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Proceedings of the Chemical Society, Vol. 7, No. 103 |
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Proceedings of the Chemical Society, London,
Volume 7,
Issue 103,
1891,
Page 155-170
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摘要:
PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 103. Session 1891-92. December 3rd, 1891. Professor A.Crum Brown, F.R.S., President, in the Chair. Messrs. T. M. Wyatt and Peter MacEuan were formally admitted FelIows of the Society. Certificates were read for the first time in favour of Messrs. Frederick Edward Adams, Town Hall, Bolton; John Edward Whitley M. Fall, Bankfield Road, West Derby, Liverpool ; John C. Hewlett, 40, Charlotke Street, E.C. ; Robert Ludwig Mond, 20, Avenue Road, Regent’s Park, N.W. ; William Shields Myers, New Pork ; George P. Daniel1 Smith, 26, Colebrooke Row, Islington, N. The following were duly elected Fellows of the Society :-Harold Alger ; George Alfred Ashcroft ; George James Allen ; Edward Charles Cyril Baly ; Thomas William Berry ; Samuel Francis Bur- ford ; John Bairstow ; J.Treeby Barratt ; John Redman Bovell ; John C. Chorley; William A. S. Calder; George Edward Cory; Thomas Darling ; Charles E. Eastwick ; Percy Elford ; Lionel William Fulcher ; George German, Jun. ; Alfred Daniel Hall ;John William Heath ; Archibald Hall ; John Holliday ; John Walter Leather ; Lionel Ludlow ; Robert Lennox ; Rudolf Laurentz Leffler ; John Willis Marshall ; Daniel McLaren, B.Sc. ; Joseph Morris ; William Naylor; William P. R. Newlands ; Thomas Neilson ;Laurence Priestley ; Abhayacharnn Sauyal, M.A.; Charles K. Scott ; Thomas Stephenson ;Walter Thorp ; A. W. Winterton ; John Henry Wilson Thomas Armistead Ward ;Henry White. The following papers were read :- 156 68."Phosphorous oxide. Part 11." By T. E. Thorpe, F.R.S., and A. E. Tutton. In this paper the authors continue their description of the pro- perties of phosphorous oxide, P,06. In their first communication (Trans., 1890, 553) it was stated that the oxide rapidly became red when exposed to light : they have since obtained phosphorous oxide in large, well-defined crystals, unaffected by light, by repeatedly exposing a quantity of the freshly distilled oxide to sunshine for several months at a time, and decanting the melted oxide from the red phosphorus produced. Large crystals of the oxide may also be obtained by spontaneous sublimation in a vacuum, which remain unaffected by light, so long as they retain their crystalline form ; but if they are melted by the warmth of the hand, and then allowed to cool to the wax-like form, reddening occurs on exposure to light.Hence it appears not improbable that the permanency of the crystal- lised oxide is in some way connected with its crystalline character. Bromine acts energetically on phosphorous oxide in a manner similar, in the end, to the action of chlorine. In a closed apparatus, however, an intermediate change occurs, crystals of phosphorus penta- bromide subliming, and phosphoric anhydride being also formed; 5P406 + 20Brz = 8PBr5 + GP205. The pentabromide is afterwards washed down by the excess of bromine, and acts on the phosphoric anhydride, the ultimate result being that products are obtained cor- responding to the equation P,06 + 4Brz = 2POBr3 + 2POzBr.Iodine acts more slowly than bromine, forming crystals of PJ4. The interaction is best carried out in carbon bieulphide solution in a sealed tube at a temperature of 150": 5Y406+ ST, =4P214j-6P,O,. Hydrogen chloride gas acts on phosphorous oxide, forming phos- phorus trichloride and phosphorous acid: P40s + 6HC1 = ZPCl, + 3H,P03. A subsidiary chauge also occurs between the two products of the reaction, wit,h formation of more or less phosphorus, orthophos- phoric acid and hydrogen chloride: PCI, + 4H3P03= 3H3POa+ Pz+ 3HC1. On distillation a weight of phosphorus trichloride is obtained equal to that of the oxide employed. When sulphur is heated with phosphorous oxide in a closed tube at about 160°,a most violent action takes place, the product of which is phosphorus sulphozide, which is obtained in colourless, tetragonal crystals upon sublimation in a vacuum.The crystals melt at about 102", and the liquid boils constantly at 295" (corr.). Vapour density determinations show that the molecular formula of the sulphoxide is P406Sd. It is a highly deliquescent substance, which rapidly dissolves in water, forming at first meta-, and subsequently ortho-phosphoric acid 157 