,Cf + Z n R I = ZnClI + R*O*CH,R'. The yield of ether increases and that of ketone diminishes as the temperature of reaction rises. The proportion of ether increases also with the molecular weight of the zinc salt; thus from zinc n-heptyl iodide only ethyl octyl ether was obtained. When R or K' are cyclic only the ketone is formed ; thus ethoxyacetyl chloride and zinc p-tolyl bromide gave p-tolyl ethoxymethyl ketone OEt*CH2*C0*C7H7 b. p. 135'/9*5 mm. ; the oxime has m. p. 57O and the p-nitrophenylhydrc~xmze m. p. 80". The yield of ketone increases also with the weight of R. isoButoxyacety1 chloride and zinc ethyl iodide gave n-propyl isobutyl ether (10%) and ethyl isobutoxymethyl ketone (50%) b.p. 68-69'/13 mm. ; oxime b. F. 116-1 17"/14 mm. ; semicurbazone m. p. 72". Phenoxyacetyl chloride gave only phenoxymethyl ethyl ketone b. p. 129'114 mm.; senxicarb- axone m. p. 102" ; p-nitrop~enylhydrr.axone prisms m. p. 153'. w. 0. w. 0 2i. 176 ABSTRACTS OF CHEMICAL PAPERS. The Preparation of P-Alkyloxy-compounde. M. H. PALOMAA and SULO KILPI (Chenz. Zent?.. 1910 ii 1453 ; from Ann. Finn. Akad. Wiss. A 2 No. 3).-The preparation of the esters of hydracrylic acid by the action of sodium alkyloxides on ethyl @-chloropropionate gave unsatisfactory results; the action was better in the case of the P-iodopropiona te. Meth y 2 /3-methoxypropionate OMe*CH,*CH,*CO,Me is a colourless liquid b. p. 143*4-143.6'/750 mm. DiE 1-0148. Ethyl P-ethoxypropionate has b.p. 49*5-49.8'/7 mm. Di 0.9536. Propyl P-propoxypropionate is a colourless agreeably smelling liquid b. p. A Green Crystalline Manganitartrate. ANDR~ JOB and P. GOISSEDET (Compt. read. 191 1 152 265-268. Compare Abstr. 1907 ii 553 ; Durrant Trans. 1905 8'7 1781)-Eighteen grams of manganous sulphate dissolved in water (20 c.c.) are added to a solution of sodium tartrate (450 grams) in a litre of water. The solution is shaken in an atmospliere of oxygen and 100 grams of sodium hydroxide in 250 C.C. of water added slowly. The red liquid gradually deposits green crystals of sodium manganitartrate 74-5-75-5'/7 mm. DiE 0.9386 N. c. CO,Na*$lH 0 CO,Na* CH* 0 >Mn*O*CH(C02Na)*CH(ONa)*C02Na,l 1H,O. This salt dissolves in water forming an alkaline solution which deposits manganic hydroxide and irobably through hydrolysis >Mn*OH.On the having occurred contains the salt; CO,Na*FH*O C0,Na.CH.O addition of sodium tartrate the liquii becomes green and remains stable. The green solutions are unable t o afford green crystals although these appear on the addition of an alkali carbonate when the liquid becomes red. An explanation of this fact is suggested. w. 0 w. Basic Citrates and Tartrates of Barium. ANTONIO QUARTAROLI (Chem. Zentr. 1910 ii 1131-1132; from Xtax. sperim. agrur. itccl. 1910 43 396-408).-The author states than when excess of barium hydroxide is added to a solution of citric acid a t a temperature of at least 1 8 O a tetrabasic citrate is formed ; at lower temperatures ( + 5-10') a less basic citrate is formed which is more soluble. The citrate formed above 18' dissolves to the extent of 10-13% in water. With tartaric acid in the same way a tribasic tartrate is obtained ; the same modification is formed at 18' and at 5-10' but at loo3 a crystal- line form is obtained.N. c. Preparation of Formaldehyde from Methyl Alcohol by the Contact Process. MAX LR BLANC and E. PLASCHKE (Zeitsch. Ekktrochem. 191 1 17 45-57).-A constant measured current of air is passed through methyl alcohol kept at a constant temperature. The mixture of air and alcohol vapour then passes over a spiral of silver silver-plated copper or copper gauze and the products (consist- ing of formaldehyde unchanged methyl alcohol carbon monoxide and dioxide hydrogen and nitrogen) are collected and analysed.ORGANIC CHEMISTRY.i. 177 The maximum yield of formaldehyde is always obtained a t about the same temperature. Measured near the end of the silver gauze spiral at which the gases entered it the best temperature is 450° but this is not the maximum temperature of the spiral which often reaches a bright red heat in the middle When the temperature of the contact is kept constant and the ratio of air to alcohol in the mixture is gradually increased the yield of aldehyde increases to a maximum and then diminishes again. The maximum yield is obtained with about 0.46 gram of oxygen to 1 gram of alcohol. The loss of alcohol (the part not accounted for by aldehyde or unchanged alcohol in the products) increases rapidly and continuously as the oxygen is increased. The length of the contact layer also affects t b e results ; in the 30 mm.tube used by the authors the most favourable length was 70 mm. which gave the highest yield of formaldehyde observed namely 58% of the theoretical quantity. The results with copper were very similar to those obtained with silver the best length of layer being 80-90 mm. and the best mixture containing 0.39 gram of oxygen per gram of methyl alcohol. A consideration of the composition of the gaseous products (which always contain more hydrogen than the sum of the carbon monoxide and dioxide) leads t o the conclusion that the formation of form- aldehyde is due not to oxidation of methyl alcohol but rather to its decomposition thus CH,*OH = CH,O + H,. The main source of loss is the decomposition of formaldehyde by heat @H,O = CO + H,. To test this methyl alcohol vapour was passed over freshly reduced copper at 700'.The yield of formaldehyde is fairly good at first but falls off rapidly. (In six experiments with the same spiral it fell from 28% in the first to 4% in the sixth.) The activity of the copper is restored by oxidising it and reducing it again. It appears therefore that the function of the air in the usual contact process is to keep the copper constantly in its most active form by continually oxidising it the reduction being brought about by the hydrogen and carbon monoxide present. T. E. Electrosyntheses. VI. SIMA M. LOSANITSCH (Ber. 19 1 1 44 312-315. Compare Abstr. 1910 i 542).-It has been shown previously (Abstr. 1897 i 179) that under the action of the silent discharge a mixture of carbon monoxide and hydrogen gives form- aldehyde which immediately condenses to yellow aldehydic products.Further investigation shows that these products consist of a liquid portion soluble in water alcohol and ether and a solid portion which is only soluble in water. The liquid portion is viscous has the odour of paraldehyde and contains formic acid. The yellow solid portion has a composition corresponding with C,,H,,O,,. It is probably the first anhydride of C,H,,O since cryoscopic experiments shorn t h a t the freshly made aqueous solution contains molecules corresponding with C,,H,,O, and these on keeping split up into C,H,,06 molecules. Xvaporation of the aqueous solution on the water-bath leaves a dark residue with the composition C,H,O,; if the evaporation is carried out in a vacuum the yellow compound U,,H1,O,! is left.The aqueous solution of the yellow solid readily gives glyoxali. 178 ABSTRACTS OF CHEMICAL PAPERS. phenylosazone with phenylhydrazine and glyoxime with hydroxyl- amine from which i t is probable that the yellow solid is a readily decomposable condensation product of glyoxal. The formaldehyde produced from the carbon monoxide and hydrogen by the silent discharge probably condenses to the two following aldehydes 2CH,O = OH*CH,*CHO and 2CH,O = CHO-CHO + H and these then form the compound CHO*CH0,20H*CH2*CH0 which is the yellow solid. The condensation product obtained from carbon monoxide and methane (Abstr. 1908 i 866) also contains a part soluble and a part insoluble in water.The former is identical with the above yellow solid C12H,,01,. A mixture of carbon dioxide and hydrogen behaves similarly t o a mixture of carbon monoxide and hydrogen towards the silent discharge since the carbon dioxide is first reduced to the monoxide. T. S. P. a-Bromocrotonaldehyde. PAUL L. VIGUIER (Compt. vend. 191 1 152 269-271. Compare Abstr. 1909 i 691; 1910 i 461).- a-Bromocrotonaldehyde forms an oxirne m. p. 110-1 1 I" which becomes pasty on keeping. The semicnrbazone has m. p. 228-230". 5-Methylpyrazole is produced when the aldehyde is added to an alcoholic solut ion of hydrazine hydrate. The phenylhydrazone lamella ni. p. 124-125" is unstable; when treated with alcoholic potassium hydroxide it forms 1 -phenyl-5-methylpyrazole ; on heating with excoss of phenylhydrazine it furnishes a compound C1G€€,8N4 m.p. 117-119'. When a-bromocrotonaldehyde or its acetal is allowed to act on urethane in aqueous solution in presence of a little hydrochloric acid a con~pound C,,H,,O,N,Br is obtained. This crystallises in coloarless slender needles -m. p. 124-125' and is useful for Photochemical Synthesis of Carbohydrates from Carbon Dioxide and Hydrogen in the Absence of Chlorophyll. JULIUS STOKLASA and WENZEL ZDOBNICKP (Biochem Zeitsch. 191 1 30 433-456; Monatsh. 1911 32 53-75).-A figure is given of the apparatus employed for carrying out experiments in the presence of ultra-violet light the chief feature of which is the form of the basin in which the reactions were investigated which was suspended from a mercury-quartz lamp which served as the source of light.It mas found t h a t water does not act on carbon dioxide in ultra-violet light in the absence of potassium hydroxide neither formaldehyde nor carbohydrate being formed in this case. If potassium hydroxide is added however formaldehyde but no carbohydrate is formed. The hydrogen must be in the Dascent state for the reaction t o take place and ultra-violet light must be present. I n the absence of the latter formic acid is formed. A sugar is also formed when nascent hydrogen reacts with carbon dioxide in the presence of ultra-violet rays. The oature of the carbohydrate has not yet been definitely established. The osazone melts a t 11,6-SOO0 and is not therefore either formose p-formose or characterishg the aldehyde.w. 0. w. p-acrose. s. B. 8.0 RG ANIC CHEMISTRY. i. 179 Nomenclature of the Sugara. EMIL VOTO~EK (Bey. 1311 44 360-361).-The prefix epi is used to denote the new carbohydrate formed by the interchange of the H and OH groups on the a-carbon atom ; thus mannose becomes epiglucose ribose becomes epiarabinose talose becomes epigalactose etc. The isomeric pair are spoken of as epirnerirles and the change as epimerism. The nomenclature is extended to the alcohols and acids of the carbohydrates. E. F. A. epiRhodeose. EMIL VOTO~EK and CYRILL KRAUZ (Ber. 191 I 44 362-365. See preceding abstract).-Hhodeonic acid prepared by oxidation of rhodeose with bromine is partly converted on heating with pyridine at 150-160° into epivhodeonic acid. The barium salt forms colourless matted crystals which are optically inactive.The crystalline lactone is reduced by sodium amalgam i n the usual manner to epiyhodeose; this is a syrup yielding the same phenylosazone as rhodeose but the methylp~enylhydraxone has m. p. 175'. On oxidation with nitric acid the trihydroxyglutaric acid obtained has m. p. 184-185O [ a ] + 12' fal!ing to + 2 * 5 O on boiling and differs slightly from the inactive lactone described by Fischer and Yiloty (m. p. 170-171°; compare Abstr. 1892 440). It is pointed out that ribohydroxyglutaric acid although itself completely symmetric forms a lactone which is not symmetric. Fischer's lactone is an equi- molecular mixture of d- and I-lactones but t h a t from epirhodeose is possibly completely derived from d-lactone or from a mixture of d- and 2-lactones in unequal proportions.E. F. A. Solubility of Lime in Aqueous S o l u t i o n s of Sucrose and of Glycerol. FRANK K. CAMERON and HARRISON E. PATTEN (J. Physical Chem. 1911 15 67-72).-When lime in excess is added to sucrose solution a soluble compound of lime and sugar is formed but some of the sucrose passes into the solid phase. The relation between the amount of lime dissolvsd and the amount of sucrose in solution is not a linear one since the liquid is in equilibrium with a series of solid solutions of the lime-sucrose compound in lime. The solid phase consisting of fine globular granules was separated by a centrifuge and contained upwards of 10.8% of sucrose. Solutions containing more than 20% of sucrose could not be investigated owing to their high viscosity.The 20% solution dissolves about 6% of lime at 25'. The presence of glycerol increases the solubility of lime to 1.34% in a 55% solution of glycerol. The ratio of lime to glycerol is a strictly linear one and no glycerol passes into the solid phase. R. J. C. Cellobiose and the Acetolysis of Cellulose. WILEIELN ScHLIEnrmN (AnnuZen 191 1 378 366-381).-The treatment of cellulose (filter-paper or cotton wool) with a mixture of acetic anhydride and concentrated sulphuric acid at low temperatures yields products quite different from those obtained at higher temperatures because the acetolysis (that is the acetylation and hydrolysis of the cellulose molecule) is less quickened by the sulphoacetic acid produced i n the acetylating mixture at high temperatures (Stillich,i.180 ABSTRACTS OF CHEMICAL PAPERS. Abstr. 190cT i 318; 1906 i 552 626) than by the acetyleulphuric acid formed a t low temperatures. The product obtained by acetylating cellulose by Skraup and Konig's method (Abstr. 1902 i 135) or by Maquenne and Goodwin's process (Abstr. 1904 i 799) after hydrolysis by alcoholic potassium hydroxide yields cellobiose which after being completely dried at loo' has the formula C,,H,,O, and [u] 34-6' in 2-17% aqueous solutions. It can be estimated by Pehling's solution by Wein's method and forms a phenylosaxone m. p. 2OS-21O0 [a] - 1 7 ~ 5 ~ in alcoholic solution. By treatment with acetic anhydride and sulphuric acid (or a little zinc chloride) i t yields the same octa-acetylcellobiose m.p. 221.5-222' [u]~41*5' in chloroform as is produced by the action of this acetylating mixture on cellulose (Maquenne and Goodwin Zoc. cit.). The isomeric octs-acetylcellobiose m. p. 191.5-192° obtained by boiling cellobiose with acetic anhydride and sodium acetate has [a]2$' -7.8' in chloroform and - 24.9' in benzene. Both octa-rtcetylcello bioses can be converted into tho acetochloro-compound m. p. 186-187' (Geinspergerp Abstr. 1906 i 57 ; Hardt-Stremayr Abstr. 1907 i 389) from which according to the author silver acetate produces the octa-acetylcellobiose m. p. 191' [u] - 7.5' in chloroform whilst Geineperger obtained an acetate [u] - 30.05' in chloroform and Hrtrdt-Stremayr an acetate [aJD 30.51' ; the discrepancy is inexplicable. I n view of Jungius' experiments on the equilibrium of the penta- acetyldextroses (Abstr.1905 i 573) cellobiose and its two octa-acetyl derivatives have been treated with acetic anhydride and iulphuric acid acetic anhydride and zinc chloride and acetic anhydride and sodium acetate. The last-mentioned reagent does not change either of the octa-acetylcellobioses once it has been formed; with the other two reagents mixtures of the two acetates are obtained containing respectively 84% and 77% of the octa-acetpl compound which has [a] 41.5' in chloroform. The two acetates in the mixture can be separated by cold benzene in which the acetate m. p. 19l0 [a]? -7.7' in chloroform is the more soluble. Evidence is stated which indicates that the octa-acetylcellobiose m. p. 19l0 belongs to the P-Feries.The amorphous by-productp obtained in addition to octa-acetyl- cellobiose by the acetolysis of cellulose have been examined in regard to the content of acetic acid liberated by hydrolysis; the author is of opinion that the products containing 66.3-67*3% of acetic acid are the immediate precursors of the octa-acetylcellobiose. c. s. Action of Water and of Alkali on Cotton Wool Cellulose. CARL C. SCHWALRE and MICHAEL ROBINOFF (Zeitsch. angew. Chem. 19 1 1 24 256-258. Compare Tauss Dingier's Yolyt. JOUY. 1889 2'73 276 ; 1890 276 411).-It is shown that the formation of hydrocelluloses that is compounds with strongly reducing properties under the influence of water occurs only when the cellulose is partly altered; for example filter-paper or strongly-bleached cellulose.With pure cellulose the formation of hydrocellulose is extremely small evenORGANlC CHEMISTRY. i. 181 under a pressure of 20 atmospheres. When a temperature of 150' is reached marked decomposition of the cellulose occurs. The action of dilute sodium hydroxide solutions on cellulose has been studied; the maximum effect at the ordinary temperature is obtained with a 4% alkali solution as shown by the fact that the product after such treatment gives the highest copper values (corrected). At temperatures of 100' and above the solubility increases but diminishes as the concentration of the alkali is increased ; at 150" the solubility is appreciable. The " gum value " has been obtained for f number of samples; by gum value is under- stood the weight of amorphous precipitate obtained by neutralising the alkaline extract.Pure cellulose has a '' gum value " of practically nil whereas impure forms have higher values. At 150' however the differences are small and here i t is also noticeable that the 4% alkali has the maximum effect. I n treatment of cellulose temperatures above 150° and an alkali concentration of 4% are to be avoided. The acid used after bleaching should not be stronger than 0.1% ; with still more dilute acid a purer white is obtained but the amount of oxycellulose is increased. J. J. S. Action of Hydracide on Starch. 11. WILLIAM OECIISNER DE CONINCK (BUZZ. Acad. soy. Belg. 1910 848-849. Compare Abstr. 1910 i 655).-Starch (1.7 grams) water (50 grams) and hydrochloric acid ( 8 c.c.) after being left for seven minutes a t 18.5' and then heated for four minutes gave a reddish-orange precipitate with Fehling'e solution.Hydrobrornic acid (1 -5 c.c.) behaved similarly; hydriodic acid (1 c.c.) produced only a slight although distinct precipitate. After four hours at 17' each acid had acted on starch sufficiently to cause WILLIAM OECESNER DE CONINCK and A. REYNAUD (Bull. Acad. roy. BeZg. 1910 846-847).-A mixture of 0.8 gram of dextrin 40 grams of water and twenty drops of concentrated hydrochloric acid gave a yellow precipitate with Fehling's solution (Cu20,H20) after twenty-four hours at 22'. With hydrobromic acid (twelve drops) the reduction (Cu20) was marked i n five hours; with five drops of hydriodic acid cuprous oxide (CusO) was precipitated after five minutes' or five hours' action.With live drops of hydrochloric acid the precipitate with Fehling's solution was cuprous oxide ; with ten drops it consisted o€ a mixture of cumous oxide and its hvdrate and with slight reduction of Fehling's solution. E. F. A. Dextrin. fifteen drops it was entirely t h i hydrated oxide Cu,O;H,O. ' E. F. A. Formation of Crystalline Polysaccharides (Dextrins) from Starch Paste by Microbes. FRANZ SCHARDINGEB (Centr. Bakt. Par. 191 1 ii 29 188-1 97).-Certain micro-organisms convert starch paste into substances soluble in water closely resembling dextrins. Bacillus rnaceruns renders potato-starch completely soluble arrowroot- starch nearly completely so but has far less effect on rice and wheat starch. Part of the dextrin formed about 25-30% of the starch taken is crystalline the rest being amorphous and gum-like. Two different crystalline dextrins distinguished as a and p have beeni. 182 ABSTRACTS OF CHEMICAL PAPERS.obtained from all four varieties of btarch the a-isomeride pre- dominating. It crystallises in colourlesP hexagonal plates or lancet- shaped needles and is doubly refractive + 128' ; the coloration of the crystalline precipitate with iodine is blue in thin layers when wet greyish-green when dry. The P-isornoride crystallises in reniform aggregates of rhombic crystals [.ID + 136' ; the crystalline precipitate with iodine is a reddish-brown both wet and dry; it sinters and decomposes at 26OC. Both dextrins are precipitated from aqueous solution by alcohol ether chloroform and iodine solution ; they do not reduce Fehling's solution and are not fermented by yeast. E.F. A. Tellurium. ALEXANDER GUTBIER and FERDINAND FLURY (J. pr. Chem. 1911 [ii] 83 145-163. Compare Abstr. 1907 ii 255).- The majority of the results recorded by previous investigators on the tellurichlorides and the telluribromides of the alkali metals and of aliphatic ammonium compounds have been confirmed ; the existence of Rammelsberg's compounds 8KC1,3TeC14 and 8NH4C1,3TeCI4 and of the hydrated potassium tellurichloride described by von Hauer and by Wheeler (Abstr. 1893 ii 457) is denied. The salts described below are irepared by mixing a n excess generally one half to three-quarters of a solution of carefully purified tellurium dioxide in the halogen acid with a solution of the alkali or substituted ammonium halide ; with suitably selected con- centrations the desired salt crystallises more or lees rapidly and is recrystallised from the dilute halogen acid.The tellurium is estimated by Lenher and Homberger's process (hbstr. 1908 ii 426). The salts are characterised by their splendid colour and cryatallise well generally in the regular system. They dissolve without decomposition in a small quantity of water at the ordinary temperature or by gentle warming but are extensively decomposed by even a small excess of water with the separation of tellurous acid. The telluri- bromides are stable in the air. [With H. MICHELER.] -The following salts have been obtained Ammonium tellurichloride is prepared best from dilute solutions and by spontaneous evaporation ; i t crystallises in sulphur-yellow octa- hedra.Trimethylammonium tellurichloyide 2NAle,,H2TeC16 pale yellow needles ; diethylammoniurn 2NHEt2,H2TeCl sulphur-yellow monoclinic crystals ; triethylammonium 2 NEt,,H2TeC16 yellow needles; propylarnmonium 2NH,Pra,H2TeCI yellow rhombic plates ; isopropyl- ummoniuni 2 NH,PrP H,TeCI greenis h-yellow monoclinic plates ; dipropplanzmoniunz 2NHl-'ra2 H2TeC'I 6 yellow rhombic (or te tragonal) crystals ; butplamnzonium 2C4H,*NH2,H2TeC16 long pale yellow needles ; isobutylammonium 2C4H,*NH,,B,TaCI like the preceding salt. Bieth~larnmonium telluribromide 2NHEt2,H2TeBr6 orange-red needles ; triethylammonium 2NEt,-H2TeBr6 orange-red monoclinic crystals ; propylarnmonium 2NH2Pra,H2TeBr6 orange-red plates ; isopropylammonium 2NH2PrP H2TeBr6 oran ge-red t e tragonal needles ; dipropylammonium 2NHPra2,H,'reBr orange-red monoclinic plates ; butylammo?ziunz 2C41S,*N11,,H,'l'eBrG orange-red needles! ; isobutpl- cinzmonium 2C,H,*N H 2,1-12TeBr6 orange-red plates. c.s.ORGANIC CHEMISTRY. i. 183 Salts of Pertitanic Acid with Organic Bases. EDUARD KUROWSKI and L. NISSENMANN (Ber. 1911 44 224-229).-The authors describe the preparation and properties of a number of salts of pertitanic acid with primary and secondary aliphatic amioes. The method of preparation adopted consists in the gradual addition of a mixture of the amine and 30% hydrogen peroxide to titanium trioxide and subsequent precipitation of the salt by the addition of a mixture of alcohol and ether the temperature being maintained at - 10' The salts are all unstable dissolve in water with a green colour and decompose rapidly at the ordinary temperature.They dissolve in dilute sulphuric acid with the formation of hydrogen peroxide. The methylamine salt (NH3Me*O),Ti0,,3H,0 has a yellowish-green colour; when exposed to the air i t forms oily drops and then decomposes with the liberation of carbon. The ethyEcmine salt NH,Et*O-TiO,H,l &H,O is a yellow powder. The propylamine salt 2NH3Pr~~O*Ti0,H,H,02,ZH,0 has a yellowish-green colour; a second less stable salt has also been obtained. Of the salts with secondary aliphatic amines only the diethyZcrnine salt 2NH,Et2-O*Ti0,H,H202 1 4H20 was obtained in a pure condition ; it is a yellow powder. The dimethylamine and dipropylamine salts so readily decompose that their composition has not been determined.Attempts to prepare salts of pertitanic acid with tertiary amines and also with aniline were upsuccessful. to - 15'. F. B. Ruthenihalides. ALEXANDER GUTBIER [with G. A. LEUCHS] (Ber. 191 1 44 306-308).-The following compounds were prepared according to a method previously described (Abstr. 1907 i 289) Z'riethylcmmoniurn ruthenicldoride (NHEt3),RuCI fcrms large broad blackish-red plates. Triethylammonium ruthenibromide ( NHEt3)2RuBr6 crystallises in large black plates. is0 Propylammonium ruthenichloride (N €13PrP),RuC1 forms glistening dark greenish-brown or black needles. isoPropylnm.monium ruthenibronzide (NH,PrP),RuBr is obtained in dark bluish-black needles. n-Butylammoniunz rutheni- chloride (C,H,*NH,),RuCI forms dark greenish- brown glistening needles.n-Butylammoniunz vuthenibromide (C,H,*NH,),RuBr forms deep bluish-black needles. Benzylammonium ruthenichlode crystallises in greenish-brown slender needles. Benxylammonium ruthenibromide (C7H7*NH,),RuBr forms black felted needles. Pyridinium ruthenachloride ( C,H,N),RuCI forms brown needles Pyridinium ruthenibromide (C,H6N),RuBr6 crystallises in light bluish-blsck needles. a-Picolinium ruthenichloride ( C,NH,Me),RuCl is obtained in small bronze-coloured leaflets. a-Picolinium mtheni- bromide (C,N H,&le)&u Br forms s h ini ng bluish - black needles. ( C p *N H,),RuCI 6 T. s. Y.i. 184 ABSTRACTS OF CHEMICAL PAPERS. Labile Hydrated F o r m s Fixed by means of an Organic Base.GIUSEPPE A. BARBIERI and F. CALZOLARI (Atti R. Accad. Lincei 1910 [v] lQ,ii 584-590).-The authors have acted on various metallic salts in aqueous solution with hexamethylenetetramine and on the hypothesis that this substance combines with hydrates already exist- ing in t.he solution the composition of the solid substances which separate yields information as to the nature of the hydrates in question (compare Kurnakoff Abstr. 1898 ii 475). The following facts accord with the supposition that the hexamethylenetetramine is not united with the metallic atom but is added t o the molecule of the hydrated salt present in the solution (1) anhydrous cobalt chloride forms with hexamethylenetetramine a compound in which the base is attached to the metal and t h i s compound is blue; (2) a compound (AcONa,3H,0),C,Hl,N4 exists and it is not probable that the base could be attached to sodium; (3) with salts which usually are an hydrous or give hydrates containing little water hexamethylene- tetramine compounds are obtained which contain little or no water. The compounds described are therefore to be regarded as amines of hydrated salts. The following compounds are prepared by acting on concentrated (20%) aqueous solutions of the chlorides bromides and iodides of magnesium manganese cobalt and nickel with concentrated aqueous solutions of hexamethylenetetramine (2-4 mols.).They form large measurable crystals which are not deliqiiescent. The tendency to effloresce in contact with dehydrating agents is greatest in the case of the chlorides least with the iodides which are stable to air and light. I n solution the manganese derivatives gradually deposit manganous hydroxide. The compowmd MgCI2,1OH,0,2C,Hl,N4 Forms colourless transparent tabular crystals belonging to the triclinic system (holo- symmetric) The compound MnC1,,10H20,2C,H,,N4 forms minute crystals of a pale flesh colour.The compound CoCl,,10H,0,2C,H,,N4 crystal- lises i n reddish-violet laminae which in contact with phosphoric oxide lose all their water and become intensely blue. NiCl 1 OH,O 2C,Hi2N4 crystallises in green laminq which on dehydration in an oven become first yellow then violet. The compound MgBr 1 OH& 2C,H12N4 forms plates which are almost square; they belong to the monoclinic system (holosymmetric) [a b c = 0.9022 1 0.51 11 ; p = 90’40’1.The compound MnBr 10H,0,2C,H,,N4 forms almost colourless crystals. The compound CoBr 1 OH20,2C6Hl2N4 forms reddish-violet crystals. The conipound NiBr 1 OH,O 2C,HI,N crystallises in green laminae. The compound MgI 10H20,2C6H12N4 forms long colourless trans- parent crybtals which belong to the monoclinic system (holosym- metric) [a b c = 0.8802 1 0-495 ; /3 = 90’1’1. MnI,,l OH20,2C6Hl,N4 is a white powder. The compound CoI 10H,0,2C,H,2N-4 forms rose-coloured tabular crystals. ‘J’he compou?zd NiI 1 OH20,ZC6H,,N4 [ ~ c b ~ = 0 . 8 3 2 1 1 :0*8573; a=125’43’ p=50°21’ y=I23’56’]. The compound The cornpound,ORGANC CHEMISTRY. i. 185 forms emerald-green crystals. I n some cases where the analytical results do not permit of the exact determination of the amount of contained water the question can be settled from relations of isomorphism and power to form mixed crystals which exist between many of the substances.The crystallographic measurements were executed by E. Billows. MOTOOKI NATSUI (Mem. Coll. Xci. Eng. Kyoto 1910 2 397-400).-1n the alkylation of amides silver oxide may be replaced by cuprous oxide lead oxide or anhydrous potassium carbonate. When a mixture of acetamide and ethyl iodide is heated for three to four hours on the water-bath with one of these substances ethyl imino- acetate is produced. Benzamide under the same conditions yields ethyl iminobenzoate. It is therefore highly probable that in alkylating with silver oxide and an alkyl iodide the silver oxide accelerates the reaction merely by the removal of the hydriodic acid produced and not by the inter- mediate formation of a silver derivative (compare Lander Trans.1900 77 729). The author considers it probable that the formation of imino-esters by the action of methyl sulphate on amides is due to the direct alkylation of the enolic form NH:CR*OH and not to the addition of methyl sulphate to the ketonic form as suggested by Buhner (Abstr. 1904 i 882). F. B. R. V. S. Alkylation of Acid Amides. Formation and Decomposition of Calcium Cyanamide. MAX LE BLANC and M. ESCHMANN (Zeitsch. Elektrochem. 1911 17 20-34).-1t is shown that the reaction CaC + N2 ZZ CaCN + C is reversible. The equilibrium pressure of nitrogen however is dependent on the quantity of nitrogen which has been taken up by the carbide.Measurements of the pressures are made at 1200' and 1300'. After almost saturating a quantity of carbide with nitrogen successive quantities of nitrogen are removed from it by diminishing the pressure and the corresponding equilibrium pressures are measured ; the quantity of combined nitrogen is then increased by adding fresh nitrogen and the pressures again measured The two curves do not agree with each other the pressure corresponding with a given per- centage of combined nitrogen constantly decreases with the duration of the experiments ; apparently the cyanamide becomes more stable. A careful chemical examination of the reaction shows that the reversible formation of calcium cyanamide is really the reaction being observed but the calcium cyanamide gradually volatilises out of the mixture and condenses in the cooler parts of the apparatus where it can no longer decompose partly owing to the lower temperature and partly owing t o the absence of carbon.T. E. Some Solid Ammoniates. CARLO GASTALDI (Gazxetta 19 10,40 ii 475-481).-W hen a concentrated aqueous solution of potassium ferricyanide is added t o an ammoniacal solution of silver nitrate a fine-grained deep red crystalline precipitate is deposited which has thei. 186 ABSTRACTS OF CHEMICAL PAPERS. composition 2[Ag3Fe(CN),],5NI€,. By varying the conditions the substance can be obtained as an amorphous flocculent precipitate or by dissolving freshly precipitated silver ferricyanide in ammozia and evaporating the solution a t the ordinary temperature in large crystals.I n all cases the composition is the same. When the ammonia is re- placed by methylamine or ethylamine methyl- and etl&!-ammoniates of similar composition are obtained. The qualitative test for the ferricyanic radicle may be masked by the presence of simple cyanides in a solution under investigation. If aluminium and hydrochloric acid are added to theliquid however the production of a coloration with an iron salt will indicate the presence of a ferricyanide for in these circumstances the formation of the complex from a cyanide and the iron salt cannot occur R. V. S. Action of Hydroxylamine on Nitrosochlorid es and Nitro- sates. 111. ap-Amylenehydroxylamineoxime and Derivatives. GUIDO CUSMANO (Gazxetta 1910 40 i 525-536.Compare Abstr. 19 10 i 86 3).-~-Hydrox~~lamino-~-mmethylbutan-y-oneoxime (amylene- hydroxylamineoxime) OH*NH*CMe,-CMe NOOH is prepared by sus- pending amylene nitrosate in a mixture of methyl alcohol and ether containing hydroxylamine (2 mols.). The reaction commences on warming and then proceeds spontaneously. After removal of the solvent the residue is dissolved in a little water and treated with sodium carbonate to dissolve the hydroxylamine nitrate present and from the solution P-hydroxylamino-p-methylbutan-y-oneoxime crystal- lises out on cooling. It forms rhombohedra or laminar hexagonal prisms m. p. about 112O (previously softening) and reduces Fehling's solution readily in the cold. The hydrochzoride C,H1,02N,,HCI forms clusters of crystalline leaflets m.p. 125-130' and are very deliquescent. The nitroso-oxime is obtained as an oil of a blue tinge by oxidising the hydroxylamino-oxime with the calculated quantity of permanganate. The p-nitrobenzylidene derivativo OH*N:C,H,*N-C*C,H,*NO (from p-nitrobenzaldehyde) forms pale yellow hexagonal laminae m. p. about 187". P-Hydroxylamino-P-methylbutan-y-oneoxime reacts readily with nitrous acid yielding P-nitrosohy droxy lamino-p-met h y I but an- y-oneoxime OH*N(NO)*CMe,*CMe:N*OH which is a very stable substance crystal- lising in long colourless needles m. p. 81-82O. It does not reduce Fehling'spolution but yields a bluish-green coloration with a solution of phenol in sulphuric acid. It can be boiled with water without suffering decomposition but it is readily decomposed by dilute acids even in the cold.It dissolves in sodium carbonate with effervescence and the solution on concentration yields the sodium salt of the isonitroamine. The isonitroamine can displace nitrous acid so that this sodium salt can be prepared by mixing concentrated solutions of hydroxylamino- oxime and sodium nitrite in the presence of a little sulphuric acid. It crystallises with 3H,O which i t loses a t 116'. The anhyd~ou8 salt C,H,,O,N,Na has m. p. 130' (decomp.). P-Hydroxylamino-/3-methylbutan-y-oneoxime when kept in an alcoholic ethereal solution saturated with hydrogen chloride eventually deposits '0' It dissolves in alkalis producing a red coloration.ORGANIC CHEMISTRY. i. 187 a hydrocldoride C,Z~,,O,N,HCl in tufts of long scicular crystals m.p. 145” (decomp.) which are not deliquescent. On treatment with sodium carbonate a base is obtained crystallising in long colourless prisms m. p. 96-98’. This base readily reduces Fehling’s solution in the cold. To i t is ascribed the constitution of p.~~ydroxylamino-P-metJ~~l- butawy-one OH*NH*CMe,*COMe and this is confirmed by the exrst- ence of a p-nitrobenzylidene derivative C H 1104N2 which crystallises in yellow rectangular tablets decomposing a t 176”. Jf hydroxylaminoruethylbutanoneoxime is dissolved in concentrated alkali and the solution after some days is treated with carbon dioxide a precipitate is obtained from which two substances can be isolated. One crystallises in small colourless prisms m. p. 96-looo and from its composition and proper ties is P-?~ydi.oxy-P-~1.LetT~yl~utan-y-oneoxifme OH-CMe,*CMe:NOH.The other compound forms long colourless prisms m. p. 184’ (decomp.). To explain the differences between the hydroxylamino-oximes of pinene and amylene arid that of limonene it is suggested t h a t the two first being saturated compoimds exist solely or chiefly as trans- forms whilst the unsaturated limonene compound can also assume the labile cis-form. R. V. 8. Unsaturated Lead Alkyls. JULIUS TAFEL ( B e y . 