摘要:

1572 CEATTAWAY : THE CONSTITUTION OF THE CI.V.-The Constitytion qf the so-called (' Nitrogen Iodide. " By FREDERICK D. CHATTAWAT, M.A., Christ Church, Oxford. FROY the beginning of the present century, the black explosive com- pound, formed when a solution of ammonia, acts on iodine, has almost continuously engaged the attention of chemists. No definite con- clusion, however, as to its constitution has been arrived at, although from time t o time different forniuls have been assigned to i t ; whilst on account of its apparently variable composition several distinct compounds have been assumed to exist. The so-called iodide of nitrogen was first prepared by Bernard Courtois," the discoverer of iodine. It was almost the first derivative of iodine made, and was described in the paper announcing the discovery of the element, read before the Institute, on November 29th, 1813.Courtois being too much occupied, as a chemical manufacturer, to take up the systematic investigation of iodine, this was undertaken, by Gay Lussac, and in his lnborat40ry and under his directioxj nitrogen iodide was first studied by Colin. Colin, adopting Gay Lussac's views, regarded i t as a substitution derivative of ammonia, of the formula NIs, and Gay Lusssc himself, in his great memoir o n iodine, expIains its formation on the assumption that it has t h b formula. Tho compound, about this time, was also investigated by Vauquelin and Davy, and their conclusions agree with that of * References to thc bibliography of the subject are collected nt the end of the pa; er.SO-CALLED ‘‘ KITROQEN IODIDE.” 1573 Gay Lussac.They both regard it as analogous to nitrogen chloride, that is, as ammonia in which all t,he hydrogen has been replaced by iodine. Mitscherlich, later, was led to assign t.0 it the formula NI from the observation that it and ammonium chloride were produced by the action of iodine trichloride on ammonia. Serullas, who next, studied it, concerned himself mainly with some of its reactions, and expressed no opinion as to its constitution. Soon after this, Millon, who observed that hydrochloric acid added to m excess of nitrogen iodide was nentralised, and Marchand who showed that the dry componnd, on explosion, yielded small quanti- ties of ammonium iodide, came independently to the conclusion t h a t it must contain hydrogen, and agree in considering the formula, NH21, as the most probable.Bineau, however, showed that this must be incorrect and that tho formula should rather be NH12, since in the compound the nitrogen and iodine were present in the ratio of one atom of nitrogen to two of iodine, He did this by decomposing the compound with hydrogen sulphide, and noting that two molecules of bydriodic acid were formed to one of ammonia. He also decomposed it by ammonium sulphite, and found the same ratio. Gladstone, some years afterwards, repeated Bineau’s observations, using, however, sulphurous acid in place of ammonium sulphite, and confirmed his results. Bunsen, about the same time, investigated the substance, adopting a slightly different method of analysis.He definitely states that nothing but iodide of nitrogen and ammonium iodide is formed in the action between ammonia and iodine, and that consequently nitrogen iodide must be a substitution derivative. From this and the result of his itn~lyses, he concludes that the black substance has the formula NH3N13, and that it is composed of a molecule OE ammonia with the whole of its hydrogen replaced by iodine, united with a molecule of unsubstitu ted ammocia. Bunsen, however, found that the composition varied with the mode of preparation, and believed that several allied suhstances of different compositions existed. Gladstone thereupon repeated his analyses, and still found one molecule of ammonia to two atoms of iodine among the decomposi- tion products of the substance.Schonbein, in a very interesting study of the reaction between ammonia solution and iodine, showed that Bunsen’s statement was incorrect, and that ammonium hypoiodite as well as ammonium iodide was formed in the reaction, and suggested that the formation of the black iodide depended on this. A11 the researches of this period, though differing in certain VOL. LXIX. 5 01574 CHATTAWAY : THE CONSTITUTION OF THE points, agree in regarding hydrogen as a constituent of the com- pound. A little later, Stahlschmidt, from the results of a few analyses, revived the statement that under certain circumstances the simple triiodide N13 could be formed, but he also obtained another product containing less iodine. He analysed products prepared in various ways from iodine and ammonia, and also found that the composition varied with differences in the mode of preparation.From his own and other previous analyses, he concluded that a series of compounds existed, each containing two pentad nitrogen atoms doubly linked together, that they were in fact substitution derivatives of a hypothetical substance, H3N:NH3, with the hydrogen more or less replaced by iodine in one or both rNH, groups. The substance has more recently been stndied by Guyard, Raschig, Szuhay, and Selimanoff. But few new facts have been brought forward by these observers, although all agree in assuming the exist- ence of a series of compounds ; they agree also in regarding all these as substitution products of ammonia, the last-named considering them to be amides of hypoiodous acid.Nitrogen iodide having always been looked on as a substitution product of ammonia, it seemed probable that a synthesis of hydrnzine derivatives might be effected by its agency, and a series of experi- ments was made with that object. These experiments, giving in every case a negative result, threw some doubt on the usually accepted views as to its constitution, and led to the present research. It is very remarkable that almost all coriclusions as t o the consti- tution of this substance have been drawn from the ratio between the arnounts of ammonia and of iodine that could be obtained from it, scarcely any attempt having been made to deduce its constitution from its reactions. The author therefore undertook the re-examination of the sub- stance, and has especially studied the various reactions in which it takes part.Owing to the extremely unstable nature of nitrogen iodide, i t cannot be obtained dry in a condition suitable for analysis, and on that account and f,i-om the fact that i t is not crystallisable, no cri- terion of its purity or constancy of composition is available. When dry, i t can hardly be manipulated a t all, exploding violently as it does at the slightest touch, and even when moist, it is very unstable. In certain conditions, it explodes violently on friction under water, and when wet and in the state of a thin pulp, the impact of a jet of water from a wash bottle is frequently sufficient to cause it to After some years, Mallet took up the investigation.SO-CALLED ‘: NITROGEN IODIDE.” 1573 detonate.As a consequence, all experiments with the substance have to be conducted on an unknown quantity and in presence of water, which frequently introduces complications. Nitrogen iodide, t o use the name by which it has long been known, is best prepared by pouring a coucentrated solution of iodine i n potassinn iodide into a strong solution of ammonia ; the substance is then precipitated as a soft, black powder, which is best washed first with a weak solution of ammonia, and finally rapidly with very cold water until the filtrate is no longer alkaline. These operations fihould be conducted entirely in the dark. Alcoholic solutions of iodine o r ammonia should be avoided alto- gether, as alcohol rapidly decomposes the compound, forming iodo- form, which is not easy to remove.The method of digesting finely powdered iodine with strong ammonia is also not a very suitable one, for the iodine being in particles of some size is not only slowly acted on, and iodine superficially coated thus with the iodide is diffi- cult to remove, but the product being more compact is very liable to explode on being touched, Any method, however, may be used and will give the same substance, provided sufficient precautions are taken to remove iodoform or any ammonia or iodine that may be in excess. As the substauce cannot be weighed, only the ratio between the nitrogen and the iodine in an unknown quantity can be determined, leaving the structure of the molecule to be decided by its various reactions. Several methods of analysis have been made use of in this research, the most convenient being based upon the decomposi- tion of the substance by a solution of sodium thiosulphate. When a solution of sodium tbiosnlphate acts on iodide of nitrogen suspended in water, all the iodine in the compound reacts as if it were free iodine, whilst all the nitrogen is liberated as ammonia.To obtain exact results, the solutions must be sufficiently dilute, and the decomposition must be conducted rapidly in a dark room. The operation is best carried out as follows: A small quantity of moist iodide of nitrogen is brought into a measured qnautity of a dilute solution of sodium thiosnlphate more than sufficient to decompose it, and shaken till black grains have entirely disappeared. The ammo- nia is then titrated with standard acid, and finally the excess of thio- sulphate is estimated by a standard solution of iodine.The results, if necessary, can be confirmed by distilling one part of the solution with iron alum, and d p h u r i c or hydrochloric acid, and another part with caustic potash, and estimating the iodine and ammonia liberated. In some cases, the compound has been decomposed by hydrogen sulphide or by sodium snlphite, and the iodine and ammonia distilled off as above anti estimated volumetrically. Many 5 0 21576 CHATTAWAY : THE CONSTITUTION OF THE specimens of the black substance, prepared in various ways, have been analysed, and always with the same result if adequate precau- tions have been taken to free theni completely from uncombined iodine and ammonia.The proportion between the ammonia and the iodine found is always very nearly that of one molecule of ammonia to two atoms of iodine. Practically, all previously published analyses have giren this ratio, or have found the proportion of iodine to be larger than this, only one observer having obtained a less pro- portion of iodine. The discrepancies, however, are very probably due to imperfectly washed or partially decomposed products having been used in the analyses. The substance retains some of the ammonia, in presence of which it is thrown down, with great persistence, and when this is removed, it is exceedingly unstable. I n presence of water, it decomposes very rapidly, especially on exposure to light; even diffused light very much accelerates the decomposition. It is only when the washing is carried just to the point when the filtrate is no longer alkaline t h a t the ratio of the nitrogen t o iodine is 1 : 2.If the washing be pushecl beyond this point, the compound begins at once to decompose, and this progresses continuously during the washing. When decomposi- tion begins, the wash water becomes slightly yellow, and the corn- pound acquires a strong odour of iodine. If a considerable quantity of the substance be subjected to sys- tematic washing for many hours, and if portions be removed at regular intervals and andysed, the ratio hetween the ammonia and iodine becomes progressidy less and lew, until after some days a small quantity of practically pure iodine alone remains. This appears to be a sufficient explanation of the variations of composi- tion observed ; they are probably due to a decomposition of greater or less extent having taken place during the treatment of the sub- stance after precipitation.Obvioasly any composition is possible, from that yielding one molecule of ammonia and two atoms of iodine, to pure iodine. At any stage of the operation, i f the iodine formed be removed, the undecomposed nitrogen iodide is found still to have its normal composition. This seems t o show that only a single compound really exists in which two atoms of iodine are associated! with one atom of nitrogen, and that the compounds of other com- positions which have been described are really admixtures of this with iodine. Nitrogen iodide has always been assumed to be a substitution derivative of ammonia, mainly on the ground that in its preparation from iodine and ammonia, :L large amount of ammonium iodide is formed, the amount being supposed to be proportional to the amounf.of nitrogen iodide produced. It has been frequently stated that it i,eSO-CA4LLED “ NITROGEN IODIDE.” 1577 the only other product, and equations hare been given representing its formation, thus : 4NH3 + 61 = NT3 + SNHJ. 3NH3 + 41 = NHIZ + ‘LNHJ. This fundamental statement is, however, incorrect. Ammonium iodide :is not the only other product of the reaction, nor are the amounts produced dependent on the amount of nitrogen iodide tbrown down, but depend on the dilution of the solutions, and on the conditions under which the precipitation is effected.When very dilute solutions of iodine and ammonia are mixed, they form a per- fectly clear liquid ; no nitrogen iodide is precipitated, but ammonium iodide and ammonium hypoiodite are formed, according t o the equation, and although the hgpoiodite is unstable, the iodine used can nearly all be set free again by the addition of excess of acid. I f somewhat stronger solutions are mixed, a slight precipitation of nitrogen iodide takes place, and the amount formed increases with the concentration of the solutions, up to a certain point, propor- tionally decreasing amounts of ammonium iodide and hypoiodite being produced. The amounts of the various products are affected, however, very noticeably by the conditions under which the solutions are brought together ; solutions which will give a copious precipitate of nitrogen iodide if the solution of iodine in potassium iodide be added t o the ammonia, fail to give any turbidity when the ammonia is added to the iodine.Further, as each drop of iodine solntion falls into the ammonia, an immediate local precipitation of nitrogen iodide takes place; this, however, at first disappears on shaking, not being permanent until a certain amount of iodine has been added, These effects are due to the presence of water, potassium iodide, and ammonia, all of which are able to decompose the nitrogen iodide. The amount of hypoiodite found after the nitrogen iodide has been precipitated is seldom equivalent in amount t o the ammonium iodide, as it seems to decompose some of*the nitrogen iodide with liberation of nitrogen.This behaviour indicates that the compound may not be a substitution product of ammonia at all. If it were a substitu- tion product, whatever its formula, the nitrogen iodide produced cmld never contain more than half the total quantity of iodine used, as the remaining half would form hydriodic acid, which would com- bine with the excess of ammonia present, according to the equation, 2NH4*OH + 1, = NHdI + NHJO + HZO, (X + i)NH, + 221 = NHS-ZT, + zNHJ. Now, even using a compwatively weak solution of iodine, for example, a decinormal solution, considerably more than half the1578 CHATTAWAT : THE CONSTITUTION OF THE iodine employed can be obtained, under proper conditions, i n the nitrogen iodide precipitated. The yield depends to a large extent on the iodine being dissolved in the least possible quantity of potassinm iodide, and on the solution being rapidly mixed with t,he ammonia, and, up to a certain point, is increased by using an excess of very strong nmmonia.This, again, seems to show that the black explosive compound cannot be a substitution product. If nitrogen iodide were a substitution derivative of ammonia, one would expect to be able by suitable reagents to replace the iodine by other groups, no such replacement, however, has ever been observed. One would expect, for example, t o be able to replace the iodine by hydroxyl by the action of water or caustic alkalis, or moist oxides of silver or lead, obtaining NH2*OH, NH( OH),, N(OH),, or products formed from these by loss of water, according as one, two, or three of the hydrogen atoms were replaced.No hydroxylamine, hyponitrous acid, or nitrous acid has ever been detected among the products of such reactions, indeed, they follow an entirely different, coume. This seems the more convincing, because nitrogen chloride, which on many grounds must be regarded as having the formula NCI,, always yields nitric acid in such reactions. Further, iodine only substitutes with extraordinary difficulty, if at all, and yet here we have an almost instantaneous substitution, and in a group into which iodine is not known otherwise to enter, For example, iodine does not substitute in the NH, group, either in aniline, or urea, or hydroxylamine, although all are basic. The conclusion is again strengthened by the difference in be- haviour of the two elements, chlorine and iodine, towards ammonia and ammonium compounds.Xitrogen chloride is only formed when chlorine acts on an ammonium s a l t ; as long as free ammonia is present, nitrogen is liberated. On the other hand, iodine forms nitrogen iodide only in the presence of free ammonia, and it has no substituting action on any ammonium salt, even in presence of iodic acid. Again, one would hardly expect ammonium iodide to be formed as one of the products of its detonation if it were a, substitution pro- duct. Also, if the compound N13, which has often been supposed t o exist, were possible, one would expect it to be formed when a solution of potassium iodide acts on nitrogen chloride. Actually no such compound is formed, but nitrogen is evolved, and iodine liber- ated.Some of the strongest arguments in favour of the view that it is not a substitution product, are found i n the reactions of the com- pound, which do not admit of any simple explanation on the theory - A number of other facts support this conclusion.SO-CALLET) “ NITROGEN IODIDE.” 1579 of substitution. Whenerer the substance is decomposed, ammonia and iodine ase always liberated. According to the conditions of the reaction, these may be free, or partially combined, or they may react with the agent effecting the decomposition. This seems to show that the substance may really be formed by the direct union OE ninnionia and iodine, and considering the ratio found between the ammonia and iodine, that it may be iodo-ammonium iodide, NH312.* This view of its constitution not only agrees with its composition and modes of formation, but gives the simplest explanation possible o f its entire chemical behaviour.The decomposition of the sub- stance by water is very characteristic. Tf it be placed in a large quantity of water, light being excluded, it slowly disappears, forming a clear brown solution containing free iodine. If to this solution an excess of acid be added, a further quantity of iodine is liberated approximately equal in amount to that already free in the liquid. If, however, light be admitted, the decomposition is much more rapid, and nitrogen is evolved, the rapidity of its evolution being determined by the intensity of the light ; somewhat more iodine is then set free in the liquid, but on adding an acid the further amount liberated is not so great.These actions seem best explained thus. The iodo-ammonium iodide reacts slowly with water, liberating iodine, and forming ammonium iodide and ammonium hypoiodite, half the total amount of iodine present in the compound being set free. 2NH3Tz + H2O = NHII + NHAIO + 1 2 . On the addition of acid, the hydriodic and hypoiodous acids formed immediately react, liberating a second portion of iodine, equal in amount to that a t first set free. NHdI + NHAIO + 2HCl = 2NHiCl + H I + HIO. HI + HI0 = HzO + 1 2 . If light be admitted, some of the compound decomposes, formirlg ammonium iodide, setting nitrogen and iodine free. 8NH3TZ = 6NHJ + Nz + 512. The hypoiodite formed at first, however, really seems to oxidise some of the undecomposed compound.* Guthie (J. Chem. SOC., 1863,16, 239) assigns this formula to a liquid obtained by adding finely powdered iodine to a saturated solution of some easily soluble ammonium salt, pal-tially decomposed by about one- third of the equivalent quan- tity of caustic potash. Neither the mode of purification nor the analytical results, however, justify the assumption that a single pure substance is thus obtained, A similar liquefaction of iodine is noticed when the solid is added to a solution already containing free iodine and free ammonia, obtained by heating the black explosivo compound with strong aqueous ammonia.1580 CHATTAWAT : THE CONSTITUTION OF THE This decomposition by water may be the action by which the ammonium iodide and hgpoiodite are obtained in the preparation of the compound.This is rendered probable by the rapid disappearance, on standing or shaking, of the black compound first produced when a dilute solution of iodine is added t o a dilute solution of ammonia. It also explains the decomposition of the substance by prolonged washing, and the accompanying accumulation of iodine in the residue ; the ammonium iotiide and hypoiodite formed can dissolve a little of the liberated iodine, and therefore the wash water is always some- what yellow, b u t some of the iodine produced cannot thus be taken into solution, and cousequcntIy remains adhering to the undecom- posed compound ; the percentage o l iodine in the residue, therefoi*e, continually increases, and ultimately o n l j a smaIl quantity of prac- tically pure iodine is left.A solution of potassium iodide appears to decompose the black iodide very readily ; this, however, is only apparent ; it has no action on it other than fncilitaking the action of water by dissolving the iodine as it is formed, so that the decomposition is much more rapid and legs water is required. A solution of ammonia of moderate strength seems to render t.he compound somewhat more stable, but if the solution be very dilute, or, on the other hand, if a very large excess be present, the decom- position is still rapid, the liberated iodine forming with the ammo- nium hydrate, ammonium hypoiodite, and ammonium iodide. NHJ, + NH40H = NHJ + NHJO. The hydrates of sodium and potassium very rapidly decompose the compound, libcrating ammonia and forming iodide and hypo- iodite, or, if the solution be heated, iodide and iodate.The oxides of lead and silver in presence of water similarly decom- pose the substance on standing 01. warming, setting ammonia free, and forming iodide and iodate of the met'al. Finely divided metals, such as silver, copper, or zinc, suspended together with the compound in water, assist the action of the water by combining with the liberated iodine, a further action sometimes taking pIace between the ammonium hypoiodite and the iodide of the metal. The action of acids, generally speaking, appears to be to decom- pose the compound, setting the iodine free and combining with the ammonia ; thus, sulphuric acid and hydriodic acid liberate iodine, and form ammonium sulphate and ammonium iodide.2NH3Tz + HZSO, = (NH,)zSO, + 21,. NHJz -+ HI = NHJ + I,. The action of hydrochloric acid is, however, peculiar; the sub-SO-CALLED ‘‘ NITROGEN IODIDE.” 1581 stance dissolves, giving a pale yellow solution, which appears to con- tain only ammonium iodide and iodine chloride ; no iodine is set free at first, although, on stacding, the colour of the soliition deepens, and the free element makes its appearance. If excess of potassium iodide be added, iodine is at once set frec. It appears at first sight unlikely that iodine chloride and ammonium iodide should exist together in solution ; it may, however, be that a combination with the iodine of the ammonium iodide really takes place, and that we have in solution a compound, NH41<C1, similar to that formed by chlorine with iodo- 1 c1 benzene, CsH51<C1.This is not, however, absolutely necessary, for in the course of the research many instances have been met with of uncombined substances existing together in solutioii which are able to react at once if an excess of one or the other is present. Thus, iodine can exist under certain circumstances in presence of a very large excess of ammonia, and it can also exist as iodine in the presence of a very considerable excess of caustic soda or potash. The black explosive compounii is at once acted on by all substances capable of reacting with iodine, for instance, when hydrogen sul- phide is passed through water containing i t in suspension, it is rapidly decomposed, sulphur being deposited, and the solution becoming strongly acid, whilst ammonium iodide and hydriodic acid are formeci. Sulphurous acid and snlphites also readily decompose it, a sulphate and an iodide or hydriodic acid being formed.In all decompositions, however, which take place in presence of an acid, or in which an acid is formed, a further and more complicated action appears also to take place. Sodium tliiosulphate very readily reacts with the compound, liberating ammonia, and forming sodium iodide and sodium tetra- thionate. This reaction under proper conditions affords a ready method of analysis. If the compound be suspended in water containing arsenites in solution, they are oxidised to arsenates, hydriodic acid and ammonia being formed.Alka.line solutions of antimony trioxide also decom- pose the compound, antimony pentoxide and hydriodic acid being formed. Pot,assium cyanide in solution also at, once decomposes the sub- stance, ammonia being liberated, and potassium iodide and cyanogen iodide formed. It is very necessary to note that most of these reactions are not quantitative. The substance is so very un~table that results which differ considerably are obtained when working under apparently1582 CONSTITUTION OF THE SO-CALLED “ NITROGEN IODIDE.” similar conditions. Some approach near to the equations required by the formula NHJ, ; others, again, agree better with the assump- tion that the compouiid is a substitution derivative. I f that mere tbe case, howerer, the reactions would not be so simple, and watev mould have to be assumed to take part in every reaction. Certain facts, too, seem to shorn that this introduction of water into the equations is inadmissible.For example, if water be assumed to take part in the reaction with sodium thiosulphate, it must be expressed thus : NHT, + H,O + 4Na,S,O, = NH, + 2NaOH + 2NaI + 2Na,S40,. This would explain the decomposition of the substance and the pro- duction of an1 monin, sodium iodide, and sodium tetrathionate. Bn t in this case the solution would bc alkaline after distilling off t h e animonia, whilst actual17 it is always found to be neutral 01- slightly acid, and the amount of alkali indicated by direct titration is obtained as ammonia on distillation with potash. It appears more probable that the variations froin theory are due to the peculiar chemical behcviour of iodine. If the substance be regarded as ail additive product, the manner of its formation wit,!i liberation of ammonia, when a solution of calcium hypochlorite acts on ammonium iodide, is clear ; the calcium hypochlorite oxidises some of the hydriodic acid corn bined with the ammonia, liberating iodine which is able to combine with half of the ammonia present to form the csplosive substance, leaving the other half free.o c 1 4NH4T + Ca<OC1 = ZNH, + BNHJ, + CaCl, + ZH,O. The action described by Willgerodt, where nitrogen iodide sus- pended in water is used as an agent to substitute iodine in various phenols, can also be explained. I n presence of the water used, a hypoiodite is produced, which is almost certainly the active agent in the substitution.That this is so is shown by the work of Messingel- and Vortmann (Ber., 1889, 22, 2314), who obtained a similar sub- stitution in phenols by using a solution of iodine in caustic alkali. Here, again, hypoiodite is formed, and the action in both cases is probably analogous to the well known substituting action of hypo- chlori tes. The view brought forward as to the constitution of the explosive compound receives considerable support from the fact recently observed by Remsen and Norris (Amer. Chem. J., 1896, 18, go), that, with iodine, trimethylamiue yields an additive product, N(CH3)3Tc, which can be weighed and analysed, and which resemb!es the ammonia compound in many of its reactions.POSITION-ISOMERISM AND OPTICAL ACTIVITY. I583 On the whole, therefore, i t seems that only one compound is formed by the action of animonia on iodine, and that in this, one atom of nitrogen is associated with two atoms of iodine. Whether the simplest molecular formula that can be given to the substance must be NH,T, or NHI, can only be finally settled by a prolonged and careful inves- tigation of all its reactions under the most varied conditions ; but a t present the formula NHJ, seems best to accord with the reactions of the compound as a whole, and best to group all the known facts regarding it. A further investigation of the reactions of the com- pound is proceeding. Appended is a list of previous researches on the subject. Courtois, Ann. de Chimie, 1813, 88, 304; Vauquelin, ihid., 1814, 90, 230; Gas- Lussac, ibid., 1814, 91, 5 ; Colin, Ann. de Chimie, 1814, 91, 252; Davy, Aun. ae Chimie, 92, 89, and Tram. Roy. SOC., 1814, 86; Serullae, An?&. Chim. Phys., 1825, [2], 22, 172, and 1829, 42, 200 ; Mitschcrlioh, Gmelin’s Chemistry, rol. 2, 465; Andre, Jozwn. Pharm., 1836, 22, 13’7 j Millon, Ann. China. P?&ys., 1838, [ S ] , 69, 78; Marchand, J. p r . Chem., 1840, 19, 1; Bineau, Ann. Chim. Phys., 1838 [ 2 ] , 67,226, and 1845, [3], 15,51; Bunsen, Annalen, 1852,84,1; Gladstone, Chem. Soc J., 1852, 4, 34, and 1853, 7, 51 ; Schonbein, J. pr. Chem., 1861, 84, 385; Stahl- Schmidt, Ann. Phys. Chent., 1863, 29, 421 j Champion et Pellet, Bull. Soc. Chim., 1875, [2], 24, 447; Mallet, Amer. Chem. J., 1879-1880, 1, 4; Guyard, Compf. rend., 1883, 97, 536, and Ann. Chim. Phys., 1884 [S], 1, 358; Raschig, Aianalen, 1885, 230, 212 ; Willgerodt, J . pi-. Chem., 1888,145, 446; Szuhay, Ber., 1893,26, 1933 ; Seliwanom, Ber., 1894, 27, 1012.

