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Proceedings of the Chemical Society, Vol. 28, No. 402 |
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Proceedings of the Chemical Society, London,
Volume 28,
Issue 402,
1912,
Page 135-150
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[ISSUC~30/5/13 PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 28. No.402. Thursday, &fay 16th, 1912, at 8.30 p.m., Dr. M. 0. FORSTER, F.R.S., Vice-president, in the Chair. Certificates were read for the first time in favour of Messrs.: Arthur Fred Campbell, M.Sc., Westwood, Middleton, Manchester. Leslie Melville Clark, 3, Harley Road, Hampstead, N.W. Bhupati Nath Das, M.A., B.Sc., Wari, Dacca, Eastern Bengal. Gerard Irvine Davys, Cape. I.M.S., B.A., M.D., B.Ch., Beechview, Kidbrook Grove, Blackheath, S.E. Donald M. Fergusson, c/o Acadia Sugar Refining Co., Ltd., Halifax, Nova Scotia. Harold Hartley, M.Sc., Fernbank: Little Switzerland, Douglas, I. of M. Henry Medley Hatherly, 14, Stackpool Road, Southville, Bristol. Max Henius, Ph.D., 1135, Fullerton Avenue, Chicago, Ill., U.S.A.Edward Lewis James, Holly Lodge, Larkhall Rise, Clapham, S.W. William Jewell, 44,Highfield Road, Dartford, Kent. Frederick James Meister, 1, Stanley Terrace, Alva. Robert Charles Menzies, 27, Cluny Drive, Edinburgh. Sidney Morgan, Rubber Growers' Association Laboratory, Pataling, Kuala Lunipur, F. 31. States. George Ernest Pearson, Prospect Cottage, Sutton, nr. Hounslow. William Daveridge Hamilton Shaw, B.Sc., c/o Coppbe Coke Oven Co., Ltd., King’s House, Kingsway, W.C. William Thgvenaz, D. 6s Sc., 48, Grey Street, Hdl. ‘William Leonard Thomas, 10, Victor Road, Bradford. Certificates have been authorised by the Council for presentation to ballot under Eye-law I (3) in favour of Messrs. : Chatindra Nohan Dutta, M.A., Dacca College, Dacca, India.Anakul Cliandra Sircar, M.A., Dacca College, Dacca, India. Of the following papers, t,hose marked * were read: *116. ‘‘Aniline-black and allied compounds. Part 11.” By Arthur George areen and Arthur Edmund Woodhead. Willstatter and Cramer (Ber., 1911, 44, 2162) have advanced the view that the product of reduction of emeraldine or nigraniline with titanium trichloride or phenylhydrazine in the cold is not as the authors have stated leueoemeraldine, C,H,*NH. [CbH,*N13J,*CGH,*NH,, but the mono-quinonoid compound, C,H,*NH-[ CbH,*NH],: C,H,:NH. Such a view is improbable in face of the fact that the base is practically colourless, but in order to remove all doubt the com-pound has been subjected to the action of boiling titanium tri- chloride in an atmosphere of carbon dioxide.The compound remained unaltered, and only a slight change in the titre of the titanium trichloride (due to air oxidation) occurred. It must therefore be concluded that the base is actually the leuco-compound, and does- not contain a quinonoid group. The true mono-quinonoid compound (protoemeraldine) was prepared by reduction of emeraldine with sulphurous acid. It is a violet base forming yellowish-green salts, and dissolves in 80 per cent. acetic acid with a grass-green colour. These observations confirm the previous conclusions of the authors as to the number of quinonoid groups in the primary oxidation products of aniline. The “ aniline-blacks ” of Willstatter and Dorogi are mixtures of these primary products with polymerised derivatives, due to the action of the mineral acid used in purification, and cannot be regarded as identical with the true aniline-black formed on the fibre.137 “117. ‘(Azo-dyestuffsof the triphenylmethane group.” By Arthur aeorge Green and Bajendra Bath Sen. With the object of ascertaining the effect on the colour exerted by two chromophors, the azo-group and the carbinol group present in the para-position with respect to each other, the authors have prepared a series of azotriphenylmethane and azotriphenylcarbinol dyestuffs by condensing azoaldehydes, such as phenetoleazobenz-aldehydesulphonic acid, OEt-C,€3,-N,*C6H3(bO,E€)*CHO, witn 2-hydroxytoluic and salicylic acids.The condensation