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Proceedings of the Chemical Society, Vol. 29, No. 418 |
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Proceedings of the Chemical Society, London,
Volume 29,
Issue 418,
1913,
Page 215-237
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[Issued 28/6/ 13 PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 29 No.418. Thursday, June 19tli, 1913, at 8.30 p.m., Prof. W. H. PERKIN, LL.D., F.R.S., President, in the Chair. The PRESIDENTannounced that, in future, a list of the papers to be read at each Ordinary Scientific Meeting will be advertised in the Morning Post on the Wednesday previous to the day of meeting. Messrs. A. J. Berry and It. Robison were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs.: Alan Milsom Bailey, Lanhill, Chippenham. George Bernard Butler, 10, Malvern Street, Elswick Road, Newcastle-on-T yne. Alexander Houghton Hay, Essex Wharf, Narrow Street, Lime- house, E. Harold Frank Tayler, 105, Barrow Road, Streatham, S.W.A ballot for the election of Fellows was held, and the following -were subsequently declared duly llected : William Love Biggart. Ralph Richard Oliver. Archibald Joseph Brooks. Percy Bernard Phillips. William Rhys-Davies. William Gilbert Saundcrs. Jack Cecil Drummond, B.Sc. Montagu George Smith. Horace Freeman. Ebenezer Bees Thomas, M.Sc. Roy Gonpalves Glenday, R.A. Percy Cyril Lesley Tliorne, B. A. James Joseph Hutchinson. Jeremiah Twomey, RLSc. Victor Lefcbure, B.Sc. John Stewart Walker. Duncan James Macnaughtan. Edmin Longstaff Watson. Ghulam Ali Mahamadi. Ernest John Wilson, M.A. Mttrius Maxwell. Thomas Howard Young. 216 Of the following papers, those marked * were read: W9. ‘(Absorption spectra and chemical reactivity.Part 111. Trinitrobenzene, trinitroanisole, and picric acid.” By Edward Charles Cyril Baly and Francis Owen Rice. The absorption spectra of trinitrobenzene, trinitroanisole, and picric acid were described, and it was shown how the closed force fields surrounding the molecules of these substances are opened up by the use of various basic solvents. In a previous paper (T.,1912, 101, 1469) a theory of fluorescence was put forward based on the existence of several stages in the opening up of these closed systems. Whereas previously only one stage had been recognised, three stages have been proved to be produced with the three trinitro-compounds. It was shown how the results explain the formation of the picrates of the hydrocarbons and the nitration of the aromatic compounds.DISCUS~ION. Referring to the views on the origin of residual affinity advanced by Prof. Baly, and to the remark that previous explanations were ‘(not satisfactory and connected,” Dr. FLURSCHEIMsaid that he was unable to discern any substantial difference between Prof. Baly’s views and those he had himself published years before. In support of this he read some passages from one of his papers (J. pr. Chem., 1907, [ii], 76, 185), in which the idea of an equilibrium between the combined and free affinity of an atom was clearly developed. He had repeatedly referred to this publication in subsequent com- munications to the Society, and based on it some further chemical generalisations, some of which he had already been able to confirm by chemical experiment.Prof. Baly had merely used different words to express the same meaning. Thus, the term force lines ” used by Baly had already ‘I been previously employed by Hugo Kauffmann as a synonym for the term chemical energy ” adhered to by him (Dr. Fliirscheim), and it was difficult to imagine chemical energy acting otherwise than in force lines. Similarly, the term “ principal and secondary valencies,” introduced by Werner and used by Prof. Baly, was, when applied to the problem of residual affinity, merely a synonym for the term “ affinity” used by him (Dr. Flurscheim). He would therefore be glad to know in what way the views published by Prof. Baly differed from, and represented an advance on, those which he had himself published previously.217 *190. Derivatives of o-xylene. Part V. 5-Bromo-o-4-xylenol and 6-bromo-o-4-xylenol.” By Arthur William Crossley and Dorothy Jessie Bartlett. 5-Bromo-o-4-xyleno1, prepared by replacing the amino-group in 5-amino-o-4-xylenol by bromine, crystallises in glistening needles, melting at 80’. The benzoyl derivative forms transparent plates, melting at 51°, and the o-nitrobenzoyl derivative crystallises from ethyl acetate in transparent, rectangular plates, melting at 151-152’. 6-Bromo-o-4-zyZenoZ was prepared from 5-nitro-3-o-xylidine by replacing the amino-group by a bromine atom and the nitro-group by hydroxyl. It separates from light petroleum (b. p. 80-looo) in masses of silken needles, melting at 103O.The benzoyl derivative crystallises from methyl alcohol in transparent, six-sided platee, melting at 85O, and the o-nitrobeizaoyl derivative forms glistening needles, melting at 132’. *191. The presence of neon in hydrogen after the passage of the electric discharge through the latter at low pressures, Part 11.” By John Norman Collie and Hubert Sutton Patterson. Since the authors’ former communication on this subject (T., 1913, 103,419), many further experiments have been made. That electrodes are necessary for Lhe production of neon and helium has been disproved ;for if a powerful oscillating discharge be passed through a coil of wire wound round a glass bulb containing a little hydrogen, helium with some neon can be detected in the residual hydrogen.It is necessary to free the gas in the bulb as completely as possible from mercury vapour. The experiment was frequently repeated in the same bulb, and even after many weeks’ working, helium and neon could still be obtained from the apparatus. The hydrogen and oxygen used in these experiments was repeatedly tested in quantities up to 100 c.c., but not a trace of helium or neon was found. The experimental bulb before use was heated to 250’ and washed out with oxygen; the oxygen residue did not show the presence of either helium or neon. Also an apparatus was made where the tube through which tlie discharge took place was surrounded by a vacuous outer tube. The wires connected to the electrodes in the inner tube passed through the outer tube in glass tubes, so that there could be no