ISSN:0368-1645    

DOI:10.1039/CT8966901572

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

POSITION-ISOMERISM AND OPTICAL ACTIVITY. I583 CV.--Positioiz-isomerisrrL and Optical Activity ; the Comparative Rotatoy P o i v e u 9 f the Dibenxoyl and Ditoluyltnrtru t es. By PERCY FRANKLAND, Ph.D ., F.R.S., and FREDERICK MAr,coLw mTHARTON, A.1.c. WE hare recently shown (Trans., 1896, 1309) that the rotatory effect of the para-toluyl radicle is greater than that of the meta-, and this, again, greater than that of the ortho-toluyl grouping; and we have also pointed out that this relationship is in harmony with the relative position of the centre of gravity in these sereral groups ; for, assum- ing that the centre of gravity of the benzene ring is the geometrical centre of a regular hexagon, it is obvious that in the ortho-arrange- ment of the tolnyl group the centre of gravity is somewhat nearer,, in the meta-arrangement somewhat further, and, in the para-arrange- mcnt, still further than that geometrical centre from the carbon atom (the carbonyl carbon), by means of which the ring is attached to the asymmetric carbon atom of the tartaric acid.1584 FRANKLAND AND WHARTON : Thus, in Fig.1, with the CH3 group in the ortho-position relatively to the CO group, the centre of gravity of the toluene ring would be at g', with the CH3 group in the nieta-position i t would be at g", and, with the CH3 group i n the para-position it would be a$ gttr. Now, the moment ofthe mass of the toluene group around CH3(0) the carbonyl carbon atom will obviously be greatest when the centre of gravity i s at g"', and least when i t is at 9'. If, then, the op- tical activity is affected by the moment of this mass, the rotatory power of the para-toluyl compound should be the greatest, that of the ortho-toluyl compound the least, and that of the meta-toluyl compound intermediate between those of the other two.This rela- tionship was, indeed, shown to hold good in the case of the methyl aiid ethyl salts of ortho-, meta-, and para-ditolayltartaric acid. The question naturally arises as t o how the rotation of these tolujl compounds will be related to the correspondiiig benzoyl deri- vatives, I n the latter we have a smaller mass (by CH,) ; but this mass, which has its centre of gravity practically coincident with the geometrical centre of the hexagon, acts through a longer arm than in the case of the larger mass of the ortho-toluyl arrangement, and through a shorter arm than in either the meta- or para-toluyl arrangements.In order to institute this comparison, the rotatory power of methylic and ethylic dibenzoyl tartrates was required. Both of these com- pounds have already been prepared (Pictet, Guge aAnd Fayollat, Freundler ; Thesis, Paris, 1894), but in both cases their rotation had only been determined in solution, and the results were, therefore, of no value for the purpose we had i n view. We have, consequently, prepared both of these substances again, and have determined their rotation over a wide range of temperature, i n the liquid 01' superfused state, for comparison with the rotation of the methylic and ethylic ditoluyltartrates recently described by us.Preparation of Meth ylic Dibenzoy1tart~ate.-Fifteen grams of pure FIQ. 1. co I CH3(m)POSITION-ISOMERIShf AND OPTICAL ACTIVITY. 158 3 methylic tartrate (obtained by the hydrochloric acid method) were run from a dropping funnel into 38 grams of benzoic chloride heated to 1 4 5 O , the temperature being gradually raised to 180'. When the evolution of hydrogen chloride had ceased, the excess of benzoic chloride was distilled off under reduced pressure, the ethereal salt subsequently passing over at 275-282' (about 1'3 mm. pressure) ; 21 grams were obtainel which crystallised immediately on cooling. The substance was repeatedly recrystallised from methylated spirit until of constant, melting point; it is but very slightly soluble irt this solvent, and is obtained as long needles melting at 135.5'.On combustion, the following results were obtained. 0.2004 gave 0.4561 COz and 0.0855 H20. The density taken at 150' and at 160°, was C = 62.07 ; H = 4.74. C20H1808 requires C = 62.18 ; H = 4-66 per cent. ai500/4~ = 1 . 1 ' ~ ~ . d160°/4' = 1.1191, from which, by extra- and in tra-polation, were calculated d 100°/4" = 1.1755. d 137'/4' = 1.1407. d 183"/4' = 1.0975. and, at these latter temperatures, the rotation was determined with the following results : Eotat ion of Methy lic Di benzoy ltartrnte. (Length of polarimeter tube in each case was 44 mm.). Preparation of Ethylic Dibenzoy1tartrate.-The method pursued was the same as that described above for the methyl compound; after distilling off the excess of benzoic chloride, the ethereal salt passed over at 270-280' (about 10 mm.pressure). The distillate did not solidify, nor could crystallisation be induced by employing the most varied solvents ; it was, therefore, redistilled, 2nd washed in ethereal solution with sodium carbonate, after which, on standing for about * [FJD is the rotation constant which Guye ha3 introduced under the name of " niolecular deviation " ; it is calculated from the formula a = observed rotation; E = length of tube; M = molecular weight; d = density. Repeated reference has been made to this constant by one of us in previous papers.1586 FRANKLAND AND WHARTON : t,hree weeks in the vacuum desiccator, crystah began to appear, and then, on stirring, the whole cryst,allised. The solid was subsequently purified by repeated recry stallisation from methylated spirit until of constant melting point, 62.5'.03618 gave 0.8437 CO, and 0.1772 H20. C = 63.60 ; H = 5.44. 0.1958 ,, 0.4571 ,, ,, 0.0957 ,, C = 63.67; H = 3.43. C2,H2,08 requires C = 63.77 ; H = 5.31 per cent. The density was determined at 70', 90°, loo', and 136*5O, d 70°,/40 = 1,1537, d 9Oo/4O = 1,1368, d 100'/4' = 1.1280, d 136*5'/4O = 1.0970, from which by extra- and intra-polation were calculated : d 1*3'/4O = 1.2122. d 18'/4' = 1.1979. d 38'14' = 1.1809. d 4!a0/4' = 1.1758. d 53.5°/40 = 1.1677. d 60'/4' = 1.1622. d 77*5"/4' = 1,1472. d 109.5'/4' = 1.1199. d 18S~5°/40 = 10571. and at these temperatures the rotation was determined, with the following results : Rotation of Ethylic Dibeitzoylta?-trate. (Length of polarimeter tube in each case was 44 mm.). -30.06° - A t 1.3' [a,]= = - - -56.36'; [S], = -477.5, 0.44 x 1.2121 -31.29' - - -59.36 - 61.70 - At 18.0 ,, - At 38.0 ,, - At 44.0 ,, - At 535 ,, - 0.44 x 1.1979 0.44 x 1.18- - U.44 x 1.1758 0.44 x l.lm7 - 0.4h x 1.1622 - 0.44 x 1.1472 - - -3206' - -32.10' - - -G2*@5 - - -32*000 - -62.28 At 60.0 ,, - -31*850 - -63.28 - 62.15 - -31.37' - At 77.5 ,, - At 100.0 ,, - -60.77 - -30.16' - 0.M x 1.1280 - - -29.51" - 0.44 x 1.1199 - -27.38' - 0.44 x 1.09iO - At 109.5 ,, - - -59.89 - 56.i2 At 136.5 ,, - A t 182.5 ,, - -24.03' - - -51.G6 - 0-44 x 1.0571 - ,, - -4499.0, - ,, - -514.0.- ,, - -515.0. - ,, - -514.5. - 5130. - Y 2 - -- ,, - -507.0. - ,, - -490.5. - ), - -481.0. - ,, - -4500. ,, = -3399.5.POSITION-ISOMERISM AND OPTICAL ACTIVITY.1587 This is a very remarkable series of rotations, exhibiting, as it does, a phenomenon which, as far as me are aware, has not hitherto been observed, namely, the passage through a maximum in the chaltge of rotation, brought about by change of temperatwe, or, in other words, the occurrence of a change in the s i g n of the seizsitivelzess of the rotation to the temperature, Thus, from the above figures it mill be seen that the greatest observed rot ation was attained between the temperatures of 38" and 53*5", whilst the maximum specific rotation was reached and remained practically constant between 53.5' and 77.5' ; again, the maximum molecular deviation is found, and remains practically constant between 38" and 60'. It is noticesble that this maximum rotation occurs in the vicinity of the melting point of the substance, namely, 62.5'.Indeed, from the figures and curves given in our recent communication on the inethylic and ethylic ditoluyltartrates, and which are reproduced below, it will be seen that in those case3 in which we examined the rotation of these compounds in the super- fused state, the sensitiveness of the rotation to temperature had a tendency to change io the vicinity of and below the temperature of fusion ; in fact, in the cage of the methylic orthoditoluyltartrate there was some evidence of a maximum rotation, although not nearly so pronounced as in the case of this ethylic dibenzoyltartrate. Thinking that possibly the above results might be due to the ethylic dibenzoyltnrtrate possessiiig an abnormal density in a state of superfusion, and as the densities employed in the above calcula- tions for specific rotsation at temperatures below the melting point had all been arrived at by extrapolation, we subsequently made the following direct determinations of the density in the superf used state : By experiment.By extrapolat,ion. d42*0'/4' = 1.1751 1.1 775 d 535'/4' = 1.1658 1.1677 d 59*0'/4' = 1.1602 1.1630 These differences, however, produce so little eifect on the specific rotation that the recalculation of the specific rotations on the basis of these direct density determinations is quite unnecessary, and the attainment of the maximum rotation referred to above is not influ- enced thereby, thus : Using extrapo!ated Using direct density density.determination. [a],, at 44.0' = -62.05' - 62.1 5'" ,, ,, 53.5 = -62.28 -62.38 ,, ,, 60.0 = -62.28 -62.44 In the following diagram we have, f o r comparison, graphically represented the sensiti-ceness to temperature of the specific rotation1558 FRANKLAND AND WHARTON : will be seen tbat the specific rotation of the methylic dibenzoyltar- trate is markedy greater than that of the methylio orthoditoluyl- tartrate for the same temperatures, and similarly the ethylicPOSITION-ISOMERISM AND OPTICAL ACTIVITY. 158 9 dibenzoyltarbrate has a greater specific rotation than the ethyltc orthoditoluyltai-trate, excepting at those lower temperatures at which t'he rotation of the ethylic dibenzoyltartrate becomes abnormal in the sense indicated above. In order to ascertain whether the same relationship between the several compounds i n question is maintained when the rotation pro- duced by an equal number OF moleciiles of each is submitted to com- parison, we have also calculated the " molecular deviation " (see note, p.1585) for the six ditolnyltartrates. Thus, using the formula MoleculaT Deriation of Methylic Ortho-ditolu~ltartrate. = -dm - -668.0. -42.30' 414 - At 12.0" At 19.0 ,, ____ 414 - At 33.5 ,, .- --G53.5. At 54.5 ,, = -625.0. At 100.0 ,, -- - -34.470dz = -557.0. 0.4 4 At 100.0 ,, - - - -0.44-dm 34.55' 414 = -558.0. At 136.0 ,, - - ___- --30*13*d= - - -492.0. - -4495.0. 0.44 424 - - At 137.0 ,, - At 1830 ,, - Td& -24.89' = -412.0. Molecular Deriation of Ethylic Ortho-diioluyltartrate. VOL. LXIX. 5 P1590 FRANKLAND AND WHARTON : - 30.30" drnSrn 442 = -500.At 48-49.5' [a], = - 0-44 At 70.0 ,7 At 100.0 ), -26.7 7" - -405. - 24.01' Molecular Deviation of Slethglic ~~eta-ditolzL?lltartrnte. -39~62~ 414 - - 34.44" At loo'oo [ 6 ] ~ = - - = -564.0. At 136.0 ,, At 183.0 ,) - rd m2 - -475.0. Molecular Deztiation of Ethylic nleta-ditolu yltartrate. - 583.5. -~ - -28.68' 414 - _- -35.43O 448 - At 20.5" [ = ~4 m7 - At 24.5 ,) - 379.0. - -34.75" 3/ 442 - -575.5, At 44-5 ,, - ~ - 34.54" At 50.0 ,, - - o.44.- 0.44 2. FlFO - dgi = -573.0. 442 c -522.0, -- At 100.0 ,, - =d& -30.76' = -516.0. At 136.0 ,, - =dm -27.5f" 442 = -467.0. Xolecula~ Der id ion of Met h y 1 ic Para- dito I 169 I f (1 r t ra t e . - 51.57" At 100.0" [a], = -~ - 44.68O 414 - At 135-5 ,, - .~ = - i 3 1 .0.44 2 1.1095 At 153.0 ,, - - -mdFoB7 -36.16" 4 14 = -599.POSITION-ISOMERISM AND OPTICAL ACTIVITY. 1591 A. Methylic para-ditoluyltartrate. ,, meta- ), ,, ortho-ditoluyltartrate. 7, d i benaoy 1 tartrate. Ilfolecular Deviation of Ethylic Pam-ditoluyltart,rate. B. E thylic para-ditoluyl t str trate. ), meta- 9 9 ,) dibenzoyltartrate. ,, ortho-ditoluyltartrate. Xethylic Dibenzoyltartrate. At 100 '0' [MID = - 280 '1" At 137.0 ) ) = -258 '0 At 183.0 ,) = -227.5 Eth.yZic DibenzoyItarlmte. At 1'3" [bl], = -233.3" At 18.0 )) = -245'7 At 38.0 ,) = - 2 j j . 4 At 4 . 0 ) ) =- --256 '9 At 53.5 ), = -257'8 At 60.0 ), = -257'8 At 77.5 ) ) = -257.3 At 100'0 ), = -251 *G At 109.5 ,, = -247.9 At 136.5 ,) = -234.8 At 182.5 )) = -213'9 2fethyZic 3-Ditoluyltart?-ate. At 12-Oo[M]D = -32'3'2O At 33.5 ,) 2 -318'8 At 54.5 ), = -30'7 '3 Ati 70'0 ), -- --298 -2 At 19.0 ,, = -324'7 At100.O ,, = -2281.6 A t 100.0 ) ? = -282.3 At 136.0 ,) = -253.7 At 137'0 ), = -255.6 At 183'0 ) ) = -218.4 Ethylic o - DitoLuyEtart,rate.At At 30.0 ), = -266'7 At 48-49 '5 ,) = -263 *1 At 70.0 .) = -256.2 At 100'0 ,, = -241.9 At 135'0 ,, = -222.6 11 *O" [MID = -266.8" Methylic p-Bitoluyltartrate. At 100'0" [MID = -425 *7" At 135'0 )) = -378.9 At 183.0 ) ) = -318.4 Ethylic p-Ditoluyltartyate. At 100'0" [nix]D = -39'7.7" At 137'0 ,) = -3360.0 At 183'5 ), = --307'2 5 P S15 92 POSITION-ISOMERISM AND OPTICAL ACTIVITP. Methylic m- Ditolzcyltavtrate. I Ethylic m- DitoZuyZtartrate. At 100'0" [MID = -327.1' At 136.0 ,, = -292'2 At 183.0 ,, = -252.4 At 20'5' [MID = -306'4° At 24-5 ,, - -304.4 At 44.5 ,, = -305.7 At 50'0 , l = -305.0 At 39.5 , l = -284.6 At 100'0 ,, = -281.7 At 136'0 ,, = -259.5 - These figures show that the relationship between the molecular rotations of the dibenzoyl- and o-ditoluyltartrates is somewhat more complex than in the case of the specific rotations and the moleculai- deviations.Thus, at high temperatures, the molecular rotation of the methylic and ethylic dibenzoyltartrates is markedly greater than that of the corresponding o-ditoluyltartrates, whilst a t low tempera- tures the latter compounds have the higher rotation. This relation- ship is best observed by means of the accompanying diagram, from which it will be seen that above 1 0 8 O , the methylic dibenzoyltartrate has a greater molecular rotation than the met,hylic orthoditoluylfar- trate, and that above 62' the ethylic dibenzoyltartrate has a greater molecular rotation than the ethylic orthoditoluyltartrate ; now the methylic dibenzoyltartrate melts a t 135*5', and the cthylic dibenzoyl- tartrate at 62*5", so that it is in both cases at temperatures below their melting points that they exhibit a molecular rotation inferior to that of the corresponding ortho-ditoluyl compounds.But it is just below the melting point that we should expect to find, and in some of the cases referred to we have actually found, abnormal rotations occurring. These results furnish, therefore, an answer to the question raised at the beginning of this paper, showing, as they do, that the smaller mass present in the benzoyl compound, but with the more distant centre of gravity, and acting, therefore, through a longer arm, has, in this particular case, a greater rotatory effect than the larger mass present in the ortho-toluyl compound with its centre of gravity nearer to the carbonyl carbon atom, by means of which, in each of these componnds, the groups in question are attached to the asym- metric atom of carbon. The result is, moreover, the same, whether we measure t.he " rotatory effect " by specific rotation, by molecular deviation, or by molecular rotation, provided that the comparisons are only made at temperatures above the melting points of the com- pounds in question. Mason College, B iwniningh am.PIG. 3.-Influence of Temperature on the Molecular Rotation of Methylic and Ethylic Diberlzoyltartrates and Ortho-, Meta-, and Para-ditoluyltartrates. Temperature. X.B.-The diagram also indimtee the melting points in t,he eltees of those compounds known in the solid &ate ; t,liose only known 38 liquids are marked “ liquid.”