19 11 44 3 2 3-3 3 7). -In his electrolytic experiments on organic substances with mercury or lead cathodes the author has frequently observed the formation of small quantities of oily products ; with lead cathodes the oil is red. A t his suggestion Renger (following abstract) has studied the formation of these oily products and has obtained the red oil in larger quantities from acetone; he considers that it consists essentially of lead tetra-isopropyl since lead di-isopropyl dibromide is produced from it by the action of bromine.Since the lead tetra-alkyl compounds are colourleas and the formation of a di-alkyl compound from a tetra-alkyl has hitherto been unknown the author has extended the investigation of these oils. The apparatus consists of a glass cathodic vessel shaped like a separating funnel and provided with a closely fitting lead cover through apertures in which are fitted a thermometer an inlet-tube for the delivery of carbon dioxide into the cathodic compartment and the porcelain anodic eell. The cathode consists of six strips of lead and the anode of a lead cylinder.The anodic liquor is 20% sulphuric acid ; the cathodic solution is a mixture of 20% sulphuric acid and acetone (in the case of higher ketones a little alcohol must also be added). The temperature is kept at 45-50° and the cathodic current density at about 0.5 amp./sq. cm. During the experiment tho cathodic solution is well agitated by a current of carbon dioxide and the red oil collects together with a white precipitate at the bottom of the vessel. It is run out into an apparatus (figured and described) in which it can be washed with dilute potassium hydroxide and with water dried over sodium sulphate and filtered all of the operations being performed with the exclusion of air. The purified product is a viscous oil with the colour of bromine and an unpleasant odour.It loses its red colour rapidly in the light leaving a golden-yellow oil consistingi. 1.88 ABSTRACTS OF CHEMICAL PAPERS. chiefly of lead tetraisopropyl. When rapidly heated the red oil decomposes a t 150' with separation of finely divided lead ; it deconi- poses at S 5 O in a vacuum. I n contact with oxygen the oil becomes coated with a yellowish-brown strongly alkaline skin. When a solu- tion of the red oil in an indifferent solvent is treated with oxygen it acquires a pale yellow colour and after filtration contains lead tetra- isopropyl and lead di-isopropyl oxide; the latter is extracted with dilute acetic acid and is isolated in the form of lead di-isoprupyl dibrornide PbPrpBr2. This salt which crystallises in felted needles and decomposes when kept even in darkness is also obtained by carefully treating the red oil in well-cooled ether or ethyl acetate with bromine until the latter only slowly disappears.The corre- sponding dichloride dinitrate and chromate are described. When the oxidised filtered solution of the red oil is distilled at 40' in a vacuum and the yellowish residue which exhibits the properties of lead tetra-isopropyl is triturated with concentrated hydrochloric acid lead iri-isopropyl chloride PbPrPCl is obtained. It has a very unpleasant odour is more volatile with steam and is less stable than the dichloride. The corresponding iodide is described. The author is of opinion that the red oil consists essentially of lead tetra- isopropyl together with about 20% of lead di-isopropyl to which the colour is due.Pure lead tetra-isopropyl has hot been obtained on account oE its great instability but the behaviour of lead tetra-ethyl is quite analogous to that of the red oil mentioned above; thus with bromine (1 mol.) in well-cooled ether or ethyl acetate i t yields lead triethyl bromide P bEt,Br which crystallises in large colourless needles and has an unpleasant odour; with 2 mols. of the halogen lead tetra-ethyl yields lead diethy2 dibpomide PbEt,Br2 the properties of which are quite analogous to those of the di-isopropyl dibromide. c. s. Lead Alkyl Compounds from Methyl Ethyl Ketone and Diethyl Ketone. GEORG RENGER (Ber. 1911 44 337-33s. Compare preceding abstract). -The electrolytic reduction of methyl ethyl ketone and of diethyl ketone (in the presence of alcohol) at lead cathodes proceeds in a manner quite analogous to that of acetone.The resulting red oils have been characterised by chlorination and bromination in chloroform or ether whereby the following salts which are even more unstable than the isopropyl compounds have been obtained. Lead tri-sec. -butyl chloride Pb(C,H9),Cl forms pale yellow needles has an unpleasant odour and melts and suddenly explodes at about 1 30° when heated rapidly. Lead di-sec.-butyl bromide crystallises in yellow needles. Lead di-y-arrql dibromide Pb( C,H,,),Br2 obtained from the oil from diethyl ketone forms extremely unstable Pb( C4H9)2Br2 brownish-yello w crps tals. c. s. Constitution of Copper Acetylide. 11. JOHAN-NES SCHEIBER and HANS RECKLEBEN [and in part K.STRAUSS] (Brvr. 1911 44 210-223. Compare Scheiber Abstr. 19OS i 933).-Further experi-ORGANIC CHEMISTRY. i. 189 ments have confirmed the existence of coppsr acetylide in the hydrated form C,Cu2,E20 and in the anhydrous form C,Cu,. The fact that when the acetylide is decomposed by mild chemical reagents for example hydrogen sulphide and' potassium cyanide quantitative yields of acetylene are obtained points to the conclusion that its constitution must be closely related t o that of acetylene. No indication of the conversion of the hydrate into an aldehyde derivative has been observed either by leaving in contact with water or ammonia by drying or under the influence of substances which mpy be present during its formation. The structural formulae of the compounds depend on that of acetylene.According to Nef's schenie the anhydrous compound would be Cu,C:C and the hydrate Cu,C:C-**OH,. The black carbonaceous material usually obtained when copper acetylide is decomposed is shown to be due to oxidation; if oxygen or oxidising substances are excluded during the preparation and decom- position of the acetylide no carbonaceous residue is obtained. IF on the other hand the water used contains dissolved air or i F the pure car- bide is heated in an atmosphere of carbon dioxide at looo or if oxidising agents such as cupric or ferric salts are used for washing the acetylide appreciable amounts of black residue are obtained (compare Soder- biturn Abstr. 1897 i 309). Analyses of the carbonaceous compound agree with the formulae (CllH60Jx for the product when dilute hydro- chloric acid is used and (C11H603)2 for the product when Concentrated acid is used.Tbe detection by means of acetylene of copper in solutions of ammoniacal cupric salts reduced by means of hydroxylamine can be carried out at a dilution of 1 in 1,100,000 or in the presence of large quantities OF ammonium acetate or tartrate of 1 in 200,000. J J. S. Sulphonation of Banzene. ROBERT BEIIREND and MARTIN MEKTELSMANN (Annalen 19 11 3'78 352-365).-The sulphonation of benzene by pure concentrated sulphuric acid at 240-250° results almost exclusively in the formation of the m-disulphonic acid less than 1% of the para-isomeride being produced after one and a-half- hours' heating. The addition of a little mercury causes the formation of the m- and the p-disulphonic acids in the proportion 2 1 ; ferrous sulphate acts similarly about 10% of benzene p-disulphonic acid being produced.The two acids are readily separated in the form of their sodium salts since sodium benzene-p-disulphonate is practically insoluble in a concentrated solution of sodium benzene-m-disulphonate. The two acids are interconvertible by heating with concentrated sulphuric acid and a little mercury a t 240-250° an equilibrium mixture of about 2 parts of the m-disulphonic acid and 1 part of the para- isomeride being formed; the same result is attained but extremely slowly in the absence of the mercury. The sodium salts of both acids by treatment with pure concentrated sulphuric acid a t 240-250" are converted into benzene-1 3 5-tri- sulphonic acid which is also formed to some extent by heating benzene VOL.c. i. Pi. 190 ABSTRACTS OF CfiEMZCAL PAPERS with concentrated sulphuric acid and potassium pyrosulphate at 240-250'. c. 5. Action of Strong Tertiary Bases on Sulphonyl Chlorides. EDGAR WEDEKIND and D. SCHENK (Ber. 191 1,44,198-202).-Triethyl- amine reacts with sulphonyl chlorides when dissolved in indifferent solvents for example benzene provided a hydrogen atom is attached to the a-carbon atom with respect to the sulphonyl group Hydrogen chloride is eliminated as in the case of the chlorides of carboxylic acids (Abstr. 1906 i 437; 1909 i 459) but the phenylsulphens for example CHPh:SO cannot be isolated. With benzylsulphonyl chloride stilbene is obtained by the elimination of sulphur dioxide and the union of the two CHPh groups.The chlorides of aromatic sulphonic acids do not react with tertiary bases. DiphenyZmethanesuZphonic acid CHPh,*SO,H 1 *5H20 crys tallises from benzene in hygroscopic needles m. p. 94-96'; when fused with potassium bydroxide i t yields p-hydroxydiphenylmetbane (Trans. 1882 41 34) and when heated with water a t 240' for eight hours i t yields diphenylmethane. The acid chloride has not been prepared. Sodium sulphite solution and w-chlorodiphenylmethane at 120-1 25' yield benxhydrol ethev C,,H,,O m. p. 109'. Phenanthrene-2-sulphonic Acid and Some of its Deriv- atives. H ~ K A N SANDQVIST (Annalen 191 1 379 79-90).-The phenanthrene-2-sulphonic acid used in the experiments is obtained in the form of the potaesium salt from the by-products of the sulphonation of phenanthrene by Kunz's process.The acid is prepared from the acid chloride and water at 130-135' from the barium salt and sulphuric acid or from the lead salt and hydrogen sulphide. The acid contains H,O has m. p. about 150° and is freed from its solvents only with difficulty ; its electrical conductivity does not differ much from that of the 3-sulphonic acid (Abstr. 1909 i 779). The following salts are described the solubilities being expressed as before (Zoc. cit.) potassium (4H20) sol. 0.273 ; ammonium sol. 0.37 ; sodium (&H,O) white leaflets or needles sol. 0.42 ; caZcium sol. 0.024 ; barium (4H20) sol. 0.016 ; magnesium (6H20) elongated leaflets sol. 0.051 ; zinc (6H,O) sol. 0.083 ; ferrous (5H,O) sol.0.044 ; lead (H,O) sol. 0.014 ; copper (H,O) bluish-green crystals sol. 0.25 ; siZver sol. 0.099. Phencc?zthrene-2-sulphonyZ chloride obtained from the potassium salt and phosphorus penta- chloride has m. p. 156' is oxidised by acetic and chromic acids to phenanthruquinone - 2 - sulphonyl chloride yellow leaflets or needles m. p. 245-246O (decomp.) and forms a sulphonamide m. p. 253-254' and sulphonanilide C,,H9*S0,*NHPh m. p- 157-1584 by the usual met hods. Methyl phenanthrene-2-sulphonate is dimorphous the stable modifi- cation forming rhombic plates the labile modification leaflets. The fact that many derivatives of phenanthrene have two m. p.'s may be due to dimorphism ; the preceding ester crystallised from methyl alcohol has m. p.92.5-93' and 101*5' whilst in a capillary tube the m. p. is either 85O 98' or 101-5°. By oxidation with chromic J. J. S.ORGANIC CHEMISTRY. i. 191 and acetic acids the ester yields methyl ~,~~P,naizlhi.~quinone-S-sul~?~on- ate yellow leaflets 1x1. p. 196-197' or elongated leaflets m. p. 192-1 92.5'. Ethpl phenaiztfirene-21-szllp~~onate has m. p. 88.5'. c. s. An Organo-metallic Compound of the Aniline Series. E. RATTENBURY HODGES (Chem. News 1910 103 52).-Sy slow addition of zinc chloride sdution to a saturated aqueous solution of aniline slender colourless highly refractive crystals of a compound of zinc chloride with aniline chloride mere obtained. ALEXANDER GUTBIER [with P. WALBINGER] (Ber. 191 1 44 308-3 12).-The following osmichlorides were prepared by interaction of sodium osmichloride (Abstr.1910 ii 45) and aryl substituted ammonium chlorides. They were purified by rscrystailisa- tion from dilute hydrochloric acid ; the aqueous sultitions undergo decomposition. PllLenylammonium osmichlogide (N K,Ph),OsCl forms brownish-red rhombic leaflets. Yhen ylrnethylc6mmonium osmichloride ( NH3MePh),OsCl6 forms brownish-red monoclinic crystals showing pleochroism. 0- TolyZ- ammonium osmichloride ( C,H,Me*NH,),OsCI is obtained in yellow or brownish-red rhombic needles which are pleochroic. m-l'olyl- ammonium osmichloride forms slender pleochroic brownish-red rhombic needles. p-Tolylarnmonium osinichlorzde crystallises in yellowish-red rhombic pleochroic leaflets. 0-4-X~Zylnmmonium osmichloride forms shining red monoclinic needles.m-4-Xyl~lammonium osmi- crllloride forms strong pleochroic ruby-red rhom bic crystals. p-5- Xylylammonium osmichloride is obtained in red rhombic pleochroic needles Pyridinium osmichloride (C,H,N),OsCI forms red rhomhic plates. a-PicoZinium osmichloride (C,NH,Me),OsCI forms yellowish- red rhombic leaflets. Quinoliniurn osmichloride (C,NH,),OaCI is obtained in yellowish-red feebly pleochroic monoclinic needles. Berrxyl- ammonium osmicltloride ( C7H7-NH,),0sC16 forms brownish-red mono- clinic plates. a-Nap~ithyZc6mmonium osmichloride (C,oH,*NH3),0sCI crystaliises in brownish-red pleochroic rhombic needles. P-Xaph- thylc6mmonium osmicldoride forms brownish-red pleochroic rhorn bic leaflets T. s. P. Lactyl Compounds of Primary Aromatic Amines. KARL ELBS (J.p ~ . Chem. 1911 [ii] 83 1-21) [with K. SINNER.]-The Iactylation of several primary aromatic amines has been studied quantitatively a t about 100' by heating mixtures of the amine and lactic acid with or without water in a water-bath and titrating the unchanged acid after definite intervals of time phenolphthalein being used as indicator. I n the experiments without water the lactate of the amine is used. The results which are expressed graphically show t h a t the formation of the lactyl compound is retarded by the presence of water but is facilitated contrary to Menschutkin's experience in the case of acetanilide by using an excess of the amine (p-toloidine). N. c. Osmichlorides. The salts are all anhydrous and stable in the air. ( C,H,Me2NH3),0sC1 23 21.192 ABSTRACTS OF CHEMICAL PAPERS. The lactylation of different amines under the same conditions namely 1 mol. OF base 1 mol. of acid and 1.66 mols. of water a t loo' shows that the reactivity of the amino-group in aniline is affected slightly by the presence of a methyl group in the para-position considerably and unfavourably by methyl in the ortho-position and favourably by the ethoxy-group in the para- and still more so in the ortho-posi tion [With FR. M~~~E.]-~actophenin in glacial acetic 'acid at 0" is converted by nitric acid D 1 *40 into 2-nitro-4-ethoxylactanilide (2-nitrolactophenin) OEt-C,H,(NO,)*NH*CO*CHMe*OH yellow needles or leaflets m. p. 1 1 2 O the position of the nitro-group being determined by the fact that the substance and nitrophenacetin give the same nitrophenetidine by hydrolysis.Nitric acid D 1-40) converts powdered lactophenin into 2 6-dinitroethoxyZactani2icle yellow needles or leaflets m. p. 1 3 5 O which yields the known dinitrophenacetin by hydrolysis and treatment oE the product with acetic anhydride. Concentrated sulphuric and nitric acids a t 0' convert dinitrolactophenin into the nitrate OEt*C,H,(NO,),*NH+CO* CHMe* ONO yell0 w leaflets m. p. 19 2 O {decomp. ) which yields dini trop henet idine amongst other pro- ducts by hydrolysis with dilute alcoholic potassium hydroxide. [With A. ScHusTE~.]-3-~itro~acto-p-to~u~d~de NO,* C,H ,;Me*NH* GO* CHMe* OH yellow needles m. p. 86-87' obtained from an acetic acid solution of lacto-p-toluidide and nitric acid D 1 *48 at Oo yields 3-nitro-p-toluidine by hydrolysis.3 5-D.initroZucto-p-toluidide yellow needles m. p. 139-1 10° obtained from the preceding compound and concentrated nitric and sulphuric acids at Oo yields 3 5-dinitro-p-toluidine by hydrolysis. The nitrate C,H,Me(NO,),'NH*CO*CHMeoONO~ white needles decomp. 1 60° obtained from lacto-p-toluidide and concentrated sulphuric acid and nitric acid D 1-48 a t Oo also yields 3 5-dinitro-p- toluidine by hydrolysis. Owing to the ease with which lactotoluidides are hydrolysed even by dilute alkali the electrolytic reduction of 3-nitrolacto-p-toluidide must be effected in an approximately neutral solution which is slightly alkaline in the immediate neighbourhood of the cathode. Even then the reduction does not proceed smoothly for with an anodic liquid consisting of cold saturated sodium carbonate and a cathodic solution of acetic acid and sodium acetate and a cathodic current density of 3-3.5 amperes per sq.dcm. the nitrolactotoluidide yields a number of products from which 3 3'-axoxylacto-p-toluidide ON,( C6H3Me NH COO CHMe. OH) yellow needles or leaflets m. p. 234' (decomp.) is isolated. By hydrolysis by dilute alcoholic potassium hydroxide it yields 3 3'-azoxy- p-tohidine red needles m. p. 18S0 which is converted by electrolytic reduction in sulphuric acid into the sparingly soluble sulphate of 3 4-tolylenediamine. The electrolytic reduction of 3-nitrolac to-p-toluidide in acid solution by Boehringer's process yields amongst other pro- ducts acetaldehyde and 40 -60% of 5-methyZbenziminaxolone C,H3Me<g>CO white crystals rn.p. 292-295O (acetyl derivative m. p. 1 7 6 O ) thoORGANIC CHEMISTRY. i. 193 constitution of which is proved by the formation of the same substance from 3 4-tolylenediamine and carbamide. [With F R . METTE and A. SCHUSTER.]-The electrolytic reduction of 2-ni troet hox ylac tanilide in approximately neu t ral (cathodic) solution at the b. p. yields 2 2'-axoethoxyZactaniZide N,[C,H,(OEt)*NH*CO*CHMe*OH] yellowish-red needles m. p. 269" in 15-20% yield. By hydrolysis the azo-compound yields axo-p-phenetidine m. p. 143O which forms an acetyl derivative m. p. 3 0 6 O identical with the azophenacetin obtained by the electrolytic reduction of nitrophenacetin. The electrolytic reduction of 2-nitroethoxylactanilide in acid solution yields acetaldehyde several unidentified products one of which has m.p. 161" and ethoxybenziminazolone (Cohn Abstr. 1899 i 944) the diacetyl derivative of which has m. p. 163O. c. s. The Solubility of Sodium Picrate in Solutions of Sodium Salts. WOLDEMAR FISCHER and P. MILOSZEWSKI (CAem. Zentr. 1910 ii 1048 ; from Kosmos 19 10 35 Radxisxewski-Pestband 638-542). -The solubility of sodium picrate in aqueous solutions of sodium carbonate chloride sulphate phosphate nitrate bromide and hydr- oxide of various strengths at 25' was determined. The measurements have proved that contrary to the statement of Reinhard (Zeitsch. anal. Chern. 1910 49 269) the solubility of sodium picrate is lowered by the presence of the sodium ions in accordance with the law of mass action. N. C. New Derivatives of Indene.VICTOR GRIGNARD and CHARLES COURTOT (Compt. rend. 191 1 152 272-274).-0rgano-magneeium bromides act on indene giving rise to a sparingly soluble magnesium indenyl bvomide O H < $ ~ ~ C H * M g S r . When treated in the usual way this yields the two following compounds 1-Indenol C,H,P yellow prisms m. p. 57-58" b. p. 140"/10 mm. with partial dehydration. Indene - 1 - carboxylic acid CH<$g$CH*CO,H chamois-coloured prismatic needles m. p. 16 lo. Magnesium indenyl bromide reacts with fluorenone at 120" to give a theoretical yield of tert.-1-indenyZfEuorenol (I) fiH*Q6H4 7 H - fiH*?BH4 CK*CH*CPh,*OH e ti 4>C,H C H CH- C( OH) (1.1 (11.) This compound crystallises in colourless needles m. p. 151-152". I n the same way benzophenone gives 1-indenyldipheicylcnrbinol (IT) a substance occurring in pale yellow tablets m.p. 131-132O. A portion of the carbinol undergoes dehydration during the preparation forming dipphenylbenzfulvene CH<$::>C:CPh orange-yellow Anthracene. I. Anthranol and Anthraquinol. KURT H. RIEYER (Annalen 191 1 379 37-73).-Dimroth's dianthrone and spangles m. p. 1 1 1-1 12O. w. 0. w.i. 194 ABSTRACTS OF CHEMICAL PAPERS Meyer’s diantbranol (Abstr. 1909 i 168) which sre stable separately not only in the solid state but also in solution and are mutually interconvertible only by energetic chemical means are distinct isomerides not tautomerides of the enol-keto- type claimed by Thiele and by Baly for phenols of the benzene series. I n the present paper the author shows that the monohydric and dihydric meso-phenols of the anthracene series anthranol and anthraquinol can each exist in two stable desmotropic forms.The substance long known as anthranol reacts sometimes as a phenol sometimes as a ketone ; it is colourless completely insoluble in cold aqueous alkalis and its solutions generally are non-fluorescent. When its 5-10% solution in boiling sodium hydroxide is cooled rapidly to -5’ and treated with cold 5% sulphuric acid a new substance C,,H,,O is obtained which crystallises in brownish-yellow leaflets is easily soluble in cold aqueous alkalis and forms solutions with an intense blue fluorescence; it sinters at 120° and melts completely at about l5Zo but when placed in a bath previously heated to 130° it melts at once. This substance is called anthranol the name anthrone being reserved for the older substance.Anthranol changes into anthrone by keeping in a desiccator. The two substances attain a state of equilibrium when fused or dissolved the change being easily followed by the formation or the disappearance OF the blue fluorescence. Since both substances separately are stable for a long time in alcohol iti is possible to answer the question whether the activity of phenols is due to the enolic or to the keto-modification. I n cold alcohol anthrone is not attacked by iodine bromine ferric chloride or amyl nitrite ; on boiling however,. particularly in solvents which cause a rapid transformation of anthrone into anthranol reactions occur. I n cold alcohol anthranol is attacked a t once by bromine or iodine and is oxidised to dianthrone by ferric chloride; also amyl nitrite in benzene at the ordinary temperature oxidises anthranol t o dianthrone ; dianthranol is never produced not even when anthranol ia oxidised by alkaline potassium ferricyanide. An alcoholic solution of anthranol at 25’ couples readily with p-nitroantidiazobenzene hydrate to form Kaufler and Suchannek’s anthraquinone-p-nitro- phenylhydrazone ; under similar conditions anthrone does not couple ; also nitrosodimethplaniiine condenses with anthranol but not with anthrone in alcoholic solution.Thus the reactivity of the hydroxylic modification supports Dimroth’s results in connexion with the reactivity of enol-keto-tautomerides in the aliphatic series (Abstr. 1907 i 662). As is well known anthraquinol (oxanthranol) obtained by reducing anthraquinone with zinc dust and alkali forms brown leaflets dissolves in cold aqueous sodium hydroxide to form a red disodium salt yields solutions with an intense green fluorescence and is rapidly oxidised to anthraquinone by iodine bromine or oxygen; its dibenxoate has m.p. 2 9 2 O and is non-fluorescent. Consequently oxnnthranol is the true anthraquinol C,H,<F(OH)>C,H,. It cannot be readily transformed into the keto-modification oxanthrone O H )ORGANIC CHEMISTRY. i. 105 C H 4 < ~ ~ ~ ~ > C 6 H 4 which is readily obtained however by \ I hydrolysing bromoanthrone (Goldmann’d bromoanthranol) by boiling 50% aqueous acetone (see also following abstract). Oxanthrone m. p. 1 6 7 O forms yellow almost colourless needles gives colourless solutions which are non-fluorescent and are not attacked by oxygen iodine or bromine in the cold is easily reduced t o anthranol by zinc dust and acetic acid (anthraquinol is not reduced) and is unchanged by cold aqueous alkalis. Boiling alkalis convert oxanthrone into anthraquinol.The two substances can be fused withqut changing the one into the other. Also i n boiling solvents they are for the most part unchanged ; the addition of a catalyst however such as hydrogen chloride or sodium acetate t o the alcoholic solutions causes an almost complete change of the oxanthrone into anthraquinol. Oxanthvone acetate c~H4<CII(OAc)>C~H4 nl. p. 108° is obtained from bromo- anthrone and potassium acetate in hot glacial acetic acid ; the action of acetyl chloride on oxanthrone i n pyridine yields Liebermann’s anthraquiny 1 diacet ate.Meisenheimer’s methoxganthrone C H 4 < ~ ~ ~ ~ & ; > C 6 H 4 ob- tained by boiling bromoanthrone with methyl alcohol is partly converted by boiling alcohol and hydrochloric acid or by luke-warm dilute sodium hydroxide into anthraquinyl methyl ether -co- C H 4 < X ~ ~ ~ ~ > C H 4 m. p. 1 6 4 O which is also obtained by shaking an alkaline solution of anthraquinol with methyl sulphate filtering in hydrogen aud extractiog the filtrate with ether in an atmosphere of carbon dioxide. The ether forms an ucetute m. p. 1 7 4 O and a bmzzoate m. p. 2 2 1 O separates in stout brown crystals yields solutions with a bluish- green fluorescence and dissolves i u cold alkalis forming reddish- yellow solutions which are easily oxidieed by iodine bromine or oxygen to anthraquinone and 9 9‘-dimsthoxydianthrone C O < ~ ~ ~ ~ > C ( O ~ ~ ~ ) * C ( O ~ ~ ~ ) < ~ ~ > C O 0 4 C(0Rle) m.p. 202” obtained as a by-product in the reaction between anthra- quinol and methyl sulphate forms colourless plates with a blue fluorescence; its solutions also are fluorescent and are not attacked by iodine or bromine in the cold. Anthraquinyl diethyl ether m. p. 148O obtained from antbraquinol and ethyl sulphate and purified by means of 80% alcohol forms colourless needles with a blue fluores- cence ; its solution in chloroform or carbon disulphide is decolorised by bromine anthrsquinone being formed. The alcoholic mother- liquor contains Liebermann’s ethyloxanthrone m.p. 107’. By a consideration of the distribution of the residual affinity Meisenheimer Inas shown that addition takes place at the nzeso-carbon 6 4 m. p. 239 -240’. Anthraquinyl disnaethyl ether C6H4<6(0Me)>c6H4,i. 196 ABSTRACTS OF CHEMICAL PAPERS. atoms in derivatives of antbracene and a t the oxygen atom in thoke of anthrone and anthraquinone. The author shows that this theory is applicable not only to explain but also to predict the preceding results. c. s. Anthracene. 11. Oxidation of Anthracene. KURT H. MEYER (Annalen 1911 379 73-78. Compare preceding abstract).-Most oxidising agents which attack anthracene convert it into anthraquinone. By using lead dioxide and glacial acetic acid Schulze obtained a sub- stance which was supposed to be different from anthraquinol (oxanthranol) and was called P-oxanthranol.It is however anthraquinol itself produced as the sequel shows from the initially- formed oxanthrone acetate by the boiling alkali used by Schulze in the process of purification. By oxidising anthracene in glacial acetic acid a t 50' by lead dioxide (1 mol.) the a.uthor obtains 40-50% of anthranyl acetate together with a little oxanthrone acetate and anthraquinone. When the oxidation is effected at 70° by 2 mols. of lead dioxide the main product is oxanthrone acetate. The oxidation of anthracene by manganese dioxide cerium acetate or vanadic acid proceeds in a similar manner provided that glacial acetic acid is used as the solvent ; a solution of anthracene in alcohol and toluene is oxidised by manganese dioxide and a drop of sulphuric acid to viscous products amongst which occurs dianthrone.Anthracene is oxidised very smoothly to oxanthrone by bromine in aqueous acetone only a trace of anthraquinone being formed; the action of chlorine on an aqueous suspension of anthracene is similar but less satisfactory as regards purity of product. By allowing solutions of anthracene in glacial acetic acid and of bromine in methyl alcohol to Bow simultaneously into a large volume of methyl alcohol rnethoxyanthrone together with a little antbraquinone and unchanged p-Xglyl Sulphide and its Derivatives. Z. MARTYNOWICZ (Chena. Zentr. 1910 ii 1048; from Kosmos 1910 35 Radxiszewski- Testband 5 94-5 9 6).-p-Xylyl aulphide S( CH,*C,H,Me) obtained by the action of an alcoholic solution of potassium sulphide on p-xylyl bromide forms colourless needles m.p. 76'. By oxidation with nitric acid it forms p-xylylsulphoxide SO(CH,*C',H,Me) which crystallises in silky needles m. p. 117'. Both these substances form on oxidation with potassium permanganate pxyt?ylsut?phoize SO2( CH,*C,H,Me) The Action of Ammonia on Aromatic Thiocyanates. MARYA STRZELECKA (Chem. Zentr. 1910 ii 1135 ; from Kosmos 1910 35 Radziszewski-Festbccnd 585-589).-When aromatic thiocyanates are boiled for a loug time with alcoholic ammonia ammonium cyanide is split off with the forniation of disulphides. I n this way the following disulphides were prepared benzyl disulphide (CH,Ph) white crystals m. p. 71-72' ; p-xylyl clisulphide white radiating t u f t s of needles m.p. 43'; 0-xylyl disulphide white plates m. p. 83-85O. anthracene are produced. c. s. which forms shining plates m. p. 197'. N. c. The metcc-cornpoiind could not be obtained in this way. N. c.ORGANIC CHEMISTRY. i. 197 Phenyl Thiocarbonate. ANGELO CASOLARI (Gazzettn 19 10 40 ii 38~-403).-Potassium trithiocarbonate reacts with diazobenzene chloride in aqueous solution with formation of phenyl trithiocarbonc~ite CS3Ph2 which is a red oil D! 1.2668 Dig'' 1.2497. It has the normal molecular weight. Heat decomposes the substance somewhat readily with formation of hydrogen sulphide and carbon disulphide among other products. When subjected to distillation the compound evolves vapour at 210-215°/30 mm. and the distillate consists of phenyl disulphide.The action of alcoholic potassium hydroxide alcoholic ammonia or aqueous ammonia in a sealed tube leads to the production of thiophenol carbon disulphide a carbonate and a thio- sulphate. As secondary products from the carbon disulphide are formed thiocyanic acid a r d hydrogen sulphide (when ammonia is used) and xanthic acid (with alcoholic potassium hydroxide). Thiosulphates give a characteristic blue coloration when treated with a few drops of a 5% solution of sodium nitroprusside which has been exposed to light and air until it has assumed a chestnut-brown colour. The coloration is green in very dilute solutions ; i t is stable in neutral solutions or in the presence of potassium hydrogen tartrate but becomes green and finally yellow in the presence of alkali acid or oxidisers.Tbe reaction is not given by sulphites or by tetrathionates. The reagent may also be made by treating a fresh solution of sodium ni troprussi d o with potassi um f erricyanide then with potassium hydroxide and finally rendering the liquid just acid with potassium hydrogen tartrate. R. V. S. S u l p h u r Derivatives of o-Cresol. THEODOR ZINCKE and R. BRUNE (Ber. 1911 44 185-197. Compare Zincke and Glahn A bstr . 1 9 07 i 6 98).-3- Bromo -o-cresol-5-sulp~on?l chloride OH*C,H2BrMe*S0,Cl prepared by the action of phosphoryl chloride on potassium bromo- 0-cresol-sulphonate (Claus and Jackson Abstr. 1889 129) at 1 50° crystallises from light petroleum in colourless needles m. p. 94" and yields an acetyl derivative i n the form of colorirless prisms m.p. 131". The methyl ester OH*C,H,MeBr *S02Me forms colourless plates m. p. 141-142' ; the ethJ ester compact needles m.. p. 1 1 3 O and the anilide minute crystals m. p. 165-1 66". Potassium acetate reacts with an acetone solution of the chloride yielding a polymeric bronzosuZy,l~onyZ-p-tolupzcinone [,,,:C<~~&~~~>C:O]n which crys- tallises from nitrobenzene in small colourless needles with no definite m. p. 3 -Brorno-5-~~ioZ-o-cresol SH*C,H,MeBr*OH obtained by reducing the sulphonyl chloride with zinc dust alcohol and hydro- chloric acid crystallises from light petroleum in colourless needles m. p. 51-42". The diacetyl derivative CI,H,,03SBr forms small compact plates m. p. 11 1-1 12". Concentrated ferric chloride solution oxidises the thiol in the presence of glacial acetic acid t o 3-bromo-o-cresol 5-disuZphide S,(C,H2BrMe*OH)2 which cryst allises from l i g h t petroleum in thick yellow plates m.p. 123-124". The corresponding cxcatyl derivative C,8HI,@,S,Bt-2 forms colourless plates,i. 198 ABSTRACTS OF CHEMICAL PAPERS. m. p. 101-102' and is also formed when the thiol is warmed with acetic anhydride and a little sulphuric acid. 3-Bromo-5-metl~y~lhio~-o-creso~ OH* C H,MeBr*SMe obtained by methylating the thiol with methyl iodide and sodium methoxide in the cold is a colourless oil b. p. 167-169'/20-21 mm. and yields an acetyl derivative C,,H,,O,S Rr in the form of glistening rhombic plates m. p. 53". When shaken with water the methyl sulpbide yields a yellow amorphous powder C32H3304S4Br m.p. about 90° after sintering at 50-6O0. Dilute alkali hjdroxide solutions react in much the same manner as water. Sodium nitrite reacts with a glacial acetic acid solution of the methyl sulphide yielding 3-nitro-5-methyl- tlhiol-0-cresol s~e*C,H,~~e(NO,)*oH which crystallises in orange-red needles m. p. 78-79'; i t s acetyl derivative forms yellow needles m. p. '70'. 3-Bromo-o-creso2 5-methyZsuZphoxide OH-C,H,MeBr*SOMe obtained by oxidising a glacial acetic acid solution of the methyl sulphide with hydrogen peroxide crystallises from benzene in well- developed colourless needles m. p. 121'; i t dissolves in alkalis without decomposition and yields a perbromide. The corresponding sulphone OH*C,H,MeBr*SO,Me obtained by using excess of hydrogen peroxide crystallises in colourless needles or prisms m.p. 168'. 3 6-Dibronao- 5-methy2thiol-o-cresol perbromide O~*C,H~feBr,*SMeBr exists in two modifications namely orange-red plates from acetic acid and brownish-violet needles from chloroform. Both forms lose bromine yielding 3 6-dibrorno-5-rnethyZthioZ-o-cresoZ C,H80SBr2 which crys- tallises from light petroleum in colourless needles or rhombic plates m. p. 11 1-1 12O. 3 6-Dibromo-o-cresoZ-5-methylsuZphoxide OH*C,HMeBr,*SMeO prepared by the action of water on the perbromide crystallises from benzene in stout colourless needles m. p. 16S0 and the corresponding sulphone CsHS0,SBr2 forms colourless needles m. p. 169'. 3-Bromo-o-cresol-5 -dirnethylsuZphinium iodide OH*C6H2eMeBr *S Me2& prepared by the action of methyl iodide on the thiol derivative in the presence of an excess of alkali crystallises i n felted needles m.p. 114O (decomp.). The corresponding chloride C9H,,0SClBr forms slender needles m. p. 15 1' (decomp.) and the platinichloride crystallises in brownish-yellow needles. The alzhydro-compound C9Hll.0SBr obtained by the action of moist silver oxide on the sulphinium iodide crystallises in colourless needles m. p. 1S5-187' after darkening at 170'. It must be represented by one or other of the formulze C-0-Me /CMe CH\ S-C or O:C<CB,-CH CMe:CIH>C aMe,. \CBr-&// - The corresponding nitrothioniwm quinone - O:C,CMe== C(N0,) CH CH>C SMe crystalliees in glistening yellow -needles m. p. 245-246" and when boiled for some time with dilute alkalis yields the nitrorngthylthiolcresol.The nitrate C,H,,O,NS,HNO forms stout yellow prisms m. p. 150-151O (decomp.); the cldoride forms pale yellow plates ni. p. 99-100' (decomp.) arid the plutiizichloride 2C19€€,,0,NS,H,PtC1 forms compact yellow needles. J. J. S.ORGANIC CHEMISTRY. i. 199 Action of Magnesium Phenyl Bromide on Heptaldehyde. U. COLACICCHI (Atti R. Accad. Lincei 1910 [v] 19 ii 600-605).- I'/~enyZ/~ex~ZcarbinoZ C13H200 (from magnesium phenyl bromide and heptaldehyde) is a colourless liquid b. p. 156'/25 mrn. 176"/40 mm or 275' at the ordinary pressure D 0.9455 n (yellow) 1.501. Its phenylurethane C,,H,,O,N forms rosettes of colourless crystals m. p. 77". The phenykhaourethcme crystallises in laminze m. p. 147'. Phenylhexylcarbinol when reduced with iodine and phosphorus yields the corresponding iodide which is a liquid b.p. 140°/38 mm. and a substance (probably a hydrocarbon) distilling at 290-360'. Eg oxidation of the carbinol phenyl hexyl ketone is obtained identical with that described by Auger (hbstr. 1887 814). The 8em;carbaxone of the ketone C,,H,ION forms colourless needles m. p. 1 18-119'. The p-nitvophenylhydraxone C191X2302N3 cry s t a k e s in yeliow needles m. p. 127-128". Experiments on the physiological action of the compounds dewribed show that the toxicity of the alcohol is somewhat greater than thitt of the ketone both for warm-blooded (Mus musculus) and cold-blooded ( R a m esculentcb) animals. B Jth substances eventually cause paralysis of the central nervous system and diminish the amplitude of the beats of t h e heart which finally stops in diastole.R. V. S. Dextrorotatory Phytosterols of Anthemis nobilis ( A n t h e - sterols). TIMOTH~E KLOBB (Compt. rend. 19 11 152 327-330. Compare Abstr. 1909 i 471).