occurs readily in cold concentrated sulphuric acid solution, giving azotriphenyl- methane derivatives, which by reason of the presence of the azo- group are yellow dyestuffs. On oxidation with nitroiyl sulphate they are converted into azotriphenylcarbinols, as, for example, the compo und Me /-\ \-/Me The latter are well defined polygenetic dyestuffs, dyeing wool directly in red shades, and producing various colours with different metallic mordants. The chromium lakes, which are black, can also be produced on the wool fibre by dyeing with the azotriphenyl- methane dyestuffs, and then boiling the wool with an acidified solution of sodium dichromate, when both oxidation and combina- tion with chromium occur together, and the colour changes from yellow through maroan to black.The conclusion is drawn that the colour of these dyestuffs is an additive eifect produced by the two chromophors acting separately. *118. Investigations on the dependence of rotatory power on chemical constitution. Part 111. The rotatory powers of ac-tetrahydro-2-naphtholand some of its esters.’’ By Robert Howson Pickard and Joseph Kengon. ac-Tetrahydro-2-naphthol has been resolved into its optically active components by the fractional crystallisation from acetone of the brucine and cinchonidine salts of the hydrogen pkthalic ester. The active alcohols have a considerably higher rotatory power ([a]D+67*2O in 5 per cent. chloroform solution) than that previ- ously given (Pickard and Littlebury, Trans., 1906, 89, 1254), and 138 crystallise very readily from light petroleum in long needles which melt at SOo.A series of esters of the active alcohols with normal fatty aci& (acetic to lauric) has been prepared. The values of the molecular rotatory powers of these gradually diminish from the propionate until the nonoate term is reached, after which the value increases. In close agreement with these results are the determinations of the efFect of temperature on the rotatory power of these esters. The acetate with [MI: 109.2O, propionate with [M]F116*2O, n-valerate with [MI: 113’7O, n-heptoate with [Mg 111.5°, and the n-nonoate with [M]~102.0° were obtained as viscid oils at the ordinary temperature, whilst the Zaurat e with [MJF107.9O solidifies to a crystalline mass and melts at 36O.DISCUSSION. Dr. A. E. DUNSTANpointed out that it would be possible, by means of viscosity determinations, to find out whether the mixture of the d-and Z-tetrahydronaphthols was a racemic mixture or a true compound, seeing that the melting points of the optical antipodes were low enough to enable measurements to be made in the liquid state. *119. “Chemical examination iof the bark of Euonymus atro-purpureus.” By Harold Rogerson. A description was given of a complete examination of the root-bark of Emruymus atropurpureus, Jacquin (Nat. Ord. Cekstraceae). The new substances which have been isolated and characterised comprise a new crystalline acid, furan-fl-carboxylic acid, C,H40, (m.p. 121-122O) ;a new crystalline alcohol designated euonymol, Cz,H,04 (m. p. 248-250°), and a series of new alcoholic substances which eve colour reactions similar to the phytosterols, and have been designated euonysterol, C3,H,,0-OH (m. p. 137--138O), homo-euonysterol, C4,H6,0*OH (m. p. 133-134O), and atropurol, CnH,(OH), (m. p. 283-285O) respectively. Various other definite substances have also been isolated and identified, amongst which may be mentioned dulcitol, C6HI4O6; citrullol, CBH360?