ISSN:0368-1645    

DOI:10.1039/CT8966901583

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

1593 CV1.--Thiocarbimides derived f?.orn Complex Ehlt y Acids, By AuGusrrus EDWARD DIXON, M.D. OUR acquaintance with the fatty acidic thiocarbimides is at present limited to those derived from acids relatively poor in carbon, the highest member of this class hitherto obtained being a raleryl com- pound, CaH9*CO*NCS (Dixon, Trans., 1895, 67, 1040). The lead tbiocyanete process already described for preparing these and allied substances is apparently generic ; it seemed, therefore, of interest to endeavour t o apply it to some of the higher terms of the fatty acid series, and experiments were accordingly carried out in this direc- tion. The results obtained form the subject of the present commu- nication. The process above referred to consists in heating, in a reflux apparatus, the corresponding acid chloride and dry lead thiocyanate, with anhydrous benzene, to the boiling point of the mixture; occa- sionally toluene is preferable, and sometimes even cumene, on account of the higher temperature thereby attainable ; the presence of a solvent is generally essential, for, in its absence, the acid chlor- ide often fails to completely moisten the thiocyanate ; moreover, in some cases, violent action occurs, accompanicd by charring of the materials, if they be heated together without a diluent.Using charges of 20 to 30 grams of chloride, and 50 to 60 C.C. of benzene, with 1& times the theoretical quantity of finely divided lead salt (preferably mixed with about its own weight of dry sand), and keeping the contents of the flask in constant motion, 10 to 15 minutes’ heating, as a rule, is sufficient ; interaction is complete when, after allowing the solid products to completely subside, the clear super- natant liquid no longer affords a green flame coloration, when used to moisten a fragment of copper oxide.Occasionally it prores difficult to obtain a solution free from chlorine; if this end is not attained within 30 minutes, it is generally best to filter a t once through dry paper, by aid of the pump, mix the filtrate (including washings) with a little fresh thiocpanate, and boil up again. As soon as the inter- action is a t an end, the mixture is filtered, well washed with dry benzene, and the filtrate diluted further with the same solvent, so that each litre contains 1 gram-molecule of product; if pure materials are employed and moisture carefully excluded, the yield of dissolved thiocarbiniide is, in most cases, practically quantitative.If possible, the solut,ions should be used without delay; they are apt to decompose on keeping f o r a few days, or it may be, hours, with1594 DIXON : THIOCARBIMIDES DERIVED FROM formation of brownish, insoluble amorphous solids-polymeric forms, very likely, of the thiocarbimides. Unfortunately, no really satisfactory method has yet been found of isolating the dissolved products ; steam distillation is out of the question, as they are all readily attacked by water ; some of them do not distil unchanged under diminished pressure, and even if they do, there is generally heavy loss, owing to the substance being freely carried over with the vapour of the solvent.I. PALMITYLTHIOCARBIMIDE, C15H31*CO*NCS, AND ITS DERIVATIVES. Pure palmitic acid, melting a t 61°, was treated with phosphorus pentachloride, as prescribed by Krafft and Burger (Rer., 1884, 17, 1379) ; the organic chloride, on further treatment with lead thio- cyanate, afforded a yellowish solution of the corresponding thiocarb- imide, the yield of the latter being nearly quantitative, When shaken up with cold water, the solution gave, on the addi- tion of ferric chloride, a distinct red coloration ; if previously boiled with water, the tliiocyanic reaction so obtainable was greatly intensified. C15H3,*CO*NCS + H,O = C15H31*COOH + HSCN. But the dissolved substance is, nevertheless, a thiocarbimide, or, at least, can act as such, for the solution, when mixed with alkaline lead tartrate, is copiously desulphurised on boiling ; ammoniacal nitrate of silver, when added to the alcoholic mixture, affords a curdy white precipitate, which readily blackens on warming ; and, more- over, on treatment with organic bases, union occurs directly, with evolution of heat and production of the corresponding substituted thioureas.Unless, therefore, this compound and its congeners are to be regarded as tautomeric, in the sense of being capable o f acting either as thiocyanate or thiocarbimide, according to the conditions under which they are placed, there seems to be only one way of satisfactorily accounting for the production of thiocyaaic acid, namely, that hydrogen thiocarbimide is initially formed, together with an acid, R*CO*NCS + HZO = R*CO*OH + H*N:C:S, but thereupon undergoes, more or less rapidly, metameric rearrange- ment into the more stable configuration, H*S*CiN. The suggestion here made has already been mentioned in a former paper (Dixon and Doran, Trans., 1895, 67, 5 i 5 ) ; I hope later on ti? investigate the phenomena more fully, particularly with a view to obtain, if possible, the hypothetical intermediate product, H-NCS.In preparing the addition compounds described below, the freshCOMPLEX FATTY ACIDS. 1595 benzene solution was employed ; when cold, it is practically devoid of odour, save that of benzene, but i f heated, ft slight acid thiocarb- imidic smell becomes perceptible ; on exposure to ordinary moist air, it slowly decomposes, owing to hydration, crystals of palmitic acid being deposited.Isolation of the Thiocarbi?wide.-In order to completely expel the solvent, a benzene solution, obtained from 25.6 grams of palmitic acid, was heated to 150' in an oil bath at 12 mm. pressure; on cool- ing, and ullowing i t to remain, the residue solidified to a dark brown, warty-looking mass. On attempting to distil this, a few grams of a clear, pale yellowish liquid of slightly pungent odour were collected, boiling between 200' and 205' under a, pressure of 10 mm. Much decomposition now occurred, gas being evolved, and the pressure riving to about 100 mm. ; ths residue became dark and treacly in consistence, but no more liquid came over. Continuing the heating, the pressure gradually diminished to almost 9 mm., bat still nothing distilled over, and frothing now became so troublesome that the pro- cess had to be stopped.After keeping a few hours, the distillate had darkened somewhat, and presently changed to a brownish solid, melting at the temperature of the hand. It gave reactions similar to those of the benzene solu- tion, and when pressed between folds of bibulous paper, formed a softish mass, which was dried over sulphuric acid and analysed. 0.2029 gare 0.1554 BaSOa. 0.2248 ,, 9.1 C.C. moist nitrogen at 11' and 764 mm. N = 4.85. S = 10.52. ClaHslCO*NCS requires S = 10.78; N = 4-72? per cent. ab-PuEmitylphenyZthiocu~~a~ide, C15H31*CO*NHCS*NH*C6H5, Molecular proportions of aniline, dissolved in benzene, and the thiocarbimide were mixed; heat was at once evolved, the mixture becoming slightly turbid, and, on cooling, the whole gradually solidi- fied.By several recrystallisations from absolute alcohol, very fine, hair-like, interlacing needles were obtained, having a somewhat greasy feel and waxy appearance, and melting at 62-63" (uucorr.). A sulphur determination afforded the following result. 0.2512 gave 0.1476 BaS04. S = 8.08. C,H,,N2S0 requires S = 8-18 per cent. When heated with water, the powder melts, forming a colonrless oil, specifically lighter than the water ; it is quite insoluble in the latter, even at the boiling point, and, on cooling, again solidifies to a crystalline cake ; it dissolves easily in hot alcohol aiid light petro- leum, much more sparing in cold, and freely in ether, chloroform, or benzene.The alcoholic solution gives no colour reaction with ferric1596 DIXON : THIOCARBIMIDES DERIVED FROM chloride; it is desulphurised at once in the cold by ammoniacal nitrate of silver, or by alkaline lead t a trate on boiling. Action of Silver Nitrate.-To a hot alcoholic solution of the above thiocarbamide, a little more than the calculated quantity of silver nitrate, in weak spirit, was added ; silver sulphide was precipitated instantly, and after a few minutes' boiling, the mixture was filtered ; as it cooled, the filtrate deposited palmitylphenylurea, in microscopic needles, melting, after recrystallisation from alcohol, at 90-91' (uncorr.), apparently without decomposition. 0.2228 gave 14 C.C. moist nitrogen at 18' and 777 mm. N = 7-42.C2,H,,N2O, requires N = 7.50 per cent.. The urea is insoluble in water, but when heated with it melts to a colourless, floating oil, which solidifies again on cooling ; it is freely soluble in chloroform, carbon bisulphide, hot alcohol, and hot light petroleum, sparingly in the oold ; very freely in hot, and moderately in cold, benzene, F ab-Palmitylorthotolylfhiocarbamide, C16H31*C O*NH*CS*NH*C6H4*CH3. Heat was evolved on mixing the thiocarbimide with orthotoluidine in benzene solution ; on cooling, tbe mixture remained clear, but pre- sently solidified ; the product, when drained, pressed, and recrystal- lised from boiling absolute alcohol, formed a felted mass of very fine, white needles, melting at 65.5-66.5O (uncorr.). The yield of recrystallised material was 72 per cent.of the theoretical. 0.265 gave 0.1548 BaS04. S = 8.03. C,~H&N,SO requires S = 7.93 per cent. It is insoluble in water, with which, on heating, it behaves like the corresponding phenyl derivative (to aroid repetition, it may here be stated that all the compounds described in the present communi- cation resemble one another in this respect), freely soluble in boiling alcohol, rather sparingly in cold, easily in benzene, ether, and chloro- form. Ferric chioride, added to the solution in dilute alcohol, produces no colour change; silver sulphide is precipitated in the cold on treatment with ammoniacal silver nitrate; the sulphur is also readily withdrawn by boiling with alkaline lead tartrate. Unlike its lower homologues, i t does not appear to give up the contained acid radicle when warmed with dilute aqueous potash.DesuZphurisation.-By treating a boiling dilute alcoholic solution of the thiocarbamide with silver nitrate, as described for the corre- sponding phenyl compound, ab-palmitylorthotolylzcrea was obtained in woolly mawes of very slender, flexible needles ; when recrystallised from spirit, they melted at 98" (uncorr.) without undergoing decom-COMPLEX FATTY AClDS. I597 position, forming a clear brown liquid, and afforded the following result on analysis. 0.2 gave 12.4 C.C. moist nitrogen at 18" and '775 mm. C,,H40N20z requires N = 7-23 per cent. The compound is insoluble i n water, freely soluble in hot alcohol, but only sparingly in cold ; it dissolves easily in chloroform, from which it is precipitated on the addition of light petroleum.N = 7.30. ab-PaZrnity~aratoZyZthiocarbamide, C15H31*CO*NH*CIS*NH*C6H4*CH3. The constituents, dissolved in benzene, united at once wit,h evolu- tion of heat, and, on cooling, the whole solidified to a rather greasy- looking crystalline mass ; by concentrating the mother liquor expressed from this, another less pure crop was obtained, the sum of the two weights amounting to a practically quantitative yield. On recrystallisation from boiling absolute alcohol, beautiful tufts of very delicate, white needles were deposited, melting without decom- position a t 75-76' (uncorr.). 0.2052 gave 0.12 BaS04. In relation to solvents, ferric chloride, silver and lead salts, thi compound resembles, in the main, its ortho-analogue.Desul23hurisutiorz.-The boiling, dilute, alcoholic solution, when treated with silver nitrate, afforded a good yield of the corresponding ab-pairnity Zparatolylurea ; the latter separated in very fiue, flexible needles, melting at 89--90' (uncorr.), without decomposition, and having properties similar to Chose of its isomer already described. On analysis the following figures were obtained. S = 8.04. CzrH40NzS0 requires S = 7.93 per cent. 0.2 gave 12.5 C.C. moist nitrogen at 20' and 775 mm. Cz4H40N202 requires N = 7.23 per cent. N = '7.29. n-PaZm.it y Z-v-methylphenylthiourea, C15H31*CO*N:C (SH) *N(CH3)*C6H,. Obtained, with evolution of hcat, from palmitylthiocarbimide and alcoholic methylaniline ; on slightly concentrating the brownish solution, and allowing it to cool, it solidified ; the product, drained and pressed, as usual, on the pump, was dissolved in boiling absolute alcohol, treated with animal charcoal, and thus obtained in Yery slender, white needles, melting a t 59-60" (uncorr.).The yield of purified substance was nearly 63 per cent. of the theoretical. The formula was checked by analysis. 0.2256 gave 0,1314 BaS04. S = 8.00. Cz4BroNzS0 requires S = 7.93 per cent.1598 DIXON : TBIOCARBIMIDES DERIVED FROJI Palmitylmethylphenylthioureao is insoluble in water, very freely soluble in chloroform, benzene, and hot alcohol, moderateIy in cold. Its alcoholic solution is not affected by boiling wit,h alkaline lead tartrate, and, if treated with ammoniacal nitrate of silver, affords a white precipitate, which darkens only slightly on boiling.If, how- ever, the hot solution be mixed with caustic alkali, and silver nitrate then added, the brownish precipitate of silver oxide at first pro- duced rapidly blackens, owing to the formation of silver sulphide. n-Palmity I- v-phemyl benz y 1 tkiourea, C15H31.CO*N:C (S H)*N( CGH5) *CHP*C6H5. Benzg laniline and the thiocarbimide, in alcohol and benzene res- pectively, interacted spontaneously with evolution of heat, and a clear, brownish liquid was formed, which presently solidified ; the amount of yellowish residue, after draining and pressing, was approximately quantitative. By dissolving in hot alcohol, and adding sufficient water to cause incipient precipitation, the solution, as it cooled, depo- sited the thiourea in very slender needles, melting ac 62-63" (uncorr.).A portion was analysed. 0.2208 gave 0.105 BaS04. S = 6.53. C,,,H,,N,SO requires S = 6.65 per oent. The compound is insoluble in water, easily soluble i n hot alcohol, and moderately in cold ; it is not affected by treatment with alkaline lead tartrate, and, in alcoholic solution, yields a white precipitate, with ammoniacal nitrate of silver, which is barely darkened, even on boiling the mixture. Wsubstitu ted thionreas not uncommonly prove difficult to attack by neutral or ammoniacal silver salts, and occasionally withhold their sulphur altogether ; it is generally possible, nevertheless, t o desul- phurise such compounds by modifying the conditioas, its described in the following experiment. a- PaZinity Z- b-pheny lbenzylurea, C ,,H,,*CO.NH*C O*N (C,H,) .CH,-CsH,. The corresponding thiourea (1 mol.), dissolved in hot absolute alcohol, was mixed with normal caustic alkali (2 mols.), and to the clear mixture, silver nitrate (2 mol.), dissolved in hot, dilute spirit, was added.A brown precipitate of silver oxide formed at once, but after a few seconds, began to darken, and rapidly changed to full black. 'The mixture was boiled for some minutes, a small quantity of strong ammonia added, and the silver sulphide removed with the aid of the pump ; a clear, colourless solution was thus obtained, which was treated with water to incipient precipitation; on cooling, a, white solid separated, which on recrystallisation from boiling spirit,COJIPLEX FATTY ACIDS. 1599 separated in beautiful tufts of pearly needles, becoiiiing moist a t 67", and melting a t 6s-69' (uncorr.).A nitrogen determination gave figures agreeing with those required for the urea. 0.2554 gave 14 C.C. moist nitrogen t i t 17'3' and 748 mm. N = 6.24. C,,H4,N,O2 requires N = 6.05 per cent. This treatment with hot alkali and silver nitrate is more effica- cious in desulphurisiiig thiourea derivatives than a n j other wet method that I am acquainted with ; I have not yet had an opportunity to try it upon a tetra-substitution derivative, but every tri-substituted thiourea. so far examiiied-and a considerable number were tested- yields up its snlphur with ease. Moreover, certain other sulphur- etted compounds, f o r example, the perithiazoline derivatives lately described (Trans., 1896,69, 17 ; 851), and Volhard's '' thiocarbimido- acetic acid " (dioxytliiazole), substances whose sulphur is included in a closed chain, and which are, in consequence, refractory under the ordinary treatment with nmmoniacal silver, or alkaline lead, salts, yield more or less completely to the attack by hot, alkaline silver oxide, It seemed probable that this p~ocess might be applied to trisub- stituted thioureas other than those containing acidic groups ; but, judging from experiments made with n-benzyl-v-methylphenyl-, n-ethyl-v-phenylbcnzyl-, a d tribenzylthioureas, the interaction does not r u n sufficiently smoothly to afford the basis of a satisfactory general method for preparing tri-substituted ureas.11. S TEARY LTH IOCAR BI 31 ID E , C H,.C 0 *NC S , AND ITS D EKIVATIVE s . Stearyl chloride, prepared from pure stearic acid by Krafft. arid Biirger's method (Eoc. cit.), was digested, as already described, with dry lead thiocyanate, shaking constantly. I n about 20 minutes, the benzene solution was free from chlorine; i t was filteied from the insoluble lead salts, the latter well washed, and the filtrate diluted as in the case OE the palmitjl homologue. The clear, golden-yellow solution, when hot, possessed the usual acid thiocarbimidic smell, though only in a slight degree; when cold, it was nearly devoid of odour, excepting that of the solvent. When shaken up with water and treated with ferric chloride, the mixture reacted dis- tinctly for thiocyanic acid, but the full red colorakion was, as usual, developed only after heating.Care was taken, during the preparation, to avoid, as far as practicable, access of moisture, but nevertheless, a certain amount of hydration occurred, and the solu- tions in the course of 24 hours, deposited small quantities of a white crystalline solid, free from sulphur, melting a t 68-69", and consist- ing of stearic acid. The presence of dissolved thiocarbimide was1600 DIXON : THIOCARBIMIDES DERIVED FROM recognised, as before, by its re.ady desulphurisstion under the in- fluence of alkaline lead and silver salts. It is worth mentioning that the course of the former interaction appears to depend largely on the way in which it is carried out ; if, for example, the soiution be mixed with dilute caustic alkali, and the mixture boiled for a few minutes, the product, on .further treatment with alkaline lead solution, will be desulphurised only feebly, whilst another portion, similarly boiled and acidified with dilute hydrochloric acid, gives, on the addition of ferric chloride, an intense thiocyanic reaction.If, however, the sub- stance be directly mixed with the lead solution, and forthwith heated, desulphurisation occurs freely, whilst another portion, mixed with cold alkali, then acidified as before, and treated with ferric chloride, gives only a faint, reaction for tliiocyanic acid. Palmitylt.hiocarb- imide, when similarly treated gave substantially the same resulta ; in this case, however, the alternative behaviour, as thiocyanate, or thio- carbimide, was less sharply marked than with the stearyl homologue.ab- St ear y ~ r t h o tol y Z thiocar banzide, C H,* C 0 *NH C S *NH* CsHd C H,. This was obtained, with evolution of heat, from the thiocarbimide and orthotoluidine, the latter dissolved in absolute alcohol. On cooling, the mixture became solid, owing to the separation of very fine needles, the yield of which amounted t o 93 per cent. of the theoretical ; after being recrystallised from absolute alcohol, they melted at 67-68" (uncorr.), without decomposition, and afforded the following results on analysis. 0.2579 gave 0.1401 BaS04. S = 7.4'7. C26H44N2S0 require8 s = 7-41 per cent. Stearylorthotolylthiocarbamide is insoluble in water, very freely soluble in boiling alcohol, sparingly in cold, freely in chloroform, ether, benzene, and warm light petroleum. I t s alcoholic solution gives no colour with ferric chloride, b u t is blackened at once, on the addition of ammoniacal silver nitrate; t4he substance is also readily desulphurised by boiling with alkaline solution of lead. Steal-ylorthoto1ylurea.-By desulphurisation with silver nitrate, a practically quantitative yield of the above symmetrical urea was obtained ; the crude product had a slightly brownish colour, which it still retained after recrystallisation from spirit ; it melted a t 9 6 9 3 ' (uncorr.).0.2448 gave 14.8 C.C. moist nitrogen a t 19' and 762 mm. N = 6.96. C,sH44N202 requires N = 6.75 per cent. It. is easily soluble in hot alcohol, sparingly in cold, insoluble in water.COMPLEX FATTY ACIDS. 1601 ab- Stear!/ Zme t aay Zy Zthiocarbamid e, C ,,Ha5*C O*NH* C S.NH*C,H, (C H,) 2 .Prepared under the same conditions as the preceding thiocarb- amide; similar phenomena were observed, and the weight of solid product amounted to 92 per cent. of that theoretically obtainable. By recrystallisation f porn absolute alcohol, and treatment with animal charcual, a dark purplish coloration was easily removed, and the solution, as it cooled, deposited fine, lustrous, white needles, becoming moist a t 70", and melting at 71-72" (uncorr.). A sulphur determination gave the following result. 0.2592 gave 0.1385 BaS04. S = 7.34. C21H16N2S0 requires S = 7.18 per cent. The compound is insoluble in water, freely soluble in chloroform, benzene, hot alcohol and ether, moderately in cold, and easily in boil- ing light petroleum, b u t rather sparingly in cold ; it crystallises very well from the last named solvent. DesuZlphurisation.-This was carried out as usual, and a clear, dark red solution obtained, which, on cooling, deposited nearly 77 per cent.of the theoretical yield of ab-stearlllmetaxylyluren, in microscopic needles, melting, without decomposition, a t 92-93" (uncorr.). 0.205 gave 11.6 C.C. moist nitrogeu at 19" and 773 mm. N = 6.62. C2,H,,N,O, requires N = 6*,52 per cent. ab- Steary Z- 2- nap7~t 7~9 It hioca~bamide, C HS5* C 0 *NH*C S*NH*CloH,. Obtained as beEore, using a-naphthylamine ; the product, already practically pure, when recrystallised from absolute alcohol, formed microscopic, white needles melting at 80-81" (nncorr.). 0.2578 gave 0.1266 BaS04.C2gH44N2S0 requires S = 6.84 per cent. The compound is insoluble in water, moderately soluble in hot, and sparingly in cold, alcohol ; with other solvents, and with silver o r lead salts, ii; behaves like tbe metaxylyl analogue. DeszcZphurisatioi~.-A greyish solid was obtained, melting at 114- 115" (uncorr.), and this melting point was not raised by recrystallisa- tioa from alcohol. The very fine needles are insoluble in water, rather sparingly soluble in boiling alcohol, almost insoluble in cold, and consist, as shown by the result of analysis, of the expected stearyl- a-naphth ylu~ea. 0.2046 gave 11-2 C.C. moist nitrogen at 20' and 773 mm. N = 6.40, S = 6.75. C'29H44N202 requires N = 6.21 per cent.DIXON : THIOCARBIMIDES DERIVED FROM n- Steary 1- v-pheizy Ebenzy It hiourea, C17H3s*CO*N:C (SH)*N (C+jHj)* CH,*C,Hj.Stearglthiocarbimide and alcoholic beuzylaniline were mixed ; heat was at once evolved, and a clear, yellowish solution obtained, which, after standing for less than a day, solidified; the yield was very sntisfactory-over 95 per cent. of the theoretical. By recrystallisa- tion from boiling absolute alcohol, extremely fine needles were obtained, free from colour, and melting at 66-66-5' (uncorr.) to it clear, yellow liquid. The composition wits checked by a sulphur determination. 0.2581 gave 0.119 BaS04. S = 6.33. CZHaN2SO requires S = 6.30 per cent. The compound is insoluble in water, freely soluble in boiling alcohol, rather sparingly in cold. Its hot alcoholic solution, on the addition of ammoniacal nitrate of silver, gives a white precipitate, which darkens very slightly on boiling ; it is not perceptibly desul- phurised by heating with alkaline lead tartrate.a- Stearyl-b-pheny Zbenzy EzLrea, C17Hs5*COgNH*C 0.N ( c6&)*C H2*C6Hj. Desulphurisation was carried out by means of caustic alkali and silver nitrate, as already described under the corresponding palmityl compound ; the product, d ter recgstallisation from spirit and further treitment with animal charcoal, was obtained in pure white needles, becoming highly electrical on friction, snd melting at 74-75' (.uncorr.) to a slightly turbid liquid. N = 5.84. 0.2152 gave'll C.C. moist nitrogen a t 19' and 756 mm. C,,H~,N,O, requires N = 5.70 per cent. Iu relation to scilvents, it resembles the thiourea.IU addition to the experiments above mentioned, stearylthiocarb- imide was brought into contact with (1) alcoholic ammonia, (2) piperidine, (3) phenylhydrazine, and (4) benzglamine. With the first, as usual, much decomposition occurred, though only the calcu- lated quantity of ammonia was used, the chief products being thio- cyanic acid and stearamide ; (2) and (3) gave poor yields, and the products could not be obtained in a pure condition ; (4) gave a poor yield of a solid, which, after two recrystallisations from alcohol, occurred in brilliant, pearly plates, becoming slightly moist at 91°, and melting at 96-95' ; it contained no sulphur, and, when burnt for carbon an6 hydrogen, gave figures agreeing nemly wit,h those required for stearylbenzidide, C,,H,,C0.NH.CH,.C6Hj.Two att,emptsCOMPLEX FATTY ACIDS. 1603 to obtain pure stearylphenylthiocarbamide were also unsuccessful, owing, apparently, to contamination of the product with stearic acid. ADDENDUM .-Bewoy 1 thiocarbimide and Die thy la mine. Miquel has placed on record (Ann. Chirn. Phys., 1877, [ 5 ] , 11, 316) the failure of repeated attempts to combine oxygsnated tbiocarb- imides with secondary and tertiary amines ; as an instance, he men- tions that benzoylthiocarbimide, even when heated at 200° with diphenylamine or diethylamine, remains unaltered ; but no further details are given. The selection of diphenylamine for experiment was unfortunate, thie compound being exceptionally difficult to unite with the thio- carbimides ; in fact, the only product of such combination, so far as I know, is a triphenylthiourea, obtained in very small quantity by Gebhardt (Bei-., 1884, 17, 2092) on heating phenylthiocarhimide for several days at 280" with the secondary base.In a, similar experi- ment, made several years ago by myself, using ethylthiocarbimide, and heating under pressure for two hours at 160°, slight decomposi- tion occurred, with formation of sticky bye-products, but no additive compound was obtained. But as regards secondary bases, which are non-, or only partially, benzenoyd in character, union with acidic thiocarbimides takes place, as a rule, quite as rendilyas where primaryare employed; the above- mentioned failure in the case of diet.hylamine was, consequently, rather puzzling ; and it seemed, therefore, desirable to make a,nothei.attempt to ascertain whether combination between these two sub- stances cannot be brought about. Instead of employing the somewhat laborious method described by Miquel for preparing the necessary benzoylthiocarbimide, a sdution of it was made from benzoic chloride (7 grams) and lead thiocyanate by boiling them together in dry benzene, using a reflux condenser ; in about 10 minutes the action was complete, and, on filtering off the insoluble lead compounds, a clear, brown liquid was obtained, to which a trifle over the calculated quantity of diethylamine, in abso- lute alcohol, was added. Marked evolution of heat at once occurred, which was checked by external cooling with water, arid the resultant clear solution, on concentration, deposited yellowish crystals amount- ing to about 90 per cent. of the quantity theoretically obtainable from the weight of materials employed. By washing with benzene, the colour was removed ; the residue, when recrystallised from boiling alcohol, formed long, pure white, brilliant prisms melting at 100-lO1° (corr.), and giving the following result on analysis. 0,2056 gave 0.206 BaS04. S = 13.77. C~HB*CO*N:C(S~)*N(CzH5)2 requires S = 13-57 per cent.1604 CROSS, REVAN, ASD SMITH: Benzoyldiethylthioui*en is sparingly soluble in boiling water, practically insoluble in cold ; almost indefinitely soluble in boiling ethylic or methylic alcohol, moderately in the cold, very freely in chloroform and acetone, less so in ether and benzene. It dissolves easily in cold dilute caustic alkali ; but if to this solution a lead salt be added, and the mixture boiled, no desulphurisation occurs. Ammoniacal nitrate of silver prodnces in the alcoholic solution a white precipitate dissolving on heating and appearing again on cool- ing; if a few drops of caustic alkali be added to the clear, heated solution, silver snlphide is at once formed. Ferric chloride, added to the solution in weak spirit, yields a purplish, amorphous precipitate ; this dissolves on the addition of hydrochloric acid, but reappears on cautious treatment with alkali ; if excess of the latter be used, the colour is destroyed and ferric hydroxide is formed. In carrying out the work described in the present communication, I have received much assistance from Mr. R. E. Doran, to whom I wish t o express my thanks. Chemical Deyavtment, Queen's College, Cork.

ISSN:0368-1645    

DOI:10.1039/CT8966901593

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

1604 CROSS, REVAN, ASD SMITH: CVI1.-The Carbohydi*ates of Barley Straiv. By c. F. CROSS, E. J. BEVAN, and CLAUD S M I n r . IN a previous communication (this Journal, 69, 804), we showed that the furEuroYd constituents of the cereal celluloses, by a simple process of acid hydrolysis, can be sharply separated froin a presum- ably normal hesose complex which is left as an insoluble residue, that is, a resistant cellulose. The furfuro’ids in the sohtion had the characteristics of fully resolved groups (monoses), and their quantitative reactions were expressed by the formula, representing a pentose monoformal. The aim of these investigations, which so far was realised by the above results, was to extend the scope of the inquiry from empirical numbers to constitutional problems; that is, from furfural as an empirical and aggregate measure of a group of carbohydrates, to the actual constitution of those members of the group, for which, in the meantime, we employ the designation of “ furfuroids.” In the seasons 1894-95, using the methods then available, we endeavoured to show the relation between the furfuro’id constituents of these plants and the general assimilation and conditions ofTHE CARBOHYDRATES OF BARLEY STRAW, 1605 growth. The conclusions me arrived at are recorded in previous papers (Rei.., 27, [l], 1061 ; 28, 2604, and J.Amer. Cltenz. Xoc., 17, 286; 18, 8), and appear rather in a negttive form, since we were met a t this stage of the inquiry by the assumption then prevalent, that the furfural-yielding carbohydrates are exclusively pentoses, and that they are not formed as direct products of assimilation or elabo- ration, but from hexoses previously assimilated, the process, regarded molecularly, being one of oxidation of the terminal CH2*OH group (De Chztlmot, Ber., 27, 2722), and its elimination as carbonic an- hydride, or as a CO derivative.Without again discussing these conclusions, we may take ndvnn- tnge of the confirmatory evidence which has since accumulated to express them in a simpler and more positive form. It appears, in fact, that the furfuro’ids of the cereals are elaborated as such, that is, that they are originally built u p into tissue with the special con- stitution or configuration brought into evidence by the characteristic manner in which they afford furfnral, the circumstance from which they take their group-name.We may distinguish here, as a parenthesis, between “ Assimila- tion ” and “ Elaboration.”* Assirnilation is the initial process of building up complex carbon compou’;Lds, for example, carbohydrates from carbon dioxide, whilst elaboratior, is the working up of pre- viously assimilated matter into organised forms or living structures. No doubt, these processes are concurrent in the living cell, cellu- losic tissues being built up directly from assimilated carbohydrates, which have never existed outside the cell in a condition of lower molecular weight; on the other hand, the plant-cell works up into its permanent tissue, carbohydrate material which has been assirni- lated and stored in other forms, such as starch or sugars. The operations, therefore, arc! to be regarded as distinct, even when con- current and apparently simultaneous.This parenthesis is necessary t o show that we disclaim the state- ment that the furfuro’ids are assimiiated as such. It is possible that it may be the case, but familiar as we are with the molecular mobility of the simple carbohydrates, we think it equally probable that a dextrose or fructose molecule undergoes an internal rearrangement in the process of elaboration to tissue material in which it then per- sists as a “ furfuro’id.” That this is the case is a general conclusion to which all our obser- vations converge. To emphasise this me have recalculated our numbers for furfural * This distinction has, perhaps, little significance to the physiologist, as in the process of “ constructive metabolism ” the supply of carbohydrate materiul is taliell for granted.VOL. LXIX. 5 Q1606 GROSS, BEVAN, AND SMITH: estimations--the meastrre of the furfuroyds-on the basis of the carbohydrates alone. I n our scheme of examination of the barley crops of 1895, we included, in addition to furfural estimations, deter- minations of ash and albuminoids; subtracting the sum of these from the total dry matter, and calculating the furfural percentages on the residue, we have tl direct measure of the proportion of furfurojids t o carbohydrates in the plant at successive stages. The two sets of numbers are subjoined in parallel columns representing the pro- portion of furfural, (A) to the whole plant, (B) to the total carbohy- drates of the plant.A. B. 7 yh- -7 Date. Age of Crop. Plot 1. Plot 6. Plot 1. Plot 6. May 15 6 weeks 6.6 5.8 10.3 10.0 June 18 11 ,, 8.0 7.6 9.6 9.8 July 16 15 ,, 12.1 10.6 13% 12.0 Bug. 16 19 ,, 9.2 9.8 10.8 11.3 Sept. 3 22 ,, 10.5 10.2 11.6 11.4 The increases in the figures under (A) disappear to a large extent under (B) ; in other words, the plant elaborates its tissue in an approximately constant ratio of farfuroyds [Furfural x 21 to total carbohydrates, namely, 1 : 4. It is clear also that the essential constitution of these compounds is preserved throughout the life of the tissue, although they may be subject to secondary changes of a minor order which will be subse- quently dealt with. In reference to the small variations in the numbers, it must be remembered that the plant is a complex of structural elements, which vary in relative proportion with its development.Thus, lignification, with an increasing proportion of lignocelluloses, is a prominent feature of its growth. In a previous paper (J. Amer. Chem. Xoc., 1896,18,8), we have giren a scheme of proximate analysis of the plant in respect of its main constituents, but as furfurojida are present in large pro- portion in all of them, i t is impossible to differentiate in respect of this factor. For the cereal stems, therefore, we must be satisfied with an aggregate and approximate demonstration of the constant chemical characteristics of these tissue constituents. In dealing with a simple tissue, such as can be mechanically separated and examined after isolation, the same point may be, and, in fact, has been, much more satisfactorily demonstrated.I n con- junction with our friend, Mr. A. Pears, we made in 1892-3 similar observations on the bast tissue (lignocellulose) of the jute plant, and showed that this much more complex compound is constant in composition throughout the life of the plant. [Pears, Trans., 63, 964 ; 65, 470 ; see also J. Inaperial Ittst., 1895, 398.1 r-Jc-THE CARBOHYDRATES OF BARLEY STRAW. 1607 That we find itl necessary to insist on this point is due to the fact that the chemical history of the “ permanent tissue ” of plants is a comparatively neglected subject, and in reducing it to system it is of fundamental importance to distinguish between the constant and the variable features of composition ; between the primary con- stituents oE tissues and the products of secondary change.Thus, the lignocelluloses are primary products ; they are not celluloses previously elab~rat~ed, on which encrusting substances (lignin) have been deposited as a result of secondary actions. The fnrfuroid celluloses are not mixtures of a hexose complex, originally elaborated as such, with furfnral yielding groups (penfoses) produced from the former by secondary oxidation. These characteristic features of composition are present from the first appearance of the tissue. In reference to the latter group, which is the main subject of our present inquiry, we have already indicated that the furfuroids of the cereal straws are subject to secondary constitutional changes of a, minor order, of which we are able to give some account from the results of investigations of the growing crops (barley) of the past season.In investigating the furfnroids isolated from the cereal celluloses, the following are the methods which chiefly contributed to determine their constitutional features : (a) Copper oxide reduction (Fehling’s solution). ( b ) Osazones : analysis and melting point. (c) Reaction with hydrogen peroxide at 80°, and estimation of the carbonic anhydride evolved. ( d ) Yeast fermentation and estimations of furfural and ‘‘ sugar ” before and after fermentation, showing the extent to which the furfuroid is broken down, that is, fermented. The application of these methods to the products isolated from the barley plant at successive stages of growth by the process of acid hydrolysis constituted our scheme of investigation of the 1896 crop.The numbers we have obtained give unmistakable evidence of a progressive constitutional change of the furfuro’ids. A completeseries was carried out on Plot 6 (barley) of the Royal Agricultnral Society’s experimental station at Woburn, this plot representing maximum yields of straw and grain ; the plants from Plot 1 (minimum yield) were also investigated in the later periods. The numbers of both are recorded in the subjoined table, which only requires a brief explanation. The green plants were under investi- gation within 24 hours of cutting; they were exhausted with boiling alcohol, and the well dried residue treated in a digester with five times its weight of 1 per cent.sulphuric acid at 3 atmos. 5 Q dDate. May 26 June 16 July 14 Aug. 4 Bug. 13 July 14 Aug. 4 Aug. 13 Total organic solids in acid extract. Per cent. of dry weight of tissue. -- 30 *1 33 *2 53 -0 25 -0 33'8 50 *O 24 -4 28 -1 Fermentation investigation. Furfural, per cent. of dry extract." Before fer- mentation. -- 16 -1 24 *1 20 -4 28 - 4 26.8 21 *4 31 -2 27 -5 After fer- mentation. I_- - - 3 .2 7 -7 15 *3 4 -4 8.1 13 *7 CuO reduction. Before fer- mentation. -- 52 *1 81 -1 49 *6 80.1 77 -1 59 a5 82 *2 92 -6 After fer- mentation. -- 7.1 5 -4 8 *8 25 -0 26 *77 13 -0 22 -3 28 -8 Fur furdids fermented. Per cent,. of total, -- 100 100 80 74 43 79 74 50 K20, reac- tion. Per cent. of CO? evolved. -- nil nil trace 4 -0 5 *5 trace 4.1 5 -1 Osazones. 31.p. Q w w a % 195 2 .- 185' 176 -' 17.5 178 m 175 125 127 5 ~ 2 Bug. 4 was t,he date of cutting. The period Aug. 4-13 is the time elapsing between cutting and carrjing. Matured straw.. ,. .. .. .. I 22.8 I 42.0 1 25.7 I 110'0 1 57.0 1 39 I 11 *7 I 145' Straw cellulose . . . . . . . . . 1 17.0 1 48.0 1 23.5 I 118'0 1 57 0 * The percentages of furfural are not calculated on the original plant-substance, but on the estmct, including nitrogenous and mineral constituents.THE CARBOHYDRATES OF BARLEY STRAW. 1609 $team pressure for 15 minutes. The determinations recorded in the table were carried out on the acid extract ; in the fermentstion es- periments, this solution, previously neutralised with chalk and filtered, was employed, using washed yeast.The results, taken together, have a very decided significance when compared with the numbers obtained with a fully matured straw and with straw cellulose, which are included in the table for comparison, and this notwithstanding the extracts from the plants in the earlier stages of growth are complicated mixtures. That the extraction of the furfuro'ids was satisfactorily complete, was established by est,imations of fnrEural in the residues. The pro- portion of residue was from 45-55 per cent. of the original, yielding fnrfural amounting to 0.9 to 1.4 per cent. calculated on the original weight. This extraction is not selective, as it is in the case of the matured straw, for the furfuro'ids in solution are accompanied by other constituents, and amount t o only 33 to 5 0 per cent. of the whole extract.Whilst this fact lessens the value of the observations taken individually, we are able none the less to draw the following definite conclusions respecting the condition of the fiirfui.oid con- stituents of the plant when extracted. ( a ) Up to the flowering period, the furfnro'ids are in such a con- dition as to be capable of being completely broken down by yeast, fermentation ; but, with increasing age, a constitutional change ensues attended by a progressive resistance to the action of the yeast organism. ( b ) In the early stages-in fact, until the period of ripening of the grain-the failure to react with hydrogen peroxide indicates the absence of a second CO group in the (assumed) C, unit, that is, the absence of the constitutional features which correspond with a pen- t ose- form al.( c ) The osazones show a characteristic fall in melting point, such as would correspond with the change from the condition of a hexose to that of a pentose, or a pentose derivative. As stated before, me regard these changes as of a minor or secon- dary order ; they are not such as to affect the specific character of the carbohydrate ; that is, the property of directly yielding furfural. This, no doubt, depends on a C5 residue of special configuration which persists, wlde the sixth C group may be subject to structural changes . These conclusions are in accordance with our anticipation that the plant fuifuro'ids will be found to represent a hexose-pentose series of which the intermediate terms can be recognised in mature cereal straws ; the probable intermediate forms, that is, those existing in the condition of complex collo'ids or celluloses, are, of course,1610 DIVERS AND HAGA: numerous ; but when reduced to the simplest terms, that of a monose, the only stable compound would be the one formulated generally as a pentose-formal. The formation of a pentose-monoformal from a hexose is most simply explained, if we regard it as produced by the oxidation of the terminal C atom of the hexose to formaldehyde by internal re- arrangement, -CIH(OH)*CH,*OH becoming -CH2*OH i- HCOH, the formaldehyde and pentose residues remaining united by condensation. This is a species of fermentation change which cannot be regarded as an improbable occurrence in the plant; the evidence which we have now adduced strengthens the hypothesis that it does occur.It may be objected that this hypothesis involves the assumption of n hexose directly converted t o furfural by the condensing action of acids ; this, however, is not exactly the ctdse. We have no criterion of configuration, and very little of constitution, in the amorphous and complex collo'id formv of the carbohydrates. I t is not improb- able that the mode of aggregation of hexoses to complex anhydrides may have an inhenee on their hydrolysis by dilute acid, c)r con- densation by stronger acids. Without, however, labouring the argn- ment, it is more consistent, with the evidence before us, to regard these tissue furfuroi'ds as consisting of hexose groups which readily pass into pentose derivatives and, ultimately, into pentoses, by a series of internal changes, the latter occurring spontaneously in the life of the plant, or being determinable by the action of condensing acids. The alternative view that they are pentoses is inconsistent with the evidence fully set out in previous papers, and now strengthened by the observations contained in the present paper, namely, that the furfuroids in the early stages of growth are, when hydrolysed, completely fermented by yeast, yield osazones of high melting point, and change progressively with age in their reactions, developing the property of being decomposed by hydrogen peroxide with formation of carbonic anhydride ; these changes, moreover, are most marked at the critical periods of the life history of the plant, that is, at flowering, and at the period of the ripening of the grain.