-The existence of isomeric benzoates and the variable composition of its bromo-daivatives suggest that anthesterol is not a single substance. To throw light on this point the alcohol was treated with acetic anhydride,' when three isomeric acetates were obtained. A. Hexagonal litmellae m. p. 245-248" [a] + 91 -2" ; this yields a-anthesterol on hydrolysis. B. Hexagonal l a m e h m. p. 225-230' [a]D +73*9'; /3-anthesterol is obtained on hydrolysis. (C) Confused crystals m. p. 185-195' giving on hydrolysis needles having a double m. p. 158-160' and 185-190'.On bromination the acetate (A) yields two monobronzo-derivatives C,,H,,OBrAc m. p. about 180° but having [a] + 133' and + 58.8' respectively. (B) gives a dibromo-additive product C31H510Br2A~ m. p. 170-175'. (C) forms zl mixture of the homo-acetate from (A) with a substance corresponding in composition with a mixture of the (A) and (S) bromo-derivatives containing 45% of the latter. The interpretation placed on these results is that anthesterol hss the formula C,,H,,0,3H20,. and is an individual substance homologous with amyrin and paltreubin (Jungfleisch and Lwoux Abstr. 1906 i 525; 1907 i 783; 1908 i 1000). It is not identical with lupeol as suggested by Cohen (Abstr. 1908 i SS2). w. 0. w. Esterification of Benzamide and the Preparation of N-Sub- stituted Benzamides. E.EMMET REID (Amer. Chem. J. 1911 45 38-47).-Bonz (Abstr. 1889 335) made a study of the reversible reaction CH,*CO*NH + EtOH ZZ CH,*CO,Et + NH and identified ethylamine among the reaction products. H e assumed that the amine mas produced by the action of ammonia on the ester previously formed,i. 200 ABSTRACTS OF CHEMICAL PAPERS. thus CH,*CO,Et + NH = CH,*CO,*NH,Et but his results are more simply accounted for by supposing that the amide and alcohol react directly t o form acetoethylamide CH,*CO*NH + EtOH = CH,*CO*NHEt + H,O. I n connexion with certain other work (Abstr. 1910 i 481 701) the author studied the action of alcohol on benzamide and found that benzoethylamide could be readily obtained. The work has been continued and extended to other alcohols. The reactions which take place when ethyl alcohol is heated with benzamide are as follows C,H,*CO-NH + EtOH Tj C,H,*CO,Et + NH C,H,*CO*NH + EtOH = C,H:*CO*N HEt + H,O.The benzoethylamide undergoes hydrolysis according to the reaction which finally reaches equilibrium. Benzamide was heated with a slight excess of the alcobol in a sealed tube a t 220-230" for periods varying from two to seven days. I n an experiment with methyl alcohol S9% of benzomethylamide was isolated but no methyl benzoate was obtained and 61% of the amide underwent hydrolysis. I n two experiments with ethyl alcohol the yields of bgnzoethylamide mere 61.1 and 62.6% of ethyl benzoate 1.27 and 1.580& whilst the amounts of amide hydrolysed were 38.1 and 36.4%. With prop91 alcohol the yield of benzopropylamide was 72.9% of propyl benzoate 5*2% and the amide hydrolysed amounted to 23.1%.I n the case of isobutyl alcohol 69.4% of benzoisobutylamide was obtained and 8.3% of isobutyl benzoate whilst 24.3% of the amide suffered hydrolysis. The amount of benzamide transformed into the ester seems t o increase with the molecular weight of the alcohol. I n the case of the experiment with methyl alcohol a small quantity of water was present and a large amount of hydrolysis therefore occurred. The action of alcohols on benzamide affords a convenient method for preparing certain benzoalkylamides and may also be of service for the preparation of tbe amines which are obtained as by-products. C,H,*CO*NHEt + H,O C,H,*C02H,NH,Et E. G. Study of o-Amino-p-sulphobeneoic Acid with Special Reference t o its Fluorescence.JOSEPH H. KASTLE (Amer. Chem. J. 19 11 45 58-78).-Aqueous solutions of p-aminobenzoic sulphinide exhibit a bluish-purple fluorescence but solutions in concentrated hydrochloric acid are not fluorescent. Since several difficulties arise in attempting to elucidate the causes of this phenomenon the author has studied o-amino-p-sulphobenzoic acid (Hart Abstr. 1881 1146) which on account of its simpler constitution appeared more suitable for a n investigation of the influence of simple chemical changes on fluorescence. o-Amino-p-sulphobenzoic acid crystallises with &H,O and in dilute aqueous solution exhibits a bluish-purple fluorescence which within certain wide limits is inversely proportional to the concentration.The intensity of the fluorescence of both the acid and its salts is diminished by heat. The fluorescence of aqueous solutions of the acid is weakened or destroyed by strong acids and alkalis the power ofORGANIC CHEMISTRY. i. 201 effecting this change being roughly proportional to the degree of ionisation of the reagent. The intensity of the fluorescence of sodium potassium ammonium calcium barium and magnesium o-amino- p-sulphobenzoates is independent of the nature of the base. Solutions of the acid and of the acid salts are much more fluorescent than those of the normal salts whilst the fluorescence of solutions of the acid salts is somewhat more intense than that of solutions of the free acid. Di-silver o-amino-p-sulphobenzooate exists in two forms one amorphous and unstable above 27*5' the other crystalline stable at 27.5' and at higher temperatures and less soluble in water than the amorphous variety.By the action of ethyl iodide on the crystalline di-silver salt a compound probably o-et h ylami?zo-p-su~!p?~obenzoic acz'd C0,H*CGH3(NHEt)*S03H,H,0 m. p. 243' (decomp.) is produced which forms colourless rhombic crystals and exhibits a blue fluor- escence in dilute aqueous solution. I n one experiment another cornpound m. p. 160' probably either the true diethyl ester or the acid ester of tho ethylamino-acid C0,Et*C,H3(NHEt)*S0,H was obtained which forms pale yellow crystals and when boiled with water is converted into the substance melting at 343'. A barium salt probably [C0,Et*CGH,(NHEt)*S03]2Ba has also been prepared.E. G. Iminosulphides. I. The Condensation of Thiobenzamide with Benzonitrile. MOTOOKI MATSUI (Mem. COIL Xci. Eng. Qoto 1910 2 401-404).-Under the influence of hydrochloric acid thiamides combine with nitriles to form irninosulphides of the constitution S(CR:NH),. BenziminosuZphide S(CPh:NH) obtained in the form of its hydro- chloride by the action of hydrochloric acid on an ethereal solution of thiobenzamide and benzonitrile crystallises in light red needles m. p. 71'; the acetyl derivative crystallises in orange needles The hydrochloride C,,Hl,NS,2HCl forms orange needles m. p. 110-1 1 lo and is decomposed by water yielding the free base. The picrate Ci,Hl,NS,C,H30,N crystallises in light red prismatic plates con- taining one molecule of alcohol; when heated at SO' the alcohol of crystallisation is lost and the picrate is obtained as an amorphous yellow substance m.p. 114'. F. B. Degradation of Amino-acids by Fermentation with Yeast. OTTO NEUBAUER and KONRAD FROMHERZ (Zeitsch. pltysiol. Chern. 19 1 1 70 326-350. Compare Abstr. 1909 ii 750).-Stress is laid on the possible analogy between the conversion of an amino-acid into alcohol by means of yeast and into fatty-acid in the mammalian organism. I n each case it is considered that the ketmic acid R*CO*CO,H is the intermediate product. It is shown that by the action of yeast on a-aminophenylacetic acid benzoyl alcohol phenylglyoxylic acid I-mandelic acid and I-acetyl aminophenylacetic acid are formed. Yeast is able to effect a partial reduction of phenylglyoxy lic acid to I-mandelic acid.The ketonic acid p-hydroxylphenylpyruvic acid is converted by yeast to a large extenti. 202 ABSTRACTS OF CHEMICAL PAPERS. into p-hydroxyphenyletbyl alcohol. p-Hydroxyphenyl-a-lactic acid on the other hand,is not converted to any extent intop-hydroxyphenylethyl alcohol proving that this alcohol acid is not. the intermediate product between keto-acid and alcohol. The conversion of amino-acid into alcohol involves a series of alternate oxidative and reducing changes. E. F. A. Transformation of 8-Phenyl-A'-pentenoic Acid i n t o the A?-Isorneride. J. BOUGAULT (Compt. rend. 19 11 152 196-197).- Fittig (Abstr. 1895 ii 204) has shown t h a t ,L?-hydroxyvaleric acid is formed on boiling 6-phenyl-Aa-pen tenoic acid with aqueous a1 kalis together with a substance which he supposed to be 8-phenyl-As-pentenoic acid.The present author has been unable to obtain the latter substance but finds that the AY-acid is an important product of the transforma- tion under the most favourablo conditions the yield amounting to 50%. The formation of P-hydroxy valeric acid was confirmed. An acidic liquid possibly a mixture is also produced in small quantity. w. 0. w. Introduction of the Carboxylic Group into Polynuclear Aromatic Hydrocarbons. CARL LIEBERMANN and M. ZSUFFA (Ber. 1911 44 202-21O).-The methods of Graebe and Liebermann (Bey. 1869,2 678) Friedel and Crafts (this Journ. 1877 ii 725) and Gattermann (Abstr. 1888 574) for the introduction of the carboxylic group into polynuclear aromatic hydrocarbons give but poor yields and in many cases do not work.The authors have prepared the following acids by treating the corresponding hydrocarbons with 2.5 times their weight of oxalyl chloride a t 160-170° and extracting with cold sodium carbonate solution; the numbers indicate the percentage yields anthracene-9-carboxylic acid m. p. 2 17' (70-80%); fiuorenecarboxylic acid (this Journ. 1877 ii 493) (7-10%) ; indene- carboxylic acid by using a temperature of 140-145' (15%) m. p. 234' (compare Perkin and RQvay Trans. 1893 65 238); acenaph- thenecarboxylic acid also obtained by heating at 180' for fourteen hours (30%) (compare Gattermann Abstr. 1888 574); phenanthrene-9- carboxylic acid (yield poor) ; chrysenecarboxylic acid by heating for two days at 170° yield poor.Better yields are obtained when aluminium chloride is added to the hydrocarbon and oxalyl chloride. The mixture becomes quite black even when carbon disulphide is present but on adding water the colour changes to yellow or red. The yields are better but the products less pure. Naphthalene gives a mixture of 80% of a- and /I-naphthoic acids and anthracene yields anthracene-9-cnrboxylic acid (30%) and ace- antbrenequinone (60%). Benzene and naphthalene are not carboxylated in the absence of aluminium chloride and when anthracene is heated with excess of oxalyl chloride at ZOO0 10-chloroant bracene-9-carboxylic acid is formed (70%) (compare Behla Abstr. 1886 248; 1887 593). ChrysenecarboxyGc acid C1,H,,*CO,H crystallises from alcohol in colourless needles m. p.3 0 3 O and the sodium salt C19H1102Na crystallises from water in long plates.ORGANIC CHEMISTRY. i. 203 Aceantlbenequinone (annexed formula) crystallises from benzene in brilliant red prisms m. p. 270' and when sublimed /\/\/\ has the appearance of alizarin. It combines with I I I I 1 sodium hydrogen sulphite is oxidised by chromic \/\ /\/ acid to anthraquinonecarboxylic acid and an acetic I I acid solution reacts with an alcoholic solution of ''-'O o-toluylenediamine yielding nceanthrenetokazin This crystnllises in orange-red needles or plates m. p. 237' and its alcoholic solution has a green fluorescence. J. J. S. Preparation of 3 ; 5-Di-iodotyrosine from Iodoprotein. ADOLF OSWALD (Zeitsch. physiol. Clwm. 1911 70 310-313).-3 5-Di-iodo- tyrosine has been isolated among the products of the hydrolysis of iodo-albacid with barium hydroxide (Blum and Vaubel Abstr.1898 i 610). It is suggested that iodine is in part attached to tyrosine in the natural iodoproteins. Conversion of Goumarins into Coumarinic Acids and o-Coumaric Acids. 11. KARL FRIES and W. VOLK (Annulen 1911 379 90-110. Compare -4bstr. 1908 i 820).-Experiments similar to those already recorded (loc. cit.) have been performed on 4-met h ylcoumarin 3-me t h ylcoumarin and 3- et h ylcoumarin. The conversion of 4-methylcoumarin into P-methylcoumarinates by aqueous alkalis is slower than that of coumarin into a coumarinate but convetsely its conversion by concentrated alkali into P-methyl- o-coumaric acid OH*C,H,*CMe:CH*CO,H m. p. 154O (decomp.) proceeds more readily (five hours' boiling with 33% potassium hydroxide) than that of couniarin into o-coumaric acid.When 4-methylcoumarin is heated with alcoholic potassium ethoxide at 140-150' for fifteen hours and the product is acidified l-(Z-meth.ql- coumaran)-3-( 4-metl~ylcoumarin) ketone (3-[2-meth ylhydrocoumarilyl]- 4-methyZcoumarin) CIOHI6O4 rn. p. 224' is obtained the constitution and behnviour of which are similar to those of the ketone obtained in the same manner from 4 7-dimethylcoumarin (Zoc. cit.) ; when boiled for a short time with dilute aqueous alkali it loses carbon dioxide and yields di-l-(2-methyZcouma~a.n) ketone (1-[Z-methylhydro- cournari~yl~-~-methy~hydl.ocournccrolze) (C,H,<-~->CH),CO CHMe m. p. 183-185' solidifying to a glassy mass which has m.p. about 95' re- solidifies at about 145' and melts again a t 184'. This substance forms yellow solutions in alkalis and yields an oxime m. p. 213'. 3-Methyl-(or ethyl-)coumarin behaves towards aqueous alkalis and sodium ethoxide like those coumarins which are not alkplated in the pyrone nucleus. After being boiled for five hours with 33% potassium hydroxide only salts of the alkylcoumarinic acid are formed since carbon dioxide causes the precipitation of the 3-alkylcoumarin. When boiled for five hours with alcoholic sodium ethoxide however the 3-alkylcoumarins yield salts of the a-alkyl-o-coumaric acids although more slowly than is the case with coumarin and its Bz-homologues. E. F. A.i. 204 ABSTRACTS OF CHEMICAL PAPERS. a-Metliyl-o-coumaric ucid OH*C,~,-CH:C'Me-CO,H m.p. 1 3S0 (decomp.) aud a-et/iyZ-o-coui)aa1.ic acid m p. 1 8 1 O (decornp.) form yellow solutions in concentrated sulphuric acid yield alkali salts which exhibit a yellowish-green fluorescence in solution (the alkali salts of P-alkyl-o-coumaric acids do not show fluorescence) and are not reconverted into the 3-alkylcoumarins very smoothly in t h i s respect resembling o-coumaric acid but differing from /I-alkyl-o-coumaric acids. The replacement by methyl groups of hydrogen atoms in the benzene nucleus of coumarins does not affect greatly the behaviour of the resulting alkylcoumarins except in so far as slight variations in the velocity of formation of the o-coumaric acids are concerned. It is very striking therefore that the introduction of hydroxy- methoxy- or dimethylamino-groups in the Bx-nucleus prevents completely the formation of the corresponding o-coumaric acids ; thus 4-methyl- um bellif erone its methyl ether and 7-dime t h ylttmino- 4-me t h ylco umarin are only converted into the corresponding coumarinates even after prolonged boiling with alcoholic sodium ethoxide or concm trated aqueous potassium hydroxide.7-Dimethylamino-4-methylcoumarin is decomposed completely by boiling for six hours with 40% potassium hydroxide m-dimethplaminophenol being formed. ~-Methylcoumarinn-4-cccetic acid C,H,Me<-o,c-,- CH m. p. 1 909 (decomp. ; thereby yielding 4 7-dimethylcoumarin) obtained together with i t s ethyl and m-tolyl esters by the interaction of rn-cresol ethyl acetonedicar boxylttte and concentrated sulphuric acid at Oo does not; behave like 4-methylcoumarin ; with aqueous alkalis i t does not form an o-coumarate and with alcoholic sodium ethoxide a ketone is not produced in both cases a coumarinate being formed which is easily reconverted into the coumarin by acids.The ethyl ester ClPHI4O4 m. p. 132O behaves in a similar manner being hydrolysed by aqueous alkalis and yielding a coumarinate with sodium ethoxide. The m-tolyl ester C,,H,,O m. p. 2 1 4 O hgwever behaves differently. By prolonged boiling with 20% potassium hydroxide it is partly hydrolpsed partly unchanged and partly converted into the following o-coumario acid and a substance which yields 2 2 4 6-tetrabromo-3-keto-2 3-dihydrotoluene (Foster Dissert. Marburg 1898) by treatment with bromine.By treatment with alcoholic potassium ethoxide at 130-140" for fifteen hours the m-tolyl ester yields after acidilying the product the m-toZyZ ester of a-acetic-4-methyl-o-cournaric acid OH*C,H,Me*C( CH,*CO,*C,H,Me):CH*CO,TI which sintera at 95O melts and decomposes at about looo resolidifies at about 120° and melts again a t 214O the m. p. of the corresponding coumarin. The acid is remarkably unstable being converted into the coumarin by acids or organic solvents. The following two ketones obtained from 4 6-dimethylcoumarin correspond in constitution with those prepared from 4 7-dimethyl- coumarin (Zoc. cit.). By treatment with alcoholic potassium ethoxide at 160" for twenty-four hours and acidification of the product 4 6-diniethylcouinarin yields 1-( 2 4-climeth~?couniaran)-3-(4 6-dimetJ~yZ- C(C H,*CO,H)>ORGANIC CHEMISTRY.i. 205 coumarinn) ketone (3-[2 4-dimethylhydrocournariEyE]-4 6-dimathylcozc- marin) C2zHao04 m. p. 275-280° which is convertad by boiling aqueous-alcoholic alkali into an intensely yellow solution from which by acidification the ketone C21H2203 m. p. 199O already described (Zoc. cit.) is obtained. The ketone C,,H,,O is converted by ethereal magnesium methyl iodide in the usual way into the compound C,H3Me<~HOM~C:CMegCH<~~~>c6H3111e m. p. 164O which reacts with bromine in glacial acetic acid to form the substccnce C6H,Me<_0__>CBr*CMeEr.C13r<_0>C6H,i\le CHMe CHMe m. p. 200'. The corresponding compound C,,H,,O obtained from 4 7-dimethyl- coumarin (Zoc.cit.) yields by bromination a substance C22H2102Br5 m. p. 225O which has the annexed constitution /CHMe\/\Br '-0-'\/ 1 /Me* CBr*CMeBr* CBr Br/\/CHMe\ Me(/\& I / c. s. Method for the Preparation of Derivatives of a-Cyano- acrylic Acids. C. H. CLARKE and FRANCIS FRANCIS (Be?*. 1911 44 273-276).-Instead of condensing aldehydes with cyanoacetic acid or its ester the authors use substances which will form cyanoacetic acid for example potassium bromoacetnte and potassium cyanide CH,Br.CO,K + KCN + R*CHO = R*CH:C(CN)*CO,K + KBr + H,O. The best yields are obtained when the potassium salt of the bromo- acetic acid is added t o an aqueous solution of the cyanide and aldehyde. Potassium cyanide accelerates the reaction between aromatic aldehydes and salts of cyanoacetic acid j u s t as sodium ethoxide does (Carrick Abstr.1890 1270; 1893 1086). The following compounds have been prepared by this method a-cyanocinnamic acid a-cyano-/3- anisylacrylic acid a-cyano-P-styrylacrylic acid a-cyano-P-piperonyl- acrylic acid and a-cyano-/3-furfurylacrylic acid. Ethyl a-cyano - P - piperonylacrylate C13Hl10,N crystallises from alcohol in colourless plates m. p. 1 0 4 O . Oh1e*C613[,( OH) CH:C( CN)*CO,H prepared from vanillin potassium bromoacetate and potassium cyanide crystallises from dilute alcohol in pale yellow needles m. p. 2 15'. The corresponding ethyl ester C13H130,N has m. p. 11 1'. a-Cyano-o-coumaric acid OH*C,H,*CH:C(CPr').CO,H could not be obtained crystalline ; its benxoyl derivative C17fit104N crystallises in needles m. p.210'. The acid is hydrolysed with great readiness to coumarinic acid. J. J. S. Isomeric Phenylphthalimides and Some Allied Compounds. 11. MITSURU KUHARA and SHIGERU KOMATSU (Bern. CoZZ. Sci. Eng. Kyota 1910 2 365-386).-By the action of acetyl chloride on phenylphthalanuic acid the authors (Abstr. 1909 j 484) have previously obtained two isomeric phenylphthalimides. Of these two isomerides the colourlees form was represented by the formula a-Cyanojhdic cccicl C( NYh) c6B4<-- (J O-->O 7 YOL. c i. IIi. 206 ABSTRACTS OF CHEMICAL PAPERS. whilst the yellow variety was supposed to possess a peroxide str uc t ure. The authors now consider that the colour of the yellow isomeride is due to the presence of the chromophoric group C:NPh and have therefore assigned to this form the unsymmetrical formula given above.The constitution of the colourless isomeride remains undetermined. Two isomeric substituted phenylphthalimides colourless and yellow are also produced by the action of phthalgl chloride on o-toluidine p-toluidine m-4-xylidine 0-3-xylidine p-xylidine and $-cumidine. The colourless isomerides possess the symmetrical constitution C,H,<CO>NAr whilst the colourod varieties are co C( :NAr)>O . represented by the unsymmetrical formula C6H4<-,o- The colourless and yellow modifications of p-methoxyphenylphthal- imide . p-ethoxyphenylphthalimide and p-methoxyphenyl-A'-dihydlo- phthalimide (Piuti and Abati Abstr. 1903 i 424) are considered by t h e authors t o be structural isomerides the yellow forms having an unsymmetrical and the colourless varieties a symmetrical structure.The formula assigned by Piutti (Abstr. 1908 i 783) t o the two modifications of p-hydroxyphenylmaleimide are to be interchanged. The behaviour of the isomeric arylphthalimides towards alkylmag- nesium halides has also been investigated and it is found that both isomerides yield the same 3-hydroxy-2-aryl-3-alkylivoindolinone C,H4<cR(oH))NAr -coy (compare Sachs and Ludwig Abstr. 1904 i 266). It is suggested that the latter compounds are formed from the us-aryl phthalimides by a molecular arrangement according to the followin,o scheme as-o-ToZyZphthuZimide CO<~~->C:N*C6H,Me obtained together with s-o-tolylphthalimide by the action of phthalyl chloride on o-tolui- dine in ethereal solution at - loo crystallises in canary-yellow needles m.p. 136-137'. On treatment with magnesium methyl iodide it yields 3-hy&roxy-2-o-tolyZisoindoZinone 6 4 'GH4<-C0- CMe(oHbN*CAH,3!Ie ; the Iatter forms colourless crystals m. p. 161-162' and is also pro- duced by the action of magnesium methyl iodide on 0- tolylphthalimide. 3-E.tydroxy-2-o-toZyZ-3-e~hylisoindoZinone ClPH1702N crystallises in colourless plates m. p. 169-1 7 lo. as-p-12ZyZ~l~lhll~aZin~ide C+,H,,O,N crystallises in light yellow needles m. p. 109-1 loo and is iormed simultaneously with s-p-tolylphthal- iinide by the action of yhthalyl chloride on p-toluidine; mith mag- nesium ethyl iodide both these cornpouods yield 3-hydroxy-2-p-tolyZ-3-ORGANIC CHEMISTRY. i. 207 ethylisoindolinone C17H1702N which crystallises in colourless needles m.p. 177-178". as-rn-4-XyZyZphthaZimide CO<o->C:N*C,H,Me yellow needles m. p. 142-1437 m-4-xyZyZphthaZamide C,H4(CO*NH-C6H3Me,) silky needles m. p. 202-203') and s-m-4-xylylphthalimide C6H4 C,H4<Eg>K* C(jH3Me 9 slender needles m. p. 154O are produced by the interaction of phthalyl chloride and nz-4-xylidine in ethereal solution. The first-named substance is converted by mineral acids or alkali into s-m-4-xylyl pht,halimide which is readily obtained by heating m-4-xylidine with phthalic anhydride or phthalyl chloride. Di-m-4-xy Zy ZphthaZdi-imide is produced to gether with s-m-4-xylylphthalimide by the interaction of phosphorus pentachloride and rn-4-xylylphthalamide i n chloroform solution ; i t forms yellow plates m.p. 149-150'. Y6H4* $? :N*C,H,Me2 CO-N* C,H,Me 3-Hy droxy-2 -m- 4-xyly Z - 3 -eth y Zisoindolinone c(j H4<-C CE (OH)>N O- *C,H,Me prepared from both as-m-4-xylylphthalimide and s-m-4-xy lylphthalimide by the action of magnesium ethyl iodide crystallises in colourless plates m. p. 176-177". 3-Nydroxy-2-m-4-xylyZ-3-methylisoindoZinone C17H1702N has m. p. 161-162' ; from methyl- and ethyl-alcoholic solutions it crystallises with one molecule of alcohol. o-3-XyZy~hthalamitZe) C?,H,,O,N slender needles m. p. 192-1 93' is obtained by the interaction of o-3-xylidine and phtbalyl chloride in ethereal solution ; small quantities of a yellow substance consisting probably of as-o-3-xylyZphthccZirnide C,,H,,O,N and of s-0-3-xylyl phthcdirnide Ci,HIHO,N are produced simultaneously.The latter compound crystallises in colourless needles m. p. 143-144") and is readily obtained by heating o-3-xylidine with phtbalic anhydride or phthalyl chloride. Di-o-3-xyZyZphthnZdi-imide C24H220N2 prepared by the action of phosphorus pentachloride on 0-3-xylylphthalitrnide crystallises from alcohol in yellow plates m. p. 123-124O. p-XyZyZphthaZamide C,,H,,O,N silky needles m. p. 209-2 1 O' s-p-xylyl~htltalimide C11(jH,302N slender needles m. p. 147-148O and as-p-xylylphthalimide C,,H,,O,N amber-coloured needles m. p. 178-181" are obtained by the action of p-xylidine on phtbalyl chloride in ethereal solution at a low temperature. The last-named substance is unstable and readily changes into s-p-xylylphthalimide which is more easily obtained by heating p-xylidine with phthalic anhydride.D i- p-x y l y Zph t ha Zdi-imide C 4Hz20N2 obtained from p - x y 1 y I p h t h a 1- amide and phosphorus pentachloride crystallises in yellow plates m. p. q-Cumylpltthdamide C,H,(CO*NH*CBHzMe& silky needles m. p. 133-134O. s I 2i. 208 ABSTRACTS OF CHEMICAL PAPERS yellow needles m. p. 11 7-1 18' are obtained togethir with s-+-cumyl- phthalimide by the interaction of q-cumidine and phthalyl chloride. L)i-~-cumy~lTLthaZdi-imide 3 is formed when yhxmylphthalamide is treated with phosphorus pentachloride in chloroform solution ; it crystallises in yellow plates m. p. 136-1 37'. y6H4*y :N*C6H,Me CO-N C,H,Me 3-IIyd?*oxy-2-+- cumyl- 3-eth y2isoindo Zinone c6H4<!,!~f!.>N* c(3H2 Mes colourless plates m.p. 152-153' is ohtained by the action of magnesium ethyl iodide on both forms of $-cumglphthalimide. F. B. Spectrometric Examination of Guthzeit's cycZoBntane Derivatives. ERICH HARTMANN (J. pr. Chenz. 1911 [ii] 83 1 YO- 194).-The stereoisomerides C,,H,,016 m. p. 103O and 8 8 O respectively (Guthzeit Weiss and Schiifer Abstr. 1909 i 933) and the ester C30H42016 m. p. 86' (Guthzeit and Hartmann Abstr. 1910 i 386) have been examined by the spectrograph. The first two esters give almost identical absorption spectra in alcoholic solution ; also in the presence of sodium ethoxide (2 mols.) they give spectra identical not only with each other but also with that of ethyl sodiodicarboxy- glutaconate; when the three solutions have been acidified they show the spectrum of ethyl dicarboxyglutaconate.Tbe ester C,,H,,O, gives an absorption spectrum which is changed by the addition of sodium ethoxide (2 mols.) but is recovered by acidifying the alkaline alcoholic solution. The results which prove that the first two esters are depolymerised by the addition of sodium ethoxide whilst the third merely forms a sodium derivative are in complete harmony with the constitutions ascribed to the three substances (Zoc. cit.). c. s. Lichens and their Characteristic Constituents. XIL. OSWALD HESSE (J. pr. Chem. 1911 [ii] 83 22-96).-A scientific clasification of the lichens must be based on a chemical examination of their characteristic constituents. The present paper is very largely a repetition of the author's work in this region during the last fifty years.The new work deals mainly with the divergencies of the author's results from those of other observers. Usnic acid is not a constant constituent of Euemia prunnsti as claimed by Zopf (Rlechtenstofe 1907 356) since the author failed to detect it in several samples of the lichen obtained from different localities. The same statement is true of Evernia divaricnta. A large quantity of E. illyrica collected on the Trnovaner Walde hear Gorz has been worked up in the usual way and the divaricatic acid isolated. It has not the formula C2,H2,07 as stated previously but C21H2t07 which is in agreement with Zopf's analyses. I t s decomposition by concentrated hydriodic acid yields methyl iodide carbon dioxide and divurinol not orcinol as erIoneonJy statedORGANIC CHEMISTRY.i. 209 elsewhere (Biochemischss Handlexicon 7 63). The potassium sodium barium calcium copper and silver salts the methyl and ethyl esters and the anhydride are described. The acid C,,H,,O obtained by the author by boiling divaricatic acid with aqueous barium hydroxide (Abstr. 1898 i 531) is identical with Zopf's divaricatinic acid prepared by treating divaricatic acid with potacsium hydroxide (Abstr. 1891 i 489). The barium salt silver salt and ethyl ester m. p. 42' are described. By treating aqueous sodium divrtricatate with a n equivalent amount of aqueous ammonia potassinm hydroxide or sodium hydroxide for forty-eight hours a t the ordinary temperature divayic acid C,,H1,O m. p. 169' (decomp.) is obtained which in alcoholic solution reddens litmus and develops a purple-violet colora- tion with ferric chloride It does not contain a methoxy-group and is easily decomposed by boiling water yielding carbon dioxide and divarinol.Pure hydrated divarinol C,H,,O,,H,O has m. p. 44O and loses its water corupletely in a desiccator at the ordinary temperature foriuing a yellowish-red mass ; its diacetate has m. p. 12-15'. Divnrinol which resembles orcinol in its behaviour has the constitution ' C 1'1 H)>CH ; the annexed formuh are those of divsric CH.C( OH) a cicl divaricatinic acid and divaricatic acid respectively CO,H CO,H n - r r OH OH V:Lrious samples of E. fu?fui*acea have been examined by the author and found to contain atranorin and evernuric acid but not farinaceaic acid as stated by Rave (Dissert.1908). Ecernici furfuracea var. olivetorina (Pscudevernia odivetorina) contains atranorin and olivetoric acid the potassium barium and ccclcium salts of which are described. The decomposition of olivetoric acid by boiliilg aqueous barium hydroxide in the absence of air yields carbon dioxide and a substance olivetorol C20H2605 which develops a purple-violet coloration with ferric chloride and a blood-red coloration with calcium hypochlorite ; its further examination has been postponed owing to lack of material. Since Zopf found Z-usnic acid destrictic acid and a colourless crystalline substance in CZadonia destrictci (Abstr. 1903 i 76Z) whilst the author isolated Z-usnic acid squamatic acid cladestin and some coloured substances (Abstr. 1.905 i 138) the lichen has been again examined with the result that Z-usnic acid cladestin squamatic acid destrictic acid and two new acids destrictasic acid and cladestic acid have been isolated. Destrictasic acid C,3H,,0 m.p. 202O sintering at 1 7 5 O forms white leaflets from dilute alcohol ; its alcoholic solution reddens litmus but does not develop colorations with ferric chloride or calcium hypochlorite. The following new facts are stated with respect to cladestin its m. p. is 242-245O not 252' it crystallises anhydrous and it does not yield ethyl iodide by treatment with hydriodic acid although it i s so changed that its alcoholic solution no longer gives a colorationi. 210 ABSTRACTS OF CHEMICAL PAPERS. with ferric chloride. Cladestic acid C50HZ4012 is a flesh-coloured amorphous powder m.p. 82' (decornp.). It does not contain a n alkyloxy-group has a distinctly acid reaction in alcoholic solution and develops an intense dark brown coloration with ferric chloride. Cetraria stuppea contains dilichesteric acid proto-a-lichesteric acid and two new substances called cornicularin and stuppeaic acid. Cornicularin C28H4405 rn. p. 230° is crystalline does not dissolve in potassium hydroxide or carbonate and in alcoholic solution gives a dark brown coloration with ferric chloride. Stuppertic acid CJ9Hz604 rn. p. 222' (decornp.) is a crystalline powder dissolves sparingly in the ordinary solvents gives only a slight brown coloration with ferric chloride and does not contain an alkyloxy-group. Cetraria uculeccta contains in addition to protolichesteric acid and proto-a- lichesteric acid a new substance called acanthellin C18H3Q05 m.p. 1 8 8 O which is apparently crystalline sparingly soluble and does not give a coloration with ferric chloride. Stictaic acid isolated from Xticta pulmonaria probably has the composition C19€€,409 rather than C,,H,,O as stated previously. I t is shown that conspersaic acid isolated from Parrnelia conspema 1s not identical with salazic acid as suggested by Zopf (Abstr. 1905 i 789). CTrceoZaria albissima is stated by Zopf (Abstr. 1897 i 436) to contain zeorin and atranorin in addition to the lecanoric acid discovered by the author (Abstr 1899 i 381) but a repetition of his experiments on 400 grams of the lichen has failed t o disclose the presence of these two substances ; in one sample however atranorin has been discovered.Zopf has stated (Abstr. 1906 i 672) that the lecauoric acid obtained by the author from Urceolaria scruposa (Abstr. 1901 i 595) is diploschistessic acid ; it is now shown that the latter is a mixture of lecanoric and patellaric acids. c. s. o-Tolylacetaldehyde and its Derivatives. M. KRONIK (Chem. Zentr. 1910 ii 1051 ; from Kosmos 1910 35 Radziszewski-Yestband 590-593).-o-ToZylacetuldehyde C,H,Me*CH,*CHO is obtained by the dry distillation under reduced pressure of the barium salts of o-tolylacetic arid formic acids; i t forms an oily yellow liquid b. p. 219-221'/742 mm. b. p. 142-143'/90 mm. Die 1,0241 and when diluted has an odour resembling that of jasmine. The oxirns forms colourless needles m.p. 99-100'. The thiosernicarbaxone crystallises The Carbonyl Group in the Nascent State. ALFRED W. STEWART (J. p ~ . Chem. 1911 [ii] 83 194-197).-Reply to in rhornbic plates. N. c. Petrenko-Kritschenko (Abstr. 1910 i 177). c. s. Halogenated Alicyclic Ketones. I. Monohalogenides of cgcZoHexanones. ARTHUR KOTZ and H. STEINHORST (Annulen 191 1 379 1-27).-The paper deals with the conditions for the direct introduction of one chlorine or bromine atom into cyclohexanone and its homologues with the orientation of the halogen atom and with the influence exerted by one or more alkyl groups in the cyclic ketone onORaANIC CHEMISTRY. i. 211 the position of the halogen. It is found t h a t the halogen always enters the ring in the ortho-position t o the keto-group and in the meta- or para-position t o a methyl group when such is present except in the case of carvomenthone.The halogenation of the cyclic ketones is effected by Kotz and GGtz's process (Abstr. 1908 i 173) by the action of chlorine or of bromine vapour mixed with air in the presence of calcium carbonate and water. The halogenated ketones are deprived of the elements of the hydrogen halogenide by ethereal aniline and are converted by aqueous potassium carbonate into the corresponding tiydroxy-compound from which the elements of water are removed by anhydrous oxnlic acid a t 110'; the same cyclohexenone is always obtained by the two processes. Thus cyclohexanone itself has already been shown t o yield 2-chloro-(or bromo-)cycZohexanone (Kotz and Gotz Zoc. cit.).1-MethylcycZohexan- 2-one yields 3 -chloro- 1 -methylcyclohexan-2-one b. p. 98-100'/15 mm. and 3-&orno~l-methyZcgclohexanone b. p. 105-107°/12 mm. ; the former is converted into 3-hydroxy-1-methyl- cyclohexan-2-one b. p. S5-87'/13 mm. from which and also from the bromo-compound l-methyl-A3-cyclohemn-2-one b. p. 172-1 73' (semi- cadmzone m. p. 177-178') is obtained. l-~letliylcycZohexan-3-one yields 4-chloro-l-methylcyclohexan-2-one m. p. 61-65!' and 4-bromo- l-methyZcyclohexan-3-one m. p. 83-84' ; 4-hydroxy-1 -methyZcyclohexan- %one has b. p. SS-9O0/1 4 mm. and 1-methyl-A3-cyclohexen-3-one b. p. 188-190° forms a sernicarbazone m. p. 159-160". 1-Methylcyclo- hexan-4-one yields 3-cMoro-l-meth~lcyclohexan-4-one b. p. 99 -1 Ol'/ 14 mm. from which 3-hydroxy-l-methylcycloh~xa~a-4-ons b.p. 90-92"/ 14 mm. is obtained ; the latter is oxidised to P-methyladipic acid and yields with anhydrous oxalic acid l-meth$-A2-cyclohexen-4-one b. p. 175-176" (sernicarbazone m. p. 184-185') which is also obtained from 3-bromo-l-methylcyclohexnn-4-one b. p. 112-1 13'114 mm. Menthone yields 4-brornomenthane-3-one b. p. 180-122'/16 mm. and 4-chZoromenthc~ne-3-one b. p. 115-117°/15 mm. from which Wallach's A'-menthene-3-one is obtained ; a n ethereal solution of the last yields with hydrogen chloride 5-chZoromenthane-3-one m. p. 135-1 36". Carvomenthone yields 1 -chZoromenthane-2-on~ b. p. 130-1 32"/14 mm. and 1 - brornomernthane-2-one b. p. 138-1 40'1 14 mm.; 1-hydroxymenthane-2-om has b. p. 128-130°/14 mm. The constitutions of the last two compounds are determined by their conversion into carvotanacetone.c. s. Tetrahydroxybenzenea. GIUSEPPE BARGELLINI and LEDA BINI (Atti €2. Accnd. Lincei 1910 [v] 19 ii 595-600).