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Proceedings of the Chemical Society, Vol. 12, No. 168 |
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Proceedings of the Chemical Society, London,
Volume 12,
Issue 168,
1896,
Page 137-162
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摘要:
PROCEEDINGS OF TlfE CHEMICAL SOCIETY. EDITED BY THE SECRETARIES. No.168. Session 1895-96. Julie 18th, 1896. Mr. A. G. Vernon Harcourt, President, in the Chair. Mesers. J. K. Burbridge and James Proude were formally admitted I?ellows of the Society. A certificate was read foy the first time in favour of hlr. Hugh Manners, Academy House, Airdrie, N.B. Dr. Tate was reinstated as a Fellow of the Society. The following were duly elected Fellows of the Society : Messrs. Xobert Addie, John Csley, Charles Matthew Crossmann, B.Sc., Llewellyn John navies, Leon Felix Goldstand, I,L.D., Ralph Hamil- ton Hanger, Frederick William Harris, Ernest George Hill, B.A., Joshua Arthur Hughes, John Burnett Knight, Herbert E. Law, William Arthur Finch Lethbridge, B.A., Cecil Rudolf Lidgey, Percy Sykes Marshall, William McConnell, jun., Loxley Meggitt, Asutosh Rai Bahadur Mitra, James Stanley Muir., B.Sc., James Hadden Overton, Hastings Montague Page, drthur Pape, Sigmund Georgje- witsch Rosenblum, Samuel Thomas Skelton, George Egerton Scott Smith, Douglas Stuart Spens Stuart, B.Sc., James Whitehead.Of the following papers, those marked * were read. ‘75. The action of bromine on pinene with reference to the question ‘I of its constitution.” By W. A. Tilden, D.Sc.,F.R.S. Experiments made by the author in 1888 led him to believe that pinene combines not only with two atoms, but with four atoms of bromine. This conclusion was confirmed by the independent experi- 138 nients of Stschukareff in 1893.Wallach, however, maintains that pinene can unite with only two atoms of bromine, and the various formula proposed by different chemists for this hydrocarbon are based on that assumption. The authoi*has, therefore, undertaken a fresh inquiry, as the result of which he is confirmed in his original opinion that pinene combines directly with four atoms of bromine, the amount of bromine entering the molecule by substitution for-hydrogen being comparatively insignificant. He therefore proposes for pinene a formula, QHz*fl*QHCH, , derived from a ring of sixC3H,CH* C-CH, carbon atoms with a double para-linkage, the disruption of which at once gives a cycloid closely related to benzene, and accounts for the ready formation of cymene, &c."76. ''Preliminary note on some products from pinene tetrabromide." By W. A. Tilden, D.Sc., F.R.S,, and A. Nicholls. '..'lie liquid tetrabromide formed by the addition of pinene to four atonis cf bromine, as described in the preceding paper, is a very unstabIe compound, for it begins to evolve hydrogen bromide soon after its formation if kept at or near the temperature of the air. In order to investigate the products of this decomposition, a considerable quantity oE the bromide was prepared. From the resulting colour- less solution the carbon tetrachloride was distilled by a water bath, and the residual liquid subjected to distillation alone with the object of expelling as much as possible of the hydrogen bromide, which escaped for the most part as gas.A colourless distillate was Obtained, ltaving a small quantity of a brown oily residue, which boils at a high temperature with further decomposition. On redistilling the perfectly colourless distillate under pressure reduced to about 10 mm., it came over between 125' and 175O, leaving R small additional quan- tity of the dark residue, from which, after standing a few hours or days, a crystalline substance was deposited, which was identified by analysis and melting point RS Wallach's dibromide, C,,H,,Br,, m. p. 169-170' (Annalen, 264, 7). In order to decompose the last portions of bromide in the distilled liquid, it was heated with excess of aniline to the boiling point of the latter, and subsequently steam distilled, The distillate, acidified with dilute sulphuric acid in order to fix the small quantity of aniline present, and again steamed, gnvo r2 colourless hydrocarbon lighter than water. By fractionation, this was found to yield a portion boil-ing at 155-1557', which contains solid camphene crystallisable by cooling.The larger part comes over between 158' and 162O, and deposih no solid at -15". Smaller fractions up to 1%"were obtained, and these remain to be examined. Thc chief fraction, 139 158-162", reduced aqueous solution of permanganate at 16-18", and fixed a quantity of bromine corresponding approximately to Br2 for C,,,. As with the quantity of hydrocarbon at our command it seemed improbable that a fraction could be separated in a pure state, it was thought best to submit the liquid to oxidation.Two portions, the product of one preparation of bromide, were taken, namely, 30 grams, boiling between 155" and 160°, from which the cani-phene had been frozen out as completely as possible, and 30 grams boiling between 160" and 170". Oxidation with aqueous permanga- nate at a temperature which never rose above 26' gave the same chief product, and the two products were therefore supposed to contain a common ingredient. The unchanged hydrocarbon and precipitated oxide of manganese having been removed, the clear solution ivas mined with a quantity of sulphuric acid calculated to neutralise the alkali contained in it. A white cloud made its appearance, which way removed on shaking with ether.The ethereal extract, submitted to distillation, left a watery residue, in which floated a nearly coIourless oil of about,the same density as water. The 30 grams of hydrocarbon at 155-160' gave 7.5 grams of this fluid, and the 30 grams at 160-170" gave 6 grams. This substance is a well-marked acid, having a sour and astringent taste ; it decomposes carbonates, and, when mixed with solutions of soda develops much heat. Distilled under a pressure of 20 mm., it partly passed over at 200-210", but evidently nndey- goes decomposition. It yields a crystalline, slightly soluble sodium salt. A solution of this salt gives with copper sulphate a greenish precipitate, which seems to be a basic salt, and with silver nitrate a white precipitate, which becomes brownish on exposure to light, but does not blacken on boiling.Analyscs were made of the acid (left in a vacuum till it ceased to lose weight) and of the crystallised sorlium salt, with results corresponding to the formuls C,,H,,O, and CIOH1SNa03. This compound does not appear to be a ketonic acid, and the remarkable properties of its sodium salt lead to the suspicion, not- withstanding that it has not yet been crystallised, that it may be identical with Baeyer's nopic acid, a, bye-product recently obtained in the oxidation of crude pinene by permsnganate (Bey., 29, 25,). This, however, can only be settled by further inquiry, for which materials are already partly prepared. "77. "An apparatus for showing experiments with ozone." ByG.S. Newth. The special feature of this apparatus consists in the device for introducing reagents into the ozonised oxygen without disturbing the 140 volume of the gas. The reagent is contained in a sealed capillary tube, which is retained in position by means of four small raised points of glass upon tbe walls of the inner and outer tubes of the ozone apparatus. The inner tube is ground to fit the outer one, and by a slight turn of the former the tube containing the reagent can be broken. In this way it is possible to show that the contraction in ~olumeduo to the absorption of ozone by tuypentine is exactly twice as great as that which is produced by ozonising the oxygen, and also that when ozone is acted upon by potassium iodide a volume of oxygen equal to that of the ozone is liberated."78. "Note on santalal and some of its derivatives." By Alfred C. Chapman, F.I.C.,and Herbert E. Burgess. In connection with a study of certain hydrocarbons allied to the sesquiterpenes, upoii which one