and hydrogen sulphide : Y,O,S1 + 68,O = 4HPO3 + 4H2S. It is also soluble in carbon bisulphide, from which it is again obtained upon evaporation in tetragonal prisms. Sulphur trioxide is reduced by phosphorous oxide, the sole pro- ducts being sulphur dioxide and phosphoric anhydride.Sulphuric acid dropped upon phosphorous oxide occasions great rise of temperature ; with quantities of a gram and upwards incmd- escence occurs. Sulphur dioxide is liberated, and phosphoric acid formed. Sulphur chloride, S2C12, also acts with violence, forming phos- phoryl and thiophosphoryl chlorides,) sulphur and sulphur dioxide : PaOG+ 6S2C12= 2POC1, + BPSCI, + 2S02 + 85. Ammonia gas acts slowly in the cold, but with incandescence on warming to 30". When ammonia is led over the oxide dissolved in ether, a white solid product is deposited, consisting of the diamide of phosphorous acid, P(0H) (NH,),, and a small quantity of the corre- sponding ammonium salt: P406+ 8NH3 = 3P(OH)(NH2)2 + P(OH)z(ONH4)z. Phosphorous diamide is a white powder which is instantly dissolved by water with sufficient rise of temperature to induce incandescence. Treated with dilute hydrogen chloride solu-tion, it evolves pure, non-spontaneously inflammable phosphoretted hydrogen, formed by the decomposition at the high temperature of the reaction of the phosphorous acid first formed : P(0H) (NH& + 2HC1 -J-2HzO = 2NH4C1 + P(0H)s.Nitrogen peroxide vapour oxidises phosphorous oxide in the cold to phosphoric anhydride, being reduced to nitrogen tri- or di-oxide. Phosphorus pentachloride acts with great energy on phosphorons oxide. The action may be controlled by cooling with ice. A liquid mixture of phosphorus and phosphory1 trichlorides is produced : P40s+ 6PC1, = 6POC13 + 4PC13.Phosphorus trichloride and phosphorous oxide only interact at a temperature near the boiling point (173")of the latter, and in a closed vessel : under these circumstances, no phosphoryl trichloride is formed, but a solid mixture of pentachloride and pentoxide of phoephorns together with amorphous phosphorus. Hydrogen, phosphoretted hydrogen, carbon monoxide, carbon di- oxide, sulphur dioxide, nitrogen, nitric oxide, cyanogen and ethylene have apparently no action upon either cold or warm phosphorous oxide. DISCUSSION. Professor RAMSAYenquired on what grounds the authors came to the conclusion that the amide described was a phosphorous and not a phosphoric compound, such as is represented by the formula OPH(NH,), corresponding to the formula OPH(OH), for phosphorous 158 acid, which latter he thought was undoubtedly a phosphoric com-pound.The low boiling point and other properties of the sulphoxide described seemed to lend additional support to the view that phos-phoric oxide was a compound of high molecular weight. Dr. ARnrsliRowG remarked that the conventional view that the affinity of phosphorus for oxygen was very great was somewhat disturbed by the observations now described, showing that in many cases the phosphorus and oxygen in phosphorous oxide were readily separated; it would seem that the extreme stability of phosphoric oxide was probably conditioned by peculiarity of structure. The authors, in their reply, said that they had no special experi- mental proof of the constitution of the dianiide formed by the action of ammonia ; Professor THORPE, however, expressed the opinion that the balance of evidence was in favour of the view that phosphorous acid is P(OH),.69. “Prangulin. Part II.” By T. E. Thorpe, F.R.S,, and A. K. Miller, Ph.D. In the first communication to the Society by one of the authors, in conjunction with Mr. H. H. Robinson (Trans., 1890, 38), ih was con- cluded that frangulin had the composition C,,H,,O,. This conclusion was based on analytical results alone, and it was, in fact, pointed out that the percentage yield of emodin obtained on hydrolysing frangulin apeed better with Schwabe’s formula C21H2009. The authors have now prepared a larger quantity of frangulin, and have succeeded in obtaining it more nearly in a state of purity than was previously possible.They find, however, that crude frangulin contains a substance isomeric with emodin, which clings to it very persistently, and which it is very difficult to completely remove from the frangulin : they ascribe the conflicting statements of previous experimenters to the presence of this substance. They have succeeded in proving the correctness of Schwabe’s formula C21H2009. Their conclusions are based not only on their more recent analyses of