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BISSETT: THE REMOVAL OF SULPHUR FROM SILVER. 2829CCLXV.-The Removal of Sulphur from Silver.By CRELLYN COLGRAVE BISSETT.THE fact that sulphur is found a t times in silver, especially in thecase of metal recovered from materials containing thiocyanates, hasbeen mentioned by hhe aathor in a previous paper (this vol., p.1223). When recovering metal from such residues the danger canbe removed to a large extent by a preliminary digestion of thematerial with warm ccacentrated hydrochloric acid. The lasttraces of sulphur can be removed by the addition of a little potass-ium nitrate to the sodium carbonate used in the recovery.The removal of sulphur from metallic silver by fusion withpotassium nitrate is very tedious, as the oxidation proceeds veryslowly. It appeared possible that the sulphur could be removedmore readily by the addition of the necessary quantity of a secondmetal.The results obtained by adding copper and iron respec-tively have been studied to some extent. The effect produced byblowing air through the molten metal has also been determined.VOL. cv. 8 2830 BISSETT: THZ REMOVAL OF SULPHUR FROM SILVER.The results obtained by the metallic additions have a furtherinterest, since they show the nature of the chemical equilibriumin these cases at moderately high temperatures.I. Znfiuence of Copper on Silver containin,g Sulphur.The freezing-point diagram for the mixture silver sulphide-cuprous sulphide has been determined by Friedrich (Metallurgie,1907, 4, 671), who found that mixtures of these substances forman unbroken series of solid solutions, the freezing-point curve fallingto a minimum a t 70 per cent.of silver sulphide, the freezing pointof this mixture being 67F.Cuprous sulphide is the only sulphide of copper stable a t hightemperatures.The results given below tend to show that the equilibriumbetween the eulphides is not affected by the presence of excessof either or both of the metals.The effect produced by adding copper to silver containing 13.5per cent. of silver sulphide was first studied. It was found that theaddition of small amounts of copper caused the first freezing pointof thei alloy to be lowered, whilst a t the1 same time the temperatureof the halt in the cooling curve due to the' materials being incom-pletely niiscible in the liquid state was raised.This change con-tinued until 2 per cent. of copper had been added; the mixturethen had only one main freezing point. An examination of thevertical section of the ingot a t this stage showed that the mixturehad separated into two ldyers in the liquid state. A further addi-tion caused the freezing point t o rise to a maximum, with approxi-mately 3.5 per cent. of copper, and then to fall gradually. Whenabout 9 per cent. of copper had been added, the cooling curve ofthe mixture showed a second break after the first freezing point,due to the separation of the copper-silver eutectic. The eutecticarrest, when it first appeared, occurred a t a temperature consider-ably below the average value.The mixture gave only one freezingpoint wheil approximately 31 per cent. of copper had been added.It was evident after the first few determinations that copper wasof little use for removing sulphur from silver.The effect of small additions of copper can only be explained onthe principlo that part alloys with the silver, whilst the remainderreplaces the silver in a portion of the silver sulphide, formingcuprous sulphide which dissolves in the excess of silver sulphidepresent in the mixture. The initial rise in the temperature ofincomplete miscibility is apparently due t o the influence of thecopper in lessening the solubility of the sulphide. This is to bBISSETT: THE REMOVAL OF SULPHUR FROM SILVER. 2831expected since cuprous sulphide is insoluble in copper.The lowtemperature of the eutectic halt in its early stages may be due t othe presence of sulphur in solution.Microscopic evidence supports the above interpretation, since theamount of sulphide present remains fairly constant until 2 percent. of copper has been added. A further addition of copperlessens the area of sulphide slightly, whilst the addition of morethan 3.5 per cent. of copper rapidly removes practically the wholeof the sulphide from the silver.I n order to follow the changes a little more completely the effectof heating practically pure silver sulphide with varying percentagesof copper was examined to some extent. It was found that thebehaviour was very similar to that described above. The mixtureseparated into two layers in the liquid &ate, when about 3 per cent.of copper had been added.The freezing point of the layer rich insulphide was determined in a number of cases. As was to beexpected, since cuprous sulphide and silver sulphide forni a con-tinuous series of solid solutions when melted together, these freezingpoints were very poorly defined. The temperature of the freezingpoint was lowered rapidly by the addition of copper.On examining these parts of the alloys under the microscope, itwas found that tho metallic portion of the mixtures had a veryconsiderable solubility, especially in the case of mixtures containinga moderately high percentage of copper.EXPERIMENTAL,The determinations were carried out in a manner analogous tothat described in the previous paper (Zoc. cit.).It was necessaryto stir t'he various mixtures very thoroughly in order t o ensureequilibrium.The following tables give information obtained from tlie coolingcurves :TABLE r.Ttzpuences of Copper o n Silver containing 13.5 per cent. ofSilver Sulphide.Alloy number.A.C. 1718192021222324Percentage of First freezing Second freezingcopper. point. point.0 920" 903"0.5 917 90s1.0 916 9101.5 915 9112.0 9122.8 9173.5 917 -4.3 9106.2 903--8 . Y 2832 BISSETT: THE REMOVAL OF SULPHUR FROM SILVER.Alloy number.A.C. 2526272829303132 . 333435TABLE I (continued).Percentage of First freezingcopper. point.6.2 gooo7.3 8929.0 87311.9 86315.6 84019.8 81227.1 78230.0 77337.5 79645.6 83754.5 867Second freezingpoint.-752O764771768772771771773772TABLE 11.Influence of Copper on Silver Sulphide containing 1 per cent.of Free Silver.Percentage of First freezingAlloy number.copper. point.- 0 802'A.C. 36 0.6 85937 1.2 88339 2-5 89840 3.2 90041 4.0 90343 7.5 91844 10.8 92045 14.1 92 146 16.9 92147 19.3 92149 23.2 91060 28.4 89261 33.3 84752 39.9 7 8253 47.2 803Second freezingpoint.798'794777766756-720674-761770774774The second ,series of points for alloys A.C. 36-A.C. 44 are inevery case the freezing points of the layer rich in sulphur. It wasfound impossible to determine similar freezing points in mixturescontaining a higher percentage of copper with any degree of accu-racy.So far as could be determined, the freezing point appeared t orise steadily as the percentage oi' copper was increased.The compositions of the inixtures tabulated above were deter-mined from the weights of material used, since in the majority ofcases there wese two liquid layers, and it was found difficult todetermine exactly the relative amounts of these.The curves obtained by plotting the above results are shown inFig, 1BISSETT: THE REMOVAL OF SULPHUR FROM SILVER. 2833II. Influence of Iron, on Silver containing Sulphur.The relation between siIver sulphide and ferrous sulphide hasbeen determined by Schoen (Uetallurgie, 1911, 8, 737), who foundthat mixtures of these substances form a simple eutectif erous series,the eutectic containing 11 per cent.of ferrous sulphide, with amelting point of 6 1 5 O .It appeared highly probable that iron would be a suitable metal930"91 0"890"870"850"8 30"810"790"770"750"730"710"690"670-__. 13.5 per cent. solution.99'0 ,, - - - - - - - - 9 ,Percentage of copper.to add in order to remove sulphur, since silver and iron areimmiscible eves a t 1600O (Petrenko, Zeitsch. unorg. Chem., 1907,53, 212), and also ferrous sulphide is stable in comparison with themajority of other sulphides.I n the present investigation the effect produced by adding vary-ing percentages of iron to molten silver containing 11.6 per cent.of silver sulphide has been studied2834 BISSETT: THE REMOVAL OF SULPHUR FROM SILVER.Three mixtures only were examined, since these gave sufficientThe following table' gives the result of the thermal investigation :information.TABLE In.Alloy number.Percentage of First freezing Second freezing - iron. point. point.A.F. 1 0 927' 903"A.F. 2 1.2 95 1 904A.F. 3 5.8 960 noneA.F. 4 10 960 noneAlloys after A.F. 1 were found to contain two layers in the liquidstate. The lower layer was rich in silver, whilst the upper layerwas rich in sulphur. Tho freezing points given refer in all cases tothe layer rich in silver. The upper layer in A.F. 4 appeared tofreeze a t a temperature above 1000°.Alloy A.F. 2 contains sufficient iron to saturate half the sulphurpresent. It will be seen that whilst the first freezing point israised to 951°, the second freezing point is practically constant.It seems probable, thesefore, that the iron combines with as muchas possible of the sulphur present, and a t the same time thesulphide formed is insoluble in silver.Microscopic evidencesupports this view, since the sulphide remaining in solution in thesilver in this alloy behaves in a manner similar to that of silversulphide, towards etching media. The freezing point, 951°, corre-sponds with that of an alloy containing 4.5 per cent. of silversulphide. Apparently , therefore, the ferrous sulphide formed dis-solves a considerable portion of the silver sulphide left in themetal. This is made the more probable by the fact that a polishedsection of the upper layer of the ingot shows traces of a eutecticstructure.Alloy A.F.3 contains sufficient iron to saturate the whole of thesulphur present. Apparently this is what does occur, since thefreezing point of the mixture rises t o that of pure silver, and thereis no second freezing point. It was found, however, on examiningthe layer rich in sulphur under the microscope that silver sulphidewas present. On adding a considerable excess of iron above that'required to saturate the sulphur, the silver present in the upperlayer was displaced by iron, the upper layer then consisting ofpractically pure ferrous sulphide.Iron, theref ore, when added to molten silver containing silversulphide appears to remove the sulphur from solutionBISSETT: THE REMOVAL OF SULPHUR FROM SILVER.2835111. Effect Produced by Blowing Air through Molten Silvercontaining Sulphur.I n the experiments being described dry air was blown throughthe molten metal a t about 1000°, the rate being approximately thesame in every case.The alloy contained 16 per cent. of silver sulphide, and 30 gramsof alloy were used in each experiment. Table I V gives the resultsobtained.TABLE IV.Experiment Time of blowing air.number. Minutes. Freezing point.1 0 907'960"950"940'930"92G"910"900-27162944 -FIG. 2.91392 193394394595910 20 30 40 50Time of blowing air: in minutes.I n experiment 7 the material from experiment 6 was re-melted.Charcoal was added, and the mixture was well stirred.The curve obtained by plotting the results is shown in Fig. 2.It will be seen that the removal of sulphur is somewhat slow underthe conditions of the experiments. The rate a t which air wasblown through the material was of necessity slow, owing to theviolent spitting caused by a rapid stream of gas.Charcoal was added in experiment 7 to remove the oxygenpresent in solution in the silver, in order to determine whether theproduct a t that stage was pure silver. The freezing point obtaine2836 MARTIN: RESEARCHES ON SILICON COMPOUNDS. PART VI.is slightly lower hhan that of pure silver. Microscopic examinationBhowed that no sulphide was present. The low freezing pointobtained was due probably t o the small weight of material used.I wish to thank Mr. C. T. Heycock for suggesting the w.ork t ome, and the Research Fund Committee of the Chemical Societyf o r a grant towards the cost of apparatus.METALLURGICAL DEPARTMENT,CHEMICALABORATORIES,CAMBRIDGE