discharge from any electrodes in the outer vessel; in this case, also, helium and some neon were found in the outer vessel.The above experi- ment was made in the following mnnncr. After the tube had been 218 externally heated and pumped until no more gas would come off, a strong current was passed. At once hydrogen began to be evolved from the electrodes; this was pumped off, and an electric spark passed through it to see whether any oxygen was present. A very small contraction occurred; 4.6 C.C. remained. This was then gradually put back into the tube, whilst a powerful current was passed through the tube, which was at the same time externally heated with a gas flame.At the end of three hours’ sparking, 2.2 C.C. of gas remained. This was again put back into the tube and the sparking repeated; at the end of another three hours it had shrunk to about 1.0 c.c., and by further treatment it went to 0.4 C.C. This hydrogen contained a trace of neon. At this point a crack appeared in the inner tube. From the outer tube only 0.4 C.C. had been pumped off; this contained both helium and neon. The inner tube was broken up at once, the two aluminium electrodes were put into a hard glass tube, and fused by a blowpipe in a vacuum; 0.2 C.C. of hydrogen was collected. The glass ends of the inner tube were powdered and also heated by means of a blowpipe in a hard glass tube that had been entirely pumped out.Too small an amount of hydrogen to be measured was pumped off. From the above experiment 4.6 -1.0=3.6 C.C. of hydrogen had apparently disappeared. In the capillary tube between the two ends of the inner tube some black substance had collected where the tube had been very highly heated by the electric discharge. This substance was carbon, for on heating it with a little oxygen it suddenly burnt away with a bright flash, and the oxygen gave a milkiness with baryta solution. Many esperiments have also been made with a double tube so constructed that mercury can be run up so as to fill the outer vessel, and drive the gas there up into a small capillary tube with a platinum wire fused through the end of it. The gas can under these conditions be examined by means of an electric discharge from the platinum wire to the mercury.During the whole of an experiment gas is perpetually appearing in the outer tube. It consists largely of hydrogen, together with traces of helium and neon, and of a gas that gives a spectrum of carbon. If it is sparked it rapidly decreases in volume, usually to about one-half and sometimes even less, the carbon spectrum almost entirely disappears, and the hydrogen (and the traces of helium and neon) remain. This same phenomenon also invariably occurs when testing for helium and neon. After the residual hydrogen has been exploded with excess of oxygen, and the residual oxygen has been absorbed by charcoal cooled in liquid air, the gas that remains should be pure helium or neon or a mixture of the two. The spectrum, however, is always a carbon spectrum, and it is only 219 after sparking for some time that the carbon spectrum goes and the pure spectrum of helium and neon takes its place.There is always at the same time a diminution usually of over 50 per cent. in the volume of the gas. This gas also is produced in the bulb, round which a wire has been coiled, and through which an oscillating discharge has been passed. It also is produced in a tube containing a piece of platinum foil, placed in the focus of a concave cathode of aluminium, bombarded by cathode stream, so that it becomes red-hot. At first, hydrogen is given, then hydrogen mixed with helium and some neon, then less hydrogen and helium, and some of the gas already mentioned that gives a carbon spectrum.After this apparently no more helium is produced, but an increasingly relatively larger amount of the gas giving the carbon spectrum. If this gas is sparked in contact with mercury vapour, it almost instantaneously disappears, and ib has been found impos- sible to reproduce it, by heating the tube, or varying the pressure in the tube. As it can be separated from the hydrogen in which it is found by exploding with excess of oxygen and removing that excess by means of charcoal cooled with liquid air, it appears to be a highly uncondensable gas, and not readily oxidised. This result, taken in conjunction with the fact that it gives a carbon spectrum, is very difficult to explain.It is possible that this gas may be the same as that discovered by Sir J. J. Thomson and called by him X,. Various experiments have also been made with electrodes other than aluminium. In the case of copper, interesting results were obtained. The hydrogen seemed to disappear more rapidly than when aluminium electrodes were used. Possibly this is due to the fact that a more powerful current can be passed through the tube, and the electrodes therefore heated to a higher temperature. The splashed copper was in parts of a black colour. Even after as much as 5 C.C. of hydrogen had been absorbed by a tube, no amount of heating made the gas come off again. The copper splash was dissolved in aqua regia, and evaporated to dryness, some water and a little hydrochloric acid added, and the clear solution of the copper salt was then tested with barium chloride.A small, white precipitate was obtained. This has been repeated many times; the copper splash always gives this precipitate. Presumably it is barium sulphate; but it is somewhat difficult to prove the presence of sulphur in the minute amount produced. The actual amount from four different experiments weighed about one-tenth of a milligram. Some of it was heated with a little sodium carbonate and carbon, and gave a faint brown stain on silver; also, with hydrochloric acid, a very faint odour of hydrogen siilphide. As B 220 ordinary glass contains traces of sulphur, four more experiments were made with lead glass tubes that are quite free from sulphur.Again in every case a precipitate was obtained in acid solution by barium chloride. Three other tubes with respectively magnesium, platinum, and palladium electrodes all gave this precipitate. Every conceivable precaution was taken to test the metals, the reagents, and the electrodes for sulphur, and, except in the case of soda-glass tubes, sulphur was invariably absent. The results at present arrived at froin the experiments given in this note are the following: (1) Electrodes apparently are not necessary for the production of She helium and neon. (2) Hydrogen in considerable quantities can be made to apparently entirely disappear in tubes through which a heavy discharge passes.