(OH)2;and a mixture of fatty acids. No evidence waa obtained of the presence of a glucoside in the bark. DISCUSSION. Mr. FINNEMOREasked if the substance euonymol obtained in small quantities from the aqueous extract had been tested pharma- 139 cologically.Seeing that the drug had been shown by "eyer to contain a heart poison, it seemed to be of some interest, as eaonymol appeared to give the same colour reactions as cynotoxin, the heart poison obtained from Apcynum. Mr. ROGERSON,in reply to Mr. Finnemore, stated that euonymol had not been physiologically tested; and in reply to Dr. Harden said that Euonymus atroprpureuu, Jacquin, was a good source of dulcitol, the yield being equivalent to 2.09 per cent. of the weight of root-bark taken. *120. ('Furan-2 : 5-dialdehyde." By William Francis Cooper and Walter Harold Nuttall. In the preparation oi dehydromucic acid by the oxidation of o-chloromethylfurfuraldehyde with nitric acid, a considerable quantity of furan-2 :5-dialdehyde is produced if the reaction is retarded by cooling.A small quantity of a crystalline acid (m. p. 196--197O), probably furan-2-alcTehyde-5-carboxylicacid (pyromucic aldehyde), is also formed. Furan-2 :5-dialdehyde is a white, crystalline compound melting at 109*5-110°, which on oxidation gives dehydromucic acid. It is characterised by the blue colour which it gives with thymol and excess of sulphuric acid. The diphenylhydrazone (m. p. 206--207°), dioxime (m. p. 212~5-213°), dknilide (m. p. 160-161°), and 8-naphthylamine derivative (m. p. above 230O) were described. The dialdehyde is also formed in the ret'arded oxidation of o-hydroxymethylfurfuraldehyde with nitric acid.o-Hydroxy-methylfurfuraldehyde is most conveniently prepared by pouring crude w-chloromethylfurfuraldehydeinto a large excess of almost boiling wa.ter, without the presence of any reagent capable of reacting with the liberated hydrogen chloride (namely, silver nitrate or barium carbonate) as recommended hitherto. B-Naphthylamine is a very convenient reagent for the identifica- tion of aldehydes of the furan series. The rS-naphthyZamine derivatives of methylfurfuraldehyde (m. p. 87-88O) and w-hydroxymethylfurfuraldehyde (m. p. 131-132O) were described. "121. Researches on aantalin. Part I. Santalin and its derivatives." By John Cannell Cain and John Lionel Simonsen. The authors have examined the saplings of Pterocarpas santalkus (red sanderswood), and have investigated the colouring matter, santalin, contained in the wood of the tree.140 The colourless saplings conta.in free sugar and a glucoside, which on hydrolysis decomposes into a pMobup7t etz and dextrose. Santaliii, whether obtained from the wood as grown in India, from the rasped wood imported into England, or from the commercial dyestuff, has the formula C,,H,O,, and melts at 226O. It forms diacetyl, nitro-diacetyl, and dz‘benioyl derivatives, and the Tzitro-and benzeneaeo-derivatives have been prepared, as well as the oxinie and dimethyl ether and its nitro-derivative. Oxidation of the dimethyl ether furnishes veratric and anisic *acids, and the nitrodimethyl ether when oxidised yields anisic acid and probably a nitroveratric acid.122. “Action of Grignard reagents on esters of dibasic acids.” (Preliminary note.) By John Theodore Hewitt and David Bernard Steinberg. By the action of magnesium phenyl bromide on diethyl phthalate, Shibata (Trans., 1909, 95, 1449) obtained a compound of the formula C”,,H,,O, melting at 194--195O, to which he assigned the constitution : Certain theoretical conclusions as to the nature of the benzene nucleus were based on the assumption that the compound contained $he phenylene group attached to a single carbon atom. Following Shibata’s directions, a compound is obtained identical with diphenylanthrone synthesised by Haller’s method from phenyl- oxanthroa yl chloride and benzene in presence of aluminium chloride, as shown by appearance, solubilities, and mixed melting point, 193O.Shibata’s observaiion that the compound is stable towards bromine and potassium permanganate is thus readily explained. 123. ‘‘The constitution of aminotgrosine and the action of oxgdnses on some tyrosine derivatives.” By Casimir Funk. An attempt has been made to prepare an optically active 3 :4-dihydroxyphenylalanineby the action of nitrous acid on amino- tyrosine, which was considered to be 3-aminotyrosine. In this way an optically inactive compound was isolated, which possessed the composition of the initial product, but differed from the latter in the colour of the crystals, melting point, and behavionr towards oxgdases. It was concluded therefore that aminotyrosine is a mixture of 141 2- and 3-aniinotyrosine7 the product obtained being 2-aminotyrosine.Further, the action of laccase and tyrosinase on amino-and hydroxy-tyrosine and adrenaline was testled, and it was found that both ferments are able to oxidise these substances. 