摘要:

THE POLYSULPHIDES OB THE ALKALI METALS. PART 111. 1063 XCIV.-The Pol ysdphides of the Alkali Metals. Part III. The Solidifying Points of' the Systems Sodium Monosulp hide-Sulp 12 ur and Potassium i l l 0 7 1 o-sulph id e-Sulplzur. By JOHN SMEATH THOMAS and ALEXANDER RULE. THE formation of polysulphides by the action of sulphur on alcoholic solutions of the arthydrous hydrosulphides of sodium and potassium has previously been investigated and described by the authors (T. 1914 105 177 2819). By means of this reaction it was found possible t o prepare sodium tetrasulphide and potassium pentasulphide in the pure and anhydrous form but it was observed that when attempts were made t o utilise i t for the preparation of other polysulphides of lower sulphur content the above-mentioned compounds contaminated t o a greater or less extent with the corresponding hydrosulphides were always obtained.This result is in general agreement with the work of Bloxam (T. 1900 77, By measuring the quantities of hydrogen sulphide evolved when known weights of the hydrosulphides of sodium and potassium were treated in boiling alcoholic solution with varying amounts of sulphur the present authors (Zoc. cit.) have shown that the reaction between sulphur and the hydrosulphides of the alkali metals in solution tends t o the formation of one polysulphide only; in the case of sodium the tetrasulphide and in the case of potassium the pentasulphide. The only polysulphide of sodium that Bloxam succeeded in pre-paring was the hydrated enneasulphide to which he assigned the formula Na,S,,14H20.He described however a regular series of the potassium compounds including an enneasulphide which he claimed t o have isolated in the anhydrous state. The question of the existence of enneasulphides of the alkali metals will be dis-cussed later. It may however be pointed out here that the present authors have failed to obtain any such compound either of sodium o r potassium. Further in view of the ease with which the polysulphides of these metals undergo hydrolysis and taking into consideration the fact that Bloxam's preparations were carried out in aqueous solutions the 1,urity of the anhydrous polysulphides described by him seems open to question. There is however considerable evidence of the existence in aqueous solution of a series of sodium polysulphides lrom the disulphide t o the hexasulphide and possibly beyond the work of 753) 1064 THOMAS AND RULE THE POLYSULPHIDES Euster and Heberlein on this point being specially important (Zeitsch.anorg. Chem. 1905 43 53; 44 431). These authors found that their results could only be explained satisfactorily by assuming that the solutions dealt with contained a number of anions of the type W SN2 Sllg etc. in equilibrium with each other. The present investigation was undertaken with the view of resolving the present uncertainty as to the number and the relative stabilities of the solid polysulphides of sodium and potassium. Two main objects were kept in view. I n the first,place it seemed desirable to decide whether higher polysulphides of these metals than those which have been described can exist in the solid state, and secondly the nature of the lower polysulphides and the ques-tion of the existence of intermediate compounds required to be settled.The last-mentioned point is of especial interest in view of Bloxam’s conclusion (Zoc. cit. and T. 1895 67 277) that the enneasulphides of sodium potassium and ammoniuin can exist as stable compounds. I n order to account for these intermediate compounds Bloxam suggested that the polysulphides of the alkali metals really consist of solid solutions of sulphur in fundamental compounds of the type R,S, and that therefore the general formula assigned t o them should be R,S, where ~ 1 may be any whole number greater than 5. I n the case of rubidium and cmium Biltz and Wilke-Dorfurt (Zeitsch.aitorg. Chem. 1906 40 297; 50 67; see also Rer. 1905 43 53) who thoroughly investigated the polysulphides of these metals by a thermo-analytical method found no indica-tion of the existence of the intermediate compounds required by this theory and the present authors similarly have failed t’o con-firm the existence of such compounds of sodium and pot.assium. On the other hand positive evidence has been obt>ained in support of the simpler general formula R,S,. E X P E R I M E N T A L . The main portion of the experimental work described in this paper consisted of the determination of the freezing-point curves for the systems sodium monosulphide-sulphur and potassium mono-sulphide-sulphur. These curves were constructed in each case in two sections the first coiisisting of that portion relating to mix-tures in which the percentage of sulphur exceeded that required for the formation of potassium pentasulphide or sodium tetra-sulphide as the case might be the second dealing with mixtures intermediate in composition between potassium pentasulphide or sodium tetrasulphide and the corresponding disulphide OF THE ALEALI METALS.PART 111. 1066 In a second series of experiments the higher polysulphides were heated in a steady stream of hydrogen alld the rate of desulphur-isation was determined by weighing at regular intervals. During each period of heating the temperature was kept as nearly constant as possible but i t was regularly increased for successive periods.Finally in order to decide between the simpler formula R,S, and the double formula advocated by Bloxam molecular weight determinations were carried out in the cases of those compounds which could be obtained in the pure state. For this the ebullio-scopic method was employed alcohol being the solvent. The hygroscopic nature of the substances dealt with made it necessary carefully to exclude moisture a t every stage whilst, owing to the ease with which they oxidise ali solidifying-point measurements had to be made in a stream of pure dry nitrogen. Frequently mixtures were ob t ainecl especially when the composi-tioh was not that of a compound which supercooled to a remark-able extent and it was sometimes possible t o keep these mixtures in the supercooled condition for several days a t the ordinary temperature.The crystallisation of these supercooled mixtures was usually accompanied by considerable increase in volume and it often took place so rapidly that the crucible containing the mixture was shattered. Preliminary experiments showed that a t temperatures above 400° the fused substances attacked glass to an appreciable extent, the disulphides being more active in this respect than the tetra-or the penta-sulphides. Except at much higher temperatures, they are however all without marked action on glazed porcelain, and vessels of this material were therefore used t o contain them. For the determination of solidifying points below 300° the apparatus used was very simple. It consisted of a weighed crucible of glazed porcelain in which the weighed substance from 15 to 20 grams in amount was placed.The crucible was then lowered to the bottom of a hard glass tube about 30 cm. long the lower end of which was sealed. This tube was clamped in a vertical position and its upper end was fitted with a rubber stopper through which passed a thermometer a porcelain stirrer, the exact weight of each having previously been determined and two gas-delivery tubes. One of these tubes just passed through the stopper whilst the other reached almost to the bottom of the apparatus. By their means the air was displaced by dry nitrogen. The mixtures were fused by heating the apparatus in an oil-bath, and a similar bath was used to maintain a constant external temperature during solidification.u u 1066 THOMAS AND RULE THE POLYSULPHIDES In consequence of the high melting points observed in the region of the disulphides it became necessary to employ a form of apparatus more suited to their measurement than the one just described. An electrically heated arrangement was finally adopted. This consisted of an internally glazed porcelain tub0 of approximately 3.5 cm. in diameter and 50 cm. long clamped in an upright position. A portion of this tube was wound with nickel-chromium wire; current from the lighting circuit was used and loss of heat by radiation and oxidation of the wire were prevented by surrounding the wound section of the tube with a thick layer of kieselguhr. It was found that temperatures up to 800° could easily be attained and that when equilibrium conditions had been estab-lished any desired temperature could be maintained with very slight variation over considerable periods of time.The pyrometer consisted of a platinum-platinum-iridium thermoelement in con-junction with a millivoltmeter which was carefully calibrated. The hot junction was protected from the action of the fused sub-stances by enclosing it in a very thin-walled porcelain tube. For the reasons previously mentioned silica could not be used for this purpose and it was found inadvisable to employ platinum.* The lower portion of the furnace tube was packed with kiesel-guhr through which a silica tube of small bore passed. On the kieselguhr the crucible was supported so as to rest in that region of the furnace where the temperature was most uniform.It was placed in position and removed by means of a stout platinum wire looped round it. A rubber stopper pierced with four holes closed the upper end of the tube. Through these holes passed the pyro-meter tube the stirrer the platinum wire referred to and lastly, a delivery tube which used in conjunction with the silica tube a t the lower end allowed of the displacement of the air by dry hydrogen or nitrogen. The pure potassium pentasulphide and the di- and tetra-sulphides of sodium used in these experiments were prepared by the methods described in earlier papers of this series (Zoc. cit.). After preparation they were kept iii a vacuum desiccator over phosphoric oxide. It has previously been pointed out that potassium disulphide 1 In some early experiments the hot junction was protected by a platinum tube but a t the close of the series the metal was found t o be considerably lighter in weight.On dissolving the fusion a brown insoluble powder was obtained which from a partial examination appeared to be platinum mono-sulphide. The quantity obtained however was insufficient to allow of a complete examination OF THE ALKALI METALS. PART fff. 1067 cannot be Qbtained by a method analogous to that employed for t.he preparation of the corresponding sodium compound since the reduction of the pentasulphide by metallic potassium yields a poly-sulphide mixture consisting mainly of the trisulphide but contain-ing a considerable amount of other substances the removal of which is very difficult.In their work on the polysulphides of rubidium and msium Biltz and Wilke-Dorfurt ( l o c . c i t . ) obtained mixtures of low sulphur content by strongly heating the penta-sulphides in a stream of hydrogen. It was decided to use this method for the preparation of potassiuin disulphide. F o r purposes of comparison sodium disulphide was also prepared in this way, and a series of solidifying-point determinations was made with material so prepared as the starting point. The results obtained in this series were found to agree very closely with those recorded in experiments in which sodium disulphide prepared by reduction formed the starting materisl. The sulphur used was twice recrystallised from carbon disulphide and then heated f o r several hours a t looo in order to remove the last traces of solvent.This substance was also preserved in a desiccator over phosphoric oxide. The Desulphurisalion of Sodium Tetrasulphide aud Potassium Pent a s d p hid e . The primary object of these experiments as has already been mentioned was the preparation of the materials necessary for the construction of the complete solidifying-point diagrams of the systems under consideration. The removal of sulphur from the easily prepared higher polysulphides was effected by heating them in a steady stream of hydrogen. At half-hourly intervals the heating was interrupted and after cooling the amount of sulphur lost by the substance was determined by weighing. During each period of heating the temperature was kept as nearly constant as possible and its value was 2 5 O higher for each period than for the one immediately preceding.The variations in the rate of removal of sulphur yielded valuable information with regard to the exist-ence of lower compounds and especially as to their relative stabilities. The heatings were carried out in a slightly modified form of the electrically heated furnace already described. A porcelain crucible of known weight and containing the weighed substance was intro-duced into the furnace tube and the stream of pure dry hydrogen started. The gas was prepared by the electrolysis of a solution of barium hydroxide using a current of constant strength thus u u* 1U08 THOMAS AND RULE THE POLYSULPHIDES avoiding variations in its rate of flow. During the time that the temperature of the furnace was being adjusted to the constant, value desired the crucible was drawn into the cool upper pottion of the tube and on the expiration of each heating period the sub-stance was cooled quickly in the same way.Frc. 1 . IO(700) 9( 650) S(600) 7(55fl) G(500) 4(400! j.( 350) 2( 300) Z(350) O( 200) 0 5 1 0 1 Na2M, Loss in weight per 100 grams of sodium tetrasulphide. The weight of sodiuiii tetrasulphide taken was 15.673 gram and 0.5657 gave 0.4624 Na,SO,. 0.2464 , 1.3178 BaSO,. S=73*47. Na,S4 reqclires Na = 26.44 ; S = 73.56 per cent. The results obtained are represented graphically in Fig. 1 in which the loss in weight per 100 grams of sodium tetrasulphide is an analysis of the substance gave the following figures : Na = 26.47 0s THE ALKALI METALS.PART 111. 1060 pIotted against the total time of heating. The temperature main-tained during the previous half-hour is shown and points are given a t which from the loss of weight. the fused material should have the compositjion of the inone di- and t ri-sulphides. As will be seen from the curve the tetrasulphide undergoes considerable decomposition below 300° aiid from this point the velocity with which the sulphur is reniovetl increases regularly as the temperature rises until the composition of the fusion approaches t h a t of the disulphide the temperature by this timc having risen t o between 625O and 650O. Before the loss reaches t h a t calculated for the disulphide however the direction of the curve changes markedly and the removal of sulphur proceeds much more slowly.This retardation is indeed so marked as to render the preparation of the monosulphide by this method a t the temperatures attain-able in the apparatus described practically impossible. The values given on the curve are of course only relative since the rate of loss of sulphur must obviously depend on the surface area exposed by the fused substance and also on the rate of flow of the hydrogen stream. They do however indicate the existence of a disulphide the stability of which towards heat far exceeds t h a t of the higher compounds. The total loss of weight in the course of the experiment was 6.575 grams and the composition of the product should therefore be Na =45*43 ; S = 54.57 per cent.Analysis of the product gave the following results which agree well with the composition calculated from the loss in weight : 0.4846 gave 0.6795 Na,SO,. 0.3725 , 1.4810 BaSO,. S=54.62. NazSe requires Na=41*76; S=58*24 per cent. From the excellent agreement between the composition of the product as determined analytically and that calculated from the loss in weight it is clear t h a t the sodium polysulphides do not volatilise to any appreciable extent when they are heated a t temperatures within the limits mentioned and this was found to be equally true in the case of the potassium compounds. Biltz and WilkeDorfurt (loc. cit.) found however t h a t when the disulphides of rubidium and czsium were prepared by this method volatilisa-tion invariably occurred and to a greater extent in tho case of the czsium compounds than in the case of those of rubidium.It would seem therefore that the polysulphides of the alkali metals, like the halogen salts show an increasing tendency t o volatilise with rise in the atomic weights of the metals from which they are derived. Na = 45.40 1070 THOMAS AND RULE THE POLYSULPHIDES Turning to the preparation of potassium disulphide the weight of the pentasulphide taken was 17.853 grams. The purity of the salts was established by analysis in which the following results were obtained : 0.3587 gave 0.2816 K,SO,. K=32-76. 0.2752 , 1.3429 BaSO,. S=67*09. K2S requires K=32.78; S=67*22 per cent. FIU. 2. K2SS K,S* K 8 K,S, Loss i n weight per 100 grams of potassium pentasulphate.The removal of sulphur was effect,ed and controlled in the manner already described and the results obtained are shown graphically in Fig. 2 OF THE ALKALI METALS. PART 111. 1071 Whereas sodium tetrasulphide decomposes slightly a t its melt-ing point 274O and loss of sulphur is appreciable a t 300°, potassium pentasulphide appears to be more stable at its melting point although in this case also appreciable loss of sulphur occurs a t 300O. As in the case of the sodium compound the rate of removal of sulphur increases regularly as the temperature is raised but the curve appears t o indicate a slight retardation when the composition of the fusion approximates to that of the trisulphide thus furnish-ing evidence of the existence of that compound as a substance the sulphur pressure of which remains constant betwen definite temperature limits.I n the case of potassium also the great stability of the disulphide may be deduced from the marked change in the direction of the curve when the composition of the fusion approaches that of that compound. Even a t 750° the further removal of sulphur takes place very slowly indeed. The final product of the experiment after cooling was analysed, and gave the following figures: 0.3935 gave 0.4838 K,SO,. K = 55.17. 0.4017 , 1-3008 BaSO,. S=44*49. K,S requires K=54*94; S=45.06 per cent. The total loss in weight was 7.306 grams and from this assuming that no volatilisation of the sulphides had taken place the com-position of the product should have been K-55-46; S=44*54 per cent.It is evident that sulphur had been removed in excess of the amount required for the formation of potassium disulphide. The agreement between the values obtained and those calculated from the loss in weight is not so good as in the previous experiment, but the divergence lies within the limits of reasonable experimental error. Since on examination of the furnace tube no trace of sub-limed sulphide such as Biltz and WilkeDiirfurt describe in the cases of the rubidium and casium compounds was found it was concluded that as in the case of the sodium compounds no appreci-able volatilisation had occurred. Both potassium pentasulphide and sodium tetrasulphide fuse to deep red almost black liquids and this is also true of the various products obtained from them by the removal of sulphur.On solidification the penta- and tetra-sulphides crystallise quickly with very little supercooling and the disulphides also crystallise quite readily although supercooling is more marked in their case. Between the di- and the tetra-sulphides however and especially in the neighbourhood of the trisulphides red glass-like substances were always obtained. I n these cases inoculation often failed t 1072 THOMAS AND RULE THE POLYSTJLPEIDES promote crystallisation and the amorphous substances thus obtained could be kept for considerable periods a t the temperature of the laboratory. Crystallisation usually took place with great rapidity when the temperature was raised and owing t o its being accompanied by considerable increase of volume shattering of the containing vessel commonly resulted.After crystallisation the mass usually remained transparent and red but presented the appearance of fracture in all directions. When the substances after crystallisation were allowed t o remain the crystalline form apparently changed and the mass became opaque and pale yellow, the depth of the colour depending on the percentage of sulphur in the substance. I n all cases the products were soluble in water, forming clear yellow solutions which however rapidly became cloudy owing to oxidation. The solutions of the disulphides were only faintly coloured but increase in the sulphur content was in each case accompanied by a progressive increase in the intensity of the coloration. The System Sodium Monosulphide-Sulphur.The apparatus employed in the investigation of this system has already been described. Every experiment was carried out in a &ream of nitrogen which had been passed over red-hot copper and then over phosphoric oxide, During the cooling of the mixtures the temperatare was read every fifteen seconds. The accuracy of the measurements depended not only on the exactness of the temperature readings which in the case of the thermometer could be trusted to 0.2O and in that of the pyrometer to 1-1.5O but also on the general tendency of the curve and the ease with which crystallisation could be induced. Thus the error in the neighbourhood of the disulphide where the curve is steep is probably far greater than in the regions where the curve is comparatively flat.Similarly higher accuracy is attainable in the case of those mixtures which solidify sharply without supercooling than in thel case of those in which the tendency to supercooling is very great and crystallisation even in the most f avourable circumstances only proceeds slowly. I n these cases the error in single determinations may be relatively great. The results obtained in the analysis of the original material used for the construction of the section of the diagram lying between the disulphide and the tetrasulphide have already been given. On analysis the tetrasulphide employed as starting material for the mapping out of the remaining portion of the curve gave the following figures OF THE ALKALI METALS. PART 111. 1073 0.4931 gave 0.4019 Na,SO,.0.2785 , 1.4904 BaSO,. S=73*52. Na,S requires Na = 26-44 ; S = 73.56 per cent. At the commencement of each series of experiments the sub-stance the crucible containing it and also the thermometer and stirrer employed were weighed. After each solidifying-point determination the fusion was allowed to cool in an atmosphere of nitrogen and when cold after removing the volatilised sulphur, the substance etc. were re-weighed. The increase in weight gave Na =26.39. the amount of sulphur actually added and from this the per-centage composition of each fusion was calculated. As a check on the compositions determined in this way the final mixture obtained in each series of measurements was analysed. I n every case the analytical results agreed well with the percentage compositions calculated from the total increase in weight.I n table I the experimental results obtained f o r the different mixtures investigated are given and they are also graphically represented in Fig. 3. In this diagram the solidifying points o 1074 Ji 0 - r 9; -5.g 2s -3 % &PI M 54.57 55-25 56.39 67.9 1 59.04 60.18 6 1.08 61-91 62.38 62-92 63-63 64.25 64.95 65-74 66.10 66-32 66.74 67-14 67-69 68.05 68-61 69.29 69.67 70-13 70.42 71.25 72.35 73-56 74- 15 74.45 74-62 74-96 75.38 75-72 76.29 76-37 76.97 77.43 77-71 78-03 78.31 78.41 78-63 79.15 80.15 75-1.7 THOMAS AND RULE THE POLYSULPHIDES 8 1 W E %& 3 p 1 j iL P i o d 3% 0 0-723 0.771 0.855 0-970 1.067 1.168 1.252 1.330 1-380 1.437 1.513 1,580 1.662 1.752 1.800 1.829 1.883 1-935 2.010 2.060 2.140 2-241 2.301 2-364 2.42 1 2.550 2.760 3.000 3.114 3-180 3.217 3.294 3.342 3.392 3.522 3.615 3.636 3.794 3.921 4-00 1 4.094 4.179 4.209 4.278 4.445 4.792 81.18 5-200 3 c PI .d .- in $ 3 4 M 504 455 439 445 44 0 432.5 421.5 413 403-5 300 374 356.5 322 290 206 214.5 218 220 223 223.5 235.5 246 252 256 263 2 73 2 75 272.5 269 266 267.5 260.5 257.4 253.5 248.7 250 250 251 251.8 251-7 250 249.5 249.7 249.7 249-5 249.6 249.4 TABLE I.Remarks. Eutectic point doubtful Approximate m.p., Naps,. These points were doter-mined pyro-metrically. Probably m. p. eut,ectic This point is taken from he curve. The eutectic solidified amorphous and this accounts for the wide difference in the values observed. = 206. .m.p. Na,S, taken as 223.5". Mean solidifying point = 222.6". of eutectic Solidifying point of Na,S,. Mean solidifying point of eutectic = 247.6". Solidifying point of Na,S,. Saturated solutions of sulphur in The other layer was sulphur with Na,S with rn. p. 249.6". solidifying point 11 8" OF THE ALKALI METALS. PART 111. 