(3) A gas is produced in the tubes that gives a carbon spectrum. It entirely disappears when sparked in contact with mercury. It is not readily condensed by charcoal cooled in liquid air, nor easily oxidised by sparking with oxygen. (4) When copper, platinum, palladium, or magnesium are splashed off in an ordinary vacuum tube containing hydrogen, something is produced that, after dissolving in aqua regia, gives a precipitate in acid solution with barium chloride. ,l'ote.-Only one of the authors (J. N. C.) is responsible for the statement that the nietallic splashes give, after solution in acids, a precipitate with barium chloride. Since the paper was read he has made further experiments that probably account fcr its production .(1) Copper electrodes were used. The sslution of the splash in acids was evaporated in silica vessels. iVo precipitate was obtained. (2) The same tube was used again, and the solution of the splash was divided in half. One half (a) was evaporated in glass test-tubes, the other half (b) was evaporated in silica vessels: (a) gaue Q precipitate, (b) yave tjo precipitate. A blank experiment was made with the acids and considerable evaporation in glass test-tubes, and a precipitate was obtained with barium chloride in acid solution. The hydrochloric acid had been boiled with, and then distilled from, solid barium chloride, and the nitric acid had been treated in the same way with barium nitrate. There also might be another explanation of the precipitate.The copper electrodes were sealed to the platinum by a little silver solder; some of the silver splashes off; this gives silver chloride, that on evaporation with strong hydrochloric acid dissolves, and is reprecipitated on dilution and addition of barium chloride. b4*192. The rotatory dispersive power of organic compounds. Part 111. The measurement of magnetic rotatory dispersion.” By Thomas Martin Lowry. A description was given of apparatus and methods for the measurement of magnetic rotations over a wide range of the visible spectrum. “193. The rotatory dispersive power of organic compounds. Part IV. Magnetic rotation and dispersion in some simple organic liquids.” By Thomas Martin Lowry. Numerical values were given for the magcetic rotation and dispersion in (1) inactive primary alcohols, (2) active secondary alcohols prepared by Dr.R. H. Pickard, (3) fatty acids, including active valeric acid, (4)ketones, (5) esters and paraffins prepared by Prof. Young, (6) carbon disulphide. *194. 66 The isomerism of p-azophenol.” By Philip Wilfred Robertson. pAzopheno1, HO*C,H,*N:N*C,H,*OH, as ordinarily prepared, forms yellow crystals containing one molecule of water; there appear, however, to be two yellow modifications, one of which yields, on heating, the anhydrous compound as a dark green, the other as a brick-red variety. Both of these forms have been shown to be stable in dry air under ordinary conditions; at higher tem- peratures the red is converted into the green, the transition temperature being about 50°.This is possibly not a case of polymorphism, because the difference seems to persist in solution. In addition to this a-azophenol, Willstatter has obtained, by oxidation and subgequent reduction, a 8-modification, a red sub-stance incapable of being reconverted into the original compound by physical means. Hantzsch has shown that both substances have exactly the same absorption spectra, and calls this a case of homo- chromisomerism. The chemical reactions of the two substances have now been examined. On broniination, they yield different tetrabromo-derivatives, melting at 252O and 271”, and these have also identical absorption spectra. On nitration, a-azophenol yields a tetranitro- compound (I), whilst the @-modification, even with considerable excess of nitric acid, forms only a disubstituted derivative (11) : 222 KO, NO” H (1.1 (11.1 It is possible that this difference is due to stereoisomerism, ae is indicated in the above formula.DIs CUSS ION. Prof. MELDOLAconsidered that Dr. Robertson had made out a good case in favour of the stereoisomerism of the two forms in the sense of their being the syn-and anti-modifications. He had no doubt the author had considered the possibility of quinonoid i8omerism, since one-half of the molecule admitted of such rearrangement. He asked whether this point had been tested by checking the mobility of the hydroxylic hydrogens by preparing the methyl derivatives, and, if so, whether the two isomerides gave isomeric or identical methyl derivatives.In reply to Prof. Meldola, Dr. ROBERTSONsaid that the fact of the two isomerides having the same absorption spectrum precluded the possibility of either possessing a quinonoid constitution. The author differed from Prof. Baly in his contention that an equilibrium mixture in solution might yield two different substances on removal of the solvent, according to whether one started from one or the other isomeride. “195. “The action of ozone on cellulose. Part IV. Cellulose peroxide.” By Charles DorBe. Ozone acting on purified cotton-cellulose was stated to furnish a peroxide, recognised by its oxidising action on potassium iodide solution (T., 1912, 101, 498).Doubts having been cast on the existence of this product, the question has been reinvestigated. In the absence of water, a small amount of peroxide alone is produced, but in air-dry material the quantity of peroxide formed is very much greater, and at the same time the solid insoluble acid and oxycellulose are formed (Zoc. cit.). The amount of ‘‘ active oxygen ” fixed by air-dry cotton, mercerised cotton, and lustra-cellulose after eighteen hours’ exposure to ozone was 0.0056, 0-0106,and 0.0248 per cent. respectively. The peroxide is slowly decomposed on treatment with water, hydrogen peroxide being produced. It is decomposed to the extent of 25 per cent., after heating for two 223 hours at 37O, and almost entirely after two hours at 95O.The activity soon disappears if the material