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Proceedings of the Chemical Society, Vol. 30, No. 432 |
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Proceedings of the Chemical Society, London,
Volume 30,
Issue 432,
1914,
Page 195-214
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[Imwed 301'7114 PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 30 No. 432. Thursday, June 18th, 1914, at 8.30 p.m., Professor W. H. PERKIN,LL.D., F.R.S., President, in the Chair. The PRESIDENTreferred to the loss the Society had sustained, through death on June 6th, 1914, of Professor Dr. Adolf Lieben, who was elected an Honorary and Foreign Member on June 16th, 1892. Messrs. H, C. Reynard and R. L. Collett were formally admitted Fellows of the Chemical Society. Certificates were read for the first time in favour of Messrs. : Frederick Raine Ennos, B.A., B.Sc., 98, Rectory Road, Stoke Newington, N. Leon Maurice Hirchberg, Ph.D., 20, Birchington Road, Crouch End, N. Benjamin Stanley Mellor, M.Sc., 42, Hill Crest View, Leeds. Olin Freeman Tower, Ph.D., Adelbert College, Cleveland, Ohio, U.S.A.Arthur Henry Wardle, Ford House, Leek. The following Certificate has been authorised by the Council for presentation to ballot under Bye-law 1(3) : Ernest George, B.Sc., Victoria Square, King William's Town, S. Africa. 196 Messrs. F. P. Dunn and R. Gaunt were elected Scrutators, and a ballot for the election of Fellows was held. The following were subsequently declared as duly elected : Nicholas Alexander Aufilogoff. Alfred Holt. Harry Berry. John Cyril Jennings. Alfred Archibald Boon, D. Sc. John Orrou Leighton. Probodha Chundra Chattopadhyay, M. A. Robert Ernest blachin, B. Sc. Stanley Winter Collins, B.Sc. Ernest lrerguson Pollock, Ph. D. Herbert William Cremer, B.Sc. Hashmat Rai, B.A., M.Sc. John Verne11 Cutler. Charles Edward Roberts, B. A., B. Sc. Shanazar Galstaun Gslstaun, B.A. Frederic Robinson, M.Sc. Tech. James Mylam Gittins, M.Sc. Walter Edward Rowbottam. Frederick George Henderson. Thomas William Thompson, M. A. Victor Henri. Alfred John White, B.Sc. Leonard Eric Hinkel, B.Sc. Of $he following papers, those marked * were read: *172. ‘‘Nitrogenous constituents of hops.” By Alfred Chaston Chapman. In the case of a number of samples of hops nnalysed, the total percentage of nitrogen varied from 1.7 to 4 per cent, the per- centages of soluble nitrogen varying from 0.44 to 0-9 per cent. The nitrogenous substances soluble in hot water consisted of soluble proteins, albumoses, ammonium salts, amino-compounds and amides, bases precipitable by phosphotungstic acid, and unclassified nitrogenous substances not precipitated by that reagent.Results were given showing the proportions in which these various classes of compounds occur. In the course of the work, large quantities of hops and hop extract were worked with, and four distinct methods for the separation and isolation of the nitrogenous sub-stances were employed. The following substances were isolated and identified : I-asparagine, aspartic acid, betaine, choline, histidine, hypoxanthine, and adenine. Of these, asparagine and choline have been previously detected. Two other bases were obtained, but in quantities too small to permit of their complete identification. One of these, however, wm almost certainly arginine.Although considerable quantities of hops of various growths were employed, in no case was morphine, or any alkaloid closely resembling it, obtained. Potassium nitrate wi~s present in appreciable quantities. DIscusSION. Dr. POWERremarked, concerning the reference by Mr. Chapman to the alleged pretsence of morphine in hops, that no evidence had 197 ever been adduced to justify the assumption that this alkaloid occurs in either wild or cultivated hops. The fact was recalled that about thirty years ago a preparation was introduced under the name of “hopeine,” which was first stated to have been obtained from (‘wild Virginian hops,” and subsequently from “Arizona h0pt3,’~ but neither of these districts was known to produoe hops in any amount.The so-called hopeine ” was examined by Laden- burg (Ber., 1886, 19,783) and others, who found it to consist of morphine or a mixture of the latter with a more readily soluble base. Dr. B. IX. Paul (Phiarm. J., 1886, [iii], 16, 877) likewise showed it to be a variable product, consisting either chiefly of morphine or a mixture of morphine and cocaine, whilst in some samples the latter base predominated. The only presumption for the presence of morphine in hops appears thus to have been based on the statements concerning a product which was shown many years ago to have been of a purely fictitious character. Mr. E. GRANTHOOPERinquired whether any investigation had been made of the solubili€,y of the nitrogenous constituents of hops when a sugar or other carbohydrate solution was used instead of water.Considering that hops were chiefly used for brewing purposes, he thought that the solubility of the nitrogenous constitu- ents in carbohydrate solutions was of some importance, and might be appreciably different from the solubility in water alone. Mr. ROGERSONasked if the amount of betaine obtained by the lime method of extracting the hops was greater than the amount obtained by the other methods described. It was conceivable that some oxidation of choline might take place. Mr. CHAPMANsaid that he was aware of the episode to which Dr. Power had referred. So far as he knew, there was no evidence that certain kinds of wild hops did not contain small quantities of morphine or some similar alkaloid, but he thought it was quite clearly established that cultivated hops did not contain more than, at most, insignificant traces.Choline did not undergo con-version into betaine as readily as Mr. Rogerson seemed to imply, and having regard to the methods of extraction adopted in his (Mr. Chapman’s) experiments, there could be no doubt that the betaine wits actually present in the hops, and had not been formed from the choline during the process of examination. He had specially searched for the presence of tyrosine and guanine, but with negative results. He had, moreover, been unable to obtain any evidence of the presence of lysine. 