124. (‘The dynamic isomerism of ammonium thiocyanate and thio- carbamide.” By William Ringrose Gelston Atkins and Emil Alphonse Werner. A careful study of the freezing points of mixtures of the two isomerides at temperatures above 130° shows a deviation from the simple form of the freezing-point composition diagram given by Findlay (Trans., 1904, 84, 403). Evidence has been obtained indicatibg the presence in the fusioii of the compound (CSN,H,),NH,SCN ; this undergoes dissociation, even below its apparent melting point (144O).The form of the curve obtained clearly shows that the true melting point of thiocarbamide itself lies at about 200O; the very rapid reversion which takes place before this temperature can be reached renders its experimental realisation impracticable. The reversion has also been studied in aqueous and in alcoholic solution; the results obtained in the former case confirm the work of Dutoit and Gagnaux (J. G%m. phys., 1906, 4, 261). Values were given for the velocity constant of the reversion of ammonium thiocyanate in the liquid phase; the mean value of Kl is 0.00295, as compared with Ii1=0.00633 found by Waddell (J. Physical Cheiiz., 1898, 2, 525).The series of tetrathiocarbamide alkali iodide compounds has been completed by the preparation of the rubidium and msium derivatives. (CSN,H,),RbI (m. p. 202O) and (CSN?H,),CsI (m. p. 1910). Lithium and sodium iodides do not form any compounds with thiocarbamide. The compound (CSN2H,),KI has already been described (Werner, PTOC.,1906, 22,245). Thiocarbaniide and potassium thiocyanate unite to form the compound (CSN,H,),KSCN (m. p. 143O), analogous to the above ammonium compound. 126. “Properties of mixtures of ally1 alcohol and water. Part I,” By Thomas Arthur Wallace and William Ringrose Gelston Atkins. In order to be able to analyse accurately the mixtures of the alcohol with water during the subsequent work, a complete density- 142 composition diagram was plotted for Oo.Analysis may also be satisfactorily carried out by a slight modification of the bromine absorption method. A large contraction in volume was found, amounting to 2-54 per cent. with a mixture containing 39 per cent. of alcohol when determined at 0“. The pure alcohol had D: 0.86929 and boiling point 96.95O. The alcohol and water afford a binary mixture of constant boiling point, as already known. The composi- tion of thisis 72 per cent. of alcohol and 28 per cent. of water, and its boiling point is 88*0°. In determinations of the above composi- tion, the middle-point distillation method of S. Young gave values which agreed closely with those obtained from the density curve. The behaviour of the alcohol on distillation with benzene and water is at present under investigation.126. ‘‘Amodification of the Beckmann apparatus.” By Edmund Knecht and John Percy Batey. The authors find that by employing a heating coil pf suitable resistance, internal electrical heating can be used in the Beckmann apparatus for determining the molecular weight of substances in aqueous solution without electrolysis taking place. Quite constant readings are obtained without any special precautions. The appara- tus has been used for determining the molecular weights of certain dyestuffs, such as benzopurpurine and indigo-white. 127. b4 Alkaline cupri-compounds.” By Spencer Umfreville Pickering. Twenty-four cupri-compounds of tartaric aud racemic acids were described, representable by ten general formulz, derived either from a molecule of the copper salt or of the double salt of copper and the alkali metal, by the copper atom becoming quadrivalent., and the introduction of OH, OM’, or OzCuN groups through the action of alkali. Four of the salts are represented by the empirical formula (R&uM’,),,EiCuO; in the others, which are alkaline in reaction, the ratio of copper to alkali metal is 1:1, 1 :2, 1:2.5, 1:3, 1:4, 1:5, and 1:6.All the compounds except those with the ratio 1:1 are crystalline. Copper racemate itself exists in two different forms, one of which is probably a “cupri”-salt, and ia much more soluble than the ordinary racemate. 