摘要:

154 JAPP AND LANDER : REDUCTION OF DESYLEKEACETIC ACID, XI.-Reductioii of Desyleneacetic Acid, and the Constitu- tion of Zinids Pyl-oamaric A c i d . By FRANCIS ROBERT JAPP, F.R.S., and GEORGE DRUCE LANDER, B.Sc. THE ease with which desyleneacetic acid may be prepared by the oxidation of anhydracetonebenzil with sodium hypobromite led us to study some of the reactions of this munication, we give an account of agents. When dissolved in acetic acid and acetic acid is converted into Victor m i d , compound. I n the present com- its behaviour towards reducing treated with zinc dust, desylene- Meyer and Oelkers’s desykacetic C,H,* YH* CH,* COOH C,H,* CO By the limited action of sodium amalgam on an aqueous solution of sodium desyleneacetate, the same product is obtained, Excess of sodium amalgam, however, carries the reduction further, and By-diphenyl-y- C,H,*$?H* OH,* COOH IL?/d9*oxybutylrr.ic acid, , is formed, which, when C,H,*CH* OH liberated from its salts, speedily changes into the Zactone C,H5*~H*~H2 C,H,*CH CO ‘4 0 By boiling desyleneacetic acid for a few minutes with fuming rydriodic acid, it yields a mixture of desylacetic acid and dip?mayZcs.o- Polactone, behaving, in this respect, like desylenemalonic acid, except That, in the case of the latter compound, the reaction is attended with elimination of carbon dioxide (Japp and Davidson, Trans., 1895, 67, 136).By boiling desyleneacetic acid for some hours with hydriodic acid and amorphous phosphorus, the reaction is carried further, and both the primary products of the reduction are converted into Py- diphenylbutyric acid, C,H,* CH,* CH(C,H,)* CH,* COOH.Comparison of this substance with a specimen of pyroamaric mid* showed that the two were identical. Pyroamaric acid was first obtained by Zinin (Jcchresbericht, 1877, 813) by fusing amaric acid with caustic potash, and was regarded by him as an ethylbenzylbenzoic acid. Klingemann * We were indebted for this specimen to Dr. Felix Klingemann, who prepared it by the fusion of B-dehydroamaric acid with caustic potash-a reaction discovered by him.AND THE CONSTITUTION OF ZININ'S PPROAJIARIC ACID. 155 (A~n?~cder~, 1893, 275, 81) first suggested that it might be a diphenyl- butyric acid, and showed that it was not identical with a-diphenylbutyric acid, Incidentally, it was observed that when desyleneacetic acid is boiled with aqueous caustic potash it is hydrolysed, yielding deoxybenzoin.Desylenemalonic acid is stable under these conditions, EXPERIMENTAL. Recluction of Desyleilzeacetic Acid with Zinc Dust cmd Acetic Acid.- Five grams of desyleneacetic acid were dissolved in glacial acetic acid, excess of zinc dust was added, and the whole was boiled for about an hour, after which the liquid was filtered and poured into water. The Precipitated substance was recrystallised twice from benzene, from which it was deposited in the characteristic octahedra of desylacetic acid melting a t 160". It was stable towards permanganate in the cold, showing that it was free from desyleneacetic acid. Found : C = 75.57 ; H = 5.65. Calculated for C,,H,,O, : C = 75-59 ; H = 5.51 per cent.Reduction of Desyleneticetic Acid with Soditcna Arncdgcm.--Five grams of desyleneacetic acid were dissolved in sodium carbonate and treated with 180 grams of 2.5 per cent. sodium amalgam, passing a current of carbon dioxide through the liquid during the entire process. On acidifying t h e solution, a gummy substance mas precipitated, from which, by crystallisation from benzene, three substances were isolated : (1) unchanged desyleneacetic acid ; (2) desylacetic acid, which formed colourless octahedra melting a t 161' ; and (3) a substance crystallising in needles melting at 112-113°. The two former were deposited together and could he separated mechanically, the brownish colour of the crystals of impure desyleneacetic acid allowing of their being readily distinguished from the colourless octahedra of desylacetic acid.The third substance separated from the benzene mother liquor. The experiment was repeated, using 400 grams of 2.5 per cent. sodium amalgam to 5 grams of desyleneacetic acid. This time, only the compound melting a t 1 1 2 - - 1 1 3 O was obtained. It was purified by recrystallisation from a mixture of benzene and light petroleum. On analysis, it gave figures agreeing with the formula C,,H,,O,. 0.1284 gave 0.3799 CO, and 0.0685 H,O. 0.1214 ,, 0,3586 CO, ,, 0.0644 H,O. C,,H,,O, requires C = 80.67 ; H This compound is, as already mentioned, C = 80.69; H = 5.92. C = 80.54; H = 5.89. = 5.88 per cent.156 JAPP AKD LANDER : REDUCTION OF DESYLENEACETIC ACID. derived from py-diphenyl-y-hydroxybutyric acid.The acid, freshly precipitated from solutions of its salts, redissolves in sodium carbonate, but the crystallised lactone is apparently quite insoluble in sodium carbonate, and dissolves only with difficulty in a warm solution of sodium hydroxide. Keduction of Desylenecccetic Acid with Puming HydiGodic A c i d - Three grams of desyleneacetic acid were boiled with the strongest fuming hydriodic acid (sp. gr. 2.0) for 5 minutes. The product of the action was washed with water, dissolved in ether., and freed from iodine by treatment with sulphurous acid. From the ethereal solution, sodium carbonate extracted an acid which crystallised from benzene in octahedra melting a t 160°, and was in all respects indistinguishable from desylacetic acid.The non-acid substance, which remained after expelling the ether, crystallised from benzene in tufts of needles melting at 15 1 -5' and was identical with Klingemann's diphenylcroto- lactone (Annalen, 1892, 269, 134; d. also Japp and Davidson, Zoc. Reduction of Desylenecccetic Acid with I€ydyiodic Acid and Amorphous Pl~osp7~orus.--Five grams of desyleneacetic acid were boiled with 75 grams of hydriodic acid (sp. gr. 1.7) and 7 grams of amorphous phosphorus for 4 hours. The organic substance was extracted with ether, and, after the usual treatment of the ethereal solution with sulphurous acid, the organic acid was extracted twice with a solution of sodium carbonate. A small quantity of a neutral oil, which was not further examined, remained dissolved in the ether.Two organic acids were obtained. One of these, which was precipitated in a crystalline form from the first sodium carbonate extract, was sparingly soluble in ether and melted at 228-230'; the quantity was too small for further investigation. The second extract gave an acid which was oily when first precipitated, but speedily solidified. It was obtained in large crystals by spontaneous evaporation of its ethereal solution, and these were further purified by recrystallisation from a mixture of ethylic acetate and light petroleum, which deposited the compound in oblique plates melting constantly a t 96--97'. Analysis gave figures agreeing with the expected formula of py-diphenylbutyric acid, cit.). C6H5' CH2* CH(C6H,) CH,* COOH. 0-1457 gave 0.4270 CO, and 0.0877 H,O.C= 79.93 ; H= 6.68. C16H1602 requires C = 80.00 ; H = 6.66 per cent. A comparison of this Substance with a specimen of Zinin's pyroamaric acid (v. supra) showed that the two substances were identical. Both crystallised from a mixture of ethylic acetate and light petroleum in the same oblique plates, and a simultaneous deter-BENTLEP AND PERKIN: REDUCTION OF XYLIC ACID, ETC. 157 mination of the melting points, made in the same bath, gave 96-97O in both cases. As already pointed out, the hitherto unknown constitution of pyroamaric acid is thus ascertained. ActioN of Aqueous Caustic PotasfL om Deayleneacetic Acid.--In an experiment made with a different object, it was noticed that, when desyleneacetic acid was boiled with aqueous caustic potash, an oil, smelling like a benzenoid ketone, separated.Two grams of the acid mere therefore boiled with excess of strong caustic potash for 4--5 hours. After extracting the oily substance with ether, the alkaline solution was acidified, but gave only a slight turbidity, showing that practically no desyleneacetic acid mas left. The substance which remained on evaporating the ether solidified to a crystalline mass. It was purified by recrystallisation, first from benzene, and afterwards twice from alcohol, and was thus obtained in colourless leaflets, melting a t 59'. Analysis gave figures agreeing with the formula C,,H,,O. Found : C = 85-38 ; H = 6.28. This is the formula of deoxybenzoin, which melts at 60°, and t,he other physical properties are also those of that compound. A cold, supersaturated alcoholic solution of the compound a t once began to crystallise on adding a crystal of deoxybenzoin. We did not attempt to isolate the other product of the hydrolysis. As Japp and Davidson (Trans., 1895,67, 135), in preparing desylene- malonic acid, heated it for a long time with caustic soda, i t was of interest to know whether it was in any way decomposed by this treat- ment. We therefore heated desylenemalonic acid for many hours, both with caustic potash and with caustic soda, but no separation of neutral substance occurred, and the acid was recovered unchanged. Calculated : C = 85-71 ; H = 6.12 per cent. CHEMICAL DEPARTMENT, UNIVERSITY OF ABERDEEN.

