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Proceedings of the Chemical Society, Vol. 9, No. 121 |
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Proceedings of the Chemical Society, London,
Volume 9,
Issue 121,
1893,
Page 51-72
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摘要:
Issued 15/3/1893. PROCEEDINGS OF THE C HOE M I C A L S 0 C I E TY. No. 121. Session 189 2-93. March 2nd, 1893. Dr. J. H. Gladstone, F.R.S., Vice-president, in the Chair. Messrs. T. I(. Rose, K. I(.Hacker and C. M. Luxmoore were formally‘admitted Fellows oE the Society. It WRS announced that the following additions to the bye-laws proposed by the Council would be presented for consideration at the corning General Meeting :-1.-In Bye-Law XI, afber the words “The ordinary Scientific Meetings of the Society shall be held twice in every month, from November to June inclusive, except in the month of January, when the Society shall meet once only,” to add the words “and also at Easter, when, if the Council see fit, there shall also be only one meeting in the month.” %--In Bye-Law XIII, to add the following paragraph :-“At all General Meetings of the Society, whether annual or extraordinary, no motion of a proposal to alter the bye-laws shall be considered of which due notice has not been given, at least 14 days previously, either at an ordinary Scientific Meeting, or through the agency of the “ Proceedings,’’ or by means of a printed notice addressed to all the resident Fellows.” Attention was directed to the following resolutions passed at n meeting held on March lst, 1893, at the Royal Agricultural Society’s rooms, H.R.H.the Prince of. Wales, K.G., in the chair :-“ That, having regard to the great national importance of the series of experiments which have been carried on at, Rothamsted during the last 50 years, it is desirable that some public recogni- tion should be ma3e of the invaluable services tAus rendered to agriculture by Sir John Lavres, and also by Ih.Gilbert, who has been associated with the experiments during the wholc period, "That, with this object, subscriptions, to be limited to two guineas, be invited from all interested in agriculture, whether scientific or practical. "That, in the opinion of this meet,ing, the testimonial might advantageously take the form of (1) a granite memorial, with a, suitable inscription, to be erected at the head of the field where the experiments have taken place ; (2) addresses to Sir John Lnwes and Dr. Gilbert, accompanied (if funds permit) by a commemorative piece of plate." Ordinary certificates were read for the first time in favour of Messrs John Charles Burnham, 179, Griffin Road, Plumpstead ; James Cameron, Nobel's Explosive Go., Polmont Station, A.B.; Henry Williamson Uixon, 2 ;8, Hunslet Road, Leeds ; Thomas Edwards, Brewery House, Rhymney ; Hedley Gordon Jones, 15, Rectory Place, Woolwich. Of the following papers those marked * were read :-"121. "The magnetic rotation and refractive power of ethylene oxide." By W. H. Perkin, Ph.D., F.R.S. Thc following values are recorded in the paper :-a 4*/4= = 0.8909; d 70140 = 0.~8654; CE ,0170 = 0.88~7; d 10°/lOo= G.8824. Molecular magnetic rotation at 8" = 1.935. Molecular refraction at 7", A = 17.680. Dispersion, G -A = 0.5494.It is pointed out that the magnetic rotation is most remarkably low, and the refractive power also below the calculated value (A =18). "152. "The origin of colour (including fluorescence\. VII. The phthd-eins and fluoresceins.'' By Henry E. Armstrong. Jn the first of these communications on the origin of colour (these Proceedings, 1888, No. 4,p. 27), exception was taken to the fotmulm assigned to phenolphthalein and its congeners. Although the ex- bibition of colour by these substances could not be accouuted for by the formulae ascribed to them. the data then available were insufficient to permit of more satisfactory formulte being devised. The! subse- qumt discovery of the rhodaniines streiigthened this conviction, and The inteiitioti to make these the subject of experimental study a3 soon as an opportunity occui~ed has long been kept in mind ; fortuiiatelg tliis is 110 longer necessary, the technical value of these subshnctls having led to their fui-ther investigation in various works laboratories, with tlle result that they liave been shown, as was anticipated, to exhibit properties proving that they also are quinonoid compoands. The C'henviker Zeitung.No. 104, December 28, 1892, contains an account of a communicntiun made ta the Heidelberg Chemical Society on Dccember 16, by Professor Brrnthsen, who poiuts out that tlie 1.1iod;tmines afford true ethereal salts when subjected to the coil- joint action of alcohol and clilorliydric acid : in other words, tliat they a,ffurd cai.boxy-compoi~nds and not lactone derivatives.After tlii-eoting attention to otlier evidence in favour of the view that the colours of tliis class are members of the triphenjlnietliane group, lie points out, in so many WOY~E,that the characteristic development of colour on adding alkali to ~iiieiiolplit,h;llein is, in all probability, clue to tlie fact that the colourless lactone phenolphthidein is thereby hydrolysed and converted into a yiiinolic cnmpouiid, which sutfers dehjdrat ion, affording a coloured quinonoid compound : C6H4{ 'O>O r COzH C-(C,H,*OH), 4-Hzo = CsH41C(OH)(C,H,*OH), In a more recent paper (Berichte, 1893, 172), Friedlander-who does not appear to be aware of Bernthsen's communication-has st'ated that pbenolphthaleiu and hydroxylamine readily interact in an alkaline solution and form a hydroxime ; this and other evidence he iiientions leads him to express the opinion that in their coloured state phenolphthalein and the allied phthaleins which behave similarly in presenct? of alkali are all puisionoid compounds.ButJ, as EO frequently happens at the present day, the patent lit~ra- ture contains statements which anticipate the views of Bernthsen and Friedlander, eg., a description being given of the forruation of ethereal salts of rhodaulines by the action of alcohol and chlorhydric acid in the French patent specification No. 224603, of tlie " Farbenfabriken vorrrials Friedr. Bayer uiid Go." (Elbei feld), dated September 28, 1892. It is pointod out in this specification that the rlodnminr~s are to be regarded