143 128. 6‘ The constituents of West Indian satinwood.” By Samuel James Manson Auld and Samuel Shrowder Pickles.An investigation of West Indian satinwood (Zanthoxylum flauum, Vahl. ;Fagara flava, Kr. et Urb.) has been made, the primary object of which was to determine whether it contained irritating or poisonous principles, such as have already been shown to be present in East Indian satinwood (Auld, Trans., 1909, 95, 964). The exgination has shown it to contain several interesting compounds of a lactonic character, together with a number of non-crystalline resins. These include a colourless, crystalline compozcnd, C11H1003 (m. p. 124-126O), and a pale yellow, crystalline substance, CI4Hl2O3 (m. p. 133O). Derivatives of the latter have been obtained, and its general behaviour has been studied.It yields a characteristic &bromide, Ci4Hl2O3Br, (m. p. 125O), in which, on treatment with water, one of the bromine atoms is replaced by a hydroxyl group, giving a compound, Ci4H,30,Br (m. p. 168-169O). A series of resins has also been separated, as well as a further crystalline cornpownd (m. p. 112-114cj. The pharmacological action of the various constituents of the wood is at present under investigation by Prof. Cash, of Aberdeen University. 129. ‘(Optically active derivatives of Z-methoxy- and d-dimethoxy- succinic acids.’’ (Preliminary note.) By Charles Robert Young. In continuation of previous work (Purdie and Young, Tram., 1910, 97, 1524), d-dimethoxysuccinanilide and d-dimethoxyysuccilzr anildc acid have been prepared by the action of aniline on d-di-methoxysuccinic acid and its anhydride respectively.The anilide crystallism from benzene in slender needles (m. p. 137-139O), aiid in dilute acetone solution has a, +259O. The anilic acid (m. p. 120-122O) separates from solution in acetone in small prisms; in the same solvent it has a, + 134O. Attempts are now being made to prepare, from the anilic acid, the corresponding anil and isosnil. Other active derivatives of Cmethoxy- and d-di-methoxy-succinic acids of these types are under investigation with the view of studying their optical behaviour. 130. The mechanism of the racemisation of some hydroxy-acids 64 by heat.” By Dan Ivor James and Humphrey Owen Jones. The process of racemisation of malic acid in aqueous solutions (concentration about 8 per cent.) at about 160° has been studied, 144 and it has been found that racemisation takes place through the intermediate formation of fumaric acid, a change which is reversible.The corresponding change in the case of tartaric acid would produce hydroxyfumaric acid, as suggested by Nef ;this acid itself or its isomeride, oxalacetic acid, would be expected to lose carbon dioxide and yield pyruvic acid. The formation of considerable quantities of pyruvic acid has been established, and it is probable that the following changes take place: CO,H*~H*OH -CO,H*g*OH -CH(OH)*CO,H .-CH-CO,€€ --CO,H*yO * Co2HeSo + co,.CH,*CO,H CH3 131. ‘‘ The action of sodium hgpobromite on carbamide derivatives.” By Frank William Linch.The author has studied the regulated oxidation of certain carb- amide derivatives by means of sodium hypobromite. With semicarbazide the main product is purazine (yield, 80 per cent. of the theoretical) when the substances are allowed to react in the proportions indicated by the following equation : 2CO<sE:NH2 + 3NaORr = L NH*NHCO<NH.NH>CO i-R’, + 3NaBr + 3H,O. The reaction proceeds in stages, with the intermediate formation of hydrazodicarboiiamide. p-Urazine is very sensitive towards oxidising agents, the first product being 3 :6-diketo-l:2 :3 :6-tetrahyd?