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Isued 9/2/1893. P -R0C E E D I N G-S OF THE CHEMICAL SOCIETY. No. 119. Session 1892-93. Fchrnary Bad, 1893. Dr. W. H. Perkin, F.R.S., Vice-Presidelit, in the Chair. Mr. Walter H. Ince was formally tLdiiiitted a Fellow of the Society. Ordinary certificates were read for tlie first time in favour of Messrs. John Frederick Briggs, c/o Messrs. Parry & Co., Madras ; J ulian L. Raker, Stamford, Hendharn Road, Upper ‘looting, 8.W. ; William A. Bone, Schlossberg 3, Heidelberg; H. W. Dickinson, Kent Place, Ulverston, Lancashire ; John Addyman Gardner, 5, Bath Place, Oxford ; John Alan Murray, 60,Marine Terrace, Aberyst- wyth ; Alan E. Munby, 44,Holly Avenue, Newcastle-on-‘l’gne ; J. E’rnnk &Gregory, M.A., Hamilton, N.Y., U.S.A. ; James Henry Robbina, 4,Roderick Road, Haverstock Hill, N.W.; William Rintoul, 48. Cnimirvon Street, Glasgow ; George Rudd Thompson, 5, Clythn Square, Newport, Mon. Of the following papers, those marked * were read:- *106, “The connection between the atomic weight of the contained metals and the magnitude of the angles of crystals of isomorph-ous series” By Alfred E. Tutton, Assoc. R.C.S. The author has subjected the crystals of 22 salts of thc series of double sulphates R,M( SO,),*SH,O containing as the aikali metal R potassium, rnbidium and cesium respectively, and as the second (dyad) metal R! magnesium, zinc, iron, niagancse, nickel, cobalt, copper and cadmium respectively, to a detailed goniometrical inres- tigation, with the piirpose of ascertaining thc nature of the connection specified in the title.The measurements have been made in great detail, at least 10 crystals of each salt, of the highest procurable depee of purity and perfection, selected from Feveral different CI-OPS, haring been completely measared : an average of over 400 measure-ments have thus been made in the case of each salt, 40 separate values of each of the principal angles being frequently obtained ; this being considered necessary in view of the smallness of the differences under investigation, in order that on taking the mean of all the v;llues of each angle fhe errors due to slight distnrbances during deposition, and also the instrumental errors, might be elimin- ated. The purity of each salt was established by direct, analysis.The 22 salts are fiilly described in the paper, and complete tables of their angles given. -4fter each set of three salts containing the same second metal and potassium, rubidium and cmium, respectively, as the alkali metal have been thus described, their angles are conipared and the morphological relations "are discussed. The results of the investigation are embodied in the following summary : -1. The salts contsining czesium as tile alkali nieial are the mosf readily obtained in hhe form of crystals ; those containing potassium. the least ; the salts containing rubidium occupying an intermediate position in this respect. 2. Though bounded by tile same common planes, the crystds of the potassium, rubidium and caesium salts of the series exhibit specific characteristic habits, the characteristic habit of the crystals of the potassium salts being widely different from that exhibited by the crystals of the cesium salts, and the habit usually assumed by the crystals of the rubidium salts being of an intermediste character. T'lie relations betwcen the chai acteristic habits of the potassium, rubidium and cmiuin salts rcspectively are tlius found to be in dircct correlation M ith the atomic weights of the alkali metals.3. The axial angle /il increases with the iricrease in the atomic: weight oi the alkali metal, its magnitude in any rubidium salt of the series beicg approximately midway between that in the potassium and that in the cesium salt containing the same second metal; in other words, the differences between the mstgnitudes of the axial angle in crystals of this series contailling potassium, rubidium and czsium respectively as the alkali metal are in direct simple propor- tion to the differences between the atomic weights of these metals.The changes in the magnitude of the axial angle on passing from a potassium to a rubidium salt, and from a rubidium to a caesium salt, ;we vc.1-y considerable, usually exceeding a wliolt. degree in each case ; they are therefore far outside thc limits of possible expel-imental or forniatioiial crror. 