of the authors is engaged, it became a matter of interest to determine more carefully the chemical pro- perties of cedrene, and to coinpare it with the hydrocarbon obtained by the action of phosphorus pentoxide on santalal, with which it is generally said to be identical. The cedrene was prepared by the fractional distillation of about 1 litre of cedarwood oil under reduced pressure, and had a corrected boiling point of 261-262'. Tts density at 15'/15O was 0.9359, and it produced, in a lOO-mrr,.tube, a lzevorotation of 60'. Its refrac-tire index for the red hydrogen line and for the sodium line was pH, = 1.4991; 14D = 1.5015. Although ccdrenc is unsaturated, and combines readily with hy-drogen chloride and bromine, no definite compounds with these substances could be isolated. Negative results were also obtained in the case of the oxides of nitrogen and nitrosyl chloride. Santalal was next prepared by the fractional distillation of santal-wood oil. Its corrccted boiling point was found to be 301--306", some deconiposition occurring at this temperature. Its density was d 15O/15" = 0.9793 ; d 3Oo/2O0 = 0.9761, and its specific rotatory power at 27" was -14' 42' for sodium light. Its refractive index for the lines C anti D was pHa = 1.5051; ,uD = 1.5085.Its specific refractive energy is, therefore, 0.3039, and its molecular refractive energy 66.8. C,,H,,O requires 66.3. Its general propcrtics are those of an aldehyde. On oxidatioii ItGth an aqueous solution of potassium pernianganate it yielded an acid crystallising from dilute alcohol in thin, pearly plates melting at 76". For this substancc the name "santaleiiic acid " is suggested. This acid is strill under investigation. From santalal the hydrocarbon, C,,H,,, was prepared by treatment wit<hphosphorns pentoxide and subsequent fractionation under rc- 141 duced pressure. The main fraction was then obtained as a colourless liquid boiling between 140-145’ (25 mm.). Its density at 15’115’ was 0.9359.In a 100-mm. tube at 16” it produced a rotation of 5’ 45‘ to the right. This hydrocarbon is unsaturated, combining directly with hydrogen chloride and bromine, bnt no definite compound could be obtained. Attempts to prepare compounds with the oxides of nitrogen and ni trosyl chloride were equally unsuccessful. So far as these results go they show that cedrene and the hydro- carbon from sltntalal are very similar, but not identical. *79. “Second note 011 the liberation of chlorine during the heating of a mixture of potassic chlorate and manganic peroxide.” ByHerbert McLeod, F.R.S, This paper is a reply to a criticism by 0. Rrunck (Zeit. anorg. Chem., 1895, 10,222) on a previous note, in which it was shown that chlorine is produced by heating a mixture of potassic chlorate and mmganic peroxide. Brunck considers that the evidence is insufficient, and that the author was misled by the presence of potassic chloride mechanically carried over by the gas.Further experiments have been carried out in a different manner, arising from a suggestion of Dr. Armstz-ong. The mixtui-e of potassic chlorate and maiiganic peroxide was heated in R test-tube by the vspour of boiling mercury, and the gas passed into an exhausted flask. After the lapse of some days, during which the snspended matter settled, the gas was pumped out through U-tubes containing solutions of sodic carbonate and potmassiciodide. When the gas tilaversed the sodic carbonate first, no colouration was seen in the potassic iodide, even when this was done immediately after the gas was collected, showing the absence of ozone.On acidifying the sodic carbonate solution with nitric acid, and adding argentic nitrate, a precipitate of chloride was formed which was weighed, and from it the quantity of chlorine was calculated. In three experimeiits the quantities of chlorine were 0.064, 0.063 and 0.057 per cent. on the quantity of potassic chlorate used. When the gas, after three days’ rest, was passed through a solution of potassic iodide and then through sodic carbonate, the latter did not contain chloride, and the former solution was coloured ; on determining the liberated iodine volumetrically it was found to correspond to a, quantity Qf chlorine equal to 0.063 per cent.on the chlorate. Sodic hydrate solution that was used for washing oxygen, prepared by heating the usual mixture, was found to contain permanganate, some oxide of manganese having been mechanically carried into the solu-tion, showing that the gas contained chlorine, for ozone does not produce permanganate when in contact with sodic hydrate containing manganic peroxide. 142 *SO. Polymorphism as an explanation of the thermocliemical pecu-liarities of chloral and bromal hydrates.” By William Jackson Pope. Berthelot has observed that the heat of combustion OF chloral hydrate decreases as the time elapsing since fusiop and solidification of the sample increases; the same observation has been made by Bruner respecting bromal hydrat,e.No explanation of this peculiarity is offered by either of these chemists, although Bruner statfes that other substances such as thymol and nieiithol, which are pasty after solidification, do not show the same behaviour. In the case of chloral hydrate at least, the explanation of the gradually dect*easing heat of combustion is a purely crystallographic one. On cautiously melting the hydrate 011 a microscopic slide under a’cover slip, and allowiiig the slide to cool, solidification readily occurs, niid a thin crystalline film of the substaiice suitable for micro-crys- tallographic examination is obtained ; it consists entirely of felted micular crjstnls, most of which are so orientated that the optic axial direction of an optically negative uniasial substance is perpendicular to the surface of the slide ; in other crystals the optic axis emerges obliquely, and sometimes the crystals arc slightly biaxial.A few of the ncedles may be truly biaxial, but this can hardly be stated defin- itel9. After several hours at, the ordinary temperature, micute rhomboidal plates make their appearance amongst the needles, and, after 24 hours have become sufficiently large for crystallographic examination. The number and size of these plates which belong apparently to the monosymmetric system, increase continuously, whilst the number of needles decreases nntil, a€ter six or eight days, none but the monosymmetric plates remain. It is thus evident that on solidification o€ chloral hydrate it uniaxial form is obtained which very slowly changes into a biaxial modification stable at ordinary temperatures ; this change must be accompanied by an evolution of heat, as are all changes of the kind, SO t,hat freshly solidified chloral hjdratc: has a larger heat of combustion than a sample solidified several days before burning.The cliarige of any particular spot in the slide may be best observed and rccorded photlographically, and several good series of micro-photographs have been taken between crossed Nicols at definite intervals of time, which show the transition in 8 very perfect’ manner. On similarly examining broninl tiyclrate, no very distinct evidence of change is obtained, the solidified inass being scarcely suitable for micro-crystallographic examination.The photographic record, how-ej-er, seems to indicate a change of some kind in the plate. ‘The therniochemicnl heliaviour. of tli ymol must, as found by 143 Bruuer, be quite normal, because no crystalline change of any kind occurs in it after solidification has once occurred. After melting menthol, the other instance quoted by Bruner, it fiolidifies from centres giving a radially crystallised film. There is usually just time to give a photographic plate an exposure of three minutes on the preparation, however, before a change of crystalline foym sets in and tlhe menthol becomes rapidly converted into a mass of very minute crystals which show aggregate polarisation ; after this no further change occurs.Since the time elapsing between cooling and the formation of the crystalline