as carboxylic compounds, and the absence froin the ethereal salts of the propetty which the rhodamines exhibit of forming salts and lakes is referred to as confirmatory of this view.54 Friedlander is led to regard the fluoresceiris as perhaps different from the phthaleins, as he was unable to obtain hydroximes from them, and speaks of their colour as conditioned by their xanthone- like structure. There appears to be no reason, however, why a dis-tinction should be drawn between the intensely fluorescent rhod- amiries and tbe analogous oxygenated compounds-the fluoi~esceiris. Even regarding them as xanthone derivatives, the appearance of colour in fhese latter is, it can scarcely be doubted, consequent; on the occurrence of isodynarnic change (cf, these Proceedings, 1892, 103).0 Colourless. Coloured. The problem, therefore, remains practically the same ; nevertheless, there call be little doubt that the phthalein-flnorescein group still offers ii~terest~ingmatter requiring further study. Perhaps the point of chief interest claiming attention is the extra- ordinary ease with which the hydroljsis of the lactone is effected in the case of phenolphthalein, as evidenced by the fact that it is among thc most sensitive of the known indicators of alkali : in con- templating the changes which niay attend the dissolution of sub-htltrices by water., such facts are undoubtedly of high importance. Perhaps the change is less a consequence of the inst(abi1ity of the lactone ring, and is mainly couditioned by the hydroxyl present in the para-position relatively to the carbon atoni to which tlie phenolic 3 adicles are aktached-it is conceivable that a hydrated metallic derivative of the phenol is initially produced, aiid that the metal and water necessary to effect the hydrolytic change are thus brought into the inti*ainolecular sphere of interaction. From this point of view, it would be interesting to determilie the degrees of readiness with which pht,halid and its various derivatives undergo hydrolysis.It is also worth noticiiig that8, according to Bernthsen, the anhydrous ihodamine base forms a colourless solution in benzene and may be obtained in large, colourless crystals, while its solution in water is coloured and it forms an int'ensely coloured pentaliydrate.The recognition of the quiiionoid character of such eminently fluorescent substances as the fluoresceins and rhodamines may be claimed as a most important argumcrit on behalf of the view that fliioresceuce is a foim of colour : indeed that-taken in coqjuiiction with bthr facts-it goes Far towards justifyiiig the contention that all quinonoid derivatives would be visibly fluorescent, were it not that, as in the case of certain quinine saits, 8s Hartley has pointled out, the rays which are the cause of the fluorescence sometimes become absorbed in the solution. “123. “The origin of colour. VIII. The limitation of colour to truly J quinonoid compounds.Change of solour as indicative of change of structure, as in the case of alizarin.” By Henry E. Armstrong. A quinonoid componnd may be defined as a hexuphene, i.s., an un- saturated cycloid composed o€ six “elements ” (cf. these Proceedings, 1892, 129), two “elements” of which are CCR” groups in either para-or ortho-positions. Colonred substances generally appear to fall within tlhisdefinition, as there do not appear to be any established cases of the existence of colourecl substances-(a) containing a single CGR” group, or (b) in which two such groups are present in a cgclane or saturated ring, or (c) in which the cycloid coutaiiis any other number of elements than six. The succinosuccinic derivatives, &c., are but apparent excep- t.ons to b, as those which are coloured may be regarded as isodynamic forms of t>he saturated compounds.Diacetgl and dibenzoyl (bead) may be mentioned as exceptions to the general definition, but for this very reason it appears likely that they will eventually be obtained colourless; if is easy to account for the appearance of colpur in diacetyl, as it undergoes condensation with extreme facility, yielding dimethylquinorie (paraxj loquinone), an intensely yellow siubstance. Such a change is riot likely to occur in tlhe case of benzil, but this compound is so faintly yellow that the colour may well be due to impurity. Some of the keto-chlorides described by Zincke appear to be ex-Cl2 A/\() ceptions to a, “g., the compound I I ,prepared by chlorinating I \/ \/betanaphthol, the colour of which is a yellow of considerable inten- sity, and there is no reason to suppose that this is not characteristic of the pure compound.It is not improbable, however, that the gronp CCI, in this and similar substances may be the true equivalent of a CCR” group. In an article on “ The determination of the consti- tution of carbon compounds from thermochemical data,” published in the PhiE. Mug., in February, 1887, summarising and briefly dis- cussing the results described in the fourth volume o€ J. Thornsen’s ITAermuchemische Untersuchtingen, it, was suggested that the greater. demlopment of htat which attends the formation of sgmmetric.tl dichloro-derivatives may be due to the partial neutralisation of the (residual) affinity of the one chlorine atom by the other: in other words.that chlorine atoms are possessed of the power of directly entrrinp into aqsocintion while combined with another atom ; in which case 2C1 would be the equivalent of El’. As the presence of two ortho-or para-carbonyl groups in a saturated ring apparently does not condition colour, it would seem that the two CGR” gronps are concerned together with the “ethenoid linkages ” in tho unsaturated ring in the production of colour ; hence, the fact that compounds such as the naphthaquinones and the ketochloride before referred to are coloured is of importance, as evidence that perhaps a single ethenoid linkage in the ring is sufficient, and that it is not necessary that there shodd be two sucli, symmetrically situated with reference to the two CGR“ groups as in the benzoquinones; this, however, is on the assumption that the naphthayuinones are derivatives of centric and not of ethe~oidbenzene, hence the perhaps ; the importance of this consideration will be more clearly realised after reference to the arguments made use of in the two following