is kept in the air, but persists for some weeks in a dry atmosphere. The peroxide acts strongly on a photographic plate, sharp negative images of the fibres being obtained in twenty days at 14O, or in six hours at 37O. These properties recall the photographic action of the natural woods described by Russell (Phil. Trans., 1904, 197, 251, etc.), and were shown to be due probably to a similar cause, namely, the gradual production of hydrogen peroxide. The question of the position in the cellulose complex at which the peroxide oxygen may be attached was discussed, together with the part played by the peroxide in the oxidation of cellulose by ozone. DISCUSSION.Mi. C. F. CROSSbelieved that the author’s paper would be found to explain these observations in terms of a cyclic formula for the unit ((26) constituent group of the cellulose complex with the “potential ” unsaturated position. He call’ed attention to current articles by H. Gebhardt (especially Chem. Zeit., 1913, 37, 663), discussing the constitution of cellulose from the point of view of its affinities for colouring matters. Thie author arrived independently at similar conclusions. *196. bb Sylvestrene. The constitution of d-sylvestrene and its derivatives.” By Walter Norman Haworth, William Henry Perkin, jun., and Otto Wallach. The authors have been engaged on a detailed investigation of d-sylvestrene, prepared from the dihydrochloride by the elimination of hydrogen chloride, and they find that it is mainly a mixture of A1:3 :Q-and AG:*:Q-m-menthadiene: H2<CH2*CH,C”e=CH>CH*CMe: CH, 71 A1: :9-m- Menthadiene.CMeC1*cH2>CH*CMe,C1 ’ Sylvestrene dihydrochloride.\% CH<~H,-CHz>~~~~~e:~~,CMe-CH AG :;:g-m-Menthadiene. They have also prepared a large number of derivative8 of sylvestrene and determined their constitutions. 224 197. The refractivities of acenaphthene and its monohalogen derivatives." By Holland Crompton and Wilhelmina blebecca Smyth. The following values have been obtained for the molecular refractions of acenaphthene and its monohalogen derivatives : Mc. MD. ivE. Acenaphthene ............... 50.84 51.33 52.84 3-Chloroacenaphthene ......55-53 56.07 57 -55 5-Bromoacenaphthene ...... 58.97 59-58 61.22 3-Iodoacennphthene .......... 63 '42 64 '10 66'02 The molecular refraction, M,, of acenaphthene, calculated from that of naphthalene, is 50.94, and in the case of the halogen derivatives, the values calculated for the molecular refractions from that of acenaphthene agree with the observed. There is therefore nothing abnormal in the behaviour of these compounds. 198. "The formation of cyclic bases from aromatic imides." (Preliminary note.) By Edward Hope and Frederick Russell Lankshear. The authors have studied the electrolytic reduction of phthalimidine and of N-methylphthalimidine (prepared from phthalimide and N-methylphthalimide respectively), and have succeeded in obtaining excellent yields of dihydroisoindole (I) and N-methyldihydroisoindole (11): (1.) (11.) The properties of dihydroisoindole thus prepared agree with those given by Gabriel and Pinkus (Ber., 1893, 26, 2210) and by Frankel (Be?., 1900, 33, 2809).As stated by the latter, methyl iodide reacts with dihydroisoindole, giving a mixture of the hydriodide and the methiodide. N-Methyldihydroisoindole is a colourless oil with a strong basic odour, and boils at 195--196O/750 mm. It is very soluble in water, and readily distils over in steam, separating in the distillate as a sparingly soluble hydrate, which coiitains two molecules of water. The compound also reacts vigorously with methyl iodide, giving a quantitative yield of the methiodide (m.p. 246O). This is identical with the methiodide obtained under similar conditions from dihydroisoindole. This electrolytic reduction process renders simple the preparation of isoindole bases, which have hitherto been obtained only by 225 somewhat laborious methods. The authors are engaged in an investigation of these bases, and are carrying out experiments with a view to apply the reduction process to a variety of similar imides. 199. L6 The action of sulphur dioxide on copper at high temperatures.” By Clifford Morgan Stubbs. The depression of the freezing point of copper by dissolved sulphur dioxide has been found to be about 2-54 times that expected if the molecules of the gas remained intact in the sblution.This result can be explained on the hypothesis of a partial reaction of the dissolved gas with the molten metal according to the equation : 6Cu+SO, Cu,S +2Cu,O. Complete reaction would give three times the depression calculated from the molecular formula SO,. It has been shown that this hypothesis of an equilibrium in the molten metal can be brought into harmony with the solubility results of Sieverts and Krumbhaar. The equilibrium pressures of sulphur dioxide in the univariant system Cu, Cu,O, Cu,S (all as solids) have also been measured between 700° and 1050°, the pressure rising in this range of temperature from less than one atmosphere to about seven atmospheres. 200. The change of colour of metallic haloid solutions.” By Charles Scott Garrett.Solutions of coloured metallic haloids in general undergo con-siderable changes of colour on varying the concentration, tem-perature, or solvent, as well as on the addition of colourless haloid salts. The phenomenon is connected with the presence of varying valency in the parent metal. It was pointed out that these changes most probably are due to the formation of complex radicles of two types, acidic and metallic radicles, and by quantitative spectrophotometric measure-ments it has been shown how these two types of complex formation may be distinguished. Copper haloids form acidic complexes, whilst chromium haloids form metallic complexes, but the solvent must be regarded as playing some part in the change. Bands of selective absorption due to the complexes were found in the case of cupric bromide, cupric chloride, and nickel bromide solutions, by photographing the saturated aqueous solutions in very thin layers.In the typical cases of copper and chromium haloid solutions it was shown that the various parts of the absorption spectra may be attributed to various entities in the molecules of the salts. 