ISSN:0368-1645    

DOI:10.1039/CT8966901604

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

1610 DIVERS AND HAGA: CVII1.- The Reduction of Nity*ososulphcctes. By EDWARP DIVERS, M. D., F.R.S., and TAMEMASA HAGA, D.Sc. (Japan), F.C.S. IN 1885 (J. Chem. SOC., 47, 203), we studied the action of sodium amalgam on a solution of potassium nitrososulphate, and found that it produced sodium hyponitrite and sulphite, besides nitrous oxide,THE REDUCTION OF KlTKOSOSULPHATES. 1611 hydroxylamine, and ammonia. In 1894, Duden (Ber., 27, 3498) ex- amined this action, and found that hydraxine was produced in small quantity. This interesting result has caused us to re-examine the subject with the object of ascertaining whether what we judged to be hydroxylamine might not have been hydrczxine ; for, at the time of our former work, liydrazine had not been discovered, and it would have given the reactions we relied on as evidence of the presence of hydroxylamine. We felt it desirable also to ascertain whether hydr- oxylamine or hydrazine was the strongly reducing substance which, in very small proportion, accompanied the hyponitrite formed from a nitrite by the action of sodium.The results of our irivestigation have not only cleared up these two points, but have shown that, besides hyponitrite and nitrous oxide, sulphite, hydrazine, and ammonia,, both sul phate and amidosulphonate are also produced in large quantities. Before treating of these results, we desire to give some details which may be foand useful in the preparation of potas- sium nitrososulphate. Preparation of Potassium Nitrososu1phate.-It is a mistake to sup- pose that nitric oxide unites but slowly with potassium sulphite ; it is only the insolubility of nitric oxide in water that retards this union, as the use of suitably shaped vessels shows.We have arranged four flattened, conical bottles in series by means of corks and tubes ; the diameter of the flat bottom of each bottle being, on the inside, 19.5 cm., and the height, t o the commencement of the neck, 3 cm. only. With 100 C.C. of solution in each, the depth of the liquid is only 3-4 mm., whilst the free surface is nearly 300 sq. cm., so that the four bottles give a surface of 1200 E q . cm. to 400 C.C. of solution ; this is further increased by the circumstance that the salt, as it forms, grows up in small heaps above the level of the liquid. A con- centrated solution, containing 40 per cent.potassium sulphite and 5 per cent. of potassium hydroxide, will give 70 grams of crystals or more in three hours. In cold o r temperate seasons, external cooling is of little use ; motion of the bottles, beyond an occasional tilting, is also uncalled for. It is, of course, necessary to replace the air a t the beginning, and the nitric oxide at the end, by hydrogen ; but the pro- duction of a little oximidosulphonate or nitrite is of little moment, since these remain in solution. The salt, when drained on tiles, is pure enough for most purposes, but, for special work like the present, it can be purified and obt'ained in good crystals by dissolving it quickly at 50--60° in 4-5 times its weight of water containing 1-1-5 per cent. of potassium hydroxide, but this involves considerable loss.Reduction bg Sodium Amalgam-The amount of water present with the salt seems to be without effect on the course of the re- duction ; the extremes we hare used have been from 3 to 10 parts of1612 DIVERS AND HAGA: water to 1 part of salt, one per cent. of its weight of sodium hydr- oxide being added to the water at starting as a precaution. Wheu much less than LO parts of alkaline water are taken, some of the salt remains undissolved during the earlier stages, and less than 3 parts of water are insufficient. The amalgam we used was one contain- ingabout 2.5 per cent. sodium. The reduction goes on rapidly at the ordinary temperature, and much heat is developed, whilst if the nitro- sosulyhate solution is cooled below Oo, the amalgam acts on it only when it first comes in contact with i t ; perhaps it would not, even then, if it itself were first cooled down.At this low temperature, action is arrested for any period, but, soon after the vessel is removed from the water bath, action begins, and, once started, is not easily checked by returning the vessel to the bath, as the solution is kept warm by the heat developed by the action. A moderate rise of tem- perature to 40°, for instance, does not seem to lessen the production of either hydrazine or hyponit.rite. The sodium requisite to reduce the nitrososulphate is, as nearly as could be estimated, 3Na : K(,N,SO,-; but to destroy all the hydrazine much more is required (we nsed 2Na additional for this purpose). After the maill change is com- plete, the interaction between the amalgam and solution is very slow, the solution remaining cold, and hydrogen making its appearance, along with much ammonia.The contact of the amalgam with the solution has been maintained, in our experiments, f o r 24 hours, and for two days, but, with continuous shaking during the second stage, much less time would have sufficed. We used a stoppered vessel, the loose stopper acting effectively as a valve in keeping air out. Eydroxylamine, a Product of the Reduction of a Nitrite by Sodixirz Amalgarn.-As the testing for small quantities of hydroxylamine, alone or in presence of hydrazine, possesses some novelty, i t is well to describe the positive result. in the case of sodium nitrite before the negative one with potassium nitrososulphate is alluded to.The process we adopted consisted in shaking the solution with acetone, distilling with steam to get over the acetoxime, and evaporating the distillate with hydrochloric acid, in order to recover the hydroxyl- amine as its hydrochloride. Concerning the formation of acetoxime, we found that when the acetone was left in contact with the solution made neutral to litmus, so as to have the hydroxylamine free, but no alkali present, the action was very slow and unsatisfactory, but that it was quickly completed when the potassium hydroxide was present in some excess. The strongly alkaline solution was distilled with the '' superheated " steam. Having proved the absence OF hydrazine in the product of the action of sodium amalgam on a soluteion of sodium nitrite, we mere able, in the above WRY, t o get crystals of liydroxylamine hydrochloride from it.THE REDUCTIO~ OF NITROSOSULPHATES.1813 Hydyoxylamine not a Pyodzict of the Reduction o j Nitrososulphate by Sodium.-After removing hydrazine from the solution of reduced nitrososul?hate by means of benzaldehyde and ether, and evaporating the residual ether, m-e tested the solution for hydroxylamine by the acetone method, and failed t o find any. Moreover, after the removal of the hydrazine the solution no longer had any reducing power 011 cupric oxide. Hydruzine.-Hydrazine is quickly formed from nitrososulphate by the action of sodium amalgam, and is then slowly decomposed by it, but so long as any nitrososulphate remains, the action of the sodium is diverted from t'he hydrazine.Ainmonia can hardly be ranked as a product of the reduction of iiitrososuiphatc, beicg the result of the hydrogenisat>ion of the hydrazine. During the reduction proper, it is almost entirely absent, but makes its appearance in quantity when the sodium is able to act on the water and liberate hydrogen. Hypoizitrite.-The hyponitrite produced by the reduction of the nitrososulphate is unstable, and continuously decomposes in the alkaline solution, with evolution of gas. After treating the nitroso- Rulphate with sodium for 24 hours only, the solution was mixed with excess of barium nitrate, and filtered from the precipitate pro- duced. Silver nitrate and some nitric acid added to the filtrate gale first a little reduced silver, and then precipitated silver hypo- nitrite equivalent to almost one-fifth of the total nitrogen of the nitrososulphate.Nitrous Oxide and Nitrogeir.--No estimate of the nitrous oxide has been attempted, b u t it is formed in large quantity. I t appears to be generated along with amidosulphonic acid, as well as witoh hyponitrite. Nitrogen probably accompanies it, since hydrazine is produced. Sulphate. -There being so much sulphite produced, we expected difficiilty in determining whether sulphate mas a direct product of t'he reduction of the nitrososulphate, or only the result of incidental oxidation of sulphite by the a i r ; we experienced none, however. When the water present is not more than 3 parts to 1 of nitroso- sulphate, anhydrons sodium sulphate is deposited before the solutioii has been removed fmm the amalgam, and comes in coiitact with ail-.We hare in this way got 4 grams of anhydrous sodium sulphate (containing only R very little sulphite) from 40 grams of potassium iiitrososulphate ; but little sulphate then remained in solution, as the barium precipitate obtained from it largely dissolved in hydro- chloric acid. It should be remembered that salts are only sparingly soluble in concentrated solutions of alkali. It would seem safe to say that, on reduct,iou, one-seventh of the total sulphur appears as sulphate. The quantitative determination of the sulphate produczd1614 DIVERS AKD HhCA: in this way is liot only interfered with bay the presence of sul- phite, but by thzt of much amidosulphonate, for the latter greatly retards, even if it does not prevent, precipitation of barium sulphate and sulphite, unless excess of barium nitrate is u3ed and the solu- tion is largely diluted.In the cold, barium nitrate, in bare excess, precipitates 43 per cent. of tlie sulphur as (very impure) sulphate atid sulphite, the estimation being based on the quantity of barium nitrate used, and not on that of the precipitate. When the sulphur dioxide is rapidly removed from the acidified solution by a current of air, the precipitate, obtained on adding a very slight excess of barium nitrate, shows by its weight, after purification, that 12.5 per cent. of the sulphur is precipitated as sulphate. But whether the sulphur dioxide has been expelled or not, and whether the solution is alkaline, neutral, or acid, if it is mixed with excess of barium nitrate and allowed to stand, much more snlphate is obtained; and after renioving the amidosulphonic acid by mercuric nitrate, still more barium sulphate is slowly deposited.The sulphate pre- cipitated later is not formed by the hydrolysis of some compound in solution, for that would be accompanied with acidification, whereas the neutral solution, after it has deposited the snlphate, remains neutral. The difficulties due to the presence OE amidosulphonnte, as well as sulphite, are, doubtless, not insuperable, and although, for the present, we are not prepared with a closely approximate determina- tion of the quantity of snlphate present, we can assert that thc amount produced lies between the limits of 12 and 20 per cent.of the total sulphur, an important fact enough. Sui@hile.-The sulphite formed in tlie reduction of the nitroso- snlphate, estimated iodometrically, is equal to 31 per cent. of the sul- phur. The actual determination presented no difficulty, but as the previous neutrslisation with dilute sulphuric acid and the other unavoidable slight exposure to air in preparing the solution, mast have reduced the quantity of sulphite, it would be unjusti- fiable refinement to assert that more than about one-third of the sulphur becomes snlphite. A s hydrazine acts slowly on iodine solutioa, the sulphite solution used for the determination was f I eed from it by prolonged treatment with the amalgam. According to the first, note by oneof us to the Royal Society, on the “ Formation oE Salts of Nitrous Oxide,” the presence of hyponitrite should have interfered, but, thanks to Thum’s valuable contribution (1894) to the knowledge of hyponitrous acid, in which it is correctly pointed out that hyponitrous acid does not act on iodine (evidence to the contrary having been iiue to the presence of acid silver hyponitrite in the crude sclution), we had learned that i t was without influence.I n titrating, the sulphite solution was poured at once into the iodineTHE REDUCTION OF ISITROSOSULPHATES. 1615 solution, and the excess of iodine estimated by sodium thiosulphate. One other point about the sulphite is that, after the sulphate and sulphite have been precipitated from the alkaline solution by barium nitrate barely in excess, the clear solution, after more barium nitrate bad been added to it, continued for a day or two to deposit barium sulphite, as well as the sulphate already mentioned. Awzidoszdpphonate.-The sulphur which is not precipitated by the barium nitrate remains in solution as amidosulphouate. The pre- cipitate contains some amidosulphonate, although the barium salt of this acid is soluble in water; it can be extracted, however, from the precipitate by washing it with water. Having added a small excess of barium nitrate, and filtered off tbe precipitate after two or three days’ standing, the mother liquor, slightly acidified with nitric acid, is poured into a moderate excess of niercuric nitrate solution, in order to precipitate the amidosulphonate as the oxy- mercuric salt (see “ Amidosulphonic acid,” p.1649); this is collected, washed, and decomposed by hydrogen sulphide. The mercuric sul- phide requires much washing i n order to extract all the amido- sulpho.nic acid from it. The filtrate and washings when evaporated to dryness in a desiccator leave tho acid in an impure form, but it, can be purified without much loss by washing it with dilute sulphuric acid (see p. 1640). Another way of examinicg the mercury precipi- tate is to boil it with hydrochloric acid and potassium chlorate, or to hydrolyse it at 150°, arid then precipitate the sulphate by barium chloride. By working in these ways, we have ascertained the amount of amidosulphonic acid to be equal to nearly half the sulphur of the nitrososulphate. Collection and Analysis of Results.-Not less than essentially three independent equations have to be employed to express the results of the interaction of sodium amalgam with potassium nitrososulphate. For convenience, we write thcse equations as four, namely,- 3[2K2N,S05 + 8Na + 7H,O = 2H2NS03K + N,O + 2KOH 4[K,N,S05 + 2Na + 8NaOHI.= (NaON), + K,SO9]. = &SO4 + N, + 2NaOH K2N,S0, + 6Na + 5H20 = K2S04 + (NH,), + 6NaOH 1 * K,N,SO, + 2Na + H,O If these reactions do occur, and in the proportions indicated by the numbers prefixed to them, the products will correspond in their proportions to those found, namely : amidosulphonate equal to half the sulphur and one-fourth of the nitrogen ; one-third of the nitrogen as hyponitrite (three-fifths of this were secured as hyponitrate before further decomposition) ; one-third of the sulphur as sulphite ; and one-sixth of the salphnr as snlphate ; together with one-sixth of the 2[1616 DIVERS h S D HAGA: nitrogen, partly as hydrazine, partly as elemental nitrogen ; and one-fourth of the nitrogen as nitrous oxide (besides t,hat from the hyponitrite reaction), these being as yet unmeasured.Further, the above reactions, in the proportions marked, represent one molecule bf the nitrososulphate as being acted on by sodium in the mean propor- tion of 3 to 3$ atoms, according to the relative quantities of hydra- zine and nitrogen produced, a result which agrees well with observalion , Theoretical Considerations. -The cause of the variety and number of the products obtained in the reduction of a nitrososulphate by sodium is undonbtedly to be found in the different points a t which fission of the molecule of the salt must so easily occur, as shown by the formula we have deduced for it.Under the action of sodium, the salt shows the same disposition to give both sulphite and sulphate that it does when heated and when moistened; bitherto, it has been possible to say of the latter changes that, supposing t h e salt to be a sulphonate, it might give a sulphate by an oxidising process, bat the present observation of the generation of much sulphate by the action of wdium, in strongly alkaline solution, affords another proof of the impossibility of regarding a, nitrososulphate as a sulphoriic compound. For sodium to produce n sulphate out of a sulphite seems incredible.Nevertheless, Duden, having adopted for potassium nitrososulphate the constitution given i t by Raschig, has not hesitated to derive a sulphate from it by the action of sodium, in an equation framed to express the formation of hydrazine. Raschig's formula is and is one well suited to explain the decomposition of the salt into sulphate and nitrous oxide,--too well suited, indeed, for it is hardly conceivable how, with such a constitution, a nitrososulphate could exist at all and, if existing, could ever give back sulphite when heated, If we are to believe that sodium amalgam would act on a salt of this constitution i n such a way as to produce a sulphate, we must ignore what we know to be true of every other snlphonate. Duden detaches the OK as potassiuni hydroxide and then, armed with this alkali, puts its hydrogen in the place of the S03K, and gets sulphate outl of this and the KO.But not a single instance can be found of an organic sulphonnte in reaction with potassium hydroxidc yielding a aulphate instead of a sulphite. So also with the sulphonated hydroxylamines, both of which decompose in concentrated potassium hydroxide solution, for they, too, give potassium sulphite. When Duden obtained hydrazine from a nitrososulphate, he furnished another proof that the salt is not a sulphonate. There is a fact which we have not yet brought forward in supportTHE REDUCTION OF NITROSOSULPHATES. 1617 of the non-sulphonic constitution of nitrososulphates, which we may now give account of in this connection. It is that sodium amalga.m, as Such, is wizhont action on a true aminesulphonate or hydroxyl.aminesulphonate ; me have, indeed, just been showing in this parper that amidosulphonic acid is producible by the action of sodium; it and imidosulphonate (no doubt, also nitrilosulphonate) are entirely unaffected by sodium. Oxyamidosulphonic acid, in alkaline solution, is also untouched by it and, in acid or neiitral solution, is merely reduced to amidosulphonic acid (see p. 1636). Hantzscli and Semple (Bey., 1895, 28, 274s) have stated that Schatzmann found Fremy’s potassium sulphazilati to be reducible by sodium, but only back to the oximidosulphonate from which it is pre- pared by oxidation: as a sulphonate, it is not affected. Since, then, all aminesulphonates, oxygenated or otherwise, resist, as sul- phonates, the action of sodium amalgam, while a nitrososulphate a t Once yields to it, the latter is not of the same class, that is, is noi a sulphonat e .A similar objection to nitrososulphates being regarded a9 sul- phonic compounds has been raised by Lachmann and Thiele (AnnuZen, 1895, 288, 267). It is that, whereas all undoubted sulphonic derivatives of ammonia, when mixed with nitric and sulph- uric acids in the cold (see Divers and Haga, Trans., 1892, 61, 9G;<), give pure nitrous oxide, and sometimes even a little nitramide itself, potassium nitrososulphate does not. We come now to the formation of amidosulphonate, which is essentially that of the reduction of a sulphate to the corresponding sulphite, a thing hitherto unknown t o occur in alkaline solutioti.But we have here to do with a sulphate of the group -N20K, and it would seem that, just as EtSO3K and AgSO3K do not oxidise to sulphate, whereas KSOsK does, because it has the oxidisable pot,as- sium atom, whilst they have a, non-oxidisable atom, that is ethyl or silver; so, conversely, nitrososulphate is reducible to a virtual sulphite, because it is the sulphate of a hydrogenisable radicle, whereas other sulphates have radicles (metal, alkyl, or ammonium) which cannot be hydrogenised. If it stood alone, the conversion of nitroso- sulphate into amidosulp honate would point t o a sulphonic constitution for it, but other reactions make the acceptance OE this impossible, unless, indeed, it could be a half sulphonic, half sulphatic salt, which also seems impossible.Were it of sulphonic constitution, it ought to yield, by reduction, a hydrazinesulphonnte, but! none of this can be found. When, after reduction, the solution is acidified and all the sulphur dioxide blown out of it, it yields up all its hjdrazine to benzaldehyde and retains no discoverable hgdrazine derivative. The formation of hydrazine presents a difficulty, whatever con-1618 DIVERS AND HAQA: stitution is given to the nitrososulphates, in that it requires the reduc- tion of the KON group. That this radicle can resist the attack of sodium amalgam is shown by the formation of the hyponitrite from a nitrite and from a nitrososulphate ; besides, Dunstan and Dymond (Trans., 1887,51, 657) specialiy tested the matter, and found a hypo- nitrite to be irreducible by sodium amalgam.Two ways out of the difficulty present themselves. It may be admitted that the group KON, detached when the sodium forms alkali sulphate, is reducible to hydrazine and potassium hydroxide, although (KON), is not. Or, considering that a nitrososulphate reverts, when heated, to sulphite and nitric oxide, even in its strongly alkaline solution, as we have shown (1895) in the case of the sodium salt, we may assume that to a slight extent this reversion occurs during the heating caused by the action of the sodicm amalgam, and gives nitric oxide, or rather dinitrosyl, (NO),, ready to be reduced by the sodium aud water to hydrazine. In studying the action of alcohol on nitrososulphates, we have already had occasion t o recognise this possibility of slight rever- sion occurring at the ordinary temperatures, in order to account for the Froduction of a little aldehyde.I t was shown by us (Trans., 1895,67,1038) that potassium nitroso- sulphate decomposes more slowly when dissolved in aqueous alcohol than in water, and that from the salt and the alcohol there are formed potassium hydroxide and potassium ethyl mlpbate, besides nitrous oxide and a very little aldehyde. In a cold saturated solution of the salt in 23 per cent.. spirit, about 14 per cent. of the salt, it was then stated, interacted witth the alcohol in this way, the rest decomposing into potassium sulphate and nitrous oxide as usual. Another experi- ment, in which 14 per cent. spirit was used, seemed to indicate that weaker spirit was more effective than stronger in forming alkali and ethyl sulphate, but the experiment was quantitatively incomplete.We have since ascertained the effect of using 15, 5, and 2.5 per cent. spirit, estimating in each case, as before, the extent to which the alcohol had been active by titrating the potassium hydroxide. With the 15 per cent. spirit, 10.8 per cent. of the salt interacted with the alcohol; with 5 per cent. spirit, only 48 per cent.; and with 2-5 per cent., less than 1 per cent. of the salt. Evidently, there- fore, water lessens the power of the alcohol to form potassium ethyl sulpbate. Luxmoore (Trans., 1895, 67, 1021) has opportunely shown that a thermometer with its bulb embedded in potassium nitrososulphnte subjected to heat marks from 127" to 148O, according to circumstances,THE REDUCTION O F NITROSOSULPHATES.1619 as the temperature a t which the salt explodes ; this observation agrees with P6louze’s statement that i t does so at about 130°, which was the only part of his description we had failed to adequately justify. We had ascertained that the medium (air, oil) surrounding the salt needed to be only from 91” to lo$’, according to circumstances, to bring about the explosion, and i t has now been established by Lux- moore that then the temperature of the salt ri’ses of itself to about l S O o before it explodes. By the above observation, Luxmoore has cleared away a difficulty in P15louze’s description of the nitrososnlphates, but he has raised another without in our judgment having reason for so doing.Bemuse he has found the salt to lose 2.5 per cent. in five minutes when at a temperature a little below 105O, he considers it impossible to explain how PBlouze could have found that it did not lose weight at all. I n another of his experi- ments, it was little more than half as fast as the rate just quoted, while our observation had shown that the loss med be only 10 per cent. in ?+ hours, and t,his seems t o explain how PBlouze might have failed t o notice sufficient loss to be deemed worth recording. We have merely to assume that he exposed his salt to heat for a short time only, and in a very dry atmosphere, and that he attributed the slight loss that even then must have occurred to the presence of a little moisture i n his salt as prepared.No doubt the salt loses weight rapidly when heated in ordinarydamp air; underthose circumstnnces,itdoes so slowly even at the ordinary temperature, whilst the sodium salt loses weight rapidly. But in a weZZ dried atmosphere, either of air or hydrogen, such as was used in our experiments, the well dried, powdered salt loses weight much more slowly, so that it becomes probable that, with abso- lute dryness of salt and atmosphere, there would be no loss at all. It is surely on account of dampness of the salt that the rate of loss is most rapid a t first, as Luxmoore rightly observed, and we must therefore also assume that P6louze worked on a well desiccated salt. But the rate of loss varies greatly. I n concluding this paper, we would call attention to the compara- tively small part which Sir Humphry navy had i n the discovery of the nitrososulphat~es ; so small indeed is it that we must demur to the habit which prevails of naming him as their discoverer, for it is an injustice to the memory of Pt5louze. In the year 1800, thirty-five years before PBlonze published his work on these salts, Davy made known that apparently a combination of nitrous acid with potash was obtain- able by subjecting a mixture of potassium hydroside and sulphite in the solid state to the prolonged action of nitric oxide, dissolving the product in water, crystallising out potassium snlphate, and evapo- rating the mother liquor to dryness. The residue was a mass which,1620 DIVERS AND HhGA : IMIDO SULPHONATES. when heated, yielded about a fourth of its weight of pure nitrous oxide. There can b3 no doubt that he had obtained potassium nitroso- d p h a t e , but there can be no doubt also that he did not know it, that he did not isolate the salt, and that he thought the product t o be potassium hyponitrite, formed from nascent nitrous oxide, the nitric oxide having been deoxidised by the sulphite. It was, no doubt, Davy’s observation that led P6louze to investigate the nature of the action, and consequently to the discovery of the nitrososulph- ates ; ‘but that is all that Davy had to do with the matter. Imperial Univemit y, Tokyo, Japan.