inodification of menthol stable at ordinary temperatures, is too short to allow of the substance being weighed and introduced into the calorimetric bomb, the heat of combustion determined has always been that of the modification stable at ordinary temperatures. The crystallographic examination of these substances shows that’ thermochemical data respecting solid organic substances should always be accompanied by a crystallographic description of the material used. 81. “Explosion and detection of acetylene in air.” By Frank Clowes, D.Sc. The behaviour of mixtures of air with gradually increased propor-tions of acetylene, when brought into contact with flame, were studied by a method recently described by the author.The method enables mixtures in varied and accurately known pro-portion to be rapidly prepared. The proportion of acetylene was progressively increased from 1to 82 per cent. The mixture containing 3 per cent. of acetylene was the first which was affected by contact with the flame placed either above or below. A pale green flame slowly traversed the mixture, showing that it,was feebly explosive. As the proportion of acetylene was increased, the rapidity of combustion increased, and even a small volume of the mixture gave decidedly explosive effect, When 22 pev cent. of acetylene was present, the explosive combus- tion of the mixture was attended with a slight separation of unburnt carbon.As the proportion of acetylene was increased the separation of carbon was more marked. The limit of explosibility, as judged by the flanie traversing the mixture, was reached when 81 per cent. of acetylene was present. The range of explosibility of mixtures of air with acetylene, ex- tending from 3 per cent. of acetylene to 81 per cent., is extraordi-narily wide, exceeding that of any combustible gas yet experimented with. It seems highly probable that the appearance of combustion extending through the mixture with the higher proportions of 144 acetylene is partly due to acetylene being an endothermic compound. Accordingly, the combustion of a small portion of the acetylene in contact with the kindling flame, starts the decomposition of the remainder of the acetylene, with the production o€ heat and the appearance of combustion.This probably explains why air contain- ing much acetylene becomes heated throughout, when it is kindled at one point, and thus extends the range of explosibility of mixtuiw of acetylene with air. In estimating the percentage of acetylene in air, if the amouirt does not reach the lower explosive limit of 3 per cent., the most coil- venient method was the passage of the air over a standard hydiaogcn flame, and an esaniination and measurement of the halo 01-“ flarn? cap ” which was seen in a darkened room over the hydrogen flamc. A laboratory apparatus suitable for this purpose is nearly perfected, and will probably be fouud convenient ns a means for measuring accu- rately the percentage of any combustible gas present in air.hboiit 600 C.C.of the mixture are required for the estimation, which is corn-pleted in a few seconds. When air containing less than 3 per cent. of acetylene was passed over the standard 10-mm. hydrogen flame, the flame at once became yellowish-green in tint. A halo or “ cap ” mas at the snmc time seen, the height of which increased so rapidly with the increase in the percentage of acetylene, that the last estimation was made by the usc of a reduced 5-mm. hydrogen flame. The measure merit^ of the “ cap ” over the 10-mm. hydrogen flame were as follows :-O% pel. cent., 17-mm. cap ; 0.5 per cent., 19 mm.; 1per cent., 28 nim.; 2 per per cent., 48 mm. OveY the 5-ui111. flamc 3.5 per cent. gave 56-mm. cap, and 2.75 per cent. i9-mm. cap. When the percentage reached 3 per cent. it bnrn t th rougliout, giving no cap. 82, “On the occurrence of quercetin in the outer skins of the bulb of the onion (Allium Cepa).” By A. G. Perkin and J. J. Hummel. Zeuch (.Fcwbelz ?end B’wbenEiiiade, 1825, 1,434) has described the dyeing properties of these skins. Tlie colouring matter was obtained by the authors in the form of glistening, yellow needles of the formula C,,H,,,O,, which yielded compounds with mineral acids, the sulphuric acid compound C15H,,0,,H,SOI was analysed. On acetyln-tion, a compound, C,,H,O,(C,H,O),, forming colourless needles, melt- ing point 190-191”, was obtained, and by decomposition with fused alkali, phloroglucin and protocatechuic acid formed the principal products.With mordants it dyed shades similar to those given by quercetin the colouring matter of quercitron bark, and wa,s thus proved to be identical with this substance. Comparative dyeing experiments showed that the colouring niattcr 143 of onion skins was quite equal to that of such well-known dye-stuiTs RS old fustic and quercitron bark. 83. “On the colouring mattcr contained in the bark of Myrica nagi.” By A. G.Perkin and J. 3. Hummel. Jlyi-ica 7~agiis an evergreen tree, belonging to the Myricacea: occnrring in the sub-tropical Hiinslayas, in the Khasin mountains, the Malay Islands, and Japan. The bark, which is used as a tanning agent, and occasionally for medicinal purposes, was found to contain jellow colouring matter. This formed yellow needles, closely resembling quercetin, having the formula C15HiO08,and yielding coin- pounds with mineral St?ids, C15H100SI€2SO~, C,iHiJIJICI,C15H100YHBr, and Cl5HloO8*HI, orange to orange-red needles, decomposed by water into the free acid and colouring matter.In strong solutions of alkali it dissolves with an orange colonr, which, on dilution and exposure to air, becomes first green, then deep blue, and finally red violet. It dyes shades which, in their general character, closely resemble those produced by yuercetin and fisetin. The acetyl derivative, C,,H,08(C2H30),, colourless needles, m. p. 203--204”, and the benzoyl CDmpouud, Cl,H,O8( CiH,O),, m.p. 23S--236°, are described. With fused alkali it yields phZorogZzwoZ and gallic acid, and with bromine a compound (orange-brown needles, m. p. 235-%No), tlie analytical numbers for which agree with the formula C,5H60,Br,. This is probably a teti*sbromo-derivative of the colouring matter, but, on account of its somewhat peculiar properties, it will mquire further examination. The results of this investigation show t4hat this colour- ing matter, for which the name myq.iceti?L is proposed, is most prob- ably an hydroxyquercetin, 0 OH and experiments with its alkyl ethers will be carried‘out, to confirm this point. Its colour reactions with dilute alkali are probably due tv the oxidation of tlie pjrogallol nucleus it contains.The amount of colouring matter, isolated by the method described, varied from 0*2;3 to 0.27 per cent., and the nrnount of tannin it contained: estimated under the direction of Rilr. H. H. Procter, Lecturer on Leatlicia Industries, Yorkshire College, was found to be 27.30 per cent. 84. “Preliminary ncite on a new base derived from camphoroxime.” By Martin 0. Forster, Ph.D. Camphoroxinie undergoes no change when treated with boiling methylic iodide in a reflux apparatus, but on heating it with this 146 agent iii sealed tubes at 170-180", the hydriodide of a new base is produced, along with campholenonitrile. The quantity of the salt obtained frdm 15 grams of camphoroxime and 30 grams of methylic iodide was 9.5 grams.The base is a colourless, limpid oil, having the odour of piperidine ; it Inoils at 206-207", and is markedly lzvorotatory. It is tertiary in character, and analysis p3ints to the formula C12HT,,Nas representing its composition. (Found: C = 81.06; €1 = 30.66. Calculated for C,,H,,N, C = 81.35; H = 10.73 per cent.). Thc platinichloride, (C,,H,,N),PtC~,, crystallises from alcohol in magnificent orange needles, and melts, decomposing at 214.5' ; the hydyioditle, C12H,,N,HI, separates from water in lustrous straw-yellow six-sided plates, and effervesces vigorously when heated at 285O. The picyate and rnexurichloride are well-defined salts, melting at 190" and 126-128" respectively, whilst the chyonznte crystallises in microscopic pale brown square plates, becoming purple on exposure to light.Incidentally, the hydrobromide, and the acetyl, and methyl derivatives o€ camphoroximo have been obtained. 