-The preparation is described of some derivatives of 1 2 3 5-tetrahydroxy benzene including 2 3 4 6-tetrnmethoxyacetophenone the corresponding tetramethoxychalkone and 4 2' 3' 4' 6'-pentamethoxychalkone. When 1 2 3 5-tetramethoxybenzene is treated with acetyl chloride in presence of aluminium chloride in carbon disulphide solution a mixture of the dimethyl (in small quantity) trimethyl and tetra- methyl ethers of 2 3 4 6-tetrahydroxyacetophenone is produced. Thei. 212 ABSTRACTS OF CHEMICAL PAPERS. first two are soluble in sodium hydroxide; they can be precipitated from it by addition of acid and separated with the aid of solvents.2 13 4 6-lbtrahydroxyacetophenone dimethyl ether CIOHI2O5 i s a bright yellow crystalline powder m. p. 162-163'. It dissolves in concen- t r a ted sulphuric acid with production of an orange-yellow coloration which on addition of nitric acid becomes intensely red. I t s ucetyl derivative has m. p. 110-112°. 2 3 4 6-Tetrahydroxyacetop?~enone trimethyl ether C1,H1405 forms slightly yellow prismatic crystals m. p. 105-107" and dissolves in concentrated sulphuric acid giving a yellow coloration which becomes red on addition of nitric acid. Its cccetyl derivative C13H160A crystallises in small colourless needles m. p. 106O. The benxoyl derivative has m. p. 120-122O. 2 3 4 6 ~~tra~~?/droxyaceto~~~enone tetramethgl ether C12H1605 has m.p. 43-45O b. p. about. 310° and gives a yellow solution in concentrated sulphuric acid which becomes intensely red when treated with nitric acid. I t s serniccwbaxone C33H1~105N3 forms small colourless needles m. p. 128-130". 2' 3' 4' 6'-Tetranzethox?/chnlLone (from benzaldehyde) crystallises in tufts of small very pale yellow needles m. p. 74-75O (softening at 70"). It dissolves in concentrated sulphuric acid with Production of an orange-red coloration. 4 2' 3' 4' 6'-Pentanzethoxy- chalkone C20H2206 (from anisaldehyde) fornis small straw-yellow needles in. p. 88-90° (previously softening) and dissolves in con- centrated sulphuric acid with production of an orange-red coloration. R. V. S. a-Amino-ketones. SIEGMUND GABRIEL (Bey.191 1 44 57-69). -A description is given of the preparation of some u-amino-ketones of the type X*CO*CR,*NH hitherto unknown. a-Phthcdiminoiso- butyi-ic acid C,H,<CO>N*CMe2*C0,H m. p. 153-1 54O obtained from a-aminoisobutyric acid and phthalic anhydride at 180° is con- verted by phosphorus pentachloride into the chloride C6B4<~~>N*CMe,*cocI m. p. 82-84O. By treat'ment with benzene and aluminium chloride and subsequently with cold dilute hydrochloric acid the chloride is con- verted into a-phthaliminoisobutyrophenone m. p. 122-1 23*5O which on hydrolysis by hot 10% potassium hydroxide and subsequent treatment with hydrochloric acid yields a-arninoisobutyrophenone hydmchloride COPh*CMe,-NH,,HCI,&H,O sintering a t about 137O ; the anhydrous salt has m.p. 187-18W; the picrate m. p. 175'. Unlike other a-amino-ketones the salt of this new amino-ketone does not reduce Fehliag's solution. a-Arninoisobutyrophenone liberated from the hydro- chloride by strong potassium hydroxide has b. p. 254-255"/752 mm. and is the first a-amino-ketone that has been isolated in the pure state others suffering condensation and oxidation to substituted pyrazines (Abstr. 1908 i 464). A suspension of ethyl sodiomalonate in benzene is treated with a benzene solution of a-phthaliminoisobutyryl chloride and the yellow solu- tion obtained is boiled for eighteen hours neutralised by a little hydro- chloric acid and distilled with steam ; the yellow residue is extracted COORGANIC CHEMISTRY. i. 213 with ether (the insoluble yellow crystalline powder is described in the following abstract) the ethereal filtrate after being shaken with aqueous sodium carbonate is evaporated and the residue is dissolved in lukewarm amyl alcohol the solution being kept for six hours a t the ordinary temperature whereby ethyl a-phthdiminoisob~tyryl- malonate C,H,<GO>N*CMe2*CO*CH(C0,Et)2 co m.p. 76-77*5' is obtained. When boiled with hydriodic acid b. p. 127' for half an hour the ester is decomposed into phthalic acid carbon dioxide ethyl iodide and methyl P-aminoisopropyl ketone hydriodide CH,*CO*CMe2*NH2,HI m. p. 169-170'. The nitrute m. p. 132-1335' hydrochlode m. p. 210-21 lo platin&?doride m. p. 201' (decomp.) aurichloride m. p. 165' giving turbid liquid clarifying a t 190°,picrate m. p.142 -143.5' benxoyl derivative m. p. 124-125' and phti'alyl compound m. p. 105-106' are described. The aqueous solutions of the salts of this a-amino- ketone do not reduce Fehling's solution. Unlike a-amino- isobutyrophenone however this amino-ketone cannot be isolated in a pure state. When an aqueous solution of its hydriodide is treated with an equivalent amount of N-sodium hydroxide a certain amount of the amino-ketone is obtained together with a crystalline substance with an odour of menthol. The latter is obtained better by shaking the solid hydriodide with an excess of 33% potassium hydroxide ; i t has m. p. 88-89' and is tbe hexahydrate of a base C,,Hl,N2 b. p. 180-88 Lo m. p. 69-695' which volatilises very readily and appears to be 2 ; 3 3 ; 5 6 ; 6-hexamethyl-3 6-dihydropyruxine CMe* CMe N%Me2*CMe 2>N ; its hydrochloride picrate m.p. 232' (decomp.) platinic?'loride and aurichloride decomp. 180° are described. By reducing the base with sodium and alcohol and treating the product with hydrochloric acid and potassium nitrite dinitrosohexarnethylpiperaxine C10H2002N4 m. p. 248-249' (decomp.) is obtained which is converted by boiling hydro- chloric and a little acetic acids into hexamethylpiperazine hydvochloride C1,H2,N2~2HC1 from which the hydrated base C,oH2,N2,2H,0 m. p. 65-66.5 is obtained by the action of concentrated potassium hydroxide ; the nitruta platinichloride uurichloride picrate decom p. 260' and mercurichloride are mentioned. A by-product of the action of very concentrated potassium hydroxide on methyl P-aminoisopropyl ketone hydriodide is a basic substance C10H18NZ which forms a Iqdroch,Zoride C,,H,,N,,2HC1,2H,O m.p. about 17 1-1 72' pkatini- chloride Cl,H,,N,,H,PtCI,,~ benxoyl derivative CloH17N2Bz m. p. 105O picrate m. p. 198' and aurachloride. Its constitution has not yet been ascertained ; probably it is an aminopyrrole or pyridine derivative. c. s. The Beckmann Rearrangement. 11. MITSURU KUHARA and YOSHINORI TODO (Mem. Coll. Xci. Eng. Kydto 1910 2 387-396).- The influence of acetyl chloride chloroacetyl chloride and benzene-i. 214 ABSTRACTS OF CHEMICAL PAPERS. sulphonyl chloride on the rate of rearrangement of diphenylketoxime has been determined by heating a chloroform solution of the acid chloride and the oxime in molecular proportions at SO’ and weighing the ben zanilide produced.I n $-molar solutions diphenylketoxime is almost completely trans- formed into benzanilide by benzenesulphonyl chloride in five minutes whilst with chloroacetyl chloride 61% undergoes change in the same time ; in the case of acetyl chloride the rate of rearrangement is much slower only 9.6% of the oxime being transformed in fifteen minutes. The rates of rearrangement thus stand in the order of magnitude of the dissociation constants of the acids and the conclusion is there- fore drawn that the velocity of transformation of the oxime esters CPh,:N*O*CO*R is dependent on the negative character of the acid residue R*CO*O. Measurements of the velocity of rearrangement of acetyldiphenyl- ketoxime in the presence of hydrochloric acid and of diphenylketoxime in the presence of acetyl chloride both in &-molar chloroform solutions indicate that these reactions are unimolecular. With respect to the mechanism of the rearrangement the authors propose the following scheme P h E P h (1) P h g P h (2) Ph$*OAc HCIN*OAc -+- IIClNPh +AcCl -+ N*OH + AcCI (3) P h y O -+ HNPh in which the changes (1) and (3) take place rapidly whilst the reaction (2) occurs slowly thus accounting for the transformation being apparently of the unimolecular type.According to the authors the primary cause of the change R*$?3 R* I;; *O*COR’ (‘1 N.O.COR’ -+ (I1) N.R is the negative character of the acid residue R’CO.0 ; with strongly negative residues dissociation of (I) into K,C:N- and R’CO.0 readily takes place and these dissociation products then react to form (11).It has been shown (Kuhara and Kainosho Abstr. 1907 i 1027) that the presence of hydrochloric acid is necessary for the rearrange- ment of acetyldiphenylketoxime and the authors therefore draw the conclusion that in the case of the oxime-acetates hydrochlorides of the type CR,:N*OAc,IICl are produced ; under the iufluence of the hydro- chloric acid the tendency of t h e OAc group to separate from the nitrogen atom is increased to such an extent that a similar dissociation to that mentioned above takes place. A compound of the constitution OAc-CPhXPh has been obtained as a viscid yellow oil by the interaction of the imide-chloride CPhCI:NPh and silver acetate. On passing hydrochloric acid into its cold ethereal solution the hydrochloride separates out as a canary- yellow precipitate which is converted by excess of the acid into acetyl- benzanilide.When the hydrochloride in chloroform solution is heated above 60° i t yields benzanilide. This change corresponds with the last phase of the rearrangement in the authors scheme given above. F. €3.ORGANIC CHEMISTRY. i. 215 Ketene. XV. Action of Diphenylketen on Nitroso-corn- pounds. HERMANN STAUDINGER and SERGIUS .JELAGIN (Ber. 191 1 44 365-374. Compare Abstr. 1910 i 46).-By the action of nitrosodimethylaniline in ethereal solution in 2 mols. of diphenyl- keten carbon dioxide is liberated the green colour a t once vanishes and the Schiff's base first formed combines with diphenylketen to form a /3-Zactum of ~-dimethyZccminoaniZino-aa~~-t~t~~a~~en~Z~o~~acid -co- CPh2<CPh,>N.CBH,*NMe2.This forms colourless crystals which sinter at 196O m. p. above 200' (decomp. t o an orange-red liquid). The composition of this lactam was proved by its synthesis from diphenylketen and benzopbenone-p-dimethylaminoanil. Nitrosobenzene reacts differently with di pheny 1 keten forming GO nnhydrod~pl~e~ylg2ycolZ~Zp~~nyZhydrox~Zumine CPh,<-O->NPh which separates in well formed colourless crystals m. p. 7 2 - 6 O . T t is stable at the melting point but on further heating decomposes explosively into benzophenone and phenylcarbimide. When boiled with con- centratod hydrochloric acid chEorocliph~nyZaceto~henyZhydroxyZnrnine CPh,Cl*CO*NPh*OH colourless crystals m. p. 158.5- 159.5' is formed.The four-membered ring-compound is obtained synthetically by the action of chlorodiphenglacetyl chloride on phenylhydroxyl- amine. Nitrosobenzene and 2 mols. of diphenylketen also react t o form small quantities of the p-lccctam of p-anilino-aapp-tetraphen?ll2-,?.opionic acid CPh,<c,h2>NPb m. P. 191" which is also formed on con- densing benzophenoneanil with diphenplketen. The four-membered CO- co- ring CPh2<Nph>0 is possibly formed in small quantity during the action of nitrosobenzane on diphenylketen but decomposes in the cold into benzophenoneanil and carbon dioxide. Diphenyl- and dimethyl-nitrosoarnines do not react with diphenyl- keten. E. F. A. Action of Nitric Acid on Halogen Derivatives of o-Alkylated Phenols. 11. TIIEODOR ZINCKE and W. BREITWEISER (Ber.191 1 44 li6-184).-The products formed by the action of nitric acid on tribromo-p-xylenol are similar to those obtained previously from tetra- bromo-o-cresol (Abstr. 1907 i 322). They are three in number namely (a) 3 5 6-tribromo-1 4-dirnethylquinonitrole CM e < ~ ~ ? ~ ~ ~ > C M e * N 0 2 . ( b ) An additive compound of the quinonitrole with nitric acid CBr==== CBr CMe<CBr*c(oH)(o*No2) >CMe.NO ( c ) An open-chain compound N02*C H Me*CBr:CBr*CMe CBr*CO*ON O which can also be obtained by the action of Eodium carbonate solution on the additive compound. The quinonitrole is identical with the product deccribed by Auwers (Abstr. 1899 i 30) but is regarded as an ortho- and not a para-i. 216 ABSTRACTS OF CKEMICAL PAPERS. derivative since the quinole obtained by the action of cold benzene on the nitro-compound does not lose hydrogen bromide and form dibromo-p-xyloquinone and does not yield a p-xyloquinone derivative when heated with sodium acetate and acetic anhydride but loses nitrous acid extremely readily under the influence of moist ether The conversion of the quinonitrole into dibromo-p-xyloquinone by boiling with benzene or light petroleum and of the quioole into dibrorno-p-xyloquinone by warming with acetic anhydride and concen- trated sulphuric acid is accompanied by molecular rearrangements.3 4 6-Tribromo-1 4-dimethylqiiinonitrole is most readily prepared by the action of concentrated nitric acid on tribromo-p-xylenol in the presence of glacial acetic acid. It reacts with cold methyl alcohol yielding 3 6 - dibromo-5 - nitro - p - 2 - xylenol NO,-C,Me,Br,*OH as colourless needles m.p. 154O together with a product m. p. 186-190° insoluble in alkalis and with acetic anhydride and a few drops of concentrated sul phuric acid yields dibrorno-p-x~loquinol diacetate in the form of yellowish-white needles m. p. 218". 3 5 6-Tribromo-l 4- dirneth~ZquinoZ CSHS02Br3 cry stallises from light petroleum in colour- less needles m. p. 111". 3 5 6 - l'ribromo-4-methyl-o-methyZenequinone C,H,OBr crystallises from acetic anhydride in yellow plates m. p. 220-230' (decomp.) and is not chemically active. The acetyl derivative of 3 6-dibromo-5-nitro- p-2-xylenol crystallises in colourless glistening prisms m. p. 116O and 3 6-dibrorno-4-amino-p-2-xylenol crystallises from benzene in colourless plates m.p. 186-1S8'. The additive compound of the quinonitrole with nitric acid C,H70,N2?r crystallises in colourless well-developed prisms m. p. 1 O5-107 (decomp.). The open-chain compound CsH706N2Br3 crystallises in colourless needles m. p. 1 41' (decomp.). J. J. S. Oxidation of Aniline. 11. R I K ~ MAJIMA (Ber. 1911 44 229-234. Compare W illstatter and Majima Abstr. 1910 i 748).- By the oxidation of aniline with sodium bromate in aqueous acetic acid solution at O' a mixture of 2 5-dianilino-p-benzoquinoneanil and amino-ani Zino-p-ben~quinonean~z C( NHPh). CH 0 C<cHIC(NH2'>C :NPh or 0 C<C(?H2)=CH>C CH.C(NHPh) NPh is produced. The latter compound isolated by means of its sparingly sol uble sulphate crystallises in bluish-red prisms.It dissolves in concentrated sulphuric acid with a green colour has feebly basic properties and yields 2 5-dianilino-p-benzoquinoneanil when heated with aniline in glacial acetic acid solution. The hydrochloride C,,HI,ON HCl forms dark green crystals. 2 5-Dianilino-p-benzoquinoneimine (Willstatter and Majima Zoc. c h . ) is more conveniently prepared by oxidising aniline with sodium persulphate. When hydrolysed with hydrochloric acid in aqueous alcoholic solution it yields 2 5-dianilino-p-benzoquinone. F. B,ORGANIC CHEMISTRY. i. 217 Synthesis of P-Menthol-lactoside and its Behaviour in the Organism. HANS FISCHER (Zeitsch. physiot. Chem. 19 1 1 70 256-263. Compare E. and H. Fischer Abstr. 1910 i 716)- Heptwzcet y~-P-menthoZ-Zactoside prepared by the interaction of aceto- bromolactose and menthol in presence of silver carbonate and chloro- form crystallises i n long prisms m.p. 125-1 30° [a] - 29.65' ( k 0.2). It resists hydrolysis by dilute mineral acids ; barium hydroxide con- verts it into J-nzenthol-Zactoside. This crystallises with 4H20 in concentrically-grouped prismatic needles m. p. 1 lo" [U]? - 38.04". It is hydrolysed by mineral acids to menthol and reducing sugar and by emulsin t o menthol lactose and some dextrose. Kephir lactose hydrolyses it slowly. When injected subcutaneously into the organism i t is excreted unchanged ; neither ment holglycuronic acid nor menthol-lacturonic acid are formed. Mentholglycuronic acid (l+H,O) sinters at 92' m. p. l l O o and has [uJZ - 104.4'. Some Derivatives of Dicamphor.VINCENZO CASTELLANA and R. P'ERBERO (Gazxetta 1910 40 ii 482-491. Compare Angeli Castellana and Ferrero Abstr. 1909 i 739).-When pernitrosodi- camphor is boiled with an excess of alcoholic potassium hydroxide the potassium salt separates as a precipitate. If water is added to dissolve this the boiling continued for an hour and then the alcohol removed by distillation dicccmphenoneimine remains as a n oil which on cooling solidifies and after recrystallisation forms needles m. p. 191'. If the ebullition is prolonged for several hours an amorphous grey powder having the properties of an acid is obtained on acidifying the wash water of the preceding compound. To the imine the structure CsHI4< C:NH I It forms a pics.de E. F. A. C- C Ob>C,H,4 is ascribed.C,,H,SON,C,H2(N0,),0H m. p. 195'. When warmed with dilute sulphuric acid the imine yields the corresponding diketone dicamphenone C,H14<b0 Ob>CsR14 which crystallises in lemon- c-c yellow needles m. p. 192-193" and is identical with the di- camphanehexmedione of Odd0 (Abstr. 1897 i 577). With hydrazine it yields the mine as stated by that author and at the same time a small quantity of a yellow sub.utance m. p. 153" is formed. The same aziue is obtained from hydrazine and pernitrosodicamphor. Its picrate C20H28N2,C6H307N3 has m. p. 220'. Pernitrosodicamphor when treated with an excess of hydroxylamine yields two products which can be separated wit,h the aid of solvents and are apparently stereoisomeric dioximes C2,H,,0,N2. One is crystalline and has m.p about 240' (decomp.); the other is formed in very small amount and has m. p. about 275-280'. The authors have also prepared pernitrosocamphor and some of its derivatives from inactive camphor and find them to have similar properties but somewhat lower melting points pernitroso-i-canip~~oo. has m. p. 32' ; per~itrosodi-i-ca~phor m. p. 163' ; i-dioamphenoneinaine m. p. 179'. R. V. 8.i. 215 ABSTRACTS OF CHEMICAL PAPERS. Behaviour of Iodine towards Terpine Hydrate Eucalyptol and Terpineol. CARLO CASANOVA (BoEZ. chirn. fkrm. 1910 49 957-960. Compare Abstr. 1909 i 813).-The above terpenes react with iodine on warming and the liquid compounds produced are heavier than water and give no reaction with starch. They readily decompose in the course of a few hours if exposed t o light and air large quantities of iodine and hydrogen iodide being set free.R. V. S. Constituents of Ethereal OilrJ. Constitution of Perill- aldehyde C,,H,,O. FRIEDHICR W. SEMMLER and B. ZAAR (Be?.. 1911 44 52-57).-The aldehyde isolated from Perilla nankinensis leaf oil and described by Schimmel & Co. (Abstr. 1910 i 758) has been isolated and examined by the authors. I n addition to the properties already recorded (Zoc. cit.) the aldehyde which is called perillaldehyde shows the following behaviour. The semicaybaxone has m. p. 199-200'. By reduction with zinc dust and glacial acetic acid on the water-bath the aldehyde yields perillyl alcohol in the form of its acetate b. p. 123-126",43 mm. DZo 0.9785 nD 1.48142 [a] -48'; the alcohol C,,H,,O obtained by hydrolysing the ester by alcoholic potassiumhydroxide has b.p. 119-121°/11 mm. D20 0*9640,nD1.49964 [a] -6S-5" and is converted by phosphorus pentachloride in petroleum solution into the chloride ClnH1,Cl b. p. 99-l0lo/12 rnm. D20 0.9861 n 1.49728 [.ID - 60'. By treatment with sodium and alcohol the chloride is converted into Z-limonene. Perillaldoxime is changed by boiling acetic anhydride and sodium acetate into perillonifirile C,,H,,N b. p. 116-118°/1 1 mm. D20 0.9439 n 1.49775 [a] - 115" which by hydrolysis yields perillic acid Ci nHi40p b. p. 164-165"/10 mm. m. p. 130-1~1' [.ID - 20" in 25% alcoholic solution. The acid forms n &bromide CloH,,O,Br m. p. 166-167' arid is reduced by sodium and boiling amyl alcohol to dihydroperillic acid C,,H,,O b.p. 152-153°/10.5 mm. m. p. 107-log" [.ID 0' in 25% alcoholic solution which forms a dihyomide m. p. 116-117° and a methyl ester (from the silver salt and methyl iodide) b. p. 105-106"/ 11 mm. DlS 0.9732 n 1.46768 [.ID O' from which dihgd~*operiZEyl alcohol C,,H,,O b. p. 114-115°/10 mm. DI9 0.9284 n 1.48191 [.I) Oo is obtained by the action of sodium in the usual way. The formation of the preceding derivatives particularly of Z-limonene and the fact that the molecular refraction of perillaldehyde indicates the presence of two ethylenic lingings afford good evidence of the con- stitution C€I,:CXe* C H < ~ ~ ~ ~ \ ~ > C * CHO for the aldehyde. C,,HlEPZ~ c. 8. Curcumin. C. LORING JACKSON and I A T H m CLARKE (Amer. Chem. J. 191 I 45 48-58).-Mitobedzka Kostanecki and Lnmpe's state- ment (Abstr.1910 i 629) that curcumin should be represented by the formula C,,H,,O first proposed by Ciamician and Silber (Abstr. 1897 i 229) instead of C,4H1404 as suggested by Jackson and Menke (Anrsr. Chm. J. 1884 4 77) is confirmed. Curcumin has xu. p. 1789ORGANIC CHEMISTRY. i. 219 as found by and Silber. as recorded quantitative heat. Jackson and Menke and not 1 8 3 O as stated by Ciamician Curcumin dimetbyl ether has m. p. 1 3 7 O instead of 135O by Ciamician and Silber and can be obtained in a yield by using a shaking machine instead of applying The brown coloration produced by the action of hydrogen chloride on curcumin is due to t h e formation of an additive compound which is dark brown when only a little hydrogen chloride is used but becomes dark violet when an excess is employed; it is very unstable and is instantly decomposed by water.C2 H2006,3HBr is formed by the action of hydrogen bromide. The reddish-purple substance formed by the action of phosphoryl chloride on curcumin (Jackson and Menke Zoc. c i t . ) is probably either the hydrogen chloride additive compound or a similar product containing chlorine and phosphorus since i t is reconverted into curcumin by the action of water. This substance if left in a desiccator becomes black owing to the further action of the phosphoryl chloride. When an dcoholic solution of curcumin is shaken for rz long time with hydroxylamine hydrochloride a compound m. p. 162O probably the mono-oxime is produced which forms stout orange-yellow needles.If the mixture is heated on the steam-bath instead of being shaken a t the ordinary temperature a yellowish-white compound m. p. 163O is obtained which is probably identical with the foregoing ait,hough of a different colour. This substance is not identical with the isooxazole described by Ciamician and Silber (Zoc. cit.). A similar compound E. G. Pyronone Synthesis by means of the “Tertiary Bases Reaction.” 11. EDGAR WEDEKIND [and JOHANNES HAUSSERNANN W. WEISSWANGE and MORIZ MILLER] (Anrmlen 1911 378 261-232).-The “ tertiary bases reaction ” (Wedekind and Hiiusser- mann Abstr. 1908 i 671) has been applied t o phenylacetyl chloride phenylpropionyl chloride p-nitrophenylacetyl chloride and loutyryl chloride ; pyronone derivatives are formed the production of a diketo- cyclobutane as in the case of isobutyryl chloride (Wedekind and Weiss- wange Abstr.1906 i 437) not being observed. Thus by slowly adding a solution of phenylacetyl chloride (1 mol.) in dry carbon disulphide to a solution of a tertiary base (tripropyl- amine pyridine 1-methylpiperidine or best of all triethylamine) in the same solvent a t Oo moisture being rigorously excluded by passing a slow stream of dry hydrogen through the apparatus 3 S-diphenyt-2- ‘O>O m. p. 173-174” is CHPh- benxyl-1 4 6-pyronone C O < ~ ~ ~ . ~ ( ~ ~ ~ ~ ~ ) obtained in 50% yield its formation‘ beiLg kxplained in the same way as that of 3 5-dimethyl-2-ethyl-1 4 6-pyronone from propionyl chloride (Wedekind and Haussermann doc. cit.). The substance is remarkably stable to reducing agents behaves as a monobasic acid (sodium salt C2,H170,Na,3EtOH cnlourless crystals from alcohol) but not as an oxoniurn base and is decomposed by 20% potassium hydroxide into diphenylacetone phenylacetic acid and carbon dioxide.This reaction suggedts that the substance might be s-triphenylphloro-i. 220 ABSTRACTS OF CHEMICAL PAPERS. glucinol produced by the polymerisation of 3 mols. of phenylketeo. Its pyronone constitution however is indicated by the formation of a mo!uo-oxime m. p. 157' (decomp.) acetate C,,H,,04 m. p. 124-125O and benzoate C,,H,?O m. p. 126O by the non-formation of triphenyl- benzene by reduction with zinc dust and by its behaviour with concentrated aqueous ammonia at 80-100" and finally a t 130-1403 whereby 4 6-dihydroxy-3 ; 5-diphenyZ-2-benxylpyridine C( CH2Ph) CPh>C. OH N<C( OH)==CPh m.p. 260° is obtained. This substance has acidic properties does not decolorise bromine develops a reddish-brown coloration with alcoholic ferric chloride (distinction from the pyronone) and forms a diacetate m. p. 165'. The ready formation of an oxime from diphenylbenzyl- pyronone is unusual; its oximic structure is proved by the regeneration of hydroxylamine and the pyronone by hydrolysis with concentrated hydrochloric acid. Phenylpropionyl chloride and tripropylamine reacting under the preceding conditions yield 3 5-dibenzyl-2-/3-phenylethyZ-l ; 4 6-pyronone CH,Ph*CH,-C<~(CH2Ph)*~~>CH*CH,Ph m. p. 167-1 68O which resembles diphenylbenzylpyronone but is less acidic does not form an oxime and is more readily decomposed by 25% qotassium hydroxide at 120' yielding dibenzylacetone phenylpropionic acid and carbon dioxide. Butyryl chloride and triethylamine react in carbon disulphide to form a pyronone derivative which is so unstable however that its production is indicated only by the formation of dipropyl ketone resulting from its decomposition.p-Nitrophenyhcetyl chloride b. p. 135-138O/0*1 mm. m. p. 4 7 O obtained from the acid and phosphorus pentachloride reacts with triethylamine in dry ether cooled by a freezing mixture 3 5-cli-p- nitrophen?/t-2-p-nitrobenm~l-l ; 4 6-pyronone NO,*C,H,* CH,*Cg~(C6H40NO~)'Co>CH*C,H,.N0 co m. p. 146" (decomp.) a yellow microcrystalline powder being produced which has pronounced acidic properties and is decomposed by 20% potassium hydroxide at 1 60° yielding p-nitrophenylacetic acid and pp'-dinitrodiphenylacetone decomp.205-206" (phenylhydraxone decomp. 1 10-1 12'). The "tertiary bases reaction" has also been applied to isovaleryl chloride and crotonyl chloride ; the former with ethereal tripropyl- amine yields ethyl isovalerate and isovaleric anhydride whilst the latter with triethylamine in benzene forms crotonic anhydride. ' c. s. '' Oxindigo " [2:2-Diketo-A1'*'-dicoumaran]. RICHARD STOERMER and K. BRACHMANN (Ber. 191 1,44,315-319).-The yellow substance m. p. 276" (decomp,) obtained by acidifying the potassium salt of aci- nitrocoumaranone and formerly regarded as (' leuco-oxindigo " (Abstr. 1909 i 174) is now found to be 2 2'-diket0-3~'~'-dicoumsran itself since it is produced from the potassium salt by the action of iodine inORGANIC CHEMISTRY.i. 221 bqueous potassium iodide or alcohol a reaction in which the formation of ‘ 6 leuco-oxindigo ” [2 2’-dihydroxy-l 1’-dicoumaran] is impossible. The properties of the substance correspond almost exactly with those of 2 2‘-diketo-A1:”-dicoumaran prepared by Fries and Hasselbach (this vol. i 150). The action of chlorine water on potassium aci-nitrocoumaranone yields I-chloro-l-nitg*ocozcmaranone C,H,O,NCl m. p. 102’. 1-Bronao- l-nit9-ocoumamnone m. p 105’ is obtained by shaking the potassium salt with bromine in benzene or by rapidly adding bromine water to its aqueous solution; when the bromine water is added very slowly Coffee. IV. K. GORTER (Annnalen 1911 378 110-130 Compare Abstr.1908 i lS6 345),-The author replies to Lendrich and Nottbohm’s criticism (Abstr. 1909 ii 449) of his method for the estimation of the caffeine in raw coffee (Zoc. cit.) and describes experiments which show that the caffeine in Liberian coffee is all piesent as potassium caffeine chlorogenate. All formuh previously suggested for hemichlorogenic acid are withdrawn and are replaced by the constitution given below for the following reasons (1) I n its fission by acids and alkalis hemichloro- genic acid behaves like a /3-ketonic acid. (2) The non-formation of a n oxime phenyl hydrazone and semicarbazone indicates the absence of a carbonyl group. (3) If the tetrahydropyrone formula previously suggested is correct the acid should yield 3’ 4’-dihydroxyflavone by the elimination of 3H20 and of the carboxyl group This result has not been effected by heating chlorogenic acid with hydriodic acid with water a t 220-230’ or alone a t 240-250’ in a vacuum.(4) By treatment with bromine (I mol.) in chloroform in sunlight penta- acetyl hemichlorogenic acid yields a crystalline additive compound Cl6Hl3O9Ac5Br2 m. p. 214-215’ which cannot be acetyliited quantitatively regenerates penta-acetylhemichlorogenic acid with alcohol and potassium iodide and is converted by boiling potassium hydroxide into quinic and broiriocaffeic acids. (5) The fact that only ,five of the six hydroxyl groups in hemichlorogenic acid can be :acetylated is proved by showing by Zerewitinoff’s method with magnesium methyl iodide in amyl ether that penta-acetylhemichlsro- genic acid which cannot be further acetylated even by acetyl chloride in pyridine still contains a hg droxyl group.If hemichlorogenic acid were identical with a-quinylcaffeic acid diketo-A’’l’-dicoumaran is proddced. c. 8. 0,H,(OH)2*CH:C(C02H)*CO*C(OH)<~~~~~(~~~>CE€*OH dhe non-acetylated hydroxyl gronp would be the tertiary one a view whish is untenable since this group i n quinic acid itself is easily atoetydated. ( 6 ) Chlorogenic and penta-acetylhemichlorogenic acids m e nat reduced by zinc dust and acetic acid and therefore do not con- h i n au ethylenic linking in the up-position to a carbonyl group. For these aeasons and others already recorded hemichlorogenic acid is represented by the constitution I 0 I C,H,(OH)2*CH:C(C0,H)*C(OH)*C(OH)<~$~H~.~>CH* i OH VOL.C. i. Ti. 222 ABSTRACTS OF CHEMICAL PAPERS. in which the * denotes the hydroxyl group which cannot be acetylated. Consequently chlorogenic acid has the constitution I I o- which is in harmony with the result obtained by reducing the acid by sodium amalgam in a solution which is kept slightly acidic by the continuous addition of sulphuric acid. The product of reduction is dihydrohemichlorogenic u&& C,,H,,O m. p. 167-168' which forms a pentcc-acetate m. p. 182' and IS decomposed by hydrochloric acid or potassium hydroxide into quinic acid and dihydrocufleic acid C,H m. p. 139'. I t s formation is explained by the conversion of the chlorogenic acid into hemichlorogenic acid which as an ap-unsaturated Dioscorine.K. GORTER (Chem. Zentr. 1910 ii 1228-1229 from A m . Jardirn Bot. Buitenxorg. 1909 [ii] Suppl. 3 3S5-392).- From the bulbs of Dioscorea hirsuta Boorsma and later Schutte (Abstr. 1898 i 341) isolated a crystalline alkaloid dioscorine Cl,H1902N. The base was isolated from the bulbs by extraction with alcohol acidified with acetic acid; it can be distilled unchanged in a vacuum. The following salts are depcribed hydrobromide white crystals m. p. 213-214' ; oxcclate white prisms m. p. 69.5-70.5' ; metlhiodids 113. p. 213O ; methocldoride aurichloride plates m. p. 188' ; methochloride platinichloride orange tufts rn. p. 21 8'. Dioscorine is not acted on by acetic anhydride and it must be considered to be a tertiary base not containing a n OH group.On heating with potassium hydroxide it gives a potassium salt which again yields dioscorine by the action of hydrochloric acid. It must there- C H s * N < b ~ - y H - ~ H * ax >" fore be considered that dioscorine is CH,.CH:CH.CH a y-lactone. When dioscorine is heated with concentrated potassium hydroxide a t 200-250° in the presence of air methylamine is evolved; dioscorine methiodide gives dimethylamine under similar cooditions a phenol-like substance being also formed. An acid solution of potassium permanganate is a t once decolorised by dioscorine. The annexed Alkaloid of Eschscholtzia Californica. GEORGES BRINDEJONC (Bull. Xoc. chirn. 1911 [iv] 9 97-100).-This plant contains 0.25% of a new alkaloid ionidiae. No other alkaloid is present (compare R.Fischer 'Abstr. 1901 i 743). An alcoholic extract of the plant deposits potassium nitrate on concentration and when extracted with warm water deposits resin. From the filtrate after defaecation with lead acetate and addition of alkali ether extracts ionidine C,,H,,O,N m. p. 154-156' which crystallises in short flattened colourless transparent prisms. Its solubility in cold aIcohol (90') is 0*46% and in water 1 in 2500. The alkaloid is strongly basic and yields bitter very soluble gummy salts acid is easily reduced to the dihjdro-compound. c. s. CH*CH,*yH-O constitution for dioscorine is suggested. N. c.ORGANIC CHEMISTRY. i. 223 with acids The aurichloride platinichloride and rnercurichloride are all amorphous. It is precipitated from dilute solutions by iodine pici*ic acid or gold chloride and gives characteristic colour reactions with various reagents of which t h e most useful a r e the following sulphuric acid gives no coloration but with sulphuric acid containing a tvace of nitrous acid a deep violet t i n t is produced and a similar coloration is given with Frijbde's reagent.In both cased the violet t i n t changes t o brown when kept. Codeine Oxide. GUSTAV MOSSLER and ERICH TSCIIEBULL (Ber. 191 1 44 105-1OY).-By not too prolonged treatment with 1.5% hydrogen peroxide on the water-bath codeine yields a biniolecular codeine oxide C3,H4,09N2,7H20 m. p. 200-2@2°(decornp.) crystallising in elongated rectangular plates. 'I.'he substance loses 6H20 in a vacuum and 7H,O at 100-110" and then has m. p. 211-215' (tteromp.).It contains two atoms of active oxygen; the monohydrate has [.ID - 9'7.6' in water and - 105.9' in 97% alcohol the values for tho anhydrous substance being -99.6O and - 107.2c. The molecular weight is determined by the ebullioscopic method in water. The hyclrochlo?*ide OlsH?,04N,HC1,H20 obtained by treating a hot alcoholic solution of the bimolecuInr oxide with hydrochloric acid haa m. p. 219-220' when anhydrous and has [.ID - 105.8O in water. By treating its aqueous solution with sodium carbonate. the hydrochloride yields a unimolecular oxide C,,H,,O,N,H,O m. p. %15O [.ID - 97.1' in water (compare Freund and Speyer this vol. i 76). T. A. H. c. s. Aldehyde Sulphites of Vegetable Alkaloids. MARIO MAY ER (Gaxzetta 1910 40 ii 402-414).-Bvucine benzaldehyde suZpluite is prepared by treating a suspension of brucine in water with sulphur dioxide until solution is complete and then shaking the liquid with benzaldehyde. It forms a colourless crystalline precipitate m.p 1 2 5 O (decomp.). The following similar' compounds were prepared in the same way. The analytical figures mostly indicate an excess of alka- loid. Brucine anisuldehyde sulphite C23H2604N2,~aS03,C8H802 is a white powder which softens at 108" and decomposes at 115". Brucine scclzcy~a~dehyde sulphite C,,H2,04N,,H,S03,C7H602 is a colourless powder decomposing at 1 ZOO. Brucme heptaldehyde sulphite is a white crystalline substance decomposing at 102'. Brucine prupakdehyde sulphite C2,H,,0,N2,H2S0,,0,H60 separates only when the solution is kept in presence of sulphuric acid ; i t decomposes at 135'.Brucine ucetune sulphite C,3H2,04N2,H2S0,,C,H,0 is a colour- less crystalline substance decomposing a t 190". Brucine benzophenone sulphite ~,,H,,04N2,H,S03,C1,Hlo0 is prepared in alcoholic solution ; it is a colourless crystalline substance decomposing at 120". Brucine acetophenone sulphite C23H2604N2,H2S03,CSH,0 forins a yellow crystalline powder decomposing at 108". Brucinic mid benzaldehyde sulphite C23H2805N2 H2S03 C7H,0 crystal- lises in clusters of small needles decomposing at 122'. -Brzccinic acid ethiodide C2,H3,05N,I,H,0 prepared by the method C23H,,04N2 H,S03,C7Hf50 C,3H260,N2,H2S03 C7H140 r 2i. 224 ABSTRACTS OF CHEMICAL PAPERS. used by JkIoufarig and Tafel (Abstr. 1899 i 309) for the methyl derivative is a grey mass m.p. 205' (decornp.). It yields with sulphur dioxide and benzaldeliyde a small quantity of n substance m. p. 145' (decornp.) which does not contain iodine. Bwberine sulphite is obtained by acting on the hydrochloride with a saturated solution of sulphur dioxide in couceritrated sodium hydrogen sulphite (compare Yerkin Trans. 