frangulin, but also, and in fact nlainly, on the esults obtained from the hydrolysis of frangulin. The two products of the hydrolysis are emodirz, Cl,HloO,, as shown in the first paper, and rhamnose, CsH,,O,.The latter substance was obtained in a crys- talline form, and was identified by its chemical and physical proper- ties and by the properties of its osazone. The percentage yield of emodin shows that one molecular proportion of frangulin yields one molecular proportlion of emodin, and the diiference represents one molecular proportion of rhamnose. It is thus possible to build up the formula of frangulin from its constituents, and since the result agrees 159 with the formula deduced from the analyses of the glucoside, the conclusion is justified that frangulin has the composition C21H2009, and that its hydrolysis takes place in accordance with the equation C21Hz009 + HzO = C15H1005 + CsHI2O5,which was given by Schwabe as highly probable.The substance which has been mentioned as clinging so persistently to the frangulin has been isolated, and is found to have the same percentage composition as emodin. It melts at 202-203”, and is, without. doubt, the same substance which Schwabe found and de- scribed as melting at 199”. It differs from ernodin also in that it crystallises in golden-yellow needles, in the greater readiness with which it sublimes and in its reaction with alkalis. It is probably an isomeric trihydroxymethylanthraquinone. 70. “The structure and chemistry of flames.” By Arthur Smithells, B.Sc., and Harry Ingle, B.Sc., Yorkshire College, Leeds. The authors have been engaged for twelve months in investigating the chemistry of flames produced by burning known hydrocarbons, and are still continuing their experiments.The publication of their results in the present form is consequent on the appearance of a paper by N. Tech (Journ. prakt. Ohem., 44, 246), who describes the phenomenon which served as a starting point in the authors’ enquiry. If a long glass tube be fitted by means of a cork over the metal tube of a Bunsen burner, so as to form a wider continuation of it, the flame can be caused to burn at the top of the glass tube. When the gas is turned slowly off, the flame becomes smaller, and develops a sharply defined inner cone of a greenish colour ; this cone ultimately becomes almost a flat disc of flame and enters the glass tube. It will, as a rule, descend at a rapid rate for some distance, then begin to oscillate and finally either detonate and light the gas at the bottom of the metal tube, or else go out.If the gas supply be very carefully regulated, the flame may be got into such a state that it will descend the tube for a short distance and then re-ascend, and in this state it is very easy to see that whilst the lower cone is moving there remains at the top of the tube a steady cone of flame of a pale-lilac colour. By heating the glass tube at one point, so as to increase at that point the rate of inflammation, it is possible to fix the oscillating inner cone-that is, to prevent its re-ascent. It is also possible to effect this by narrowing the bore of the glass tube at one point, so as to diminish the rate of inflammation, i.e., to prevent the descent of the inner cone past that point.In this way it is possible to separate the two hollow cones of combustion which constitute the Bunsen flame, 160 and to keep them any distance apart for any length of time. This permits of the aspiration of the gases from the space between the cones without any chance of admixture of outside air 01-of pro-ducts of combustion fyom the upper cone. The apparatus used by the authors in most of their experiments consisted of two glass tubes, one of which slides very easily within the other. The inner tube (G), which is the longer one, is united to the outer one by an india-rubber collqr (a), through which it slides freely, and the two tubes are kept coaxial by a ring of asbestos packing (b).The projecting end of the inner tube qay be fitted to a Bunsen burner, but the authors have usually led separate supplies of gas and air into the apparatus by a, T-tube, instead of using a Bunsen burner, in order to have a better control of the flame. With this apparatus a non-luminous flame is easily obtained, and the two cones can be separated in two ways. If the apparatus is arranged so that the flame is formed at the orifice of the wider tube (d) and the orifice of the narrower one (e) is 8 or 10 cm. below it, on increasing the air sup- ply the inner