85. "The rotation of aspartic acid," By B. M. C. Marshall, A.R.C.S. In view of the contradictory statements concerning tlie rotation of aspartic acid in aqueous solution, the author has re-examined the subject. Landolt (Ber., 13, 2334) and Becker (Bey., 14,1035) obtained a Zrero-rotation for aspartic acid, prepared from ordinary asparagine. Piutti (Ber., 19, 1691), on the other hand, stat'es that ordinary aspa-ragine yields dextro-aspartic acid, which is convertible into ordinary lzlevo-malic acid, while the dextro-asparagine yields Imo-aspartic acid, which gives dextro-malic acid.The results obtained by tlie author confirm the observations of I'iutti. The solubility of the aspartic acid in water was found to be in agreement with thc results of Pasteur, Guareszlii (Jahyesber., 1876, 7/7), and Eiigel (Compt. rend., 106, 1736), and to be much less than that deduced from Becker's data. 86. "Synthesis of pentacarbon rings. Part 111. Condensation of benzil with hvulic acid." By Francis R. Japp, F.R.S.,and T. S. Murray, D.Sc. When lsenzil ancl lzvulic acid are heated with a solution of caustic 1)otash in dilute alcohol, they condense to form two isomeric com-poundH. a-Anhjrdrobenzill~vulicacid P-Anhydrobenzill~vulicacid (m. p. 187-189'). (known oiily in its salts). 147 These two di23henylkyd~ozycyclope~tteizo~zylaceticacids arc allied to anhydracetonebenzil, which is a di23he~aylhydroxycyclo~enteszone(Japp and Lander, Proc., 1896, 107).The a-acid is stable; the /I-acid, when liberated from its salts, spontaneously changes into the lactone, CsH,*Q:CH>GOC,H,*Q*CH (m. p. 151-1.52‘).0,CO >CH2 Both the a-acid and the lactone of the /3-acid, when boiled for from one to two minutes with fuming hydriodic acid, are converted into diphenylcyclopenteuonylaceticmid, C,H,*E*CH,>co (m. P.C,H,*C*CH -CH,.COH 126-127”), a change in the position of the double bonds occurring during the process. The latter acid, on oxidation with sodium hypo- bromite, yields a mixture of dipheiaylmaleic and diphewylfumnric acids. Oximes arid other deriratii-es of the foregoing conipouiids have also been prepared. 87.“Absorption of dilute acids by silk.” By James Walker and and James R. Appleyard. When silk is dyed with picric acid a real equilibrium is attained which is independent of the original distribution of the materials. If the equilibrinni concentration of the picric acid in the silk be denoted by s, and in the water by w,the relation s/gG=const. exists between these magnitudes. This formula wonld indicate, according to the solid solution theory of dyeing, that the weight of the molecule of picric acid dissolved in the water would be ?z times that of the molecule of picric acid ‘‘dissolved ” in the silk ; but this we know to be incorrect, as n is greater than unity, and the molecular weight of picric acid in water is the smallest consistent with its formula.When other solvents than water are used the rate and amount of dyeing with picric acid seem to be connected with the dissociative power of the solvent. Silk will not take up picric acid from benzene or from carbon tetrachloride, but does so readily from alcohol, less readily from ether and acetone. The ratio of the final concentrations of aqueous and alcoholic solutions of picric acid required to dje siik to a given standard was fouiid to be approximately the ratio of the solnbilities of picric acid in water and in alcohol. A comparison of the extents to which the various acids are ab-sorbed by silk shows that the acids fall into two classes,-the aromatic acids where the absorption is great, and the non-aromatic acids where the absorption is relatirely small.In each class there 148 is a rough parallelism between the strength of the acids and the amount absorbed. The addition of calcium benzoate to a solution of benzoic acid greatly diminishes the strength of the acid, and the absorption also is thereby much diminished. If dyeing mere n pure chemical addition of the dye to the fibi-e, the theory of insss-action predicts that the equilibrium concentra-tion of the dye-bath should be constant at any given temperature independently of the quantities of material taken. This is not known to be the case for actual dyeing, but it was experimentally verified by “dyeing ” diphenylamine brown vith picric acid from aqueous solution.88. ‘‘Position-isomerism and optical activity ; the methylic and ethylic salts of ortho-, meta-, and para-ditoluyltartaric acid.” By Percy Frankland, Ph.D., F.R.S.,and Frederick Malcolm Wharton, A.I.C. The authors have commenced the systematic study of the connec- tion between position-isomerism and rotatory power in optically active substances containing the benzene-ring. The present paper contains an account of the preparation and properties of the inethylic and ethylic salts of the three isonieric ditoluyltartaric acids. These mbstances were obtained by the action of the three toluyl chlorides on methylic and ethylic tartrates respectively. With the exception of the ethylic salts of the diorttio- and dimeta-toluyltartaric acids, they were all obtained as beautifully crystalline bodies, the two ethylic salts in question only as viscid liquids.All six compounds are powerfully laevoi*otatory, the methylic salts more so than the corresponding ethylic ones, and the para-compounds have the highest, the ortho- the lowest, and the meta- an intermediate rotation. As regards other physical properties, in the case of the methyl corn-pounds, all of which are solids at the ordinary temperahwe, the para- also has the highest, the ortho- the lowest, and the meta-com- pound an intermediate melting point, whilst the density is distinctly greatest in the case of the ortho-compounds, the meta- and para- compounds having almost exactly equal densities.In all cases the yotatory power was determined in the liquid state, no use being made of solutions, and the rotations were compared over wide ranges of temperature. With rise in temperature the laevorotatory power is in all cases diminished, and since the Ievorotation is conditioned by the presence of the aromatic groups (methylic and cthylic tartrates being dextrorotntory) the dominant influence of these groups is reduced with increasing temperature ; a perfectly analogous phenomenon has already been shown by one of the authors to take place in the case of the dibenzoylglycerates (Trans., 1896, 149 106). Moreover, as the laevorotation is conditioned by the toluyl groups, it follows from a comparison of the rotations of the com-pounds described that the meta-toluyl group has a higher rotatory value than the ortho-, and the para- an even higher one thau the meta-.89. ‘I Double sulphides of gold and other metals, or the action at a red heat of sulphur upon gold when alloyed with other metals.’’ By J. S. Maclaurin, B.Sc., University College, Auckland, New Zealand. It is shown that, when alloyed with silver, lead, copper, or iron, gold is readily converted into a sulphide by the action of sulphur vapour on the melted alloys. Analyses of the compounds so pre-pared are given which prove that the gold snlphide has t,he formula, Au~S. 90. “The relative weights of gold and silver dissolved by potassium cyanide solutions from alloys of these metals.” By J.S. Mac-laurin, B.Sc. The author finds that gold and silver are dissolved by solution of potassium cyanide from an alloy of these metals in the proportions by weight in which they exist in it. He shows that this is the ratio of their atomic volumes, and deduces it from the results previously obtained by him (Trans., 1895, 199) 91. The three chlorobenzeneazosalicylic acids.” By J. T. Hewitt, Ph.D., and H. E. Stevenson. O?.thoc7Llorobcizzelzeazosnlicy~c acid, CGH,-(1) Cl(2) -N:N-(4) CsH,-(2) COZB(1)OH, prepared by the addition of diazotised orthochloraniline hyd~o-chloride to an alkaline solution of salicylic acid forms yellow or buff aggregates of small crystals (ni. p. 194‘). Besides metallic salts, the methyl and ethyl esters are described.Methyl orthochlorobeiLzeneazosnlicy2nte, in. p. 109”. Ethyl orthochloro-benzeneazosalicylnte, m. p. 90-96’. Attempts to remove hydrochloric acid by inorganic bases were fruitless, and dipheneleneazo-derivatives were not produced. Boiled with aniline, in a flask provided with a reflux tube, a, sub-limate of ammonium chloride was observed, the chief prodnct of the reaction being a substance of the formula C,,H,,N30,. To effect its isolation, the contents of the flask are freed from aniline by steam distillation, subsequent treatment with soda removes an acid prob-ably having the formula C,,H,,N,03 ; after washing with hydrochIoric 150 acid, the residug is dissolved in chloroform and precipitated by ligroin as a violet crystalline powder.The formation of the substance C,jHl,N,02 niay be thus repre- sented : C13H,C1Nz03+ 2C6H5N8,= C,5H,,N30,+ NH4C1 + H,O. The substance possesses neutral properties, and ir probably the nnilide of a benzeneindulonecarboxylic acid, Metachlorobe?aze,Leazosalicy~cacid, G,H4--(1)C 1- (3)N IN-(4) C6H3-(2) CO2H (1)0H, has been previously described (Ber., 1894, 28, 803). An account is now given of some of its metallic salts. Metl~yl?,zetnchlo~.obe?azenecr2.o-salicylate forins yellow needles which melt at 114". Ethyl metachloro-benzeneazosalicylate, ni. p. 102-103°. Pni.aclalorobenzeneazosalicy~~c acid, C6H4-(l)Cl-(4)N:N-(4) C6H3-(2)C02Z3(I)OH,was prepared in the usual manner ; it melts at 237". The potassium, ain?noniTGm,silmcr, and burizcm salts are described.Methyl yas.achlol.obei2zeneazosaZicylnte, m. p. 152'. Ethyl parachlorobeizzeiaeazosalicylate, in. p. 113". For purposes of comparison the methyl and ethyl esters of benzene-szosalicylic acid (Stebbins, Bey., 1880, 13, 716) have also been prepared. Methyl l~eizzeneazosalicylate, ni. p. 106". -Ethyl bemenetrzo- salicylate, ni. p. 88-89". 92. " Condensation of chloral with resorcinol." By J. T. Hewitt, M.A., D,Sc., Ph.D., and F. G. Pope. H. Causse studied the condensation of chloral with resorcinol in dilute aqueous solution under the influence of sodium hydrogen sulphate (BzdI. SOC.Chz'm., [3], 3,861-467). In this manner he obtained a colourless compound of the formula CllHlZO6; whilst working with hot solutions, yellow crystals of the formula C,,H,,,O, were obtained.He assigned to these two substances the following constitutional formulze (CaH4(OH)O)zCH*COOHand ~6"H'(O")O,>CH.CC). c6&<0 The authors of the present comniunication have studied the latter substance, and find that it furnishes a triacetyl derivative (m. p. 152") crystallising in glittering leaflets. The substance C1,HlOO5dissolves in cold alkalis with an intense purple colour which disappears on warming, salts of tlhe type M*Cl,H,,O6 being produced. The purple 151 alkaline solution of the formula C,,H,,O, gives a precipitate on acidi-fication, solutions of salts M*C,,H,,O, only on boiling for some time. The conclusion can be drawn that the compound C,,HO, is the lactone of an acid, C,,H,,O,, which is itself readily soluble in water.This acid must contain four hydroxyl groups, and is, therefore, tet~aIiydrozydiphenylaceticacid. Probably the acid and lactoiie possess the following constitutioiial formulz. and \IdOOH The authors reserve their views as to the cause of the colo~atiun produced when the lactone is dissolved in cold alkalis. 93. "The atomic weight of Japanese tellurium." By Masumi Chika- shig6, B.Sc., Imperial University, Japan. A redetermination of the atomic weight of tellurium has been made by means of its tetrabromide, and by closely following Brauner in all the details. The result has been to get in the three experi- ments made, the numbers 127.57, 127.61, and 127.58, which, there-fore, agree with his in making the atomic weight 127%.This work was undertaken by the advice of Dr. Divers, in order to asceytain whether tellurium found under mineralogical conditions quite unlike those pertaining to the tellurium employed by Brauner, Stauden- maier, and all others who have investigated the subject, has the same atomic weight as the latter. That, as is well known, occws in Hungary and elsewhere, in union with bismuth, gold, silver., &c., while the tellurium einploged in this research was obtained from the red native sulphur, or telluro-sulphur, of Japan, dis-covered and described in 1883 by Divers, Shimose, and Shiniiclzu. It is extremely improbable that, if the substance known as tellurium is compound, as it has been considered to be by Brauner, its com-position should be identical when occurring in association with sulphur as a sulphur-like body in Japan, as when occurring in metallic combination in Europe or America.Since Staudenmaicr has got the same atomic weight for tellurium of European origin as that found by Brauner, but by a totally different method, and that the author has again got the same atomic weight by Brauner's pro- cess, but working on a tellurium of quite dissimilar origin, the point may be regarded as settled that its atomic weight exceeds that of iodine. Its occurrence with sulphur and selenium in the Japanese 152 mineral at the same time furnishes additional proof that it belongs to the sulphur group. by EDWARD ns.-l'he case of tellurium and iodine, ADDENDUM, DIVE with atomic weights in the reverse order of their places in the periodic series, is not the only one.Cobalt belongs, undoubtedly, to the second division of Group VIII, arid nickel to the thiid division, according to both Mendeleeff and Lothar Meyer ; yet all tJhe elabo- rate work done on the subject has left cobalt with an atomic weight slightly higher than, or at least equal to, that of nickel. Hence we find in most books cobalt and nickel misplaced in the reproduction of Mendel6eff or Meyer's table. It is to be hoped no onc will ven- ture now to misplace tellurium and iodine. 94. '' Derivatives of camphens sulphonic acids." By Arthur Lapworth and Frederic Stanley Kipping. The two chlorocamphenesulphonic chlorides obtained as bye-products in the sulphonntion of camphor (compare Proc., 1895, 57) have been submitted to a further examinatioii.Although no experi- mental proof of their relationship to campbene has yet been obtained, their characterisation has now been completed, and a number of new derivatives have been prepared from them. a-Chlorocumphene suZplaochZoride, C,,Hl,C1*SO,C1, is dimorphous, as was at first suspected (Zoc. cit.). It crystallises from light petroleum or cold methylic alcohol in massive transparent anorthic prisms or plates, which melt at 83-44'; from hot methylic alcohol it is de-posited in small orthorhonibic tables which melt at 87-88'. Tho latter modification is also obtained when the melted substance is quickly cooled, and undergoes gradual reversion to the anorthic niodification at the ordinary temperature.Both forms have been goniometrically measured. a-Chlorocamphene sulplmnilide, C,,Hl,Cl*S0,*NHC6H5,crystallises in small flattened needles, which probably belong to the anorthic system ; it is readily soluble in alcohol, but only sparingly soluble in ether or chloroform ; it melts and decomposes about 232-234'. a-ChZo~ocanzplwnesulphonic acid, C,,H,,Cl*SO,H, crystallises from ether in beautiful glistening elongated plates ; it dissolves sparingly in ether and in chloroform, but is insoluble in petroleuni. When heated it gradually darkens, and at 264-265' swells up aid evolves gases, finally forming a dark-coloured, liquid mass.p-ChZorocumphe?ze suZphochZoride, C,,H,,Cl*SO,CI, crystallises from anhydrous methylic alcohol in long needles which belong to the tetragonal system, and melts at 83-84'; the low meltillg point 153 (78') originally observed was probably due to some slight admixture with the isomeric sulphochloride, the latter being almost impossible to eliminate by crystallisation from petroleum. /?