198 *173. ‘‘The isomerism of the oximes.Part IV. The constitution of the N-methyl ethers of the aldoximes and the absorption spectra of oximes, their sodium salts and methyl ethers.” By Oscar Lisle Brady. The author is of opinion that the constitution proposed by Angeli, Alessandri and Aizzi-Mancini (Atti R.Accad. Lincei, 1911, [v], 20, i, 546) for the N-methyl ethers of the oximes, namely, R*CH:N(CH,):O, is more in accordance with the facts than the R*CH-N*CH, more generally accepted iso-oxime structure, \/0 The consideration of the absorption spectra of the oximes, their sodium salts, and their methyl ethers, obtained from benzaldehyde and pnitrobenzaldehyde, supports t.he views of Baly, Tuck and Marsden (T., 1910, 97, 571), that no trustworthy evidence can be obtained from spectroscopic considerations with regard to the struct.ure of such compounds as the nitrophenols and their sodium salts.*174. “The wet oxidation of metals. Part 111. The corrosion of lead.” By Bertram Lambert and Herbert Edwin Cullis. Metallic lead, made by Stas’ method, was fractionated by dis- tilling in a quartz tube in a vacuum, and the middle fraction taken. This fraction was then distilled again, in a vacuum, in an apparatus so constructed that the distilled metal could be brought into con- tact with pure water and pure oxygen. It was found that corrosion took place very rapidly if the oxygen was allowed to come into contact with the lead and water within a few days after the distillation of the lead.If, however, t.he lead was left in contact with the pure water in a vacuum for twelve months, and then oxygen allowed to enter, the rate of corrosion was very slow. The metal retained a silvery- white appearance for more than a week, and even after six months the coating of oxide was so thin that it gave rise to interference colours. The electrolytic theory of corrosion was considered in connexion with lead. “175. ‘4Studies in the camphane series. Part XXXV. Isomeric bydrazoximes of camphorqninone, and some derivatives of aminocamphor.” By Martin Onslow Forster and Ernest Kanr. In order to investigate the possibility of stereoisomerism among hydrazoximes of camphorquinone, a systematic attempt was made 199 to prepare the eight modifications required by theoretical con-siderations.Only two of these have been realised, however, C:N-NHnamely, camphorpinonehydrazoxime, C8H,,<&NOH 2, melting at 130°, from P-isonitrosoepicamphor, and the structural isomeride, C8H14<~:~.~~,’melting at 142O, from unstable isonitroso-camphor. Several derivatives of these compounds were described, together with various materials prepared from aminocamphor in the hope of obtaining the missing isomerides by indirect methods. 176. (( The velocities of combination of sodium derivatives of phenols with olefine oxides.’’ By David Rnnciman Boyd and Ernest Bobert Marle. The velocities with which ethxlene and propylene oxides combine with sodium derivatives of phenols have been determined, approxi- mately, for twenty-five phenols by estimating the yields of glycol aryl ethers produced when the olefine oxides are heated with N/2O-alcoholic solutioas of the phenolic salts.The values found for l/tlog100/100-x vary in the case of ethylene oxide from 0.34 for q-cumenol to 0.0073 for o-nitrophenol, and in the case of propylene oxide from 0.13 for q-cumenol to 0.0035 for o-nitrophenol. The following general conclusions are drawn : (1) The reactivity of the sodium derivative towards ethylene oxide is increased by ths presence of positive groups, for example, 4H3, *C3H7, *CH,*CH:CH,, and diminished by the presence of negative groups, such as *O*CH3, *CB:CH-CH:CH*,*C1, *Br, C,H,*N:N*, *CN, -NO,. (2) In general, the reactivity diminishes with increase in the acidity of the phenol.2 : 4: 6-Trichlorophenol, however, forms an exception to this rule, its sodium salt having a much higher re activity than would be expected. (3) The phenols stand in almost the same order in the case of propylene as in the case of ethylene oxide. The most important except’ions are 2 : 4: 6-trichloro-and 2 : 4: 6-tribromo-phenol, a-naphthol, and o-chlorophenol. The sodium salts of these four phenols are much more reactive towards propylene oxide than would be antJcipated from a consideration of the results obtained for the same phenols in the case of ethylene oxide. (4) There is no evidence of steric hindrance in the caw of diortho-substituted phenols. The process of combination in the case of ethylene, and particularly in that of propylene oxide, seem8 200 rather to be facilitate’d by the presence of the two ortho-substituents. Several new glycol aryl ethers were