226 201. Hydroxyazo-compounds. The action of semicarbazide hydro-chloride on the p-quinones.” By Isidor Morris Heilbron and James Alexander Russell Henderson. As indicated in a recent communication (P., 1912, 28, 256), the condensation products obtained by the action of semicarbazide hydrochloride on the p-quinones in equimolecular quantities must, from spectrographic evidence, be regarded as hydroxyazo-derivatives. A further examination of these condensation products has, however, made evident that under certain conditions a few of these hydroxyazo-compounds undoubtedly react tautomerically as semi- carbazones.The authors find further that on salt-formation the hydroxyazo-compounds assume a quinonoid constitution, as is proved by the great similarity of their absorption curves with the typical quinone, tetraphenylquinodimethane. This compound shows a very characteristic band of great persistence in M/ 10,000-solution, differ- ing in position from the band of pbenzoquinone and its homologues, but resembling closely the absorption curves of the nitrophenol salts, and the authors adduce from this that such salts are undoubtedly quinonoid.A direct relationship has also been found to exist between the molecular weight and position of the absorption band in this series of similarly constituted compounds. 202. c6 The alkaloids of ipecacuanha.’’ (Preliminary note.) By Francis Howard Carr and Frank Lee Pyman. In spite of the medicinal importance of ipecacuanha, very little is known about the alkaloids which it contains, although the subject has received a considerable amount of attention. A number of earlier investigations were carried out with a purified amorphous total alkaloid, formerly known as “emetine,” but later Paul and Cownley (Pharm. J., 1894, [iii], 24, 111) showed that this product contains at least two alkaloids, emetine and cephaeline, the latter being a phenolic baae, and described methods for their separation and purification.They attributed to emetine the formula C30H4404N2or C,,H2,04N2, and the cephaeline, C2,H4@4N2 or C,4H2004N2,whilst 0. Hesse (Pharm. J., 1898 [iv], 7, 98), repeating the work at their request, preferred the formula C,H4,04N2 for emetine and C2,H,,0,N2 for cephzline. Hesse showed that emetine contains four methoxyl groups, whilst the results for cephaeline lie between those required for two and three. The subject has recently been reinvestigated by Keller (Arch Pharm., 1911, 249, 512), who has brought out the important result 227 that emetine forms a nitrosoarnine, and therefore contains an imino-group. He regards it as a secondary tertiary base, containing two methoxyls and at least one hydroxyl group.In the course of an extended investigation of these alkaloids, the authors have obtained results having an important bearing on the constitution of emetine and cephxline, and think it well to record briefly at the present stage some of their principal conclusions. A large number of analyses of emetine, and of its hydrochloride, hydrobromide, hydriodide, and nitrate have now been carried out, and these indicate the formula C29H4004N2 for this base. This formula is also in better agreement on the whole with the few results obtained by previous investigators than any of the formulae suggested by them. Cephzline is probably correctly represented by the formula C2,H,804N2. These formulz, which are supported by molecular-weight determinations, indicate that each alkaloid contains two nitrogen atoms.In the stable neutral salts, the bases are combined with two equivalents of acid. Evidence of the existence of basic salts has also been adduced. In each base both nitrogen atoms are present as imino-groups ; and these alkaloids are therefore disecondary bases. Emetine contains four, and cephzeline three, methoxyl groups, whilst the latter also contains a phenolic hydroxyl group. All the oxygen atom8 contained in them are thus accounted for. Both alkaloids are optically active, the bases being lzvorotatory, emetine having [aID -22O, and cephzline [aID-18O, whilst the salts are dextrorotatory, anhydrous emetine hydrochloride [a],,+16O corre-sponding with [a], +18O for the basic ion. Emetine yields, on oxidation with ferric chloride in aqueous solution, a scarlet, crystalline hydrochloride, which is termed rubremetine hydrochloride. Being formed by the removal of eight hydrogen atoms from emetine, it has the formula C29H3204N2,HCl,6H20.It melts at 127-1 28O (corr.), contains four methoxyl groups, and is monobasic.When emetine is oxidised with a large amount of potassium permanganate in aqueous acetone solution, 6 : 7-dimethoxyisoquinolin~+l-carboxylicacid is formed, identical with the substance previously obtained by Goldschmidt by the oxidation of papaverine; m-hemipinic acid has also been observed amongst the oxidation products.Cephaeline, on oxidation, behaves differently from emetine, ferric chloride giving rise to two crystalline oxidation products: (i) a hydrochloride, C2,H2,07N2,HC1,5H,0, melting at 249-250O (corr.), and containing three rnethoxyl groups but no hydroxyl group, (ii) a hydrochloride, CI7H2,O,N,HC1,4H20, melting and decom- posing at 158O (corr.), after drying at looo, and containing two methoxyl groups and a hydroxyl group. A crystalline N-methyl derivative of cephaeline, melting at 194O (corr.), has also been obtained. The results are beihg elaborated and extended, and it is hoped to communicate them fully to the Society later in the year. 203. (‘Dibenzoyldiaminoacetic acid.” By Paul Haas. When a-hydroxyhippuric acid, C6H5*CO0NH*CH(0H)*CO2H,is heated to 150°, it is converted into dibenzoyldiaminoacetic acid, (C6H50CO*NH)2CH*C02H,in a 40 per cent.yield; the latter sub-stance, on hydrolysis, decomposes into benzamide and glyoxylic acid, 204. 6L The so-called calcium P-diglycerglphosphate : A correction.” By Frank Tutin. In a paper published by the present author and Mr. Hann (T.,1906, 89, 1754), a calcium salt, melting at 249-250°, was described, which, on hydrolysis with dilute acids, gave a small yield of 8-glycerylphosphoric acid. Analyses of the calcium salt men-tioned gave results in harmony with the conclusion that it had the composition C12H2s0,6PzCa, provided it were assumed that thirteen molecules of water of crystallisation were also present.It was theref ore regarded as hydrated calcium 8-diglycerylphosphate. It has now been ascertained that this conclusion cannot be correct, since the calcium salt in question contains chlorine (about 38 per cent. on the air-dried material). This fact, however, does not aEect the identity of the P-glycerylphosphoric acid prepared by the hydrolysis of the calcium salt, the formation of which was one of the objects of the above-mentioned investigation. 