notes :-0 0 Centric ” p-naphthaquinone. ‘‘Etlienoid ” P-naphthaquinone.Anthraquinone-whicli, it may be remarked, has scarcely any OE the properties of a true quinonc-may be referred to in this con-nection : if reprenanted as it derivative of centric benzene, thus, /\PO\A1 c 1 1 c I, the median group would appear to be saturated; yet, as anthrayuinone may be regarded as formed by the superposition of benzene and quinone, it would seem that the median group is 8till possessed of quinonoid characteristics ; unless it be that the effect of the two CO groups is supplemented by that of the two symmetrically placed centric cycloids.It would seem appropriate to here direct wttention to the colour of aliznrin in comparison with that of anthraquinone. The colour of paraqninones and their derivatives, in all cases in which the struct,ure appears to be in no way open to question, is uniformly yellow ; and red is characteristeristic of orthoquinoiies. How comes it then that alizarin is red ? The conventional formula is not in accord with this 57 fact, but the colour may be accounted for by regarding alizarin as an isodynamic form of dihydroxyanthraquinone, e.g., II On this assumption there is no difficulty in understanding why tho monhyclroxyanthrnquinones are of no use as dye-stuffs ; and why the int,roduction of two contiguous hydroxyls into anthraquinone is of such importance ; furthermore, it is to be expected that a monethoxy- derivative prepared from alizarin if it contained an a-ethoxy-group would resemble anthraquinone while one containing a p-ethoxy-group would more nearly resemble alizarin in colour : and, as a matter of fact, two such compounds have been described, one of which is yellow and the other red.In like manner, it may be suggested as probable that the chlor-anilates are not ‘derivatives of pnraquinone, and that their formation involves the occurrence of isodynainic change, thus :-0 0 The arguments advanced in proof of their paraquinonoid nature do not appear to be in any way conclusive.Lastly, reference may be made to the phcnoquinones and puinhydrones: it is diEcult to re-gard these as being other than members of that ill-understood and vaguely-defined class of substances termed molecular compounds. If so, the changes in the colour of quinones involved in their formation may arise from the weighting of the CCR“ groups by the attachment thereto of the phenol. “124,“ Note on optical properties as indicative of structure.” ByHenry E. Armstrong. In his “Notes on some recent determinations of molecular refraction and dispersion,” recently communicated to the Physical Society (Phil.May., 1893, 203), Dr.Gladstone directs atttention to a number of curiously suggestive observations of special interest in connection with the all-fascinating enquiry into the correlations of properties and structure. The metallic carbonyls to which he refers, in respect of physical propcrties as in many other respects, are compounds oE extraordinary interest. The conclusion which both Mond and Gladstone favour that they are cycloids is undoubtedly that most in harmony with their general behzviour, affording as it does an explanation of the complete masking of the metal, com- parable, for example, with. that which snlphur suffers in thiophen.The excessive refractive and dispersive power which the metallic carbonyls exhibit is probably, as Gladstone suggests, to be sought in the peculiar arrangement of the carbonyls; one object of this note is to call attention to the evidence which the optical data ap- parently afford of their cooperative action. The ketonic compounds hitherto studied from which the value GO =8.4 has been derived have been cornpounds containing single or isolated carbonyls, whereas-if reprevented as cpcloids-the metallic carbonyls contain two " ortho-systems," thus- Ni Fe \/co In this sense, they are in fact diorthoquinonoid and are comparable with coloured substances, but they are not truly quinonoid, the cycloid being saturated, and hence should not be coloured.(The nickel compound is colourless, but the iron compound is described as yellow ;the instability of the latter, however, is such that this colour may be due to impurity.) There are only two orthoquinonoid systems, although there are five carbonyls in iron pentacarboiiyl, so that one of the cnrhonyls should have the ordinary value and only four the value they apparently exhibit in nickel tetrncarbonyl (11.9) : con-sequently the molecular refraction should be 4CO (ortboquinonoid) = 4. 11.9 = 47.6 CO (ketonic) = 8.4 We" = 11.6 b7.6 a value not far removed from that found, viz., 67.4. If this argument be a sound one, it is to be anticipated that quin- onoid compounds generally will be found to possesses specially high refractive powers ; and there is some evidence that this is the case : thus among the compounds examined by Gladstone (C.S.Journ., 1870, 101-147 ; Trans., 1884, 241) anthracene--s hydrocarbon which, as more than once pointed out, is probably quinonoid in struc ture---is credited with B very high value, considerably above that calculated even if the value 6.1 be assigned to carbon. Giad-stone has also stated that p-nitraniline has an abriormally high refractive power. I learn from Professor Mills that the compounds referred to as a-and 8-nitraniline which he gave to Gladstone were the meta- and para-derivatives ;apparently, therefore, this result is in accord with the view previously advocated (these Proceedings, 1892, 101) that paranitraniline and similar coZoured nitro-compounds are in reality quinonoid. nr.Gladstone states, however, that both sub- stances were examined in weak solutions, and, therefore, less than the usual confidence can be felt in the accuracy of the data. Liveing and Dewar’s determination of the molecular refraction of nitrous oxide in the liquid state is also referred to by Gladstone, who points out that the value observed (11.418) favours the view that the nitrogen in nitrous oxide has the low value which this element exhibits in nitriles, viz., 4.1. The determination of the structure of nitrous oxide is of special importance, as it; is one of a group of com-pounds, including trimetbylene, ethylene oxide and diazoimide, all of which it is the fashion at the moment to formulate as cyc1oids:- CH2 0 NH /\ /\ ’‘7HZC-C