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Proceedings of the Chemical Society, Vol. 8, No. 112 |
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Proceedings of the Chemical Society, London,
Volume 8,
Issue 112,
1892,
Page 99-118
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摘要:
Issued 28/5/1892. PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 112. Session 1892-93. May 19th, '~892. Professor A. Crum Brown, F.R.S., President, in the Chair. Certificates were read for the first time in favour of Messrs. Arthur Edward Barrows, Bloomfield Iron Works, Tipton, Staffs ; Horiitio Ballantyne, 260, Rerifrew Street, Glasgow ; Thomas Cockerill, 105, Derby Sheet, Bolton ; John Evans, Trsas. R.S., Kash Mills, Heme1 Hempstead ; John Gibson, Ph.D., 15, Hsrtington Gardens, Edinburgh ; Henry Ramsden Redman, 10, The Gardens, East Dul- wich, S.E. The President announced that the Council at their meeting that af Iernoon had adopted the following resolution expressive of the loss the Society and chemists generally had suflered by the death on Nay 5 of Professor von Hofmann.The resolution would be com-mrinicated to the family of tbe deceased and to the German Chemical Society :-" The President and Council of the Chemical Society, at their first moeting since the death of their illustrious colleague Augustus William von Hofmnnn, desire to record their sense of his eminence and of the great scientific work he achieved both in England and in Germany. "Invited to Londonin 1845 to organise and superintend the Rojal College of Chemistry, he spent nearly twenty Sears in this country, and during that time made many brilliant discoveries, and trained a body of investigators who have followed his example in extending the bounds of the science and in applying chemical ?rinciples to the industrial arts." Many of t>h=Fellows of the Chemical Socicty were introduced by 100 him to the science, and look back with gratitude to his inspiriiig teaching. “Hofmann’s influence on science in this country still remains, though the country of his birth has, since 1865, received the imme- diate benefit of his persoual labours as an investigator, teacher, and organiser. “The President, and Council of the Chemical Society of London desire to exprcss to their colleagues of the German Chemical Society their profound sorrow at the death of the great chemist so closely corinected with both, and tlieir sympitthy with the sister Society in the loss of its distinguished President.” Of the following papers those marked were read :-*16. “ The magnetic rotation of compounds supposed to contain acetyl or of ketonic origin.” By W.H. Perkin, Ph.D., F.R.S. The author, nfher referring to the diverse view8 which are held as to the constitution of ethylic acetoacetate, draws attention to Brnhl’s determination of the refractive powers of’this substance, which favours a, ketonic constituhn, and to its magnetic I-otatiun, which was deter-mined several years ago by himself, and which also snpports this view; a list is then given of seven acetyl compounds of which he has ascertained the magnetic rotations, all giving numbers point- ing to a ketonic constitution. But as such compounds behave sometimes as ketonic and sometimes as hyilroxy-derivatives, it was thought desii-able to exaizlhe a larger number of compounds supposed to contain acetyl or of ketonic origin under different circumstances ; the following were selected :-F’yruvic acid ; levulinic acid, fused and in solution ; ethylic acetonedicai*boxylate ; ethjlic acetoacetate ; acetyl-acetone ; methylacetj lacetone ; ethjlic P-amidocrotonate. The last-mentioned four were examined at widely different temperatures. The rotation of the first five compounds gxve numbers correspond- ing to a ketonic constitution, though those obtuiiled with ethylic acetonedicarLoxylate were rather high, arid it is therefore proposed to re-examine this substance at higher teniperatuiw.The rotation of acetylacetone was found to be very high, showing it to be an unsakjurated or hydroxy-compound, wliilst the value obtained for methylncetylacetone stitlids between the hydroxy- and ketonic rotations.At teniperaturc s approaching that of boiiing water, it was found, however, that these compounds give much lower rotations than whtn cold : in the case of the former, the values fall between the hydroxy- and the ketonic rotations, and in the case of the latter, they neaily correspond to the ketonic rotation, showing 101 apparently that t,hey change into t,he more stable or ketonic form when heated. The refractive and dispersive powers of the same compounds, determined at different temperatures, confirmed the magnetic rotations. The magnetic rotatory power of ethglic P-amidocrotonate was found to be remarkably higb, as was its refractive and dispersive power, showing it to be an unsaturated compound ; the author pro-poses to continue the examination of sukstances of this class.DISCUSSION. Dr. COLLIEremarked that he had long held the view that ethjlic P-amidocrotonate was an imido-derivative, the correctness of which appeared to be demonstrated by Dr. Perkin’s measurements. Dr. PERKIN,answer to Dr. Morley, said that he had not yet in ascertained whether acetone was abnormally affected by heating. “17. “The origin of colour. 