ISSN:0368-1645    

DOI:10.1039/CT8977100154

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

BENTLEP AND PERKIN: REDUCTION OF XYLIC ACID, ETC. 157 XIL-The reductiou of Xylic Acid, of Paraxylic Acid and of Methylterephth,aZic Acid, and the preparci- tion of Metlzylterephthulic Acid crnd of Methyl- isophthulic Acid. By WILLIAM HENRY BENTLEY and WILLIAM HENRY PERKIN, Jun. KACHLER (Annalelz, 1813, 169, 183) first showed that sulphocamphylic acid, U,H,,SO',, is decomposed when fused with potash with formation of a monobasic acid, C,H1,O,, melting at 148'. C9Hl,S05 = G,H,,O, + SO, + H,O,158 BENTLEY AND PERKIN : REDUCTION OF XYLIC, PARAXYLIC, and subsequently Damsky (Bey., 1887, 20, 2965) obtained, by the same reaction, a second acidof this formula melting a t 99O. This action of fused soda or potash on sulphocamphylic acid has been made the subject of an extended investigation by one of us (compare Proceedings, 1893, 109 ; 1895, 23 ; 1896, lS9), in the hope of discovering the con- stitution of the two isomeric acids C,H,,O,, and of thus obtaining evidence as to the constitution of sulphocamphylic acid and, indirectly, also, of that of camphoric acid itself.During the course of the examination of these two acids, which mere named a-camphylic acid (m. p. 14S0) and P-camphylic acid (m. p. about lo$"), some facts came to light which seemed to point t o the conclusion that these substances might be closely allied to xyZic ucid, I, or pa?*ccz~~~c COOH CH, acid, 11, and this seemed all the more probable when it was remembered that sulphocamphylic acid itself could be converted into derivatives of these acids by two widely different processes.When sulphocamphylic acid is oxidised with potassium permanganate (Proc., 1893, log), it yields a dibasic acid of the formula C,,H,,07, which, by the action of concentrated sulphuric acid, is converted into a hydroxyxylic acid of the probable coiistitution COOH 0 H o H 3 \/ CH3 Again, Koenigs and Meyer (Be?*., 1894, 2'7, isokc~u~onoZic acid, CgH1402, which is formed 3465) found that when by the action of heat on sulphocamphylic acid (CgH,,SO,,H,O = CgH,,O, + H,SO,) is oxidised with permanganate it yields isolauronic acid, CgH,,03, and that the latter acid, when warmed on the water bath with sulphuric acid, is converted into paraxylic acid, C=, (+3 \/ COOH. As these xylic and paraxylic acids may be obtained in this way from sulphocamphylic acid, it seemed possible that the two camphylic acids, C,H120,.might be dihydro-derivative? of these acids and that the acids,AND METHYLTEREPHTHALIC ACIDS, ETC. 159 C9HI4O2, which may be obtained from them by reduction with sodium amalgam, were the corresponding tetrahydro-acids. I n order to deter- mine whether this view was correct, we decided to investigate the action of reducing agents on the xylic acids, and beg t o lay an account, of the results of our experiments before the Society. The xylic and paraxylic acids required for this research were first prepared by the method described by Fittig and Laubinger (Annulen, 1869, 151, 269), which consists in oxidising pseudocumene by means of dilute nitric acid. The product of this reaction contains, besides the two xylic acids, methylisophthalic acid, UH,* C,H,(COOH), [CH, : COOH : COOH = 1 : 2 : 41, rnethylterephthalic acid, and also nitro-derivatives of these acids and of pseudocumene, and as the separation of these various substances by the method given by Fittig and Laubinger is exceedingly tedious, many experiments were made, in the hope of being able to devise a more simple method for preparing these acids. I n the first place, pseudocumene was brominated a t 150' and the bromo-derivative C,H,(CH,),* CH,Br converted into the ethylic ether C,H,(CH,),* CH,* OC,H, by treatment with sodium ethoxide, this was then oxidised in the way recommended by Kipping (Trans., lSS8, 53, 45) for preparing isophthalic acid, but the results were not, satisfactory, and as the irritating vapours of the bromopseudocumene made the process very objectionable, it was abandoned.The next method of preparing paraxylic acid which was investigated was that devised by Armstrong and Kipping (Trans., 1893, 63, 75), who showed that camphor, when digested with sulphuric acid yields acetyl-2-ortho-xylene [Me, : Ac = 1 : 2 : 41, and that this, on oxidation with nitric acid, yields pure paraxylic acid. We, however, soon found that this method is not suitable for the preparation of large quantities of the acid, owing to the difficulty of obtaining acetyl-2-ortho-xylene in a sufficiently pure condition for giving good results on oxidation. Ultimately, we found it necessary to return to the oxidation of pseudocumene with nitric acid, but it very soon became evident that some improvement must be made in the method of separating the products of oxidation, in order to obtain sufficient material for this investigation.The chief objection to Fittig and Laubinger's process is the distilla- tion in steam which they recommend as a means of partially separating the oxidation products, because the xylic acids volatilise with diffi- culty in steam, and therefore, when working with large quantities of160 BEKTLEY AND PERKIN : REDUCTION OF XYLIC, PARAXYLIC, material, this operation takes a considerable length of time and involves the evaporation of large quantities of liquid ; even then, the products obtained are in a very impure condition. Several experiments were made with the object of avoiding this steam distillation, and ultimately the following method was devised, which was found t o work well.After oxidising the pseudocumene in the way recommended by Fittig and Laubinger, the semi-solid product is dissolved in an excess of sodium carbonate, and the nitro-compounds and unaltered pseudocumene removed by extraction with ether. The alkaline solution is then acidified, and the precipitated acids, collected by means of the pump, are dried and con- verted into their methylic salts, which are then fractionated under reduced pressure. I n this way, two principal fractions are obtained, namely, one boiling a t 140-160° (40 mm.), which contains the methylic salts of the two xylic acids, and the other boiling at 180-200" (40 mm.), consist- ing principally of the mixed methylic salts of methylisophthalic acid and methylterephthalic acids ; the former fraction always remained liquid, whilst the latter quickly solidified. The fraction 140-160° (40 mm.) is hydrolysed, the mixed xylic acids thus obtained are converted into their calcium salts, and the latter are then separated by repeated recrystallisation from water ; the separa- tion of methylisophthalic acid and methylterephthalic acid is described later on in this paper. I n our first experiments on the reduction of the xylic acids, the action of sodium amalgam on paraxylic acid was investigated, but even when the alkaline solution of the acid was boiled with sodium amalgam in the way recommended by Aschan (Afinalen, 1892, 271, 234) very little action took place, and nearly all the acid was recovered unchanged.This method was then abandoned, and the reduction of xylic acid and paraxylic acid with sodium and isoamylic alcohol was next tried and found to give satisfactory results, the acids being converted in this way always into a mixture of the tetrahydro- and hexahydro-derivatives ; i t was not found possible to reduce the whole of the acid to the hexa- hydro-derivative, although many experiments were made with this object under very varying conditions, as even after the acids had been subjected repeatedly to the action of the reducing agent, a considerable quantity of tetrahydro-acid was always present. As a rule, after several successive treatments with sodium and isoamylic alcohol, the reduced acid, in each case, was found to contain 50-60 per cent.of the hexahydro- and 40-50 per cent. of the tetrahydro-derivative. On fractionation, the mixed acids distil in each case a t about 160-170O (40 mm.), and the purified product, when leftASD METHYLTEREPHTHALIC ACIDS, ETC. 161 for some time in a freezing mixture, deposits small quantities of solid acid which, on examination, proved to be the tetrahydro-acid. Fetruhyd~~o~u~~ccx~Z~c acid, C,H,,O,, melts a t 83O, and unites with bromine, forming dibromhexahydroparaxylic acid, C9H14Br202, which melts a t 124'. Feti*ahyd~o-xgZic acid, C9HI4O2, melts at I 04O, and also a,bsorbs bromine. The oily reduced acid from both reductions, and from which no more crystals could be obtained, still contains a large proportion of the tetrahydro-cornpound, and attempts were made to convert the whole of it into the hexahydro-acid by repeated reduction with sodium and isoamylic alcohol, and by adding on hydrogen bromide and heating the bromide with zinc dust and acetic acid, but without success.As we were unable to reduce the acids completely to the hexa- hydro-derivatives, we decided to separate the hexahydro-acid from the accompanying tetrahydro-acid, and for this purpose we employed two methods, namely, (1) oxidation of the mixture with potassium perman- ganate, by which means the tehahydro-acids are converted into syrupy hydroxy-compounds, leaving the hexahydro-acids unchanged ; (2) the conversion of the mixed acids into their anilides, by treating the acid chlorides with aniline, and subsequently separating the hexahydro- anilide from the product by fractional crystallisation.The oxidation with permanganate mas performed in very dilute the unaltered hexahydro-acids being subsequently non-volatile hydroxy-acids by distillation in steam. H COOH and cold solutions, separated ifroni the /\ CH, H as a colourless liquid, which on standing solidifies to colonrless crystals melting a t 76-78". H CH, /\ H COOH and does not show any signs of crystallisation, even on long standing. The syrupy hydroxy-acids obtained during the above oxidations could not be obtained in a crystalline condition, and as, on further oxidation VOL. LXXI. M162 BENTLEP AND PERKIN : REDUCTION OF XYLIC, PARAXYLIC, with chromic acid, they did not yield any solid products, their examina- tion was not continued further. It will be seen that, by the above method of separating the hexahydro- acids, the tetrahydro-acids are always destroyed, and as it was especially important t o carefully study these tetrahydro-acids and their derivatives the separation by means of the anilides was tried, but with little success.The acids were converted into the anilides in each case, but on subse- quent crystallisation only the anilides of the hexahydro-acids could be isolated in any quantity in the pure state. This want of success was apparently due t o the presence of a considerable amount of resinous matter, produced, probably, by the action of phosphorus trichloride on the unsaturated tetrahydro-acids ; in both cases, however, besides the anilides of the hexahydro-acids, small amounts of other anilides were isolated, but in quantities too small for further identification.The anilide of hexahydroparaxylic acid melts at 1 1 5 O , whilst that of hexahy- dro-xylic acid melts a t 188'; these anilides are best hydrolysed by heating them with a solution of hydrogen chloride in acetic acid, the yield of acid obtained in this way being quantitative. Prepared by this process, hexahydroparaxylic acid still remained liquid, even when cooled to - 10' ; hexahydro-xylic acid, however, quickly solidified, forming colourless plates which melted at 76-78' : both acids possess a peculiar, pungent smell, somewhat resembling that of the higher fatty acids. Owing t o the difficulty of obtaining the pure tetrahydro-acids in any quantity, experiments were next instituted with the object of preparing these acids from the hexahydro-acids, and in order t o do this the hexahydro-acids were brominated, and the monobromo-derivatives, after conversion into the ethereal salts, hydrolysed, in the first place, with alcoholic potash.It was thought that this method might give very interesting results, as very probably the tetrahydro-acids obtained would be isomeric, and not identical with the tetrahydro-acids prepared by the direct reduction of the xylic acids. However, although the experiments were very much varied, instead of the pure tetrahydro- acids, the products in each case mere semi-solid, uninviting-looking masses, which evidently contained several substances, and as the quantities at our disposal were small, it was impossible t o effect a separation of the various constituents.Apparently, the tetrahydro-acids first formed by this reaction are in part oxidised during the treatment with potash, because, in our experi- ments with hexahydroparaxylic acid, an acid was obtained in this way which had the approximate constitution of a dihydroparaxylic acid. In the case of hexahydro-xylic acid, the bromination did not take place very satisfactorily, as the product, after treatment with alcohol,AXD METHYLTEREPHTHALIC ACIDS, ETC. 163 appeared to contain, besides eth-ylic bromohexahydro-xylate, traces of the ethylic salt of a bromo-xylic acid. The formation of the latter is probably due to the bromine converting part of the hexahydro-acid into xylic acid, which then, by the further action of the bromine, was converted into bromoxylic acid.When the ethereal salts of the bromohexahydro- xylic acids are digested with diethylaniline, they are converted fairly quantitatively into the ethylic salts of the corresponding tetrahydro- acids, which are colourless, sweet-smelling oils, distilling without decomposition at about 1 5 5 O (60 mm.), but these ethereal salts on hydrolysis do not yield the pure tetrahydro-acids ; unfortunately, owing to the nature of the product and to the small quantity of material at our disposal, we were unable to investigate this matter further. Although we have had so much difficulty in obtaining the tetrahy- droderivatives of xylic acid and paraxylic acid in any quantity, we were, nevertheless, able to prepare sufficient of each acid to prove conclusively that these tetrahydro-acids are not identical with the acids which have been obtained by the reduction of the a- and P-camphylic acids.This does not, of course, prove that the a- and P-camphylic acids are not derivatives of the xylic acids, because there are many theoretically possible isomeric tetrahydro-xylic acids which are not described in this paper. As, however, the further study of tho camphylic acids has made it appear unlikely that these acids are closely connected with the xylic acids, we have decided, in the meantime, t o discontinue these experiments, and to publish the results which have so far been obtained. Sepmtion of MetlqZisopAthalic Acid f y o m Nethyltes.ephthalic hi Preparation of Teetralqdrometh ylterephthalic Acid. During the separation of the acids formed by the oxidation of pseudocumene by means of their methylic salts, as explained on page 160, a considerable quantity of a fraction boiling at 180-200' (40 mm.) was obtained, and on investigating this product we were ultimately able to show that it consisted of the methylic salts of methylisophthalic acid, I, and methylterephthalic acid, 11, COOH but no methylphthalic acid could be isolated from the mixture.The above fraction, on cooling, solidified to a crystalline mass, melting roughly a t 40--50°, and by subjecting it to a series of fractional crystallisations, we ultimately succeeded in separating i t into two portions, A, melting at 73-74O, and B, at about 58-60'. Each of these, on analysis, gave M 2164 BENTLEY AND PERKIN : REDUCTION OF XYLIC, PARAXYLIC, numbers agreeing with the formula CH,*C,H,(COOCH,),, and as further recrystallisation did not appear to affect the melting points, we concluded that they were the pure methylic salts of two distinct dibasic acids of the formula CH,* C,H,(COOH),. On hydrolysis with potash, the methylic salt A (m.p. 7 3 - 7 4 O ) yielded an acid melting at 325-330°,* which did not form an anhydride and which, in its properties, agreed so closely with methylisophthalic acid,? that we concluded at first that it was identical with this acid, and that the methylic salt A was methylic methylisophthalate. The methylic salt B (m. p. 58-60'), on hydrolysis, yielded an acid, CH,*C,H,(COOH),, which melted a t 293-295' and gave no anhydride, and consequently we supposed it to be .IrLetl7LyZte~~eio~t~~a~~c cmk?, especially as Fittig and Laubinger (Annalen, 1869, 151, 276) had described methylterephthalic acid as melting at 280-283", and, after sublimation, at 291'. On treating the supposed methylisophthalic and methyltereph thalic acids with sodium amalgam, it was observed that the acid (m.p. 325- 330") corresponding with the methylic salt A (m. p. 73-74°) was readily and completely reduced to a tetrahydro-acid, whereas the acid (m. p. 293-295') obtained from the methylic salt B (m. p. 58-60°) was only partially reduced, yielding a tetrahydro-acid which was evidently identical with that obtained from the acid of higher melting point. The acid which had not been reduced during this treatment was carefully purified, and found to have the formula CH,* C,H,(COOH), ; it melted now at 320-33,0°, and yielded a methylic salt which fused sharply a t SO', and which may be called C.This acid is not in the least degree affected by boiling with sodium amalgam, and, as it does not give an anhydride, it must obviously be either methylisophthalic acid or methylterephthalic acid, and the acid which Fittig and Laubinger described as methylterephthalic acid must be a mixture of this acid with methylisophthalic acid, one of which is reduced by sodium amalgam, leaving the other entirely unattacked. I n order to determine which of these two acids is reducible by sodium amalgam, we made a number of experiments, with the object of IC With regard to the melting point of methylisophthalic acid, compare Clam, J.gr, Chem., 1890, [ 2 ] , 42, 510. j. Methylisophthalic acid has been prepared by Jacobsen (Ew., 1881, 14, 2112) by the oxidation 1 : 4-dimethylbenzoic acid with permangsnate ; by Claus (Ber., 1886, 19, 233 ; J. pr. Chem., 1890, [ 2 ] , 42, 509) by the oxidation of methyl cymyl ketone, CH,*CO.C,H,(CH,)'C,H,, and of the acid CH,*C,H,(C,H,)~CO~COOH [CH,: CO : C,H,= 1 : 3 : 51, and by Hjelt and Gadd (Ber., 1886, 19, 868) by the oxidation of pscudocumenyl alcohol, CH3.C6H3(CH,*OH),.AND METHYLTEREPHTHALIC ACIDS, ETC. 165 deciding which of the two acids formed a methylic salt melting a t 73-74", and which a mcthylic sa,lt melting a t 80'. By oxidising xylic acid and paraxylic acid with potassium perman- ganate, we obtained, in both cases, an acid melting a t 325-330" which did not give an anhydride, and which must, therefore, be metlqyZtes*eph- thulic acid.coo H CH, COOH f \ C H 3 and f j c ~ 3 give \j \/ COOH \/ COOH CH3 As the methylic salt of this acid melts a t 73-74', it follows that the methylic salt A is methyZic terephthdute. When iso-xylic acid is oxidised with permanganate, it yields a dibasic acid which does not form an anhydride, and which must, therefore, be meth$isopI~thalic acid. CH3 CH3 OCooH- ( Y O O H gives COOH \/ CH, This acid melts a t 320-330', and yields a methylic salt melting at SO". On treatment with sodium amalgam at 1 O O O , met'hylisophthalic acid remains unchanged, whereas, on the other hand, mebhylterephthalic acid, under the same conditions, is apparently completely reduced to a tetrahydro-derivative.T~trahydrornethylterep~~t~alic acid, CH,. C,H7(COOH),, is moderately easily soluble in water, and melts a t 240-245'; it yields a dimethylic salt, CH,* C,H7(COOCH,),, which is a colourless oil boiling a t 165-170' (20 mm.). Although the solution of the acid in sodium carbonate very quickly decolourisea permanganate, pet the free acid does not appear to absorb bromine or hydrogen bromide a t all readily. When heated with a saturated solution of hydrogen bromide in glacial acetic acid a t 100' in a sealed tube, it yields a black, oily maPs containing bromine, but which could not be purified. Experiments on the reduction of this crude hydrobromide with zinc dust and acetic acid were instituted, but we have so far not been able to isolate the hexahydromethyltere- phthalic acid, which should be formed in this way.The methylic salt C is, theref ore, meth?jlic isophthabte. EXPERIMENTAL. Oxidution of Pseudocumene.-For this purpose, as stated in the introduction, we employed a modification of the process devised by166 BENTLEY AND PERKIN : REDUCTION OF XYLIC, PARAXYLIC, Fittig and Laubinger (Ann., 1869, 151, 269), their method of separat- ing the products by distilling in a current of steam being very trouble- some and inconvenient when working with large quantities. As the result of numerous experiments, we ultimately adopted the following method in preparing the acids required for this research. Pseudocumene (250 grams), mixed with dilute nitric acid (700 grams of acid, sp. gr. 3.4, diluted with 24 volumes of water), is heated to boiling for 18 hours in a large flask connected with a reflux condenser.The cold liquid is then largely diluted, the semi-eoli d precipitate collected with the aid of the pump, washed well with water, and dissolved in a solution of sodium carbonate. The nitro-compounds and un- altered pseudocumene which remain undissolved are removed by agitation with ether, and the aqueous solution is heated to boiling and acidified with hydrochloric acid. The precipitate thus obtained is col- lected, washed with water, and after being pressed on porous plates to remove oily matter, is dried a t 100'. The mixed acids are then con- verted into their methylic salts by saturating their solution in methylic alcohol with dry hydrogen chloride ; the mixed methylic salts, after being precipitated with water and extracted with ether, &c., in the usual way, are fractionated several times under a pressure of 40 mm.Of the two fractions obtained, the larger distilling at 140-155', consists princi- pally of the methylic salts of xylic and paraxylic acids; whilst the smaller fraction, which distils at 1 80-200°, and quickly solidifies on cooling, contains the methylic salts of methylterephthalic and methylisophthalic acids. A third, but very small, fraction, boiling at 250-270', was also obtained; this was a very viscid liquid, which possibly contained the methylic salts of trimellitic acid, but it was not further investigated. Xepwation of the Xylic and Pamxylic Acids.--In order t o isolate these acids, the fraction (135 grams) containing their methylic salts is hydrolysed by boiling with a solution of alcoholic potash (80 grams) in a reflux apparatus for 3 hours, the alcohol distilled off, the residue dissolved in water, and the solution evaporated to a moderately small bulk.While still hot, t.his is acidified with hydrochloric acid, and the precipitate, which is somewhat oily a t first, but on cooling becomes quite hard, is first roughly freed from oily matter and other impurities by crystallisation from acetic acid; if his is not done, the subsequent separation of the isomerides by means of their calcium salts becomes a very difficult matter. The mixture of acids which separates from the hot, concentrated solution in glacial acetic acid in the form of a crystalline precipitate melting roughly at 1 0 5 O , is collected, washed first with acetic acid and then with water, and dis- solved in a slight excess of hot sodium carbonate solution; on mixingAND METHYLTEREPHTHALIC ACIDS, ETC.167 this with a strong, hot solution of rather more than the calculated quantity of calcium chloride, and cooling, a mixture of the calcium salts of the two xylic acids separates almost completely; the salts, after being collected and washed with a little water, are crystallised from a considerable quantity of boiling water. If the acids are puri- fied as described above, the f i s t crystallisation yields the almost pure calcium salt of paraxylic acid, this being the least soluble. It is, however, a matter of considerable difficulty to separate the calcium salts contained in the mother liquor, but this may be effected in the following manner.When the solutions of the calcium salts have yielded as much pure calcium paraxylate as possible, the mother liquors are acidified, and the precipitated acids collected and crystallised from acetic acid. A considerable quantity of nearly pure xylic acid separates first in beautiful, long needles. After this has been collected, and the acetic acid removed from the mother liquors by distillation, the acids are again converted into the calcium salts and crystallised from water. By a repetition of this process, it is possible to separate the whole of the material into calcium paraxylate and xylic acid. The paraxylic acid obtained from the pure calcium salts by precipitation with hydrochloric acid was recrystallised from acetic aci-d.Xylic acid, U,H,(CH,),* COOH [CH, : CH, : COOH = 1 : 3 : 41, crystallises from acetic acid in beautiful, long, prismatic needles melting at 126'. Paraxylic acid, [CH, : OH, : COOH = 1 : 2 : 41, crystnllises in short needles melting a t 163'. As stated in the introduction, this acid is one of the products of the reduction of paraxylic acid by means of sodium and isoamylic alcohol. Pure paraxylic acid (30 grams) is dissolved in isoamylic alcohol (1% litres) contained in a large, round-bottomed flask attached to a long reflux condenser. The liquid is heated to the boiling point, and then sodium (10 grams) is dropped in ; a violent action takes place, and as soon as this has subsided more sodium (20.grams) is added. When the sodium has all dissolved (the mixture being heated if necessary), the contents of the flask are allowed to cool, diluted with water and acidifled with hydrochloric acid; the liquid then separates into two layers, the upper of which is isoamylic alcohol containing the organic acid in solution. The lower layer, consisting of sodium chloride soln- tion and some hydrochloric acid, is shaken with pure isoamylic alcohol, in order to extract any traces of the organic acid which it may contain, and the whole of the isoamylic alcohol solution is dehydrated by dis- tillation until the temperature of the vapour rises to 120'. It is then treated with sodium (30 grams) exactly as before, and the process of168 BENTLEY AND PEHKIN : REDUCTION OF XTLIC, PARAXTLIC, extraction again repeated.After thrice treating with sodium, the product is diluted with a large quantity of water, the upper layer of isoamylic alcohol is distilled almost to dryness, and the residue dissolved in water and mixed with the aqueous layer. I f this is not done, there is a very considerable loss of product, as the isoamylic alcohol retains a quantity of the sodium salts of the reduced acids, even after it has been repeatedly washed with water, The aqueous solution, after being boiled until free from isoamylic alcohol, is acidified and extracted with pure ether, the ethereal solution is dried over calcium chloride, the ether distilled off, and the oily residue fractionated under diminished pressure. Nearly the whole distils at about 160-170° under a pressure of 40 mm.When, however, about three-quarters of the acid has distilled, the receiver is changed and the last portion collected separately ; the latter, when exposed to the cold for about a week, deposits crystals of tetrahydro- paraxylic acid, whereas the first fraction if similarly treated yields very few crystals. The crystals were collected with the aid of the pump, pressed on a porous plate, and recrystallised several times from light petroleum (b. p. 60-80"). I. 0.1020 gave 0.2618 CO, and 0.0830 H,O. C = 70.00 ; H = 9.04. 11. 0.1096 ,, 0.2820 CO, ,, 0*0900 H,O. C = 70.17 ; H = 9.12. C6H7(CH,),.COOH requires C = 70.13 ; H = 9.09 per cent. It is easily soluble in benzene, alcohol, ether, and acetic acid ; sparingly so in cold, easily in hot, light petroleum.I t s solution in sodium carbonate immediately reduces potassium permanganate in the cold, and bromine is quickly absorbed by a solution of the acid in chloroform. The yield of reduced acid, after distillation, was usually about 75 per cent. of the theoretical quantity, but of this only about 10 per cent. separated in the form of crystals of tetrahydroparaxylic acid. Tetruhydroparuxylic cccid crystallises in prisms melting a t 83". Dibromhexcc?~yds.o~aruxylic Acid, CSH1,Br,O,. This was prepared by dissolving pure tetrahydroparaxylic acid in dry chloroform and adding a chloroform solution of bromine until the colour of the bromine remained permanent. The oil which was deposited, on allowing the chloroform to evaporate spontaneously, slowly solidified.This crude product purified by recrystallisation from dilute acetic acid saturated with hydrogen bromide, separated in colourless plates melting at 124' 0.0532 gave 0.0640 AgBr. Br=51*17. Dibromhexahydro~uraxyEic cccid melts a t 124". C9H,,Br,02 requires Br = 50.95 per cent. It dissolves readily in most organic solvents on boiling, being apparently decomposed at the same time, as we could not succeed in recovering it from them inAND METHYLTEREPHTHALIC ACIDS, ETC. 169 a crystalline form. It separates, however, readily from dilute acetic acid if decomposition is prevented by previously saturating the solution with hydrogen bromide. NexcchydropcwaxyZic acid, C,H,(CH,),*COOH, CH, I CH. CH, PH\\ Hzf! I II,C CH, ‘CH” I COOH This acid is formed when paraxylic acid is reduced by sodium and iso- amylic alcohol as explained on page 167, and is present in considerable quantities in the mother liquor of the reduced acid after the bulk of the crystalline tetrahydroparaxylic acid has been removed by cooling in a freezing mixture.I n order to isolate it, two methods were employed. 1. The crude product was treated with permanganate so as to oxidise the tetrahydroparaxylic acid, the hexahydroparaxylic acid remaining unchanged. 2. The mixed acids were converted into the anilides, and these sepa- rated by fractional crystallisation. iMetftod I.-The oxidation mas carried out in the following manner. The oily mixture of tetrahydro- and hexahydro-paraxylic acids was dis- solved in a small quantity of sodium carbonate solution, diluted with a large quantity of water, and oxidised by running in slowly a weak solution of potassium permanganate.During the whole operation, a rapid current of carbon dioxide was passed through the liquid, which was vigorously stirred by means of a turbine, and kept cold by adding ice from time to time. When the colour of the permanganate re- mained permanent, the liquid was mixed with a little alcohol, boiled, and the manganese dioxide filtered off, well washed with hot water, and the filtrate evaporated to a small bulk. This was then acidified and subjected to distillation in a rapid current of steam until the condensed water was quite clear and had only a very slight acid reaction. The dis- tillate was extracted three times with ether, and the oily residue left on evaporating the dried ethereal solution was fractionated at the ordi- nary pressure. Nearly the whole distilled at 251’ (748 mm.) as a colourless oil which gave the following results on analysis.0.1480 gave 0.3760 CO, and 0.1336 H,O. C = 69.28 ; H = 10.03. CGH9(CH,),* COOH rcquires C = 69.23 ; H = 10.25 per cent.170 BENTLEY AND PERKIN : REDUCTION OF XYLIC, PARAXYLIC, Hexahydroparaxylic acid is an oil of peculiar odour, somewhat similar to that of the higher fatty acids; it remains liquid even when cooled to a temperature of - 10". Method II.-The separation of hexahydroparaxylic acid by means of its anilide was conducted as follows. The crude mixture of acids (30 grams) was first converted into the acid chlorides by heating with phos- phorus trichloride (15 grams) in a reflux apparatus for 10 minutes ; the liquid was then decanted from the layer of phosphorus acid, and distilled under reduced pressure.The fraction boiling a t 135-145' (60 mm.) was dissolved in pure, dry ether, and slowly mixed with an ethe- real solution of aniline (60 grams) ; after standing some time, water was added, the ethereal solution separated, washed with dilute hydro- chloric acid until free from aniline, dried, and the ether distilled off. The oily residue, on standing, quickly solidified, and the product, after two crystallisations from light petroleum (b. p. 100--120°), was ob- tained in colourless prisms melting at 115'. This substance is the anilide of hexahydroparaxylic acid, as was proved by comparing it with a sample of the anilide prepared from the pure acid.I n order to obtain the hexahydro-acid from its anilicle, the latter is heated for 12 hours a t 150' in a sealed tube with acetic acid saturated with hydrogen chloride, and containing a little aqueous hydrochloric acid. The pro- duct was then diluted with water and extracted several times with ether. I n order to remove the aniline, the ethereal solution was shaken with excess of sodium carbonate solution, and the alkaline liquid acidified and again extracted with ether. This ethereal solution was washed, dried, and evaporated, the oily residue being purified by fractional distillation. Even when prepared from the pure anilide in this way, hexahydroparaxylic acid is an oil which does not solidify, even at low temperatures.The yield of hexahydroparaxylic acid obtained from the crude mixture of acids by this method is from 30 to 40 per cent. The petroleum mother liquors of the anilide of hexahydroparaxylic acid, after the removal of the light petroleum by distillation, deposited an oil from which a small quantity of solid separated on standing. This, after being crystallised from petroleum, melted a t 140-145" ; the quantity, however, was too small for further examination. The attempts made with the object of obtaining tetrahydroparaxylic acid from the oily anilide which remained after the above crystalline products had been extracted as completely as possible, were unsatis- factory. Hexahy dr opcwaxy Zp? ch Zoyide, C,H,( CH,), COO1. This was prepared by gently heating pure hexahydroparaxylic acid (4 grams) with phosphorus trichloride (2 grams) for 10 minutes ; the liquid was decanted from the phosphorous acid and distilled under reduced pressure.It is a disagreeably-smelling liquid boiling at 110" (25 mm.).AND METHYLTEHEPHTHALIC ACIDS, ETC. 171 0.2406 gave 0.1996 Ag C1. C1=20*52. C8H,,*COC1 requires C1= 20.34 per cent. Eth ylic hexuh ydropccrccx ylcte, C,H, (CH,),. COOC,H5. This was prepared by pouring the acid chloride into three times its volume of alcohol, and after allowing it to stand a short time, diluting with water, extracting with ether, &c. The brownish oil thus obtained was purified by fractional distillation. Ethylic hexahydroparaxylate is an oil of pleasant odour, and lighter than water; it boils at 224' (758 mm.).0.12'72 gave 0.3334 CO, and 0.1210 H,O. C = 71.48 ; H = 10.65. C,H,,*COOC,H, requires C = 71-74 ; H = 10.87 per cent. Artilide of hexuhydyopuraxyZic w i d , C,H,,* CO* NH- C6H5. This anilide was prepared by mixing ethereal solutions of equal quantities of the acid chloride and aniline. After standing for some time, water was added, and the ethereal solution washed first several times with small quantities of dilute hydrochloric acid until free from aniline, and then once with water. It was then dried andthe ether distilled off; the oily residue gradually solidified, and after being purified by crystallisation from light petroleum (b. p. SO--looo) the. anilide was obtained in prisms melting a t 115'. N = 6-39 ; C,H,,* CO *NH* C,H, requires N = 6-06.The anilide of hexahydroparaxylic acid is moderately soluble in ben-- zene and alcohol, but only slightly in cold light petroleum (b. p. 80- loo'), although it dissolves readily in the boiling solvent. Analysis ; found Etlqlic bronahexahyd~.opi~raxylute, C,HsBr(CH,)2* COOEt YH3 CH* CH, P"\ I I COOC,H, This was prepared, for reasons explained in the introduction, by brominating hexahydroparaxylic acid and subsequently pouring the product into absolute alcohol. Hexahydroparaxylic acid (5 grams) was carefully mixed with phosphorus pentabromide (5 grams) and bromine (6 grams), and gently heated on the water bath until the bromine had disappeared. The product, poured into twice its volume of alcohol, was allowed to stand for some time, and then diluted with water, the heavy oil which172 BENTJ,EY AND PERKIN : REDUCTION OF XYLIC, PARAXYLIC, separated being extracted with ether, kc., in the usual manner.The residue thus obtained, when fractionated under reduced pressure, yielded ethylic bromhexahydroparaxylate as a heavy oil boiling without decompo- sition a t 170-180' (55 mm.); the yield was about 70-80 per cent. 0.1928 gave 0.1376 AgBr. C,H,,Br* COOC,H, requires Br = 30.112 per cent. When hydrolysed with potash, this ethereal salt yields a mixture of acids, a behaviour which is probably due in part to the oxidation of the tetrahydroparaxylic acid formed in the first instance. The only sub- stance we were able to isolate from this mixture was a small quantity of a crystalline acid which melted roughly a t 135-140°, and on analysis gave numbers corresponding with those required by dihydro- paraxylic acid, C,H,,O,.Br = 30.37. Ethylic tetrahydroparaxylute, C,H7( CH,),* COOC,H,. This is formed when ethylic bromhexahydroparaxylate is digested with diethylaniline. Pure ethylic bromhexahydroparaxylate mixed with twice its weight of diethylaniline was heated to gentle ebullition €or 4 hours, and then poured into dilute hydrochloric acid. The dark- coloured oil which separated was extracted with ether, washed, and treated in the usual way. The product on being fractionated under re- duced pressure, yielded a colourless, sweet-smelling oil which distilled at 155' (60' mm.), and on analysis gave numbers showing that it was of ethylic tetrahydroparaxylate. 0-0814 gave 0.2162 CO, and 0.0720 H,O.C,H,,*COOC,H, requires C = 72.52 ; H = 9.89 per cent. I n order, if possible, to prepare the corresponding tetrahydroparaxylic acid, the ethylic salt was hydrolysed. Ethylic tetrahydroparaxylate (3 grams) was heated on the water bath with potash (3 grams) dissolved in methylic alcohol for 2 hours, the alcohol distilled off, the residue evaporated with water until free from alcohol, and then acidified and extracted with ether. The dried ethereal solution, on distillation, left an oil which partially solidified. The crystals, after being pressed upon a porous plate and crystallised from light petroleum (b. p. 100-120°), formed prisms melting a t 135-140°, and on analysis gave numbers agreeing with the formula C,H,,O,. C = 71.14; H = 7.93. C = 72.43 ; H= 9.82.0.1180 gram gave 0.3068 GO, and 0.0842 H,O. CgH,,O2 requires C = 71.05 ; H = 7.88. C,H,,O, requires C = 70.13 ; H = 9.09 per cent. This substance is, therefore, probably a dihydroparaxylic acid identical with the substance described above.AND METHYLTEREPETHALIC ACIDS, ETC. 173 Reduction of Xylic Acid. The reduction of xylic acid with sodivm and isoamylic alcohol, and the methods used in the separation of t,he acids thus formed, were con- ducted in almost exactly the same manner as in the case of paraxylic acid ; a brief description of the process, therefore, is all that is needful. Pure xylic acid (30 grams), dissolved in isoamylic alcohol (I$ litres), was heated t o boiling and treated three times in succession with sodium (30 grams), the same precautions and methods of extraction being adopted as in the reduction of paraxylic acid.The oily acid thus obtained when fractionated under reduced pressure passed over entirely a t about 160--170° (40 mni.). When three-quarters of the acid had distilled, the last portion was collected separately ; this soon deposited crystals when exposed to the cold, whilst the first fract.ion usually remained liquid. Tetvahydyo-xylic Acid, C,H7(CH3),*COOH. This was obtained from the higher fraction of the reduced xylic acid, the crystals which were deposited being pressed, and recrystallised several times from light petroleum (b. p. SO-looo). It forms plates which melt a t 103’. 0.1000 gave 0.2570 CO, and 0.0830 H,O. C,H7(CH3),*COOH requires C = 70.13; H = 9.09 per cent. Tetrahydro-xylic acid is readily soluble in benzene, alcohol, and acetic acid; sparingly so in cold petroleum, but very soluble in the hot solvent.When dissolved in sodium carbonate solution, it instantly decolorises potassium permanganate ; its solution in chloroform also decolorises bromine very readily, but, unfortunately, we were not able to isolate the product owing to the small amount of material a t our disposal. He.xcchyZi*o-xyZic Acid, C,H,(CH,),*COOH. C = 70.09 ; H = 9.22. COOH I PH\ CH*CH, I CH, This acid, like the corresponding hexahydroparaxylic acid, was isolated from the mixture of reduced acids by two processes, viz., (1) oxidation with potassium permanganate, and ( 2 ) hydrolysis of the anilide. I n both cases, a liquid is obtained which, when prepared from the anilide, solidifies quickly, whereas the product obtained by oxidation solidifies but slowly and vcry incompletely. The second method gives the purer product.174 BENTLEY AND PERKIN : REDUCTION OF XYLIC, PARAXYLIC, 0.1694 gave 0.4288 CO, and 0.1568 H,O.Hexahydro-xylic acid crystallises from light petroleum (I 00-1 20') in thick plates melting a t 76-78". It boils at 250-255", and is readily soluble in benzene, alcohol, and acetic acid ; sparingly in cold, easily in hot, light petroleum. I t s solution in cold dilute sodium carbonate decolorises permanganate only very slowly. C = 69.03 ; H = 10.28. C,H9(CH,),COOH requires C = 69.23; H = 10.25 per cent. Anilide of Hexahy&o-xylic Acid, C,H9(CH,),*CO*NH*C,H,. This anilide was obtained from reduced xylic acid, and employed for the preparation of the foregoing hexahydro-xylic acid.Reduced xylic acid (28 grams) was heated for about 15 minutes with phosphorus trichloride (14 grams), and the liquid decanted from the phosphorous acid and distilled under reduced pressure ; the acid chloride (30 grams), which came over a t about 130-140" (40 mm.), was then dissolved in pure, dry ether, and carefully added to an ethereal solution of aniline (56 grams); after a short time water was added and the ethereal solution washed, dried, &c., as before. The oil obtained in this way soon solidified, and after being four times recrystallised from a mixture of alcohol and petroleum (b.p. 100-120"), was obtained in needles melting a t 180'. On analysis, nitrogen was found = 6.26 per cent.; C,H,,- CO *NH* C,H, requires N r= 6-06 per cent.The anilide of hexah?/dyo-xylic acid is sparingly soluble in cold ben- zene and alcohol, but dissolves readily in these solvents on boiling ; i t is almost insoluble in cold petroleum (b.p. 100-120°) and only sparingly soluble in the hot solvent. These properties, together with its unusually high melting point, distinguish this anilide from the cor- responding anilide of hexahydropnraxylic acid. It is hydrolysed on heating with an acetic acid solution of hydrogen chloride in a sealed tube for 12 hours at 150", an almost quantitative yield of hexahydro-xylic acid being produced. Ethylic 61wom~exa~~yd.1.o-xyZute, C,H,,Br*COOC,H5. COOC,H, I CH* CH, PBr\ H27 H,C CH2 CH3 'CR' I This mas prepared in the same manner as the isomeric ethylic brom- hexahydroparaxylate.The specimen prepared boiled a t 160-1 70"AND OF XETHYLTEREPHTHALIC ACIDS, ETC. 175 (40 mm.), but was apparently not quite pure and probably contained traces of the ethylic salt of bromo-xylic acid, C,H,Br*COOC,H,. We were led to these conclusions from the fact that a bromine determina- tion gave too high a result, and, secondly, that the oil on hydrolysis with potash yielded a small quantity of a solid acid which melted at 170" and contained bromine, apparently a monobrorno-xylic acid. The ethylic bromhexahydro-xylate, prepared as explained above, gave the following results on analysis. 0.3010 gave 0.2222 AgBr. Br = 31-41. CsH,4Br*COOC,H5 requires Br = 30.42 per cent. Ethylic tetmhydyo-xybte, C,H,,* COOC,H,.This was obtained by the action of diethylaniline on the brom- It is a pleasant-smelling liquid boiling ethereal salt just described. a t 228O (752 mm.). 0.1293 gave 0.3418 CO, and 0.1122 H,O. C,H,,* COOC,H, requires C = 72.52 ; H = 9.89 per cent. A small quantity of this ethylic salt was hydrolysed with potash and yielded an acid melting at 98-110", but the quantity was insufficient for further examination. C =72*02 H= 9.64. Pt*epcwcction of Methylisophthalic Acid und of Methylterepltthcclc Acid. As was explained in the introduction, the oxidation of pseudocumene with dilute nitric acid gives rise to two dibasic acids, namely, methyl- isophthalic acid, CH,. C,H,(COOH), [CH, : COOH : COOH = 1 : 2 : 41, and methylterephthalic acid, and when the acids contained in the crude product of the oxidation are converted into their methylic salts and these are fractionated (see p.160), the fraction lS0-200' (40 mm.), consists almost entirely of the methylic salts of these two acids. This fraction solidifies on cooling, and the solid mass, when subjected to a series of crystallisations from methylic alcohol, separates into two portions, A, the least soluble, melting a t 73-74', and B, which melts at about 58-60'. The melting point of the fraction B does not rise on further crystallisation, and it was, therefore, at first supposed that this substance was pure, especially as, on analysis, it gave numbers agree- ing closely with those required by the formula CH,* C,H,(COOCH,),. 0.1280 gave 0.2986 GO, and 0.0686 H,O. CH,*C,H,(COOCH,), requires C = 63.46 ; H = 5.76 per cent.Further experiments showed, however, that it is a mixture of methylic methylisophthalate and methylic methylterephthalate, and the only way which we could find to separate the methylisophthalic from the methylterephthalic acid was by treatment with sodium amalgam. C = 63.62 ; H = 5.95.176 BENTLEY AND PERKIN : REDUCTION OF XYLTC, PARAXTLIC, Met?~yliso~~?~tl~clic Acid, [CH, : (COOH), = 1 : 2 : 41. I n order to prepare this acid, the methylic salts B, melting a t 58-60' (70 grams) were dissolved in alcohol, mixed with an alcoholic solution of potash (65 grams), and heated on the water bath for 2 hours. The alcohol was then distilled off, the residue diluted with water, evaporated until entirely free from alcohol, and the aqueous solution, after filtration, was acidified ; the copious, flocculent precipitate which separated was collocted with tho aid of the pump, washed well with water, and dried, first on porous plates, and then a t 100".It melted a t 285-290', but on repeated recrystallisation from glacial acetic acid the melting point rose to 293-295", but no higher. This substance is a mixture of methylisophthalic and methylterephthalic acids, and in order to obtain the former acid from it in a pure state, the mixture, in quantities of 10 grams at a time, was dissolved in sodium carbonate solution in a strong porcelain beaker and 3 per cent. sodium amalgam (1 kilo.) added in quantities of 100 grams a t a time. The temperature of the reaction was kept at about 100" by immersing the beaker in a boiling water bath, a rapid current of carbon dioxide was also passed into the mixture during the whole operation, and the separation of sodium salts was prevented by the addition from time to time of small quantities of boiling water.When the sodium amalgam had all been used up, the aqueous solu- tion was decanted from the mercury, filtered, and acidified; the bulky precipitate then thrown down consisted of nearly pure methylisophthalic acid, as the tetrahydromethylterephthalic acid which is formed during the reduction is soluble in water, and remains dissolved in the mother liquor. The precipitate was collected with aid of the pump, waslied well with water, dried first on a porous plate, and then at looo, and purified by conversion into the methylic salt.For this purpose, the well-powdered dry acid was suspended in methylic alcohol, the mixture saturated with hydrogen chloride and allowed to stand for some hours; water was then added and the methylic salt extracted with ether. The ethereal solution, after being washed with water and sodium carbonate solution, was dried over calcium chloride, and the ether distilled off, when an oil was left which quickly solidified. After crystallising three times from methylic alcohol, the methylic salt was obtained pure in the form of prismatic needles, which, when heated in a capillary tube, sintered somewhat a t 77", and melted a t 80'. I. 0-1592 gave 0.3710 CO, and 0.0864 H,O. C=63*55; H=6*03. II. 0.1172 ,, 0.2726 CO, ,, 0.0628 H,O. C=63*43; H=5*95.CH,* C,H,(COOCH,), requires C = 63-46 ; H = 5.76 per cent. Methylic methylisophthalate is readily soluble in most of the ordinary organic solvents, it is, however, but sparingly soluble in cold methylicAND O F METHYLTEREPHTHALIC ACIDS, ETC. 177 or ethylic alcohol, although it dissolves readily in these solvents on boiling. On hydrolysis with potash, it yields pure ~ ~ t ~ y Z i s o p ~ ~ t ~ u Z ~ acid, which separates from acetic acid as a white, apparently amorphous, powder, and melts at about 320-330". 0.1188 gave 0.2618 CO, and 0.0480 H,O. CH;C,H,(COOH), requires C = 60.00 ; H = 4.44 per cent. Methylisophthalic acid is practically insoluble in most organic sol- vents ; it dissolves slightly, however, in boiling water, and, on cooling, separates almost completely in white, flocculent masses.When treated with acetic anhydride or acetyl chloride, it does not yield an anhydride. Prolonged treatment with sodium amalgam does not appear to have any action on this acid, nearly the whole being recovered unchanged on acidifying the alkaline product of the reaction. I n purifying methylisophthalic acid in the way described above, the tetrahydroterephthalic acid formed during the reduction remains dissolved in the liquors from which the former acid separates on acidi- fication. To obtain this tetrahydro-acid, the solution was evaporated to dryness, and the residue extracted with ether in a Soxhlet apparatus ; after distilling off the ether and crystallising the extract from water, pure tetrahydromethylterephthalic acid was obt-ained, melting at 240-245" (see p.178). C = 60.01 ; H = 4.48. 0.11 10 gave 0.2386 CO, and 0,0642 H,O. C = 58.62 ; H = 6-42. CH,* C,H;(COOH), requires C = 58.69 ; H = 6.62 per cent. i ~ ~ ~ t l ~ ~ Z t e l . e y , l ~ t h c ~ Z ~ c Acid, [Me : (COOH), = 1 : 2 : 51 The methylic salt A, the preparation of which is given on p. 163, consists of pure methylic met h ylt erephthalate. 0.1052 gave 0.2450 CO, and 0.0540 H,O. C=63-51; H=5.70. CH,-C,H,(COOCH,), requires C = 63.46 ; H = 5.76 per cent. Methylic ~,zethyltes.e~htl~alcl.te is very readily soluble in benzene, ethylic acetate, light petroleum, and hot alcohol, but comparatively sparingly in cold methylic or ethylic alcohol. In order to prepare nzethylterephthalic acid, the pure methylic salt (7 grams) was dissolved in alcohol, and heated on the water bath with alcoholic potash (7 grams) for 2 hours.The product was diluted with water, evaporated until free from alcohol, filtered, and acidified, when a very voluminous precipitate was thrown down. This was collected with the aid of the pump, washed well with water, dried, and purified by crystallisation from hot glacial acetic acid, from which it separates as an apparently amorphous powder melting at 325-330'. It melts at 73-76'. VOL. LXXI. N178 BENTLEY AJSD PERKIK : HEDUCTION O F XYLIC, PARAXYLIC, 0.1106 gave 0.2420 CO, and 0.0458 H,O. I~eth?/Zterep~~thacEic acid resembles methylisophthalic acid very closely in its properties. It is practically insoluble in most organic solvents, such as benzene, chloroform, light petroleum, and ether, and although more readily soluble in boiling xylene and glacial acetic acid, it is practi- cally insoluble in these solvents in the cold.When heated, it sublimes without forming an anhydride. Methylterephthalic acid is moderately easily reduced when its solution in sodium carbonate is boiled with sodium amalgam, and in this respect it differs remarkably from methylisophthalic acid, which does not appear to be affected a t all by this treatment. C=59*67; H=4-61. CH,* C,H,(COOH), requires C = 60.00 ; H : 4-44. per cent. ~etrcc~?/drometl~yhterepl~~~aEic Acid, CH,*C,H7(COOH),. I n order to prepare this acid, methylterephthalic acid (18 grams) was dissolved in a little sodium carbonate solution, heated to about 100" by means of a water bath, and sodium amalgam (2 kilos.) added in small quantities at a time, a current of carbon dioxide being passed through the liquid during the operation. When the sodium amalgam had all been added, the aqueous solution was filtered, acidified, and the precipi- tate, collected by the aid of the filter-pump, was washed with a little water, and purified by crystallisation from hot water. It is thus obtained apparently in the amorphous condition ; it melts at 240-245", sintering a t about 230".0.1 182 gave 0.2554 CO, and 0.0696 H,O. CH,*C,H, (COOH), requires C = 58.69 ; H = 6.52 per cent. ~etra~~ydiwonzethylterep~~t~~alic acid is fairly soluble in organic solvents, and especially readily in glacial acetic acid ; it is easily soluble i n hot water,-and as it is also fairly soluble in cold water, a considerable quan- tity remains in the mother liquors after the acid has been collected.This can be recovered by evaporating and extracting the solid residue with ether in a Soxhlet's apparatus (see p. 177). A solution of the acid in sodium carbonate decolourises potassium permanganate very quickly, but the acid itself appears t o have little affinity for bromine or hydrogen bromide. An attempt was made to prepare the bromhexahydro-acid by heating the tetrahydro-acid with a solution of hydrogen bromide in glacial acetic acid in a sealed tube a t 100" for several hours. On diluting the product with water, a black, oily-looking precipitate was obtained, but all attempts to isolate a pure bromhexahydro-acid for it were unsuc- cessful. When the black mass was dissolved in acetic acid and treated C = 58.82 ; H = 6.53.AND OF METHYLTEREPHTHALIC ACIDS, ETC.179 with zinc dust, a small quantity of what appeared to be impure tetra- hydromethylterephthalic acid was obtained. The experiment was repeated several times, and in one instance an acid was obtained which decomposed permanganate only very slowly, and melted a t 210-220" ; the quantity, however, was too small t o permit of further investigation. This compound mas prepared by saturating a solution of the acid in methylic alcohol with dry hydrogen chloride, and adding water after the mixture had been left for several hours. The oil which separated was extracted with ether, the ethereal solution washed with sodium car- bonate and then with water, and dried by calcium chloride ; the ether was distilled off and the oily residue distilled under reduced pressure.C = 61.83 ; H = 7-59, 0.1676 gave 0.3800 CO, and 0.1146 H,O. Methylic tet.r.c~hydromethyEt~~ep~~tl~abte is an oil possessing compara- CH,*C,H7(COOCH,), requires C = 62.26; H = 7.55 per cent. tively little odour ; it boils at 165-170' (20 mm.). Preprution of i~et~&yltei.e~~~t~~uZic A cid 69 the Oxidation of Xylic Acid und of Paraxglic Acid. These experiments were instituted, as explained in the introduction, with the object of obtaining pure methylterephthalic acid for comparison with the acids obtained by the oxidation of pseudocumene. Xylic acid (2 grams) was dissolved in sodium carbonate solution and heated on a water bath with a dilute solution of potassium permanganate (4 grams) until the pink colour had disappeared.The manganese dioxide was then removed by filtration, washed with hot water, and the filtrate evaporated to a small bulk; on acidifying the liquid a volu- minous precipitate of methylterephthalic acid was thrown down. This was collected, dried on rz porous plate, and crystallised from glacial acetic acid, when it separated as an apparently amorphous powder melting at 320-330'. The acid was converted into its methylic salt by means of methylic alcohol and hydrogen chloride in the usual way ; after crystallising from methylic alcohol, it melted a t 73-74', and was found to be identical with the methylic salt of this melting point, already described as methylic methylterephthalate (p. 177). On oxidising yamxylic acid in precisely the same way, an acid was obtained which again melted at 320-330" and yielded a methylic salt melting at 73-74" identical with that obtained from xylic acid. These two experiments prove that this substance, melting at 73-74', must be the methylic salt of methylterephthalic acid.180 BENTLEY AND PERKIN : REDUCTION OF XYLIC ACID, ETC. Preparation of MethyZisophthaZiic Acid by the oxidution of Isoxylic Acid. The isoxylic acid required for these experiments was obtained by the oxidation of paraxylyl methyl ketone (CH,),C,H,*CO-CII,, this being prepared by a met'hod similar to that recomicended by Claus ancl Wollner (Bey., 1885, 18, 1856), namely, by treating a mixture of paraxylene and acetyl chloride with aluminium chloride. Paraxylene (20 grams) was mixed with acetyl chloride (25 grams) and carbon bisulphide (60 grams), and finely-powdered aluminium chloride (26 grams) was gradually added t o the mixture, which was well shaken during the operation. The whole was then heated on the water bath for a few minutes, and afterwards poured on t o ice. The oil containing carbon bisulphicle was extracted with ether, the ethereal solution mashed with sodium carbonate, then with water and dried over calcium chloride ; the ether and carbon bisulphide were then distilled OG, and the residue fractionated under the ordinary pressure. About 7 grams of an oil boiling a t 220-230', and consisting of nearly pure paraxylyl methyl ketone, were obtained, ancl 10 grams of paraxylene were recovered unchanged. Oxichtion of paraxpIg2 naethy2 ketone,-The fraction boiling a t 220-230' was mixed with about 30 grams of dilute nitric acid (I vol. of acid, sp. gr. 1.4, and 3 vols. of water) and heated just to boiling for 2 hours. On cooling the mixture, the oily product solidified to a hard mass ; this was collected, washed with water, a i d boiled for a consider- able time with sodium carbonate solution. The liquid was filtered from the insoluble matter, extracted once with ether and then acidified ; the bulky precipitate thus produced was collected, washed with water, dried on a porous plate, and recrystallised from acetic acid. In this way isoxylic acid, C,H,B'Ie,.C0OI3[Me2 : COOH = 1 : 2 : 41, mas obtained quite pure, melting a t 132'. The oxidation of isoxylic acid with permanganate was conducted in exactly the same manner as described in the case of xylic acid (p. 179), and a dibasic acid was obtained which, as it did not give an anhydride, was evideutly methylisophthalic acid. It melted at 320-330°, and yielded a methylic salt which, after crystallisation from alcohol, melted a t 79-80' ; this was identical with the substance of the same melting point described on page 177 as methylic methylisophthalate. OWENS COLLEGE, MANCHESTER.