205. ‘‘ Some derivatives of desylamine.” By Alex. McKenzie and Fred Barrow. The authors have studied the conversion of phenylaminoacetic acid into desylamine, with the primary object of aiding an invest,i- gation, which is at present in progress, on the isolation of the optically active modifications of the base.a-Phthalyliminophenylacetyl chloride, when acted on by benzene and aluminium chloride, gave desylphthalimide (compare Pfaehler, Ber., 1913, 46, 1700), from which desylamine can be obtained. A mixture of desylphthalimide and dibenzoylstilbene was pro-duced by the interaction of desyl chloride and potassium phthalimide in presence of nitrobenzene at 150-I6O0. 229 2: 4: 5-Triphenyloxazole waa prepared by the dehydration of benzodesylamide with concentrated sulphuric acid. The action of various Grignard reagents on desylamine hydro- chloride has also been investigated. 206. LL Influence of substitution on the reactivity of p-phenglene-diamine.” By Qilbert T. Xorgan and Joseph Allen Pickard. This investigation, which is a contribution to the study of the inhibition of chemical change, was initiated with the object of ascertaining the part played by substituents in modifying the reactivity of p-phenylenediamine and its homologues.The follow- ing preliminary experiments were carried out on two derivatives of this diamine containing negative substituents. I.-The Reactivity of Xitro-p-phe n y 1e I ediumiti c. 1. d cetyZatiou.-One acetyl group only was introduced into the molecule of this nitrodiamine by suspending the base in water, adding excess of acetic anhydride, and subsequently heating to boiling. The product, which crystallised from water in light red, felted needles, melting at 189O, was identical with the monoacetyl derivative previously obtained by half hydrolysing nitrodiacetyl- pphenylenediamine with ammonia, dilute aqueous alkalis, or prefer- ably with baryta water (Ber., 1884, 17, 148; 1886, 19, 339; 1897, 30,980; 1903, 36,415).As the constitution of this compound has been assumed without proof, it was dissolved in cold alcohol and treated successively with hydrogen chloride and nitrous fumes, the diazonium chloride being precipitated with dry ether. This salt was suspended in absolute alcohol, the mixture warmed with copper powder, and the solution neutralised with calcium carbonate, filtered, and evaporated nearly to dryness. m-Nitroacetanilide (m. p. 150O) separated, and was further identified by hydrolysis to m-nitroaniline (ni. p. 112O). These reactions fix the constitution of the acetyl derivative as 2-n it ro-4-acetyl-p-pheny 1eI? ediamine, NO2 NO2 NH,/---\NHA~ -+ CIN,~NHA~\-/ -+ NO* ~N AuH ~. Acetylation with acetic anhydride in the presence of water leads to diacetyl derivatives with p-phenylenediamine and its homologue, 230 2 : 5-tolylenediamine; it is also pract,icable with m-and p-nitro- anilines, but not with o-nitroaniline.2. Picrylation.-Only one picryl group is introduced by boiling nitro-p-phenylenediamine for twelve hours with excess of picryl chloride (3 mols.) in dry toluene over anhydrous sodium acetate. Nitro-4-pcryE-p-phenylenediamine,which separated in dark red crystals melting at 255O, dissolved in aqueous or alcoholic sodium hydroxide, and was only sparingly soluble in alcohol, glacial acetic acid, or concentrated hydrochloric acid : 0.2028 gave 39.1 C.C.N, at 15O and 766 mm. N=22*77. CI2H,O,N, requires N =23.10 per cent. Comparative experiments with o-nitroaniline and 2 :4-dinitro-aniline showed that these bases are not picrylated under the fore- going conditions, and it is accordingly highly probable that in nitro-p-phenylenediamine picrylation occurs in the amino-group remote from the nitro-radicle. Direct evidence was obtained by dissolving the picryl derivative in concentrated sulphuric acid and adding successively to the bright yellow solution nitrosyl sulphate and alcohol, the temperature being kept below 5O. The solution of diazonium sulphate thus produced gave a deep red azo-&naphthol derivative, dissolving in concentrated sulphuric acid to a bluish-green aolution.When boiled with copper powder, the alcoholic solution of the diazonium salt evolved nitrogen, and yielded picryl-m-nitroaniline (m. p. 207O), thus indicating the following constitution for the picrylat'ed diamine : 3. Diazotisation.-Although nitro-p-phenylenediamine diazotises most readily to the monodiazonium salt (Bulow, Ber., 1896, 29, 2285) in 50 per cent. sulphuric acid, the second amino-group is attacked, with the production of the bisdiazonium sulphate. These reactions have been turned to account in the preparation of 4-nitro- m-tohidine. The homologous base, 4-nitro-2 :5-tolylenediamine, behaved in a similar manner, diazotising chiefly to 4-nitro-5-amino- toluene-2-diazonium chloride with a smaller proportion of 4-nitro-toluene-2 :5-bisdiazonium chloride.11.-The Reactivity of 2 :6-Dichloro-p-phenylenediamine. 1. Acety1ation.-When boiled with acetyl chloride, 2 :6-dichloro-p-phenylenediamine yielded 2 :6-dichlorodiacetyl-p-phenylenedi- 231 amine, which crystallised from alcohol or hot water in colourless needles, melting at 253-254O : 0.1722 gave 15.4 C.C. N, at 12O and 757 mm. M=10.5. C,,H,,0,N,C12 requires N =10.73 per cent. When boiled for fifteen minutes with N-sodium hydroxide solution (30 parts), the diacetyl derivative yielded a monoacetyl compound, crystallising from alcohol in lustrous, colourless plates,' melting at 218O, and dissolving in dilute hydrochloric acid, the soluble hydro- chloride being readily diazotised.2 : 6-DichZo~o-4-acetyl-p-phenylenediamine, CI NH /-\.NH*CO*CH,.2\-/ c1 This isomeric rnonoacetyl derivative was produced by shaking 2 : 6-dichloro-p-phenylenediarninewith excess of acetic anhydride and water. It crystallised from alcohol or water in colourlesa needles, melting at ZOOo: 0.1553 gave 17.3 C.C. N, at 18O and 759 mm. N= 12.85. C,H,ON,Cl, requires N =12-70 per cent. The constitution of this compound was determined by adding nitrosyl sulphate to its slightly warm solution in absolute alcohol. The diazonium sulphate, which separated in colourless, feathery needles, was suspended in alcohol and treated with copper powder, when a brisk evolution of nitrogen occurred.3 : 5-Dichloroacet-anilide (m. p. 187O) separated in colourless crystals on diluting the filtered solution with water, and this product, when hydrolysed with concentrated hydrochloric acid, yielded 3 : 5-dichloroaniline (m. p. 51O). 