cone of flame will ultimately descend and rest upon the orifice of the inner tube. If, on the other hand, the inner tube be made to project beyond the outer one and the non-luminous flame be formed on it, then, if there be a sufficient air supply, on sliding UP the outer tube it will as it passes the flame cleanly detach and carry up the outer cone, leaving t'he inner one still burning on the inner tube.The authors have made similar experiments with flames of liquid hydrocarbons by charging air with the vapour of the liquid by passing it through A " saturator " such as is used for producing the ether-oxygen lime-light. The vapour-charged air is afterwards mixed with more air, and by suitably regulating the proportions a non-luminous flame is obtained and divided into two cones. In the case of liquid hydrocarbons, the lower cone of flame usually appears to be divided by dark spaces into several petal-like divisions which are in rapid rotat.ion.In the case of benzene vaponr the following sequence of appearances is presented: starting with the orifice of the inner tube, 8 or 10 cm. below that of the outer one, a luminous smoky flame is first obtained at the latter; as air is gradually added the flame becomes less and less luminous, and an inner cone begins to develop, but before this has become non-luminous it descends to the inner tube ; more air makes both it and the upper cone non-luminous, and this state may be maintained. If now somewhat less air is sup-plied, ;I luminous streak appears at the tip of the inner cone, and passes right up and through the tip of the upper cone. If more air is supplied, the upper cone of flame begins to disappear, and only the upper part of it remains ; this also gradually fades away, and then there is only the lower cone left.Still more air produces a visible effect on the inner cone, the colonr changing and the combustion becoming less intense until the cone rises from its seat, passes upwards and disappears. There is thus a gradual transition from the richly luminous flame to one consisting of a simple pale-blue cone just on the point of extinction through excess of air. The hydrocarbons examined by the authors were ethylene, methane, pentane, heptane and beozene. Coal-gas was also used. The gases from the regions between the two cones of flame were analysed in all these cases volumetrically or gravimetricallg. The followiug are some of the results obtained :-- 162 -Substance.CH4. Coal gas. mm. mm. mm. mm. mm. mm. Diameter of outer tube ......... 29 29 29 29 19 05 28 Diameter of inner tube ......... 20 20 20 20 12 8 Gt (gavimetric) or V (volumetric). Gt V v G V V 002 ............ 3-8 3 *6 6 -8 3 -8 4.2 4.8 HzO............ 9 -5 9 -5 17.6 14 *9 16 -0 15 -9 co ............ 15 -3 15 *6 4.5 10 -2 8.8 7.1 -IHydrocarbons ... 0 *8 1 -3 --H2 ............. 9 -5 9 '4 3.9 10 -9 9 -3 7.7 N2 ............. jl.1 60-6 67 *2 60.3 62.0 64 -4 I These results, which are obtained in the preliminary survey, are not quite accurate owing to the impurity of the hydrocarbons and certain difficulties which are described in the paper. They show, however, that the products of combustion of the first cone are essentially CO,, H20, CO and H,, and that the second zone is due to the combustion of the CO and H2with the external air.The results are in harmony with the conclusions of Blochmann, obtained indirectly, and with the not generally known work of Dalton on the explosion of methane and ethylene with oxygen in quantities insufficient for complete combustion, which was repeated in 1861by Kersten. The authors point out (i) that carbon, according to Raker's experi- ments, even in excess of oxygen, burns preferentially to CO, and not to CO,; (ii) that the heat of combustion of gaseous carbon to CO is probably greater than that of hydrogen to H,O ; (iii) that, according to Dalton, CH4 when burnt with its own volume of oxygen gives pro- ducts represented in the equation CH, + O2 = GO + H20 + H2; and they conclude that this equation represents the character of the change first taking place in the inner cone.But as the two sub- stances CO and Hi0 act upon one another (CO + H,O =C02 + H?), the case is one of reversible change, and four products will result, viz., COz, H20,CO and H2. The conditions of equilibrium of this system, according to Dixon, are expressed by the coefficient H20 = 4.0. This is subjectco2 x l3* to certain conditions of temperature and dilution. The authors in their most reliable experiments (viz., the gravimetric ones), with