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Proceedings of the Chemical Society, Vol. 7, No. 94 |
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Proceedings of the Chemical Society, London,
Volume 7,
Issue 94,
1891,
Page 29-34
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摘要:
Issued 17/3/1891. PROCEEDINGS OF THE CHEMICAL SOCIETY. ~~ No.94. Session 1890-91. March 5th, 1891. Dr. W. J. Russell, F.R.S., President, in the Chair. Mr. A. W. Oxford was formally admitted a Fellow of the Society. Certificates were read for the first time in favour of Messrs. William Bate, National Explosives Company, Hayle, Cornwall; Alexander Lander, University Coilege, Bangor, North Wales ; Cecil George Freer Tlionger, Colonial College, Hollesley Bltj, Suffulk. The following papers were read :-14. "Crystalline form of the calcium salt of opt'ically active glyceric acid." By Slfred E. Tutton, Royal College of Science, London. This paper presents the results of a complete crystallographical inrestigation of the calcium salt, Ca(C,H,04)2,2H20, of the optically active (dextrorotatory) form of glyceric acid described (Trans., 1891, p.96) by Frankland and Frew. The crystals belong to the mono-clinic system, and are hemihedral, the forms (111) and (011) being only developed at the right-hand extremity of the symmetry axis, and the forms (sil) and (211) at the left extremity. The hemi- hedrism is also manifested by a difference in the prism faces of the fo~m(IlO), those upon the right side of the symmetry plane being much more brilliant than those upon the left side. The ratio of the axes is a : b : c = 1.4469 : 1 : 0.6694. A complete table of angles is given, the result of the measurement of a dozen crystals. The optic axial plane is perpendicular to the symmetry plane, and the first median line is nearly perpendicular to the basal plane.The true angle of the optic axes is 2Va,, = 34" 5G', 2Vax, = 35" 28', 30 2Va,, = 36" 16'. The mean refractjive index is 1.4496, 1.4521and 1.4545 for lithium, sodium and thallium light respectively. The sign of double refraction is positive. The calcium salt of this dextro- rotatory glyceric acid must therefore be added to the list, of optically active substances whose crystals are also hemihedral, a list which includes all the hitherto well investigated cases. 15. " Fermentations induced by the Pnezcmococczm of Friedliinder." By Percy F. Frankland, Ph.D., B.Sc. (Lond.), Arthur Stanley and Wm. Prew. That this well known micro-organism is capable of inducing fer- mentative changes in suitable solutions of glucose and cane-sugar was first pointed out by Brieger (Zeit.f.pkysiol. Chem, 8, 306-331, and 9, 1-7). The authors have confirmed these observations of Brieger's, and have further found that the orgaiiism ferments maltose, niilk-sugar, raffinose, dextrin and mannitol, but that, like the Racittzc,~ ethaceticus, it does not attack dulcitol. They have made a special study of the fermentations of glucose and mannitol, determining quantitatively the proportioils in which the several products are formed. These products are in each case ethyl alcohol, acetic acid, generally accompanied by a little formic acid and a trace of succinic acid, carbon dioxide and hydrogen. Both the glucose and mannitol were in all cases only partially fexnented, and the decomposition of the glucose was especially incomplete, glucose being apparently less readily attacked by the organism than mannitol and cane-sugar.The fermentation was not rendered more complete by furnishing the organism with a more abundant supply of' nitrogenous food. In the first iristaiice, fermentations were condiicted on 60 grams of glucose and mannitol respectively, with the following resnl ts :-I. 11. IIT. Glucose. Munnitol. Mannitol. Ethyl alcohol . . .. 0.5897 gram 4.11 gram 5-06 grams. Volatile acids cal- culated as acetic 1.6578 ,, 2.9921 ,, 3.1617 ,, acid . . ..... . . . I The products of the mannitol fermentations are not only qualitatively similar to those obtained in the fermentation of the same substauce by the BaciZZus ethaceticzcs, but the relative proportions in which they are formed are almost identical, the ratio corresponding closely to the molecular proportions 2C2H5*OH: CH,3.COOH.In the subsequent experiments, in which the volume and composi- of the evolved gases were determined, only 12 grams of mannitol were employed ; in this case also very similar ratios were obtained, 31 although a period of two years had elapsed since the above fermenta- tions had beeu carried on. The following results of analysis show the composition of the gas evolved in a fermentation with 12 grams mannitol, after the air in the appamtus had been displaced :-16th day. 23rd day. 34th day. 4lst day. Average.CO, .. . .. 