2. Picrylation.-Only one amino-group is picrylated on boiling e2 :6-dicliloro~pphenylenediamin with picryl chloride in toluene solution over anhydrous sodium acetate. 2 : 6-DichZo~op'cryl-p-phen,ylenediamine, NH2~C6H,CI,*NH0C6H2(N0,),, separated from glacial acetic acid in lustrous, dark red crystals, sintering at 220°, and melting at 227-228O: 0.1516 gave 0.1119 AgC1. C1=18-25. Cl,H707N,C1, requires C1= 18.27 per cent. The compound was soluble in aqueous or alcoholic alkali hydroxides, but dissolved only very sparingly in hydrochloric acid.3. Diazotisation. -2 : 6-Dichloro-pphenylenediamine did not diazotise smoothly in aqueous solutions of the mineral acids, and 232 although the reaction proceeded more readily in alcoholic or glacial acetic acid solution, even then only one amino-group was diazotised with the formation of 2 : 6-dichloro-l-aminobenzene-4-diazonium chloride or sulphate. On treatment with absolute alcohol and copper powder, these diazonium salts yielded '2 : 6-dichloroaniline, thus showing that the amino-group diazotised is the one in the meta-position with respect to the chlorine atoms. sum rnrrry. 1. The introduction of a negative radicle into the arcmatic nucleus of pphenylenediamine hinders very considerably the acetylation of the amino-group contiguous to this substituent.The picrylation of this amino-group is completely inhibited. 2. The introduction of one nitro-group into the p-phenylene- diamine or 2 : 5-tolylenediamine nucleus diminishes very consider- ably the diazotisability of the contiguous amino-group. The presence of two chlorine atoms in ortho-positions with respect to one amino-group of y-phenylenediamine inhibits completely the diazo- tisation of this group. 207. '' The constitution of the ortho-diazoimines. Part 111. The a-and 13-acyl-3 :4-tolylenediazoimides as structural isomerides." By Qilbert T. "organ and Frances Mary Gore Xicklethwait. 3 : 4-Tolylenediazoimine or its metallic derivatives yield on acetylation a mixture of two acetyl derivatives, which have hitherto been regarded as (' physical isomerides " (Zincke and Lawson, Annulen, 1887, 240, 119).The authors have shown that these compounds are structural isomerides having the constitutional formulz : CH,*C,H,< --N*CO*CH,. 3 IN:N . . . . . . . 4 a-M.1'. 132". 8-M. 1). 93-94". arising respectively as sole products of the diazotisation of 4-acetyl- 3 : 4-tolylenediamine and 3-acetyl-3 : 4-tolylenediamitre. The chemical nature of the foregoing case of isomerism was con- firmed by obtainin-g, from 4-benzoyI-3: 4-tolylenediamine and 3-benzoyl-3: 4-tolylenediarniize respectively, the isomeric pair of benroyl-3 : 4-tolyleii edictzoirriidrs having coiistitutions represented FY the following formulze : 3 4 a-31.p. 127-128". 8-nf. p. 122-423". The existence of these two pairs of isomerides affords additional coiifirmation of KekulB’s formula for diazoimines as opposed to the configuration for these diazo-derivatives advocated by Griess. 208. ‘‘The occurrence of neon in vacuum-tubes containing hydrogen.” By Irvine Masson. Experiments are in progress to test further the results of Collie and Patterson (T., 1913, 103,419), and have yielded independent evidence of the fact that neon appears after the passage of an electrical discharge through a vessel containing a gas previously free from neon. When pure dry hydrogen was sparked in a discharge-tube bearing a perforated aluminium disk cathode and having a vacuous jacket surrounding it, it was found that after a time neon ceased to be formed; on then admitting a mixture of oxygen and hydrogen and passing the discharge, the tube appeared to be rendered “active ” once more, for thereafter neon was steadily produced when hydrogen was sparked. In all these experiments, hydrogen accumulated in the initially vacuous jacket, and had apparently passed through from the discharge-tube.Quantities up to about one-third of a C.C. could be so obtained. This gas was found to contain no other, except carbon monoxide in small and varying amounts. 209. “A himple and efficient method of dehydrating substances by electrical heating in a vacuum.” By William Ernest Stephen Turner and Crellyn Colgrave Bissett.Methods of electrical heating within a vacuum desiccator have already been described by Skita (Chenz. Zeit., 1902, 26, 898) and by Scheermesser (;bid., 190.3, 27, 175). The first-named author used two 16-candle-power lamps promoting a temperature of 70° ; the second, a plate; and both methods are suitable more for the evaporation of liquids than for dehydration at higher temperatures. The authors’ own method, which was in use some time before they were aware of previous arrangements, is not only much more e5cient, but also far simpler. It consists in introducing into a vacuum desiccator a heating coil made of manganin wire, a length of 90 cm. of No. 20 wire gauge being very suitable, so as to give a coil of about 4 cm. internal diameter. A cover for the coil is made by wrapping round it a strip of asbestos paper, previously moistened.Connexion is made with the coil by two leads of stcut copper wire, which pass through two pieces of narrow quill glass 234 tubes inserted in the rubber stopper of the desiccator, the upper ends of the glass tubes being then closed by sealing wax. Using a small platinum dish, weighing 12 grams, 3.5 grams of powdered silica were maintained in the exhausted desiccator at a temperature of 36O with a current of 2 amperes, 92O with 4 amperes, and 154O with 5.8. Still higher temperatures may be reached if desired. The drying agent used in the desiccator is phosphoric oxide. The value of the method will be realised by the two following cases, in which dehydration by previous methods appears to have been both difficult and not entirely successful.Lithium