ISSN:0368-1645    

DOI:10.1039/CT8966901610

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

DIVERS AND HhGA : IMIDO SULPHONATES. C1X.- Euzidosu@honates. Part 11. By EDWARD DIVERS, M.D., P.R.S., and TAMsMAsA HAGA, D.Sc. (Japan), Y.C.S. THIS communication to the Society is supplementary to that which appeared in 1892 (Trans., 61, 943). I t contains an account of some imidosulphonates not there described, and a collation of our results with those obtained by Berglund, called for by the existence of some radical differences between them. It was this chemist, now deceased, who first made known the existence of imidosulphonates, although several of them had been already obtained and described by others, under various names and formule His important memoir on these salts was published in Swedish, but summaries of it by C l h e and by himself, respectively, appeared in the journals of the French and German Chemical Societies.References to all are given in our first paper. In English, also, a good summary was first published by Watts in the 2nd Supplement of his Dictionary ; this had escaped our notice, and, up to the time of publishing our first paper, we had only seen the account in the Berichte, and an appreciative notice of the Swedish paper in Raschig’s paper on “ Fremy’s Sulphazotised Salts.’’ But, soon after that, Dr. Raschig spontaneously sent us, with the greatest kindness, his own copies of Berglund’s Swedish papers on ‘‘ Imidosulphonic acid ” and “ Amidosulphonic acid.” A perusal of these led pus to resume work on the subject, with the intention only of examining into the differences between his results and onrs, but we went further afield, and prepared a few new salts, because they promised to be of interest.F o r convenience of reference, we follow in this paper the order of description observed in the former paper, and reproduce, as brieflyDIYERS AND HAGA : IMIDOSULPHONATES. 1621 as possible, matters of interest in Berglutid’s paper in Swedish, not t o be found in chemical literature outside it. A full list of the salts prepared by him is given by Watts (op. cit.). Berglund’s first source of imidosulphonates was ammonia and chlorosulphonic acid, but afterwards he prepared them from potas- sium nitrite and mlphite, following Fremy, with modifications, which do not call for notice here. Alkali Imidosulphonates. Ammonium ImidosuZphonates.-Berglund failed to get normal am- monium imidosulphonate, the statement i n Watts’ Dictionary that he did being erroneous. He believed Rose’s “ vitreous sulphat- ammon ” to be this salt, but we find that, both before and after its crystallisation from water, i t is the two-thirds normal imidosulphon- ate, and that Rose’s “ flocculent sulphatammon,” not noticed by Berglund, is anhydrous normal ammonium imidosulphonate.TO Woronin is due the accurate distinction between the two salts. The mother liquor of the crystals of the two-thirds normal ammo- nium imidosulphonate (“ parasulphatammon ”) gave Rose, on evapo- ration, his so-called “ deliquescent salt ; ” this, Berglnnd, judging from his later paper on “ Amidosulphonic acid,” considered to have been a mixture of amidosulphonate and the two-thirds normal imidosulphonate with ammonium acid sulphate.S o d i u m 1midosulphonnte.s.-That, contrary to Frem y’s experience, sodium nitrite can be sulphonated as easily as potassium nitrite, was ascertained independently by Raschig and by us about the same time ; later, me prepared the normal and two-thirds normal sodium salts, as well as some compound salts. Berglund, however, had pre- pared the normal aodium salt (and also the mercury sodium salt) from ammoninm imidosulphonate by boiling it with sodium hydroxide till all ammonia had been expelled; he found it more satisfactory, however, to precipitate the two-thirds normal potassium salt by adding potassium chloride to the ammonium salt, and to boil the product with a solution of sodium hydroxide and chloride ; on cool- ing, the normal sodium salt was deposited.His description of this salt, so far as it goes, agrees with ours. The crystalline salt, which Le sometimes got, in place of the ordinary normal sodium salt, and which he believed to be that salt in the anhjdrous state, we take to have been a double salt of normal sodium imidosulphonate and potassium chloride. He did not obtain the two- thirds normal sodium irnidosulphonate, or its compounds wich ammonium nitrate and with potassium nitrate, or sodium ammonium imidosulphonate. VOL. LXIX. 5 R1622 DIVERS AND HAGA : INIDOSULPHOKATES. Barium I ~ ~ i d o ~ d p h onat es. Berglund's account of normal barium imidosulphonate agrees with ours ; he was really the first to prepare this salt, and did himself an injnsthe in crediting Woronin and Jacquelain with its previous pre- paration.Woronin never anxlysed his preparation, which was almost certainly a double salt, and, although Jacquelain did carefully analyse his, the result shows it t o have been a barium ammonium salt. Berglund found that the normal barium salt gave up its 5H,O almost entirely a t 100'; we maintain the accuracy of our statement that i t loses water only very slowly, even a t 115' (see further on this point, our account of the strontium salt). Barium imidosulphonate is soluble in a solution of ammonium chloride. T wo-thirds normal barium imidosulphonate was fully described by Berglund, his account agreeing with ours. Double salts of barium with the alkalis received peculiar treatment by Berglund. He did not formally recognise their existence, and relegated to footnotes observations which, he admitted, made their existence probable.He could not satisfactorily formulate the com- position he found them to have, and for him they remained as impure barium salt only. Our own work confirms his results, and m&es it possible to give formulE to his preparations. First, there is Ba12K8H(NS20,),,,llH20, which he constantly obtained when he added normal potassium imidosulphonate to barium chloride. Had he thought of introducing the atom of hydrogen there is in the abol--e formula, he would probably not hare considered his analytical results as incapable of interpretation. A sodium salt, described by us, comes very near to this salt, being R~,,Na,(NSzO,),,,l~HzO ; for, if we sub- tract a molecule of the tlwo-thirds normal barium salt, BaHNS,O,, from his formula and write Na for K, we get ours.Evidently, either salt is mainly BaK(or Na)NS206 with a little Ba,(NS,O,),. By adding two-thirds normal potassium salt to ammonia and barium chloride, he got Ba,,K7(NH,)2(NS,0,J,l,f9H,0. Lastly, the salts ~a6(NH,),H(N8,0,),,21H,C and Ba7(NH4) (NS20,),,22H,0 ; all three having an obvious relation to the first. We have described a still more ammoniated salt, Bas,( NH4 ),( N S,O,) (,8Hz0. A 11 these double salts of barium are granular and powdery, and quite unlike the peculiarly soft, clinging, pure barium salt. Stroii tium Irniclosz~~pl~ onates. According to Berglund, normal strontium and normal calcinm imidosulphonates are, in properties, water of crystallisation, arid con - ditions of formation, as like each other as two salts can be, but unlike the normal barium salt.This account of the normal salts puzzledDITTVRS AND HAGA : IRIIDOSULPHONATES. 1623 US, but when we found hih description of the properties and method of preparstion clf tho calcium salt applied perfectly, so far as it goes, to a salt described 1 q us in our first paper, which we had found to be calcium sodium imidosulphonate, we lnst all confidence as to the accuracy of his accomt. We therefore studied the strontium salts for ourselves, having omitted to do SO when preparing our first paper. Morrnal strontium imidosulphonate, according to Berglund, gradu- ally separates in acicnlar prisms when a solution of strontinm chloride, moderately concentrated, is mixed with one of either noi-ma] sodium imidosulphonate or of diammonium imidosulphonate to which ammonia has been added.Its composition is expressed by the formula Sr,(NSz06)2,6Hz0, ana it loses only two-thirds of its water, even a t 130-140°. I n preparing it, it is iinnecessaig, he said, to take any care to have the strontium chloride ii. excess, although it is very important to keep the barium chloride in excess when preparing the normal barium imidosulphonate. Normal strontium im idosu7,phonate, according to our experience, cannot be obtained by mixing together strontium chloride and normal sodium imidosulphonate, strontium sodium imidosulphonate being formed in this way ; the normal salt, however, can be obtained from this in the same way as the normal barium salt is prepared from a barium potassium or barium sodium salt, namely, by dissolr- ing it in dilute hydrochloric acid and pouring the solution at once into a slight excess of a warm, concentrated solution of strontium Iipdroxide, repeating the operation twice, or until a,ll the sodium has been removed.So long as the reprecipitated salt contains sodium, it is a hard, granular precipitate, but, when it is free irom sodium, it separates in glistening, thin, scaly crystals, which felt together into soft, roluminous flocks, and these, dried on the tile, form coherent flakes, retaining water in their interstices with great obstinacy, like the barium salt, to which i t has, indeed, much resemblance. It is more soluble in water than the barium salt, and is actually soluble in hot water to a considerable extent. For analysis, we comminuted its flaky masses, and pressed the particles between filter paper till it seemed quite dry ; but, on exposure to air for days, such a prepara- tion continuously loses water, and much of it before the crystalline lustrc sensibly dim in is hes.The freshly dried salt contains 12H20, m the following numbers show : Strontium. Sulphur. Water. Calculated ....... 31-75 15-51 26.13 Found. ...... .... 31-86 15.49 - Tested fifter 14 days’ exposure, ihe water amounted to only 7 mds., 5 R 21624 DITERS AND RAGA : IMIDOSULPHONATES. although efflorescence had only then just become apparent. The strontium was then 35.61 per cent., calculation for 7H20 giving 35.66 per cent. By decomposing the normal hydroxy-lead imidosulphonate with ammonium hydrogen carbonate, so as to obtain a weak solution of normal ammonium imidosulphonate, and then evaporating to a small volume, we obtained a concentrated solution of the two-thirds normal ammoniam salt, the strength of which we determined by analysis.To it we added enough ammonia to make i t a little more alkaline than the normal salt, and then mixed it with w slight excess of a con- centrated solution of strontium chloride and left it to stand. Only a very small quantity of precipitate formed, but, on adding excess of somewhat concentrated ammonia water, allowing the whole to evapo- rate nearly to dryness in a desiccator over anhydrous potassium carbonate, and then adding water, a white, opaque powder was left, which, on analysis, proved to be normal strontium imidosulpho- nate, with a slight quantity of ammonia in addition.Our calculation i 3 fcr a pure strontium salt with 53 mols. water. The salt may, however, be regarded as having only 5 mols. water. We determined the alkalinity of the salt, and this expressed as strontium, shows i t t o be more than a third of the total strontium. The excess of base may be regarded as consisting of ammonium, the presence of a little of which wa8 established. Calc. Found. Strontium.. ................ 37.00 37.02 Alkalinity, as strontium. ..... 12.33 12-66 Sulphur.. .................. 18-04 17-98 When a solution of the normal strontium salt, with 12R20, is boiled, a nearly insoluble sandy precipitate is formed; this is a slightly basic* strontium salt with about 5H20.The calculation given is for normal strontium imidosulphonate with 5H20. Calc. Found. Strontium.. ................ 37.47 39.02 Sulphur.. .................. 18.27 18.36 An opaque, powdery salt is also precipitated when the mixed solutions of strontium chloride and normal ammonium imido- sulphonate are boiled ; it contains a very little ammonia, and is, no doubt, a, slightly basic ammoniacal strontium salt. We have not quantitatively analysed it. We have not attempted to prepare the two-thirds normal strontium * We have got results indicating the existence of a heinihydroxy-salt, (HOSr)3NS206, corresponding with the lead salt, but hare not had time to establish t h e fact.DIVERS AND HAGA : IMIDOSULPHONATES.1625 salt, although it could, no doubt, be easily got like the calcium salt (p. 1626). Berglund prepared a solution of it, but found the salt so soluble and so difficult to crystallise that he did not examine it. Strontium sodium irnidosulphonate is obtained when solutions of normal sodium imidosulphonate and strontium chloride are mixed. Probably, the proportions matter little, but we have used 2 mols of the imidosulphonate to 3 mols. of the strontium salt in moderately concentrated solutions. When the salts are mixed, precipitation occurs, but the precipitate redissolves on shaking, and soon small prisms of the strontium sodium salt separate. The salt is sparingly soluble, and resembles the calcium sodium salt described in our first paper. Like that salt, too, it contains 3H20, its formula being SrNaN S2O6,3H2O.Found. Celc. rL- 7 Strontium ..... 25.84 25.96 25.97 Sodium.. ...... 6-81 - 6.69 Water 15.95 - - Berglund got granular precipitates of a strontium potassium salt soon after mixing normal potassium imidosulphonate solutions with strontium chloride solutions. Calculating from his results, we find the salt waa represented by the formula Sr,,fCBH(NS,0s),1,13H,0, in close agreement with the composition of his barium potassium pre- cipitates, as calculated by us. Sulphnr ....... 18-93 18.89 - ......... Calcium Imidosu ?phonates. Berglund states that, on mixing solutions of normal sodium imido- sulphonate and of calcium chloride, he got the normal calcium salt, whereas we always got the calcium sodium salt described in our first paper.Berglund’s description and ours agree, and, as Berglund estimated the calcium from the weight of the residue left on ignition, the difference between this and the weight of the residue left by the sodium calcium salt would be within the limits of error of an ordinary analysis. Berglund’s salt is qaite unlike the normal calcium salt which we now describe for the first time. Norm a1 Calcium I?~aidosulphonate.-The true normal salt can be prepared by acting on the insoluble normal silver salt with its eqni- valent of calcium chloride in solution, decanting from silver chloride, and evaporating the solution in a desiccator till the new salt crystal- lises out. It is only sparingly soluble in water when once separated from solution, and crptallises i n rectangular prisms and tables, stablo in the air.Its composition is expressed by Ca3(NS,0s),,8H,0. It is strongly alkaline to litmus.DIVERS AXD HAGX : I3IIDOSULPHONATES. Calc. Found. Calcium.. ................ 19.60 19.60 Sulphur.. ................ 20.92 21.06 Bei-glund states that the normal calcium salt is also got from a niixed solution of ammonium imidosulphonate, s.mmonia, and calcium chloride. Two-thirds Norvial Culcium Im.idosulphonate.--This salt is obtained by decomposing normal silrer imidmulphonate by two-thirds of its equivalent of calcium chloride and one-third of its equivalent, or, for safety, just a, very little less, of hydrochloric acid. The solution, when evaporated in a desiecator, becomes a mass of radiating prisms. Crushed and drained dry, the salt is permanent in the air, at least for some days.Its formula is CaHNSz06,~H~0. This mixture gave us no insoluble sz,lt. Its reaction is slightly aci.1 t o litmus. Cdc. Found. Calcium ................ 14.87 14-70 Sulphur ................ 23 '79 23-59 Calcium Sodium Inaidc,sdphonate, CaNa.XS2O6,3H2O, is described in our first paper, and has been referred to tibove as being what we get by following Berglund's directions for preparing his normal calcium salt. The mercury calcium salt. will be found demribed on page 1630. Lead Iwtidosulphonates. We have indicated the existence of 8-2 unstable salt, PbHNS,06, in solution, and Berglund has done the sami?. The crystalline, normal hjdroxy-lead irnidosulphonate, (HO),Pb4NS2O6, has also been de- scribed by both of us, ar-d our accounts agree ; his way of preparing it, however, was to add ammonia gradually to mixed solutions of cliammonium imidosnlphonate and lead acetate so long as the amorphous precipitate at 6rst produced gives place to a crystalline one ; when t h e last formed e.morphous precipitate no longer changes, acetic acid is added until this has just been converted into the crjs- talline precipitate.The amorphous precipitate he found t o be a basic lead imido- sulphonate of varying composition. We have shown in our first Faper, however, that a basic salt can be uniformly obtained of the composition, (HOPb)JVS,O,. Xi 1 c e: Imid osu lp Lona t es. We have described t h i s and two otlier crystalline, well characterised salts, Ag,NaNS,06 and AgNazlTS2O6, the latter being obtained when silver nitrate is added to excess of xiorma1 sodium imidosulphonate.Accord- ing to Berglund, however, the precipitate in that case is richer in Bergluud has described only the normal silver salt.DIVERS AND HhGA : INIDOSULPHOXATES. 1627 silver than the normal salt. This is explicable when we consider that he worked with very dilute solutions, for, as we have pointed out, the salt, AgNa2NS206, is partly decomposed by much water into silver oxide and t wo-thirds normal sodium imidosulphonate. Mercury Tmidosulphonatcs. Oxyrnercuric Hydrogen Imidosulphonate, HN( S03HgO)2Hg (Divers and Haga) ; Normal Oqmerczwic Imidosulphonate, Hg[N( SO3Hg),0I2 (Berglund).-These basic mercuric imidosulphonates differ i n that the proportion of sulphur to mercury in ours is S,: Hg6, whilst in Berglund's it is S,: Hg6.His salt was prepared from mercury potassium imidosulphonate and mercuric nitrate, and ours from normal sodium imidosulphouate and mercuric nitrate ; they ought, therefore, to have been the same. Berglund tried the use of normal potassiurii imido- sulphonate, and thus got a more basic product, but this he attributed to the presence of mercuric oxide or basic nitrate in the precipitate. As Berglund was strongly impressed by the tendency of mercury to displace the imidic hydrogen, whilst we were similarly struck with bhe fact that whenever sulphuryl occurs in combination with oxylic mercury in a Precipitated salt, that mercury functions as the bivalent radicle, -IlgOHgOHg-, it will be seen that Berglund's ratio of sulphur to mercury accords with his preconception, and not with oum, and that our ratio accords with our preconception, and not with his.To make sure that we had not been mistaken, we made further experiments ; but, before describing these, we have two adverse com- ments to make on, Berglund's experiments. One is as to the precipitation of mercuric oxide or basic nitrate inferred by him. However prepared, our product has always been one of the whitest of precipitates, only assuming a faint buff tint when kept for some time at 100" or higher, in the dry state. The presence of very little oxide of basic nitrate should have shown itself by a yellowish tinge. No precipitate that we have tested either of the present salt, of the oxymercuric sodium salt (first paper, p.9831, of the mercurous salt (this paper, p. 1630), or of the rnercurosic salts (this paper, p. 1632), has ever shown the presence of nitric acid in it. Moreover, Berglund's supposition that mercnri c oxide or basic nitrate might be precipitated is not probable, when it is considered that the mother liquor of the precipitating salt is much more strongly acid than the solution of mercuric nitrate used. The other matter is the unlikelihood of mercury taking o r retaining the imidic relation in a salt precipitating from such very acid mother liquors ; for, as we have shown in our first paper, dilute nitric acid replaces such mercury by hydrogen. Directly the attempt is made t o lessen the quantity of nitric acid sufficiently to permit of mercury1628 DIVERS AND HAGA : 13IlDOSULPHONhTES.taking the imidic relation, sodium or potassium also enters the salt, displacing half the oxylic mercury. For we then find that we pass abruptly from HN( SO,ElgO),Hg to Hg<N(S033Na)2 “SO HgO),Hg . ,Experiment 1.-To excess of very dilute mercuric nitrate (neces- sarily acid) was added a very dilute solution (1 in 50) of mercury sodium imidosulphonate. The crystalloidal precipitate, washed by decantation with much water, was dried on a tile ; both the salt and the mother liquor were free from sulphate. Composition : Mercury, 73.70 per cent. ; sulphur, 7.98 per cent. ; sodiua, 0.08 per cent. Experiment 11.-Mercuric nitrate solution, 250 c.c., prepared from 6 grams of mercuric oxide dissolved in l i t h equivalent of nitric acid, 250 C.C.of a solution containing 4 grams of mercury sodium imido- sulphomte ; the voluminous, crystalline precipitate formed on mixing these solutions, after being washed once with dilute nitric acid, and then repeatedly with water, was drained dry on a tile; it weighed 6+ grams, or four-fifths of the calculated quantity. It was free from sulphate, as was also the mother liquor. Composition: Mer- cury, 73.44 per cent. ; sulphur, 7.94 per cent. ; sodium, 0.08 per cent, Experiment 111.-Dissolred 2.8 grams of mercury potassium imido- sulphonate i n 230 C.C. water, and added it t o 3 granis of concentrated mercuric nitrate solution containing almost 1.5 grams of mercury as nitrate. A crystalline precipitate formed at once; after a few moments’ active stirring, the precipitate was allowed to settle, and the bright mother liquor was decanted into another vessel containing 4.5 grams more of the mercuric nitrate solution ; a second precipi- tate was thus obtained.Both were washed bg decantation, and drained on tiles. The first weighed 2 grams ; the second, 1.5 grams ; by calculation, each would have weighed 2.9 grams, bad none remained dissolved, according to the equations, 1. HgN,(SOs)*Kd + 2Hg(NOS), + 2H20 = HN(SO,),Rg302 + 211(N03 + ?HN03 + IIN(SO,),K,; + 2KN03 + 4HN0,. 2. HN(SOs)ZK, + 3Hg(NOa)2 + 2HZO = HN(SO,),Hg,O2 The first precipitate contained mercury, 72.85 per cent. ; sulphur, 8.03 per cent. ; potassium, 0.3 per cent. The second contained mer- cury, 72.61 per cent. ; sulphur, 8.11 per cent.; potassium, 0.38 per cent. It will be seen that in no case is alkali metal absent, the quantity present being markedly greater in the case of potassium than in that of sodium, and that the potassium is slightly higher if more nitric acid is present. This apparently strange result is due t o the fact that nitric acid dissolves mercuric imidosulphonate, but has no action on the two-thirds normal potassium or sodium salts.DIVERS AND HAQh : IMIDOSULPHONATES. 1629 The results of the above experiments, together with those described in our first paper, can, we think, leave no doubt that the basic mer- curic salt has the composition HN( SO,HgO)zHg, the percentage numbers for which are-mercury, 74.35 ; sulphur, 7.93 ; the potas- sium in the precipitates of Experiment 111 fully accounts for the slight deficiency of mercury in them.As alreadF stated, it is probable that Berglund got his analytical results as a consequence of the presence of unobserved potassium. Nercury Ammonium 1midosuZphonate.-W hen the mercury calcium salt, described later (p. 1630), was decomposed with just enough am- monium hydrogen carbonate, a secondary decomposition set in after a very few minutes; that is to say, at first calcium carbonate was precipitated with effervescence due t o escape of carbon dioxide ; but after stirring well, till the effervescence had subsided, the solu- tion began again to effervesce and deposit a basic mercuric calcium salt, possibly analogous to the sodium salt, and, therefore, The precipitate proved to be a mixture of calcium carbonate and basic mercuric calcium imidosulphonate, roughly separable by dilute nitric acid ; whilst the mother liquor was a solution of normal and two- thirds normal ammonium imidosulphonate, with a very little mercury calcium imidosulphonate, or the equivalent of these salts.No ami- dated mercury salt was produced. Berglund also tried to make the mercury ammonium salt from the mercury barium salt and ammonium sulphate, but failed. The salt, therefore, appears t o be incapable of continued existence. Mercury potassium Imidosu1phonate.-According to Berglund, dilute nitric acid has no action on this salt, but, as we have pointed out, i t is converted into the insoluble two-thirds normal potassium salt. and mercuric nitrate. Jfercury Sodium Imidosu lyhonate.-This salt was described by us fully, under the belief that Berglund had not prepared it, iii which, we were mistaken.We hare agaiu prepared and examined the salt, and now find it contains 5 atoms of water, and not 6, which agrees with Berglund’s results. The formula is therefore HgN,( 80,),Nal,5Hz0, We have also found now that the salt left in a vacuum over sulphurio acid for weeks loses all its water, and not merely two-thirds of it, as stated in our first paper. Berglund dried his salt. at looo. Oxymercuric Sodium Imidosulphonate.-Berglund had no know- ledge of such a salt as the basic mercury sodium salt, described i n our first paper, or of a corresponding potassium salt. I t is interest- ing, however, to find that on mixing normal mercury potassium, imidosulphonate with silver nitrate even in excess, he was unable to1630 DIVERS AND HAGh : IJIIDOSULPBOSATES.get the mercury silver salt, but only a mercury silver potassium salt. ' ( so"g)2,3H20, is strictly analo- N( SO&) 2 His formula for this salt, Hg< p u s to ours for the basic mercury sodium salt, (instead of 4H20, formerly adopted by us). Mercury Calcium Imidosu7phonate.-Although Berglund obtained and described mercury barium, mercury strontium, and mercury magnesium imidosulphonates, he failed t o get the corresponding calcium salt, on account of its being so soluble in water. We have prep:tred it by dissolving mercuric oxide in a warm solution of two- thirds normal calcium imidosulphonate, filtering, evaporating, crjs- tallising, and, finally, recryetallising from water.It forms small, brilliant prisms. Mercury. Calcium. Sulphur. Calculated . . . . . . 25.90 10.36 16-58 Found .. .... .... 25.92 10.20 16.61 A compound of this salt with mercuric chloride, which can be formulated as C1Hg2(NSz0,Ca)3,12Hz0, and, therefore, be compared with apatite, was got in good, although small, crystals by treating oxymercuric hydrogen imidosulphonate with calcium chloride solu- fiou in the proportion IINS206Hg~Oz : CaC1,. The solution, filtered from tho mercuric oxychloride, and evaporated in a desiccator, gave the salt i n question. By dissolving this in water and precipitating by absolute alcohol, the mercuric chloride can, for the most part, be removed, but only with great loss of the imidosulphonate, as the latter also is soluble in alcohol.Mercury. Calcium. Sulphur. Chlorine. Calculated. . . . 30.92 9.28 14.84 2-74! Found ... .... 31.00 9.35 14-55 2.63 ,Vemirous lmidosui$honate.--No mercurous imidosulphonate has yet been described. There seems to be only one, a basic salt, having Hg', : S2, formed when two-thirds normal sodium imidosulphonate is added to mercurous nitrate in powder which has been stirred up with h u t water until it has all passed into solution except a little of the soft, voluminous, basic nitrate, the latter being quite free from any yellow, granular particles. As the nitric acid liberated dissolves some of the salt, a third, at least, of the imidosulphonate remains in solution ; tile normal sodium imidosulphonate would, therefore, be preferable t o use, were its use not subject to a disturbing effect, t o be noticed presently.The mercuric nitrate should be i n someDIVERS AND HAGA : IMIDOSULPHONATES. 1631 excess, about one-fifth more than the calculated quantity. tion expressing the reaction is The equa- 4(HgNOs), + H,O + 2HN(SO,Wa), = O[Hg4N(S0J2], + 4NaN0, t- 4HN03. Of the sodium salt, 1.05 gram, dissolved in about 150 C.C. water, added, with stirring, gradually to 4.5 grams of mercurous nitrate in about 20 C.C. of water, gave a precipitate weighing 2.i5 grams, and nitric acid in solution weighing 0.33 gram, the ratio of these weights being in accordance with the above equation. The precipitate was free from nitrate and sulphate, and the mother liquor contained no sulpliuric acid. The new salt is flocculent and quite white, and, most probably, has the constitution expressed by the formula 0 [ Hg’2N(S0,)2Hg’,],,6H20.Calculated ........ 77.22 6-18 Found ........... 77.27 6.18 It loses very little i n weight at 100’ or 120°, and part of that loss will be due to volatilisation of mercury, for the salt becomes very grey; when more strongly heated, it becomes nearly black tem- porarily, and then white again. Then, or while still black, the altered salt gives some mercuric chloride as well as mercurous chloride when triturated with a solution of sodium chloride. A t an incipient red heat, the whitened, altered salt fuses and effer- vesces, evolving nitrogen, but no sulphur dioxide. The black-red liquid consists mainly of the mercury sulphates. Mercurous imidosulphonate dissolves in dilute nitric acid much more readily than mercuric; imidosul phonate does, and the addition of sodium chloride to the solution precipitates all the mercury. Triturated with sodium chloride solution, the salt becomes of a per- manent, dull, and somewhat greenish-orange colour, though quite free from the mercuric radicle ; and the sodium chloride solution becomes very alkaline to litmus, no doubt because of the formation of normal sodium imidosulphonate.Concentrated hydrochloric acid soon causes, even in the cold, the formation of some mercury and mercuric chloride and, cn heating, this change becomes complete.* Concentrated solu- tion of potassium iodide at once, in the cold, dissolves it, all but half its mercury left as metal. Normal sodium imidosulphonate converts it into mercury and the sparingly soluble mercuric sodium imidosulphonate, and this makes it undesirable to use the normal sodium salt for preparing the mer- curous salt.When it is used, a blue-grey cloud of niercurg is Mercury. Sulphur. * Ox-ing to the production of amidosulphonic acid (see our paper on this acid).1632 DIVERS AND HAGA : IMIDOSULPHONATES. formed, but by incessant and violent stirring for 10 minutes from the time of adding the normal sodium salt, not in excess, to the mer- curous nitrate (which may here be used in a very dilute nitric acid solution), the grey precipitate becomes almost completely white, and is then the mercurous imidosulphonate. Thus prepared, we have found i t to contain 78.20 and 78.55, instead of 77.22 per cent.of mercury, but the right quantity of sulphur, namely, 6.20 (twice), theory requiring 6.18 per cent. Mercurosic ImidosuZphonates.-Berglund found that mercuric potas- sium imidosulphonate when added to a solution of mercurous nitrate deposited some oxymercuric imidosulphonate only after standing 6ome time. He must ttierefore have used a solution of mercuroua nitrate containing an unnecessary excess of nitric acid, for precipita- tion is immediate if but little nitric acid is present. The precipitate varies in composition with the proportions of the salts used, but, siill within well-marked limits. The variation is very great in the quantities of bivalent and univalent mercury, but very small indeed in the total quantities of mercury and of sulphur.The composition of the precipitates is such that they may be regarded as the oxymercurous imidosulphonate just described, modified in having one-half to three-eighths of its mercurous radicles replaced by mercuric radicles, for it varies within the limits expressed by They differ from the purely mercurous salt in having only half as much water of hydration, and they cannot be represented as mixtures of the known oxymercurous salt with the known oxymercuric salt. O[Hg”N(S0,),Hg‘2~~,3H,0 (atomic ratios Hg”, : Hg‘, : S,) is obtained by adding mercuric sodium imidosulphonate, a salt neutral to litmus, to half its weight of normal mercurous nitrate, which makes 3Hg” be present for every 2Hg’,, and leaves a neutral, or even alkaline, mother liquor. The mercurous nitrate is used in the form described in the preparation of oxymercurous imidosulpho- nate.After adding the mercuric sodium imidosulphonate to. it, the mixture is well stirred t o insure the completion of the action, and until the mother liquor has just lost its acidity. The precipitate s white, settles quickly, and can be freely washed; when dry, its colour is dull. It contains nearly all (+;) of the mercury of t h e nitrate, but only $- of the mercuric radicle, and even only f of the imidosulphonic radicle, its moi,her liquor being very rich in imido- sulphonate, and this gives assurance that there is no mercurous The compoundDIVERS AND HAGA : IMIDOSULPHONATES. 1633 nitrate in the precipitate. contains any snlphate. Neither precipitate nor mother liquor Calc.Found. Univalent mercury. , . 49-45} 74,1, 5p.76} 73.99 Bivalent mercury .... 24.72 23-23 Sulphur ............ 7.91 Sodium - ............ '7.87 0-04 I n the analysis, the two mercury radicles were estimated by dis- solving the salt in dilute nitric acid, diluting the solution, precipita- ting mercurous chloride by dilute hydrochioric acid, and precipitating the mercury in the filtrate as sulpbide. After the salt has been hydrolysed in a sealed tube by hydrochloric acid for sulphur estima- tion, the mercuric radicle is found increased in quantity at the expense of the mercurous radicle; the oxjgen in the air sealed up in the tube having given rise to the increase of mercuric radicle, as shown by the lessened pressure (Hada, this vol., p. 1676). (atomic ratios Hg", : Hg',, T S,) is obtained if the mercurous nitrate is in excess, about five parts being taken for every two parts of mer- curic sodium imidosulphonate, which provides 7Hgf2 for every 2Hg". The precipitate has much the same appearance as that obtained when the imidosulphonate is taken i n excess, and contains nearly 3 of the mercuric and imidosulphonic radicles, but only a little more than + of the mercury of the nitrate used. The mother liquor is accord- ingly comparatively rich in mercurous salt ; i t is also acid. Both the mother liquor and precipitate are free from sulphate, and the pre- cipitate from nitrate. The dry precipitate is dull white. Calc. Found. UnivaleQt mercury.. 63.89) 73.37. 62.11 } 73.57. Bivalent mercury ... 10.48 11.46 Sulphur ............ 7.22 7.20 Sodium.. .......... - 0.01 It will now be seen how remarkably the percentages of sulphur and of total mercury approach each other in the two precipitates, widely as the ratio of the two mercury radicles varies. We append the results of analyses of two other preparations; they support the conclusions drawn from the above extremes.1634 DIVERS AND HhaA : AMIDOSULPHONIO ACID. A. B. Univalent mercury.. . 59.90) '72.78s Bivalent mercury.. . . 12.88 73.46t Sulphur. . . . . . , . . . . . 7.04 7.56 Imperial University , Tokyo, Japan.