0,........ H? .... . .. 51.7’7 0.09 47.97 61.29 0.15 38 26 66.18 0.22 33.47 65.47 0.09 54-19 61.18 0.14 38.47 N?....... . 0-17 0.30 1-13 0.25 0.21 - ~ 100~00 100~00 100.00 lGO.00 100.00 The lower proportion of carbon dioxide in the earlier part of the fermentation is doubtless due to thc liquid saturating itsel€ with the gas, and the excess at the end to the slow decomposition of the calcium bicarbonate formed in the first instance. The average com- position of the gas may be taken to be G volumes or molecules of carbon dioxide to 4 volumes or molecules of hydrogen. Taking into account the actual volume of gas given off, the several pro-ducts are in very close accord with the molecular proportions: 9C,H60 .4C2H40,: 12C0, : 8H2, derived from 6 mol. props. of mannitol, 2 mol. props. of carbon dioxide being formed by the action of the acetic acid on the added calcium carbonate. By plotting out the roluines oE evolved gas on a diagram, in which the ordinates represent the volumes in cubic centimetres, and the abscissz the time of fermentation in days fkom the date of inocula-tion, tlie authors obtain a CLIWO for which the equation is 6*73t2 ‘u= 1 -O-OOtjt + 0*00574t2’ 16. “ The volunietric estimation of tellurium. Part 11.” By B. Brauner, Ph.D. The author finds that although a solution of iodine in potassium iodide acts on alkaline tellurates in accordance with the equation NaLTeO, + I, + ZNaOH = Na2Te04 + 2NaI + H20, the action is very slow and incomplete at the ordinary temperature, so that heat must be applied for its completion.On acidification the excess of iodine is set free, but it has hitherto been found impossible to exactly determine tlie end of reaction by titration with thiosulphate. The titration of solutions of tellurium dioxide in chlorhydric acid wit>h permanganate is found to be impracticable, as varying quanti-ties of chlorine are evolved during the process. 32 When a solution of telluyium dioxide in sulpliuric acid is titrated with permanganate, the following interchange occurs :-2KMn04 + 4H2S04 + 4Te0, = K2S04 + Mn2(S04)3+ 4H,O + 4Te0,. In order to destroy the manganic salt which is formed, either cleci-normal ferrous sulphate or oxalic acid is added until decolorisation takes place, after which permanganatc is added in slight excess.After subtracting the volume of permangnnnte corresponding to the ferrous salt or to oxalic acid from the kotal of permanganRte added, the quantity of tellurium dioxide is calculated from the volume of permanganate uecessary for its oxidation, as if the following action had taken place: 2KMn0, +-3i3,S04 + 5Te02 = K2S04+ 2MnS04 + 3H20 + 5Te0,. Owing to the evolution of some oxygen, the quantity of tellurium dioxide found is greater by 1 per cent. than that calculated from the equation. In alkaline solution the change which takes place is that indicated by the equation 2KMn04 + 3Te0, = K,O + 2MnOz + 3Te0,. After addition of an excess of sulphuric acid oxalic acid is used for retitra-tion in the manner previously stated, but the results are 0.35 per cent.too high. The results obtained by both methods are accurate when the corrections mentioned are applied. 17. “ Chloro- and bromo-derivatives of naphthol and iiaphthyl- amine.” By Henry E. Armstrong and E. C. Rossiter. This communication is a continuation of one published in these Proceedings in 1889. 1: 4-DicFvZo~o-/3-naphthol.-A bettei. yield of this compound than is obtained by Zincke’s method appears to result from the gradual interaction of chloro-&naphthol and sulphuryl chloride at ordinary temperatures, about 50 per cent. of the chloro- being converted into the dich loro-compound. The mixt ui-e obtained on steam-distilling the crude product is sulphonated, and the mixture of salts resulting From the direct neutralisation of the acid solution with potassium carbonate is extracted with boiling alcohol, which dissolves the dichloro- but not the monochloro-sulphonate.The dichloronaphthol is recovered by heating the sulphonate with dilute snlphuric acid at 210”. 1 :4 : 4‘-T/.ichloro-/3-nu~h~hoZ.-The oily by-product obtained in preparing a large quantity of trichloro-p-ketonaphthalene,when allowed to stand during many months, was found to slowly give off hydrogen chloride and to become partially solid ; the solid was freed from oil by washing with acetic acid and was recrystallised from this solvent. The substance thus obtained proves to be a trichloro-/3-naphthol, and as it yields 1 : 2 : 3-chlorophthalic acid on oxiclat,ion, and is reduced by sodium amalgam to 1: 4-dichloro-p-naphthol, it is most probably the 1:4 : 4'-modification.It crystallises in short, soft needles melting at 15'7-158" ; its acetyl derivative melts at 129". C'hlol.o-P-n,aplitholsu~honicacid.