iodide at the ordinary temperature occur8 as the tri-hydrate, although the commercial samples are usually parily dehydrated. In Abegg’s “Handbuch der anorganischen Chemie,” Vol. 11,p. 130, it is stated that the anhydrous form may be pro- duced by heating above 300°, but that the substance so obtained is not pure, since at this temperature it attacks glass and porcelain. From the authors’ tests, a sample of the salt of composition corre- sponding precisely with the monohydrate did not lose moisture by standing over phosphoric oxide in an exhausted desiccator for three weeks. By the new process, pure anhydrous lithium iodide (Found, I=94*9.Calc., I=94.8 per cent.) was obtained after raising the temperature to about looo for several hours. The iodide so obtained is quite white. Rhamnose is another substance the dehydration of which up to now has proved very difficult. It occurs ordinarily combined with one molecule of water, and its dehydration not only requires pro- longed heating on a water-bath, but the process is also accompanied by at least a partial conversion into the &form. Purdie and Young (T., 1906, 89,1194) state that dehydration is incomplete after prolonged heating at 70-90° under diminished pressure and in presence of phosphoric oxide, and is accompanied in this case also by partial conversion into the &form. The authors have been successful in completely dehydrating rhamnose during t’he course of a week by raising the temperature within the exhausted desiccator very slowly to about 90°.Moreover, polarimetric observations (made by Mr. C. R. Young) point to the absence of the ,&form from the dehydrated sugar. 210. ‘(The vapour density of ammonium nitrate, benzoate, and acetate.” By Prafulla Chandra RAy and Sarat Chandra Jana. A detailed description of work of which a preliminary account has already appeared (this vol., p. 28). 235 211 ‘‘ The action of nitric oxide on a neutral solution of potassium permanganate.” By Barum Chandra Putt, Bamacharan Chatterji, and Haridas Banerji. When nitric oxide is passed througli a solution of potassium permanganate in an atmosphere of hydrogen, the reaction which takes place is represented by the equation: KMnO, +NO =KNO, +MnOz.There is no intermediate formation of nitrous acid. ADDITIONS TO THE LIBRARY. I. Donations. [Beale, Sir WiZZicbm Phipso?~] ‘‘On the utilization of sewage by phosphsto of alumina,” ‘‘Some further observations on the analysis of water,” and “Primeval chemistry.” [‘l B I’ Club Rhymes, 1867, etc.] (RPf8rence.) [Brough, .7oh Cargill.] Meidern chemistry.” [“ B ” Club Rhyme, 1868.1 (Rpfirence.) [Field, Frederick] ‘‘C. B,” and ‘(A quiet sort of way.” [“ B ” Club Rhymes.] (Reference.) From Sir William Tilden, F.R.S. Haas, Pad, and Hill, T.G. An introduction to the chemistry of plant products. London 1913. pp. xiif401. 7s. 6d. net.(Recd. 16/6/13.) From the Publishers : Messrs. Lmgmans, Green and Co. Heredia, Carlos E. Observaciones sobre el m6todo criosc6pico y relaciones entre 10s cuerpos simples. Buenos Aires 1912. pp. 244. (Recd. 5/6/13.) From the Author. 11. By Purciinse. Boyle, Robert. Memoirs for the natural history of Humane Blood, Especially the Spirit of that Liqux. London 1682. pp. [xvi]+ 289 +[vii]. (Refirence.) Browning, Philip E. Introduction to the rarer elements. 3rd edition. Kew York 1913. pp. xii+232. 6s. 6d. net. (12ecd. 12/6/13.) Loschmidt, Joseph. Konstitutions-Formeln der organischen Chemie in graphischer Darstellung. Edited by Ricliard Anschtitz. (Ostwald’s A’Zassiker, No. 190.) Leipzig. pp. 154. M. 5.-. (Recd. 19/6/13.j Ildatthews, J.Jlerrritt. Tbe textile fibres : their physical, microscopical and chemical properties. 3rd edition. New York 1913. pp. xi + 630. ill. 17s. net. (Bed. 12/6/13.) 236 Neubauer, Carl I'heodoy Ludwig, and Huppert, Rarl Hugo. Analyse des Harns. 11th editiou. 2nd half. Wiesbaden 1913. pp. xxi+ 683 to 1657. ill. M. 27.-. (Recd. 13/6/13.) Scheele, Karl Wilhelm. The chemical essays of . . . Translated from the Tracsactions of the Academy of Sciences at Stockholm. First published. .. in 1786. [Re-issued] with a sketch of the life of Karl Wilhelm Scheole by John Geddes M'Intosh. London 1901. pp, xxx + 294. 5s. (Recd. 17/6/13.) Scheithauer, W, Shale oils and tars, and their products. Trans-lated by Charles Salter. London 1913. pp. viii + 183.ill. 89.6d. net. (Recd. 15/6/13.) Thresh, John C. The examination of waters and water supplies. 2nd edition. London 1913. pp. xx + 644. ill. 188. Od. net. (Recd 12/6/13.) III. Pamphlets. Butterfield, William John Atkinson. Lectures on chemistry in gas- works. pp. 71. London 191 3. Egypt. Survey Department. Report on the work of the Laboratories and of the Assay Office during 1912. By AIfi.ed Lucas. pp. 28. Cairo 1913. Hatton, John. Notes on the therapeutics of radium in the Bath waters. [Bath 1913.1 Hill, Charles Alexander. Lecture on the functiou and scope of the chemist in a pharmaceutical works. pp. 43. London 1913. Metropolitan Water Board. Ninth research report. By Alexaizder Cruikshank Houston, pp. 26. London 1913. Osterhout, W.J. V. Plants which require sodium. (From the Bot. Gaz., 1912, 54.) Parnas, Jcdiob. Ueber Bildung von Glykogen aus Glyzerinaldehyd in der Leber. (From the Zentr. Physiol., 1912, 26.) Ruttan, Robert E., and Hardisty, R. H. M. A new reagent for detecting occult blood. (From the Canudian Afecl. Assoc. J.,1912.) West Indies, Itnipeiiul Department of Agriculture. Sugar-cane experiments in the Leeward Islands. pp. 11 1. Barbados 19 13. 237 THE LIBRARY. The Library will be closed for Stocktaking from Monday, August llth, until Saturday, August 23rd, 1913, inclusive. Fellows are particularly requested to return all Library Books in their possession not later than Wednesday, August 6th. LIST OF FELLOWS, 1913. The List of Fellows for 1913 is now in active preparation, and changes of address received after July 31st cannot be included in it. In order that the new List may be as complete as possible, those Fellows whose degrees and Christian names do not appear in full are requested t,o communicate them to the Assistant Secretary. B. CLAY AND SC"9, LTD., BBUKSWICK ST., STAYPOBD BT., f3.E., hND BUNOAY. SUPPOLX.
ISSN:0369-8718
DOI:10.1039/PL9132900215
出版商:RSC
年代:1913
数据来源: RSC
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