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TssaceJ 8/7/1892, PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 114. Session 1892-93. .June 16th, 1892. Professor A.Crum Brown, F.R.P., President, in tilt? Chair. Certificates were iiead for the first time in favoui. of Messrs. Lionel Cooper, 173, Marylebone Road, London, N. w’.; James Robson, 1, Naxwell Street, Paislty, S.B.;,Jolin King WarrF, 15, Grafton Street, Mile End, F:. The follo~ving were elected Fellows of the Society :-As Foreign Members :-Emil Fischer, Wiirzburg ; Carl G raebe, Geneva ; Adolph Lieben, Vienna ; Hugo Schiff, Florence ; Th. Schloesing, Paris. As Ordinary Fellows :-Percy Targett Adams, John W. Alcock, Arthur Edward Bmrows, Horatio Ballantyne, Arthur Sanderson Bleckly, Charles Bayliss, Henry Couldery, Thomas Cockerill, Sir John Evans, K.C.B., Herbert Entwistle, John Gibson, Ph.D., John Fenton Ne wall, Charles James Korris, Henry Ramsden Redman, Ernest Heber Smith, Fred Whiteley, B.A.Of the following papers those marked * were read :-*33. “ Contributions to an international sjstem of n~menclat~are. ‘l’he nomenclature of cycloids.” By Henry E. Armstrong. An account was given of the proceedings at the recent Conference on Chetnical Nomenclatui*e at Geneva, and attention was directed to the sigiiificance of the chief resolutions. The main recommendation of the Conference may be said to be that functional terminations should be given to all names, i.e., terminations indicative of the class to which the compound belongs. This is a 128 principle which is familar to English chemists, through the operation of the rules laid down by the Publication Committee of the Chemical Society for the guidance of Abstractors, and one, therefore, which will readily find favour in this country. In the case of hydrocarbons, those of the paraffin series, as hereto..fore, are to receive names ending in me. The termination me, is, however, to be restricted to hydrocarbons containing carbon atoms united as in ethylene or ethene, the number of such ethenoid unions being indicated by a prefix, e.g., propadiene = CH2:C:CH,. It is proposed that hydrocarbons containing acetylenic unions should re- ceive names ending in iiie ;this is a somewhat unfortunate recom- mendation, as this termination ine has long been consistently applied to alkaloids by English chemists, and is an illustration of one of the difficulties met with in devising a systematic nomenclature.Reference was made to the discussion which arose at the Con- ference on the question whether carboxyl should be treated as a substituting gronp or no, and to the inconvenience involved in many cases in adopting the recommendation to refer acids to the hydro- carbon from which they might be regarded as derived by oxidation, a proposal which would necessitate that citric acid, for example, CO,H-CH,*C(OH) (CO,H).CH,*CO,H, should he named methyl-pen tanoltrioic acid, numbers being added to indicate the position of the OH and COzH groups. The motive for this recommendation is doubtless to be found in the desire to maintain a mental picture of a relationship such as exists between alcohol, aldehyde and acetic tzcid ; but if it be remembered that only primary carbinols are con- veintible into corresponding aldehydes and acids on oxidation, and that there are no acids corresponding to secondary and tertiary alcohols and phenols, this argument does not appear of great weight.As 02 is indicative of an OH derivative, there seems no reason why the simple word acid should not connote carboxyl, and why al should not connote COH ; the names ethanol ethanal and ethaioic acid or simply ethane acid would then stand for the OH, COH and COOH derivatives of ethane; citric acid, on this system, would be named propanoltrioic acid or simply propaiiol tri-acid.An explanation was then given at some length of the author’s pro- posed system of nomenclature for cycloids, on which he was request’ed by the Conference to prepare a report. Up to the present time, the termination_ awe, applied to paraflins, has been the only one which has served to connote something more trhan the possession of a particular function ; it has also served to convey definite information regarding the cha~a~ter and constitution of the compound as a whole, as