107 5; the mixtures used are plotted against their compositions the latter being expressed as the number of gram-atoms of sulphur added per gram-molecule of sodium monosulphide.As will be seen by reference to the curve the system contains two well-defined eutectics the first of which lies between the tri-sulphide and the tetrasulphide contains 68-15 per cent. of sulphur, and melts a t 222'6O whilst the second lies between the tetra- and penta-sulphide. The melting point of this second eutectic is 247*6O and it contains 75.48 per cent. of sulphur. I n addition t o these there can be no doubt from the general tendency of the curve that eutectics also exist between the di- and tri-sulphides, and also between the monosulphide and the disulphide. Owing to undercooling the melting point of the di-tri eutectic could not be determined accurately hut it is in the neighbourhood of 206O, and the mixture contains approximately 65 per cent.of sulphur. For the definition of the monosulphide-disulphide eutectic only one observation was obtained and this was made pyrometrically . The halt which was fairly distinct occurred a t a temperature of 432O. Although the existence and especially the exact solidify-ing point of this eutectic mixture cannot be considered to be determined by such a single measurement it should be pointed out that the observation is in agreement with the general direc-tion of the curve so that, on the whole the conclusion is justified that the mono-di eutectic does exist and that its solidifying point is probably in the neighbourhood of 430O. It contains approxim-ately 55.8 per cent. of sulphur. The solidifying point of the monosulphide has not been deter-mined since a sufficiently high temperature could not be obtained in the apparatus employed.It would seem probable however, from the direction of that portion of the curve which lies between the monosulphide and the mono-di eutectic as defined by the two points actually observed that the melting point of the mono-sulphide must exceed 800O. Turning to the maxima exhibited by the diagram the first maximum occurs when the composition of the mixture corresponds with the disulphide the temperature being 445O. From t.he fact that on either side of this point the curves fall away very steeply, it follows that the disulphide is quite stable towards heat a t its melting point. From the disulphide the mlidifying points of the mixtures fall nearly 250° until the di-tri eutectic is reached from which point they again rise but much less rapidly.I n the case of the tri-sulphide a definite maximum is not shown but the existence of this compound is established first by the pronounced break whic 1076 THOMAS AND RULE THE POLYSULPHIDES is observed in the curve when the mixture has the composition of the trisulphide and secondly by the presence of both di-tri and tri-tetra eutectics. The absence of a definite maximum is evidence of the unstable character of the trisulphide which must decompose at a tempera-ture below its melting point. From the break indicating the existence of the trisulphide the curve again rises t o a maximurn at 2'75O at which point the fusion has the composition of the tetrasulphide. Thus the existence of this compouiid as a substance stable a t its meltisg point is established.The behaviour of mixtures containing a higher percentage of sulphur than the tetrasulphide is interesting. As the sulphur content is increased the solidifying points become lower until the tetra-penta eutectic melting at 247'6O is reached. From this point the curve appears to be almost horizontal but' on closer inspection a very slight rise can be seen which reaches a maximum a t 251-8O the rise therefore being only 4 - 2 O . A t this maximum point the substance has a composition practically identical with that of the pentasulphide. Kremapn (Moizats?b. 1904 25 1311) has shown that in the case of additive compounds dissociation must theoretically result in the flattening of the maximum and that this flattening must be the greater the greater the extent to which dissociation takes place.Ile has investigated cases for example trinitrobenzene-naphthalene in which the solidifying points of both eutectics and that of the compound only differ by one o r two degrees. It would appear that in the case of sodium pentasulphide the fused sub-stance is so strosgly dissociated that the dissociation products are able to lower the maximum t o a point very little above the tetra-penta eutectic on the one hand and the solidifying point of the saturated solution of sulphur in sodium inonosulphide on the other. Abegg and Hamburger (Zeitach. anorg. Chem. 1906 50, 435) have recorded a similar observation in the case of the poly-iodides of potassium and their results have been confirmed by Kremsnn (Monatsh.1912 33 1081). I n this case the differ-epce between the maximum and the eutectic temperatures was found to be 3.7O. The results obtained by the authors in their present investiga-tion lead to the conclysion that the pentasulphide is the highest polysulphide obtainable by fusiog together sodium monosulphide and sulphur for immediately beyond the pentasulphide maximum the curve becomes horizontal indicating the formation of a saturated solution of sulphur in the latter compound. The melt OF THE ALKALI METALS. PART 111. 1077 ing point of the saturated solution is 249.6") and several points were obtained differing from this value by only 0*1-0-2* although the sulphur content was varied considerably. In order to make quite certain that this horizontal line really represented the formation of a saturated solution the solidifying point of a mixture of equal sinounts of sodium tetrasnlphide and sulphur was determined.After the fused mixture had been thoroughly stirred it separated into two layers the lower of which, the saturated solution solidified a t 249*4O whilst the upper layer of sulphur remained liquid until the temperature had fallen to 11S0 when it solidified to a pale yellow mass. From the appear-ance of the sulphur so obtained and also from its solidifying point, it would seem that the sodium polysulphicles do not dissolve in molten sulphur to any appreciable extent. No evidence whatever is furnished by the results obtained in this investmigation of the existence of intermediate compouiids Such as the enneasulphide.If intermediate compounds exist at all they can only do so a t low temperatures. The System Potassium i~onosulphide-Sulph.2cr. The methods and apparatus employed in the investigation of this system were exactly similar t o those already described when dealing with the sodium series. As starting materials the pure pentasulphide was used in one case and mixtures obtained by expelling sulphur from the penta-sulphide by heating it in a stream of hydrogen were employed in other series. Analyses of the peiitasulphide and of a mixture con-taining less sulphur than the disulphide have already been given. I n addition to these a third material was employed which on analysis gave the following results : 0.4971 gave 0.4639 Ii,SO,.K = 41.88. 0.2333 , 0.9856 BaSO,. S=58*04. These figures agree well with the composition calculated from the loss in weight and the substance therefore approximates to the t r isulphide . A t the end of each series of determinations the final product was analysed. I n every case the figures obtained were found to be in good agreement with the composition calculated from the weight of sulphur added in the course of the series. The results obtained are given in table 11 and in Fig. 4 they are represented graphically 1.078 \ 1.i-t.i sutectic. J Mean m. p. = 250.9. 1 THOMAS AND RULE THE POLYSULPHIDES These points were deter-' mined pyro-metrically. TABLE 11. 44.55 45.56 46.89 48.09 49.18 50.63 51-97 53-02 54.32 55.51 57.06 57-78 68.93 69.62 60.15 60-55 60.95 62.02 62.38 62.72 63.70 64.58 65.74 66.79 67.22 67.99 68.73 69.2 1 69.59 69.81 70.26 70.57 70.86 71.21 71.56 72.26 74.11 76.42 0.959 1-041 1.145 1.259 1-360 1-501 1.638 1-752 1.900 2.042 2-240 2.342 2.499 2.600 2.691 2.743 2.807 2.983 3-043 3.102 3-279 3.445 3.680 3.905 4-00 1 4.179 4-360 4-480 4.550 4.637 4.709 4.847 4-930 6.03 1 5.135 5.352 6-98 1 6.902 467.5 464-5 452.5 433 390.5 3GO 311 25 1-5 251.6 238 217.4 189 160.5 101 ? 130.7 141.6 145-5 152 166 178.2 192 20 1.9 204.3 206.5 204.2 200 196.7 192.3 190 187 185.2 188.6 1ss.9 188 188.1 187.9 185.3 468 -264 249 249 251.5 --101 ? --144 142.5 145 142 --183 183.7 183.1 182.4 182.2 -I I Remarks.Aniorphous. Probably tri-tetra eutectic. Tetra-pen ta eutec tic. Mean m. p. = 143.4. Pcnta-hexa eutectic. Mean m. p. = 182.9". Saturated solution of sulphur in I<,S6 m. p. = 188.1. I The sulphur layer solidified a t 117.5". An examinat,ion of the diagram renders quite clear the existence of three well-defined eutectic horizontal lines which lie between the di- and tri-sulphides the tetra- and penta-sulphides and the penta- and hexa-sulphides respectively. The eutectic mixtures corresponding with these horizontal lines have the following com-positions and melting points OF THE ALKALI METALS.PART 111. 1079 Di-tri eutectic S=54.32 per cent. m. p. 250.9'. Tetra-penta eutectic S = 62-31 per cent. m. p. 143.4O. Penta-hexa eutectic S=70*39 per cent. m. p. 182.9'. Owing t o the difficulty of obtaining the necessary material and the previously mentioned limitation of the apparatus employed the region between the mono- and di-sulphides has not been investi-gated. a region was encountered in which the tendency of the fusions to form highly supercooled amorphous masses was very marked and here no trust-Between the trisulphide and the tetrasulphide worthy transition points could be obtained. It seems probable that the amorphous substance referred t o in the table really consists of the tri-tetra eutectic mixture. The curve exhibits five maxima oE which those corresponding with the di- tri- and penta-sulphides are quite distinct.They occur a t temperatures of 470° 252O and 206.5O respectively. The compounds mentioned therefore can exist as stable substances a t their melting points. Of the two remaining maxima that which indicates the exist-ence of the hexasulphide and is found a t 1 8 9 O is flatbned in th 1080 THOMAS AND RULE THE POLYSULPHIDES same way as the previously discussed sodium pentasulphide maximum being but lo higher than the saturated solution line on the one hand and 6 O above the penta-hexa eutectic on the other. Potassium hexasulphide is therefore very considerably dis-sociated a t its melting point. I n the case of the tetrasulphide the curve shows no definite maximum but the existence of this compound the least stable towards heat of the polysulphides of potassium is indicated by the decided break observed in the curve at the point where the com-position of the fusion corresponds with that of this compound.The temperature a t which this break occurs is 145'5O. A t 18B0 when the mixture contains 71.5 per cent. of sulphur, the curve becomes horizontal and the addition of comparatively large amounts of sulphur does not affect the solidifying point. When a sufficiently larg0 amount of sulphur is added separation into two layers can be observed the one consisting of a saturated solution of sulphur in the hexasulphide solidifying a t 1 8 8 O whilst the other solidifies a t 1 1 7 * 5 O and is practically pure sulphur. As in the case of the sodium series this investigation furnished nos evidence whatever of the existence of intermediate compounds.A comparison of the results of this investigation with the work of Biltz and Wilke-Dorfurt (Zoc. cit.) on the polysulphides of rubidium and cmium is interesting and brings out more clearly the observation made by the authors in an earlier paper that, whilst the polysulphides of potassium rubidium and caesium resemble one another very closely the sodium compounds exhibit notable differences. Thus whilst the three elements first named all form hexasulphides and stable pentasulphides in the case of sodium no trace of the existence of a hexasulphide could be detected and the pentasulphide is relatively unstable. On the other hand sodium tetrasulphide is stable and the trisulphide unstable this order being reversed for the potassium rubidium, and caesium compounds.As regards their appearance stability, and eolidifying points all the disulphides appear to be similar in character. Towards heat these compounds show greater stability than any other of the polysulphides of the alkali metals. For purposes of comparison the solidifying points of the com-pounds and eutectic mixtures investigated by the authors together with the values obtained by Biltz and Wilke-Dorfurt in the rubidium and czsium series are given in table 111 OF THE ALKALI METALS. PSRT 111. 1081 Compound or eutectic. Disulphido ..................... Di-tri eutectic ............... Trisulphide ..................... Tri-tetra eutectic ............Tetrasulphide .................. Tetra-penta eutectic ......... Pent asulphide ............... Penta-hexa eutectic ......... Hexnsulp hide .................. Saturated solution ............ TABLE 111. Sodium. Potassium. 445.0' 471.0" 206.0 250.9 223.5 252.0 222.6 ?(amorphous) 275.0 > 145.0 24i.6 143.4 251.8 206.0 - 182.9 - 189.0 249.6 1SS.l R,ubidinm. Czsi urn. 420.0" 480.0" 200.0 205.5 213.0 217.0 148.5 151-0 > 160.0 > 160.0 159.5 159.6 232.0 210.0 189.8 178.0 201.0 186.0 184.6 172.5 The Molecular Weights of t h e Polysulphides of Sodium and Potassium in Alcoholic Solution. The view expressed by Rloxani (loc. cit.) that the character of the polysulphides of the alkali metals is better denoted by the general formula R,S than by the usually accepted formula R,S,, and that they are to be regarded as derivatives of a compound of the type R4S5 has already been referred to.The existence of compounds of the last-mentioned type has not been established by substantial experimental evidence but the theory was put forward as an attempt to bring the various intermediate conipounds which Rloxam clainied to have isolated of which the socalled ennea-sulphides are the best examples into line with those compounds, such as the tetra- and peiit?a-sulphides the existence of which was generally recognised. As regards the rubidium and ca%uiii compounds Biltz and Wilke-Dorfurt (loc. cit.) found no trace of any such intermediate compounds and the present authors conclude similarly in the cases of the sodium and potassium compounds.Intermediate com-pounds if they exist at all must be of an extremely unstable character. In order to obtain further evidence as to whether the single or the double formula is to be preferred for these compounds the molecular weights in alcoholic solution have been determined for such of them as can readily be obtained in the pure state. For this purpose the ebullioscopic method was employed. Carefully dried alcohol was used and the polysulphides employed had also remained for several days over phosphoric oxide. I n every case their purity was established by analysis. Several determinations were carried out with each substance, solutions of different concentrations being used. It' should be pointed out however that owiiig to the sparing solubilities of sodium sulphide and potassium pentasulphide it was not possibl 1082 THOMAS AND RULE THE POLYSULPHIDES in the cases of these substances to vary the concentration of the solutions used to any considerable extent.The following results were obtained : Sodium Disvlphide. Weight of substance Weightl of Number of taken. alcohol. experiment. Gram. Grams. E. M. W. 3 0,3684 3 1.67 0.184 73.97J 70.57 1 1 0.2396 32-20 0.098" 2 0.3441 31.24 0-173 74-49 Mean = 73.01. Na,S requires M.W. = 220.28. Na$ , , = 110.14. Sodium Te t ?.as u 1p12 ide. Weight of substance Number of t,aken. experiment. Grams. 1 0.2210 2 0.4278 3 0-6194 4 0.8988 5 1.1836 Weight of alcohol. Grams. E. M. w. 31.46 0*071° 115.76 30-91 30.13 30.65 0-290 118.05 31.07 0.358 123-07 Na,S8 requires M.W.= 348.56. Na,S 9 , = 174.28. Potassium Pentaszdphide. Weight of substanca Weight of Number of taken. alcohol. experiment. Gram. Grams. E. M.W. 30.69 E:;: ig;:::} Mean = 157.25 1 0,2761 2 0.3478 31.41 K,S:, requires M.W. = 467.1. K,S Y , = 238.55. I n the case of each polysulphide investigated the mean observed value for the molecular weight was found to be considerably lower than that required by even the simple formula R,S, and there can therefore be little doubt that under these conditions the double formula is quite out of the question. The uniformly low results obtained require however some further explanation. They may be accounted for in two ways. I n the first place alcoholysis of the solution may occur in accord-ance with the equation The result of such a reaction would be to reduce the weight of alcohol actually acting as solvent whilst a t the same time the R,S + 2C2H,*OH 2C2H,*OR + H,S + S - 1 OF THE AT;RAtI METALS.PART 111. 1083 number of molecules in solution would be increased. Both these results would tend to lower the observed molecular weight. That alcoholysis does occur to some extent is certain for in every determination the solution obtained was bright green. This phenomenon has been noted in an earlier paper (T, 1914 105, 188) and was there shown t o be due to the separation of minute particles of sulphur formed by the decomposition of the poly-sulphide by alcohol. Since however the amounts of hydrogen sulphide given off from such solutions even during prolonged boil-ing were so small as to be practically negligible the alcoholysis cannot be very considerable.In the case of sodium tetrasulphide if one supposes the above equation to represent the reaction and the sulphur produced to be insoluble the substance would have to be alcoholysed to the extent of more than 45 per cent. in order that the molecular weight might have the observed value. Taking all the known facts can-cerning the polysulphides of the alkali metals into consideration, this cannot be deemed probable. This opinion is strengthened by the behaviour of sodium tetrasulphide in aqueous solution. One would naturally expect this compound to be decomposed by water to a far greater extent than by alcohol yet Kuster and Heberlein (Zoc.cit.) have shown that in O.1N-solution at 25O the extent of the hydrolysis is only 11.8 per cent. On the other hand the low values obtained by the ebullioscopic method for the molecular weights may be due to the ionisation of the polysulphides in alcoholic solution. Supposing this to be the case and assuming that the alcoholysis is so slight as t o be negligible in order t o account for the difference between the observed and the theoretical values the degree of ionisation must be of the order of 25 per cent. Turner (Amer. Chem. J . 1908 40 588) has studied the ionisa-tion of alcoholic solutions of various halogen salts of the alkali metah in particular of potassium iodide. He employed the con-ductivity method and the results of his work lead to the con-clusion that a 0-1N-solution of this salt is ionised to the extent of 35 per cent.a t its boiling point'. Whilst therefore the evidence is insufficient t o permit of a definite conclusion being drawn the authors are of the opinion that although alcoholysis may in some measure give rise to the observed abnormalities its effect must be comparatively slight and the main cause must be looked f o r in the direction of ionisation of the polysulphide solutions. With the view of gaining further information on this point the conductivities of alcoholic solutions of the polysulphides will be investigated a t a later date 1084 THOMAS AND RULE THE POLYSULPHIDES Surn?tzury and Con el us i o n s. The systems sodium monosulphide-sulphur anci potassium monosulphide-sulphur have been investigated by a thermo-analytical method and in each case the existence has been estab-lished of a complete series of compounds to which the general formula R,S may be assigned where x is a whole number having the maximum value 5 in the sodium series and 6 in the case of the potassium series.No evidence whatever has been obtained of the existence of intermediate compounds such as the enneasulphide described by Bloxam. The thermal diagram for the potassium series closely resembles those obtained by Biltz and Wilke-DSrfurt for rubidium anci czsium. In the sodium series however the resemblance is much less striking. The sodium compounds differ in appearance and properties the maximum combining power of the metal is less anti strict parallelism can no longer be observed between this series and the potassium rubidium and czsium series as regards the com-parative stabilities of compounds of corresponding compositions.This is in accordance with the behaviour of the alkali metals in their compounds with other elements notably with iodine. I n connexion with the preparation of the materials necessary for the main research the rate at which sodium tetrasulphide and potassium pentasulphide lose sulphur when they are heated in a steady stream of hydrogen a t regularly increasing temperatures has been investigated. The results obtained lead to the coiiclusioii that the disulphides in each case are extremely stable compounds from which sulphur can only be removed with difficulty.The bearing of this on the constitution of the polysulphides is of some interest. This question has been discussed by many authors but the views put forward by Spring and Demarteau (Bull. SOC. chim. 1889 [iii] 1 11) and Kuster and Heberlein (Zeitsch. anorg. Chent. 1905 43 72) appear to be the most important. The first-mentioned authors point out that whilst towards inorganic substances the polysulphides behave in accord-ance with the general formula R,SS, their reactions with alkyl haloids are best explained by assuming that they possess the formula R,S,S, in which the first two sulphur atoms in the mole-cule play quite a different part from the remainder. Spring and Demarteau favour the latter formula considering the higher poly-sulphides merely to be solutions of sulphur in the disulphides.Kiister and Heberlein criticise this view on the ground that if it were true all polysulphides being essentially salts of hydroge OF THE ALKALI METALS. PART 111. 1085 disulphide should be hydrolysed in solution t o the same extent, f o r the hydrolysis could not be influenced by the mere physical solution of sulphur. They consider that the constitutions of the polysulphides and the polyiodides are analogous and since it is generally recognised that the latter compounds are best repre-sented by the formula RI,Iz they conclude that the constitution of the polysulphides is best expressed by the formula R,S,S,. With the criticism of Kiister and Heberlein the present authors are in agreement. Nevertheless their results certainly favour the view that in the polysulphide molecule two atoms of sulphur are in a different state of combination from the remainder.They suggest that the disulphides should be regarded as being derived from the form of hydrogen disulphide analogous to the tautomeric form of hydrogen peroxide. They would thus possess the formula R*S*S*R. From this substance the higher polysulphides are obtained not by solution of Thus the trisulphide would R.q:S R*S:S’ the tetrasulphide by I n this way the criticism sulphur but by further combination. be represented by the formula E?:S , R*S etc. of Kiister and Heberlein is obviated, whilst still retaining an explanation of the difference in behaviour of two sulphur atoms in the molecule from that of the remainder. Taken in conjunction with the work of Biltz and Wilke-Dorfurt, the results of the present investigation establish that the volatili-ties of the polysulphides of the alkali metals increase with rise in the atomic weight of the metal. This is in agreement with the well-known behaviour of the halogen salts of these metals. With the object of deciding between the simple formula R,S, and the doubled formula R,S, the molecular weights of several polysulphides in alcoholic solution have ,been determined by the ebullioscopic method. Under these conditions there can be no doubt that the simpler forinula is the correct one. The results obtained were however very considerably lower than even the simple formulz require. The authors attribute this to the ionisa-tion of the solutions and i t is calculated that assuming alcoholysis t o be negligible such ionisation takes place to the extent of about 25 per cent. In conclusioii the authors wish to express their thanks to Mr. F. Hughes who has rendered valuable assistance in the prepara-tion of some of the materials used in the work. INO~WANIC LABORATORIES, UNIVECSITY OF LIVERPOOL. Llteceiued S e p t e t i d m 7th 1t)l’i.