-Chlorocnmphene sulrphmilide, ClnHI4Cl*SO2*NHC6H5, slightlyis soluble in hot water, and crystallises from dilnte alcohol in branched aggregates of plates ; it melts at 101-103'. /?-ChZoi~ocnmrzphei~e is readily soluble sdphoizic acitl, C,,,HlrCl*SOJH, in watw, and crystallises from ether in minute ill-defined leaflets ; it melts at 73-74", and decomposes and evolves gases at about 142'. When the solution of this acid is evaporated to dryness on the water bath, and the residue extracted with water, a substance remains undissolved which is isomeric with /hhlorocarnphene sulph- onic acid.This compound crystallises from inefhylic alcohol ill well-defined plates, which aggregate on pressure to a camphor-like mass ; it melts at 183*5-184*5". It is not altered by hot aniline, but is gradually dissolved Iny boiling baryta, water, forming an ill-defined salt. Its behaviour is in accordance with tlie supposition that it is the lactone of a hydroxy-sulphonic acid. 95. " Iodoso- and iodoxy-benzaldehydes." By Victor Meyer and T. S. Patterson. It is shown that m-and p-iocloso- and iodoxy-benzaldehydes are much easier to prepare than o-iodoso-benzaldehyde, which is contrary to tlhe hitherto observed rule.The preparation of the following new substances is described. m-Todo-benzaldehyde, ni. p. 57". rn-Iodo-benzaldehyde-bichloride. ,m-Iodoso-benzaldehSde ; decomposes (eii-cn) 190". m-Iodoso-benz-aldehyde-acetate, m. p. 15i". m-Iodoxy-benzaldehyde. p-Iodo-benz- aldehyde-bichloride. y-Iodoso-benzaldehyde ; decomposes at 115". p-Iodoxy-benzaldehyde ; decomposes at 216'. o-Iodo-benzaldehyde-bichloride. o-Iodoso-benzaldehyde ; decomposes at 2015-210". 0-Iodo-benzaldouime, m. p. 107-108". m-lodo-benzaldoxime, m. p. 62-63". y-Iodo-benzaldoxime, ni. p. 111". o-lodo-benzaldehyde-phenylhydr-azone, m. p. 79". m-Iodo-benzaldehyde-phenylhydrazone,m. p.155'. y-Iodo-benzalclehyde-phenylhyclrazone,m. p. 121". 96. '' a-Isopropylglutaric acid." By W.H,Perkin, jun., F.R.S. During the course OE experiments on derivatives of glutaric acid, the author had occasion to carefully study the action of alkalis ou ethylic mefhylisopropyl-a-bromacetate, and also the action of this ethereal salt on the sodium derivative of etliylic nialonate. (CH3),*CH.C(CH,)Br*COOC2H,, ethylic. inethyZisopropyl-~-b701,zace-t utc, was pi epared by broiuinating methylisopropylact.tic: acid in the 154 presence of phosphorus, and pouring the product into alcohol; it boils constantly at 130" (100 mm.). When heated with quinoline, this ethereal salt yields a mixture of the ethereal salts of a-isopropyl-acrylic and of trimethylacrylic acids, elimination of hydrogen bromide taking place in two directions, thus : 1.(CH,>,CH*C(CH~)BYCOOC~H,= (CH3),CH*#*COO,H, + HBr. CH, 11. Me,CH*C(Me)Br*COOEt = Me2*C:C(Me)*COOEt+ HBr. And, when digested with alcoholic potash, the bromethereal salt yields a mixture of the above acrylic acids, together with small quantities of methylisopropyl-a-hydroxyaceticacid. Trimethylacrylic acid, (CH,),*C:C (CH3)*COOH, crystallises in colourless prisms, and melts at 71"; it combines with bromine, yield-ing a~-dibromotrimethy~ps.opionicacid, (CH,),CBr*CBr( CH,) *COOH (m. p. 190°), and with hydrogen bromide and hydrogen iodide with formation of (CHs),*CBr.CH(CH3)*COOH,~-b,.omotrimethy~pr~~ionic ilcid (m, p. 79O), and (CH,),*CI*CH(CH,)*COOH, 13 iodotrinzethylpro-pionic acid,(in.p. 81") respectively. a-Isopyopylacrylic acid, (CH,),*CHf*COOH , has not been obtainedCH,in a pure state. H(CHJ)**C a C(0H)mCH,*COOH, methylisopropyI-x-hyth-oxyaceticucitl, crystallises in colourless prisms and nielts at 75 -76". Condensatiou of Ethylic Isopopylacrylate with the rSodium C'omponnd of Etlzylic MaEonate.-When the mixed ethereal salts of isopropyl glutaric acid and trimethylglutaric acid (as obtained by the actioii of quinoline on ethylic methylisopropyl-a-bromacetate) are digested with the sodium derivative of ethylic malonate in alcoholic solution, condensation takes place, curiously enough, only in the case of tlic former substance. Me,CH*Q:CH, + CH,( COOEt), - Me,*CH*~H*CH,*~K COOEt COOEt (COOEt), The ethylic isopropylpropunetrica,.bolel/late thus formed is a thick colourless oil which boils constaiitlg at 209' (45 mm.), and, on hydrolysis, yields the corresponding isopropylpropanetricarboxylic acid ; this acid melts at 165' with decomposition into C02and a-iso-propylglutaric acid.(CH3)zC H*9H*CH,*yH2ar.-Isopropylglutaric acid, melts at 94-COOH COOH' 95", and in its propert,ies shows considerable resemblance to the isomeric COOH*CH,*C(CH3),*CH(CH3)*COOH,aPP-trimethylglutaric acid, which Balbiano (Ber., 1895, 28,1507) obtained from the pro- 155 ducts of the oxidation of camphoric acid with cold potassium perman- ganate. It yields an ethereal salt which boils at 158-160’ (45 mm.), an anhydride, C,H,,O, (m.p. 53O), an anilic acid, CldH8o3,which melts at 159O, and it is oxidised by cbromic acid with formation of acetic and succinic acids. Action of Ethylic Metl~ylisopropyl-x-Bronancetate OTL the Sodium Compound of Ethylic &talonate.-This reaction was studied under a variety of conditions, using alcohol and xylene as solvents, but in all cases the product was found to be identical with the ethylic isopropyl- propanetricarboxylate, obtained, as described above, by the con-densation of ethylic isopropylacrylate wit,h the sodium derivative of ethylic malonate. During this reaction the et,hylic methylisopropyl- brornacetate is obviously first converted into ethylic isopropylacryl- ate, which then condenses with the sodinm compound of the ethylic malonate in the manner described above.97. “The action of ethylic B-iodopropionate on the sodium derivative of ethylic isopropylmalonate.” By J. Z. Heinke and W,H. Perkin, jun., F.R.S. These experiments mere instituted with the object of obtaining additional evidence as to the constitution of the isopropylglutaric acid described in the preceding abstract. When ethylic p-iodopro- pionate is digested in alcoholic solution with the sodium derivative of ethylic isopropylmalonate, the reaction proceeds as follows. and the product formed was found to be identical with tbe ethylic isopropylpropanetricarboxylatedescribed in the preceding abstract. The ethereal salt on hydrolysis yielded isopropylpropanetricarboxylic acid (m.p. 165O), and this at 180’ yielded isopropylglutaric acid (m. p. 94-95’). A number of derivatives of this acid were pre-pared, and in this way its identity with the isopropylglutaric acid, described in the preceding abshact, was conclusively proved. 98. ‘‘ The condensation of halogen derivatives of fatty ethereal salts with ketones and ketonic acids.” By W,H. Perkin, jun., F.R.S., and J. F. Thorpe. The condensation of substance containing the group >CO with halogen derivatives in the presence of zinc appears to have been first studied by Frankland and Duppa (Annulen, 133,80) ;these chemists 156 synthesisecl e thylic hydroxyisobutyrate, (CH,),C( OH)4300C2H5,by acting on a mixture of methylic iodide and ethylic oxalate with zinc.Since then work has been done on this condensation by several chemists, and qn te lately by Reformatzky (Bey., 1895, 28, ZSSS), and we have lately employed it with success in preparing the follow- ing interesting substances, of which we give a brief account, in order to reserve them for further investigation in the autnmn. (1) COOC,H,*CH2*C(OH) (CH,).C( CH,),*COOC,H,, ethylic /3-hydy-oxy-aap-tyimethylgl?Ltnrate,is produced by the action of zinc on a mixture of ethylacetoacetatc and ethylic z-bi*omisobictyr.ate,or of ethybic byornoacetate and ethylic diniethylnccJtcacetate. It is a thick, colourless oil, which boils at 165" (35 mm.), and which, on hydrolysis, is decom-posed, wihh formation of acetic and iso5utyric acids.When treated with a mixture of tribromide and pentabromide of phosphorous, it is converted into COOC,H,-CH2*C Br(CH3)*C(CH,)2*COOC,H5,ethylic f3-brorno-aap-trimethylglutamte7which distils with slight decomptxi- tion at 170-175' (30 mm.), and, when digested with potassium cyanide in alcoholic solution, is reduced, with formation of C00C,H,*CB,*CH(CH,) C( CH,).