definite in its way as that afforded by the term phenol applied to a particular kind of ol or alcohol. It is proposed to apply the term phene 123 (perhaps phen) to all unsaturated cycloids, and phane (perhaps phan) to saturated cycloids, the number of terms or members in the cycle to be indiczted by the appropriate prefix, although, probably in the case of hexa<phene (benzene) derivatives, it would be unnecessary to use any prefix.For example, names such as furf oran, thiophen, pyrol, indol are purely empirical and mea,ning-less, in no way serving to indicate the similarity in structure which obtains between the compounds to which they refer, and such names cannot be countenanced mnch longer; a clear idea of their structure and relationship is at once given, however, by naming such compounds respectively osy-(perhaps om-), thio-, azo-and pheirazo-yentaphem. 0ther examples are the following : 0 SH co 3-ii 'i\c/o Y 1:4-Oxyketophrne 1 :4-Imidoketophene 1 :4-Diketophene 1 :4-Diazoplieiie (PYrone)* (pyridone).(quinone). (aldine). S N\/\IIII\/\NJHV Dipheno-1 :4-diketophene Dipheno-1:4-thioiinitlol~l1cr~c (anthraquinone). (thiodiphenplamine). 'l'rimethylene, regarded as a cycloicl, might be t~iphaiie,the nuine hexaphnne, or simply phane, being assigned to hexamethylene in- stead of cyclohexane, as proposed by the Conference. The Zactonep, irnines, betnines-in fact, cycloids generally, may be easily named on this same principle, thereby rendering unnecessary a number of specific terminations proposed by the Conference. Thus ethenimine, yH">N€€, is an inzidotriphane; the lactone, 0--So isICH2 CH,*OH,-CH2' Me,N--?1 :2-oxyketopentayhane; betaine, IHZC-CO' is trimef haxonoxyI; D to-fetraphane ;and uric acid, adopting the formula proposed by Medicus, NH It is proposed to diwuss the subject at length in a, comprehensivr~ paper.DISCUPSIOX. Professor Meldola, MI.. Priswell, Mi-. Groves and Mr. Page all spoke in defence of trivial names, and urged the importance of retaining them. MI-. FRISWELL thought the use of azo to denote nitrogen in a ring might give rise to confusion, as the term had acquired significance in connexioii with compounds of a different character. Mr. PAGEdwelt on the importance of giving new names, instead of transferring old ones, to new compounds. Professor P. F. FRANKLANDthought names nunecessary, and that it would be hetteiz for the purposes of a register to use formuh. The PRESIDEKTsaid that we must keep in mind that such systematic names as had been suggested were really names of formd!x? rather than names of substances. Thus, a name had been suggested for uric acid on the assumption that Medicus's formula correctly yepresents the constitution of the acid.He thought it did, and so do most chemists, but some do not, and for them the name suggest,ed will not be the name of uric acid. Again, a new substance is discovered ; its discoverer has no doubt as to its constitution aiid gives it the corre- sponding name-it is written about, is used for preparing ot'her substances, perhaps comes to be made on n large scale, but after a time it is found not to have the constitution iiidicated by its iiariie : it must then get a new narne, and its old name will be given to a substance now supposed to have the constitution it indicates.Hence will arise confusion, for when we come across the word in reading WP may have some difficulty in ascertaining which substance is iiieaiit. Mr. Page gave an instance of this kind of confusion-the old hylw sulphite had its name correctly enough changed to thiosulphate, but unfortunately the old name, supposed now to be free, was gireii to Schutzenberger's salt. The best way out of this confusion is to abandon the name hyposulphite altogether and speak of thiosulphates and hydrosulphites. With a, rigorously systematic nomenclature we should have no such rcsource, for the old, misapplied name would be wanted for another substance, and confusioii woiild be unavoidable, except by adding in all such cases words suflicient, to identify the substance.These words would then be the iznnze; the systematic name would be a statement of our opinion as to the constitution. In reference to the objection to the termination -ine foi. hydrocarbons with an acetylene union, we could get over this