ISSN:0368-1645    

DOI:10.1039/CT9171101063

出版商:RSC    

年代:1917

数据来源: RSC

摘要:

1086 LEWIS STUDIES IN CATALYSIS. PART mf. XCV.-Studies in Catalysis. Part VIIL Thermo-chemical Data and the Quantum Theory. High Ten ipera t ure Reactions. By TVILLIAM CUDMORE MCCULLABH LEWIS. IT was shown in Part VII. (this vol. p. 457) that on the basis of the radiation theory the heat of a reaction is connected with the critical frequencies of the reactants and resultants by the relation : where N is the number of molecules in 1 gram-molecule h the Planck constant and v the critical frequency of any given molecular species taking part in the reaction. It has already been pointed out that this relation was first deduced by Haber (Ber. Bezct. physik~il. Ges. 1911 13 1117) who also attempted to verify it in three cases, namely the formation of potassium chloride potassium iodide and sodium chloride from their elements.I n the present paper it is proposed t o consider the experimental data available a t the present time with the object of obtaining if possible a wider experimental basis for the relationship. Incident-ally it. is necessary t o reconsider Haber’s calculations. F o r our present purpose it is convenient t o divide reactions into high tem-perature reactions and low temperature reactions respectively indi-cating by the former that the chemical clianges require quanta of great size correspondiiig with the visible and ultra-violet regions of the spectrum indicating by the latter that the reactions are such that quanta belonging to the short. infra-red region are sufficient to account for the critical increments involved.High Temperature Reactions. As examples of this class we are concerned mainly with the heats of formation of inorganic salts. To test the relation already given, i t is necessary to know the critical frequency of each of the sub-stances participating in the reaction. I n a large number of cases these frequencies have not yet been directly observed. Haber (Zoc. cit.) has suggested however a very simple relation which, although semi-empirical may be employed in this connexion. This relation which will be referred to as the square-root rule states that the characteristic infra-red frequency I+ of a substance that is, the frequency of the residual ray which is capable of accounting approximately for the specific heat of the substance is connecte LEWIS STUDIES IN CATALYSIS.PART VIII. 1087 with the characteristic frequency v, in the ultra-violet region in the following way : where m is the mass of an electron and M is the inolecular weight of the subst.ance. The ultra-violet frequency vv referred to is that which coi-responds with the maximum of the selective photo-electric effect. Employing the atomic weight f o r M in the case of a number of elements the alkali metals Haber has shown that the calculated and observed frequencies agree satisfactorily. Haber has extended the application of the square-root rule t o the calculation of the characteristic ultra-violet frequency of solid coin-pounds (salts). Thus in the case of sock salt Rubens and Asch-kinass have observed the characteristic infra-red band a t 51.2 p.Taking dl as 58.46 the normal molecular weight of sodium chloride, the ultra-violet wave-length thus calculated is 156.4 ,UP which agrees extremely well with the value 1 5 6 . 3 ~ ~ obtained by Martens from dispersion measurements. I n the case of potassium chloride the infra-red band occurs a t 61.1 p whence employing the normal molecular weight of the salt in the square-root rule Haber finds that the ultra-violet wavelength is 165.3 ,up whilst Martens obtained 160.7 pp from the dispersion. The values quoted are those given by Haber. So far as these data go they indicate the general applica-bility of the rule. Haber further points out that in addition to the characteristic ultra-violet f r squencies referred to in the above cases, the dispersion measurements indicate the existence of a still shorter wave-length.It is an interesting fact although not bearing directly on the present problem that these shorter wave-lengths may also be calculated with considerable accuracy by means of the squareroot rule provided we employ twice the molecular weight of the salt for the quantity 171. Thus in the case of rock salt the second ultra-violet absorption band is calculated to be 110.6 pp, whilst Martens’s value obtained from dispersion data is 110.7 pp. I n the case of sylvine Haber calculates in a similar manner that tlie shorter ultra-violet dispersional band should occur a t 11 6.7 pp, whilst Martens has calculated the value 115.3 pp. As already mentioned Haber has applied the square-root relatioil t o elements such as tho alkali metals and to iodine in which M is taken to represent the atomic weight with satisfactory results.In the case of iodine M obviously represents one-half of the molecular weight of the substance in the dissolved or gaseous state. I n general, tlierefore the term M may refer t o tlie normal molecular weight or to one-half this quantity. That the relation is largely empirical is evidenced by this lack of precision as to tht? significance of M 1088 LEWIS STUDIES IN CATALYSIS. PART VIII. especially when we consider that the investigation of the solid state by means of the X-ray spectrometer lias led t o a quite new concep-tion of the molecular weights of solids. It would appear that in the large majority of salts the term iil denotes the usually accepted value for the molecular weight.It will be shown later however. that one-half of the molecular weight appears to be the correct quantity t o employ in the case of the thallium haloids The significance t o be attached to M is not entirely arbitrary. The following considerations serve as a guide. If we restrict ourselves to the chlorides bromides and iodides of a given metal we would expect on general grounds t o find a certain sequence in the ultra-violet frequencies such 2s is found in the far infra-red region (com-pare Rubens and von Wartenberg Sitzzingsber. K . Aknd. Wiss. Berlin 1914 169). That is we would expect the bromide to occupy an intermediate position between the chloride and iodide. I n the cam of the thallium Ealoids using the nornial molecular weights, we obt ,in f o r the ultra-violet frequencies 15-52 x 1014 for the chloride 18.3 x 1014 for the bromide and 15-21 x 1014 f o r the iodide.Using the half -molecular weights the corresponding values are : 15.21 x 1014 12.93 x 1014 and 10.76 x 1014. I n the first case the sequence is broken in the latter it remains. We conclude there-fore that the latter values are more nearly correct. It will be shown later that ths conclusions here tentatively drawn are borne out from the point of view of the heat determinations. I n Raber’s consideration of the heats of formation of salts the process is regarded as involving the removal of electrons from certain atoms and their addition to others. Haber visualises the process in the following way for the union of a halogen with an alkali metal.Let us imagine an electric space lattice containing halogen atoms and atoms of the metal which have not yet reacted with one another to give the solid salt. The electric space lattice is supposed to possess properties which may be regarded as the mean of those exhibited by solid halogen and solid metal separately. This mean o r average state is then characterised by the single ultra-violet fre-quency (u1+v2)/2 where v3 is the frequency of the alkali metal by itself and v2 is that of the solid halogen. When transfer of the elec-tron has taken place the nature of the space lattice is altered the frequency being now that of the alkali salt. Haber then proceeds to determine whether the work % term Ziv involved in the removal of * Haber regards the quantum as measuring the \vork of removing nil It would appear more justifiable t o idcntify the quantum with the electron.total energy change involved in the transfer of the electron LEWIS STUDIES IN CATALYSIS. PART VIII. 1089 an electron from the alkali haloid salt space lattice is equal to the heat of formation reckoned per grnm-molecule together with the work term J t ( 0 . 5 ~ ~ + 0 . 5 ~ ~ ) . The first case considered by Haber is that of potassium iodide. The heat evolved by the union of the solid elements to produce the solid salt is 80,100 cals. per gram-molecule of the salt. Pohl and Pringsheim have observed the selective photo-electric effect of potass-ium the frequency being v,=0*685 x 1015. From measurements of the atomic heat of iodine it follows that the characteristic iodine frequency in the infra-red is 2-0 x 1012.Employing the square-root rule with M = 127 Haber calculates the ultra-violet frequency of solid iodine to be v1 = 0.9646 x 1015. Hence, N k ( 0 . 5 ~ ~ + 0 . 5 ~ ~ ) = 79,630 cals. The heat of union of K and 1=80,100 Hence for the salt NhvKI := 159,730 From this result Haber calculates the ultra-violet frequency of the salt to be 1.654 x 1015. Applying the square-root rule in the inverse manner Haber calculates from this value the characteristic fre-quency of the salt in the far infra-red region. The result expressed in wave-length is 100 p. The value observed by Rubens (Zoc. c i t . , 1914) is 94.1 p. Haber next considers the formation of sodium chloride.The lieat of reaction between solid chloride and sodium is taken to be 94,600 cals. The ultra-violet frequency of rock salt obtained from disper-sion measurements is 1.918 x 10'5 or A,= 156.4 pp. This corresponds with the value 185,200 cals. for NJLV~;,,:, the radiant energy re-quired to activate one grsm-molecule of the salt. Subtracting the heat of formation from this quantity we find the ~ i l u e l of ( 0 . 5 ~ ~ ~ + 0*5vX,,) namely 0.9382 x 1015 for half the sum of the frequencies of sodium and chlorine. On doubling this value and subtracting from i t the ultra-violet frequency of sodium which Pohl and Pringsheim have found by experiment to be vSn =0*947 x lO15,* we obtain the value vc = 0.9294 x 1015 for the ultra-violet frequency of solid chlorine.Haber uses this to calculate the density of solid chlorine, employing a relation of Lindemann and finds a number of the order which would be anticipated. This however is not a rigid test. Haber therefore considers the two following reactions simul-taneously K + C1= KCl and Na + Cl = NaCl. On subtracting the second equation from the first we obtain : ,, ,, The agreement is fairly good. K+ NaCl=KCl-+ Na. * The above value is that. quoted by Haber. The corresponding wave-length is 317 pp. Recent measurements by Pohl and Pringsheim however, give the value 340 pp for the maximum of the selective photo-electric effect of sodium (compare Hughes " Photo-electricity," p. 84). VOL. CXI. x 1090 LEWIS STUDIES IN CATALYSIS. PART VIII. The corresponding energy expressions are : which give on subtraction N'(VKC - V N ~ C I - Oa5VK f O*'v~a) = QKCI - QN~CI.If we now write vK =0*685 x 1015 vNRCl = 1.918 x 1016 vSa =0*947 x we can calculate the ultra-violet frequency of sylvine. The value thus obtained is 1.8683 x 1015 or ~ = 1 6 0 * 5 pp which is in excellent agreement with the value calculated by Martens from dis-persion measurements namely 160.7 pp. Reviewing Haber's treatment of the problem it is evident that considerable 'doubt exists as regards the mechanism whereby half the sum of the frequencies of the halogen and metal is introduced, although it is evident that the results obtained by this means are in good agreement with the observed values. On the basis of the expression for the heat of a reaction quoted a t the beginning of this paper we should have expected the sum of these two quanti-h s not half the sum.Haber's concept of the mechanism of union of the halogen atom with the atom of the alkali metal seems to involve a rather artificial mean stage which is itself regarded as the starting point of the process. An alternative view might be taken of the mechanism and this view has the advantage that it does not restrict us to the solid state only. If we suppose that the ultra-violet quantum corre-qmnding with the selective photo-electric effect breaks the bond between two adjacent atoms that is activates two atoms in a chemical sense then one quantum characteristic of sodium plus one quantum characteristic of chlorine serves to bring about the following reaction 2Na + 2C1= 2NaC1.Hence the heat of forma-tion 20 reckoned for two gram-molecules of the salt would be given by or the heat of formation of one gram-molecule is given by which is simply Haber's expression without any assumption beiiig made as t o a mean stage. [ 2 N h V N a C 1 - (NhVNa + VCJ]? [ N ~ v - 0*5Nh(~, + vc)], Dissociation of the Halogens. The dissociation of chlorine bromine and iodine may be con-sidered before the question of the formation of salts as the data are required for later calculations LEWIS STUDIES IN CATALYSIS. PART VIII. 1091 It will be observed that the relat,ion is identical with Q = (Eresultaiits - E,e.rctallt6). where E stands for the critical increment as defined i n previous papers. I n the case of gaseous iodine and bromine Evans (Astrophys.J. 1910 32 I 291) has fouiicl that on raising the temperature, the bands in the visible region finally disappear the lowest observed temperature of disappearance being 950O. The tempera-ture of disappearance of colour is a function of the pressure of the gas the greater the pressure the higher being the temperature of disappearance. I n view of this behaviour Evans has concluded that the disappearance of colour is due to dissociation into atoms, which evidently do not absorb in the visible region. The atoms must absorb either in the ultra-violet or the infra-red region. The heat of dissociation of the halogens is negative heat being absorbed in the process. I n order that Q may be negative the critical increment of the reactant (molecular form) must be greater than the increment of the resultant (atomic form).Hence on taking Evans’s results into account and applying the radiation expression we conclude that the critical increments of the atoms correspond with quanta .in the infra-red region. Further the heats of dissociation represent quantities of energy considerably greater than those obtainable from the infra-red region. It is obvious that in the case of gaseous dissociation the critical incre-ment of the reactant must exceed the observed heat of dissocia-tion. If however the critical increments of the resultants are small as in the present case the heat of dissociation cannot be very different from the critical increments of the corresponding tindissociated molecules. The observed heats of dissociation per gram-molecule a t a fairly high temperature that is at a temperature a t which the dissocia-tion becomes measurable are in round numbers as follow: chlorine - 113,000 cals.(compare Pollitzer Ahrens “ Sammlung,” 1912 17 434) ; bromine - 50,000 cals. (Bodenstein and Cramer, Zeitsch. Elektrochem. 1916 22 327) ; iodine - 36,860 cals. (Bodenstein and Starck ibid. 1910 16 961). The values in the case OF bromine and iodine are known with considerable exactness ; that for chlorine is a rough approximation only. From a consideration of the temperature range a t which these gas- dissociate sensibly i t is evident that we are dealing with high temperature reactions that is reactions which require larger quanta than those which correspond with the short infra-x x 1092 LEWIS STUDIES IN CATALYSIS.PART VIII. red region. Further iodine dissociates more easily than bromine and bromine more easily than chlorine. We woi-lld expect there-fore that the critical energy and hence the size of the correspond-ing quantum would increase in the order iodine bromine, chlorine. This sequence is also exhibited by the values of the respective heats of dissociation. To show that radiation in the visible region is capable of sup-plying quanta of the necessary size we may proceed in the follow-ing approximate manner. As indicated by its violet colour iodine absorbs largely in the red end of the visible spectrum. Assuming that the characteristic wave-length is of the order 700,up it follows that the critical increment per gram-molecule is 41,000 cals.in round numbers. This is slightly greater than the observed heat of dissociation. It is therefore a possible value. Similarly if we take the wave-length 500 ,up to be characteristic of bromine this wave-length corresponding with absorption in the green region we find the critical increment per gram-molecule t o be 57,000 cals. This quantity is somewhat greater than the observed heat of dis-sociation of bromine. Owing to the very extensive absorption of both iodine and bromine throughout the visible region i t is impossible at the present time to ascribe the critical increment t o ar,y particular band. The investigations of Hasselberg and of Konen (compare Konen Ann. Ph?ys. C'hen2. 1898 [iii] 65 257) show that iodine possesses numerous bands in the visible region.The same is probably true of bromine although a recent investiga-tion by Peskov (,7. Physicnl C'hem. 1917 21 382) indicates a broad maximum a t 436,up with considerable absorption down to 600pp. I n the case of chlorine a well-defined band has been measured by Brannigan and Macbeth (T. 1916 109 1277) in the near ultra-violet occurring at h = 327 pp. Peskov (Zoc. c i f .) places the maximuin a t 334 p,u. Taking Brannigan and Macbeth's value, i t is found that the critical increment of chlorine is 86,750 cals. per gram-molecule. This is considerably less than the value quoted for the heat of dissociation but it is to be remembered that the latter is a rough approximation and the quantity 86,750 is theoretically an upper limit for the heat effect.We require the critical increments of the halogens in the gaseous state in dealing subsequently with the formation of salts. For this purpose we shall employ the following average values chlorine 86,750 cals. per gram-molecule; bromine 57,000 cals. ; and iodine 41,000 cals. It may be mentioned that the process of dissociation of chlorine, bromine and iodine is one which requires larger quanta than are required for the decompositJon of the corresponding halogen hydr-acids. The only exact measurements available in this connexio LEWIS STUDIES IN CATALYSIS. PART VIII. 1093 refer to hydrogen iodide for which the critical increment per gram-molecule is 20,000 cals. a quantity which corresponds with the short infra-red region. H e a t o f F o r m a t i o n o f S a l t s Potassium Chloride.The characteristic ultra-violet freclilency of this salt as obtaiiied from dispersion measurements is 18.6 x 1014 or A,,= 160.3 pp. The value of the critical iiicrerneiit NhvKC is therefore 175,960 cals. per grain-molecule. As regards the critical increment of potassium the maximum of the selective photo-electric effect occurs a t A = 440 pp whence the increment’ is 64,517 cals. This amount of energy 011 the view already suggested represents the ainouiit required to activate two adjacent atoms of potassium. The stoicheiometric equation requires one-half of this quantity. Similarly the critical iiicreineiit of oiie gram-molecule of chlorine or two gram-atoms of chlorine is 86,750 cals. The total critical iiicremeiit of one gram-atom of each reactant is (64,517 + 86,750) 12, or 75,634 cals.Applying the equation it follows t h a t & = 175,960 - 75,634 = i- 100,330 caIs. in round numbers whilst & &served (Thornsen) = + 105,600 cals. Hack-spill (“Tables Aiinuelles,” 3 p. 588) gives the value 99,650 cals. for the heat of formation. The agreement between observed and calculated values is moderately good. It may be mentioned t h a t if the square-root rule had been employed with M=74.5 in the case of the salt and the infra-red frequency as determined by Rubeiis the critical iiicreiiient per gram-molecule would have bee11 164,000 cals. which is somewhat lower than t h a t obtained from dispersion measurements. As regards the observed heats of forma-tion of salts it may be pointed out that the values given are in general obtained indirectly so t h a t the result is liable to a certain amount of error.Potassium Bromide. The characteristic infra-red band as observed by Rubens (coni-pare Rubens and voii Wartenberg #itzungsber. Ii. A kad. Wiss., Berlitt 1914 169) occurs a t A-82.61“. Measurements of the molecular heat of the salt require the wave-length 82.4 p (Nernst, A72n. Physik 1911 [iv] 36 395) in the Nernst-Liiidemann formula that is v r =0.036 x 1014. Usiiig the squareroot rule an 1094 LEWIS STUDIES IN CATALYSIS. PART VIII. the normal molecular weight of the salt the ultra-violet frequency vv= 16.67 x 1014 or A = 180 ,up. Hence the critical increment, NhvKBr per gram-molecule is 157,700 cals.As before the energy required for two gram-atoms of potassium is 64,517 cals. For bromine the critical increment for two gram-atoms is 57,000 cals. Hence for the formation of one gram-molecule of the salt the t o t a l critical increment of the reactants is (64,517 + 57,000)/2 = 60,758 cals. Hence Q = 157,700 - 60,758= + 96,940 cals. The observed heat of reaction between liquid bromine and solid potassium is +95,310 cals. The calculated value refers to gaseous bromine so that it is necessary t o add the heat of vaporisation of bromine namely 3500 cals. t o the observed value thereby obtaiii-ing the quantity 98,810 cals. The agreement between calculated and observed values is moderately good. Sodium Chloride. The observed infra-red band of the salt occurs a t 52p.The value 51p is required to account f o r the molecular heat (compare Nernst loc. cit.). The infra-red frequency is therefore 0.0577 x 1014. Using the square-root rule and the normal mole-cular weight of the salt, the ultra-violet frequency vV= 19-27 x 1014, or A = 155 ,up which agrees excellently with the value calculated from dispersion measurements. It follows that the critical incre-ment NhvNaC, per gram-molecule of the salt is 182,290 cals. The critical increment of two atoms of sodium is obtained from the position of the selective photo-electric effect which occurs at h=340 pp or vxa =8-8 x 1014 the value of the increment being 83,250 cals. Hence the total critical increment of one gram-atom of sodium and one gram-atom of chlorine is (83,250+86,750)/2 or 85,000 cals.Hence, Q = 182,290 - 85,000 = 97,290 cals. Q (observed) =97,800 ,, The agreement is good. Potnssiunt Iodide. It has already been pointed out that Haber demonstrated the validity of the heat expression in connexion with this substance. Haber considers the reaction as taking place between the elements in the solid state. For iodine he makes use therefore of the square-root rule t o calculate the characteristic ultra-violet fre LEWIS STUDIES IN CATALYSIS. PART VIII. 1095 quency. On the other hand considering the reaction between gaseous iodine and solid potassium and employing therefore the value 41,000 cals. for the critical increment of two gram-atoms of iodine vapour the agreement between the observed and the calcu-lated heat effect is far from satisfactory.We are dependent of course upon the correctness of the infra-red characteristic fre-quency of the salt which has been observed to occur a t v?. =0*0319 x 1014. Using the square-root rule and the normal inolecular weight of the salt we obtain for the ultra-violet fre-quency the value 17.45 x 1014 or At.= 172 p p whence Nhv, = 165,077 cals. Employing the values already given for the critical increments of solid potassium and iodine vapour the calculated heat effect is 112,320 cals. whilst the observed is 83,100 cals. The discrepancy is very great. If we employ one-half of the normal molecular weight of the salt in the square-root rule we obtain, finally the value 63,680 cals. for the calculated heat of the reac-tion. This is now considerably less than the observed value.There does not appear to be any justification however for this mode of calculation in view of the results obtained in the case of the other alkali haloids in which the normal molecular weight of the salt is employed. The agreement obtained by Haber rests on the fact that in the case of iodine he applied the square-root rule to the infra-red frequency given by Lindeniann’s melting-point formula. The resulting value for the critical increment for solid iodine is 91,300 cals. The value which we have taken f o r gaseous iodine is widely different namely 41,000 cals. It may be pointed out however that> the value A,=172pp for the ultra-violet wave-length of the salt-a quantity which is employed by Haber and by the author-is almost certainly in-correct as it involves a breaking down in the expected sequence of the chloride bromide and iodide.Thus since hKcl = 160.7 pp and hRBr= 180 p p we should expect A, to lie somewhere in the region of 200pp. If we take the observed value for the heat of formation together with the critical increments of solid potassium and gaseous iodine already employed we can calculate the critical increment of the salt. Thea value thus obtained is 135,860 cals. per gram-molecule. It follows from this that the ultra-violet fre-quency of the salt is 14.4 x 1014 or A, =208 ~ p . This value occupies roughly the expected position with respect to potassium chloride and potassium bromide but a t the present time there is no means of further testing its accuracy.Taking this value to be correct and applying the squareroot rule in the inveres sense we find that the characteristic infra-red wave-length is 115 p 1096 LEWIS STUDIES IN CATALYSIS. PART VIII. Silver Chloride. The observed infra-red band of the salt occurs a t X-81.5p. Hence v,.=0'0368 x Using the square-root rule and the normal molecular weight' of the salt we obtain for the ultra-violet frequency ~ = l 8 - 6 6 x or A,= 160pp. That is Nhv,,, = 166,520 cals. For silver the infra-red frequency given by Biltz (Zeitsclz. E'ZektrocJwm. 1911 17 676) on the basis of the Linde-mann melting-point formula is lrl. = 0.0436 x l O I 4 (compare also Lindemann B e y . D e u f . physikrrl. G'es. 1911 13 1114). Using the squareroot' rule with M= 108 we obtain for the! ultra-violet frequency I!,,= 19-23 x or A,.= 156 pp. The corresponding value of Nhv, is 182,016 cals. for the activatioii of two gram-atoms. Hence the total critical increment of one gram-atom of each of the reactants is (182,016 + 86,750)/2 OK 134,383 cals. Hence Q = 166,520 - 134,383 = 32,140 cals. whilst Q observed (Fischer Zeitsch. Elektrochei~i. 1912 18 283) = 29,940 cals. The agreement is moderate. Silver Bromide. The observed infra-red band of the salt occurs a t 127~1 or v,. =0-0266 x 1014. Proceeding as in the previous case the ultra-violet frequency is 15-48 x 1014 or A,= 194 pp. Hence Nh,VAIIBr = 146,440 cals. From the data already given i t follows that the critical increment of the reactants per gram-atom of each is (182,016 + 57,000)/2 = 119,508 cals.Hence the heat of formation ($ = 146,440 - 119,508 = 26,930 cals. in round numbers. The observed heat of formation for liquid bromine and solid silver is 22,700 cals. Hence for the reaction involving gaseous bromine the observed heat is 26,200 cals. which is in good agreement with the calculated value. I n all cases the calculated heat effect is a relatively small diff ereiice between two large quantities. It is not to be expected in general that the result can be an accurate one. Silver Iodide. The characteristic iiifra-red band of this salt has not yet been measured. It is possible however to obtain a moderately exact value by comparing the observed values of the three thallium haloids with the two silver haloids all of which have been measured by Rubens.These are as follows TlCl 9 1 . 6 ~ ; TlBr 117-0p; TlI 1 5 1 . 8 ~ . For the silver haloids AgCl 8 1 . 5 ~ ; AgBr, 112.7 p. On plotting these figures the lines run approxim LEWIS STUDIES IN CATALYSIS. PART VIII. 1097 ably parallel aiid an extrapolation iiidicates h = 145 /L for silver iodide. This value is probably correct to k5 per cent. The infra-red frequency is therefore 0.0207 x 1014. Using the square-root rule and the normal molecular weight of the salt the ultra-violet frequency is 13-46 x 1014 or A = 223 pp Hence Nhv,, = 127,332 cals. Employing the values already obtained for silver and gaseous iodine the total critical increment of the reactants per gram-atom is (182,016 + 41,000)/2 =111,508 cals. Hence the heat formation = 127,332 - 111,508 = + 15,820 cals.in round numbers. The heat of formation of the salt. from the elements in the solid state has been accurately measured by Fischer (Zoc. c i f . ) the value being + 15,100 cals. Taking the heat of sub-limation of iodine to be 3000 cals. per gram-atom the observed heat of the reaction involving gaseous iodine is 18,100 cals. which agrees approximately with that calculated on the radiation theory. It will be observed that in the above calculation we have made use of the value 41,000 cals. for the gram-molecular increment of gaseous iodine. Had we employed the value 91,300 cals. obtained from the infra-red band by means of the square-root rule (which Haber has employed in the case of potassium iodide) the heat of the reaction between the solid elements calculated on this basis would have been a negative quantity namely -9300 cals.in place of the observed positive quantity + 15,100 cals. This further emphasises the difficulty met with in the formation of potassium iodide. The result serves to throw still further doubt on the value 172 pp as being the ultra-violet wave-length of potassium iodide. Q T hnl li u m Nnlo ids. T~c~ZZiwn C'liloride.-Direct measurement of the infra-red band of the salt gives the value A=91.6p or v,=0.0327 x 1014. Using the squareroot rule and the normal molecular weight the value obtained for the ultra-violet frequency is 15-52 x 1014 or A = 193 pp. Hence NhvTlc = 146,820 cals. For thallium metal, Biltz (lor. c i t . ) gives the value v,.=0*0184 x 1014. Using the squareroot rule the ultra-violet frequency v,.= 11.15 x or h,=269 pp. The value of Nhv, for two gram-atoms of the metal is therefore 105,480 cals. Hence the critical increment of the reactants per gram-atom is (105,480 + 86,750)/2= 96,115 cals. and the heat of formation Q = 146,820 - 96,115 = 50,700 cals. in round numbers. The observed heat of formation is 48,600 cals. The agreement is satisfactory. Thallium Broniide.-The infra-red band occurs at h = 117 p or v,. =0.0256 x Using the square-root rule and the normal x s 1098 LEWIS STUDIES IN CATALYSIS. PART VIfI. molecular weight we obtain for vv the value 18.3 x 1014 or A,= 164 pp. Hence NhvB = 173,120 cals. The critical increment of thallium and of bromine have already been given. The total critical increment of the reactants is (105,480 + 57,000)/2 or 82,240 cals.The observed heat effect for the reaction involving liquid bromine is 41,300 cals. and therefore for gaseous bromine 44,800 cals. The discrepancy is very great. Thallium Zodide.-The infra-red band occurs a t 151.8 p or vY = 0.0197 x 1014. Using the square-root rule and the normal mole-cular weight of the salt we obtain vv=15*21 x 1014 or A,=197ppu. Hence Nhv,, =143,890 cals. The critical increment of the reactants is (105,480 + 41,000)/2 = 73,240 cals. Hence Q = 143,890 -73,240=70,650 cals. whilst Q observed is 30,200 cals. As this refers to solid iodine the observed value for the reaction involving gaseous iodine is 33,200 cals. The discrepancy is even greater than in the case of the bromide.It has already been pointed out however that the values obtained for the ultra-violet frequencies of the thallium haloids suggests that the square-root rule should be employed in conjunc-tion with half the molecular weight of the salt in order to give the correct sequence in the ultra-violet frequencies of the +,hree salts. Carrying out the calculation we obtain the following results : Hence Nhv for the salt is 143,890 cals. and therefore Q=47,780 cals., whilst the observed value is 48,600 cals. I-Ience Nhv for the salt is 122,320 cals. and therefore Q=40,080 cals., whilst Q observed is 44,800 cals. Thallium Zodide.-v,, = 10.76 x 1014 o r A,= 278 ,up. Hence Nhv= 101,790 cals. and therefore Q = 28,550 cals. The observed value is 33,200 cals. All three thallium haloids exhibit satisfac-tory agreement between the observed and calculated heats of formation on the assumption that one-half of the molecular weight should be employed in conjunction with the square-root rule.This is scarcely likely to be accidental although no reason for the choice can as yet be given. Hence Q = 173,120 - 82,240 = 90,880 cals. Thallium Chloride.-v,,c = 15.21 x 1014 or A,,= 197 pp. Thallium Bromide.-v.r,,3 = 12.93 x 1014 or hv= 232 pp. Lead Chloride. The characteristic infra-red band of lead chloride has been observed by Rubens at Ar=91.0 p that is v,=OaO33 x 1014. Using the normal molecular weight we obtain for the ultra-violet fre-quency vv = 23.33 x 1014 whence the critical increment per gram LEWIS STUDIES IN CATALYSIS. PART VIII.1099 inolecule is 220,700 cals. The infra-red frequency for metallic lead is 0.0195 x 1014 (Neriist Zoc. cit.) whence the ultra-violet frequency is 11.9 x 1014 o r hv= 252 p p ; whence the critical increment of two gram-atoms is 112,574 cals. and the increment per gram-atom is 56,290 cals. The critical increment per gram-molecule (Cl,) is 86,750 cals. Hence the heat of formation of one gram-molecule of lead chloride is 220,700 - (56,290 + 86,750) = 77,660 cals. The observed heat of formation (involving gaseous chlorine) is + 85,570 cals. according t o Braune and Koref (Zeitsch. EZektrochem. 1912, 18 818) and 85,380 cals. according to Gunther (ibid. 1917 23, 197). The agreement is only approximate the discrepancy being due probably to error in the value taken for the critical increment of the salt.Assuming the observed value of Braune and Koref we can calculate a corrected ' value for the critical incre-ment of the salt namely 228,610 cals. By applying the square-root rule we find the infra-red frequency to be 0'034xlOf4 or A,. =89*2p7 which is not greatly different from that observed by Rubens (91.0 p). This illustrates how sensitive the final value for the heat effect. is to error in the infra-red frequency. Mercu~ic Chloride. The infra-red band of the salt occurs a t 95p. Employing t.he normal molecular weight the ultra-violet frequency is found to be 22-06 x 1014 or hv= 136 pp. The critical increment is therefore 208,690 cals. per gram-molecule. The corresponding quantity f o r one gram-molecule of chlorine is 86,750 cals.Lindemann (Zoc. (,it.> finds the infra-red frequency of mercury t o be 0.022 x 1014 whence the ultra-violet frequency is 13.2 x 1Ol4 or hv=227 pp. Hence the critical increment of mercury is 124,872 cals. for two gram-atoms, or 62,436 cals. per gram-atom. The heat of formation per gram-molecule of mercuric chloride is therefore 208,690 - (86,750 + 62,43$) = 59,504 cals. The observed heat of the reaction between liquid mercury and gaseous chlorine is 53,300 cals. Lindeniann's value for the infra-red frequency refers t o solid mercury. On correcting for the latent heat of fusion the calculated heat of the react'ion is 59,000 cals. Mer carotts C?L loride. Let us assume in the first place t,hat the molecule of the salt is represented by HgCl.The observed infra-red band is 98*8p or v,. =0.0304 x 1014. Using the normal molecular weight we find i t u = 19-76 x 1014 or A,= 152 pp whence the increment is 186,930 x x" 1100 LEWIS STUDIES IN CATALYSIS. PART VIIT. cals. per grani-molecule. The critical increinerit per gram-atom of mercury we have already taken to be 62,436 cals. the correspond-ing quantity per gram-atom of chlorine being 43,375 cals. Hence the heat of formation of the salt is 186,930-(43,375+62,436)= 81,120 cals. The observed heat of formation (Nernst Zeitsch. pJ~ysikal. Chptn. 1888 2 23) is 31,300 cals. The discrepancy is very great. Let us now assume that the salt is represented by the formula Hg,CI,. Using the square-root rule with this molecular weight we find v,=27.97 x 1014 or hV=107pp.Hence the increment is 264,600 cals. The reaction is now represented by 2Hg + C1 = Hg2Cl2 hence the critical increment of the reactanh is double the value given above. The heat of formation is thus calculated to be 264,600 - 211,620 =53,000 cals. in round numbers. As the observed heatl of reaction refers t o one-half the quantities here con-sidered it is necessary to calculate the heat effect per gram-atom of mercury namely 26,500 cals. This is in much better agreement with the observed value than the result obtained by the previous method. It appears therefore that the correct formula is Hg2C1,, and not HgCl a conclusion which is borne out by measurements on the salt' in the dissolved state. Employing the observed value for the heat effect we can calculate a ' corrected ' value for the increment of the salt namely 274,000 cals.in round numbers. Thence, calculating backwards we obtain the value v,.=0*0302 x 1014 or A = 101 ,u for the salt which is not very different from the observed value (98.8 p ) . The Reaction Pb + 2AgC1= PbCl 1- 2Ag. The' lieat of this reactlion per gram-atom of lead is according t o Magiius ( Z e i t s c h . ElektrochPrn. 1910 16 273) 24,590 cals. As we have already ohtained the critical increments for the substances participating i i i this reactioii it should be possible t o calculate the heat eflect. Thus: Jncrementr for two gram-inolec~iles of AgCl ... = 2 x 106,620 cals. - ......... Y S .. one grain-atom o f l e d 56,290 Henco total critical increment of re- - actants ......................................389,330 cals. - Increment for one grani-molecule of PbCl ... - 228,610 9 9 , two gram-atoms of silver - 182,016 - ...... Hence total critical iiicrement of re-sultnnts .................................... - - 410,626 cals. Hence Q = 410,626 - 389,330 = + 21,300 cals. in round numbers. This is of the correct order of magnitude and the result is satisfac LEWIS STUDIES IN CATALYSIS. PART VIJI. 1101 tory in view of the fact t h a t we are dealing with a small difference between two very large quantities. The I?eaction P b + Hg,Cl = PbCl -t- 2Hg. Proceeding as in the previous case we obtain : Increment for one gram-atom of lead ......... = 56,290 9 , gram-inolecule of Hg,Cl,. .. = 374,000 Hence total critical increment of re-actants ....................................- :1:30,290 cals. lncreiiiciit fur one gram-iiioleciilr~ of l’hC1 ... = 228,610 1 9 , two grain-atoms of inereury ... =124,870 Hence total critical iiicrement. of re-sultitilts .................................... = 363,480 C ~ S . Hence Q = 353,480 - 330,290 = 23,190 cals. Tlie value observed is 21,800 cals. approximately Giinther (loc. The agreement is satisfactory especially as the critical incre- ,.it.). ments are very large. LYji w r Cyun i d e . The heat of formation of this salt froiri silver aiid gaseous cyaiio-gen as determined by Thomsen is 1393 cals. per gram-molecule. This quantity i q so small t h a t it would be impossible to calculate it with any degree of precision by the method employed in previous cases.I n addition the question of the critical frequency of cyano-gen is in an involved state (compare Grotrian and Runge PAysikuZ. Zeitsch. 1914 15 545). We may use the available data t o calcu-late the critical frequency of cyanogen. Rubens and von Warteiiberg (Zoc. c i t . ) have observed the infra-red band of silver cyanide a t A,.=% p approximately. That is I!,.= 0.0323 x lo** and employing the square-root rule in coiljunction with the normal molecular weight of the salt as we have done in tlie case of the silver Iialoids we obtain 15.86 x 101.‘ for the ultra-violet frequency and A,= 189 ,up. Hence tlie critical iiicrement per gram-molecule is 150,000 cals. The stoicheioirietric equation considered is Ag+ CN=AgCN. We have already seen that the increment of one gram-atom of silver is 91,010 cals.The heat of formation being 1393 cals. the total critical increment of the reactants is (150,000 -1393) cals. On subtracting the value for one gram-atom of silver, we find t h a t the critical increment of the cyanogen group is 57,600 cals. or f o r one gram-molecule of cyanogen the value is 115,200 cals. Hence the frequency is 12.2 x 1014 or h,=246 pp. Tlie author is unaware whether any measurements have been carried out wit 1102 LEWIS STUDIES Ih’ CATALYSIS. PART VIII. cyanogen in this region of the spectrum. In the process considered. tlie energy term 115,200 cals. is t h a t required t.0 break the link between the two carbon atoms in the molecule (CN), thereby giving rise to two nascent groups of monocyanogen.This is quite distinct from the mechanism involved in tlie dissociation of gaseous cyanogen into carbon and nitrogen in which the carbon-nitrogen linking is broken. This would probably require a vory different amount of energy. Sumniury. 1. I n spite of tlie fact that. many of the available data are inac-curate and incomplete the foregoing consideration of liigh-tempera-ture reactions indicates t h a t the radiation expression is borne out in a fairly satisfactory manner. 2. The following table contains the observed and calculated values of the heat effects in those cases in which the necessary data are avaiIable to permit of the complete calculation being carried out. For the reactions considered positive t h a t is heat is evolved. Reaction.K+C1 - KC1 ........................... K+Br -. KBr ........................... Na+Cl -+ NaCl ........................ K+I 4 KI .............................. Ag+CI + AgCl ........................ Ag+Br - AgBr ........................ ;Ag+I -- AgI ........................... TI+Br - TlBr ........................ Tl+I - T1I .............................. Pb+C1 - PbCl ........................ Hg+CI - HgCl ........................ Hg+CI - &Hg,CI ..................... Pb+2AgC1 4 PbCI,+SAg ............ .ri+ci - ~ i c i ........................... Pb-tHg,Cl -t PhCI,+SHg ........ the heat effect is in all cases Heat effect per gram-atom of - Q observed. Q calculated. first reac t,a nt. 98,810 97,800 83,100 29,940 26,200 18,100 48,600 44,800 3 3,2 00 85,570 53,900 3 1,300 24,500 21,800 100,330 96,910 97,290 112,320 ? 32,140 26,930 15,820 47,780 40,080 28,550 59,000 26,500 21,300 23,190 77,660 I n a subsequent paper i t is proposed to consider the data avail-able in connexion with reactions which proceed a t a sensible velocity a t the ordinary temperature that is reactions which require quanta belonging to the short infra-red region to supply the energy neces-sary for the critical increments. MUSPRATT LABOBATORY OF PHYSICAL AND ELECTRO-CHEMISTRY, UNIVERSITY OF LIVERPOOL. [Received October 9 t h 1917.