11. The constitution of coloured nitro-compounds.” By Henry E. Armstrong. In a communication to the Society in Narch, 1888 (Proceedings 1888, 27), iu which the relation between colour and constitution wns discussed, it was maintained thak in the case of azo-dyes, the rosanil- ines, methylene-blue, &c., colour was conditioned by a quinonoid structure.Although the general correctness of this view has never yet been nckiiowledged, a study of the literature relating to coloured compounds which has appeared in the interval clearly shows that it is more and more recommending itself; it should a1.o be nlentioned that Nietzki, in the introduction to his r)rgctr,ische Farhstofe (Berlin, lS89), makes reference to the quinonoid cllaracter of a, number of dye-stuffs, although he does not seek to apply such a view of their structura at all generally. The subject has continually occnpied my attention since I first brought it before the Society, and I think it is justifiable that I should now state the opinion at which I have arrived ; viz., that in the case of coloured compounds which have been fairly well studied, it is so generally true that a quinonoid formula is applicable, that the reconsideration of the formula of amy coloured substance is warrantable iE it do not come within the rulc.‘aThe term quirionoid” must, however, be understood to include coni-pounds of the type of benzil; and it is to be noted that in the case of closed chain compounds, it appears to be essential that at least one of tlhe quinonoid carbon atoms be associated with a dyad radicle, and that the ring itself be unsaturated: the presence of two ortho-or para-carbonyl groups in a saturated ring apparently does not ccndi- tion colour.102 Nitro-compounds have from an early period attracted my atten-tion, as they do not come within the suggested " colour-rule." It is well known, however, that nitro-compounds are not all coloured, many which are commonly described as yellow being obtained white when prepared from pure materials and precaution is taken to t~movethe phenolic compounds which are so frequently formed even fi*om hydrocarbons during nitration; from this it follows that the nitro-group does not per se condition colour. A comparison of ortho- with para-nitrophenol affords striking confirmation of the coixctness of this conclusion: the former alone is coloured, being intensely yellow, very volatile and insoluble in water ; whereas pmanitro-phenol does not, volatilise with steam, and is fairly soluble in water.To what is the difference ascribable ? It can scarcely be otherwise than to a difference in structure beyond that involved in a mere difference in the relative positions of the radicles. Dr. Kipping and I, in the course of an investigation of coloured nitro-conipounds in which we are engaged, have had occasion to compare the methoxy- nitrobenzenes prepared from ortho- and para-nitrophenol, and we find not only that they are both colourless, but that they agree as closely in their. general properties as do most isomeric compounds containing the same radicles ; it' is particularly noteworthy that they are about equally volatile with steam. The non-correspondence of the two nitrophenols is rendered far more striking by the correspondence of the conipounds prepared from them by methylation, and the conclu- sion is strengthened thereby that they are not mere position isomer- ides : it therefore appears justifiable to represent orthonitrophenol by a quinonoid formula, which may readily be done by transferring the hydroxylic hydrogen to the NO, group, thus ti*aasforming it into a dyad gronp, NO,H, a change which admittedly attends the fot niation of so-called nitrosophenol (quinonehydroxime) (cf. Nietzki, op.cit., p. 9). On this hypothesis, the name piGiizo1aeortjionitroxime may be sug-gested for "orthonitrophenol." Paranitrophenol, although itself colourless, yields coloured metal- lic derivatives, in the formation of which a change of structure must be involved, according to the view here advocated.As only para- and ort>ho-compounds can have quinonoid formula?, it would follow that metanitro-derivatives must be colourlcss ; but actually metanitraniline has an intense yellow colour. There are but two ways out of this difficulty : to assume that metanitraniline either is not (as ordinarily obtained) an uniform substance, or that its struc-ture is not really that of an amidollitrobenzene. There is, however, no obvious other mode of representing it ; and although Er. Killping and I have spent much time in trying to deprive it of its colour, we have been unsuccessful; we have found, however, that it jields a 103 practically colourless benzoate, R result which we regard as strong presumptive proof in favour of the view tha8t metanitraniline is not whet it is supposed to be, and me therefore propose to submit it and similar compounds to exhaustive study.If it be granted that in the case of ortho-and para-nitrophenol there may be a transference of hydrogen or metal to the NOz group, leading to the formation of nitroximes, it is conceivable that. a similar change may take piace in other cases ;for example, in the case of the primiiyy aitroparaffins, the properties of which are in many respects compatible with the view that they are nitrosimes. Moreover, the explanation woinld gain support which is afforded of the “ acid ” properties mani- fested by a compound such as benxyl cyanide, by regardiug it as, at least potentially, an imide, C,H,.CH:C:NH. A consist,ent explanation of the formation of metallic derivatives could be given, and it would be unnecessary to assume that “hydro-carbon ’’ hydrogen other than acctylenic is displaceable by metal, if the view here suggested were accepted. *18. “The origin of colour. 