1890,57 1097). When to a solution of the salt in the cold benzaldehyde and alcohol me added and the liquid is treated with sulphur dioxide berberine benzaldehyde sulphite C2,H,,0,N,H2S0,,C7H60 is obtained in golden-yellow silky needles which become brown at 180'. Morphine benxaldehyde suZphite Ci~Hi,0,N,H2S03,C7H60,is a crystalline substance m. p. 1 15' (decomp.). Namotine benxaldehyde suZphite C2,H2,O7N,H2SO3,C7II60 is a colour- less crystalline powder m.p. 70" (partial decornp.). Cocaine benzaldehyde sulplrite C i ~ ~ 2 1 0 ~ H 2 S 0 3 ~ ~ ~ 6 ~ is obtained in alcoholic solution and forms a colourless deliquescent mass. Quinine benxaldehyde sulphite C20H2402N2,2 H2S0,,2C7H60 prepared in alcoholic solution is a powder which decomposes a t 8 5 O arid at ordinary temperatures and pressures evolves sulphur dioxide. Cinchon- ine benxaldehyde sulphite C,,H2,0N,,2H2S0 2C7H,0 forms a white powder which decomposes a t go" and loses sulphur dioxide when kept in a desiccator. Benzaldehyde anhydrosulphites of the alkaloids are obtained when chloroform or benzene solutions of the alkaloids are treated with dry sulphur dioxide and benzaldehyde is subsequently added. The anhydrosulphites appear as crystalline or resinous residues when the liquids are evaporated and have properties similar to those of the sulphites. Pilocarpine benxaldehyde anhydrosulphite is a colourless,crystalline substance decomposing at 105'.The nnnrcoline compound C22H2,0,N,S02,C7H,0 is also colourlese and crystalline ; it decomposes a t 80". The brucine4compound C23H~604N2,S02,C7HGo is crystalline and has m. p. 105' (decomp.). It dissolves readily in water the sulphite being precipitated. The brucinic acid compoufzd C23H,,0,N,,S02,C7H60 is a crystalline mass decomposing at 95". Xtrychnine although a monoacidic base yields an anhydrosulphite to which the formula C 2 H 2 ~ 0 2 ~ 2 2 ~ 0 2 C 7 ~ G ~ may be ascribed although the analytical figures differ somewhat from those required by this formula.The substance is a yellow resinous mass m. p. 110". (decomp.) which continually evolves sulphur dioxide. When dissolved in water it loses sulphur dioxide and benzaldehyde and on evaporation of the solution a solid resin is obtained m. p. 95" (decornp.) which is probably strychnine benxaldehyde sulphite C,H2202N2~~2S03,~7H60. It is suggested that the sulphites described in this paper have the structure C,H,* CH<-O->Ni R Nil< representing the alkaloid. C1,HI,02N2,S02,C7H60 R. V. S. so2 Action of Sulphuryl Chloride on s-Dimethylpyrrole. u. COLACICCH~ (Atti IZ. Accad. Lincei 1910 [v] 19 ii 645-648).- Sulphuryl chloride (2 mols.) reacts with 2 5-dimethylpyrrole inORGANIC CHEMISTRY. i. 225 ethereal solution a t 0". The liquid after remaining f o r two days a t the ordinary temperature was treated with ice and the residue from the ethereal solution was subjected to steam distillation.No dis- tillate was obtained but the aqueous residue in the distilling vessel d+posited crystals on cooling from which by the aid of solvents two bubst:mces were obbained in very small quantity. One of these did not melt at 300'; it behaved as an acid and gave an unstable silver salt The other substance crystallised in stellate clusters of needles m. p. 228' (deccjmp.) had the composition C,HSO,NCl and the reactions of an aldehyde. It reduced ammoniacal silver solution gave a white substance with ammonia yielded a p-nitrophenylhydraxone m. p. 237". and formed a naphthacinchooinic derivative m. p. 265" with py.ruvic acid and P-naphthylamine.Por these reasons the substance is assigned the structure of 3 4-dichloro-2 5-diuldehydopy~roZe >NH QCl:C(CHO) CC1 C(CH0) whilst the acid above-mentioned' is pr'obably the corresponding dibasic acid 3 ; 4-clichloropyrrole-2 5-dicarboxylic acid. The Ferriammines. GIUSEPPE A. BARBIEEI and G. PAMPANINI (Atti R. Accad. Lincei 1910 [v] 19 ii 591-594).-Ferric thiocyanate yields with certain organic bases crystalline compounds containing for every molecule of thiocyanate three molecules of the base. They have a constitution similar to that of the tripyridinechrornium chloride of Pfeiffer (Abstr. 1907 i 872). Bipyridineferric thiocyanate Fe(SCN)3 is prepared by mixing the calculated quantities of ferric thiocyanate and pyridine in aqueous or better in ethereal solution.It forms dark green crystals which are insoluble in water but are soluble in various organic solvents with production of either red or violet solutions. Trriquinolineferric thiocyunute Fe(SCN),(CpH7N) is similar to the pyridine derivative; it forms crystals which are almost black. Triccntipyrinefewic thiocyanate Fe(SCN),( C1,H,,ON,) forms red crystals. Rupture of the Pgridine Ring. FRITZ REITENSTEIN and WILHELM BREUNING (J. pr. Chem. 1911 [ii] 83 9'7-130).- Vongerichten (Abstr. 1900 i 51 ; compare Spiegel ibid. 1901 i 752) has shown that 1-chloro-2 4-dinitrobenzene and pyridine form an additive compound containing a quinquevalent nitrogen atom and Zincke (Abstr. 1904 i 448 921 ; 1905 i 241 923) has proved that this additive compound reacts with primary and secondary arylamines yielding 2 4-dinitroaniline and derivatives of glutaconaldehyde of the type NHPhCl:CH*CH:CH*CH:CH*NHPh due t o the rupture of the pyridine ring (compare Yieckmann Abstr.1905 i a l l ) . It is now shown that other substances containing negative groups can form quaternary ammonium salts with pyridine for example diaryl- oxalirninochlorides benzanilideimidechlorjde phosphorus pentachloride etc. and that these additive compounds react with primary aryl- amines producing a rupture of the pyridine ring and the formation of red dyes of the same type as those described by Zincke. It has R. V. S. (C,NH,) R. V. S.i. 226 ABSTRACTS OF CHEMICAL PAPERS. not been found possible t o isolate definite additive compounds in all the cases studied but the subsequent formation of a red dye by the action of an amine is regarded as proof of the formation of an additive compound between the pyridine and the compound containing the negative groups.Di-o-tolyloxa Zi minoch Zoride-py&iinium chloride C,NH,Cl*C( N* C6H,Me)*CCI :N - C !,Me obtained by warming a mixture of anhydrous pyridine and di-o-tolyl- oxalimino chloride (Bauer Abstr. 1907 i 603) with toluene extract- ing the crude product with hot acetone and crystallising the residue three times from methyl alcohol forms intensely yellow-coloured plates m. p. 180". When boiled with water acids or alkalis i t is decomposed and yields carbylamine derivatives. I t s solution in con- centrated sulphuric acid has a blood-red colour and when poured into water yields oxaI yl-o- toluid id e.2C,1H,,N,C12 H,PtCI forms orange-yellow crystals decomposing a t 2 10 -212'. The plutinich Zoride Diphen?/loxaliminoc~~Zoride-p?/ridinizlm chloride C,NH,Cl*C( :NPh) *CCl NPh prepared in a similar manner from pyridine and diphenyloxalimino chloride crystallises from methyl alcohol i n yellow plates which turn brown at 200" and melt at 2 0 3 O . When the di-o-tolyl derivative is warmed for a short time with an alcoholic solution of p-toluidine Zincke's glutacondi-ptoluidide hydro- chloride is obtained and with an alcoholic solution of B-naphthylamine the corresponding P-naphthalide. The additive compound of pyridine and bezanilidedi-imidechloride (Wallach this Journ.. 1877 ii 187) could not be isolated but by the action of aniline Zincke's dianilide was obtained together with anilinobenzylideneaniline (Bernthsen Anmden 1877 184 353).A mixture of carbodiphenylimide (Schall Abstr. 1895 i 42) pyridine hydrochloride and p-toluidine yields Zincke's p-toluidide and a mixture of phosphorus pentachloride pyridine and aniline gives the corresponding anilide. Ppridine dibromide and potassium cyanide react yielding the product obtained by Kijnig from pyridine cyanogen bromide and this with aniline yields the glutacondianilide. For the preparation of the anilide it is not necessary to isolate the intermediate compound. Experiments on the chlorination of pyridine have been carried out. Ry chlorinating in dry ethereal solution an unstable colourless derivative is formed which readily loses chlorine and reacts explosively with ether alcohol or aniline.With water it yields dichlornpyridine hydrochloride C,NH,Cl,,HCI,H20 which turns brown at 1 EOO and melts at 168' (decornp.). The product of chlorination yields a precipitate with mercuric chloride solution,and when this precipitate is decomposed by boiling with concentrated potassium chloride solution dichloropyridine distils over and this forms a mercurichloride C,NH5Cl,Hg which crystallises from mpthyl alcohol in brilliant colourless needles m. p. 190'. When pyridine is chlorinated without the addition of a solvent but in the presence of zinc chloride or sea-sand and a t low temperatures,ORGANIC CHEMISTRY. i. 227 a white precipitate is first obtained but-this re-dissolves and ultimately a dark brown viscous product is formed.The behaviour of the various chlorinated products towards primary amines has been studied. The white precipitate obtained by chlorinating pyridine in dry ethereal solution when distilled under reduced pressure gave fractions which did not yield dyes with primary arylamines. Similarly the distillates obtained from the dark viscous liquid formed by chlorinating pyridine in the presence of zinc chloride did not give colorations with P-naphthylamine neither did tri- tetra- and penta-chloropyridines. On the other hand the white precipitate when left in contact with ether and the air underwent partial decomposition and then reacted with aromatic bases yielding red dyes of varying composition and the undistilled dark viscid oil gave a red product with p-toluidine melting at 197-198' with /3-naphthylitmine a compound Cs5Hz7N3 in the form of strongly electrical dark red needles m.p. 245' and with a-methyldihydroindole a product in the form of a cochineal-red pre- cipitate which has not been analysed. The cis- and trans-tolane dichlorides and phosphorus trichloride do not yield dyes with mixtures of pyridine and an aromatic aniine. A list of the various amines which react with the chlorinated pyridine is given together with the colours produced. The character- istic line in the spectra of the various coloured condensation products is also given. J. J. S. Condensation Product of E thy1 Phthaliminoisobutyryl- malonate. SIEGMUND GABRIEL (Ber. 19 11 44,70-91. Compare this vol. i 212).-The yellow by-product obtained by the interaction of ethyl sodiomalonate and a-phthaliminoisobutyryl chloride in benzene becomes the main product when 13 mols.of ethyl sodiomalonate are employed. (In the former method of preparation [Zoc. cit.1 the yellow by-product is mixed with a colourless substance m. p. 168-16S.5' which is shown to be a-p1ILthaZiminoisobutyric anhydride by its form- ation also from a-phthaliminoisobutyric acid and its chloride a t 170O.) The same substance C,,H,,O,N,. yellow prisms m. p. 176-177O is produced when ethyl a-phthaliminoisobutyrylmalonate is boiled with sodium in benzene. I t no longer yields phthalic acid by hydrolysis with hydrochloric acid and its behaviour described below points to the constitution of an ethyl benzoylenedimethylpyrrolonecarboxy late (I) obtained in accordance with the equation When the ester is hydrolysed by equal volumes of water and concentrated sulphuric acid it-yields -3-kato-2 2-dimethyl-2 3-dihydro- pyrrole-5 -0-benzoic acid >C C,H,*CO,H (11) [hydrobromide yMe,*NH CO-CH C1,E1,O,N HBr,H,O m.p. 200' (decornp.)] which readily suffers ring closure at its m. p. 191O (decomp.,rapidly heated) or by prolonged boiling1. 228 ABSTRACTS OF CHEMICAL PAPERS. with mineral acids yielding 6enzoyEenedimethyZpyrrolone (111) >GO yGH,*f?=CH CO--N CMe m. p. 125-126O. This is reconverted into (11) by warm alkalis and C H *v=CBr forms 6enzoyZene-4-bromodimethylpyrrolone (IV) CO-N*CMe I )CO m. p. 224-225' with bromine in glacial acetic acid. Substance (111) is reduced by hydriodic acid and red phosphorus to benxoylene- C H *yH*CH2>C0 dimethylpyrrolidone (VII) I ' m.p. 172-1 73O which CO-X CBle is also formed from (I) and from (11) by the same reducing agent. Substance (VII) unlike (111) is not ruptured by warm alkalis forms a pheizyZhyclracxone m. p. 215-217*5' and an oxirne 220-221.5O and yields a nityo-compound C13H12O4N2 m. p. 172-1 73' (decornp.) with warm fuming nitric acid. When substance (111) is treated with fuming nitric acid below ZOO it is converted into benxoyleae-4-lnitrodinzethylpyrrolone (V) Y6H4*y :C(NO,) GO-N-CMe >co m. p. 264-265" (decornp.) which is reduced by hydriodic and glacial acetic acids partly t o substance (VII) partly to benzoylene-4-amino- dimethylpyrrolone (VI) Cl,Hl,02N orange-red prisms m. p. 2 1 2 O .By treatment with methyl-alcoholic hydrogen chloride substance (11) yields the hydrochloride m. p. 199-199*5' (decomp.) of its methyl ester an aqueous solution of which is reconverted into (11) by an excess of sodium carbonate. Bromine in glacial acetic acid converts (11) into 4- bromo- 3-keto-2 2-dimethyl-2 3-dihydropgrrole-5-0- benxoic acid ( VI 11) ~ - _ CBr.70 ~ C02H*CGH4* '<NH .cM~,. m. p. 223' (slowly heated) which is re-con- verted into (11) and anothzr (unexamined) substance by 20% potassium hydroxide on the water-bath; is almost unattacked by aniline at 150' (substance IV is produced in this experiment) and reacts with alcoholic ammonia at 100' to form a substccnce C1,Hl2O2N (XI) m. p. 303-304' and with methylamine to form a substance C,,HllMe0,N2 (XIII) m.p. 222-223' the constitutions of which are discussed below. By the action of cold hydrochloric acid and potassium nitrite substance (11) is changed into 1 4-dinitroso-3-keto-2 2-dimethyl-2 3- dihydropyrroZe-5-o-be.nxoic acid (IX) C(N0) G O C02H*CGH4* '<N(No). &+,J-~ 9 m. p. aboiit 160' (decomp,) which is converted by warm aqueous sodium carbonate into 4-r~itroso-3-keto-2 2-dimethyl-2 S-dihydropyrrole- 5-o-benzoic acid (X) CO,H*C,H,*C<NII CMe,' m. p. 182' (decornp.). This substance (X) which is obtained more conveniently by treating (11) with 50% alcohol 50% acetic acid and potassium nitrite forms a silver salt C,,H,10,N,Ag,H20 decornp. 260-270° and is C( N 0) 70ORGANIC CHEMISTRY. i. 229 regarded as containing the nitroso-group in position 4 for the following reason&.It yields substance (VIII) with alcoholic bromine is converted by nitric acid D 1.2 into the 4-nitro-acid ( X a ) m. p. 262-264' (decomp) (which is changed into V by boiling acetic anhydride) and is reduced as also is ( X a ) by hydriodic and glacial acetic acids to substance (XI). This substance forms yellow crystals givesabluish-green fluorescent solution in boiling water and a malachite- green solution in concentrated sulphuric acid from which a blue powder is precipitated by the addition of water. Its insolubility in aqueous ammonia proves the absence of a carboxyl group and its formation from substances (VIII) and (X) is explained by the formation of the same (unisolated) intermediate comDound. from which substance (XI) (annexed constitution) is obtained by the elimination of water.The substance which is called gyrolone is isomeric with substance (VT) ; in fact (VI) can C-NH*CMe be converted into gyrolone by the action of /\/\c--bo alcoholic potassium hydroxide and treatment of the product with aqneous ammonium chloride. That the solubility of gyrolone in alkali hydr- oxides is due to the presence of the acidic imino-group is indicated by the fact that sub- stance (XIIT) which contains NRle is insoluble in these solvents; (XI) is converted into (XIII) by methyl-alcoholic potassium hydroxide and methyl iodide. By treatment with phosphoryl chloride on the water- bath gyrolone is converted into a substance Cl,Hl1ON2CI pale yellow needles which sublimes under diminished pressure has m. p.1 9 6 O develops a malachite-green coloration in concentrated sulphuric acid is insoluble in aqueous ammonia but dissolves in alkali hydroxides ; these properties point to the annexed con- C-N stitution. The substance which is called /\/\,c- 6ZcMe2 chloroyyrilone is converted by methylation I I \Ah co into the same N-methyl homologue CI,Hl,MeON2Cl m.p. 128-128~5',asisobtained by theaction of phosphoryl chloride on substance (XIII). By reduction with hydriodic acid b. p. 127" and red phosphorus chlorogyrilone is converted into a base C HI6O2N2 citron-yellow needles m. p. 196-19So which loses H,O in a vacuum yielding >CMe m. p. l9O-19So clari- dihydrogyrilons C6H,< fying completely a t 210° a solution of which in dilute sulphuric acid reduces gold and silver salts and also Fehling's solution.The product of the oxidation C,,HI,0N2 m. p. 212' (decomp.) (the hydrochloride chyomate aurichloridc and platinichlorids are mentioned) is obtained best by oxidising a solution of dibydrogyrilons or of its hydrate in I I ' VVNH co - p H CO*NH*C*CH,i. 230 ABSTRACTS OF CHEMICAL PAPERS. hydrochloric acid with an excess of bromine ; the substance probably has the constitution C H '-- *'CO*NH*C*CH >CMe,. fi*y- When a solution of gyrilone in fuming hydrochloric acid is heated at 135O for two hours and the resulting green powder is distilled in a vacuum a substance C,,HI20N2 isomeric with gyrilone but devoid of basic properties is obtained. It crystallises in yellow leaflets melts and decomposes above 300° and sublimes when heated carefully on a watch-glass ; its constitution is as yet unascertained.c. s. Transformation of Naphthalimide into Naphthastyril. ELIE E. PISOVSCIII (Bull. Soc. chiin. 1911 [iv] 9 86-88).-& the processes described by Francescmi and ltecchi (Abstr. 1901 i 721) and by Ullmann and Crtssirer (Abstr. 1910 i Sol) do not give good yields the following new proceq which gives a quaatitative yield has been devised. Naphthaiimide (40 grams) dissolved in 600 C.C. of sodium hydroxide solution (3%) is treated a t 40" with 480 C.C. of sodium hypochlorite solution containing 5.5% by weight of active chlorine and the mixture warmed for thirty minutes a t 65'. To this 172 C.C. of sodium hydrogen sulphite solution (30%) are added and the cooled mixture filtered and the filtrate diluted to 2750 C.C.From this naphthastyril is precipitated in three fractions by ( a ) adding acetic acid ( b ) adding dilute sulphuric acid and ( c ) concentrating the mother liquors. The product may be crystallised from acetic acid. Dilute solutions of naphthastyril in organic solvents show a green fluoreacence. The solution in sulphuric acid is yellow (compare Ekstrand Abstr. 1886 715; 1889 52). T. A. H. Diacetyl. Diacetylmonophenylhydraeones and their Con- densations. OTTO DIELS and ANTON KOLLISCH (Bey. 1911 44 263-268. Compare Abstr. 1903 i 400 ; 1905 i 509 ; 1907 i 480 ; 1909 i 455).-Although diacetylphenylhydrazone is not de- composed when boiled with hydrochloric acid the corresponding phenylmethylhydrazone is readily transformed into l-acetyl-2-methyl- indole when well shaken with warm hydrochloric acid.The phenyl- hydrazone and the phenylmethylhydrazme condense readily with ethyl oxalate yielding hydrazones of ethyl diacetyloxalate but so far it has not been found possible to remove the hydrazo-group from the condensation products. DiacetyZphenylmcthyZhy~ra~one COMe*CMe:N*NMePh is formed together with a small amount of the corresponding osszone by the action of phenylmethylhydrazine on diacetyl in acetic acid solution. It is a deep yellow oil has b. p. 154-155"/14 mm. (corr.) and D20 1.0809 and condenses with ethyl oxalate in the presence of dry sodium ethoxide and anhydrous ether yielding the phenylmethyl- hydrazone of ethyl diacetylozalate CO Et*CO*CH,*CO*CMe:N*NMePh which crystalliaes from methyl alcohol in red needles m.p. 88' afterORUANIC CHEMISTRY. i. 231 sintering. The corresponding phenylhydrazone C,,H,,O,N crystallises from alcohol in golden-yellow plates m. p. 148-149' (corr.). 1 - Acetyl-2-meth ylindole C6H,<N:>CA~ crystal lises from light petroleum in stout colourless plates m. p. 72O and yields a picrute C,7H,,0,N in the form of long orange needles m. p. 1 1 7 O and a phen@ydraxone C,,H17N in the form of long nearly colourless needles m. p. 117-118". J. J. S. Isatinanils. IV. Cases of Desmotropism. RUDOLF PUMMERER [with F. GRUBE] (Be?.. 1911 44 338-345. Compare Abstr. 1910 i 5 1 l).-Isatin-2-anil crystallises from benzene in brownish-violet prisms m. p. 126' but is precipitated by sodium carbonate from solutions of its salts in brown crystalline flakes which crystallise from dilute alcohol in large yellowish-brown plates m.p. 126'. At about l l O o partial transference into the violet form is observed. The two modifications are not identical the yeliow leaflets representing isatin- - NH 2-ani1 C H,(CO>C NPh and the violet prism,c isatin-2-anilide C,H,<cE>C*NHPh. The violet iorm immediately gives red solutions ; the yellow form yields yellowish-brown sdutions in anhydrous solvents at low temperatures which soon become red. l-LVethyZisatin-2-aniZ C,H,<F:G>C:NPh is obtained by the action of sodium methoxide and methyl iodide; it crystallises in yellowish-red prisms m p. 132' aud is hydrolysed by acids to 1 -methylisatin and aniline. Isutin-2-nzethyZanilide C,H,<&C*NMePh -N prepared by the inter- action of isatin chloride with methylaniline in benzene solution crystallises in long bluish-violet plates m.p. 103-104'. It is hydrolysed into isatin and methylaniline. I n the ca.w of both isomerides the introduction of methyl causes a deepening of the colour. There is a considerable difference in the basicity of the two forms; the methyl-anil does not react with concentrated sodium hydrogen sulphite solution whereas the methyl- anilide forms almost quantitatively a sparingly soluble bisulphite compound. A similar isomerism has been studied in the case of thioindigo- scarlet-2-anil which is red and thioindigoscarletanilide which is greenish-brown (compare following abstract). In t h i s example the anil form is more stable and has been studied in solution.It is best converted into the anilide by means of acids boiling with pyridine being the most satisfactory method of effecting the reverse change. E. F. A. Indirubinanils Substances with Reactive Carbon Double Bonds. KUDOLF PUMMERER [with MAXIMILTAN GOETTLER] ( B e y . 191 1 44 346-356. Compare preceding abstract ; also A bstr. 19 10 i 5 11). -1satin-2-anil reacts in alkaline solution with indoxyl formingi. 232 ABSTRACTS OF CHEMICAL PAPERS. indirubin-2-anil in which the anil residue being no longer in the neighbourhood of a CO group is firmly fixed. In a similar manner indirubin-p-dimethylamino-2-anil and the corresponding sulphur compound have been.prepared both are blue dyes. Thioindigo-scarlet-p-dimethylamino-2-anil on prolonged heating with 1% hydrogen chloride is decomposed quantitatively into aminodimethyl- aniHne and thioindigo-scarlet but the indirubin compound under similar treament only gives small quantities of indirubin the main part being converted into a reddish-brown compound C,,H,,O,N which has not been further investigated.Indirubin-2-anil is decomposed by indoxyl into an indigo dye and oxindoleanil C6H,<:2>C:NPh. The reaction is quantitative and takes place rapidly in hot dilute acetic acid. The carbon double bond in indirubinanil is opened by the action of phenylhydrazine and isatin-2-phenylhydrazone is formed. Oxidoleanil forms colourless flakes m. p. 90-92'; it rapidly becomes violet on exposure to moist air. The hydrochloride forms short lancet-shaped crystals m.p- 21 9-220'. When warmed with nitrosobenzene isatindianil is formed. The brown modification of thioindigo-scarlet-2-anilids [3( 1 ')-thionaph- thenyl-~-indole-2-anilide] c6H,<zi>C c<;$z$ (see preced- ing abstract) formed by the interaction of isatin-2-anil with 2-hydroxy- thionaphthen crystallises in long narrow brown prisms m. p. pre- pared by boiling the brown form in dry pyridine crystallises in carmine-red prisms with a coppery lustre. 3( ~')-~?~ionaphthenyl-~-indole-p-dimet~ylacrrLino-~-anil crystallises in lustrous violet-black plates m. p. 220-221'. Indirdin-p-dimet h ylarnino- 2 -annil forms bluish -viole t plates m . p. 357-258O. The sulphate forms rectangular violet-black plates of metallic lustre m. p. 255-256'. 226-227'. The red anil form C H < C O > C C < ~ ~ ~ ~ ~ ~ ~ H -S - E.F. A. 1-Nitro- and 1 -Amino-derivatives of Antipyrine Thiopyrine and Anilopyrine. AUGUST MICHAELIS [with WALTER GRAFF RICHARD GESING and HEINRICH BOIE] (Annalen 19 1 1 378 293-351).-A previous attempt to prepare p-nitroantipyrine from methyl iodide and 5-chloro-1-p-nitrophenyl-3-methylpyrazole failed because the two reagents yielded an iodo-p-nitrophenylmethylpyrazole methiodide from which the p-nitroantipyrine could not be obtained by the action of alkalis or of silver oxide (Michaelis and Behn Abstr. 1900 i 693). Success has now been attained by treating the chloro- p-nitrophenylmethylpyrazole with an excess of methyl sulphate a t 1 loo a n d treating the neutralised aqueous solution of the methosulphate with potassium iodide whereby 5-chloro- 1 -p-nityopheny I-3-methylp ynmole methiodide I I CMe>N,MeI yellow crystals m.p. 196' is obtainad ; an aqueous solution of this methiodide by treatment with CH-- CCl*N( C,H *NO,)ORGANIC CHEMISTRY. i. 233 silver oxide and subsequent evaporation yields p-nitroantipyrine (1 -p-nitropheny/E-2 3-dimethyZ-5-pyraxoZone) (annexed formula) yellow prisms m. p. 132'. p-Nitroantipyrine CMe :TMe which can also be prepared although less I 0 \N*C&&'NO satisfactorily by warming an aqueous solu- tion of the preceding methiodide with the calculated quantity of hydroxylamine / I CH=&- hydrochloride and sodium carbonate forms a hydrocktoride m. p. 1 '31~5~ which is decomposed by water ; pkatinichloride large red crystals; hydriodide m.p. 163' (decomp.) and picrate m. p. 101". The methiae hydrogen atom in position 4 exhibits its customary activity. Thus by treatment with sodium nitrite in glacial acetic acid p-nitroantipyrine yields p-nitro-4-nitrosoantipyrine a green cryatal- line powder which becomes yellow a t 176' and has m. p. 1S8-1S9°. ~-4-Dinitroanti~yrine (annexed formula) colourless needles m. p. 276O is prepared by the action of nitric and CMe=rMe sulphuric acids on antipyrine by treat- I Q \N-C,H,*NO ing p-nitroantipyrine with nitric acid C(N0,) C- / or by heating 5-chloro-4-nitro-l-p-nitro- p?henyZ - 3 - methylpyraxole m. p. 1 8 1' (obtained by the action of nitric and sulphuric acids on 5-chloro- 1-plenyl-3-methylpyrazole) with methyl sulphate at 115-1 20' and decomposing the resulting methosulphate with sodium carbonate.4-Bromo- p-nitroantipyrine obtained from the nit roanti py rin e and bromine in chloroform solution has 1x1. p. 173'. By reduction with tin and hydrochloric acid p-nitroantipyrine yields p-aminoantipyrine m. p. 21 O' which does not condense with aldehydes ; its h!/drochloride C11Hl,0N3,SHCl has m. p. 220' (decomp.). The cccetyl derivative m. p. 22 lo forms 4-nitroso-p-acetyla~inoant~pyrin~ green needles m. p. 237' (decomp.) with potassium nitrite in acetic acid solution and 4-bromo-p-ncetyZaminoantip~rir~e m. p. 240' with bromine in chloroform. p-Benzoyluminountipyrine m. p. 26 lo yields 4-nitroso- p-beiaxoyZurrLinoantipyi.ine m. p. 2 14' and 4-bromo-p-benxoylcLminou~~ti- pyrine m. p. 33T0 by similar procetses.y-Benzenesulp?honyZamino- antipyrine m. p. 251' obtained from 1,-aminoantipyrine and benzene- sulphonyl chloride in alcoholic solution yields a 4-nitroso-compound m. p. 211' (decomp.) and a 4-bro~~o-compoui~d m. p. 235". p:4-Di- aminountipyrine m. p. 279" obtained by reducing dinitroantipyrine by tin and hydrochloric acid forms a dsiacetyl derivative ni. IJ. 291' which has only a slight antipyretic action. The following compounds of m-nitroantipyrine and of o-nitroanti- pyrine are obtained in the main by processes similar to those mentioned above. 5-C~~Zoro-l-m-nitropl~enyZ-~-~e~~ylp~razoZe rnethiodide m. p. 222O yellow needles. m-Nitroantipyrine m. p. 98' yellow needles forms a hydrochZos.ide m. p. 188" which is decomposed by water ; platinichloride BC,,Hl103N3,H,PtCI,,2H,0 m.p. 140" ; hyd?*iodide m. p. 171'; picrate m. p. 165" and nitrate m. p. 143". m-Nitro-4-nitrosoantipyrine .green crystals decomp. 165' complete a t 188-1 90'. m-4-DinitroantzpyriIze prepared from m-nitroan tipprine and nitric acid with cooling decomposes at 203'. 4-Bromo-rn-nitro- C11H1103N39HCJ Ii. 234 ABSTRACTS OF CHEMICAL PAPERS. antipyrine m. p. 184'. m-Aminoantipyrine m. p. 14S0 does not react with aldehydes phenylthiocarbimide or carbon disulphide ; it forms a hydrochloride C1,H,,ON3,2HC1 m. p. 228" which is very unstable ; platinichloride 2CI,HI,0N,,H,PtC16,2H20 decomp. above ZOO" and an acetyl derivative C,,H,,O,N,,H,O m. p. 127' (hydrated) 167' (anhydrous) which has only a slight antipyretic action. 4-Bro??io- m-ace2yZrcminocsntipyrine has m.p. 21 7". m-dlenzo?lZaminoccnli~?/ril/e has m. p. 1 1 9". m-Dirnethylami?coanti- CMe ?Me pyrine (+-pyramidone) (annexed formula) \N C6H4*NMe2 obtained by heating m-a mi noan ti py r i ne and methyl sulphate nearly a t the b. p. CH=C- for half an hour and basifying the aqueous solution of the resulting methosulphate is a n oil wbich forms a platiniclJoride reddish-brown needles m. p. 210' (decornp.). m-4-Bi- arninoantipyrine m. p. 170" forms a hydrochloride CllHl,ON,,BTICl m. p. 2 4 5 O and a diucet3l derivxtive m. p. 273". 5-Chloro-l-o-nitrophen?/l-3-n~et?b~rpyraxo~e nzetibiodide ID. p. 183" yellow prisms is converted by silver oxide in the preceding manner into o-nitroantipyrine m. p. 1S8' which forms a hydrochloride m. p. 2 0 1 O and ylatinichloride 2C1,Hl102N,,H,PtCJ6,2€~20,~ m.p. 133' (hydrated) decomp. abovo 300" (anhydrous). o 4-Dinztrountipyrine white needles has m. p. 244'. o-Arriinountipyrine has M. p. 165". 2 5 - Thio-1-m-nitrophenyl-2 ; 3-dimethyZpyi~tcxoZone (m-nitrot?biopyri?2e) (nnnexodforrnula) m. p. 204O yellow leaflets YMe T I e obtained by treatinga suspension of 5-chloro- 1 -m-nitropheay1-3-methylpyrazole meth- 1 7 )N*c6H4*N02 iodide in chloroform with a concentrated UH=C- alcoholic solution of potausium sulphide (the use of aqueous solutions is to be avoided since the hydrogen sulphide liberated reduces the nitro-group to the amino-group) forms a Iqdrochloride C11H1102N,S,HCI m. p. 1 a?' which is decomposed by water plati&hlorids m. p. 225' i ydriodide m. p. 185' methiodide m. p.2 0 9 O and trioxide Cl,Hl105N,S m. p. above 350" the last being obtained by passing chlorine through a hot aqueous solution of the nitrothiopyrine. 5 -Meth ylthio I-1. m-nitrophen yZ - 3 -rneth yZpyraxo Ze (m-nitro- $-thioy yrine) I ' ? / YMe===N CH C( Slsll e ) >No C,H,*N O m. p. 84' white needles is obtained by carefully heating m-nitrothio- pyrine methiodide under reduced pressure ; by oxidation by potassium permanganate in glacial acetic acid i t yields the sulphone m. p. 135'. m.Arninothiopyrine in. p. 1 9 9 O obtained by reducing the nitrothiopyrine by tin and hydrochloric 'acid forms a hydrochloride m. p. 226' and platinichloride an amorphous red powder. The following compounds are obtained by methods similar to the pre- ceding 2 5-thio-1-o-nitropheql-2 3-dimethylpymxolone (o-nitrothio- pyrine) m.p. 1 90° blood-red-crystals forms a hydrochloride m.. p. 125' pZatinichZoride decornp. 230° hydriodide m. p. 152' methiodzde m. p. 1814 and trioxide m. p. 298'. o-Nitro-$-thiopyrie and its Eulphone have m. p. 61° and 160" respectively. o-Aminothiopyrine C11H1104N3S,ORGANIC CHEMISTRY. i. 235 m. p. 172" forms a platinichloride decomp. 300'. 2 5-Thio-I-p-nitro- pl~ertyl-2 3-dimetlq?pgraxolone (p-)aitrotZbio~yrine) m. p. 241" red crystals is obtained by treating a hot aqueous solution of 5-chloro- 1 -p-nitrophenyl-3-methylpyrazole methiodide with concentrated aqueous sodium sulphide ; it forms a hydrochloride M. p. 175" methioclids m. p. 196' and trioxide decornp. above 3'70'. p-Nitro-pthiopyrine (Michaelis and Besson Abstr.1904 i 750) forms a hydrochloride m. p. 85' and a sulphone m. p. 154' ; 4-bromo-p-nitro-~-t~~~~p~/ri?ae has m. p. 120". p-4-Dinitrot~~iop?/rilze m. p. 240° yellow crystals obtained in a similar manner t o the dinitroantipyrine forms a met?ciodiLEe m. p. 154-155' which by heating under reduced pressure yields the dinitro-$-thiopyrine m. p. 123'; the corresponding sulphone has In. p. 177". p-AminotlAio- pyrine rn. p. 255-2256' obtained by the red iiction of p-nitrothiopyrine forms a hydrochloride CllH13N3S,2HCl a n acetyl derivative m. p. 2 71' and benxoyl derivative m. p. 265'. p-Ami?Lo-$-thiop?lrine m p. 133' white leaflets obtained by the reduction of p-nitro-$-thiopyrine forms a hydrochloride C,,Hl,N3S,2HC1 m. p. 221' and an acetyl derivative m. p.137". p-4-Biaminothiopyrine m. p. 207' obtained in it similar manner t o the diaminoantipyrine forms a dicbcetyk derivative "1.. p. 273'. p-4-Diumino-~-thiopyrine m. p. 115O white needles is obtained by the reduction of the dinitro-+-tbiopyrine ; i t s diacetgl derivative has m. p. 235". (rn-nitromilo- pyvine) (annexed formula) m. p. 1 lo" reddish-brown needles is obtained by heating 5-chloro-1-m-nitro- plienyl-3-methylpyrszole rriethiodide and \ aniline (2 mols.) a t 125' for two hours. CISle:NMe I IkPh I N'CGH~*xo2 It reduces Fehling's solution and silver CH=C-/ salts and is a strong base; the hy?riodide m. p. 1 66' platinicltloride picrccte tfiio- cyanate m. p. 1 6 8 O methiodide in. p. 2 2 P ethz'odide m. p. 176' and propiodide m. p. 130° are described. By treatment with benzoyl- chloride in benzene m-nitroanilopyrine forms a benzogl chloride which is isolated a s the platinichloride 2(C'l~H,,02N,,C,H~*COCl)~ tC I 4 m.p 235O ; from this by aqueous potmsium iodide the benxo?+?iodide m. p. 198" is obtained ; the acetyliodide C17Hl,0qN,,CIJ,.COI has m. p. 21 4'. When heated at 200° m-nitroanilopyrine hydrochloride loses methyl chloride and is converted into 5-unilino-l-m-nitropl~enyl-3- methylpymxole m. p. 122-1 23' yellow needles. 2 5-endoAnilo-l -o-nitrophenyl- 2 3-dimethy?pyrccxob (0-nitroanilo- pyrine) m. p . lll' dark red prisms is obtained in a similar manner to the meta-compound using 4 mols. of aniline at 110'. It is like- wise a strong base forming a plutinichloride m. p. 206' hpdriodide m. p. 198" picrate m.p. 167' thiocpaate m. p. 193' znntliiodide m. p. 97' ethiodide m. p. 1 7 7 O propiodide m. p. 168' acetyliodide m. p. 225' benxoyliodide m. p. 19'io and beneoyl chloride m. p. 124"; by heating the last at 50-8OC/40 mni . 5-benzoylanilino-1-o-nitrophenyl- 3-methyZpyraxole m. p. 156-157' white prisms is obtained. 1-Azo-o- aniEopyrine N2( C,H,-C,N,Me,:NPh) red needles m. p. 225' is pre- pared by heating a n aIcoholic solution of o-nitroanilopyrine with aluminium amalgam and a little water on the water-bath. 2 5-endo Anilo-1 -m-nitrophan yl-2 3-dimethylpyraxolei. 236 ABSTRACTS OF CEEMICAL PAPERS 2 5-endoAni20-l -p-nitrophenyZ-2 3-dimethylpyraxob (p-nitroanilo- pyrine) m. p. 168' dark red crystals is prepared by heating 6-chloro-1-p-nitrophenyl-3-methylpyrazole with methyl sulphate and treating the resulting methosulphate with aniline a t 125-130O for five hours; the hydriodide has m.p. 192O and the methiodide m. p. 182'. By heating the latter at 200' under reduced pressure p-nitro- . A FMe:N- CH:C(NPhMe) ->N*c,H,*No~ m. p. 1000 yellow $-anilopyrine needles is obtained.' p 4-binitroanilo~yrine m. p. 192" yellow leaflets is prepared by heating 5-chloro-4-nitro-l-p-nitrophenyl-3- methylpyrazole with methyl sulphate a t 115-120' for six hours and treating the resulting methosulphate with an excess of aniline a t 130° for four hours. p-Nitronnilopyrine yields p-aminoanilop?Jrine m.. p. 175' by reduction with tin and hydrochloric acid and p-axoaniZopyro.ne m. p. 224' dark red crystals by reduction in alcohol-chloroform Action of Diethylmalonyl Chloride on Some Substances Containing Nitrogen.MARTIN FREUND and KARL FLEISCHER (Annalen 191 1 379 27-46. Compare Abstr. 1910 i 490).-When warmed with acetamide (2 mols.) diethylmalonyl chloride yields 4 6- d iketo-2-meth yl- 5 ; 5 - diet72yltetrahydro~y~~i~nid~ne h ydroch Zoride decomp. 