ISSN:0368-1645    

DOI:10.1039/CT9171101086

出版商:RSC    

年代:1917

数据来源: RSC

摘要:

RELATION BETWEEN CHEMICAL CONSTITUTION EFC. 1103 The Relation Bet ween Ch.emical Constitution and Physiological A c t io n. A Lecture delivered before the Chemical Society 011 December 6th, 1917. By FRANK LEE PYMAN. THE study of the relation between chemical constitutioii and physiological action is a branch of research which has a definite place in the investigation of medicinal substances. Chemical research on a drug begins with the attempt t o isolate the priii-ciple to which its physiological action is due and when this has proved successful the next step is the determination of the con-stitution of the active principle by analytic and synthetic methods. The knowledge is thus gained that some compound of known chemical structure has a particular physiological effect and the way is then clear for the study of the relation between chemical constitution and physiological action by the preparation of a number of substances related to the parent compound and com-parison of their actions on the living organism.The history of quinine affords an illustration of this sequence. Cinchona bark was employed as a remedy for malarial fevers in the fifteenth century. Later on the alkaloid quinine was isolated and recog-nised as the chief active principle of the drug. Chemical investi-gation eventually established the structure of the alkaloid and attempts have since been made to improve or vary its medicinal properties by slight alterations of the molecular structure such as reduction of the vinyl group and replacement of the methoxyl by higher alkyloxyl groups.Moreover a number of compounds with the following general formula have been synthesised which, in common with quinine are distinguished as powerful febrifuges combining a low toxicity to man and a high toxicity to infusoria and paramoecia. The study of the relation between chemical constitution and physiological action may have various objects philosophic o 1104 PYMAN THE RELATION RETWEEN CHEMICAL practical. From the purely scientific point of view it is of great interest to determine the change in physiological action resulting from modification of the chemical structure of an active compound and to elucidate the groups within its molecule to which its pre-dominant physiological action is due ; whilst from the practical standpoint the work may be directed to the physiological, chemical or physical improvement of a drug-for instance it may be desired to eliminate some undesirable secondary effect while maintaining the chief physiological action of the drug or to pre-pare a derivative more stable or more soluble than the parent compound.The relatioil betweeii chemical constitutioii and physiological action has a significance in the discovery of new drugs similar to the relation between chemical constitution and colour in the dis-covery of new dyes. I n the latter case however a single physical property the absorption of light of different wave-lengths is studied ; whereas the term physiological action has no simple meaning but covers any action on the living organism. The bactericidal action of phenol the hypnotic properties of diethyl-barbituric acid and the local anzesthetic action of cocaine are ex-amples of physiological action which are no more comparable with one another than are the chemical structures of the three drugs.Moreover it should be borne in mind that the same superficial signs of physiological action may be due to different causes. Purga-tion for instance is caused by saline cathartics such as magnesium sulphate which act by increasing the bulk of fluid in the intes-tines; and by vegetable purgatives such as derivatives of anthra-quinone which act by irritating the epithelium of the intestines, thus promoting peristalsis. The difficulty of generalisation in the relation under discussion may be instanced by the effect of intro ducing a methyl group into the ortho-position of a phenol, where in the case of the pareiit compuiid the resulting 0-cresol is a more powerful germicide than phenol whilst a similar substi-tution in phydroxy-B-phenylethylamine leads to a substance, 4-hydroxy-/3-m-tolylethylamine which has only one-half of the llressor properties of the parent compound.The subject of this paper must therefore be subdivided eventually into a number of fragments on the relation between chemical constitution and a particular physiological effect ; but before proceeding with these, some general remarks on the action of drugs may be made. An example of physiological action which everyone can appreciate without special knowledge is the effect of certain volatile compounds on the terminations of the olfactory nerves producing the sense of smell.Many compounds of similar constitutioll hav CONSTITUTION AND PHYSIOLOOICAT~ ACTION. 1 105 the same type of smell-for inst'ance the lower fatty acids whilst each member may have a specific odour-which in this particular case serves to distinguish the individual members from formic to valeric acids. Sense of taste also provides an occasional means of discrimination not only between side chains of different lengths -p-ethoxyphenylcarbamide (dulcine) being sweet whilst the higher alkylphenylcarbamides are not-but also in certain cases between stereoisomerides-cl-histidine for example tasting sweet whilst I-histidine is tasteless. It is noteworthy that stereo-chemical influences often have profound effects on the physio-logical actions of quite different classes of compouiids particularly in actions on nerve-endings as Cushiiy has poiiitetl out ( L a n c e / , September 9th 1916 459) ; thus 7-hyoscyamine has about 100 times the niydriatic action of the d-variety and [-adrenaline has many times the pressor eflect of d-adrenaline.In the case of pilocarpine which contains Cwo asyinrrietric carbon atoms a chaiige of sign of one of these results in the formation of the stereoisomeric isopilocarpine which has only a fraction of the activity of pilo-carpine itself. The asymmetry of a nitrogen atom may also con-dition a difference in pllysiological action ; when Icanadine is methylated a mixture of the a- and P-methochlorides is obtained, the isomerism of which is due t o the asymmetry of the nitrogen atom; these produce a typical curare effect (paralysis of nerve endings in voluntary muscle) in the frog the &salt being how-ever twelve times as powerful as the a-salt.Stereoisomerides, however do not always show large diff ereiices in physiological action even in actions on nerve-endings ; cl- and I-homatropine differ little from each other and dZ-homatropine in mydriatic action, whilst &cocaine a stereoisomeride of natural lzvorotatory cocaine, has a local anasthetic action which although quicker and more intense is also more evanescent than that of cocaine. Very little is known about the cause of the variatioii in the physiological actions of stereoisomerides but recently an explana-tion has been suggested by Windaus (Ntrcl~r.K. Ges. Wiss. Cfittingen 1916 301) for the different physiological behaviour of the stereoisomerides 8- and 6:-eholestanol. These compounds differ greatly in their power of inhibiting the hzmolytic action of saponins such as digitonin the former having this property in a high degree whilst the latter has oiily slight preventive proper-ties. Now the &compound has been found to combine with digitonin t o give an almost inactive additive product whilst ocholestanol does not combine with digitonin. This case is of special importance because of the close relation of the cholestanols to cholesterol a constituent of the livin 1106 PYMAN THE RELATION BETWEEN CHEMICAL organism; it may be that a similar difference in the ability of stereoisonierides t o combine with constituents of the nerve cells is the cause of their different action in other cases also.A point to be considered in connexion with the relation between chemical constitution and physiological action is the effect of the physical and chemical properties of the substance on its distribu-tion in the organism. The influence of physical properties such as aolubility in different media may be of great importance as in the case of hypnotics where Meyer and Overton found that the narcotic effect of a series of aliphatic compounds on tadpoles was proportional to the partition coefficients of their solubilitaies in oil and water. An indication of the effect of chemical properties on the distribution of drugs in the organism was afforded by the work of Ehrlich (compare ‘‘ v.Leyden-.Festschrift,” 1898). He showed that basic dyes such as methylene-blue stained tha grey nerve substance whereas their sulphonic acids did not and this difference suggested that bases which are liberated in the blood-stream by the alkali are extracted by the nerve substances whilst their sulphonic acids remain in solution as alkali salts. Similarly, the facility with which an alkaloid is extracted from aqueous alkaline solutions by immiscible solvents may reasonably be sup-posed to affect its distribution in the organism and Ehrlich gave examples of the change of action when certain basic drugs are converted into derivatives containing a free acid grouping or into quaternary salts. I n the case of alkaloids it is a general rule that the introduc-tion of a free carboxyl group into the molecule profoundly modifies the physiological action of the parent compound.Benzoylecgonine, of which cocaine is the methyl ester has no local anzesthetic action; quitenine the acid obtained by oxidising the vinyl group of quinine to a carboxyl group is non-toxic but regains its toxicity on ethylation ; the lactone pilocarpine becomes inactive on the addi-tion of a molecule of alkali hydroxide which forms the alkali salt of the corresponding hydroxy-acid whilst a similar loss of physio-logical activity is shown by a series of tropeines containing a lactone group which lose their atropine-like action on the addition of a molecule of alkali hydroxide. The formation of quaternary salts likewise very largely affects the physiological properties of alkaloids and was the subject of study many years ago by Crum-Brown and Fraser.To give an example from more recent work Laidlaw (Biochem. J. 1910 5, 243) found that 6 7-dimethoxy-3 4-dihydroisoquinoline (I) had a strychnine-like effect whilst its methochloride (11) was devoid o CONSTITUTION AND PHYSIOLOGICAL ACTION. 1 107 this property which however reappeared in its reduction product G 7-climethoxy-2-methyltetrahydroisoquinoline (111). CH CH CH2 /\/\N /\/\NMeCl MeO/\/)Nl\le MeO\/\/CH2 nzeol I I 'CH2 CH2 (111. ) CH2 3feo\/\/ (11. j CH2 ( 1 9 1 A similar relation was observed with papaverine (IV) its metho-chloride (V) and the reductioii product of the latter laudanosine $JH2*C6H3(0Mf1).2 f H,*C,H,(OBle), C C M ~ o / \ / \ N w.1 p32*CGH,(OM42 CH M eO/\/\NMe M"o\/\/ I ICH2 WI.1 CH2 (VI) ; here also the tertiary bases were characterised by strychnine-like action which was not obtained with papaverine niethochloride.Having directed attention to the complication introduced into the relation under discussion by the effect of physical and chemical properties on the distribution of drugs we may now consider certain difficulties of generalisation. We have seen that certain compounds closely allied in chemical constitution differ remarkably in their action and we find on the other hand groups of substances which are almost indistinguishable physiologically but have little in common from the point of view of chemical constitution; one such group is formed by the alkaloids nicotine lobeline and cytisine, another by muscarine arecoline and pilocarpine.Experience has shown however that the members of a group of chemical com-pounds of similar constitution often resemble one another in physiological action and in such cases it is of interest to observe the effect of slight alterations in chemical structure. Many such investigations have been carried out and will be known to you. To-night I shall confine my attention to a few lines of work i 1108 PYMAN THE EELATION BETWEEN CHEMICAL this field which have been carried out or materially advanced wit.hin the last ten years selecting especially those with which the Wellcome Research -Laboratories have Trope ines. The compounds knowii as tropeiiies the amino-alcohol tropine.Atropine, group is the dl-tropyl ester of tropine, CH2-CH-CH2 I I I been a,ssociated. are the and the acyl derivatives of parent inember of the readily yields this sub-I NMe CH*O*CO*CHYh*CH,*Of1. CH2-CH-CH, I t 1 stance on hydrolysis. By esterifyiiig tropine with other acids, tropeines containing different acyl groups may be prepared. A number of these have been examined physiologically the best known being homatropine; the mandelyl ester of tropine which was described by Ladenburg in 1883. I n this paper I propose to give an account of the work on the relation between chemical constitution and physiological action in the tropeines carried out some years ago by Dr. H. A. D. Jowett and myself with the co-operation of Dr.H. H. Dale F.R.S. (Srventh Interlfat. C'ongr. Appl. Chenz. 1909 IVA 1 335) in coiitinuatioii of an investi-gation coinmeiiced by Dr. Jowett in collaboration with Dr. C. R. Marshall. The tropeines appeared to us to be specially suitable for a study of the relation between chemical constitution and physiological action since they are easily prepared give neutral salts readily soluble in water and can be tested physiologically under uniform conditions. Their salts were dissolved in distilled water to give solutions equivalent in tropine content to a 1 per cent. solution of homatropine hydrobromide and the niydriatic effects of these solutions were then compared. By means of two pipettes delivering drops of equal size a drop of one of the two solutions to be compared was allowed to fall into the right eye of a cat and a drop of the other exactly a t the same moment into the left eye the head being held until all was absorbed so that none escaped by overflow of tears.I n the case of the less active tropeines the times required to produce the maximum mydriatic effect were much the same in all cases so that the more active of two was easily recognised. I n the case of the highly active tropeines the rapidity of actio'n as well as the maximum mydriatic effect had to be considerecl. It should be iioted that the mydriasis caused by the mor CONSTITUTION AND PHYSIOLOGICAL ACTION. 1 109 powerful tends to produce consensual niyosis in the other eye so that a small difference of activity is exaggerated and easily de twted.The effect of concentrated solutions has not been tested but tropeines which produce no perceptible effect in dilute solutions may give evidence of mydriatic effect when applied in concentrated form; thus Gottlieb ( . ~ T c ? z . e s p . Pnth. I’hnrnl. 1896 37 218) has stated that lactyltropeine and hippuryltropeine produce no mydriasis when introduced into the conjunctival sac in 2 per cent. solution but that 10 t o 20 per cent. solutions produce mydriasis commencing in half an hour. Further it must be pointed out that only the effect of lortd application has been tested; tropine itself although it has no local action on the eye pro’duces a striking mydriasis .in cats when given internally in large doxs and certain tropeines which have no local action for example the lactone of o-carboxyphenylglyceryltropeine produce mydriasis on injection.Briefly the problem investigated was the relation between the chemical constitution of the acyl group of a tropeine and the mydriatic effect produced by the instillation of a neutral solution equivalent in tropine content to a 1 per cent. solution of hom-atropine hydrobromide into the conjunctival sac of a cat. NO attempt was made to determine the cause of the mydriatic effect, which may have been due to action of the atropine type that is, paralysis of the motor nerve-endings of the sphincter (contractor) muscle of the pupil or t o action of the cocaine type that is, stimulation of the nerve-endings in the dilator muscle. Thirty tropeines were prepared and exanlined comparatively by this method.The mydriatic action of many of these had been recorded previously and references to the earlier results are given below. The mydriatic action of a further fifteen tropeines which we ourselves did not examine is also taken into consideration. For the purpose of discussion the forty-five tropeines inay be divided conveniently into six groups. T. Tropeines of aliphatic acids ................................. 8 11. Tropeiiies of substituted benzoic acids .................. (i 111. Tropeines of substituted hydratropic acids ............... 1 1 1V. Tropeines of substituted phenylacetic acids ............ 1 3 V. Tropeincs of sizbstituted phenylpropionic acids ......... 5 VC. Tropeines of acids in which the phenyl and cnrhosyl gronps are separated by an imino-group ............2 The tropeines of each group have been tabulated in order to show the results obtained a t a glance 1110 PYMAN THE RELATION BETWEEN CHEMICAL I . Tropeines of Aliphatic Acids. Mydriatic action A f Present Previous results corn--*- parison. Tropeine. Pormnls. Action. Observer. Actioii. 1. Acetyl- - Gottlieb ............... CH3*C0,T 2. Glycollyl- ............ CH2( OH)'CO,T - Marshall' 3. Lactyl- ............... CH;CH(OH)'CO,T + lo'& Gottlieb 4. Succinyl- ............ ('CH,'CO,T) - Gottlieb 5. Tartryl- ............... [*CH(OH)'CO,T] -6. Fumsroyl- ............ (:CH*CO,T) -7. Methylparaconyl- ... I I - Marshall1 -............... -1- Marshall' -l - y / CHMe*CHCO,T 0 'CO 'CH, CMe,-CH.CO,T O'CO 'CH, 8.Terebyl- I I Jowett and Hann T. 1906 89 357. Gottlieb stated that acetyl- and succinyl-tropeines can be brought in the solid state on to the conjunctival sac of a cat without. per-ceptible mydriatic effect but that lactyltropeine produces mydriasis commencing in half an hour under these conditions although it is inactive when applied as a 2 per cent. solution. The above table shows that previous observers had only reported mydriatic activity of dilute solutions in one instance that of terebyltropeine. This compound was again examined in the course of the present work and found t o be inactive. Tartryl-and fumaroyl-tropeines were also inactive so that no aliphatic tropeine that has yet been tested possesses mydriatic properties when applied as a dilute solution t o the eyes of a cat.11. Tropeines of Substituted Benzoic Acids. Mydriatic action. Previous results. comparison. && - Present Order of Tropeine. Formula. Action. Observer. Action. a.ctivity. 9. Benzoyl- ............ C,H;CO,T + Schmiede- 4- 3 10. Phthaloyl- ......... C6H,(COaT) -11. o-Hydroxybenzoyl- HO'C,H;CO,T - FaIck 4 1 12. m-Hydroxybenzoyl- HO*C,,H,'CO,T + Volkers _I_ 2 13. p-Hydroxybenzoyl- HO'C,H,*CO,T -14. Protocatechoyl- ... (HO)2C6H3'C02T - Marshall -berg. R'. Buchheim Arch. exp. Path. Pharm. 1876 5 463. Ladenburg AnnuZen 1883 217 82 CONSTITUTION AND PHYSIOLOGICAL ACTION. 11 11 Our examination of the above tropeines confirmed the state-ments of previous observers except in the case of o-hydroxy-benzoyltropeine.So far from being inactive this proved to be the most active of the tropeines of substituted benzoic acids, m-hydroxybenzoyltropeine being the next in order of activity. The tropeines of phydroxy- and 3 4-dihydroxy-benzoic acids both containing a para-hydroxyl group were inactive. 111. Tropeines of Substituted Hydratropic Acids. Mgdriatic action. Previous Present I- - results. comparison. i 2 2 . ' .r( g $ & F 4 Tropeine. Formula 0 4 8 Cushny' 4- 1 ;] CH,*OH + Laidlaw2 + Erbe3 + Lewinand 16. I-Tropyl-(hyoscyamine) I 17. d-Tropyl-(d-hyoscyamine) CHPh'C0,T 15. dl-Tropyl-(atropine) 18. Atropine methonitrate. I CH,-OH CHPh*CO,T,MeNO Grube4 CH,*O~CO*CH, CHPh*C02T CH,C1 CHPh'C0,T CH,Br Guillery5 CIIPh'C0,T CII;O *SO,H 22.Atropinesulphuric acid I - Trendel-CIIPh'C0,T onhurg CII,*OH CPh( OH)-CO,T i ............... Guillery5 Guillery5 19. Acetyltropyl- 1 20. Chlorohydratropyl- I 2 1. Bromohydratropyl- 1 ...... + Lewiii and ...... + Lewin and 23. Atroglyceryl- ............... 1 -b 2 26. Atropyl- ..................... CPh(:CH,)*CO,T - Lewin and 24. Atrolactyl- .................. CI'hMe( OH)'CO,T -1- Volkers Guillerys J . physioE. 1904,30 176. Barrowcliff and Tutin T. 1909 95 1906. Inaug. Diss. Miinchen 1903. Inaug. Diss. Gottingen 1905. " Die Wirkungen von Arzneiinitteln und Giften auf das Auge," Berlin, Arch. exp. Path. Pharm. 1913,73 118. 1905 p. 209. The tropeines of substituted hydratropic acids present several points of interest the most striking being the difference in activity between I- and d-hyoscyamine.Cushny working with the partly racemised substances found that Ehyoscyamine was about fourtee 11 12 PYMAN THE RELATION BETWEEN CHEMICAL times as active a inydriatic as d-hyoscyarniae. Later Laidlaw showed that the ratio of activity between the pure salts was much greater the mydriatic action of the Z-compound being about one hundred times that of the dextro-compound. The mydriatic action of atropine is therefore mainly due to the 7-constituent. Methylation of the nitrogen atom of atropine decreases the mydriatic action atropine methonitrate being apparently inter-mediate in action between atropine and homatropine. Acetylatropine is stsated by Lewin and Guillery to cause mydriasis and paralysis of the accommodation when applied in 1 per cent.solution whilst the same authors report that chloro-and bromo-hydratropyltropeines in 2 per cent. solution cause greater irritation to the eyes than atropine. The chloro-com-pound although less active than atropine gives sufficient mydriasis for ophthalmic purposes whilst t'he action of the bromo-compound is even slower and less intense than that of the chloro-compound. They found that atropyltropeine caused 110 mydriasis in 2 per cent. solution. Atropinesulphuric acid the acid sulphuric ester of atropine and a t the same time an internal salt' has no mydriatic action in 1 per cent. solution. Atroglyceryltropeine is of particular interest since it contains two hydroxyl groups in the positions of those of atropine and hornatropine respectively.CH,*OH CH,*OH H I C,II,*C CO,T C,H~&CO,T C,B ,*d*c4 qr. k J tz O H I Atsro p i 11 c. A t roglycerylt ropcine. HornatPopine. When examined on cats by the comparative method i t proved to be intermediate in activity between atropine and homatropine, but was less active than homatropine for the human eye. Atrolactyltropine is described as a powerful mydriatic strikingly similar in this respect t o homatropine. With the exceptioii of homatropiiiesulpliuric acid which is in-active like atropiiiesulphuric acid in the previous s,ection all the tropeines of substituted phenylacetic acids have mydriatic proper-ties. The effect of stereoisomerism on the activity is much less marked than in the previous section the enantiomorphous forms of homatropine differing only slightly in action the lmo-form being again the more active.Homatropine methobromide dilates the pupils of cats' eyes more completely and more quickly than a solution of hornatropin CONSTITUTION AND PHYSIOLOGICAL ACTION. 11 13 2 6. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. IV. Tropeines of Substituted Pheiiylacetic Acids. Mydriatic action. - Present Previous results. com-parisoil. Tropeine. Formula. Phenylacetyl- ... CH,Ph*CO,T (homatropine) *. CHPh(OH) *CO,T 1 ...... dl-Mandelyl-d-Mandelyl-Z-Mandelyl- ......... dl-MandeIyI-dl-Mandelyl-etho -Homatropine-sul-methobromide C'HPh(OH)'W2T,1L1eSr bromide ......... CHPh(OH)'CO,T,Et.B1. nhurir acid ......CHPh(O'SO.H)'CO,T " I I m-Methylmandelyl- C ,H,Mo 'CH( OH) *CO,T o -Methylmandelyl -p-Methylmrtndelyl -Phenvlchloro -acetyl- ......... CHPhC:1'C02T acetyl- ......... CHPh( NH2)'C0,T Phenylamino-Pht halidecarbosyl- C ,H;CH 'CO ,T I I co-0 Jowett and Pyman T. 1907, Action. Observer. Actioii. -I- + VOlkers + + i-4- Symoris . j -+ Symons -I-- Trendel-enbnrg 4-4- + 4 t--k Marshall 3-91 92. hydrobromide of the same strength but is less active for human eyes. Homatropine ethobromide is less active than the metho-bromide. Of the three methylmandelyltropeines the ortho- and meta-compounds equal each other and are more powerful than hornatropine in mydriatic power when tested on cats but the para-compound is slightly less active.Phenylacetyl- phenylchloroacetyl- phenylaminoacetyl- and phthalidecarboxyl-tropeines which contain 110 free alcoholic hydroxyl group are all active but much less so than honiatropine. Cinnamoyltropeine reported by Ladenburg as " hardly inydriatic," was found to have no mydriatic properties under the conditions of our investigation. 8-Phenyl-a-hydroxypropionyl-t r opeine is isomeric with atropine (u-p hen y l-P-h y d r oxy pr opionyl-tropeine) and also with atrolactyltropeine (a-phenyl-a-hydroxy-propionyltropeine) ; it only differs from honiatropine in that the phenyl and secondary alcohol groups are separated by a methylene group. It is a powerful mydriatic for cats' eyes and begins to dilate the pupil considerably earlier than atropine but the atropine dilation when it once begins quickly overtakes the othe 11 14 PYMAN THE RELATION BETWEEN CHEMICAL V.Tropei?i.es of Substit7ited Phenylpropionic Acids. Mydriatic action. Tropoine. Formula. 40. Lactone of o-carb- C,H4'CH(OH)'CH'C0,T 41. isocoumarincarb- ~6H,*CH:C.C02'I! 43. b-Phenvl-a-hvdr-39. Cinnamoyl- ...... CHPh:CH*CO,T I 0 oxyphenyl- I glyceryl- co oxyl- I I co- 0 > Present Previous com-results. parison. - 7-- Ladenburg -- Symons -- Symons -+ 1 oxypiopioiyl- CH,Ph'CH(OH)'CO,T 43. B-2-Pyridyl-a-hydroxfpro-pionyl- ......... C,H4N'CH,'CH(OH)'C0,T aiid becomes maximal a little earlier. When tested on human eyes it was found to be inferior to homatropine hydrobromide. &2-Pyridyl-a-hydroxypropionyltropeine has been included in the above group.It differs from the preceding member by the substitution of pyridine for benzene and although active is con-siderably weaker. VI. Tropeines of Acids in which the Groups are Separated b y an Pheityl and Cccrboxyl Imin 0-group. Mydriatic action. Present com-Previous results. parison. Troneine. Formula. Action. Observer. A4ction. 7-44. Hiipuryl- C,H,'CO'NH'CH,'CO,T { T:$ to 207; Gottlieb 45. Phenvlcarb-amo- ...... C,H,*NH*CO,T -I-Gottlieb states that hippuryltropeine behaves similarly t o lactyltropeine that is to say it only exercises a mydriatic effect when the solid substance is introduced into the conjunctival sac t o give a concentrated solution and is inactive in dilute solution. Phenylcarbamot,ropeine proved to have a slight mydriatic action.I n the foregoing tables the tropeines are classified according t CONSTITUTIOX AND PHYSIOLOGICAL ACTION. 11 15 their chemical constitution. The thirty members which we com-pared by the method given above may be grouped also in order of their 1. 11. 