*o-l:2 :4:5-letrazine, Thiosemicarbazide and hydrazodicarbonthioamide when oxidised by hypobromite produce hydrazodicarbonthioamidesulphonic acid : 2SH*C(:NH)*NH*NH,-t.5NaOBr = SO,H*C(:NH)*NH*NH*C(:NH)*SH+ 5NaBr_+2H,O. No condensation product could be obtained from carbamide, but acetylcarbamide condenses as foliows : ZNHAc*CO*NH,+ NaOBr = NHAc*CO*NH*NH-CO*NHAc+ NaBr + H,O. The author proposes to extend the investigation to other carb- amide der iv atives. 145 132. ‘6 Keto-enolic ethers and derivatives of dibenzoylmethane.” By Robert Duncombe Abell. The object of this work was to prepare ethers of the type *C(OR):CH*CO*by the silver oxide method, which did not appear to have been applied to the keto-enolic forms of the 1:3-diketones. Phenyl a-hydroxystyryl ketone, OH*CPh:CH*COPh, reacting with methyl iodide gave aa-dibenzoylethane, CHBz,-CH3;and with ethyl iodide gave aa-dibenzoylpropane, CHB%*CR,*CH,, and a small quantity of phenyl a-ethoxystyrpl ketone, OEt*CPh:CH*COPh.The methyl and ethyl esters of phenyl a-hydroxystyryl ketone were obtained in good yield from phenyl a-bromostyryl ketone by the action of sodium methoxide and ethoxide respectively. Further, the sodium derivative of phenyl a-hydroxystyryl ketone reacts, under suitable conditions, with : (1) Methyl iodide to give aa-dibenzoylethane. (2) Ethyl iodide to form aa-dibenzoylpropane (compare Miss Smedley, Truns., 1910, 97, 1492). (3) Ethyl iodoacetate to produce et?zyZ P-cliben$oylproyionate, CHB%-CH,-CO,Et. (4) Iodine to give s-teti.cibe?z=o!/Zet~~u/~~,C’HBz,*CHBz2, and dibenzoyliodom ethane, CHBz21.(5) Benzyl iodide to form aa-dibenzoyl-P-phenglethane, CHBz,*CH,Ph. (6) Benzoyl chloride to give the a-or diketo-enolic form of tribenzoyl rnet hane, CBz,: CPh-0 13, and not the triket o-f orrn (corn’- pare Claisen, AnnaEen, 1896, 291,95; Baeyer and Perkin, Ber., 1883, 16, 2135; Perkin, TTLI~ZS.,1885, 47, 253). Dibenzoyliodomethane and aa-dibenzoyl-P-phenylethane show feeble enolic properties. 183. ‘‘Derivatives of phenyl styryl ketone. Part I. The tautomeric forms of dibenzoylmethane.” By Robert Duncornbe Abell. This revision of Wislicenus’s work (A nnalen, 1899, 308, 219), undertaken after identifying phenyl a-ethoxystyryl ketone with ‘’dibenzoylmethane,” was continued even after the appearance of Ruhemann and Watson’s paper (Trctns., 1904, 85, 456) as several new results had already been obtained.Phenyl styryi ketone combines with bromine to form two isomeric dibromides, CHPhBr*CHBr*COPh, the one melting at 158O (Claisen and Clapar&de, Uer., 1881, 14, 2464 ; Wislicenus, Zoc. cit.), the other in very small yield melting at 122O (Miss Smedley, PTOC., 146 1909, 25, 259, gives 1135, and Pond, York, and Moore, Anzer. Chem. J.,1901,23, 789, 108-109°). The. dibrornide, melting at 122O, can be obtained in 90 per cent. yield by the union of hydrogen bromide with phenyl a-bromostyryl ketone, CBrPh:CH*COPh, in carbon disulphide solution. Phenyl a-bromostyryl ketone was prepared from the dibroinide melting at 158O by the action of excess of potassium acetate in alcoholic solution (compare Wislicenus, Zoc.cit.). According to Wislicenus, equimolecular quantities of phenyl a-bromostyryl ketone and sodium hydroxide in alcoholic solution when heated for half an hour gave a trace of phenyl a-hydroxy- styryl ketone and “ dibenzoylmethane,” now known to be phenyl a-ethoxystyryl ketone. The author finds that under these conditions phenyl styryl ketone is also formed. If the same quantities of the reacting substances are heated only until the alkaline reaction disappears, phenyl a-hydroxystyryl ketone is not formed. Wislicenus’s “ dibenzoylmethane ” is phenyl a-ethoxystyryl ketone. The “ dibenzoylmethane ” of Eaeyer and Perkin (Bcr., 1883, 16,2134) and of Claisen (Ber., 1887, 20, 655) is phenyl a-hydroxystyryl ketone.Dibenzoylmethane, CGH,*CO*CH2*CO*C6H,, is still unknown. 