described.177. “Colouring matters contained as glucoside in the flowers of some Indian plants.” By Arthur George Perkin and Isaac Shulman. These flowers, the description of which is given below, were specially collect’ed in India, in the anticipation that they contained some quantity of dyestuff. This has not proved to be the case, the amount of colouring matter isolated being extremely small, and, indeed, not always sufficient for analysis. The method of examination in each instance has consisted of treating the concen- trated alcoholic extract with water, removal of suspended waxy matter, digestion of the aqueous solution with boiling hydrochloric acid to hydrolyse the glucosides, and isolation of the colouring matter by means of ether.Incidentally, the use of sodium hydrogen carbonate solution has been found of much service in purifying minute amounts of these substances. To this the crude product dissolved in alcohol is added, and, after agitation, ether now removes a fairly pure compound. Poinciana regia (Bengal) .-Three hundred and fifty grams gave 0.31 gram of colouring matter, which crystallised in yellow needles, dissolved in alkalis with a yellow coloration, and proved to be quercetin. The acetyl compound, colourless needles, m. p. 194-196O, gave C=58.75; H=3.84 per cent.An extract of these flowers had practically no dyeing action on mordanted cotton. Impatiens balsamina (Chansili Pass) yielded but a trace of sub-stance, evidently kaempferol. It separated from acetic acid in needles, m. p. 275-278O, and gave with sulphuric acid a fluores-cent solution, whereas the acetyl derivative, colourless needles (Found, C=61.18; H=4.06 per cent.), fused at about 120°, re-solidified, and finally melted at 181-183O. Woodf ordia flom’bunda.-Seven hundred grams gave 0.84 gram of crude colouring matter, and this consisted of two substances readily separated by means of alcohol. The sparingly soluble com- pound (0.61 gram) crystallised from pyridine in needles, and was recognised by analysis (Found, C =55- 62 ;H =2-40), the melting point of the acetyl derivative (343--345O), and the Griessmayer reaction as ellagic acid. The soluble colouring matter (yellow needles, m.p. 285-291°), of which but a minute amount was avail- able, was possibly an impure quercetin. It gave the general tests for this substance, but the acetyl compound, obtained in colourless needles, melted at 135-137O. 201 Erythriita stricta (vernacular name, (( Konkathet ”), from Chief Conservator of Forests (Mamyo, Burmah), gave a trace of kaemp- ferol insufficient for analysis, which was recognised by the peculiar melting point of the acetyl compound (see above), the fluorescence of its sulphuric acid solution, and its general properties. For the samples of these flowers, the authors are indebted to Mr.D. Hooper, Reporter on Economic Products to the Govern- ment of India. Mention may also be made here of the flowers of the common fuschia, F. mncrostema globosa, which was found to yield traces of ellagic acid, identified by means of the acetyl compound (m. p. 343-345O), and quercetin, which gave acetylquercetin, m. p. 193-195’. 178. (r Note on quercitrin.” By Arthur George Perkin. The statements (this vol., p. 151; T., 1914, 105, 1411) that quercitrin has the formula C2~H20011and m. p. 183--185O, con-sidered by the author at the time to be novel, are, in reality, not so, these facts having been previously ascertained by Brauns (Arch. Pharm., 1904, 242, 561) and C. W. Moore (P., 1910, 26, 182). 179. ‘‘ A new chlorocamphor.” (Preliminary note.) By Thomas Martin Lowry and Victor Steele.By using the method described by Kipping in 1905 (P., 21, l25), a-chlorocamphor has been converted into the stsreoisomeric a‘-chlorocamphor, which melts at 117O. A direct comparison gave the following values for the specific rotatory powers of the two compounds in alcoholic solution (5 grams per 100 c.c.) : Li 6708. Nu 5893. Hg 5461. Hg 4359. a-Chlorocamphor . . . . . . . . .... 70.0 97.0 119.2 242.9 a’-Chlorocamphor.......,.... 27.5 41.4 64.1 140.9 180. Ideal refractivities of gases.” By William Jacob Jones and James Riddick Partington. An equation has been deduced which permits of the correction of observed refractivities of gases at normal pressure, P,,=760 mm., and absolute temperature, To=273.09, for the deviations of the gases from the ideal state.This equation, which is based on D. Berthelot’s characteristic equation, is : 9p‘ -1 = (p-1)[1+ --m( 1 -h2)]128 202 where ,u and ,d are the observed and ideal refractive indices re- spectively, r=P,/P,, 7=TC/To (P, and T, are the critical constants). In the case of the permanent gases, the correction is inconsiderable, but it is appreciable in the case of the more easily liquefiable gases. Wave- Refractive index Ideal refractive Gas. length. at N.T.P. index. Methane.................. Hydrogen ............... 589 559 1.0001 392 1.0004410 1-0001393 1.0004403 Xenon .................. 486 1.0007 130 1*0007078 Carbon dioxide......... 589 1.0004498 1.0004467 Chlorine .................. Sulphur dioxide ...... 589 589 1.00067 60 1.0007730 1.0006628 1.0007608 Cyanogen ............... 