29 4. The magnitudes of all the aiigles betweeii the faces of the crystals of the salts of this series containing rn1)idiuni as the alkali metal lie between tbe magnitudes of the coi*responding angles upon the cr,ystals of the salts containing potassium and cx?siunl respec- tively.The differences between the magnitudes of the angles, other than the axial angle, in crystals of this series containing potassium, riibidiuni and cssium respectively as the alkali metal are not gene-rally in direct simple proportion to the differences between the atomic weights of these metals. The maximum deviation from simple proportionality occurs in the prism zone, in which the ratio of the differences varies, according to the uature of the second metal present, from 1:2 to 1:3 The fact that the differences betweeii the magnitudes of many of the angles of the caesium and rubidium salts are so much larger than those between the rubidium and potassium salts would appear to indicate that as the atomic weight increases it exercises an influence on these angles in excess of the mere numerica,l proportion to its increase.This influence is most apparent in the case of tlie angles of the prism zone, and becomes less and less evident in the zones approaching more and niore neai4y to the plane of symmetry, until at length, in the case of the axial angle lying in the plane of sym-metry, all evidence of it disappears, and the differences are then directly proportional to the numerical differences in atomic weight. 5. The alkali metals exert a preponderating influence in determin- ing the geometrical form of the crystals, the magnitudes of the angles being altered on displacing one alkali metal R by the next higher or lower to an extent attaining a maximum in certain anglea of more than a whole degree, while the displacenient of the second (dyad) metal M by any other of the same group is unattended by any material change in the angular magnitudes.6. The importance of the axial ratios as indicative of the change of geometrical form on displacing one alkali metal in any salt of the series by another is greatly diminished by the fact that simultaneous changes, more or less neutralising each other, occur in the angles which determine them, thus causing the differences to be small. It is generally observed, however, that in any set of three salts contain- ing the same second metal the ratios in the case of t.he rubidium salt lie between those of the potassium and czsiiim salts, and soinewhak nearer to those of the potassium salt.The changes in the angles themselves af'ford the only complete information concerning the change in geometrical form. The optical properties of the crystals of the salts mw considered will be described and discussed in a subsequent communication. D~SCUSSION. Mr. MIEM remarked that Mr. Tuttoii appeared to attribute the intermediate position occupied by the rubidiiini sulphates to the fact that the atomic weight of rubidiuiri is the ai-ithnietic mean of those of potassium and caesium ; if this were the simple caiise, we should expect similar relatioris to obtain in the lithiiim, sodium and potas- sium, or the calcium, strontium and barium series, or iii the case of an homologous series of l-iydrocarbon radicles.The stronti urn salts, however, are not)intermediate in form between those of barium and calcium in the case of the bromates, tlie sulphates or the carbonates, and even in the potassium-rubidium-caxium series the platinonitrites and the platiniodonitri tes prepni*ed by Nilson afford results showing that the rubidium salt does not necessarily occupy an intell-mediate position. Hence it is impossible at present io draw simple general conclusions froiu the results afforded by these or other iso-morphons series, as the relatioris obtaining in one series do not genernlly prevail in others. Mi*. Miers expressed the hope that Mr.Tutoon would extend liis observations to the isomorphous selenates. "107. "The preparation of phosphoric oxide free from the lower oxide." By W. A. Shenstone and C. R. Beck. A description is given of a method of preparing phosphoric oxide free froin the lower oxides by distilling it over platinum sponge iii the presence c;f excess of oxygen. Thc authors refer to a sirniltbr process lately described by Professor Threlfnll (Phil. Mag., January, 1893),and call attention to certain points in this process which in their experieiice considerably improve its efiiciency and value. DIS c usSIOS. Professor TFIOBPE,referring to the strictures passed on the com-mercial phosphoric oxide by Mr. Shenstone, said that in his experi- ence it was by no means unsatisfactory in quality.Mr. Tutton and he had failed in extract,ing more than a minute proportion of phos-phorous oxide from it. Mr. H. B. BAKERagreed with Professor Thorpe ; he had been in the habitlof testing for the tetroxide by means of carbon tetrachlor- ide, which dissolves it but not phosphoric oxide. Mil. SHENSTONF,iii rcplj-, said tliat lie liad not int,ended to imply more than that the commercial product was impiire ; the porcentnge of impurity was probably small. 