ISSN:0368-1645    

DOI:10.1039/CT9140502829

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

2836 MARTIN: RESEARCHES ON SILICON COMPOUNDS, PART VI.CCLXV1.-Researches on Silicon Compounds. Part VI.Preparation o j Silicon Tetrachloride, DisiliconHexachloride, and the Higher Chlorides of Siliconby the Action of Chlorine on 50 p e r cent.Perrosilicon, Together with a Discussion on Theiq-Mode of Formation.By GEOFFREY MARTIN.THE method once exclusively used for preparing silicon tetra-chloride in the laboratory was Oersted's process (Ann. Phys.Chem., 1825, [ii], 5, 132) of passing chlorine over a red-hot mixtureof silica and carbon.A great improvement was introduced by Gattermann andWeinlig in 1894 (Ber., 1894, 27, 1943; see also Gattermann andEllery, Ber., 1899, 32, 1114), when they passed chlorine overcrude silicon contained in a glass tube heated to 300-310°.Theyobtained by this process a producb containing 80 per cent. of silicontetrachloride, 20 per cent. of disilicon hexachloride, Si,Cl,, and0.5 to 1 per cent. of trisilicon octachloride, Si,Cl,.Up to the present time this has proved by far the easiwt methodof preparing, not only silic~n tet'rachloride, but also disilicon hexa-chloride and the higher chlorides of silicon.The cost, however, of preparing disilicon hexachloride inquantity by this method is almost prohibitive, and consequentlydisilicon hexachloride is sold a t an extremely high price.As some kilos. of this costly product were necmsary in orderto carry out some of the research work on which t,he author iMARTIN: RESEARCHES ON SILICON COMPOUNDS. PART VI. 2837engaged, it became necessary to devise some cheap and convenientmethod of preparing disilicon hexachloride in quantity.After much preliminary work it was found that commercial 50per cent.ferrosilicon, such as is used for refining steel, can be usedinstead of the expensive silicon itself for the purpose of preparingdisilicon hexachloride in quantity, and that this material formsby far the most economical known method of preparing silicontetrachloride.I n fact there can be no doubt that, in future, 50 per cent. ferro-silicon must prove the starting point for the preparation of allchlorinated compounds of silicon.*Consequently, a description of the method of using this materialfor preparing silicon tetrachloride, disilicon hexachloride, and theother chloridee of silicon, will be of some value to other workerson silicon compounds, as the optimum conditions were onlyarrived a t after much troublesome experimenting and many pre-liminary failures.I n order to give some idea of the extent to which the difficul-ties attached to the preparation of these highly hygroscopic liquidchlorides of silicon were overcome by means of the final form ofapparatus described below, the author may state that he succeededin isolating 3 kilos.of pure disilicon hexachloride, 200 grams oftrisilicon octachloride, and more than 54 kilos. of pure, silicontetrachloride by passing 143 kilos. of chlorine over 50 kilos. offerrosilicon. This was done in an ordinary chemical laboratory,and all leakage of chlorine and of the volatile silicon tetrachloridewas so completely overcome, in the final stages of this preparationthat ordinary class work went on around the apparatus while thepreparation was actively proceeding.Since water causes the instant decomposition of these chlorides,all traces of atmospheric moisture must be carefully excluded fromall parts of the apparatus, and it is this necessity that makes theirpreparation a matter of so much trouble.The large amount of disilicon hexachloride prepared by thisprocess enabled the author to obtain it in a state, of very greatpurity, and so he was able to investigate its properties more care-fully than wa6 possible with earlier workers.It was found, forexample, that Gattermann and Weinlig’s value for the boilingpoint of disilicon hexachloride, Si2C16, namely, 145-146O, wasundoubtedly a little too high, the true boiling point being144--145*5O/760 mm.The boiling points of the substance under* The silicon purchased as 50 per cent. ferrosilicon is nearly eighteen times cheaperthan when purchased as pure silicon ; moreover, 50 per cent. ferrosilicon is readilyavailable, the other grades being made only on the small scale2838 MARTIN: RESEARCHES ON SILICON COMPOUNDS. PART VI.pressures ranging from 12 mm. to ordinary atmospheric pressurewere also accurately determined. They are tabulated on p. 2852.The density of pure disilicon hexachloride was found to beDi5 1.5624; Troost and Hautsfeuille gave D 1.58.The refractive index for sodium light (D line) was found to be1.4748 a t 18O.Gattermann and Weinlig (Zoc. cit.) give the re-fractive index for “red light” as 1’45.It was also shown that although a t the ordinary temperaturedisilicon hexachloride does not combine with chlorine (althoughthe latter is very soluble in it), yet a t about 300° it takes fire inthis gas and burns to silicon Getrachloride, thus, Si2C1,+C?l,=2SiC1,.This is a new fact of considerable importance, since it throwslight on the mode of formation of disilicon hexachloride by theaction of chlorine on silicon or ferrosilicon (see below).Although Gattermann and Weinlig (Zoc. cit.) showed that whenwater a c b on disilicon hexachloride there is produced silico-oxalicacid, (Si02H),, yet they Beem to have overlooked the fact thatthere are also soluble colloidal forms of silico-oxalic acid produceda t the same time, as the author proved in the course of this work.These colloidal forms are t o be investigated.After the disilicon hexachloride had distilled, about 200 gramsof crude trisilicon octachloride passed over.This, after carefulfractionation, yielded a b u t 150 grams of pure octachloride, whichboiled a t 210-213O under atmospheric pressure (Gattermann andWeinlig, Zoc. cit., give 210-215O, and Besson and Fournier, Cornpt.rend., 1909, 148, 840, give 215-218O. This value is undoubtedlytoo high). However, it was shown that trisilicon octachloride gradu-ally decompowd when distilled under the ordinary pressure, givingrise t o a dark-coloured residue.To avoid decomposition it wasfound advisable to distil it under diminished pressure. It couldbe repeatedly distilled without decomposition ati pressures below110 mm. (when it boiled a t about 149O). Trisilicon octachloride isconsiderably less &able than disilicon hexachloride. The density isDY 1-61, and the refractive index (D ‘line) 1.5135 a t 14.5O.After the trisilicon octachloride had been removed the liquidremaining was €ractionated under greatly diminished pressure, andhigher chlorides were isolated in small quantities. These weredecomposed by water, giving rise to white, amorphous products,which dissolved in alkalis with the evolution of hydrogen. Alater communication will be made on this subject. Besson andFournier (Compt.Tend., 1909, 148, 839; 149, 34) recentlydescribed higher chlorides, which were isolated by a differentmethodMARTIN: RESEARCHES ON SILICON COMPOUNDS. PART VI. 2839The residues left after removal of these chlorides consisted of( a ) about 13 grams of a viscid, black, tar-like mass and ( b ) about160 grams of a black powder like animal charcoal. These productsare now being investigated.It is thus shown that the product obtained by the action ofchlorine on silicon and ferrosilicon is no simple substance, but avery complex mixture of silicon compounds, the different compon-ents of which are now in process of isolation.Gattermann and Weinlig (Zoc. cit.) explained the formation ofdisilicon hexachloride when chlorine passes over silicon a t 300’ byassuming that the chlorine first directly unites with the silicon toform silicon tetrachloride, thus :Si + 2C1, = SiC1,.’Next they supposed that the silicon tetrachloride thus formed a tonce reacts with more silicon to produce the hexachloride, thus:3SiC1, + Si = 2Si2C1,.For the last twenty years this explanation of Gatkermann andWeinlig has been universally accepted as the correct one.However,this explanation is certainly quite erroneous for the simple reasonthat a t the low temperatures employed by Gattermann and Weinlig,and also by the author in the preparation of disilicon hexachlorideby the action of chlorine on ferrosilicon, silicon tetrachloride doesnot react with silicon to produce disilicon hexachloride in noticeablequantity. This is conclusively shown in the experiments quotedbelow. Gattermann and Weinlig made not the slightest attempt toverify their theory experimentally.Indeed, on theoretical groundsthis formation a t a low tempetrature of disilicon hexachloride fromsilicon and silicon tetrachloride would appear to be most improb-able since disilicon hexachloride is an endothermic compound, andits formation requirm the absorption of a considerable amount ofheat.A white heat would favour its formation (as in the similar case ofnitric oxide), but a low temperature would not be expected t o actin this way. Troost and Hautefeuille showed that a t a temperatureapproaching the fusing point of porcelain (that is, a t a white heat)the formation of disilicon hexachloride from silicon and silicontetrachloride does take place to a limited extent (Ann.Chim. Phys.,1876, [v], 7, 459), but the conditions under which the formationtakes place in Troost and Hautefeuille’s experiments are entirelydifferent from those under which it occurs in Gattermann andWeinlig’s experiments, where the temperature is kept quite low,and also in the author’s experiments, whereby disilicon hexachlorideis produced by the action of chlorine on ferrosilicon, where also onl2840 MARTIN: RESEARCHES Oh' SILICON COMPOUNDS. PART VI.low temperatures are employed, so that arguments derived fromTroost and Hautefeuille's experiments do no€ apply in any way t othe case now under consideration.The problem to be explained is how a large proportion, amount-ing to something like 20 per cent.of disilicon hexachloride, isproduced by the action of chlorine on silicon a t the low tempera-tures (about 300O) employed by Gattermann and Weinlig.The conclusive refutation of Gattermann and Weinlig's theory isgiven by the following experimental facts established by the author.(1) When silicon tetrachloride is distilled over either silicon orferrosilicon heated to any temperature between 200° and 340" nonoticeable1 amounts of disilicon hexachloride can be detected inthe resulting silicon tetrachloride ; in other words, disilicon hexa-chloride is Fot formed by the action of silicon tetrachloride onsilicon a t moderately low temperatures, as Gattermann and Weinligsupposed.(2) Silicon tetrachloride was prepared by allowing chlorine toact on ferrosilicon at one end of a long tube packed with ferro-silicon, and the silicon tetrachloride thus produced was passedover the long length of heated ferrosilicon in the later portionsof the same tube.Less disilicon hexachloride was found to bepresent in the resulting silicon tetrachloride than when only shortlengths of ferrosilicon were used. According to the Gattermannand Weinlig theory, the longer the length of ferrosilicon traversedby the vapour of the silicon tetrachloride the better would be theopportunity for the reaction, SSiCl, + Si = 2Si2C1,, to proceed, sothat an increased yield of disilicon hexachloride should have re-sulted.(3) Moreo'ver, the lower the temperatures employed the higherthe yield of disilicon hexachloride.For example, when the tubescontaining ferrosilicon were kept a t 180-200°, in some cases morethan 8.6 per cent. of disilicon hexachloride was produced; a t250-260° about 4.6 per cent., whilst a t 300-310° only about4 per cent. was obtained. This should not be the case if theGattermann-Weinlig theory be correct.It is therefore obvious that some other explanation of theformation of disilicon hexachloride and trisilicon octachloride mustbe sought for.The.theory now advanced, which explains all the known factgin a satisfactory manner, is the following:Ordinary silicon (and also the metallic silicides) consists ofcomplex chains of silicon atoms directly united together. Thefirst action of chlorine on silicon (or metallic silicides) is, con-sequently, a complex one.The chain of silicon atoms is noMARTIN: RESEARCEES ON SILICON COMPOUNDS. PART VI. 2841immediately disrupted by the chlorine, but there are first pro-duced complex chlorinated products still containing chains ofsilicon atoms directly united. These complex chlorides are thenattacked by more chlorine, and decompose into simpler chlorides,such as Si6Cl14, Si5Cl12, Si4Cl10, Si3Cll0, and Si,Cl,, all of whichhave been isolated. Lastly, the chlorine then attacks thesechlorides and produces therefrom silicon tetrachloride. Thussilicon tetrachloride is not the first product of chlorination (asGattermann and Weinlig supposed), but rather is the final pro-duct of chlorination, as indicated in the following scheme :I II I I II I II C1 I c1 c1 c1I I I1 I I II I-Si- C1-Si-C1 SiCI, SiC1, SiC1,-Si- Cl-Si-Cl C1-Si-CI SiC1, SiC1,-Si- C1-Si-Cl SiC1, SiC1, S iC1,-Si- --+ C1-Si-C1 -+ Sic], --+ SiCI, --+ SiCI,-Si- C1-Si-Cl C1-Si-CI SiC1, SiC1,-Si- C1-Si-Cl SiC1, SiC1, SiC1,Chain of silicon First stage of Second stage Third stage Final stageatoms in crude chlorination. showing how showing the s h o w i n gsilicon.the chain of production the com-silicon atoms of disilicon pletechlor-is broken hexachloride ination ofdown by the and silicon the chainschlorine. tetrachloride. of siliconatoms t oSicloConsequently, silicon tetrachloride is the main product of theaction, but small quantities of complex chlorides still containingdirectly linked silicon atoms remain in the silicon tetrachloride,thus indicating its mode of origin.The amount contained in the silicon tetrachloride of disiliconhexachloride, which possesses only two silicon atoms directly linked,is much greater than the amount of chlorides containing longerchains of silicon atoms, such as trisilicon octachloride, because thelonger chains of silicon atoms are the first to be broken under thefurther action of the chlorine.The same considerations apply to the case of the metallicsilicides, and the fact that silicides, such as 50 per cent.ferro-silicon, can be used for preparing disilicon hexachloride and higherchlorides containing directly linked silicon atoms (see above), maybe taken as evidence that in these metallic silicides chains ofdirectly linked silicon atoms are present, and that the smallamounts of higher chlorides containing directly linked siliconatoms produced in theIr chlorination contain parts of the unbrokenchains of silicon atoms which were originally present in thes2842 MARTIN: RESEARCHES ON SILICON COMPOUNDS.PART VI.silicides, but which have been for t,he most part broken down, bythe further action of chlorine, into silicon tetrachloride.The formation of disilicon hexachloride from f errosilicon, forexample, would be very simply explained thus :SiC1,S~CI,’Fe<Si si -.