ethylene and coal gas, get numbers not greatly differing from 4 ; but they are stmill engaged in studying this question, 163 The authors have succeeded in dividing into two cones flames pro- duced by admixture of air with cyanogen, sulphuretted hydroge n, carbon bisulphide and decomposed ammonia (Le., N, + 3H,).The products of the inner cone in the case of cyanogen were found in one experiment to consist of CO and CO, in the proportion of 2 vols. of the former to 1vol. of the latter. Professor Smithells is continuing the expeciments, with a view of elucidating the following points :-(i.) The influence of differences of diameter of the tubes and rates of efflux on the fractional combustion. (ii.) The exact composition of the interconal gases in the case of hydrocarbons, and also of mixtures of CO + H,, so as to ascer-tain if, and in what way, the coefficient (hO,Xx H2°H, = 4)varies with the composition of the gases and other conditions.(iii.) The composition of the interconal gases from hydrocarbon flames whilst carbon is being liberated, so as to ascertain whethei- the luminosity of flames is due to simple decomposition of hydro-carbons by heat, to preferential combustion of hydrogen, to partial decomposition, or to other change. (iv.) The exact nature of the flame of cyanogen, so as to ascer-tain wha’t governs the proportions of CO and COz formed in the inner cone. (v.) The manner in which the partition of oxygen takes place in the inner cone between C and H, H and S, C and S, so as to obtain information as to the affinities of C, H and S for oxygen.(vi.) The spectroscopic appearances of the flames. DISCUSSION. Professor THORPE,after expressing regret that time did not per- mit of the discussion of the numerous interesting questions which had been raised, referred to Professor Smithells’ remark, that the books failed to notice the fact that carbonic oxide was produced on partial combustion of methane. He pointed out that Mr. Thomas, several years ago, made a special study of this question, having been led to do so by the observation that in cases of undoubted marsh gas explosions in coal mines the men killed often exhibited an appearance suggestive of carbonic-oxide poisoning. Mr. Thomas found that carb- onic oxide and hydrogen were regular products of the incomp lete combustion of marsh gas.(Cf.Coal-mine Gases a?td Veiztilation, by J. W. Thomas. Longmans and Co., 1878. Also Imn, 1875). 71. “Note OIL the structure of luminous flames.” By Arthur Smithells, B.Sc. The author gives a brief summary of the various views that have been held on this subject. With one or two exceptions, there has been general agreement since the time of Berzelins that an ordi-nary candle flame, or the flame of coal gas escaping from a circular hole, is divisible into four chief regions: (i) the dark inner part; (ii) the luminous part; (iii) a small, bright-blue part at the base of the flame, thinning off rapidly as it extends upwards; (iv) a dim, scarcely visible, faintly luminous mantle surrounding the whole flame.The explanation which the author would give of these regions is as follows :-The gas or vaporised wax, on issuing from the orifice or wick, becomes mixed with air and burns. Whether or not the flame is luminous depends on the rate at which the combustible is supplied. If slowly supplied, sufficient air is admixed with the gas for non-luminous combustion. Thus a very small gas fla,me is non-luminous, and so also the flame of a candle, with the wick cropped close to the wax. It is conventionally said that coal gas burns with a luminous flame ; it is just as true to say that it burns with a non-luminous flame. The small, non-luminoas flame of coal gas, or of a short wick candle, is seen to have the same structure as a Bunsen burner, viz., a bright- blue, inner cone, and a, pale-lilac cone superposed upon it.The author supposes that we have here the same chemical changes occurring as are dealt with in the previous paper, viz., that the first combustion in the inner cone is mainly to CO,, H20,CO and H,, and the final me in the outer cone is mainly that of CO and H, to CO, and H20. This is made more probable by the fact that if the gas supply be increased, the luminous tip appears just at the point where it appears in the experiment with benzene, and that even after it is considerably developed the shape of the flame betrays the persistence of the inner cone. As the gas supply is further increased, the luminous area becomes increasingly great, the relics of the two original cones being very small.The author’s view is further enforced by the simple experiment of taking a flame about 5 cm. high from a Bunsen burner with the air holes stopped, noting the blue region at the base of the flame and the dim mantle outside it and then gradually turning on the air. The gradual transition shows unmistakably that the blue part and the mantle are the ‘‘ rudiments ” of the two cones of a Bunsen flame. With regard to the luminous part, everything goes to show that it is mainly a region where hydrocarbons are decomposed by the heat of the outer parts of the flame. The precise mature of the change is being studied by the auhhor. 