by returning to the old termination -a or -ia for bases-morpliia, quinia, niethylia, &c. He thought that in translating the French names into English we should as far as possible drop the final e, aiid su hsing our ~)roiitinciation nearw tliat of our brehhren on tlie Continent. When the French nomcii- 131 clature of salts was first introduced into this country, some chemists dropped the final e in snlphate, nitrate, &c., and, no doubt, pronounc- ing these words with the a of 7mt, not as we now do with the a of hate.The confusion mould be serious with -ane, -ene, -ine, for an English- man, unless carefully trained and warned, would be sure to pronounce fane almost exactly as a Frenchman pronounces -me, and -ene almost exactly as a Frenchman pronounces -ine. This would be avoided if we mere to spell -an, -en, -in, for, although the pronunciation mould not be identical with the French, there would be no risk of mistaking the one for the other, except perhaps in the extremest form of south English,,in which -ancornes so near -en as to appear almost identical to those unaccustomed to that dialect. Nr. GROVESquoted words such as fat and fate to show that in English we could not dispense with the terminal e.Dr. h?JfSTRONG, in reply, s;tid that notwithstanding its disadvan-tages, a sgstern of nomenclature based on formuh had become a riecessity of the times ; trivial narnx would necessarily still be used, but their use would probably become more and more restricted to substances in daily use. H3 was satistied that within a very few 3-ears a system of nomenclature would be devised, and, therefore, it was all-important that we should contribute our due share to it, and do our best to establish as good a system as possible, adapted for use by English-speaking chemists. *34. "The production of pyridine derivatives from the lactone of triacetic acid." By N. Collie, Ph.D., and W.S. Myers. The authors have studied the compound obtained by the interaction of ammonia and triacetic lxtone referred to by one of them in a pre-vious communication (C.S. Trans., 1891, 617) ; they show that most probably it is an ay-dihydroxy-a-~icolinerather than the imidodiketo- compound isomeric therewith. Af t,er various attempts t,o displace the oxygen by chlorine, they at last succeeded in effecting this by means of phosphorus oxychloride ; the product possessed all the pro-perties of a dichloropicoline, and when passed together with hydrogen over heated zinc-dust gave a-picoline boiling at 128-129". The melting points of the platini- and auri-chlorides, and of the picrate prepared from the synthetic alkaloid, were found to be considerably higher than those not'iced by former workers, but substances having the same melting points were ultimately obtained from pure z-pic3liue, prepwed by heating pyridim rnethidicie.The following are the melting points observed :- Platinichloride, Aurichloride, Picrate. B.p. m. p. m. p. m. p. Picoline from lactone.. .. about 128" 216-217" 183-184" 169-171" (221-222' (186-18i' (1'72-173" corr.) corr.) corr.) Picoline from pyridine .. 127-129" do. tio. do. The platinichloride prepared from R specimen of bone-oil picoline (b p. 128-129"), after more than 20 recrystallisations, melted at 'L10--211', and the melting point could not be further raised. *35. " The fermentation of arabinose by Bacillzis ethacelicus." By Percy F.Frankland, F.R.S., and John MacGregor. The products are qualitatively t,he same as were obtained in the fermentations of glycerol by the same organism, consisting of ethyl alcohol, acetic acid, carbon dioxide, hydrogen, and traces of succinic acid, together with another acid, which was not identified, although Its carbon dioxide equivalent was determined. When. how-ever, the feimentation is conducted in a space closed by a mercury seal instead of cotton wool, a notable proportion of formic acid also occurs amongst the products. The carbonic anhydride and hydrogen are evolved in equimolecul~r proportions. When the fermentation is condiicted in a closed space, the products are formed approximate17 in the proportions 3CzH60:3CzH,Oz :4CH?02, the formic acid, as well as the carbon dioxide and hydrogen found, being all collected together as formic acid in this statement.In the fermentations conducted in