2 5 3 O white needles from which dilute aqueous ammonia solution by aluminium amdgam and water. C. s. C9H,pO,N,,HCl CO-N liberates the base itself CEt,<CO.NH>CMe m. p. 125'. The constitution follows from the ready decomposition of the base into diethylmalonamide by warm alkalis. It separates from methyl alcohol in long needles C,H,,O,N,,MeOH m. p. 1 35-140' which a t 100-1 10' lose methyl alcohol and are converted into a vitreous yellow mass which has pronounced acidic properties and is probably the enolic form of t h e base sirice it is converted by 20% hydrochloric acid into the preceding hydrochloride.Formamide and propionamide do not form pyrimidines with diethylmalonyl chloride. By the prolonged interaction of benzamide and diethylrnalonyl chloride with warming diethylmalonamic acid together with a little cyaphenine are produced. By short careful heating however the two substances yield 6enxoyZdiethylmaZonanzic acid NHBz*CO*CEt2*C0,H m. p. 127-1 28' (decomp.) together wikh diethylacetylbenxamide NHBz*CO*CHEt m. p. 138-139' which is also formed by heating t h e preceding acid above its m. p. When warmed with diethylmalonyl chloride benzylidenesemicarb- :azone is converted into 3 5-diketo-1 2-diethylmalonyl-4 4-diethyl- pyraxolidine CEt,<Co*~'C~>CEt2 m.p. 202-203'. This is con- verted by warm dilute sodium hydroxide and subsequent acidification 5nto b.isdiethylmaZonhydrc6zinic acid N,H,(CO*C Et,*CO,H) m. p. 233-234" (decomp.) which is very stable to alkalis and to sulphuric acid but is converted by careful heating into bis-a-etiLyZbutyryZr'lydraxide N,H,*CO*CHEt m. p. 234". CO*N-COORCANIC CHEMISTRY. i. 237 [IVith MAX Ro~ssc~~r~n.]-~enzy~idenesemicarbazono and dipropyl- malonyl chlorido yield the corresponding 3 5-diketo-1 2-dipropyl- mccZon?jl-4 4-~il3ro~yZp?/~azoZicline C H,,O,N m. p. 189'. C. S. [ Benzoylenecarbamide.] HERMANN FINGER and H. GUNZLER (J. pr. Chem. 19 11 [ii] 83 198-199).-The substance designated as ethyl cyanoanilide-o-carboxylate (Finger and Zeh Abstr.19 10 i 382) has been described previously by Griess under the name ethoxycysnoaminobenzene (4-keto-2-ethoxy-1 4-dibydro- 1 3-benzdi- azine) ; he also mentions its conversion into benzoylenccarbamide. If this constitution is correct the substance obtained from i t by the action of methyl snlphste and described a s o-carbethoxyphenylmethyl- carbodi-imide (Finger Abstr. 1910 i 383) may very possibly be 4-keto-2-ethoxy-3-methyl-3 4-dihydro-1 3-benzdiazine c. s. Condensation of Esters of Alkyloxy-acids with Cyanides REINHOLD VON WALTIIER (J. pi.. Chem. 1911 [ii] 83 and Ketones 1 7 I - 1 S2).- [With H. Lri~~~.]-Pl~enoxyncetyZacetop~eszon~ OPh*CH,*CO* CH,* COPh m. p. 79-80° white needles obtained by acidifying the product of the condensation OF cquimolecular quantities of ethyl phenoxyacetate and acetopheuone in the presence of sodium ethoxide gives a red coloration with alcoholic ferric chloride does not react with phenyl- carbimidc or with benzoyl chloride and sodium hydroxide but condenses with phenylhydrazine i o form 1 3-tl~~henyl-5~pheizoxymethylpyraxole OPh*CH,.C<Nph.# m. p.S 8 O which is reduced by sodium and CH-C P h alcohol to 1 3-diphenyl-5-methylpyrazoline phenol being eliminated. 3- PhenyE-5-pheszoxymeth~lpyrazoZe m. p. 104" is obtained by boiling a n alcoholic solution of phenoxyacetylacetophenone with aqueous hydrazine whilst 3-pJ~enyl-5-pJ~enoxymethylisooxcmoZe m. p. 6 lo is produced in a similar manner with hydroxylamine hydrochloride. [With P. HERSCHEL.] - cr-Phenoxyacetyzplien ykuetonitri~e OPh*CH,*CO- CHPh* CN m.p. 125-1 26',preparedfrom ethyl phenoxyacetate,. phenylacetonitrile and sodium ethoxide dissolves in aqueous ammonia and reacts with phenylhydrazine i n boiling glacial acetic acid to form 5-imino-1 4- m. p. diphenyl-3-phenoxymeth ylpyraxolone OPh* CH,*C< 1 20-l2lo the hydrocldoride p!atinic?tZos*ide m. p. 192' (decomp.) picrate m. p. 1 6 3 O benxoyl derivative m. p. 163-169O and acetyl derivative m. p. 174-175' of which are described. Phenoxyacetyl phenylacetonitrile reacts with dry ammonia at 150' t o form @-amino- y -phenoxy -a -phen ylcrotononitrile OPh*CH,*C(NH,) CPh*CN m. p. 88-89' and with aniline p-toluidine and a-naphthylamine t o form corresponding /3-anilino- /3-p-toluidino- and P-naphthylamino-deriv- atives m.p. 131° 1 1 8 O and 145-150'respecti~ely ; also by saturating N-- Y P h CHPh' C :NH' VOL. c. i. s1. 238 ABSYhCTS OF CHEMICAL PAPERY. its solution in hot glacial acetic acid with hydrogen chloride it yields y-phenoxy-a-pl~enylacetoucetamide OPh* CH2*C0.CHPh*CO*NH m.. p. 151-152c which reacts with hydroxylamine hydrochloride in boiling acetic acid t o form 4phe~~yl-3-pher~ox~~wiethylisooxuxoZone N-.- 0 oPh*CH,*C<C HPh.&O' m. p. 160-162" (decomp.) and with phenylhydrazine to form 2 4- diphn?/Z- 3 -pl~eiLoxynaeth?l~yraxolone OPh-CH2*C<Cph b0 m. p. 145') a substance which is soluble in sodium hydroxide carbonate or hydrogen carbonate. Ethyl phenoxyacetate condenses withp-chloro- phenylacetonitrile t o form p-clLloro-a-plLenoxyacetylphenyZncetonitrile OPh* CH,* CO*CH( C,H,CI).CN m.p. 168") from which the following substances are produced by reactions similar t o the preceding 5-haino-I -pl~enyl-4-p-chlorophenyZ- 3-ivl~enorcymethyZpyrazoZone m. p. 107' (7qdrochZoride picrate m. p. 165O acat9l deiivative m. p. 219O benxoyl derivative m. p. 219-220') ; P-amino-y -phenoxy-a- p - chlorophenylcrotononitde m. p. 1 3 2 O ; the corresponding p-anilino- and P-p-toluidino-derivatives have m. p. 122' and 135' respectively. p-Chloro-a-phenoxyacetylphenylaceto- nitrile unlike the non-halogenated cyanide reacts with hydroxylamine hydrochloride in boiling alcohol to form 5-irnino-4-p-chloropl~enyZ- 3-plienozymethyZisooxuzolone OPh*CH2qN Also i t does not form an amide but with alcoholic hydrogen chloride yields e t h j l y -phenoxy-a-p-chlorophenylacetoucetate OPh*CH,*CO.CH(C H CI)*CO,Et m.p. 70"; the methyl ester has m. p.6874'. boiling alcohol the ester yields a phenylhyldrazide OPh* CH,*CO*CH( C,H,CI) CO*NH =NHPh m. p. 125-126") which is easily converted by alcoholic sodium hydroxide into the pyraxolone OPh-CH,*C< NPh*NH CH( C,H,CI).$?:NH ,In. p. loso. 0 With phenylhydrazine in C(C6H'%C1).yo m p 1660. NH' NPh-- c. s. Reaction Products of Potassium isocyanate and Diamino- acetone Hydrochloride. Amino- and Carbamido-propylene- ureine [Carbamidomethylglyoxalonel. ANTOINE P. N. FRANCHI- MONT and J. V. DUBSKY (Proc. K. Akad. Wetensch. Amsterdam 1911 13 625-628).-16 is shown t h a t when potassium isocyanate and diaminoacetone hydrochloride interact the products are riot those described by Rugheimer (Abstr.1892 ii 952) but 4-carbamidomethyl- glyoxalone and aminopropy leneureine C4-aminomethy lglyoxalone] hvdrochl oride. d AminorrLethylgl~oxaline hydrochloride ~ ~ ~ ~ ~ C * C H 2 * N ~ € H C crystallises in small needles which a r e very soluble in water The free base has not yet been isolated but some of its compounds and derivatives are described. The nitrate and normal and acid sulphates all form small colourless needles with no definite melting point. TheORGANIC CHEMISTRY. i. 239 triacety? derivative forms needle.c m. p. 141". ~ A c * c H > ~ ~ 2 * N A c 2 crystallises in plates C 0-NAc The tetra-cccetllZ derivative m. p. 163-1664'. The caTboxymethyZ derivative forms leaflets m. p. 23S0 and when boiled with acetic anhydride yields a monotccetyl derivative m.p. 215'. 125-1 2 6 O . glittering crystals m. p. 208". m. p. 218-219' and a diacetyl compound m. p. 101-lOSo. 4-Ca~barr~i~lomat?~~Z~~~oxaZo~~~ C,N2H?-C H,*NH Ac The diacetyl derivative crystallises i n needles m. p. The corresponding carboxyethpl derivative forms small It yields a ntonoacetyZ compound TH*CH CO*NH2 '. C€€ *NI€*CO*NH \VW ~ b - tained from diaminoxe tone hydrochloride with 2 molecules of potassium isocyanate ixnd also from arninomethylglyoxalone hydro- chloride with 1 molecule oE the isocyanate. It for1ri.i snow-white leaflets decomposing at 220" and gives no precipitate with silver nitrate or mercuric chloride unless ammmia is added but is precipitated by mercuric nitrate. N. c. Phenanthrene Series.XXIX. Phenantriazines. JULI us SCHMIDT OTTO SCHAIRER and EHNST G L A m (Ber. 1911 44 276-282. Compare Thiele and Bihan Abstr. 1S99 i 47).-- F6H4*$XN*7 0 Q,H,$.~:N$-oH ' Hydroxyphenantriazine or is C,,H; C N N H C,;H,*C N*N formed when phenanthray;inonemonoxime is boded for ten hours with an alcoholic solution of semicnrbazide hydrochloride hydroxyl- amine being formed at the same time. Substituted derivatives of phenanthraquinonemonoxime react in much the same manner and by using the 4-nitro-derivative i t lilts been found possible t o isolate the semicarbszone of the morioxime as a n intermediate product. I t has not beon found possible to obtain the phenantriazirie directly from phenant hraquinonemonosemicar bazone. P~enccnt~Tapuinonesen~icarbct;zone 9 8 3 4 .y:N*NH*C**NH crystsI- C,H,*CO lises from alcohol in golden crystalline nodules or i n long brilliant golden-yellow needles containing 0.5 mol. of ethyl alcohol. Both forms have m. p. 220" (decomp.). 3-Ilydroxyphenantriaxine C1,H,0N3 crystallises from alcohol in pale yellow nodules m. p. 285' (decomp.) and does not give the usual reactions for ketones. 4-Nitrophenanthraqwinonemonmemicccr6azone C1,H,,04N forms a yellow crystalline powder m. p. 210-21 1' (decomp.). ~ - ~ ~ ~ t r o ~ h e n a ~ z t h r a ~ u ~ ~ ~ o ~ e o x ~ m e s e m ~ c a ~ ~ ~ a z o n e U,,H,,O,N forms a yellowish-green powder m. p. 240" (decomp.) and yields 8-nitro- 3-hydroxyphenantriaxine C,,H,03N4 as a yellow powder m. p. 285" (decomp.) when heated with alcohol and concentrated hydrochloric acid.3 - B1.omophenant7Lrapuinoizeoxilr~esemicccrbazone form pale yellow crystals m. p. 274-2 754 and 7-bromo-3-I~?/cErox~p?~enant~.~~z~yellow crystals m. p. 304". s 2i. 240 ABSTRACTS OF CHEMICAL PAPERS. 3- iVityopl~enanthrnpluino?zeoxirneserrL~on~ has m. p. 249-250" (decomp.) and 7-nitro-3-iLydl.ox~piLerzccntriaxine forms ochre-yellow crystals m. p. 273-274' (decomp.). Hypocaffeine and its Decomposition. HEINRICH EILTZ and PAUL KKEBS (Bey. 1911 44 282-305. Compare Abstr. 1910 i 521 524,526).-The products described by Fischer (Abstr 1882,217; 1883 356) under the names of hypocaffeine caffoline and acecaffeine have been re-examined. The formula for hypocaffeine is shown to be CSHl0O4N4 and not CGH703N3 as suggested by Fischer. A 60% yield of the compound is formed when trimethyluric-acid-glycol ether is decom- posed by a n alcoholic solution of hydrogen chloride in the absence of water ; when aqueous hydrochloric acid is used the yield is only 30% and apocaffeine is also formed.The formulae for the silver and barium salts are CsH,04N,Ag and ( CsH,0,N,)2Ba respectively. When tri- methy luric-acid-glycol ether is decomposed by concentrated sulphuric acid apocaffeine and not hypocaffeine is formed. Caffoline has the formula C7HI2O3N4 and in the conversion of hypocaffeine into caffoline by warming with barium carbonate solution a molecule of water is added and one of carbon dioxide eliminated and the conversion of caffoline into acecaffeine by boiling with acetic anhydride and hydrolysing the resulting acetyl derivative also consists in the addition of water and the removal of carbon dioxide and ammonia.These conclusions have been confirmed by molecular-weight determinations and the rnethylation of hypocaffeine t o oxytetramethyluric acid (Fischer Abstr. 1898 i 180). I n the conversion of the glycol ether into hypocaffeine trimethyluric-acid-glycol is probably first formed ; this is however unstable and is ruptured at the 3 4 position yielding 5-hydroxy-1-methylhydantoyl-7 9-dimethylcarbamide J. J. S. >GO NHMe*CO*NMe* GO*$!( OH)-NMe CO-NH by the hydrolytic decomposition of tliis in the 8 9 position and ( a ) subsequent formation of a lactone apocaffeine rMe*CO NMe*?O c O--O>C<CO-NH' is formed or ( b ) ring formation between carbon No. 5 and nitrogen NMe.yo is obtained.According No. 9 hypocaffeine lfMe*CO CO*NMe >C<co-NH? t o Baeyer's nomenclature (Ber. 1900 33 3771) hypocaffeine is thus 1 7 9-trimethyl-spiro-5 5-iLydantoin and oxytetramethyluric acid the corresponding 1 3 7 9-tetramethyl derivative. This constitution of oxytetramethyluric acid has been confirmed by its synthesis from dimethglcarbamide and 5-hydroxy-1 3-dirnethylhydantoylamide or 6-hydroxy-1 3-dimethplhydantoylmethylamide (Zoc. cit. p. 521) (nlZo- NHMe NH,*CO*Y(OH) = CO-NMe caff uric acid) CO<NHMe + y M e * GO CO*NMe + NH,+H,O. Hypocaffeine is not formed when methylcarbamide is fused with 5-hy droxy- 1 3-dimethylhydantoylamide or yet by heating dimetbyl-ORGANIC CHEMISTRY. i. 241 carbamide with caff uric acid alone or in presence of solvents but can be synthesised together with oxytetramethyluric acid by heating dimetbyl- car bamide with 5 -hydrox y- 1 -met hy 1 h y d antoyl me t hylami d e at 1 5 0' for eight t o ten minutes whilst hydrogen chloride is passed through the mixture.A spiro-dihydantoin is not formed by the decomposition of 7:9- dimethyluric-acid-glycol as the rupture then occurs at the 8 9 position only. These facts are in perfect harmony with Biltz's views on the stability of the C*N union (Zoc. cit. p. 324) when methyl is attached to the nitrogen. The formation of spiro-hydantoins is to be expected only when the uric acid is alkylated in positmion 3. Fischer's hypo- ethyltheobromine (Abstr. 1883 357) is undoubtedly 1 9-dirneth3yZ-7- ethyl spiro-5 5-dihydnntoin. Further support for the constitutional formula for hypocaffeine is afforded by a n examination of the decomposition products of caffoline namely dimethylcarbamide or cholesterophan and methylcarbamide from which it is argued that caff oline must be 1 3 6-trimet?~?/ZalZarctoin (annexed formula) the formula of To<Nv kMe*$O e*CH*NMe*Co*NH2 5 6 7 8 which is in harmony with most of the properties deecri bed by Fischer.Caff oline and acetic anhydride yield acetylacecaff eine carbon dioxide and acetamide C7H,,03N + (CH,*CO),O = C8H,,03K3 + (20 + CH,*CO*NH and the scetyl derivative when heated with concentrated hydrochloric acid yields acecaff eine hydrochloride from which the free base is formed by the action of magnesium oxide and extracting the dry mass with benzene. The constitution 5-rnethwlamino-1 3-dinzethyl- is suggested for acecaffeine and this NMe*FO NMe*CH*NHMe' hydantoin CO< agrees with its basic properties with the readiness with which it can be oxidised to cholesterophan and with the formation of methylamine dimethylcarbamide and glyoxylic acid on hydrolysis. Caffoline can be synthesised by evaporating an aqueous solution of acecaffeine hydrochloride and potassium cyanate t o dryness on the water-bath.Free acecaffeine condenses readily with alkyl cnrbimides or thio- carbimides yielding alkylated allantoins and thioallantoins and this appears to be an extremely convenient method for the preparation of these types of compounds. It is pointed out that the oxidation of uric acid and its monomethyl derivatives cannot be due t o the intermediate formation of spiro- hydantoins as according to such a scheme both 1-methyl and 9-methyl- uric acids should yield 3-methylallantoin and the 3-methyl and 7-methyl acids should yield 1-methylallantoin whereas Pischer and S c h (Abstr.1900 i 63) have shown that 3-methylallantoin is formed from the 1- and 7-methylsted acids and 1-methylallantoin from the 3- and 9-methylated acids. Hypocaffeine has m. p. 185-186O (corr.) and 1 3 6-trimethyl- allantoin (caffoline) m. p. 197O (corr.). Hypocaffeine can also be obtained from 5-cbloro-1 3 '/-t,rirnethylisouric acid (Abstr. 1911 i 168) and the corresponding 5-alkyloxy-compounds but this methodi 242 ABSTRACTS OF CHEMICATA PAPERS. is not so convenient as Fischer’s. I n the alkylation of silver hypocaff eine by methyl iodide the yield of oxytetramethyluric acid is only about 25-30% and appreciable quantities of free hypocaff eine are formed.This is attributed to the conversion of a portion of the methyl iodide into hydrogen iodide and ethylene. When ethyl iodide is used the silver compound is not rtlkylated. It has not been found possible to oxidise trimethyluric acid t o a trimethylallantoin. 1 3 6 S-~e~rametl~~Znlla~~toilz C,H1403N4 is readily formed when acecaffeine and methylcarbimide in benzene solution are sealed in a glass tube and left for twelve hours ; i t is also formed by the action of barium hydroxide solution on oxytetramethyluric acid. It absorbs water rapidly g i e l d i ~ g a monohydrate which crjstallises in rectangular prisms m.p. 9 8 O after sintering at S 5 O . The anhydrous compound has m. p. 112-113°. 8-Phenpl-l 3 6-trirnet~ylccllcntoin C,,HI,03N obtained from phenyl- carbimide and acecaffeine in benzene solution and in the absence of ’ moisture crystallises from ethyl acetate and has m. p. 197-19SO. 7-y1?hio-1 3 6 S-tetrccmetl~~ZnZlantoi~~ C,H140,N,S crystallises from benzene in prisms m. p. 15S-159°. ’7-Thi0-1 3 6-trimethyZ-S- ethyZcLZZantoin C,H1602N4S has m. p. 135O and is not readily desulphurised. J. J. S. Purines. 11. An Isomeride of Xanthine ; 2 8-Dioxy- purine. CARL 0. JOHNS (Amer. Chem. J. 1911 45 79-87).-In an earlier paper (hbstr. 1909 i 192) a n account was given of 2:s-dioxy- 6-methylpurine which was prepared by the condensation of 5 6-di- amino-2 4-methylpyrimidono with carbamide. 2 8-Dioxypurine has now been obtained in a similar manner.2 8-Bioxypurine (annexed f o r m u l ~ ) obtained in a yield of 92% of the theoretical by heating a mixture of 5 6-diamino-2-pyrimidone (Johnson Johns arid Heyl CH NH CH NH Abstr. 1906 i 771) and /\/\ /\/\ carbamide at 180-190° re- 8 70 or HT $ 70 sembles xanthine (2 6-dioxy- OC C-NH ()C C--NH’ purine) in many respects and gives the murexide reaction. If carbon dioxide is passed into a solution of the substance i n potassium hydroxide or if a solution in a mineral acid is poured into water the free base is precipitated. 2 S-Dioxypurine can be distinguished from xantbine by means of its sodium salt which forms stout prisms containing 4H,O. The hydrocldoride dinitrute and ammonium and pottcssium salts are also described ; the last-mentioned crystallises with 2H,O.5 6-Diamino-2-pyrimidone can be obtained in a yield of 65% of the theoretical by reducing 5-nitsocytosine with ferrous hydroxide ; its hydrochloride C,H,ON 2 NC 1 szc2pl~nts C,HGON ,H $O H20 and nitrate C,H60N,,4HN0 are described. When this compound is heated with sulphuric acid of 20% strength in a sealed tribe a t 140-150° it is converted into isobarbituric acid. \/ N \/’ NH E. G.ORGANIC CHEMISTRY. i 243 Quadriurates. RUDOLF KOHLER (Zeitsch. physioZ. Chem. 191 I 70 360-387).-Bttempts were made to prepare the quadriurates first described by Bence Jones (this Journ. 1862 15 201) by mixing saturated sodium biurate solution with a primary phosphate and by introducing uric acid into hot acetate solutions of varying con- centration The salts have not the composition H,C,H,O,N,,R!t HC,H,O,N attributed to them by Bence Jones but appear to be a mixture of primary urate and uric acid in the proportion of 1 1.By varying the concentration of the acetate solution mixtures varying in cmcentration to biurate may be obtained. It is shown that this is in agreement with theoretical considerations. The hydrolysis by water is not characteristic of the so-called quadriurates as some do not show it at all whereas some biurates are hydrolysed. It is due to the partial absorption of acid during the formation of the salt this pssses out into water and causes de- composition. The same reasoning applies to the decomposition of soake excrement by water and to simultaneous precipitation of biumte and uric acid from human urine as witnessed by the decrease in acidity after the formation of sediment.The salts were also sought for in snake excrement. E. F. A. Action of Azoimide on the Carbylamines. E. OLIVERI- MANDALA and B. ALAGNA (Gaxzetta 1910 40 ii 441-444. Compare Abstr. 1910 i 343).-By the action of azoiinide on the corresponding carbylamines other homologous tetrazoles can be pre- pared in the manner already described for 1-methyltetrazole. l-EthyZtetiwzoZe CSH6N4 is a liquid b. p. 155-156"/14 mm. ; i t forms a stable platiniddoride ( C,H,N,)2PtCI,. 1 -Phenyltetrazole (compare Freund and Paradies Abstr. 1901 i 770) has m. p. 65-66'. R. V. S. The Course of the Sandmeyer Reaction. GUSTAV HELLER and WALTER TISCHNER (Bey.1911 44 250-255. Compare Abstr. 19 10 i 240).-The authors have investigated the velocity of decom- position of benzenedinzonium chloride and also of 0- and p-toluene- diazonium chlorides in aqueous hydrochloric acid solution in the presence of cuprous chloride by measuring the rate of evolution of nitrogen. It is found that the velocity depends not only on the temperature and concentration both of the acid and of the diazonium compound but also to a great extent on the nature of the diazonium compound ihelf slight changes i n the constitution producing considerable differ- ences in the course of the decomposition ; catalytic influences also play a considerable part in determining tbe rate of decomposition. I n the case of benzenediazonium chloride free nitrous acid and also excess of cuprous chloride influence the decomposition in a marked but irregular manner.W ithp-toluenediazoniurn chloride the velocity a t the beginning of the reaction is very small and then gradually increases ; this increase is followed by a gradual diminution in the rate of decomposition and finally by a rapid rise to a maximum when the reaction quickly conies t o an end.i. 21.4 ABSTRACTS OF CHEMICAL PAPERS. I n the case of o-toluenediazonium chloride the rate of decom- position is very slow a t first then rises rapidly to a maximum in about two hours and slowly diminishes. F. B. o-Arylazo-compounds of Heterocyclic Phenols 3 Methyl- 4-arylaz:,-5-hydroxyisooxazole. CARL BULOW and ARNULF HECK- ING ( B e y . 191 1 44 238-250).-Knorr and Reuter's 4-benzeneazo- 5 -h ydroxy -3 -met hylisooxazol e 0 C(OH) >C*N:NPh (Abstr.1894 N CIXe- i 371 ; compare Schiff Abstr. 1896 i 83) can be readily prepared by the addition of an aqueous solution of sodiiim acetate and hydroxyl- amine hydrochloride to a boiling alcoholic solution of ethyl benzeneazo- acetoacetate. It dissolves in alkalis and is reprecipitated by carbon dioxide. The silver salt C,,H,O,N,Ag when slowly heated has m. p. 208-210° (decomp.). The sodium salt C,?H,,O,N,Na,H,O~ was prepared by Schiff and Viciani (Abstr. 1897 1 444) who considered it to be sodium P-oximino-a-phenylhydrazonoacetoacetate HO *N CMe * C( N NHPh ) C0,Na. The authors find however that this sodium salt loses one molecule of water of crystallisation when kept in a vacuum over sulphuric acid and is readily hydrolysed with the formation 4-benzeneazo-5- hydroxy-3-methylisooxazole ; when treated with hydrochloric acid it yields the original heterocyclic phenol (compare Schiff and Viciani JOG.cit.). These facts are in contradiction to the view that the solubility of 4-benzeneazo-5-hydroxy-3-methylisooxazole in alkalis is due t o the rupture of the isooxazole ring with the formation of salts of oximino- phenylhydrazonoacetoacetic acid and support tshe contention of Biiiow and Haas (Abstr. 1910 i 902) that the products obtained by the action of diazonium salts on 3-substituted isooxazolones are azo- derivatives of heterocyclic phenols y C(OH)>C. N N . R. N== CR The isooxazolones themselves are also represented by the hydroxylic and riot the ketonic formulz.When 4-benzeneazo-5-hydroxy-3-methylisooxazole is boiled with concentrated potassium hydroxide solution 2-phonyl-4-methyl-2 1 3 - triazole 1 l N * P h (von Pechmann Abstr. 1888 1287) and a-methylglyoxztl-a-oxinie-/3-phenylhydrazone are produced. The authors consider that the first stage in this reaction consists in the rupture of the isooxazole ring and the formation of NaO-N :CMe*C( N,Ph):C(ONa)2 which then loses sodium carbonate yielding the oxime-hydrazonc. HON:CMe-CH:N*NI'IPh forms yellow crystals m. p. 147-14So which become yellowish- brown on keeping ; it reduces silver nitrate and Fehling's solutions and gives a n intense reddish-violet coloration when its solution in concentrated sulphuric acid is treated with ferric chloride or potassium dichromate.When heated with phenylhydrazine i t is converted into CISle:N CH-N' a- Met A y lg l y oxal - a-ozim e- P-pherq Z h yds-azone,ORGANIC CHEMISTRY. i. 245 methylglyoxalosazone NHPh-N :CMe*C I€ N*NHPh (von Pechmann Abstr. 1887 1103). 4-p-Nitrobenxeneaxo-5-~ydrox~-3-~~~ethylisoo.xuzole C,,H,O,N is pre- parec1 by the interaction of equal molecular quantities of nitric acid and 4-benzeneazo-5-hydroxy-3-methylisooxazole i n concentrated sul- phuric acid solution ; it forms felted needles ID. p. 176-177' dissolves in strong sulphuric acid with a greenish-yellow colour and does not give the Eulow reaction for hydrazones. 4-Dinitrobenxeneuxo-~-?~~d~oxy-3-met~~~Zisooxc~xoZe CIOH70dN6 pre- pared in a similar manner from two mols.of nitric acid crystallises in yellow leaflets m. p. 184-1 85'. 4 - o - i r ' o l u e ~ a e u x o - 5 - h p d ~ o x y - 3 - m e t h y C,,H,,O,N is prepared by the gradual addition of an aqueous solution of hydroxylamine and sodium acetate t o a boiling alcoholic solution of ethyl o-tolueneazo- acetoacetate; it has m. p. 154-155' and dissolves in alkalis with a yellow colour. 4-p-Tolueneazo-5-hydroxy-3-methylisooxazole C,,H,,O,N obtained in a similar manner from ethyl p-tolueneazoacetoacetate crystallises in yellow needles rn. p. 203"(Schiff 202'). 4-rn-Xyleneazo -5 -hydroxy-3-met?iylisooxazole C,,H,,O,N forms orange-yellow needles m. .p. 134-135'; its salts with alkalis are decomposed by carbon dioxide. C,,Hl,O,N crystallises in brick-red leaflets m. p. 172-173' (Schiff 168-170') and dissolves in concentrated sulphuric acid with a deep bluish-red colour.4-P-Nupl~thaleneuxo-5 -hydroxy- 3-methyl isooxccxole C,,K,,O,N3 for ins stout brownish-yellow needles m. p. 201-202' ; its solutions in strong sul phuric acid have a reddish-orange colour. By the interaction of sodium acetate hydroxylamine hydrochloride and ethyl o-csrboxybenzeneazoacetoacetate in alcoholic solution ethyl a-o-carboxybenzeneuzo- p-oxi~minoncetoncetate HON CMe* CH (N,*C,H,*CO,H)* CO Et is produced. The latter compound bas m. p. S07-2OSu and yields 4-o-carbozybenxeneuzo-5 -Aydroxy-3 -methylisooxcczole C H904N3 yellow leaflets m. p. 232' when boiled in glacial acetic acid solution. &thpl nitroccrboxybenzeneccxoacetoucetate C13M1307N3 obtained by nitrating ethyl carboxybenzeneazoacetoacetate crystallises in feltetl yellow needles m.p. lSS-189'; the oxinbe Cl,H,,07N4 has m. 1). 222' and could not be converted into the correbponding zsooxazolone. 4 -a - Naphthaleneazo - 5 - hydroxy - 3 - methylisooxazole F. B. The State of Aggregation of Matter. 1-111. SAMUEL B. SCHRYVER (Proc. Roy. ~Soc. 1910 B 83 96-123).-1. Action of Salts in Heterogeneous Systems und the Nature of the Globulins.-When formaldehyde acts on a solution of Witte's peptone a precipitate is formed. This precipitation can however as Sollman has shown be inhibited by the presence of salts. The titratiop of the mixture by alkali even in the absence of precipitate formation shows that the formaldehyde has acted on the amino-groups with the formation of methyleneimino-peptones.The inhibitory action of salts on pre-i. 246 ABSTRACTS OF CHEMICAL PAPERS. cipitate formation can however be explained if the methyleneimino- peptones undergo polymerisation or condensation to form more com- plex molecules and behave in the same way as methyleneasparagine behaves according to the investigations of Schiff. If the unpolymer- ised or uncondensed methyleneimino-peptones are of such complexity as to form colloidal solutions they can adsorb salt molecules from solution which sterically inhibit their reactions with one another and prevent the formation of the insoluble complexes. A quantitative investigation of the inhibitory action of a large number of salt solutions showed that (with certain explicable exceptions) those which possessed the greatest power in this wspect were the best solvents of the globulins.This suggested an explanation of the nature of these substances wbich are soluble in salt solution but insoluble in water. The author gives reasons for supposing that the undissolved globulins are aggregates formed by the combination of a carboxyl group in one molecule with an amino-group in another by means of which a salt is formed which undergoes a slight but definite hydrolysis in the presence of water. Owing to adsorptions of salt the dissociated globulin molecules are sterically inhibited from reaggregation ; the more readily a salt is adsorbed the greater the solvent or (diaggregat- ing) capacity as regards the globulin. The results indicate that owing to their adsorption capacities chemical reactions of colloids do not follow the ordinary lams of mass action.The solvent capacity of salts for globulins can be correlated with two physical properties of their aqueous solutions namely their surface tensions and their viscosities ; the higher the surface tension and the viscosity of a salt the smaller i t s solvent capacity for the globulins. The influence of the former property can be deduced from a general study of adsorption phenomena and of the latter by an extension of Noyes and Whitney’s and of Nernst’s generalisations on the rate of action in heterogeneous systems with t h e assumption of the existence of a diffusion layer a t the limit- ing surfaces. Salts also exert similar action in systems other than those containing proteins.Thus the critical solution temperature of phenol and salt solutions is shown to be a function of the surface tension of the latter. Furthermore the solubility of certain crystal- line substances in salt solutions especially of amphoteric substances is shown to follow similar laws to the globulins. The surface tensions and viscosities of a series of salt solutions together with the solubility of edestin and serum-globulin in these solutions are tabulated. 11. Action of .Formaldehyde on Witte’s Peptone.-It is shown that the precipitate is formed from the more complex constituents of the peptones. Owing to the acidic nature of the methyleneimino-peptones the salts of the weaker acids exert a greater inhibitory capacity on precipitate formation than would be deduced from their surface tensions and viscosities as double decomposition can take place.111. The Solubility (f Phenol and Certain Crystalline Substancerr in Salt Solutions.-The solubilities of dl-leucine dl-phenylalanine caffeine. benzamide and p-toluidine in the series of salt solutions employed in the investigations on the globulins are tabulated. S. B. S.ORGANIC CI-IEMISTRY. i. 247 Organic Colloids. S. J. LEVITES (Zeitsch. Chem. Ind. Kolloide 1911 8 4-S).-Observations are recorded in reference to the solubility and precipitability of proteins and the adsorption of tannin by gelatin. Glutin is readily soluble in solutions of iodides and thiocyanates ; casein in solutions of potassium iodide sodium thiocyanate potassium nitrate and sodium phosphate. Aqueous pyridine is a good solvent for various proteins.Glutin and casein are both insoluble in water and in anhydrous pyridine but dissolve in water-pyridine mixtures the maximum solubility corresponding with a solvent of the composition C,H,N+2H20. Glutin and Witte’s peptone are readily soluble in formamide and the solutions can be diluted with water without precipitation. The formamide and aqueous pyridine solutions of the proteins are very viscous. I n regard t o the precipitation of proteins i t has been found that Witte’a peptone and gelatin are precipitated by cadmium iodide in very dilute solution. Solutions of zinc and cadmium sulphates only give rise to a slight opalescence when added t o With’s peptone and have no effect on a gelatin solution. From experiments on the adsorption of tannin by gelatin from tannin solutions of different concentrations it has been found that the proportion of adsorbed substance diminishes as the concentration increases.For a given solution the adsorption increases with the period of smelling of the gelatin. I n presence of an electrolyte (potassium aluminium sulphate) the adsorption of tannin by gelatin is diminished and the influence of the concentration of the tannin solution on the magnitude of the adsorption is very greatly reduced. H. M. D. Methylation of Gelatin ZUENKO H. SKRAUP and B. E~TTCIIER (Monatsh. 1910 31 1035-1050).-The authors find that gelatin contains a small quantity of methyl in the form of the groups *OMe and :NMe and t h a t the percentage of methyl in both forms increases on methylation. When hydrolysed the methyl derivative yields histidine and arginine in quantities amounting to 10% of those furnished by gelatin itself traces of glutamic acid and no lysine; leucine alanine glycine pyrrolidinecarboxylic acid and phenylalanine were also found amongst the products of hydrolysis. The hexone bases and glutamic acid are ‘ thus destroyed on methylation whereas the leucine alanine etc. remain unchanged. Comparing these results with those obtained in the case of casein (Abstr. 1909 i 74S) the authors draw the conclusion t h a t the arrangement of the glutamic acid residue in the latter compound is different from that in gelatin. Methylgelatin pFepared by boiling a solution of gelatin in alcoholic potassium hydroxide with methyl iodide forms an amorphous yellow mass which when powdered is almost white ; it is soluble in water and is precipitated on the addition of ammonium sulphate. The xantho- protein reaction is more marked than with ordinary gelatin. F. B.i. 248 ABS’I’RACTS OF CIIEMICAL PAPERS. The Pepsin-chymosin Question. J. F. B. VAN HASSELT (Zezlsclt. ph,ysioZ. Chem. 1910 70 171-185). -The experiments quoted bear against the view that pepsin and rennin (chymosin) are one and the same substance. It is possible to obtain preparations which exhibit only one action ; anti-substances also inhibit differently the two enzymatic actions. W. D. H. Diastase and Commercial Lecithin Preparations. HERMAN LAPIDUS (Biochem. Zeitsch. 1910 30 39-55).-The amount of action was determined by estimating the reducing sugars formed (calculated as maltose for which the author has worked out tables). Wohlgemuth’s iodine method was not available owing to the action of this snbstsnce on the lecithin. The lecithin inhibits the action of ptyalin to a marked extent but not t o a relatively greater extent when small amounts of saliva are employed as compared with its inhibitory action on larger amounts oE saliva. There does not appear therefore t o be any evidence of combination between saliva and lecithin. The inhibitory influence is more marked a t room temperature than a t body tempera- ture. The action of lecithin on pancreas diastase is similar although here there is not such a marked difference between the action a t room temperature and body tempei ature. With serum diaslase the results obtained are somewhat complicated as the amount of diastase in the serum alters (increases) with age and diminishes after extraction with ether. The lecithin in this case diminishes the action a t room tern- perature ; at body temperature i t sometimes increases and sometimes diminishes the action. Generally the action is weakly inhibitory. I f however the serum which has been extracted with ether is employed lecithin markedly increases the diastatic action. The above experi- ments were carried out with ox-serum. I n human seIum (from placenta) the diastatic action was weak but was inct eased by addition of lecithin. Similar results were obtained with syphillitic sera in which the diastatic action is stronger than in the normal. S. 6. S. Hmmoglobin as a Peroxydase. GABRIEL BERTRAND and FELIX ROGOSINSKI (Compt. rend. 1911 152,148-151 ; Bull. Soc. chim. 1911 [iv] 9 148-152. Compare Wolff and Stcecklin Abstr. 1910 i 802).-The peroxydase character of oxyhaemoglobin is also shared by carboxyhzmoglobin and cyanohzemoglobin ; it appears therefore not to be due to the ability of oxyhtlemoglobin t o part with oxggen but to depend on the presence of iron in the molecule. W. 0. W. Extraction of Zymase by Simple Maceration. A. VON LEBEDEFF (Compt. rend. 1911 152 49-51).-.It is not necessary to employ Buchner’s method to obtain a preparation of zymase from yeast. The solution obtained by macerating one part of dried yeast with 2.5-3 parts of water on filtering through paper after being allowed to remain overnight has greater activity and stabiiity than that prepared by the usual method. w. 0. w.