111. Colour as an evidence of iso-dynamic change : tbe existence of isodynamic acids.” By Henry K. Armstrong. The application of the colonr-rule dwelt on iri the foresoing note must lead not only to the modification of mail7 of the formulae attri- buted to colonred substances, but’ also to tile recognition OE equiva-lent or isodynamic forms (cf. Morley and Muir’s Watts’ Dictionavy of Chemi.str!y,3,Art. “Isomerism ”) of a verie ty of compounds, as I have already partialIy indicated.Thus it appears to me to be impossible any longer to regard the caloured substances known as paradihydr-oxyterephthalic acid, dihydroxypyromellithic acid and the corre-sponding “diamido-” acids (cf. Nef, Annalen, 237,38) as constituted in the manner suggested by these names, and there is no difficulty in representing them as quinonoid compounds, thereby accounting for their being coloured, thus :-In principle this idea is not novel (cf. Hantzsch and Herrmann, Ber., 1887, 2800); indeed, it has already been rejected (Iheyer, 104 A,nnalen, 245, 189; Nef, iCid., 258, 26l), hut on grounds which T regard as altogether insufficient, holding, as I do, the opinion that the character of such substances is scarcely to be detcrniiried by purely chemical methods, owing to the readiness with which a change in type sets in.This is well illustrated in the case of the ethylic salts of "diamido-" terephthalic and pyromellithic acids, which are both red-coloured substances, but yield colourlpss salts with acids, the addition of HCZ heing suEcient, it would seem, to suppress the chromophoric group C(NH)*C(OH) (OEt)), which becomes C(NH,*HCl)*COOEt, so that in presence of acids such substances would tend to behave as amido-compounds. If it be surmised on the evidence afforded by colour that acids exist which are not true carboxylic, but curbhydrilic, acids, there is no reason to deny the possible existence of such acids among colourless compounds, and it is conceivable that some of the reputed geometri- cally isomeric acids are of this character; von Baeyer's two hexa- hydrot,erephthalic acids perhaps afford an example of such isomerism.At present, however, we have no means of differentiating such acids from carboxylic acids. There are a number of cases in which a suggestive explanation of peculiarities may he given with the aid of the hypohhesis adTocated in these notes. Thus, although orthonitromethoxybenzene is colourless when solid, the fused substance is yellow; if not due to the pre- sence of impurity, or to slight decomposition, the appearance of colour in such a case may be conditioned by the occurrence of isodynamic change on heating.Then it is conceivable that the slight intensity of the colour exhibited by some substances may be due to the fact that the coloured and colourless isodynamic forms are both present, the coloured form in but small amount. On this view, it would be possible to understand the marked difference in intensity of colour sometimes apparent between derivatives of a coloured substance. Thus, in the case of the substituted nitrophcnols, the silver deriva- tire has frequently a much deeper colour than the potassium deriva- tire ; and the metallic derivatives of iododiorthonitrophenol are crimson, while those of the corresponding chloro-compound are bright- red; it may be that. one metal more than another, and one halogen more than another, favours tlie occurrence of the isodgnamic change on which the colour is dependent.I)1scuss10rj. Dr. ARMSTRONG,in reply to a remark by Professor Ramsay, said that although it, was true t,hat all substances exhibited absorptive power in scme region of the spect'rum, it was R remarkable fact that compounds which are coloured in the conventional sense clearly di-fl'er 105 in constitution from colourless compounds, and it therefore appeared justifiable to discuss the oriqin of visible colour apart from the general question of absorption. It wa? very noteworthy that satu-rated compounds had but slight absorptive power even for invisible rays, and there appeared to be a connexion between the power of exercising selective absorption and what liaq been termed residual affinity : so much was this the case, that it appeared probable to him that ultimately colour wonld be tiwxd to that peculiar condition represented conventionally by a double bond, the atoms being regarded as altogether subordinate.*19. " Studies on isomeric change. No. IV. Halogen derivatires of qninoiie. Part I." By Arthur R. Ling. DicliZol.ob,.omoplienoZ [OH : C1, : Rr = 1: 2 : 6 : 41, prepared from pnrabromophenol and sulphuryl chloride, crystallises from light petrolcum in silky needles melting at 66 5" ; it gives metadichloro- quinone when treated cold with nitric acid (1.5), and a mixture of d ichlorop arani trop henol (m. p. 125") and chlororthoparadi ni trophenol (m. p. 110-111") when warmed with nitric acid in glacial acetic acid solution.~~efackloi-obromoq?