+ c1 FeCI, -I- IThe fact seem6 definitely established that many of these silicides,such as ferrosilicon, are simply mixtures of complex silicides, andin many cases there is reason to believe that the silicides are not‘(compounds” at all, but are merely solid solutions of metal insilicon.The following facts are in favour of this view of the formationof the higher chlorides of silicon:(1) Complex chlorides of silicon are invariably produced whenchlorine acts on silicon or silicides, but (as shown above and below)their formation cannot be accounted for by the action of siliconon silicon tetrachloride.(2) That the disruption in the presence of chlorine of directlylinked silicon atoms, such as exist in disilicon hexachloride, intosilicon tetrachloride does actually take place was proved by pass-ing vapours of disilicon hexachloride mixed with chlorine througha tube heated to about 300°, when the disilicon he’xachloride caughtfire and burnt to silicon tetrachloride, thus : Si,Cl, + Cl, = 2SiC1,.It was also proved that at the ordinary temperature disilicon hexa-chloride does not combine with chlorine to form silicon tetra,-chloride.It is therefore practically certain that the small amounts ofsilicon hexachloride, octachloride, etc., found in the silicon tetra-chloride produced by chlorinating silicon or ferroeilicon, aresimply the residue or debris of much larger quantities of siliconhexachloride or octachloride originally present, this residue havingescaped destruction by the chlorine present owing to the fact thatit was quickly removed from the sphere of action of the latterby quick cooling.(3) This theory also accounts ~~atisfactorily for the fact that thelower the temperature a t which chlorine acts on ferrosilicon thegreater is the yield of disilicon hexachloride and other chloridesof silicon containing chains of directly united silicon atoms in themolecule.On the Gattermann-Weinlig theory the reverse effect wouldrather be expected to take place.(4) Next to carbon, silicon is the element having the most highlydeveloped power of self-combination.Elementary silicon, there-fore, cannot be regarded as a mere aggregate of single silicoMARTIN : RESEARCHES ON SILICON COMPOUNDS. PART VI. 2843atoms, but rather the element must be thought of as composed ofcomplex molecules consisting of many silicon atoms directly unitedtogether, possibly in rings or chains, as in the case of carbon.Itwould, therefore, appear to be unreasonable to suppoee that at themoment the chlorine atoms act on these molecules they immedi-ately fly to pieces with the production of single atoms of silicon,which are hhen acted on by the chlorine to produce silicon tetra-chloride. It is more reasonable to’ suppose that the chlorinationtakes place slowly and the whole complex silicon molecule isattacked, forming first complex chloro-compounds, which later, bythe further action of the chlorine, break down into simplechlorides, the end-product of the whole complex chain of eventsbeing silicon tetrachloride. I n this connexion there is the curiousexperimental fact (see p. 2847) that when chlorine is passed overferrosilicon heated to a suitable temperature, the formation ofsilicon tetrachloride does not begin at once.First of all, a periodelapses (which may last any time from thirty minutes to one hour,or even, under special and not well-understood conditions, to threehours) during which no silicon tetrachloride at all passes over, butin which it is possible that the surface of the ferrosilicon is beingacted on with the production of complex chlorinated silicon com-pounds, by the further chlorination of which the silicon tetra-chloride is produced.Once this initial stage is over, the formation of silicon tetra-chloride takes place with great rapidity.EXPERIMENTAL.Preliminary Experiments.-Some preliminary experiments werecarried out by placing 50 per cent.ferrosilicon in g1,ass tubes andpassing chlorine through them while the latter were heated tovarious temperatures in a Gattermann’s bomb furnace.It wassoon found, however, that glass tubes were quite unsuitable foruse with ferrosilicon. I n the first place, the ferric chloride pro-duced by the chlorination of the iron sublimed down the tube,and soon caused it to block up, and the tubes usually broke whenbeing cleaned out. Moreover, unless the stream of chlorine isvery carefully regulated, the temperature of the reaction may riseso high that the glass may fuse a t certain points.The we of glass tubes, therefore, was abandoned in favour ofordinary iron gas-piping, 30 mm. bore, fitted a t the end withordinary corks.It was found that the iron piping was soon burntthrough by the chlorine a t that end of the tube where the chlorineentered and began t;o react with the ferrosilicon. The expedientA t first a temperature of 300-310° was maintained2844 MARTIN: RESEARCHES ON SILICON COMPOUNDS. PART VI.of placing the ferrosilicon on movable iron troughs inside t'he tubewas tried, but was abandoned, as the troughs stuck firmly to theinside of the tube (owing to the ferric chloride acting as a lute),and the latter could not be effectively cleaned out.Although, when the temperature of the furnace was maintaineda t 3OC-310°, the iron tube was very rapidly attacked by thechlorine, it was found that by employing a lower temperature thecorrosive action of the chlorine was very much diminished. A tem-perature of 180--200° was found to be very suitable.A tempera-ture of 170° caused the action of the chlorine on the ferrosilicon tobecome so slow that it was abandoned in favour of the higher tem-perature. Moreover, by keeping the temperatures low, the yield ofdisilicon hexachloride (the substance i t was desired to obtain inquantity) was practically doubled. Thus in the initial experiments,when the furnace was maintained a t 300-310°, the yield of disiliconhexachloride in the crude silicon tetrachloride was about 4 per cent.When the furnace was kept a t 250--260° the yield of disiliconhexachloride rose t o 4.6 per cent., whilst a t 180-200° the yieldrose to 8.6 pe'r cent. A t 170° the action of chlorine on ferrosilicontook place too slowly for effective work.Apparatus for the Production of Silicon Tetrachloride andDisilicon Hexachloride in Quantity.As the result of these preliminary experiments an apparatus forproducing silicon tetrachloride in quantity was built up.I n itchlorine from a cylinder was dried by passing through sulphuricacid, and then, by means of a T-piece, was led alternately throughtwo iron tubes set in a Gattermann bomb iurnace and charged withferrosilicon. The ends of the tubes were fitted with ordinary corksthrough which glass leading-tubes passed.The corks were best coated with paraffin-wax o r bakelite varnish.A plug of glass-wool a t the far end of the tubes arrested the ferricchloride, which slowly distilled down the tube, and tended to blockup the leading tubes.The silicon tetrachloride was collected in aWinchester bottle.This apparatus worked well for the production of a few kilos.of silicon tetrachloride and a few hundred grams of disilicon hexa-chloride. Whea, however, it became necessary to prepare about50 kilos. of silicon tetrachloride, so that about 3 kilos. of disiliconhexachloride, could be isolated therefrom, grave defects soonrevealed its& in the apparatus.I n the first place the corks needed constant replacement andrepair even when well coated with bakelite varnish. Moreover,they often become impregnated with disilicon hexachloride and thMARTIN : RESEARCHES ON SILICON COMPOUNDS. PART VI. 2845higher chlorides, which on contact with atmospheric moisture soondecomposed with the production o€ explosive silicon oxy-compounds.Consequently, the corks, after a time, became unpleasant to handle,since in forcing them into or withdrawing them from the tubeexplosions occurred, which, when much disilicon hexachloride hadaccumulated, could cause injury to the hands.It should be notedthat all these compounds of silicon which contlain silicon atomsdirectly united in the chain are, apparently, formed with theabsorption of heat, and so are capable of explosion under suitableconditions.Frequently in the course of the experiment the corks blew offwithout warning with considerable violence, either as the result ofa sudden blockage in the tube by the sublimed ferric chloride, orpossibly, on certain occasions, by the presence of excess of chlorineexplosively causing the ignition of the higher chlorides formed inthe tube (see p.2859).Leakage of chlorine from the corks could only be prevented withgreat difficulty, and as about 143 kilos. of chlorine were requiredfor the production of the amount of silicon hexa- and tetra-chloridesneeded, the leakage of chlorine became serious. It was, there-fore, essential t o devise chlorine-tight end-pieces, and after someexperimenting, the corks were finally displaced by detachable ironcaps screwed on to the ends of the tubes.The threads were made gas-tight a t first by the use of ordinaryyellow soap (which acted admirably as a lute for chlorine), butlater fine fibres of asbestos introduced into the threads were foundto act better. The difficulty of chlorine leakage was thus sur-mounted, and the ends of the tube could be screwed off with easeand the tube withdrawn, washed out, and recharged when this wasnecessary.Since blockages in the tubes invariably occurred after a certaininterval of time, explosions could easily arise unless the pressureprevailing inside the tubes was properly controlled.This was doneby attaching mercury manometers t o the mouths of the tubes, anyincrease of pressure inside the tubes being indicated by the rise ofmercury in these manometers, which also acted as safety valves.Lastly, it was necessary to absorb chlorine and other corrosivevapours which passed through the apparatus. This was very effi-ciently done by means of a lime absorber.It consisted of a woodenbox, 100 cm. long by 70 cm. wide, fitted with shelves so shapedthat the chlorine passed over them in a zigzag fashion. The wastegases entered a t the bottom, and escaped into the flues a t the topthrough holes of about 3 cm. diameter bored in the shelves. Thelime had to be changed every week, the face of tdhe box being soVOL. cv. 8 2846 MARTIN: RES~ARCEIES ON SILICON COMPOUNDS. PART vr.arranged that the front opened like a door, so that the shelvescould be cleaned out when necessary. The box was made chlorine-tight by luting with ordinary yellow soap. The complete apparatusis Ejhown in Fig. 1. A and A1 are two chlorine cylinders, eachholding about, 42.5 kilos. of liquid chlorine.13 and B1 are the twogeries of sulphuric acid wash-bottles, whilst D and B1 are the two3-cm. gas-pipe ifon tubes, about 120 cm. long, fitted with ironieadiag pipes attached to iron screw-on caps, C and C1. F and F1aye the two mercury manometers attached by means of glass andrubber tubing to the leading tubes of D and D1, so that the pres-sures prevailing inside the pipes D and D1 are accurately known,an increase of pressure being indicated by the rise of mercury inP and F1.The mercury in the reservoirs of F and 3’1 is covered with a layerFIG. 1.of concentrated sulphuric acid, which protects the mercury to alarge extent from vigorous attack by the chlorine gas. 2 is a Gatter-mann bomb furnace, the internal temperaturs of which is indicatedby the thermometer K.In these experiments the tlemperature waskept on the average between 180° and 200O. The tubes D and Dlend in iron screw-on elbow joints E and El, from which a piece ofiron pipe of 12 mm. bore projects into the two receiving vessels,Q and Q1. These consisted of two 2-litre filter-flasks, in whichalmost all the crude silicon tetrachloride passing over from theapparatus condensed, only a very small amount passing awaythrough the condensers ill and MI and collecting in tlie bottle N .An air-pump P provided with a mercury trap R and a dryingtube S is directly united t o the flasks Q and Q’, and by forcing airinto Q and &1 (after closing sundry clips controlling the exits froMARTIN: RESEARCEES ON SILICON COMPOUNDS. PART VI.2847the flasks) the crude silicon tetrachloride could be forced up thetubes X and X1 (which reach almost to the bottom of the filter-flasks @ and Ql), along the pipe X X into the fractionating columnT, and thus into the fractionating flask U, which is heated on awater-bath 7.The fractionating column employed was a Young's three-bulbevaporator still-head, which was fused on to a litre flask. Theleading tube from the top of the distilling column T passes througha condenser H into a receiver J (a Winchester bottle). From J aleading tube L runs to the catch-bottle N , and thence a wide lead-ing tube runs to the lime absorber WW. Here any chlorine andsilicon tetrachloride vapours enter a t the bott'om, and after circu-lating over the lime on shelves in zigzag fashion, escape a t the topinto the flues.The absorption of chlorine and silicon tetrachlorideby the apparatus was almost complete.The iron piping was packed with coarsely crushed ferrosilicon,which commenced a few em. in front of the place where the tubesenter the furnace, and extended for some 20 to 30 em. down thetube, about 1 to 2 kilos. of ferrosilicon being used for each charge.This short length of ferrosilicon was found advantageous in thatthe chlorine was found t o be completely absorbed by the shortlayers, and a, longer length only tended to cause the tube to blockup owing to the sublimed iron chloride condensing in the ferro-silicon a t the far end of the tube. With short lengths of packinga considerable space was left in which the iron chloride could con-dense without choking the tube.The method of working the apparatus was as follows: The tubesDD and DID1 were charged with ferrosilicon, placed in the furnace,and their temperature was raised to 180-200°, the temperaturebeing indicated by the thermometer K.Chlorine was then admittedin a moderately rapid stream, the rate being controlled by thescrew valves attached t o the cylinders A and Al.The action does not take place immediately. Usually the silicontetrachloride begins t o pass over in about thirty minutes afterstarting the operation. Occasionally, however, it was found thatan hour's, two hours', and in some cases three hours' passage of thechlorine through the heated tube was necessary before the silicontetrachloride began to pass over in