flasks plugged only with cotton wool, on the other hand, the alcohol and acPti9 acid were in the pro-portion 2C2H60: 3C?H40z. It appears therefore that in the fermen-tation of arabinose by Bacillus ethaceficus the proportion of ace tic acid to alcohol is greater than in that of dextrose, and still greater than in that of mannitol and gljcerol, but less than in that of qlj-ceric acid. *36. "Resolution of lactic acid into its opticxlly active com-ponents." By T. Purdie, Ph.D., B.Sc., and J. Wallace Walker, M.A. The object of the investigation described in this paper is to show by direct analytical methods that ordinary lactic acid, in accordance with the theory of Van't Hoff and Le Bel, is composed of two oppo-.sitely active constituents. Applying the method of Pasteur, which depends on the difference of solnbility of the alkaloid salts of actire 133 isomeric acids, the authors have resolved ordinary lactic acid into a dextro-and a lsevo-acid by means of the strychnine salt. The strychnine salts of both the active acids are crystallisable, but the strychnine laevolactate is considerably less soluble in water than its isomeride. By the fractional crystallisation of the mixed salts and the removal of the strychnine from the crystals and mother liquors by means of ammoria or barium hydrate, they obtained salt solutions which were respectively dextro- and laevo-gyrate.The dextrogyrate ammonium salt yielded a dextrogyrate zinc salt having the same composition and solubility as zinc sarcolactate. Its specific rotation, +5-63”,indicated, however, that it contained some inactive lactate. A dextrogyrate zinc ammonium salt, CsHloO6Zn*C3H5OjRH4.2H~0, crystallising in well-defined prisms, and having a specific rotation of about +6.49” in an 8$ per cent. solution, was also prepared. No corresponding salt of ordinary lactic acid could be obtained. The dextrogyrate salts yielded a laevogyrate acid, which, like sarcolactic acid, yielded an oppositely active anhydride. The laevogyrate salts obtained from the more soluble strychnine sah were mixed with much inactive lactate, which, however, was mostly eliminated by fractional cry stallisation of the zinc salt.Lawogyrate zinc and zinc ammonium salts, similar in composition to the corresponding dextrogyrate salts were also prepared. The specific rotation of the laevogyrate zinc salt was similar in amount to that of the oppositely active isomeride, that of the zinc ammonium salt being somewhat lower, owing to the presence of inactive salt. A special experiment proved thatl the quantities of oppositely active acids separated from each other by means of the strychnine salt possessed equal amounts of optical activity. When the dextro- and lavo-gyrate zinc salts with 2 mols. of water were mixed, the less soluble inactive zinc salt was at once precipi- tated.Fermentation lactic acid is thus shown by analysis to consist of two oppositely active isomeric acids, one of which is identical with dex trogyrate sarcolactic acid, and the other with the laevogyrate acid obtained by Schardinger (C.X. Abstr., 60, 1891, 666) by the bacterial decomposition of cane sugar. 37. ‘‘A method for determining the number of NH, groups in certain organia bases.” By R. Meldola, F.R.S., and E. M. Hawkins. In the course of an investigation upon which the authors are still engaged, the question has arisen as to whether a certain base contains two NH, groups, or one NH, and one NH group. The ordinary methods of acetylating, diazotising, the formation of azo-deriva-tives, &c., having given ambiguous results, the authors have made experiments to ascertain whether in snch cases the azoimide could be formed by Griess's method (action of ammonia on the diazo- perbromide), as the determination of nitrogen in the pure product would leave no doubt as to the number of NH, groups which had been diazotised.As a test case they have started with the sym- metrical p-diamidoazobenzene, (~)NHZ*C~H,*~~*C~H,*NH~(p) : this base is not easy to prepare in quantity by the methods usually de- scribed, and it was only after many experiments that they found the method patented by the SOC.Anon. des Mat. Color. de St. Denis (Eng. Pat., 1579, January 29, 1890) to be the most direct, although the yield it affords is not very large. According