~inone[O, : C1 :Br = 1: 4 : 2 : 63, prepared by adding chlorodibromophenol [OH : Cl : Br, = 1: 2 : 4 : 61 to cooled nitric acid (1.5), crystallises from alcohol in yellow needles melting at 114-115". The quinol melts at 154-155'. I'aradicl~lorobro?izoquinone[02: C1, : Br = 1:4 :2 : 5 : 61, obtained by bromin%ting paradichloroquinone (m. p. 161"), melts at 160--161". The quinol crystallises from water in monohydrated needles melting at 124-126° ; the anhydrous substance melts at 135.5". The diacetyl derivative melts at 158-159". nletad~hromochlororuino~~e[0, : Cl, : Br = 1: 4 : 2 : 6 : 51, pro-duced by brominating metadichloroquinone (m. p. 121"), melts at 168". The quinol crptallises from water in anhydrous needles melting at 135", its diacetyl derivative melting at 173-1 74".Paradichloroqninone does not yield metadichlorodibromoquinone on hromination, as stated by Hantzsch and Schniter, but the normal product-paradichlorodibrornoquinone-is obtained. Paradicldorodi-b~onzoquinone [02: C12 : Br, = 1: 4 : 2 : 6 : 3 : 51. produced in this way, forms six-sided plates melting at 292"; the qui~z/11melts at 235-236", its diacetyl derivative me1 ting ah 269-2iO". The quinone does not yield chlorobromanilic acid on treatment with alkali, as Levy has etated, but a compound consisting of 1 mol. proportion of cliloranilate and 2 mol. proportions of bromanilate. It is then shown that metadichloroquinone yields paradichlorodibromoquinone, identi- 106 cal in all respects with the last-mentioned, when it is brominated in boiling glacial acet,ic acid solution ; when, however, the bromination is conducted at the ordinary temperature, the product consists chiefly of the norma.1 product, metadichlorodibromoquinone. Metndi~lilorodibromoquinone [02: C1, : Br, = 1 : 4 : 2 : 6 : 3 : 51 is obtained exclusively when metadichlorobromoquinol (m.p. 135") is suspended in carbon tetrachloride and heated in a closed bottle in a bath of boiling water, and the product oxidised ; it cryst,allises from benzene in six-sided plates melting at 291" ; the corresponding quinol melts at 231-2:32', its diacetyl derivative melting at 265-266". The quinone yields chlorobromanilic acid on heating it wit.11 alkali.*20. " Halogen derivatives of quinone. Part IT." By Arthur R. Ling and Julian L. Baker. Chlorotribrornoquinone, prepared by brominating monochloroquinol in acetic acid solution, and subsequently oxidising, crjstallises from benzene in yellow, six-sided plates, and melts at 292". The formation of chlorobromanilic acid on treatment with alkali, as previously stated by one of the authors, was only observed in one experiment ; in all others the molecular CO~Z~OZL'IL~,C6C1Br(ONa),O, + 2C,Br,( ONa),Oz + 12H20, was obtained. Chlorotribromoquinol crystallises from benzene in small, colourless needles melting ah 233-234" ; the diacetyl derivatire separates from benzene in needles melting at 275". Trichlorobromoquinone is obtained by brominating trichloroquinone : it separates from benzene in yellow, six-sided plates and melts at 289-290".On treatment with soda, it yields the coinpwund C6C1,(ONa),O2 + 2C,ClBr( ONa),Oz + 10$H,O. The formation of chlorobromanilic acid, as stated by Levy and Schul tz, was not observed. Trichlorobromoquinol, prepared by re-ducing the quinone, crystallises from benzene in flat needles melting at 230-231 its diucetyl derivative crystallising from acetic acid inO, oolourless needles melting at 261 -262". The authors draw attention to the fact that in the interaction of' the tetrahalogen qninone8 and alkali at least 3 mols. of the quinone appear to be simultaneously concerned (campare also preceding abstract). "21. "The crystalline forms of the sodium derivatives of substi-tuted anilic acids." By William J.Pope. A comparison of the crystallographic dimensions of the sodium of the brominated and chlorinated anilic acids referred to in the pre- ceding abstracts shows that the crystals possess considerable simi- 107 larity. The salts examined crystallise in the anorthic system and have the following axial relations :-Sodium bromanilate, C6(ONa)zBrzOz,4Hz0, EC : b : c = 0.8768 : 1 : 0.8100; u = 69" 28'; /3 = 87" 56'; "I = 71" 4'3'. Sodium chloranilate, C6(ONa)2C12~2,4H20, a :b : c = 0 8743 : 1: :j ; a: = 88" 8'; p = 89" 51'; 7 = 72" 30'. Sodium chlorobromanilate, C6(ONa)2C1Br0z,4H2n,a : b : c = 0.888 : 1 : 0.814; u = 69" 59'; /3 = 87" 3'; = 71" 58'.A double salt, composed of 2 mol. proportlions of sodium brom- anilate and 1of sodium chloranilate, having the composition 2C,( ONa),Br2O2,4H,O ; c6(ONaj2C120z,4E20, is obtained by the action of caustic soda on paradichlorodibromo- quinone and crystallises in the anorthic system. It possesses the constants a :b : c = 0.8825 : 1:0.8163; a: = 69" 48'; p = 87" 14'; '1 = 72" 11'. The same double salt, prepared by siniply crystallising a mixture of the two constituents in the requibite proportions, gives numbers pactically the same as these :--a : b :c r= 0.8825 :1:0-8143; cc = 69" 56'; /3 = 87" 7'; "1 = 7%' 11'. The identity of the two samples of double salt, prepared in different ways is thus establishcd. The crystals of the above substances consist of small, distorted prisms, exhibiting the forms a(100), b{Q10), c(OOl), p(ll0) and m{xOl). The form m(I0l) is not met with on crystals of sodium chloranilate, SO that the axial ratio h : c is in this case indeterminate.It is to be remarked that the chloranilate differs considerably in angular dimensions from the salts containing bromine, which approxi- mate very closely to one another in geometrical properties. The crystals of these salts nearly always show a curious step-like structure, which extends in the direction of the c-axis and frequently obliterates the forms m(x0l) and c{OOl) at the end of the crystal. A note-worthy fact is the great resemblance between the simple salts and the double salt of sodium brom-and chlor-anilate.The crystals of all the above-mentioned substances are, under ordinary Conditions, opaque, but, when crushed to powder and examined microscopically, are seen to tmnsmit light of a claret colour. 