ISSN:0368-1645    

DOI:10.1039/CT8977100157

出版商:RSC    

年代:1897

数据来源: RSC

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LORD l:APT,ElGIT: ON THE OXIDATI@X OF NITROGEN GAS. 181 By LORD RAYLEIGH. THE observations here described were made in connection with the isolation of argon by removal of the nitrogen from air, but they may, perhaps, possess a wider interest as throwing light upon the behaviour of nitrogen itself. According to Davy,* the dissolved nitrogen of water is oxidised to nitrous (or nitric) acid when the liquid is submitted to electrolysis. “TO make the experiment in as refined a form as possible, I procured two hollow cones of pure gold containing about 25 grains of water each, they were filled with distilled water connected together by a moistened piece of amianthus which had been used in the former experiments, and exposed t o the action of a voltaic battery of 100 pairs. , .. I n 10 minutes the water in the negative tube had gained the power of giving a slight blue tint to litmus paper : and the water in the positive tube rendered i t red. The process was continued for 14 hours ; the acid increased in quantity during the whole time, and the water became a t last very sour t.0 the taste. . . . The acid, as f a r as its properties were examined, agreed with pure nitrous acid having an excess of nitrous gas ” (p. 6). Further (p. lo), ‘‘ 1 had never made any experiments, in which acid matter having the properties of nitrous acid was not produced, and the longer the operation the greater was the quantity which appeared. . . . It was natural t o account for both these appearances, from the corn- bination of nascent oxygene and hydrogene respectively ; with the nitrogene of the common air dissolved in the water,” Davy was confirmed in his conclusion by experiments in which the electrolytic vessels were placed in a vacuum or in an atmosphere of hydrogen.There was then little or no reddening of the litmus, even after prolonged action of the battery. If nitrogen could be oxidised in this way, the process would be a convenient one for the isolation of’argon, for it could be worked on a large scale aud be made self-acting. But it did not appear a t all probable that nitrogen could take a direct part in the electrolysis. I n that case, its oxidation would be a secondary action, due, perhaps, to the forma- tion of peroxide of hydrogen. This consideration led me to t r y the effect of peroxide of sodium on dissolved nitrogen, but without success.The nitrogen dissolved in 1250 C.C. of tap water and liberated by boiling, was found t o be 19.1 c.c., and i t was not diminished by a previous addition of peroxide of sodium, with or without acid. Having failed in this direction, I endeavoured t o repeat Davy’s experiment * Phil. Tr(tms., 1807, p. 1. VOL. LXXI. 0IS2 T,ORD RAYLEIGH : OBSERVATIONS ON nearly in its original form. bored in a block of paraffin, and connected by a wick of asbestos which had been previously ignited. By means of platinum terminals con- nected with a secondary battery, a potential difference of 100 volts was maintained between the cups. The whole was covered by a glass shade, to exclude any saline matter that might be introduced from the atmosphere, But, under these conditions, no difference in the behaviour of litmus when moistened with water from the two cups could be detected, even after 14 days' exposure to the 100 volts.When, however, the cover was removed, the litmus responded markedly after a day or two. The failure of several attempts of this kind lead me to doubt the correctness of Davy's view, that the dissolved nitrogen of water is oxidised during electrolysis. At any rate, the action is so slow that tho process holds out no promise of usefulness on a large scale. The water mas contained in two cavitie I n the oxidation of nitrogen by gaseous oxygen under the action of electric discharge, a question arises as to the influence of pressure. If the mass absorbed were proportional to pressure, or the volume inde- pendent of psessure, the electrical energy expended being the same, it might be desirable to work with highly condensed gases, in spite of the serious difficulties that must necessarily be encountered.That pressure would be favourable seems probable a p i o r i , and is suggested by certain observations of Dr. Frankland. My own early experiments pointed also in the same direction. A suitable mixture of nitrogen and oxygen, standing in an inverted test-tube over alkali, was sparked from a Rhumhorff coil actuated by five Grove cells; when the total pressure was about three atmospheres, the mass absorbed was about three times that absorbed in the same time at theordinary pressure. This result made i t necessary to proceed to operations upon a larger scale with the a1 ternate current discharge.Experiments were first tried in a small vessel (of 250 c.c.), which would be more easily capable of withstanding internal pressure than a larger one. I n order to protect the glass, which at the top was almost in contact with the electric flame, and to promote absorption of the combined nitrogen, the alkali was used in the form of cz fountain, which struck the glass immediately over the flame, and washed the whole of the internal surface." But, to my surprise, preliminary trials, conducted a t atmospheric pressure, showed that this apparatus was not effective. The rates of absorption were about 1600 C.C. per hour, the runs themselves being for half-an-hour. About double this rate had already been obtained with the same electrical appliances and with stationary alkali.Care having been taken that the quality of the * Rayleigh and Ramsay, Phib. Trans., 1895, p. 217.THE OXInATtON O F NITROGEN GAS. 1s:; mixture within the working vessel was maintained throughout the ruu, the smaller efficiency could only be connected with the coufined space. As to the reason why a confined space should be unfavourable, it is difficult to give a decided opinion. Other things being the same, the surface presented by the alkali mill be diminished in a smaller vessel, and the absorption of the combined nitrogen may consequently be less rapid. But it is difficult to accept this explanation, in view of the favourable conditions secured by the use of a fountain. The gases, as they rise from the flame, impinge directly upon the alkali, which is itself in rapid motion over the whole internal surface.It would almost seem as if the combined nitrogen, as it leaves the flame, is not yet ready for absorption, and only becomes so after the lapse of LZ certain time. However this may be, the efficiency is in practice improved by largely increasing the capacity of the working vessel. A larger bottle, of 370 C.C. capacity, allowed n rate of 2000 C.C. per hour. A flask of still greater capacity gave 3300 C.C. per hour, whilst with a larger globe capable of holding 4; litres, a rate of 6800 C.C. per hour was obtained. These experiments were all made a t atmospheric pressure with a fountain of alkali and with the electric flame in as nearly as possible a constant condition.I n the case of the smallest vessel, i t was thought that the separation of the platinuni terminals may have been insufficient for the best effect, but the loss due to this cause must have been relatively small, Electrical instruments connected with the primary circuit of the Rhumhorff gave readings of 10 amperes and 41 volts. When the comparatively small vessel of 370 C.C. was used a t a pres- sure of about one additional atmosphere, the volume absorbed was about the same as in the experiments with the same vessel a t atmos- pheric pressure, thus indicating a doubled efficiency. This increased efficiency is, however, of no practical importance, inasmuch as a higher efficiency still can be obtained a t atmospheric pressure by use of a larger vessel.I n order to clear up the question, it was necessary to compare the efficiencies in a Inrye vessel a t different pressures, an operation involving considerable difficulty and even danger. For this purpose, a glass globe, nearly spherical in form, and having a capacity of about 7 litres, was employed. The extra pressure was nearly an atmosphere and was obtained by gravity, the feed and return pipes for the alkaline fountain, as well as the pipe for the supply of water to the gas-holder, being carried to a higher level thars that at which the rest of the apparatus stood. The rate of absorption (reduced to atmospheric pressure) was 6880 C.C. per hour. Experiments con- ducted a t atmospheric pressure gave as a mean 6600 C.C. In order to examine still further the influence of pressure, two 0 2184 LORD RAYLEICH : OBSERVATIONS ON experiments were tried under a total pressure of llnrf an atmosphere.The reduced numbers were 5600, 5700 C.C. per hour. From these results, it would appear' that the influence of pressure is slightly favour- able. But, in comparing the results for one atmosphere and for half an atmosphere, it should be remembered that, in the latter case, aqueous vapour is responsible for a sensible part of the total pressure. At any rate, the results are much more nearly independent of pressure than proportional to pressure ; so that the cases of large and small vessels are sharply distinguished, pressure appearing to be advantageous only where the space is too confined to admit of Dhe best efficiency at a given pressure being reached.Not sorry to be relieved from the obligation of designing a Iarge scale apparatus to be worked at a high pressure, such as 20 or 100 atmospheres, I reverted to the ordinary pressure, and sought to obtain n high rate of absorption by employing a powerful electric flame con- tained in cz large vessel whose walls were washed internally by an alkaline fountain. The electrical arrangements have been the subject of much consideration, and require to be different From what would naturally be expected. Since the voltage on the final platinurns during discharge is only from 1600 to 2000, as measured by one of Lord Kelvin's instruments, it might be supposed that a commercial trans- former, transforming from 100 volts. to 2400 volts., would suffice for the purpose.When, however, the attempt is made, it is soon dis- covered that such an arrangement is quite unmanageable. When, after some difficulty, the arc is started, it is found that the electrical con- ditions are unstable. Things may go well for a time, but after perhaps some hours the current will rise and the platinurns will become over- heated and may melt. Even when two transformers were employed, so connected as to give an open secondary circuit nearly 4800 volts., the conditions were not steady enough for convenient practice. The transformer used in the experiments about to be described is by Messrs. Swinburne, and is insulated with oil. On open secondary, the voltage is nearly 8000," but it falls to 2000 or less when the discharge is running.Even with this transformer, it was necessary to include in its primary (thick wire) circuit a self-induction coil, provided with a core consisting of a bundle of iron wires, and adjustable in position. As finally used, the adjustment was such that the electromotive force actually operative on the primary was only about 30 volts. out of the 100 volts. available at the mains of the public supply. This reduction of voltage does not, at any rate from a theoretical point of view, involve any loss of economy, and some such reduction seems to be essential to steadiness. Under these conditions, the current taken amounted to 40 amperes. * Probably 6,000 would have sufficed.THE OXIDATION OF NITROGEN GAS. 185 It is scarcely necessary to say that the watts actually delivered to the primary circuit of tho transformer are less than the number (1200) derived by multiplication of volts.and amp8res. From some experiments made under similar conditions,* I have found that the factor of reduction -the cosine of the angle of lag-is about two-thirds, so that the watts taken in the above arrangement are about 800, representing a little more than a horse-power. The working vessel, A, was of glass, spherical in forin, and of 50 litres capacity. The neck was placed down- wards, and was closed by a large rubber stopper, through which five tubes of glass penetrated. Two tubes of substantial construction carried the electrodes, B, C, arranged much as in a foriner apparatus? ; two more, D and E, were required for the supply tube of the fountain and for the drain of liquid, whilst the fifth, F, was for the supply of gas.The external drown- ing of the vessel, formerly necessary, mas now dispensed with ; but a suitable cool- ing arrangement for the alkali (some- thing like the worm of a condenser) had to be provided to obviate excessive accu- mulation of heat. As the solution of alkali circulated entirely in the closed apparatus, it could lose none of its dissolved argon. I t was maintained in circulation by a small centrifugal pump constructed of iron and driven from an electric motor. The mixed gases (about 11 parts of oxygen to 9 parts of air) were supplied from a large gas-holder; but an auxiliary holder was also necessary in order t o observe the rate of absorption. When the rate became unsatisfactory, the mixed gas in the working vessel was analysed and the necessary rectification effected. In the earlier stages of the operation, the rate of absorption was about 21 litres per hour, and this, by proper attention, could be main- tained without much loss until the accumulation of argon began to tell. If we take 20 litres as corresponding to 800 watts, we have 25 C.C. per watt-hour, an eficiency not very different from that found in operations on a much smaller scale. The present apparatus works about three times as fast as the former one, in which the vessel was smaller and the alkali stationary. .It ’ I hope shortly to publish ail accouiit of the iiietliod cml)lojcd. + liayleigh a i d Rainsay, Pliil. Trans., 1895, 1). 218.186 PERKIN : DERIVATIVES OF MACLURIN. is also more interesting to watch, as the electric flame is fully exposed to view. On the other hand, it is more complicated, owing to the use of a circulating pump, and probably requires closer attention. A failure of the fountain whilst the flame was established mould doubtless soon lead to a disaster. I have been efficiently aided throughout by Mr. Gordon, who has not only fitted the apparatus, but has devised many of the contrivances necessary to meet the ever-recurring difficulties which must be expected in work of this character.

ISSN:0368-1645    

DOI:10.1039/CT8977100181

出版商:RSC    

年代:1897

数据来源: RSC

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186 PERKIN : DERIVATIVES OF MACLURIN. x 1 v. -Be I iva t itw 0 f lia ClU? * i? 1. Part 11. By A. G. PERKIN, F.R.S.E. I:: a previous communication (Eedford and Perkio, Trans., 1895, S7, 933), it was shown that maclurin, one of the colouring matters of old fustic (Mows tincto~icc), reacts with 2 molecules of diazobenzene and analogous substances, yielding crystalline compounds. Based upon the fact that maclurin forms a pentabenzoyl derivative, C,,R,0,(C7H,0), (Konig and Kostanecki, Bw., 1893, 26, 1994), and when fused with alkali yields protocatechuic acid and phloroglucinol, i t appears to be iL pentahydrosybenzophenone ; conse Iueiitly, the constitution of maclu- rine-azobenzene was represented as follows. OH OH/\-CO--/\N:N- C,H, 0110 OH\,/OH I I N:N*C,H, Ciamician and Silber (L’er., 1894, 27, 162s) found that maclurin, when digested with acetic anhydride and excess of anhydrous sodium acetate, behaves peculiarly, yielding, not a pentacetyl compound, but a substance having this composition less 1 molecule of water.Further, by the activn of hydriodic acid, this is converted, riot into rnaclurin, but into a compound, C,,IT,oO,, isomeric with fisetin. Phlore- tin, C,,H,,O,, also, a product obtained by the decomposition of the glucoside phloridzin, which exists in the root bark of the apple tree, behaved similarly. These authors point out that in this respect both phloretin and macliirin behave like cotoin, which had been previously examined by them (L’el.., 1894, 27, 400), and found to be a mono- methyl ether of benzoylphloroglucinol. This, when treated with acetic anhydride and sodium acetate, is converted into a substame having the coiistitution of a diucetyl derivative less 1 molecule of water, shown ultimately to be the acetyl compound of a inonomethyl 3ther of lvetadionyplienylcoumnrin.PERKIN : DERIVATIVES O F MACLURIN.187 Certain natural colouring matters and allied substances, a t present undergoing investigation, which possess the property of reacting with diazobenzene, yield by the ordinary method of acetylisation sticky pro- ducts difficult to purify, resembling maclurin in this respect. Their behaviour, when treated according to the process of Ciamician and Silber, has not at present been studied, for the derivatives formed not being normal acetyl compounds, cannot be used as a sure indication of the number of hydroxyl groups present in them.Having observed that the diazobenzene derivatives of maclurin, cyanomaclurin, &c., are considerably more stable towards reagents than the substances themselves, it appeared possible that the acetyli- sation might proceed in the normal manner, and further that by Lieber- mann’s method, the number of acetyl groups present could be deter- mined with accuracy and rapidity. The difficulty experienced in preparing a quantity of the substances under examination made it ad- visable t o first test the accuracy of such a method with maclurin itself, for not only is this colouring matter more readily procurable, but from Kostanecki’s results, the number of its hydroxyl groups is no longer open to doubt.It was at first intended to embody the results of this paper in an investigation of cyanomaclurin and catechin which is now proceeding, but having noticed that Herzig (Monatsh., 1896, 17, 421) has expressed his intention t o further study the acetylisation products of maclurin obtained by Ciamician and Silber, I thought it desirable t o submit this communication to the Society, so as to conclude for the present my study of maclurin. EXPERIMENTAL. A mixture of 1 gram of finely-powdered maclurinazobenzene, 1 gram of anhydrous sodium acetate, and 30 grams of acetic anhydride was digested at the boiling heat ; the maclurinazobenzene, without appearing to dissolve entirely, became slightly yellower, and after a few minutes the whole was transformed into a semi-solid mass, owing to the separation of yellow crystals.Excess of acetic anhydride was now added, and the mixture digested until complete solution was attained, the heating being continued for an hour longer. After diluting with acetic acid, the product was poured into a large volume of water, and the red precipitate collected and washed. Before drying at looo, it was found preferable to strongly press the product between bibulous paper, otherwise, when much water was present, the whole aggregated to a dark-coloured, resinous mass, whilst, if this was avoided, a friable red powder was obtained, which could be more readily purified. Treatment with alcohol removed a dark-coloured impurity, and the residue was then crystallised from boiling cumene ; this was greatly facilitated by188 PERKIN : DERIVATIYES OF MACLURIN.the addition of a trace of alcohol t o the hot cumene solution, the mass then separating entirely in the crystalline form, and the tendency of a portion t o gelatinise was avoided. 0.1420 gave 11 C.C. nitrogen a t 18' and 772 mm. 0.1230 gave O.ZS17 CO, and 0.0495 H,O. per cent. CI,H,O,(C,H,O),(N,* C,H,), requires N = 8-77 per cent'. Although the production of a triacetyl derivative was readily to be accounted for, it appeared advisable t o study the action of acetic anhy- dride when continued for a longer period, and for this purpose the heating was continued for 7 hours. The chief product of the acetylisa- tion was again found to be the above acetyl compound, accompanied, however, in this instance, by a larger quantity of the resinous impurity previously referred to.N = 9-09. C = 62.45 ; H = 4.47. C,3H,0,(C,H,0),(N,* C,H,), requires C = 62.42. H = 4.02 ; X = 9 40 An analysis gave the following result. 0*1708 gave 13.6 C.C. nitrogen a t 15' and 770 mm. Theory requires N = 9.40 per cent. I n order to determine the number of acetyl groups contained in this substance, it was suspended in a very little boiling acetic acid, a few drops of sulphuric acid added, and the clear solution heated to boiling for a short time; the cautious addition of boiling water caused the separation of crystals, and after the mixture had stood for 12 hours, they were collected and washed with water. The filtrate was pale yellow, evidently containing a trace of the substance still in solution ; it was therefore concentrated to a small bulk, treated with boiling water, and again evaporated, this process being repeated until but a faint odour of acetic acid was perceptible.After standing 1 2 hours, the minute quantity of crystals which had then separated was added t o the main bulk, which was dried first a t 100' and then a t 160". 0.7716 gave 0.6109 C,,H,O,(N,C,H,),. C1,HjOa(C2H30),(N,*C,H,), requiresC,,H,O,(N,C,H,), = 7S%6 per cent. To be sure that the decomposition product thus obtained was in reality maclurinazobenzene, it was analy sed, with the following result. 0.1222 gave 13 C.C. moist nitrogen a t 19" and 743 mm. N = 11.94. 0.1193 ,, 0.2786 CO, and 0.0430 H,O. C = 63.69 ; H = 4 00 C,,H,O,(N,* C,H,), requires C = 63.83 ; H = 3.S3 ; N = 11 -91 per cent.Its melting point also was found t o be identical with that of maclurinazobenzene, for when heated, both showed signs of decompo- sition a t 265", and melted at 276-277" with evolution of gas. It WRS observed that the melting point of maclurinazobenzene varied within a few degrees, according to the rapidity with which it was heated; if heated slowly it melted even as low as 270". The crystals obtained N = 9-45, Found, 79.17 per cent.PERRIN : DERIVATIVES O F RIBCLURIN. IS9 on decomposing the acetyl compound in this manner were remark- able for their size and beauty, as compared with those produced by the methods described in the previous paper (Eoc. cit.), a fact which a t first caused a doubt as to their identity. It mas, however, found subsequently that, on cautiously adding water to the unacetylised substance dissolved in zt hot dilute solution of sulphuric acid in acetic acid, crystals separate, identical with those obtained from the acetyl compound, ~twicccet~E.lncccl.uri~z,tcLxo6eizxene forms a mass of glistening, hair-like, orange yellow needles, melting at 240-243" with decomposition, sparingly soluble in boiling acetic acid and cumene.It is not aLtt;Lcked by cold, dilute alkalis, but on heating gradually dissolves, yielding an orange-red liquid from which acids precipitate red flocks of the free diazobenzene compound. It has been stated above that when maclurinazobenzene i d digested with acetic anhydride and sodium acetate, the mixtnre quickly solidifies unless a very large excess of the former reagent is present.I n order t o examine this product, the mass thus produced was stirred up with a small quantity of acetic acid, and the crystals collected, mashed .repeatedly with alcohol, then with water and dried. The glistening mass of yellow needles thus obtained was found t o consist entirely of the above triacetylmaclurin- azobenzene, it being thus evident that the process of acetylisation takes place with extreme rapidity, prolonged digestion being unneces- sary. I n this way, nioreovei-, the yield is considerably increased. Maclurin, as is well known, contains a phloroglucinol nucleus, and it therefore appeared of interest to study the acetylisation of phloro- glucinolazobenzene ; this was prepared according to the directions of Weselsky and Benedikt (Uer., 12, 2%)) and purified by crystallisation from alcohol.A nitrogen estimation gave N = 16.43 per cent., theory requiring 16-76 per cent. I n acetylising this substance, the method employed was identical with that described above with maclurinszobenzene. As the digestion proceeded, the bright orange-red solution a t first obtained gradually became browner and finally very dark, as if decomposition mas taking place. The addition of water caused the separatioii of a chocolate- coloured precipitate, which, after standing for 1 2 hours, was collected, washed, and dried. Treatment with slightly warm acetic acid removed from this product a dark-brownish, resinous substance, a small quantity of a red powder remaining undissolved; this was purified by crystalli- sation from acetic acid.0'0882 gave 11.4 C.C. nitrogen a t 16', aild 754 111111. I? = l.l*O-i. CGH,O,(N,* C61i15)2* C,H,O i,ecluires N = 14.89 per cent. The yield of the ncetyl compound olhained in this may being small,190 PERKIN : DERIVATIVES O F MACLURIN. it seemediprobable that, if digested for a shorter time, a larger quantity might be produced ; this was found to be the case. As soon as it was completely dissolved, the whole was allowed to cool, and the crystals, after treatment with acetic acid, were collected, washed with alcohol, then with water, and finally purified by crystallisation from acetic acid. 0.1357 gave 17.7 C.C. nitrogen a t 17", and 740 mm. H = 14.73 ; 0.1178 ,, C,H,O,(C,H30)(N,CGH,), requires C = 63-82 ; H= 4.25; N = 14.89'p.c. To determine the number of acetyl groups present, a similar method was employed as with the maclurin compound.0.6664 gave 0.5887 C,H,O;(N,* C,H,),. CGK303(C.LHSO)(COH5N,)~ requires CoH,O,(N,* C,H,), = 88.83 per cent. It was evidently a monacetyl compound. The regenerated phloro- glucinolazobenzene was analysod. 0.1342 gave 19.7 C.C. nitrogen a t 16', and 748 mm. N = 16 83. Phloroglucinolazobenzene melts and decomposes at 228-230". I~~oiLacet~Z~)~lo~o~lzcciizoZa,-obeil~e?ie was obtained as an orange-red mass of glistening needles meltring a t 222-223" wit'h decomposition, readily soluble in boiling glacial acetic acicl. Cold alkaline solutions do not dissolve it, but on warming, orange-red liquids are obtained, from which acids precipitate red flocks of the azo-compound.The above results show that, although in maclurin five hydroxyls exist, three only are present in its diazobenzene derivative. This is readily accounted f o r on examining the constitution shown above, two hydroxyls in the ortho-position relatively to the diazobenzene groups being in the ketonic condition. The same also is the case with phloroglucinolazobenzenc, which consequently contains, as found above, but one free hydroxyl group, and, if further proof were needed, there is here conclusive evidence of the existence in maclurin of five hydroxyl groups. It is interesting to notice that the peculiar reaction of maclurin with acetic anhydride and sodium acetate investigated by Ciamician and Silber (Zoc. cit.) does not, under the conditions here employed, take place with its diazobenzene derivative, as this behaves in the normal manner with these re-agents, I t s behaviour in this respect, and its stability when compared with maclurin, would appear, therefore, t o be due to the ketonic condition of the two hydroxylsabove referred to.Moreover, it appears probable that the acetylisation of the diazo- benzene derivatives of substances analogous to maclurin will yield a ready means of estimating their hydroxyl groups, in case these cannot! 0.2745 GO,, and 0.0495 H,O. C: = 63.55 ; H= 4.67. Found, 88.19 per cent. Theory requires N = 16.76 per cent.FORSTER : CONVERSION OF CAMPHOROXTME, ETC. 191 be determined in the ordinary way; and further experiments that are being carried out on the azobenzene derivative of catechin seem likely to corroborate this supposition, I n such substances, but little difficulty presents itself in determining the group or groups present to which this reactive capacity with diazo-compounds is due, and should ortho- azo derivatives be formed, the ketonic condition of such hydroxyl groups must thus be allowed for.LuteoZim.-Since the publication of my last communication on this colouring matter, a paper has appeared by Herzig (Nonatsh., Zoc. cit.) which confirms those results excepting as regards a slight difference in the melting point of luteolin triethyl ether. He, however, mentions a second product formed during the ethylation of luteolin, although its nature and composition were not determined. Although no account of this substance appears in my paper, I was fully aware of its existence, but did not consider it necessary t o mention i t at that time, believing that the prior publication of my results was sufficient to reserve f o r me the further study of this reaction. Vnderstanding, however, from a private communication from him, that he is investigating this product, I have withdrawn my claim to it, This, howcver, renders it necessary for me t o point out that, during the methylation of luteolin, the results of which I have already partly desc~ibed, rz second substance is similarly produced in conjunction with luteolin trimethyl ether. An account of this, now partly investiguted, I hope shortly to lay before the Society. For reasons similar to those given above, it has not been before men- tioned, although I have been aware of its existence for many months. I reserve this entirely for myself. CLOTH\VORKERS’ RESESRCII LABORATORY, DYEING DEPARTMENT. YORKSHIEE COLLEGE.