H2, H2C-C H,, Pu’rN.But, apparently, thew is no valid evidence to justify the practice, and it is in no way necessary to adopt such a course. Unfortunately we are without knowledge of the optical properties of trimethylene, but we have J. Thornsen’s remarkable observation that its heat of combustion exceeds that of the isomeric propjlene by 6690 units. I have on several occasions discussed the properties of this hydro- carbon and have pointed out how its unique behaviour with bromine and bromhydric acid may be explained by electrolytic considerations (cf. Morley and Muir’s Watts’ Dictionary of Chemistyy, 3, Art. “Isomerism.”) Granting the accuracy of Thornsen’s figures, there appears to be no way of avoiding the conc!usion that it is an open cbain hydroca,rbon, and, thei-efore, that free affinities may exist at the end of a chain; its dissimilar behaviour towards bromine and bromhydric acid precludes the application of von Baeyer’s explanation of the instability of a ring of three atoms, as such a ring should prove unstable to bromine as well as to bromhydric acid, the former being in all other cases the more active agent in attacking hydrocarbons.Ethylene oxide, in li~emanner, has an abnormally low heat of formation ; in fact, on this account, J. Thomsen has gone so far as to represent it by the forniula CH2.0.CH2,an expression offending against all recognised canons. If, however, trimethylene be writt.cn CH,*CH,*CHr, ethylene oxide may be writ ten CH,*CH,.O.Ferkin’s results, referred to in a previous note (ante, p. 52), show that it is abnormal in it.s optical behaviour; they are most significant as affording evidence-assuming an open chain formula-that the optical effect of free aEnities is below the normal, and it may be anticipated that trimethylene will afford low values. It is worth noting that carbonic oxide, in which we believe that certain of the affinities of the carbon atom, if not free, are “ self engaged,” has a molecular refrac- tion (7.5) considerably below the value of CO in ketonic compounds : it would seem that the ordinarily accepted refraction eqnivalents are not to be regarded as measures of the effect of the “affinities ” proper, but of the affinities engaged between atoms.Passing now to the nitriles and nitrous oxide, we have the most in-definite ideas as to the former; they we conventionally represented as compounds of triad nitrogen, but this practice is but the outcome of formal obedience to certain artificial and dogmatic rules of valency, and has no real justification. As we must admit the existcnce of latent afltinities in carbonic oxide-which may be written <CO--we may also admit the possibility of their existence in nitrogen, and may v n represent the nitriles as compounds of the form I . Nitrous<C--N> oxide, on .this assumption, would be <N-0-N>. Diazoimide might, in like manner, be regarded as <N-NH-N>, a formula which is implied in Mendeleef’s a,ssumption that it is a dinitrile.No diazoimide derivatives have hitherto been examined : Dr. Perkin had the kindness to determine the refractive power of the phenyl deriva- tive, of which a quantity was placed at my disposal by Professor Tilden : t,he results are as follows :-d ioopoo 1.0980 ;d i5°/i~o 1.09318 ; a 25~125”1.08527. t. w. 98-1 Ct- 1c -lP.d A. ...... 11.7 1.54719 0.49943 60.431 c ....... ,, 1.53407 0.50571 61.191 D . . . .... ,, 1.560t33 0.51170 61.916 F ... . . . . ,, 1.57i93 0.52749 63.126 Deducting from the value of aniline, 52.09, tho value of two hydro- gen atoms, 2 6, and adding twice the highest value of nitrogen, 2 .5.1, the theoretical value is ‘A = 59.89, which is lower by 0.54than that found ; so that diazophenimide has proportionally a somewhat higher molecular refraction than even aniline.These results do not indicate that diazophenimide is a dinitrile ; neither is it possible to deduce from them any special argument in favour of the formnla Ph*N<#: the problem, in fact, remains iiiis 01ved . Consideration of the facts makes it appear probable that a solntion of tfhe diEculty may be fonnd, and not only so, but that it may be possible ere long to carry on the enquiry into the interrelationship of structure and physical propertied on more fruitful lines than has of late been possible. In the case of parreffinoid componnds generally, both carbon and hvdrogen seem to have R fixed opticaJ value, and it may bs supposed also that this is true of hydrogen in all case$ ;seemingly also, ethenoid carbon-carbon as it is in ethylene, whatever may be the mode in which the atoms are united-has a constant value.The variations which are noticed in paraffinoid and ehhenoid derivatives mixst on these assumptions be ascribed to variations in the radicles displacing hydrogen ; and it shoiild be easy therefore, by studying a considerable number of pyoperly chosen compounds, to determine which radicles are, and which are not, subject to variation and the circumstances which condition variation. In the case of benzenoid componnds, there is no evidence of con-stancy. Even in the case of the hydrocarbons, the value of the C, group rises from C = 6 (very nearly) in benzene to C = 6.15 in mesitylene, the only apptrent alteration made consisting in intro- ducing methyl in place of hydrogen.As all the evidence derived from the study of paraffinoids seemingly shows that CH, has an invariable value, it is only logical to suppose that the variation arises in the cycloid ; in other words, tbat whereas the ethenoid C, system apparently has an invariable optical effect, the beiizenoid C6system hhs a variable optical effect. There is nothing surprising in this con- conclusion-it is in absolute accordance with the experience derived from the study of the chemical behaviour of the benzenoid com- pounds. The variation, in many cases, is very considerable : that of aniline, for example, which has a molecular refractive power A = 52.09.Assuming NH2to be 5.1 + 2. 