22. "Formation of a hydrocarbon, C18H12,fmm phenylpropionic acid." By F. Stanley Kipping, Ph.D., D.Sc. Having studied the action of phosphoric anhydride on a number of' fatty acids (Chem. SOC.Trans., 1890, 532, 980), it appeared desirable to ascertain whether benzenoid acids would yield ketones under similar conditions ; phenylpropionic acid was chosen. When this acid is heated with phosphoric anhydride, a reddish-brown, resinous 108 mass is obtained; from this product I have so far succeeded in isolating three compounds, but others are doubtless formed.1. A 7iydrorarbon, which after recrjstdlisation from boiling xylene, gnre on analysis resultq corresponing to the formula C3Hz,0.1515 gram substa,tico yielding 0.5250 gram COz = 94-51 per cent. carbon, and 0.0710 gram H,O = 5.21 per cent. hydrogen ; the calc~ilnted vtilucs are carbon 94.74, hydrogen 5.26 per cenl). The hydrocarbon crystailises in pale-yellow plates, does not melt at 250", and is insoluble in most ordinary solvents, and only very sparingly soluble in boiling xylene ; it is evident from its properties that it has a high molecular weight, its molecular formula being probably C18HL2.It dissolves in hot, concentrated sulphuric acid, jielding R sulphonic acid which is readily soluble in water. On prolonged boiling with a mixture of potassium bichromute and sulphuric acid the hydrocarbon is converted into a deep-yellow 3r orange compound ; this substance is doubtless a quinone of the com-position C18H1002,but as it is insoluble in all the ordinary solvents, and only very sparingly soluble in m7ch liquids as boiling xylene, &c., it, is not easily obtained in a pure condition ; analyses gave about 1 per cent.ol: carbon too much, probably owiug to the presence of un-changed hydrocarbon. A diCroruLo-derivat,ive of the composition ClsHloBrzis formed when the hydrocarbon is treated with bromine ; this substance crystallises from boiling xylene in microscopic needles, and does not melt at 300". 2. The second compound which is formed by the interaction of phosphoric anhydride and phenylpropionic acid is of greater interest than the hydrocarbon ; it is, however, produced in such small qnanti-ties that up to the present I have only obtained its hydrazone in a pure condition.This hydrazone crystallises from dilute alcohol in yellow needles, melts at 127-128" with decomposition, and on a,nalysis gives results agreeing well with those required by a com-pound of the composition C,,H,,NZ; when heated with concentrated hydrochloric acid it is converted into a colourless, crystalline com-pound which melts ai; about 245", is insoluble in water and contains nitrogen. The constitution of the ketone (or aldehyde) from which this hydrazone is derived is, of course, at present quite a matter of speculation, but is possibly represented by the formula This view is supported by the fact that, by treating phenylpropionic acid with phosphnrus pentachloride in order to convert it into the chloride CH,Ph*CH,*COCl,and then warming an ethereal sdu tion of this chloride with aiuminium chloride, I obtained an oil which is 109 insoluble in mdiurll carbonate, and which gives with phenylhydrazine a hydrazone identical with that described above.3. The third product, obtained by t’he action of phosphoric an-hydride on phenylpropionic acid seems to be an organic derivative ot‘phosphoric acid. The experiments here described are still Fery incomplete, but it appears desirable to call attention to them as, if ketoliydrindene derivatives are rea>lly produced in this way, their investigation cannot fail to be of interest.23. “Metallic deriratives of acetylene.” By R. T. Plimpton, Ph.D. A report in the Chemical News (65, 169) of a preliminary paper read by Dr. Kaiser before the Chemical Section of the Franklin Institute, on the copper and silver compounds of acetylene, leads me to publish some of the results of an investigation of these and other metallic derivatives with which I have been engaged for some time past. 1. Silver Compounds. SiEuer Nitrate and Ammonia. -The precipitate formed by acetyleiie in ammoniacal silver nitrate is in dilute solutions (decinormal) bright- yellow ; in strong solutions the yellow, curdy substance first thrown down is prone to pass inlo a white and less bulky form.The yellow substance often undergoes the same change when allowed to stand under water containing acetylene and protected from light. The white substance usually yields a somewhat higher percentage of silver. Strong ammonia appears to be without action on the yellow acetylide, and the quantity present during precipitation does not in- fluence the composition of the precipitate. Silver estimations in eight specimens dried over sulphuric acid gave percentages of silver ranging from 87-38to 88.85. Of these two had been dried for three and six weeks respectively, and yielded 88.7 and 88.8. Blockmann’s formula C2Ag,,H20requires 8.37; that of Berthelot, C,A~,~H,Oor (C2HAg2),0,86.7. An attempt to prepare silver acetylide in neutral or acid solution, SO as to diminish the risk of the precipitate carrying down with it silver oxide, was successful.Silver acetate is completely prctcipitrtted by acetylene with separation of the whole of the acetic acid. The acetylide, so prepared, has the same properties as that obtained in ammoniacal solution, but has not the same tendency to turn brownish on drying; and, like the latter, separates as a yellow, curdy pre- cipitate, but mzy become white under the same conditions. The silver was estimated in fifteen specimens carefully dried in n 110 vacuum over sulphuric acid until they ceased to lose weight, and in some cases at 60-70". The results lay between 86.6, tha percentage of silver required for C2Ag2,$H20,and 87.9,nearly that required for C2A.g2.