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Proceedings of the Chemical Society, Vol. 12, No. 165 |
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Proceedings of the Chemical Society, London,
Volume 12,
Issue 165,
1896,
Page 103-112
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摘要:
PROCEEDINGS OX' THE CHEMICAL SOCIETY, EDITED BY THE SECRETARIES. No. 165. Session 1895-96. May 7th, 1896. Mi*. A. G. Vernon Harcourt, President, in the C:hair. Certificates were read for the first time in favour of Mews. Llewellyn John Davies, 8, Wordsworth Avenue, Cardiff ; Frederick William Harris, 62, Rectoyy Road, Burnley ; John Burnett Knight, Bushwwd, Wanstead, Essex ; Percy Sykes Marshall, Church School House, Lockwood, Huddersfeld ; Loxley Meggitt, The Laurels, SC. John's Street, Mansfield ; Sigmund Georgjewitsch Rosenblurn, 19, Russell Road, Kensington ; Douglas Stuart Spens Stewart, 9, Thistle Grove, Fulham Road, S.W. ; James Whitehead, R,oach Place, Roch-dale. The following were duly elected Fellows of the Society :-Henry Thomas Durant,, Ernest Hunter Fisher, W.Goodwiu, Edgar Hawkins, John Percival Jenkins, Robeyt Hazlewood Jones, Herbert Edwin Macadam, John McCrae, jun ., William Henry Merrett, Joseph W. Patterson, H. voii Pechmann, Thomas William Pilley, Robert Barnabas Pollitt, James Pronde, Charles El. Reissmann, Henry Fishwick Robinson, Otto Rosenheirn, Raymond St. George Ross, Walter Dalrymple Severn, John Christopher Stead, James Edward Shun1 Tuckett, Edward Chaning Wills, John Henry Wolfenden. Of the followiiig papers those marked * were read :-"60. " Carbon dioxide, its volumetric determination." By W. H. Syrnons and F. R. Stephens. After reviewing the various methods for estimating carbon dioxide in air, the authors describe one which they find to be reliable and at the same time convenient, For collecting the samples of air they use flasks from which all air has been expelled by means of steam, their vacuity being ascertained by weighing before and aftOr use.For ahsorbing the carbon dioxide, mixed solutions of sodinin Eiydroxide and barium chloride are used. The pressure of the sample of air in the flask is made equal to the atmospheric pressure by admitting a measured volume of air free from carbon dioxide, and the true volume is found by calculntion ; thus the pressure, and temperature at the time of taking the sampIe need not, be noted. The residual hydroxide is titrated, without being removed from the flask, with dilute acetic acid and phenolphthnle’in. The nse of thc same flask for collecting and cultivating micro- organisms, estimating albnmino’icl ammonia and oxygen absorbing matter, is suggested, and it is pointed out that ihe carbon dioxide may be estimated in the same sample of air, provided the number of organisms is not sufficient to influence the results throngh the carbon dioxide they produce.Examples of the trustwortliy nature of the process are given ; in some cases carefully measiired volumes of carbon dioxide have been estimated; in others, a series of samples have been taken from a closed space occupied by the authors. A compound pipette for accurately measuring volumes of gas or liquids is also described. “61. “On certain views concerning the condition of the dissolved sub-stance in solutions of sodium sulphate.” By R.F.D’Arcy, M.A. The differences in the solubilities of anhydrous sodium sulphate and its two well-defined hydrates, and the existence of a maximum solubility of the decahydrate at a temperature just below that at which it breaks up in the solid state into anhydrous salt and water, are properties which have been thought to indicate that these sub-stances dissolve as such. Other facts have been shown to be in accordance with the view that the condition of the dissolved salt is the same in all cases-the differences in solubilities being explained as being deteimined by the condition of the undissolved solid in contact with tlhe liquid. The experiments described wer2 undertaken with the object of finding if any evidence in favour oE the former, and now rather discredited, theory could be obtained by making careful experirllents on the viscosities of strong solutionc, of this salt, prepared in differ- ent ways and at different temperatures.The rcsulls obtained are in accordance with the view of the identity of the condition of the dis- solved substance in all cases. The experimental method, which differs in some respects from those used in other researches, is believed to give results which are free from ambiguity. 