quantity.Temperature did not ceem to play a great part in shortening thelength of this preliminary period, as even when the furnace wasmaintained a t as high a t'emperature as 300-310° the same pheno-menon was observed, and keeping the temperature a t 190-200'did not cause a sensible prolongation of this period of waitingbefore the silicon tetrachloride began to pass over.Also a very8 2 2848 MARTIN: RESEARCHES ON SILICON COMPOUNDS. PART VI.rapid initial stream of chlorine did not shorten sensibly the initialperiod.This effect is, possibly, due to the fact that the chlorine musthave time t o attack the surface of the ferrosilicon and produce inter-mediate complex silicon chlorinated compounds before the produc-tion of silicon tetrachloride takes place.When, however, the actionstarted it took place moderately rapidly with a considerable riseof temperature, and the silicon tetrachloride passed over in a steadystream and collected in the vessels Q and Q1 as a yellow, fumingliquid.The tubes are worked for about three hours a t a time eithersimultaneously or alternately, but as a rule matters were soarranged that one tube was in full action whilst the other one wasbeing pulled out and re-charged. The silicon tet'rachloride con-densed in the filter-flasks Q and Q 1 , and was from time t o timeforced by the pressure of the chlorine from the cylinders up thepipes X and X 1 into the fractionating flask U . When this wasdone the screw clips were once more opened and the action con-tinued.When, for any reason, it was inconvenient to use thepressure of the chlorine from the cylinders A and A1 for forcingthe liquid from Q into U , air-pressure applied by the air-pump Pwas used for this purpose.The silicoil tetrachloride collecting in U was then fractionallydistilled, the distillate being collected in the Winchester bottle J .J when filled is removed and replaced by another Winchesterbcttle. The silicon tetrachloride is stored in them bot'tles, usingordinary corks well boiled in paraffin wax, the corks being takenout of the paraffin bath and while still warm being forced intothe neck of the bottle, and covered over with a layer of meltedparaffin, so as to prevent any danger of atmospheric moisture reach-ing the silicon tetrachloride.When sealed in this way the silicontetrachloride can be stored for months without depreciation.When the flask U became nearly full of residues of high boilingpoint, the water-bath was replaced by an oil-bath heated to ahigher temperature.The disilicon hexachloride passed over a t 147--149OJ and wascollected separately and fractionated in a separate flask, also pro-vided with a fused-on Young evaporator still-head. There wasthus left behind in U a gradually increasing amount of residuesof high boiling point, which were later proved to consist of higherchlorides of silicon (see below), besides a mass of tarry materialand a black, solid residue, much like animal charcoal in appelar-ance.Uothod of Charging and Discharging the Tubes.-When it waMARTIN: RESEARCBES ON SILICON COMFOUNDS. PART VI.2849observed that the supply of silicon tetrachloride dropping into Qor Q1 from one of the tubes diminished, or when the pressure inthe tube began to increase rapidly (as indicated by the mano-meters F or FI), it wae known that either the tube was becomingexhausted, or that i t was becoming choked up by sublimed ferricchloride. This occurred, on the average', every three hours. Con-sequently, it became necessary at the end of this time to withdrawthe tube, clean it out, recharge it with ferrosilicon, and replacei t in the furnace.To do this, the supply of chlorine is cut off from the tube, thenthe end caps C and E are rapidly unscrewed (these caps are coldenough to be touched by the hand, since they project nearly 30 cm.from the furnace), the tube is drawn out over iron rollers (notshown in the illustration), then, while hot, rapidly transferredto a sink, a cmk fitted with a leading tube is attached to oneend (after first withdrawing the plug of glass wool), and a supplyof cold water allowed to flow into the tube.This water, enter-ing the tube, is soon heated to boiling, and largely convertedinto steam, which blows the contents of the tube through the openend of the tube and effectively and rapidly cleans out the ferricchloride in the tube. The stream of cold water is allowed to flowthrough the tdbe until it runs clear, when the ferric chloride hasbeen completely removed.The iron rod with a pointed end isthen applied to clear out any particles of ferrosilicon still adheringto the tube, and the wet, clean tube is then transferred to a com-bustion furnace and dried by heating, while a current of air isblown through it. The tube is then removed from the combustionfurnace, rapidly charged with 50 per cent. ferrosilicon, as describedon page 2847, and replaced in the furnace (being run in over theiron rollers above-mentioned), the caps a t C and D are screwed on,and the stream of chlorine is once more let into the apparatus.As each iron tube corroded very rapidly just at one point,namely, a t the end where the chlorine enters and acts on the ferro-silicon, in recharging care was taken to place the charge a t theend of the tube opposite to that end previously used, so that thecorrosion should take place equally a t each end.However, evenwith this precaution, the average life of each iron tube was notmore than six experiments, the chlorine burning a hole throughthe iron piping a t the point where the action was mostintense.The 50 per cent. ferrosilicon washed out of the tube is wellwashed with water until free from iron chloride, dried in an air-oven, and once more was used for recharging a second tube. Theferrosilicon was thus used over and over again until consumed2850 MARTIN : RESEARCHES ON SILICON COMPOUNDS. PART VI.A t thO same time considerable wastage occurred, owing to particlesof the ferrosilicon escaping as a suspension in the washing water.Too finely powdered ferrosilicon was found not to be suitablefo,r use, as blockages in the tube were thereby easily occasioned.Since traces of higher chlorides accumulate at the ends of thetube and are converted by the washing water into’ explosive oxy-compounds, these, on striking with the iron rod or on scraping,may-explode if in considerable amount, so that a certain amountof care must be taken not to allow these residues to accumulateto any great extent in the tubes.This apparatus, which was gradually evolved out of repeatedfailures and mishaps, worked very smoothly and efficiently, andby means of it about 54 kilos.of silicon tetrachloride were p r epared by the passage of 143 kilos. of chlorine gas over about50 kilos.of 50 per cent. ferrosilicon.From the crude silicon tetrachloride, which was distilled asfast as it was produced in the continuous fractionating apparatus,there were produced about 3 kilos. of disilicon hexachloride andabout 500 grams of residues which contained nearly 200 grams oftrisilicon octachloride.Apparatus for Distilling the Crude Silicon TetrachZom’de so as toSeparate the Higher Chlorides.The problem of dealing with large quantities of the highlyvolatile silicon tetrachloride (b. p. 59O) is complicated by the factthat atmospheric moisture decomposes it, with tlhe formation ofhydrochloric acid and the deposition of silicic acid.Consequently, all the vessels in which the liquid is kept mustbe most carefully dried before allowing the silicon tetrachloride toenter.A description of the apparatus used for distilling and fraction-ating this silicon tetrachloride in the absence of atmosphericmoisture may prove useful to other workers, as the final form wasarrived a t only after much troublesome experimenting.Theapparatus finally used is shown in Fig. 2.A is a vessel filled with coarsely granulated calcium chloride.To this vessel an air-pump, P, is att’ached, connexion being madethrough a mercury trap, T, to prevent the silicon tetrachloridevapours reaching the pump. By this means dry air can be forcedinto the Winchestm bottle, B, contlaining the crude silicon tetra-chloride to be dist4illed. As a result of this increased air-pressure,the crude silicon tetrachloride is forced up the tube K K into thefractionating flask D, which is fitted with a Young’s three-bulbevaporator still-head, C, fused on to D.A t the top of t’he stillMARTIN: RESEARCHES ON SILICON COMPOUNDS. PART VI. 2851head C is a thermometer, M . The leading tube from the still-head passes through a condenser, N , as shown. The flask D isplaced on a water-bath, H , and after the proper amount of crudesilicon tetrachloride has been forced into D from the reservoir B,it is fractionated, the residual disilicon hexachloride (b. p. 1 4 5 O ) ,together with the higher chlorides, remaining behind in D, whilsttlhe volatile silicon tetrachloride (b. p. 59O) passes up the columnC and, condensing in N , runs into the receiver E.F is a catchFIG 2.for any silicon tetrachloride vapour that does not condense in E,C being an auxiliary condenser. I n hot weather F should beimmersed in ice. P leads out to the flues.The bottle B, the distilling column C, the bottle E, and theflask F are all fitted with corks which have been boiled in paraffinwax.By means of this apparatus many kilos. of silicon tetrachloridecan be continuously distilled free from contact with atmosphericmoisture, and separated from the residues of high boiling point,which thus accumulate in the flask D2852 MARTIN: RESEARCHES ON SILICON COMPOUNDS. PART VI.Pressure. Pressure.mm. B. p. mm. B. p.12 40" 41 61"12.5 43 50 6513 46 53 6614 47 90 8017 48.5 95 8119 49 105 8420 50 110 8622 53.5 119 8927 56 122 9031 60 126 91 .As the liquid concentrates in I) it becomes dark brown, almostblack, whilst the liquid in E consists of almost pure silicon tetra-chloride containing a little dissolved chlorine.It is of a yellowishcolour, but can be rendered colourless by allowing i t to remain forsome days in contact with freshly-ignited animal charcoal, followedby redistillation.When a sufficient quantity of residues has collected in D, thewater-bath, H , is replaced by an oil-bath, and the residues aredistilled, the bulk of the material passing over (after the silicontetrachloride has been removed) a t 147-148O under the ordinaryatmospheric pressure. There remains in I) some black fluid resi-dues, and a black powder resembling animal charcoal.Pressure.mm.B. p.130 92"135 93140 94150 95181 98195 101200 102222 103.5760 144-145.5Redistillation of the Crude DisiZicon Hexachloride.The crude disilicon hexachloride distilled, as above described,from the residues was now purified by keeping it over freshlyignited animal charcoal, and was then fractionally distilled from anapparatus made entJrely of glass, the fractionating column employedbeing a Young's three-bulb evaporator still-head fused to the flask.During this operation the most rigorous precautions had to be takento dry most thoroughly all the vessels used in the distillation, other-wise a turbid distillate would result.Ordinary drying by washing out with alcohol followed by etherand blowing warm air through the apparatus was not efficientenough. The flasks had to be heated nearly to redness (after thepreliminary washing with alcohol and ether), and then, after blow-ing out with hot, air, must be attached still fairly hot t o the receiver.The pure substance boils a t 144-145*5°/760 mm.The boilingpoint, 145--146O, given by Gattermann and Weinlig (Zoc. cit.) isundoubtedly a little too high. The boiling points under diminishedpressures were also determined as follows MARTIN: RESEARCHES ON SILICON COMPOUNDS. PART VI. 2853The density of disilicon hexachloride determined with 200‘6684grams was found to be DY 1.5624. Troost and Hautefeuille gave1.58 a t Oo.The refractive index for sodium light (D line) as determined bythe hollow prism method was found to be 1.4748 a t 18O.Anotherdetermination by a drop method gave 1.4775 a t 14.5O. Gatter-mann and Weinlig gave the refractive index for “red light”as 1-45.Although Gattermann and Weinlig showed (Zoc. c i t .) that whenwater acts on disilicon hexachloride, silico-oxalic acid is produced,thus :Si,Cl, + 4H,O = (SiO,H), + 6HC1,in the form of a white precipitate, insoluble in acids, but solublein alkalis with the evolution of hydrogen, yet it seems to haveescaped their notice that soluble colloidal forms of silico-oxalic acidare produced a t the same time. This was proved as follows:disilicon hexachloride was treated with a little water, when awhite precipitate of silico-oxalic acid separated, which was col-lected. The residual clear liquid, however, still contained somesilico-oxalic acid in colloidal solution, as was proved by adding t othe liquid a ferw drops of concentrated ammonia solution, when acmsiderable gelatinous precipitate was obtained, This colloidalform of si1ico:oxalic acid is now being further investigated, and anaccount will be given in another paper.,4 nalysis of Disilicon I€extrddoride.