-1-Chloro-, 1:3-and 1:4-dichloro-, and 1: 3 : 4'- and 1: 4 : 4'4t~richloro-~-naphtholare all sulphonated with the greatest ease, each yielding a derivative of 1:3'-(Schaefer's) p-naphtholsulphonic acid, proof that this is the case being afforded by the formation of this acid from each of the chloro-acids on reduc- tion. This result is noteworthy inasmuch as 3' : 1-dibronlo- and brotnochloro-@-naphthol-in which the position occupied by the sulpho-group in Schaeier's acid iR occupied by bromine-are distiqtly less rea(di1y sulphonated than any of the chloronaphthols referred to ; and it is a matter of interest also that neither is a derivative of the Weinberg P-acid, isomeric with Schaefer's, formed from them : hence it would seem that a ~-sulplionic acid only results when the p-3'-posi-tion is free, viz., that mhich is symmetrically situated relatively to the /I-OH group. 1: 3'-Dib~omo-and bronzochloi-o-P-napl~t~ol.-In the previous com- munication it was stated, tbnt on brominating either bromo- or cliloro-P-naphthol, the bromine is introduced into the second nucleus.To determine the position taken up by the bromine, the broniochloro- naphthol was distilled with PCI, ; 1 : 2 : 3'-trichloronaphthalene was one of the products obtained, and it would seem therefore that it occupies the position 3'-.As both dibromo- and bromochloronaph-tho1 afford 1: 3 :4-bromophthalic acid cin oxidation, this conclusion may be regarded as establishod. Independent confirmation of this result is afforded by the observation that chloro-p-acennphthalide is converted by bromine almost quantitatively into a bromochlorace-naphthalide (m. p. 21Go), which affords a bromochloronaphthylamine (m. p. 119.) and a bromochloronaphtlialene (m. p. SO0) in which the bromine atom occupies the p-3'-position; also by Claus's recent ,statement that when brominated bromo-p-acenaphthalide in like niauner yields 1:3'-dibromo-p-naphthylamine(J.pi*.Chenz.). The conclusion thus arrived at, however, is in opposition to that to be deduced from Smith's and Meldola's statement, thatl tetrabromo-,& naphthol, when oxidised, yields the bromophthalic acid whose an-hydride melts at 134", i.e., the 1 : 2: %acid.The authors hsve, therefore, studied the action of bromine in excess on @naphthol. They find that, contrary to Smith's statement, the preparation of tetrabromonaphthol is attended with very considerable difficulty, the product chiefly consisting of tribromonaphthol ; the separation of this latter by crystallisation is difficult, but is easily accomplished by acetylating the crude product and recrystallising the acetate from benzene and from acetic acid. The acetate crystallises in long, fine 34 needles melting at 184”, an3 is very easily hydrol~sed.Trihromo- naphthol melts at 155-156” ; on oxidation with alkaline permnn- ganate it yields 1 : 3 : 4-bromophthalic acid. The authors are still engaged in investigatkg this compound and the other products of the action of bromine in excess on P-naphthol. Actio?z of nitric acid and of oxicJising agents on chloro-and byonzn-naphthok-Nearly all the chloro-and bromo-derivatit-es of p-naphthol yield characteristic quinone derivatives when submitted to the action of nitric acid ; in most cases the formation of these is pre-ceded by that of an unstable intermediate compound, the deterininn- tion of whose composition presents great difficulties. The final product of the action of nitric acid is a phthalic acid.Alkaline per- manganate is not always a suitable agent to employ if the object be to completely oxidise the naphthol: thus the main product of its action on dibromo-/3-naphthol, for example, is the acid C6H3Br<gz>0---COOH, IT hich, on distil lation, yields bromophthalide. ANNIVERSARY MEETING. Wednesday, March 25th,at 8 P.M. At, the next meeting, on March 19th, the following papers will be read :-“ The molecular refraction and dispersion of various substances.” By Dr. Gladstone, F.R.S. “ Contribntions to our knowledge of the aconite alkaloids. Part T. On the crystalline alkaloid of Aconitum napellus.” By Professor Dunstan and Dr. W. H. Iuce. ‘(The crystallographic; characters of aconitine from Bco7iitwn napellus.” By Mr. A. E. Tuttan. HANILISON AXD SONS, PRINTERS 119 ORDINARY TO HEX MAJESTY,ST.MARTIN’S LAKE.
ISSN:0369-8718
DOI:10.1039/PL8910700029
出版商:RSC
年代:1891
数据来源: RSC
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