105 *62. “Luteolin. 11.” By A. G. Perkin. In EL previons communication (Tmns., 1896, 69, 206), it was shown that thc formula of luteolin is CI5H1,,O6,a fact determined by means of its compounds with mineral acids and with bromine.The production of its tetracetyl nncl benzoyl compounds proved it to contain four hydroxyl groups, and 011 methylation it yielded a product containing three metlioxy-groups. Since the publication of this paper: Herzig (Bey., 29, 6, 1013) has stated that he is also working upon luteolin. He mentions the methyl ether of the acetyl cornpoiid, and the decomposition of luteolin with fused alkalis. It is now shown that the product previously described, m. p. 210°, which, together with protocatechuic acid is formed by the action of fused alkalis npon luteolin, which did not then appear to be phloroglucol, is really this substancc, as surmised by Herzig (Zoc. cit.). On etliylntion, luteolin yields a triethyl ether, C,5H,06(O~2H5)~, (yellow needles, m.p.131--132’), insoluble in alkalis, which gives a monacetyl dei*isative, C,,H,06(OC,~c,),.C2~~0(coloudess needles, m. p. 185-186’). Decomposed by alcoEiolic potash this ether yields a crystalline yellow potapsium salt’, which is resolved by water into the free etlzcr. These reactions pave that the hydroxyl group in luteolin which resists etbylation is in the ortho-position to a carbonyl group. When heated with alcoliolic potash to 130-140”, luteolin triethyl ether yields the diethyletlier of protocatechuic acid, and a small qunn- tity of a substance which gives the phloroglucol reaction. The product of the methylation of luteolin (Zoc. cit.) closely resembles the ethyl ether in its reaction, as it contains three methoxy-groups, yields an acetyl compound, in.p. 174-1’75°, and a yellow potassium salt. Herzig (Zoc. cit.) gives the melting point of acetyl-luteolin 225-5227’, but an examination of the melting point previously obtained, 213-215’, shows that this must be considered as correct. A close resemblance of luteolin to ynercetin and fisetin is traced, and it is considered that quercetin, which is an hydroxyfisetin, is most probably also an hydroxyluteolin. 0 OH 0 OH op4/\-/-\OH *H/\/\-/-\oH I I \-/I\A,jiOH\--/ k/-L,dOH Fisctin. Quercetin. 0 OH Luteolin. "63. "Morin. Part L" By Hermann Bablich, Ph.D., and Arthur George Perkin. The yellow colouring matter, inorin, exists, as has been known for some time in old fustic (Mo~iistinetoria), and has lately been shown by one of us and P.Cope (Trans., 1895, 937) to be also contained in tho Indian dyestuff, Jackwood (A~tocn~pusintegrifolia). By means of its compounds with mineral acids the true formula of morin mas established by one of us and L. Pats (Trans., 1895, 67, 644) to be Cl,H,,O,. The principal reactions of morin described by previous workers arc its behaviour towards alkaline reducing agents (Hlasiwetz and Pfaundler, Jahi-es., 1864, 537), by which means it yields phloroglucol and p-resorcyclic acid, and towards fused alkali, when it gives phloroglncol and resorcinol. Of the substitiition products of moriu but three are described, viz., morinsulphonic acid, Cl5H9O,HSO3 (Benedikt and Hazura, Monatsh., 5,16T),tetrabromomorin,'Ci5H6Br407, and tetrabromomorinetbyl ether, C15H,Br40,.C,Ha. The latter is formed by brominating morin in alcoholic solution, andl can be con- verted into tetrabromomorin by means of zinc chloride and fuming hydi~ochloric acid.The action of fused alkalis and of bromine upon nioriii lias been investigated, and it is shown that by the foriiier means at 150-160" plllorogluc 01 and /3-resorcjlic acid are the principal products, and with the latter the results of Beiiedikt and Hazura have been con-firmed. Incidentally it has been found that, by the action of bromine on morin in presence of acetic acid, a considerably increased yield of tetmbromomorin is obtained. On acetylisation, tetrsbroinomorin yielcls pentacetjltetrabronio- morin, C15HBr,0,(C,H,O), (colourless needles, in.p. 192--293"), from which it is evident that moiain contains five hydroxyl groups. The principal product of the methylation of moriii is a tetramethyl ekher, C1,H6O,(OCH3), (light yellow