1.3 = 7.7, and deducting the value of 5H = 6.5, the value of C, in aniline is 52-09 -7.7 -6.5 = 37.89, and C = 6.31. There is no reason why the value should not be still bigher in diazophenimide : to determine the value of the NS, either N,H or one of its pamffinyl derivatives shonld be examined. The chemical properties of diazophenimide are such-its nitro-deriva-tives are hydrolysed with such facility-as entirely to justify the assumption that the N,has a very special influelice on the properties of the cycloid. The strongest confirmation of the view here put forward is afforded 62 by dipheiiyl, in which each carbon npparently has the value 6-39: the two radicles of which this hjdrocarbon is composed being alike, and being both benzene residues and directly conjoined-putting the hydrogen aside-there can be no pestion that the variation is due to the variation in the optical effect of the C6group.If it can thus be shown either that the ethenoid group has an in- variable effect whatever number OF such groups may be present in the compound or that its effect is invariable except in certain cases in which a co-operative effect is traceable, and the benzenoid group be proved to have a variable optical effect, the most absolute denronstra- tioii will have been secured of the existence in benzenoid compounds of R peculiar structure such as is foreshadowed in the centric formula first proposed by me in February, 1887.The following may be referred to as illustrative of the problems requiring consideration. Among haloid compounds, methylene iodide is altogether peculiar, its refraction equivalent (58.22) being much above the calculated value (52.1); this may be a case of co-operative action. The high dispersive power of carbon bisulphide is perhaps to be accounted for in some such manner. In iodoform, an eminently remarkable substance on account of its colour and other exceptional properties, the third iodine atom appears to exert an influence comparable with that of an ethenoid group in quinone and to determine the appearance of colour. In this case the effect is seemingly produced within the sphere of afflnity aroiiud the carbon atom, much as in the case of quinonoid compounds it, is produced within the cycloid sphere of affinity.Bromopicrin, if the value found hy Gladstone be correct, appears to be an example involving a negative influence, a cause which, perhaps, also prevails in the case of acetylenic compounds, the abnormally low refractive power of which is highly remarkable. The aldehydes offer many peculiarities. It is to be remembered that Thomsen has represented aldehyde as CH,*C(OH) ; the oxygen in such a compound would have a lower value than in ketones, but the one atom of carbon, being in the carbonic oxide or dyad state, would probably have a lower value than 5: so that, by assigning the full value to both carbon atoms and the ketonic value to oxygen, the equivalent would be over-estimated.But no indica-tion tthat such is the case is actually afforded by aldehyde. T’he refraction equivalent of benzaldehyde is about two, and that of salicylic aldehyde about three, units above the calculated value ; this may be due to an increase in the cjcloid value, but it is conceivable that the cycloid and the ketonic groups in some way co-operate ; and it, is even possible to represent salicylic aldebyde as a qiiinonoid com- pound. It is noteworthy that both these aldehydes are very active substances, and prone to yield condensation products. Cinnamic 63 aldehyde is one of the most refractive and dispersive of known sub- stances, and its refraction equivalent (75.3) is much above the cal- culated value, 6.3.4.It may be represented as C,H,*CHZCH-CCOH, or even as CsH,-CHCCCCH*OH,and it would seem probable that the high refractive power is conditioned by co-operative influence of the contignotis cycloid and ethenoid groups.From this point of view, it is important to examine allene, CH,CCCCH,. Stilbene, C,H,*CHZCK*C,H,, is another equally striking instance, its refrac-tion equivalent (113.39) being also very much higher than the cal- culated value (101). The arguments here made use of in correlating optical properties and structure are undoubtedly applicable to the discussion of other physical properties, and, as some of these are apparently the measure OE intra- and others of extra-molecular effects, it is all important that a careful comparison should be made with the object of elucidating reciprocal relationships.In conclusion, attention may be directed to the aiaonialous colour dispersion displayed by rosaniline and other colouring matters. In these compounds the two CCR” groups are of totally distiwt tjpes, md apparently the effect has not been noticed in the case of com-pounds in which the-quinonoid groups are alike or similar. Biot has shown that the phenomena of anomalous ~otato~ydispersion exhibited by tartaric acid solutions are-simulated by a mixture of two optically active mutually indifferent substances having different rotatory dis- persive powers; it seems not improbable that the two dissimilar qninonoid groups which condition colour in rosaniline a.nd substaiices which behave .like it condition anomalous colour dispersion in con-sequence of their dissimilarity.125. “The origin of colour. IX. Note on the appearance of colour in auinoline derivatives and of fluorescence in quinine.” By HenryE. Armstrong. The arguments put forward in the previous note have far-reaching consequences. The increase in refractive power observed on corn-pariug the homologues of benzene with benzene might be ascribed to a passage from the centric to the ethenoid form-assuming the former to have a slightly lower optical value than the latter; and such a view would be in accordance with the observed change in chemical behaviour, bnt it would not account for the change in the case of aniline and other compounds, as the optical vaiue of carbon in these rises above that which is seemingly characteristic of the ethenoid form.That the change takes place in some cases, there can be little doubt, especially when von Baeyer’s researches are taken into account. The object of the present note is to point out that its occurrence would account for the appearance of fluorescence and colour in quinoline derivatives which lins been discussed in a previous note (thew Proceedings, 1892, 143). Assuming quinoline to be a centric cycloid and that the introduction of NH, has a. very marked effect, as in the case of aniline, it is posjible that tlie compound may t,hert.l)y be caused to acquire an ethenoid structure; but such an ethenoid cornpoutid would be quinonoid, as may be seen on reference to the formula N NH.i/v) ; in other