+H20,87.8.Drying at 60-70" caused a slight loss of weight, but caused the precipitates to darken. Those specimens which had become white yielded higher results tha.n those which remained yellow. Two por-tions of the same precipitate, of which the one was left in contact with strong ammonia for several days, were dried and yielded the same percentage of silver, 86-56. The aceeylene given off froni a known weight of the dry substance with chlorhydric acid was measured and the silver chloride weighed ; ratio of silver to acetylene, as 38 to 20 or 10.3 per cent. carbon, C,Ag.,,+H,O, 9.7. Percentage of silver, 87.47. Other experiments by the Rame method, made with acetylide from ammoniacal silver nitrate and from silver acetate, also gave 1 mol.of acetylene to 2 atoms of silver. Xiher cltloiide dissolved in ammonia gave a yellow acetylide con-taining 87.85 per cent. silver, and free from silver chloride. Silver nitrate, in aqueous solutiori (decinormal), is precipitated by acetylene, three-fourths of the acid being liberated. Precipitates prepared from solutions of different strepgths contained varjing pi-+ portions of silver nitrate. Alcoholic silver nitrate yields a precipitate much richer in nitrate, containing equal amounts of silver as acetylide and as iiitrate. The action of hydrocarboils of the acetylene series on alcoholic silver nitrate has been studied by BehaI. My analyses of precipitates from the nitrate gave as limits 3C2A,g$AgN0,Aq and C2Ag2AgN0,Ay, the latter being obtained from alcoholic solutions.Silver szilphate solutions are also completely precipitated by acetylene, and with a solution containing 0.2 gmm in 100 C.C. two-thirds of the snlphuric acid was set free. Precipitates obtained from such a solution give results corresponding to 2CzAg2Ag2S0,Ay. 2. Mercury CYon,pmnds. Mercuric acetate solutions yield white precipitates which become grey towards the end of hhe precipit'ation. If the solutions are not too strong fhe whole of fhe metal is thrown down with separation of all the acetic acid. When washed with alcohol and dried in uucuo over sulphuric acid the substance has the composition required by the formula 3Hg02C,H2. It resembles the compound 3Hg02C3H43HgCIz, obtained by Rutcheroff (Ber., 17,13) from allylene, for, unlike the acetylides generally, it does not give off acetylene on treatment with chlorhrdric acid, and is not explosive.111 Iodine athacks it, apparently, with formation of iodoform. Mercwrous acetate freshly precipitated and suspended in water is decomposed by acetylene and is converted into a greyish substance which differs entirely from the mercuric compound, and seems to be similar to silver acetylide in composition and properties. It detonates when heated suddenly, and gives acetylene on treatment with chlor- hydric acid. Iodine acts upon it in the Bame way as upon silver acetylide, yielding di-iodace tylene. The acetylene used was prepared from the copper compound ob- tained from the incomplete combustion of coal gas, and was purified by caustic soda. I propose to continue the study of the mercurous compound and the action of iodine on this and other acetylides.24. " Isomeihm amongst the substituted thioureas." By Augustus E. Dixon, M.D. The author notes that, while it has been established that the addi- tion product of a thiocarbimide XNCS with a primary amine YNH, is ident,ical with that resulting from the combination of the thio- carbimide Y-t'CS with the amine XNH2, no investigation appears, as jet, to have been conducted with the object of determining whether identical or isomeric forms would result if the substituting groups are similarly transposed in thiocarbimide and secondary amine.In a communication recently made to the Society (C.S. Trans., 1891, 551), two isomeric forms of methylphenylbenzylthiourea were incidentally described, but it was left undecided whether two ethyl- phenylbenzyl compounds resulting from the action of ethylthio-carbimide on benzylaniline, and of benzylthioca.rbimide on ethyl-aniline, respectively, were identical or isomeric. Their isomerism has since been established by the observation that when heated with alcoholic ammonia, under pressure, the former yields ethylthiourea and benzylaniline, the latter benzylthiourea and ethylaniline. Fur-thermore, a third isomer is now described, produced from phenylthio-carbimide and ethylbenzylamine ; this occurs in vitreous prisms in- soluble in cold water, freely soluble in hot alcohol, chloroform, benz- ene and carbon disulphide, and melting at 94-95".An isomer of Gebhardt's (Bey., 17,3037) di~iieth~lphenylthiourea (m.p. 114",from MeNCS and MeNHPh) was also obtained, by tJhe interaction of PhNCS and Me2NH. It forms long, white pi*isms, melting, wihhout decomposition, at 234-13s". It is moderately soluble in boiling water, very freely in hot alcohol, and when boiled with aniline yields diniethy lamine md thiocarbanilide. 