to this method diazot- ised paranitraniline is combined with P-naphtholdisulphonic acid in alkaline soliition (the G-and R-salts need not be separated), and the purified colouring matter is reduced by boiling with caustic soda and grape sugar.The base thus prepared was purified, diazotised in the presence of chlorhg dric acid and converted into the tetrazoperbromide in the usual way. The latter, which forms an orange, crystalline powder, was allowed to remain for some hours in contact with cold dilute ammonia. The product, after several crystallisations from alcohol, forms lustrous silvery scales, melting sharply at 142". A little above this temperature it explodes. Analysis confirmed the formula :-Calculated.. .. C, 54.54; H, 3-03; N, 42.42 p. c. Found .......C, 54.58; H, 3.33; N, 42.30 ,, The substance is readily soluble in benzene, slightly soluble in petroleum, and crystallises beautifully from hot glacial acetic acid. Nitric acid or sodium nitrite added to the acetic acid solution produces an evanescent magenta-red coloration. The compound is easily reduced both by acid and alkaline reducing agents to para- phenylenediamine; the authors were unable to convert it into a diphenyl base by means of cold stannous chloride. The method described is recommended for compounds containing NH, groups in different nuclei, as the azoimides are well characteriscd and easily crystallisable compounds. The method which is some-times adopted, viz., the displacement of the NH, groups by a halogen, of course gives the same information, but in many cases this process does not work satisfactorily, and in laboratories where the vacuum method of determining nitrogen is in constant use, the determination of this element is a much simpler operation than the determination of a halogen.135 38. "The existence of t'mo acetaldoximes. Second Notice." By Wyndham R. Ihnstan and T. S. Dymond. The authors are now able to furnish further information on the change undergone by acetaldoxime when heated (cf. C.S. Trans., 1892; Proc., 1892, SSj. The melting point of the pure crystals, thoroughly freed from adhering crystals by pressure between blotting- pnper, is 46~~5"(coi-r.), the determination being made in n capillary tube. When these crystals are melted and heated at 100" for a few minutes, no apparent chemical change takes place, but the liquid cannot now be crystalliaed until 13' (con'.).A similar change in the original substance takes place more slowly at 50", the freezing point) of the liquid gradually falling to the minimum of 13' ; even at 20" this alteration slowly takes place, the crystals gradually melting and furnisliing, at last, a liquid freezing at 13". At temperatures above 100" the change is very rapid, but unless decomposition occur, the freezing point of the resulting liquid never falls below 13",however long the heating may be continued. This liquid, on exposure at 0", is very slowly entirely reconverted into the 01-iginal aldoxime melting at 46.5". At first it was thought that the liquid crystallising at 13" entirely consisted of a new modification of acetaldoxime.This, however, is not the case, and so far it has not been possible to crystalliee the new modification or even to obtain it in a pure state. The liquid never completely solidifies at L3". On separating the crystals from the liquid and thoroughly dryiq them, they melt at 46*5",and therefore consist of the original substance. The liquid from which these crystals were separated now freezes at a lower temperature than 13", producing more crystals of the original substance, but on cooling the new residual liquid, the freezing point is found to have risen, and on repeating the operation, the freezing point of the separated liquids rises each time, so that by degrees the whole of the substance is ob- tained in its original form (m p.46.5"). It is therefore evident that the liquid freezing at 13" is a solution of the original hydroxime in a new liquid modification. This liquid modification cannot be obtained pure, because, on the one hand, there is a limit to the amouut of it which can be produced by heating the solid, whilst on the other hand, although a somewhat stronger solution can be made by removing the crjstals which separate at 13", this opera- tion cannot be repeated so as to produce stronger and stronger solutions a'nd finally the pure snbstauce, because at these low temperatures the liquid modification gradually undergoes conversion into the original aldoxinie (m.p. 46.5') ; and, therefore, solutions containing less and not more of the new modification are obtained. 