摘要:

398 LXII.-Orb Dihydroqbeiizoic Acids and Ioclosalicy lic Acids. By ALEX. K. MILLER Ph.D. OF the six acids of the formula C6H3(OH),.COOH theoretically possible five are already known and it was with the view of com-pleting the series that the following research was undert,aken. The acid remaining as yet undescribed is that represented by the for-mula,-COOEI and may be conveniently termed catecho~-o1-t7Locnrbox?jlic acid. In order to prepare this acid I have tried two different methods in the one case starting from catechol (pyrocatechin) and in the other from salicylic acid. It is evident that if the same acid should he formed both by the introduction of a carboxyl group into catechol, and by replacing a hydrogen-atom in salicylic acid by hydroxyl this acid must necessarily have the structure represented by the above formula.Preparation of Dikydroxybenzoic Acids f y o m Catechol. I n order to prepare dihydroxybeneoic acids from catechol the method described by Senhofer and Brunner for the direct introduc-tion of carboxyl into phenols &c. ( W e n . Akad. Ber. 1879 2 Abth., 504) was made use of. According to this method a phenol is heated in sealed tubes for several hours to a temperature of about 110" with a concentrated solution of ammonium carbonate. I n this way Sen-hofer and Brunner obtained from resorcinol the following two dihydroxjbenzoic acids :-OH OH I n tho first of these two acids the carboxyl takes up the ortho-and para-positions respectively to the two hydroxyl groups and in the second acid the ortho-position to both hJ-droxyl groups.The symmetrical acid MILLER ON DIHYDROXYBENZOIC ACIDS ETC. 399 CGOH was not formed in tho reaction. St,arting from catechol there are only acids possible namely protocatechuic acid, two dihydroxybenzoic OH 0 I€ and since in the former the carboxyl is in the para-position to one of the hydroxyl groups and in the latter in the ortho-position to a hydroxyl group it was thought possible that both acids might be formed. 1 pftrt catechol 4 parts ammonium carbonate and 5 parts water were heated in sealed tubes a t a temperature of 130-140" for 14-16 hours. The tubes were then opened and after nearly neutralising with hydrochloric acid the liquid was filtered and the unaltered catechol extracted with ether. An excess of hydrochloric acid was then added to liberate any dihydroxybenzoic acid t h a t might have been formed and this was separated from the ammonium chloride by again shaking up with ether.After evaporating the ether a dark strongly acid residue was left behind the weight of which amounted to about one-third that of the catechol employed. After repeated crystallisations from hot water, this residue was found to consist of two distinct acids which had, however been formed in very unequal proportions. One of these, which formed by far the greater part of the product was found to be protocatechuic acid as seen from the following properties :-It crys-tallised in needles and plates with 1 mol. of water of crystallisation, which it lost a t loo" and it melted at 199'.With lead acetate it gave in aqueous solution a white flocculent precipitate and with ferric chloride an intense blue-green colour which changed to red on the addition of sodium carbonate. On heating it with pamice-stone, carbonic anhydride was given off and a sublimate of catechol was obtained. The catechol was recognised by the characteristic green colour which it gives with ferric chloride changing to violet on addi-tion of sodium carbonate ; also by the precipitate which it gives with lead acetate. The second dihydroxybenzoic acid was found in the mother-liquor from the protocatechuic acid. It had been formed only in minute ::OH The experiment was carried out as follows:-It melted a t 100" 400 MILLER OK DIHYDROXYBENZOIC ACIDS quantities and could therefore not be obtained in the pure state or of constant melting point this difficulty being further increased by its partial decomposition below the melting point.The highest melting point obtained was 192". This acid differed from protocatechuic acid in its crystalline appear-ance and in its colour reaction with ferric chloride producing a pure blue coloration which on addition of sodium carbonate changed to violet-red. By the slow evaporation of its solution in ether the acid was obtained in nodules which presented an appearance totally dis-tinct from that of the needles of protocatechuic acid. On account of the very poor yield of the second acid only a single analysis could be made. 0.0979 gram substance gave 0.1980 gram CO and 0.0375 gram HZO. Calculated for C;H,04.Found. C = 54.54 per cent. H = 3.90 , 4.25 ,, 55-15 per cent. 0 = 41.56 , -100~00 Although the small quantity of this body which was at my disposal allowed so few experiments to be made they are still sufficient to show that two dihydroxybenzoic acids can be obtained from catechol, one of which is protocatechuic acid. But since two only of these dihydroxy-acids can be derived from catechol the only formula possible for the second acid is-OH and that this constitution is the correct one is further confirmed by the experiments described below. In the second method employed for obtaining the acid just men-tioned salicylic acid was submitted to the direct action of iodine and the resulting iodosalicylic acids were converted into dihydroxybenzoic acids by melting with potash.Although different chemists have already worked upon this reaction, the results obtained differ so much among themselves that it appeared desirable to repeat the investigation. Lautemann (Annalen 120 301) for instance prepared iodosalicylic acid by boiling a solution of salicylic acid and iodine in Icohol. The acid he obtained melted a t 196". On heating with pctash it gave an oxysalicylic acid (Le. dihydroxybenzoic mid) which he characterise AXD IODOSALICTLIC ACIDS. 401 a s follows :-It melted a t 193" crystnllised anhydrous and gave with ferric chloride a deep blue colour changing t o violet on addition of sodium carbonate. Wit,h acetate of lead a yellowish-white precipitate was produced. On heating his oxysalicylic acid with pumice-stone, Lautemann obtained a distillate which hd found to be a mixture of catechol and quinol.Liechtli (Amzalen. Suppl. 7 133) made iodosalicylic acid by heating salicylic acid in aqueous solution with iodine and iodic acid. He gives 184" as the melting point of his acid. On melting his mono-iodosalicylic acid with potash he obtained a dihydroxybenzoic acid which melted at 183". Like Lautemann's acid it gave a deep blue colour reaction with ferric chloride. Demole (Bey. 7 1437) prepared iodosalicylic acid according to Liechti's method and confirmed his melting point. He also converted the iodosalicylic acid into dihydroxybenzoic acid and here again obtained the same results as Liechti. On heating his dihydroxybenzoic acid with pumice-stone Demole obtained either pure quinol or a mix-ture of the latter with small and rariable quantities of catechol.Be says that more or less catechol is formed according to the temperature a t which the acid is distilled and that in some experiments he found scarcely any ; so that since quinol is the chief and essential product of the reaction it seems fair to suppose that were dealing with quinolcarboxylic acid : OH Demole and also Liechti Demole examined further the action of melted potash on di-iodo-salicylic acid and through the unexpected results which he obtained, he thought he could explain the discrepancies between his own and Lautemann's results. From pure di-iodosalicylic acid he obtained :t mixture of two dihydroxybenzoic acids (instead of a trihydroxybenzoic acid as he expected) one of which was quinolcarboxylic acid, OH COOH Demole found further that a mixture of monoiodosalicylic acid with about b di-iodosalicylic acid melted a t 196" i.e.a t the same temperature which Lautemitnn gave for his monoiodosalicylic acid, supposed to be pure. On melting this mixture with pot,ash Demol 402 MILLER ON DIHYDROXYBENZOIC ACIDS obtained a mixture of quinolcarboxylic acid and protocatechuic acid, the latter resulting as already mentioned from the di-iodosalicylic acid. By the action of heat on these two dihydroxybenzoic acids both gave off carbonic anhydride the former yielding quinol and the latter catechol. In this way Demole tried to explain the high melting point of Lautemann’s iodosalicylic acid and the fact of a considerable quantity of catecliol being formed on heating his dihydroxybenzoic acid.Goldberg (Dissertation Wurzburg 1878) prepared iodosalicylic acid from salicylic acid by means of the diazo-compound. His acid also melted at 196” and yielded a dihydroxybenzoic acid of melting point 197” by the dry distillation of which Goldberg obtained pure quinol so that there can be no doubt that he really had pure quinolcarboxylic acid. The acid is characterised by giving a deep blue colour-reaction with ferric chloride also by not being precipitated by acetate of lead. Although the iodosalicylic acids of Lautemann and Goldberg agree in melting point important differences are found in the dihydroxy-acids obtained from them and in the products of their decomposition, Lauternanu’s acid yielding principally catechol which was however, always accompanied by quinol while Goldberg’s acid yielded pure quinol.I n order to decide whether Lnutemann’s acid was identical with Goldberg’s or with an isomeride having the same melting point or, finally a mixture of mono- and di-iodosalicylic acids as imagined by Demole I have prepared iodosalicylic acid by Lautemann’s method (see page 400). For the separation of the mono- from the di-iodosalicylic acid and from unaltered salicylic acid the mixture was boiled with water and barium carbonate and the barium salts so obtained were repeatedly crystallised from hot water. I n this way it is comparatively easy to obtain a product which analysis shows to be barium mono-iodosali-cylate.That the same was however not a definite body was shown by the fact that the products of different preparations had different melting points ; also that in recrystallising the barium salts the iodo-salicylic acid separated from different fractions showed the same chemical composition though different melt’ing points. Finally this method had to be given up and the attempt was made to get a pure product by crystallising the acid itself‘ from water. Although on account of the very slight solubility of iodosalicylic acid in water, this method has the disadvantage that large quantities of liquid have to be employed it seems to be the best for the separation of the isomeric acids. I n preparing iodosalicylic acid by Lautomann’s method two isomeric acids are in fact formed which melt a t nearly the same temperature AND IODOSALICYLIC ACIDS.403 They differ however in crystalline appearance and in their solubility in water and yield on melt,ing with potash two different dihydroxy-benzoic acids as will be seen below. The separation and purification of these two iodosalicylic acids was systematically carried out as shown in the following scheme :-c 5 4a c 0 m B 404 MILLER ON DIHYDROSYBENZOIC AClDS This scheme represents bp way of example a small part of that made up in the course of the work which is much too lengthy and complicated to reproduce in full. The portion communicated will suffice to show to some extent the difficulty of separating the two acids. The following short explanation will serve to make this scheme intelligible :-A small fraction of the whole iodosalicylic acid mixture A (melting at 171-175') was dissolved in hot water.Tile crystals a (melting a t 172-173") separated out on cooling while the evaporated mother-liquor yielded the crystals /3 (melting a t 181-1S6°). By the further treatment of a in the same fashion y and 6 were obtained, &c. &c. the find result being two crops of constant melting point, the more difficultly soluble acid melting a t 157" and the more easily soluble a t 1%". The former acid (197" m. p.) is identical as will be hereafter shown, with that obtained by Goldberg. It is para-iodosalicylic acid and has the constitution-COOH (1) c~H,.L/oH (a) 'I ( 5 ) It crystalliees from water in splendid long needles.a violet coloration with ferric chloride. Its solution gives On analysis the following numbers were obtained :-Calculated for C,H,I(OH).COOH. C = 31.82 per cent. H = 1.89 ,, I = 48.10 ,, 0 = 18.19 ,, Found. 31-68 per cent. 1-92 ,, 48.12 ,, The barium salt of this para-iodosalicylic acid obtained by boiling its aqueous solution with barium carbonate crystallises with 4 mols. of water of crystallisation in warty conglomerations of scales. The dry salt requires for solution 120-125 parts water a t 8". Conversion of Para-ioclosalicy 1 ic Acid into Dihydroxy benxoic Acid. The moist iodosalicylic acid was heated with an excess of potash till decomposition was complete. This was ascertained by acidulating a small portion with hydrochloric acid which produced a precipitate so long as iodosalicylic acid remained undecomposed.The alkaline mass was left to cool dissolved in water and treated with an excess of hydrochloric acid and the liberated dihydroxybenzoic acid was then separated by shaking out with ether. On evaporating the etherea AND IODOSALICPLIC ACIDS. 405 solution a brown residue was obtained which was purified by crystal-lisation from water. The acid crystallises in anhydrous needles. I t s aqueous solution gives with acetate of lead 980 precipitate with ferric chloride a deep blue coloration changing to red on addition of sodium carbonate. This red colour is however very unstable and is at once destroyed by an excess of the reagent. The acid melts a t 200" i.e. 3" higher than the melting point given by Goldberg.There can however be no doubt that the two are identical and it may here be mid that, for recognising the different isomeric dihydroxybenzoic acids the melting points cannot well be depended upon first because most of these acids melt a t temperatures very close to one another ; and secondly because they for the most part begin to decompose either on melting or below their melting points, into carbonic anhydride and dihydroxybenzene. I n order better to establish the constitut,ion of this acid and its identity with that of Goldberg it was cautiously heated in an oil-bath to a temperature of 215". Carbonic anhydride was given off and a sublimate obtained of pure quinol which was identified by its melting point (169") and by its yielding the powerful and highly characteristic odour of quinone when warmed with ferric chloride.The absence of catechol was proved by the fact of lead acetate giving no precipitate. The barium salt of t h i s dihydroxybenzoic acid crystallised in rosette-like groups as described by Goldberg. In water it is very soluble, 1 part of salt requiring only 2.3 parts of water. On analysing the acid the following numbers were obtained :-Calculated for C = 54.54 per cent. H = 3.90 ,, C~HS(OH)~.COO H. Found. 54-96 per cent. 4-19 ,, From the undoubted constitution of this quinolcarboxylic acid i t is evident that the iodosalicylic acid from which it was obtained is also identical with that prepared by Goldberg and tliat it has the con-stitution-COOH (1) C6H,LOH (2).'I ( 5 ) The second or more easily soluble iodosalicylic acid obtained by the scheme of crystallisation referred to above (page 403) separated from its hot aqueous solution usually as an indistinct crystalline mass but could be obtained by very slow cooling in well-formed needles which, however have a very different crystalline appearance from those of para-iodosalicylic acid. It will be shown to be the ortho-iodosalicylic acid sought after 40 6 MILLER ON DIHYDROXYBENZOIC ACJDS This acid melts a t 198" i.e. one degree higher than the para-iodo-Both give a violet colour-reaction with ferric chloride. On analysis the following results were obtained :-salicylic acid. Calonlat~ed for C,H,T(OH).COOH. C = 31.82 per cent. H = 1.89 ,, I = 48.10 ,, 0 = 18-19 ) ) Found.31.91 per cent. 1-89 ,, 47.98 ,, For the readier coniparison of the two isomeric iodosalicylic acids, the barium salt of the last described acid was also made (see page 404). At 8" it requires for solution 190 times its weight of water and is con-sequently much less soluble than the para-compound. It crystallises with 3$ mols. of water in concentrically grouped needles. On melting this second iodo-salicylic acid (ortho-iodosalicylic acid) with potash a dihydrosybenzoic acid was obtained which by its colour reaction with ferric chloride could be easily mistaken for quinolcarboxylic acid but by its other properties was shown to be a distinct acid. Ferric chloride produced a deep blue colour which changed to violet-red on addition of sodium carbonate.This last colour is however distinguished from that which quinolcarboxylic acid gives by not being destroyed by an excess of the sodic solu-tion. This new dihydroxybenzoic acid differs further from quinolcarboxylic acid in its crystalline appemance and by sometimes containing water of crystallisation ; also by giving a precipitate with acetate of lead and by yielding on heating carbonic anhydride and catechol. From water it crystallises either in anhydrous warty masses or in Fell-formed needles with 2 mols. of water. On analysis the following numbers were obtained :-Calculated for C,H,O,. C = 54.54 per cent. H = 3.90 ,, Found. 54.70 per cent. 4.28 ,, By the slow evaporation of an ethereal solution of this acid i t was obtained in small nodules which had exactly the appearance of the acid obtained from catechol and ammonium carbonate (see page 399).The two are in fact identica,l ; with ferric chloride and sodium carbo-nate they both give exactly the same colour reactions; both give white precipitates with lead acetate and both decompose on heating into carbonic anhydride and catechol. In order to determine the temperatnre a t which decomposition commences the acid was mixed with powdered pumice and gradually The acid melts a t 204" AXD IODOSALIGPLIC ACIDS. 407 heated in an oil-bath a slow current of carbonic anhydride being a t the same time passed through the retort in which the mixture was con-tained. A sublimate of catechol began to be formed when the tem-perature had risen to 160-170”.This was resublimed between watch-glasses to free it from traces of undecomposed acid and was then found to consist of pure catechol. It melted a t 102-103” gave the characteristic green coloration with ferric chloride the colour chang-i n g to violet-red on adding sodium carbonate. With lead acetate it gave a white precipitate. The barium salt of this dihydroxybenzoic acid crystallises in small transparent well formed prisms which are difficultly soluble in cold water one part of the salt requiring a t 18” 95-100 parts water. The salt crystallises with 5 mols. of water. The fact that the above dihydroxybenzoic acid prepared from sali-cylic acid yields catechol on heating is of itself proof that this acid must have the constitution COOH Buk this constitution is also the only one possible for the acid which was obtained together with prntocatechuic acid by the introduction of a carboxyl-group into catechol (page 398).And since both of these methods have yielded one and the same product there cannot be the least doubt as to its constitution. Since in preparing the iodosalicylic acids Lantemann’s instructions have been followed it is in the highest degree probable. that Laute-mann was also dealing with a mixture of two isomerides. On fusing with potash he would in this case naturally have got a mixture of the two dihydroxybenzoic acids. In this way it is easy to explain how the distillate from his dihydroxybenzoic acids contained bolh catechol and quinol instead of assuming as Demole did that Lautemann’s m ono-iodosalicylic acid consisted principally of di-iodosalicylic acid.The low melting points of Liechti’s and Demole’s iodosalicylic and dihydroxybenzoic acids and the formation of small quantities of cate-chol by the distillation of the latter acid may also perhaps find their true explanation in the assumption that the acids prepared by Liechti and Demole also contained small quantities of the isomeric ortho-acid. The series of the six dihydroxybenzoic acids being now complete, I have compiled for comparison a table (pp. 409 410) showing their principal properties methods of preparation &c. The readiness with which these acids split up on heating seemR to be connected with the relative positions of the carboxyl- and hy-VOL. XLT. 2 408 MILLER ON DIHYDROXYBENZOIC ACIDS droxyl-groups to one another.It will be seen for instance that the acid which most easily gives off carbonic anhydride is the one in which the two hydroxyl-groups are in the ortho-position to the carboxyl-group. Then follow the acids in which the carboxyl is in the ortho-position to only one hydroxyl-group and last of all the most difficultly decornposible symmetrical acid. It will also he seen from the table that the solubility or insolubility of %he lead compounds of these acids depends upon the relative posi-tion of the two hydroxyl-groups to one another. Of the three phenols, C6E4(OH), catechol alone gives a precipitate with lead aceta.te and of the six acids C6H3(OH),.COOH none yield precipitates with acetate of lead except the two which are obtainedfrom catechol.I n conclusion I beg to thank Professor Wisliceniis in whose laboratory this research was carried out for valuable advice and assistance received during the progress of the investigation TAnr,E OF 1'1113 DIHTDROXYRE~-ZOIC ACIDS. Name. CO,Nn,Z t,he c.olollr being ~ -.I--1 2 3 Catzechol-ortho-car-boxylic acid. I 1 2 4 -a-Dihy-droxyben-zoic acid. I 1,2,5, By 1 From Q,uinolcar-boxylic acid. -Author. -Brunner and Senhof er. 4sher. Blomstrand. L'icmann and Parrisius. -Liechti n e -mole Gold-berg Author Mowski and Leppert. icllllofcr and Sarlcy . :-Catechol and arninonic carbonate. rodosalicylic acid. -__ Resorcinol mid ammo-nic carbon-ate. phonic acid.phonic acid. ronc. p-Crcsolsul-Tolnoldisul-Umbcllife--lo dosalicylic acid. Rromsalicylic acid. 3uinol and I< I i c'o,. Crystalline form and water oi crystallisa-tion. -_. Wart-like groups (an-hydrous). Keedles with 2&0. _I-Yeedles and plates with S 19 or 3H20. -Lnhydrous needles and prisms. Melting point. --204OC. de-composes -_e-LY4-2OO0 decomposes. according to Tiemann. 20t-206°, --197' accord-ing to Rakowski and Gold-berg. !0O0 accord-iilg t o A ut 1101'. Reaction with PepC1,. Deep blue coloration, which with CO,Na, changes to violet -red. The colour is not de-stroyed by excess of re-agent. Red colour. -Deep bl Lie colour, which changes to dirty red wit TABLE OF THE DIHYDR,OXYBENZOIC ACIDS. 1 3,4 techuic acid. -I__-39 Symmetri-cal dihj-droxyben-zoic acid. Prepared Crystalline form and water of cqstallisa-tion. Reaction with Fe2C16. Melting point. From -I-When di-lute violet j concentra-ted intense blue colora-tion. Resomino1 and mnnio-nic carbon-ate. Long needles with 1 mol. H20. Ip-Dihy-1 2 6 1 droxyben-I zOic acid-48-16'7". decomposes. 3enhofer and Yrunner. -Bromanisic acid. droxyben-zoic acid. lulphanisic acid. 2atechol and ammonium carbonate. lodo -p-hy---I-1 9 9 O . Barth. B1 ue-green coloration, vhnnging to red onaddi-tion of CO,Na2. Needles and plates mit,h 1 m01. H2O. I Protoca-Rlalin. Author. -No colora-tion. Barth and Senhofer. Disulphoben-zoic acid. Prisms and needles. 232-233"