111, IV. v. VI. rnydriatic properties. Atropine B-Pheiiyl-a-hydroxypropionyl- I- Most active. t ropeine I A troglyceryl tropeiii e Intermediate i l l activity be-tween atropine and hom-atropine . dl-Homat ropiiie d - and Z-Homatropine Quaternary salts of hoinatropiiie 0- m- and p-Rlethylhomatropine J 8- 2-Pyridyl -a-hydroxypropionyl-Phthalidecarboxyltropeine Phenylchloroacetyltropeine Phenylaminoacet~yltropeine Phenylacetyltropeine Benzoyltropeine o -Hydroxybenzoyltropeine nz-Hydroxybcnzoyltropeine Phenylcarbamotropeine Tar tryltropeine Fumaroyltropeine rile t hylparaconyltropeinc Terebyltropeine Lactone of o-carbosyphenylglyceryl-is2Coumarincarboxyltropeine P hthalo ylt ropeine.p-Hydroxybenzoyltropeine Protocatechoyltropeine Cinnamoylt ropeine 1 Of a similar order of activity. All active but less so than i homstropine. t ropei ne Faintly active. i Inactive. I tropeine Of the fifteen tropeines which we did not examine by the com-parative method natural hyoscyaniine which is the lzvo-variety, is nearly twice as active as atropine d-hyoscyamine much less so. Acetylatropine chlorohydratropyltropeine bromohydratropyl-tropeiiie atrolactyltropeine and atropine metrhonitrate appear to be equivalent in niydriatic power t o the members of groups I1 and I11 of the above table whilst the following are stated to be inactive in dilute solutioii : Acetyltropeine.Atropyltropeine. Glycollyltropeine. Hippuryltropeine. Lactyltropeine. Atropinesulphuric acid. Succin yltropeine. Homatropinesulphuric acid. Before considering whether any general conclusions can be drawn froin these results attention inay be directed to the general-isatioii which has found its way into the literature sometimes i 11 16 PYMAN THE RELATION BETWEEN CHEMICAL association with Ladenburg’s name. This generalisation states that a tropeine to have mydriatic properties must contain (1) a benzene nucleus and (2) an alcoholic hydroxyl group in the side chain containing the carboxyl group.Now Ladenburg stated in 1883 that rri-hydroxybenzoyltropine had mydriatic properties so it seemed unlikely that the geiieral-isation was due to him. Accordingly after a careful but unsuccessful search of the literature for such a generalisation under Professor Ladeliburg’s name we coniiiiuiiicated with him, arid learned that he was unable to recollect framing it. In the light of the evidence afforded above i t would appear that the first postulate of this generalisation is approximately correct ; 110 tropeine of an aliphatic acid has yet been found to possess mydriatic properties in dilute solution but on the other hand, the closed chain need not necessarily be that of benzene since /3-2-pyridyl-a-hydroxypropionyltropeiiie which contains a pyridine instead of a benzene residue is active.The second postulate that a tropeine to be inydriatic must have ail alcoholic hydroxyl group in the side chain containing the carboxyl group is incorrect for mydriatic substances are obtained when the hydroxyl group of atropine is exchanged for acetoxyl, chlorine or bromine and when the hydroxyl group of hornatropine is exchanged for hydrogen chlorine o r an amino-group or when i t is closed by the formation of a lactone; moreover benzoyl- and 0- and nz-hydroxybenzoyl-tropeines are mydriatic. The loss of mydriatic properties on the replacement of the hydroxyl group in atropine and honiatropine by the sulphuric acid residue is possibly due to the same cause which operates in the case of substances containing a free carboxyl group such as benzoylecgonine and quitenine.Whilst however the second postulate is incorrect as regards the qualitative mydriatic action of tropeines i t must be remem-bered that those tropeiiies which we found more active than or equal to homatropine in mydriatic properties contained an alcoholic hydroxyl group. Of the tropeines of hydroxybenzoic acids the o- and m-sub-stituted compounds were active whilst the p and also the 3 4-di-hydroxy-compounds were inactive. Substitution in the pposition in this case causes the mydriatic action to vanish and in the case of the methylmandelyltropeines also the para-compound is less active than the ortho- and meta-isomerides. The tropeines of substituted hydratropic phenylacetic and phenylpropionic acids were all active with the exception of atropinesulphuric acid homatropinesulphuric acid the lactone o CONSTITUTION AND PHYSIOLOGICAL ACTION.1 117 o-carboxyphenylglyceryltropeine and those containing an un-saturated linking in the side-chain containing the carboxyl group. Consideration of the above material led us to conclude that no generalisation as to the relation between niydriatic action and chemical constitution could be made which would offer a strict explanation of the) results obtained. Before leaving the subject of the tropeines attention may be directed to some points of' interest in connexim with allied mydriatics. Norhyoscyamine which differs from hyoscyamine in containing an imino- in the place of an N-methyl group has only one-eighth of the mydriatic effect of hyoscyamine and the racemic form noratropine is again about one-eighth as active as atropine (Carr and .Reynolds T.1912 101 946. Physiological tests by Laidlaw). I t has already been pointed out that the steric structure of the acyl radicle of a tropeine influences its niydriatic properties. The steric structure of the basic portion of the molecule is also important for the tropyl and mandelyl esters of +-tropine have 110 mydriatic properties (Liebermann and Limpach Her. 1892 25, 933. Physiological tests by Liebreich). A iriinoctlkyl Esters. The question as to what portions of the cocaine molecule (I) are essential to the local anaesthetic action of the alkaloid has long been the subject of investigation and the collated results of numerous workers have shown by a series of eliminations that the anaesthetic properties of cocaine are a,ssociated with its func-tion as an aminoalkyl ester.It has been found that the carboxy-methyl (C0,Me) group is not an essential factor since tropa-cocaine (11) which contains no such group produces the same effect; and further the presence of a bridged or simple ring containing nitrogen is unnecessary since eucaine (111) which possesses only a simple not a bridged ring and stovaine (IV), alypine (V) and novocaine (VI) which contain no such ring have well-marked local anathetic properties. CH2*CH-CH*C0,&le CH,*CH-CH I &Me CI1*O*COPh 1 kMe bH-O*COPh I i i I C H,*CH-CH, (11.1 CH,*CM6-CH2 CH,*Nhfe, AH bH-O*COPh C,H ,*C*O*COPh I I I I C H ;CH-CH C*3 (111.) W. 1118 PYMAN THE RELATION BETWEEN CHEMICAL CH2*NMe2 C,H,*i<O*COPh ( C2H5)2N*CH2*CH2*O*CO*C,H,*NH2 (21) From the above considerations it follows that local aimsthetic action is associated with the aininoalkyl ester structure and we may now inquire what complexes in such eaters are necessary for the possession of local anzesthetic properties. Aminoalkyl esters have the general formula R*CO-O-(CR,R2),-NR,R4 ; they are formed by the esterification of an acid with an alcohol containing an umino-pap and may be dealt with conveniently from this point 0f view. The ucyl group of aminoalkyl esters possessing local anathetic properties is in most cases aromatic and in the majority of sub-stances of practical application is the benzoyl group as instanced by the compounds numbered I to V.Fourneau (J. Pharm. C'kim., 1910 [vii] 2 337 397) has however recorded that the valeryl, bromovaleryl and bromoheptoyl esters of dimethylaminodi-methylethylcarbinol (the benzoate of which is stovaine) have anzsthetic properties so that the presence of a ring complex in the acid does not appear to be essential. I n the case of cocaine replacement of the benzoyl by substi-tuted benzoyl or other acid radicles leads to substances with much weaker local anzesthetic properties. Thus the phenylacetyl deriv-ative is much less powerful the o-chlorobenzoyl and m-niixobenzoyl derivatives have only a slight local anmthetic action and the m-hydroxybenzoyl compound still less whilst the substances in which the benzoyl is replaced by the valeryl rrL-aminobenzoyl, phthaloyl cinnamoyl or isatropyl radicles are inactive (Ehrlich, Liebreich and Poulsson.Compare Ehrlich and Einhorn BeT., 1894 27 1870). Substitution i n the benzoic acid nucleus of aminoalkyl benzoates is not however necessarily associated with weak local anzesthetic action for the p-aminobenzoyl esters of many amino-alcohols are strong local anaesthetics novocaine being diethylaminoethyl p-aminobenzoate whilst the dialkylaminoalkyl 3 4-diaminobenzoates have also considerable local anzesthetic properties (Einhorn D.R.-P. 194365). I n the case of cocaine, the mbstitution of phthaloyl f o r benzoyl gave an inactive com-pound and similarly whilst diethylaminoethyl benzoate, NEh=CH,*CH,*O*COPh is stated to have local .anzesthetic proper-ties (E.Schering D.R.-P. 175080) diethylaminoethyl phthalate proved to be inactive (Pyman T. 1908 93 1793. Physiologica CONSTITUTION AND PHYSIOLOGICAL ACTION. 1 1 19 tests by Dale and Symons). Passing now to aromatic acids in which the carboxyl of the acyl group is not directly attached to the benzene nucleus w0 have seen that the replacement’ of the benzoyl by the phenylacetyl group in cocaine gives a substance having local anaesthetic properties ; with a-eucaine also the phenyl-acetyl compound has well-marked local anaesthetic properties (Vinci Virch. -4rch. 1898 154 549); i t was found however that replacement of the paminobenzoyl group by the paminophenyl-acetyl group in novocaine and anEdhesine (ethyl p-aminobenzoate) gave inactive compounds diethylaminoethyl and ethyl p-amino-phenylacetates (Pyman this vol.p. 167. Physiological tests hy Dale and Symons). Cinnamic acid usually but not invariably confers local anaes-thetic properties on aminoalkyl esters. As we have seen cinnamoyl-cocaine is inactive but the a-eucaine derivative has local anaesthetic properties (Vinci loc. cit .). Tetramethyldiamino-dimethylethylcarbinyl cinnamate that is an ‘( alypine ” in which cinnamic acid takes the place of benzoic acid produces an anzesthetic effect lasting twice as long as that brought about by the same quantity of cocaine (Farbenfabriken vorm. F. Bayer & Co. D.R.-P. 173631) whiIst y-diethylaminopropyl cinnamate (apothesine) also has well-marked local anaesthetic properties (E. A. Wildman and L. Thorp U.S.Pat. 1193649). It may be noted that the aminoalkyl esters of aminocinnamic acid are stated to have several times the local anzsthetic power of those of aminobenzoic acid (Meister Lucius & Bruning D.R.-P., 187593). With regard to the nature of the substituted amino-group required in an alkamine ester having local anmthetic properties, there is little available information. Most of the best known local anzesthetics contain a tertiary amino-group but Peucaine which has powerful local anaesthetic properties contains a secondary amino-group. Norcocaine in which the N-methyl group is re-placed by the imino-group has greater local anaesthetic properties than cocaine (compare Ehrlich and Einhorn Zoc. c i t . ) but the primary amine corresponding with novocaine namely &amino-ethyl paminobenzoate (VII) (Forster T.1908 93 1865. Physiological tests by Dale) is devoid of local anasthetic action. The nature of the alkyl groups replacing the hydrogen atoms of the amino-group appears t o affect the local anzesthetic properties in some degree; thus piperidylethyl benzoate (VIII) is only slightly active whilst s-di-/3-benzoyloxy-l 4-diethylpiperazine (IX) has very distinct action and pB-dibenzoyloxytriethylamine (X) i 1120 PYMAN THE RELATION BETWEEN CHEMICAL slightly active whilst BP-dibenzoyloxymethyldiethylamine (XI) (Pyman loc. c i t . ) is inactive. NH2* C H,*CH,*O*CO* CGH,*N H C,H,oN*CH3*CH,*0.C'OPh (VII.) (vzrr.) PhCO.O*CH,.CH,*N<~~~:~~~>N.CH,*CHB*O*COPh (IX) NEt(CH,*CH,*O*COPh) N Me( CH,*CH,-O*COPh), (X.) (XI.1 The ct7colmZ residues of these esters are very varied in character; they may be primary secondary or tertiary and may separate the acyl residue and the substituted amino-group by chains of a varying number of carbon atoms. As inst'ances of active aminoalkyl esters derived from primary alcohols we have novocaine and the dialkylaminoethyl benzoat es ; in these oiily two carbon at'oms separate the acyl- and amino-groups. y-Diethylaminopropyl cinnamate is an example of an ester of a primary alcohol in which the two groups referred t o are separated by three carbon atoms. Cocaine tropacocaine and the eucaines are derived from secondary alcohols containing a chain of three carbon atoms between the acyl- and amino-groups whilst instances of local anaesthetic property in secondary alcohols in which these groups are separated by only two carbon atoms are furnished by P-benzoyloxy-/3-3 4-methylenedioxyphenylethyldi-methylamine (I) and By-dibenzoyloxydimethylpropylamine (11) (Pymaii loc.cit .). 0-C H +' 1 1 C H N Me, dlH*O-COPb . dH,*@*COPh Finally typical examples of local anaesthetics derived from tertiary alcohols are stovaine and alypine in which the acyl and amino-groups are also separated by a chain of two carbon atoms. The general conclusions to be drawn from the above summary are that in aminoalkyl esters having local anmthetic properties (1) the acyl group is usually aromatic (2) the amino-group may be secondary or tertiary and may be associated with simple or bridged ring complexes and (3) the alcohol group may be primary CONSTITUTfON AND PIIYSIOLOaICAL ACTION.112 1 secondary or tertiary and may separate the acyl and amino-groups by a chain of either two or three carbon atoms. Adrenaline and the Amines. Adrenaline the active principle of the suprarenal gland is a substance of powerful physiological action. Its action simulates the effects of exciting sympathetic nerves and in consequence has been termed I ‘ sympathomimetic.” Therapeutically it is chiefly used to prevent bleeding by its vasoconstrictor action when applied locally ; when injected intra-venously it causes amongsi; other symptoms a large rise of blood pressure also partly due to vasoconstriction and the measure of this pressor effect when accompanied by other symptoms of sympathomimetic action serves for the comparison of adrenaline with allied compounds.Adrenaline is of comparatively simple constitution being 8-3 4-trihydroxy-&phenylethylmethylamine (I) and the question as to the relative influences of the different portions of its mole-cular structure has been the subject of much investigation. It was a t one time suggested that the catechol nucleus (11) was the essential active group for catechol causes a rise of blood pressure on intravenous injection whilst the other half of the molecule, 8-hydroxyethylmethylamiiie (111) has no such action. OH O H ()OH I ’ ’\OH CH2*OH \/ \/ CH,*NHMe I CH*OH 6H2*NHMe (1.) (11.) (111.) Barger and Dale ( J . Physiol. 1910 41 19) however showed that the rise of blood pressure produced by catechol was not due to sympathomimetic action hut t o an action of an entirely different type whilst on the other hand many aliphatic and aromatic amines had an action very similar t o that of adrenaline.They studied the relation between chemical constitution and sympatho-mimetic action in a large number of amines gradually appro,aching adrenaline in constitution and as a quantitative index of the activity of the compounds they adopted the effect on arterial blood pressure. The aliphatic amines were first examined then those containing a phenyl group and finally phenylalkylamines in which one two or three hydroxyl groups were introduced as substituents into the benzene nucleus. I n the aliphatic series the following VOL. UXI. Y 1122 PYMAN THE RELATION BETWEEN CHEMICAL results were obtained with primary amines under comparable con-ditions : Substance.Pressor effect. 'i J (1) Methylamine (2) Ethylamine (3) iaoPropylamine - insignificant. (4) n-Propylamine ( 5 ) isoButylamine (6) n-Butylamine positive. (7) isoamylamine, (8) n-Amylamine, (9) n-Hexylamine, (10) n-Heptylamine, (1 1) n-Octylamine, several times that of No. 6. distinctly greater than that of No. 7. greater than that of No. 8. less than that of No. 9. less than that of No. 10. With still higher members of the series comparison was difficult, since they became increasingly toxic. Of mcolndary amines diethylamine was found to be inactive, methylisoamylamine C,H,,*NHMe was considerably weaker than isoamylamine whilst diisoamylamine had very little of the action.In the aliphatic series therefore the most active member proved t o be n-hexylamine. The next group examined consisted of aromatic amines in which the benzene nucleus was otherwise unsubstituted. (1) Aniline Ph'NH, did not show the specifio action. (2) Benzylamine Ph*CH;NH, had a mere trace of the aotion. (3) a-Phenylethylamine Ph'CHMe'NH, was very feebly active. (4) B-Phenylethylamine Ph*CH,'CH,'NH, was more active than Nos. (3) and (a) and its activity was distinctly greater than that of n-hexylamine the most active of the aliphatic amines. (5) y-Phenylpropylamine Ph*[CH,];NH, was No. much (4). less active than B-Phenylethylamine which proved to be the most active of this series contains the skeleton of adrenaline but differs from it in lacking (1) the 3 4dihydroxyl substituents of the benzene nucleus, (2) the hydroxyl substituent of the &carbon atom and (3) the methyl group attached to the nitrogen atom.The effect of the two last substitutions singly or together on P-phenylethylamine was tested by the examination of 8-hydroxy-0-phenylethylamine, Ph-CH(OH)*CH,*NH, P-phenylethylmethylamine, P h* CH,*CH,*NH Me, and fi-hydroxy-8-phenylethylmethylamine, P h* CH (OH) CH,* NHMe, none of which differed noticeably in activity from P-phenylethyl-amine. Further work was directed to determining the influence of phenolic hydroxyl groups on the action of these phenylalkyl CONSTITUTION AND PHYSIOLOGICAL ACTION. 1 123 amines and in the first place the effect of introducing a single hydroxyl group was ascertained with the following result8 : ( 1) p-Hydroxy-B-phenylethylamine, HO*C6H;CH;CH2~NH *.( 2) m-Hydroxy -B-phenylethylamine, (3) o-Hydroxy-8-phenylethylarnine, (4) 4-Hydroxy -B -m-t olylethylamine, Me HO(->CH;CH,*NH,. 8-p-Dihydr&y-B-phenylethylamine, HO'C,H;CH( OH)*CH;NH,. p -Hydroxy - i-aminoacetophenone, HO~C,H;CO*CH,'NH,. p -Hy droxy - 8-phenylethylm et hylaminc HO*C6H;CH,'CH,'NHMe. p -Hydroxy-b -phenylet h ylet h ylamine , HO*C6H;CH;CH;NH Et. p-Hydroxy-8-phenylethyldimethylami HO*CIH4*CH,'CH;NMe2. p-Hydroxy-B-phenylethyltrimethyl . . _.-ammonium iodide, HO'C6H4'CH,'CH,'NMe,~. dl-p -Hydroxy -a -p henylet hylamine, HO'C,H;CHMe*NH,. I-p-Hydroxy-a-phenylethylemine, ( 13) p-Hydroxyphenylethylacetarnide, (14) Tyrosine ethyl ester, HO *C ,H4*CH2*CH2*NHA~.HO *C 6H4*CH2'CH( CO ,El t) *NH,. 9 .ne, 3 to 5 times as active as 8-phenylethylamine. Had about 1-20th of the activity of adrenaline. Equal to (1). No more active than 8-phenyl-ethylamine. Half as active as (1). Less active than (1). Feebly about 1-10th as About the same as (1). Considerably less active than (1) and (7). Very much less active than (1) and (7). Action entirely different from that of adrenaline resemb-ling that of nicotine. Very slightly active. Very slightly active; not Inactive. active as (1). different from (1 1). Inactive. The foregoing results show that the introduction of a hydroxyl group into phenylethylamirie is accompanied by an increase in activity in the case of the p- and m-compounds but not in that of the o-substituted compound.Here again as in the unsubstituted phenyl series neither the introduction of a hydroxyl group in the &position (5) nor methyl-ation of the nitrogen (7) increases the activity of the parent com-pound whilst the introduction of a larger alkyl group (8) or second methyl group (9) on the nitrogen atom seriously diminishes the activity of the compound. The next group of compounds examined contained two phenolic hydroxyl groups and included (a) derivatives of acetocatechol, ( 6 ) derivatives of ethylcatechol and ( c ) derivatives of hydroxy-ethylcatechol. By determining the doses which produced rises of blood pressure to equal submaximal heights the approximate average activity values were found t o be ae follows 1124 PYMAN THE RELATION BETWEEN CHEMICAL (a) ( 1) 3 4-Dihydroxy-o-aminoacetophenone, (OH),C,H,*CO'CH;NH ..........................................1.5 (OH),C,H,'CO*CH;NHMe Weaker (1); greater i t h ~ ~ ~ o * No. (4) (2) 3 4-Dihydroxy-o-methylaminoacetophenone, (3) 3 4-Dihydroxy-w-ethylaminoacetophenone, (4) 3 4-Dihydroxy-o-propylaminoacetophenone, (OH)2C,H,'CO'CH,'NHEt ....................................... 2.25 (OH),C,H;CO'CH,'NHPr ....................................... 0.25 (OH),C6H,*CH;CH,*NH ....................................... 1 (OH),C,H,'CH;CH,'NHMe .................................... 5 ( 13) ( 5 ) 3 4-Dihydroxy-B-phenylethylamine, (6) 3 4 -Dihydroxy - 8-phenylethylmethylamine, (7) 3 4-Dihydroxy-8-phenylethylethylamine, ( 8 ) 3 4-Dihydroxy-8-phenylethylpropylaminey (OH)2C,H3.CH,*CH,*NHEt ....................................1.5 (OH),C,H,*CH(OH)*CH;NH ................................. 50 (OH),C,H3*CH2~CH;NHPr .................................... 0.25 (c) (9) d1-8-3 4-Trihydroxy-j3-phenylethylamine, ( 10) dE-8-3 4-Trihydrosy-~-phenylethylmethylamine (dl-adren-(1 1) 1-8-3 4-Trihydroxy-~-phenylethylmethylarnine (Z-adren-aline) (OH),C,H;CH( 0H)'CH;NHMe.. ...................... 35 aline) .................................................................. 50 In these series the N-propyl derivatives were much less active than the N-methyl and N-ethyl derivatives but there is no con-sistency in the relative values of the amino- N-methyl and N-ethyl derivatives; in the (a) series the N-ethyl in the ( b ) series the N-methyl and in the ( c ) series the amino-compound was the most active of those examined.Two amines containing three phenolic hydroxyl groups were also examined namely 2 3 4-trihydroxy-o-aminoacetophenone, and 2 3 4-trihydroxy-P-phenylethylamine, (OH),C,H,*CO*CH,-NH , (OH),C,H,*CH,= CH,-NH,. I n each case the pressor action was somewhat weaker than that of the corresponding catechol base. Consideration of the above results led Barger and Dale t o the following conclusions '' The optimum carbon-skeleton for sympathomimetic activity consists of a benzene ring with a side-chain of two carbon atoms the terminal one bearing the amino-group. Another optimum condition is the presence of two phenolic hydroxyls in the 3 4-position relative t o the side-chain ; when these are present an alcoholic hydroxyl still further intensifies the activity.A phenolic hydroxyl in the ortho-position does not increase the activity. Many physiologically active amines occur in nature as the result of decarboxylation of amino-acids by bacteria. Of those men CONSTITUTION ,4ND PHYSIOLOGICAL ACTION. 11 25 tioned above for instance isoamylamine and p-hydroxy-fl-phenyl-ethylamine are derived from leucine and tyrosine respectively. HO*C6H4*CH,*CH(NH,)*C0&l + HO*C,H4*CH2*CH2*NH,. Tyrosine. p-Hydroxy -B-phenylethylamine. Derivatives of ethylamine containing heterocyclic nuclei are formed similarly thus indole-ethylamine from tryptophan and aminoethylglyoxaline from histidine.Aminoethylglyoxaline occurs naturally in ergot and is an intense stimulant of plain muscle; several of its derivatives and allied compounds listed below have been prepared and compared with it physiologically (Ewins T., 1911 99 2052; Pyman ibid. 2172; 1916 109 186. Physio-logical tests by Laidlaw and Dale): ( 1) 4-Aminomethylglyoxaline.. ...................... C3H3N2'CH,'NH2. (2) 5-Methyl-4-aminomethylglyoxaline.. .......... Me'C3H2N2'CH2*NH,. (3) 5-Methyl-4-methylaminomethylglyoxaline Me'C3H2N2'CH2 'NHMe, (4) 4-B-Aminoethylglyoxaline ..................... C,H3N,'CH2'CH,*NH2. i t C,H,N,'CH'CH,*NH,. ( 5 ) By-bis( 4-Glyoxaline) -propylamine (6) B-Hydroxy-B-glyoxaline-4-ethylamine ...... C,H3N,'CH(OH)'CH,'NH2.(7) 5-Methyl-4-aminoethylglyoxaline ............ Me'C3H2N2*CH,'CH,*NH,. ( 8 ) l-Methyl-4-aminoethylglyoxaline ............ MeC,H,N:CH,'CH,*NH,. (9) l-Methyl-5-aminoethylglyoxaline ............ Me'C,H N;CH,*CH,'NH,. C3H3N2'CH2. ............ ( 10) 4 -7 . Aminobutylglyoxaline .................... .C,H3NS*CH;CH,'CHMe"H, Of these compounds No. 6 was found to be less active than aminoethylglyoxaline (No. 4)) and No. 7 had only about a 1/2OOth of the characteristic stimulant action of No. 4 whilst the remain-ing members of the series only showed this action to a slight extent. Here also the optimum side-chain has two carbon atoms between the cyclic system and the amino-group the compounds in which one (No. 1) and three (No. 10) carbon atoms separated these groups being much less active.The introduction of an alcoholic hydroxyl group (No. 6) o r of methyl substituents into the nucleus (No. 7) or into the imino-group (Nor:. 8 and 9) also gave less active compounds. Protozoacidal Drzigs. The fourth and last exainple of the relation which I desire t o discuss to-night concerns the action of certain alkaloids in proto-zoal diseases. Malaria is a condition in which the blood is infested with plasmodia and is treated by means of quinine which has a specific action on the parasites. Amebic dysentery is similarly due to infection with the E n t a m a b a histolytica and responds best to the. action of emeiine. Experiments have recently been conducted in both fields to determine whether some derivative of the alkaloid8 mentioned.or one of the alkaloids associated wit 1126 PYMAN THE RELATION BETWEEN CHEMICAL them in cinchona bark or ipecacuanha root respectively have any advantages therapeutically. The line of attack has been some-what similar in the two cases; the toxicities of the drug and a number of its derivatives to protozoa and mammals were first deter-mined in the laboratory and the more promising derivatives were then tested clinically. I n the case of the inquiry into the value of certain cinchona derivatives (A. C. MacGilchrist Znd. J . Med. Res. 1914-1915, 2 315 336 516; 1915-1916 3 l) the relative lethality of each derivative to different species of infusoria (as representing protozoa) and to guinea-pigs (as representing mammds) was determined with the object of finding some indication as to which derivative would be most useful for the treatment of malaria that is would kill the parasite and yet cause least inconvenience or harm to the host.The results obtained are tabulated below the substances being given in the order of their lethality t o infusoria ethylhydro-cupreine hydrochloride being the most toxic. The minimum lethal dose to guinea-pigs is also given together with formulz designed to show the structural differences a t a glance; the two1 pairs of stereoisomerides quinine and quinidine cinchonine and cinchon-idine differ in the sign of the carbon atom bearing the alcoholic hydroxyl group. M.L.D. for guinea-pigs mg per Substances in order of lethality to infusoria. kil og. Formula. 1. Ethylhydrocupreine hydrochloride 0.65 EtO'C1,H18ON2*CH,*CH,.2. Cinchonine sulphate .................. 0.425 H'C17HI8ON2'CH:CHa 3. Quinine sulphate ..................... 0.525 Me0 'C ,H,,ON,*CH:CH,. 4. Hydroquinine hydrochloride ......... 0.6 MeO*C ,Hl8ON,*CH,'CH,. 5 . Quinidine sulphate ..................... 0.4 MeO'C ,H,,ON,'CH:CH,. 6. Cinchonidine sulphate.. ................ 0.6 R~C,,H,,ON,~CH:CH,. From these results it appeared that ethylhydrocupreine in which the vinyl group of quinine is reduced whilst ethoxyl takes the place of methoxyl was a promising subject for clinical trial in malaria. On a clinical comparison however the order of their value was found to be as follows: 1. Hydroquinine hydrochloride. 2. Quinine sulphate. { Quinidine sulphate. 5. Ethylhydrocupreine hydrochloride.6. Cinchonidine sulphate. Cinchonine sulphate. I n the case of the alkaloids of ipecacuanha determinations of the relative toxicity of a number of compounds t o free living amcebz gave the following results (Pyman and Wenyon J . Pharmacol. 1917 in the press). Emetine cephaeline #-methyl CONSTITUTION AND PHYSIOLO~ICAL AOTION. 1127 emetine and N-methylcephaeline were approximately equally amcebacidal ; N-methylemetine methochloride rubremetino hydro-chloride noremetine and the hydrochloride B, C,,H,70,NC1,,HC1 ,5H20, obtained by the oxidation of cephaeline were inferior to these, whilst psychotrine su1phat.e was much inferior. These results indicate that the full amcebacidal action characteristic of emetine is only exhibited when the nucleus is intact.The exact constitu-tion of the nucleus of these alkaloids is a t present unknown but it is certainly present intact and fully reduced in emetine, cephaeline N-methylemetine N-methylcephaeline and noremetine, for these substances are interconvertible in a simple manner differ-ing only in the number of methyl groups attached to the oxygen and nit,rogen atoms of the :molecule. Noremetine. Cephieline. Emetine. Psychotrine. N-Methylcephaeline. N-Methylemetine. It is interwting t o note that four of these compounds were very active. The inferiority of noremetine may conceivably be due to the fact that this compound contains four hydroxyl groups in place of the four methoxyl groups of emetine for Laidlaw (Zoc. cit.) has shown that amongst other isoquinoline derivatives a similar change of constitution produces an alteration in physio-logical action.N-Methylemetine methochloride is a biquaternary salt and as such a difference in its action from that of the parent tertiary base is not surprising. The fact that the hydro-chloride B still retains some amcebacidal properties is interesting, because of the comparatively simple constitution of this substance, which is devoid of the guaiacol residue and one of the nitrogen atoms of cephaeline. The hwo remaining substances rubremetine and psychotrine are not fully saturated rubremetine hydrochloride containing eight hydrogen atoms fewer than emetine hydrochloride, whilst psychotrine contains two atoms of hydrogen fewer than cephaeline. Some of the above compounds and certain others have also been tested on Entamaba histolytica in vitro (Dale and Dobell J .Pharmacol. 1917 in the press) and here again emetine cephaeline 1128 RELATION BETWEEN CHEMICAL CONSTITUTION ETC. and N-methylemetine proved to be active as was also the 0-methyl ether of psychotrine (which had not been tested on free living amoebae) whilst psychotrine again proved to have only a slight action. It is curious to contrast the similarity of action between cephae-line and its methyl ether emetine with the difference between psychot>rine and its methyl ether. The toxicity of many of the above compounds was determined and the laboratory results indicated that N-me t h yleme t ine and 0-me t h y 1 p syc hot ri n e were 1 ess toxic than emetine to mammals. Since t,hey were at the same time equal to emetine in amoebacidal properties it was thought that they might prove to be superior to this alkaloid in the treatment of amoebic dysent'ery but unfortunately clinical trials have shown that this is not the case (G. C. Low Brit. Med. J. November 13th 1915; C. M. Wenyon and F. W. O'Connor J . Roy. Army Med. Corps 1917 28 473; M. W. Jepps and J. C. Meakins Brit. Med. J. November 17th 1917 648). A review of the subjects discussed b n i g h t leads to the con-clusion that i t is very difficult to improve upon naturally occurring active principles the use of which in medicine is due to accumu-lated experience. I n point of maximum effect none of the natural compounds discussed to-night-hyoscyamine cocaine adrenaline, quinine emetine-is surpassed by its derivatives; but on the other hand it has been possible in some of the cases to prepare derivatives o r synthetic analogues which have proved to be of service in medicine. In conclusion I should like t o thank Dr. €3. H. Dale F.R.S., of the staff of the Medical Research Committee for help on the physiological side and Dr. H. A. D. Jowett for his collaboration in the previous paper which forms the basis of much of the work recorded above