*C 00C2H5,dlr y7ic ax/%frimethylglzb-tarufe. This ethereal salt boils at 162' (40 mm.), and, on hydrolysis, yields au/3-t?.imethylgZutnric n&d, a colourless crystalline substance, which melts at 147". (2) The ethereal salt of the lactone of aag-ti.ir)zethyl-P-hy~ro,,,y-(L~@cacid, COOC,H5.C (CHs),.? (CH,) .CH2*7 H2 ,is produced by clis-O--co tilling the product of the condensation of ethylic levulinate and ethylic bromoisobutyrate. It boils at 187-188" (30 mm.), and dis- solves in ammonia and aqueous potash, being precipitated on the addition of acids unchanged.When hydrolysed with aqueous potash at 0", it yields the corresponding acid, a colourless crystalline sub-stance, which melts at 105-106". (3) Ethylic pyruvate and ethylic P-bromoisovalerate condense readily in the presence of zinc, with formation of efhylic a-hyd~oxy a/3~-trimethylgtz~tnrccte, CO0Et.C (OH) (Me)*CMe,.CH,*COOEt, n colourless oil, which boils at 160-110" (60 mm.). (4) Ethyl a-methyl-~~-hydroxyznlei.crfe,Ale,.C(OH)*CH(Me)*COOEt, is produced by the condensation of ethylic bromopropionate with acetone. It; is a colourless oil, which distils at 105' (30 mm.), and on hydrolysis yields the corresponding a-methlJZ-S-l/ydr.oxy~aZericacid, a thick colonrless syrup, boiling at 160" (35 mm.).From this acid the following derivatives h nve been prepared. a-~~ethyZ-P-bromiso.LaEeyicmid, (CH,),*CBr*CH(CH,)*COOH, a white, crystalline solid, melting at 79', and yielding an oily ethereal salt, which distils in n vacuum almost without decomposition, 137 a-MethyZ-p-ioduisovaZel.ic acid, (C H,),-CI*CH(CH,) *COOH, me1 ts at 81". l'rimethylacrylic acid, (CH,)2C:C(CH,)*COOH, is formecl by the hydrolysis of ethybic a-mcthyl-~-brorni.snval~atcwith alcoliolic potash. It crysta.lliscsfrom water iii colourless prisms, which melt at 'iO--'il", and distils without decomposition at 145-150" (50 mrn.).It com-bines with bromine readily, yieldiiig dibromotrilnethylpropionic acid, (CH,) ,CBr*CHBr*C0OH, niclting at 190". 99. (( The electrolysis of the salts of nionhydroxy acids." ByJ. Wallace Walker, M.A., Ph.D. An unsuccessful attempt was made to synthesise the alcohols of the glycollic series by electrolysis of strong solutions of the salts of tlie monhydroxy-acids. 100. (( The action of formic aldehyde on phenylhydrazine, and on some hydrazones." By J. Wallace Walker, M.A., P1i.D. Besides the already known compound, (C,H,N,),( CH,),, obtained by the interaction of these substances, the author has prepamd a number of others by varying the conditions of tlie reaction. The relation-ships of the different substances is fully discussed iu the paper.101. '(The colouring matter of Sicilian sumach, Rhus coriariz," ByA. G. Perkin and George Young Allen. Sumach, which consists of the dried and powdered leaves of the genus lihus, especially R.corinria (Sicilian), and R. cotinus (Venetian sumach), is used in tanning, and also in dyeing and calico printing, on account of the tannin matter it contains, which according to Liiwe is gallotannic acid (Presenius, Zeit. unul. Chem, 12, 128). According also to Chevrenl, it contains a yeilo\v colouring matter (WattsDict. Chew,., 1874, 5, 614). Lowe (Zeit. anal. Chem., 12,187), who examined the clifferelit varieties of sumach, stated that they contain quercetin and quercitrin, but this is certainly incorrect as regards Sicilian sumach, The colouring matter, C,,H,,,O,, forms glistening yellow needles, having dyeing properties similar to those of quercetin and fisetin, but is distinguished from these by its colour reactions with dilute alkalis.The sulphuric acid compound, C,5H,,0,*H;SOa,forms orange red needles, arid the acetyl derivative, C,,H,O,( C,H,O),, colourless needles, 111. 1'. 203-204". Fused with alkali, it yields pliloroy ZucoZ and gallic wl. These reactions show it to be idelltical with myricetin, tlte colouring matter of My~ic;anagi (see prcvious abstract). Sicilian sumach also contains some qLiaritity of free gallic acid. I58 102. The colouring matter of Querbracho Colorado,” By Arthur G. Perkin and Oswald Gunnell. The wood of Querbmcho colorado conbtitutes the tannin matter ‘‘ querbracho,” which is suitnble for the production of Morocco leather, aud, moreover, in conjunction with aluni, it gives the leathcr a bright yellow shade, instead of the darker colours prepayed in the ordinary way.Jean (BUZZ.SOC.Chim., 33,6) found it to contain a tannin differing froin thosc of oak bark and chestnut wood. According to hrnandon (Watts Dict. Chew., 8, 1732), it colitains a yellow colouring matter. The colouring matter, C1,H,,,O,,forms glistening yellow needles, dye- ing shades similar to those of quercetin, and yielding compounds with mineral acids. The beuzoyl derivative, C15H606(CjH50)4,colourless needles, ni. p. 180-181”, and the acetyl derivative, C,,H606(CzH30)a, colourless needles, m.p. 196-198”, were prepared. Fused with alkali, it yields protocatechuic acid, and probably resorcinol. Its dyeing properties were identical with those of fisetin, (-:15H1006,the oolouiing iiiatter of young fustic (Rhtrs cofimis), and tlierc could be liltle doubt that it was jisctin. A second substance, C,,H,,,O,,,, forming minute prisms, was also isolated, and was found to bt: eZZagic mid, and further, the presence of a considerable quantity of ynllic acid was deteeted, these latter being, 110 doubt, chiefly foriiied during the isolation of the fisetiii from the querbracho. 103. On atisine, the alkaloid of Aconitum lieterophyllum.” By H.A,D,Jowett, D.Sc. The autliou has investigated the nature and properties of the alka- loid contained in tlie roots of the noii-toxic Acowitunz heterophyZhm.This alkaloid was examined by Broughton in 1873, who named it atisine, and ascribed to it the formula C4SHia205;it was subsequently examined by Wasowicz and by Alder Wright. The powdered roots were extracted by percolation with a mixture of methyl and amyl alcohol, slid from this percolate was obtained tlie crystalline hydro- chloride or hydriodide by the method described in the paper. Atisiize, for which tlic author adopts the formula C2,H,,N02,could only be obtained as a colourless nwnish, soluble in alcohol, ether., or chIoroform, slightly soluble in water, and insolublc in petroleum ether. Its alcoholic solution is kevorotrttory, [a]D = -19*6”, aid though the base is amorphous it yields a series of crystalline salts.Atisine hydrochloride, C,,H,~NOZ*HC1,crystallises eithe~ from water or from a mixture of alcohol and ether iii well-defined prisms, which melt at 296‘ (cow.), and aye freely soluble in water or alcoliol, but insoluble in ether. The aqueous solution of the salt is dextrorotatory, [a]== +18.46'. Atisirze hydYobrorn!de, C22€€31N0,*HBr,cryst allises from water or a mixture of alcohol and ether, either singly or in rosettes of needles, which melt at 273' (corr.). The salt is freely soluble in water and alcohol, but insoluble in ether or petroleum ether, and in aqueous solution is dextrorotatory, [x]D = +24.3". Atisine hydriodidp, C22H31NOa*HI,crystallises from hot water or alcohol in well-defined plates or tables, melting at 279-280" (corr.), soluble in hot water or alcohol, but sparingly soluble in cold water.Its aqueous solution is dextrorotntory, [a]D = +27*4". This salt cannot apparently be prepared by the direct action of hydrogen iodide upon the base, but is easily prepared by precipitating a solution of any salt of atisine with potassio-mercuric iodide, and decomposing the precipitate with hydrogen sulphide. The riitrate (m. p. 252", corr.) and pEatinic7do~ide(m. p. 229", corr.) were also obtained as \vell-detined, crystalline salts, but the auri-chloride could only be obtained as an amorphous powder. The results of the analyses of a number of pure salts led to the adop- tion of the formula C,,H,,TU'02for the base.The hydriodide, when treated with hydrogen iodide, yielded no methyl iodide, and thm the alkaloid was shown to contain no met,hoxyl groups. When either the base or its salts are mixed with alkalis or acids in either alcoholic or aqueous solution, no fission of the molecule takes place, but a new base, atisine monohydrate, C22H31K02*H20,is formed. Neither this base nor any of its salts could be obtained in the crystalline condition, but analyses of the nzwichloride and platini-chloride confirmed the formula given above. A preliminary examination of the physiological action of the nitrate by Dr. Cash, F.R.S., showed that the alkaloid is non-toxic, and that its action somewhat resembles aconine. 