words, any amido-derivati\*oof quinoline might \\ A,be quinonoid, and therefore coloured, probably eith r orange or red.Xti like manner, an ethenoid form of naphthalene would be quinonoid ; it is, therefore, possible that the fluowscence exhibited by many naph tho1 and naph thylaniine derivatives is characteristic of the piire substances, and does not always originate in impurities. If t,he argument here used be justified, the non-appearance of colour and fluorescence in naphthalene derivatives will afford evidence of a ceutric structure similar in character to that which the peculiar optical behnviour of benzerioid compounds affords of a special struc- ture different from the ehhenoid form in benzene.DISCUSSIOX. The CHAIRMAN(Dr. Gladstone) said that, he would like to consider the snggestive remarks of Profewor Srmstrong on m deoular refrac- tion more carefully before committing himself to R definite opinion ; the idea of a “co-opmafive iiifluence,” such as had been put forward, was, he thought, worthy of all attention. It had long struck him as an unexplained phenomenon, that while in the aromatic substances in general 6.1 is indicated as the atomic refraction of each of the double-linked carbons, the value was very appreciably lower in benzene itself and in toluene ; and that when the compound becomes very complex, the value becomes larger than 6.1. Thus aniline is certainly more refractjive than would be anticipated from the mual run of benzene componnds and compound slmmonias.Carbon in such compounds as naphthalene or pbenanthrene has a much higher refractive power, to which he had, sotlie yews ago, prc‘visioiially assigned the value of 8.8. It had been remarked that the ethjleiie bonds in open-chain compounds ought to retard light different iy from the double bonds in the aromatic series. This was not to be easily recognised in the refraction of A, but it was, undoubtedly, the case in the dispersion. Such considerations must have much weight in t’ie discussion of the structure of caibbon compouuds exhihitin special properties. 65 Dr. PEREINsaid, in iderence to Dr. Armstrong's remarks on tbe very high values obtained for the refractive power of the carbonyl compounds of nickel and iron, it must be remembered that these compounds were examined in the pure condition, whereas all other determinations of the refractive power of nickel and iron were made with dissolved salts and do not necessarily give tne values for these metals.In the case of zinc componnds, he had found that the value of this metal in zinc ethyl was 15.9, whereas solutions of zinc salts gave only 9.8. Therefore itnwas not safe to infer that in the csi*bonyl compounds nickel and iyon had the value; they appavently possessed in salts. 'I'hrough the kindness of Mi.. Mond, he had had the oppor- tunity of measuring the magnetic rotation of the nickel and iron carbonyl compounds, and had found that they gave very high rota- tions ; but at present no other compounds of these metals had been examined. As to the values given for the refraction of carbon and hydrogen being perfectly constant, even iu saturated compoiinds this appears to be doubtful.Taking the case of ethyleiie oxide, they must be somewhat lower than usually given, and, in some of the amines, they appear to be higher; this is seen on comparing primary and tertisry amines, the refraction, but more especially the dispersion, increasing as we pass from the former to the latter. In the aromatic series this is very evident. Aniline itself has an abnormally high value, but, a8 inethjl is introduced into this compound, the refract'ion increases with each methyl introduced much more than the change of composition requires, the incpease for the first methyl being 8.36, and the change of dispersion no less than 1-37,and that for the second methyl 8 51, and of dispersion 1-22; whereas the calculated difference in each case is 7.6 only, and for the dispersion 0.34.Corresponding resnlts me observed in reference to the magnetic rotation of all these com- pounds, though in a much more striking mannw. lh. Armstrong had also made reference to the refractive power of two nitrmilities ; that these should be high is only consistent with their being derivatives of aniline. As to whether the difference of position of the NO2 group would influence the refractive power of these substances in any marked degree, the data we have would be against such an assumption.Dr. Gladstone had measured several series of ortho-, meta- arid para-componnds at his request., and had found them to give nearly identical results. Mr. MONDdrew attention to the very different values deducible for nickel, the atomic refraction calculated from Kundt's observations with the metal being 6.12, while that calculated from the oxide is 9.82 (cf. Mond aud Nasini, 2;it.yhys. Chern., 8,150). Ethereal Salts of Glycwic Acid. Inactive. Ethereal salt. Density, 15'/15". Difference. Boiliog point. Methyl. ...................... 1 *28L4 0-0905 119-120" (14 nlm.). Ethyl ........................ 1.1903) 120-121" (14 mni.). Propyl (normal) ..............1 -145.31 0*O -1.56 126-127' (14 inm.). Isobuty1 ...................... 1-1024 128-139" (13 miii.). Active. _-c__-Observed Densihy, Differ-rotation in Specific Ethereal salt. 15'/15'. ence. 198 -4 mm. rotation, Boiling point, tube, a. "lib -------I-----_ -Methyl ............. 0-0877 -12 *2O -4'81" -5.76" -5-43O 120" (13 mm.) Ethyl .............. .2798 1 -21 -7 -9'18 -12 *30 -11-60 'lg21I 0-0473 -29 -4 -1'2.9,ii -19 -15 -18 *07Propyl (normal) ..... 1'1448 Ieopropyl ........... t':;:;} 0 -0293 -26.5 -11.82 -17-49 -16 -50 114-116" (13 mm.). Rutyl (noimal) ...... 0 *0232 -2A .4 -11*05 -17 '85 -16 '84 LYl-lii93 (14m.n.). Iso3ut.yl ............ 1a1052 ' -31 *2 -14*23 -23 *05 -21 *75 123-126'(13-5 urn.). Buutyl (sec0ndai.J).... 