ISSN:0368-1769    

DOI:10.1039/CA9110000173

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

ii. 200 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. Influence of Organic Liquids on the Interaction of Hydrogen Sulphide and Sulphur Dioxide. DAVID KLEIN (J. Physical Chem. 1910 15 l-l9).-Dry hydrogen sulphide will not react with dry mlphur dioxide (Cluzel Ann. Chim. Phys. 1812 84 162). Brereton Baker has recently stated that liquid alcohol and liquid sulphur dioxide can liberate sulphur from the dried mixture of gases whereas carbon tetrachloride is inert (Mem. Manchester Phil. Xoc. 1909 53 Part 3). The+ author’s experiments confirm and extend these observations. Immediate action is produced by water ethyl alcohol isobutyl alc9ho1 isoamyl alcohol acetone propyl acetate benzaldehyde and carvone. A slower decomposition occurs with methyl ethyl ketone acetonitrile propionitrile valeronitrile phenylacetonitrile methyl benzoate isobutyl acetate and ethyl ether.On the other hand carbon disulphide ethyl disulphide benzene amylene chloroform nitrobenzene acetyl chloride benzoyl chloride ethyl chloride and carbon tetrachloride are quite inert There appears t o be no connexion between the dielectric capacity or association factor of a liquid and i t s activity as a catalyst in this reaction. Many of the active liquids are known to form compounds with hydrogen sulphide notably the nitriles the aldehydes and carvone. The results generally support the intermediate compound theory of catalysis. Care was taken to eliminate water as far as possible from the mixed gases and the various solvents but it is admittedly impossible t o prove that water was entirely absent in those cases where action occurred.R. J. C. Nitrosulphonic Acid 4‘ Blue Acid ”. FRITZ RASCHIG (Zeitsch. angew. Chern. 1911 24 160. Compare Abstr. 1910 ii 1055).- Polemical. A reply to Manchot (this vol. ii 107). T. S. P.INORGANIC CHEMISTRY. ii. 201 Tellurium. ALEXANDER GUTBIER and FERDINAND FLURY (J. pr. Chern. [ii] 83 145-163).-See this vol. i 182. ROBEIXT STOLL~ (J. pr. Chern. 1911 [ii] 200).-Almost anhydrous hydrazine is obtained by distilling sodamide and hydrazine hydrate in a vacuum (compare Raschig Ahstr. 1910 ii 706). The quantity of sodamide must be rather smaller than that calculated from the equation N,H,,H20 + NH2Na = N2H + NH + NaOH ; when an excess is used a violent explosion occurs a t about 70° probably due to the formation and decomposition of sodium hydrazide (compare Ebler Abstr.19 10 Action of Hydrazine Hydrate on Sodamide. ii 614). c. s. Experiments on the Inertness of Oxygen towards Phos- phorus. MIECZYSLAW CENTNERSZWER (Chew,. Zentr. 1910 ii 1022 ; from Kosmos 1910,35 Radxisxewsl%i-~estbunc2,526-527).-The author determined the partial pressure of oxygen at which luminosity commences in solutions of phosphorus in castor oil petroleum and vaselin oil between 0' and 25'. He also measured the speed of oxidatkn of phosphorus in castor oil a t 25'. The experiments shorn that the apparent inertness of phosphorus for oxygen occurs also in solutions of phosphorus and that with the decreasing partial pressure of the phosphorus the luminosity pressure decreases for the oxygen.It is also shown that by the solution of phosphorus in non-volatile oils its oxidation power is increased. During the oxidation of phosphorus an unknown compound is formed which inhibits the oxidation process autocatalytically; this compound is evidently identical with that which inhibits the oxidation of solid phosphorus by oxygen at atmospheric pressure. N. c. Density of Hydrogen Phosphide and Atomic Weight of Phosphorus. G. TER-GAZARIAN (J. Chim. Phys. 1911,9 101-102). -Replying to the criticism of Baxter and Jones (Abstr. 1910 ii 288) the author contends that the hydrogen phosphide used in his atomic weight determinations could not have been contaminated with hydrogen and ammonia Some error may however have been introduced by calculating the compression constants from the critical data instead of from the compressibility of the phosphide.R. J. C. The Volatile Matter of Coal. HORACE C. PORTER and F. K. OVITZ (Bull. Bu!recm of Mines 19 10 I 1-56).-Nine different coals from various parts of the United States have been investigated with a view to determining the composition of the volatile products evolved at different temperatures. The by-products of coking were determined by tests in an iron retort on 400 grams of coal whilst the gas evolved was determined by tests on 10 grams of coal using a platinum retort. The furnace temperatures varied from 500-1 100'. The main features of the results are the comparatively large amounts of inert constituents such as carbon dioxide and water in the products from certain western coals the large amounts of higherii.202 ABSTKACTS OF CEEMICAL PAPERS. methane hydrocarbons such as ethane in the products obtained at moderate temperatures particularly from the Appalachian coals and the larger amounts of gas and tarry vapours produced qnickly at moderate temperatures from the younger western coals. The bearing of these results on smoke-producing tendencies on studies of the nature of coal substance and on the calculation of heat value from ultimate analysis is discussed. Any statement as to the character of the gases or volatile products evolved from coal at specified temperatures has little value unless i t is accompanied by a clear description of the conditions prevailing during the testing and particularly of the points at which temperatures were taken and of the mass of cod which mas heated.The temperature varies throughout the mass and is affected by the rate and time of heating. The same temperatures outside the containing vessel produce different temperatures in the coal itself according to the kind of vessel and the duration of heating. The distance of the vessel from the point where temperatures are read influences the difference between the observed temperature and that of the coal within the vessel. T. s. I?. Fractional Crystallisation a n d Atomic W e i g h t of Argon. FRANZ FISCHEB and VICTOR FROBOESE (Bey. 1911 44 92-104).- The discrepancy in the periodic arrangement of the elements which occurs with the pair argon and potassium is due very probably to an error in the atomic weight of argon.The authors have therefore tested the individuality of this element by a process of fractional cry stallisation. An apparatus for this purpose is figured and described; the most important part is the fractionating vessel which is designed to effect a separation of the liquid and the solid phases at any pressure and in the complete absence of air. Forty litres of argon 1) 19.94 isolated from air by the aid of glowing calcium carbide (Pischer and lxinge Abstr. 1908 ii 688 ; Fischer and Hahnel Abstt. 1910 ii 608) are used. Argon has b. p. - 186.9O/560 mm. and f . p. - 189.6' arid its freezing and thawing by the aid of freshly-prepaxed liquid air b. p. about - 19l0 and of stored liquid air b. p. about - 1 8 3 4 O is a practical operation. The experiments show that argon cannot be separated into t w o fractions of different density by fractional crystallisation ; the densities of the gaseous argon obtained from the liquid and tnhe solid phases are both 19.95(4) corresponding with an atomic weight of 39.9.I n some experiments fractions have been obtained having D 19.86 ; the depression is due to the presence of neon and air for when the latter is removed by chemical means the density is increased to 19.92. c. 8. Isotherms of Monatomic Gases and of their Binary Mixtures. VI. Go-existing Liquid and Vapour Densities of Argon; Calculation of the Critical Density of Argon. C. A. CROMMELIN (Proc. K. Akud. Wetensch. Arnstwdam 1910 13 607-613).-From the data obtained in a previous investigation (Abstr. 1910 ii 709) the author has calculated the differencesINORGANIC CHEMISTRY. ii.203 between the demities of liquid and gaseous argon at a series of temperatures. By combination of these differences with the sum of the densities as represented by the law of rectilinear diameters values have been obtained for the deosity of both liquid and saturated vapour. The respective densities are 1.0268 and 0,1073 a t - 140-8" 0.9339 and 0.1621 at - 134*72" 0.8581 and 0.2079 at - 129*83" and 0,7557 arid 0.2Cf43 at - 125.49'. It is shown that the observat,ions can be satisfactorily represented by means of Keesom's formula. H. M. D. Isotherms of Monatomic Gaees a n d o1 their Binary Mixtures. VII. Isotherms of Argon between +20° and -150". H KAMERLINGH ONNES and C. A. CROMMELIN (Proc.A'. Akad. Wetmsch. Amstos-dam 19 10 13 6 14-625).-The pressure volume relationships of argon have been determined at temperatures between + 20" and - 150" for pressures ranging up t o 60 atmospheres. Precipitation of Soluble Chlorides by Hydrochloric Acid. JOHN GIBSON arid ROBERT B. DENISON (Proc. Roy. SOC. &din. 19N-10 30 562-568).-From the point of view of the dissociation theory the precipitation of sodium chloride from solution by the addition of hydrochloric acid is due to a decrease in the dissociation of the salt and consequent increase in the concentration of the undissociated molecules. Precipitation should occur therefore only when the concerltration of the chloride ions in the solution of hydro- chloric acid is greater than the concentration of the chloride ions in the saturated solution to which it is added.Experiments at 18' with saturated solutions of sodium potassium rubidium and ammonium chlorides and at 0" with saturated solutions of sodium and potassium chloride? showed that precipitation occurred only when the concentration of the hydrochloric acid added was l8-19% or higher that is when acid of maximum conductivity was added. Calculation of the chloride-ion concentrations of the saturated solutions from measurements of the electrical conductivity shows that only in the case of sodium chloride is it less than the concentration of the chloride ion in hydrochloric acid of maximum conductivity so that if the explanation mentioned above is the correct one the ionic concentrations calculated from the electrical conductivities cannot be even approximately correct.Even if the concentration of t h e chloride ions is a t least equal to that of the saturated salt solutions there is no explanation as to why such solutions which are all precipitated by hydrochloric acid of the same concentration are in no case p~ ecipitated by a solution containing less hydrogen chloride. The insufficiency of the dissociation theory to explain these phenomena is probably due to i t s taking into account only the following equilibria solid salt t undissociated salt in solution ions whereas probably there are otber factors such as the hydration of the ions and undiesociated molecules and the formation of complex ions. H. M. D.ii. 204 ABSTRACTS OF CHEMICAL PAPERS The above experiments are further instances of A tendency towards maximum specific conductivity in chemical reactions (compare Abstr.1897 ii 437; 1900 ii 198); the hypothesis of such a tendency is thus shown to be useful for by it the conditions necessary for these precipitations are correlated and were predicted Revision of the Atomic W e i g h t of Calcium. 11. Analysis of Calcium Chloride. THEODORE W. RICHARDS and OTTO HONIG- SCHNID (itfonatsh. 1911 32 41-51." Compare Abstr. 1902 ii 394 and this vol. ii 112).-The calcium chloride was prepared from calcium carbonate and hydrochloric acid and was subjected to three recrystal- lisations. The calcium carbonate was from two different sources. The first specimen was prepared from calcium nitrate by precipitation with freshly distilled ammonium carbonate the calcium nitrate having been obtained from marble and nitric acid and recrystallised ten times.The second specimen was obtained in a similar manner from a pixre specimen of precipitated calcium carbonate the nitrate being recrystallised four times. Calcium chloride was prepared from each of these specimens of calcium carbonate and also by concentration of the mother liquors resulting from the recrystallisations ; this third specimen of calcium chloride was recrystallised four times. The calcium chloride used in each determination was fused in a current of hydrogen chloride and cooled in an atmosphere of nitrogen and finally of air. It was then analysed by the gravimetric titration method (Abstr. 1910 ii 292) the chlorine being precipitated by silver nitrate prepared from three different specimens of pure silver.Allow- ance had to be made for any acidity or alkalinity of the calcium chloride. The average of seven determinations gave the ratio CaCl Ag = 0.514405 corresponding with 40.074 0,002 a s the atomic weight of calcium [Ag = 107.88 and C1= 35.4571. This result is con- sidered to be more accurate than those obtained by analysis of calcium bromide (Zoc. cit.). As a mean of all results the authors consider Ca = 40.075 as the most accurate number. The Chemical Action of Sea-Water on Portland Cement. LUCIEN POIRSON (Zentr. hydraul. Zemente 1910 1 151-159).- Experiments in which powdered Portland cement was shaken with solutions of the salts contained in sea-water show that the only stable compound formed is calcium sulpho-aluminate 3CaO,Al20,,3CaSO,.Solutions of chlorides react with cement and form insoluble compounds such as 2( 3Ca0,A1,03),CaCl but these compounds are rapidly decom- posed by solution of sulphates yielding the sulpho-aluminate. Calcium ferrite forms an insoluble compound 3CaO,Fe,O,,CaSO,. The Ternary Alloys of Lead Tin and Antimony. RICHARD LOEBE (34etaUurgie 191 1 8 7-10 33-49).-The thermal analysis of the tin-antimony alloys confirms the results of Williams (Abstr. 1907 ii 783) as to the existence of three series of solid solutions the discontinuities in the freezing-point curve being at 422O and 244O respectively. Thus two components of the ternary system form three solid solutions with one another whilst the third component does not * and J.Amer. Chem. SOC. 1911 33 28-35. T. S. P. T. S. P. C. H. D.INORGANIC CHEMISTRY. ii. 205 form solid solutions with either. The limited miscibility of solid lead and tin may be neglected under the conditions of the investigation. The freezing-point surface of the space-model is made up of four surfaces of which three represent the primary crystallisation of the solid solutions of tin and antimony and the fourth t h a t of lead. There is no ternary eutectic the lowest point of the surface being the lead- tin eutectic point at 183'. There are two horizontal planes of invariant equilibrium at 245' and 19l0 limiting the regions of stability of the saturated solid solutions. The process of diffusion in the solid alloys is so slow that equilibrium is not readily reached and small discrep- ancies are observed between the thermal and microscopical results The great differences of density between the phases formed also lead to much segregation during freezing.The lead in these alloys only plays the part of a solvent and does not otherwise affect the relations of tin and antimony. C. H. D. A New Property of Copper and the Rapid Combustion of Gases without Flame or Convergent Combustion. JEAN MEUNIER (Compt. rend. 1911 152,194-196 Compare Abstr. 1908 ii 11 276 376 463 ; 1909 ii 311).-Copper is able to bring about the flameless combustion of mixtures of coal gas and air at its surface in the same way as the metals mentioned in previous communications. The phenomenon may be observed by passing a copper wire into the interior of the luminous flame from a Bunsen burner in such a way that the surface becomes bright by reduction ; on allowing air to enter and pushing the metal into the cool portion of the mixed gases the wire glows and the flame above becomes green probably through the formation of a hydride of copper.This property appears to be attributable to the crystalline condition of the metal ; electrolytic copper shows it particularly well. w. 0. w. Colloidal Mercury. CONRAD AMBERGER (Zeitsch. Clknz. 1w.Z. Kolloide 19 11 8 8S-93).-Colloidal preparations containing about 50% of mercury can be obtained by the reduction of mercurous nitrate in presence of protalbic and lysalbic acid$ as protective agents. Five grams of sodium protalbate are dissolved in 250 C.C. of water and sodium hydroxide is added to this solution in quantity somewhat greater than that corresponding with 7 grams of mercurous nitrate.This is also dissolved in 250 C.C. of water acidified with a few drops of nitric acid and the mercurous salt solution is added in successive small portions to the protalbste solution. On addition of excess of hydrazine hydrate to the reddish-brown solution the mercurous salt is reduced. Acetic acid is then added and the dark brown flaky precipitate after washing is dried in a vacuum at the ordinary temperature. The substance thus obtained is an adsorption compound of solid colloidal mercury and protalbic acid. I f the flaky precipitate is dissolved in the minimum amount of sodium hydroxide solution before evaporation a similar absorption compound of colloidal mercury and sodium protalbate is obtained. Experiments are also described which show that colloidal mercury preparations are obtained by the reduction of mercurous nitrate byii.206 ABSTRACTS OF CHEMICAL PAPERS. means of sodium hyposulphite in presence of sodium protnlhate or lysltlbate as protective colloid. All these preparations appear to be quite stable but coagulation takes place when they are dissolved in water. The stability of solutions of the preparations obtained by the hyposulphite reduction is however relatively much greater tban that of the preparations which result from the reduction w i t h hydrszine. This is attributed to the presence of colloidal mercuric sulphide which acts as second protective colloid. 13. M.D. Formulae of Aluminium Salts. S. C . J. OLIVIER (Chem. Feek- A reply to Coops (this vol. ii hlc~d 1911 8 56-59).-Po!emical. 116). A. J. W. The Influence of Manganese on the Properties of Mild Steel. GEORG LANG (Metullurgie 191 1 8 15-21 49-53).-The addition of aluminottiermic manganese to iron prepared in an electric furnace and containing 0.1% of carbon yields alloys the tenacity and hardness of which increases up to 3% of manganese. The ductility is not diminished until the manganese exceeds 1.5%. The electrical resistance is increased arid is independent of the thermal treatment. The magnetic coercive force and hysteresis of iron are increased and the permeability diminished by t h e addition of manganese. C. H. D. Action of Water Containing Carbon Dioxide on Iron.W. TH. CLOUS (Chem. U’eekblad 1911 8 lo).-When carbon dioxide is passed through a wash-bottle containing water and powdered iron int>o a eudiometer filled with a concentrated solution of potassium hydroxide u n t i l the hydroxide solution is nearly saturated with the gas a small amount of gas insoluble in the potassium hydroxide is obtained. I n t h e author’s experiment 2.5 C.C. of this gas were collected and it was proved to be hydrogen by introducing a small amount of oxygen and exploding the mixture by an electric spark. A. J. W. Preparation of the Hydrosol of Tungatic Acid. ARTHUR MULLEK (Zeitsch. Chem. Ind. Kolloide 1911 8 93-95).-Five grams of tungstic tetrachloride are dissolved in about 50 C.C. of a mixture containing equal volumes of ethyl alcohol and ethyl ether and the filtered solution is then diluted to 250 C.C.with ethyl alcohol. If this solution is mixed with an equal volume of water a colloidal solution of tungstic acid is obtained which can be kept for some days without any appreciable opalescence being observed. With larger quantities of water coagulation takes place much more quickly. On addition of small quantities of neutral salts or of hydroxides coagulation occurs ‘immediately ; strong acids produce a similar effect after some minutes but weak organic acids appear to exert no influence on the stability of the colloidal solutions. Ri*e of temperature is also without influence but coagulation takes place if the volume is reduced to about a fourth of the original by evaporation. When an electric current is passed through the colloidal solution a deep blue precipitate is formed a t the cathode.This is attributed toINORGANIC CHEMISTRY. ii. 207 reduction of the positively charged colloidal particles by the discharged hydrogen. The behaviour of the colloidal solutions towards electrolytes is consistent with the supposition that the tungstic acid is a positive colloid and the spontaneous coagulation of the solutions obtained by the author’s method is probably due to the presence of chlorine ions in the solutions. H. M. D. Metallic Uranium. WILLEN P. J-OR~SSEN and A. P. H. TRIVELLI (Chem. tVeekbZad 1911 8 59-62. Corn pare Kohlschutter Abstr. 1901 ii 598 ; Jorissen and Ringer Abstr. 1907 422 731 ; Olie and also Jorissen Abstr. 1909 ii 10; Olie Abstr.1909 ii 783).-When metallic uranium is exposed to cathode rays nitrogen is evolved. To ascertain whether this nitrogen is derived from Kohlschutter’s uranium nitride U,N a sample of uranium was heated i n a vacuum with lead chromate. The results indicated the presence in the metal of 0.94% of nitrogen and 1.25% of carbon. The formula U,N requires 12.9% of uranium. A. J. W. A New Uranium Colloid. ALEXANDER SAMSONOW (Zeitsch. Chent. Ind. KoZloide 1911 8 96-97).-When a solution of uranyl chloride is electrolysed a black precipitate is formed by reduction a t the cathode. The precipitate is soluble in wttter giving a dark-coloured solution which shows the presence of ultra-microscopic particles. A very dilute solution has a yellow tinge and the absorption spectrum indicates that neither a uranous nor a uranyl salt is present.I n an electric field tho solution becomes decolorised a t the anode and precipitation takes place at the cathode. On addition of electrolytes coagulation phenomena characteristic of the positive colloids are observed. By titration of the solution with potassium permanganate before and after reduction with zinc i t has been found that the colloidal suspension consists of uranous oxide. The same substance is also obtained in the reduction of uranyl chloride by zinc or copper in dilute acid solution. Uranous chloride acts as a protective and increases the stability of the colloidal solution. H. 31. D. Thorium Arsenates. GIUSEPPE A. BARBIERI ( A t t i R. Accad. Lincei 1910 [v] 19 ii 642-645. Compare Bdrbieri and Calzolari Abstr.1910 ii 779).-The author has succeeded in preparing two thorium arsenates similar in constitution and appearance to the two cerium arseriates previously described. Thorium hydyogen arsenccte Th( HAsO4),,6H,O is precipitated in crystalline form when to a boiling solution of thorium nitrate (containing 2% of Tho,) a 40% aqueous solution of arsenic acid (4 mols.) is added. If less arsenic acid is employed an amorphous precipitate of variable composition is obtained whilst if the reaction with the quantities mentioned is carried out with dilute solutions in the cold no precipitate may bo formed but instead a gelatinous mass which eventually becomes crystalline and then has the above coin posi ti on. Thos*iurn dihydrogen arsenate T h( H AsO,) * 4 H,OI is precipitated in colourless ct ystals when a solution of thoriumii. 208 ABSTRACTS OF CHEMICAL PAPERS. nitrate (containing 5% of Tho,) is treated with a 50% solution of arsenic acid (8 mols.). Water converts it into the monohydrogen salt. R. V. S. Brown Gold. MAURICE HANRIOT (Compt. rend. 1911 152 138-141. Compare this vol. ii 118).-A further study of the influence of temperature dimensions mode of heating impurities and composition of the original alloy on the contraction undergone when brown gold the product of the action of nitric acid on gold- silver alloys is heated. Contraction is not complete below 950° or until after about six hours’ heating. \v. 0. w.

ISSN:0368-1769    

DOI:10.1039/CA9110005200

出版商:RSC    

年代:1911

数据来源: RSC

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ii. 208 ABSTRACTS OF CHEMICAL PAPERS. Miner a l o gi c a1 C h e mi s t r y. Pyrites and Marcasite. VIKTOR POSCHL (Zeitsch. Kryst. Min. 1911 48 572-618).-Descriptions are given of the surface characters of crystals of pyrites and marcasite as seen under a metallographic microscope. The characters of the faces and the form and orientation of the arti- ficially-produced etched figures suggest that the symmetry of pyrites is tetrahedral-pentagonal-dodecahedra1 rather than pentagonal-dodeca- hedral. Numerous determinations were made of the hardness of natural and of artificially-cut faces. The degree of hardness is assumed to be proportional to the volume of material removed (that is proportional t o the square of the width of the scratches produced) by a weighted diamond point moved across the surface.The hardness of pyrites relative to that of topaz = 1000 is 199.1 under a load of 50 grams and 182.2 under a load of 20 grams ; of marcasite 134.1 and 140.2 under the same loads respectively. On on0 and the same crystal no differ- ences in hardness were detected on different faces or along different directions on the same face. Different crystals however differ slightly in hardness and it is noticed that those which are softer are at the same time less dense. The specifically lightest and heaviest crystals of each lot experimented on were analysed with the following results but no essential differences are shown in chemical composition Fe. Ni. Go. Cu. I. 46.02 0'04 - 0.59 11. 46.19 0.07 - 0-63 111. 96-32 trace 0-06 0'09 IV. 46'18 trace 0'09 0,04 V.46-07 0'03 0'16 0'26 VI. 45'98 0'02 0.18 0.29 ++ Trace Ag. S. 51-70 51.55 51-78 51 '90 51-83 51.95 -t. Trace As. Total. Sp. gr. 0.93 99-28 5.098* 0.78 99-22 5.153" 1.52 99.77 5.078 1.73 99'94 5-113 1'28 99'63 5.068-f 1.19 99-61 5.lOlf. Mn. I and I I pentagonal-dodecahedra1 crystals (2lO} oE pyrites fromMINERALOGICAL CHEMISTRY. ii. 209 Elba ; I11 and IV ditto from Huttenberg Carinthia; V and VI ditto from Seegraben near Leoben Styria. L. J. S. Composition of Jamesonite and Warrenite. WALDEMAR T. SCHALLER (Zeitsch. Kryst. Min. 191 1 48 562-565).-The jamesonite formulct propobed by Spencer (Abstr. 1907 ii 700) is replaced by the simpler formula 4PbS,FeS,3Sb2S proposed by Loczka (Abstr. 1909 ii 153) the calculated percentages corresponding with these formulze being 7(l'b:,Fe:)S,4Sb,S3 ...............21-70 34'23 41.29 2-78 S. Sb. Pb. Fe. 4PbS,FeS,3Sb2S .................. 21 86 35-10 40'32 2 T 2 Warrenite (Eakins 1888) is shown to be a mixture of the brittle '' feather-ore " jamesonite and the flexible " feather-ore " plumosite (PbS,S b,S,). L. J. s. Optical Characters of the Q- and P-Modifications of Quartz and Leucite. FRITZ RINNE and R. KOLB (Jalwb. Afi~. 1910 ii 138-158).-The refractive indices are given for lines of several wave-lengths at various temperatures ranging from - 140' to + 765'. These were determined with prisms enclosed in a specially constructed electric oven or cooling chamber attached to the goniometer. The curves showing the results obtained with quartz exhibit an abrupt break at 570° corresponding with the change from a- t o @-quartz.The values for a-quartz a t 23' are W = 105442 E = 15533; for /3-quartz at 580° w = 1.5328 E = 1.5404 (line DJ. Leucite becomes optically isotropic at 714' and the plotted curves of the refracGive indices deviate in direction near this point but show no sudden break ; the change from Q- to p-leucite therefore takes place over a considerable interval of temperature. L. J. 8. Artificial Production of Nesquehoiiite. GIUSEPPE CESARO (Bull. Acad. Roy. Belg. 1910 844-845. Compare ?bid. 1910 749; Abstr. 1910 ii 49,613).-9 solution of sodium hydrogen carbonate and magnesium chloride was exposed outside to the low temperature at the end of November and the next day there were formed small transparent crystals of lansfordite (MgCO3,5H,O) together with crystalline globules composed of fine needles having the optical charactlers of nesqnehonite ( MgC0,,3H20).The simultaneous forma- tion of these two substances thus depends on the low temperature and not on pressure. Thaumasite from Beaver County Utah. 33. S. BUTLER and WALDEMAR T. SCHALLER (Amer. J. Sci. 1911 [iv] 31 131-134).- 'I'his mineral has hitherto been found only in Sweden and a t Yaterson in New Jersey. It has now been found as a filling in small fissures in metamorphosed dolomitic limestone in the Old Hickory copper and magnetite mine in the Rocky Range of Beaver Co. Utah. It is a pure white mineral with a fibrous structure and silky lustre and its lightness (sp. gr. 1.84) is a noticeable feature. Between crossed nicols the minute slender prisms give btraight extinction ; the L.J. S.ii. 210 ABSTRACTS OF CHEMICAL PAPERS. refractive indices are w > 1.500 E > 1,464. Analysis agrees w usual formula 3Ca0,Si02,S0,,C02 15H,O. SiO,. SO,. CO,. CaO. H,O. (Al,Fe),O,. MgO. Alkalis P,O,. 10'14 12-60 6-98 26'81 42.97 0.20 0-23 trace. th the Total. 99'93 L. J. S. Are Allophane Halloysite and Montmorillonite Simple Minerals or Mixtures of Colloidal Alumina and Silica? STANISLAUS J. THUGUTT (Centr. Min. 191 1 9$-103).-A review of the literature on this question is given (compare Stremme Abstr. 1908 ii 1041). The various clay minerals are capable of taking up organic colouring matters (methylene-blue rhodamine methyl-orange) but t h e varying nature of the colour reactions suggests that these minerals possess individuality and are not merely mixtures of colloidal hydrated alumina and silica.When moistened with cobalt nitrate solution and ignited some of these minerals do not give a blue colour Whilst others become blue only in part. This indicates that the alumina and silica must be chemically combined. The patchy distribution of the colours sometimes obtained indicates that the materials are not a1 ways homogeneous. L. J. S. Deposit of Alunite in the Liparite of Torniella in the Province of Grotweto. UGO PANICHI (Atti R. Accnd. Lincei 1910 Lv] 19 ii 666-664).-Analysis of a typical liparite of the district gave Loss on SiO,. Also,. Fe,O,. FeO. CaO. MgO. K,O. Na,O. heating Total. 72.29 14-40 1.69 0.31 1-34 0-48 4-18 2.67 2.39 99-75 A white deposit which occurs in abundance a t Marmaio and Pimale is not kaolin as has been hitherto believed but consists of alunite containing a little more silica and iron than the alunite of Tolfa. The mineral loses sulphur trioxide when heated and this loss of weight has been assumed to be due to water by previous investigators. Analysis of a sample of the mineral ga.ve SiO,. A1,0,. Fe,O,. SO,. H,O. K,O. Na,O. Total 1'99 39-04 0.53 33'26 13.74 9.77 2.94 100.27 The rock a t the base of the deposit a t Marrnaio is impregnated with the substance which when separated by levigat,ion gave similar analytical figures. It is noted that the rocks of the aeighbourhood of the deposit of alunite have suffered more change into kaolin than other similar rocks of the same district further removed from it. R. V. S.