136 The process by which the new acetaldoxime is formed is there€ore a reversible one. There is only a, small difference (O*OOS) between the relative density of the original substance at its melting point and that of the solution (f. p. 13")at the same temperature. Determinations by Dr. Perkin of the magnetic rotations of the two liquids also sxhibit only slight differences ; the molecular rotation of the liquid freezing at 46.5" being 3.400 and that of the liquid fi-eez- ing at 13", 3.491. The molecular weight of the original crystals determined by Raonlt's method, using benzene as the solvent, is nearly twice as great as that corresponding with the formula CzH5N0(59).The same result was obtained with the solution (f. p. 13"). The two modifications, there- fore, have the same molecular weight. When acetic acid is used in the determination of the molecular weight instead of benzene, both the crystals and the solution give numbers closely agreeing with that representing the weight of the gaseous inoleculule C,H,NO. The two modifications of acetaldoxime are therefore isomeric and not polymeric. When acted on by acetic chloride or aiihydride, acetaldoxime is stated to furnish acetonitrile and not an acebyl derivative. In the light of the observations recorded above, it seemed not unlikely that previous observations have been made with a substance consisting largely of P-aeetaldoxime.Experiments have therefore been made with a-acetaldoxime (m. p. 46*5O), under such conditions that isomeric change into the p-modification cannot occur during the interaction, as it undoubtedly would if acetic chloride or anhydride were caused to act in the ordinary manner. In this way the authors have obtained what, appears to be acetyl-ct-acetaldoxime. The crystals were gradually dissolved in acetic anhydride, cooled to 0", and after some hours the liquid was pourad inbo a weak alkaline solution, when an oily liquid separated. Tliis liquid cannot be crystallised, and it does not distil without decomposition. When heated with water it decomposes into acetic acid and acetaldoxime. Solid potash converts it into ammonia nud acetic acid.The properties of this compound are being furtheit investigated. The facts now recorded demonstrate the existence of two isomeric acetaldoximes which seem to correspond in their principal properties miih the two benzaldoximes, which, however, are far from stable. The isomerism of the benzaldoximes is now generally adjudged to be stereochemical : although it is probable that this is also true of the acetaldoximes, the authors consider that further experiments are needed before it can confident,ly be asserted thpt the isomerism is incapable of a structural explanation. Although it might at first 137 seem that the small diffeiience observed in the magnetic rotations is in harmony with the stereochemical theory, when the magnetic rotations are calculated for the possible structural formule, it is found that the differenccs are also small mid are actually too slight to rtfford trustworthy criteria of structural isomerism. :39.“ The dihsociatioii (-onstants of’ o~ganic acids.” Ry James Walker, D.Sc., Ph.D. Tb.e author has cletemiined the dissociation constants of various alkyl derivatives of pimelic acid ; of dimethyl- and diethyl-pentane- tet racarboxylic acids, (HOOC)?-CMe.