ISSN:0368-1645    

DOI:10.1039/CT8977100186

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

FORSTER : CONVERSION OF CAMPHOROXTME, ETC. 191 By MARTIN ONSLOW FORSTER, Ph.D, IN studying the properties of the methyl ether of camphoroxime-a substance which is readily obtained on heating the oxime in a reflux apparatus with sodium methoxide, methylic iodide, and rnethylic alcohol-it became of interest to ascertain whether ethers are pro- duced under the direct influence of alkylic iodide on csmphoroxime. The latter was therefore heated with methylic iodide in sealed tubes a t temperatures above loo”, and it was found that, under these192 FOKSTER : CONVERSION OF CAMPHOROXIME INTO circumstances, the product consisted of the hydriodide of a base, which proved to be the methyl derivative of cainphorlmine. Csmphoriiiiine was first obtained by ‘l‘iemann on treating camphor- oxime with nitrous acid (Ber., lS95, 28, lOSO), which gives rise simultaneously to camphorimine nitrate and carnphenylnitramine.The identity of the prodnct of the action of iiiethylic iodide on cam- phoroxime with meth~lcamp~orimiiie, which, according to Tiernann, has the constitution (CH,,),C--~H-CH, I CH,,* CH* CH--C:N* CH,,, was at once suggested by the conversion of the former into camphor and methylitmine under the influence of concentrated hydrochloric acid a t high temperatures, the point being placed beyond doubt by com- parison with a specimen of the methj 1 derivative prepared directly from camphorimine by the method described in a recent payer by Mahla and Tiemann (L’ei.., 18cjG, 29, 2809). As the examination of methylcamphorimine was aliiiost completed when Mahls and Tiemam’s paper appeared, and its properties have not yet been described, these are recorded in the present communication.Although caniphoriniine is a coniparatively unstable substance, which undergoes partial deconiposition a t its melting point (95*), and evolves aiiinionia when exposed to the air for a considerable period (ZOC. cit.), the methyl derivative, which boils a t 203”, may be preserved indefinitely without change ; as already stated, however, the base gives rise t o camphor when heated with concentrated hydrochloric acid in sealed tubes? and the same change takes place when an acid solution of the hydrochloride is evaporated on the water bath. Camphor is also regenerated when an aqueous solution of methylcamphorimine methiodide is treated ~ i t h cold, dilute caustic soda, or boiled with sodium carbonate ; the quantity obtained in this way approximates t o the theoretical proportion.Net liylcamphorimine immediately decolo- rises bromine when the solution in chloroform is treated with the lialogen in the same medium, an additive compound being formed. This behavioui-, however, cannot be regarded as evidence of the un- saturated linking between carbon and nitrogen, because a solution of iodine gives rise to a s i i d a r product ; moreover, the dibromide, oh- tnined in the manner described, readily loses bromine when treated with warm, dilute hydrochloric acid, and is therefore most probably :I perbromide in which both bromine atonis are attached to nitrogen. It has been pointed out by Tieinann (Zoc.c i t . ) that the production of cainphorimine and cai33pl~en?ilnitramine, by the action of nitrous acid on camphoroxime, admits of explanation on the assumption that theMETHYLCAMPHORIMINE AND INTO CAMPHENYLNITRAMINE. 193 nitrite of camphoroxime, C,,H,,:KOH,HNO,--mhich is probably incapable of existence in the free state-constitutes the intermediate product of the change, and undergoes molecular rearrangement, yield- ing the nitrate of camphorimine, C,,H,G:hTH,HNO, ; the greater portion, on the other hand, loses the elements of water, and becomes converted into crtmphenylnitramine, CloHlj* NH* NO,. No simple explanation of the direct production of methylcamphorimine hydriodide by the action of methylic iodide on camphoroxime is apparent at present, and this curious result was certainly not anticipated at the time the experiments were nndertaken ; as expressed by the equation CI,Hl,:NOH + CH31 = C,,H,,N,HI + 0, one methylic group is intro- duced into the oxime, and aii atomic proportion of oxygen eliminated from the product.I have been unable to meet with the record of any experiments in which oximes have been submitted to the direct action of alkylic iodides, excepting those of Luxmoore (Trans., 1806, 69, 185)? who obtained the hydriodide of benz-antiddoxime nitrogen methyl ether on heating the oxime with methylic iodide; attempts to apply this action t o the preparation of the alkyl isoxi- mido-derivative of benzophenone were unsnccessf ul (footnote, Zoc. cit.). Whilst the production of the hydriodide of benz-antialdoxime nitrogen methyl ether constitutes an additive action, involving n change in the valency of nitrogen, no such simple course is followed in the action of methylic iodide on camphoroxime, and in view of the fact that the yield of methylcamphorimine hydriodide does not approximate to the amount required by theory, it would be premature to discuss the mechanism of the change until fresh evidence is forthcoming.Ex PER I MENTAL. Although the first experiments which led to the direct conversion of camphoroxime into methylcamphorimine -were carried out at tempera- tures approaching 200°, it is unnecessary to heat the contents of the tube above looo. Ten grams of camphoroxime are enclosed in a hard glass tube with 20 grams of methylic iodide, and heated during 1-2 hours at 120-140" : on opening the capillary, there is a considerable escape of gas, and the tube contains a dark-brown oil, impregnated with a crystallino deposit of methylcamphorimine hy d riodide.The viscous liquid, which has the odour of campholenonitrile, is allowed t o drain as cpmpletely as possible from the hydriodide, which is then transferred to the filter pump, washed several times with ether, and finally with alcohol ; the quantity of salt obtained from 10 grams of camphoroxinie amounts to 7.5 grams. The recrystallised hydriodide is dissolved in hot water and treated with caustic soda, which liberates the base as a194 FORSTER : CONVERSION OF CARIPHOROXI;~IE INTO pale yellow oil ; the liquid is extracted with ether, which is then dried with caustic potash, and removed by distillation.IlIethylcamphorimine is a limpid, almost colourless oil, which boils a t 203' (uncori-,) under a pressrrre of 757 mm., and has the sp. gr. = 0.9226 a t 22-75'; it is I~vorotntory, and the mean of seven concordant readings i n a 2 decimetre tube gave a, = - 43'39' at 22-75', whence the specific rotatory power [a],= - 23.6'. The base has the odour of piperidine, and the vapour produces dense white fumes with hydrogen chloride ; it is readily volatile in a n atmosphere of steam, and on boiling it with water the odour suggests .both camphor and ammonia. The vapour is inflammable, and will ignite a t the mouth of the test-tube in which water is boiled along with the base. Although a preliminary examination of this substance pointed to the formula C1,H,,N (Proceedings, 1895, 146), the preparation of the compound on a larger scale, and the investigation of new derivatives, have established the formula C,,H,,N as representing its composition.The following results were ob tnined on analysis. 0.2222 gave 0.6480 CO,, and 0.2266 H,O. C = '79.53 ; H= 11.33. 0.1419 ,, 0.4159 CO,, and 0.1476 H,O. C = 79493 ; H = 11-55. C,,H,,N requires C = 80.00 ; H= 11.51 per cent, Methylcnmphorimine has no reducing action on ammoniacal silver or Fehling's solutions ; unlike camphorimine, it does not yield camphor when treated with a hot solution of sodium hydrogen sulphite. It is indifferent towards an acid solution of potassium permanganate, an ice-cold solution of the oxidising agent merely precipitating the crystalline permanganate, which separates in lustrous, violet scales, and becomes brown when exposed to the air ; a neutral solution is reduced on boiling, but dilute nitric acid has no immediate action on the substance.Sccissio n d' Met ?L $ccowaph oil-inzine. --W he n a so 1 u t io n of camphor im i n e in cold, alcoholic, oxalic acid is kept for some days, it is found that a certain amount of camphor is formed, and it is also produced when a n acid solution of the hydrochloride is heated on the water bath; the quantity of camphor obtained in this may, however, is comparatively small, the greater proportion of the base being easily recovered on treating the filtered liquid with alkali. The hydrolytic action proceeds almost quantitatively, however, when the base is heated with concen- trated hydrochloric acid.Three C.C. of methylcamphorimine were heated in a-sealed tube with 10 C.C. of concentrated hydrochloric acid for 2 hours a t 180--200°, it having been previously ascertained that no separation of camphor occurs at 120'. After being submitted to the higher temperature, the tube was found to contain a solid cake of camphor ; the contents were therefore transferred to a distilling flask in which steam was driven throughthe liquid, and a quantity of camphor weighing 2 grams was carried over. Assuming the action to take place in accordance with the equation C,,H,,N + H,O = Cl,I1l,iO + CH,*NH,, 2.6 grams of camphor should have been expected. The residual liquid was filtered, concentrated on the water bath, and extracted with chloroform in order to remove a small quantity of methylcaniphorimine hydrochloride which escapes hydrolysis ; the solution answered to the qualitative tests for methylamine hydrochloride, remaining clear on treatment with soda, and yielding a gaseous base which fumed with hydrogen chloride, and burnt readily.On mixing the liquid with a solution of platinum tetrachloride, an orange-coloured platinochloride was obtained. This was analysed with the following result. 0.0504 gave 0.0206 Pt. Pt = 409. 0.0407 ,, 0'0167 Pt. Pt=41*0. (CH:,*NH,),H,PtCl, requires Pt = 41.3 per cent. The camphor obtained in this manner was identified by conversion into the oxime, which melted at 118", and did not depress the melting point of puriGed camphoroxime when mixed with it.Meth~?llcccnz~~l~os.ir)zilze h y c l i w clL lo &?e, C , H, ,N, H C 1, is prepared by dissolving the base in hydrochloric acid, and extracting the liquid with chloroform, which on evaporation deposits the salt as a friable, amorphous mass; it is very readily soluble in alcohol and water, crystallising slowly from the latter in colourless needles. It melts and effervesces a t 270°, and becomes yellow on exposure t o the air. 0-1308 gave 0.0943 AgCl. C1 = 18.0. C,,H,,N,HCl requires C1 = 17.6 per cent. 0.1203 ,y 0.0866 AgCl. C1 = 17.8. Me thy I cccnyAo&ntisze Izycl~ ioclicle, C,, H, ,N, HI, i s obtain ecl from cam- phoroxime in the manner already described ; i t is also produced when potassium iodide is added to an aqueous solution of methylcamphori- mine hydrochloride, separating from the liquid in lustrous needles ; it is identical with the substance obtained by Tiemann on treating an ethereal solution of camphorimine with methylic iodide (Zoc.cit.), and crystallises from water and alcohol in long, coiourlese, lustrous needles, which become yellow on exposure to air. It darkens above ZOO", and melts with effervescence above 285". The salt was analysed with the following results. 0.3131 gave 0.3560 CO,, and 0.1387 H,O. C = 45.56 ; H = 7.23. 0.1853 ,, 0.3082 CO,, and 0.1170 H,O. C = 45.36 ; H = 7.01. 0.4626 ,, 17.2 C.C. moist nitrogen at 16" and 761 mm. N = 4-3. 0.2583 ,, 0.3081 AgT. I = 43.50. 0.2126 ,, 0.1712 AgI. I = 43.48. ,H,,N,HI requires C = 45.05 ; H = 6.82 ; N = 4.7 ; I = 43.34 per cent.C196 BORSTER : CONVERSION OF CARIPHOROXIMR INTO N e tlqlcccmph o rinzisae pl ci ti? 1 och To~icle, (C, ,H ,K ),,H,P t C1 G, separa t c R in woolly masses of pale yellow needles on adding aqueous platinum tetrachloride t o the alcoholic hydrochloride ; the crystals rapidly become trsnspnren t and orange-coloured. Recrystxllised from absolute slcohol, i t melts autl effervesces a t 219.5'. Pt = 26.16. 0.2542 gave 0.0665 Pt. 0,1895 ,, 0,0493 P t . Y t = 26.02. 0.1816 ,7 0.0475 Pt-. Pt = 36.15. 0.5130 ), 17.9 C.C. of moist nitrogenat 15.5'and 769mm. N = 4.12. (C,,H,,N),,H,PtCI, requires Pt = 26.28; N = 3.79 per cent. ille th y lccinzph o ~ i 2 z iize me t?L io dide, C, H, ,N, C H, I, rapid 1 y separates from a mixture of the base with a n equal weight of methylic iodide, until a solid mass of crystals is obtained ; the substance is precipitated in minute, lustrous leaflets on adding ether to the solution in chloro- form, whilst from benzene containing a very small proportion of absolute alcohol it crystallises in lustrous, square plates, and melts a t 231-232' without undergoing decomposition, 0 3476 gave 0.2634 AgI.I = 40.92. Cl,H,9N,CH,,I requires I = 41 -36 per cent. The methiodide dissolves sparingly in hot benzene, and is insoluble in ether and petroleum, but dissolves very readily in methylic and ethylic alcohols and acetone, crystallising from the latter in stout needles. When crystallised from ethylic acetate, it yields lustrous, transparent leaflets, which effloresce in the desiccator. Met~~~Zcccnz~~l~oi.inki~ae picyate crystallises from absolute alcohol in slender, sulphur-yellow needIes, and melts at 190'. The chromccte crystallises from hot water in square, orange-coloured plates, and becomes purple when exposed to light.The mercu~iclrZomk?e is obtained on adding excess of mercuric chloride to a n aqueous solution of the hydrochloride; it is readily soluble in water, and separates in slender, white needles, melting at 126-1 28". The substance dissolves readily in water, and on adding cold, dilute caustic soda to the solution, a precipitate of camphor immediately separates ; the same effect is produced by hot sodium carbomte. 0.2648 7, 0.2015 AgI. 1=41*09. treating a solution of the base in petroleum with one molecnlar proportion of bromine dissolved in the same medium, the colour of the halogen being immediately destroyed ; no hydrogen bromide is liberated, and the perbromide separates as a pale yellow, amorphous precipitate, which is collected, washed with petroleum, and dried in the desiccator.METHYLCAJIPHORIMJNE AND INTO CAMPHENYLNITRAMINE.197 It does not dissolve readily in cold absolute alcohol, but, on warming, a red solution is obtained; when this is diluted, the perbromide sepa- rates in lustrous, reddish needles, and melts a t 133-1 3 4 O . The perbromide is insoluble in cold water, but very readily dis- solves in chloroform. When the substance is treated with boiling water, it gradually passes into solution, yielding methylcamphorimine hydrobromide, whilst cold, aqueous alkali also removes the bromine, and regenerates the base ; hot dilute hydrochloric acid eliminates bromine, and gives rise to methylcamphorimine hydrochloride. Concurrently with the examination of methylcamphorimine, atten- tion has been paid to the behaviour of camphoroxime towards oxidising agents, and although the experiments have not thrown any fresh light on the nature of the substance, the results are not altogether devoid of interest, Action of Nitric Acid on Canzplmoxinae.By heating camphoroxime for some time with nitric acid of sp. gr. = 1.38 diluted with an equal volume of water, Koenigs obtained carnphoric and isocamphoronic acids, along with a nitrogenous compound which is stated to melt a t 215-218”, evolving red gas and hydrogen cyanide (Bey., 1893, 2G, 2340); I find, however, that if a more dilute acid is employed, and the action is arrested after a few minutes, camphenyl- nitramine, C,,H,,N,O,, is obtained almost exclusively, along with about 2 per cent.of a substance which crystallises from alcohol in six-sided plates, and melts, evolving red gas, a t 222’) being probably identical with the compound mentioned by Koenigs (Zoc. cit.). Camphoroxime is dissolved in 10 parts of dilute nitric acid (sp. gr. = 1.42, mixed with five volumes of water), the liquid being warmed on the water bath in a reflux apparatus until a clear, colourless solution is obtained; on heating it by means of a Bunsen flame, it is noticed that, as the temperature rises, the liquid gradually acquires a green tint, and then suddenly becomes turbid, owing to the separation of a green oil.At this stage, red nitrous fumes are liberated in smallquantity, and a brisk action then sets up, continuing for some time without further application of heat. After about 20 minutes, when the oil-which is now colourless, and has a faint odour of cam- phor-becomes semi-solid if cooled, it is extracted with ether, the extract washed with dilute caustic soda until the alkaline washings are colourless, freed from mineral matter by repeated agitation with water, and finally dried with calcium chloride; on evaporation, the soIvent deposits a translucent, camphor-like mass, which is then sub- mitted to distillation in an atmosphere of steam. The solid distillate, which melts at 44O, gives Liebermann’s reaction, and dissolves readily VOL.LXXI. P198 FORSTER : CIONVERSiON OF CAMPHOROSIME INTO in alcoholic potash, ether precipitating the potassium derivative of camphenylnitramine from the liquid ; on decomposing this potassium derivative with hydrochloric acid, and comparing the product with camphenylnitramine obtained by the action of nitrous acid on cam- phoroxime (Angeli and Rimini, Ber., 1896, 28, 1078 ; also Tiemmi), Gid., 28, 1080, and 29, ZSlO), they were found to be identical. Employing 50 grams of camphoroxime, 35 grams of camphenylni- tramine were obtained, and when this quantity of substance had been carried over by the steam, it was found that the distillate no longer fused in warm water, but remained as a solid deposit in the tube of the condenser, even during the passage of steam.The quantity of substance exhibiting this property, however, amounted to less than one gram, and consequently was not further investigated; it gives Liebermann's reaction, crystallises from alcohol in lustrous, six-sided plates, melting sharply a t 222' with brisk evolution of red fumes, and differs from camphenylnitramine in its behaviour towards concentrated sulphuric acid, which does not liberate gas from the substance. Uamphenylnitramine is also produced when nitrogen peroxide acts on camphoroxime. On dissolving 10 grams in chloroform, cooling the liquid by immersion in a mixture of ice and salt, and submitting it to a current of the gas obtained by heating lead nitrate, the solutiou assumed a green tint, and on evaporating the chloroform, a yellow oil mas deposited; the product was distilled in an atmosphere of steam, 5.5 grams of carnphenylnitramine being obtained.Scholl and Born have also studied the behaviour of camphoroxime towards nitrogen peroxide, and obtained camphorimine nitrate (Bey., 1895,28, 1361), the product, t h a t is, of the action of nitrous acid on camphoroxime. Assuming that camphenylnitramine has the structure (CH,),U--CH-CH I 1 7% ; CH,* CH - CH- C *NH*NO,, ascribed to i t by Tiemann (Seq-., 1896, 29, SSlO), it is possilJIe t o explain the production of this substance by the action of nitrogeu peroxide on camphoroxime in the following manner. This scheme depends on elimination of the elements of nitric acid from an intermediate additive compound of nitrogen peroxide andMETHYLCAMPHORIMINE AND INTO Ch3IPHENYLNITRAMINE.199 camphoroxime ; the action of dilute nitric acid, however, is less easy to follow, and considering the somewhat complex course which is prob- ably pursued, it would be unprofitable to discuss the change,.until it has been more closely investigated. Actioiz of Potcissizcir~ PeiwuqCiiiate OVL C'aull'l~oi.o,r;ii,re. 1.n the paper already quoted, Koenigs alludes to the production of cam- phoric and nitrous acids on oxidising camphoroxime with an alkaline solution of potassium permanganate ; a very different result has been obtained, however, by employing an acidified solution of the oxidising agent. Ten grams of recrystallised camphoroxime are dissolved in 200 c.c, of cold, dilute sulphuric acid, containing one part of the concentrated acid and seven parts of water ; the filtered liquid is cooled by immersioii in crushed ice, and treated with a 3 per cent.solution of potassium permanganate in dilute sulphuric acid, which is cooled to about 0", and added to the liquid in small quantities a t a time. After the first few C.C. are decolorised, the colour becomes discharged immediately the osidising agent is added, and this continues until a considerablc quantity of the solution has been reduced; during treatment with the agent, the liquid acquires a green tinge, and a bright green oil slowly separates, and solidi6es t o a sticky, opaque mass. The substance obtained in this manner does not admit of further purification, as it is excessively unstable. It has a somewhat pungent odour, and when exposed to the air, rapidly deliquesces, losing its bright tint, and becomes translucent and yellow, the product yielding camphor on dis- tillation with steam ; the green substance changes in the same way when left in the desiccator, and yields camphor immediately when heated with aqueous alkali, being insoluble in the cold agent.The camphor obtained in this manner was identified by conversion into the oxime, which melted at 118", and did not depress the melting point of purified camphoroxime when mixed with it. The product of the action of an acidic solution of potassium per- iiianganate on camphoroxime has the properties of a very unstable nitroso-derivative. It is readily soluble in alcohol and acetic acid, yielding bright emerald green solutions, which rapidly become colour- less when boiled ; the solution i n acetic acid also loses its bright green colour when treated with aniline dissolved in the same medium, pass- ing through olive green, and greenish-brown, to brownish-red. On adding a mixture of finely-powdered ice and zinc dust to an ice-cold solution of the Substance in glacial acetic acid, the green colour is rapidly destroyed, and on filtering off the zinc, and rendering the liqnid alkaline with soda, a current of steam carries over a consider- able quantity of camphor. P d200 YOUNG AND ANNABLE : FORMATION OF SUBSTITUTED The formation of a nitroso-derivative on oxidising camphoroxime is probably due to the double linking between carbon and nitrogen. It is conceivable that an intermediate compound arises from the initial action of the agent, and losing the elements of water, is converted into an unstable nitroso-derivative, as represented by the following scheme. Camphorosime. Interiiiediate compound. Nitroso-derivative. Elimination of the elements of hyponitrous acid from a substance of this constitution would lead to the production of camphor. Oxidised camphoroxime gives Lie bermann’s reaction ; when the alco- holic solution is boiled, the odour of aldehyde becomes perceptible, and the liquid exerts n vigorous reducing action on an amrnoniacal solution of silver nitrate.