134. The interaction between di-iodoacetylene and organic sodio-derivatives.” By Hugh Vernon Thompson. Di-iodoacetylene, although a very unstable substance, resembles the metallic derivatives of acetylene in that it exhibits but little tendency to react with the ordinary organic reagenb; it therefore appeared of interest to examine its behaviour towards such highly reactive compounds as sodiomalonic and sodioacetoacetic esters. Preparation oj Dkiodoacetylene. The metihod for preparing di-iodoacetylene given by Dehu (J. Amer. Chem., Soc., 1911, 33, 1598) only yields satisfactory results if certain precautions not mentioned by that author are taken.It is desirable to, purify the acetylene obtained by the action of water on commercial calcium carbide, by passing it through an aqueous solution of ammonium persulphate. The sodium hypochlorite solution, which is dropped into the solution of potassium iodide during the passage of the acetylene gas, should 147 be prepared by passing chlorine into a 10 per cent. solution of sodium hydroxide, and care must be taken that no excess of chlorine is ultimately present ;if more concentrated sodium hypo- chlorite solutions are used, or if they contain free chlorine, the formation of di-iodoacetylene is considerably or completely inhi- bited. The preparation of the di-iodoacetylene should be carried out as rapidly as possible, and the precipitated substance collected immediately, washed, dried on porous earthenware, and dissolved in light petroleum; if left in contact with the mother liquor the di-iodoacetylene redissolves in part, leaving an unstable material, which explodes with violence when separated and left in contact with the air.When the precautions indicated above are taken, the yield of crude di-iodoacetylene represents 80 to 90 per cent. of that theo- retically obtainable from the amount of potassium iodide used ; after purification by crystallisation from light petroleum, the yield is found to be smaller, because of the presence of a material insoluble in that solvent. Dihydroxy buta.net e tracarb oxylic Ester, CH(C02Et),*CH(OH) CH(0H)*CH(CO,Et),. One molecular proportion of di-iodoacetylene is boiled with four molecular proportions of monosodiomalonic ester in alcoholic solution for several hours on the water-bath; the reaction is performed in the dark in order to prevent decomposition of the di-iodoacetylene by light.The alcohol is then distilled off, and the residue, after addition of water, extracted with ether ;the ethereal extract on evaporation yields a viscous, reddish-brown residue, which contains no halogen, and which could not be caused to crystallise. This residue is distilled under ordinary pressure, and then undergoes considerable decomposition ; the distillate, however, is cz colourless oil, which slowly becomes partly crystalline. The crystalline material after separation and recrystallisation from ether is obtained in small, compact., colourless crystals, which melt at 72O: 0.2062 gave 0.1250 H,O and 0.3835 CO,.C;=50*72; €€=6.79. C,,H2,0,, requires C =50.77 ;H =6-93 per cent. 1.9917 Grams dissolved in 26-45 grams of glacial acetic acid depressed t'he freezing point of the solvent by 0*8lo. The molecular weight indicated is thus 363. 1.6347 Grams in 25.68 grams of the same solvent; similarly depressed the freezing point by 0'64O, indi-cating a molecular weight of 390. The mean of the two determina- tions, namely, 376, agrees well with that corresponding with the, molecular composition stated, namely, 378. 148 There seems iittle doubt that the substance is the dihydrosy- butanet,etracarboxylic ester which Polonowsky obtained (Annulei?, 1888, 246, 3) as a yellow syrup by the action of glyoxal and malonic ester in presence of zinc chloride.The formation of this product by the reaction now described may be represented by the equation : C,I, + 2CHNa(CO,Et), + 2H,O = 2llu’aI +CH(CO,Et),*CH(OH,)-CH(OH)*CH(CO,Et),. On preserving the oily residue from which the above-described crystalline product had been separated, it gradually crystallised, and the crystalline compound thus obtained, after recrystallisation from ether, yielded colourless crystals melting at 47--48O. The quantity of material obtained was too small for further examins- tion, but it is probable that the two crystalline substances melting at 72O and at 47--48O are the cis-and tram-modifications of dihydroxyhutanetetracarboxylic