--By means of a small pipettemade of a piece of small-bore glass tubing drawn out a t one endand fitted with a rubber teat a t the’ other end (the whole pipettebeing most carefully dried before use), 1.3029 grams of disiliconhexachloride were transferred to a dry weighing bottle, exactlyweighed, and then decomposed by water rendered alkaline withammonia. The contents of the weighing bottle were finally rinsedout, the precipitated silicic acids collected, the washings exactlyneutralised with nitric acid and titrated with silver nitrate, usingpotassium chromate as indicator. (Found, C1= 78.9.Calc., C1= 78.9per cent.)Isolation and Properties of Trisilicon Octachloride, Si,Cl,.After the crude disilicon hexachloride had been distilled over,there remained in the flask a dark-coloured mass, consisting ofliquid and solid. The liquid was poured into a fractionating flask,and there remained a black, amorphous powder resembling animalcharcoal, and weighing 160 grams. This powder is undergoingexamination.The black liquid, weighing about 377 grams, was now distilled2854 MARTIN: RESEARCHES ON SILICON COMPOUNDS.PART VI.using a rod-and-disk fractionating column fused on to the flask,and heating on it metal bath.After separating the disilicon hexachloride still in the liquidbetween 141O and 147O (atmospheric pressure), the’ temperaturerose rapidly to 170°, and then more slowly to 185O. The weightof the fraction boiling a t 141-185° was 128 grams.The temperature then ros0 rapidly from 185O to ZOOo, when thereceiver was again changed, 64 grams distilling between 1 8 5 O and200O. The bulk of the liquid, amounting to 185 grams, passedover, however, a t 200-220°, a large portion of which distilled a tabout 215-217O.There remained in the flask about 20 C.C. of a dark-colouredliquid boiling at above 220°, which was worked up separately (seebelow).The distillates, which consisted of yellow, fuming liquids, werenow subjected t o careful fractionation under diminished pressure,using a 21 rod-and-disk fractionating column fused on to a glassflask, and heating from an oil-bath.The liquids were easilyseparated into some disilicon hexachloride and trisilicon octa-chloride, the latter being obtained pure after one or two fractiona-tions. The amount of pure trisilicon octachloride was about 150grams, about 30 grams of impure liquid being simultaneouslyisolated.The published accounts of the boiling point of this substancevary considerably. Thus, Gattermann and Weinlig (Zoc. c i t . ) give210-215°, whilst Besson and Fournier (Zoc. cit.) give 215-218O.There is no doubt, however, that Besson and Fournier’s productwas not pure.The boiling point of the above product was210-213O under the atmospheric pressure, agreeing closely withGattermann’s value. The substance slowly decomposes whenboiled under the ordinary pressure, giving rise to a dark-colouredresidue. It is this partial decomposition of the trisilicon octa-chloride that is responsible f o r the fact that the boiling pointis not very sharp under atmospheric pressure. When the liquidis distilled, however, under diminished pressure, no decomposi-tion occurs; the liquid can be repeatedly distilled under dimin-ished pressure to the last drop, without any discoloured residueappearing in the flask. The boiling points were determined asf ollows MARTIN : RESEARCHES ON SILICON COMPOUNDS. PART VI.2855Pressure.mm.17222430475360666972B. p.100"106110113124129133134.5135.5126.5Pressure.111111. B. p.74 137"80 13983 14190 14393 14495 145108 147110 149760 210-213The density was found to be DY 1.61, and the refractive indexfor sodium light (D line) 1.5135 a t 14.5O. Gattermann and Weinlig(Eoc. cit.) gave the refractive index for "red light" as 1.52.The liquid was analysed in the same way as disilicon hexa-chloride (p. 2853). (Found, Cl= 76.99. Calc., C1= 76.97 per cent.)Isolation of Higher Chlorides.After separating the trisilicon octachloride as above describedthere remained in the flask about 20 C.C. of a black liquid whichboiled a t above 220O. This was now subjected to fractional distilla-tion under diminished pressure in a specially constructed smallglass flask, fitted with a rod-and-disk fractionating column, theflask and fractionating column being fused together.After very considerable difficulties, founded principally on thefact that the silicon chlorides must not be exposed to moist air,and the fact that only very small quantities were distilled, a t leastthree distinct substances were separated after repeated distillation :(1) a viscous, colourless liquid (3 grams), boiling a t about 150°/15 mm.; (2) a viscous, colourless liquid (2 grams), boiling a t about190°/15 mm.; and (3) a white, crystalline solid (0.5 gram), whichmelted a t about 21B0, and distilled a t about 210°/12 mm.It wassoluble1 in dry benzene or light petroleum, and could be crystallisedtherefrom.The examination of these substances is being continued.These chlorides, when thrown into water, yield white, amorphousproducts, easily combustible, which are no doubt the higheranalogues of silico-oxalic and mesoxalic acid. These white sub-stances also dissolve in potassium hydroxide t o a clear solutionwith the evolution of hydrogen.The examination of these products is being continued.There remained in the flask a t least 13 grams of a black, viscousmass, like t a r or pitch, which was soluble in ether, insoluble inabsolute alcohol, and evolved hydrogen with sodium hydroxide.The latter product, however, is still undergoing examination2856 MARTIN: RESEARCHES ON SILICON COMPOUNDS.PART VI.Distillatio~~ of Silicon Tetrachloride over Silicon.According to Gattermann and Weinlig (loc. cit.), silicon andsilicon tetrachloride interact as follows :SSiCl, + Si= 2Si2C1,.I n order to test this the following apparatus was employed:FIG. 3.By means of air pressure (from an air-pump) applied to the Win-chester bottle F , pure silicon tetrachloride contained therein couldbe forced into the weighed flask B , which is heated on the water-bath. This silicon tetrachloride was then distilled from the flaskB through an iron pipe C packed with commercial silicon brokeninto a coarse powder and heated in a Gattermann’s bomb furnace A .The iron tube was about 120 cm. long and 3.1 cm. in internaldiameter, with screwed-on iron terminal caps and connecting pieces,the screw-threads being made gas-tight by asbestos packing.Thesilicon tetrachloride passing through the tube Q is condensed in thetwo-litre filter flask D. By means of an air-pump attached to Hthe silicon tetrachloride accumulated in B could (after closingcertain clips connected with the exit tubes from the apparatus) beforced back up the tube EEE into the reservoir F , and thence, ifrequired, up the tube GG back into the flask 23, so that thesilicon tetrachloride in F could be repeatedly distilled over thesilicon in CC as many times as desired.By means of this apparatus 3 kilos. of silicon tetrachloride freefrom disilicon liexachloride were repeatedly distilled over silicoMARTIN: RESEARCHES ON SILICON COMPOUNDS.PART VI. 2857in the tube 0, first of all when the latter was maintained a t ZOOo,then a t 280°, then a t 310°, and lastly a t 340O.However, in no case were noticeable amounts of disilicon hexa-chloride found to have been formed in the distilled silicon tetra-chloride.Hence it is proved that the 20 per cent. yield of disilicon hexa-chloride stated by Gattermann and Weinlig to have been producedby the action of chlorine on silicon at 300-310° could not possiblyhave arisen, as they supposed, from the action of silicon tetra-chloride on silicon.Uistillation of Silicon Tetrachloride over Ferrosilicon.The preceding experiment was repeated, the silicon in the tubebeing now replaced by 50 per cent. ferrosilicon. However, in thiscase, also, no noticeable amounts of disilicomn hexachloride couldbe proved to be produced when 3 kilos.of silicon tetrachloridewere distilled over the mass, even when the tubes were heated to300° and 340O.It was thought that although ordinary silicon tetrachloride whendistilled over ferrosilicon will not give rise t o disilicon hexachloride,nevertheless it might be possible that silicon tetrachloride a t itsmoment of formation might react, with ferrosilicon to produce somedisilicon hexachloride.The easiest way to test this was to pass chlorine over a verylong length of ferrosilicon, so that the silicon tetrachloride pro-duced in the first part of the tube would then react with moreferrosilicon as i t passed in the vaporous condition down the tube.Consequently, the following experiment was carried out :A piece of Jena combustion tube, about 200 cm.long and 2 cm.bore, was drawn out a t one end and bent at right angles. It wasfilled with a long layer of 50 per cent. ferrosilicon in the form ofa coarse powder, and the tube was placed through two bombfurnaces in succession, and was therein heated to 300-310°, whilea slow current of dry chlorine was passed through the tube. Theresulting silicon tetrachloride was received in a distilling flaskimmersed in cold water.It was found that when the action commenced, the chlorine waspractically completely absorbed by the first 15 or 17 cm. of heatedferrosilicon, so that the silicon tetrachloride would have everyopportunity as i t passed over the succeeding lengths of ferrosiliconto react with more silicon to produce disilicon hexachloride.How-ever, the resulting silicon tetrachloride was found on distillationto contain less than 4 per cent. of disilicon hexachlmide. Sincethe average yield of disilicon hexachloride produced by passin2858 MARTIN: RESEARCHES ow SILICON COMPOUNDS. PART VI.chlorine over short lengths of ferrosilicon considerably exceeds this,it is quite certain that the effect of passing silicon tetrachlorideover a long length of heated ferrosilicon is not to increase theyield of disilicon hexachloride. I f anything, i t led to a diminu-tion of the yield.These experiments prove conclusively that the Gattermann-Weinlig reaction certainly does not proceed to a noticeable extenta t low temperatures, and that therefore their explanation of thepresence of disilicon hexachloride and higher chlorides in t,hesilicon tetrachloride produced by chlorinating silicon or ferrosiliconis inadmissible.Action of Chlorine on Didicon Hexachloride.The author’s theory that complicated chlorinated silicon com-pounds are first*,produckd when chlorine acts on silicon or metallicsilicides, and that silicon tetrachloride is foxmed from these by thefurther action of chlorine, was now put t o the test of experiment,and it was definitely poved that chlorine acts vigorously ondisilicon tetrachloride (and no doubt still more vigorously on themore unstable higher chlorides) a t 300-340° so as to break upthe chain of directly united silicon atoms, with the production ofsilicon tetrachloride, thus :Cl,Si=SiCl, + C1, = 2SiC1,.It was proved that disilicon hexachloride burns directly to silicontetrachloride in the presence of chlorine, the experiment beingcarried out as follows :A stream of chlorine (dried by passing through concentratedsulphuric acid) was passed into a 150 C.C.flask containing about50 grams of pure disilicon hexachloride and heated on an oil-bath,the bmperature of which was gradually raised to 165O or 166O.The leading tube of the distilling flask was inserted firmly througha cork a t one end of an iron tube, whilst a t the other end of theiron tub0 there was an iron elbow joint screwed on, which wasfitted with a reducer. A piece of iron piping from this projectedinto a receiving flask, passing in through a rubber stopper. Thereceiving flask had its leading tube projecting into a similar flask,the two latter flasks being immersed in ice.The iron tube was contained in a Gattermann’s bomb furnace,the temperature of which was maintained a t about 340O.A continuous stream of chlorine was now passed through theapparatus. So long as the temperature of the oil-bath in which thefirst flask was immersed was not sufficiently high to cause thedisilicon hexachloride to boil, the t3ilicon tetrachloride was noMARTIN: RESEARCHES ON SILICON COMPOUNDS. PART VI.2859noticed to be passing over rapidly into the receiving flask. Also, ifthe iron tube was kept a t about 120-130° and the disilicon hexa-chloride was allowed to distil through i t in a stream of chlorine, noinflammation followed.If, however, the temperat'ure of the tubewas kept a t 300-340°, as soon as the vapour from the boilingdisilicon hexachloride, mixed with chlorine, reached the iron tubea mild explosion took place, a red flame shot back into the flask,and the disilicon hexachloride could be observed burning with areddish flame all over its surface in the atmosphere of chlorine.When the supply of chlorine was checked the flame rose andburnt round the end of the tube projecting into the flask throughwhich the chlorine entered, the chlorine here burning in an atmo-sphere of disilicon hexachloride vapour. Dense, brown fumesaccompanied the combustion of the disilicon hexachloride, and a tthe same time the silicon tetrachloride produced as the result of thecombustion streamed through the iron tube, and rapidly collectedin the receiving flask, the liquid being of a dark colour.The experiment, however, must be carried out with caution, orit may become dangerous.Although on one occasion about45 grams of pure disilicon hexachloride were burnt to silicon tetra-chloride in this manner with only a mild initial explosion, yet inanother experiment a violent explosion suddenly occurred towardsthe end of th'e operation, the first flask being hurled with greatviolence into the air and shattered with a loud report.The liquid which distilled over was proved to be almost entirelysilicon tetrachloride, distilling almost to the last drop between 50°and 70°, and leaving an inappreciable weight of a brown film inthe flask. Disilicon liexachloride boils a t 1 4 5 O , whereas silicontetrachloride boils a t 5 9 O .Although disilicon hexachloride will thus catch fire and burn ina stream of chlorine to silicon tetrachloride, yet it was proved thatthis action only took place a t temperatures higher than the boilingpoint of t$e hexachloride. At the ordinary temperature disiliconhexachlorida does not combine with chlorine to a noticeable extent.This was proved as follows: Dry chlorine' from a cylinder waspassed first through a wash-bottle containing concentrated sulphuricacid, and then into a distilling flask cont'aining about 270 grams ofpure disilicon hexachloride, the chlorine escaping through anotherwash-bottle also containing concentrated sulphuric acid.A very considerable amount of chlorine was observed t o dissolvein the disilicon hexachloride in the flask, without, however, anyvisible signs of a chemical action taking place; thus no sensibleevolution of heat, could be detected as the chlorine entered theflask. The stream of chlorine was passed through the disilico2860 MARTIN : RESEARCHES ON SILICON COMPOUNDS. PART VII.hexachloride for about four hours, and the liquid containing thedissolved chlorine was then allowed to remain for twenty-four hours.When the liquid in the flask was heated (being connected for thispurpose with a condenser and a receiver rendered moisture-proof bycalcium chloride tubes), on the first application of heat the disiliconhexachloride appeared to boil a t quite a low temperature. Thiseffect, however, was entirely due to the, escape of the dissolvedchlorine, and on distilling the 270 grams of disilicon hexacliloridecertainly less than 1 C.C. of liquid passed over below looo, thusconclusively proving that no appreciable amount of silicon tetra-chloride (b. p. 5 9 O ) was produced by t<he prolonged action of chlorineon disilicon hexachloride.This experiment also proved the very great solubility of chlorinein disilicon hexachloride, a fact which does not appear t o havebeen noted before.The refractive indices of disilicon hexachloride and trisiliconoctachloride were kindly determined for the author by Mr. H. R.Nettleton.The author desires to thank the Senate of London University fora grant from the Dixon Fund which nearly covered the heavyexpenses of the investigation. He also desires to thank the ChemicalSociety for likewise giving him a grant for the same purpose.BIRKBECK COLLEGE,LONDON