( CH2)3*CMe( CO0H)? and (HOOC)2*CEt-(CH,),.CEt(COOH),; of several carboxyl derivatives of the polymethylenes ; of citric, aconitic and tricarballylic acids ; ticd of a number of acid ethereal salts of dibasic organic acids, R’OOC*R”*COOH. He finds that the introduction of an alkyl gi-oup into the molecule of piinelic acid has little influence on the streiigtli of the acid, which corresponds with Walden‘s observations on the substituted glutaric acids.The closing of a carbon chain to form a, polymethylene ring is not accompanied by any marked change in the constant. The constants of tricarballylic, aconitic and citric acids form a series payallel to that formed by the constants of succinic, fumaric and malic acids, their. -\-slues being considerably greater. l~owe~ei*,corresponding with the greatel, number of carboxyl groups in the molecule. Hthj1 liydrogen stilts of dibasic acids have constants equal iii geiiei.al to about half tlie constants of the corresponding dihydi*ogen salts. Exceytioiis to this yule are only fouiid in the case of (libansic itcids with constants abnormally high.Methyl hydrogen salts posscss constants somewhat greater than those of tlie coi*respondiug ethyl hydrogen salts, so that the group COOMe has a somewhat nioi*e maiaked acid character than the group COOEt. 40. “Note on the preparation of alkyl iodides.” By James Walker D.Sc., Ph.D. The anthor describes a method for the convenient and. rapid pre- paration of considerable quantities (500-1000 grams) of methyl or ethyl iodide from iodine, methyl or ethyl alcohol, and a mixtare of red and yellow phosphorus. The apparatus employed is a niodific;i-tioii of a fat extraction appai-atus, by means of which the iodine is dissolved hy the condensed :tlcohol or iodide, and runs into a vessel t*oiitaiiiing thc phosphorus xiid itlooliol.The nietliod requires little attention, and gives a good yield--570 grams of ethyl iodide froi~i 138 500 grams of iodine. It may also be applied to the preparahion of higher iodides. 41. “ An examination of the products obtained by the dry distilla- tion of bran with lime. Preliminary communicat’ion.” By W. F. Laycock, Ph.D., and F. Elingeniann, Ph.D. Considerable quantities of bran and unslaked lime, in the propor- tions of 1 to 2 by weight, were subjected to dry distillation. The resulting distillate col-isisted of n black oil floating on an aqueous solution. The aqiieous solution sniells of herring-brine and contains large quantities of ammonia. On boiling the solution, gases are evolved, which burn on ignition with a slightly luminous flame.Anlines and furfurau are probably ?resent. The oil, after repeated fractionation, was found to have no constant boiling point. Analysis of different fractions showed that they all contained about 4 per cent. of nitrogen. Thej- were heated successively with (1) water, (2) sodium bisulph- ite solution (t,lie resulting solution contained aldehydes or ketones) and (3) phenylhydrazine. The oils which remained unaffected by thid treatment were distilled three times over excess of sodium and eventually fractionated. Analysis showed that the percentage of nitrogen had not been affected to any great extent, but that the substances containing oxygen had been for the greatel.part destroyed. The percentage of carbon was higher than in the original oil, and, judging fi*oni the behavionr of the oil towwds agents, indifferent substances, probably hydrocarbons, were present. The oil is evidently a comples mixture, and fractional distilla tiori appears to be of limited use as a means of isolating its constituents. 42. “ The atomic weight of ldladiuin.” By (3. H. Bailey, L).dc.: Ph.I)., and Thornton Lamb. The authors have been eilg:iged during the past tliree years on thz investigation of palladium salts and the redetermination of the atomic weight of palladium. After an examination of the values obtained from vayious salts, especially potassium palladious chloride (the salt used by Berzelius) and the palladamrnonium salts, they come to the conclusion that the most reliable substance for the estimation of the atomic weight is palladammonium chloride, Pd (NH,Cl),.They prepared a series of fractions, and determined the relation between the weight of salt taken and the palladium and chlorine obtained on reducing tlie compound in hydrogen. Thc mean of their results fi*oin the palladium is 105.46. They point out that the chlorine determinations afford far from accordant values, owing to irregularities arising in the course of the decomposition of the salt and to the difficulty of arresting the whole of the ammoriium chloride. The atomic weights of all the platinum metals have now undergone revision, and it is interesting to note that the relations already pointed out by Seubert (Liebig's AnnuZen, 261,279) are even more pronounced when the new value is introduced in place of that obtained by Berzelius (106.35).Rutlieniuui. Rhodium. Palladium. Silver. 