needles, m. p. 131-13P). This substance is insoluble iii alkalis, but yields a monacetyl derivative, C,5H503(OCH,)4*CzH30(colourless needles, ni. p. 167O), and a crys-talline yellow potassium salt, which is decoinposed by water, regene- rating the ether. When digested with alcoholic potash at 150-160", the tetramethyl ether yields the dimethyl ether of /3-resorcylic acid (m. p. 107-108") and a sniall quantity of a product which gave the phloroglucol reaction. lllorin dimctlijl ether, C,H8Os(OCH,),, forms yellow needles melting at 225-227'.These results denioiistrate a close similarity between quercetin and morin, €or both contain five bydroxyl groups, one in the ortho-position to a carbonyl group, and both combine with mineral acids. Quercetin 107 yields with fused alkali pliloi~oglii~nland protocatechuic acid, mopin, ph 1o~oglu coi atid /&wsorcy1i c acid . The furinula of qnelrcetiii appears to he (Ilcrzig, 7kr.. 1895, 28, moriii is represented by that of quercetin, in which the catechol nucleus has been dis- placed by a resorciiiol group thus-0 OII 64. '' Synthesis of pentacarbon rings. Part I. Anhydracetonebenzil and its homologues." By Francis R. Japp, F.R.S., and G. Druce Lander, B.Sc. Anhj.dracetonebenzi1, which i(s obtained by the condensation of betizil with acetone, was first prepared arid investigated by Japp and Miller (Ti*aiis,,1885, 47, 27), and was afterwards further studied by Japp and Bui*tuu (Trans., 1887, 51, 420).In both of these earlier communications the opinion was expressed that in the condensation R closed chain of carbon atoms was formed. By osi2ation with sodium hypobrornite it gives an almost quanti- t ative yield of' Japp and Daviclson's desglemacetic acid, C,H,*Q:CH*COOH 7cpjH,.cO a reaction xhich constitutes the best means at present known of pre-paring this compound, and at the same time proves the configuration Tlie oxidation of anhydracetoiiebenzil by heating it with chromium trioxide in acetic acid solution was studied by Japp and Miller (Zoc.cit.). They thus obtained a product to which they assigned the con-stitution of a /3-benzoylhydrocinnarnic (des-jlacetic) acid. Desylacetic acid has, however, been since prepared by Victor Meyer and Oelkers. The present authors find that tlhe two substances are quite distinct. 108 Thcy also find that Japp and Millcr's acid is not the primary product of oxidation, for, when the process is conducted in the cold, sininltaneous oxidation and hydration occiii-, and dip72Pn?Jldil22/1~1.~~~yglzitai-ic mid, C6H5.~(OH).cH2*COOH c6H5.C(oH.) COOH (m. p. 120°, when rapidly heated), is formed. On heating this acid for some time at 100" it decomposes, parting with carbon dioxide and water, and yielding Japp and &Iiller's acid, mhicli has the formulu of an isoci?i~za112e.lzylnza12deZic acid, c68,*C?:CH, and which melts at 159-160°.(The meltingCsH,.C (0H)mCOOH' point, 152O, given by Japp and Miller is too low.) When boiled with funiing hydriodic acid, or with fuming hydrochloric acid, di-phenyldihydrosygluta~,icacid also parts with carbon dioxide and water ; but the carbon dioxide is in this case furnished by thc other C,H+ H.CH,.COOHcarboxyl group, and desy Zacctic acid, C,Hj*c0 (ni. p. 162'), is formed. Beyond the close approximation of the melting Foints, there is hardly any resemblance, either pli~sical or chemical, between these two isomel-ides, clesjlacetic acid and isocinnamenyl-mandelic acid. By partial reduction of isocinnamenylniaitdelic acid by boiling it for a few minutes with hydriodic wid, it is converted into isopherL-C6Hj* HaCH, .ethy 1wzde1ic ncid,C,H5.C(OH)*COOH (m.p. 1:34!--1 %P) By partial reduction of anhydracetonebenzil with hydi,iodic acid, Japp and Burton obtained R compound, Cl7HI10,melting at 110", which yielded a hydrazcjne, and therefore contained the origins1 carbonyl group of' the anhydracetonebenzi!. The authors show t!iat this reduction compound has the formula of a di~~e7L~lcycZope1Lteizoize, C,H,.g'CH2 >CO. That the foregoing cliaiige in the pvsition of the C:,H,j*C.CH, doublc boncts: li~staken place during the reducttion is shown by the fact that the compound yields, on oxidation with sodium hjpo-brornite, dipheny lrnalcic acid, which, when liberated from its salts, changes into the very characteristic anhydride, CGH5'fl*U0>0 (m.p.c6135. c'c0 1560). The hydrocarbon, C,,H,, (m. p. 47"), obtained by Japp and Burton by the complete reduction of anhydrncetonebenzil \vit#h hydriodio acid and amorphous phosphorus is a diphen~lcyclo~entane, C,H,.YII-CH, >CK2.C6H5*CH.CH, The various compounds obtained by .Jnpp and Burton (Trans, 1887, 51, 431) by the coBdensation of herdl with homologues of acetone of the general formulas CH2R‘-CO*CH3and CH,R’*CO*CH,R’ must be regarded as hoinologues of anh ydracetonebenzil. 