ISSN:0368-1645    

DOI:10.1039/CT8824100398

出版商:RSC    

年代:1882

数据来源: RSC

摘要:

411 LXIII.-CrystalEiize Molecular Compounds of Naphthalene and Benzene with Antimony Trich lo ride. By WATSON SM~TR and G. W. DAVIS. IT was observed by one of us some time ago (this Journal June 1879) that on melting a mixture of antimony trichloride and naphthalene, after removing the source of heat a beautiful crystallisation com-mences in the still liquid mass the minute but perfectly symmetrical clinorhombic tables in their rapid growth performing during the pro-cess singular gyrations upon the liquid surface on which they float. Although these crystals are formed with great facility it is no easy matter to separate them perfectly from the melted mixture in which they float owing t o the rapidity with which on removal of the crys-tals the adhering fluid solidifies upon them.This must be rapidly performed with a small platinum spatula previously warmed. It was found best to adopt the proportions by weight of 3 parts of antimony trichloride t o 2 of naphthalene. The crystals on removal froni the melted fluid in which they float must be at once placed in a dry stoppered bottle as they are very deliquescent. Immediately on removal they are observed to be transparent but a few moments later become whitish and opaque. They form perfect clinorhombic tables, and on analysis gave the following numbers :-0.5425 gram gave 0.293 gram Sb& = 0.2093 Sb = 38.58 per cent. 0.4990 , 0.269 , SbzS3 = 0.1914 Sb = 38-56 ,, Calculated for Found Sb 38-94 (i) 38.58 (ii) 38.56 3SbC1,,2CloH8 per cent. per cent. Molecular Compound of Benzene with Antimony Trichloride.Crystallised antimony trichloride is dissolved in benzene so as to give a concentrated solution. It is besi to take about 3 parts of the former to 4 of the latter. Solution may be promoted by gentle warming in a small flask which is afterwards loosely corked and then set aside for a few days. Large well-defined clinorhombic plates, much thinner and also more irregular than the naphthalene compound, are formed. They are perfectly colourless and transparent and per-manently so thus differing from the naphthalene compound. They me also exceedingly deliquescent. Analytical numbers as follows were obtained :-V O L XLJ. 2 f 412 SMITH AND DAVIS ON THE Weight taken = 0.594 gram. Antimony trisnlphide obtained = 0.3615 gram = 0.2582 gram Sb. A chlorine determination gave . . . . . . . . . . . = 43-46 per cent. 37.62 ,, Calculated for Found 3SbC1,,2C6H6 per cent. per cent. Sb = 43.57 43.46 C1 = 37.90 37.6

ISSN:0368-1645    

DOI:10.1039/CT8824100411

出版商:RSC    

年代:1882

数据来源: RSC

摘要:

412 SMITH AND DAVIS ON THE LXIV.-An Additional Evidence by Analysis of the Qwholirze Hole-c d e that this Base belongs to the Aromatic Series of Organic Subs f ances. By WATSON SMITH and G. W. DAVIS. MERZ in conjunction with Ruoff Moe Zetter (Innug. Disserts.) and other pupils of his showed that on exhaustive perchlorination all iiiembers of the aromatic series break up so as to yield perchloroben-zene unaccompanied or accompanied with perchlorinated paraffin groups according to circumstances. An exception occurs in the case of diphenyl which forms perchlorodiphenyl and this body refused to disintegrate on further chlorination. The formation of perchloro-diphenyl was found to be of very rare occurrence. Of course in many cases the formation and separation of perchlorobenzene made it pos-sible to predict what the perchlorinated members of the paraffin group formed at the same time in the general disintegration of the aromatic molecule must be.Thus light was obtained and thrown upon the constitution of several aromatic compounds besides which a remarkable confirmation of the truth lying at the root benzene-ring hypothesis was obtained. I f quinoline has the constitution now generally assigned CH CH of Kekul6's to it-(and this has been made clear to a considerable extent by the several rasearches of Dewar Baeyer Konigs and Skraup) then by an exhaustive perchlorination according to the method of V. Merz it might be expected that in the disintegration following that portion o ,4ROMATIC SERIES OF ORGANIC SUBSTANCES. 413 the compound nucleus containing nitrogen would prove least stable as being most complex and would consequently give way yielding per-chlorethane perchloromethane and nitrogen whilst the other portion would yield perchlorohenzene.It will now be interesting to examine what the actual experience of Xerz and Ruoff was in their perchlorination of naphthalene. They found that on repeated treatment in sealed tubes with antimony penta-chloride at gradually increased temperatures finally at 350" to about 400" C. naphthalene first changes to perchlornaphthalene becomes disintegrated gradually and yields perchlorobenzene perchlorethane, and perchlormethane, This reaction as regards the appearance both of perchlor-methane and -ethane is better interpreted by assuming as Graebe proposes the presence in the naphthalene molecule of the group (CJ&)" which becomes spIit off from the chlorinatsd benzene-ring as the first step of disintegration and by the action of the chlorine is converted into per-chlorbutane which then immgdiately after its formation (as Krafft and Merz (Ber.1875 1300) have actually shown in the case of per-chlorbutane) at the high temperature is first broken up into perchlor-propane and perchlormethane and the former later on into perchlor-ethane and perchlormethane thus :-cl()c1 + 4C12 = CljCI + c&cl,,. c,c1, + c12 = C3C1 -I- CCI, C3CIs + c12 = C,c& + ccl& In our experiments then we might expect to realise the following, possibly :-C,CI,?? t 7c1 = cljc16 c3CIs N. C3C18 + c1 = c,c1 + CClJ.Perchlornaphthalene has of course been. prepared and studied by Berthelot and Jungfleisch (Ann. Chim. Phys. [4] 15 331) ; perchlor-quinoline has so far as we are aware not been prepared as yet. We took 1.7' grams of chemically pure quinoline and placed it in a strong tube of hard glass together with ten times its weight of anti-mony pentachloride slowly and cautiously added. The tube was well sealed up and heated to 170" then to 280" to 320° and finally to 400" about each for a space of five hours leaving the contents to cool and 2 K 414 SMITE AND DAVIS ON THE AROMATIC SERIES ETC. opening the tube after each heating to allow hydrochloric acid gas and nitrogen t o escape. Dry chlorine gas was then passed into the brown mass for about 20 minutes and the tube after re-sealing was again heated at the above intervals as before.The chlorinating and heating were repeated till on opening the tube no more hydrogen chloride was evolved. The contents of the tube were now quite black from separation of carbon but the m8ss was also crysta,lline. This black mass was now washed out with strong hydrochloric acid into a beaker and washed by decantation several times with strong hydro-chloric acid and afterwards with a strong tartaric acid solution till a portion of the filtrate from the mass gave no longer a precipitate of antimony snlphide with H,S. The residue dried and a portion sub-mitted to sublimation yielded vapours haring the characteristic camphor-like odour of perchlorethane which condensed to small white needles having a melting point of 210".Now the melting point of perchlorethane is 193" hence probably this first crop was contaminated with some perchlorbenzene which melts at 2.20-223". This crop first obtained was submitted to a careful re-sublimation when a melting point in the crop now obtained was exactly 182" the correct melting point of perchlorethane. After the perchlorethane was all sublimed and expelled from the black mass the iemperature was further raised, when after some time long white needle-shaped crystals formed them-selves on the surface of the dark mass in the sublimation apparatus. A quantity of these needles was carefully collected and it was ob-served on heating a portion of them that the vapour possessed only an extremely faint odour unlike that of the perchlorethane ; in fact the vapour might be described as odourless.The melting point of these crystals ww 223" which is the cc3rrect melting point of per-chlorobenzene. Quinoline is a substance which is exhaustively perchlorinated with the greatest difficulty and in future experiments we should recom-mend a 10-hours' heating at each successive temperature already mentioned. The opening of the sealed tubes is by no means unat-tended with danger and for the sake of safety we should recommend that after heaking and leaving it to cool the tube should be opened by just allowing the drawn-out point to project from the oven and then t o let the flame of a lamp play upon it. No perclilormethane could be detected and this was probably owing to the volatilityof the substance by virtue of which it would be carried off in the violent rushes of gas ensuing on opening the tube from time to time.The danger of the operation of opening the tube illdeed prevented any observations of the nature of gaseous bodies galerated during the proceps from being made. It may now just be pointed out how our experience just describe NEVILE AND WlNTHER ON ORCaTOL ETC. 415 coincides with that of Dewar who in 1877 obtained quinoIinic acid (this Journal 1881 p. 1044) (C6H4(NH2) .CH,.CO.COOH) by the oxidation of quinoline this acid on distilling with soda-lime yielding aniline (C6&,.NH2). Dewar thus by an oxidation process obtains analytically proof of the aromatic nature of quinoline actually getting the benzene-nucleus with the still adherent nitrogen now in the form of an amido-group. We have succeeded in obtaining analytically by a chlorination process the perchlorinated benzene-nucleus (c,c16), together with half the remainder of the residue containing the nitro-gen-atom also as a perchlorinated group vie as perchlorethane (c2c16) I I Writing quinoline as CGH1.N C2H2 CIE we have obtained by ch1or.i-- + + nation the following groups . . . . . . . -. . C$16 as perchlorinated products - whereas-Dewar obtained . . C6H5.NH2 (aniline) as the result of an oxidation process followed by a distillation of the product with soda-lime. CzC1

ISSN:0368-1645    

DOI:10.1039/CT8824100412

出版商:RSC    

年代:1882

数据来源: RSC

摘要:

NEVILE AND WlNTHER ON ORCaTOL ETC. 415 LXV.-On O/rcinol and some of the other Dihydroxytoluene. By R. H. C NEVILE and DrA. WINTBER, VARIOUS considerations had some time sinae led US to consider it highly probable that orcinol was a dihydroxytoluene of the constitu-tion 1 3 5 a supposition which has since been shown to be true by Tiemann and Streag (Bey. 1881 1999). In order to satisfy our-selves upon this point and to ascertain if some practicable method for its artificial production could not be found we undertook the research recorded in the present notes. As we were endeavouring to obtain satisfactory proof o$ its exae.t; constitutiou we avoided all methods involving the fusion of a corn-pouiici with a caustic alkali as this method has in some cases been found to cause the hydroxyl-group to attach itself at a position in the benzene-nucleus different from that occupied by the halogen or othei-group which has been eliminated.For this reason we started with the dinitrotoluene 1 3 5 which has bean prepared by Staedel (Ber. 1881 902) from both dinitro-orthotoluidine and dinitro-paratoluidine. We prepared it from tho latter 416 NEVILE AND WINTHER ON ORCIKOL As obtained by us it crystallised in bright yellow needles melting at 92.4". Aaalysis. Empl. 0.2503 gram; val. M = 32.5 C.C. ; t = 11" ; b = 743.5 = 15.13 per cent. N. Theory requires 15.38 per cent. We obtained a yield of from 60 per cent. to 65 per cent. of the theoretical amount. On dissolving the dinitrotoltlene in an alcoholic solution of ammo-nium sulphide it gets warm and the addition of water then causes the precipitation of an orange-red substance.This was dissolved in dilute hydrochloric acid filtered and reprecipitated by ammonia. This nitrotoluidine crystallises from alcohol and ether in red-brown lancet-shaped needles. There is frequently mixed with it a lighter-coloured . body which is less easily soluble in ether- or dilute hydro-chloric acid and may modify the characteristics of the nitrotoluidine. The best method of purification appears to be to dissolve the nitro-toluidine in hydrochloric acid and leave it for 12-24 hours in a warm place when a white precipitate gradually forms. This must be filtered out and the liquid again left and the filtration repeated until no further precipitat,e separates on standing or warming.This white substance melts at from 170-180" and appears to be the result of imperfect reduction. The purified solution will now give by neutralisation with ammonia, a precipitate which should be washed dried and crystallised from ether or alcohol. We thus obtained it in thick needles melting at 98-98-4". It is very easily soluble in ether also in alcohol and benzene and somewhat so in water. The salts appear to dissolve freely in water only in presence of an excess of acid. The chloride appears to give up a portion of' its acid on drying in the air or washing with ether. Analyeis. Empl. 0.2893 gram; vol. N = 45.5 C.C. ; t = 13.2'; b = 758.6 = lS.47 per cent. N. Theory requires 18.42 per cent. N. We obtained a yield equal t o about 50 per cent.of the dinitrotoluene used. The nitrotolliidine wits now dissolved in a warm mixt'ure of equal uolumes of sulphuric acid and water and cooled whereupon the sul-phate crystallised out. An aqueous solution of potassium nitrite was now gradnally added until the salphate was all redissolved. An equal volume of water was now added and the mixture warmed wherFupo AND SOhIE OF THE OTHER DIHYDROXYTOLUENES. 417 the diazo-compound was decomposed with evolution of gas and nitro-wesol formed. This oil and the ethereal extract of the mother-liquid were boiled with water and filtered hot. By this means most of the pitch &c. was left on the tilter and the filtrate on cooling gave thick bright yellow needles of nearly pure nitro-cresol. These were purified by crystallisation from benzene or water.Thus obtained it crystallised in bright yellow needles or prisms, very soluble in ether or alcohol less so in benzene and still less in water easily soluble with a dark yellow colour in alkalis or their car-bonates. It does not distil with steam. When crystallised from benzene its melting point is 90-91" but when crystallised from water., 60-62". This arises from its crystallising with water as will be seen below. By heating to 100" a sample which melted at 60-6Z0 or by drying it over sulphuric acid or by recrystallising i t from ether or benzene, its melting point was raised to 90-91". If this was left long iit the open air it attracted moisture and then again melted at 60-62". In order to determine the amount of water of crystallisation some was left over sulphuric acid for various times.This separated as a brown oil. Gram. M.p. Gram. Percent. M . p Empl. 0.1549 60-61" left for 7 days lost 0.0161 = 10.39 81-86'" , 0.5307 60-61 , 6 , 0.0534 = 10.06 81-85 , 0.3160 61-62 , 5 , 0.0330 = 10.44 87-89 1 molecular proportion of water would amount to 10.52 per cent. Ana.lysis of some Crystallised from Benzene and then Dried over Sulp huric Acid. Empl. 0.2171 gram; vol. N = 17.5 C.C. ; t = 12.5"; b = 742.2 = 9.3 per cent. N. Theory requires 9.15 per cent. The yield was about 65 per cent. of the theoretical amount. The nitro-cresol was now reduced with tin and hydrochloric acid : after removal of the tin the liquid was evaporated during which pro-vess it turned brown.The crystalline chloride was washed with ether to remove uiireduced nitro-cresol and was then used for con-version into dihydroxytoluene. In order to obtain dihydroxy-toluene 1 3 5 from the chloride 1 gram of this latter was dis-solved in a hot mixture of 13 grams sulphuric acid with an equal volume of water the solution was diluted with 100 grams of water. cooled by a freezing mixture and a solution containing 0.6 gram of potassium nitrite added. The decomposition of the diazo-compound The base itself was not isolated 418 NEVILE AKD RIXTHER ON ORCINOL thus formed commences between 30" and 50". The liquid was warmed to expel all the gas and complete the decomposition; then filtered and extracted with ether. In this way we obtained a red-brown oil which was purified by frequent distillation and crystallisation from benzene or chloroform.Thus we obtained it from chloroform in glittering white leaves and from benzene in long needles or prisms. After drying for 14 days over snlphuric acid it melted at 106-108". Analysis. R C Empl. 0.1653 H,O = 0.0932 = 6-26 p. c. Theory for C6H,,CHI, (OH), requires. . . . . . . . . . . . . . . . = 6.45 ,, The question now remained ms this identical with the orcinol obtained in other ways? We compared it in all its reactions (viz., ammonia and moist air chloride of lime ferric chloride sodium hydrate in air sodium hydrate in chloroform) with orcinol otherwise obtained and found them all to agree perfectly with the exception of the melting point. Lamparter (Juhresb.1865 589) gives 8s the melting point of anhy-drous orcinol obtained from lichens 86" and when crystallised from water 58'. Vogt and Henniger (Jahresb. 18i2 410) find €or the melting point of the orcinol they obtained from chlorotoluene-sulphonic acid 57*1" when crystallised from water. We examined some orcinol obtained from Messrs. Hopkin and Williams and found that although it agreed in all other respects with the descriptions usually given of orcinol yet that the melting point varied from 56" to 107" accordingly as crystals or fine powders were taken and according to whether the temperature was raised slowly or fast. It appears certain that by very slow raising of the tempera-ture the combined water is driven off and then the orcinol melts at the higher point.In frying the dihydroxytoluene prepared by our method (when crystallised from water) we got sometimes from 54-56' sometimes By distilling the orcinol from Hopkin and Williams between two watch-glasses and by fractionating the distillate by changing the upper glass we got-9 0.1611 H20 = 0.0911 = 6.28 , COZ = 0.4007 = 67.83 P.C. 67.74 ,, 54-105". For 1st distillate m. p. 5 6 81.6" 77 2nd Y , $2- 83.0 9 9 3rd 9 107-108.5 , 4th and 5th , , 107-108. AND SOME O F THE OTHER DIHYDROXYTOLUENES. 419 Treating the substance obtained by u s in a similar way we got-For 1st distillate m.p. 54- 55O 9 2nd 9 , 90- 98 9 3rd 9 , 98-103 7 4th 7 , 97-104 It does not appear that by merely raising tbe temperature to 100" On placing Messrs. Hopkin and Williams' orcinol in a partial vacuum the whole of the water can be satisfactorily driven off.over sulphuric acid the melting point after 24 hours was-106.5-107.5" After 8 days 106~5-10b~O and the same after 14 days. Our substance similarly treated gave after 24 hours m.p. 104-105" After 8 days , 105-107 9 14 9 9 , 106-108 Some of Messrs. Hopkin and Williams' orcino1 which had been dried Theory = 67-74 H20 = 0.1253 = 6-16 , H. , = 6.45 It appears therefore cei-tain that the dihydroxytoluene 1 3 5 , obtained in the manner we have described is identical with orcinol. The melting point of orcinol when containing water seems to be about 56" but the actual point of complete fusion is very hard to determine. When the compound is anhydrous or nearly so the melting point seems to be 106*5-108".It appears very hard to remove the last traces of water. Some orcinol from Messrs. Hopkin and Williams was placed in vacuo over sulphuric acid. Empl. 0.3230 gram; after 45 hours it had lost 0.0254 = 7.86 per cent. 5 days , , 0.0301 = 9-32 per cent. for 14 days and which melted at 106.5-108" was analysed-Empl. 0.2261 gram ; CO = 0.5561 = 67.08 p.c. C. (m.p. 106*5-7.07.5"). 12 9 , , 0.0373 = 11.55 ,, (m.p. 106*5-108"). Again-Empl. 0.3496 gram; after 25 hours it had lost 0,0321 = 9.18 per cent. 10days , , 0*0408 = 1'1.5 ,, 12 9 , , 0.0411 = 11.73 per cent. (m.p. 107-108"). (m.p. 107-108'). Theory for C6H3,CH3(0H) + H20 requires 12.67 per cent 420 NEVILE AND WINTHER ON ORCINOL The artificially-prepared orcinol appears to behave in the same way.Empl. 0.1 gram ; after 4 days it had lost 0.0114 = 11.4 per cent. , 12 , , 0.0125 = 12.5 ,, I n further prosecution of our researches we have succeeded in preparing orcinol by other methods viz. from metabromo-toluene-metasulphonic acid. This was described by us in this Journal 1880, 627 and Ber. 1880 1944-1948. By taking the potash salt of this and fusing it with twice its weight of caustic potash at a temperature of about 280-300" for from half-an-hour to one hour a mass was obtained which was dissolved in water and acidulated extracted first with benzene to remove bye-products and then with ether. The ethereal extract on evaporation left a brown oil which by distillation gave a white distillate slowly becoming crystalline. A fractional distillation of this substance after cry stallisation from water gave distillates as follows :-1st m.p. 54- 56" 2nd , 54-100 2rd , 98-103 4th , 100-104 Some dried over sulphuric acid had the melting point 103-10S0. Aitaly sis. Theory for C,H3,CH3 (0%. Empl. 0.1863 gram HzO = 0.1057 = 6.31 per cent. H ; 6.45 per cent. CO = 0.4648 = 67.92 , C; 67.74 ,, It gave all the reactions of orcinol with chloride of lime ferric chloride sodium hydrate and air sodium hydrate and chloroform, and ammonia and moist air; and we may therefore conclude that it is identical with the above. We have also prepared orcinol from metabromometatoluidine (described by us in this Journal 1880 432). We dissolved it in a warm mixture of equal volumes of sulphuric acid and water ; on cooling the sulpha$e crystallised out.A solution of potassium nitrite was now gradually added until the crystals were dissolved. Water was now added and the solution warmed when gas was evolved and an oil separated out. This was purified by distilla-tion with steam. The oil slowly solidifies into a mass of white crystals which may be completely purified by solution in dilute caustic soda filtration short boiling acidification and then repeated distillations with steam. The boiling with caustic soda seems t o drive off a substance volatile with steam and insoluble in the soda. As th AND SOME OF THE OTHER DIHTDROXTTOLUENES. 421 substance is slightly soluble in water the mother-liquids should be extracted with ether. This substance melts at 56-57," is very easily soluble in ether and alcohol and somewhat in water.An alysis. requires 42-98 per cent. for monobromocresol. Empl. 0.4120 gram; AgBr = 0.4097 = 42-32 per cent. Br. Theory The metabromo-metacresol thus obtained was heated to 280-300" with twice its weighh of caustic potash for one hour. The melt was acidified and extracted by ether. The ethereal extract was distilled, and in this w.ay we oMained a distillate solidifying into crystals and possessing all the characteristics of orcinol. Orcinol was also obtained from metadibromotoluene by heating it in a closed iron tube with twice its weight of potassium hydrate dis-solved in a small quantity of water for two hours from 280-300". It was further obtained from toluene-metndisulphonic acid. As a starting point we took ortho-amido-toluene-metasulphonic acid and heated 5 grams of it with 15 grams of strongly fuming sul-phuric acid to 150-170" for between half-an-hour and an hour.The miss then dissolved easily in water and was treated with barium carbonate to remove the excess of sulphuric acid. The barium salt filtered a very small excess of sulphuric acid added to remove the barium and the filtered solution evaporated to dryness and dis-solved in alcohol re-evaporated to dryness and redissolved in alcohol and again evaporated. The mass thus obtained was very easily soluble in water ar alcohol but not in benzene. Analysis. Empl. 0.4720 gram ; BaSOI = 0.8234 = 59.89 per cent. SOs. Theory for amido-toluol-disulphonic acid requires 59.92 per cent,.In a previous communication (this Journal 1880 625) we have pointed out that the sulpho-group in the moaosulphonic acid occupies the position para to NH and meta to C&. In order to determine the position of the other sulpho-group we converted the nmido-sul-phonic acid into a diazo-compound by introducing nitrous gas into a mixture of it with alcohol or benzene. The diazo-compound was bailed with water a few drops of nitric acid then added and the whole boiled until crystals appeared on cooling. These were filtered out a few drops more nitric acid added and the liquid boiled again, this operation being repeated as often as any further crop of crystals mas obtained. In this manner six crops of crystals were obtained 422 NEVILE ASD WINTHER ON ORCINOL which all had the melting point 85" and possessed all the properties of dinitroorthocresol.Now this last has the two nitro-groups in the two positions meta to CH, as was pointed out by as in a former communication (this Journal 1880 631) also by Staedel (Ber. 1882 901).