101.4 102.7 105.5 107.7 Osmium. Iridium. Platinum. Gold. 190.3 192-5 194.3 196.7 Differences. 88.9 89.a 88.8 89.0 43. " The action of sulphuryl chloride on acetorthotoluiclide and acetparatoluidide." By W. P. Wynne, D.Sc. I : 2 :5-Metachloracetorthotoluidide is almost the sole proclnct of the interaction of equal weights of sulphuryl chloride and acetortho- toluidide whea the latter is suspended in five times its weight of carbon bieulphide. 1:2 :5-Ijichlorotoluene, obtained by hydrolysis of pure potassium 1: 2 :5-dichlorotoluenesulphonate,boils at 200" under 770 mm.pressure ; on sulphonation with 10 per cent. anhydro- sulphuric acid at 70-100", this dichlorotoluene yields a single sulph-onic acid, the bai-ium (+ H,O), potassium and sodium (+ l&H,O)salts of which are described ; the chloride, C6H,MeCl,-S0,C1, crystallises in large tables melting at 43". When acetparatol uidide, suspended in carbon bisulphide, is treated with an equal weight of sulphuryl chloride, 1: 3 : 4-metnchloi-met-paratoluidide is the chief product ; small quantities of 1: 3 : 4 : 5-dichloracetparatoluidide and the tri- and t~etr.a-chloro-derivativcfi being also formed. The corresponding chlorotoluidines are converted into chlorotoluenes by Sandmryer's method, and these may be sepa- rated partly by fractional distillation and partly by fractional sulph- onation, since pal-achlorotoluene is almost exclusively sulphonated by 100 per cent.sulpliuric acid, 1: 3 : 4-dichlorotoluene by 5 per cent. anhydrosulphuric acid and 1: 3 : 4 : 5-trichlorotoluene by 10 per cent. anhydrosulphuric acid at temperatures below 100". 1:3 : 4-Dichlorotoluene, on treatment with 5 per cent. anhydrosnlph- uric acid, yields snlphonic acid, the barium (+ 2H,O), potassium and sodium (+ H,O) salts of which are described; the chloride, CsHzMeCl,~S02C1, crystallises in long, probably monosymmetric prisms melting at 82". On hydrolysis of the potassium salt, pure 140 1 :3 :4-dichlorotoluene is obtained, boiling at 207" under 764 mm.pressure. 1:3 :4:5-Trichlorotoluene, on treatment with 10 per cent. anhydrosulphuric acid, yields a single aulphonic acid, of which the barium (+ H,O), potassiunz and sodium (++H,O) salts are described ; the chloride, C6HMeCI3-SO2CI,crystallises in short, slender needles melting at 88". On hydrolysis of the potassium salt, 1:3 :4 :5-trichlorotoluene is obtained ; this melts at 42*5", boils at 24.5-5-247" under 768 mm. pressure, and, on oxidation with dilute nitric acid, yields the corresponding trichlorobenzoic acid melting at 203". The action of sulphuryl chloride, therefore, corresponds very closely with that of chlorine on acetortho- and acetpara-toluidide, as de-scribed by Lellmann and Klotz (Annulen, 231,310). Orthochlorotoluene, on sulphonation with 100 per cent.sulphuric acid at 60", seems to yield only one sulphonic acid, the buriuw~ (+ 2H20),potassizcm (+ &H,O) and .sodium (+ $H,O) salts of which are described ; the chloi-ide, C,H,&IeCl-SO,Cl, crystallises iii long, flattened, irregularly-developed prisms melting at 59". M etachlorotoluene, under like conditions, seems to i'01~111 only one ssnlphonic acid, the buriunz (+ H,O), potassium and .soJ'L'?L~L(+ H,O) sitlts of which are descrihed ; the chlor-itle, C6H,MeCI*S02Cl, wystnl- lises in brilliant, long, orthorhoiiibic prisms melting at 53". Parachlorotoluene is less readilj- sulphonated by 100 per cent. sulphuric acid than its isonierides, and yields two isomeric sulphouic acids, which have not yet been completely separated. Two series of salts are described, one of which is beyond question derived from the mixed acids, as shown by an investigation of the sulpho-chloride. The results obtained agree in the main with those of Vogt and Henninger (Ann. Chim.Phys. [4],27, 130), and tend to show that the 1 : 2 :4-isorneride, identified by conversion into the 1 :2 :4-pmchlorotolueneorthosulphonarnide described by Heater (Awaalmr, 221, 'Log), is the rninor product of sulphonxtion. The Society's rooms are closed until further notice, to permit of alterations, the introduction of the electric light and re-decoration. HARRISON AND soss,PRINTERS LN ORDINARY TO HER MAJESTY. ST. NAZLTIN'SLANE.

ISSN:0369-8718    

DOI:10.1039/PL8920800127

出版商:RSC    

年代:1892

数据来源: RSC