ester.Di-iodoacetylene reacts with sodioacetoacet’ic ester in alcoholic solution, and after evaporation of the alcohol, treatment of the residue with water, extraction of the aqueous solution with benzene, and evaporation of the benzene, an oily residue was obtained which was obviously a mixture ;it could not be caused to crystallise, and decomposed when distilled under diminished pressure. The attempt to cause di-iodoacetylene to condense with sodium ethoxide under various conditions led in each case to the isolation of a small yield of a dark-coloured, pungent-smelling liquid corre-sponding in properties with the ethyl iodo-orthoacetate, CH,I*C(OEt),, prepared by Nef (A.uiiaie?b, 1897, 298, 350) in the same way.This investigation, commenced at the suggestion of Prof. Pope, will be continued. 135. ‘‘The rotatory powers of the d-and I-methylethylphenacyl-thetine salts.” Clara Millicent Taylor. Externally compensated methylethylphenacylthetine bromide has been prepared in quantity, and resolved into its optically active components by the aid of the corresponding salts formed with d-a-bromocarnphor-.lr-sulphonic acid. An extensive series of deter-minations of the rotation constants for the mercury green, mercury yellow, and sodium yellow lines has been made of the salts of d-and I-methylethylphenacylthetine with the latter acid, picric acid, and styphnic acid in various solvents. 149 ADDITIONS TO THE LIBRARY.1. Boltcctions. International Institute of Agriculture. Bulletin of the Bureau of Agricultural Intelligence and of Plant-diseases. 2nd year, No. 7, etc. Rome 1911 + . (Referencs.) From the Board of Agriculture. Tibbles, WiiEZiccm. Foods : t,heir origin, composition and manu-facture. London 1912. pp. viii + 950. IS/-net. (Rccd. 4/5/12.) From the Publishers : Messrs. Baillihre, Tindall and Cox. 11. By Puwhase. Allen, Alfred €Zenrp. Commercial organic analysis. Vol. VI. 4th edition. Edited by W.A. Davis and Samuel X.Sadtler. London 1912. pp. ix + 726. 21/- net. (RpJeerence.) Furth, Olto von. Problerne der physiologischen und pathologischen Chemie. I Band. Gewebschemie. Leipzig 1912. pp. xv + 634. M. 16.-. (Recd. 9/5/12.) Stahl, Gaovge Ernest.Philosophical principles of universal chemistry : or, the foundation of a scientifical manner of inquiring into and prepar -ing the natural and artificial bodies for the uses of life : Both in the way of experiment, and the larger way of business. Designed as ;G general introduction to the knowledge and practice of artificial philo-sophy: or, genuine chemistry in all its branches. Drawn from the Collegiwm Jenanse of Dr. George Ernest Stnhl by Peter Shaw. London 1730. pp. xxviii + 424 + [xxiv]. (Refwence.) Tauber, Ernst, and Norman, Ragnar. Die Derivate des Naphtslins. Berlin 1896. pp. viii+ 219. (Recd. 13/5/12.) Thompson, M. de Ray. Applied electrochemistry. New York 19 1 1. pp. xii + 329. 9/- net. (Recd. 9/5/12.) ERRATUM.PROCEEDINGS,1913. Page 126, line 2 from bolow, in formula, for I I read 1 I . N--CH, N--0 CANNIZZARO MEMORIAL LECTURE. An Extra Meeting will be held on Wednesday, June 26th, at 8.30 p.m., when the Cannizzaro Memorial Lecture will be delivered by Sir William Tilden, F.R.S. The next Ordinary Scientific Meeting will be held on Thursday, June 6th, at 8.30 p.m., when the following papers will be com-municated : ‘(The absorption spectra of various derivatives of naphthalene in solution and as vapours.” By J. E. Purvis. “The veiocity of the hydrogen ion, and a general dissociation formula for acids.” By J. Eendall. “ Cihloroamino-derivatives of benzylidenediamides.” By F. D. Chattaway and A. E. Swinton. “ The refractivity of sulphur in various aliphatic compounds.” By T. S. Price and D. F. Twiss. “The conditions of isodynamic change in the aliphatic ketones. Part I. The auto-catalytic reaction between acetone and iodine.” By H. M. Dawson and F. Powis. B. CLAY AND SONS, L’PD., BRIJXSWICK ST., STAMFORD HI’., S.E., AND BUNGAY, SGFFOLK.
ISSN:0369-8718
DOI:10.1039/PL9122800135
出版商:RSC
年代:1912
数据来源: RSC
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