436 1*0008710 1.0008536 181. a-Bromonaphthalene: its physical properties and its appli-cation to the determination of water in moist alcohol.” By Marian Jones and Arthur Lapworth. The work referred to in a previous note on a-bromonaphthalene has been confirmed and extended (compare Crabtree and Lapworth, P., 1912, 28, 264). The temperatures at which homogeneow mixtures of a-bromo-naphthalene and moist alcohol separate into two phases can be determined with exceptional readiness, and as these temperatur- are very sensitive to alterations in the proportion of water present the aut’hors use a-bromonaphthalene for ascertaining the composi- tion of moist alcohol within the range, H2O=1*45-10*3 per cent.Data were quoted by means of which the percentage of water in small quantities of moist alcohol may be determined in a very simple manner, and with an error of less than 0-03 per cent. 182. ib Colour and constitution of azo-compounds. Part VI,” By John Theodore Hewitt, Gladys Ruby Mann, and Frank George Pope. In previous communications attention has been drawn to the marked changes in colour which occur when solutions of para-nitrated azophenols are reandered alkaline, and certain chemical evidence has been adduced in favour of the assumption that the salts possess a quinonoid structure. Considering the possibility of enolisation taking place when an azo-compound contains a ketonic as well as a hydroxyl group, a number of azophenols have been prepared by diazotising pamino- acetophenone and paminobenzophenone, and coupling them with phenol, p-cresol, and the naphthols.Alcoholic solutions of these compounds exhibit marked cdour changes on addition of alkali. 203 183. ‘‘ Studies in phototropy and thermotropy. Part IV. +Nitro-benzylidenearylamines and their photoisomeric change.” By Alfred Senier and Rosalind Clarke. The authors have made a further search for examples of photo-tropy and thermotropy. The bases examined were o-nitrobenzyl-idenearylamines. -All are thermotropic, and several exhibit photo- tropy. Prolonged exposure to light leads, however, to a non-reversible change in colour, and in many cases to a change in melt- ing point.This change is ascribed to dimorphism. The interest-ing fact was discovered that these bases undergo photoieomeric change, like the compounds studied by Ciamician and Silber (Ber., 1901, 34, 2040), and that examined by Sachs and Kempf (Ber., 1902, 35, 2704). 184. 4‘ Contributions to the chemistry of the terpenes. Part XVIIr. Camphenanic acid and its isomerides.” By George Gerald Henderson and Maggie Xillen Jeffs Sutherland. The four isomeric acids of the formula C,H,,*CO,H, which have been obtained by the oxidation both of camphene and of bornylene, were converted into their methyl esters; these are somewhat viscid, colourless liquids, which all boil at about the same temperature, 103-104°/ 22 mm. The esters of camphenilanic, isocamphenilanic, and camphenanic acids yield the respective acids when hydrolysed, but the product obtained on hydrolysis of the supposed ester of isocamphenanic acid was found to be a mixture of camphenilanic and isocamphenilanic acids.It is concluded that isocamphenanic acid is, in reality, a mixture of camphenilanic and isocamphenilanic acids, or else is converted into these, acids during esterification. Each of the esters, when treated with sodium and alcohol, yields the same alcohol, camphenilanol, CsH,,*CH2*OH,a crystalline solid melting at 77O, which is converted into camphenilanaldehyde by oxidation with chromic acid mixture.Its hydrogen phthalate crystallises in colourless plates, m. p. 153O, and its p-nitroberzzoate in yellow needles, m. p. 90°. During the reduction of each of the esters, a small quantity of an acid was produced, and in every case this proved to be isocamphenilanic acid. Thus camphenilanic and camphenanic acids can be transformed into isocamphenilanic acid by a method different from those formerly described. 204 185. ‘‘2 :3-Dibromonnphthalene.” (Preliminary note.) By William Palmer Wynne. Different views have been held regarding the composition of the product obtained by dibrominating naphthalene; 1: 4- and 1:5-dibromonaphthalenes have been isolated from it, but the nature of a third substance, m. p. 68O (circa), is still in doubt!.Guareschi, who first recorded its presence in the dibromination producb (Gazzetta, 1881, 11,542), and Canzoneri, who obtained it by the interaction of phosphorus tribromide and bromo-P-naphthol (ibid., 1882, 12, 424), regard it as a single substance, but Armstrong and Rossiter consider it to be a definite compound of I :4-and 1 :5-dibromonaphthalene (P., 1891, 7, 184). On the assumption that it is an individual, the only available structure1 is that of the 2 :3-derivative, although this orientation is improbable on several grounds. For example, it would be the one exception to the rule that dibromonaphthalenes melt at temperatures higher than the corresponding dichloro-derivatives, 2 :3-dichloronaphthalene melb ing at 119.5O. Through the kindness of the Badische Anilin- & Soda-Fabrik in supplying the author with 3-amino-P-naphthoic acid, an opportunity has arisen for the preparation of 2 : 3-dibromonaphthalene, hitherto unknown.The following compounds were described : 3-brOm0-b-naphthoic acid, CIoH,Br*CO,H, needles, m. p. 220O; the methyl ester, needles, m. p. 67O; the hydrazide, minute needles, m. p. 218O; the, urethane, needles, m. p. 114O; 3-bromo-2-nnpl~thylamine, CIoH,Br*NH2, scales, m. p. 16S0, and its acetyl derivative, clusters of scales, m. p. 172O. 2: 3-Dibromonnphthalene, which forms silvery, rectangular scales, m. p. 140°, has the same melting point as recorded for the 2: 7-derivative by Jolin (Bull. SOC.chirn, 