31 *108. " Contributions to our knowledge of the aconite alkaloids. Part IV. On isaconitine (napelline)." By Wyndham R. Dunstan and E. F. Harrison; The authors have investigated the nature and properties of the alkaloid found together with aconitine in the roots of Aconitunt wapeZZus (see Part II), to which it was proposed to assign the old, disused name of napelline ; this alkaloid always occurs in the roots to as large an extent as aconitine and in some cases to a larger extent.The preparation of the pure substance is fully described in the paper. Its separation from aconitine is based on the superior solubility of the latter in ether, while its superior solubility in chloroform affords a means of separating it in greater part from the other associated alkaloids ; it is finally purified by recrystallising its hydrochloride. It is found to be isomeric with aconitine, and the name isaconitine is therefore now adopted instead of napelline, to which objections were raised ou a former occasion.Isaconitine has hitherto always been obtained in a colonrless, friable, varnish-like form, resisting all attempts to crystallise it ; it is readily dissolved by alcohol and chloroform, less readily by ether, and it is only slightly soluble in waier, though more so than aconitine. The alcoholic solution is feebly dextro-rotatory. The hydrochloride, C3,H4,N0,,*HC1,crystallises from water in rosettes soluble in alcohol, containing 1 mol. prop. of water. The aqueous solution is intensely bitter, and is laevorotatory to almost the same extent as the aconitine salt, [a]== -28.74". The corresponding hydrobromide and hydriodide form similar crystals, but are anhydrous ; the latter salt is lmvorotatory, [a]D = -26.94".All these compounds somewhat resemble the corresponding aconitine salts in their physical properties. Isaconitine exhibits a remarkable behaviour with auric chloride which sharply distinguishes it from aconitine, and, indeed from most other alkaloids. Hitherto no definite aurichloride has been obtained, but it is found that when solutions of the hydrochloride and of auric chloride are mixed, a yellow, amorphous precipitate is produced as in the case of aconitine ; on recrystallising this from alcohol, nearly colourless crystals are obtained of an aurochZorisaconit~ne,of the formula C3,H4,(AuC12)NO12.This is apparently a derivative of the alkaloid in which one atom of hydrogen is displaced by the group AuCl,. The first known alkaloidal derivative of this type, namely, aurochlorcaffeine, was described a short time ago by Dunstan and Shepheard (cf.Trans., Feb., 1893). The production of such a com- pound from napelline was altogether unexpected. Aurochlorisacon- itinc differs, however, from aurochlorcaffeiiic in not being rcconvertcd into the aurochloride by the action of hydrogen chloride. When isaconitine is heated either with water in closed tubes or under ordinary pressure with mineral acids, it' is gradually hydro- lysed. The hydrolysis is more rapidly effected by aqueous solu-tions of soda or potash, which act even in the cold. It yields thc same products as aconitine and the same proportions, viz., aconine and benzoic acid, C,H,,NO,, + H,O = C26H4,N0,,+ CiH,02.The physiological action of isaconitine has been compared with that of aconitine hy Professor Cash, who finds that the action of the two alkaloids is entirely distinct. A solution of a pure isaconitine salt docs not produce the tingling sensation on the tongue which is so character-istic of aconitine; and while aconitine is a most violent poison, even in excessively minute doses, relatively considerable quantities of isaconitine must be administered to small animals in order to pro-duce a toxic effect, which effect is the result of a physiological action in the main distinct from that of aconitine. It seems doubt- ful whether isaconitine would prove toxic to man, except when given in very large doses. It may be added that the new alkaloid now described under the name of isaconitine is entirely different from the mixtures of amorphous alkaloids called napelline by thc earlier workers.It also differs in composition and properties from the picraconitine of Wright and the amorphous bases since obtaiiied from the roots of Aconitum napellus by other investigators. Having regard to thc manner in which these amorphous bases were prepared, and to the extreme difficulty which is expcrienccd in preparing purc isaconitinc, it may be safely concluded that they were not single substances. "109. " Contributions