165 The dark, inner zone contains mainly unburned gas, mixed with some products of combustion from surrounding regions.A commonly held view that the mantle of a luminons flnme is due to heated air and products of combustion is inconsistent with the above explanation, and also with the fact that in recent experi- ments it has been found impossible to render air luminous at the, highest attainable temperatures. The view ihat carbon is separated in a flame owing to the pre- ferential combination of oxygen with hydrogen, is opposed, the author thinks, to all experimental evidence, which he is of opinion goes to show that if the oxygen supplj- be limited carbon will burn befoye hydrogen. The author would describe a luminous flame as follows :-(i.) An outer sheath or mantle, with (ii) an inner, bright-blue portion visible at the base of the flame.These two parts correspond respectively to the outer and inner flame cones of a Bunsen flame, and mark t>he region where the coal gas or candle gas is burning with a large quantity of air. (iii.) The yellow, luminous part marking the region where the heat of the parts (i) and (ii) is decomposing hydrocarbons, setting free carbon, which rapidly glows and burns. (iv.) The dark, inner region, consisting of unburned gas, mixed with products of combustion of surrounding parts. Novelty is not claimed for this description, but the author considers that the experiments described in the preceding paper put the matter in a somewhat new light. 72. “ The existence of hyoscynmine in lettuce.” By T. S. Dgmond. Lettuce has been used in medicine from early times as a sedative, but the active constituent has never been with certainty determined.The author’s attention was drawn a few months ago to the mydriatic action of an extract of lettuce used in medicine. It had been pre- pared from the flowering plant of common lettuce according to the directions of the British Pharmawpczia. An examination showed that the mydriatic action was due to an alkaloid. Commercial specimens of the extract of wild lettuce and of the variety of the edible plant known as cos lettuce, obtained from three different sources, together with a specimen of the dried flowering plant of wild lettuce, were all found to contain this alkaloid. The alkaloid was most easily isolated by mixing the commercial extract with water acidified with acetic acid, adding alcohol till pre-cipitatioii of nearly all the constituents of the exti*act occurred, filter- 166 ing, evaporating the filtrate to a low bulk, :filtering again, washing the filtrate with ether till free from fat, then rendering it alkaline and extracting the alkaloid with ether.The impure alkaloid thus obtained was purified by conversion into the oxalate, and the precipi- tation of this salt by ether from itls alcoholic solution. On recovering the alkaloid and crystallising it from chloroform, it was obtained in silky rleedles having approximately the same melting point and other properties as hyoscyamine, the poisonous mydriatic alkaloid existing in belladonna, henbane and other plants belonging to the natural order Solanacece.The identity of tohe alkaloid with hyoscyamine was confirmed by conversion into the aurichloride which melted at 159.75",the melting point given by Ladenburg for hyoscyamine aurichloride being 159". The determination of the gold and the alkaloid in the compound afforded results corresponding with the formula of liyoscyamine auri-chloride, C1,HBNO3*HAuC14. The amount of hyoscyamine in the extract of common lettuce does not exceed 0.02 per cent., while in the flowering plant itself, it cannot be more than 0.001 per cent. It appears that this is the first occasion on which hyoscyamine or any other alkaloid belonging to that mydriatic group has been found in a plant not a member of the natural order XoZanacece, lettuce belonging to the natural order Conzpositm.DISCUSSION. Proiessor DUNSTANpointed out that it had been known from the time of the Greeks that lettuce had a. soporific action, and as Laden- burg and others had shown hyoscyainine to be a soporific, it was now possible for the first time tc explain an ancient Grecian practice. 