1877, ([ii], 28, 514), but. as the method used by him is open to criticism, the preparation of the 2 :7-compound is being undertaken for the, purpose of comparison by reactions which avoid the use of phosphorus pentabromide at high temperatures.186. “Calcium nitrate. Part 111. The three-component system : calcium nitrate-lime-water.” By Henry Bassett, jun., and Hugh Stott Taylor. The conditions of equilibrium in this system have been studied at 25O and at looo. The compounds capable of existing in equilibrium with solution at 25O are : Ca(OH)% Ca,Nz0,,3H,0, and Ca(N0,),,4H20 ;whilst at looo they are : Ca(OH),, Ca,N,07,2H,0, Ca,N,O,,~H,O, and Ca(N03)2. The series of solid solutions Ca0,zN,0,,yH20, which according to Cameron and Robinson (J. physical Chem., 1907, 11, 273) exists at 25O, has not been confirmed. It has, on the con-trary, been shown that the region of solid solutions described by these authors is really a portion of the region where Ca(OH), is the stable solid phase.It was suggested that the presence of a trace of magnesia in the calcium nitrate used by Cameron and Robinson may have led them to erroneous conclusions. 187. ‘(Some arylidenedimethglpyrones and their salts.’’ By Alfred Archibald Boon, Kenneth John McKenzie, and John Trotter. Not long after Collie suggested the bridged formula for dimethyl- pyrone (T., 1904, 85, 973), one of the authors was induced to study the action of furfuraldehyde on this base with the view of effecting the following condensation : For this purpose many experiments were undertaken under varying conditions, but in every case both the methyl groups of dimethylpyrone took part in the reaction.More recently (P., 1910, 26, 95) it wa indicated that the condensation of dimethylpyrone with an aldehyde could be represented by the following scheme: 0 0 and that the resulting coloured base formed intensely coloured salts with acids, the colour of the salts depending on the nature of the aldehyde used in condensation ag well as that of the acids employed in their production. Attention is now called to three of these bases, namely, bisfurylidenedimet hylpyrone, basbenzylid ene-dimethylpyrone, and bisariisylidenedimeth~lp~rone,and some of their salts. All these salts undergo hydrolysis when boiled with water.In a subsequent paper the constitution of the various compounds indicated here will be discussed by one of the authors with other collaborators. Each of the bases just mentioned was prepared by the action of the aldehyde on dimethylpyrone in the presence of alcoholic 206 sodium hydroxide. Basf~r~li~enedimet~yl~Tone,CI7Hl2O4, is yellow, and melts at 200O. Each of the following salts, which are red, was obtained in the following way: A 20 per cent. solution of the acid was allowed to act on the base dissolved in an alcohol, in the case of the hydrochloride amyl alcohol being used, and for the other salts methyl alcohol. Each salt was washed with light petroleum, and dried in a vacuum. The hydrochloride, C,7H,204,HC1,m.p. 196O (becoming yellow at about 115O). Found : HC1= 11.29. Calc., HC1= 11-50 per cent. The nitrate, C,,H,20,,HN0,, m. p. 166-167O (changes colour at 102O). Found : HNO,= 18*02. Calc., HNO,= 18.38 per cent. The sulphate, CI7Hl2O4,H2SO4,m. p. 202-203O. Found : 3S04=24-70. Calc., H2S04=25-92 per cent. Bisbensytidenedimethylpjrone, C2,HI6O2, forms faintly yellow, crystalline flakes, melting at 168O. The following yellow salts were isolated, and in the preparation of each of them the respective acids were allowed to act on the base dissolved in chloroform. For the nitrate a 20 per cent. solution of nitric acid was used, and for the hydrochloride and the sulphate, acids having respec- tively D 1-11and D 1-32 were employed. The hydrochloride, ~21H,60,,HC1,m.p. 166-167O. Found : HCl= 10.65. Calc., HC1= 10.85 per cent. The nitrade, C2,H1602,HN03, m. p. 141-142O (with decomposi- tion). Found : HNO,= 16.98. Calc., HNO,= 17.38 per cent. The sulphate, C2,H1602,H2S04, m p. 155-156O, darkens about 104O. Found : H,S04 =25.80. Calc., H,SO, =24.68 per cent. BisaizisylicFertedimethylp~rone, C2,H,04, forms faintly yellow, crystalline flakes, melting at 199O. With the exception of the deliquescent, bright red sulphate, the inorganic and organic salts prepased from this base lose weight when exposed to the air, during periods varying from eleven to thirty days, the nitrate being most stable, the formate losing all its acid, and the hydriodide becoming dark violet. Inorganic Salts.-The hydrofluoride is yellow, but all the other salts are red. Unless otherwise stated, each salt was prepared by allowing an excess of the concentrated acid dissolved in alcohol to act on a boiling alcoholic solution containing 2 grams of the base.In some wcs the freshly prepareld salt was dried and imm+ 207 diately analysed (for example, the bright red sulphate), whilst in other cases it was either washed with alcohol (for example, the nitrate) or recrystallised from methyl alcohol (for example, the hydrochloride) before being dried and analysed. The hydrochloride, Ci,H,,O,,HCl, m. p. 147-148'. Found : HCl =8.89. Calc., HCl= 9-20 per cent. The hgdrohromidt., C2,H,,04,HBr (melting point not sharp). Found : HBr= 18-08. Calc., HBr =18.36 per cent.The, IiydrofEuoride, C,,H,,O,,HF, decomposes when heated. In its preparation at least four times the calculated quantity of acid must be used. The salt when freshly prepared is red, but