to our knowledge of the aconite alkaloids. Part V. The composition of some commercial specimens of aconitine." By Wyndham R. Dunstan and Francis H. Carr. The authors have examined a number of Englisli and foi-eign specimens of aconitine.For several of these they are indebted to Dr. J. W. L. Thudichum, who collected them some years ago ;others have been purchased during the last two years. Dr. Thudichum had found that the various specimens differed enormously in their toxic power, many being nearly inert, while a few were highly poisonous. The process uscd in examining these '' aconitines " was essentially that described in the preceding communication by mcans of which aconitine, isaconitine, homisaconitine (homonapelline) and aconinc could be isolated, and the quantity of each appr.oximatcly detcrmincci. The nietliod of estimating aconitixic first proposcd by Wright, and recently advocated in it slightly modified form by Allen, in which the benzoic acid produced on hydrolysis of the mixture of alkaloids is reckoned as derived froni aconitine, is valueless, since isaconitine furnishes benzoic acid in the same proportion as aconitine when hydrolysed.Sixteen specimens of “aconitine from A. napellus ” and its salts wei’e examined. Most of the samples were amorphous ; these were invariably tound to contain but a very small proportion of aconitine, in some cases none, but were chiefly composed of the amorphous a1kaloids aconine, isaconitine and homisaconitine, a11 of which appear to he very slightly, if at all, toxic. It would seem that, as a rule, ’‘ amorphous aconitine ” represents the total alkaloids of the root. Of the crystalline specimens of alkaloid only two were pure, most of them bt4ng contaminated with more or less amorphous alkaloid.The specimens of aconitine salts examined were found, in nearly every case, to be chiefly isaconitine salts containing only small quantities of aconitine compounds. Hence it is not surprising that great differences have been observed in the mode of action and toxic power of commercial “aconitine.” Zt is most important that in future nothing but pure crystalline aconitine possessing the cha-racters fully described in Part; I of the enquiry should be used in medicine, and it is satisfactory that a pure alkaloid can now be obtained in conimerce. MY.HOWARDcharacterised the discovery of the extraordinary difference between aconitiue and the isaconitine now Ciesciibed as a striking example of the value of high “ theoretical ” chemistry ; the discovery of the explanation of the difference would be of the deepest interest.Ur. STEVENSOX,atter alluding to the impure nature of German commercial aconitine, dwelt on the importance of using crystallised material, which gave fairly constant results ; such was the virulence of the alkaloid that ‘L/l,OOOthsof a gmin never failed to kill a large mouse, arid 3 milligrams usually proved fatal to an adult man. Dr. BRUNTONspoke of the fear of prescribing “aconitine,” which existed owing to its irregular character; in the course of experiments made 22 years ago, he bad liirnself obtained most conflicting results, having, doubtless, used different “ aconitines.” He then remarked 011 the scientific interest attaching to the determination of the nature of’ the alkaloidal constituonts of the various species of aconite, and the light which might thereby be shed on the origin of the diflerent alkaloids : A.heteq*ophyZlu?n,unlike most species, contained no poison-ous principle, and it would be specially interesting to examine this. 34 Pr.Dfessor DUNSTAX, iii reply, said that (&rrnaii aconitines we~enot dl amorphous and valueless ; moreover it was a mistake to suppose that a sample was pure because it was orystalline. A. heterophyllum, td which Dr. Brunton had allndcd, had a vei-y bitter taste ; as this was characteristic of isaconitine, perhaps this alkaloid was present. 110.‘‘Sjnthesis of oxazoles from benzoin and nitriles.” By Francis R. Japp, F.R.S., and T. S. Murray, D.Sc. The authors find that nitriles aud benzoin interact when a mixture of the two compounds is dissolved in concentrated sulphuric acid, water being eliminated, an oxazole being formed in which the hydro-carbon radicle attached to the cyanogen of the nitrile occupies the meso-position, e.g., in the case of acetonitrile, which yields up-di- CsH5*7pheny 1-p-methy loxazole (m. p. H.0 H + NC*CHI,= **”)’ CsH,*CO In addition to the foregoing, t’hey have prepared a,3-diphetzylozazole, C,H,,NO (m. p. 44’)) Prom benzoin and hydyogen cjanide; zp-di-phenyl-~~-ethyloxcczole,C1,H,5N0(m. p. 32”), from benzoir, and propio-nitrile ; and tri’henyloxuzole, C2,Hl,N0 (m.p. 