1-1052 -23.2 -10 '58 -17 '14 -16.17 67 "126. '' The ethereal salts of glyceric acid, active and inactive." By Percy Frankland, Ph.D., B.Sc., F.R.S,, and John MacGregor, M.A. The following table contahs the names of the glycerates, inactive and laevorotatory, wLich the authors have prepared, together with their densities, observed specific and molecular rotations, as well as the specific rotation of glyceric acid as deduced from the rotations cf the several salts. The method of preparation adopted for the methylic, ethylio, normal propylic and normal butylic glycerates consisted in heating 813 ceric. acid (either inactive or active) with an excess OF the part'icular alcoliol in a sealed tube at about 180" C., and then fractioning the resultirly products by distillation under greatly reduced pressn re.In the CRW of the secondary alcohols, this method yielded an unsatisfactory ye-sult, and consequently the isopropJlic and secondary but,ylic salts werch prepared by saturating a mixture of glyceric acid and the alcohol ill question with hydrogen chloride gas, and then fractioning under re-duced pressure. This method was also adopted in the case df isbbntylic glycerate, although this compound could also, doubtless, have been satisfactorily prepared by tlie staled tiibe method. It tvas foutid that the facility of etherification was much greater in the case of the primary than in that of the secondary alcoliols, whilst in the case of the tertiary butyl alcoliol (the only tertiary alcohol experimentc cl with) it was not found possible to obtain an ethereal salt.In preparing the isopropylic and secondary butjlic salts, a coilsideti-able quantity of a white substance was formed which was Found to be an anhydride of glyceric acid, whilst in the attempt to prepare tlie tertiary butylic salts, this anhydride a>ppeared to be the sole pi.oduc*t. The active ethylic glycerate was prepared by both the sealed tulw and hydrogen chlokide methods, and tlie resnlting products were found to have the same rotatory power, thus shaJwing that tlic activity is in 110 way impaired by the Ligh temperature (180' C.) crnplojeil in the sealed tube method. Attention is directed to the relationship between the moleculai~ rotations of the several gljceric cthereal salts experikented with.This rotation increases alniost quite regularly f~ommetliylic to ethylic, to normal propylic glycerate. Isopropylic glycei ate has a soinev h:ir lowe~rotation than the i~ormal propylic compound, but the isobutylic gljcerate lies much more nearly on the L' main liiie " of molecultli-rotatory increase than either the normal or secondary butjlic com- pounds, the rotations of which correspond closely with that of the isopropylic glycerate. It is pointed out that the addition of CH, io the alkyl group increases the molecular rotation by 6.54ia the case of methylic and ethplic, and of 6.85 iu the case of the ethylic and noimal propylie glycerates, wliilst the increase is only 5 56 it1 the case of the ispropylic and.isobutylic glycerates. These values fur CH, are very similar to those which can be deduced in the case of ethereal salts of tartaric acid, in which, also, the rotatory value of CH, is less in the case of the isothnn of the normal compouds. In reviewir,g the rotatory pcwer of these active glyceric ethereal salts in relation to the recently advanced theories of Gnye and of Crum Brown, they are of opinion that, although in the first three terms of the scries, the iricrease in rotation follows the increase in the weighting of one of the groups attached to the asymmetric carbon atom, yet that by a consideration of the rattitory powers of the higher tepms, as well as by a comparison of the rotations of ethylic zlycerate and etliylic lactate (the only active lactic echereal salt hitherto prepared), it is obvious that the moleculgr rotation is affected by the qualitative nature of the groups as well as by the relative mapitude of their masses.127. " Formation of the ketone 2 : 6-dimethyl-1-ketohexaphinefrom di -methylpimelic acid." By F. Stanley Kipping, Ph.D., DSc. In a recent paper by the anthor and Mackcnzie (C.S. Y'ruris., 1891, SSO), it was stated that " when dimethyl pitnelic acid is heated with phosphoric anhylride at. a moderately high temperature, it yields an oil, having a strong turpentine-like odonr; this reastion will be further investigated by one of us." Although, on continuing thn experiments, only a Fery small quan-tity of the oil was obtained in the manner indicated, owing to the formation of resinon3 products, the investigation was not relinqnished as it seemed probable that the product would prove to be a, dimethyl-ketohexamethylene (2 :6-dimethyl-l-ketohexaphane,qf.these Pro-ceedings, 1892) CH2<CH,.CHYeCHz'c*Me> CO, the formation of which in tbis way wonld be of considerable interest, not only on account of the iinture of the product, but also at^ showing that dicarboxylic acids are capable of undergoing a change sitnilar to that already studied in the case of the fatty acids (Trans., 1890, 532,980). Ultimately, by distilling the calcium salt of dimetliylpimelic acid with ~odalime under rcduced pressure, an oil was obtained which, after agitation with soda solution, was distilled, and t,he portion boiling at about 180" collected separately ; this fraction contained a ketone of the composition C,,H,,O (bund, C = 76.5, H = 11.1 per cent.; cal-culated, C = 76 2, H = 11l per cent.), capable of interacting with hydroxylnmine, f ormiiig a kyhoxirne of the c3mposibiora CeH,,:N OH, crystiillising from light petroleum in colonrless prisms melting at ahoiit 112'; the hydroxime had an odour wry similar to that of cam ph or h 1dmxim e . 69 The ketone is, in all probability, a dimethylketohexamethylene : it has a peppermint-like odour, which'seems to be characteristic of the cyclic ketones of this class, ketopentamethylene (Wislicenus and Hentschel), methylketopentamethylene (Semmler, (Ber., 25, 3517) and suberone, which is probably a methylketohexamethylene (com- pare Kipping and Perkin, Trans., 1891, 217), being all described as having this particular odour.The publication of this note at present time seems to be desirable in view of the fact that in the last number of the Berichte (p. 231) von Baeyer has described a ketone, obtained by the distillation of calcium pimelate with soda lime, which is doubtkss a homologue of the compound prepared by the author. The investigation is being continued. 