ISSN:0368-1645    

DOI:10.1039/CT9140502836

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

2860 MARTIN : RESEARCHES ON SILICON COMPOUNDS. PART VII.CCLXVI1.-Researches on Silicon Compounds. PartThe Action of Ethyl Alcohol on Disilicon VII.Hexachloride.By GEOFFREY MARTIN.WHEN ethyl alcohol acts on disilicon hexachloride, Si2Cl,, thefollowing nine substances are, theoretically, capable of being pro-duced, none of which has hitherto been described:SiCl, SiCI, SiCl,*OEt Sic 1, SiCl,*OEtI ISiCI,*OEt dia(OEt), \ SiCI,*OEt J &i(OEt), L &Cl(OEt), 2One form. Two forms. Two forms. Y YSi(OEt), SiCl(OEt), Si(OEt), Si(OEt),ISiCl,*OEt diCl(OEt), diCl(OEt), di(OEt),Two forms. One form. One form.MARTIN : RESEARCHES ON SILICON COMPOUNDS. PART VII. 2861The production of these substances has also considerabletheoretical importance, because the chlorine atoms containedtherein can be easily replaced by hydroxy-groups merely by treat-ment' with water, and the properties of the resulting hydroxy-com-pounds have some interest', as they afford means of verifying theauthor's theory* (Be?-., 1912, 45, 2097; 1913, 46, 3289) thatdirectly united silicon atoms, in the presence of attached oxygenatoms, are decomposed by alkalis with the evolution of hydrogen,according t o the scheme:III -51-1Thus each direct Si-Si linking corresponds with the evolution ofone molecule of evolved hydrogen.The properties and descrip-tion of these hydroxy-compounds are best left t o a laher paper.The present paper is confined t o the preparation and propertiesof the above-mentioned chlorinated compounds.Having prepared a considerable amount of pure disilicon hexa-chloride as a starting point, the author was able t o prepare in apure condition compounds of the following formulze : Si,Cl,*OEt,Si,C"l,(OEt),, Si,Cl,(OEt),, Si,Cl(OEt),, and Si,(OEt),.It will be noticed that' each of the substances Si,Cl,(OEt),,Si,Cl,(OEt),, and Si,Cl,(OEt), can, theoretically, exist - in twostructurally different forms.However, in actual practice theauthor up to the present was unable to find more than one modifi-cation of each of the& forms. Either the t'wo modifications ofeach variety boil a t the same temperature, or, what is more likely,the action proceeds almost t o completion in one direction only, theone modification being produced in overwhelming amount and theother in traces, so that i t is tlifficult t o isolate the two isomerides.One curious fact that appears when alcohol is added t o disiliconhexachloride is the circumstance that, apparently, a most vigorousaction sets in, the mixture appearing to boil with the copiousevolution of hydrogen chloride. Nevertheless, such an intense coldis produced t h a t hoar-frost collects on the sides of the flask.* I n view of Kipping's footnote (this vol., p.484) I wish to draw attention to thepaper (T,, 1913, 103, 119) in which I have dealt in detail with the accusations nowrepeated by him. With Kipt'ing's suggestion that readers should refer t o andcoinpare the original papers bearing on the matter a t issue I am in full agreement.Iu regard t o Kipping's statement that my preliminary note (Bey., 1912, 45,2097) was published without his permission, I would poiiit out that as theexperiment^, were desigued and carried out by myself aloire, Kipping's pernissionwas not necessary.VOL. cv.9 2862 MARTIN : RESEARCHES ON SILICON COMPOUNDS. PART VII.This is an example of a vigorous chemical action taking placewith the absorption of so much heat that water can easily be frozenthereby.The feebleness of the chemical forces tending t o bring about theinterchange of the chlorine atoms of the disilicon hexachloride forethoxy-groups is also, no doubt, responsible for the fact that whendisilicon hexachloride is treated with excess of alcohol, substitutionof ethoxy-groups for chlorine does not proceed quantitatively withthe production of the compound Si,(OEt),, thus :Si,Cl, + 6EtOH = Si,(OEt), + 6HC1,but a mixture of lower chlorides is formed, and the last chlorineatoms of the disilicon hexachloride are quite difficult to displaceby ethoxy-groups, repeated heating and distillation with excess ofalcohol being necessary befosre the last traces of chlorine are ex-pelled and the compound Si,(OEt), is obtained.It is true that the first equivalents of chlorine of the disiliconhsxachloride molecule are readily displaced by ethoxy-groups, yetas each successive chlorine atom is removed the displacement pro-ceeds with greater and greater difficulty, so that the substancesSi,Cl,(OEt), and Si,Cl(OEt), do not any longer fume very notice-ably in air, and are scarcely acted on by ethyl alcohol a t theordinary temperature.They must be heated with alcohol to. loooand above before any visible action, such as the evolution ofhydrogen chloride, takes place.The separation of these chlorinated silicon compounds by frac-tional distillation in a pure state proved a most difficult task, veryprolonged and numerous fractionations being necessary beforecomplete separation of the various components was effected. Thedifficulties were enormously increased by the fact that these sub-stancm react with traces of moisture, giving white, explosive pre-cipitates, and causing a turbidity i n the resulting liquids. Con-sequently, every vessel used in these repeated fractionations hadto be most carefully freed from every trace of moisture by carefullywashing out with alcohol, followed by ether, heating almost t oredness in a luminous gas flame while a current of dry air waspassed through the flask, and affixing fresh from the heating andwhile still fairly hot to the fractionating apparatus.Only thuscan absolutely clear, colourless fluids, free from every trace ofturbidity, be obtained. Moreover, in the fractionating apparatuscorks had to be dispensed with as far as possible, and f o r this reasonthe long fractionating columns had to be fused on to the flasks,the union by means of a cork proving unsatisfactory.Rubber corks, after a time, were attacked by the liquids, be-coming hard and crackedMARTIN : RESEARCHES ON SILICON COMPOUNDS.PART VII. 2863Other difficulties also arose, on account of the corrosive actionof these liquids on the skin. They set up painful sores which tooka long time to heal, and as in the repeated fractionations the changing of the vessels made contact of the fingers with t'hese liquidsalmost unavoidable (owing to traces adhering to the sides, etc., ofthe vessels), i t was found highly advisable to protect the thumband fingers with indiarubber coverings.I n the following table are compared the physical properties ofthe different members of the, series:Substance.Si,Cl,( OEt)Si,Cl,( OEt),Si,Cl,( OEt),Si,Cl,( OEt),Si,Cl(OEt),Sizc16si2( OEt),Boiling pointunder 34 mm. Density.60.5" 1 * 5 624:"84 1 * 3 8 8:'104 1 27 Ojo122 1.163y138 1-092i7141 0.97 1 8:7- -Refractiveindex(D line).1.4748 at 18"1.4688 ,, 14.5"1.4432 ,, 14.5"1.4333 y y 14.5"1.4205 y y 14.5"1.4134 ,, 14.5"-It will be seen that as we proceed down the series from Si,Cl,to Si,(OEt),, there is a progressive increase in the value of theboiling points; the substitution of a single chlorine atom in Si,CI,for an ethoxy-group causes an increase in the boiling point of23*5O/34 rnm., but the successive displacements of chlorine byethoxyl effeds a rapidly diminishing value in the rise of the boil-ing point, until finally the last two members of the series, namely,Si,Cl(OEt), and Si,(OEt),, boil a t nearly the same temperature-so near together, in fact, that it is difficult t o separate a mixtureof these two substances by fractional distillation.The same gradation of physical properties is apparent when thedensities are compared.Thus, whilst disilicon hexachloride has adensity of 1 *56, hexaethoxysilico-ethare, Si,(OEt), (D 0*97), isactually lighter than water ; the intermediate members of the serieshave intermediate values.EXPERIMENTAL.Some preliminary experiments were first, made. In one case7 grams of disilicon hexachlaride were treated with about 100 C.C.of ethyl alcohol (99.8 per cent'.), and in another case 21 grams ofdisilicon hexachloride were treated with 50 C.C. of ethyl alcohol.In each case a vigorous action took place, much hydrogenchloride was evolved, and the liquid became so cold that the flaskscontaining t'he liquid became covered with ice, whilst a thermo-meter placed in one flask registered - go.Two layers of liquid wereobserved t o form.After distilling over the excess of alcohol the residual oils decom-9 a 2864 MARTIN : RESEARCEES ON SILICON COMPOUNDS. PART VII.posed on distillation under the ordinary pressures, the thermometerrising rapidly t o 200°, and dense brown fumes appeared in the flaskand a brown mass remained behind.Under diminished pressure, however, colourless oils distilled overwithout decomposition, but they were evidently mixtures, sinceunder 15 mm. pressure some liquid distilled at, 65-96O, but about75 per cent. passed over at 110-115°/15 mm., after which thethermometer rose and a small quantity of liquid distilled over a t170-180a/ 15 mm.Attempts t o fractionate these liquids showed that they consistedof compIex mixtures of different substances, and that when disiliconhexachloride is treated with excess of alcohol the action does notproceed quantitatively, thus : Si,Cl, + 6EtOH = Si,(OEt), + 6HC1,but leads to the production of intermediate chlorinated products invery considerable quantity.All these colourless oils cmtained chlorine', and when thrown intowater they produced white precipitates, which dissolved on warming(but not in the cold) with sodium or potassium hydroxides with theevolution of hydrogen. They also evolved hydrogen with ammonia.When thrown into water, however, the change, from an oil t o awhite solid took some little time, aiid no heat perceptibls to thehand (although perceptible t o a thermometer) was evolved.When exposed to the air in a dish the oils became transformedinto transparent, solid glassss, which also possessed the power ofdissolving in warm potassium hydroxide' with thel evolution ofhydrogen.That it was atmospheric moisiure (and not oxygen) that con-verted t'lie oils into glasses on exposure to air was proved by thefact that when equal qiantities of the oils were exposed (1) to dryair in a desiccator (over sulphuric acid), and (2) to the ordinarymoist air outside the desiccator, i t was found that, only the surfaceexposed to the moist air outside the desiccator exhibited this solidi-fying effect.These preliminary experiments proved that the action of ethylalcohol on disilicon hexachloride was no simple one, and that inorder to isolate pure' products considerable quantities of disiliconhexachloride would have to be treated with alcohol, and the result-ing liquid very carefully fractionated.Accordirgly, in all, some 600 grams of disilicon hexachloridewere treated with ethyl alcohol, and the products isolated aftermany months' fractional distillation, as described belowMARTIN : RESEARCHES ON SILICON COMPOUNDS. PART VII.2865Pen tuc hloro e t hoxysilico-e t hane , Si,Cl,=OEt, and T e trachloro-diethoxysilico-ethane, Si,Cl,(OEt),.Eighty-four grams of disilicon hexachloride (1 mol.) were placedin a flask fitted with a reflux Condenser, and 15 grams (1.05 mol.)of ethyl alcohol were gradually run in (with continual shaking)through a stoppered funnel.A vigorous action took place as the alcohol entered, much hydro-gen chloride was evolved, and the liquid in the flask becameslightly yellow and very cold, so that ice was deposited on the sidesof the containing flask.A few drops of an orange-coloured liquidappeared to float’ on the surface of the liquid in the flask.On heating, however, under a reflug condenser on the water-bath for one hour these orange-coloured drops gradually dissp-peared, the liquid finally appearing almost colourless. After leavingovernight fhe liquid was distilled under diminished pressure, usinga Young’s 15-rod-and-disk fractionating column fused on t o thedistilling flask.However, a great many fractionations proved that the fraction-ating column used was not efficient enough t o separate sharply thevarious components of the mixture, and i t was also evident thatlarger quantities of material would have t o be employed in orderto obtain pure products. Four main fractions were isolated:The liquid boiled fairly con-s€antly a t 60-65O/35 mm., then for some time a t 75O/35 mm.Thethermometer rose slowly t o 80°/35 mm.The bulk passed over a t S2--S7°,/35 mm.Fraction 1.-Up to S0°/35 mm.Fraction 2.-80-90°/35 mm.Fraction 3.-90-100°/35 mm.Fraction 4.-100-110°/35 mm.The experiment was repeated three times, using the followingquantities : (I) 101 grams of disilicon hexachloride and 21 grams ofethyl alcohol. (3) 105grams and 22 grams respectively.This makes in all about 390 gramsof disilicon hexachloride treated with 79 grams of ethyl alcohol.Each of these fractions was then fractionated, using a Young’s20-rod-and-disk fractionating column, with the result that therewere finally obtained, after a very prolonged series of fractiona-tions :(1) A colourless, fuming liquid, boiling a t 50-5Z0/35 mm. and131-136O/ 767 mm., which contained silicon and chlorine#, but wasnot disilicon hexachloride (which boils a t 145O/760 mm.). The yieldwas, however, only 8 c.c., and it was certainly not pure, so that i twas not further examined.(2) 100 grams and 21 grams respectively2866 MARTIN : RESEARCHES ON SILICON COMPOUNDS. PART VII.(2) About 17 C.C. of a fuming, colourless liquid, boiling a t59-61°/35 mm.and 144--146O/767 mm., which was unchangeddisilicon hexachloride,(3) One hundred grams of a colourlem, mobile, fuming liquid,boiling a t 83'5-84*5O/34 nim., which was pentachloroethoxysilico-ethane, Si,Cl,*OEt (see below).(4) Fifty-four grams of a colourless, fuming liquid, boiling a t1 0 4 O / 35 mm., which proved to be tetrachlorodiethoxysilico-ethane.