112 25. “Note on &static action.” By E. R. Moritz and T. A. Glendinning. It has been observed by one of the authors that brewers’ worts, as they issue from the mash tun, remain constant in respect to their starch transformation products when digested for two Eionrs at the same temperature as that at whicbh the conversion was conducted.The diastase in these solut.ions therefore exercises within such a period no action on the starch prodiicts contained in it; but if fresh starch be added, the residual diastase is found pet, to possess consider-able power of liquefying and sncghnrifying starch, although its energy is distinctly inferior to that of the original malt. The authors describe a series of experiments made with the object of comparing the energy of the original with that of the residual diastase. They consider that the results entitle them to form the following conclusions :-The attaiiiment of a resting stage in the transformation of starch by diastase bv no means shows that the energy of tlie diastase is exhausted.The energy of the “ residual ” diastase is, in fact, very considerable, even under conditions adverse to its activity, It is somewhat weakened hy increasing the amount of starch it has to convert, but it is wcakened to a marked extent by subjecting it for some time to a temperature exceeding the optimum one for sacecharifi-cation. When, however, it is not exposed for any length of time, whether precious to the first or to subsequent transformations, to R temperature exceeding the optimum, it appears capable, after trans- forming a considerable amount of starch, to transform further quan- tities to iieerly the same point, when such further quantities are added successively and subsequent to the attainment of the resting stage in the preceding transformation. ADDITIONS TO THE LIBRARY.I. Donation. Sopra alcune proprieta dsl Fosforo, esperienze ed observazioni di G. Branchi. Pisa, l@l& From A. X.Sibson, Esq. IT. By PurcJmse. An Introduct,ion to ModcAm Therapeutics ; being the Croonian Lectures on the Relationship between Chemical Structure and Phy-amlogical Action, by T. L. Brunton. London 1892. Watts’ Dictionary of Chemistry, revised and entirely rewritten by H. F. Morlcy and M. 35. P. Muir, assisted by eminent contributors. Vol. 111. London 1892. RESEA.RCH FUND. A meeting of the Committee will be held in June. Fellowv desiring grants are requested to make application to the Secretaries before June 9th. At the next meeting, on June 2nd, the following papers will be read :-‘‘ Ethylene derivatives of diazo-amido-compounds.” By R.Meldola, F.R.S., and F. W.Strentfeild. “The action of light on silver chloride.” By H. Brcreton Baker. “ The zyniic function of yeast. I.” .By James O’Sullivan. ‘‘ The estimation of slag in wrought iron.” By A. E. Barrows and Thomas Turner. “ The constitution of Iapachic acid and its derivatives.” By S. C. Hooker, Ph.D. CERTIFICATES OF CANDIDATES FOR ELECTION AT THE NEXT BALLOT. N.B.-The names of those who sign from “ General Knowledge ” are printed in italics. The following Candidates will be balloted for on June l&h, 1892 :-Adams,Percy Targett, 0phthalmic Hospital ,Maid stone. Surgeon.Diploma in Public Health, R. C. of P. and S. Lond. Student in Chemistry as applied to Sanitary Science and Food Bnalysis (in my father’s laboratories), Maidstone. 0tt.o Hehner. Thos. Stevenson. Matthew A. Adams. I;.W. Stamsell. Laurence Green. Alcock, John W., Central Brewery, 45, Mott Street, Birmingham. Practical Brewer and Maltster. I have been a student in the Chemistry Classes (Practical and Theoretical, Organic and Inorganic) at the Birmingham and Midland Institute for the past four years, and have passed the Science and Art Department Examinations in these subjects. My object in application for Fellowship being to furt8her my knowledge in the chemistry in connection with my occupation. William W. Butler. H. J. Mousley. William McCowan.J. Cuthbert Welch. Arthur Adams. Thoinas Turner. Ballantyne, Horatio, 260, Renfrew Street,, Glasgow. Analytical Chemist. For six years Assistant with R. R. Tatlock, F.R.S.E., F.I.C., F.C.S., Public Analyst for the cities of Glasgowand Perth, &c. Read paper on “ The Effects of Exposure under certain conditions upon some Constant’s of Oils,” SOC. Chem. Ind., March, 18 1 (Journul, p. 29, 1891). In conjunction with R. T. Thornson, F.I.C., “ On the Revision of Constants employed in Oil Analysis,” 115 Part I, SOC.Chem. Ind. (Journal, 1890). Also “On the Rsvision, ditto, ditto,” Part TI, SOC.Chern. Ind. (Journal, 3891). Robert R. Tatlock. Alfred H. Allen. John Clark. G. G. Henderson. A. Humboldt Sexton. W. MncKean. D.A. Sutherland. George Wdson, Jular. IZowlannd Willian?~. Barrows, Arthur Edward, Bloomfield Iron Works, Tipton, Staffordshire. Iron Manufacturer. Student for three sessions in the Metallurgical Laboratory at Mason College. Passed Senior Practical Examination. Have been engaged during the present session with Mr. Turner upon it Research on the Chemistry of Wrought Iron, the results of which will shortly be communicated to the Society. William A. Tilden. Thomas Turner. W. W. G. Nicol. Harold G. Colman. Sidney Williamson. Bleckly, Arthur Sanderson, Thelwall Len, near Wfirrington. Analytical Chemist to Messrs. Pearson and Knowles’ Coal and Iron Company, Limited, Warrington. Was at Polytechnicum, Hanorer, Germany, for six months; also at Liverpool College of Chemistry for one term.Was then in a Works Laboratory in -Middlesbrougli for two yesrs. Thos. G. Rylands. H. Wilson Hake. C. H. Ridsdale. Charles Will more. George Tatc. J. Rymer Yonng. Bayliss, Charles, Selly Park, near Birmingham. Assayer and Chemist. Ten years Assayer and Chemist at tlie Bir-mingham Assay Office. B William V?. Butler. H. J. Monsley. Wm. Whitehouse. Arthur Adams. Wm. Tate. WilliamA. Ti7den. TTi. W. 19.NicoZ. A. Percy Smith. Cockerill, Thomas, 