73. " Cryptopine." By D. Rainy Brown and W. H. Perkin, Junr., Ph.D., F.R.S. The authors have commenced an investigation on the rare alkaloid cryptopine, which occurs in small quantity in opium, and which was first isolated by J. and H. Smith (Jnhresbericht, 1867, 523), and sub- sequently analysed by Hesse (Annalen, Suppl. 8, 209). Analyses of the base and of several of its salts led Hesse to assign to cryptopine the formula C21H,,N0,.The authors have prepared and analysed several samples which had been purified by conversion into the oxalate and subsequent recrystallisation from isobutyl alco- hol. The mean result of five analyses was- Theory for C21H23X05. C ... . .. 68*2:3 per cent. 68-29 per cent. H ...... 6.34 ,, 6-23 ,, N ...... 4.15 ,, 3.79 ,, The oxalake, after repeated recrystallisalion from water, was ob- tained in the form of beautiful glistening prisms, which, on analysis, gave the following numbers as the mean of four experiments :-Theory for C21H23NO,C?H?O,. C. ...... 59.82 per cent. 60.13 per cent. H....... 5.55 ,, 5-44 ), N.. ..... 3.31 ,, 3.05 ,, These analyses confil-in Hesse's results, and show that cryptopine has the formula C21H?3N05.On oxidstion with potassium permanganate, cryptopine yields among other products a crystalline acid, C10H1006,m. p. 179-180", which proves to be metahemipinic acid, C6H2(CH30)2(COOH), [l : 2 :4 :51, the acid which Goldschmidt obtained from papaverine ; this result is interesting in view of the fact that metahemipinic acid, up to the present time, has only been obtained from papaverine. The identity of the acid obtained from cryptopine with that from papaverine was proved by the fact that both yield an anhydride, C,,H,O,, m. p. 175", and an ethylimide, Cl2Hl3N04,melting at 226O. Cryptopine contains only two methoxy-groups, as shown by its behaviour when treated with hydrogen iodide, these two groups being situated in that part of the molecule which is converted into meta- hemipinic acid on oxidation.74. "The action of sodium on ethereal salts. Part 111. Benzylic orthotohate." By W. R. Hodgkinson. The behaviour of the different ethylic toluylates towards sodium was briefly referred to in these Proceedings in 1886 (p. 188). In all cases their behaviour is different to that of the ethylic salts of phenylacetic acid. No trace of any substituted acetic or benzenoid fatty acid could be found, and the action differs moreover in that no ring condensation appears to take place as is the case with ethylic phenylacetate, which affords "triphenylphloroglucol". In the case of the benzylic salt of orthotoluic acid, it was thought that either the CH, might act in a similar manner to the CH, in phenyl- acetic acid, or that two molecules would condense, forming dimethyl- ant hraquinone and benzylic alcohol. Benzylic orthotoluate, C6H,Me*C0,*CH2Ph,which does not appear to have been previously formed, is a, liquid of very pale-yellow coIour which boils without the least decomposition at 315" (thermometer in vapour).Rel. den. at 17" 1.12. A s mentioned in connection with triphenylphloroglucol, the pro- 168 ducts of the action of sodium on these ethereal salts differ consider- ably according to the conditions of the experiment. On adding the sodium to the oil previously heated to 200" it dissolved, and the tem- perature rose to 250", when an oil distilled over.This, on fractional distillation, separated into toluene and benzyl alcohol for the most part, with a smaller quantum of the original ethereal salt. The sodium salt in the retort dissolved in water, and gave on treatment in the usual manner an oil and an acid. Thi3 acid is pare o-toluic acid, The oil was found to consist of unchanged benzylic orthotoluate and a substance boiling at 350" (nitrogen thermometer in vapour) 360". This substance remained liquid at -10" and could scarcely be a derivative of anthraquinone. Analysis shows it to have the composi- tion C22H2002,which is that of a substance of the formula C6H4Me*CO2.CHPh(CH,Ph) . The quantity at present disposal has allowed only of hydrolysis with potassium hydroxide, from which it appears that only o-toluic acid is formed, and an oil which boils at about 250-280".The matter is still under investigation. 