115”), from benzoin and benzonitrile. Tripbenyloxazole is identical with Lanrent’s beneilam and Zinin’s azobenzil. By heating a~-diphenyl-~-methyloxazolewith ammonia, it is con- verted into the corresponding imidmole, identical with Japp and Wpne’s methyldiphenylglyoxaline, the oxygen atom in the ring being displaced by NH. 111. “The action of nitrosyl chloride and of nitric peroxide on some members of the olefine series.” By William A. Tilden and J. J. Sudborough. The authors have examined the action of nitrosyl chloride on the first five members of the olefine series with the following results :-Ethylene forms only the dichloride ; propylene and butylene R mix-ture of dichloride and nitrosochloride, while trimethylene (amylene) is almost entirely converted into a nitrosochloride.Phenylet,hylene (cinnamene) behaves like trimethylethylene. Further, it is now found that propylene affords a compound similar to that prepared by Guthrie many years ago from nitric peroxide and amylene. The study of these compounds has been undertaken with the view of elucidating the constitution of the nitrosochlorides formed by the terpenes. 112. '' Piperazine." By W.Majert and A.Schmidt, Erroneous statements have appeared in several modern text books regarding the physical and chemical charac ters of piperazine, CaHloNz,which have been confused with those ascribed by A. W. von Hofma8nn and by Ladenburg to the impure substances of like composition discovered by them, and termed respectively diethylene- diamine and ethylenimine or diethylenediimine ; our attention has been directed to the fact that this misunderstanding has partly arisen from a misconstruction of our views (Ber.,1890, 3719) as to the identity of these substances : we, therefore, desire to correct this impression. Piperazine, which was not known in its pure crystaIline condition until prepared by us in August, 1890, by treatment OE dinitroso-diphenylpiperazine with alkali, is a crystallinc substance melting at 104-107" in capillary tubes, althongh when the melting point is de-termined on large quantities it is found to be 112",the differences being due to the hygroscopic nature of the base ; it boils at 140-145".It is very readily soluble in water and alcohol, the aqueous solution having a distinctly alkaline action.It is ve1.y hygroscopic and readily absorbs carbon dioxide, being thereby converted into the carbonate melting at 162-165'. Piperazine is especially characterised by the formation of an in-soluble pomegranate-red double salt with bismuth iodide and liy a dibenzoyl compound melting at 191O. The basic substance diethylenediamiiie prepared by Hofmann by the interaction of ammonia and ethylene bromide consisted of a liquid mixture of bases boiling approximately at 170". That this mixture contained a small quantity of' a base identical wilh piperazine is undoubted, but it was only after piperazine had been prepared from dinitrosodiphenylpiperazine that Hof mann succecded in identifying it and isolating the pure crystalline product fror: the mixture, which, besides higher ethylene bases, contained also a number of vinyl compounds. Owing to the difficulty of purifying smd1 quantities of the base, Ladenburg's experiments .with diethylcnediimine, obtained by the decomposition by heat, of ethylcnediamine hydrochloride, were unsuc- cessful: the product described by Ladenburg as the base was undoubtedly impure piperazine carbonate, as proved by its melt iiig point, 159-163'. In conclusion, it, may be interesting to mention that we have suc-ceeded in preparing the following series of hydrates of piperazine, that most readily fGrmed being a hexhydrnte which crystallises from dilute aqueous solutions :- 36 C1H,,,N2*H20,m. p.75", ,, 2H20, ,, 56", ,, 3H20, ,, 39-40', ,, 4H20, ,, 42-43", !, EiH20, ,, 45", ,, 6H20, ,, $8". KOPP MEMORIAL LECTURE. An extra meeting of the Society will be held on February 20th, 1893, at 8 P.M., the aniiiversary of the death of Herinann Kopp, when a lecture will be delivered by Professor Thorpe, F.R.S. At the next meeting, 011 E'cbruai-y 16th, there will be a ballot for the election of Fellows ; and the following papers will be read :--'( Platinous chloride." By W. A. Shenstone. " The rrielting point,s of compounds of similar constitii tion ." BJ-F. S. Kipping.'' The electrolysis of sodic ethylic camphorate." By James Wa1kt.r. c' Note on optical properties as icdicative of StriicturC." By H. E. Armstrong. " A new base from Coqdalis cuca." By J. J. lhbbie nnd A. Lsuder. tl ARRlSOPi AND SONS, PRINTERS 1sORDINARY TO HRlt 3?.4JIISTY, ST. MARTIN'S IANE,

ISSN:0369-8718    

DOI:10.1039/PL8930900027

出版商:RSC    

年代:1893

数据来源: RSC