* Hence we conclude that the two sulpho-groups displaced by the nitro-groups had the same position and that the acid thus obtained is ortho-amido-toluene-metadisulphonic acid. The para-amidotoluene-metadisulphonic acid may be obtained in an analogous manner. When the diazo-compound of either of these acids is heated with absolute alcohol under pressure the toluene-metadisulphonic acid is formed. The solution is then evaporated after neutralisation with an alkali or alkaline carbonate and on heating the resulting aalt with caustic alkali to from 200" to 300" orcinol is produced in all respects iden-tical with that produced by the other methods described.In pursuing these researches we prepared also the dihydroxytoluene 1 2 4 proceeding as follows :-We start from ortho-nitro-para-toluidine (m. p. 77-78"). 40 grams of thi8 was dissolved in 300 grams of a mixture of 1 vol. sulpburic acid with 16 vols. of water and the solution cooled. This causes the separation of crystals of the sulphate. A solution of potassium nitrite was now gradnally added until all the crystals of sulphate were dissolved. It is best to add the potassium nitrite by a tube reaching to the bottoni of the vessel. 3200 grams of a mixture of equal parts of sulphuric acid and water were now added, and the whole heated gradually until the evolution of gas ceased.On cooling crystals of nitrocresol separated out. The mother-liquor was extracted with ether after the addition of water ; and by evaporation of the ether a further quantity of nitrocresol was obtained. In this manner the total yield of nitrocresol reached about 80 per cent. of the theoretical quantity. In order to purify it the ethereal solution was shaken with animal charcoal or the nitrocresol was crystallised from water. By slow evaporation of an ethereal solution it was obt,ained in hard yellow prisms of m. p. 77-'77*4". It dissolves in alkalis and their carbonates with an orange-red colour but the aqueous solutions of the salts partially decompose on heating. It is easily soluble in ether and alcohol.A finahpis. Empl. 0.3313 gram ; vol. N = 25.5 C.C. ; t = 8" ; b = 747-5 mm. N per cent. = 9.14. Theory for CsH3,CH3,N0,,0H = 9.15. * We in common with Nolting and SaIis (Ber. 1881 982) found the melting point of pure dinitro-ortho-cresol higher than did Staedel viz. 85-8' ; Nolting and Sdia give 86" AND SOME OF THE OTHER DIHYDROSTTOLUENES. 423 This nitrocresol is easily reduced by tin and hydrochloric acid. The solution may be freed from tin by hydrogen sulphide and the fil-tered liquid evaporated to dryness. In this way a crystalline residue of chloride of amidocresol is obtained but it is always coloured brown in the process of evaporation. Any unreduced nitrocresol remaining inay be removed by washing with ether. The chloride is easily soluble in water but on the addition of an alkali or alkaline carbonate or ammonia the liquid becomes brown or green.In order to prepare from this the dihydroxytoluene 1 2 4 one gram of it was dissolved in 13 grams of a warm mixture of equal volumes of sulphnric acid and water. The mixture was now diluted with 100 grams of water cooled by a freezing-mixture and a dilute solution of potassium nitrite added until a slight smell of nitrous acid remained permanent ; an excess of nitrite injures the reaction. The liquid was now warmed from 90" to 95" filtered and exhausted with ether. The ether by evaporation left a brown oil which was boiled with benzene. The benzene was decanted off and distilled and the residue remaining after the benzene had distilled off further distilled.In this way an oily distillate was obtained which after some time crystallised. This was purified by frequent sublimations and cry stallisations from ben-zene or toluene and was thus eventually obtained of melting point Analysis. 104-105". Empl. 0.0953 gram ; H20 = 0-0566 = 6.61 per cent. H. Theory for C6&,CH3,(OH), CO = 0.2364 = 6'7.65 , C. requires,. . . . . . . . . . H = 6-45 per cent. C = 6'7.74 ,, The reactions agree pretty closely with those described by Hakan-son (Ber. 1872 1087) for the dihydroxytoluene obtained by him from the toluenedisulphonic acid prepared from toluene and f aming sulphuric acid and it is probable that they are identical. Since this paper was written Knecht (Ber. 1882 298) has obtained this dihydroxytoluene in a similar manner and gives 103' as the melting point.We have also prepared the dihydroxytoluene 1 2 5. For this purpose we start from the nitro-orthotoluidine produced by the nitration of ortho-acetotoluid and which we showed (this Journal 1880 436) had that constitution. 40 grams of metanitro-orthotoluidine (m. p. 127-129") were dissolved in 300 grams of a warm mixture of equal volumes of sul-phuric acid and water. The mixture cooled and a solution of potassium nitrite carefully added until the crystals of sulphat 424 NEVILE AND WIN'L'HER ON ORCINOL deposited on cooling were all dissolved. 1600 grams of a mixture of 1 vol. sulphnric acid to 2 vols. of water were then added and the mixture gently warmed. The decompositioii of the diazo-compound takes place at a temperature of 70-90'.A brown oil separates out which crystallises on cooling and fine needles form in the liquid. These crystals and a further portion extracted from the mother-liquid with ether were dissolved in ether and purified with animal char-coal. Owing to the formation by the above process of dinitro-ortho cresol as well as mono-nitrocresol the perfect isolation of the latter is difficult. We found that the best method was to dissolve the mixed cresols in potash solution and separate the more from the less soluble portion. (The potassium salt of dinitro-orthocresol is much less soluble in cold potash-solution than the salt of the mono-nitrocresol). We then reprecipitated the cresol with sulphuric acid. By repeating these operations we got the compound tolerably pure.The metanitro-orthocresol thus obtained crystallises from water in fine glittering bright yellow needles melting at 30-34" ; but by drying it on paper or on a water-bath or by crystallising it from ether its melting point is raised to 94.6-95". It is not freely soluble in water but easily in alcohol or ether and also in solutions of alkalis or their carbonates. The salts of the alkalis dissolve in water with an orange-yellow colour. Anal p i s . Empl. 0.2267 gram; vol. N = 17.5 c . ~ ; t = 7.8"; b = 750.3 mm. = 9.02 per cent. N. Theory for C6H3,CH3,NO,,O;H requires 8.15 per cent. N. An easier way of obtaining the pure mononitrocresol was found to consist in boiling the metanitro-orthotoluidine with moderately con-centrated solution of soda until it dissolved.In this way few if any, bye-products except a little pitch seem to be formed. The pitch is easily removed by filtration and by then precipitating the nitrocresol with sulphnric acid extracting with ether and shaking with animal charcoal it may be obtained at once nearly pure and the yield is very nearly theoretical. The nitrocresol obtained in this manner presented exactly the same characteristics as that obtained in the other manner-Amalysis. Empl. 0.2895 gram; vol. N = 23.25 C.C. ; t = 9.6'; b = 757 mm. = It appears from the above that the fluid nitro-orthocresol which Hofmann and Miller (Ber. 1881 571) consider to have the constitution 1 2 5 must have some other constitution. 960 per cent. N. Theory requires 9.15 per cent.N ASD SO^ OF THE OTHER DIHTDROSSTOLUESES. 425 The nitrocresol obtained by either of the above processes is easily yeduced by tin and hydrochloric acid. After the tin has been removed by hydrogen sulphide the chloride of the amidocresol is easily ob-tained by evaporation in good crystals coloured brown by the slight products of decomposition. These were washed with ether to free them from undecomposed nitrocresol. The free amidocresol was not obtained as it decomposed immediately on being set free from its salts giving a greenish-yellow or red-brown colonr to the solution from which ether extracted nothing but a red-brown pitch. In order to obtain the dihydroxytoluene 1 2 5 the chloride of tbe amidocresol was dissolved in a considerable quantity of a very dilute sulphuric acid.To this was added a dilute solution of potassium nitrite until the smell of nitrous acid remained permanent for a short time. More water was then added and the mixture boiled until all disengagement of gas ceased. The cooled and filtered liquid was then exhausted with ether. On evaporation the ether gave red-brown' crystals which were purified by sublimation and recrystallisation from benzene in which they are not freely soluble. It was obtained from benzene in white pearly leaves melting at 124-123" freely soluble in alcohol ether or water. From water it crystallises in colourless crystals which melt at 123-125" and do not appear to contain any water of crystallisation. This dihydroxytoluene was prepared from the nitrocresol obtained from nitro-orthotoluidine by both the above-mentioned methods and in both cases appeared identical.Analysis. Theory for requires H = 6-45 p. c. C,H&H, (OH) 2 Empl. 0.2247 gram; H,O = 0.1480 = 7-31 p. c. H. CO = 0.5567 = 67.56 , C. C = 67.74 ,, This dihydroxytoluene appears to be identical with the hgdrotolu-quinone of Nietzki (Bey. 1877 834) prepared from toluquinone from orthoamidoazotoluene. With soda-solution it gives a pretty blue-green colour which very quickly turns to dark brown. With chloride of lime it turns blue-green as with soda t,hen brown ; but with a weak solution of chloride of lime a brownish-red. Chloroform and soda produce a brown colour ; ferric chloride a brownish-red or in a dilute solution yellow. Ammonia in presence of moisture changes it into a dark brown mass which dissolves in alkalis with a brown colour and the addition of acetic acid to the solution causes the precipitation of brown flocks 426 NEVILE AND WINTHER ON ORCINOL We also made some investigations into the preparation of hydroxy-toluene 1 3 4 starting from metanitroparatoluidine (m.p. 114-115"). Armstrong and Thorpe (Jahresb. 1876 452) obtained by nitration of paracresol a nitrocresol identical with that which Wagner (Ber., 1 874 537) obtained by heating metanitroparacetotoluid with sodium hydrate. This nitrocresol must have the required constitution viz., 1 3 4 unless some molecular change takes place. Wagner by this method however obtained only small quantities. We therefore tried t o prepareit from the diazo-compound in the hopes of getting a better yield.10 grams metanitroparatoluidine was dissolved in 100 grams of a mixture of equal parts of sulphuric acid and water and a solution of potassium nitrite was added until a sample of the solution no longer gave a precipitate of nitrotoluidine on addition of water. The solu-tion was then decomposed by heating 800 grams of a mixture of 1 vol. sulphuric acid and lk-2 vols. of water having first been added. The result however was unsatisfactory as neither in the distillate nor in t,he et,hereal extract was any large quantity of nitrocresol obtained, but only a very little melting at 33". We therefore tried Wagner's method and after some experiments succeeded in getting a very good yield. The best plan is to take say 10 grams and heat it with about 50-100 grams of a 20 per cent.solution of sodium hydrate for 15 hours ; then pour off the liquid and boil the remaining nitrotoluidine with a fresh charge of sodium hydrate repeating this process until it is all dissolved. All the sodium hydrate liquors are then mixed acidified with sulphuric acid and distilled. In this way an almost theoretical yield is obtained ; from 20 grams of nitrotoluidine we obtained 19 grams of nitrocresol. This good yield allows us to assume that no molecular change takes place, and that the nitrocresol has the constitution 1 3 4. The substance when purified was obtained from benzene in yellow crystals melting at 33-33-4O easily soluble in caustic alkalis ether or alcohol but scarcely soluble in water.A portion of this nitrocresol was reduced by tin and hydrochloric acid. After removal of the tin by a current of hydro-gen sulphide the filtrate was evaporated to dryness. The chloride (1 gram) dissolved in 100 grams water and 13 grams sulphuric acid, cooled by a freezing mixture and 0.6 gram of potassium nitrite in solution added. The solution was then warmed filtered and extracted with ether. An oil was thus obtained which dissolved easily in water. The aqueous solution was coloured green by ferric chloride, on adding ammonia or sodium carbonate gradually the colour became first blue and then violet. Its properties This oil is probably the dihydroxytoluene 1 3 E AND SOME OF THE OTHER DIHYDROXPTOLUENES. 427 - - - - ~ -coincide with those of homocatechol which Tiemann (.Ber.1877, 210; and 1878 672) obtained by heating the calcium salt of alpha-homoprotocatechuic acid and from coniferyl alcohol. They also re-garded it as a dihydroxytoluene 1 3 4. It would appear from our investigations as well as those of others, that inasmuch as orcinol evidently has the constitution 1 3 5 those reactions by which it has been obtained from substances of other con-stitution such as chlorotoluene-sulphonic acid (1 2 4) must have involved a molecular change. We subjoin a table of the reactions of the different dihydroxy-toluenes above described. Circumstances have prevented us from investigating the dihydroxytoluene 1 3 4 as fully as we could have wished as also the two others viz. 1 2 3 and 1 2 6 ; but we hope to iwume the investigation at some later date.brown. Reagent. 1 -2 *4. --Ammoniaand damp air. 2. '3 *4. Cliloride of lime. Red after a while a green fluorescence, yellow by transmitted light. Ferric chlo-ride. Brown. Sodium hy-drate and air. Chloroform and sodium hydrate on heating. Orcinol 1 *3 *5. Intense re6 vio-let diss. in alkalis with red-violet co-lour. Acetic acid precipi-tates redflocks. -Deep violet-red, then brown and yellow. Deep black-vio-let. Red. 1.2 -5. Dark brown dis solves in alka-lis with brown colour. Acetic acid precipi. tates brown flocks. --Blue-green then brown. When dilute brown-ish-red. B rownish-red, yellow in di-lute solutions. Pretty blue-green chang-ing to dark-I Reddish then brown then green then blue. Blue changing tc red by additior of acetic acid without an5 precipitation. ~ Yellow. Blue scarcely clraiiging. Rose-red then brownish. Rose-red. ' -Green j on gradual addi-tion of NH, or Na2C03, became blue and then violet. TOL. XLI. 2 428 NEVILE AND WlNTHER ON ORCINOL ETC. NOTE. The above p p e r was written principally in the autumn of 1881, but its publication has been delayed owing to our having applied for protection for the method of manufacturing orcinol and since it was written independent workers have published some of the above results. We have however thought it better to publish the paper in its entirety, at the risk of repenting work already done. We may perhaps take this opportunity of noticing a paper by C. Langer (Ber. 1882 1061-l065) on the law of substitution of aromatic amines and point out that the law he there enunciates is really nothing else than the law which we showed to be true in a communication to this Society in 1880 (this Journal 1880 430) stated in other words