on drying in a vacuum over sodium hydroxide until its weight is constant it becomes yellow, Found: HF=5.23. Calc., HF=5.26 per cent. (From various experiments the action of hydrofluoric acid on the base appears to be abnormal.) The nitrate, C,,H,,O,,HNO,, decompose at 146O. Found : HN03= 14.78. Calc., HNO, =14-89 per cent. The sulphate, (C23H,,0,)2,H2S0,, forms dark red crystals, m. p. 86-87O. The, calculated quantity of concentrated sulphuric acid mixed with 10 C.C. of alcohol was used in its preparation. Found : H,SO,= 12.25.Calc., H2S04=11.98 per cent. The mlphade, C,,H,0,,H2S0,, bright red crystals. m. p. 101O. To a solution containing 50 C.C. of alcohol and 20 C.C. of concen-trated sulphuric acid 2 grams of the bam were added, and the mixture was heated for half-an-hour on a water-bath. Found : H,SO,= 21-42. Calc., H2So,=21*39 per cent. The platinichloride, (C,3H~o04)z,H2PtClG.-A slight excess of a concentrated alcoholic solution of platinic chloride wm added to a boiling alcoholic mixture containing the base and 0xcw of concen-trated hydrochloric acid. Found : Pt= 17.11. Calc., Pt =17.25 per cent. Organic Salts.-These are mostly yellow compounds, but a formate, a tartrate, and the picrate are red, whilst the salicylate is yell0 wis h-r ed. The formate, C23H2004,(CHz0,),, is a red salt, m.p. 99O, unstable when exposed to the air, becoming yellow, and finally losing all its acid. It is prepared by heating a solution of the base in pure formic acid on a water-bath, then allowing the solution to remain at the ordinary temperature, washing the salt with 50 per cent. formic acid, drying, and immediately analysing. Found : CH202=19.62. Calc., CH,O, =20.35 per cent. 208 The formale, C23H2@4,a202, consists of yellow, hair-like crys- tals, and suffers decomposition when heated. It is obtained by the action of 90 per cent. formic acid on the base. Found : CH,02= 11.20. Calc., CH,02= 11.33 per cent. The acetate, C23H2004,C2H402,forms yellow, hair-like crystals, and is obtained by gently warming a solution of the base in 90 per cent.acetic acid, and allowing the mixture to remain at the ordinary temperature. The crystals were washed with 50 per cent. acetic acid, dried, and immediately analyaed. Found : C2H4O2=14.44. Calc., C2H402 =14-30 per cent. The oxaZa.te, (C2,H2004)2,C2H204,which forms yellow needles, was obtained by adding a slight excess of the calculated quantity of anhydrous oxalic acid to a solution of the base dissolved in toluene (some alcohol being added to keep the base in solution). The mixture was boiled for six hours on the water-bath, and then allowed to cool at the ordinary temperature. Found : C2H204= 11.75. Calc., C2H204= 11.11 per cent. The oxalate, C23€€200i,C2H204,which separates in yellow crystals, m.p. 174--175O, was prepared by gradually adding 1 gram of anhydrous oxalic acid to a boiling toluene solution of 2 grams of the base. The solution was allowed to remain at the ordinary temperature after being boiled for six hours. Found : C,H20, =19-62. Calc., C2H204 =20.00 per cent. The tartrate, (C23H2004)2,C4H606,forms red crystals, and was obtained in a manner similar to that employed for the preparation of the corresponding oxalate. Found : C4H606=17-45. Calc., C4H606 =17.24 per cent. The succina.te, (~23H2,04),,C,H604,is yellow, and the salicylate, (~23H2,0,)2C,H603,yellowish-red. These were obtained by heating the base for a number of hours with a concentrated alcoholic solution of the respective acids. In the meof the salicylate, the alcohol contained about 5 per cent.of toluene. =14-65, Calc., C4H604Found : C4H604 =14-42 per cent. 28-57. Calc., c7H,03=27.71 per cent. Found : C7H603= The picrate, C,3H2004,C6H30,??3,prepared by adding an alcoholic 601UtiOn of picric acid to a boiling alcoholic solution of the base, forms red needles, m. p. 211O. Found: N=7.62. Calc., N=7*13 per cent. 209 188. L6 The constitution of the arylidenedimethglpyrones and their salts.” By Alfred Archibald Boon, Forsyth James Wilson. and Isidor Morris Heilbron. The authors have examined the absorption spectra of bis-p-methoxybenzylidenedimethylpyrone, bisbenzylidenedimethylpyrone, and bisfurfurylidenedimethylpyrone. They find that the absorption curves of these substances are all practically identical, and, more- over, are very similar to the curve of the alcohol compound of dimethylpyrone.They theref ore conclude that the arylidene-dimethylpvrones possess symmetrical f ormulz of the type : 0 /\CHR:CH*g $*CH:CHR CH CH \/C..0 The absorption cum- of the salts which these arylidenedimethyl- pyrones form with acids show two bands, a small colour band with head about A 1/2200, and a large, well-defined band quite similar in intensity and position to the parent substances. The authors therefore believe that these salts are structurally similar to the free arylidenedimethylpyrones, thus : HX \/0 CHR:CH*fl/\g*CH:CHR CH CH \/C.. 0 (X=acidic radicle.) On bromination, bis-p-methoxybenzylidenedimethylpyrone yields a tetrabromo-additive product, which does not form salts with acids, and, like dimethylpyrone, shows only general absorption.Accord-ingly, the authors ascribe to this compound the bridged structure: /y\ ,MeO*C,H,*CHBr*CHBr*E C*CHBr*CHBr*C,H,*OMe 210 The addition of bromine apparently has the effect of making the whole molecule too acidic for saltiformation with acids, as is the case with diacetyldimethylpyrone (compare Collie, T., 1904, 85, 971). The authors conclude from these results that acidic or weakly basic pyrones, such as those examined by Baly, Collie, and Watson (T., 1909, 95, 144), possess bridged structures, whilst the arylidene- diniethylpyrones, which are more basic in character, yielding as they do stable salts with acids, possess symmetrical structures.189. 