ISSN:0368-1645    

DOI:10.1039/CT8966901620

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

1634 DIVERS AND HhaA : AMIDOSULPHONIO ACID. CX.-Amidosulphonic acid. By EDWARD DIVERS, M.D., F.R.S., arid TAMEMASA HAGA, D.Sc. (Japan), P.C.S. A MIDOS~LPHONIC acid, erroneously supposed to be known nearly 40 years ago, was not actually discovered and prepared until 1876, by Rerglund, and has only attracted the attention of chemists to any extent since 1887, when Raschig made known an easy way of pre- paring i t by a new process. The contents of this paper comprise a summary, not elsewhere found, of the work of others ; new ways of forming the acid ; a study of the interaction of oxyamidosulphonic acid and sodium amalgam, and of the same acid and sulphur dioxide ; improvements in known methods of preparing amidosulphonic acid ; a very productive 2nd economical method of preparing it ; some of its properties hitherto undescribed ; some new salts of it ; remarkable points in the behariour of its silver and mercury salts ; and an investigation of the decom- position of the acid by heat.Our colleagues, Professors Sakurai, Loew, and Takahashi, haye helped u s in adding to what was known of the acid, the first-named by investigating its molecular conductivity, the other two its physio- logical action. Both these investigations hare a special interest, an; form the subjects of separate communications following this. ~Vame of the Acid.-Berglund accepted su7phamic acid, then in USC, as an alternative name for the acid he had discovered, but employed that of amidosulphonic acid. This name, the use of which is now general, is analogically incorrect, and needs to be changed into eithei- arninesulphonic acid or amidosulphuric acid.Similarly, irnidosul- phonic acid and nitrilosulphonic acid should be altered to aminc- * This preparation rims found to be damp when analysed. t The numbers obtained for uniralent and bivalent mercury in this csse, namelv, 51 98 and 21.48 per cent., are in accordance with the others, but 8s they were determined in the salt after it had been hydrolysed, they are not trustworthy, and therefore withheld from the table.DIVERS AND HAGA : AMIDOSULPHONIC ACID. 1 is35 disulphonic and aminetrisulphonic acids, o r to imidosulphuric and nitrilodphuric acids. But it seems of little moment to make tlie change so long as ethylsulphonic acid remains in use in place of ethanesulphonic acid, and ethyvlsulphuric acid is misapplied to ethyl hydrogen sulphate.Sulpharnic acid must remain in the background until such time a s sulphimic acid becomes acceptable for imidosalph- uric acid, and some analogous name has suggested itself as suitable for nitrilosulphuric acid. Formation of the Acid. 1. Sulphur trioxide and ammonia, if the latter is kept in large excess, sometimes yield, according to Berglund, a very little ammo- nium amidosulphonate along with the imidosulpLonate which is the chief product. He gives no details of his method of testing for it, and, before he states that he had occasionally found it in very small quantity, he guardedly says that probably it can be formed in this way. The difficulty presents itself that, even a t 135O, ammonium amidosulphonate begins to change in to imidosulphonate, whilst the temperature caused by the iinion of sulphur trioxide and nmnionin is much higher than that, and Bergliind mentions that he did nothing to keep down the temperature.But, although the amidosulptonate does begin to change at so low a temperature as 13.i0,a IittJe of it can remain unchanged a t temperatures not very far below 300'. So that, 011 the whole, when it is considered that it was Berglund who first recognised that the product of the interaction of sulphur trionide and ammonia is not amidosulphonate but imidosulphonate, it seems wise to accept as well founded his assertion that occasionally amido- sulphonate is also formed in very small quantity. 2. Ammonium imidosulphonate readily hydrolyses into the amido- sulphonate (Berglund, 1876).The imidosulphonate is obtainable from chlorosulphonic acid, from pyrosulphuryl chloride, and from suIphury1 chloride (after the action of water), as well as from sulphur trioxide and ammonia. 3. Sulphamide, which is a product of the intemction of sulpburyl chloride and ammonia (Regnault, W. Traube), is decomposed by alkalis into amidosulphonate and ammonia (Traube, lS9:3). 4. Bx actiiig on acetonitrile with fuming sulphuric acid, a derira- t ive of' amidosulphonic acid, namely, acetyl acetamidinesulphonic acid, is obtained, and this hydrolyses, with extreme readiness, into d iacetsmide and amidosulphonic acid (Eitner, 1892). In the above four cases, amidosulphonic acid comes out as a sulph- uric clei*ivative ; in those which follow it comes from sulphur dioxide.In the first of them imidosulphonafes appear again. 5. Nitrites, fnlly sulphonated by sulphur dioxide, become nitrilo-1636 DIVERS AND HAGlA : AMIUOSULPHONIC ACID. sulphonates, which very easily hpdrolyse into imidosulphonates, and these, again, can be hy drolysed into amidosulphonates (Rergiund, 1876). The hydrolysis of potassium imidosulphonate was studied by Fremy and by Claus and Koch long before Berglund, but without amidosulphonic acid being discovered by them. Its production was overlooked, no doubt, through the great solubility of its potassium salt, and through its being liable to be destroyed by further hydro- lysis. 6. Oxyamidosulphonic acid is produced by the hydrolysis of oximidosulphonic acid, which is formed by the sulphonation of a nitrite, and, by reducing this acid with sodium amalgam, sodium amidosulphonate is obtained (Berglund, 1876).Bergland’s work was admittedly incomplete; he did not isolate the mid, and he did not state the conditions for success. Oxyamidosulphonic acid is not attacked by sodium amalgam, except in acid solution, and we have proved that it is then changed into amidosulphonic acid, having obtained crystals of the latter in this way. Zinc and sulphuric acid, or the Gladstone-Tribe copper-zinc couple, may also be used with perfect success for the reduction. Another, but indirect, way of effecting the conversion is given lower down (10). 7. Potassium nitrososulphate, which is prepared from potassium sulphite and nitric oxide, and is not a sulphonate, also yields amido- sulphonic acid among the products formed when it is reduced by sodium amalgam (see p.1615). 8. The simplest and most direct of all the processes for preparing amidosnlphonic acid is the sulphonation of hydroxylamine, which may be effected by allowing sulphur dioxide to act long enough on a solution of one of its salts (Raschig, 1887). 9. Acetoxime also yields amidosulphonic acid, when treated with aqueous sulphur dioxide (M. Schmidt, 1891). Sodium metasulphite acts on the oxime to form a hydrolysable compound (v. Pechmann, 1887), dirnethylmethyleneimidosulphonic acid (a monosnlphonic, and, therefore, an amidosulphonic, not imidosulphonic, derivative), and this, on hydrolysis, yields acetone and amidosulphonic acid (Krafft, Bourgeois, and Dambmann, 1892).10. The reduction of oxyamidosulphonic acid by sodium and by zinc has already been treated of (6), but this acid can also be con- verted by sulphur dioxide into imidosulphonic acid, from which amidosulphonic acid may be obtained by hydrolysis. That this would be the case was recognised by Raschig, but he did not attempt t o effect the change. We find that when a solution of potassium oxyamidosulphonate mixed with a molecule of potassium hydrogen carbonate is submitted t o the action of sulphur dioxide, as i n sul- phonating pot#assium nitrite, it is converted, apparently completely,DIVERS AND HAGCA : AMIDOSULPHONIC ACID. 1637 into the sparingly soluble, two- thirds normal potassium imidosul- phonate. The conditions resemble those of the sulphonation of hydroxylamine, for the change is not immediate, but requires hours for completion at the common temperature, whilst at or near Oo it seems not t o take place at all.X e t h y l i c sulphate and ammonia do not form methylic amidosulphon- ate, as they were long supposed to do, but primary, secondary, and tertiary methylammonium sulphates and ammonium sulphate (Berg- lund, 18i6). Ammonia acts, therefore, on an nlkylic sulphate, as Berglund pointed out, in the same way as i t does 0x1 an alkylic nitrate (Carey Lea, 1860). Although the nature of the interaction of ammonia and methylic sulphate mas discovered and worked out in detail by Berglund, his name is not even mentioned in connection with the suhject in chemical literature, as represented by Beilstein’s Hundbuch and Morley and Muir’s Dictionary. The whole credit of the discovery is given to Claesson and Lundvall, and i t is remarkable that, although these chemists dated their -paper from Lund, in 1880, only four years after Berglund’s memoir on amidosulphonio acid had appeared in that university town, they make no reference to it.In all points, so far as methylic sulphate and ammonia are concerned, Claesson and Lundvall had been anticipated by their countryman, except that they improved on Berglund’s process of dissolving the alkylic salt in ether and passing gaseous ammonia into the solution, by first saturating the ether with ammonia and then adding the sulphate gradually, and, i n this way, reduced to a minimum the production of the secondary and tertiary ammonium salts.The only chemists who worked on the action of ammonia on methyliu sulphate before Berglund were Dumas and Peligot, in 1836, and they only observed that the two substanees interact violently, when an aqueous solution of ammonia is added to the undiluted methylic sulphate, and, with- out giving quantitative analyses of the products, represented them t o be methylic alcohol and methylic amidosulphonate (“ sulphomethyl- ane ”). Strecker, in 1850, had, indeed, found that ethyl sulphate and ammonia combine, giving what he called ammonium sulphefhamate ; and it used, therefore, to be supposed that the action of ammonia on that sulphate was quite different from what it was on methylic sulphate. Strecker, however, did observe that his complex salt gave ethylamine when heated, although, from this weighty fact, he deduced no thing .Prpparation of the Acid. Amidosulphonic acid may be advantageously prepared in two ways, one being based upon the sulphonation of hydroxylamine, and the other upon the hydrolysis of imidosulphonic acid. Although both VOL. LXIX, 5 s1638 DIVERS AND HAGA : ABIIDOSULPHONIC ACID. hydroxylamine and imidosnlphonic acid are obtainable in several ways, the best for both of them is the sulphonation of sodium nitrite, and hydrolysis of the suitable sulphonate. It is, therefore, from sodium nitrite that amidosulphonic acid will, on economical grounds, be pre- pared in either case. The production of the acid through imido- sulphonic acid is much more profitable as regards time, labour, and yield, than its production through hydroxylamine ; but a t present it, must be taken into Consideration that hydroxylamine hydrocliloride is a t hand in most laboratories, and that if we take this as the starting point, it is easier to prepare the acid from it than to begin with sodium nitrite.This renders the hydroxylamine method the most convenient, pending the time when amidosulphonic acid itself becomes purchasable. Prepay-ation from Hydroxy lamine Sulph ate.-Baschig's account of this process, using the hpdrochloride,is brief, and as follows. '' Saturate an aqueous solution of hydroxylamine hydrochloride with sulphur dioxide, allow it to staiid some time, and then evaporate until a pellicle of crystals forms. A large quantity of the acid crystallises out by cooling, and the mother liquor yields a little more, but mixed with ammonium sulphate." Kraff t and Bourgeois (1892) used the solution of hydroxylamine hydrochloride very concentrated, sntui-ated it with sulphur dioxide to begin witb, and, for a day o r two, supplied inore as needed.I n t'his way they got fully three-sevenths of the calculated quantity of the acid to crystallise out without any evapora- Although sulphur dioxide takes some hours t o complete its action oil hydroxylamine, it acts rapidly a t first, and occasions a sensible rise of temperature. Cold checks its action, and a t 0" there appears t o be none. Saturation of the hydroxylamine solution at this tem- perature with sulphur dioxide is sufficient, once for all, unless it is st very concentrat)ed one, or is left exposed to the air.Some of t,be amidosulphonic acid becomes hydrolysed, i f the solution is evapo- rated on the water bath, but there is no appreciable decomposition if it is evaporated in the cold. Two points had to be investigated, the one being as to whether the acid of the hydroxylamine salt had any influence on the reaction, and the other whether hydroxylamine and sulphur dioxide suffer corn- plcte conversion into amidosulphonic acid, o r yield other products, such as ammonium sulphate, nitrogen, or nitrous oxide. The out- come of these investigations was that the action of sulphur dioxide is quantitatively the same, whether the hydrochloride, the sulphate, o r tlie base itself is used, and that, besides amidosulphonic acid, ammonium hydrogen sulphate is the only other direct product of t h e actmion.Very closel~, about one-tenth of the hydrdxylamine alwaysDIVERS ASD HAGA : AMIDOSULPHONIC ACID. 1639 becomes ammonia, the solution being cold (not much excee3ing 25"), and of moderate concentration. When the solution, a day after pre- paring it,, is distilled with potassium hydroxide, it gives a, tenth of the nitroZen as ammonia, whether sulphate or hydrochloride has been used, or, whether or not, along with either of these salts, just enough sodium carbonate has been added to combine with its acid, lea~--ing the hydroxjlamine free, or whether more sodium carbonate has been added and converted into metnsulphite. If, instead of a t Once distilling off the ammonia, the solutioa, deprived of its excess of sulphur dioxide, is heated for some hours a t 150-160", so as to hydrolyse all the amidosulphonic acid, and it is then distilled with potassium hydroxide, the ammonia obtained is closely equivalent to the hydroxylamine taken ; no nitrogen, therefore, has been lost as gas.The stability of amidosulphonic acid is such that the decomposition of the asid is quite insignificant,, and, therefore, that nearly all the ammonium hydrogen sulphate comm direotly from hydroxylamine, sulphur dioxide, and water. Although the action of sulphur dioxide on hydroxylamine is not affected by the acid present, there are several circumstances which make it advantageous to use the sulphate rather than the hydro- chloride? in preparing amidosulphonic acid. In the first place, the sulphate is easy to get i n large crystals, which are practically non- deliquescent, and it is a much cheaper salt to prepare" ; in the second place, sulphuric acid very greatly reduces the solubility of amid+ eulphonic: acid in water, and hydrochloric acid hardly a t all.To prepare amidosulphonic acid from hydroxylamine sulphate, it is dissoived in four or fire times its weight of water, the solution nearly saturated ice-cold wihh sulphur dioxide, and set aside a t the ordinary temperature for a day in a flask closed not quite air-tight ; the sulphur dioxide remaining is then expelled by a current of air, and the solution placed in a good desiccator, where the acid soon begins to crystallise out in t>hick plates. The crystals are well drained, and washed two or three times with a little ice-cold water.The yield should approar:h four-fifths of the weight of the hydroxylninine sulphate. As, however, amidosulphonic acid itself can be obtained from sodium nitrite more easily than hydroxylamine sulphate can, it will mver be prepared from the latter on the large scale. Pwprcration of Anaidosulphonic acid from Sodium N i t r i t e through I?nidoszilphon,ic acid. -Briefly, this process consists in fully sulphonat- ing sodium nitrite by means of sulphur dioxide and sodium carbonate, bydrolysing the nit'rilosulphonate to acid sulphate and amidosulph- * See '' Economical Preparation of Hydroxylaruine Sidphate," p. 1665. 3 a 21640 DIVERS AXD HAGA : AMIDOSULPHONIC ACID. onic acid, neutralising with sodium carbonate, separating the sodium sulphate by crystallisation, and precipitating the amidosulphonic acid by the addition of a large excess of coiicentrnted sulphuric acid.To get a l a ~ g e yield easily, the following details must be observed. Sodium nitrite (2 mols.) and sodium carbonate (3 mols.) are put into enough water to make the whole weigh 18 times as much as the sodium nitrite, and sulphur dioxide is passed in until the solution is acid to litmus. Usually the solution undergoes change very quickly if left to itself, but a drop of st,rong sulphuric acid may be added to start it, the nitrilosulphonate being converted into imidosnlphonnte and acid sulphate. There is a marked development of heat, and 8 large amount of sulphur dioxide is evolved, due to the interaction of the acid sulphate and sodium metasulphite, the latter salt haring had to be produced in order to secure the sharp sulphonation of the nitrite (Trans., 1892, 61, 955).Much of the loss of t,he sulpbur dioxide, and also the inconvenience camed by its escape, can be easily avoided by distributing the nitrite solution in several flasks for sepa- rate sulphonation, and then allowing the sulphur dioxide regenerated by the hydrolysi8 of one portion to help in sulphonating another ; in doing so, the sulphur dioxide may be driren o u t of the hydrolysed solution, without detriment to it, by heating, provided this is not, too prolonged. In any case, either a short heating is requisite in order to hasten the second stage in the hydrolysis (that of imido- sulphonate into amidosulphonate and acid sulphate), or eIse a, setting aside of the solution for a few hours (after expelling its sulphur dioxide by a current of air) in order to allow this hydrolysis to become complete.The solution is next neutralised by adding 1 moll, sodium carbonate, that is, a third as much as the quantity taken a t first, and the solution evaporated, by boiling or otherwise, until it again weighs only 18 times as much as the nitrite taken. Tf i t is then exposed i n an open vessel for a night, where the temperature may fall to 0' o r below, nearly all the sulphate present will separate in large crystals, from which the mother liquor can be well drained. If these conditions are not observed, it becomes necessary to concen- trate the mother liquor, and the sulpliate, which then separates on cooling, seldom crystallises in so good a form for draining.It is worth while to redissolve the separated sodium sulphate in a third of its weight of hot water and recrystallise it, the mother liquor being then evaporated to one-fifth, cooled, and, after separation of the sulphat-e, added to the main quantity of mother liquor. The solu- tion of sodium amidosulphonate, after being filtered, is now mixed with concentrated sulphuric acid, weighing 3-34 times that of the nitrate taken, and set aside for a day in a cool place. Most of the amidosulphonic acid separates immediately ; more crystallises o u tDIVERS ASD HAGA : AIIIDOSULPHO~IC ACID. 1641 during the cooling and standing. It is well drained on porous tiles, and washed with a little ice-cold water.Tho yield of acid by this process is affected by the tendency of the acid to form crystals with sodium hydrogen sulphate (see the account of the salts, p. 1646), so that the sodium sulphate should be separated as far as possible before adding the sulphuric acid. A yield of 75 per cent. of the calculated quantity may be reckoned on, while with care much more can be obtained. To obtain the acid in good crjstals, it must be purified by recrys- tallisation ; this can be done without any considerable waste by grind- ing it fine, adding it to 22 times its weight of boiling hot water, and stirring diligently on a water bath until it is all dissolved. The solution set aside deposits about three-fiftlis of it, and the mother liquor by cold evaporation mill yield nearly all the remainder in fine crystals in spite of the hydrolysis which the hot water will have caused.Mother liquors may also be worked up by precipitating the acid by means of strong sulphuric acid or by alcohol.* Properties of the Acid. Amidosulphonic acid is colourless and odourless, and has a sharp, purely acid taste (Berglund). I t crystallises readily from its aqueous solution, and better than most of its salts (Berglund). Its crystals are orthorhombic plates ; Pock (see Raschig's memoir) has examined it crystallographically, and shown i t to be isomorphous with its potassium salt. We took its sp. gr. in ether, and found it to be 2.03 a t 12O. Nothing has been published as to its melting point, except that M. Schmidt placed it as near 200' ; it has, in fact, no real melting point, for, as will be shown later on in this paper (p.1650 et seq.) in the act of melting it t o a great extent decomposes. Its apparent melting point, as near probably as can be determined, is 205O, the observa- tion being made on the driest acid in a capillary tube, beside a Jena thermometer with thread immersed in a bath of sulphuric acid; it melts but very slowly at this temperature. Even a t its melting point, it begins to evolve vapours produced by its decomposition, but this is very slight in dry air. I n fact, this volatilisation and the .melting point are greatly affected by the access of moist air and by any dampness in the acid used. Berglund described it as being quite easily soluble in water, and i t is so, though slowly ; it is, howcver, less soluble than any of its salts, except that of silver (not counting its basic mercury salt).It requires 5 parts of water at Oo, and 2Q parts at 70" t o dissolve it. The fact that hot water is not without chemical action on it ren- * For another, sometimes useful, way of preparing the acid, see p. 1646.1662 DIVERS BUD HAOA : AMIDOSULPHONIC ACID. ders a close determination of its solubility in hot water impossible, There is no known solvent for it but water. Sulphuric acid greatly diminishes the solubility of the acid in water, and readily precipitates it from its solutions and from SOIU- tiona of its salts ; its solubility is also greatly reduced by the pre- sence of sodium hydrogen sulphate. These facts, as already rnen- tioned, greatly facilitate the preparation of the acid.Not more than 3 parts of the acid for each 100 of water remain dissolved after concentrated sulphuric acid, amounting to 5-i of the volume of the solution has been added, and the mixture left to itself for a day, A 5 per cent. solution of the acid very soon deposited some of it when mixed with sulphuric acid; a 2 i per cent. solution deposits none, even on standing, but if it has been previously nearly saturated with sodium hydrogen sulphate, it yields some of the acid on standing, after admixture with sulphuric acid. Nitric acid also precipitates arnidosulphonic acid from its solution, but to a much less extent than sulphuric acid does. A fuming solution of hydrochloric acid does not precipitate it.Glacial acetic acid acts well as a precipitant, but more of it must be used than of sulphuric acid. It is stable in the air (even when crude) and non-deliquescent in the cold, but it generally holds about 1 per cent. of water, either hygroscopically or, to a slight extent, as ammonium acid snlphate. It is also stable in cold solution (Berglund), or very nearly so. Neither dilute hydrochloric acid nor a mixture of this acid with barium chloride seem to affect its stability in the cold. A solution of the acid may be boiled for a, moment, or be kept at 100' for a very few minutes, and still fail to show sulphuric acid with barium chloride; at 45" there is just enough hydrolysis in two hours to give a turbidity with barium chloride in 20 seconds. The presence of hydrochloric acid in a boiling solution quickens the destruction of the acid very much, but, even then, it is not completed in the course of a few hours; heating with the acid a t 150°, however, makes the hydrolysis complete in three or fonr hours (Raschig).Berglund stated that the acid in aqueous solution can be boiled for an hour without decomposition occurring, a1t)hough continued boiling decomposes it ; moreover, although hydrochloric acid hastens matters, the solution may be boiled with this acid and barium chloride for an hour before barium sulphate begins to sepzrate. Raschig also stated that, in its boiling solution, the acid is practi- cally undecomposed, and only very slowly decomposes in presence of acids. According to our experience, just recorded, Berglund and Rascbig have exaggerated the stability of the acid in boiling solu- tions, whilst Krafft and Bourgeois, on the other hand, exaggemtedDIVERS AND HAGA : AMIDOSULPHONIC ACID.1643 still more its instability when, in purifying the acid, they only ventured to dissolve it in slightly warm water. Crystals of the acid will lie for months in concentrated sulphuric acid unchanged; heated with it till dissolved, the acid undergoes essentially the same change as when heated by itself. Berglund found the acid not to be decomposed by boiling with potassium hydroxide ; whilst,, according to Raschig, alkalis seem to make the gcid more unstable. We find the decomposition caused by con- tinuous boiling to be very slight, and no greater than that in a solution of the neutral potasoium salt kept at the same tempera- ture.A solution of the potassium salt along with potassium hydroxide can be evaporated on the water bath, without the salt suffering noticeable change. Were it otherwise, how could sulphamide, boiled with alkali, pro- duce amidosnlphonate, half the nitrogen only escaping as ammonia (Traube) ? HePted in ordinary damp air at loo', amidosulphouic acid very slowly fixes water, through hydrolyaing, and becomes sticky on the snrface of its crystals. Krafft and Bourgeois found this change to proceed freely a t 130-140'. Berglund, on the contrary, found that the acid does not change in this may until above 190' ; but the facts observed by Berglund are such as occur without the intervention of moisture, as will be made clear when the effects of heating the acid are described.Amidosulphonic acid retards the precipitation of small quantities of sulphuric acid hy barium chloride, a fact that must be taken into account when testing for the beginnings of decomposition of the acid itself. A cold saturated solution of :~midosulphonic acid containing one part of sulphuric acid to ?O,OOO of water, gives no precipitate €or some minutes after barium chloride solution is shaken with it, and then only slowly and sparingly, although in 20 hours precipita- tion seems to be nearly complete. With only half as much sulphuric acid present, barium chloride takes half an hour to cause any pre- cipitate, and this remains very slight for a long time. I n strong, neutral, or alkaline solutions, alkali amidosulphonates also retard, for a day or two, the complete precipitation of a sulphite by barium chloride.Amidosulphonic acid, when acted on by sodium, changes into its sodium salt with evolution of hydrogen. It also dissolves zinc and iron (Berglund). It does not decompose an alkali chloride o r nitrate when mixed with the salt in the damp state, or in solution. Heated dry with