104. '' The action of methyl alcohol on aconitine.Formation of methylbenzaconine." By Wyndham R. Dunstan, F.R.S.,Thomas Tickle, and D. H.Jackson, Ph.D. When aconitirie (or a salt) is heated with methyl alcohol in a closed tube between 120-130", the alkaloid loses one molecular pro- portion o€ acetic acid and takes up one methyl group, forniing mefhyl benaaconine, C33H&NO,2 + CH30H = C32H45N01,+ CH,COOH. The composition of the new base has been ascertained by combustion and verified by estimation of the quantity of acetic acid separated in its production from aconitine, by estimation of the amount of benzoic acid separated on hydrolysis, and also by the determination of the 160 iinmber of methoxyl groups present, which has shown that the base contains one more than aconitine.Methyl benzaconine is a well crystallised base (m.p. 210-211”, corr.): soluble in alcohol ether and benzene, and most readily crystal- lised by adding light petroleum to its ethereal solution. It forms crystalline salts ; the hydrochloride aid the hydrobromide have been examined. On hydrolysis, methylbenzaconine loses benzoic acid, forming a base which appears to be methyl aconine, but has not so far been completely investigated. Methyl benzaconine produces a well-marked physiological effect when administered to animals, but, unlike aco-nitine, it is not a powerful poison. The authors are at present engaged in investigating the mechanism of the remarkable reaction which has led to the formation of this alkaloid, the acetyl group of aconitine being apparently replaced by methyl 105.“The chemical inactivity of Rontgen rays.” By H. B. Dixon and H. Brereton Baker. The authors have investigated the question whether Rontgen i’ays are able to influence chemical change, either by starting it or by accelerating or diminishing it after it has been started by ordinary light. In all cases examined negative results were obtained. These were carbon monoxide and oxygen (dried and moist), hydrogen and oxygen, hydrogen and chlorine, carbon monoxide and chlorine, hydrogen sulphide and sulphur dioxide, solutions of sodium snlphitc and oxygen, slow oxidation of phosphorus, decomposition of hydrogen peroxide. 106. ‘I Colloidal chromsulphuric acid.” By H. T. Calvert and T.Ewan. By heating together 1molecular proportion of chromium sulphate and 4-6 molecular proportions of sulphuric acid at 115O foy one 01’ two days, Recoura (Ann. Chinz. PIqs., 1895, [7], 4, 516) bas pre- pared a series of bodies having the forrnulce :-Cia,( SOJ34H,S04, Crz(S04)3*5HzS04,&c., which he calls chr omopol y sulphuric acids. These compounds dissolve readily in water, yielding yellowish-green, opalescent solutions. The behaviour of these solutions makes it appear probable that the cliromosulphuric acids do not exist in them as SUCZI, but are hydroljsed, foisming a colloidal substance, Crz(SO,),*H,SO4,and free snlphuric acid. Recoura does not attempt to decide whether this is so or not. Experiments recently made by W. R. Whitney (Zeit.physiknl. Chem, 1896, 20, 59) lead him to thc conclusion that the above view is the correct, one. The following 161 experiments, which were carried out in part more than a year ago, may be of interest as yielding further evidence in the same direction. The green, opalescent solutions were filtered through porous earthennilare (a " Pasteur-Chamberland candle " was used). A dark green, gelatinous deposit remained on the outside of the pot; the filtrate was almost colourless, and contained a mere trace of chromium together with the excess of sulphuric acid over and above that required to form the compound Cr2(S0&*H2S01.There was thus no doubt that the gelatinous substance removed from the solution possessed this composition ; the same body was obtained from acids of the formuls Cr2(S0,),3H2SO~and Crz( S04),5H2S04.The following are the details of the experiments. Chromium sulphate was prepared by reducing chromic acid with pure alcohol in presence of sulphuric acid (Traube, Annulen, 1848, 66, 168). It was recrysiallised by precipitating its aqueous solution with alcohol, and dried in a vacuum. On prolonged heating to 200' it lost about 11mols. of water ; a determination of the sulphuric acid, how- ever, showed that its formula was Cr,( S04),12.75H20. 1. One molecule of this salt was mixed with 3 mols. of concentrated sulphuric acid, and the mixture heated to 115-120' for seven days, The mass dissolved readily in water ; 10 C.C. of the pale green, opal- escent solution yielded 0.0596 gram Cr203 and 0 5177 gram J3aSO4.The liquid was then fi!tered through the moist; porous pot by evacuat-ing the latter internally ; the first portion of the filtrate was rejected, Since the filtration was very slow the filtrate probably became some- what too concentrated by evaporation. 10 C.C. of the filtrate gave 0.1674 gram BaSO1. The solution therefore contained : Cr.(SO,), + 2*68H2S04,and the filtrate coutained Cr2(S01), + 1.84H2S04. The composition of the gelatinous compound was Ci*,(S04),.0.8~H2S0,. 11. This experiment was made in the same way, the results being :-The original solution contained : C1.2(S04)3 + 5*OOH2S04; the filtrate contained Cr2(SO4), + 4*25HzS04.The substance removed was thus : cr2(sO4),+ 0*75H2S0,. The formation of the colloidal substance was not observed when 1 inolecular propoytion of chromium sulphate was heated with 1molecular proportion of sulphuric acid for two weeks.I 62 ADDITIONS TO THH LIBRARY. I. By Purchtsse. The Liquefaction of Gases. Papers by Michael Paraday, F.R.S. (1823-BG), with an Appendix, consisting of Papers by Thomas Northmore. On the Compression of Gases (1605-1806). i9 pp. London 1896. (Alembic Club Reprints, No. 12.) Lacroix, A. Min6ralogie de la France ct de ses Colonies. Toii~e premier. xx +723 pp. Paris 1893-95. Liebisch, Theodor. Grundriss der Physikalischen Krystallogmph ie init 898 Fignren im Text. viii+506 pp. Leipzig 1896. 11. nowntiollc. Bamber, 31. Kelway. A Text-Book 011 the Chemistry and Agricultme of Tea, iricludirig the growth and manufactui*e.858 + xxii pp. Calcutla 1893. From the Buihor Clowes. Frank, and Coleman J. Bernard. Eleiiientary Practical Cliemistry and Qnalitatim Analysis. xvi +284 pp. London 1896. From the Anthors. Cornish, Vaughan, 1siI.S~. Practical Proofs of Chemical Laws : a Course of Experiments upon the Combining Proportions of the Chemical Elements. xii +9;! pp. London 1895. Prom the Author. Podi. Annali della R. Stazione dgraria di Forli. Fascicoli xxi, xxii, xuiii, 1892-- 1894. Modena and Forli 1894-- 1895. From the Station. Heusler, Dr. Fr. Die Terpene. xii +183pp. Braunschweig 1896. From the Author. Dr. Lassnr-Colin. Chemistyy in Daily Life. Popular Lccturcs. Translated by 3131. Pattison-Muir, MA. With 21 woodcuts in text. x+ 321 pp. London 1896. Prom the Pnblisliers. Sanford, P. Gerald. Nitro-explosives. A Practical Treatise coil- cerning the Properties, Manufacture, and Analysis of Nitrated Sub-st,ances,including the Fulniinates, Smokeless Powders, and Celluloid. xii +270 pp. London. From the Authoi*. LIBRARY. The Library will be closed during the last fortniglit8 in August for cleaning and the annual revision of the Catalogue. Fellows are requested to return all booksin theirpossession not later than August 15. -.__ ___ -__~~--_____ AKD SOPIS,li~x1i1-0~ Yrintcrs in Orclinuq to HPPMajestj-, St. JI;Lrtiii’sT,~,;~.
ISSN:0369-8718
DOI:10.1039/PL8961200137
出版商:RSC
年代:1896
数据来源: RSC
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