105, Derby Street. Bolton. Elect,rical Engineer. Engaged in the electro-deposition of metals. Had ten years’ study in Electro-chemistry, and engaged in this pr-snit today, specially in deposition of alloys. Taken Silver Medal at 116 the City and Guilds of l~ondon Institute for this sub.ject, and elected an Associate of the Institute of Electrical Engineers in 1891.J. Campbell Brown. H. B. Dixou. TisT. W. Haldane Gee. J. B. Cohen. W. B. Mason. W.Collingwood Williams. Charles A. Kohn. Couldrey, Henry, H.M. Nint, Bombay, India. Assistant Assay Master. Studied Chemistry in the Royal College of Science, South Kensington. Assistant Assay Master in the Bombay Mint since 1873. T. F. Thorpe. W. P. Wynne. Edwin J. Ball. Alfred E. Tuttou. William Tate. Entwistle,Herbert, Crosshill Terrace, 476, Padiham Road, Burnley . Head Instructor of Burnley and District Pupil Teachers’ Central Classes. (Appointed January, 1899.) From 1877 to 1884, pupil in Theoretical and Practical Chemistry (Organic arid Inorganic) at Man-Chester Grammar School, under Francis Jones, Esq., P.R.S.E., F.C.S.Jn 1883 and 1884, Teacher of Theoretical and Practical Chemistry (Science and Art Department) under the Mancheater School Board. In 1887 and 1888, Assistant Chemical Demonstrator to J. Howard, Esq., F.C.S., at Borough Road College, London. In 1889, 1890, 1891 and 1892 (to March), was a Science Demonstrator to the Liverpool School Board. Commenced tbe Chemistry teaching in their Schools. Had more than 100 pupils iii each year in Theoretical Chemistry (Science and Art DepartinerLt), and in 1591 and 1892 had nearly 100 pupils i 11 Practical Chemistry. Francis Jones. R. L. Taylor. J. Howard. John Angell. Wm. John Wateyhouse. A.Norman Tate. C. E.Buckmaster. Edward Davies. .J. Campbell B~owyt. Evans, Sir John,K.C.B., Nash Xills, Heniel Hempstead. President Xlect of the Society of Chemical Industry. Treasurer :rnd Vice-president of the Royal Societ,y ; D.C.L. (Oxon) ; LL.D. Dublin) ; z).Sc. (Cambyidge) ; Trustee of the British Museum ; P.S.A., F.S.L., &c. Alex. Crum B~owir. T. $1. Thorpe. E. Frankland. Hugo ;\luller. William Crookes. At. Foster. W~i1dh:ixi1K. Du tistan. 117 Gibson, John,Ph.D., F.R.S.E.,F.I.C., 15, Hartington Gardens, Edinburgh. C hie€ Assistant in the University Chemical Laboratory, Edinburgh. Chief Assistant in the University Chemical Laboratory Edinburgh since 1881. Author of numerous papers in scientific journals, among which may be mentioned-“ On Laboratory Fittings,” XOC.of Chern-Ind., March, 1887 ; “ Report on Physics and Chemistry of the North Sea during 1888 and 1889;” “Seventh Annual Report of Fisheries Board for Scotland ;” ‘‘Report on Analytical Examination of Man-ganese Nodules, with special reference to the presence of the Rarer Elements,” Challenger Expedition Reports.Alex. Crnm Brown. Henry E. Armstrong. William Ramsay.. John Norman Collie. T. E. Thorpc. John M. Thoinson. Newall, John Fent on, Mai-ple (also 8, Market Place, Manchester). IJerchant. I studied Chemistry under Professor Maden, at Eton, fyom two to three years, and have since then always had at my house a physical and chemical laboratory in which I have carried on researches in connection with my business, and with other matters not connected therewith.I have also studied Chemistry for some time in the Royal Institution Laboratory of Manchester. I am Managing Director of a large Oil Works, and have the laboratory and works under my sole control. I have also experimented a great deal in the manufacture of chemical wood pulp, and I am one of the largest dealers in that article iz the kingdom. William Thomson. Thomas Fairley. J. Carter Bell. Wna. Odling. -4lfred H. Allen. C. Estcozwl. Bowlaud Williarns. W.Lazoreitce Gadcl. 8. Lees. Norris, Charles James, Skipton Grammar School. Science Master in the Skipton Grammar School. Has studied Chemistry and Physics at the Royal College of Science, South Kensington. 1’.E.Thorpe. A. E. Tutton. Wllliam Tate. Chupman Jones. C. W.Priestley. Lionel ill. Jones. Redman, Henry Ramsden, 10, The Gardens, East Dulwich, S.E. Htwl Master of the Slafford Street Higher Grade Schools. Foimrrly a student at 0wens College, Xanchester, and for some 118 time Chemistry-Assist aut to the Principal of Melbourne Training College. Has been engaged in teaching Chemistry during the last eight years at the Stafford Street Schools. Desirous of joining the Society in order to attend the Meetings, and to keep in touch with rfost recent work. Gerald T. Moody. W. J. Pope. Holland Crompton. Thos. Goddard Nicholson. Jnnaes Hendrick. Percy A.E. Richads. F. Stanley Ripping. Smith, Ernest Heber, 54,Cambrian View, Chester. Head Science Master, Chester Science and Art Technical Schools.Associate of R2yal Colleqe of Science (London) in Chemistry. Esperience as a teacher of the subject. T. E. Thorpe. Chapman Jones. A. E. Tutton. D. S. Macnair. William R. Eaton Hodgkinson. Whiteley, Fred.,B.A., Clare College, 20, Dunkerley Street, Oldham. Science Teacher. Student of Chemistry for the last seven years, having obtained Honours in Parts I and I1 of the Natural Science+ Tripos (1890 and lS9l), and of late chiefly engaged in Agricultural and Analytical Chemistry in the UnirersitJ-Chemical Lnboratorr, Cambridge. A1exander Scott,. S.Rclwmnnn. Thomas H. Easterfield. G. 11. Liveing. 111. J. H. Fenton. HARRISON AND SONS, PRINTEXIS 1N ORDINARY TO HER MAJ1;S:TY. S1‘. MARTIN’S LANE.
ISSN:0369-8718
DOI:10.1039/PL8920800099
出版商:RSC
年代:1892
数据来源: RSC
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