75. '' The gas-volumeter and gravivolumeter. By G. Lunge. In this note the author comments on Professor Japp's reply to his criticisms (Bey., 24,1656). 76. "The action of sulphuric acid on the bromides of hydrogen, potassium and sodium." By F. T. Addyman, B.Sc. The author has sought to determine the extent to which hydrogen bromide is oxidised by sulphiiric acid under varying conditions of mass and dilution. He first describes experiments in which sulphuric acid (d = 1-84) was allowed to act on potassium bromide, from which he infers that She amount of decomposition which the hydrogen bromide undergoes is very nearly proportional to the amount of sulphuric acid used ; but it is subsequently admitted that the extent to which the hydrogen bromide and acid come into contact greatly affects the result, so that a higher percentage would be decomposed in a, deep than in a shallow vessel. In the second section of the paper, a method of preparing a solution of hydrogen bromide is described, very similar to that of Feit and Kubierschky (C.S.Abstracts, 1891, 1320). An account is then given of observations on the amount o€ change produced by sulphuric acid in solutions of hydrogen, potassium and sodium bromides. But mere traces of bromine are liberated in solutions containing not more 169 than about 30 per cent. of sulphuric acid; and the percentage of hydrogen bromide decomposed is but small, even when as much as about 70 per cent.of sulphurie acid is present. 77. “ The iodometric estimation of chlorates.” By G. DiIcGowan Ph.D. Attention is called to Finkener’s statement, that when Bunsen’s method is applied to chlorates, less than the theoretical amount of chlorine is evolved. Experiments are then described, made in accordance with the method, and wit11 the apparatus of which an account is given at pp. 530-536 of this year’s volume of the Society’s Transactions, which corroborate the results of de Koninck and Nihoul, and prove the accuracy of the Bunsen method; Finkener’s error doubtless arose from a slight loss of chlorine. The author emphasises the importance of carrying out all such deter- minations in an apparatus in which the chlorine does not come into contact with india-rubber.ADDITIONS TO THE LIBRARY. I. Donations. Laboratory Practice : A Series of Experiments on the Fundamental Principles of Chemistry, by J. P. Cooke. New Pork 1691. From the Author. Reprints of Three Editorials regarding the Priority in Demonstrat- ing the Toxic Effect of Matter accompanying the Tubercle Bacillus and its Nidus. Philadelphia 1891. From the Bacteriological Laboratory, Acad. Nat. Sci. Philadelphia. The Organic Analysis of Potable Waters, by J. Blair. 2nd Edition 1891. From the Publishers. The Chemistry of Illuminating Gas, by N. H. Humphreys. London 1891. From the Author. Quantitative Chemical Analysis, by F.Clowes and J. B. Coleman. London 1891. From Professor Clowes. Engineering. Vols. I11 to XLIV. London 1867-1887. From Dr. W. S. Squire. The Principles of Chemistry, by D. MendelBeff. Translated from the Russian (3rd Edition) by G. Kamensky and edited by A. J. Greenaway. 2 vols. London 1891. From the Publishers. The Alkali-Maker’s Handbook, by G. Lunge and F. Hurter. 2nd Edition. London 1891. From the Publishers. 170 Examinations by the StnLe Board of Health of the Water Supplies and Inland Waters of Massachusetts 1887-1890. Parts I and 11. Report on Water Supply and Sewerage. Boston 1890. From R. Warington, Esq. At the next meeting, on December 17th, the following papers will be read :-1. “ The composition of cooked vegetables.” By Miss Williams.2. “ Some metallic hydrosulphides.” By S. E. Linder and Harold Picton. 3. “ The physical constitution of some solutions of insoluble sulphides.” By Harold Picton. 4. “ Solution and pseudo-solution,” By Harold Picton and S. E. Linder. 5. “The change proceeding in acidified solution of sodium thio- sulphate when the products are retained within the system.” By Dr. A. Colefax. 6. “The action of sulphurous acid on flowers of sulphur.” By 7. ‘‘ The a-and p-modifications of chlorobenzenc hexachloride.” Dr. A. Colefnx. By Dr. Matthews. 8. “ Camphrone, a product of the action of dehydrating agents on camphor.” By Drs. Armstrong and Ripping. 9. “ Studies of the dibromonaphthalenes.” By Dr. Armstrong and Mr. Rossiter. HAI<RISON AND SONS, PEINTERS IN ORDINARY TO HER MAJESTY, ST.MARTIN’S LANE.
ISSN:0369-8718
DOI:10.1039/PL8910700155
出版商:RSC
年代:1891
数据来源: RSC
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