65. ‘I Synthesis of pentacarbon rings. Part 11. Condensation of benzil with acetonedicarboxylic acid.” By Francis R. Japp, F.R.S., and G. Druce Lander, B.Sc.Bemil and acetonedicarboxylic acid, when gently warmed with dilute alcoholic potash, condense according to the equation yielding adiydraeeton ebenzilc arbuzylic acid (111. p. 16 7--268O), which corrcsponds with isophenanthroxyleneacetoacetic acid (.Tapp and Klingemann, Trans., 1891, 59, 2). When anhydracetonebenzilcarboxglic acid is boiled for a few minutes with fuming Hydriodic acid, it is reduced, simultaneously parting with carbon dioxide and yielding a diphenylcyclopentenone (m. p. llOo), identical with that obtained from anhydracetonebenzil itself (see preceding note). By oxidation with sodium hypobromite ,anhydracetonebenzilcarb-oxylic acid yields a mixture of diphenylm aleic and diphenylfurnaric acids, these two substances being produced in approximately equal quantity. A change in the position of the double bonds takes place during this process. When oxidiaed with chromiuni trioxide in acetic acid solution it parts with 2 atoms of hydrogen, yielding an acid of the formula C18H2204(m.p. 201”, with decomposition). The action of phenylhydraxine is complex. The primary product is a yellow compound, apparently the hydrazom ; but this readily changes, especially on recrystallisation, into dark red needles of a substance melting indefinitely above 200°, formed by elimination of 1mol. of water from 2 mols. of the hydrazone, 2C24H20N203 -HZO = C~~H~SN,O~. 66. “Reduction of desylenea cetic acid, and the constitution of Zinin’s pyroamaric acid.” By Francis R..Japp, F.R.S.,and G.Druce Lander, B.Sc. The authors find that by the action of zinc dust and acetic acid on desyleneacetic acid the latter is converted into Victor Meyer and Oel ke rs’s desy lace tic acid, 110 By t>he limited action of sodium amalgam on an aqueous solution of sodium desyleneacetate t'he same product is obtained. Excess of sodium amalgam, however, carries the reduction further, and Py-di-C,H,*yH*CH2*COOHphe~zyl-cy-hydi.ozt.ybutyricacid, , is formed, which C6H5*CH*OH when liberated from its salts, speedily changes into the lactone C6H5*FHQH2(m. p. 1120).C,H,.CH CO b' By boiliug desyleiiencetic acid for four 1iour.s.with hydriodic acid and amorphous phosphorus, it is couverted iut:, /!Iy-dipheuylbutyric acid, C,H,.C~I,.CK(C,K,)*CH2.COOH(m.p. 96-97'). Comparison o€ this substance with a specimen of pyt-oaiiznric acid showed that the two were identical. Pyroarna~ic acid was &-st obtained by Zinin (Jahresbericht, 1877, 813) by fasing amaric acid with caustic potash, and was regarded by him as an ethylbenzylbenzoic acid. Klingemann (Anna7eiz, 275, 81) suggested that it might be ii diphenylbutyric acid. Incidentally it was observed that when desylcneasetic acid is boiled with aqueous caustic potash it is hydrolysed, yielding dcoxybenzoin. Desylenemalonic acid is stable under these conditions. 67. " Electrolysis of potassium allo-ethylic calnphorate. Part 11." ByJames Walker, Ph,D., DSc., and Janes Henlerson, B.Sc. In addition to the coiiiponnds previously desmibed (Trans., 1895, 337) the auihors have obtained from the product of electrolysis of potassium allo-ethylic camphorate, a hydrocarbon, CBH14,boiling at 120', which is formed by the decomposition of an acid, CDHIIOP,011 heating.This hydrocarlsoii is appamntly identical with Zazwolene prepared from camphanic acid. A ketonic acid, C9E140J,m. p. 228", mas also isolated and investigated. The authors conclude that cam- phoric acid contains the complex -CH,GH*(COOH)-C(CO~H). 