(5) About 155 grams of residues separated from the variousfractionations in isolating the fractions (3) and (4).Since both the liquids (3) and (4) boiled constantly, and allefforts to alter their boiling points proved unavailing, they wereanalysed as follows :The liquid was introduced into a weighing bottle (without touch-ing the sides, etc., of the latter) by means of a m a l l pipette fittedwith a rubber teat, the stopper quickly inserted, and the wholeweighed.Wa€,er was then quickly introduced into the weighingbottle in order t o decompose the chloride. The white solid whichappeared was firs€ €rested with concentrated ammonia (whichcaused the evolution of hydrogen, and thus loosened the precipitateadhering t o the sides of the vessd), and the liquid and precipitatewere rinsed out into a beaker and warmed for some time on thewater-bath with a little ammoniz until the effervescence of hydrogenceased. The liquid could be then either acidified with nitric acidand the chlorine estimated by the Volhard method, or exactlyneutralised with nitric acid, and the chlorine estimated by titratingwith _V/ 10-silver nitrate, using potassium chromate as indicator.I n the present case the clear liquid was filtered from the precipi-tate, the latter being'well washed, and the liquid was neutralisedwith nitric acid, made LIP t o 250 c.c., and titrated with N/IO-silvernitrate.Liquid (3) (b. p.83*5-84'5°/35 mm.) :0.5910 gave C1= 63.7.The liquid, therefore, was practically pure pentachloroethoxy-silico-ethane, Si,Cl,*OEt.Liquid (4) (b. p. 10P0/35 mm.):0.8990 gave Cl=49.7.This liquid, therefore, needed some pmrification.C,H,OCl,Si, requires C1= 63.6 per cent.C,H,,O,Cl,Si, requires C1= 49.1 per cent.It was treatedwith a very small amount oE alcohol to remove the excess of chlorine,and the liquid was again fractionated, the first and last portionsof the distillate being rejected.The liquid finally obtained, whichboiled a t the same temperature as that given above, was found tMARTIN : RESEARCHES ON SILICON COMPOUNDS. PAW VII. 2867contain C1= 49.2, and so was practically pure tetrachlorodiethoxy-silico-ethane, Si,Cl,(OEt),.Pentachtloroethoxysilico-ct hane, Si,Cl,-OEG, is a mobile, colourless,fuming liquid, boiling a t 83*5--84.5O/35 mm., having D? 1-388and nF5 1.4568. It does not solidify when immersed in a freezingmixture of ice and salt. When exposed t o moisture i t is convertedinto a white solid, which can be made t.0 explode by touching witha hot glass rod or even by brushing with a test-tube brush. A fulldescription of these explosive hydroxy-derivatives is reeerved for alater paper.Tetrachlorodiethozysilico-ethane, Si,Cl,(OEt),, is a mobile, colour-less, fuming liquid, boiling a t 104O/34 mm., and having Dia 1.270and 7 ~ : ’ ~ 1.4432.It does not freeze when immersed in a mixtureof ice and salt. It is decomposed by water to form an explosivewhite hydroxy-compound.The preceding results prove that in general when one equivalentof alcohol acts on disilicon hexachloride the reaction by no meansproceeds quantitatively, thus :SkC1, + EtOH = Si,Cl,*OEt + HCI.Although pentachloroethoxysilico-ethane is th0 main product, avery considerable amount (more than 30 per cent.) of tetrachloro-diethoxysilico-ethane is produced a t the same time, and the conse-quence is that some free disilicon hexachloride is left uncombined,and can actually be separated from the mixture by fractionaldistillation.Trichlorot riet htoxysilico-e t hane, Si,Cl,(OEt),.From the previous distillations there had accumulated about155 grams of residues, consisting mainly of a mixture of penta-chloroethoxy- and tetrachlorodiethoxy-silico-ethane, together withsome trichlorotriethoxysilico-ethane and similar product&. I n orderto convert this mixture into the trichloro-derivative, 55 C.C. of ethylalcohol (99.8 per cent.) wer0 gradually added and the mixture con-stantly shaken, and heated on the water-bath for one hour.Asthe ethyl alcohol entered a vigorous action ensued, much hydrogenchloride was evolved, and the flask became very cold. After leavingovernight the liquid was fractionated under diminished pressure,using a Young’s 20-rod-and-disk fractionating column fused on tothe distilling flask.At115-1 1 6 O / 35 mm.the thermometer remained constant until about10-15 C.C. of li2uid had distilled over. The bulk of the liquidpassed over between 123O and 125O’/35 mm., about 80 C.C. beinghere collected, and the thermometer then rose to 130--135O/35 mm.Only a few C.C. passed over between 60° and 115O/35 mm2868 MARTIN : RESEARCHES ON SILICON COMPOUNDS. PART VII.On cooling, the residuei in the flask solidified after standing over-night, forming a dirty grey mass, which melted when gentlyheated.The various fractions were now subjected t o a prolonged andcareful series of fractionations, whereby there was isolated about50 grams of a liquid boiling constantly a t 123--124O/35 mm.:0.5741 gave C1= 35.6.C,H,,0,C1,Si2 requires C1= 35.7 per cent.Trichlorotriethoxysilico-etha?ze is a colourless, fuming liquid,boiling a t 123--124O/35 mm., and having D;O 1.163 and Y I : ' ~1.4333.It' does not solidify when immersed in a freezing mixtureof ice1 and salt. It is soon decomposed by atmospheric moisture,yielding a white, explosive' hydroxy-compound. The liquid actsstrongly on the1 skin, causing deep and painful wounds, which donot readily heal.A t t empt to Isolate Dichloro t etrae thoxysiZico-efl~a?ze, Si2C1,(OEt),.From the previous distillations there had accumulated about11 1 grams of liquid, largely consisting of trichlorotriethoxysilico-ethane, together with some tetrachlorodietlioxy- and dichlorotetra-ethoxy-silico-ethane.This mixture was placed in a flask, and about60 C.C. of ethyl alcohol were run in with constant shaking. Muchhydrogen chloride was evolved, and the liquid became very cold.The mixture was then subjected t o fractional distillation. Nearlyall passed over between 130° and 137O/33 mm., the bulk distillinga t 131--132O/33 nim.After prolonged fractionation a colourless liquid was isolated,boiling a t 132--133O/35 mm., 121°/23 mm., 116O/18 mm., and110°/12 mm.Nearly 70 grams of this liquid were isolated, and this was shownby analysis (Found, C1=17.3) to be a mixture of dichlorotetra-ethoxy- (Cl = 23.0) and chloropentaethoxy-silico-ethane (C1= 11.2).The mixtme was subjected t o prolonged fractional distillation,whereby some of the first fractions had their chlorine contentraised to 18.7 per cent.However, i t was not found possible toobtain dichlorotetraethoxysilico-ethane, Si,Cl,(OEt),, in a purecondition, the boiling points of the mono- and di-chloro-derivativesbeing so close together as t o make a complete separation of both byfractional distillation alone a matter of considerable difficulty, a tleast with the small quantities available.Chlo ropentae t hox ysilico-e t hnn P , Si,C1 (OE t)5.With the object of isolating the above compound, some of theresidues and fractions from previous distillations, amounting in alMARTIN : RESEARCHES ON STLICON COMPOUNDS. PART VII. 2869t o about 66 grams, were collected and placed in a flask, and about9 grams of ethyl alcohol were added.On adding the alcohol, how-ever, apparently no action took place a t the ordinary temperature,the liquid becoming neither sensibly hot nor cold to the hand, norwas any visible amount of hydrogen chloride evolved. On heat-ing, however, an action set in, some hydrogen chloride beingevolved.It is thus evident that as the substitution of the chlorine forethoxy-groups in the disilicon hexachloride molecule proceeds, theaction takes place less and less readily, substances like dichloro-tetraethoxysilico-ethane not being noticeably acted on by alcohola t the ordinary t'emperature, although this action takes placereadily enough on heating.During the distillation, however, the flask, while being heatedon a metal-bath, burst, and the liquid was lost.A fresh attempt was therefore made to isolate chloropentaet'hoxy-silicoiethane by acting on disilicon hexachloride with the theoreticalamount of alcohol.Disilicon liexachloride (138 grams; 1 mol.) was placed in a flaskand treated with 99.8 ethyl alcohol (120 grams).Hydrogenchloride was evolved, and the flask became cold. The liquid,after being heat'ed on the water-bath t o complete the action, wasfractionally distilled under diminished pressure, the heating beingcarried out on a metal-bath. After about 80 grams of a liquidboiling a t 120--124O/15 mm. had distilled over, amd while theflask was nearly half full of residual liquid, a violent explosiontook place, the flask being shattered, and the fragments hurledvert8dcally into the air with such force that an indentation was madein the hard plaster on the ceiling, 4 o r 5 metres above the workingbench.The employment of a metal-bath, therefore, for heating the1 flaskappeared inadvisable, as the explosion possibly arose from over-heating the residues of high boiling point left in the flask.Aswill be shown in a subsequent paper, many compounds containingsilicon atoms directly united are explosive under certain conditions.In all the subsequent distillations the flasks were heated on oil-baths, the temperatures of which were carefully controlled so asto avoid overheating, and with this precaution no further explosionswere met with in the course of many subsequent distillations.The prece'ding experimentl was once more repeated, with precau-tions against overheating.Disilicon hexachloride (1 38 grams) wasplaced in a flask, and 99.8 per cent. ethyl alcohol (120 grams) wasgradually added. Hydrogen chloride was evolved, and cold wasproduced. The liquid was then heated on the water-bath for on28'10 MARTIN : RESEARCHES ON SILICON COMPOUNDS. PART VII.hour until the evolution of hydrogen chloride had ceased, and theflask and its contents were allowed to remain overnight.The weight of the contents of the flask after the evolution ofhydrogen chloride had ceased was 167 grams, so that 138 gramsof disilicon hexachloride had yielded about 167 grams of productand lost 91 grams of hydrogen chloride.According to the equation Si,Cl, + 5EtOH = Si,Cl(OEt), + 5IIC1,138 grams of disilicon hexachloride should give 161 grams ofchloropentaethoxysilico-ethane and lose 93 grams of hydrogenchloride.The numbers actually found agree sufficiently closely with thetheoretical to make certain that the action had taken place almostquantitatively.The liquid was therefore fractiofnally distilleld, the fractionatingflask being immersed in an oil-bath, the temperature of which wasnot allowed to rise above 175O in order to avoid the danger ofoverheating.After about 20 grams of liquid had passed over between 75Oand 120°/15 mm., the main fraction of 112 grams passed over,boiling very constantly, between 120° and 123O/15 mm.I n theflask remained about 25 grams of residue of higher boiling point.The main fraction, boiling at 120-123°/15 mm., was now sub-jected to fradioaal distillation, using a Young's 20-rod-and-diskcolumn fused on t o the distilling flask, which was heated in an oil-bath t'o about 1 6 0 O .There was thus obhined a fraction boilingvery constantly at about 121°/15 mm.However, the substance was certainly not quite pure, a chlorinedetermination, carried out as previously described, using chromatea6 indicator, giving C1=12*0 (Calc., Cl=ll.2 per cent.). Con-sequently, the excess of chlorine was removed by adding a verylittle alcohol t o the liqu*id, and then subjecting it to fractional andrepeated distillation, neglecting the first and last parts of thedistillate.There wits thus obtained the, main bulk of liquid, which, whenthree successive fractions were taken, all boiled a t the sametemperature of 126--127O/19 mm., and seemed quite pure.A chlorine estimation was next carried out with each of thethree successive fractions, and gave, respectively, C1= 11-5,There is no doubt, therefore, that the substance was fairly purechloropentaethoxysilico-ethane, which requires C1= 11-2 per cent.Chloropentae t hoxysilico-e thane, Si,Cl(OE t)5, is a colourlessliquid (D;' 1.092, ng'5 1.4205) which does not fume noticeably inthe air, but on exposure t o atmospheric moisture gives a white,c1= 11 '2, c1= 11.1MARTIN : RESEARCHES ON SILICON COMPOUNDS.PART VII. 2871amorphous, explosive hydroxy-compound. The liquid does notsolidify when immersed in a freezing mixture of ice and salt.Theboiling points were determiried under different pressures, asfollowsi :Pressure ............... 13 mm. 14mm. 15mm. 16 mm. 18 mm. 20 mm. 22 mm.Boilingpoint ......... 119" 120" 121' 122" 124' 127' 129OPressure ............... 23 mm. 24 mm. 27 mm. 30 mm. 32 mm. 36 mm.Boilingpoint ......... 130" 131' 134" 136" 137" 139'Eexae t hoxysilico-e thane, Si,(OEt),.About 151 grams of chloropentaethoxysilico-ethane, prepared aspreviously described, and boiling a t about 120-121°/15 mm., wasplaced in a flask fitted with a reflux condenser. On adding about32 C.C. of ethyl alcohol (1 mol.), no visible action appeared to takeplace. On heating on the oil-bath, however, the evolution ofhydrogen chloride began a t about looo, and became quite vigoromwhen the temperature of the oil-bath reached 1 10-120°, showingthat the action, Si2C1(OEt), + EtOH= Si,(OEt), + HC1, was pro-ceeding.On distilling the liquid, which passed over for the most partbetween 120° and 124O/15 mm., no alcohol distilled over, so thatt'he absorption of alcohol was complete.However, a little chlorinewas present in the distillate, and in order to remove this about30 C.C. of alcohol were added, and the liquid was heated on thewater-bath under a reflux condenser. The excess of alcohol couldbe distinctly seen distilling up the condenser, condensing, anddropping back on the liquid in the flask, so that excess of alcoholwas certainly present.The alco,hol was distilled over, and in i t was found a perceptibleamount, of chlorine. The liquid was therefore repeatedly boiledwith alcohol, the excess of alcohol being distilled off each time. Itwas found very difficult, even when excess of alcohol was repeatedlypresent, to expel every trace of chlorine, proving that the abovereaction by no means readily proceeds to completion.However, there was finally obtained a colourless, non-fumingliquid boiling a t 123O/ 15 mm., which, after repeated fractionationwith a Young 20-rod-and-disk fractionating column fused on to thedistilling flask, was found to be free from chlorine. In analysingthe liquid, the silicon was estimated by heating some of the sub-stance in a platinum crucible with concentrated sulphuric acid,igniting, and weighing the resulting silica :0-2800 gave 0.4499 CO, and 0.2354 H,O. C=43-8; H=9-4;1.1281 gave 0.4120 SiO,.Si = 17.2.C,,H,,O,Si, requires C= 44-07 ; H = 9.2 ; Si = 17.3 per cent2572 BRADY AND DUNN :Hexaethoxysilico-etJ~ane is a colourless, non-fuming oil whichdoes not solidify in a freezing mixture of ice and salt. It boils a t123*/15 mm., 132*/24 mm., 137*5O/30 mm., and 141°/34 mm.,and has D:' 0.9718 and 12:'~ 1.4134. The boiling points are thusvery close t o those of chloropentaethoxysilico-ethane. It is actedon by alkali, with the evolution of hydrogen.The refractive indices recorded in this paper were kindly deter-mined by Mr. H. R. Nettleton, at the author's request.The author desires to express his thanks t o the Research FundCommittee of the Chemical Society for a grant which defrayed asmall part of the cost' of this investigation; also t o the Senate ofLondon University for a grant from the Dixon Fund whichdefrayed the main part of the expenses.~ ~ 1 I : K ~ E C K COLLROE,IAox~ox, E.C