ISSN:0368-1645    

DOI:10.1039/CT9171101103

出版商:RSC    

年代:1917

数据来源: RSC

摘要:

INDEX OF AUTHORS' NAMES. TRANSACTIONS. 1917. A. Angel Andrea obituary notice of 321. B. Bagster Lancelot Salisbury compounds of calcium chloride and acetone 494. Baker Julian Levett and Henry Francis h'werurd Hulton evidence of the ex-istence in malt of an enzyme hydro-lysing the furfuroids of barley 121. Bassett Henry jun. the phosphates of calcium. Part IV. The basic phos-phates 620. Bennett George Macdonuld the crystal form and isomerism of some ferro-cyanides 490. Blount Bertram the limitations of the balance 1035. Briggr Samuel Henry Cliford the structure of inorganic compounds 253. Brightman Rainald. See Raphael Meldola. Brown (Miss) Janet Forrest AlcGilk'vray, and Robert Robinson veratricsul-phinide 952. Browne Vere Rochelle. See Frederick Palliser Worley.Browning Kendall Colin the detection of traces of mercury salts for toxico-logical purposes 236. C. Caton Frederick William obi tnary Chapman Ayred Chaston spinacene a new hydrocarbon from certain fish liver oils 56. some main lines of advance in the domain of modern analytical chem-istry 203. Chowdhnri Tarini Chnran. See Pan-chcnan Xeogi. Colson Emile the constitution of cyanamide 554. notice of 312. CXI. Cooper Christopher. See Aqtrila Forster. Copbarow Mawice the Friedel-Cra fts' reaction. Part I. Phthalyl chloride and the mechanism of its reaction with benzene 10. Cunningham (Miss) Mary and Charles Do& contributions to the chemistry of caramel. Part I. Caramelan 589. D. Davies Edward obituary notice of 323.De Rajendra Lal relationship between the physical properties of isomeric cobaltammines and the electro-valen-cies of their co-ordination complexes, 51. Debus Heinrich obituary notice of 325. Denham Henry George lead subiodide, and an improved method for prepar-ing lead suboxide. The solubility of lead iodide 29. Denham William Smith and (Miss) Hilda Woodhouse trimethyl glucose from cellulose 244. Dey Manik Lal. See Prafulla Chandra RAy. Dhar Nilratan catalysis. Part 111. Some induced reactions 690. catalysis. Part IV. Temperature co-efficients of catalysed reactions 707. Dixon Awgustus Edward salts of thio-carbamide 684. Dor'Be Charles. See (Miss) Mary Cun-ningham. Drakeley Thonms James the liberation of hydrogen sulphide from gob fire8 in coal mines 853.Druce John Gerald Prederick a simple method of preparing potassium stanni-chloride 418. E. Esson William obituary notice of 332. Z 1130 INDEX OF AUTHORS. F. Farmer Charles George Edgar obituary notice of 314. Ferguson John obituary notice of 333. Forster Aquila Christopher Cooper and George Yarrow compounds of ferric chloride with ether and with dibenzyl sulphide 809. Foster Henry Stennett. See Raphael Meldola. Francis Arthur Gordon 3~4-di-p-nitrotetraphenylfuran 1039. Friend John Albert 11-ewton notes on the effect of heat and oxidation on liuseed oil 162. G. Ohosh Jnaizendra Chandra. See Pra-fulla Chandra RQy. Ohorrh Praphulla Chandra action of acetaldehydeaminonia on qumones, 608. Ghosh Praphulla Chandra and Edwin Ruy Watson the effect of additional auxochromes on the colour of dyes.Part 11. Triphenylmethane and azo-dyes 815. Gibson Charles Stanley John Lionel Simonsen and Madyar Gopala Rau [with John Edward Purvis] the nitration of 2-acetylamino-3:4-dime-thoxybenzoic acid and 3-acetylamino-veratrole 69. Gray Harold Heath a simple apparatus for the washiug of gases 179. Green Arthur George and Frederick Haurice Rowe the conversion of o-nitroamines into isooxadiazole oxides, and of o-nitrosoamines into isooxadi-azoles 612. Qreenwell Allan. See Richard Vernon Wheeler. Griffith lZobert Ozuen AlfTed Lamble, and William Cudmore McCuZlaa(lh Lewis studies in catalysis. Part VI. The mutual influence of two reactions proceeding in the same medium 389.Oriffiths John obituary notice of 315. H. Hammick Dalziel LlewelZyn the action of sulphur dioxide on metal oxides. Part I. 379. Haward William Arthur and Sosale Garalapzcry Sastry the uniform move-ment of flame in mixtures of acetylene and air 841. Hickinbottom Wivrid John. See Joseph Reilly. Hindmarsh (Miss) Ellen MaTgaret (Miss) Isabel Knight and Robert Robinson, 5-bromognaiacol and some derivatives, 940. Eoward David obituary notice of 343. Hulton Hcnry Francis Everard. See Julian Levett Baker. J. Jones Thonzns Gilbert Henry and Robert Robinson experiments on the orientation of substituted catechol ethers 903. Joseph Alfred Francis and William Nomnan Rae chromium phosphate, 196. K. Knight (Miss) Isabel.See (Miss) Ellen Koningh Lconard de obituary notice Margarat Hindmarsh. of 348. L. Lakhumalani Jamiat Vishindas. See Joha Joseph Sudborough. Lamble AIfred. See Robert Oweit Griffith. Lapworth Arthur (Mrs. ) Leonore Kletz Pearson and Frank Albert Royle the pungent principle of ginger. Part I. The chemical characters and decom-position products of Thresh's '' gin-gerol," 777. Lapworth Arthur and Frederick Henry Wykes the pungent principles of ginger. Part 11. Synthetic prepar-ations of zingerone methylzingerone and some related acids 790. Lewis Ernest Alfred obituary notice of 348. Lewis Ft';illiana Cudmore McCuElagh, studies in catalysis. Part VII. Heat of reaction equilihrium constant, and allied quantities from the point of view of the radiation hypothesis, 457.studies in catalysis. Part VIII. Thermochemical data and the quantum theory ; high temperature reactions 1086. Lewis William Czbdmore McCzcllagh. Lloyd Percy Vivian. See Clarence See also Eobcrt Owen Oriffith. Arthur Seyler INDEX OF AUTHORS. 1131 M. Macbeth Alexander Killen and Alfred Walter Stewart the absorption spectra of substances containing conjugated and unconjugatcd systems of’ triple bonds 829. McConnan James obituary notice of, 316. McCourt Ugril Douglas obituary notice of 318. McDavid James Wallace the temper-ature of ignition of gaseous mixtures, 1003. MacDougall (Miss) Elizabeth Alfred Walter Stewart and Robert Wright, phosphorescent zinc sulphide 663. Martin Gerald Bargrave.See Qeorge Senter. Mason Walter and .&hard FTer?wn Wheeler the “uniform movement” during the propagation of flame 1044. laxted Edward Bradford disodium nitrite an additive compound of sodium nitrite and sodium 1016. Meek David B. the absorption spectra of some polyhydroxyanthraquinone dyes in concentrated sulphuric acid solutions and in the state of vapour, 969. Meldola Rephael obituary notice of, 349. Meldola RaphaeZ Henry Stennett Foster, and Rainald Brightman attempts to prepare asymmetric quinqueva-lent nitrogen compounds. Part I. 5-Aminosalicylic acid and rdated compounds 533. attempts to prepare asymmetric quin-quevalent nitrogen compounds. Part 11. Nitrated hydroxydiphenyl-amines 546. attempts to prepare asymmetric quin-quevalent nitrogen compounds.Part III. Hydroxyphenylglycine, 551. Yitter Praftdla Chandra and Jnan-endra Nath Sen action of phenyl-hydrazine on opianic nitro-opianic, and phthalonic acids ; some deriva-tives of hydrazo- and azo-phthslide, 988. Morgan Gilbert Thomas and Henry Philip Tomlins the coiistitution of internal diazo-oxides (diazophenols). Part II. 497. lorgan Gilbert Thomas and Adolph William Henry Upton acyl deriva-tives of p-diazoiminobenzene 187. Miiller Hugo obituary notice of 572. Myera James Eckersley boric anhydride and its hydrates 172. N. Neogi Panchannn and Tarini Charan Chowdhuri reduction of aliphatic nitrites to nmines 899. Newbery &?gar the hydration of ions and metal overvoltage 470. Nichols hhynmw? William obituary notice of 319.Nierenstein Maximilian the synthesis of hydroxyquercetin 4. Nomura Hiroshi the pungent principles of ginger. Part I. A new ketone, zingerone (4-hydroxv-3-methoxy-phenylethyl methyl ketoie) occurring in ginger 769. 0. Orr (Miss) Annie Mary Bleakly Robert Robinson and (Miss) Margaret Mary Williams the action of halogens on piperonal 946. P. Pearson (Mrs.) Leonore Kletz. See Pickering Spencer Percitial Umfreville, Purdie Thomas obituary notice of 359. Pnrvis John Edward. See Charles Pyman Frank Lee relation between chemical constitution and physio-logical action in certain substituted aminoalkyl esters. Part II. 167. the alkaloids of ipecacuanha. Part II. 419. the relation between chemical consti-tution and physiological action, 1103.Arthur Lapworth. the detergent action of soap 86. Stanley Gibson. R. Rae William Norman. See Alfred Francis Joseph. Ramsay (Sir) William obituary notice of 369. Rao Basrzw Sanjiva. See Francis Lawry Usher. Rau Madyar Gopala. See Charles Stanley Gibson and John Lionel Simonsen. Rly Prnfulla Chandra mercury mer-captide nitrites and their reaction with the alkyl iodides. Part 111. Chain compounds of sulphur 101. cadmium and zinc nitrites 159. alkaloidal derivatives of mercuric nitrite 507 1132 INDEX 01 Riy Prafdla Chandra and Manik Ld Dey synthesis of d-thiocrotonic acid, 510. S y Prafulla Chadra Manik La1 Dey, and Jnanendra Chandra Ghosh velo-city of decomposition and the dissocia-tion constant of nitrous acid 413.Rayleigh (Lord) the Le Chatelier-Brann principle 250. Read John and (Miss) Murgaret Mary Williams the action of bromine water on ethylene 240. Beilly Joseph the resolution of asym-metric quinquevalent nitrogen com-pounds. Part I. The salts of d- and 2-phenylbenzylmethylallylammonium hydroxide with d- and Z-a-bromocam-phor-lr-sulphonic acid 20. Reilly Joseph and WiZfrid John Hickin-bottom derivatives of n-butylaniline, 1026. Report of the Council 273. Robinson (Mrs.) Gertrude Maud azoxy-catechol ethers and related substances, 109. Robinson (Mrs.) Gertrude Maud and Robert Robinson the scission of cer-tain substituted cyclic catechol ethers 929. researches on pseudo-bases. Part 11. Note on some berberine derivatives and remarks on the mechanism of the condensation reactions of pseudo-bases 958.Robinson Robert a synthesis of tropinone, 762. a theory of the mechanism of the phytochemical synthesis of certain alkaloids 876. See also (Miss) Janet Forrest McGillivray Brown (Miss) Ellen Margaret Hindmarsh Thomas Gilbert Eenry Jones (Niss) Annie Mary Bleakly Om and (Mrs.) Gertrude Maud Robinson. Rodd Ernest Harry the properties and constitution of some new basic salts of zirconium 396. Bowe Frederick JIaurice. See Arthur George Green. Royle Frank Albert. See Arthur Lap-worth. Rule Alexaider. See John Xmeath Thomas. Robinson Robert. 8. Salway Arthur Henry methyl iionyl Bastry Sosale GaralapTy. See William ketoiie from palm kernel oil 407. Arthzcr Haward.AUTHORS. Sannders William Gilbert obituary Scott Alexander presidential address, Sen Jnanendra Nath. See Prafulla Chandra Xitter. Senter Georye and Gerald Hurgrave Martin studies on the Walden in-version. Part V. The kinetics and dissociation conatant of 8-phenyl-a-bromopropionic acid 447. Seyler Claretrce Arthur and Percy Vivian Lloyd studies of the carbon-ates. Part 11. Hydrolysis of sodium carbonate and bicarbonate and the ionisation constants of carbonic acid, 138. Part 111. Lithium calcium and magnesium carbonates 994. Simonsen John Lionel and Madyar Gopala Rau the nitration of isomeric acetylaminomethoxybenzoic acids, 220. Simonsen John Lionel. See also Charles Stanley Gibson. Stewart Alfred Walter and Robert Wright solvent effect and Beer’s law, 183.Stewart Avred Walter. See also Alex-ander Killen lacbeth and (Miss) Elizabeth MacDongall. Still Charles James. See €Tenry Wren. Stoddart Frederick WulZis obituary notice of 376. Sndborough John Joseph and Janiiat Vishindas Lakhamalani the displace-ment of sulphonic acid groups in aininosulphonic acids by halogen atoms 41. notice of 320. 288. studies of the carbonates. T. Taylor John constitution of the salts of S-alkylthiocarbamides 650. Thomas John separation of secondary arylamines from primary amines, 562. Thomas John Smedh and Alexuder Rule the polysulphides of the alkali metals. Part 111. The solidifying points of the system sodium mono-sulphide-sulphur and potassium monosulphide-snlphur 1063.Tomlins Henry Philip. See Gilbert Thomas Morgan. Turner fiatace Ebenezer T . Studies in ring formation. Part 11. The action of aromatic amines on acetylacetone and benzoylacetone 1 INDEX OF AUTHORS. 1133 U. Upton Adolph William Henry. See Gilbert Thomas Morgan. Uaher Francis Lawry and Basrur Sanjiva Wo the determination of ozone and oxides of nitrogen in the atmosphere 799. W. Watson Edwin Roy. See Praphulla Werner Emil RZphonse methylation by means of formaldehyde. Part I. The mechanism of the interaction of formaldehyde and ammonium chloride ; the preparation of methyl-smine and of dimethylamine 844. the constitution of carbamides. Part IV. The mechanism of the inter-action of urea and nitrous acid 863. Wheeler Richard Vemum the influence of pressure on the ignition o f .a mixture of methane and air by the impulsive electrical discharge 411. Wheeler Richard V e m and Allan Greenwell “ stepped ” ignition 230. Wheeler Richard Vernon and Amold Whitaker the propagation of flame in mixtures of acetone and air 267. Wheeler Richard Vernon. See also Waiter Maron. Chandra Bhoeh. Wheelwri ht Edwin Whit!ld obituary notice of 377. Whitaker Arnold. See Richard Y e m Wheeler. Williame (Miss) Margaret Mary. See (Miss) Annie Mary Bleakly Orr and John Read. Woodhonse (Miss) Hilda. See William Smith Denham. Worley E”rede&k Palliser and Vere Rochelle Browne the hydrolysis of sodium cyanide 1057. Wren Henry and Charles James 8til1, studies in the phenylsuccinic acid series. Part IV. The l-menthyl esters of the diphenylsuccinic acids, 513. studies in the phenylsuccinic acid series. Part V. The inter-conver-sion of the esters of r- and meso-diphenylsuccinic acids 10 19. Wright Robert “ spark-lengths ” in various gases and vapours 643. Wright Robert. See also (Niss) Eliza-beth MaoDongall and AZfred Walter 8tewart. Wrightson John obituary notice of, 378. Wykee Frederick Henry. See Arthur Lap worth. Y . Yarrow George. See Aquila Forrter