68. " Fluorene and acenaphthene." By W. R. Hodgk inson. Some recent communications in the AnnaleiL, by Giw be and his students, on fliiorene and acenaphthene, necessitate a short notice on my part about these substaiices in order to maintain priority. The author has worked at these hydrocarbons and their derivatives for the past 12 years, and in Proc., 1885, 36, refwence is inade to previous notes on the beliaviour of fluorane (Cl3Hi0) when heated alone, in air, or with oxidising agents.Lately he has associated Mr. A. H. Coote, with this work. In the paper above quoted, it is indicated thxt the red substance 111 obtained from fluorene (and also from acenaphthenc) can be sepnrated from the hjd~octtrbons (there called difluorylzz, C26H18.a.{3.y),and that this red substance is not a simple Iiydrwarbon, but contains oxygen. During the past three years a great number of results have been obtained. One conclusion arrived at is that no red or coloured hydrocarbon is produced by the oxidation of either fluorene or acenaphthene.The coloured compounds produced, along with the doubled rnolccule in the case of fluorene, CZ6HI6,(difluoryl), and the coloured substance along with tzcenaphthylerie in the case of acenaphthene, have been obtained almost pure. It is found that not only on heating with litharge, as Behr and Van Dorp first showed, but that almost any other oxide, and even potash, soda-lime, and chalk Iceland spar, will produce coloured oxidation products from both fluorene and acenaphthene, and especially from the latter. Phennnthrene, naphthalene, and anthracene, do not act in the same manner. On the other hand botb fluorene and acenaphthene may be passed along with hydrogen, steam, or hydrogen chloride, through tt red hot platinum tube without change.The isolation of thrse oxidation products is a difficult matter. They are not volatile alone without decomposition, and are as soluble in the usual liquids as the hydrocarbons. Picric acid also seems to precipitate them as well as the hydrocarbons. The ethereal and chloroform solutions of these oxidation products are highly fluorescent. The one from acenaphthene more 80 than that from fluorene. They form compounds with acid sulphites which are non-fluorescent. Two analyses (preps. 5 and 7) taken at random, C = 80.41, H =4.51,0 = 15.08. C = 79.89, H = 4.22, 0 = 15-89. The coloured substance from ffuorene is more difficult to obtain in quantity, or pure. The average percentage of oxygen is between 9 and 10.Sulphur behaves like oxygen towards both these hydrocarbons, and selenium also to a lesser extent. When the hydrocarbons are heated with dry sodium thiosulphate, or with some metallic sulphides, sulphur compounds of a red or orange colour are produced. Their solutions in ether and chloroform are also fluorescent. With sulphur or selenium, hydrogen sulphide and selenide are respectively pro-duced. In the case of fluorene a difluoryl is also produced on heating with sulphur. Several analyses of the red compound from acenaphthene and sulphur indicate the presence of about 13.26 per cent. of sulphur. 112 ADDITIONS TO THE LIBRARY. I. By Pwchase. 1 3rthol :t, C. L. Untersuchungen iiber die Gesetzc der Ver-wandtschaft.113 pp. Leipzig 1896. 8vo. (Ostwald’s Klassiker der Exakten Wissenschaften. 74). Berzelius, J. J. A View of the Progress and Present State of Anirna.1 Chemistry. Translated from the Swedish by Gustavus Brunnmark, D.D. viii+115 pp. London 1813. 8vo. Bouty, M., and Jamiu, M. J. Cours de Physique de L’Ecole Poly-technique. Suppl. 182 pp. Paris 1896. Svo. Comey, A. M. A Dictionary of Chemical Solubilities. Inorganic. xx+515 pp. London 1896. 8vo. Classen, Dr. Alexander. Handbuch der Analytische Chemie. 1 Theil, Qualitative Analysis. xii+242 pp. Stuttgart 1896. 8v0, RESEARCH FUND. A meeting of the Research Fund Committee will be held in June. Applications for grants, accompanied by full particulars should be sent to the Secretaries before June 8th. LOTHAR MEYER MEMORIAL LECTURE. The Lothar Meyer Memorial Lecture will be delivered by Pro-fessor P. Phillips Bedson, D.Sc., at an extra meeting of the Socisty on Thursday, May 28th, at 8 P.M. At the next meeting 011 May 21st, the following papers will be read :-“ The diphenylbenzenes. I. Meta,diphenplbenzeue.” By I?. D. Chattsway, M.A., and R. C. T. Evans. “ Derivatives of camphoric acid.” By Dr. P. S. Kipping. L‘ Some substances exhibiting rotatory power both in the liquid and crystalline states.” By W. J. Pope. RABHISON AND SONS,PHINTERS IN ORDINARY TO llEU JIAJESTY, ST. MARTIN’S LANE,
ISSN:0369-8718
DOI:10.1039/PL8961200103
出版商:RSC
年代:1896
数据来源: RSC
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