ISSN:0368-1645    

DOI:10.1039/CT8977100191

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

200 YOUNG AND ANNABLE : FORMATION OF SUBSTITUTED XVI. Fomnatioi8 of Substituted Oxyti-iaxoles fyeom P~~e?aylse172icc-s1.~uxiclc. By GEORGE YOUNG, Ph.D., and HENHY ANNABLE, Firth College, Sheffield. C,H, *N *N C,H,*C :N THE formation of diphenyloxytriazole, I >C*OH, by the oxidation of an alcoholic mixture of phenylsemicarbazide and benzalde- hyde, according to the equation I. C,I-I,*N,H,* CO 'NH, c C,HjUHO + 0 = (C,HJp(:qNy* OH + BH,O has already been described by one of us (Trans., 1895, 67, 1063). It was there shown that the action could be carried out in two stages: the first being the oxidation of phenylsemicarbazide to phenylazocar- bamide. IIcc. C,H,*NH*NHb CO*NH&, + 0 = C,H,*N:N* COaNH, + H,O, the second the condensation of phenylazocarbamide with benzaldebyde, 116.C,13,.N2* (30 *NH, + C,Hj*COH = (C6H5)2C,Ns* OH + H,O. This last equation might itself represent two stages, if, before forma- tion of the molecule of water, direct addition of benxaldehyde toOXYTRIAZOLES FROM PHENYLSE;1IICBRBAZIDE. 201 phenylazocarbamide were to take place, an action which mould prob- ably result in the formation of benzoylphenylsemicarbazide. C,;H;N*NH* CO *NH, I - 111. C,H,*N:N* CO *NH, I + C,H ,*COH qp-; C 0 Benzoylphenylsemicnrbazide niight also be formed in action I. with, out intermediate formation of phenylazocarbarnide, if oxidation took place according to the scheme IV. C,H,*NH*NH* CO*KH, C,;H;N*NH* CO *NH, - - + H,O. + C,3H,*COH + 0 C6H,* C 0 The possibility of the formation of benzoylphenylsemicarb,rl7,ide by either action 111.or action IV. WRS not overlooked, but it was thought improbable, in view & the fact that Widman (L’w., 1893, 28, 948) had prepared this substance by the action of benzoic chloride on phenylsemicarbazide, and ha‘d observed that i t showed no inclination t o undergo ring condensation, even under very varied conditions. Our attention has again been drawn to this subject by Widman’s recent paper (Ber., 1896, 29, 1946), in which i t is shown that benzoyl- phenylsemicarbazide does condense to diphenyloxytriazole, and that with surprising ease, under the influence of warm, dilute alkalis. This seemed to make a reinvestigation of action I. and of action 116. advis- able, more especially cf the latter, as the product obtained by heating benzaldehyde with phenylazocarbamide had been purified by dissolving it in warm alkali and reprecipitating i t by dilute sulphuric acid, a process which, as Widman’s results show, would lead to the condensa- tion of any benzoylphenylsemicarbazide which might be present in the product of the action.We have, therefore, repeated the experiments with benzaldehyde and phenylazocarbamide, omitting the purification by means of alkali, and we have made several experiments to determine whether benzoylphenylsemicarbazide, if formed in the course of action I. or of action IIb., mould be condensed to diphenyloxytriazole under the conditions of the action. Action of BeiaxnZdelu& o n P~~eia?/lrL,Nocniabct nzide. An alcoholic solution of benzaldehyde and phenylazocarbamide in molecular proportion was boiled for 5 minutes, similar experiments being made with the addition of ferrous chloride, and also of ferrous chloride and hydrochloric acid.In neither case m ~ s any trace of benzoylphenylsemicarbazide or of diphenyloxytriazole formed. The action was next tried in sealed tubes a t 120’; the product, after being washed with cold alcohol and with ether and recrystallised from dilute alcohol, melted a t 288--289’. Benzoylphenylsemicarbazide has been202 YOUNG AND ANNABLE : FORMATION OF SUESTITUTED observed by &Pich,zelis and Schmidt (fie).., lSS7, 20, 1715) to melt at, 203-203°, and by Widmnn (Bey-., 1593, 26, 945) a t 210--811". Tho melting point of diphenyloxytriazole is given by Widman as 290" (Be,*., 1896, 29, 1946), and me found it to be 288' (loc.cit.). As the treatment of the product with alkali was entirely omitted, there could here be 110 possibility that benzoylphenylsemicarbazide, if formed by the action, had been condensed during the process of purification. The same result was obtainel whether the benzaldehyde and phenyl- azocarbamide were heated alone, with the addition of alcohol, or with alcohol and ferrous chloride. The yield varied considerably, the best being obtained when ferrous chloride mas present ; when the latter was omitted, phenylazocarhxmide coulcl be recovered from the alcoholic and ethereal washings. ~ ' e ? 2 ~ o ? / ~ ~ 1 ~ e 1 a ? ? s ~ ~ ~ ~ ~ c ~ ~ y ~ ~ ~ ~ ~ Tide. I n order to determine whether benzoylphenylsemicarbazide would undergo condensation if formed in the course of the actions under con- sideration, i t was first necessary to prepare this compound.Of two alternative methods, namely, addition of cyanic acid to asymmetrical benzoylphenylhydrazine, first used by Miclmelis and Schmidt (Zoc. cit.), and Widman's proces?, the action of benzoic chloride on phenylsemi- carbazide suspended in benzene, me decided t o adopt the latter, and were considerably surprised t o find that the product which we obtained melted a t 202-203O, the melting point given by Michaelis and Schmidt, and not a t 210-211" (Widman). Widman also gives 2l0-21lo as the melting point of the product obtained by Michaelis and Schmidt's method. As alternate fractional recrystallisations from dcohol and benzene failed to alter the melting point of any portion of the sub- stance, the experiment was repeated, using carefully purified phenyl- semicarbazide melting sharply at 171', and the purest obtainable benzoic chloride.After boiling in a reflux apparatus until evolution of hydrogen chloride had ceased, the mixture was allowed t o cool, and the crystalline product was recrystallised from 99 per cent. alcohol ; both before and after recrystallisation it melted at 202-203'. The decanted benzene also, on standing, deposited a further crop of crystals, which melted at 202--203°. 0.3078 gave 29.0 C.C. moist nitrogen a t 12.5" and 750.1 mm. N = 16.31. CGH,*N(CO.C,Hj)*NH*CO.NH, requires N = 16.4'7 per cent. I n addition to the difference in the melting points, our preparation seemed to be considerably more soluble in benzene and i n alcoliol tlian Widman's was, The only chemical action to be compared was the condensation by means of caustic potash to diphenyloxytriazole, and in regard to this point our experience agrees with Widman's observations.The benzoylphenylsemicarbazide mas dissolved in warm caustic potash,OSYTRIAZOLES FROXI PHENYLSEJIICARRjiZInE. 203 nncl, on adding hydrochloric acid, a white, crystalline precipitate was formed which, after recrystallisation from alcohol, melted at 2S8-289", and was undoubtedly diphenyloxytriazole. I n view of these facts, it seems highly probable that there are two 1 -benzoyl-1-phenylsemicarbazides, both of which, according to the usually accepted constitution foip the semicarbazides, would be represented by formula I. C),H,-?J* N H* C(0H):NH I C,$H5* N N H CO NH, I 11.* CGHj*CO C,H,m C 0 It is quite possible that semicarbazides may contain the grouping - C(OH):NH, as in formula 11. The isomerism under consideration could hardly be due t o ono isomeride having the constitution represented by I., and the other that represented by II., as, in such a pair, one isomeride would be readily converted into the other, which does not seem to be the case in this instance. A similar objection might be urged to the suggestion that both substances may have constitution II., and that the isomerides may be represented by (' syn " and " anti " formulq similar t o those by which the isomerism of the oximes is explained by the Hantzsch- Werner theory, thus : H*N II II * C',H,*N(COC,H,)*NH* C *OH N*H and C,,H;X(COC',H;)*XR.C *OH A more probable explanation of the supposed isomerism may be founded on the fact that two of the nitrogen atoms are each attached to three different groups, The possibility of isomerism being produced by a difference in the arrangement of three different groups about a nitrogen atom has been recognised for some years (Hantzsch and Werner, Eel*., lS90, 23, 20), but it is only recently that v. Miller and Plochl (Be?*., 1896, 29, 1462) have succeeded in obtaining the first pair of isomerides in which the isomerism has been shown to be due to this cause. These authors have shown that the condensation of acetaldehyde and anisidine yields two products, both of which must be represented by the formula C,H:,(CH:~),*NH* CH(CH,)-CH.; CHO. They point out that, as neither isomeride is optically active, the iso- merism cannot be due to the asymmetric carbon atom, and that for the same reason the three valencies of the nitrogen atom must be con- sidered to lie in the same plane.To account for the isomerism, the following two formulse are suggested. C H(CH,)* CH,* COH I I I I C H(CH,)* CH,* COH N*C,H,(CH,), and NH H C,H,(CH:J,204 YOUNG AND ANNABLE : FORMATION OF SUBSTITUTED It is important to note that v. Miller and Plochl find that these two isomerides cannot be readily, if a t all, converted one into the other. I f in the case of benzoylphenylsemicarbazide we have to deal with a similar case of isom&ism, it seems probable that it is due to a differ- ence in the arrangement of the groups round that nitrogen atom to which benzoyl is attached, and the two isomerides might be repre- sented by bhe tentative formulze NH.CO *NH, O*C,H, N* CO*C,H, I and N*NH* CO*NH,. I CGH5 It might be interesting to note that the benzoylphenylsemicarbazide is not the only case in which Widman and Michaelis and Schmidt have observed different melting points for the same derivative of asym - benzoylphenylhydrazine. Benzylidenebenzoylphenylhydrazone, C,H,-N(COC,H,)*N:CH* CGH,, was observed by Widman (Bey., 1893,26, 947) to melt a t 115-116', and by Michaelis and Schmidt (loc. cit.) a t 122'. Both specimens were prepared by the action of benzaldehy de on benzoylphenylhydrazine which melted at 69-70'. As such cases of isomerism are, not only interesting, but also of great theoretical value, we regret we are unable to pursue this investi- gation," and hope that someone interested in this subject may be able to decide whether two isomeric benzoylphenylsemicarbazides exist, or a t least as to the cause of the difference in the products obtained, on the one hand by Widman, and on the other by Michaelis and Schmidt and by us, Attempts to Condense Be~a,zxoy~~en?/Zsemiccc?.bcc.2.ide. Benzoylphenylsemicarbazide (1 mol.), dissolved in boiling alcohol, was boiled with ferrous chloride (2 mols.).The product consisted wholly of unaltered benzoylphenglsemicarbazide, melting at 202-203". No trace of diphenyloxytriazole could be observed. The above ex- periment was repeated with the addition of hydrochloric acid, but the result was the same. The effect of heating the mixture under pressure at 130' for half an hour was next tried, but the benzoylphenylsemicarbazide was recovered unchanged.There was no diphenyloxytriazole formed. On * We have been compelled to cease our investigations into derivatives of phenyl- hydrazine, owing to one of us having become so extremely sensitive to these sub- stances that the merest trace of vapour or of substance in solution prodiices an acute attack of eczema on the exposed portions of the skin.OXYTRIAZOLES FROAI PHENYLSEMICARBAZIDE. 205 repeating the experiment with the addition of hydrochloric acid, hom- ever, the cooled tube showed a high internal pressure, and neither benzoylphenylsemicarbazide nor diphenyioxytriazole could be found in the alcoholic solution. We are of opinion that these failures to condense benzoylphenyl- semicarbazide, along with the resultss of the investigation on the action of benzaldehyde on pheny lazocarbamide, show that benzoylphenyl- semicarbazide is not formed by the oxidation of a mixture of phenyl- semicarbazide and benzaldehyde, or by the action of the latter on phenylazocarbamide.The equations Ilrc. and IIb., given at the com- mencement of this paper, may be, therefore, taken as fairly represent- ing the course of the action by which diphenyloxytriazole is formed from benzaldehyde and phenylsemicarbazide. I n order to obtain some idea as to the scope of this action, we have investigated the behaviour of a variety of aldehydes, and have ob- tained a series of oxytriazoles, which are described in the following pages.The aldehydes which have yielded oxybriazoles are : metanitro- benzaldehgde, paranitrobenzaldehyde, metatoluic aldehyde, terephthalic aldehyde, and cinnamic aldehyde. The following did not yield oxytriazoles : formaldehyde, acetalcle- hyde, paraldehyde, isobutaldehyde. This oxytriazole was prepared by the oxidation of an alcoholic solu- tion of phenylsemicarbazide and paranitrobenzaldehyde. The addition of water to the product precipitated a reddish-yellow substance, which, on treatment with warm ammonia, passed almost completely into solu- tion, leavinga red, tarry residue. On adding hydrochloric acid to this solution, a yellow, amorphous precipitate was obtained, which separated from 90 per cent. alcohol in the crystalline state. Dried a t looo, it gave figures agreeing with the formula which requires C = 59.57 ; H = 3.54, and N = 19-85 per cent.NO,* C,,H,C',N,* OH, I. 0,1329 gave 0.2902 CO, and 0.0441 H,O. 11. 0.2050 ,, 34.0 c.c.moist nitrogen a t 14Oand 768-0 mm. N = 19-72. Paranitrodiphenyloxytriazole is insoluble in water, easily soluble in boiling alcohol, less so in cold alcohol, and only slightly in boiling ether and benzene. It is easily soluble in alkalis, and in warm alkali carbonate solutions, and these solutions do not reduce Fehling's solu- tion,or silver nitrate, evenon prolonged boiling. No sharp melting point C = 59.55 ; H= 3.68.206 YOUNG AKD ANNABLE : FORMATION OF STJRSTITUTED could be observed, as, when heated in a capilinry tube, the su1)stanco begins to darken a t ?,TO", and melts and decomposes abont 2563-260'. The ammoniacnl sulntion is deep red, but on boiling, the red colour gradually disappeared, and, a t the samc time, a crystftllioe film formecl on the surface. When nmnionia could no longer be cletected in the steam, the liqiiid mas filtered and the filtrate acidified, but there mas no precipitation.The crystalline film melted a t about 256-260", and a nitrogen determination gave figures agreeing with the formula of the oxytriazole, C,,H1,N,O,, or N = 19.85 per cent. Found, N = 20.13 per cent, The ammonium salt is, therefore, completaly dissociated a t the temperature of boiling water. The same result followed an attempt to prepare the ammonium salt by allowing n concentrated ammoniacal solution of the oxytriazole to evaporate spontxneously.The residue consisted of unchanged oxytriazole. Paranitrodiphenyloxytrjazole is oxidised by boiling nitric acid to paranitrohenzoic acid, which was identified by its melting point, 237--238", and by a nitrogen determination. C7HSN0, requires N = 8-38 per cent. The silver salt of paranitrodiphenylox~+iazole, N0,C12H,C,N,0Ag + iH,O, is precipitated as a yellowish, crystalline powder on adcling silver nitrate to the amrnoniacal solution. It is easily soluble in excess of ammonia. When dry, i t seems to be stable, but if exposed to light while moist, it rapidly turns red. The water of crystallisa- tion is given up a t 110". Pound, N = 8.29 per cent. 0.6602 lost,, a t 110", 0.0152 II,O = 2.30. 0,6452, dried a t l l O o , gave 0,2394 AgC1. Cl,H,N,O,Ag + iH,O requires H,O = 2-26, Ag = 27.93.C1,H,N,O,Ag reqiiires Ag = 27.76 per cent. Ethg Z ~ ~ ( ~ . r . n l z i t i . o c T z J ~ e ~ ~ ~ ~ o ~ ~ t i , ~ t ~ ~ o Ze, NO, C, ?H,. C',N,O* C,H,. The ethyl derivative, prepared by the action of ethylic iodide on the dried silver salt, crystallised from alcohol in long, thin, slightly yellow plates, which melted a t 140". It is insoluble in water, slightly soluble in cold alcohol and ether, and easily in boiling alcohol and ether. The solution in benzene is precipitated by the addition of light petroleum. I t is not attacked by boiling alkalis or by boiling concentrated acids. 0.1'732 gave 26.4 C.C. moist nitrogen a t 12' and 758.9 mm. N = 18-06. CliH9N4O3*C2Hi requires N = 18.06 per cent. Acetg?ll;llniw Iziti.ocli~J~ei~yZorc?/tl.ictxole, KO; c', .H,* C,N30 C,H,O.The acetyl derivat ve, prepared by boiling the oxytriazole withOXYTRIAZOLES FROM PHENYI,SEI\IIC'ARRh%InE. 207 acetic anhydride and fused sodium acetate, was recrystallisecl from alcohol. I t formecl small, hard, fl:it needles, having a slight yellow tinge and melting a t 152". I t is easily soloblc in glacial acetic. acid, in cold ether, and in boiling alcohol. When 1)oiled with potassiiini carbonate solution, or with dilute hydrochloric acid, it is rapidly h ydrol ysed. 0.2000 gare 30.2 C.C. moist nitrogen at 12" and 722.1 mm. N = 17.02. C,,H,N,O,* C,H :O requires N = 17-28 per cent. The silver salt was warmed with benzoic chloride dissolved in ether, and t h e product recrystallised from alcohol. It formed yellowisli- white, feathery plates, which melted at 153".This derivative is insoluble in water, fairly soluble in boiling alcohol and ether, less so in cold alcohol and ether. It is easily soluble in benzene, and is pre- cipitated from the solution by the addition oE light petroleum. It is slowly hydrolysed by boiling potassium carbonate solution, and more rapidly by boiling dilute hydrochloric acid. 0.2193 gave 27.1 C.C. moist nitrogen at 15.5"and 759.1 mm. N = 1 4 4 ? . C1,H9N,03* C7H,0 requires N = 14.50 per cent. Reduct ioiz of Pnm n itraocl iph c jig Z o q t r icc zo Ze. Paranitrodipbenyloxytriazole was added in small quantities at a time to a warm mixture of stannous chloride and concentrated hydrochloric acid. After dilution, the tin was removed as sulphide, the filtrate concentrated, and the new base precipitated by the addition of am- monium acetate.Further purification was effected by dissolving i t in dilute, warm ammonia, precipitating by acetic acid, dissolving again in warm glacial acetic acid, and precipitating by water. 0.1576 gave 0-38-15 CO, and 0.0681 H.,O. 0,2155 48.0 C.C. moist nitrogen a t 1 5 5" and 748-9 m u . N = 22-42. NH,. C,,H,C',N,*OH reqnires C = 66 66 ; H = 4.76 ; N = 28-22 per cent. C: = 66.53 ; H = 4.80. ,, C,H;X*N Pn YCI nzido t l iph e 1 t g Z o q t 1- i CI Cole, I >C*OH,forms delicate, NH,.C .H C :N 4 mhite needles, which remained unchanged when heated t o 290'. It is easily soluble in dilute mineral acids and in warm glacial acetic acid ; from its solution in the latter, it is precipitated unchanged on the addition of water.It is easily soluble in dilute alkalis and in warm potassium carbonate solution, from which i t is precipitated by dilute acetic acid, The alkaline solutions do not reduce Fehlings solution,208 YOUNG AND ANNARLE : FORMATION OF SUBSTITUTED It is only slightly soluble in boiling alcohol, almost insoluhle in ether and benzene. The arnmoniacal solution, when warmed, became rapidly covered with a film of slender neeclles,whichanitrogendeterminationshowed to be the free amiclodiphenyloxytriazole. Found N = 22.44 per cent., C,+HI,N,O requiring N = 22.22 per cent. When paramidodiphenyloxgtriazole is dissolved in a small quantity of warm, concentrated hydrochloric acid, the hydrochloride crystallises out in long needles as the solution cools.These crystals, if air-dried on a porous plate, contain 3H,O; when dried in a vacuum over sul- phuric acid, or if heated to 90°, the water of crystallisation is given up, and if the temperature be raised, hydrochloric acid is also lost,, dissociation being complete at 11 0". The residue, dissolved in nitric acid, gave no precipitate with silver nitrate. 0~612810st,at90°,0~0980,andat I1O0,O*164L H,O= 15.97; HCl= 10.80. 0.8596 of the dried salt gave 0.4194 AgC1. 1.0223 lost over sulphuric acid 0.1627. Hal= 12.41. H,O = 15.93. C,,H,,N,O,HCl+ 3H,O requires H,O = 15.76 ; HC1= 10.66 per cent. C,,H,,N,O,HCl requires HCl= 13.66 per cent. The silver salt, NH,* C,,H,* C,N,OAg + H,O, is precipitated as a white, amorphous powder on adding silver nitrate to an animoniacal solu- tion of amidodiphenyloxytriazole.It is easily soluble in excess of ammonia and in nitric acid. After being dried over sulphuric acid, i t appears to be quite stable, but if exposed to light while moist i t rapidly turns red. Analysis gave the following figures agreeing with the above formula. 1.5092 lost, at 1 lo", 0.0'732 and then gave 0.5748 AgCl. H,O = 4.55 ; CI4Hl1N,OAg + H,O requires H,O = 4 77 per cent. Ag = 30.34. C1,H,,N,OAg requires Ag= 30.08 per cent. The diacetyl derivative, formed when amidodiphenyloxy triazole is boiled with acetic anhydride and fused sodium acetate, is easily soluble in glacial acetic acid, ether, and boiling alcohol ; recrystallised from 80 per cent. alcohol, it forms a white, crystalline powder which melts a t 2 15'.0.2148 gave 31.4 C.C. moist nitrogen a t 12" and 739.8 mm. N= 16-88, C,,H,,N,O*(C,H,O), requires N = 16-66 per cent.OXYTRIAZOLES FROM PHENYLSEMICARBAZIDE. 209 The diacetylamidodiphenyloxytriazole is insoluble in cold, dilute acids and alkalis, but when boiled with potassium carbonate solution, it gradually passes into solution ; on adding hydrochloric acid, the monacetyl derivative is precipitated. The same partial hydrolysis is effected by boiling with dilute hydrochloric acid. Morzucety~~ii1.a~Iiiclod;~l~esz?/ Zoxyt~iccole, LC:,H,*N*N C,II,O *NH* C,H,* C :N I YC-OH, 4 1 is easily soluble in alkalis, alcohol, and ether. dilute acids. which melt a t 278". the amidodiphenyloxy triazole is warmed with acetyl chIoride. It is insoluble in It crystallises from alcohol in white, hair-like needles, The same monacetyl derivative is formed when 0.1987 gave 32.9 C.C.moist nitrogen a t 15' and 745.4 mm. N = 19.01. C,H,O* C14H1,N40 requires N = 19 04 per cent. When the monacetyl derivative is boiled with concentrated hydro- chloric acid, it gradually becomes dissolved, and addition of dilute ammonium acetate solution precipitates p-amidodiphenyloxytriazole, as shown by the high melting point (over 290') and by a nitrogen determination. 0.1846 gave 35.8 C.C. moist nitrogen at 16-5"and 750-1 mm. N = 22.25 C,,H,,N,O requires N = 22.22 per cent. This oxytriazole was prepared by the oxidation of an alcoholic solu- tioh of phenylsemicarbazide and metanitroben zaIdeby de. As in the case of the paranitro-derivative, treatment of the product with am- monia left a small amount of a red, tarry matier undissolved; 011 acidifying the nminoniacal solution, a y ellowisli, crystalline precipi- tate was formed.This was dissolved in boiling benzene, and as the solution cooled, metanitrodiphenyloxytriazole crystallised out in yellowish, microscopic plates, which melted a t about 275-278". The melting point could not be observed sharply, as considerable decompo- sition takes place before it is reached. 0.1655 gave 0.3608 CO, and 04554 H,O*(: : 5'3.45 ; H- 3.7'1. 0.1608 ,, 27.4 C.C. moist nitrogen at 15" and 753.3 mm. N = 19.75, C1,€IE-I,,N,O, requires C = 59-57' ; H = 3.5 1 ; N = 19.S.5 per cent.210 YOUNG AND ANNABLE : FORMATION O F SUBSTITUTED Yhenylmetanitrophenyloxytriazole is very slightly soluble in water, more so in boiling alcohol, ether, benzene, and glacial acetic acid.It is easily soluble in dilute alkalis and in warm, dilute alkali carbonate solutions. It dissolves in warm, concentrated hydrochloric acid and is precipitated unchanged on the addition of water; it is not attacked by prolonged boiling with concentrated hydrochloric acid or alkalis, and the alka,line solution does not reduce Fehling's solution or silver nitrate. As the aqueous filtrates from metanitrodiphenyloxytriazoll: were found to be always more or less coloured, the solubility in water mas determined by boiling an excess of the substance with distilled water and filtering througha hot filter, It was found that 100 C.C. of water measured a t 15' dissolved, when boiling, only 0.0343 gram of metanitrodipheny loxy triazole.This oxytriazole is very easily soluble in warm, dilute ammonia, forming a somewhat opaque, deep, reddish-yellow solution. The am- monium salt is very easily dissociated, nitrodiphenyloxytriazole separating out in crystalline scales when the solution is kept warm. These melted a t 270-276", and on analysis gave N = 19.88 per cent ,, C,,H,,N,O, requiring N = 19.55 per cent. Xetanitrodiphenyloxytriazole, when boiled with dilute nitric acid, is oxidised t o metanit'robenzoic acid, which was recognised by its melt- ing point, and by a nitrogen determimation. Found, N = 8.31 per cent., NO,. C,H,* COOH requiring N = 8-38 per cent. The silver derivative, NO; C,,H,- C2Nij* OAg + 4 H,O was thrown down as a white, amorphous precipitate on adding silver nitrate t o an ammoniacal solution of the oxytriazole.It is easily soluble in excess of ammonia ; when dry, it seems t o be stable, but in the moist condition i t rapidly becomes red on exposure to light. The air-dried substance, when heated to 100-llOo, lost weight equivalent to &H,O. 0.3288 a t 110" lost 0.0082 H,O = 2.49. 0.5720, dried a t l l O o , gave 0.2113 AgCl. Ag=27*80. NO,* C1,H,C,N,*OAg + &H,O requires iH,O = 2.26 per cent. NO; C,,H,C,N; OAg requires Ag = 27.76 per cent. This derivative was prepared by the action of a n etliereal solution OF cthylic iodide on the dried silver salt. On evaporating the ethereal solu- tion, a mass of yellowish, silky needles was deposited. These needles melted at 9V, and after repeatedly recrystallising from dilute alcohol, were obtained as small, yellow, prismatic crystals, melting at 98'.N == 1S.23. 0.2105 gave 32.8 C.C. moist nitrogen at 16" and 761.11 mm. l3thylmetanitrodipheiiylosytriazole is insoluble in water, easily NO,* C,,H,:C,N,O-C,I€, requires N = lS.06 per cent.0 XY TRI AZO 1, ES FROM PHEN Y LS EJIIC ARB AZIDE. 211 soluble in alcohol and ether. alkalis. It is not acted on by boiling acids o r Acety~~izetc~~~it.i~o~l~~)~en~Zo.~~t~.icc.;oZe, NO; C,,H, : C,?J,O. C,I€,O. Prepared in the same way RS acetylparanitrodiplienyloxy triazole , it is left in clusters of small needles on evaporating the ethereal solution. It melts a t 116", and is moderately soluble in cold ether, easily in boiling ether, glacial acetic acid, or ethylic acetate.0.2173 gave 33.2 C.C. moist nitrogen at 12"and 720.1 mm. N = 17.17. NO,C,,H,* C,N,0*C2H,0 requires N = 17:28 per cent. The acetyl derivative is rapidly hjdrolysed when boiled with potas- sium carbonate solution or with dilute hydrochloric acid, giving meta- nitrodiphenyloxytriazole, melting at 275- 277". l ' e n ~ o ? / l n z e t ( ~ c l z i t . 1 ~ o ~ ~ ~ ~ J ~ e ~ ~ ~ l o ~ ~ t ~ ~ ~ ~ ~ o l ~ , NO,* C1,,Hc, : C,N,0*C7H,0, was prepared by warming the dried silver salt, suspended in dry ether, with a slight excess of benzoic chloride. The ethereal solution, after wash- ing with potassium carbonate, was dried a i d evaporated ; the yellow crystals thus obtained melted a t 148". It is fairly soluble in warm ether and in boiling alcohol. 0.1616 gave 21.1 C.C.moist nitrogen at 19.5" and 758.2 mm. N = 14-92. NO,C1,H; C,N,0*C7H,0 requires N = 14.50 per cent. Redzcct io of n-letcc )&rot1 iphe?Zy Zoxpti. icco Ze. The reduction was effected with iron filings and concentrated hydro- chloric acid, and on the completion of the reaction, water was added and the excess of hydrochloric acid removed by a current of steam. When the solution had cooled down, ammonium acetate was added to precipi- tate the new base, which was purified by dissolving it in ammonia and reprecipitating by dilute acetic acid. 0.1571 gave 0.3835 CO, and 0.0688 H,O*C = 66.57.H = 4 S7. 0.2004 ,, 35.6 C.C. moist nitrogen a t 13.5" and 752.2 mm. N = 22.35 C,,H,,N,O requires C: = 66.66 ; €I = 4.76 ; N = 22.22 per cent. in needles melting a t 278".It is easily soluble in dilute hydrochloric acid and in glacial acetic acid, and is precipitated from the latter solu- tion on adding water. It is easily soluble in dilute alkalis and in warm potassium carbonate solution, and is reprecipitated by acetic acid. It is slightly soluble in boiIing alcohol, hit insoluble in ether and benzene. The ammoniacal solution has a deep red colour which212 YOUNG AND ANNABLE : FORMATION OF STTBSTITUTED disappears on boiling, the free oxytriazole separating as a crystalline film melting at 27s"; on analysis, it gave N = 22*3'7,C1,H1,N,0 requiring N = 22.22 per cent. When metamidodiphenyloxytriazole is dissolved in a small quantity of warm, concentrated hydrochloric acid, the hydrochloride, NH,* C,,H,:C,N,* OH,HCl + 3H,O, crystallises out in brownish needles as the solution cools.The air- dried crystals contain 3H,O, which are given up a t l l O o , or when the salt is dried in a vacuum over sulphuric acid. This hydrochloride differs from the corresponding salt of paramidodiphenyloxytriazole in that at 110" dissociation into the free base and hydrochloric acid does not take place. 0.9898 lost, a t l l O o , 0.1565 H,O= 15.S2. 0 S333, dried at l l O o , gave 0.4084 AgCl. 0-9144, dried over sulphuric acid, gave 0.4415 AgCl. NH,*C,,H,:C,N,* OH,HCl+ 3H,O requires 3H,O = 15.76 per cent. NH,* C,,H,:C,N,*.OH,HCl requires HC1= 12.66 per cent. HCl = 12.47. HCl= 12.31. The silver salt, NH,. C12H!,: C,N,OAg + H,O, is a white, amorphous powder, which rapidly turns red if exposed to the light while moist, but seems to be stable when dry.It is easily soluble in ammoniaand in nitric acid. It loses its water of crystallisation a t 100-110". 1.6583 lost, at 110", 0.0799 H,O = 4*S(2. 1,5794, dried at l l O o , gave 0.6311 Ag Cl. Ag = 30.07. NH,. C,,H,:C,N,OAg + H,O requires H,O = 4-77 per cent. NH,* C,,H9:C,N,0Ag requires Ag = 30.08 per cent. B iacet yZnietaaLidod~~l~e.rL y Zoxpt&m Ze, The diacetyl derivative was prepared by boiling the oxytriazole with acetic anhydride and fused sodium acetate. The oil left on evaporating the ethereal solution was dissolved in boiling alcohol, and water added, when a white, crjstalline powder was precipitated whicb, after recrystallisation from dilute alcohol, formed small, white needles melting a t 117". 0.3678 gave 53.3 C.C.moist nitrogen at 17", and 759.5 mm. N = 16.82. ClsH16N,0~j requires N = 16.66. It is insoluble in cold, dilute alkalis and acids, but when boiled with dilute potassium carbonate solution it is rapidly converted into the mon- acetyl derivative ; the same change also takes place when the diacetyl derivative is boiled with dilute hydrochloric acid. iCloiiclcet~Z~~~etn~~~.iclotl~~7~es~~Zox.yt~~iaxoZe, C,H,O *NH* C,,-H9: C,N; OH, C,H,O*NH* C1,H,:C,N,O*C,H,O. This diacetyl derivative is easily soluble in ether and alcohol.OXYTRIAZOEES FROM PEIENYLSEMIChRBAZIDE. 213 is deposited from dilute alcohol as a white, crystalline powder which melts at 294". The same monacetyl derivative may be formed by warming amidodiphenyloxytriazole with acetic chloride.0,1682 gave 28.0 C.C. moist nitrogen a t 1 8 O , and 761.9 mm. N = 19.27. C1,H14N402 requires N = 19.04 per cent. The monacetyl derivative is easily soluble in alkalis, in warm potassium carbonate solution, in alcohol, and in ether. It is insoluble in dilute acids, but when boiled with concentrated hydrochloric acid the remaining acetyl group is removed, and on then adding ammonium acetate the free amidodiphenyloxytriazole is precipitated. It was recog- nised by its melting point, 278*, and a nitrogen determination. Found, N = 22.29 per cent., Cl,H12N,0 requiring N = 22.22 per cent. Phenylmetatolyloxytriazole was prepared by the oxidation of an alcoholic sohtion of phenylsernicarbazide and metatoluic aldehyde. Ten grams of phenylsernicarbazide yielded over 9 grams of phenyltolyl- oxytrinzole.The crude product was purified by dissolving it in ammonia and reprecipitating by sulphuric acid. It crystallised from alcohol in white, microscopic plates which melted sharply a t 256". 0.1624 gave 0,4268 CO, and 0.0767 H,O. 0.2219 C = 71.69 ; H = 5-25. ,, 32.4 C.C. moist nitrogen a t 15' and 749.1 mm. N = 16.85. C1,H,:,N30 requires C = 71.71 ; H= 5.17 ; N = 16.73 per cent. Phenylrnetatolyloxytriazole is sparingly soluble in boiling alcohol, ether, and benzene, and almost insoluble in boiling water and in light petroleum. It is easily soluble in alkalis, and in a boiiing, dilute sdution of potassium carbonate, from which it is reprecipitated by acetic acid. The alkaline solutions do not reduce Pehling's solution or silver nitrate, even on prolonged boiling.The ammoniacal solution is reddish-brown, but when boiled, it gradually becomes colourless, the oxytriazole at the same time being precipitated, The addition of silver nitrate to the aqlmoniacal solution precipitates the silver salt of phenyltolyloxytriazole as a white, amorphous powder. It is easily soluble in excess of ammonia, and separates from a warm, dilute ammoniacal solution, on cooling, in smalI, shining crystals. It becomes red when exposed to light while still moist, but seems quite stable when dry. Dried in n vacuum over sulphuric acid, i t contains lH,O, which is given up at 100-110". VOL. LXXI, Q214 YOUNG AND ANNABLE : FORMATION OF SUBSTITUTED 0,7433 lost, at l l O o , 0.0360 H,O = 4.85. 0.70'73, dried at 110', gave 0.2843 A@.Ag = 30.25. C,,H,,:C,N,OAg + H,O requires H,O = 4-78 per cent. C,,,Hl2:C,N3OAg requires Ag = 30.16 per cent. Etlz?l~J~e.n?/lnzetatol?lloxyts.iccxoZe, Cl,H12: C,N,O* C,TI,. The ethyl derivative was prepared from the silver salt by the action of ethylic iodide. On evaporating the ethereal solution, an oil was left which was dissolved in warm, light petroleum; on evaporating this solution, the ethyl derivative crystallised in clusters of plates which melted a t 59". It is easily soluble in alcohol, ether, benzene, and light petroleum, and separates from most of these solutions as an oil which solidifies on standing. 0.2086 gave 28.2 C.C. moist nitrogen at 14' and 736.6 mm. N = 15.40. It is not attacked by boiling acids or alkalis. C,,H,,- C,N,O*C,H, requires lS = 15-05 per cent.Acet?l~J~e~a?llnzetcclol~lox~t~inxole, C,,H,,: C,N,O*C,H,O. The acetyl derivative is formed on boiling the oxytriazole with acetic anhydride and fused sodium acetate ; the product was then neutralised with potassium carbonate and extracted with benzene. The brown oil left on distilling off the benzene was treated with small quantities of warm, light petroleum ; on cooling, a small quantity of oil was first de- posited and then white, crystalline nodules which melted at 65-68'. On recrystallisation from dilute alcohol, the acetyl derivative separated as an oil, which gradually solidified to white crystals melting at 69.5-70". After repeated recrystallisation, the melting point remained constant at 70". 0.2328 gave 20.2 C.C. moist nitrogen at 14' and 742.7 mm.N = 14.41. C13H12: C,N,O*C,H,O requires N = 14.33 per cent. The acetyl derivative is insoluble in water, easily soluble in alcohol, ethor, and benzene, and in warm, light petroleum. It is easily hydro- lysed by boiling potassium carbonate solution, or by boiling dilute hydrochloric acid, yielding phenyltolyloxytriazole melting at 256". Benso?ll~J~en?llbrtet~tol?llox?lt?.iwxole, C,,H,,: C,N,0*C7H,0. The benzoyl derivative, prepared by the action of benzoic chloride on the silver salt suspended in dry ether, crystallised from alcohol in clusters of small, white needles which melted at 1179 It is easily soluble in warm alcohol and ether, moderately so in benzene, insoluble in light petroleum and in water. 0,2477 gave 26.1 C.C. moist nitrogen at 14" and 755% mm.N = 12.32. C13H,,C,N,C7H,0 requires N = 12.38 per cent.OXYTRIAZOLES FROM PHENYLXEMICARBAZIDE. 215 The benzoyl derivative is hydrolysed by boiling alkalis and acids, more slowly by boiling potassium carbonate solution, yielding phenyl- metatolyloxytriazole melting at 256". This oxytriazole was prepared b y the oxidation of an alcoholic solution of rphenylsemicarbazide and cinnamaldehyde. After removnl of the alcohol by a current of steam, a yellowish, crystalline film separated, which was dissolved in dilute ammonia, filtered, and repre- cipitated by hydrochloric acid. The product, after several recrystalli- sations from alcohol, formed yellowish, shining leaves, which nielted at 2 8 4 O . 0.1404 gave 0.3'750 CO, and 0.0659 H,O. 0.2053 ,, 28.5 C.C.moist nitrogen a t 15fi"and 750.7 mm. N = 16.02. C,,H,,N,O requires C = 73.00 ; H = 4194 ; N = 15.96 per cent. Phenylstyrenyloxytriazole is only sparingly soluble in hot alcohol, and almost insoluble in ether, benzene, and water. It is easily soluble in alkalis and in warm potassium carbonate solution, from which i t is reprecipitated by acetic acid. The ammoniacal solution is slightly fluo- rescent, but, on boiling, the fluorescence gradually disappears and at the same time the oxytriazole separates as a crystalline film. The alkaline solutions do not reduce either Fehling's solution or silver nitrate. After repeated recrystallisation from alcohol and from glacial acetic acid, the substance was odourless, remained slightly yellow, and melted constantly a t 284'. Fractional recrystallisation, as also conversion into the acetyl- and the benzoyl-derivatives with subsequent hydrolysis failed to raise the melting point above 286".This was particularly noted, as Widman, who has also recently (Be?.. , 1806, 29, 1946) prepared phenylstyren yloxytriazole by the action of caustic potash on cinnamylphenylsemicarbazide, observed that i t melted at 287". I n other respects, the properties of our product agree with those described by Widman. The silver salt, CI4I3,,:C,N,OAg + l ~ H , O , is precipitated as a yel- lowish, amorphous powder on adding silver nitrate to a cold, dilute amtnoniacal solution of phenylstyrenyloxytriazolc. If the precipitatioii be carried out in a warm solution, or in one containing too great an excess of ammonia, the silver salt separates as a dark, tarry mass, which gradually changes to a yellowish powder when shaken with large quantities of water.Analysis gave figures agreeing with the above formula, the water being given off at 110'. ' " Styrenyl " is the term suggested by Widman (Bw., 1896, 29, 1946) for the nnsaturated univalent radicle C,H,* CH: CH-. C = 72.84 ; H = 5-21. Q 2216 YOUNG AND ANNABLE : FORMATION OF SUBSTITUTED 0.6573 lost, at 110', 0.0430 H,O = 6-54, 0.5887, dried at 1 loo, gave 0.2300 AgC1. Ag = 29.40. C,,I€,,:C,N,OAg + l&H,O requires H,O = 6-80 per cent. ; C,,H,,: C,N,OAg requires Ag = 29.19 per cent. The ethyl derivative, prepared by the action of ethylic iodide on the dried silver salt, crystallises from SO per cent. alcohol in clusters of white needles melting a t 89-90'.It is fairly soluble in ether, alcohol, and benzene, slightly so in lighb petroleum. 0.2635 gave 31.4 C.C. moist nitrogen at 13' and 769.3 mm. N = 14.26. C,,H,,:C,N,O*C,H, requires N = 14-44 per cent. When boiled with alkalis, the ethyl derivative is coiiverted into an oil, which, on treatment with benzene, again becomes crystalline and melts zt S9-90"; the same effect is produced by long boiling with concentrated hydrochloric acid. The acetyl derivative was prepared by the action of acetic chloride on the dry silver salt and also by boiling the oxytriazole with acetic anhydride and sodium acetate; both methods yielded an oily sub- stance which could not be properly purified. It was easily soluble in the various organic solvents, but on cooling or on evaporation of the solution, the substance separated as an oil; i t was, therefore, not analysed.It dissolved when boiled with dilute potassium carbonate solution, and on acidification phenylstyrenyloxytriazole melting at 283-284" separated. The benzoyl derivative, prepared by boiling the dry silver salt with an ethereal solution of benzoic chloride, crys tallised from alcohol in round tufts of small, yellowish needles melting a t 1 2 5 O . From benzene, it crystallised in brilliant, yellow, silky needles. It is easily soluble in warm benzene, ether, and alcohol. 0.2349 gave 23.1 C.C. moist nitrogen at 14" and 749.5 mm. N = 11.41. C,,H,,:C,N,O* C,H,O requires N = 1 1 a44 per cent. Hydrolysis takes place slowly when the benzoyl derivative is boiled with potassium carbonate solution, more quickly by the action of boiling acids and alkalis. The regenerated phenylstyrenyloxytriazole melted a t 283"-284".OXYTRIAZOLES FROM PHENPLSERIICARBAZIDE.a17 N -N C,H,C,H, N -N N=C - C,H, ---GIN HO.C< I I >C*OH. 1 4 This oxytriazole mas prepared by the oxidation of an alcoholic soh- tion of phenylsemicarbazide (2 mols.) and terephthalic aldehyde (I mol.) (melting point 11 6"). The product was washed with warm alcohol, and dissolved in dilute ammonia; on standing, the solution gradually de- posit ed the phen ylenedip h en y loxy triazole in white, cry st alline nodules, which remained unchanged when heated to over 340". 0.1563 gave 0.3802 CO; and 0.0590 H,O. C = 66.34 ; H= 4.19. 0.1283 ,, 23.5 C.C. moist nitrogen at 12Oand 747.7 mm. N = 21 -38. C,,H16N,0, requires C = 66.66 ; H = 4.04 ; N = 21.21 per cent. The substance seems to be quite insoluble in water, alcohol, ether, and benzene. It is, however, easily soluble in alkalis ; when its solution in dilute ammonia was allowed to stand, i t was reprecipitated in yellowish, minute crystals. On adding silver nitrate to the ammo- niacal solution, the silver salt was precipitated; this, when heated at l l O o , lost weight equivalent to about gH,O. 0.7773 lost, a t 110", 0.0160 H,O=2*05. 0.7613 gave 0.3590 AgC1. Ag. = 35.49. C,,H,,N,O,Ag, + $H,O requires $H,O= 2-16 per cent. C,,H1,N,jO,Ag, requires Ag, = 35.40 per cent. The acetyl derivative, prepared by boiling the oxytriazole with acetic anhydride and fused sodium acetate, crystallised from alcohol in clusters of white, delicate needles, which melted at 208-210". It mas easily soluble in alcohol, ether, and benzene. No analysis wasmscle, as me had not sufficient of the substance a t our disposal. When boiled with potassium carbonate solution, the acetyl deriva- tive rapidly passed into solution, and the addition of hydrochloric acid precipitated the high melting phenylenediphenyloxytriazole. Having shown, as described in the foregoing pages, that the forma- tion of an oxytriazole by the oxidation of a mixture of phenylsemicar- bazide and an aldehyde is a general action for aromatic and fatty aromatic aldehydes, we next turned our attention to the purely fatty aldehydes. Those which we have tried are formaldehyde, acetalde- hyde, paraldehyde, and isobutaldehyde. Alcoholic mixtures of these aldehydes with phenylsemicarbazide have been subjected to the action of various oxidising agents, both in open and in closed vessels, at temperatures varying from that of the atmosphere to 150", and for varying lengths of time, but in no instance have we been able218 SUDBOROUGEI : RESEARCHES IN TRE STIT,BENE SERIES. to isolnte an oxytrinzole as a product of the action. We have met with no better success in ~ i i r endeavours to condense these aldehydes with phenylazocnrbnmide. I n RS far as our experience goes, therefore, the action does not seem to be capable of extension t o the purely fatty aldehydes.