6b The constituents of the flowers of Anthemis nobilis.” By Frederick Belding Power and Henry Browning, jun. The material employed for this investigation consisted of the flower-heads of Anthemis nobilis, Linn6, collected from plants grown in Belgium. Apart from the essential oil yielded by distillation with steam, the flowers were found to contain the following definite compounds : (1) 3 : 4-dihydroxycinnamic acid ; (2) apigenin, C15H1005; (3) a glucoside of al3igenin, C,,H,,0,,,H20, which yields an hexa- acetyi! derivative, CT3,H,0,,4H,0 ; (4) choline, C5€Q502N; (5) i-inositol, C,H,(OH), ;(6) triacontane, C,,€€,, ;(7) taraxasterol, C,,H,,*OH; (8) a phytosterolin (m.p. 280-283O); (9) a mixture of fatty acids, consisting of cerotic, stearic, palmitdc, oleic, and linolic acids. The flowers contained, furthermore, a considerable quantity of sugar, which yielded d-phenylglucosazone (in. p. 208-210O). The amount of fatty and resinous material, from which some of the above-mentioned substances were obtained, was equivalent to about 7-4 per cent. of the weight of flowers employed. The bitter taste of chamomile flowers appears to be due to dark-coloured, amorphous material, and not to any well-defined con-stituent. 190. ‘(The constituents of Clematis vitalba.” By Frank Tutin and Hubert William Bentley Clewer. The material employed for this investigation consisted of the flowering branches of Clematis vitalba, Linn6, which had been specially collected for the purpose.Preliminary tests showed the absence of any alkaloid, and that only a trace of volatile material was present. An alcoholic extract of the dried and ground material yielded, in addition to much chlorophyll and resin, the following definite compounds : (1) 3 : 4-dihydroxycinnamic acid ; (2) caulosapogenin, 211 C42Z€660,;(3) a saponin, C54H86016,which proved to be a new glucoside of caulosapogenin ; (4) dextrose ; (5) myricyl and ceryl alcohols; (6) hentriacontane, C?31Hs4;(7) a phytosterol; (8) a phytosterolin, which apparently consisted essentially of stigmasterol glucoside ; (9) melissic, cerotic, and palmitic acids, together with a mixture of unsaturated acids, consisting largely of linolic acid, and an acid, C22H4402(m.p. 69*5O), apparently isomeric with behenic acid. The statements regarding the irritant properties of Clematis uitalba cannot be confirmed. 191. ‘‘A magnetic study of compounds of water and of aqueous solutions.” By Francis William Gray and William Milne Birse. For the constitution of compounds like copper sulphate penta- hydrate, suggestions based on magnetic measurements were made, and a magnetic study of benzoic, phthalic, maleic, succinic, and camphoric acids and their anhydrides was also described. The magnetic properties of solutions were discussed, and it was shown that aqueous potassium f erricyanide solutions obey the law of additivity throughout the whole range of concentrations.A value for the susceptibility of potassium ferricyanide is thus obtained. 192. 6‘ The rate of combinationof gaseous nitric oxide and chlorine.’’ By Joseph Edward Coates and Ada Finney. A study has been made of the kinetics of the gas reaction 2N0 + C12=2NOC1, which proceeds with measurable velocity at the ordinary tempera- ture. Known quantities of pure chlorine and nitric oxide were rapidly mixed in a glass bulb kept at constant temperature, and the gradual change of pressure at constant volume was followed by means of a mercury manometer connected with the reaction- vessel by a glass capillary tube filled with nitrogen. On mixing the gases, the temperature rose a few degrees, but soon fell to a constant value.The reaction was half completed in about five to six minutes. Satisfactory velocity constants were obtained only by the use of an equation for reactions of the third order. This is in agreement with the ordinary chemical equation, and constitutes a well-defined example of a “pure” (the walls of the vessel are almost certainly without influence) gas reaction of the third order ; such reactions, as is well known, are extremely rare. 212 19% Carajura and chica red.” (Preliminary note.) By Arthur George Perkin. “ Carajura,” a rare pigment, considered to be identical with ‘(Chica red ” (compare Erdmann, Jahresber., 1857, 487), is said to be prepared by the Indians of Central America from Bigonia chica. The material examined, obtained through the kindness of Messrs.Wright, Layman, and Umney, contains a small quantity of the calcium compounds of at least two colouring matters, which have either been precipitated on, or intermingled with, a sub-stance of the nature of ground bark or peat. After treatment with hot dilute hydrochloric acid, alcohol removes the colouring matters in the form of a resin, and from this, by means of boiling benzene, carajurin is isolated. This compound, to which the formula C18Hl,0, has been provisionally assigned (Found, C =69.09 ; H =5-28>, separates in ruby needles, melting at 204-206*, soluble in boiling dilute alkali with a red colour, and is nearly devoid of dyeing properties. With mineral acids, it very readily