the salt, i t causes decompoBition, b u t then the acid is itself decomposed. Alkalis appear, therefore, to be inactive.1 6 . . DIVERS AND HAGA : AMIDOSULPHONIC ACID. Amidosulphonic acid is decomposed with effervescence, even at the ordinary temperature, by a mixture of concentrated sulphuric acid and a nitrate or nitric acid, the gas being nitroas oxide. In this respect its hehaviour is like that of imidosulphonic acid, which, in 1892, we fully described on p.963 of our paper on " Irnidosulphonates " (Trans., 1892, 61). Soon after issuing that pa)per., we recognised the similarity of this reaction to that discovered by Franchimon t (1887)-that by which nitramide has recently been obtained by Lachmann aiid Thiele (1896) ; but we were at that time unable to study the reaction further. Lachmann and T'riiele have been the first to publish the fact that amidosulphonic acid gives nitrous oxide when treated with nitric and sulphuric acids. They also state that nitramide itself cannod be got by the reaction, but they give no parti- culars. We, too, have failed to get any nitramide, not, apparently, because it is decomposed after being formed, but because there is no action between the nitric and amidosulphonic acids in a freezing mixture.As already mentioned, amidosulphonic acid is quite in- soluble in strong sulphuric acid, and but little soluble in the dilute acid. Owing t o this property, we have been able to recover from a, mixture of the acids, which had h e n stirred up for nearly an hour, immersed in ice and salt, not only much of the nitric acid (by ether extraction), but, also, much of the amidosulphonic acid, by getting it deposited when the mixed acids, holding it suspended, were poured on to ice to dilute them. I n our experiment, we used the amidosul- phonic acid in the form of its ammonium salt, v i t h the object of having the acid present in the finest state of division. As has just been indicated, amidosulphonic acid is oxidised in the cold by nitric acid in presence of concentrated sulphuric acid.It is also oxidised by hot, or even cold, nitric acid, by potassium chlorate and hydrochloric acid (Berglund), and by chlorine and bromine. It is not acted on by chromic acid or permangaaic acid solution, or by ferric chloride, ferric amidosulphonate being as stable in hot solution as the other salts of the acid ; the acid is slowly oxidised, however, at a boiling heat by silver oxide and alkali, and then silvers the glass. This oxidation gives the solution the power, when acidified, of reducing small quantities of permanganic acid. This property, together with the fact of sulpbites in alkaline solution not being oxidisable by silver oxide, makes i t pretty certain that the reduc- tion of silver goes 011 thus (but see the account of the silver salt, p.1648) : HZNSOaK + AgaO = AgSOJC + Ag + N 3- OH,. Platinum black very slowly acts on a solution of amidosulphonic acid exposed to the air, and produces sulphuric acid-but, appa- rently, only by hydrolysis.DIT’ERS XKD HAGA : ANIDOSULPHONIC ACID. 1645 hmidosulphonic acid prevents the precipitation of silver and mercuric salts by alkalis (see the accounts of the silver and oxy- mercuyic salts, pp. 1648, 1650). Here the acid is seen acting as an amine. I t combines with boiling alcohol in tlie course of hours, becoming ammonium ethgl sulphate (Krafft and Bourgeois), and, when boiled with aniline, i t is slowly and similarly converted into ammonium phcnylamidosulphonate (Yaal and Kretschmer, 1S94) ; both reac- tions are analogous to tlic hydration of the acid, NH and 0 func- tioning alike.A description of its behaviour, when heated dry, will be Tound after the account of its salts. Preparation and Properties of the Salts. A number of the salts of amidosulphonic acid were examined by Berglund, and a comparatively full account of his work on them, condensed by ClAve from Berglund’a Swedish memoir, was published in the BUZZ. SOC. Chirn., 29, 422. The salts examined were those of potassium, sodium, lithium, ammonium, thallium, silver, barium, strontium, calcium, lead, nickel, cobalt, rnanganesc, zinc, cadmium, and copper, and the existence of a basic mercuric salt was pointed out. Raschig prepared again and analysed the potassium salt, and included, in his account of it, its crystallographic elements, as deter- mined by Fock. Krafft and Bourgeois again analysed and described the barium salt.Eitner again analysed the barium and the silver salts. Paal and Kretschmer again analysed and described the silver salt (acknowledging the previous work of Eitner), the copper salt, and the lead salt. Of these investigators, Raschig alone mentions Berglund, carefully indicating the great value of his work. The others are silent as to the work of the chemist who not only first prepared the acid and its salts, but analgsed and described them at least as fully as they have done. Yet an epitome of Berglund’s paper, drawn up by himself, appeared in the Berichte of the German Society (and not among the Beferate.), besides appearing, in another form, in the Bulletin of the French Society, as we have just said. Now that the isolation of the acid has become easier than that of any of its salts, the work of Bergluud and of Itaschig on the prepara- tion of the salts has lost its valne.Berglund, by laborious processes, prepared the barium salt by hydrolysing either the barium or the mercury barium imidosulphonate, and from this obtained the acid and the other salts. He gave himself unnecessary trouble through his belief, founded on observation, tha,t imidosulphonates have a great tendency to pass at once into ammonium sulphate, instead of stopping at the stage of amidosulphonates, although these, once1646 DIVERS AND HAGA : AMIDOSULPHONIC ACID.formed, are stable enough. Instead of describing Berglund's, now obsolete, process, we will give a very simple modification of it that may sometimes prove useful. Normal barium imidosulphonate, freed from alkali by reprecipitation, is kept on the water bath, with very slightly more dilute sulphuric acid than is equivalent to one- third of its barium, just so long AS a little of the filtered solution is found to yield barium sulphate on boiling; then, after filtering off and washing the barium snlphate, the solution of amidosulphonic acid is evaporated in the cold over sulphuric acid. Nothing need be said of the preparation of the salts from the acid, but a line o r two may be given to the direct preparation of the sodium and potassium salts from the nitrite.If, i n the preparation of the acid from sodium nitrite already described, the mother liquor from the sodium sulphate crystals is further evaporated, sodium amidosulphonate crystallises out, and can be thus obtained, but it i s far better to prepare the salt from purified acid and sodium carbon- ate. Raschig obtained the potassium salt direct, in the above way. Other amidosulphonates cannot be prepared by double decomposition of the alkali salts (see the account of the silver salt', p. 1648). All smidosulphonates (except the oxymercuric) are soluble in water, the least soluble of them being the silver salt (Berglund). Xost of them are exceedingly soluble, and form supersaturated solu- tions (Berglund). They are stable, even in solution, so far as we have observed, except the ammonium salt, which is liable to hydro- lyse, if not quite dry, moreover, their solutions may be kept for hours at loo", or even be boiled without showing decomposition.A double salt of sodium sulphate and arnidosulphonic acid has been obtained by u s a t times, when preparing amidosulphonic acid and separating it from its sodium salt by sulphuric acid ; but experiments made to deteriniue the conditions for its production at will have been unsuccessful. When obtained by us, it had crjstallised from a strongly acid solution, and formed short, thick prisms, somewhat deliquescent. Its analysis showed it to have the composition of 6 mols. amidosulphonic acid with 5 mols. disodium sulphate, and 15 mols. water. Calc. Pound. Sodium .............. 14-72 14.79 Sulphate sulphur...... 10.24 10.18 Sulphonate sulphur.. .. 12.29 12 08 Water ............... 17.28 15.70 This complex may have been only a crystal compound, but it conld not have been a mere mixture, because of its form, i t a apparent homogeneity, and its content of water. It may be written as H,N*SOsH + 5(NaO~S02~NH2*HO~S02.0Na,30H2), which, if theDIVERS AND HAGA : AnllDOSULPHONIO ACID. I647 1 mol. of amidosulphonic acid be neglected, is a salt analogous to the well dcfined and stable ammonium sodium sulphate formed under similar circumstances, the sodium amidosulphonate representing ammonia. I n our accounts of irnidosulphonates and oximidosulyh- onates, already published, we have had occasion to point out the apparent functioning of those salts as amines towards nitric acid.Hydroxylamin e anzidosulpphonate has only been obtained as an uncrystallisable, viscous, hygroscopic liquid. It was prepared by decomposing h ydroxylamine sulphate by its equivalent of barium nmidosulphona te. Ferrozts Amidoszcl~honnte.-This salt was prepared from the acid and iron wire, with exclusion of air. Since the solution of this very soluble salt has to be evaporated in a vacuum, it i3 well to use much less water than would dissolve all the acid, for this then goes into solution in proportion as it is used up in forming the iron salt. The solution and crystals have the usual blue-green colour. The solution shows supersaturation, like that of many other amidosulphonates, and the salt is consequently obtained in the form of a cake of radiating prisms, just like the zinc salt.It is deliquescent, and, unlike the sul- phate, ie not precipitated by alcohol. Pressed between filter-paper, but still slightly damp, some of the salt showed, by permanganate, the presence of 1G.48 per cent. of iron. A salt with 4H20 would have 17.5 per cent. of iron, and one with 5H,O, 16.57 per cent. ; the latter must, we think, be taken as the right expression. Analogy is not available for deciding the point, for, according to Berglund, although the zinc salt has 4H,O, the nickel, cobalt, and manganese salts Bnve 3H20, the cadmium salt 5H20, and the copper salt 2H20. The magnesium salt has not been prepared. Fewk Amidosz~lplionate.-This salt was prepared by dissolving ferric hydroxide and the acid in water. Its solution is bright brown, and dries up into an opaque, amorphous, brittle mass of the colour of ferric hydroxide.It is very soluble in water, but is not at. all deliquescent. It has the full, astringent taste of the ferric salts of inorganic acids, and not that of the citrate or tartrate. The Silver Salt.-Before passing tfo the results of our own exnmina- tion of the important silver salt, we give Berglund’s excellent account of it. ‘* It crystallises best of a l l the salts; it is also the least soluble, requiring about 15 parts of water a t the ordinary tempera- ture (19’). It forms bundles of striated prisms, looking much like those of the sodium salt, and almost as hard and brittle as glass. It blackens only extremely slowly ; its solution is quite neutral. It is best prepared from barium amidosulphonate and a solution in boiling water of its equivalent of silver snlphate.” (Then follows its1648 DlVERS AND HAQA : AMIDOSULPHONlC ACID.analysis, showing it to be anhydrous). It is, however, better to prepare it directly from the acid itself. It is noteworthy that. silver amidosulphonate cannot be prepared from the potassium salt and silver nitrate, as the most concentrated solutions of these salts, mixed in molecular proportions, yield no crystals; when dried u p in the desiccator, it leaves a mixture of crystals consisting of silver amidosulphonate in combination, appa- rently, with silver nitrate, of potassium nitrate, and of silver potas- sium amidosulphonate nitrate. On adding potassium hydroxide to a solution of the silver salt, not too dilute, a, bright jellow-ochre precipitate is produced, and if the potassium hydroxide is in moderate excess, the mother liquor is bright yellow, like a solution of gold chloride.Both precipitate a n d solution are changed by much water, becoming brown, the pre- cipitate dissolving. Blither solution, gives a brown precipitate when heated, o r when mixed with excess of potassium hydroxide, of silver nitrate, or of potassium amidosulphonate, and this precipitate cannot be redissolved. The yellow solution is also unstable, gelatinising on long standing, and becomes colourless. The yellow and brown pre- cipitates and solutions appear all to be colloidal in character. The brown substance in solution and the brown precipitate appear t o be essentially silver oxide.The yellow conipound is not blackened by light, is soluble without colour in potassium amidosulphonate, i s slowly converted to r?. whitish, pulverulent precipitate by diges- tion with silver nitrate solution, and into a white flocculent pre- cipitate by excess of potassium hydroxide. I t s solution in a minimum of potassium amidosulphonate silvers glass a t a boiling heat, so does a solution of potassium nmidosulphonate, silver nitrate, and potassium hydroxide. solution of silver amidosulphonate does not sensibly dissolve silver oxide. 4 solution containing silver nitrate and its equivalent of potassium arnidosulphonate behaves towards potassium hydroxide like silver nmidosulphonate. If the silver nitrate is present in excess, and the solution not too dilute, precipitation of the amidosulphonic compound precedes that of silver oxide, but if the proportion of potassium arnidosulphonate is as 2 mols.t o 1 of the silver nitrate, potassium hydroxide causes no precipitate in solutions of moderate concentration, t h a t is to sas, amidosulphonic acid prevents the pre- cipitation of silver oxide by alkalis. A solution of 2 mols. of potas- sium amidosuiphonate, 2 mols. of potassium hydroxide, and 1 inol. of silver nitrate dries up in the desiccator to a white homogeneous mass of minute, silky fibres, soluble i n water again without change. Alcohol extracts from it no notable quantity of potassium hydroxide.DIVERS AND HAGA : AiVfIDOSULPHOh'IC ACID. 1649 Further experiments are necessary to justify u s in speaking posi- tively, and these, for the time, are impossible, but there can be little doubt, from what has been already ascertained and from analogous facts, that one of the amido-hpdrogens is replaceable by silver, and even by potassium ; that the ochre-yellow collo'idal substance, soluble in water (when it is neither too much nor too little), is AgHNS0,K; and that the white, fibrous, very soluble salt is a compound of silver potassium amidosulphonate with dipotassium amidosulphonate, (KHNSO,K), and potassium nitrate.The power of preventing the precipitation of silver salts by alkalis exhibits amidosulphonic acid playing the part of an amine. It has no solvent effect in the case of cupric salts ; in that of cuprous salts, its action has not yet been tried.The reduction of silver by amidosulphonic acid has been already briefly discussed along with the other properties of the acid (p. 1644). Mercurous amidosulphonafe cannot exist. With a solution of mercurous nitrate, the acid gives a precipitate of metallic mercury and the salt next described. Ox y mercuric Amidosu lphonil t e.-B e rglund recorded that silver amidosulphonate, with mercuric chloride, gives a mixed precipitate of silver chloride and basic mercuric amidosulphonate, amidosulph - onic acid being set free. The normal salt cannot be obtained. When mercuric oxide and amidosulphonic acid are ground together and moistened, they slowly interact, so that, with occasional stirring, the action is complete in two or three days, but the oxymercuric salt, ( H2NSO,HgO),Hg,2H2O, alone is formed, any exceas of acid dissolv- ing out in water, without taking any mercury with it, and any excess of mercuric oxide, evident by its red coloui*, being removable by diges- tion witch much diluted nitric acid.Mercuric chloride and potassium amidosulphonate mix together i n solution without change, but, i f t h e former is not in exoess, the above-mentioned salt is obtained as a white precipitate on adding potassium hydroxide in quantity not exceeding the equivalent of the chloride. The acid can precipitate almost all the mercury from a solution of mercuric nitrate, leaving only nitric acid in solution, and is itself completely precipitated by a slight excdss of mercuric nitrate. To prepare the salt, it. is best to mix a dilute solution of the acid with a concentrated solution of mercuric nitrate in t h e minimum of nitric acid, when the salt is thrown down as a snow-white, volu- minous, and very finely divided precipitate, which is troublesome t o wash, either by decantation or on the filter, and takes long to dry on ;I tile, in consequence of its fine state of division.It is very stable, and may be washed wibh hot water. Air-dried, at the common temperature, i t contains 2H20, which it easily loses when heated at 1 1 5 O . The results of its analjsis are as follows :1650 DIVEItS AND HAGX : XNIDOSULPHONIC ACID. Mercury. 8 ill phur . Water. Calculated . . . . 69.77 7.44 4.19 Found . .. .... 70.80 7.49 4.65 The mercury found is too high through imperfect determination, for when the calculation is made, the total a little exceeds 103; the error does not affect the formula adopted.The salt requires comparat,ively strorig nitric acid to dissolve it in the cold. Hydrochloric acid dissolves it, of course; but’, what is rery remarkable, potassium hydroxide does so too. By using an in- sufficient quantity of alkali, it is possible to decompose the salt partly, znd khus to get a little yellow mercuric oxide from it, which remains insoluble i n excess of alkali; but when the alkali,in excess, is rapidly mixed with it, the salt all dissolves permanently. Mercuric chloride, in presence of enough amidosulphonic acid, is not, therefore, precipitated by potassium hydroxide in excess ; the addition of more mercuric chloride, o r of a little acid, causes the white oxymercuric salt to precipitate, but not mercuric oxide.The precipitation of the oxymercuric salt from an acid solution of mercuric nitrate indicates its nature as a basic salt, while in degree of basicity it agrees with the oxymercuric salts of sulphuric, sulph- urous, and imidosulphonic acids, that is, it contains the bivalent group, -0HgOHgO-. B u t the stability of the salt when heated, its insolubility in dilute nitric acid, and its solubility in an alkali, suggest the possibility of its having another constitution, or of its being subject to tautomery. At least in its alkaline solution, it must almost certainly exist as a potassium salt of the formula Hg”3N,(S03K)2(0H)2, which exhibits it as a sulphonated mercuram- moriium hydroxide. Like other mercurammonium salts, it does not yield up its amine (amidosulphonic acid) when treated with alkalis.I t also behaves like a mercurammonium compound, in being com- pletely resolved, i n accordance with Pesci’s reaction, into amido- sulphonic acid (its amine) and mercuric bromide by a saturated solution of ammonium bromide, ammonia being liberated, thus : Hg3N,(SOsH),(OH), + 12NH4Br = 3[HgBr2(NH4Br),] + 2NH,S03NH4 + 4NH3 + 2H20 Dilute solution of ammonium chloride converts i t into “ white prc- cipitate,” and a solution of mercury ammonium chloride and ammo- nium amidosulphonnte, without any ammonia being liberated. Effect of heating Arnidosulpphonic acid and its Salts. The only statement yet made, concerning the effect of heating amidosulphonic acid i n the absence of water, is Berglund’s, that, when rapidly heated, i t is decomposed ; sulphur dioxide, nitrogen,DIVERS AND HAGA : AMIDOSULPHONIC ACID.1651 water, and sulphuric acid being produced. This is correct, although i t is remarkable that ammonia is not mentioned, as it always occurs in combination among the products. But, much below the ternp?i*a,ture a t which the acid is converted into these pro- ducts, i t suffera a complete chemical change; this occurs to it large extent a t the temperature at which the acid appears to melt, that is a t 205". In a closely limited space, to which air h a s not free access, it sustains no loss in half an hour when heated to 220°, and only about 1 per cent. when heated to 260"; just above 260" small bubbles very slowly form in the liquid, but become re- absorbed if the temperature is lowered ; they consist, almost certainly, of ammonia.There is much expansion in the act of melt- ing, the unmelted particles sinking freely in the melted part; cn cooling, the liquid forms a vitreous mass, which contracts so much as t o partly detach itself from the glass, evert cracking this when very thin. The vitreous product is brittle, exceedingly deliquescent, and very soluble in water. If kept dry, it remains quite trans- parent, and shows no tendency to crystallise even after the lapse of several dajs. Although the vitreous mass obtained by fusing the acid must have the same ultimate composition as the acid itself, it yet contains very little of that acid; for when the mass is dissolved in water more than half the acid that has been fused appears as ammonium hydrogen sulphate, that is, has combined with the elements of water.Now as it is plainly impossible that the change into this sub- stance could arise from the effect of heat alone, it must necessarily be in part, a t least, due to the action of water when the mass is dissolved. This can easily be shown to be the fact, but in doing s o it becomes established that nearly half the acid is actually con- verted into sulphate by heat alone. When the mass is dissolved i n a solution of potassium hydroxide instead of in water, sulphuric acid and ammonia are still the principal products, but the propor- -tion of the former is now not so great as before. I n the alkaline solation, imidosulphonate is present in large quanti ty, sometimes separating out from it in crystals.Since the quantity of ammonia is the same whether the mass is dissolved in presence of potassium liydroxide or not, and since the quantity is more than would be required to form sulphate with the sulphuric acid present in the alkaline solution, it follows that some of the arnmonia must exist in t h e vitreous mass as ammonium imidosulphonate. This explains how it is that more sulphuric acid is got by dissolving the fused product in water than when alkali is present, as the acid imido- sulphonate very rapidly hydrolyses in to sulphate and amidosulphonic acid. Accordingly, the solution in water contains nothing but am-1652 DIVERS AND HAGh : A3JIDOSITLPHONIC ACID. monium hydrogen mlphafe and amidosulphonic acid ; whilst, in the alkaline solution most of the sulphur may be present as sulphate arid imidosulphonate and very little as amidosulphonic acid.Prom this it is evident that in the production of ammonium sulphate by heat alone, one part of bhe acid must yield the elements of water to the other part, being itself converted into imidosulphonate, for nothing escapes during the heating. This is only possible if both sulphate and imidosulphonate come into existence as their pyro- salts; and although neither of these is yet known or has been isolated from the vitreous mass, the analytical data point to t h e presence in it oE these two pyro-salts in molecular proportion, along with some unchanged amidosulphonic acid. The following equation expresses the formation of the pyro-salts : The formation of acid iinidosulphonate,- and t h a t of pyrosulphate,- arc not necessarily simultaneous ; b u t , within the limits of analytical determination, they appear to be so. In the case of some amido- sulphonates, however, the conversion to imidosulphonate partly precedes that into sulphate.On heating the acid much above 260°, the prodncts first formed enter into decomposition. The vapoui-s evolved at first are dense white, and apparently contain much sulphur trioxide, besides dioxide diluted with much nitrogen ; but as the temperature rises and decom- position gets more rapid, the vapours become almost transparent. The decomposition induced by this higher heating is an interesting sequel to the primary decomposition of the acid by heat, the pyro-salts becoining ordimry salts in the following way, as closely as can be traccd : 4HJTSO3H = (NHaSO3)zO + NH4N(SO2),0. 4H,NSO3H = 2NH,N(SO3H)?, 4HJYSO3H =I (wH4s03)20 + (HZN SO2)2O, 5(NH,SO,),O + 5NH,K(S02),0 = GNH4HS0, + 3HN(S03NH,), + 2N, + NH3 + 6S02 + 2S0, When this change is abont eomplet>e, the decomposition, at still higher temperatures, goes an in snch a way as to preserve a residue nearly steady in composition as regards sulphiir (29 per cent.), but t r , cause it to become richer in water and poerer in ammonia and imidosulphonate, until, quite’at the last, the residue consists of am- monium hydrogen sulphats aioiie.The Salts.-When the amidosulphonates of ammonium and potas- sium, are carefully heated, they give a very large proportion of t h e corresponding imidosulphona tes. The karinm salt under the same circunist,ances gives much two-thirds normal ammonium imidosul- phonate and an orange- coloured sublimate of nitrogen snlphid e.DIVERS AND HAQA : AMIDOSULPHONIC ACID, 1653 The silver salt is first converted into an imidosulphonate, NH1N(S03Ag)2, and this, a t a higher temperature, loses ammonia and appears to be changed into HN(S03Ag),. The oxymercuric salt does not decompose until heated nearly to redness, when it gives off sulphur dioxide and nitrogen, whilst at a red heat much mercury, as well as mercury sulphates, volatilise. In the remarks which follow, the mercury salt is not taken into consideration, its decomposition being specific. Xunimary of the Efects of heating the Acid a7id its Salts.-Varied as are the details of the decomposition of amidosulphonates by heat, according as they concern the acid or its barium salt, the ammonium or the potassium salt, the characteristics of the decomposition are the same. There is always, virtually, the change of 2 mols. of amido- sulphouate into imidosulphonate and ammonia, and, for the most part, the union of these to form a normal salt, 2HZNSO3H = NH3 + HN(SO3H)z ; (H2NS03)2Ba = NH3 + HN(S03),Ba. That change is the cumulative resolution of an amine ; next comes the cumulative resolution of the imidosnlphonate as a hydroxide or metalloxide. The elements of 1 mol. of water and, in the case of metal salts, 1 mol. of basic oxide, go from 1 mol. of the imidosul- phonate to auother mol. of it, converting this into sulphate, pyro or normal, as the case may be, and leaving either pyro-irnidosulphonate as a residue, or (when basic oxide has been also lost) nitrogen, ammonia,, and sulphur dioxide, as representatives of what, at lower femperatures, might have been sulphimide, 2NH4N(S03H)2 = (NH,FjOS)zO + NHAN(SO2)zO; 2NH4N(S03)2Ba = 2BaS04 + 2NH3 + [SHNSO,]. The complex [2HNS02] appears as 3(NH3 + N, + 3s03), or, in the case of the barium salt (infusible as that is, and acquiring a higher temperature as it does) this complex partly interacts with the 2NH,, according to the equation 2NH3 + 2HNS02 = 4H20 + 2NS + N,. We are indebted, for their kind assistance, to Mr. Y. Osaka, B.Sc., i n examining the reactions of silver amidosulphonate, and to Mr. M. Chikashig6, B.Sc., in examining the componud of aruidosulphonic acid with sodium sulphate. Imperial Univewity , Td~y6, Japan. TOL LXIX. 5 T