ISSN:0368-1645    

DOI:10.1039/CT8977100200

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

218 SUDBOROUGEI : RESEARCHES IN TRE STIT,BENE SERIES. By JOHN J. SUDBOROUGII, Ph.D., D.Sc. BY the action of phosphorus pentachloride on deoxybenzoin, C,H5* CH,. CO*C,H,, Zinin obtained an oily chlorostilbene, which he describes as being unstable and as yielding tolane, C,H,-C i C*C,H,, on distillation (Annnlen, 1869, 149, 375). Some few years ago, I showed (Bey., 1892, 25, 2237) that, when deoxybenzoyn is heated with phos- phorus pentachloride, and the product is distilled, a solid chloro- stilbene, melting a t 54O, is obtained differing materially from the oily compound described by Zinin. It was, however, found possible to obtain an oily compound by the action of the pentachloride in the cold, and decomposing the phosphorus oxychloride by pouring the product on t o ice. This oily compound differs somewhat from that described by Zinin, in that it does not yield tolane on dis- tillation, but is converted, more or less completely, into solid chloro- stilbene.Whether a liquid or solid chlorostilbene is formed by the action of phosphorus pentachloride on deoxybenzok, appears to depend largely on the temperature a t which the action takes place. Thus, when working a t as low zt temperature as possible, and then decomposing the phosphorus oxychloride with ice, an oily product is obtained which does not solidify when cooled to - 15". If, however, the pentachloride and deoxybenzoh are heated together for half-an- hour on the water bath, and the product is then poured into water, extracted with ether, and the ethereal solution well shaken with sodium hydroxide solution, the oil left on evaporating the ether becomes partially solid when cooled in x freezing mixture.The solicl, rapidly separated and recrystallised from alcohol, melts at 54'. Either of the two above-mentioned oils, when distilled under atmospheric, or even under diminished, pressure, is converted into solid chlorostilbene (m. p. 54"). Met(hy1- and ethyl-deoxybenzoin, when heated with phosphorus pentachloride, can also be made to yield oily stilbene derivatives, which, on distillation, are partially converted into solid methyl- and c th yl-chloros t ilbenes. Whether the oily substances are merely slightly impure forms ofXUDBOROUGH : RESEARCHES IN THE STILBENE SERIES. 210 the solid compounds, or whether they are stereo-isomeric forms, Iias, up to the present, not been definitely decided.This question I hope to deal with in a future communication, when the oily compounds have been subjected to a more complete investigation. The present paper contains an account of the solid compounds, chlorostilbene, methylchlorostilbene, and ethylchlorostilbene, and of certain deriva- tives which have been obtained from them. P~*epcwc&oia of Deoxgbenxo!in. For the preparation of these stilbene derivatives, it has been neces- sary to obtain large quantities of deoxybenzob. When the research was first started, some four yearsago, the best method for obtaining deoxybenzob was that recommended by v. Meyer and Oelkers (Zei*., 1888, 21, 1295) ; both this method, and also those described by Wachter (Be?.., 1892,25, 1721) and by Knoevenagel and Weisgerber (Zel.., 1893, 26, 441), have been tried.The simplest process, however, seems to be to treat benzoi'n (1 part) with zinc dust (I part) and glacial acetic acid (6 parts) ; in order to prevent caking, the zinc dust is added, while the mixture of benzoln and acetic acid is kept well stirred ; the whole is then heated on the water bath for about 15-20 hours, or until a portion, when poured into water, gives no flocculent matter, only a yellowish oil which slowly solidifies. The mixture is then poured into cold water and allowed to stand until the oil has completely solidifiecl, the solidified oil being recrystallised several times from alcohol, in which i t is readily soluble. The deoxybenzoyn is thus obtained in the form of colourless plates which melt a t 55'.The yield generally amounts to some 50 per cent. of the theoretical. Extremely interesting is the fact that benzil, C,H,* CO*CO*C,H,, is one of the products of the action of zinc dust on an acet.ic acid solu- tion of benzoin. When the mixture, in the above proportions, is heated for 15-20 hours, practically no benzil is obtained, but it can easily be isolated from the product, if the heating is continued for a shorter period. The mixture, heated at looo for 8 hours, was poured into cold water, and the flocculent precipitate, after being washed and dried, was triturated in a mortar with cold alcohol. The residue, which is almost insoluble in cold alcohol, on recrystallisation from hot alcohol, formed prismatic needles melting at 136O, and, on analysis, proved to be unaltered benzoin.Found, C=79*22 and 78.40 per cent.; H = 5.65 and 5.77 per cent. C,H,* CH(OH)*CO*C,H, requires C = 79.24 and H=5.65 per cent. The cold aIcoholic solution, after standing for several days, yielded a mixture of two different kinds of crystals; as i t was found im- possible to separate these by any chemical means, the solution was allowed to evaporate spontaneously, and the crystals, which were well220 SUDROROUGH : RESEARCHES IN THE STILRENE SERIES. developed, were separated mechanically. One of the compounds ~vhich crystallised in fairly large, flat, colourless, I ustrous plates me1 ting at 55", proved to be deoxybenzoin. The other compound, which was present in smaller quantity, crystallised in long, sulphur-yellow, pris- matic needles, and melted a t 94".It exhibited all the properties of benzil, and its identity was established by analysis. Found C = 79.92 and 80.04 per cent. H=4*73 and 4 5 0 per cent. C,H,*CO*CO*C,H, requires C = 80.00 and H = 4-76 per cent. The formation of benzil, an oxidation product of benzoi'n, by the action of zinc dust and acetic acid on benzoyn, seemed so remarkable, that I hare studied the action of hot acetic acid on benzoi'n, and find that small quantities of benzil are formed under these circumstances if the heating is continued for some 8-9 hours. Pwpccwction of P-Chloi*ostilbene, CGH,* CH: CC1* C,H,. I n order to distinguish the solid chlorostilbene previously mentioned from the oily compound described by Zinin, I propose to call the solid compound P-chlorostilbene, and Zinin's oil a-chlorostilbene ; it may be, however, that further investigation will establish the identity of the two compounds.P-Chlorostilbene is best obtained by treating deoxybenzoh in the cold with a slight excess of phosphorus pentachloride; as the action is somewhat violent, it is advisable to add the pentachloride in small quantities at a time. The mixture is heated for a short time on the water bath, poured into water, and the oil extracted with ether; the ethereal solution is then well shaken with sodium hydroxide, washed with water, dried over calcium chloride, and the ether distilled off. The residue may then be distilled under atmospheric pressure, or, still better, under reduced pressure; in the latter case, the greater part passes over at 189-190" under a pressure of 26 mm., and, as a rule, a considerable amount of hydrogen chloride is evolved during the dis- tillation.When cold, the greater part of the distillate becomes solid ; it is drained on a porous plate, and recrystallised from alcohol. The crystals usually have a yellowish tinge, which can only bc removed by repeated recrystallisation. P-Chlorostilbene cry stallises in large, colour- less, lustrous plates, melts as 53-44', and in general appearance re- sembles stilbene. Under atmospheric pressure, it distils a t 320-324', but a t the same time undergoes slight decomposition. I n the preparation of /3-chlorostilbene, it is not advisable to take the crude product obtained by the action of phosphorus pentachloride and subject it straight away to distillation, either under reduced or atmo- spheric pressure, as in both cases charring is apt to take place, and there is considerable loss.P-Chlorostilbene i s readily soluble in ether,SUDBOROUGH : RESEARCHES IN THE STILBENE SERIES. 221 chloroform, benzene, glacial acetic acid, and hot alcohol ; more sparingly in cold alcohol, and insoluble in water. 0,1640 gave 0.107 AgC1. C1 = 16.14. 0,2085 ,, 0.135 AgCI. C1 = 16.37. 0*1500 ,, 0.069 gram H,O and O*43gramC02. C! = '78.18; H = 5.11. C,,H,,Cl requires c1 = 78.32 ; H = 5.12 ; C1 = 16.55 per cent. Molecular weight determination. I. 0,328 gram dissolved in 1S.61'7 grams of glacial acetic acid lowered 11. 0.2415 gram dissolved in 16,064 grams of glacial acetic acid Theory for C',,H,,Cl, If the solid chlorostilbene is heated for 3-4 hours on the water bath with alcoholic potash, it is converted, by the loss of 1 molecule of hydrogen chloride, into tolane (diphenylacetylene) which melts at 60"; the tolane was further identified by conversion into its dibromide which melts a t 204-205".Sodium ethoxide is also capable of bringing about the same decomposition. When reduced with sodium amalgam and alcohol, P-chlorostilbene is readily converted into stilbene (m. p. 125"). Two grams of chloro- stilbene were dissolved in 30 grams of ethylic alcohol and 40 grams of 2.5 per cent. sodium amalgam were added. The mixture was left overnight, and then neutralised wibh hydrochloric acid, the alcohol evaporated, and the residue extracted with ether.The product left on evaporating the ether crystallised from alcohol in large, lustrous plates, melting a t 124-124.5O ; it gave a dibromide which melted a t 237", thus establishing its identity with stilbene. Cli,Zo+*ostilhae tZiclJok?e (trichlorodibenzyl), C,H,* C'HC11* CCl,. Cf:H5, was obtained by saturating a solution of chlorostilbene in carbon tetrachloride with dry chlorine a t 0" and in the dark. The mixture was allowed to stand for about half an hour, the excess of chlorine re- moved by drawing a rapid current of air through the solution, and the carbon tetrachloride allowed to evaporate spontaneously. The solid residue, washed with a little warm alcohol and crystallised from hot glacial acetic acid, deposited the dichloride in colourless, well-developed, hard prisms melting at 102-103°.It is almost insoluble in alcohol and ether, but readily dissolves in benzene, chloro- form, carbon tetrachloride and hot acetic acid. the freezing point 0.326". lowered the freezing point 0,274". M = 2109. 1% = 214. 31 = 214.5. 0.3668 gave 0-5427 AgC'I. C1 = 36.62 per cent. Theory requires C1 = 37.30 per cent. When the dichloride is heated for half-an-hour with a slight excess of alcoholic potash, it yields two compounds which are best separated222 SUDBOROUCH : RESEARCHES I N THE STILBENE SERIES. by fractional crystallisation from alcohol. The portion which is only sparingly soluble in alcohol crystallises in flat, colourless plates, and melts a t 141'. 0.2051 gave 0.236 RgC1. C1 = 28.46. C,,H,,Cl, requires C1 = 28.51 per cent.It is identical with Liebermann and Homeger's cis-tolane dichloride, which melts at 143' (Bey., lS79, 12, 1971). The other compound is much more readily soluble in alcohol, crystallises in prismatic needles, and melts at 63'. 0.2093 gave 0.2365 AgCl. U,,H,,Cl, requires C1 = 28.51 per cent. It is identical with tmm-tolane dichloride (m. p. 63') (Zoc. cit.). ChZoil*ostiZbene dibyoilnide? C,H,* CHBr C1U1Br*C,H6, or chlorodibromo- dibenzyl, is readily obtained by the action of a chloroform soln- tion of bromine on P-chlorostilbene dissolved in chloroform : 100 grams of a 10 per cent, solution of bromine in chloroform was gradually added to 5Igrams of chlorostilbene dissolved in 40 grams of chloroform. The solution, kept cool by surrounding it with ice- cold water, was allowed to stand for two or three hours, and the chloroform and excess of bromine were then quickly removed by pouring the solution on to a large clock glass, and blowing air over the surface.The solid residue mas washed with a little warm alcohol, and recrystallised from benzene or hot glacial acetic acid. From its solu- tion in acetic acid, it is deposited i n the form of colourless, well-deve- loped prisms ; it melts a t 127", but a t the same time undergoes decom- position. It is readily soluble in chloroform, benzene, and hot ether, but is practically insoluble in alcohol. At 1l0, 100 parts by weight of benzene dissolve 29.18 parts by weight of the dibromide. 0.2056 gram gave 0.286 gram of silver chloride and bromide, which, when reduced, gave 0.1785 gram of metallic silver.Br = 42.69 ; (21 = 9.59 per cent. If boiled for half-an-hour with a slight excess of alcoholic potash, the dibromide yields a mixture of three compounds, which are best separated by fractional crystallisation from alcohol. 1.-The compound least soluble in alcohol crystallised in hard, colourless, flat prisms, and melted at 173-174'. Analysis proved it t o be a chlorobromostilbene obtained by the elimination of a molecule of hydrogen bromide from the chlorostilbene dibromide. 0.183 gram gave 0.205 gram of silver chloride and bromide, which, when reduced, gave 0.1335 gram of metallic silver. Br and C1= 39.07 per cent. 2.-An intermediate product was obtained which melted at 71-78',; it could not, however, be obtained in a pure state.3.-The compound which was most readily soluble in alcohol crystallised in colourless needles or prisms; it melted at 62", and analysis proved it t o be a dibromostilbene. Cl = 27.95. Cl4H,,C1Br2 requires Br = 42.72 ; C1= 9.47 per cent. C,,HloBrC1 requires Br + C1= 39.35 per cent.SUDBOROUGH : RESEARCHES IN TRE STILBENE smm. 2213 0.3 gave 02215 AgBr. The compound must, therefore, be identical with Limpricht and (Be?*., 1871, 4, Br= 47.12. C,,H,,Br, requires Br = 47.33 per cent. Schwanert's dibromostilbene which melts a t 63'. 379). Nit o-de r ivcc t ives. As it was found impossible to obtain any definite nitro-derivative by the aid of nitric acid-concentrated or fuming, alone or in acetic acid solution-the action of the red fumes evolved from nitric acid and arsenious anhydride on chlorostilbene was studied.Solid chlorostil- bene was dissolved in glacial acetic acid, and the solution saturated with the nitrous fumes, while surrounded by ice-cold water. The solution became deep green, and during the course of the action a colourless, crystalline substance was deposited. When saturated, the solution mas kept f o r several hours, and the insoluble product was then collected and recrystallised from hot glacial acetic acid. It forms colourless prisms, melts at 124-125", and is apparently chlorodinitrodibenzyl? C,H,* CH(NO,)*CCl(NO,)*C,H,, formed by the addition of two nitro-groups to the unsaturated compound chloro- s ti1 bene. 0,1221 gave 9.4 C.C. moist nitrogen a t 11" and 764 mm. 0.2542 ,, 0.115 AgC1.C1=11*20 per cent. C1,Hl,CIN,O, requires N = 9.1 3 and GI= 11 *liS per cent. /3-Chlorostilbene thus resembles stilbenc itself, which, according to Gabriel (Bey., 1885,18, 2438), yields an additive compound, C,,H,,N,O,, melting a t about 300". The acetic acid filtrate from this crystalline product was poured into cold water, when an oil was deposited which became semi-solid after a time ; this, after being pressed and recrystallised from hot alcohol, gave fine, sulphur-yellow, prismatic needles, but on spontaneous evapora- tion of its alcohol solution, it is deposited in well-developed monoclinic prisms. It melts at 104-105", and is readily soluble in all organic solvents, but insoluble in water. It was found to be free from chlorine, and analyses gave the following results.N=9*22. 0.3102 gave 0 7124 CO, and 0.0974 H,O. C = 62-63 ; H = 3.48. 0.2414 ,, 0.5501 CO, ,, 0,0864 HiO. C=62.15; H=3.97. 0.236 20.4 C.C. moist nitrogen a t 15" and 760 mm. N = 10.12. 0.298 ,, 25.8 C.C. moist nitrogen a t l4"and 755 mm. N = 10.11. Molecular weight determination. 0.4978 gram dissolved in 16.904 grams of glacial acetic acid lowered the freezing point 0.49". M = 234.4. Theory for C,,HI,N,O,, M = 270. ,, C,,H,,(NO,), requires C = 62 22 ; H = 3.70 ; N = 10.37 per cent.2% SUDBOROUGH : RESEARCHES IN THE STTLBENE SERIES, A11 attempts t'o reduce the nitro-groups, and to obtain amido- compounds proved unsuccessful, the only product formed being a dark brown, tarry mass. That the nitro-groups must be attached to the ethylene carbon atoms, and not to carbon atoms in either of the benzene nuclei, was proved by oxidising the nitro-compound with an acetic acid solution of chromic anhydride.no mono- or di-nitrobenzoic acids could be isolated. If the yellow compound has the composition The only product obtained was benzoic acid CGH,* C(NO2) :C(NO,) COH,, it must be formed from the compound C,H,* CH(NO,)*CCl(NO,)* C,H,, already mentioned, by the elimination of a molecule of hydrogen chloride. Chlorodinitrodibenzyl, when heated with alcoholic potash, at once turns yellow, and Ion acidifying and distilling off the alcohol a yellow oil is obtained, but it could not be induced to solidify. Although the yellow, crystalline compound, according t o the formula just given, contains a double bond, it has been found impossible up to the present to bring about any combination with bromine.A solu- tion of the compound in chloroform does not decolorise a chloroform solution of bromine, and, even after standing for some time, the original compound can be obtained by evaporating off the chloroform. ~et~LyZchZoyostiZ6e.ne, C,H, Cy Cl : C( CH,). C,H,. Methyldeoxybenzoi'n, obtained by v. Meyer and Oel ker's method (Bey., 1888, 21, 1295), was heated with a slight excess of phosphorus pentachloride for about half-an-hour on the water bath. The liquid mass was then poured into water, allowed to stand, neutralised with sodium hydroxide, and extracted with ether; the yellow oil left on evaporating the ether gave the following results on analysis. 0.77 gave 0.539 AgCl. C1= 1'7.32. 0.476 ,, 0.331 AgC1.C1= 17.20. CGH5* CC1:CMe- C,H, requires C1= 15.54 per cent. C,H,- CCI,*.CHMe- C,H, ,, C1= 26.78 ,, ,, When the oil was distilled under diminished pressure, a consider- able quantity of hydrogen chloride was evolved, and the greater part passed over at 178' under a pressure of 18 mm. The distillate, on cooling, deposited a small quantity of colourless, prismatic crystals ; these were drained off and the oil again distilled under diminished pressure, when more of the crystalline compound was obtained. By this process of repeated distillation, a considerable portion of the oil was converted into the crystalline compound, although not 20 per cent, was converted a t any one distillation,SUDBOROUGH : RESEARCHES IhT THE STILBENE SERIES. 225 The crystals, when separated, drained on a porous plate, and re- crystallised from hot glacial acetic acid, formed colourless, lustrous plates melting at 124".0.2 gave 0.5767 GO, and 0.106 H,O. 0.233 gave 0.146 AgC1. C1= 15.51. C,H,*CMe:CCl*C,H, requires C = 78.77 ; H = 5.69 ; C1= 15.54 per cent. Molecular weight determination. 0,2065 gram dissolved in 21-12 grams of glacial acetic acid lowered the freezing point 0.17". M = 224.3. Theory for C,H,*CMe:CCl* C,H,, This crystalline methylchlorostilbene is readily soluble in ether, benzene, chloroform, and carbon tetrachloride, also in hot alcohol and in hot acetic acid. Under atmospheric pressure, it distils at about 311' undergoing but slight decomposition. It differs from the solid chlorostilbene in not being acted on by alcoholic potash, and also by not being readily reduced either by sodium amalgam and water or by zinc and acetic acid.The oily compound which was formed along with this solid methyl- ehlorostilbene on distilling the product of the action of phosphorus pentachloride on methyldeoxybenzoin mas also analysed, and gave numbers which agree with those required for methylchlorostilbene. C = 78.64 ; H = 5.88. M = 228.5. 0.25 gave 0.716 CD, and 0.126 H,O. C: := 78'11 ; H = 5.6. 0.5 ,, 0.307 AgCl. C1= 15.19. 0.58 ,, 0,355 AgCI, Cl= 15-14. Theory, C = 78.77 ; H = 5.69 ; C1= 15-54 per cent. The investigation of this oil is being continued, in order to deter- mine, if possible, whether it is merely an impure form of the solid compound, or whether it is to be regarded as a stereo-isomeride. n~etl~ylciLZol.ostiZbe~~e c l i b i - o t ~ d e , C,H,* Cl\leBr* CClBr* C,H,, or methyl- chlorodibromodibenzyl, obtained by a method exactly similar to that used for the preparation of chlorostilbene dibromide, crystallises from hot glacial acetic acid in well-developed rhombic prisms.It melts and decomposes at 122-1 25", is practically insoluble in alcohol, and only sparingly soluble in ether. 0.2324 gave 0.2966 gram silver chloride and bromide, which, when reduced, -gave 0.185 gram metallic silver. Br = 41 *05, C1= 9.12 per cent. Metl~?/lcl~lo~ostilbene dicldoride, C,H,. CMeCl* CCI,* C,H,, or methyltri- chlorodibenzyl, obtained by passing chlorine into a cold solution of methylchlorostilbene in carbon tetrachloride, crystallises from hot glacial acetic acid in well-developed, colourless prisms.It melts and decomposes at 130°, is readily soluble in benzene, chloroform, carbon Theory, Br = 41-18 and C1= 9.13 per cent.226 SUDBOROUGH : RESEARCHES I N THE STILBENE SERIES. tetrachloride and hot acetic acid, but is almost insoluble in alcohol and cold ether, 0,2722 gave 0.3978 AgCl. C1= 36.15. 0.2433 ,, 0.349 AgCl. Cl=35*49. Theory requires C1= 35.55 per cent. ~ t l ~ ~ Z c ~ Z o l . o s t i Z ~ e ~ e , C,H,* C(C,H,):CCl*C,H,, wits obtained from ethyldeoxybenzoln (Meyer and Oelkers, Zoc. cit.), in exactly the same way as methylchlorostil bene from methyldeoxybenzoi'n. When the crude, oily compound was distilled, the greater part passed over at 1S8-189* under a pressure of 27 mm., and when cold set t o a mass of crystals mixed with a certain amount of oil.The crystals, drained and crystsllised from hot alcohol, in which they are readily soluble, form very large, colourless prisms, which melt a t 60" and distil under atmospheric pressure a t 32s' (corr.). I t is extremely easily soluble in all organic solvents, but insoluble in water. Characteristic is the ease with which i t can be obtained in large, well-developed crystals. 0.1542 gave 0.4448 CO, and 0.0865 H,O. C=: 78.53 ; H=6*24. 0.1435 ,, 0.416 CO, ,, 0.0815 H,O. C-='79*06; H=6*31. 0.298 ,, 0.171 AgCI. C1=14.20. 0.2066 ,, 0.1212 AgCI. CI = 14-52, C,H,* CEt:CYCl*C,H, requires C = 79.1s ; H = 6.18 ; C1= 14.64 per cent. Molecular weight determination. 0.2925 gram dissolved in 20.567 grams of glacial acetic acid lowered the freezing point 0.234". 0.3565 gram dissolved in 19.298 grams of glacial acetic acid lowered the freezing point 0.310".Alcoholic potash has no action on the compound, as was to be expected, It was also found impossible to reduce it either with sodium amalgam and water or zinc and acetic acid. ~tl~~lc~LlorostiZbene dicldo&Ze, C,H,* CEtC11. CCl,* C,H,, or ethyltri- chlorodibenzyl, was obtained by chlorinating LZ solution of ethglchloro- stilbene in carbon tetrachloride, the solution being kept quite cold arid allowed to stand for 2 hours after saturation ; the excess of chlorine was then removed by drawing a rapid current of air through the solution, and the carbon tetrachloride left to evaporate spontaneously. The syrupy, oily residue, which became solid on treatment with cold alcohol, was washed with warm alcohol and then recrystallised from ether..The dichloride crystallises in colourless needles, melts at 90-9 lo, and is readily soluble in chloroform, benzenc, and acetic acid. M = 236.S. M = 232.4. Theory, M = 242.5. 0.214 gave 0.2938 AgCI. C1= 33.96. C!,H,- CEtU1-C'C1l2*U,H, requires C1= 33.97 per cent,SUDBOROUGH : RESEARCHES I N THE STILBENE SERIES. 224 &!h@iZos.ostil6ene clihomide, C,H,* CEtBr* CClBr* C,H,, or ethyl- chlorodibromodibenzyl, was obtained as a thick oil, which readily solidified on treatment with a little alcohol. It melts at 97-99', is insoluble in alcohol, and only sparingly soluble in ether. 0.2 gram gave 0.259 gram of silver chloride and bromide, which, when reduced, gave 0,1615 gram of metallic silver.Br=39.92 and C1= 8.83 per cent. Theory requires Br = 39.75 and C1= 8.81 per cent. The purification and investigation of the oily compounds obtained by treating deoxybenzoin and its alkylic derivatives with phosphorus pentachloride have already been begun, in order t o determine, if possible, whether these oils are only slightly impure forms of the crys- talline chloro-, methylchloro-, and ethylchloro-stilbenes described above, or whether they are to be regarded as isomerides. If the substances are isomeric, beyond a doubt almost they are stereo-isomeric, as the oils are so readily converted into the solid compounds. The best method of attacking the problem, when once the oily com- pounds have been obtained in a pure state, appears to be to study the additive compounds formed by the union of the oils with chlorine and bromine, and then to compare the products with those obtained from the solid compounds.I n the case of rnethylchlorostilbene, for example, the oil and solid, if stereo-isomeric, must bear the same relationship 60 one another as the two tolane dichlorides or as the two crotonic acids. I n other words, one must have the &-configuration A, and the other the tmms-configuration B. C,H,-C;)-CH, C .H,*C*CH, C,H,* c c1 Cl*C*C,H, A, B. ' ' 11 The effect of chlorinating the compound A would be to form an inactive mixture of the two enantiomorphic compounds I and 11. ? C,H,*C*CH, c1 I. C,I€,.b* I c1 c1 I CN; C-C,H, 11. I C1* C*C,H, I c1 or else a racemic compound of the two. compound of I11 and IT.The compound B would also yield an inactive mixture or racemic C1 CH&C,H, Y1 C,H,* C*C€I, I I v. I Cl*C*C,H, C,H,*C*Cl Cl c1228 SUDBOROUGH : RESEARCHES IN THE STILBENE SERIES. It can easily be shown by means of models that compounds I11 and IV are identical with compounds I and 11. This also follows from the fact that the compound C,H,- CCl(CH,)*CCI; C,H, contains only one asymmet'ric carbon atom, and can therefore exist, according t o the van't Hoff theory, in only two optically active modifications, which can combine to form a racemic compound. The result of brominating the compounds A and B would, however, be somewhat different. A would yield us an inactive mixture of the two enantiomorphic compounds V and VI. Sr Br c,H,- ~WH, CH,. 6 C,H, V. I V I. I 7 C,HS*C.C1 Crl*C* C,H, Er Br I I whereas B would yield an inactive mixture of the compounds VII and VIII. Br Br C,H,*bCH:, CH,. b C,H, VII. I VIII. I C1* C C,H, C,H,* C*C1 I I Br Br Compounds VII and VIII, however, are not identical with compounds V and VI. This can readily be established by means of models, and is in accord with the fact that the compound C,H,* CBr(CH,)*CClBr*C,H, contains two asymmetric carbon atoms, and can exist in four optically active and two racemic forms. Based upon these purely theoretical considerations, we should expect both the oily and solid methyl- chlorostilbenes, if they are stereoisomeric in the same way as the crotonic acids, to yield the same dichloride but different dibromides. The same applies to the chlorostilbenes and ethylchlorostilbenes. On the other hand, if the oil is merely an impure form of the solid, then both compounds should Field the same dichloride and also the same dibmmide. A third possibility, that the compounds are structurally isomeric, could be settled a t the same time, for in this case the oil and solid should yield different dichlorides, and also different dibromides. In conclusion, I wish to express to Dr. Irving W. Fay my sincere thanks for his kind assistance in some of the analytical work entailed in this investigation. UNIvEiisITY COLLEGE, NOTTJXGIIAM.