ISSN:0368-1645    

DOI:10.1039/CT8824100415

出版商:RSC    

年代:1882

数据来源: RSC

摘要:

P R O C E E D I N G S AT THE MEETINGS OF THE CHEMICAL SOCIETY, SESSION 158 1-82. November 3rd 1881. Dr. Gilbert Vice-president in the Chair. The following papers were read :-“ On Citraconic and Mesaconic Ethers and on Maleic and Fumttric “ On the Action of Potassium Cyanide on Bismuthous Nitrate ” by ‘‘ On the Atomic Weight of Bismuth ” by M. M. P. Muir. “ Additional Observations on the Halogen Salts of Bismuth ” by “Note on the Action of Sulphuric Acid on Zinc and Tin ” by “ On the Volumetric Estimation of Bismuth in the Form of “ Note on the Influence of Water on the Reaction between Potas-“ Laboratory Notes ” by M. M. P. Muir. “ On Suberone ” by C. Schorlemmer and R. S. Dale. “ On Isodinaphthyldisulphonic Acids and on Phenylnaphthalene ” “ On Dimethylmalonic Acid and Dimethylbarbituric Acid ” by Acids ” by W.H. Perkin. M. M. P. Muir. M. M. P. Muir. M. M. P. Muir and C. E. Robbs. Oxalate :” by M. M. P. Muir and C. E. Robbs. sium Iodide and Chlorine ” by M. M. P. Muir and R. Threlfall. by Watson Smith and T. Takamatsu. L. T. Thorne. November 17th 1881. Dr. Gilbert Vice-president in the Chair. The following papers were read :-“ Aluminium Alcohols (Part 11) their Products of Decomposition by Heat ” by J. H. Gladstone and A. Tribe. 2 L 430 PROCEEDINGS OF THE CHEMICAL SOCIETY. “ On thc Chemical Action of decomposing Vegetable Matter on the Rock-forming Sediment of the Carboniferous Period ” by A. Wethered. “ On a- and 6-Amylan ” by C. 0. Sullivan. “ On the Action of Oxides on Salts (Part IV) Potassic Chlorate, “ On the Steeping of Barley ” by E.J. Mills and J. Pettigrew. and Ferric Oxide ” by E. J. Mills and G. Donald. December lst 1881. Prof. H. E. Roscoe President in the Chair. The following papers were read :-“ Researches on the Laws of Substitution in the Naphthalene Series “ On Benxylphenol and its Derivatives ” by E. H. Rennie. “ Note on the Action of Ethylchlorocarbonate on Benzene in pre-“ On the Production of Oxalic Acid by Oxidation of Paraffin Oil ” (Part 11) ” by H. E. Armstrong. sence of Aluminium Chloride ” by E. H. Rennie. by J. Gallatly and J. S. Thomson. December 15th 1881. Prof. H. E. Roscoe President in the Chair. The following gentlemen were duly elected Fellows of the Society :-C. Armitage Dewsbnry ; J.Bingley Northampton ; C H. Botham-Icy Leeds; J. D. Custance Soutlh Australia; G. W H. Clements, Bilbao Spain ; E. A. Demargay Paris ; T. Farmer Liverpool ; A. B. Griffiths Dulwich; R. P. Gardener St. John’s Wood Park; W. B. Harrington Cork ; H. E. Head Landose ; J. Innes Llanelly ; W. Jackson Northampton; R. V. Jackson Glasgow; P. S. Looker, Rhymney S. Wales ; R. P. Mathews Battersea ; R. D. Naegamvale, Malabar Hill Bombay ; J. B. Orr Eltham Kent ; W. F. Reid Stow-market ; W. Rupp New York ; H. ROSS Lancaster ; F. Sear Laven-der Hill S.W. ; C. H. Sieber Whitworth ; J. W. Stevens Blandford; C. H. Slaytor Doncaster ; D. N. Steuart Broxburn N.B. ; B. E. Smith Wandsworth S.W.; C. A. Stitt Dalruth N.B.; R. Tervet, Johnstone N.B. ; J. S. Topham Exeter; Rev. E. W.Volckson, Bath ; B. Wilkinson Mmchester ; J. Whitlock Lancaster. The following papers were read :-‘‘ On Some Higher Oxides of Manganese and their Hydrates ” by V. E. Veley PROCEEDINGS OF THE CHEMICAL SOCEETY. 431 ‘‘ On a New Alkaloid from Cinchona Bark ” by D. Howard and ‘‘ Contributions to the Chemistry of the Rare Earth-metals ” by J. Hodgkin. B. Brauner. January 9th 1882. Prof. H. E. Roscoe President in the Chair:. The following gentlemen were duly elected Fellows of the Society :-F. Barkas New Zealand; E. D. Chester Venezuela; J. Gray, Somerset House W.C. ; H. E. Irons Enfield; J. P. Laws St. John’s Park N. ; I?. H. Lescher Bartholomew Close E.C. ; D. 0. Masson, Edinburgh ; H. F. Moore Hammersmith ; T. Perry Torquay ; J. R. Parker Hackney E.The following papers were read :-“The ChemistrF of Bast Fibres ” by C. F. Cross and E. J. Bevan. “ A New Apparatus for Determining Fusing Points:” by C. 3’. “ On the Action of Heat an Mercuric Chloride ” by T. Carnelley. “ Contributions to the History of Cerium Compounds ” by W. N. ‘‘ On the Reaction of Chromic Anhydride with Sulphnric Acid ” by ‘‘ On Dibenzylaniline and its Isomerides ” by A. Higgin. Cross and E. J. Bevan. Har tley. C. F. Cross and A. Higgin. February 2nd 1882. Prof. Williamson Vice-president in the Chair. Prof. Odling delivered a Lecture on ‘‘ The Unit Weight and Mode of Constitution of Compounds.” February 16th 1882. Prof. H. E. Roscoe President in the Chair. The following gentlemen were duly elected Fellows of the Society :-F.J. Slford Tauntori ; H. L. Buckeridge Duke Street W. ; A. Blaikie Edinburgh ; J. J. Beringer Cornwall ; W. E. Bush Clapton ; G. W. Davies Stockport; J. F. Heyes Liverpool ; W. Hamilton, Nadrns ; T. Isherwood Blackburn ; H. H. Phillips Manchester 432 PROCEEDINGS OF THE CHEMICAL SOCIETY. T. Pitt Coleman Street E.C. ; H. Porter Forest Hill S.E. ; G. McRobert Ardter Stevenston ; C. H. Ridsdale Stockton-on-Tees ; V. 0. Sells Newark-on-Trent; L. T. Thorne Fortess Road N.W. S. Young Bournemouth. The following papers were read :-“ On Bensyl-phenol and its Derivatives (Part 11) :” by E. H. “ On the Chemical Examination of the Buxton Thermal Water ” “ On Retrograde Phosphates ” by F. J. Lloyd. “ Contributions ko our Knowledge of the Composition of Alloys “ On the Dissociation of Chlorine:” by A.P. Smith and W. B. Rennie. by J. C. Thresh. and Metd Work for the most part Ancient ” by W. Flight. Inwe. March 2nd 1882. Prof. H. E. Roscoe President in the Chair. The following papers were read :-‘‘ On the Action of Aldehydes on Phenanthraquinone in Presence of Ammonia (3rd notice) ” by F. R. Japp a’nd F. W. Streatfeiid. “ Application of the Aldehyde and Ammonia Reaction in Deter-mining the Constitution of Quinones:” by F. R. Japp and F. W. S trestfeild. “ On the Solubility of Glass in certain Reagents ” by R. Cowper. “ Analysis of a Piece of Oxidised Iron from the Condenser of “ On the Action of Sodium Hydrate and Carbonate on Felspars and .‘‘ On the Preparation of Pure Nitrogen ” by W. Flight. “ Some Observations on the Luminous incomplete Combustion of E.M.S.‘ Spartaa ’ ” by R. Cowper. Wollastonite ” by W. Flight. Ether and other Organic Substances ” by W. H. Perkin. March 16tb 1882. Prof. H. E. Roscoe President in the Chair. The following gentlemen were duly elected Fellows of the Society :-H. L. Billing Plymouth; J. Brown Dewsbnry; H. H. Crawley, Bournemoutlh ; T. Donnelly Dubliu ; U. R. Dutt Montpelier Street, S.W.; W. Fowler Sunderland; N. Graham Tulse Hill S.W. PROCEEDINGS OF THE CI3cEMICA.L SOCIETY. 433 A. Hartley Dulwich S.E. ; A. Hill Port Glasgow; R. Mar Brisbane, Queensland ; J. T. Smith Birmingham ; F. Vacher Birkenhead. The following papers were read :-" On Valency :" by H. E. Armstrong. " On the Preparation of Diethylnaphthylamine " by B.E. Smith. " On the Action of Sulphuric Acid on Diethylnaphthylamine " by " On the Action of Phosgene Gas on Diethylnaphthylarnine " by " On some Constituents of Rosin Spirit " by G . H. Morris. " Contributions to the Chemical History of the kromatic Derivatives " On Pentathionic Acid (Part 11) " by Watson Smith. B. E. Smith. B. E. Smith. of Methane " by R. Meldola. March 30th 1882. (Annual General Meeting.) See page 229. April 6th 1882. Dr. Gilbert President in the Chair. The following papers were read :-" On the Action of Acetyl Chloride on Fumaric Acid " by W. H. " Some Arguments in favour of the Prism Formula of Benzene " '' Note on a convenient Apparatus for the Liquefaction of " On the Transformation of Urea into Cyanamide " by H.J. H. " On the Action of Halo'id Acids upon Hydrocyanic Acid " by Perkin. by W. R. Dutt. Ammonia " by J. Emmerson Reynolds. Fenton. L. Claison and F. E. Matthews. April 20th 1882. Dr. Gilbert President in the Chair. The following papers were read :-" On the Atomic Volume of Iodine " by W. Ramsay. '' On the Action of Acetone on Phenanthraquinone both alone and i n presence of Ammonia " by F. R. Japp and F. W. Streatfeild 434 PROCEEDINGS OF THE CHEMICAL SOCIETY. “ A Study of some of the Earth-metals contained in Samars-kite ” by H. E. Roscoe. “ On the Spectrum of Terbium ” by H. E. Roscoe and A . Schuster. “ On the Action of Thiophosphoryl Chloride on Silver Nitrate ” by T. E. Thorpe and S. Dyson. “ On the Behaviour of Zinc Magnesium and Iron as Reducing Agents with Acidulated Solutions of Ferric Salts ” by T.E. Thorpe. “ Experiments on the Action of Potassium Amalgam Sulphuretted Hydrogen and Potassium Hydrate respectively on Tetra- and Pentn-thionates of Potassium ” by V. Lewes-May 4th 1882. Dr. Gilbert President in the Chair. The following gentlemen were duly elected Bellows of the Socieky :-L. W. Andrews Springfield U.S.A. ; J. H. Beckett Manchester ; B. A. Burrell Leeds; ‘J. H. Bicket Kilmarnock; J. Palknier, Dublin; G. R. Faulkner Cirencester; W. J. Kemp Surrey; S. Langdon Kandy Ceylon; E. G. Love New York; A. I?. Price, San Francisco ; W. H. A. Peake Stellenbosch Cape Colony ; A. N. Palmer Wrexham ; J. Robinson Llanfairfechan ; S. P. Sadtler, Philadelphia; W. C. Samuel Heme Hill S.E.; J.H. Smith Not-tiiigham ; J. H. Stebbins New Yorli ; P. W. Squire Oxford Street W. ; L. Taylor Hackney E. ; G. Watson Glasgow. Prof. Dewar delivered a lecture “ On Recent Developments of the Theory of Dissociation.” May 1st h 1882. Dr. Gilbert President in the Chair. The following papers were read :-“ On the Precipitation of Alums by Sodic Carbonate:” by E. J. ‘‘ On the Rotary Polarisation by Chemical Substances under Mag-“ On the Constitution of Amarine and Lophine ” by F. R. Japp and Mills and R. L. Bsrr. netic Influence ” by W. K. Perkin. H. H. Robinson. Julie lst 1882. Dr. Gilbert President in the Chair. The following papers were read : PROCEEDINGS OJ!’ THE C m I C A L SOCIETY. 435 “ On the Determination of Nitric Acid in Soils ” by R.Warington. “ On a Spectroscopic Study of Chlorophyll ” by W. J. Russell and W. Lapraik. June 15th 1882. Dr. Gilbert President in the Chair. The following gentlemen were duly elected Fellows of the Society :-R. Alexander New Cross S.E. ; Br Brauner Manchester ; J. J. Dobbie Glasgow; C. J. Ellis Glasgow; W. L. Goodwin New Brunswick Canada ; D. E. Johnstone Soutshport ; T. W. Lovibond, Greenwich S.E.; R. W. Fullar Tayside Perih; R. N. Wolfenden, Welbeck Street W. The folIowing papers were read :-“ Notes on 8-Naphthaquinone ” by C. E. Groves. “ On some New Compounds of Brazile’in and HEemate’in ” by “ On the Determination of Nitric Acid as Nitric Oxide by Means of “ On a New Process of Bleaching ” by J. J. Dobbie and J. J. Hummel and A. G. Perkin.its Reaction with Ferrous Salts (Part 11) ” by R. Warington. Hutcheson. Donations to the Library 1881-82 :-“ A Treatise on Chemistry.” Vol. iii. “ Organic Chemistry.” Part 1 by Professors Roscoe and Scborlemmer. “ Practical Chemistry ” by A. Vernon Harcourt. M.A. F.R.S., and H. G. Madan M.A. F.C.S. Third Edition from tbe Authors. “ Chemical and Physical Researches ” by Josiah Parsons Cooke : from the Authoi “ Handbook of Metric Measures and their English Equivalenis ” “ Photography with Emulsions ” by Captain Abney RO.B.$ F.R.S. : “ Sprengel’s Vacuum-pump ” by H Sprengel from the Author. “ Usefiil Information in Electric Lighting ” by Killingworth “ The Scientific Roll and Magazine of Systematised Notes ” con-“ Thermometric Scales ” by Dr.T. Stevenson from the Author. by W. G. Borns from the Author. from the Author. Hedges from the Author. ducted by Alexander Ramsay. Climate Vol. i from the Editor 436 YROCEEDINGS OF THE CHEMICAL SOCIETY. “ Handbook of the Collection of the Wild Silks of India in the Indian Section of the South Kensington Mnsenm:” by Thomas Wardle from the Author. “ Water-supply of the City of New York ” by E. Waller Ph.D. : from the Author. “ Science and Industry ” an address delivered in the Town Hall, from the Author. L( The Analysis of Phosphates and Method of expressing the Results ” by T. Jarnieson from the Author. “ Ausfuhrliches Lehrbnch der Chemie ‘’ 3ter Band. Organische Chemie. Erste Abtheilung von H. E. Roscoe F.R.S. and C. Schorlemmer P.R.S.from the Authors. ‘‘ Handbuch des krystallographisch - physikalischen Theils der Mineralogih von C. RammelsErg from the Author. “ Premims Resdtats des Etudels sur la formation des Matiares colorantes par voie $lectrochemigae exposes par F. Goppelsroeder : from the Author. Periodicals :-Birmingham Bctober 2&h 1881 by Dr. C. W. Siemens: “ Philosophical Transactions for 1881 ” from the Royal Society. “ The Chemical Gazette from 1848 to 1859 ” from Dr. Francis. “Annual Reports of the Deputy Master of the Mint.” i to xi (1870-1880) from W. Chandler Roberts Esq. “ Report of the 51st Meeting of the British Association for the Advancement of Scienee held at York 1881 ” from the Association. “ Address to the Chemical Section of the British Association at York 1881 on the Growth of the Atomic Theory ” by Dr.A. W. Williamson F.R.S. from the Author. “ Army Medical Department Report for 1879 ” (‘ The Analyst for 1882 ” from the Editors. ‘( The Chemist and Druggist 1882 ” from the Editor. “ The Chemical News 1881-82 ” from the Editor. ‘( Quarterly Journd of the ,Geological Society 1882 ” ‘‘ Quartedy Journal of Science.” Vol. xii from the Editor. “ Chemical Review May 1882 ” from the Editor. “ The Dyer and Textile Colourist June 1882 ” from the Editor. ‘( Journal of the Society of Arts 1881-82 ” from the Society. “ Journal of the Society of Chemical Industry.” from the President. “ Journal of rthe &on and Steel Institute 1882 ; also 1879 No. 2 and from the Department. from the Society.No. 1 : 1881 No. 2 ” from the Institute PROCEEDINGS OF TiEX CEIEMZCAL SOCIETY. 437 “ Mineralogical Magazine 1882 ” from the Mineralogical Society. “ Pharmaceutical Journal and Transactions 1881-82 ” “ Year-book of Pharmacy I881 ” from Professor Attfield. “ Proceedings of the Physical Society of London 1881 ” from the Society. “ Catalogue of the Scientific Books in the Library of the Royal “ Transactions of the Royal Society of Edinburgh.” Vol. xxx, “ Proceedings of the same (1880-81) ” from the Society. “ Proceedings of the Philosophical Society (of Glasgow 1880-81 ’’ “ The Glasgow University Calendar for 1881-82 ” “ Reports of the Mitchell Library Glasgow 1880 and 1881 ” “ Easter Ardross Experimental Station Report for 1880-81 ’’ “ Geological Survey of Canada (1879-1880) ” : from the Director.“ Transactions of the South African Philosophical Society.” Vols. i and ii (1878-1880) from the Society. “Journal and Proceedings of the Royal Society of New South Wales 1880-81 and 1881-86 ” from Prof. Liversidge. “ Report of the School $of Mines Ballarat.” Presented at the Meeting of Governors May 24th 1882 from the Reporter. ‘‘ American Chemical Journal ” edited by Ira ICemsen. Vol. iv, Nos. 1 2 and 3 from the Editor. “ American Journal of Science and Arts.” from the Editors. ‘‘ Proceedings of the American Philosophical Society January to “ Annual Report of the Commissioner of Agriculture (U.S.) for “ Abhandlungen der Konigl-baeyrischen Akademie der Wissen-from the Royal Bavarian Academy. “ Denkschriften der Kaiserlichen Akndemie zu Wien (Mathemat.-4lter Band from the Academy.“ Sitzungsberichte derselben ’’ 82ter Band from the Academy. “ Sitzungsberichte der Koniglich-preussischen Akademie der Wis-from the Pharmaceutical Society. Society ” fpom the Society. Part I Session 1880-81. Vol. xiii No. 1 from the Society. from the University. from tohe Librarian. J. McDonald Cameron from the Author. Vols. xxiii and xxiv : December 1881 ” from the Society. 1880 ” from the Department of Agriculktnre. schaften.” Bd. xiv. Erste Abtheilung : naturw. Klasse) .” senschaften zu Berlin i-xvii 1882 from the Academy 438 PROCEEDINGS OF THE CHEMICAL SOCIETY. “ Oversigt over det Kongelige Danske Viderskabernes Selskabs from the Royal Danish Academy of Sciences.Bd. from the Royal Swedish Academy of Sciences. “ Kongliga Svenska Vet8enskaps Akademiens FGrhandlingar 187 7-“ Meddelser fra Carlsberg Laboratoriet Andet HBfte 1879 ” from the Royal Danish Academy of Sciences. ‘ I Verhandlungen der Kaiserl-Leopold Carolinischen Deutscheii from the Academj-. “ Verhandlungen nnd Sitznngsberichte der physikalisch-medicii-“ Vierteljahresschrift der naturforschenden Gesellschaft in Zurich, ‘‘ Comptes rendua des SQances et M6moires de In Soci6t6 de 6me SQrie Tomes 5 et 6 7me SQrie tome 1 1880: from the Society. Bulletin de l’Acad6mie Royale des Sciences de Belgique, ‘‘ Annuaire de 1’AcadQmie Roynle des Sciences de Belgique, Forhandlinger og des Medlemmers Arbeeten 1880-81 ” “ Kongliga Svenska Vetenskaps Akademiens Handlingar.” xiv-xvii (1876-1878) : 1880 ” from the Royal Swedish Academy of Sciences. Akademie der Natnrforscher.” xxi Band 2te Abtheilung 1880 : schen Gesellschaft zu Wurzburg 1881 ” from the Society. 1880 and 1881 :” from the Society. Biologie.’’ 1881-82. ” 1881-82 ” from the Academy