yields oxonium salts, crystallising in bright, orange needles, of which the sulphate, probably C18H,,0,,H,S0,,H,0 (Found, C=50*67; H=4.35), is the most stable, the hydrobromide and hydrochloride being decomposed at looo.From the hydro-chloride, a platinichloride was prepared. Cold acetic anhydride with a trace of pyridine, after two days, gives an almost colourless acetyl compound, crystallising in needles, whereas bromine gives an immediate precipitate with cara jurin in acetic acid, which, when boiled with this solvent, separates in orange needles. Hydriodic acid converts carajurin, with loss of two molecules of methyl iodide, into carajuretin hydriodide, bright scarlet needles, stable in the presence of cold water, and from this, by means of cold pyridine, carajuretin, probably C16H1205,scarlet needles melting above 330°, and soluble in alkalis with a reddish-violet colour, is produced.By dry distillation, carajurin evolves a trace of aromatic oil, resembling anisaldehyde in odour, and when fused with alkali, phydroxy- benzoic acid, and a colourless substance, melting at 185--187O, as yet unidentified, are obtained. In many respects carajurin resembles the anhydroliydroxybenzopyranol compounds described by Bulow and Wagner (Ber., 1901, 34, 1199). That portion of the alcoholic extract insoluble in benzene yields to ether carajurone, isolated as a scarlet powder, which readily assumes a beetlegreen lustre, and possesses strong dyeing proper- ties. Analysis indicates the presence of more oxygen in this com- pound than in carajurin.A small amount of a similar, but brighter, lake from British Guiana, and obtained from the leaves 213 of a (‘bushrope,” gave a colouring matter dyeing also alizarin-like shades. This lake, considered to be “ chica red,” appears to differ in some respects from the “ carajura ” above described. 194. (IThe interaction of nitric acid and the sulphides of &naphthol.” By Charles Graham Hutchison and Samuel Smiles. When treated with nitric acid under suitable conditions, naphthasulphonium-quinone yielded a moizonitro-derivat.ive, which was converted into a phenylhydrasone and into chloronitro-naphthathioxin. Interaction of the isosulphide and nitric acid furnished the same nitro-quinone in almost quantitative yield, but the normal sulphide, even under mild conditions, gave only a very small quantity of this nitro-compound with a relatively large amount of dinitro-P-naphthol. Experiments were also quoted to show t’hat the conversion of either sulphide into the quinone involves a loss of two atoms of hydrogen per molecule. 195.r6 Dinaphthathioxonium salts.” By Brojendranath Ghose and Samuel Smiles. It was shown that, whilst acetyl chloride reacts with naphtha- sulphonium-quinone, yielding chlorodinaphthathioxin, acetyl iodide furnishes dinaphthathioxon,ium iodide. The latter substance was converted into dinaphthathioxin by means of sodium thiosulphate. Other salts of dinaphthathioxonium were obtained by iqteraction of acids and the corresponding sulphoxides, the change being parallel to that previously observed in the phenazthionium, carbo- thionium, and thiotliionium series.The following note has been received since the meeting: 196. (‘Alizarin a-methyl ether.” By Josef Oesch and Arthur George Perkin. Alizarin a-methyl ether, which it3 present in Chay root, Olden-latzdia umbella6a (l’.,1893, 64, 1160; 1907, 91, 2068), and contains the methoxy-group in the peri-position with respect to the carbonyl group, has been prepared in small quantity by the action of an ethereal solution of diazomethane on a nitrobenzene solution of monoacetylalizarin and subsequent removal of the acetyl group (T., 1899, 75, 447). It’ was obtained in needles melting at 117-l78Oy gave the ltcetyl compound melting at 211--213O, and possessed the characteristic properties of the natural product.214 ADDITIONS TO THE LIBRARY. 1. Donations. Hale, Arthur James. The synthetic use of metals in organic chemistry. London 1914. pp. xif169. 48. 6d. net. (Recd. 21/5/ 14.) From the Publishers : Messrs. J. and A. Churchill. Harden, Arthur. Alcoholic fermentation. 2nd edition. London 1914. pp. Pi+ 156. 4s. net. (Recd.15/6/14.) From the Publishers : Messrs. Longman@,Green and Co. Philip, James C. Physical chemistry. Its bearing on biology and medicine. 2nd edition. London 1913. pp. vii+326. 78. 6d. net. (Recd. 4/6/14,) 11. By Pzlrchasa. Apolant, H. [and others]. Paul Ehrlich. Eine Darstellung seines wissenschaftlichen Wirkens.Festschrift zum 60 Geburtstage des Forschers. Jena 1914. pp. viii + 668. ill. M.16.--. (Recd. 17/6114.) Cammidge, Percy John. The faeces of children and adults. Their examination and diagnostic significance with indications for treatment. Bristol 1914. pp. viii+516. ill. 17s. 6d. net. (Recd. 17/6/14.) Ehrlich, PauE. See Apolant, H. INFORMAL MEETING. The Rooms of the Society will be open for an informal meeting of the Fellows on Thursday, October 22nd, 1914, from 8 to 10 p.m. Further particulars will be announced in due course. THE LIBRARY. The Library will be closed for Stocktaking from Monday, August 17th, until Saturday, August 29th, 1914, inclusive. Fellows are particularly requested to return all Library Books in their possession not later than Wednesday, August 12th. R. 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ISSN:0369-8718
DOI:10.1039/PL9143000195
出版商:RSC
年代:1914
数据来源: RSC
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