ISSN:0368-1645    

DOI:10.1039/CT8977100218

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

229 BY JOHN J. SUDBOROUGH, PERCY G. JACKSON, AND LORENZO L. LLOYD, IT has been previously shown by Victor Meyer and one of us (Bey., 1894, 27, 510, 1580, and 3146) that diortho-substituted benzoic acids yield no ethereal salts when their cold methyl alcoholic solutions arc saturated with dry hydrogen chloride; these salts, however, can be obtained by the action of alkylic iodides on the silver salts of the acids, or by the action of alcohols on the acid chlorides. Victor Meyer has shown that these ethereal salts are characterised by the fact that they are extremely difficult to hydrolyse (Bey., 1895, 28, 188). The acid chlorides of diortho-substituted benzoic acids, further, are remarkably stable, being only completely decomposed on prolonged boiling with potassium hydroxide solution (Sadborough, Trans., 1895, 6'7, 587 ; v.Meyer, Rev., 1894, 27,3153 ; Liitzens, Be?*., 1896, 29,2837). It has also been pointed out by one of us (Sudborough, Trans., 1895,67, 601) that probably diortho-substituted benzamides exhibit a similar degree of stability. Thns it has been shown that 2:6-dibromobenz- amide remains practically unacted on when heated a t 170" with SO per cent. sulphuric acid, whereas the isomeric 2 : 4-dibromobenzamide, under similar conditions, is completely hydrolysed. With the purpose of further investigating the properties of sub- Ortho-, meta-, and para-bromobenzamides, 2 : 4-, 2 : 6-, and 2 : 5-dibromobenzamides, 2 : 4 : 6- and 3 : 4 : 5-tribromobenzamides, 2 : 4 : 6-Trichlorobenzamide, 2 : 4 : 6-Trimet hylbenzamido, Mesitylacetamide, stituted benzamides, we have prepared the following amides.and have in each case determined the amount of amide converted into acid when heated with different strengths of sulphuric acid a t given temperatures. The general method adopted was as follows. 0.5 gram of the amide was heated with 20 or 25 C.C. of the sulphuric acid to a given temperature for different lengths of time, generally in sealed tubes. On cooling, the acid was diluted with water and the mixture extracted three times with ether ; the ethereal solution was extracted twice with dilute caustic potash, in order to remove any acid which might have been formed, and the combined alkaline extracts were acidified with hydrochloric acid and then extracted twice with ether. This ethereal extract was washed with water, dried over calcium chloride, transferred to a tared flask, and the ether slowly evaporated.VOL. LXXI, It230 SUDBOROUGH, JACKSON, AND LLOYD : During the course of this work, the following new compounds have been prepared. 3 : 5-Di~onzobenxc~micle, C,H,Br,* CONH, [ CONH, : Br, = 1 : 3 : 51, was prepared by the action of aqueous ammonia on 3 : 5-dibromobenzoic chloride. It crystallises from hot, aqueous alcohol in colourless needles, melts at 187", and is soluble in alcohol, ether, benzene, and chloroform, but more sparingly in boiling water. 0.2608 gave 0.3505 AgBr. Br = 57.19. 0.3005 ,, 12.8 C.C. moist nitrogen a t 11" and 760 mrn. N = 5.07. C,H,Br,*CONH, requires Br = 57-31 ; N = 5.02 per cent. This amide was completely hydrolysed on treaticg it with 75 per cent.sulphuric acid for 7 hours at 160". The acid thus formed melted at 209". Synametriccd tyibronzo6enxonit.l.ile, C?,H,Br,.CN [CN : Br, = 1 : 2 : 4 : 61. -This nitrile is really prepared from symmetrical tribromaniline by the Sandmeyer Reaction (as described in Bey., 1894,27, 512). It is advisable, after diazotising, to filter off from any unaltered tribromaniline before adding to the cuprous potassium cyanide solution. The reddish-coloured product which is thus obtained is best boiled in alcoholic solution with animal charcoal, and then recrystallised from dilute alcohol, when it is obtained in small, colourless needles, readily soluble in alcohol and ether, but only sparingly in boiling water. It melts a t 127", and very slowly volatilises in a current of steam.0.1452 gave 0.241 AgBr. 0.4 ,, 14.2 C.C. moist nitrogen a t 16" and 756 mm. N=4*116. Br = 70.62. Theory requires Br = $0.59 ; N = 4.12 per cent. Xymmet&cd t~ibromoben,xc6mide, C,H,Br,* CONH,, is readily obtained when the nitrile is heated in sealed tubes with 80 per cent. sulphuric acid at 160" for several hours; the nitrile is not hydrolysed when heated to the same temperature with 60 per cent. acid. Ten grams of the nitrile were heated with 200 C.C. of 80 per cent. sulphuric acid at 160" f o r 6 hours, and on cooling, the acid was diluted with water, and the solid residue collected and recrystallised from dilute alcohol or from boiling water. It crystallises in small, colourless needles, or from dilute solutions in hard prisms, melts a t 193-194", is readily soluble in alcohol, ether, and chloroform, moderately in boiling water, and almost insoluble in cold water.I. 0.1675 gave 0.264 AgBr. Rr = 67.06. 11. 0-401 HI. 0,2156 ,, 14.2 C.C. moist nitrogen at 12" and 759 mm. N=4.19. ,, sufficient NH, to neutralise 6 C.C. N/lOH,SO,. N= 3-89. Theory requires Br = 67.04 j N = 3.91 per cent,DITHIO-SUBSTITUTED BENZOIC ACIDS. 231 As regards its hydrolysis, this amide exhibits a remarkable degree of stability as compared with its isomeride, [COXH, : Br, = 1 : 3 : 4 : 51, see appended table. Unsynnzetiical tribi.onzobe,z~~cp,z~~~e, [CONH, : Br, = 1 : 3 : 4 : 51.-3 : 4 : 5- Tribromobenzoic acid was prepared by the method previously des- cribed (Bey., 1894, 27, 513), a slight modification being made by using hydrochloric instead of sulphuric acid for liberating the nitrous acid ; the yield of tribrom-acid is very good.The acid was converted into its chloride by warming it with phosphorus pentachloride, the oxychloride distilled off under diminished pressure, and the residue treated with concentrated ammonia ; the solid mass thus obtained was washed with water, and recrystallised from dilute alcohol. It is readily aoluble in ether, chloroform, and alcohol, but only sparingly so in boil- ing water. It crystallises from its dilute alcoholic solution in colourless, slender, silky needles, and melts a t 199-200", and not a t 210' as pre- viously stated (Trans., 1894, 65, 596). 0-3008 gave 0.3117 AgBr. Br = 67.32. 0.1961 gram, when heated with soda lime, gave sufficient ammonia t o neutralise 5-3 C.C. of N/10 sulphuric acid.N = 3.18. C,H,Br,* CONH, requires Br = 67.04 and N = 3.91 per cent. Xynmet&al t~ic~loi~obe~aaonitl.ile, C,H,Cl,* CN [CN : C1, = I : 2 : 4 : 61.- Trichloraniline was prepared by saturating an acetic acid solution of aniline with chlorine, filtering OR the crystalline precipitate, and decom- posing it with water. The trichloraniline was then diazotised in the cold, and poured into a warm (60") solution of cuprous potassium cyanide (10 grams of 98 per cent. potassium cyanide to 9.5 grams of copper sulphate). The precipitated nitrile, after being allowed t o stand for 12 hours, was extracted with ether, the ether evaporated, and the residue dissolved in alcohol, boiled with animal charcoal, and recrystal- lised several times from dilute alcohol. The yield is not very good, in most cases not more than 20-30 per cent.of the theoretical, and it is still worse when the diazotised solution is poured into boiling cuprous potassium cyanide solution. The nitrile crystallises in colourless, silky needles, melts at 75", and is extremely soluble in alcohol and ether, but only sparingly in boiling water. C,H,Cl,*CN requires C1= 51.57 per cent., and N=6.78 per cent. Found, C1=51*53 per cent., and N = 6.9 per cent. The nitrile is practically unacted on when heated a t 160" for 3 hours with 60 per cent. sulphuric acid, but is readily hydrolysed when heated with 80 per cent. acid ; thus 0.5 gram of the nitrile, when heated with 20 C.C. of 80 per cent, sulphuric acid a t 160" for 3 hours, gave 0.43 gram of the amide and 0.06 gram of trichlorobenzoic acid.2 : 4 : 6-~ricl~Zol.obenxan2~~e, obtained by heating the nitrile (10 grams) P 2232 SUDBOROUGH, JACKSON, AND I,T,OYD : with 80 per cent. sulphnric acid (200 grams) for 3 hours a t 160°, crys- tallises from boiling water in colourless, glistening plates, and melts at 177". It is readily soluble in most organic solvents, and moderately so in boiling water. 0.1865 gave 0.3565 AgC1. c11= 47.29. 0.1 909 gram, when heated with soda lime, gave sufficient ammonia t o neutralise 8.3 C.C. of NjlO sulphuric acid. N = 6.09. C,H,CI,* CONH, requires C1= 47.43 ; N = 6.23 per cent. This arnide is also remarkably stable when heated with 75 per cent. sulphuric acid. iClesit~la;ceto~nzicle,C,H,Me,.CH,*CONH,[CH,*CONH,:Me,=1:2:4:6]. This compound was obtained by converting mesitylacetic acid into its chloride, and pouring the chloride into ammonia; the action is violent, and the product, after recrystallisation from dilute alcohol, forms long, slender, silky needles, melting a t 209-210'. It is iden- tical with the compound obtained by Claus (J.p ~ . Clmz., 1890, [ 21, 41, 507), which melted a t 208". Results of HydYolyses. II No. - 1 2 3 4 5 6 7 8 9 10 11 12 1 3 14 15 16 17 18 19 20 21 - Amide taken. Urthobromobenzamide . . . . . , Do. Me tabromobenza.micle . . . . . . , . . Do. Do. Do. Do. Do. Do. Do. Do. Parabromobenzamide ......,.. 3 : 5-Dibromobenzamide.. . .. 2 : 4-Dibromobenzamide.. , . . . 2 : 6-Dibroniobenzan~ide . . . . I 3 : 4 : 5-Tribronio~enzamide..2 : 4 : 6-Tribromobenzaniide. 2 : 4 : 6-Trichlorobenzamide.. Mesitylacetamide . . . . . . . . . . . . . Do. D O . - 0" 3 cu 5 ba g* 4 u ) m 9 'er cent. 30 50 30 30 30 30 30 50 50 75 75 75 75 75 75 75 75 75 75 30 30 - 20 20 20 20 20 20 20 20 20 25 25 25 25 25 25 25 25 25 25 25 5 - QJ + M 2 i ~~ Boiling Do. Do. Do. Do. Do. Do. Do. Do. 160" 160" 160" 160" 160" 60-17F 160" 160" 160" 160" Boiling Do. - 15 mills 30 9 J 5 9 > 15 9 9 15 ? ? 30 9 9 30 9 2 7 9 9 7 9 9 7 9 ) 3 9 3 3 > 9 7 9 9 30 1 9 2 hour J J J 7 J 9 J 3 15 mins 2 hour - :ram, 0.5 0.5 0.5 0.5 0 -5 0-5 0.5 0 5 0.5 0.5 0.5 0.5 0.5 0 *5 0 -5 0 -5 0 *5 0.5 0.5 0.5 0.1 - gram. 0'126 0.411 0'335 0'4985 0'499 0'4056 0'4986 0.125 0.255 0'487 0'47'39 0.4718 0'498 0.058 0.0626 0'4703 0.023 0'022 0'242 0'1752 0.073 25-07 81-79 66'66 99 *20 99-30 80.71 99'22 24.91 50'81 97'05 94'44 94'02 99'24 11.56 12'47 93.80 4 '59 4'39 48'18 34-85 72'59 -DITHIO-SUBSTITUTED BENZOIC ACIDS.233 The behaviour of these acid-amides towards hy drolysing agents is extremely characteristic. Of the three monobromobenzamides, the ortho-compound is somewhat more stable than the other two. This is only what was to be expected, since V. Meyer has shown that, not only are the ethereal salts of ortho-substituted-benzoic acids more slowly formed than those of isomeric acids, but also that these ortho-substi- tuted salts are more stable than the isomeric meta- and para-substituted compounds. It has further been shown by one of us that orthobromo- benzoic chloride is somewhat more difficult to hyclrolyse- than the meta- and para-compounds.Of the di- and tri-bromobenzamides, those which have bromine atoms in the two ortho-positions are remarkably stable, yielding only 4-12 per cent. of acid when heated with 75 per cent. sulphuric acid at 160" for several hours, whilst the isomeric amides in which the two ortho- positions are not substituted yield over 90 per cent. of acid under exactly similar conditions. This, again, is in complete accord with the behaviour of the corresponding ethereal salts and acid chlorides. It is interesting to note that 2 : 4 : 6-tribromobenzamide is even more stable than 2 : 6-dibrsmobenzamide7 although both are ortho-substituted ; the introduction of a third substituting group, even when the two ortho- positions are already occupied, seems to render the amide more difficult to hydrolyse.A similar phenomenon has already been noticed in the case of substituted benzoic chlorides. 2 : 4: 6-Trichlorobenzamide proves to be difficult to hydrolyse, but not nearly so difficult as the corresponding bromine derivative. This is in accord with the results obtained with substituted benzoic acids ; it has been shown by V. Meyer t h a t the raterat which diortho-substituted benzoic acids are converted into ethereal salts depends mainly on the atomic or molecular weights of the atoms or groups which occupy the ortho-positions, Diortho-substituted acids, in which the substituting groups are methyl groups (CH, = 15), are slowly converted into ethe- real salts a t the boiling point of the alcoholic solution, whereas di- ortho-substituted acids, in which the substifuting groups are bromine atoms or nitro-groups (Br = 80, NO, = 46), do not yield a trace of the salt under similar conditions, We have also attempted t o hyilroly se mesitylformamide-2 : 4 : 6-trimethylbenzamide-by heating it with '75 per cent.sulphuric acid, in the hope of being able t o show that it mas more readily hydrolysed than the corresponding trichloro-derivative (C1= 35.5). It was, however, found impossible to carry out the pro- cess of hydrolysis, as the amide was charred and completely destroyed by the sulphuric acid. An interesting point in connection with the diortho-substituted benzoic chlorides is the fact that, although they are so dificult to hydrolyse by treatment with water or sodium hydr- oxide solution, they are yet readily acted on by aqueous ammonia,234 SUDBOROUGH, JACKSON, AND LLOYD : DITHIO-, ETC.yielding the corresponding amides. In brder t o prepare 2 : 6-dibromo- or 2 : 4 : 6-tribromo-benzamide, it is only necessary t o warm the corres- ponding chloride with aqueous ammonia for a few minutes. Some of the isomeric chlorides react with cold, aqueous ammonia ; the diortho-substi- tuted compounds, however, require heating with the smmoniacal solu- tion for a short time. There is thus a difference between the diortho-substituted chlorides and their isomerides as regards their behaviour towards aqueous ammonia, but this difference is not nearly so marked as the difference between the two series of compounds when treated with hydrolytic agent 5.Wegscheider (Momtsh., 1895,16, 75) has' suggested t h a t the reason why diortho-siibbtituLed acids do not yield ethereal salts on treatment with alcohol and hydrogen chloride, is to be sought for in the fact t h a t the substituting groups prevent the formation of a n additive compound of the acid with the alcohol, this additive compound always being an intermediate product in the preparation of these salts by the method mentioned above. It may be that, in the hydrolysis of acid chlorides and amides, an additive compound with water is also formed, and t h a t this is afterwards decomposed into the acid and hydrogen chloride, or into the acid and ammonia. The substituting groups in the ortho- positions would have a tendency to prevent the formation of such an additive compound, and would thus retard the hydrolysis. In the action of ammonia on the acid chlorides, we must suppose that no such intermediate additive product is formed, but t h a t the chlorine is at once withdrawn and replaced by the amido-group. I n conclusion, we intend taking up the study of the amides of a few methyl- and chloro-substituted benzoic acids, and also, if possible, the preparation of certain diortho-substituted benzsldehydes and benzylic alcohols, in order to determine whether they also have such well-defined characteristics. The qnestion a s t o whether a diortho-substituted benz- aldehyde can form additive conipouncls with hydrogen cyanide, &c., or whether it can enter into t'he usual aldehydic condensations ( V . Meyer, Bey., 1895, 28, 1267), seems to us to be one worthy OF closer study. UNIVERSITY COLLEGE, NOTTINGRAM,

ISSN:0368-1645    

DOI:10.1039/CT8977100229

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年代:1897

数据来源: RSC

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TUTTON : THE REFRACTJON CONSTANTS, &C. 235 XIX.-The Refraction Constants o f Cyystalliue Salts. BY ALFRED EDWIN TUTTON. IN a recent issue of this Journal (Trans., 1896, 69, 1530), there appears a contribution by Mr. Pope on the above subject, containing a criticism of certain results published by the author of the present communication earlier in the past year (Trans., 1896, 69, 502) con- cerning the molecular refraction constants of the sulphates and double sulphates containing potassium, rubidium, and cmium. I n the paper referred to, which includes no new experimental data, Mr. Pope advances a claim to originality with regard to the additive nature of the molecular refractions of crystallised compounds, to which, it appears, he is not entitled. It was clearly sbomn in the author’s memoir that this rule of additive moleculnr refraction held good in the cases of the whole of the 22 double sulphates of the series R2M(S04)2 + 6H,O, the results of the investigation of which were then presented, and i t was thereby established that the same refraction equivalents which were observed in the case of the simple alkali sulphates apply also to those salts when combined with the sulphates of magnesium, zinc, iron, nickel, cobalt, copper, manganese, and cadmium.The author did not, however, lay claim t o the discovery of the rule that the molecular refraction of a crystallised compound is the sum of the re- fractions of its components, for the reason that he considered that the valuable work of previous observers, notably that of Gladstone, in which he utilised the data of Topsoe and Christiansen andof Soret, and more recently that of Perrot (A~chiv.cles Sciences pJqs. et nut. G e n h e , 1891, 26 and 669, and 1893,3), after allowing for the fact that the experimental data were not in every case all that could be desired, had already led t o that conclusion. The author consequently only presented his results from more accurate experimental data in further confirmation of the rule, and based upon its acceptance the whole argument for the similarity of the refractive power of the simple alkali sulphates when alone and when forming part of the double sulphates. Hence, when Mr. Pope speaks of the rule as ‘‘ my view that the molecular refractions of solid salts are . . . the sums of , . . atomic or equivalent refractions,” and further states on tlie first page that ‘‘ proof is advanced in the present paper that the molecular refractions of crystalline salts are practically additive quantities,” he is not contributing anything original, such proof having alreatly been advanced.Mr. Pope further draws attention t o the fact that the author, in arriving at his values for the general molecular refractions of his salts,236 TUTTON : REFRACTION CONSTANTS OF CRYSTALLINE SALTS. all of which crystallised in systems involving biaxial optical properties, took the mean of the values corresponding to the two extreme indices, a and y, rather than the mean of those corresponding to all three, a, p, and 7, and, apparently, he considers the author to be unaware of the mathematical nature of the problem.His conclusion that this course was pursued ‘‘ merely because, in the cases of the few salts which the author compared in the two states, it happened to give practically the same molecular refraction for the crystalline salt as was found in solution ” is unfounded. The author carefully considered the question during the preparation of his memoir, and decided that i t was amply sufficient for the purpose in view (that of ascertaining whether the same refraction equivalents applied to the alkali sulphates when contained in the double sulphates as when alone) to take the mean of the two extreme values, because all the salts under considera- tion exhibited extremely feeble double refractions-that is, the two extreme values were exceptionally close together, so close, indeed, that it was evident that the differences between the results so ob- tained and those derived by taking the mean of all three values would come within the limits of experimental error, although the utmost care had been taken to reduce the latter to a minimum, and there would be no gain in accuracy in return for the extra labour entailed.I n seeking confirmation of his contention that this extra labour ought to have been incurred, Mr. Pope presents a number of tables purporting to exhibit the results, recalculated in accordance with his view, from the author’s experimental data, and also comparing the recalculated values thus obtained with the author’s values. From the comparison (Table IV, p. 1537), i t would appear that the course con- tended for by Mr.Pope leads to results which differ from the author’s values by amounts far exceeding the experimental error. The author has taken the trouble to check Mr. Pope’s recalculations, with the result that no less than thirteen mistakes were found in the first three columns of figures in Table I11 for which Mr. Pope is responsible, and a similar number in the last column consequent on the others. I n two cases, the arithmetical errors are in the whole numbers, and not in decimal places, and one of them amounts to a fifth of the whole value and is three times the amount of the real difference due to the two methods of procedure. These two cases occur in the third column of figures in Table I11 ; that opposite K,Cu should be 5.25, instead of 4-25, and that opposite Cs,Cu should be 14.51, instead of 13.51.Both these inaccurate values appear as the inferior limits in Table IV, for the increment corresponding t o the passage from potassium to rubi- dium and to cmium respectively, hence, there is no wonder that, to quote Mr. Pope’s statement following the table, ‘‘ the differences areTUTTON : REFRACTION CONSTANTS OF CRYSTALLINE SALTS. 237 Rb, t o Cs,. very much closer with my values than with Tutton’s.” When the arithmetical errors are corrected, Table IV naturally assumes a very different aspect. I n its correct form, it is as follows. K, t o cs,. Increase in rnolccular refraction in passing from ! Limits. K, to Rb,. Diff. IMoan. ! Limits. Diff. Mcan. I I Limits. ~ Diff. IMean. 1 0’91 15’15 It is obvious that the differences between the extreme values found experimentaIIy in different cases of the same chemical replacement, which are due, in part a t least, t o experimental error, are much larger than is the variation in these differences according as the experimental values have been calculated from two refractive indices or from three. Mr.Pope seeks to contro- vert the author’s statement that “the matter in a crystal has, for refraction purposes, the same average effect as the same matter uncrystallised,” and in order to do so he first quotes the case of water and ice, wherein it is observed that the molecular refraction of water, calculated from the determinations of van der Willigen for 20°, appears to be slightly lower than that of ice as calculated from the determination of Pulfrich for 0”. He then extends the dis- cussion to the sulphates of rubidium and czsium, as determined with the same material by Dr.Gladstone in solution and theauthor in the crystallised condition, and states that “just as in the case of ice and water, the molecular refraction in the crystalline state is greater than that calculated for the solution.” It appears to have escaped Mr. Pope’s notice that this is so only for caesium sulphate, and that in the case of rubidium sulphate the opposite is the fact. Both differences, however, are well within the region of experimental error as regards the numbers for solutions. Moreover, water is notEa good test substance, behaving exceptionally, as it does, in so many respects, and particularly when the comparison is made between the one at 0” and the other a t 20”. Such difference as there may in reality be between the refraction effect of a substance when dissolved and when crystallised, due to change of state, is very minute, and from the broad standpoint from which the author was regarding the matter his statement was correct. It remains to notice one further point.