ISSN:0368-1769    

DOI:10.1039/CA9110005208

出版商:RSC    

年代:1911

数据来源: RSC

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ii. 210 ABSTRACTS OF CHEMICAL PAPERS. Physiological Chemistry The Respiratory Exchange as Affected by Body Position. L. E. EMMES and J. A. RICHE (Amer. J. Physiol. 1911 2'7 406-413). -When the person investigated is sitting quietly in a chair thePHPSTOLOGICAL CHEMISTRY. ii. 211 muscular activity involved causes an increase in metabolism of 8% as compared with that in the same person when lying down. W. D. H. The Respiratory Exchange of Mice Bearing Transplanted Carcinoma. R. A. CHISOLM (J. Path. Bact 1910 15 192-206). -No noticeable difference was found in mice with carcinoma and normal mice so far as respikatory exchange is concerned. W. D. H. Influence of Preceding Diet on the Respiratory Quotient after Active Digestion has Ceased. FRANCIS G. BENEDICT L. lC. EMMES and J.A. RICHE (Amer. J. Physiol. 1911 27 383-405).- The respiratory exchange was examined twelve hours after a meal in the human subject. The most important fact which came out of the investigation is the rise in the respiratory quotient if the preceding meal is rich in carbohydrates. W. D. H. The Regulation of Breathing by the Blood. HANS WINTER- STEIN (P’iiger’s Archiv 191 1 138 167-184).-The method adopted was t h a t of artificial perfusion with Ringer’s solution of new-born mammals. If the tension of carbon dioxide in the perfusing fluid is low apncea is the result ; but the addition of more of the gas excites rhythmical breathing. Lack of oxygen during the npnceic period does not interrupt the apnma but leads without excitation t o death. The addition of acids to the fluid excites respiriitory movements and within certain limits the excitation of the respiratory centres is parallel t o the concentration of hydrogen ions.The Influence of Oxygen Breathing. W. D. H. OTTO WARBURG (Zeitsch. physiod. Chem. 19 11 70 413-432).-The microscopic appearances in red corpuscles and echinoderm eggs produced by oxygen and by agents which inhibit oxidation are described and figured. The part played by tho cell-membrane and the effect on i t of the reagents form the main points investigated. W. D. H. The Effect of Altitude on the Dissociation Curve 01 Blood. JOSEPH BARCROFT ( J . Physiol. 191 1 42 44--63).-The experiments recorded were made on certain members of the recent antituberculosis party which visited Teneriffe. Without going into details of technique and argument the main practical outcome of the investigation is that some acid substance appears in the blood in increasiog quantities as the altitude increases.This change com- pensates the change in alveolar carbon dioxide tension to such an extent that the actual dissociatior curve urrder tho conditions locally established did not alter. W. D. H. Solubility of Gases in Ox-blood and Ox-aerum. ALEXANDER FINDLAY and H. JERhlAIN M. CREIGHTON (Bio-Chem. J. 1911 5 294-305).-The solubility of oxygen carbon monoxide and carbon dioxide in blood and of carbon dioxide in serum is greater than inii. 212 ABSTRACTS OF CHEMICAL PAPERS water ; that of nitrogen and nitrous oxide in blood and serum and of oxygen and carbon monoxide in serum is less than in water.When the solubility is increased the solubility curves fall with increasing pressure ; when i t is lessened the curves rise with increasing pressure. The increased absorption of oxygen carbon monoxide and carbon dioxide is ascribed mainly to chemical combination. I n cases of diminished solubility the rise in the curve is ascribed to adsorption. W. D. H. Trimethylamine as a Normal Constituent of Human Blood Urine and Cerebro-spinal Fluid. CHARLES DORI~E and E. GOLLA (Bio-Chem J. 191 1 5 306-324).-Trimethylamine is a normal constituent of blood and cerebro-Fpinal fluid. The evidence as to urine is not so clear Filippi’s method of estimation was employed with some modifications which considerably shorten it and good results were obtained.Choline is normally absent in all these fluids. I n most of the methods at present in use for the detection of choline trimethylamine would be driven off. The acidity of laboratory aIcohol is another possibly source of error. Trimethylamine gives most of t,he reactions (including the periodide reaction) considered to be characteristic of choline. The present observations are confined to normal fluids. W. D. H. Action of Arsenic on the Red Corpuscles. MOXIZO ONAKA (Zeitsch. physiol. Chern. 191 1 70 433-440).-Arsenious acid mas found next to hydrocyanic acid t o be most powerful in reducing respiratory changes in red corpuscles. Larger doses destroy the cell- membrane. This substance in view of the lipoid constitution of this membrane has very small partition-coefficients between oil and water.W. D. H. The Absorption of Hemolytic and Agglutinating Sub- stances. J. DUNIN-BORKOWSKI (BuL?. Acad. Sci. Cracow 1910 B 608-617).-The paper consists of a brief account of the results of experiments published in detail in Polish in the Roxprawy Wydx. Mat. PYX~Y. Acad. Sci. Cracow (1910 B). I n the agglutination of red-blood corpuscles by silver nitrate mercuric nitrate and ferrous chloride the relation was determined between the concentration of the salt and the amount taken up by the corpuscles. From the value of the constant n in the equation A = el’. where A is the amount absorbed and c the concentration of the salt it was found that agglutination was accompanied by an adsorption OF the salt in the cases of both silver and mercuric nitrates.With ferrous chloride however none of the salt was taken up by the corpuscles. Agglutination may thus take place without adsorption and the theory of Arrhenius that only those substances which are absorbed have any action on the red corpuscles is not in accordance with these results. The coefficients of partition of the bemolytic agent between the red corpuscles and the solution were determined in haemolysis brought abclut by means of acetic acid boric acid and potassium cyanide. ThePHYSIOLOGICAL CHEMISTRY. ii. 213 results were found t o be in contradiction t o the hypothesis of Arrhenius t h a t in hsmolysis the red corpuscles absorb a quantity of the haemolysin sufficient to bring about their complete dieeolution. W. J. Y. The Law R e g u l a t i n g Hamolysis of Erythrocytes in Hypos- motic Saline Solution or Distilled Water.U. N. BRAHMACHARI (Bio-Chem. J. 192 1 5 291-293).-The amount of hsmoglobin dis- solved in a given volume of hyposmotic sodium chloride solution or water is proportional t o the amouct of hiemoglobin in the corpuscles presented for solution in t h e form of a suspension. In the animals examined the ratio between the above two factors is smallest for the frog and greatest for the rabbit and sheep. It is fairly constant in healthy persons but varies widely in disease. The same law regulates the solution of hEmoglobin within red corpuscles which regulates t h e solution of globulin in neutral salt solutions. W. D. H. T h e P l a t e l e t s of Human Blood. M. AYNAUD (Ann. Inst. Pasteur 1911 24 56-’iS).-The blood was collected in such a manner as to avoid contact with the tissues and all the vessels employed were lined with parafin to preserve i t from the action of the glass.Under these conditions blood may be kept for some hours (one t o five) without coagulating. The blood was allowed to sediment and the colourless plasma containing the platelets drawn ofl-‘. I n fresh plasma the platelets occur as clear round plain discs having a rapid oscillatory movement which causes them t o appear as spindle-shaped bodies. On keeping they alter in shape become granular in structure and finally disappear. Anti-coagulants vary in their action on the platelets ; thus sodium fluoride produces granular changes i n them whilst citratee oxalates and metaphosphates preserve the platelets and retard their agglutination. A number of substances such as quinine and cocaine produce changes in the form of the platelets when added to the plasma in the presence of oxalates and citrates.Human blood- platelets show very little tendency to agglutinate on the addition of peptone gelatin metallic colloids or other substances which readily bring about agglutination in the platelets of dogs’ blood. Reactions with staining agents show them to have a complex structure and to contain at least two different substances whilst no differences could be detected by these means between the platelets of human blood and those of other mammals. No numerical relation could be established between the platelets and the red corpuscles and leucocytes xnd they are considered as quite independent of the other elements of blood.W. J. Y. E f f e c t s of Copious Water Drinking with Meals on I n t e s t i n a l Putrefaction CV. 31. HATTREM and PHILIP H. HAWK (Proc. Arne?*. plujsiol. SOC. 1910 xxv ; Arner. J. Physiol. 27).-The drinking of copious (1000 c.c.) or moderate doses (500 c.c.) of water with nieals reduces the output of urinary indican but incremes that of ethereal sul pha tes . W. D. H. YOL. c. ii. 15ii. 214 ABSTRACTS OF CHEMICAL PAPERS. Effects of Copious Water Drinking with Meals on the Pancreatic Function. PHILTP B. HAWK (Proc. Amer. physiol. Xoc. 1910 xxvi; Amer. J. Physiol. 27).-The effect is that the pancreatic activity is increased as judged by the amount of amylase in the faeces. M7. D.H. Effects of Copious Water Drinking with Meals on Gastric Secretion. F. WILLS and PHILIP B. HAWK (Proc. Amer. physiol. ~Yoc. 1910 xxxii; Amer. J. Physiol. 27).-The urinary ammonia is increased and this is considered t o be an index of a rise in the secretion of gastric juice. The acid concentration of the stomach contents is thus maintained in spite of the large amount of water taken. W. D. H. Comparative Study of Four Digestive Diastases from Certain Species of Coleoptera. L. BOUNOURE (Compt. rend. 191 1 1 5 2 2 2 8 4 3 I).-The digestive enzymes of Coleoptera include a lipase a protcolytic diastase an amylase and an invertase. Experiments have been conducted on a number of different species with the object of determining the relative activity of the different ferments in each and their variation with the natural diet of the insects.The results are tabulated. It is found that the more carnivorous the species the greater the proteolytic and the smaller the lipolytic activity. Amylolytic and sucroclastic activity is at a maximum with those insects which favour a mixed diet (Nydrophiluspiceus) and a t a minimum with the carnivorous species such as Dysticus marginalis. Proteolytic enzymes are practically absent from the entirely vegetarian species (Polyphylla The Metabolism of Dogs with Functionally-resected Small Intestine. PRANK P. UNDERHILL (Amer. J. Physiol. 191 1 27 366-382).-When 39% of the small intestine is short-circuited foods are utilised for many months in a normal way. When 66% is similarly resected fat utilisation is decreased and there is a small loss of body.nitrogen and of body weight which is specially noticeable some time after the operation. When 757; is resected food utilisation is seriously impaired and this is particularly the case for fat. Indican elimina. tion is not altered as in the normal dog by replacing meat in the diet by gelatin. Ability to utilise carbohydrate is increased; this may be of importance in cases of intestinal resection in man. The Influence of Meat-extractives on the Absorption of Nutritive Material. The Physiological Value of Meat Extract. WILHELM VOLTZ and ATJQUST BAUDREXEL (PJEGgerr’a Archit 1911 138 875-291).-The addition of meat extract to a mixed diet has no effect on the absorption of nitrogenous or non- nitrogenous foods. The nitrogen of the extractives can under very favourable conditions lead t o a retention of nitrogen or a lessening of loss of nitroqen which accounts for a t least 11% of the extractive nitrogen.The g hjsiological utilisation of the extr<ictivrs averages ftdlo). w. 0. w. W. D. H. nbout tno-thirds of their potential energy. w. u. H.PEYSIOLOCfICAL CEEMISTRY. ii. 215 The Utilitation of Yeast in the Human Body. M7~r4n~~ir T’CiLTZ and AUGUST SAUDREXEL (Biochern. Zeituch. 1910 30 457-472) -Dried yeast from which the bitter principles had been extracted can be tolerated in relatively large qua.ntities by man (100 gramw within one to two hours). The food-value was determined by €ceding experiments on man in the usual way and i t was found t h a t 86% of the protein was resorbed and 88% of the caloric value mas utilihed.The physiological food-value calculated from uitrogenous equilibrinm experiments was 74.8% of its total energy content,. 8. B. S. Intravenous Injection of Pineal Extracts. J. A. E. EYSTER and H. E. JORDAN (Proc. Amer. physiol. Yoc. 19 10 xxiii-xxiv ; if m r . J. Physiol. 27).-Aqiieous extracts of the sheep’s pineal cmse H fall of arterial blood pressure i n the dog which is stated t o be greater than that obtained from other parts of the brain. This is associated with dilatation of the splanchnic vessels. W. D. H. The Dichromate Hmmatoxylin Method of Staining Tissues. J. LORRAIN SMITH and W. MAIR (J. Path. Bact. 1910 15 179-181. Compare this vol. i 44).-The substance in the nervous system which is stained in t h e Weigert method is not only cholesterol but also the cerebroside separated by the authors.The relative insolubility of this substance in f a t solvents accounts for the staining with bErna- toxylin observed i n specimens treated with alcohol and ether. It is only present in traces in the brain of the new-born infant; hence the greater difficulty in staining such tissue. The cerebroside has a fluid crjstalline phase extending over a wide range of temperature and on expo>ure t o water it gives ‘‘ myelin forms.” W. D. H. The Alleged Presence of an Alcoholic Enzyme in Animal Tissues and Organs. ARTHUR HARDEN and HUGH MACLEAN (J. YhpsioL. 191 1 42 64-92).-The experiments recorded establish a strong presumption that alcoholic ferrnen tation cannot be produced by animal tissues or juices or powders prepared from them.With the onset of putrefaction evolution of gases (carbon dioxide and hydrogen) occurs but not otherwise. W. D. H A Method of Removing Glycogen from the Human Subject. GRAHAN LUSK (Amer. J. Phpsiol. 191 1 27 427-437},- Exposure t o cold (baths in ice water) lowers the respiratory quotient in various men to 0.75 to 0.67 ; this correGponds with Benedict’s fig111 e after a prolonged fast and isbelieved to indicate the disappearance of glycogen. W. D. H. The Position Occupied by the Production of Heat in the Chain of Processes Constituting a Muscular Contraction. AHCHIBALD V. HILL (J. PIuyjsioZ. 191 1 42 1-43).-Muscle is not a heat engine for the heat may not appear until the tension has returned t o normal.On excitation some substance (or substances) is liberated which affects the colloidal tissues of the miiscle and sets up a tension proportional t o its concentration. The substance is t h m 15-2ii. 216 ABSTRACTS OF CHEMICAL PAPERS. destroyed or replaced in its original position (the presence of oxygen being favourable for both) and the heat then evolved is proportional t o the amount of the substance (for instance lactic acid) in question. W. D. H . Purine Metabolism. V. The Behaviour of the Purine Bases in Muscle during Work. V~TTORIO SCAFFIDI (Biochem. Zeitd 1911 30,473-480).-Thepurine-base contentin the striated muscles of the frog and toad is smaller than in mammals and fish and diminishes considerably after work (up to 17%) ; this diminution is derived chiefly from the combined bases the free bases remaining unchanged in quantity or even increasing.No uric acid was found in the m u d e s The Distribution of the Nitrogen of the Extractive Substances from Mammalian Muscle. OTTO VON FURTH and CARL SCHWARZ (Uiochern. Zeitsch. 191 1 30 413-432).-The nitrogen was estimated in the following fractions of the extractives total bases (precipitated by phosphotungstic acid) colloidal substances of albumose character (precipitated by zinc sulphate by Robmer’s method) creatine and creatiuine (determined by Folin’s process) ammonia (determined by distillation with magnesium oxide) purine substances (determined by Kriiper iLnd Schmidt’s method) carnosine (determined by Gulewitsch and Krimberp’s method) polypeptides and amino-acids (determined by the Soreusen-Henriques method) and urea (determined by Braunstein’s method).The materials employed were the muscles of the estremitics and of the horse’s heart. The chief constituents were found to be creatine and carnosine. No material difference could be detected in the extractives of resting and fatigued muscle in experiments carried out on the muscular tissue of dogs. The authors tabulate several series of results. s. B. s. Occurrence of Betaine in Gephalopods. MARTIN HENZE (Zuitsch. physiol. Chem. 1911 70 253-255. Compare Abstr. 1905 ii 270). -Octopus muscle in addition t o the taurine previously recorded contains betaine and two substances yielding sparingly soluble picrates. the one m. p. 215-220° (decornp. 2-25’) aud the other decomposiug still higher and giving a n aurichloride III.p. 137-.148” crystallising in slender needles (Au = 31.9%). Isolation of an Hepatic Antithrombin. Description of Some of its Properties. MAUR~CE DOYON ALBERT MOREL and A. POLICARD (Corrpt. rend. 191 1 152 147-148).-The isolated liver of a dog is perfused with blood from the carotid vein of another dog which has previously received a n injection of peptone. Antithrombin is present in the plasma after centrifugation It is not destroyed or precipitated by heating the plasma at 100’. If the medium is acid however the antithrombin is precipitated at loo’ but can be redissolved i n an alkaline solution. Demonstration of the Exclusively Hepatic Origin of Antithrombin. Extraction of this Substance by a Solvent for Nuclear Substances.MAURICE DOYON ALBERT MOREL and 8. POLICARD (Compt. read 191 1,152 282-283).-The antithrombin of the frog and toad either in rest or after work. s. B. s. E. F. A. MT. 0. w.PHYSIOLOGICAL CHEMISTRY. ii. 217 described in a previous communication (preceding abstract) can be obtained from the liver. by perfusion with a slightly alkaline physiological salt solution. The active substance contniris nitrogen and phosphorus and may be precipitated from the solution by the addition of acetic acid. It gives a sIight biuret reaction. w. 0. w. 4-/3-Aminoethylglyoxaline a Depressor Constituent of In- testinal Mucosa. GEORGE BARGER and HENRY H. DALE (J. I’hysiol. 19 11 41 499-503).-PopieIski’s vaso-dilatin to which he attributec the activities of commercial peptone and various tissue extracts con- tain.; 4-~-aminoethylglyoxaline.It was in the present research identified chemically and physiologically in intestinal extracts and is no doubt the substance which in Bayliss and Starling’s preparations of secretiu lowers blood pressure. The effect of this base in stimulating the p n c r e a s t o secrete is very feeble. It also doe.; not affect the co- agulability of the blood ; this action of vaso-dilatin must be due to borne other substance in it. W. D. H. Source of Immune Substances in Lymph. The Part Played by the Spleen in the Formation of Immune Substances. AI~NO B. LUCKHARDT and FRANK C. BECHT (Proc. Amer. physiol. Suc. 11) 10 xi-xii xvi-xvii ; Amer. J. Physiol. 2’7).-Haemolyeiu~ agglutinins and opsonins pas3 at about the same rate from the blood into the lymphs and make their appearance in the thoracic earlier than in the cervicallymph.They a r e also more concentrated in the former situation. They hardly pass at a l l in the cerebro-spinal fluid or aqueous humor. The formation of such siibstances is slow and in lessened quantity when the spleen is removed. The experiments were made on dogs. W. D. H. Experimental Hyperthyroidism. ANTON J. CARLSON J. F. ROOKS and J. F. McKm (Proc. Anzer. physiol. Soc. 1910 xiii-xiv ; Artier. J. physiol. 27).-Different animals .exhibit great variations in their resistance t o thyroid feeding but t h e most constant symptoms (emaciatiou and diarrbaea) may be absent even in fatal cases. The riervous and cardiac phases of the symptom-complex in birds and lower marnmals differ from those in man.Feeding on other organs shows that the symptoms are due t o thyroid feeding. Effects of Extracts of Different Parts of the Pituitary Body. J. I;. MILLER D. D. LEWIS and S. A. MATTHEWS (Proc. Amer. physiol. Soc. 1910 xvii-xviii ; Amer. J. Physiol. 27).-The experi- ments show t h a t the pars intermedia is the seat of origin of the pressor substance. The contents of a cyst of this region produced a distinct pressor effect. The substance which slows the heart is confined t o the pars nervosa. Extracts of t h e stalk of the ox hypophysis never gave a pressor effect. The Neutralisation of Spermotoxins and Alkaloids by Extract of the Teetis and Epididymie. S. METALNIKOFF (PfZiigey’s Archiv 1911 138 14-18).-1n animals in whose blood W.D. H. W. D. H.ii. 218 ABSTRACTS OF CHEMICAL PAPERS. strong spermotoxins are aontained the spermatozoa in the epididymis a r e normal for the testis and epididymis contain a suhstance which neutralises spermotovins or renders them harmless. This material also neritralises certain alkaloids such as nicotine which act harmf idly on spermatozoa. Curare by itself has but little action on spermatozoa but mixed with epididyrnis extract i t kills them. W. D. H. The Amount of Alcohol Excreted by the Animal Organism Under Various Conditions. WILHELM VULTZ and AuausT BAU- DREXEL (PfEiiger’s Archiv 191 1 138 85- 133).-Analytical dctails are given of the quantity of alcohol excreted in the urine expired air etc. when it is given under varying conditions of quautity volume of diIuent habituation and so forth.W. D. H. Allantoin-Purine Excretion of the Monkey. ANDREW HUNTER and MAURICE H. GIVENS (Proc. Arner. physiol. Soc. 1910 xv-xvi; Amer. J. I’hysiol. 27).-The analyses show the great relative import- ance of allantoin as an end-product in purine metabolism i n monkeys. From 500 C.C. of urine from two monkeys 172 mg. of allantoin no uric acid and 4.5 mg. of purine bases were obtained. W. D. €1. The Origin of Uric Acid in Man. FRANZ SMET~NKA (?’iiyer’s Awlhiw 19 1 I 138 217-274).-Everg protein meal including those whit h are purine-free produces a iise of uric acid excretion which three hours after the meal may rise to an 89% increase of the previous value. If the meal is taken late in the day the rise may extend through the night to the following morning.The increase is attri- huted t o metabolic changes accompimying the activity of the cells of the digestive glands. If polysaccharides are given the smaller WOI k of the digestive glands is accompnnied with a smrtller rise i n uric acid excretion. After taking honey there is a large rise which is exp1.tint.d by the intense activity of the liver cells in forming glycogen. The total excretion of nitrogen is but little altered by carbohydrate food. W. D. H. Action of Urinary Antiseptics. ANSON JORDAN (Bio-Chem. J. 19 1 1 5 274-290).-Using a defined arbitrary standard the average acidity of normal urine is about 4. With large doses of dihydrogen s dium phosphate this can be raised t o 9 and the urine can easily be made alkaline with potassium citmte.Putrefaction will readily occur and Stuphylococcus and Bacillus coli grow easily in urines of all degrees of acidity and alkalinity which cau be produced in the body ; acidity however exciting a restraining influence. Urotropine acts as a urinary antiseptic by the formation of formaldehyde; in alkaline urine i t s action is nil because no formaldehyde is then formed. In urine of a little o t e r normal acidity the antiseptic power is sufficient to prevent the growth of all micro-organisms. Sandal wood oil is quite feeble against B. coli and putrefactive organisms ; it has a specific antiseptic action against Stuphylococcus. The power of salicylic acid is not great but against B. coli andPHYSIOLOGICAL CHEMISTRY. ii. 219 putrefactive organisms it is more efficient than sandal wood oil.Neither agent can however be compared with urotropine for efficiency. W. D. H. Chemical Investigation of Atheromatous Aortm A. SELTG. Composition of Deposits in Calcified Aorta 15. PH. F. AMESBDER. Remarks on the Foregoing Investigations. RICHARD VON ZEYNEK (Zeitsch. physiol. Chem. 1911 70 451-457 458-463 464-465).- I. I n atheroma the amount of elastin is lessened the fat (light petroleum extract) is increased and the calcium in the ash is increased although the total ash may not be. 11. The second paper gives analytical details. 111. The third paper is explanatory and critical. Experimental GI gcosuria. VI. The Distribution of Glycogen over the Liver under Various Conditions. Post-mortem Glycogenolysis.JOHN J. R. MACLEOD and R. G. PEAHCE (Amer. J. Physiol 1911 27 341-366. Compare Abstr. 1910 ii 144).- The amount of glycogen in different lobes of the liver varies by about 5%. This is due to errors of analysis by Pfliiger’s method and to an unequal amount of blood and connective tissue in different parts of the organ. Glycogenolysis is accelerated after death and this varies in different lobes; it sets in within twenty minutes after death and proceeds at a uniform speed for severnl hours. The rate is lessened by absence of blood and by cutting up the liver. Nervous influences play no part in it. W. D. H. W. D. H. Uric Acid Excretion in Gout and Rheumatoid Arthritis. WILLIAM J. MALLORY (J. Path. Bact. 1910 15 207-246).-1n gout there is a slight fluctuation in the endogenous excretion a low endogenous average and a small percentage of exogenous purine nitrogen excretion excreted as uric acid.I n cases associated with lead poisoning these characteristics are more marked. Many cases of gout however are atypical. I n some cases of rheumatoid arthritis there is a somewhat similar disturbance of purine metabolism. Mr. D. H. The Wassermann Reaction in Rabbits Infected with the Trypanosomes of Nagaoa and the Effect of Treatment vit4 Arsenophenylglycine (Ehrlich). CARL H. BROWNING and IVY MCKENZ~E (J. Pccth. Bact. 1910 15 182-191).-A full account of experiments previously published (this vol. ii 59). W. D. H The Influence of Quinine and Quinine Derivatives on Experimental Trypanosome Infection. JULIUS MORGENROTH and 14. HALBERSTAEDTER (Sitxunysber K.Alcacl. Wiss. Berlin 191 1 30-37). -In continuation of previous investigations (Abstr. 1910 ii 881) the authors now show that hydroquinine which is not more toxic than quinine has a greater trypanocidal action. The method of adding the base to cakes of food-stuff was employed as in former work arid a Hagana trypanosomp was the soyrce of infection S. B. S.ii. 220 ARSTRACTS OF CHEMICAL PAPERS. Ingestion of Mineral Acids by the Dog. HENRI LAH& and L. VIOLLE (Compt. rend. 1911 152 279-281).-When dogs i n a state of nitrogenous equilibrium are dosed with hydrochloric acid in quantity insufficient t o affect their general health an increased urinary excretion of volatile bases takes place proportional t o the amount of acid administered. The ratio between the acid and the bases is practically molecular.The same thing is observed when the diet is insufficiently nitrogenous. The experiments are held to support the view t h a t the organism protects itself against acid intoxication by the increased formation of ammonia. w. 0. w. Migration of Solutions in Bodies Deprived of the Cardiac Circulation. SAMUEL J. MELTZER (I’roc. Amer. plr ysiol. Soc. 1910 xxix-xxx ; Amer. J. Physiol. 27).-The injection of adrenaline and strychnine into tbe dorsal lymph sac of the frog produres in time effects on the pupil and spinal cord respectively even although the circulation has been stopped by removal of the heart. The migration of these substances can therefore take place against gravity through the lymph spaces. W.D. H; A Second Active Ergot Base. R. ENGELAND and FRIEDRICH KUTSCFIER (Chem Zentr. 1910 ii 1394-1395 ; from Zentr. Physiol. 1910 24 479 -480).-The authors have previously obtained an active base from ergot containing a glyoxaline radicle (Abstr. 1910 ii 881). Another base is now described which bas active physiological properties and is identified with the guanido-butylaminoagmatine of Kossel both from the properties of the carbonate and sulphate and from the analyses of the aurichloride and picrate. It is precipitated by silver nitrate and baryta after removal of the bases precipitated by ammoiiacal silver nitrate. The silver compounds are then converted into the picrolonates and these into the carbonate and sulphate. Contractions were produced in a cat’s uterus suspended in 70% Ringer’s solution by 0*001 gram of the dichloride in alkaline solution and the contraction was only slightly increased by tho addition of an equal quantity of 4-~-aminoethylglyoxaline.Injections of the dichloride into rabbits temporarily increased. the blood pressure and respiration. [Physiological Action of] Pilocarpine. I. N. WATERNAN (Zeitsch. physiol. Chem. 19 11,70 441-450).-Pilocarpine in addition t o its known actions on sympathetic nerves causes in rabbits an increace in urine the appearance of sugar in that secretion and a rise of susceptibility to adrenaline. W.. J. Y. W. D. I€. [Physiological] Action of Some isoQuinoline Derivatives. PATRICK P. LAIDLAW (Bio-Chem. 2 1911 5 243-273).-A review of the action of a number of iaoquinoline bases is made and their action compared with their chemical constitution.A law of relationship for one series is put forward. 6 7-Dimethoxy-2-methyl-3 4-dihydro- isoquinolinium chloride (Pyman Trans. 1909 95 1271) has a n action very similar to that of hydrastinine. The generally acceptedVEGETABLE PHYSIOLOQY AND AGRICULTURE. ii. 521 view of the action of hydrastinine on the functions of the body is stated to be erroneous in several points. Antagonistic Action of Salts. JACQUES LOER ( I’YOC. Anier. physiol. Soc. 1910 xxxii-xxxiii ; Amer. J. Physiol. 27).-Pure potassium chloride of the same concentration as in sea-wnter kills Fwdulus in two days or less while i n sodium chloride of the Fame Concentration the fish live indefinitely. The toxicity of the potassium salts can be neutralised by sodium chloride added in a certain constant ratio. The conclusiou is drawn that a partition of some c3lloiditl anion between the two metals occurs in the gills. There is an upper limit for the concentratioti of potassium chloride beyond which its toxic action can be no longer inhibited by sodium chloride. W. D. H. W. D. H. A Case of Poisoning by Sewer-gag. WILHELM GOHLICH (Chem. Zeit. 1911 35 129-130).-The investigation arose out of a case of sudden illness ending in death i n a workman engaged in cleaning a sewer. Samples of the sewer-water were found t o contain arsenic and free sulphuric acid in such quantities that the addition of zinc or iron produced an evolution of arsenic trihydride. which could readily be detected with silver nitrate paper. Trie illress was attributed t o poisoning by arsenic trihydride formed by the action of the sewer- water on the iron tools and zinc bucket which the man was using at the time. Post-mortem examination revdaled the presence of arsenic in the organs and blood. The sulphuric acid and arsenic were eventually traced t o the drainage from a n artificial manure manufactory. W. J. Y.

ISSN:0368-1769    

DOI:10.1039/CA9110005210

出版商:RSC    

年代:1911

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOQY AND AGRICULTURE. ii. 521 Chemistry of Vegetable Physiology and Agriculture. An Automatic Pipette. CARL PERYIN (Centr. Brikt. Par. 1911 i 57 575-576).-The pipette is designe 1 for bacteriological and serological work and consists of an ordinary graduated pipette connected by a side opening with an indin-rubber ball which is situated on the stem just below the top. The ball terves to till the pipette the opening a t the top of the stem being closed with the finger. The liquid is run out by removing the finger from the top of the pipette in the usual manner. Action of the Bulgarian Ferment on Monobasic Acids Derived from Reducing Sugars. GABRIEL BERTRAND and R. VEILLON (Compt. rend. 191 1 152 330-332).-The Bulgarian ferment bas no action on solutions of calcium gluconate galactonate mannonate maltobionate or lactobionate.The first four salts have no influence on the lactic fermentation of dextrose or lactose. I n the case of solutions containing lactose and calcium lactobionate however W. J. Y.ii. 222 ABSTRACTS OF CHEMICAL PAPERS. the ferment produces more lactic acid than corresponds with the weight OC sugar present. This may be explained by supposing that a n endolactase is only liberated in media containing lactose; under these conditions the lactobionic acid becomes hydrolysed the resulting galactose then forming lactic acid. w. 0. w. Fungicidal Properties of Liver of Sulphur. FREDERICK W. FOREMAN ( J . Agric. Sci. 1911 3,400-416).-Liver of sulphur contains various oxidation products and usually frce sulphur in addition to potassium or sodium hydrosulphide sulphide and polysulphides. Experiments with spores of Botrytis cinerea showed that the oxida- tion products have little or no fungicidal properties in weak solutions and that saturated hydrogen sulphide solution and free sulphur have no effect.The chief agent in the mixture is the sodium hydroxide. Potassium hydroxide is less poisonous. Methods for the analysis of liver of sulphur are described. N. H. J. M. Influence of Manganese on the Development of Aspergillus niger. GABRIEL BERTRAND and MAURICE JAVILLIER (Compt. rend. 1911 152 235-228. Compare Rbstr. 1908 ii 134).-AspergiZlus dyer was cultivated in a manganese-free nutrient solution to which definite quantities of pure manganese sulphate were added.Special precautions were taken to avoid the presence of metals such as zinc and iron which favour the growth of the organism. It was found that manganese had a favourable influence on the development of the mould the yield increasing with the proportion of metal added from dilutions of 1/1,000,000 to 1/100. At higher concentrations manganese exerted a prejudicial action. w. 0. w. Calcium Requirements of Plants Different Relations of the Calcium and Magnesium in Nutritive Solutions. IWAN KONOWALOFF (Landw. Vemuchs-#tat. 191 1 74 343-360).-Results of water-culture and sand-culture experiments with varying amounts of calcium showed that the yields increase up to a certain point with the increase in the amount of calcium. I n most cases the highest yield was obtained with solutions containing 0.2% CaO.With varying relations of calcium (as nitrate) and magnesium the highest yield was obtained with the ratio CaO MgO = 1 1. When however the calcium was in the form of sulphate or carbonate equally good or better results were obtained with the rcttio 6.7 1. Comparing different calcium compounds (with a ratio CaO MgO = 6.7 l) it was found that tricalcium phosphate gave the best results. Calcium carbonate (marble) had no injurious effect when the ratio was 53.6 1. N. H. J. M. Basic Components of Bamboo Shoots. GINZABURO TOTANI (Zeitsch. physiol. Chem. 191 1 70 388-390).-Fresh bamboo shoots are shown to contain betaine and choline in addition to tyrosine asparagine guanine xanthine hypoxanthine and adenine. E. F. A,VEGETABLE PHYSIOLOGY AND AGRICULTURE. ii.223 Waxes of the Conifera. J. BOUGAULT (J. Pharm. Chim. 191 1 [vii] 3 101-103).-1n addition t o juniperic and sabinic acids already isolated from the wax of Juniperus sabina a small quantity of thapsic acid which has been shown to be an oxidation product of juniperic acid has been obtained (compare Abstr. 1909 i 82 ; 1910 i 297). Sabiuic acid has also now been obtained from the wax of T/m& occidentcdis. This wax may also contain a trace of thapsic acid. T. A. H. The Chromogenic Subgtances of White Grapes. SERAFINO DEZANI (Chern. Zentr. 1910 ii 1141-1142 ; from Stax. sperim. ayrar. itacl. 1910 43 428-438).-Two chromogenic substances mere found in white grapep of which one only is precipitated by lead acetate. By the action of hydrochloric acid colouring matters are obtained which are analogous t o the ‘( cenocyaoine.” The conversion OF these substances into colouring matters is due not to oxidation but probably to hydrolytic scission with simultaneous formation of a reducing substance. I n the residue from the chromogenic substances there are other substances which give a red coloration with alkalis.N. c. The Tonic Effect of Certain Organic Substances in Solution and as Vapours. HERMANN STADLER (Arch. Hygiene 1911 ’73 195-2 17).-The toxicity of the aliphatic alcohols increases as the molecular weight increases; on the other hand the toxicity of the aliphatic aldebydes falls off with increasing molecular weight. Replacement of oxygen by sulphur in aliphatic compounds leads to a marked incroasu in toxicity.The effect deperids only on the amount of the substance present and not at all on the form in which i t occurs ; the compounds examined were equally toxic whether they were used as solutions or as bvapours provided only the partial pressure was the same; indeed knowing the toxicity of a substance in the liquid form its toxicity in vapour form is readily calculated from Henry’s law. But this rule breaks down when the substance reacts with thg nutrient medium on which the organisms are growing; in t h i s case vapours act more powerfully than solutions of the same partial pressure. A table is given showing the concentrations at which a number of alcohols aldehydes and other substances totally inhibit the growth of Slaphylococcus pyogenes aureus Bact.pyocyaneum and B. coli commune. On the latter organism experiments were made both with solutions and vapours. E. J. R. Action on Green Plants of Some Substances Extracted from Coal-tar and Employed in Agriculture. MARCEL MIHANDE (Compt. rend. 1911 152 204-206. Compare Abstr. 1909 ii 824; 1910 ii 884 ; this vol. ii 64)-Insecticides prepared from coal-tar are liabb to bring about anaesthesia or blackening of the leaves of plants. Direct contact with the liquids is more injurious to the plantsii. 284 ABSTRACTS OF CHEMICAL PAPERS. than exposure to the vapours. to be due principally to the phenols present in such preparations. The action on the chlorophyll appears w. 0. w. Influence of Different Amounts of Water Different Manures and Consolidation of the S o i l on the Root Development of Wheat and Barley in the First Period of Growth.R. POLLE (J. Lundw. 1910 58 297-344; from Inaug. Diss. Gottingen).-Vegetation experiments are described in which wheat and barley were grown in boxes containing loam and sandy soil respectively both without and with manure and with low and higher percentages of water. I n sonie the soil was consolidated by pressure whilst in others it WAS employed in a looser condition. F u l l particulars as to length and weight of the main roots and side roots produced under the different conditions are given as well as the amounts of growth above ground. N. H. J. hl. Amounts of Ammonia and Nitric Acid in Rain-water in Tonquin. M. AUPRAY (Bull. Econom. Hanoi-Huiphong 1909 12 595-616. Compare Leatlier Abstr.1906 ii 487 ; Brunnich 1910 ii 647).-The amounts of nitrogen as ammonia and as nitrates were estimated in 123 samples of rain-water collected in the Botanic Gardens Hanoi from April 1902 to March 1905 and in 313 samples collectrd from June 1906 to September 1909 iu an open space in the middle of the same town. Assuming the composition of the samples to approximately represent the whole rainfall the average amounts of nitrogen per million and the total amounts per acre for the six years would be as follows N per million N per acre (Ibs.) Rainfall as as as as 7- -\ inches. ammonia. nitrates. ammonia. nitrates Total. 1902-3 ...... 90.55 0.71 0 '66 14.74 13'47 28-21 1903-4 ...... 59'68 0.99 0'80 13.34 10'89 24-23 1904-5 ...... 84'72 0.64 0.43 12-25 8 '26 20.51 1906-7 ...... 49.92 0 '54 0.36 6-13 4 '06 10.19 1907-8 ...... 57-91 0'33 0.87 4 -59 3.54 7-93 1908-9 ...... 77-72 0.23 0'15 4 -04 2'65 6-69 Of the total rainfall about 82% falls from May to October and this contains about 84% of the total nitrogen. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9110005221

出版商:RSC    

年代:1911

数据来源: RSC