ISSN:0368-1645    

DOI:10.1039/CT9171101129

出版商:RSC    

年代:1917

数据来源: RSC

摘要:

INDEX OF SUBJECTS. (MEEKj '969. A Arylamines secondary separation of, from primary arylamines (THOMAS), 662. Atmospheric air propagation of flame in mixtures of acetone and (WHEELER and WHITAKER) 267. TRAN SAC TI ON 8. I9 17. Single organic compounds of known empirical formula will be found in the Formula Index p. 1139. phosphates (BASSETT) 620. Caramel chemistry of (CUNN JNGHAM and DoR~P,) 589. -' Caramelan CI,H,,O,. Caramelin C24H28O13. Carbamides constitution of (WERNER), 863. A. Acids structure of ( BRIGGB) 261. organic reduction of nietallic salts by in presence of oxidising agents (DHAR) 690. Address presidential (SCOTT) 288. Afflnity (BRIGGS) 254. Alkali polysulphides (THOMAS and Alkaloids phytochemical synthesis of RULE) 1063. (ROBINSON) 876.ipecacuanha. See Ipecacuanha. Alkyl iodides reactions of mercury mercaptide nitrites with (RAY) 101. nitrates compounds of thiocarbamide and (TAYLOR) 657. nitrites reduction of to amines (NEOGI and CHOWDHURI) 899. phosphates compounds of thiocarb-amide and (TAYLOR) 662. sulphates compounds of thiocarbamide and (TAYLott) 655. thiocyanates compounds of thiocarb-amide and (TAYLOR) 659. Aminer aliphatic formation of from nitrites (NEOGI and CHOWDHURI), 899. aromatic action of on acetylrcetone and benzoylacetone (TURNER) 1. Ammonia structure of ( BRIGGS) 260. Ammonium salts structure of ( BRIGGS), 260. Ammonium chloride interaction of formaldehyde with (WERNER) 844. Analytical chemistry modern advance in CHAPM MAN^. 203. Atmospheric air ignition of niixtnres of acetylene and (HOWARD and SASTRY) 841.electrical ignition of mixtares of methane and (WHEELER) 411. estimation of ozone and oxides of nitrogen in (USHER and RAO) 799. Atomic theory (SCOTT) 288. Atomic weights table of 1002. B. Balance limitations of the ( BLOUNT), 1035. Balance sheets of the Chemical Society and of the Research Fund. See Annual General Meeting 273. Barley enzymic hydrolysis of the furfuroids of (BAKER and HULTON), 121. Basei structure of (BRIGGS) 261. +-Bases researches on (G. M. and R. ROBINSON) 958. Beer's law application of to various solvents (STEWART and WRIGHT), 183. Boron trioxide and its hydrates (MYERS) 172. Bromine water action of on ethylene (READ and WILLIAMS) 240.Brucine CZ3Hz,O4N2. C. Cadmium nitrite (RAY) 159. Calcium carbonate (SEYLER and LLOYD), chloride. comnounds of acetone and 994 1136 INDEX OF SUBJECTS. Carbon :-Carbonic acid ionisation constants of Carbonates (SEPLER and LLOYD) 138, Carbonates. See under Carbon. Catalysis (GRIFFITH LAMBLE and LEWIS) 389; (LEWIS) 467 1086; (DHAR) 690 707. Catechol ethers substituted orientation and scission of (JONES and ROBINSON), 903 ; (G. &I. and R. ROBINSON) 929. Cellulose trimethyl glucose from (DEN-Chemical constitution and physiological action relation between ( PYMAN), 167 1103. reactions a t high temperatures (LEWIS) 1086, Chromium phosphate (JOSEPH and RAE), Cinchonidine C,,H,,ONp Coal mines formation of hydrogon sulphide by gob fires in (DRAKELEY), 853.Cobalt baees (cobaltnmmines) isomeric, relation between the physical proper-ties and electro-valencies of (DE) 51. Cocaine C,,H,,O,N. Codeine C,,H,03N. Colouring matters absorption spectra Coniine C,H,VN. (SEYLER and LLOYD) 138. 994. HAM and WOODHOUSE) 244. 196. of (GHOSII and WATSON) 815. D. Diazo-oxides internal (diaxophenols), constitution of (MORGAN and TOM-LINS) 497. E. Electric discharge through gases Emetamine CQQH~,#~N,. (WRIGHT) 643. F. Ferric salts. See under Iron. Ferrocyanider crystal form and isomer-Fish liver oil new hydrocarbon from Flame propagation. of the uniform movement in (MASON and WHEELER) 1044. in mixtures of acetone and air (WHEELER and WHITAKEIL) 267. i n mixtures of acetylene and air (HAWARD and SASTRY) 841.ism of (BENNETT) 490. (CHAPMAN) 66. Friedel-Crafts’ reaction mechanism of Furfnroids of barley enzymic hydrolysis Fnroxans. See isoClxadiazole oxides. (COPISAROW) 10. of (BAKER and HULTON) 121. 6. # m u electric discharge through (WRIGHT) 643. electrical ignition of (WHEELER and GREENWEIJ,) 130. ignition of mixtures of (MCDAVID), 1003 ; (MASON and WHEELER), 1044. Gas-washing apparatus (GRAY) 179. Ginger pungent principles of (No-MURA) 769 ; (LAPWORTH PEARSON, and ROYLE) 777; (LAPWORTH and WYKES) 790. Gingerol preparation and properties of, and its derivatives (LAPWORTH PEAR-SON and ROYLE) 777. Qob fires in coal mines formation of hydrogen sulphide by (DRAKELEY), 853. H. Hydrogen sulphide formation of by gob fires in coal mines (DRAKELEY), 853.I. Ignition of gases (WHEELER and GREEN-WELL) 130 ; (MCDAVID) 1003 ; (MASON and WHEELER) 1044. Inorganic compounds structure of ( BKIGGS) 253. Ions hydration of (NEWBERY) 470. Ipecacaanha alkaloids (PYMAN) 419. Iron -Ferric chloride compounds of ethyl ether and beuzyl sulphide with (FORSTER COOPER and YARROW), 809. L. Lead iodide solubility of (DENHAM) 29. subiodide (DENHAM) 29. suboxide preparation of ( DENIIAM), Le Chatelier-Braun prinoiple (RAY-LEIGH) 250. Lecture delivered before the Chemical Society (CHAPMAN) 203 ; (PYMAN), 1103. Linseed oil effect of heat and oxidation on (FRIEND) 162. Lithium carbonate (SEYLER and LLOYD), 994. 29 INDEX OF SUBJECTS. 1137 1.Magnesium carbonate (SEYLER and LLOYD) 994. Mercury :-Mercuric nitrite compounds of alka-compounds of thiocarbamides Dimercuric diiododisulphide (RAY), Mercury organic compounds :-mercaptide nitrites and their reaction with alkyl iodides (RAY) 101. Mercury detection of traces of in toxi-cology (BROWNING) 236. Metallic oxides action of sulphur di-oxide on (HAYMICK) 379. salts reduction of by organic acids, in presence of oxidising agents (DHAR) 690. Metals overvoltage of (NEWBERY) 470. Methylation by means of formaldehyde (WERNER) 844. Methylemetinemethine CS2H4,O4N2. Methylpsychotrine C1,H,,O,N,. loids with (RAY) 507. with (RAY) 106. 109. N. Narcotine C22H2s0,N. Nicotine Cl0Hl4N2. o-Nitroamines conversion of into iso-oxadiazole oxides (GREEN and ROWE), 612.Nitrogen oxides estimation of in air Nitrous acid velocity of decomposi-tion and dissociation constant of (RAY DEY and GHOSH) 409. action of on urea (WERNER) 863. (USHER and RAO) 799. Nitrogen organic compounds asym-metric quinquevalent prepara-tion of (MELDOLA FOSTER and BRIGHTMAN) 533 546 551. resolution of (REILLY) 20. o-Nitrosoamines conversion of into iso-oxadiazoles (GREEN and ROWE) 612. Bitrour acid. See under Nitrogen. 0. Obituary notioes :-Andrea Angel 321. Frederick William Catoii 312. Edward Davies 323. Heinrich Debus 325. William Esson 332. Qharles George Edgar Farmer 314. John Ferguson 333. John Griffiths 316. David Howard 342. Obituary notices :-Leonard de Koningh 348. Ernest Alfred Lewis 348.James McConnan 316. Cyril Douglas McCourt 318. RaDhael Meldola. 349. HUL@;o Muller 572. Ravmond William Nichols 319. ThGmas Purdie 359. Sir William Ramsay 369. William Gilbert Sauiiders 376. Edwin Whitfield Wheelwright 377. John Wrightson 378. Opianic acid OloH~,O,. Optical inversion Walden’s (SENTER and MARTIN) 447. Overvol tage ( NE WBERY ) 4 7 0. isoOxadiazoles conversion of o-nitroso-amines into (GREEN and ROWE) 612. isooxadiazole oxides conversion of o-nitroarnines into (GREEN and ROWE), 612. Oxidation (DHAR) 707. Ozone estimation of in air (USHER and RAO) 799. P. Palm kernel oil preparation of methyl nonyl ketone from (SALWAY) 407. Phenylazomeconin C,,H,,04NP Phenylopiaeone C&,,O,Np Phenylsnccinic acid series (WREN and STILL) 513 1019.Phthalonic acid C,H,O,. Physiological action and chemical con-stitution relation between (PYMAN), 167 1103. Piperonal C,H,O,. Polymerisation (BRIGGS) 264. Potassium stannichloride preparation of (DRUCE) 418. polysulphides (THOMAS and RULE), 1063. Prout’s hypotherir (SCOTT) 288. Q. Qninidine CloHt402NP Quinine O2J&dOaN,. Quinones action of acetsldehyde-am-monia on (GHOSH) 608. B. Reduction in presence of oxidising agents Ring formation studies in (TURNER) 1. (DHAR) 690 1138 INDEX OF SUBJECTS. 8. loap detergent action of (PICKERINC), Sodium carbonates hydrolysis of (SEYLER polysulphides (THOMAS and RULE), Disodium nitrite (MAXTED) 1016. Solvents application of Beer’s law to (STEWART and WRIGHT) 183.Spectra absorption of colouiing matters (GHOSH and WATSON) 815. of polyhydroxyanthraquinone colouring matters (MEEK) 969. of unsaturated substances ( MACBETH and STEWART) 329. Spinacene C30H50. Staa work of (SCOTT) 288. Strychnine C21H220,N,. Sulphonic acids amino- displacement of sulphonic acid groups in by halo-gens (SUDBOHOUQH and LAKHUMA-LANI) 41. Sulphur dioxide action of on metallic oxides (HAMMICK) 379. 86. and LLOYD) 138. 1063. T. Temperature high chemical reactions a t (LEWIS) 1086. Thiocarbamides compounds of mercuric Tropinone C,H,,ON. nitrite and (RAY) 106. U. Unsaturated compounds absorption spectra of ( MACBETH and STEWART), 829. V. Vanillin C,H,O,. Veratric-6-eulphinide C9H,0,NS. Veratrole C,Hl0O2. W. Walden inversion (SENTER and MARTIN) 447. Z. Zinc nitrite (RAY) 159. sulphide phosphorescent (MAC-DOUQALL STEWART and WRIGHT), 663. Zingerone C,,HI,OS. Zirconium salts basic properties and constitution of (RoDD) 396

ISSN:0368-1645    

DOI:10.1039/CT9171101135

出版商:RSC    

年代:1917

数据来源: RSC

摘要:

FORMULA INDEX. THE following index of organic coinpounds of known empirical formula is arranged according to Richter’s system (see Lexikon der Kohlenstof- Verbindungen). The elements are given in the order C H 0 N C1 Br I F S P and the remainder alphabetically. The compounds are arranged-Firstly in groups according to the number of carbon atoms (thus C1 group, C group etc.). Secondly according to the number of other elements besides carbon contained in the molecule (thus 5 IV indicates that the molecule contains five carbon atoms and four other elements). Thirdly according to the nature of the elements present in the niolecule (given in the above order). Fourthly according to the number of atoms of each single element (except carbon) present in the molecule. Salts are placed with the compounds from which they are derived.The chlorides, bromides iodides and cyanides of quaternary ammonium bases however are registered as group-substances. C1 Group. CH Methane electrical ignition of mixtures of air and (WHEELER) 411. I I1 CHN CH,O CH20, CHaN, CHsN I I11 CH,ON C a r b a mid e decomposition of by nitrous acid (WERNER) 863. CH4N,S Thiocarbamide salts of (DIXON) 684 ; compounds of alkyl esters Hydrocyanic acid sodium salt hydrolysis of (WORLEY and BROWNE), Formaldehyde action of ammonium chloride with (WERNER) 844. 1057. F o r m i c acid kinetics of oxidation of and its salts (DIIAR) 707. Cyanamide constitution of (COLSON) 554. Methylamine preparation of (WERNER) 844. with (TAYLOR) 650. C2 Group. CnHa A c e t y l e n e ignition of mixtures of air and (HAWARD and SASTRY) 841.CaH4 E t h y l e n e action of bromine water on (READ and WILLIAMS) 240. 2 I1 CaHsO O x a l i c acid kinetics of oxidation of and its salts (DHAR) 707. C,H,N Dime t h y 1 a mi n e preparation of (WERNER) 844. 2 I11 C,H,ON Ace taldehyde-ammonia action of on quinones (GHOSH) 608. 2 IV CaH,OsNsS Subs t a n ce from thiocarbamide and methyl nitrate (TAYLOR) 657. C3 Group. C,H,O Acetone propagation of flame in mixtures of air and (WHEELER and CaHsOz M e t h y l a c e t a t e effect of sucrose on the hydrolysis of (GRIFFITH, WHITAKER) 267 ; conipounds of calcium chloride and (BAGSTER) 494. LAMBLE and LEWIS) T. 390. 3 I11 1139 C,H,N,& S u b s t a n c e from thiocarbamide and methyl thiocyanate (TAYLOR) 659 4 11-7 IV FORMULA INDEX.C4 Group. C4H1,,0 E t h y l e t h e r compound of ferric chloride with (FORSTER COOPER and 4 I11 C4H.,02S aS-Thiocrotonic acid and its salts (RAY and DEY) 510. 4 IV C4H,021S S-Iodo-aS-thiobntyric acid silver salt (RPY and DEY) 512. C4H1404N,S S u b s t a n ce from methyl sulphate and thiocarbamide (TAYLOR) 655. YARROW) 809. Cs Group. Cs Group. C,H,02 Acetylacetone action of aromatic amines on (TURNER) 1. C,H Benzene reaction of phthalyl chloride with (COPISAROW) 10. C,H,O C a t e c ho 1 orientation and scission of substituted ethers of (JONES and CsHaN2 Phenylhydrazine action of on opianic nitro-opianic and phthalonic 6 I1 ROBINSON) 903 ; (G. M. and R. ROBINSON) 929. acids (MLTTER and SEN) 988. 6 111 6 IV C,H,ON Benzisooxadiazole preparation of (GREEN and ROWE) 618.C,H,O,N,S Benzene d i a z 0-1-0 x i d e s u l p h o n i c a c i d s and their salts (MOR-GAN and TOMLINS) 501. Phenol-3- and -4-diazoniumsulphonates (MORGAN and TOMLINS) 503. C,H,NBr21 D i b r o m o i o d o a n i 1 i II e s (SUDBOROUGH and LAKHUMALANI) 47. C,H,,04N,S Substance from ethyl sulphate and thiocarbamide (TAYLOR) 656. C7 Group. C,H,O 2:3:4:6-Tetrahydroxybenzoic a c i d (+ H,O) (NIERENSTEIN) 5. C,H,OaNs Substance from diazotisation of 5-nitro-3-aminosalicylic acid (MEL-DOLA FOSTER and BRIGHTMAN) 541. C,H,O,Cl 4:5-Dichlorocatechol methylene e t h e r (ORR ROBINBON and WILLIAMS) 949. C,H,O,Br 4:5-Di bro m o ca t e c h o 1 m e t h y l e n e e t h e r (JONES and ROBINSON), 913.C,H,ON Form 91-p-p h eny 1 ene d i az o i mide (f liH20) (MORGAN and UPTON), 190. C,H,ON 5-Methylbenzisooxadiazole (GREEN and ROWE) 619. C7H6O2Br1 4:5-Dibromoguaiacol (HINDMARSH KNIGHT and ROBINSON) 942. C,H,O,Bp 5-Bromoguaiacol (HINDYARSH KNIGHT and ROBINSON) 941. C,H,O,N,Cl 8 u bs t a n c e from diazotisation of chloroaminosalicylic acid (MEL-C,H,0eN2C1 4-C h l o r o-5:6-d ini t r oca t e c h 01 m e t h y lene e t h e r (ORR ROBIN-C,H40nC1Br 4-C h 1 oro-5-brom o ca t e c h o 1 met h y 1 e ne e t h e r (ORR ROBINSON, C,H,O,NCl 4-Chloro-5-n i t r o ca t e c h 01 m e t h yle ne e t h e r (ORR ROBINSON 7 I11 7 IV DOLA FOSTER and BRIGHTMAN) 543. SON and WILLIAMS) 951. and WILLIAMS) 950. and WILLIAMS) 951. 114 FOHMULA INDEX. 7 IV-8 111 C,H,O,NBr 4-Br om 0-5-11 it roca t ec h 01 me t 11 y lene e t h e r (JONES and ROBIX-C,H,O,NCl 3-Chloro-5-nitrosalicylic a c i d (MELDOLA FOSTER and BRIGHT-C,H,06NaBr 5-B r o mo-4:6-d i n i t r ogua i ac o 1 ( HINDMARSH KNIGHT and C,H603NC1 3-C h 1 oro-5-am i n osa 1 i c y l i c a c i ii ( MELDOLA FOSTER and C,H,O,NBr 3-Bro m o-5-am i n osal i c y l i c a c i 6 (MELDOLA FOSTER and C,H,O,NC1 4-C h 1 or o-5-n i t r ogua i a c 01 (GIBSON SIMONSEN and RAU) 82.C,H,O,NBr 6-B romo-5-ni t roguaiac 01 (JONES and ROBINSON) 917. SON) 918. MAN) 542. ROBINSON) 942. BRIGHTMAN) 542. BRIOHTMAN) 545. Cs Group. C,H,O 2:3:4:6-Te t ra h y d r o x y a i e t o p h e n on e ( NIERENSTEIN) 6. C,HliN Coniine compound of mercuric nitrite and (RAY) 507. 8 I11 C,H,O,Cl, C,H,O,N 5-Nitro-3-cyanosalicylic a c i d (+ H,O) (MELDOLA FOSTER and C8H,03C1 6-Chloropiperonal (ORR ROBINSON and WILLIAMS) 948.C,H50,C1 6-Chloropiperonylic a c i d (ORR ROBINSON and WILLIAMS) 948. C8H50eN3 4:5:6-Trinitroe thylenedioxybenzene (G. M. and R. ROBINSON), 935. C,H,ON 8 ubs t a n ce from p-benzoquinone and acetaldehyde-ammonia (GHOBH), 611. P h t h a l y l chloride reaction of with benzene (COPISAROW) 10. BRIGHTMAN) 545. C,H,ON Acetyl-p-phenylenediazoimide (+ H,O) (MORGAN and UPTOK), 193. C,H,05N Nitromethoxybenzoic acids and their salts (SIMONSEN and RAU), 224. C,H,0,N3 4:5-D i n i t r o-6-amin oe t h y 1 en e d i o x y b e n ze n e and R. C,H,O,N Nitroaminomethoxyhenzoic acids and their salts (SIMONSEN C,H,0,N2 3:4-Dinitroveratrole (GIBSON SIMONSEN and RAU) 83 ; (JONES C8H80,N2 3:5-Dini tro-2:4-dihydroxy-8-h yd r ox ye t h oxy benzene (G.M. CeHBO,N Aminomethoxybenzoic acids and their salts (SIMONSEN and p-H y d r o x y p h en y l g l y c i n e preparation of (MELDOLA FOSTEP. and BRIGHT-(G. M. ROBINSON) 936. and RAU) 216. and ROBINSON) 911. and R. ROBINSON) 938. RAU) 224. MAN) 552. C,H,O,N Nitro-2-ethoxyphenols (G. M. and R. ROBINSON) 932. CaHB06N Dinitro-3-aminoveratroles (GIBSON SIMONSEN and RAU) 79,81. CaHloO,N 5-Nitro-3-aminovera trole and its salts (GIBSON SIMONSEN and RAU) 75. 6 - N i t r o v e r a t r y l a m i n e (JONES and ROBINSON) 914. C,Hlo05N4 3:5-Dinitro-2:4-diaminophenetole (G. M. and R. ROBINSON) 934. C8Hlo0,N4 3:5-D i n i t r o-2:4-d i a m in 0 - 8 - h ~ d r o x ye t h n x y b en z en e (G.M. and C,Hl,02N 3-Am i n o ve r a t r o 1 e and its picrate (GIBSON S ~ M O N ~ E N and RAU) 79. C,H130N Tropinone (ROBINSON) 762. K. ROBINSON) 936. 114 8 IV-10 I1 FORMULA INDEX. 8 IV C,H,O,N,Br B r o m o d i n i t r o v e r a t r o l e s (JOKES and ROBINSON) 924 ; (HIND-C,H,O,NBr 6-Bromo-5-ni t r o v e r a t role (JONES and ROBINSON) 917. C,H,O,NS N i t r o v e r a t r o l e s u l p h o n i c acid potassium salt of (BROWN and C,H,,O,NS 3- and 5-Aminoveratrole-4-sulphonic a c i d s (BROWN and C,Hl,0,N.,S2 Substance from ethyl oxalate and thiocnrbamide (TAYLOR) 661. 8 V C,H,0NBr21 Dibromoiodoscetanilides (SWDBOROUGH and LAHHUMALANI), 47. C8H8o6NC1S 5-Ni t r overa t r ole-4-sulp hon y l c h l o r i d e (BROWN and ROBIN-MARSH KNIGHT and ROBINSON) 943.ROBINSON) 953. ROBINSON) 954. SON) 953. C9 Group. CgH,O P h t h a l o n i c acid action ofphenylhydrazine on (MITTER and SEN) 988. C,H,,O Snbs tance from trimethyl glucose and hydrocyanic acid (DENIIAM and CgH180s T r i m e t h y l glucose (DENHAM and WOODHOUSE) 244. C,H,02N2 5:6-M e t 11 y 1 e n edi ox y-2-m e t h y 1 be n zim i n azol e (JONES and C,H,O,N 5-Nitro-2:3-dimethoxybenzonitrile (GIBSON SIMONSEN and C,H,O,N 5-Nitro-4-acetylaminocatechol methylene e t h e r (JONES and C,H,06N2 5-Nitr o-3-a c e t y 1 amino s a l i c y l i c a c i d ( MELDOLA FOSTER and C,H,02Br 8-Phonyl-a-bromop r o p i o n i c acid kinetics and dissociation con-CgHgO,Br 5-Bromo-2-met hoxyphenyl a c e t a t e (HINDMAHSH KNIGHT and C,H,O,N C,HlOO,N2 6-Ni t ro-2-amino-3:4-dime t hox y ben zoic acid (GIBSON SIMOS-C,H,,O,Br 6-Bromohomoveratrole (JONES and R.OBINSON) 919.C,EI,,N,S Substance from thiocarbamide and benzyl thiocyanate (TAYLOR) 660. CoH,20,N2 5(or 6)-N it r o-6(or 5)-am ino-1:2:4-t rim e t h ox y beii zene (JONES and C,H120,N 3:5-Dini tro-2A-dime t h y l a m i n o a n i s o l e (HINDMARSH KNIGHT, 9 IV WOODHOUBE) 248. 9 1x1 ROBINSON) 916. RAU) 76. ROBINSON) 914. BRIGHTMAN) 541. stant of (SENTER and MARTIN) 447. ROBINSON) 941. M e t h y l nitromethoxybenzoates (SIMONSEN and RAU) 229. SEN and RAU) 75. ROBINSON) 926. and ROBINSON) 944. C,H,O,NC1 3-C h l o r o-5-a c e t y 1 amino s a1 i c y 1 i c acid (MELDOLA FOSTER and C,H,O,NBr B r om on i t r ov e r a t r a 1 d e h y d e s (JONES and ROBINSON) 920 923.C,H,O,NS C,H,,O,NBr 6-Bromo-5-nitrohomoveratrole (JONES and ROBINSON) 919. C,H,,O,NS Homovera t ro 1 e-6-sul p h onamide (BROWN and ROBINSON) 954. BRIGHTMAN) 543. Veratric-6-sulphinide (BROWN and ROBINSON) 956. Clo Group. C,HlOO2 CloHloOs Benzoylaceton e action of aromatic amines on (TURNER) 1. 0 p i a n i c a c i d action of plienylhydrazine on (MITTER and SEN) 988. 114 FORMULA INDEX. 10 11-11 IV CloHl,05 2:6-Dihydroxy-3:4-dimethoxyacet ophenone (NIERENSTEIN) 7. C10H14N2 Nicotine compound of mercuric nitrite and (RAY) 507. C10H15N CloH,,Nn Phenyl-mbutylhydrazine and its hydrochloride (REILLY and HICKINBOTTOM) 1028. p-Phenylene-n-butyldiamine and its salts (REILLY and HICKINBOTTOM), 1032. 10 I11 CloH,0N2 Naphthisooxadiazole (GREEN and ROWE) 617.C,,H,O,N Naphthisooxadiazole oxide (GREEN and ROWE) 616. C1,H,O,N Nitro-opianic acid action of phenylhydrazine on (MITTER and SEN), C,,H,,0,N2 A c e by 1 derivatives of n i t roam i n om e t h ox y be nzoi c a c i d s C,oH,,O,N Ace t y 1 derivatives of am i n om e t h ox y b e n z oi c a c i d s (SIMONSEN CloH,,06N N i t r o p i p e r on a 1 d i in e t h y l a c e t a1 (ROBINSON) 120. C,,H,,O,N, 78 81. CloH1205N2 76. C,,H,,O,N, C,,H,,O,N, C,oH,30,N C,,H,,ON p-N i troso-92-butylaniline and its hydrochloride (REILLY and 10 IV n-Bu t y l a n i l i n e preparation of (REILLY and HICKINBOTTOM) 1026. 988. (SIMONSEN and RAU) 231. and RAU) 225. D i n i t r o-3-a ce t y 1 ami no v era t r o 1 e s (GIBSON SIMONSEN and RAU), 5-Nitro-3-acetylaminovera t r o l e (GIBSON SIMONSEN and RAU), Acetyl derivative of 6 - n i t r o v e r a t r y l a m i n e (JONES and ROBINSON) 914.4:5-Dinitrocatechol d i e t h y l e t h e r (G. M. and R. ROBINSON), p-N i t r oso-9L-b u t y l a n i l i n e n i t r o s o am i n e (REILLY and HICKIN-933. BOTTOM) 1032. 3-Acetylaminoveratrole (GIBSON SIMONSEN and RAU) 80. HICKINBOTTOM) 1030. Cl,H,,05NS C,,Hl,O,NBr N-M e t h y 1 ver a t ric-6-su 1 phi n i de (BROWN and ROBINSON) 956. 6-Br o m oac e t o v e r a t r y 1 a m i d e (JONES and ROBINSON) 912. CI1 Group. C,,H,,O E t h y l c a r b o n a t o v a n i l l i n (LAPWORTH and WYKES) 792. CllH1,06 3:4:6-Trim e t hoxy-2:5-quino a c e t o p hen one (NIERENSTEIN) 8. Cl,H,,O3 Zingerone (NOMURA) 769 ; (LAPWORTH PEARSON aud ROYLE) 785 ; CllH1405 H y d r o x y t r i m e t h oxy a c e t o p hen o n e s ( NIERENSTEIN) 8.c11H1406 2:5-D i h pdroxy-3:4:6-t r i m t t h ox y a c e t o p h e n one (NIERENSTEIN) 8. CllHnO Me t h y 1 n o n y l ketone preparation of from palm kernel oil (SALWAY), 407. (LAPWORTH and WYKES) 792. 2:3:4:6-Te t ram e t h o x y benzoi c a c i d (NIERENSTEIN) 6. I1 I11 CllN,O,C1 6-Ch lor 0-3:4-me t h y l e n edi o xys t y r y l me t h y l k e t o n e (ORR, C,,H,,O,N 6-Ni t ro-2-ace t y l n n i i n 0-3:4-dim e t hox y be nzoi c a cid and its CllH,,05C1 ROBINSON and WILLIAMS) 948. silver salt (GIBSON SIMONSEN rind RAU) 74. 2:3:4:6-Te t ram e t h o x yben zo y l chloride (NIEREKSTEIN) 6. 11 IV CllH1,,OSNC1 3-C h 1 o ro-5-d iac e t y 1 ami n o s a1 i c y l i c n c i d (MELDOLA FOSTER, and BRIGHTMAN) 542.114 12 11-14 111 FORMULA INDEX. Clg Group. C,,H,,@ Methylzingerone (NOMURA) 772 ; (LAPWORTH PEARSON and C,&O T e t r ame t h o x yace t op he no n e (NIERENSTEIN) 7. C,,H1,O6 Met h y 1 2:3:4:6-t e t rame t h 0 x y be n z o a t e ( NIERENSTEIN) 6. C,2H1809 Car amelan preparation and constitution of (CUNNINGHAM and C,,H,O, Sucrose effect of methyl acetate on the inversion of (GRIFFITH, ROYLF.) 786. DoR~E) 593. LAMBLE and LEWIS) 390. 12 I11 C12H,011N 2:4:6:3’:5’-P en t a n i t r o-4’-h y d r ox y d i p h e n ylam i n e C,,H,07N 2:4:?-T r i n i t ro-4’-hydr oxy d i p h e n y lam i ne (MELDOLA, (MErmoLA, FOSTER, Substance from 2:4:6-trinitro-4‘-hydroxydipheuylamine and nitric acid (MEL-C,,H,O,N 2:4-Din i tro-4’-h y d r o x y d i ph e n y l a m i n e ( MELDOLA FOSTER and C,,H,,O,N E t h y l a-cyanocaffeate (LAPWORTH and WYKES) 798.C,,H,,O,N 4:5-D i n i t r o-3-di ac e t ylam i n o vera t r ole (GIBSON SIMONSEN and Cl2Hl4O1,N4 Caramelan t e t r a n i t r a t e (CUNNINGHAM and DORI~E) 595. C12H,,03N Methylzingeroneoxime (NOMURA) 773 ; (LAPWORTH PEARSON, FOSTER and BRIGHTMAN) 550. and BRIQHTMAN) 548. DOLA FOSTER and BRIGHTMAN) 550. BRIGHTMAN) 547. RAU) 79. and ROYLE) 786. CI3 Group. c1&&4 3:6:3’:6‘-Te t r a h y d r o x y d i p hen yl m e t h a n e preparation of (GHOSH C13H1604 Ace t y l z i nger on e ( NOMURA) 772. C13H1803 E t h y l z i n ge r on e (NOMURA) 773. C,,H,ON Ben z o y 1-p-p h e n y 1 en e d i az oi m i d e (MORGAN and UPTON) 195. C,,H,,O,N p-Nitrobenzylbopicramic a c i d (MELDOLA FOSTER and BRIGHT-C,,H,,O,N ( MELDOLA, Cl,H,,O,N E t h y l v a n i l l y lidenec y anoace t a t e (LAPWORTH and WYKES) 796.C,,H2,0,N B-D i e t h y lamil; 0-F-p h e n o x y iso pr o p y 1 a 1 c o h o 1 aud its hydro-and WATSON) 825. 13 111 MAN) 553. FOSTER and BRIGHTMAN) 549. 2:4-D i n i t ro-4’-hydr o x y d i p h e n y 1 met h y l a rn i n e chloride (PYMAN) 170. C14 Group. C14H14S Benzyl sulphide compound of ferric chloride with (FORSTER COOPER, CI4HleO E t h ylca r b o n a t o zi n ge r on e (LAP WORTH PEARSON and ROYLE), 14 I11 C,,H,O,,N 2:4:?:?-T e t ran i t r o-4’-h y d r ox ya c e t y Id i p h e n y l a m i n e (MELDOLA, Cl,Hl,0,N4 (MELDOLA, C,,H,,O,N, C,,Hl,0sN3 and YARROW) 809. 785 ; (LAPWORTH and WYKES) 794.FOSTER and BRIGHTMAN) 549. FOSTER and BKIGHTMAN) 548. 2:4:?-Trini t r o-4’-hydr oxyace t y Id i p hen y l a mine 4:5:4‘:5‘-D i m e t h y 1 en e t e t ra o x y a zo b e nze n e (ROBINSON) 113. Ace t y 1 derivative of 2:4-d i n i t ro-4‘-hy d r o x y d i p h en y 1 a m i n (MELDOLA FOSTER and BRIGHTMAN) 548. 114 FORMULA INDEX. 14 111-16 111 Cl4Hl8O6N D i n i t r o a n i I i novera t r ol e (HINDNARSH KNIGHT and ROBINSON), 944. C14H140,N of 2:3:4:6-t e t r a h y d r o xy a c e t o p h e n on e (NIEBENSTEIN) 7. P lien y 1 h y d r a z on e C14Hm04N2 8-Dieth y l a m inoe thy1 p-ni t r op h e n y 1 ace t a t e and its salts (PYMAN). 169. Cl4HZ,O2N2 ’.B-D ie t h y laminoe t h y 1 p-amino p h en y 1 a c e t a t e ( PYMAN) 170. 14 IV C14H120,NCl C h 1 o r o b en z y l a mi n o s a1 i c y 1 i c acid ( MELDOLA FOSTER and BRIGHTMAK) 544.CIS Group. C15H,,0, C15H140, 2:3:4:6-Tetra-acetoxybenzoic acid (NIERENSTEIN) 6 . C1,HQOQN3 2-Ni t ro-4:5:4‘:5’-dime t h yle n e t e t r ao xy azo x y be nz ene-2’-carb-Cl5H1,O,N S u b s t ance from trinitroacetylaminophenol and aminosalicylic acid ClSH1205Br2 5-Bromo-2-niethoxyphenyl c a r b o n a t e (HINDMARSH KNIGHT, Cl,H1305N Nitro-2-ethoxyphenyl benzoa t e s (G. M. and R. ROBINSON), C,,H1404N2 p-Nitrobenzoyl-p-phonet i d i n e (PYMAN) 172. Hydroxyquercetin synthesis of (NIERENSTEIN) 4. 15 I11 o x y l i c a c i d (ROBINSON) 119. (MELDOLA FOSTER and BRIUHTMAN) 538. and ROBINSON) 941. 933. C,,Hla0,N2 5-N i t r o-3-ben zo y lam ino ve ra t r 01 e (GIBSON SIMONSEN and RAU) 76.C15H140,N4 C16H160,N C15H&,N3 Dinitro-p-toluidinoveratrole (HINDMARSH KNIGHT and Cl,Hl,O,N p-A m i n o b e nzo yl-p-p he n e t i d i n e ( PYMAN) 172. 3:5-D i n i tro-2:4-diamino-B-b en zoyl ox ye t hox y benz en e (G. M. 3-Bonzoylaminovera t r o l e (GIBSON SIMONSEN and RAU) 80. and R. ROBINSON) 937. ROBINSON; 946. CIS Group. C1,HI4O4 T- and meso-D i p h e 11 y 1s u c c i n i c a c ids interconversion of esters of (WREN and STILL) 1019. 16 I11 C,,H,O,N 3-h y dr o x y-5:6:4’:5’-d im e t h y l en e t e t raoxy-2-CleHlo0,N2 2:3:6:7-D i m e t h y l e n e t e t raox y an t h raqninon edi-im i d e (BROWN Cl,Hl,O,N A z ox y pi p e r o n a1 (ROBINSON) 117. C,,H,,O,N p H y d r o x y b e n z en eaz o d i h y d r o xy n a p h t h a1 e ne s (GHOSH and C,,Hl,O,N Substance from nitration of C,H,ON (GHOSH) 611.CloHI3ON o-A mino benz e neazo-a-naph t h 01 (GHOSH and WATSON) 824. Lac t on e of p 11 en y 1 i n do 1 e-2’-c a r b o x y 1 i c a c i d (ROBINSON) 118. and ROBIXSON) 957. WATSON) 823. p - H y d ro x y b en z e n e az o-8-n a p h t h y l am i n e and its hydrochloride (GHOSH and Wxrsox) 824. Cl,H1305N p-N i t r oa ce t y 1 benzoin reactions o f (FRANCIS) 1041. ClsH130,N3 P h e n y 1 a z o n i t r o m t c o n i n (MITTER and SEN) 992. Cl,H130,N3 D i ace t y 1 derivative of 2:4-d i n i t ro-4’-hydr ox y d i p h en yl am i n e C16H1403N2 P h e n y 1 o p i a z o n e (MITTER and SEN) 992, (MELDOLA FOSTER and RRIGHTMAN) 547. CXI. 1145 3 16 111-19 I11 FORMULA INDEX. C,,H,,O,N, C,,H,,O,N, C,,H,,O,N, C1,H,,0,N3 C,,H,,O,N Azoxyveratrole (ROBINSON) 114.CI,H,,ONBr C,,H,,O,N,S C,,H,,O,N,Br 6-Rrom o azoxyvera t r 01 e (ROBINSON) 11 5. C,,H1,O,NsS 6-Am i n overa tryl-4:5-t h i o t r iaz ove r a t r 01 e (JONES and C,,H,,O,N,S 8 ubstance from benzyl sulphate and thiocarbaniide (TAYLOR), Phenylazomeconin (MITTER and SEN) 991. Subs t a n ce from phenylhydrltziiie and opiunic acid (MITTER and SEN) 991. 6:6’-D i n i t r oa z ox y v e r a t ro 1 e (ROBINSON) 11 6. 6-N i t ro azox y v e r a t r 01 e (ROBINSOX) 115. 16 IV Ben z o y 1 ace t o n e-p-b r o m on n i 1 i d e (TURNER) 3. 6-N i t r o v era t ryl-4:5-t h i o t r iazo v era t r o l e (JONES and ROBINSON) 925. ROBINSON) 925. 656. C1 Group. C17H,,0N3 Ben zoy 1-1:4-n a p h t h y lene diazoim i d e (MORGAN and UPTON), 196.C17H,,0,N 4-H ydroxy-3-carboxyben z en e az 0-8-11 npli t h 01 (MELDOLA Fos-TER and HHIGHTMAN) 538. C,,H,,O,N 4:5-Dinitro-2-hydroxy-l-inethoxy-3-azo-k?-ii npli tho1 (GIBSON, SLMONGEN and RAU) 82. Cl,H,,0,N3 Form y l-B-am i n o benz en eazo-B-n a p h t h o 1 (MORGAN and UPTON), 193. C,H,,O,N 8-p-N i t r o b en z o y 1-l-m e t h yl-1:2:3:4-t e t r a h y d r o q u i n 01 i n e C1,HI7O,N (PYMAN) 171. 171. $-Ben z o y lox y-l-m e t h y 1-1 :2:3:4-te t r a h y d r o q u i n o 1 i n e (PniAN), C1,H2,0N d- and Z-P h en yl b en zy l m e t h y 1 a 11 y 1 ammonium CI,H,,O,N C,,HIlO,N,C1 5-C h 1 o r o-4-h y d r o xy-3-c arbox y b enz e n e az o-B-n a 1) h t h 01 hydro x ide, salts of with bromocamphorsulphonic acids ( REILLY) 20.Cocaine compound of mercuric nitrite and (RAY) 509. 17 IV (MELDOLA FOSTER and BRIGHTMAN) 543. CIS Group. C,,H,,O Subs t a n c e from anthraquinone aud acetaldehyde-ammonia (GHOPH), 611. C,,HIsO4 R en zo y I z i n gerone (NonruRA) 771. 18 I11 C,,H,,O,N Azoxy ve r a t r a l t l e h y de (ROBINSON) 121. C1,H2,O3N Codeine compound of mercuric nitrite and (RAY) 505. 18 IV C,,H,,O,N,S s u b s t a n ce from benzyl oxdate and thioca~baiiiide (TAYLOR) 661. clgH1406 T r i h y d r o x y a u r i n (GHOSH and WATSON) 826. C19H1407 T r i hydroxy-9-o-p-di h y d r ox y p henyl-6-f 1 u o r on es CI9 Group. (GHOSII and WATSON) 828. 19 I11 C,gHl,05C12 D i-6-c h l o r om e t h y l e n e d i o xy s t y r y l k e t o n e (ORR ROBINSON, C,,H,20N2 a i d WILLIAMS) 948.C i II c h on i d i n e compound of mercuric nitrite and (RAY) 508. 114 FORMULA INDEX. 20 11-23 I11 C,, Group. CzoH,07 2-H y (1 r o x y-3:4:6-t r i m e t h o x y p h e n y 1 3:4-d i 111 e t 11 o x j7 Y t jr r y 1 k e-5:7:8 :3’:4’-P e n t a m e t h ox y fla va n o n e (NIERENSTEIN) 9. t o n e (NIEKENS’TEIN) 8. Cz0H2,N4 C,oH130,jN CzoH,@N C2,H2,O8N C20Hz,02Nz C,0H,503N D i p h e 11 y Id i-n-bu t y I t e t r a z o n e (REILLY and H~CKINBJT~OM) 1030. D i b e u z o y l derivative of n i t r o c a t e c h o l (G. M. and R. ROBINSON), 20 I11 935. Benzoylacetone-a- and - 8 - n a p h t h a l i d e s (TURXER) 3. 3-iso Ni t r o so-5:7:8:3’:4’-pen t a m e t h o x y t l a va I I o n e ( NIEREN-STEIN) 9. Q u i i i i d i ne compound of mercuric nitrite and (RAY) 507.8-D i e t l i g l amino-B’-p h e n o x y is0 p ropy1 ben z oa te and its salts Q n i i i i ne cornpound of niercuric nitrite and (RAY) 507. (PI-MAN) 170. 20 IV C,,H,,O,N,Br D i b r o ni o t e t r a m e t h o x y i n d i g o t i n s (JONES and ROBINSON), 921 924. Cal Group. C21H,,02N2 (JONES and C2,HI5O5N p - N i t r o b e n z o y l b e nzoin constitution and hydrolysis of (FRANCIS), C,lH,80,N, C,1Hl,03N 5-D i b e n z y lain i nos a l i c y l i c a c i d (MELDOLA FOSTER and C,,Hzo0,N2 A I I 11 y d r o b e r be r i n e n i t r o me t h a n e (G. M. and R. ROBINSON), 968. C,,H,,O,N C,,H,,O,N, C2,Hl10,NzC1 1:2-Me t h y l e n e d i o x y p h e n a n t h r a p h e n a z i n e lCOBIXhON) 927. 1043. C y a n o d i h y d r o b e i .b e r i n e (G. hl. and R. KOBINSON) 366. 13RIGlIT~IAX) 537. Methoxydiliydroberberine (G. M. and R. ROBINSON) 967. S t r y c h n i n e coinpound of mercuric nitrite and (RAY) 508. 21 IV 4-C 11 loro-l:%me t li y l en e d i o x y p h e n a n t h r a p h e n a z i n e (OltR ~ ~ B I S S O N and WILLIAMS) 951. Ca2 Group. Cz2H2408 2-Acetoxy-3:4:6-trimethoxyphenyl 3 b d i m e t h o x y s t y r y l k e -22 I11 t o n e (NIERENSTEIN) 9. C2,H,,02N2 C2,H2,O,N C,H,,NS CZzH2,O,N C,,H,,O,N,Br 2:3-E t h y 1 e n e d i o x 4 p h e n a n t h r a p h e n a z i n e 2-C' a r b o x y-4-d i b e n z y l m e t h y 1 am m o n i u m-l-b e n z oqu i n o n e (G. 31. and R. ROBINSOX) 935. (bIELDOLh Fosrm A11d BBRIGHTbfAN) 538. T r i b e n z y l s u l p h i n i u n i c y a n i d e and its salts (FORSTEB COOPER, and YAKKOW) 513.N a r c o t i II c‘ conipound of mercuric nitrite and (RAY) 508. 22 IV 4-13 ro m 0-1 :2-d i m e t h o x y p h e n a n t h r a p 11 e n a z i n e (JONES and BOUINSOX) 928. C, Group. C2,HI8O3N T r i rn e t h ox yli h eiia 11 t h r a p he n a z i n es (JONES and ROBINSON), 114’7 928 23 111-30 IV FORMULA INDEX. C,H2,02N2 3-Dime t h y 1 amin o-9-p-h y d r oxy p he nyl-6-di m e t h y 1 fl uorim e C83H2z03Nz 3-D im e t h ylami no-9-o-p-d i h y d r oxy p h e nyl-6-dime t h y 1 fl uor-C,,H,,0N2 4-H y d r ox ym a 1 a c h i te-gr e e n (GHOSH and WATSON) 826. Ca3Hz4O2NZ 2:4-Di h y d r ox ym alac h i t e-gree n (GHOSH and WATSON) 826. (GHOSH and WATSON) 827. ime (GHOSH and WATSON) 827. 3:6-T e t r a m e t h y 1 d i am i n o-9-p-h y d r ox y p h en y 1 x a n t h en e (GHosa and WATSON) 827.CZ3Hzso4N2 ‘b r ucin e compound of mercuric nitrite and (RAP) 509. C2* Group. C2,H2,Ol, C2,H,,0,N2 2:3-Diethoxyphenanthraphenazine (G. M. and R. ROBINSOX), 934. C,,H,,O,N C a r a m e l i n (CUNNINGHAM aud DoRESE) 602. 24 111 D i p i p e r o n y 1 i d e n e t r o p i n o n e (ROBINSON) 765. C, Group. C26H200 T e t r a p h e n y l m e t h a n e - o - c a r b o x y l i c acid and its salts (COPI-SAKOW) 17. CaaHS2O4 Menthyl hydrogen d i p h e n y l s u c c i n a t e s (WREN and STILL) 521. C, Group. C,H,,O,N 3:4-Di-p-n i t r o t e t r a p he n y 1 f u r a n (FRANCIS) 1039. C2,&06N6 A z o x y p i p e r o n a 1 d i p h e n y 1 h y d r a zon e (ROBINSON) 118.C,sH,505N Anhydroberberineacetophcnone (G. M. and R. ROBINSON) 968. C2 Group. C3, Group. C2,H3,0,N2 Em e t a m i n e and its salts (PYMAN) 442. C2,H3,04N Methylpsychotrine and its salts (PYMAN) 431. C,,H,, Spinacene (CHAPMAN) 56. C30H24N4 C30H60BPls S pinac en e do d e c a b r om i d e (CHAPMAN) 63. C30H2604N2 Be nz oy 1 3-d im e t h y 1 am ino-9-o-p-d i h y d r o x y-p h en yl-6-dim e t h y 1 fl uor i m e (GHOSH and WATSON) 28. C30H,,0,N2 Be nz oyl derivative of 3:6-t e t r am e t hy 1 d iam i n o-9-p-h ydroxy-p h e n y l x a n t h e n e (GHOSH and WATSON) 827. 30 11 Hydrazone of substance C,,H1202 (GHOSH) 612. 30 I11 derivative of CJI2~01oN2 8 u b s t a n c e from caramelan and phenylhydrazine (CUNNINGHAM and DoR~E) 597. CsoH38015N2 C30H4,04N, C30Hh0012N6 Spinacenc n i t r o s a t e (CHAPMAN) 67.C30H6003N3C1s S p i n acen e t r i n i t r oso c h l or i d e (CHAPMAN) 64. C,oH,oO,N,C1 s p i n a c ene h exan i t roso c h l o r i d e (CHAPMAN) 66. 8 u b a t a n c e from caramelan and phenylhydraziiie (CUNNINGHAM and DoRESE) 597. Methylemetine and its salts (PYMAN) 444. 30 IV 114 FORMULA INDEX. 32 111-51 III C,2 Group. C,,H,,O,N, C,,H4,0,NZ D i b e n zo y 1 is0 p r o p y 1 i d e n e b e n z i cl i n e (TURNER) 4. Methylemetinernethiue and its salts (PYMAX) 445. C, Group. C,,H,,O,o 2:3:4:6-Te t r a ben z o ylo x y benzoi c a c i d (NIERENSTEIN) 6. 35 IV C,,H,,O,N,C1 S 1) i n ace n e d i n i t r oso c h 1 or i d e n i t r o 1 pipe r i d i d e (CHAP-MAN) 65. . C36 Group. C36H5004 D i m e t h y l d i p h e n y l s u c c i n a t e s (WREN and STILL) 520. 36 111 C3,H,,05Nz B enzo y 1 m e t li y 1 p s y c h o t r i n e (PYMAN) 436. C36H4,0,Nz B e n z o y 1 is0 e m e t i n e ( PYMAN) 439. C37 Group. 37 IV S p i n ace n e d i n i t r 0 s o c h 1 o r i d e n i t r o b en z y 1 amid e (CHAP-C3,H4,O,,N S u bs t a 11 c e from caramelan and semicarbazide (CUNNINGHAM and UORBE) 598. C3,H,,O,N,C1, MAN) 66. C4, Group. C4 Group. C, Group. C,,H,,O, Caramelan t e t r a b e n z o a t e (CUNNINGHAM and DoR&E) 595. C4,H8,,03N6 S pin ace n e t r i n i t r o 1 piper i d i d e (CHAPMAN) 65. C,,H,,O,Ne Spin ac e 11 e t r i n i t r o 1 be 11 zy lam i de (CHAPMAN) 66. 114

ISSN:0368-1645    

DOI:10.1039/CT9171101139

出版商:RSC    

年代:1917

数据来源: RSC