ISSN:0368-1645    

DOI:10.1039/CT8824100429

出版商:RSC    

年代:1882

数据来源: RSC

摘要:

INDEX OF AUTHORS’ NAMES. T R A N S A C T I O N S . 1882. A. A r n o l d A. E. obituary notice of 236. Atkinson R. W. and H. Yoshida, on peppermint camphor (menthol), and some of its derivatives 49. B. B a r r R. L. See Mills. Bevan E. J. See Cross. Bloxam W. P. See Thomson. B r a u n e r B. contributions to the chemistry of rare earth-metals 68. C. Carnelley T. action of heat on mer-curic chloride under low pressures,317. Claisen L. and F. E. Matthews on the action of halond acids upon hydro-cyanic acid 264. Clapham C. obituary notice of 236. C ow per R. analysis of a piece of oxi-dised iron from the condenser of H.M.S. “Spartan,” 256. - on the solubility of glass in certain reagents 254. Crafts J. M. See Friedel. Cross C. F. and E. J. Bevan a new apparatus for the determination of melting points 111.- the chemistry of bast fibres 90. Cross C. F. and A. Higgins on the reaction of chromic anhydride with sulphuric acid 113. D. Davis E. W. See S m i t h . Dessaignes,V. obituary notice of,236. Deville H. St. Claire obituarynotice Donald George. See Mills. Byson S. See Thorpe. of 235. F, F e n t o n H. J. H. transformation of urea into cyanamide 262. F 1 i gh t W. contributions to our know-ledge of the composition of alloys and metal-work for the most part ancient, 134. - on the action of sodium hydrate and carbonate on felspars and wollas-tonite 159. Friedel C. and J. M. Crafts on some decompositions produced by the action of chloride of aluminium, 115. G. Gerstl R.obituary notice of 237. Gladstone J. H. and A. Tribe, aluminium alcohols. Part 11. Their products of decomposition by heat 5. H. H a r t l e y W. N. contributions to the chemistry of cerium compounds 202. - note on certain photographs of the ultra-violet spectra of elementary bodies 84. - researches on the relation of the molecular structure of carbon com-pounds to their absorption-spectra, 45. - the analysis of rhabdophane a new British mineral 210. H i g g i n A. dibenzoylaniline and its isomerides 132. - SeeCross. Hodgkin J. See Howard. Howarcl,D. and J. Hodgkin on a new alkalo’id from cinchona bark, 66. Hummel J. J. and A. G. P e r k i n on some new compounds of haemate’in and brazile’in 367. J. Japp F. R. and H. H. Robinson on the constitution of amariue and lophine 323 440 IXDEX OF AUTHORS.J a p p . F. R. and F. W. S t r e a t f e i l d , application of the aldehyde and ammonia reaction in determining the constitution of quinones 157. - on the action of acetone on phenanthraquinone both alone and in presence of ammonia 270. - on the action. of aldehydes on phenanthraquinone in presence of ammonia (third notice) 146. L. L a p r a i k W. See Russell. Lemes V. experiments on the action of potassium-amalgam sulphuretted hydrogen and potassic hydrate re-spectively on tetra- and penta-thionate of potassium 300. LIoyd F. J. on the estimation of retro-grade phosphates 306. M. Mackay J. obituary notice of 23’7. Marreco A. F. obituary notice of, Matthews F. E. See Claisen.Meldola R contribut,ions to the chemical history of the aromatic deri-vatives of methane 187. Miller A. K. on dihydroxybenzoic acids and iodosalicylic acids, 398. Mills E. J. and R. L. B a r r on the precipitation of the alums by sodic carbonate 341. Mills E. J. and G. Donald on the action of osides on salts. Part IV. Potassic chlorate and ferric oxide, 18. Mills E. J. and J. P e t t i g r e w on the steeping of barley 38. Morley H. F- on oxypropyltduidine, 38’7. Morris a. H. on some constituents of resin spirit 167. Muir M. M. P. action of wateron bis-muthous iodide a lecture experiment, 4. Muir M. M. P. and C. E. Robhs on the volumetric estimation of bismuth in the form of oxalate 1. 238. N. Nevile R. H. C. and nr. W i n t h e r , on orcinol ar,d some of the other di-hydroxytoluenes 415.0. O’Sullivan C. a- and p-amylan con-stituents of some cereals 24. P. P e r k i n A. G. See Humniel. Perkin W. H. on rotary polarisa-tion by chemical substances under magnetic influence 330. - on the action of acetyl chloride on fumaric acid 268. - some observations on the luminous incomplete combustion of etber and other organic bodies 363. P e t t i g r e w J. See Mills. P l i m p t o n R. T. on some halogen compounds of acetylene 391. R. Rennie E. H. note on the action of ethyl chlorocarbonate on benzene in presence of aluminium chloride 33. - on benzyl-phenol and its deriva-tives 33 220. R e y no 1 d 8 J. E. note on a convenient apparatus for the liquefactian of am-monia 259.Robbs C. E. Bee Muir. Robinson H. H. See J a p p . Roscoe H. E. a study of some of t,he earth-metals contained in samarskite, 277. Roscoe H. E and A. Schuster the spectrum of terbium 283. Russell W. J. and W. L a p r a i k a spectroscopic study of chlorophyll, 334. S. Sakurai J. on metallic compoundscon-taining bivalent hydrocarbon radicles, Part 111 360. Schust,er A. gee Roscoe. Smith B. E. on the act,ion of carbon oxydichloride (phosgene gas) upon di-ethylnaphthylanine 185. - on the action of sulphuric acid upon diethylnaphthplamine at high temperatures 182. - on the preparation of diethyl-naphthplamine 180. Smith Wat,son and Gt. W. Davis, an additional evidence by analysis of the quinoline molecule that this base belongs to the aromatic series of or-ganic compounds 412 ISDEX OF AUTHORS.441 S m i t h Watson and G. IT Davis, crystalline molecular compounds of naphthalene and benzene with anti-mony trichloride 411. Smith Watson and T. Takamrtsu, on pentathionic acid Part 11 162. S t r e a t f eild 3'. W. See Japp. T. '1'11 omas W. R. obituary notice of 238. Takamatsu T. See Smith. Thompson J. M.,and W. P. B loxam, on the cryst(a1lisation from supersatu-rated solutions of certain compound salts 379. Thorpe T. E. note on the action of the oxychlorides of sulphur on siher nitrate 297. - on the behaviour of zinc magne-sium and iron as reducing agents with acidulated solutions of ferric salts 287. Thorpe T. E. and S. Dyson on the action of thiophosphoryl chloride on silver nitrate 297. T h r e s h J. C. chemical examination of the Buxton thermal water 11'7. Tribe AlfrecF See G l a d s t o n e . V. Veley V. H. on some higher oxides of manganese and their hydrates Part 11,5& W, Walton J. S. obituary notice of 238. Warington R. on the determination of nitric acid as nitric oxide by means of its reaction with ferrous salts, Part 11,345. -on the determination of nitric acid in soils 351. Wethered E. on the composition of Pennant grits in contaet with and a t a distance from carbonaceous deposits, 79. W i l l i s A. obituary notice of 239. Winthea. See Nevile. Y. Yoshicla H. See Atkcinson

ISSN:0368-1645    

DOI:10.1039/CT8824100439

出版商:RSC    

年代:1882

数据来源: RSC

摘要:

INDEX OF SUBJECTS. T R A N S A C T I O N S. 18 8 2. A. Abstractors instructions to 247. Acetylene bromides 391. I_ bromiodide 394. .- chlorioclide 392. - chlorobromide 393. - halogen compounds of 391. - iodides 391. Adularia action of sodium hydroxide and carbonate on 159. Albite action of sodium hydroxide and carbonate on 160. Alcohols aluminium Part 11. Their products of decomposition by heat 5. Alkaline-green 189. Alkalo'id new from cinchona bark 66. Alloys composition of ancient 13%. Alum solutions supersaturated obser-vations on 382. Aluminium alcohols Part 11. Their products of decomposition by heat 5. - chloride decompositions produced by the action of on organic com-pounds 115. - a- and /3-naphthglate action of heat on 15 16. - para-cresylate action of heat on 8.* - phenylate action of heat on 5. -. - thymolate action of heat on 11. Alums precipitation of by sodium car-Atnarine constitution of 323 329. Ammonia convenient apparatus for the a- a i d P-dmylan constituents of some Anhydrobenzoyldiamidostilbene 328. Anhydro-orthomethoxybenzoyldiamido-phenanthrene 15 k. dnhydroparahydroxybenzoyldiamido-plienanthrene and its acetyl-deriva-tive 151 152. bonate 341. liquefaction of 259. cereals 24. Anhydrosalicyldiamidobenzene 149. Anhydrosalicyldiamidophenanthrene, Aniline action of benzyl chloride on, Aniline-blue two distinct kinds of 197. Anniversary meeting 229. 150. 200. Apparatus for the liquefaction of am-Axe-heads copper from Beth Saour, monia 259. near Bethlehem analyses of 144.B, Balance-sheet of the Chemical Society from March 21 1881 to March 24, 1882,245. Research Fund from March 23 1881 to March 24,1882 246. -Barley steeping of 38. Bast fibres chemistry of 90. Bastin 102. - chloro- observations on 109. Bastose 102. Benzene action of ethyl chlorocarbonate on in presence of aluminium chloride, 33. - crystalline molecular compounds of with antimony trichloride 411. Benzenylamidochrysole 158. Benzil action of parahydroxybenzalde-hyde on in presence of ammonia, 326. Benzoylphenylamine 134. Benzylphenol 33 220. - amido- 221. - constitution of 226. - dinitro- 222. - mononitro- 221. - nitrobromo- and the action of nitric acid on 223 224. - trinitro- 36. - - oxidation of 223. Benzylphenolsulphonic acid and its saits 34 220.- bromo- potassium salt of, 35. - - nitro- potassium salt I f, 35. Benzylphenylamidodiphenylmethane I 200. Benzylphenyl methyl ether oxidation Bidmi ware India analysis of 139. Bismuth volumetric estimation of in of 227. the form of oxalate 1 ISDEX OF SUBJECTS. 443 Bismuthous iodide action of water on, Brazile'in action of hydrobromic acid - action of hydrochloric acid on, - new compounds of 367 3'73. Bronze bar from mine of temple in - figures Egypt.ian analysis of 145. Bronzes Cypriote Romano-British, Greek and Roman analyses of 1 4 . Buddha figure of ancient Indian analy-sis of 138. Bnrton thermal \vat el* cliemical eslzmi-nation of 117. a lecture experiment 4 on 3'77. 376. Bolivia analysis of 145.C. Carbon compounds relation of the molecular structure of to their ab-sorption-spectra 45. Cutechol,. preparation of diliydroxyben-zoic acids from 398. Catechol-orthocarboxylic acid 398. Cereals some constituents of 24. Ceric phosphate hydrated and ignited, composition of 209. - preparation and analysis of, 205. Cerium compounds contributions to the chemistry of 202. - delicate test for 203. - estimation of 206. Cerous phosphates preparation and analysis of 204. - salts pure preparation of 202. - tetrafluoride 69. - double salt of 70. Chemical substances under magnetic in-fluence rotary polarisation by 330. Chlorobastins observations on 109. ("hloropliyll spectroscopic study of, Chromic anhydride reaction of with Chromium sulphates insoluble 113.Chryseudiene 16. Clirysoqiiinone action of beazaldehyde 9 on in presence of ammonia 157. - constitution of 158. L'incliona bark new alkalo'id from 66. Coinage copper-nickel facts relating to Coins of ancient India analysis of, Colophonic hydrate 169. Colophonine 169. Combustion luminous incomplete. of ether and other organic bodies 363. TOL. XLT. 334. sulphuric acid 113. the history of 134. 138. Yopper axe-lieads from Beth Saour, - spear-heads from Cyprus analysis lopper-nickel coinage facts relating to Iresol nitro- 417 422 424 426. 2rystallisation from supersaturated so-lutions of compound salts 379. Zyanamide transformation of urea into, 262. Jyanuric a d constitution of 48. near Bethlehem analpis of 144. of 143. the history of 134.D. Dibenzoylanilirie and its isomerides, Dibenzylamidodipheiiylmethane 200. Didymium double fluorides of '75. - pentoxide anhydrous 73. - peroxide 71. Diethylglyoxylic ether 264. Diethylnaphthylamine action of caxbon oxydichloride (phosgene gas) on, 185. - action of sulphuric aoid on a t high temperatures 182. - hydrochloride 181. - nitroso- 182. - preparation of 180. Uiheptine 1'74. Dihydroxybenzoic acid conversion of Dihydroxybenzoic acids 398. - six preparation and proper-- preparation of from catechol, Dihydroxytoluenes preparation of 415, - reactions of 426. Diphenglamine action of benzyl chlo-ride on 198. - oily product obtained by the action of benzyl chloride on 187. Diphenylamine-green a i d its optical properties 189 190 192 193.- eulphonic acid of 194. Diphenyldiamidotriphenylcarbinol 191. Diphenylcliamidotriphenylmethane 191. Diphenylmethane derimtires of 197. Double citrates action of the consti-tuents on supersaturated solutions of, 385. - salts crystallisation from sup'r-saturated solutions of 379. - tartrates action of the consti-tuents on supersaturated solutions of, 385. 132. paraiodosalicylic acid into 406. ties of 409 410. 398. 422 423 426. 2 444 INDEX OF SUBJECTS. Doxall grit analysis of 81. Drupose 106. E. Earth-metals contained in samarskite, study of 277. Elementary bodies photographs of the ultra-violet spectra of 84. Ether and other organic bodies lumi-nous incomplete combustion of 363. Ethyl chlorocarbonate action of on benzene in presence of aluminium chloride 33.Ethylbenzene 33. F. Felspars action of sodium hydroxide and carbonate on 159. Ferric oxide action of on potassium chlorate 18. - salts behaviour of zinc magne-sium and iron as reducing agents with acidulated solutions of 287. Figure of Buddha ancient Indian, analysis of 138. Figures ancient Egyptian ‘‘ bronze,” analyses of 142. Formamidine 266. Fumaric acid action of acetic chloride on 268. G. Glass solubility of in certain reagents, Gtlycodrupose 106. Glycolignose 106. 254. H. Hsemate‘in 367. - action of hydrobromic acid on, - action of hydrochloric acid on, - action of phthalic anhydride on, - action of sulphuric acid on 368. Hebrew shekel analyses of 144. Heptine 173. - and its glycol probable constitution - oxidation of 175.Heptylene 173. - dinitro- 175. 372. 371. 377. of 177. Homoquinone and its salts 67. Hook ancient bronze Egyptian analysis of 141. Hydrocarbon radicals bivalent metallic compounds containing Part 111, 360. Hydrocyanic acid action of halord acids on 264. I. Incas pin found on mummy a t Arica, Indigo reduction of by jute 108. Iron behaviour of 8s reducing agent with acidulated solutions of ferric salts 287 294. - found in one of the air-passages of the Great Pyramid by Colonel Howard Vyse in 1837 140. - oxidised from the condenser of H.M.S. “Spartan,” analysis of a piece of 256. Peru analysis of 145. Isobrazileyn bromhydrin 377. - chlorhydrin 377. - sulphate acid 375. Isoheemate‘in 373.- chlorhydrin 372. - monobromhydrin 372. - sulphate acid 369. J. Jute substance reactions of under high pressure 107. K. Kroft Gari work India analysis of, 140. L, Lanthanum atomic weight of 75. Lecture experiment ; action of water on Linseed oil reaction of with sulphuric Lophine constitution of 323. bismuthous iodide 4. acid 108. M. Maleic anhydride 269. Magnesium behaviour of as reducing agent with acidulated solutions of ferric salts 287 292 INDEX OF SUBJECTS. 445 Manganese changes produced when the higher oxides are heated in nitrogen, 57. - some higher oxides of and their hydrates 56. - dioxide action of on potassium chlorate 23. - oxides action of hydrogen on, 63. Melting-points a new apparatus for the determination of 111.Menthene 53. - action of hydriodic acid on 54. Menthol action of hydriodic acid on, 54. I_ and soine of its derivatives 49. Menthone 50. Mercuric chloride action of heat on, under low pressures 317. - specific heat of 319. Metacresol metabromo- 421. Metacresyl ether 14. Metadihydrox;yt(oluene 417. Metal-work. contributions to our know-ledge of the composition of for the most part ancient 134. Metallic compounds containing bivalent hydrocarbon radicles Part 111 360. Metatoluidine metabromo- preparation of orcinol from 4.20. Mathane chemical history of the aro-matic derivatives of 187. Methoxybcnzopheiioiie 227 228. Methylene chloriodide monomercuric salt of 361. . Metli ylphenylamidodiphenylmethaiie, 200. Metliylpropylallyleiie and its glycol, 177 178.Metliylpropylallyleneglycol and the action of acetic anhydride on 178. Microlin action of sodium hydroxide and carbonate on 160. Microcosmic salt crystallisation of super-saturated solutions of 384. Monomercuric methylcne chloriodide, 361. N. Naphthalene crystalline molecular com-pounds of with antimony trichloride, 411. - perchlorination of 413. P-Nnphthyl ether 16. Nitrates in t+oil influence of heat and moisture in reducing 364. Nitric acid estimation of as nitric oxide by means of its reaction with ferrous salts Part 11 395. Nitric acid estimation of in soils 351. Nomenclature 247. Notation 249. 0, Obituary notices 235. Orcinol and some of the other dihydroxy-toluenes preparation of 415. Organometallic compounds 360.Orthocresol metanitro- 424. Orthomethoxybenzaldehyde action of on plieuanthraquinone 152. Orthomethoxybenzenylamidophenan-thole 155. Oxides action of on salts. Part IV. Potassic chlorate and fzrric oxide, 18. Oxypropyltoluidine and its derivatives, 387. Oxypropyltrimethplammonium hydrate, distillation of 389. P. Parabenzoylphenol 227. Paracresol nitro- 426. Pamcresyl ether 10. Parahydroxybenzddehyde action of on benzil in presence of ammonia 326. - action of on phenanthraquinone, 150. Paraliydroxylopliine and its acetyl deri-vative 327 328. Paroxybenzoplienone 227. Pennant grits composition of in con-tact with and at a distance from car-bonaceous deposits 79. Pentathionic acid 162. - _ _ effect of neutralising the dilute alcoholic solution with barium carbonate 164.- ~- solutions effect of excess or otherwise of solutions of alkalis on, 165. Peppermint cainphor (menthol) and some of its derivatives 49. Phenanthraquinone action of acetone on both alone and in presence of ammonia 270. - action of aldehydes on in pre-sence of ammonia 146. - __ action of ethyl acetoacetate on, 276. Phenanthrene ncetonquin of 276. - acetonquiiiiinide of 2’16. Phenol orthobrom-a-dinitro- 225. Phenylamidodiphenylmethane 199. Pheny lbenzoyl- benzoylamide 133. 21\1 446 INDEX OF SUBJECTS. Phenyldibenzoylamide 133. Phenyl ether 6. - ketone 8. Philippium and spectroscopic examina-tion of 277 282. Phosphates dissolved by ammonium citrate solutions composition of, 316.- retrograde estimation of 306. Photographs of the ultra-violet spectra of elementary bodies 84. Picoline constitution of 47. Pin Incas found on mummy a t Arica, Peru analysis of 145. Polarisation rotary by chemical sub-stances under magnetic influence, 330. Potassio-aluminic alum precipitation of, by sodium carbonate 342 343. Pobassio-chromic alum precipitation of, by sodium carbonate 343 344. Potassium bromobenzFlphenolsulpho-nate 35. - chlorate action of ferric oxide on, 18. - action of manganese dioxide on 23. - hydrate action of on a solution of potassium tetra- and penta-thionate, 303 304. - nitrobenzylpbenolsulphonate 35. - tetra- and penta-thionate action of potassium-amalgam sulphuretted hydrogen and potassic hydroxide on, 300.Potassium-amdgam action of on potas-sium tetra- and penta-thionate 300, 301. Pyridine constitution of 45. a- and 6-Pyridine-dicarboxylic acids, spectra of 46. Quinoline action of antimony penta-- constitution of 47. - - molecule additional evidence that this? base belongs to the aromatic series of organic substances 412. Quinones application of the aldehyde and ammonia reaction in determining the constitution of 157. chloride on 413. R. Reactions of dihydroxytoluenes 426. Research fund 244. Resin products of the dry distillation Resin spirit some constituents of 167. Rhabdophane a new British mineral, analysis and constitution of 210, 214. Rotary polarisation by chemical sub-stances under magnetic influence, 330. of 167.S. Salicylaldehyde action of on phenan-Salicylic acid para-iodo- conversion of, Salicylic acids iodo- 398 400. Salts action of oxides on. Part IT. Potassic chlorate and ferric oxide, 18. I- compound crystallisation from supersaturated solutions of 379. Samarskite study of some of the earth-metals contained in 277. Shekel Hebrew analysis of 144. Sickle ancient Egyptian analysis of, 140. Silver nitrate action of chlorosulphonic acid on 297. - action of sulphuryl chloride on 297. - action of thiophosphoryl chloride on 297. Soil influence of heat and moisture in reducing the nitrates present in, 354. thraquinone 146. into dihydroxybenzoic acid 404. - extract analysis of 356. Soils estimation of nitric acid in 351. Spear-heads copper from Cyprus ana-Spectrum of an yttrium salt obtained Sucsinic anhydride chloro- 269.Sulphonic anhydride nitro- 297 298. Sulphur oxychlorides action of on silver Sulphuretted hydrogen action of on lysis of 143. from rhabdophane 215. nitrate 297. potassium tetrathionate 302. T. Tannin Hatchett’s artificial 109. Tannins origin of 106. Terbium spectrum of 283. Thiophosphoryl chloride action of on Toluene metadibromo- preparation of silver nitrate 297. orcinol from 421 INDEX OF Toluene metadinitro- preparation of orcinol from 415. Toluenedisulphonic acid amido- position of the sulpho-group in 421. Toluenemetadisulphonic acid prepara-tion of orcinol from 421. Toluenemetasdphonic acid metabromo-, preparation of orcinol from 420. Toluidine nitro- preparation of 416. Triphenylmethane derivat,ives of 188. U. Ultra-violet spectra of elementary bodies, Urea transformation of into cyanamide, 84. 262. W. Ware Bidrai India analyses of 139. SUBJECTS. 447 Water Buxton thermal chemical exa-Wollastonite action of sodium hydroxide mination of 117. and carbonate on 169 161. Y, Yttrium salt obtained from rhabdophane, spectrum of 215. 2. Zinc behaviour of as reducing agent with acidulated solutions of ferric salts 287 288. HARRISON AND SONS PBINTEBS IN OBDINABT TO HER YAJESTT ST. HARTIN% LANP

ISSN:0368-1645    

DOI:10.1039/CT8824100442

出版商:RSC    

年代:1882

数据来源: RSC

摘要:

INDEX OF SUBJECTS. ERRATA IN VOL. XLI. Page Line 317 16 for209 1881 read 31 284. !!!} Hesd-linee for Popplewell vead Bloxsm. 386 380 24 , (RH,Cl)z 2 2 !NH,Br),. 447 HARRISON AND SONS PBINTEBS IN OBDINABT TO HER YAJESTT ST. HARTIN% LANP

ISSN:0368-1645    

DOI:10.1039/CT8824100447

出版商:RSC    

年代:1882

数据来源: RSC