ISSN:0368-1645    

DOI:10.1039/CT8977100235

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年代:1897

数据来源: RSC

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238 REVIS AND KIPPING : DERIVATIVES OF a-HYDRINDONE. XX.-Des*ivativcs of a-Hydridone. By CECIL REVIS, Assoc. C.G.Inst., and FREDERIC STANLEY KIPPINB, Ph.D., D.Sc. ALTHOUGH a-hydrindone has now been known for some years, and its preparation by the method previously described by one of us (Kipping, Trans., 1894, 66, 4SO) is a comparatively simple matter, its derivatives have not yet received much attention, and little is known of their general chemical behaviour ; for this reason, we have taken up again the study of hydrindone derivatives where it was left some years ago. I n the course of this work, we have not only prepared and character- ised a number of new derivatives, but we have also examined more closely the properties of some of the compounds previously described, more particularly in order to compare their behaviour with that of corresponding derivatives of camphor.Between a-hydrindone and camphor there is, in some respects, a con- siderable difference in constitution, but, at the same time, the two ketones are doubtless of a somewhat similar structure as each consists of two closed chains, certain carbon atoms of which are common to both. Expressing the constitution of camphor by Bredt’s formula, each compound contains a 5-carbon nucleus in which the group -CK,*CO- is present; in other words, both a-hydrindone and camphor contain tho complex H I I I - C -CH, -c- I I -c --co I upon which is built a second closed chain. Now, since all the more important reactions o r changes which these two compounds undergo are determined in a greater or less degree by the presence of the -CH,*CO- group, it might be expected that there would be an obvious and close similarity in the behaviour of the two ketones, especially as regards those reactions in which this group is known to be concerned.Investigation has shown that this is so, but only to a very limited exteut : for instance, just as camphor and a-monobromocamphor are oxidised by nitric acid, giving camphoric acid, C,H,,(COOH),, so, like- wise, hydrindone arid rnonobromhyclrindone are converted into phthalic acid, C,H,(COOH), under similar conditions. Again, dibromhydrin- done, like a-dibromocamphor is a very stable substance, and may beREVIS AND KIPPING : DERIVATIVES on ~-EIYDRINDONE. 239 crystallised unchanged from boiling nitric acid of sp. gr.1.4; in both cases, therefore, the substitution of bromine for the 2 atoms of hydrogen of the -CH,* CO- group confers great stability towards nitric acid. The formation of an isonitroso. derivative, containing the complex -C(NOH)*CO- is another point in which the two ketones resemble one another, but, without going into details, it may be stated that here any close analogy ceases to be apparent. One property stands out very prominently in the case of hydrindone, and that is the readiness with which this ketone forms condensation products, such as anhydrobishydrindone, truxene, benzylidenehydrin- done, acetonehydrindone, &c. (Zoc. cit.) ; camphor, on the other hand, shows no marked tendency either to undergo condensation with itself or to interact with aldehydes and ketones; although when treated with energetic dehydrating agents, such as phosphorus pentoxide, zinc chloride, &c., i t loses the elements of water giving cymene, or loses hydrogen giving carvacrol, it yields no compounds analogous to anhy- drobishydrindone or truxene, and although, in the form of its sodium derivative, it interacts with a number of aldehydes under particular conditions, as has been shown by Haller (Conzpt.rend., 1891, 113, 22), yet it does not seem t o do so under conditions which, in the case of hydrindone, at once cause the formation of a condensation product. This last fact is all the more remarkable, inasmuch as Wallacb has lately shown (Bey., 1896, 29, 1595) that a great number of cycloid ketones of various kinds interact readily with benzaldehyde, giving mono- and in some cases di-benzylidene derivatives.We have also found that the mono- and di-bromo-derivatives of a-hydrindone behave very differently from the corresponding deriva- tives of camphor when submitted to the action of alcoholic potash. MThereas a-monobromocamphor is very stable, and even when attacked is simply reduced t o camphor, monobromhydrindone is very readily acted on by alcoholic potash at ordinary temperatures, giving a sub- stance of the composition C18Hl:3Br02, two molecules of the monobromo- compound uniting together whilst the elements of hydrogen bromide are separated. This condensation product, which we name hycll.inclonyZbl.onz~.yd~win- done, and which has probably the constitution represented by the C,H aCH, CH,-C H formula 1 ' I I I ' ' crystallises in transparent monosym- CO--CH-- CBr -CO metric prisms and has been examined crystallographically.Dibromhydrindone, unlike a-dibromocamphor-which is simply con- verted into monobromocamphor-also gives a condensation product when treated with alcoholic potash ; this compound has the composition CISH1lErOS, so that its formation may be expressed by the equation240 REVIS AND KIPPING : DERIVATIVES OF a-HYDRINDONE. 2C,H,Br,O - HBr - Br, = C18H,,Br0,. It seems probable, therefore, that it is an ~~ndonyZbroml~?/d?.i.ndon.e of the constitution represented C H *CH, CH*Y,H, CO--CBr-C--CO by the formula l 6 I I1 This substance is interesting on account of the eagerness with which it takes up benzene, forming with it a compound of the composition ClsHl,BrO,,C,HG, which crystallises in long, flat prisms.A somewhat similar condensation product is obtained when dibrom hydrindone is treated with sodium ethoxide in alcoholic solution ; this substance seems to have the composition Cl,HloBrO,*OEt, but being of little interest, it was not examined very fully. The tendency of hydrindone to undergo condensation is brought out again by the fact that, on treating the ketone with a warm solution of bromine in excess of caustic soda, a sparingly soluble substance of the composition Cl,H1,O, is finally formed. I n some experiments, we also observed the formation of dibromhydrindone, which seemed to indicate that this might be an intermediate product in the conversion of the ketone into the condensation product', but attempts to prepare the latter directly from dibromhydrindone mere unsuccessful.The consti- tution of this condensation product is, perhaps, represented by the C,H,*CH, CH* C H formula I I II I * and for the sake of reference we name CO--C(OH)-C- CO the substance i ? z d o n ~ Z ~ 2 / d r o : 7 ~ ~ 2 / ~ ~ ~ ~ ~ z ~ ~ ~ ~ ; but in this, as in the fore- going cases, the evidence is too slight to afford a sure basis for a con- stitutional formula, The well-known conversion of camphoroxime into canipholenic nitrile being a reaction of great interest, we made experiments with hydrin- done-oxime to see whether the latter could be caused to undergo a similar change, or whether it could be converted into hydrocarbostyril by treatment with mineral acids, just as i t had been previously found to be transformed into that substance when submitted to the action of phosphorus pentachloride (Zoc.cit.). Unfortunately, these experiments gave results of little interest ; the various agents which were tried apparently resolved the oxime into the ketone, the only products being anhydrobishydrindone and truxene, both of which are produced by the condensation of the ketone. An interesting sodium derivative of isonitrosohydrindone was dis- covered in the course of our work; this crystallises from wet ether in pale yellow prisms, which, when gently heated, become bright scarlet, owing to a change in crystalline form; on keeping the scarlet modifica- tion a t the ordinary temperature, it passes spontaneously into the pale yellow form in the course of a few hours. The corresponding potassium derivative has similar properties, and both compounds are decomposed,REVIS AND KIPPING : DERIVATIVES OF WHYDRINDONE.241 to a greater or less extent, into isonitrosohydrindone and alkali hydr- oxide, when attempts are made to recrystallise them from hot water. The hydrocarbon, hydrindene, has been prepared from coal-tar indene by Krfmer and Spilker (Ber., 1890, 23, 3276) and has also been obtained synthetically by Perkin and Revny (Trans., 1894, 66, a%), but owing to the difficulties met with in both cases, our knowledge of the properties of this hydrocarbon is still incoinpIete. In the hope of obtaining it from hydrindone, we repeated and extended K6nig’s work (Insug.Diss., Leipzig, 1889), trying first to reduce the ketone directly to the corresponding alcohol, and afterwards to prepare the alcohol indirectly by reducing hydrindone-oxime and then treating the base thus obtained with nitrous acid. We can fully confirm Kijnig’s con- clusion that, owing to the formation of resinous products in most of the necessary operations, i t is impracticable to use hydrindone as n starting-point for the preparation of hydrindene. The conversion of hydrindone-oxime into amidohydrindone, however, takes place practi- cally quantitatively, and we have thus been able to further characterise the base by preparing and examining a number of its derivatives. The oxalate, acetate, and nitrate are described and also its benzoyl and benzylidene derivatives. EX PER IMENT AL.The first attempts which were made to prepare hydrindone by the method which had been so successfully employed only a year or so before (Trans., 1896, 66, 484), gave very poor results, and although particular care was taken to adhere strictly to the conditions which had previously been found to ensure success, the yield of hydrindone was very small ; i t was thus ascertained that the quality of the aluminium chloride is also a most important factor in determining the course of the action, and that if this substance has been kept for some time even in well-stoppered bottles, the slight decomposition which it undergoes through absorption of moisture renders it practically useless for the conversion of hydrocinnamic chloride into hydrindone.Freshly-pre- pared aluminium chloride, however, gave results as satisfactory as those previously recorded. Hyd~*indonesemicar6ccxoute, C,H,:N*NH* CO *NH,. This is very easily prepared by dissolving the ketone in dilute alcohol, adding solutions of semicarbazide hydrochloride and potassium acetate in dilute alcohol, and then warming on the water bath. After a short time, a white, crystalline powder begins to separate, and finally the whole solution becomes a pasty mass of crystals. The product is collected, washed with water, and recrystallised from dilute acetic acid242 REVIS AEU'D KIPPING : DERIVATIVES OF a-HYDRINDONE. from which it separates in beautiful, transparent prisms. These crys- tals are hydrated, and seem to contain 7H,O; for the combustion, a sampIe was dried at looo nntil constant in weight.0.1686 lost 0,0654 II,O a t 100'. 0 2692 lost 0,1074 II.,O at 100. 0,2265 gave 0.5256 GO, and 0,1216 H,O. H,O- 38.8. I-I,0=39*9. C = 63.3 ; H = 6.0. C',,,HllN,,O + 7H,O requires H,O = 40.0 per cent. C,,H,,N,O requires C = 6 3 5 ; H = 5.0 per cent. Hydrindonesemicarbazone is only sparingly soluble in dilute alcohol, from which it is deposited in the form of a crystalline powder; it is also rather sparingly soluble in ethylic acetate, and insoluble, or nearly so, in chloroform, benzene, and light petroleum. The hydrated crystals effloresce on exposure to the air, and rapidly lose their water of crys- tallisation when kept over sulphuric acid, crumbling to a colourless powder ; when heated moderately quickly, the anhydrous substance turns brown a t about 220°, melting and decomposing a t about 239".Oxidat ion of IIyclr.i.izdo.ize and of Il.loizobrontl~~cli.i.izdone with Nitric Acid. Kijnig has already shown that hydrindone is oxidised to phthalic acid by dilute nitric acid, and our experiments gave a similar result; homophthalic acid, even if formed at all as an intermediate product, is not present in any appreciable quantity, after the solution has been evaporated to crystallisation ; small quantities of a crystalline product, insoluble in a solution of sodium carbonate, were obtained in some experiments, but not sufficient for analysis. Monobromhydrindone (Trans., 1804, 66, 500) is also easily oxidised by boiling 10-20 per cent. nitric acid; in this case, phthalic acid is produced, together with considerable quantities of dibromhydrindone.It seemed probable a t first that the dibromo-compound was present as impurity in the sample of monobromhydrindone which we used, the former being invariably produced in small quantities on treating hydrin- done with one molecular proportion of bromine ; but as samples of the monobromo-derivative, which had been purified by distillation in steam (dibromhydrindone volntilises very slowly), and by recrystallisation, in- variably afforded the dibromo-compound on oxidation with nitric acid, we are convinced that this is due to an action analogous to that ob- served in the oxidation of a-bromocamphorsulphonic acid. As has been recently shown (Lapworth and Kiyping, this vol., p. l), this monobromosulphonic acid yields, amongs t other products, a considerable quantity of di-bromocamphorsulpholactone when it is boiled with nitric acid, the bromine liberated from that portion of the acid which undergoes oxidation to sulphocamphoric acid acting on some of the unchanged compound.I n the case of monobromhydrindone, there-REVLS AND KIPPING : DERIVATIVES OF U-HYDRINDONE. 243 fore, it mould appear that a portion is oxidised to phthalic acid with liberation of bromine, which then converts the still unchanged mono- bromo-compound into dibromhydrindone. Dibromhydrindone may be crystallised from hot nitric acid (sp. gr. 1-4), by which it does not seem to be oxidised even when the solution is boiled for some time; it is also attacked with dif-liculty by a boiling solution of potassium permanganate in acetic acid.It dissolves in hot, concentrated sulphuric acid, but is precipitated unchanged on diluting, even after the solution has been gently heated ; quinoline a t 100' seems to be without action, although at higher temperatures tarry matter is produced. These facts show that dibromhydrindone is a relntively stable substance, comparable to dibromocamphor, except that it is easily attacked by alcoholic potash, as is shown later. H y d h d o n ylbrom?u&GwZo ne, C, ,Hl 3Br 0,. When a solution of alcoholic potash is added to a cold alcoholic solution of monobromhydrindone, a beautiful violet coloration is ob- served, due possibly to the formation of an alkali derivative, somewhat analogous to that of methyl-ay-diketohydrindene (Wislicenus and Kotzle, Anncclen, 1889, 252, 80) ; on continuing the addition of the alkaline solution, the violet gives place to a red or crimson colour, and potassium bromide is precipitated.As soon as the solution acquires a faint alkaline reaction, it is diluted with water, whereupon a grey, flocculent substance is precipitated, the potassium bromide passing into solution ; this precipitate is separated, washed with water, dried, and recrystal- lised two or three times from hot chloroform, from which it separates in colourless prisms. A sample which had been kept over sulphuric acid was analysed, with the following results. 0.1532 gave 0.3564 CO, and 0.0608 H,O. 0.2212 gave 0.1220 AgBr. Br = 23.47. C,,H,,BrO, requires C = 63 *34. This substance, therefore, is a condensation product, two molecules of the monobromhydrindone having combined with separation of hydrogen bromide ; the unsaturated ketone, indone, the formation of which might have been expected, does not seem to be produced under the above conditions.Hydrindonyl bromhydrindone crystallises from hot chloroform, benzene, or acetic acid, in which it is readily aoluble, and from hot methylic alcohol, in which it is only very sparingly soluble, in small, lustrous, transparent needles or prisms, but on allo\v- ing its solutiolls in cold chloroform or ethylic acetate to evaporate spontaneously, it is deposited in massive crystals (see below). Its melting point is very indefinite, partly, doubtless, because the substance decomposes, partly, perhaps, owing t o the existence of different crystal- C = 63.45 ; H= 4.41. H = 3.81; Er = 23.46 per cent.244 REVIS AND KIPPIKG : DERIVATIVES OF a-HYDRINDONE. line modifications ; whereas, for example, large prisms obtained from chloroform or ethyIic acetate solution melt gradually from 170" t o 178' turning black, similar prisms, previously crushed to a powder, melt sharply a t about 166' when quickly heated from about 130', at which latter temperature the large crystals appear to crack and undergo some change in form; sometimes, however, the crushed prisms melt gradually from 166' to 175", whereas the minute needles deposited from hot, dilute acetic acid melt gradually between 158' and 189', decomposition taking place in both cases.When warmed with a solution of phenylhydrazine in acetic acid, hydrindonylbromhydrindone gives a deep blood-red coloration, but a crystalline hydrazone could not be isolated, the product being a tarry mass ; resinous or tarry substances are also formed when the compound is boiled with alcoholic potash.For the following description of the crystallographic properties of this substance, we are indebted to Mr. Davis, Assoc. C.G.Inst. System. --Monosynz;nzetvio. Fo~ms o6sevuecl. a = (100) c = (001) = ( i o i ) r = (101) p = (110) o = ( 2 2 i ) Angle. ap = 100 :I10 ca = OOL : 100 T'C = 101 :001 pp = 110 :110 cr = 001 :LO1 YT' = 101 : 1 0 1 ar = 100 :lo& t o = 001:22& po = 110:221 cp = 001 :110 ar' = 100 : 101 No. of observations. 24 14 26 14 5 5 1 2 4 4 3 4 Limits. 59'41'-60'59' 59"2' -59'30' 83'30'-85'3' 32'50'-34'0' 30'1 1'-30"35' 6 3"l 2'-64"3 5' 61'31'-62'1 2' 53"9' -54"5' 70"2' -71"9' 21'13'-22"40' 92"2' -93'0' Mean observations.60'22' 59'16' 84'23' 33"38' 30"23' 63"57' 61"53' 53"33' 70'49' 21'58' 92'32/ Calculated. - 59"16' - - 30"27' 64"5' 61"59' 53"56' 70"54' 21"52' 92'46'REVIS AND I~IPPING : DERIVATIVES OF ~-NYDRINDONE. 245 The crystals submitted were eminently unsuitable for goniometrical measurement. Though most of the faces were well developed, hardly one gave a distinct reflection. Many of the faces were so corroded that they gave no images a t all ; others, having a serrated surface, gave long strings of images G f equal brightness. A large number of crystals were measured, but only one or two zones of measurement could be obtained from the same crystal, the corrosion being very irregular.The faces of the form 7’’ (101) appear only as thin strips, both faces of the form not always being present. The faces of ~(101) are also very small, and give bad reflections. The pinakoid ccf100) is the best developed form, but its faces are always very much corroded. There is a fair cleavage parallel to ~(001). The extinction on ~ ( 1 0 0 ) is straight. The interference figure is visible through a cleavage plate parallel to c{OOl), the double refraction being positive. The optic axial plane is nearly parallel t o n(100). The optic axial angle is large. I f ~ d o n yZb.,.onz?~.yd.,.indo./ze, C,,H11Br02. In preparing this substance, dibromhydrindone (5 grams) is dissolved in boiling alcohol (about 25 c.c.), and the solution is then rapidly cooled, so that the substance which separates is obtained in a fine state of division; a solution of potassium hydroxide (about 2.5 grams) in aqueous alcohol is then slowly added, keeping the mixture cool, until t>he latter acquires a permanently alkaline reaction.A t first, the mixture becomes a dirty green, darkening, as the alkali is added, to an indigo, and finally to a deep brown colour, during which changes the dibromhydrindone passes gradually into solution ; potassium bromide is then deposited, together wit’h long, colourless needles of the new substance. The latter is separated, mashed with warm water, dried on porous earthenware, and then boiled with a little light petroleum, t o dissolve out any unchanged dibromhydrindone ; the residue, on being re-crystallised from boiling benzene, separates in beautiful, coloar- less needles or flat prisms.Further, small quantities of this product may be obtained by evaporating the original alcoholic filtrate and then proceeding as befoTe, but this portion is less easily purified. Analyses of a preparation which had been crystallised from benzene and then kept over sulphuric acid for some time gave results which did not agree with those required for any probable formula, and the combustions made a t different times did not give concordant results; this was due to the fact that the substance crystallises with 1 mole- cule of benzene, and although the latter is rapidIy expelled at looo, i t seems to escape only very slowly in a desiccator at the ordinary temperature. A sample, freshly crjstallised from benzene and then exposed for a short time in the air, was annlysed with the following results.VOL. LXXI. S246 REVIS AND KIPPING : DERIVATIVES OF a-HTDRINDONE. 0.2156 lost 0 0457 a t looo, darkening slightly. 0.i468 gave 0.3680 CO, and 0-0540 H,O. C',H,, = 21.2. C = 69-05 ; H = 4.1. C,,H,,BrO,, C,H, requires C = 69.0 ; H = 4.1 ; C,X6 = 15.7 per cent. Samples recrystallised from chloroform, however, gave the following results :- 0.1525 gave 0,3584 CO,, and 0.0445 H,O. C = 64.1 ; 13 = 3.2. 0.2336 gave 0.5465 CO,,and 0.0688 H,O. c1 = 63.8; H = 3.3. CISHIIBrO,, requires C: = 63.7; H = 3.2; Br = 23.6 per cent. Two determinations of the bromine gave 23.5 and 23.3 per cent. respectively, but there is some doubt as to whether the samples were obtained by crystallisation from ethylic acetate, or whether they were crgstallised from benzene, and then left over sulphuric acid f o r some months ; in any case, the abov6 analyses are sufficient to establish the composition of the substance.The crystals containing benzene are long, colourless, flat prisms which, when slowly heated from about SO", sinter and begin to turn brown at about 110"; as the temperature rises, the substance becomes solid again and lighter coloured, until, at about 150", i t decomposes and blackens, giving off gas ; when, however, the capillary tube containing the crystals is plunged into the bath, previously heated to 130", the substance melts immediately, and effervesces, turning reddish-brown, then solidifies, and melts again at about 150°to a black liquid.As already stated, these crystals seem t o lose their benzene, but only very slowly, when they are kept over sulphuric acid, as they undergo slight discoloration, and also change in form, becoming a mass of small needles ; when warmed with methylic alcohol, they become opaque, and change into a white powder consisting of microscopic needles. If, on the other hand, the substance is quickly crystallised from acetic acid, i t is obtained as a colourless powder, which, when covered with warm benzene, rapidly increases in bulk and changes to a mass of long prisms owing to combination with the solvent. Indonylbromhydrindone is very readily soluble in chloroform, but only moderately so in acetic acid, and very sparingly in cold rnethylic alcohol; it separates from a cold mixture of chloroform and methylic alcohol in well-defined, transparent prisms, which become opaque a t 95--?@0", and melt to a black liquid a t 150-165"; if heated rapidly from 150°, no visible change occurs until about 160°, and then the substance begins to darken, and decomposes completely at 175--180".On treating a solution OF the substance in chloroform with a little bromine, the halogen is slowly absorbed, hydrogen bromide being evolved in small quantities; the product is a yellowish, crystalline sparingly soluble powder, but it was not analysed. When dibromhydrindone is treated with an alcoholic solution of sodium ethoxide instead of with alcoholic potash, other conditions re-REVIS AND KIPPING : DERIVATIVES OF a-HYDRINDONE.247 maining as already described, a similar blue or violef coloration is pro- duced, and a crystalline compound is easily isolated from the solution ; a sample, purified by recrystfillisation from alcohol and dried over sul- phuric acid, gave on analysis the following results. 0.1531 gave 0.3510 CO,, and 0.0570 H,O. C = 62.6 ; H = 4.1. C,,H,oBrO,*OEt requires C = 62.6; H = 3.9 per cent. From this it would seem that this product is closely related to indonylbromhydrindone, of which it is probably an ethoxy-derivative, but it was not examined very fully, as i t appeared to be of little interest. It crystallises from alcohol in colourless lamins, or in compact prisms which melt and decompose at 173-174"; it dissolves freely in hot chloroform, acetone, and benzene, but is only moderately soluble in ethylic acetate and alcohol, and comparat,ively sparingly soluble in cold ether.I~zdoizyl~~~yds.oxyhy~~~nlone, C:,sH,20,. When hydrindone is placed i n a stoppered bottle together with a considerable quantity of a warm solution of bromine in excess of caustic soda, it melts to a colourless oil, but on warming on the water bath f o r some hours, shaking from time to time, this oil gradually turns brown and becomes more viscous, and is finally partly converted into a light brown solid ; the latter is separated, washed with dilute alcohol to free it from all impurities, and recrystallised from boiling acetic acid ; for analysis, a sample was dried over sulphuric acid. 0.14'76 gave 0,4220 CO,, and 0,0644 H,O.0,1449 gave 0.4152 CO,, and 0.0602 H,O. C = 78.0; H = 4.8. C = 7S.2 ; H I= 4.6. CIsH,,O, requires C = 7S.9 ; H = 4.4 per cent. I n some experiments, apparently when the mixture was shaken vigorously for a short time, the oil was quickly converted into a white, flocculent substance, which was proved to be dibromhydrindone by its melting point and other properties, and also by analysis. Indonylhydroxyhydrindone is only sparingly soluble in boiling ethylic acetate, benzene, chloroform, and acetic acid, from all of which it is deposited in small, colourless needles on cooling ; it has not a definite melting point, but begins to turn yellow a t about 2303, and then gradually decomposes, although it does not liquefy even at 250". Attempts to throw some light on its constitution were unsuccessful, and the name assigned to it above is therefore merely a pro-visional one.Although it seems to interact with phenylhydrazine i n acetic acid solution, the product consisted of a tar from which a crystalline compound could not be isolated. It is only sparingly soluble in boil-248 REVIS AND KIPPING : DERIVATIVES OF WHYDRINDONE. ing acetic anhydride, from which it separates in part unchanged, but if the solution is boiled during some hours, crystals are not deposited on cooling, and a brown, resinous substance is formed. Action of Minesml Acids on Hgclrindojze-oxinie. The experiments which were made in order to compare the behnviour of hydrindone-oxime towards mineral acids with that of camphor- oxime, may be very briefly described, as they led to results of little interest.When hydrindone-oxime is heated with a little concentrated hydro- chloric acid, it slowly dissolves, but after some time crystals make their appearance, and the whole gradually becomes semi-solid. This crystalline product consists of a mixture of anhydrobishydrindone and truxene, and on allowing the hydrochloric acid filtrate t o stand, it deposits a small quantity of a colourless substance melting a t about 164' ; the latter consists of the hSdrochloride of hydrindone-oxime. When concentrated hydriodic acid is employed in the place of hydrochloric acid, the solution rapidly becomes dark brown, owing to the liberation of iodine, and a considerable quantity of anhydrobis- hydrindone is obtained after heating for a short time, but apparently truxene is not formed.These results shorn that hydrindone-oxime behaves quite differently from camphor-oxime, as indeed was to be expected, assuming that the formation of campholenic nitrile takes place in the manner suggested by Bredt. AZkcc Zi Derivatives of Iso~a~ti.osol~ycli.inclo?ze. In the course of some experiments on the reduction of isonitroao- hydrindone (Trans., l894,66,492),it was noticed that, on adding sodium amalgam to an alcoholic solution of the isonitroso-compound, a bright red or scarlet substance was gradually deposited as the pieces of amal- gam passed into solution; this substance proved t o be the sodium derivative of isonitrosohydrindone, but it may be more conveniently prepared simply by dissolving the isonitroso-compound in a little sodium ethoxide, and then precipitating with alcoholic ether ; the yellow, crystalline substance thus obtained was purified by recrysballisa- tion from moist ether, dried in the air, and analysed.0.1167 gave 0.0448 Na,SO,. Na = 12.5 per cent. C,H,NO,Na requires Na = 12.6 per cent. This sodium derivative crystallises from cold alcohol, and from moist ether in pale canary-yellow prisms, and it is moderately easily soluble in hot methylic alcohol, but insoluble, or nearly 80, in dry ether, chloro- form, and light petroleum. It dissolves freely in hot water, but it is at the same time decomposed to a greater or less extent into sodiumREVIS AND KIPPIKG : DERIVATIVES OF a-HYDRINDONE. 249 hydroxide and the isonitroso-compound ; on allowing the solution t o cool, it deposits crystals which are free from sodium, and which have the same melting point as isonitrosohydrindone.When the yellow, undried crystals of the sodium derivative are heated, they change, even at temperatures below loo", into a scarlet substance, and when previously dried they also undergo this transfor- mation, but, apparently, not at so low a temperature; when, on the other hand, the scarlet substance is kept at the ordinary temperature, it gradually assumes its original pale yellow colour. This change in colour is caused by a change in the crystalline form of the substance, and the following account includes the result of an examination of the crystallographic properties of the two modifications which was made for us by Mr.W. J. Pope. '6 The crystals consist of very small, thin, flattened, transparent orthorhombio needles, which shorn the forms (1001, ( O l O ) , and { O l l ) , and are elongated in the direction of the c-axis, and flattened in that of the a-axis ; they can, therefore, be examined through the faces of (100) only. They are pleochroic, appearing colourless in light the plane of polarisation of which is parallel t o the c-axis, and of a brilliant straw yellow colour in light polarised parallel to the b-axis. The optic axial plane is (OlO), and the a-axis is a positive bisectrix ; the optic axes lie outside the field of a &th immersion objective, and the interference figure is the normal orthorhombic one ; the angle (011) : (011) = l l O o , whence 6 : c = 1 : 0.7 (approx.)." '' On heating to 70 - SOo, the transparent, yellow needles are converted into a nearly opaque red or scarlet modification, although still preserv- ing their shape ; the new crystals show aggregate polarisation, and are unsuitable for further examination. By rapid heating, the yellow crystals may be obtained partially covered with red patches; in oil, this red modification is permanent for some days a t the ordinary temperature, but in the air it becomes wholly reconverted into the yellow one in the course of a few hours." It may be noted that the scarlet modification of the sodium deriva- tive may also be obtained directly from solution by boiling down an alcoholic solution of the compound until a considerable quantity of t h e substance has separated ; in this case, the temperature is above that at which the yellow modification is stable.An aqueous solution of the sodium derivative, to which a little sodium carbonate has been added, is of a pale yellow colour, but it becomes distinctly darker, and assumes a reddish-brown hue, on warming, becoming pale yellow again on cooling ; the cause of this phenomenon is, probably, dissociation. The potccssium derivative of isonitrosohydrindone closely resembles the sodium derivative in all ordinary properties, and, like the latter, exists in a yellow and in a bright red crystalline modification.250 REVIS AND KIPPING : DERIVATIVES OF U-HYDRINDONE. Hycli-indoneccxine. Hydrindone interacts readily with hydrazine, giving a beautiful, yellow, crystalline product, which is formed in accordance with the following equation : 2C,H,O + N,H, = C9H,:N*N:C,H, + 2H20.I n preparing this substance, an aqueous solution of excess of hydra- zine sulphate is added t o an alcoholic solution of the ketone, the mixture is warmed on the water bath, and small quantities of a solution of potassium hydroxide are added from time to time ; interaction soon occurs, and dirty yellow crystals are deposited. When no further separation takes place, the solution is filtered, and the residue washed with hot water, dried, and recrystallised from boiling benzene. The ketazine is thus obtained in lustrous needles or prisms having the colour of quinone ; a sample dried at loo3 gave the following result on analysis. 0-192s gave 0.5900 GO, and 0.1110 H20.C,,H,,N,requires C = 83.08 ; H = 6.15 per cent. The ketazine separates from chloroform in large, well-defined, flat prisms, and from methylic alcohol in compact rhomboidal plates, or in large, flat, fern-like forms ; it is very readily soluble in boiling chloro- form and acetic acid, and dissolves freely in hoiling acetone and benzene, but is only sparingly soluble in boiling methylic alcohol and in light petroleum. It melts at 164-165', when heated rather rapidly from looo, decomposing slightly, and turning a darker yellow. It seems t o be insoluble in cold hydrochloric acid, but on heating, it becomes lighter coloured, and then dissolves, being decomposed, apparently with formation of hgdrindone. C= 83.46 ; H= 6.39. A.naidohycl~iizdene ccizcl its Derivatives.Amidohydrindene (hydrindamine) has already been described by Konig (loc. cit.), who prepared it by reducing hydrindone-oxime with sodium amalgam in acetic acid solution; in making large quantities of this base, we have found that the following method leaves little to be desired. The oxime is dissolved in dilute acetic acid, a small quantity of sodium amalgam added, and the whole well shaken until the amalgam is decomposed, the solution being allowed to become warm by tho heat developed during the process; the addition of amalgam is then continued, the solution being kept acid, until no precipitate is produced on treating a portion with water. The filtered solution is then rendered strongly alkaline, the base distilled in a current of steam, collected in hydrochloric acid, and the solution of the hydro- chloride evaporated ; the salt is thus obtained in colourless crystals having the properties described by Konig (loc.c i t ) .REVIS AKD KIPPING : DERIVATIVES OF U-HYDRINDONE. 2-51 I1?,2idolzy/di.inde.e oxnlaie, 2C,H,,N,H2C20,, is obtained when the base is neutralised with a solution of oxalic acid, and the mixture evapo- rated ; i t crystallises from water in rosettes of opaque, white prisms, and is only moderately soluble in water and sparingly so in cold methylic alcohol. A sample was analysed with the following result. 0.2136 gave 0.5258 CO, and 0.1318 H,O. SC,H,,N,H,C,O, requires C: =-' 6'7.4 ; H = 6.7 per cent. Anzidohyclyindene acetate, prepared in a similar manner, is obtained as a syrup when the solution is evaporated, but it gradually solidifies to a mass of Iong, silky needles, and after having been spread on a porous plate, it may be recrystallised from cold water; it is thus obtained in beautiful, transparent prisms which seem to contain water of crystallisation, as they melt gradually from about 74" to loo", giving a colourless liquid which appears to boil a t about 140" ; if, after leaving the melted substlam% at this temperature for some time, i t is caused to crystallise by cooling, i t melts a t 113-115" when heated for the second time.Amidohyclriizclene zitra rate was obtained in the course of some experi- ments on the action of nitrous fumes on an ethereal solution of the base, and may also be obtained by treating the base with dilute nitric acid ; it crystsllises in long, colourless prisms and dissolves very readily in water, but is insoluble, or only sparingly soluble, in dry ether.BenxoyZc~mido~~ydi.in~Zene, C,H,*NH- CO*C,H,, is a well-defined, crys- tallised compound which serves as a means of identifying the base. It is very easily prepared by treating t h e base or its hydrochloride with 10 per cent. potassium hydroxide and benzoyl chloride in the usual manner ; the oily base is thus rapidly converted into a solid or pasty mass, which is separated by filtration, washed with dilute alcohol and recrystallised. C=67*5 ; H = 6 9 A sample was analysed with the following result. 0,2063 gave 0.6106 CO, and 0.1195 H,O. UIGH,,NO requires C = 81.0 ; H = 6.3 per cent. Benzoylamidohydrindene is readily soluble in alcohol, from which it crystallises in colourless, silky needles melting a t 142-143' ; it is very readily soluble in chloroform, ether, acetic acid, and ethylic acetate, but insoluble or nearly so in light petroleum.It dissolves in concentrated sulphuric acid, giving a dark red or crimson solution which has a green fluorescence, but on adding water the colour vanishes. Benx~~ide?aeamidohycl~.i?~zdeize, C,H,N :CH* C,H,, is formed when the base is treated with an alcoholic solution of benzaldehyde and a few drops of potash; a better method of preparation, perhaps, is to dissolve the base, together with a slight excess of benzaldehyde, in C = 80.7 ; H = 6.4.252 REVIS AND IilPPISG : DERIVATIVES O F a-HYDRINDOSE. ether, keeping the solution at the ordinary temperature for about 6 hours. The ether is then evaporated, the residue boiled with water until free from benzaldehyde, and then recrystallised from dilute alcohol; the compound is thus obtained in clusters of transparent prisms which melt a t 74-75". 0.2506 gave 05'914 CO, and 0,1534 H,O. C = 86.2 ; H = 6 8. A great many experiments were made with the object of converting amidohydrindene into the corresponding hydroxy-compound by the action of nitrous acid, but although the conditions were modified in various ways, it was found impossible to avoid the production of a large quantity of resinous matter, and, as KGnig had previously stated,?the yield of hydroxy-compound was invariably very poor. Equally~pooresults were obtained on passing the fumes evolved by the action of nitric acid on arsenious oxide into an ethereal solution of the base ; the nitmte, already described, separated from the ethereal solution in brownish crystals, but otherwise little action seemed to occur. The direct conversion of hydrindone into the alcohol also seems to be impracticable. Konig, who tried the action of varions reducing agents, obtained in all cases a considerable quantity of a crystalline pinacone, and our experience has been the same. Even a neutral reducing agent, such as aluminium amalgam, fails to bring about the desired result, as in this case also the principal product is a crystalline compound melting a t about 143", evidently the pinacone. It may be mentioned also that this pinacone is formed by the action of nitrous acid on the base, a somewhat unusual reaction, which is probably the I esult of oxidation. We can also confirm KGnig's statement that the (impure) alcohol, prepared by treating the base with nitrous acid and purified by distillation in a current of steam, is very easily converted into resinous compounds when it is warmed with hydriodic acid. This being the case, it seemed useless to continue these attempts t o conrei t the ketone into hydrindene. C,,H,,N requires C = 86.9, 73 = 6.8 per cent. CHEMICAL I)EPdRTMENT, CENTRAL TECHRICAL COLLEGE, CITY ASD GUILDS OF LOXDON ISSI'ITUTE.

ISSN:0368-1645    

DOI:10.1039/CT8977100238

出版商:RSC    

年代:1897

数据来源: RSC