128. ''Note on the interactions of alkali-metal haloids and lead haloids and of alkali-metal haloids and bismuth haloids." By Eleanor Field, Assist ant-Demonstrator in Chemistry, Newnham College, Cambridge I By boiling potassium or ammonium iodide with lead iodide, chlor- ide, bromide or fluoride and water in the ratio of 30 parts of the former to 1part of the lead compound to 75 parts of water, pale yellow, needle-like crystals were obtained, having the composition SPbI,*$KI or 3PbI,*4NH41.By boiling potassium or ammonium chloride, or bromide, with lead iodide and water in the ratio of 6 parts of the former to 1 part of the lead compound to 50 parts of water, lead iodochloride, PbICl, was obtained. By boiling potassium or ammonium iodide with lead chloride and water, in the ratio of 1 part alkali of the former to 5 parts lead chloride to 250 parts water, iodochlorides of lead of the composition Pb12*3PbCla and Pb12.5PbC12 were obtained ; when lead bromide was used in place of lead iodide, the product was an iodobromide of lead, Pb12*2PbBr2.These results show that when a large excess of potassium or ammonium iodide is used, the whole of the lead haloid is transformed into iodide, if the lead compound was not iodide to start with, and that the lead iodide thus formed combines with the potassium or ammonium iodide to form a double salt ; but that if less alkali-metal haloid be used in proportion to the amount of lead haloid employed, the product contains the halogen of the two haloids, and it is free from alkali-metal. Thecomposition of the products of the interaction depends more on the relative quantities of the interacting haloids than 011 the nature of the metals and the halogens of the salts employed.Thc results obtained by the interactions of alkali-metal and bis- muth haloids differed from those obtained with lead haloids. The compound BiBrCl,K, was obtained by dissolving bismuth chloride in solution of potassium bromide used in the ratio BiC1, :KBr. The compound BiClBrdK, was obtained when bismuth bromide was dis- solved in solution of potassium chloride in the ratio BiBr, :KC1. But when bismuth chlorido and ammonium bromide interacted in the ratio BiC‘I, :NH4Br,the same substance was obtained as when bismuth bromide interacted with ammonium chloride in the ratio of equal numbers of molecules, viz., BiC13Br3(NH& This compound is similar to the SbC1,Br3.K3 obtained by Atkinson (C.S. Trans.,2883, p. 289) by the interaction of antimony and potassium haloids, either in the ratio SbC1, : 3KBr or in the ratio SbBr, : 3KC1. These results indicate that the composition of the products of change is dependent, not only on the relative masses of the inter- acting haloids, but also on the nature and relative affinities of the halogens and also of the metals of the interacting haloids.129. “An isomeric form of benzylphenylbenzylthiourea,” By AugustusE. Dixon, M.D. Phenylthiocarbimide and dibenzylamine interact, forming the compound C,H,N:C( SH)*N(C,H7)2, isomeric with the thiourea C,H7N:C( SH)*NCRH,*C7H7 (m. p. 103”), previously obtained by the author (Trans., 1891, 567) from benzylthiocarbimide and benzyl- aniline ; it crystallises in vitreous prisms, insoluble in water, rather sparingly soluble in ether and alcohol, and melting at 145-146” (uncorr.) ; it is converted by the action of alcoholic ammonia at 100-110” into phenylthiourea and dibenxylamine.130. “A new atomic diagram and periodic table of the elements.” By R. M, Deeley. After a reference to Lothar Meyer’s diagram of atomic volumes and Mendeleeff’s periodic table of the elements, a diagram is described in which the ordinates are “volume heats ” and “ volume atoms ” instead of atomic volumes ; a table of the elements is also given, in which the elements are arranged periodically, in accordance with their positions on the diagram. The volume heats are obtained by multiplying specific heat by re- lative density, and the volume atoms by dividing relative density by atomic weight.71 ADDITIONS TO THE LIBRARY. I. Donations. Gi-undziige der theoretischen Chemie, von L. Meyer. Z weite Auflage. Leipzig 18!33. From the Author. Carl Wilhelm Gcheele, Pharmacist and Chemist. A Brief Account of his Life and Work, 1742-1786. (Reprinted from the Pharma. centical Journal) London 1893. Frcm the Pharmaceutical Society. The Year-Book of Science, edited for 1892 by T. G. Bonne.7. London, Paris aid Melbourne 1893. From the Publishers. IT. By Purchase. Mikroskopisclie Physiographie der Mineralien und Gesteine, von H. Roiinhusch. Band I. Stuttgart 1892. Organische Reaktionen und Reagentien, von E. Seelig. Stuttgart 189.2. Guide pratique pour l'analgse quantitative, par C.Graebe. GenGve et Paris 1892. Berzelius und Liebig ; ihre Briefe von 1831-1845, hernusgegeben von J. CarriBre. Munchen und Leipzig 1892. Handbuch der physiologisch- und pathologisch-chemischen Analyse, von F. Hoppe-Seyler. Sechste Auflage neu bearbeitet von F. Hoppe-Seyler and H. Thierfelder. Berlin 1893. The First Principles of Chemisti-y, by W. Nicholson. Third edition. London 1796. Chemistry of the Organic Dye-stuffs, by R. Nietzki. Translated, wit'h additions, by A. Collin and W. Richardson. London 1892. Odorographia ; a Natural History of Raw Materials and Drngr used in the Perfume Industry, by J. C. Sawer. London 1892. Quantitative Chemical Analysis by Electrolysis, by A. Classen. Translated from the 2nd German Edition by W. H. Herrick.New York 1888. Manual of Bacteriology, by E. XI. Crookshank. Third Edition. Lo~don1890. HOFMANN MEMORIAL LECTURE. An extra meeting of the Society will be held on Friday, May 5th, 1833, the anniversary of the death of A. W. von Hofmann, when adblressm will be delivered by the Right Hon. Lord Playfair, K.C.R, >'.R.S,, V.P.C.S.; Sir F. A. Ahel, C.B., F.R.S., V.P.C.S.; Dr. TV. H. Perkiii, F.R.S., V.P.C.SI 72 At the next meeting, on Maxh 16tb, the follvwiiig papers will Le read :-“The limits of accuracy of gold-bullion assaj and the losses of gold incidental to it. The volatilisntion of gold.” By T. I(.Rose. “ The boiling point of nitrous oxide at atmospheric pressure and the melting point of solid nitrous oxide.” By Professor Ramsay.‘‘The isomerism of the paraffinoid aldoximes.” By Professor Dunstan and T. S. Dgmond. “The hydroxime of formic aldehycle.” By Professor Dunstan and Dr. Bossi. “The properties of a-benzaldoxime.” By Professor Dunstan am2 C. M. Luxmoore, B.Sc. Annual General Meeting,March 27th, at 8 p.m, UAERlSOPJ AND SONS, PBINTEHS Ih’ OPDIXARF TO HBP MAJEBTY, ST. YAETTH 8 LARF.
ISSN:0369-8718
DOI:10.1039/PL8930900051
出版商:RSC
年代:1893
数据来源: RSC
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