ISSN:0368-1645    

DOI:10.1039/CT8966901634

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

1654 (2x1.-Molecular Conducthity of Amidosulphonic acid. By J ~ J I SAKURAI, D.Sc. (Japan), Professor of Chemistry, Imperial University, Japan. A r the request of Dr. Divers, I have determined the molecular conductivity of amidosulphonic acid. The apparatus which I used for the purpose consisted of a Kohlrausch’s universal bridge, in which the measuring scale is so graduated that the index at once gives the ratio of the lengths of the arms. The essential parts of the whole arrangement are sketched out in the accompanying figure. The primary current from two Daniell’s elements, e, enters the induc- tion coil i ; the induced current divide8 at c (or d), one part passing through the solution s, and the other through the rheostat T , both to return to the coil through d (or c).ha is the measuring wire along which the index, d, is moved, until the telephone, f, no longer speaks, a t which point we have, for the resistances of the various pasts the following relation : s : r :: bd : ad or s = adlbd x r. Since the index, d, at once gives the ratio, bdlad, the resistance of the vessel containing the solution is obtained by multiplying the resistance of the rheostat by this ratio. In all the determinations, I so arranged the resistances that the index should always lie between 0.9 and 1.0 division on the scale when the telephone was silent ; in this manner, any inaccuracy arising from possible errors of calibra- tion was reduced to the minimum. This part of the scale is sub- divided into 10 parts, and it is easy to read to one half of these divisions.Instead of attempting to catch the sound minimum of the telephone, I determined the limits of the region of silence, and took the arithmetical mean of these limits as the true sound-minimum, as, for example, 0.935-0.975 = 0.965. For each dilution, I made two sets of determinations by slightly altering the resistance of theMOLECULAR CONDUCTIVITY OF AMIDOSULPHONIC ACID. 1655 rheostat, each set consisting of two separate readings, and took the mean of these four readings. The resistance vessel employed for holding the solution is of the Arrhenius form, and was made by following the directions given by Ostwald (Handbuch fur physiko-chemisehe Messwagen). Burettes and pipettes were also accurately calibrated according to the methods described in the same valuable work.The temperature at which the determinations were made was 25.00-25.05° throughout, this constant temperature being main- tained in a water thermostat worked by a small turbine. Resistance Capacity of the VesseZ.--E'or determining the resistance capacity of the vessel, I employed N/50 soIution of potassium chloride, the specific conductivity of which is accurately known to be X = 2.594 x If Z = the measured conductivity of the vessel containing N/50 solution of potassium chloride, and c = its resistance capacity, then c = X/Z. The results obtained are given below, in which r = resistance of the rheostat and R = ratio of the two arms of the scale, bdlad. at 25". R. I 1 r . (1). (2). Mean. r.R z- 111. 155 0.955-0.975 = 0.9650 0.955-0.975 = 0.9650 0.9650 149.58 156 0 -950-0 '970 = 0 '9600 0 *950-0*965 = 0 '95'75 0 -9588 149 '5'7 157 0 *940-0*965 = 0 -9525 0 -945-0 -960 = 0 -9525 0 -9525 149 *54 158 0 '935-4 '960 = 0' 9475 0 *935-0 '955 = 0 -9450 0.9463 149 '52 159 0 *930-0 *950 = 0 '9400 0.930-0'950 = 0 -9400 0 -9400 149 -46 160 0,925 -0 '945 = 0 -9350 0' 925-0 '945 = 0 '9350 0 *9350 149 60 Mean..149 *55 Hence, c = h,/Z = 2.594 x loe3 x 0.14955 x lo3 = 0.387933. Specific CGnductivity of Water.-Taking advantage of the cold weather at the time, the distilled water employed for making and diluting the solutions was purified by freezing a portion of it, the ice formed being melted and used in all the determinations. Its specific conductivity was determined with the following results : 9.. R. r.R = 111. 10,000 18-22 = 20.0 200,000 11,000 17-22 = 19.5 204,500 Mean..202,250 -- 1 LU2,250 Hence, h = c.Z = 0.387933 x = 1.9 x As the molecular conductivity of the solutions was determined for v = 32, 64, 128, 256, 512, and 1024 litres, the corrections for the conductivity of -water for the respective dilutions are 6, = 0.06, 0.12, 0.24, 0-49, 0.97, and 1.94; 5 T B1656 SAKURAI : MOLECULAR CONDUCTIVITY these corrections being obtained by multiplying the specific conduc- tivity of water, as determined above, into the molecular volume of the respective solutions, expressed in cubic centimetres. No account was taken of these corrections in the case of the molecular conduc- tivity of amidosulphonic acid, inasmuch as the latter is of a very considerable magnitude when compared with these ; moreover, it is difficult to know whether the impurities in water increase or diminish the conductivity of the acid.In the case of the sodium salt, the above corrections were duly deducted from the observed molecular conductivity. Molecular Conductiiiity of Ainidosulphonic acid.-An N/32 solution of the pure acid (NH2SOsH = 97.11) having been made by dissolving 0.1517 gram in 50 c.c., 20 C.C. of it was transferred to the resistance vessel, and, when a constant temperature of 25' had been attained, a set of conductivity determinations were carried out, with changes of resistance, in the manner already stated. Then 10 C.C. of tho solution was removed from the vessel and replaced by water, and another set of determinations made, and so on, until the strength of the solution was reduced to N/1024.The results are tabulated below, ZI being the molecular volume of the solution in litres, and T and R having the same meaning as before. R. r------------ - 21. r. (1). (2). Mean. T . R = l/t. 32 44 0.9.u)-0*965 = 0.9525 0*945-0*965 = 0'9550 0.9538 41.97 ,, 45 0 *915-0 '950 = 0 -9325 0 *920-0 *945 = 9 *9325 0 *9325 41 -96 - Mean.. 41'97 64 80 0.950-0.975 = 0.9625 0*950--0*975 = 0.9625 0.9625 77.00 ,) 82 0 '930-0*950 = 0 -9400 0.930-0 *950 ;= 0 '9400 0 .&400 77 '08 - . Maan.. 77-04 128 150 0 -956-0 -980 = 0 -95'75 0 -955-0 '980 = 0 -96'75 0.9675 149 '13 ,, 152 0 -945-0 *965 = 0.9550 0 '9454 *970 = 0 -9575 0,9563 145 -36 - Mean. . 145 '25 256 290 0,945-0 -965 = 0 -9550 0 *940--0 '965 = 0 -9525 0 '9538 276 '60 ,, 294 0 -925-0 '950 = 0 *9375 0 *930-0.955 = 0'9425 0 *9400 276 *36 Mean..25'6 -48 612 570 0 -950-0 '9'75 = 0 -9625 0 *950-0*975 = 0 -9625 0 *9625 548 '63 ), 680 0 '9304 9% = 0 -9425 0.935-0'965 = 0 -9500 0 '9463 548 *86 Mean. . 548 -74 ), 1140 0*940-0*965 = 0.9525 0.930-0.970 = 0.9500 0'9512 1084.39 Mean.. 1084 '00 1024 1120 0.955-0 '980 = 0 -9675 0 '955-0 '980 = 0.9675 0 -9675 1083 -60 __I-OF AMIDOYULPHONIC ACID. 1657 The moleoular conductivities, pw, of amidosulphonic acid for the respective dilutions are, therefore, p32 = 0.387933 X 32/0.04197 = 295.78 p64 - ,, x 64/0.07704 = 324.86 Plzs = ?, x 128/0.14525 = 341.87 D256 = ,, x 256/027648 = 359.20 p512 = ,, X 512j0.54874 = 361.95 /4024= ,, x 1024/1.08400 = 366.46 The molecular conductivity of the acid at infinite dilution, pa, has been calculated from that of the sodium salt.Molecular Conductivity of Sodium Amidosulph0nate.-A solution of pure sodium hydroxide, prepared from metallic sodium, was made, titrated witb pure and crystallised oxalic acid, and made up to N/32, phenolphthale'in being used as the indicator. About 30 C.C. of this solution was carefully neutralised with powdered amido- sulphonic acid, with addition of a trace of phenolphthaleyn, and filtered with the usual precautions. Then 20 C.C. of the neutral solution was transferred to the resistance vessel, and conductivity determinations were made in exactly the sane manner as with the acid. R. u. r. (1) (2) Mean. T . R= lil. [Po0 = 3 73-97]. The results are as follows : -7 r--------.A- -- 32 155 0 -945-0 -960 = 0 -9525 0 *935-0 -960 = 0 -9475 0 -9500 147 '25 ,) 156 0 '935-0 '955 = 0 -9450 0 '9304) '955 = 0 '945 0 -9438 147 '23 - Mean .. 147 '29 64 395 0 '940-0 -975 = 0 '9575 0*945-0*970 = 0 '95'75 0.9575 282 -46 fi 300 0 -92,- '960 = 0 -9925 0 *930--0 *960 = 0 -9400 0 -9413 282 -39 Mean . . 282 -43 128 570 0 950-0 '970 = 0 *9600 0 -9504 '9'70 = 0 .MOO 0 '9600 547 '20 ,, 575 0 '945-0 '960 = 0 -9525 0 '940-0 -960 = 0 '9500 0,9513 547 -00 Mean . . 547 -10 256 1130 0 094-0 -960 = 0 '9800 0'940-0 '960 = 0 *9500 0 -9500 1073 -50 ,) 1140 0 '930-0 '955 = 0 -9425 0 '925-0 '9.55 = 0 *9900 0,9913 1073 '08 -- Mean . . 1073 -29 612 2200 0 '935-0 '9170 = 0 '9525 0 *93O-c~9'70 - 0 -9500 0 '9513 2092 '86 ,) 2240 0 '91- '955 = 0 -9350 0.915--0*935 = 0 '9350 0 '9350 2094 -40 -- Mean .. 2093 -63 1024 4300 0 -950-0 *970 = 0 -9600 0 .W-O -970 = 0 -9550 0 '95'75 4117 '25 ), 4400 0 '925-0'950 = 0 '9375 0.925-0 -955 = 0,9350 0 -9363 4119 '72 -- Mean .. 4118'491658 SAKURAI : MOLECULAR CONDUCTIVITY The molecular conductivity of sodium amidosulphonate is, there- fore, %J* PV. ~ 3 2 = 0,367933 x 32/0*14724 = 84.31 0.06 84.25 /&it = ,, x 64,’0*28243 = 87.91 0.12 87.79 PI28 = ,, x 128/0*54710 = 90.76 0.24 90.52 p256 = ,, x 25611.07329 = 92.53 0.49 92.04 p512 = ,, x 512/2.09363 = 94.87 0.97 93.90 PI024 = Y, x 1024/4v11849 = 96.45 1.94 94-51 It may be observed that the difference, plM - b2 = 10.26, is of the same magnitude as that in the case of the sodium salts of all the monohasic acids, showing that the ions of amidosulphonic acid are XI and NH2S03.For calculating the molecular conductivity of sodium amidosulphonate at infinite dilution, I have made use of Bredig’s table (Zeits. physikal. Chem., 1894, 13, 198), which gives a more concordant result than the use of Ostwald’s values. v : 32 64 128 256 512 1024 d,: 14 11 8 6 4 3 pv : 84.25 87.79 90.52 92.04 93-90 94-51 pCa : 98.25 98.79 98.52 98.04 97.90 97.51 Mean 98.17. The velocity of migration of the Na ion being 49.2, that of the NH2B03 ion is 98.17 - 49.2 = 48.97 ; and the velocity of migration of the H ion being 325, the molecular conductivity of amidosulphonic acid a t infinite dilution, pa, is evidently 325 + 48.97 = 373.97. Discussion of the Besults.-The velocity of migration of the anion, NH,SO, = 48.97, approaches those of Br03 = 50.5 and F = 50.8; it is much greater than that of 10, = 37.9 or HZPOa = 33.5, and much less than that of C1 = 70.2, Br = 73.0, I = 72.0, or NO3 = Wl.Among the organic anions, that of formic acid, HCO, = 31.2, is the only one which exceeds NH2S03 in velocity. The ‘‘ strength ” of amidosulphonic acid may be judged of from the degree of its dissociation, pzt/,uLao = rn. The following table, in which 100 times this ratio is calculated, shows that amidosulphonic acid is already dissociated to the extent of 79 per cent. in a, K/32 solution, and that the degree of dissociation attains 98 per cent. in n N/1024 solution Amidosulphornic acid (pa = 373.97) t’: 32 64 128 256 512 1024 pV : 295.78 324.86 341.87 359.20 362.95 366.46 loom : 79.09 86.87 91.42 96.04 96.79 97.99 Amidosulphonic acid may, therefore, be ranked among the strongOF AMIDOSULPEONIC ACID. 1659 mineral acids, being nearly comparable with iodic acid, as may be seen from the following numbers : 100 nz.I------- 6. H,NH,SO,. H,I$ 32 79-09 84.60 64 86-87 90.11 128 91.42 93.96 256 96-04 95.89 512 96-79 97.27 1024 97-99 97-55 In its constitution, amidosulphonic acid is sulphurous acid in which the H directly combined with sulphur has been replaced by the group NH2 : Sulphurous acid. Amidosulphonic acid. Now it is evident, from the measurements of Ostwald (J. pr. Chem., 1885, 32, 314) and of Barth (Zeits.physika7. Chern., 1892, 9, IN), that sulphurous acid, in point of electric conductivity, behaves as a monobasic acid, its ions being H and HSO,. It is, therefore, possible to obtain a knowledge of the inffuence of the replacement of H by NH, on the strength of the acid, by comparing together the values of 100 m.of sulphurous and of amidosulphonic acids. Determinations of the electric conductivity of sulphurous acid, as well as of metallic sulphites, are, however, attended with considerable inaccuracy, owing to the unavoidable and rapid oxidation occurring during the deter- mination. The following are the numbers obtained by Barth (Zoc. cit.) at 25’: v = 32 64 128 256 512 1024 Sulphurous acid, H,SO,H.. . . 177.5 214 ‘9 248 -5 279.0 303 -3 524 -7 Hyd. sod. sulphite, Na,S03H.. 80 *9 84 *7 88 *7 92 *5 95 -8 98 ‘8 The difference, pi024 - “32, for the sodium salt, instead of being about 10, is as high as 17.9, this error arising from the partial oxidation of the sulyhite into sulphate; the numbers obtained by Barth are, consequently, admittedly too high, the higher as the soln- tion is the more dilute.We have, therefore, no means of calculating exactly the velocity of migration of the anion SO,H, but it may be approximately taken as (80.9 + 14) - 49.2 = 45.7, 80-9 being the value of pa for the aodium salt, 14 Bredig’s constant for this dilution, and 49.2 the velocity of migration of the kation Na. The approxi- mate molecular conductivity of sulphurous acid at infinite dilution is, therefore, ,urn = 325 +- 45.7 = 370.7, and the values of 100 pa/pa0 for this acid at the respective dilutions are :1660 SAKURAI : MOLECULAR CONDUCTIVITY 2, = 32 64 128 256 512 1024 100m = 47.88 57.97 67.04 75.26 81.8% 87.59 The increase of dissociation with dilution, as thus calculated, is admittedly too great, inasmuch as the oxidation of sulphurous acid gives increasingly too high values of ,up.Taking this fact into con- sideration, and comparing the above numbers with those obtained for amidosulphonic acid : v = 32 64 128 256 512 1024 100m = 79.09 86.87 91.42 96.04 96.79 97.99 it becomes evident that umidosulphonic acid is much stronger than suQhu~ous acid. This conclusion, drawn from the study of the electric conductivity of amidosulphonic acid, is interesting from the fact that the influence of the NH, group on the strength of oyganiic acids generally is quite of the opposite character. Thus, from the data given by Ostwald (Zeits. physikal. Chew., 1887, 1, 74), I have calcu- lated the following values of 109 m.fGr benzenesulphonic acid : et = 32 64 128 256 512 1024 100 m = 90.91 93.95 96.15 98.52 99.61 100.00 Benzenesulphonic acid is thus one of the strongest acids, whilst its amido-dcrivatives are far below it in strength, as may be seen from the following numbers (Ostwald, Zeits. physi2aE. Chem., 2889, 3, 406) : 100 m. Ortharmdobenz. Me tamidobenz. Paramidobenz. V . sulphonic acid. sulphonic acid. aulphonic acid. f--7--- 7 32 - - 12.79 64 SG.6 10.25 17.52 128 47.1 14.26 23.80 256 58.5 19-70 31-SO 512 69% 26.55 21.60 1024 80.0 34.70 53.00 Again, benzoic acid is stronger than its amido-derivatives, and acetic acid, though itself a very weak acid, is yet incomparably stronger than glycocine. These are facts already well established (compare J.Walker, Proc., 1894, 137). The striking contrast between the influence of NH, on the strength of organic acids generally, and that on sulphurous acid-the only inorganic acid of which the electric conductivity of the amido- derivative has been determined-has, in all probability, to be ac- counted for by the circumstance that, in the former, the basic group -R"*NHz acts on -COOH or -SOsH, forming internal ammoniam salts, as wag first suggested by Erlenmeyer (compare J. Sakurai-;01' AMIDOSULPHONIC ACID. 1661 " Constitution of Glycocoll and its Derivatives," JOW. Rc. CoZZ., Imp. Fniu., Japan,, 7; or Proc., ;1894, 137). Indeed, Ostwald, after determining the molecular conductivihy of glycocine, and finding that it increases only very slightly on dilution, goes on to remark : " The nature of this series of numbers is rather that of a neutral salt, and the conclusion already drawn from the neutral reaction of glycocinc, that it is a salt-like compound, is confirmed by the electri- cal measurements " (J.pr. Chem., 1885, 32, 369). In another paper, the same author speaks of amidoacetic acid as one " which can no longer be called an acid " (Zeits. physikal. Chern., 1889, 3, 189). I have shown in another place (Zoc. cit.) that the conclusion is inevitable, that not only glycocine, but organic amido-acids generally, are salt-like compounds ; the study of the electric conductivity of amidosulplionic acid has confirmed this view by showing that the mere presence of NH2 does not diminish the strength of an acid, and that the fact, therefore, that organic amido-acids are weaker than the non-amidated acids must be explained by assuming the nitrogen of the basic group, -R"*NH2, to be in combination with the hydrogen of the acid group, -COOH or -S03H, thus : H3N*R"*CO*0 or H3N*R"* S 02*0, the dissociation of these molecules into H, on the one hand, and L---I L - 2 H2N*R".C0*O or H2N*R"*CO*0, on the other, occurring to a much L A L I less extent than in the case of non-amidated acids, which dissociate into H and R * C 0 2 or R'*SO,.It may be observed that the intro- duction into organic amido-acids of a group that diminishes their salt -like character must facilitate their dissociation, and thus increase their conductivity and strength. The superior conductivity of aceturic and hippuric acids, as compared with that of glycocine, may be cited in favour of this view.The Lmu of Dilution.-As is well known, Ostwald's dilution formula- which expresses the relation between conductivity, pv, and dilution v, oE eiectrolytes which are only moderately dissociated, does not, apply in the case of highly dissociated electrolytes. Now, Rudolphi has shown (Zeits. physikat. Clzenz., 1895, 17, 315) that the following empirical formula well expresses this relation : and, further, van't Hoff (Zeits. physikal. Chem., 1896, 18, 300) has1662 LOEW : PHFSIOLOaICAL ACTION pointed out that the relation may be equnlly well expressed by altering Rudolphi’s formula into K = Pa which may be written as I( = C?/CS3, 1 where &!- . - = Ci is the concentration of the ion, and r , v (1 -E!.)L ,v = c, is that of the undissociated salt. I have tested the above formulae wit>h sodium amidosulphonate ; tlhe results which are tabulated below are in agreement with both of them : Xodium Amidosulphonate (pa = 98.17). z1 = 32 64 128 256 512 1029 pD = 8425 87.79 90.52 92.04 93.90 94.51 KR = 1.00 1-03 1.05 0.96 1.01 0.85 KH = 1.00 1.01 1-01 0.92 0.96 0.80 The values of K, and KH have been calculated according to Rudolphi’s and van’t Hoff’s formulae, respectively, the value found for z1 = 32 litres being, in both cases, made equal to 1. The results are almost equally constant u p to v = 512 litres, but, in both cases, there is a greater deviation for the last dilution, owing, no doubt, to a greater experimental error.

ISSN:0368-1645    

DOI:10.1039/CT8966901654

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

1662 LOEW : PHFSIOLOaICAL ACTION CX 11.-Ph ysiological Action of AmidosuZphonic acid. By OscAit LOEW, Pb.D. AT the suggestion of my colleague, Dr. Edward Divers, I have made a, series of physiological tests on plants with amidosulphonic acid (amidosulphuric acid). This acid, in 0*05-0*1 per cent. solutions, was applied in the form of its calcium or sodium salt, either alone or in conjunction with mineral nutrient salts, namely, monopotassium phosphate, 0.05 per cent. ; magnesium sulphate, 0.05 per cent, ; calcium sulphate, 0.1 per cent.; and a trace of ferrous sulphate. These solutions (500 c.c.) were applied to the whole plants, or t o the branches and isolated leaves, of different families of the phEeno- gams ; also to algze, IoweP fungi, and lower aquatic animals.OF AMIDOSULPHONIC ACID.1663 The principal result, in regard to pbsenogams, was that amido- sulphonic acid has, even in its salts, a decidedly ~zoxious actioiz, clearly established by control experiments, made at the same time and on similar organisms, kept in water and in solutions of ammoninm sulphate and sodium sulphate. Some of the experiments mere the following : Young wheat plants, carefully taken from the field, 20-25 cm. high, were placed in three vessels, containing each 500 C.C. of ( a ) common water, ( t ) 0.1 per cent.\ of neutral ammonium sulphate, (c) 0.1 per cent. solution of sodium amidosulphonate. I n ( a j and ( 6 ) new rootlets gradually developed, but not in (c). After five days, withering of the leaves commenced in (c), and complete death had happened in nine days, whilst the plants in ( a ) and ( b ) mere still perfectly healthy.Young branches of Prunus Cernsus, 40 cm. long, were placed in the same solutions and also in 0.1 per cent. of hydrated sodium sulph- ate. After three days, brown spots had appeared upon all the leaves kept in the amidosulphonate, and, two days later, all these leaves were dried up, whilst in the control solutions the branches still remained healthy, and for a long time afterwards. Isolated leaves of Bscidus and Mows behaved in these solutions in the same way. Mr. Maeno made, under my supervision, further experiments with young plants of Alliurn Jistulosunz, Soja hispida, and Brassica Rupa, and in all these cases some noxious action of calcium amidosulphonate became evident.In these experiments, all the mineral nutrients were present. In contrast to what precedes, algse (Spirogyra Mesocu?-pus) had not suffered, even in a 1 per cent. solution of calcium amidosulphonate, after a week, whilst the ammonium salt killed them, in 0.5 per cent. solution, within two days.* That mould-fungi and bacteria can utilise amidosulphonic acid as a source of nitrogen was clearly established by their development in solutions containing 1 per cent. of cane sugar, 0.1 per cent.. of niono- potassium phosphate, 0.1 per cent. of magnesium sulphate, and, as the only source of nitrogen, 0.1 per cent. of amidosulphonic acid, either free or as calcium salt. Mr. Maeno studied the matter closely with beer yeast, and observed that, although the acid can be utilised as a source of nitrogen, it is not so good for the purpose as ammo- nium sulphate.10 C.C. of thin beer yeast, corresponding t o 0.0613 gram of dry matter, was suspended in a solution containing in 100 C.C. 6.856 grams of glucose, 0.1 gram of magnesium sulphate, 0.2 gram of monopotassium phosphate, an6 0.1 gram of sodium amidosulph- * All ammonium salts are, for these kinds of algee, noxious at this concentra- tion.1664 PHYSIOLOGICAL ACTION OF AMIDOSULPHONIC ACID. oiiate (A). In a second flask, (B), the last-mentioned salt was replaced by 0.1 gram of ammonium sulphate. After five days the yeast in (A) bad ipcrensed 169 per cent., and that in (B) 223 per cent., whilst of the glucose there had been fermented in (A) 48.8 per cent., and in (B) 55.2 per cent.Finally, it may be mentioned that on lower aquatic animals as Infusoria, Rotatoria, and Copepoda, calcium amidosulphonate, in 0.1 per cent. solution, had no noxious action. The poisoncus action of amidosulphonic acid on phaenogams is of considerable interest. Ammonia, in its salts, acts noxiously also, but only in higher concentration; it never is stored up as snch in plants, as nitrates are, but is quickly converted into an indifferent substance, asparagine, as the recent investigations of Kinoshita and Suzuki, in the College of Agriculture, T6ky6, have placed beyond doubt. It is the failure of the plants to convert amidosulphonic acid into an analogous indifferent substance that, perhaps, gives time for the gradual action of the labile amido-group on the living protoplasm.The poisonous action of the labile amido-groups in hydroxylamine and diamidogen for the most varied organisms is well known. The fact that amidosulphonates are poisonous neither for lower plants like algae and low fungi, nor for animals (see t,he ADDENDA to this paper), still needs an explanation that shall be perfectly satisfactory. The corresponding carbamic acid was found by Nencki to have a poisonoils effect on animals. Imperial University , Japan. ADDENDA, by EDWARD DIVERS. Further experiments on the physio- logical action of amidosulphonic acid are i n progress in Dr. Loew’s laboratory in the Agricultural College of the University, the results of which will appear in the Bulletin of the College. When the above paper was written, the fact had not been ascertained that amidosulphonic acid acts as a reducing agent on alkaline silver solutions, apparently becoming oxidised to water, nitrogen, and sulphite. This reducing power brings i t into association with hydroxylamine, hydrazine, and amidogen, which Dr. Loew has shown to be so highly poisonous ; though only remotely, because its reducing power is so feeble, as compared with theirs. The simultaneous generation of sulphite should add to its poisonous action. Professor D. Takahashi, of the Msdical College of this University, has examined the action of sodium amidosulphonate on vertebrate animals, and has kindly communicated his results t o me. HE injected 0.2 gram of it subcutaneously into a frog, and intravenouslyPREPARATION OF HTDROSYLAMINE SULPHATE. 16 G5 1.4 grams into a young dog weighing 2 kilos., in both cases without an injurious effect or any symptoms like those observed by Nencki in experiments with sodium carbamate. Amidosulphonates, there- fore, seem not to be poisonous t o animals.

ISSN:0368-1645    

DOI:10.1039/CT8966901662

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

PREPARATION OF HTDROSYLAMINE SULPHATE. 16 G5 CXII1,-Economical Preparatdoiz of Hyclyoxylamiize Sulphate. By EDWARD DIVERS, M.D., F.R.S., and TAMEMARA HAGA, D.Sc., F.C.S. IN 1887, Raschig made known that hydroxylamine can be got from a nitrite by sulphonation followed by hydrolysis, and took out pat,ents for its manufacture in this way. As to what extent these patents may have since been worked, and with what success, we have no information; but we cannot believe that this process has been advan- tageously carried out, unless the directions he gave have been greatly modified. The one we are about t o describe is very productive and economical for the preparation of hydroxylamine sulphate, a non- deliquescent salt readily forming large crystals, and soluble in three- quarters of its weight of water at 20".Commercial sodium nitrite of 95 per cent. nitrite does not contain more than 1 per cent. of objectionable matters, such as chloride and nitrate, and is, therefore, pure enough. A qoncentrated solution of this salt (2 mols.), and of sodium carbonate (1 mol.), pretty closely adjusted in these proportions, is treated with sulphur dioxide until just acid, while it is kept well agitated at 2-3' below zero by immer- sion in ice and brine; at this temperature, the conversion of the nitrite into oximidosulplionate appears to be perfect. When gently warmed with a few drops of sulphuric acid, the oximidosulphonate rapidly hydrolyses, with marked rise of temperature, into oxgamido- sulphonate and sodium hydrogen sulphate. The solution of these salts is kept at 90-95' for two days, by the end of which time all the oxyamidosulphonate will have hydrolysed into hydroxylamine sulphate and sodium hydrogen sulphate ; the quantity of ammonium salt produced is so small that i t can only be detected in the very last, mother liquor of cry stallisation, using platinic chloride (potassium hydroxide being an unsuitable reagent in presence of hydroxylamiue).At 80--55O, five days are necessary, but then practically no ammonia is formed; at 70', three weeks, at least, are necessary; whilst at the common temperature much oxynm idosulphonic acid remains un- changed after several months, even when much sulphuric acid has beer, added. On the other hand, the solution kept boiling needs1666 PREPARATION OF HYDROXYLAMINE SULPHATE. only seven or eight hours usually to deprive it of all sulphonate, bu the effect of the boiling on the hydroxylamine is disastrous, destroy- ing at least one-third of it, by converting it (through amidosulphonic acid?) into ammonia, and wasting another third as a practically inseparable mixture of its sulphate with ammonium aulphate.To make sure that all sulphonate has been hydrolysed, it is well t o add barium chloride in excess to a little of the solution, filter and boil the filtrate with potassium chlorate, to convert any sulphonate into sulphate. When the change is complete, the solution is neutral- ised with sodium carbonate, using methyl-orange as indicator, and evaporated until it weighs only lo+-11 times as much as the sodium nitrite taken ; if now left to cool where its temperature will fall to Oo, or below, nearly all the sodium sulphate will crystallise out, and Ght: mother liquor, on being evaporated sufficiently, and allowed to cool to the common temperature, yields much hydroxylamine snlphate, the mother liquor from which, very slightly diluted and cooled below O", gives again a little sodium sulphate, and can then be worked for more hydroxylamine sulphate, as before.The crude hydroxylamine sulphate weighs about 9 parts for every 10 parts of sodium nitrite taken. It needs to be recrystallised, but the mother liquors can be closely,worked up. On the other hand, the sodium sulphate recryst,allised, or even washed with ice-water, will give up 1 part more of hydroxylamine sulphate; so that sodium nitrite will yield, on the small scale, nearly its own weight of pure hydroxylamine sulphate. No doubt, on the large scale, the theo- retical yield of 118.84 per cent. could be more nearly approached. Potassium nitrite is not well fitted for the preparation of hydroxyl- amine, because of the difficulty experienced i n closely separating the hydroxylamine sulphate from that - of potassium. After several recrjstallisations, the hydroxylamine salt still contains 1.8 per cent. of potassium sulphate. The addition of aluminium sulphate is not an improvement, €or then the hydroxylamine sulphate, sepal-ated as far as practicable from the potassium alum, leaves behind, on ignition, 5.7 per cent. of residue. Imptrial Uriil;e&ty, Tokyo, Japan.

ISSN:0368-1645    

DOI:10.1039/CT8966901665

出版商:RSC    

年代:1896

数据来源: RSC