ISSN:0368-1645    

DOI:10.1039/CT9140502860

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

2572 BRADY AND DUNN :CCLXVII1.-The Isomerism of the Oximes.p- Dimet h?ilaminobenzuldoxime.Part VI.By OSCAR LISLE BRADY and FREDERICK PERCY DUNN.ALTHOUGH p-dimethylaminobenzaldoxime, NMe,*C,H,-CH:NOH,has been described (Knofler and Boessneck, Ber., 1887, 20, 3195)it has not' been studied from the point of view of the' Hantzsch-Werner hypothesis.As this compound cont'ains no possibly labile hydrogen atom inthe para-substituting group it would be expected t o exist in thetwo isomeric forms, aizti and s y ~ z (compare Brady and Dunn, thisvol., p. 824); indeed, as the basicity of the substituting groupseems t o influence the stability of the two isomerides, it seemedpossible that the oxime prepared from p-dimethylaminobenzalde-hyde by the usual methods would be a syiz-derivative, or, if not, thesyn-isomeride would be readily obtained from it, and would bemore stable than is usually the case with these compounds.Addi-tional interest is added by the fact that no benzaldoxime containinga basic group as a substituent has been obtained in two isomericforms; indeed, compounds of this class have been little studied.As regards the preparation of a syn-derivative of this compoundthe authors' expectations have not been fulfilled, and pdiinethylTHE ISOMERISM OF THE OXIMES. PART VI. 2873aminobenzaldoxime must be added to the considerable number ofaromatic aldoxiines that appear t o exist only in one form.The oxime, as ordinarily prepared by the action of hydroxylaminehydrochloride on the aldehyde in the presence of sodium carbonatehas undoubtedly the an ti-configuration, since i t yields an acetylderivative' and not a nitrile on treatment with acetic anhydrideand sodium carbonate solution.This acetyl derivative yields theoriginal oxime on hydrolysis with alkalis. Dry hydrogen chloride,when passed into a dry ether or chloroform solution of the oxime,precipitates a hydrochloride which regenerates the original oxiineon treatment with sodium carbonate solution. Under the aboveconditions the oximel unites with only one molecule of hydrogenchloride, and it was possible that the acid was attached t o thedimethylamino- and not to the oximino-group, a fact which wouldaccount for the failure t o obtain a syrz-oxime. Support is lent t othis contingency by the behaviour of the 0-methyl ether of pdi-methylaminobenzaldoxime, which readily yields a hydrochlorideunder similar conditions, differing in this respect from the 0-methylethers of oximes which contain no basic substituent in the benzenering.On the other hand it is noteworthy that, the hydrochlorideof the 0-methyl ether, in which the1 hydrogen chloride is un-doubtedly attached t o the dimethylamino-group, does not evolvehydrogen chloride a t its melting point, whereas the hydrochlorideobtained from pdimethylaminobenzaldoxime resembles the hydro-chlorides of other oximes and suffers decomposition a t its meltingpoint owing to loss of hydrogen chloride.An attempt was made t o overcome this difficulty by preparingthe hydrcchloride directly from the aldehyde and hydroxylaminehydrochloride in the absence of alkali (Beckmann, A nirnlen, 1909,365, 201):NMe2-C,H,*CH0 + NH2*OH,HC1=This method yielded, however, a hydrochloride melting a t thesame temperature as the hydrochloride obtained from the oxime,and this hydrochloride gave the afsti-oxime on treatment withsodium carbonate solution.It is possible that by this method thehydrochloride, NMe2*C,H,*CH:NOH,HC1, is first formed which isthen decomposed with the formation of the hydrochloride,HCl,NMe,*C,H,*CH:NOH ;this seems, however, unlikely, although the basic nature of theoximino-group is much less marked than that of the dimethyl-amino-group.Diphe nyl curb am yl-p-di rn e t h ylamino 6 e n xaldoxime has been pre-pared, and like other diphenylcarbamyl derivatives of the aromaticNMe2*C,H,-CH:NOH,HCl + H202874 BRADY AND DUNN :aldoximes has the syn-configuration, yielding on hydrolysisdiphenylamine and pdimethylaminobenzonitrile (compare Bradyand Dunn, T., 1913, 103, 1613):NMe2*C6H,*R H= NMe,*C,H,*CN + NHPh, + CO,.Nil*CO*NPh2C a d anilino-pdirnet hylamino b enzaldoxime,NMe,*C6H,*CH:NO*CO*NHPh,obtained by the action of phenylcarbimide on the oxime, is ofespecial interest as it resembles carbanilino-m-nitrobenzaldoxime inthat the compound first obtained, on boiling with alcohol, changesto an isomeric compound of higher melting point, which seems stillt o be a carbanilino-oxime. Up t o the present there has been nosatisfactory explanation suggested for the existence of the threecarbanilino-derivatives obtained from the m-nitrobenzaldoximes,two from the anti- and ocne from the syn-colmpound.The authorshave been engaged f o r some time on this question, which will formthe subject of their next communication; for the present it willbe sufficient to state that the carbanilino-derivative of pdimethyl-aminobenzaldoximel as prepared by the action of phenylcarbimideon the anti-oxime is the syn-derivative, and gives on hydrolysispdimethylaminobenzonitrile and aniline, whereas the product ofhigher melting point obtained by boiling this compound withalcohol is the anti-compound, and on hydrolysis gives aniline andp-dimethylaminobenzaldoxime as its main decomposition products :NMe,*C6H4*IC;H p&NCO NMe,*C,H,*fi Hp-Dime thylamino -benzantialdoxime benzaynaldoxime.HON - + NO*CO*NHPhCarbadino -p - dime thylamino -N Me2= C,H,*CNCarbanilino -p- dimethyladno- p-Dimethylamino -NMe,*C,H,* $ HNHPh*CO*ONbenznntialdoxime.benzonitrile.EXPERIMENTAL.The p-dimethylaminobenzaldoxime employed was prepared byKnofler and Boessneck's method (Zoc. cit.) by boiling a mixture ofthe aldehyde, hydroxylamine hydrochloride, and anhydrous sodiumcarbonate in equivalent proportions with alcohol under a refluxcondenser for three hours, and pouring the product into water. As,however, in the authors' experiments the oxime separated as THE ISOMERISM OF THE OXIMES. PART VI. 2875crystalline solid on stirring the aqueous emulsion, it was removedby filtration instead of extraction with ether.After recrystallisa-tion from alcohol the oxime melted at 144O.Acetyl-p-dimethy1aminobenzantialdoxime.-The oxime was dis-s o h d in acetic anhydride, warming very gently, and left forfifteen minutes. A bright green solution was thus obtained (itmay be noted here that this colour is very generally met with inworking with dimethylaminobenzaldoxime, and is probably due toa trace of some oxidation product). The excess of acetic anhydridewas decomposed by shaking with sodium carbonate solution, whenthe acetyl derivative was obtained as a mass of pale green cryst,als,which separate from dilute alcohol in colourless needles meltinga t 108O:0.1569 gave 18.2 C.C. N, a t 1l0 and 746 mm. N=13*7.C1,H,,O,N, requires N = 13.6 per cent.This compound was boiled for ten minutes with 2N-sodium hydr-oxide when it passed completely into solution, the solution wasacidified with dilute sulphuric acid, and made faintly alkaline withsodium carbonate; the solid separating proved to be pdimethyl-aminobenzaldoxime, and acetic acid could be detected in t'he motherliquor.The formation of this acetyl derivative and its hydrolysisestablish the1 anti-configuration of the oxime.A ction of Hydrogen Chloride on p-Dimet hylaminobenzanti-ctldoxim e.The oxime was dissolved in anhydrous ether, and dry hydrogenchloride passed into the solution; a yellow, pasty mass was firstprecipitated, which rapidly became white and crystalline. Thehydrochloride obtained inTthis way melted and decomposed a t 170° :0.3078 required 15.2 C.C.N/10-AgNO,.C,H,,ON,,HCl requires C1= 17.7 per cent.When decomposed with sodium carbonate solution the originaloxime was obtained, the crude product melting a t 140°, and afterrecrystallisation from cold acetone and water at 144O, moreover,admixture with this substance did not depress the melting point ofpdimethylaminobenzamtialdoxime.The action of dry hydrogen chloride on a solution of the oxime indry chloroform was also investigated, but a hydrochloride of thesame melting point was obtained, and this also regenerated theoriginal oxime on treatment with sodium carbonate solution. Thehydrochloride was also prepared according to Beckmann's method(loc. c i t . ) . Equivalent quantities of the aldehyde and hydroxyl-amine hydrochloride were heated in alcohol for three hours a tC1= 17.52876 BRADY AND DUNN:50-55O. A copious precipitate formed, which proved t o be thesame hydrochloride as previously obtained, melting a t 170° andgiving pdimethylamiiiobenmn tialdoxime on treatment with sodiumcarbonate solution.0 - M e t fi y l Ether of p-Diwiet hy7o miti ob eii zantin1doxime.-This dasprepared in the usual way by boiling on the water-bath for fifteenminutes an alcoholic solution of the oxime with an equimolecularamount of sodium ethoxide and a slight e'xcess of methyl iodide.Tlie green product was poured into water and extracted with ether,the ethereal solution being shaken with sodium hydroxide solutionto remove unaltered oxime, washed with water, and evaporated.Apale amber-coloured oil was thus obtained, which when cooled inice set t o a greenish-white, crystalline mass. On recrystallisationfrom dilute alcohol the ether separates in colourless plates with aslight fragrant' odour, and melting a t 6 9 O :0.1638 gave 22.2 C.C. N, a€ 1 7 O and 751 mm. N=15.8.C,oH,,ON, requires N = 15.7 per cent.Hydrocli loride of t h e 0-Me tli yl E t he^ of p-Dime t h y 7nwLiizob ell z-The 0-methyl ether was dissolved in dry ether, and dry hydrogenchloride was passed into the solution. A viscid substance wasprecipitated, which soon became crystalline. This hydrochloridemelt's at 118-1 22O, but, unlike the hydrochlorides of the oximes,does not evolve hydrogen chloride a t its melting point :Cl,,Hl,0N2,H@1 requires C1= 16.5 per cent.antinl<doxime.0.2134 required 10.0 C.C.N/10-AgNO,. C1= 16.6.Decomposition of the hydrochloride with sodium carbonate solu-tion regenerated the 0-methyl ether.Diphe n ylccar bnmyl-p-disne t h ylnmin o b en zsynaldoxime.This compound was prepared by dissolving the oxime in alcoholand adding one equivalent of sodium in alcohol and one equivalentof diphenylcarbamyl chloride. On adding the latter a voluminous,pasty inass was formed, which was well shaken, heated on thewater-bath for ten minutes, cooled, filtered, and washed withwater. This substance is almost insoluble in hot alcohol, but isreadily soluble in CEJoroform, and may be recrystallised from amixture of this solvent and light petroleum, when i t separates insmall, colourless needles, melting and decomposing at 171' :0.2930 gave 29.0 C.C.N, at 16O and 751 mm.Diphenylcarbamyl-p-dimethylaminobenzsyjraldoxime was hydro-N=11*5.C,,H,,O,N, requires N = 11.7 per centTHE ISOMERISM OF THE OXIMES. PART vr. 2877lysed by boiling with alcoholic sodium hydroxide for two hours.The sodium carbonate which separated was filtered off, and thesolution diluted considerably with water and filtered. The solidso obtained was washed repeatedly with very dilute hydrochloricacid, and the residue recrystallised from alcohol; this proved t o bediphenylamine. The washings were extracted with ether to removediphenylamine, then made alkaline, and again extracted with ether,After removal of the ether the residue was crystallised from alcohol,and found to be diniethylaminobenzonitrile.From the first filtrateabove a small quantity of dimethylaminobenzaldoxime was obtainedby extracting the alkaline solution with ether to remove diphenyl-amine, etc., acidifying, making faintly alkaline with sodium car-bonate, and again extracting with ether. This ethereal solutionyielded a small quantity of solid, which was recrystallised fromalcohol and shown to be the oxime.solution ofpdimethylaminobenzanttialdoxime in ether was treated with anequimolecular amount of phenylcarbimide. After a few momentspale brown, shining plates began to separate; the solution was leftf o r twenty-four hours and then filtered. The solid was recrystal-lised from cold acetone and water, from which solution it separatedin sulphur-yellow plates, melting and decomposing a t 117O.Afurther recrystallisation from alcohol removed most of the colour,but did not raise the melting point:C'arb anilino-p-dim e thy lamiiao b enssynaldoxim e .-A0.2021 gave 25.2 C.C. N, a t 16O and 761 mm. N=14.7.This carbanilino-derivative was hydrolysed by boiling with30 per cent. sodium hydroxide solution for five minutes. Anilinewas easily recognised in the steam, whilst oily drops remainedsuspended in the liquid. These on cooling set to a solid, whichwas crystallised from dilute alcohol, and melted a t 75O; a mixturewith p-dimethylaminobenzaldehyde (m. p. 73O) melted a t 55O, andwith p-dimethylaminobenzonitrile (m.p. 75-76O) a t 75O. Themother liquor from the hydrolysis was acidified, and then madefaintly alkaline with sodium carbonate solution, when, after sometime, a small quantity of substance crystallised out, which provedto be pdimethylaminobenzaldoxime, f orrned probably by the con-version of a little of the syn- into the anti-carbanilino-compoundduring the warming and the subsequent hydrolysis of the latter.A similar decomposition takes place if the carbanilino-derivativeis boiled 'with alcohol alone for some time. Carbanilino-pdimethyl-aminobenzsynaldoxime was boiled with alcohol under a reflux con-denser for twenty-four hours; the solution so obtained was dilutedwith about half its volwne of water and cooled. The crystallineC16H1,02N3 requires N = 14.8 per cent.VOL.cv. 9 2878 BRADY AND DUNN : ISOMERISM OF THE OXIMES. PART VI.precipitate which formed proved t o be diphenylcarbamide (m. p.232O). The mother liquor was diluted, and the milky liquid acidi-fied with dilub hydrochloric acid ; silky needles which remainedsuspended in the solution were collected, and shown t o be diphenyl-carbarnide. The filtrate was again made alkaline with sodiumhydroxide, stirred, and set aside for some hours, when a quantityof dimethylaminobenzonitrile separated out. The mother liquorwas acidified a-tid made alkaline with sodium carbonate, and thesolid separating was crystallised from alcohol, and proved t o bedimethylaminobenzaldoxime.I n each of the above cases the primary products of the reactionmay be regarded as p-dimethylaminobenzonitrile and the hypo-thetical phenylcarbamic acid ; the latter in the presence of alkalisis decomposed into carbon dioxide and aniline, and in the absenceof alkalis two molecules yield water, carbon dioxide, and diphenyl-carbamide :C,H,*NH*CO,H = C,H,*NH, + CO,.2C,H,*NH*C02H = (C,H,*NH),CO + CO, + H,O.The nuch larger ainount of oxime found as the result of pro-longed boiling with alcoliol is due t o the conversion of most of thesyn- into the 0)) ti-derivative, and the subsequent hydrolysis of t h a tcompound (see below).Cccrba?tilztzo-p-dimet hylrc m in o benzantiaZdoxirne.-The freshly pre-pared syn -carbanilino-derivative described above was covered withalcohol and boiled under a reflux condenser for one hour.On cool-ing, carbanilino-pdiniethylaminobenznntialdoxime crystallised inlarge, colourless plates, melting and decomposing a t 152O :0.2646 gave 32.4 C.C. N, a t 1 3 O and 768 mm. N=14*9.C,,H,,O,N, requires N = 14.8 per cent.This compound is also formed if the syn-carbanilino-derivativeis kept for any length of time, there being formed simultaneouslya small amount of aniline and dimethylaminobenzonitrile. Carb-anilinodimethylaminobenzan tialdoxime on boiling with 2N-sodiumhydroxide passes almost completely into solution, no nitrile beingformed; the solution on treatment in the usual way yields dimethyl-aminobenzaldoxime and aniline.I n conclusion, the authors beg to express their thanks to theResearch Fund Committee of the Chemical Society for a grantwhich has defrayed the expenses of this work.ROYAL COLLEGE OF SCIENCE,SOUTH KRNSIKGTOK.THE IMPERIAL COLLEGE O F SCIENCE AND TECHX OLOGY

ISSN:0368-1645    

DOI:10.1039/CT9140502872

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

THE BEACTION BBTWEEN BENZYLAMINE, ETC. 2879CCLXI X. - The Reaction Betweeyx Benzylarnine and theDibromosuccinic Acids.By EDWARD PERCY FRANKLAND.IT has been shown by the author (T., 1911, 99, 1775) that mzpso-dibromosuccinic acid -Ic and benzylamine react to form a dibenzyl-aminosuccinic acid and, simultaneously, the dibenzylamidel ofi-tartaric acid. Analogous results have now been obtained withr-dibromosuccinic acid,* which yields an isomeric dibenzylamino-succinic acid, together with a small quantity of the dibenzylamideof racemic acid. A comparison of the properhies of the twodibenzylamino-acids suggests that the one obtained from 7neso-dibromosuccinic acid has a structure corresponding with that ofi-tartaric acid, and resembles the diaminosuccinic acid preparedby Lehrfeld from meso-dibro~nosuccinic acid, which Tafel has shownto yield i-tartaric acid when treated with nitrous acid.On theassumption that the configurakions of the groups about the twoasymmetric carbon atoms are similarly affected by the reagent(nitrous acid), the configuration of the diamino-acid will be tliesame as that of the tartaric acid derived from it. Consequently,we may be justified in calling Lehrfeld's diamino-acid meso-diaminosuccinic acid (I), and the more soluble diamino-acidobtained by Tafel, which yields racemic acid with nitrous acid, isr-diaminclsuccinic acid (11) :CO,H*$JH*NH R CO,H*FH*NHR NHR*CO*yH*OHCO,H*CH*NHR R N H* CH*CO,H OH*CH*CO*NHR(1.) (IT.) (IIr.)The new dibenzylaminosuccinic acid from r-dibromosuccinic acid,on account of its greater solubility, has most probably a structureanalogous to that of the r-diarninosuccinic acid [(11), whereR=C,H7]. It has not been possible to prove this directly, sincethe benzylamino-acids cannot be converted into the amino-acids orinto tartaric acids by any simple means.The simultaneous appear-ance of the benzylamide of racemic acid (111) cannot be taken asevidence of a racemic configuration for the dibenzylamineacid,since the former substance is pro'duced by an entirely differentreaction (first discovered by Lutz in the case of monobromosuccinicacid), and is not generated from bromofumaric acid, t.he initialstage in the formation of the dibenzylamino-acid.The smallness of the yield of racemobenzylamide (one-twentieth* It is coilsidered that these designations are more suitable than those usedIceviously, namely, s-dibromosucciuic acid and isodibromosnccini~ acid I espectively,9 B 2880 FRANKLAND : THE REACTION BETWEENt o one-thirtieth of tlie weight of the isomeric dibenzylamino-acid)is probably due to the extreme readiness with which r-dibromo-succinic acid parts with hydrogen bromide to form bromofumaricacid.The action of benzylamine on r-dibromosuccinic acid in wateror chloroform solution appears to, lead, in the first instance, t o tlieformation of a mixture of mono- and di-benzylamine salts ofbromofumaric acid ; the mono-salt being sparingly soluble in water,i t may separate out when the mixture is acidified with hydrochloricacid.This salt yields broniofumaric acid and benzylamine hydro-chloride when treated with ethereal hydrochloric acid, and whenheated with aqueous benzylamine passes into the (r)-dibmzylamino-acid. * This reaction may proceed along two different lines: eitherthe benzylamine may combine a t the double bond t o form it bromo-benzylamino-acid, and the bromine is then displaced by the benzyl-amino-group, or the bromine is displaced first, yielding a benzyl-C0,H-S*NH*C7 liH*C*CO,Haminofumaric acid, ’, which then attaches benzyl-aniine t o the double bond.I n the previous communication on meso-dibromosuccinic acid i twas suggested t h a t the corresponding formation of bromomaleicacid was followed by the addition of benzylamine a t the doublebond t o yield a bromobenzylamino-acid (benzylamine salt) (IV).Further investigations on a product isolated from the reactionmixture, and having this compoaition, C,8H,,0,N2Br, render i t mostprobable t h a t the substance in question is the isomeric dibeiizyl-amine salt of bromomaleic acid (V):$!H Er* C0,H,C7H7*NH,CH(NH*C,FI 7)*C0,H(IV.)Si*E* C0,H,C7H, *NH,HC* C0,H,C,H7*N H,(V.)Thus, when treated with ethereal hydrochloric acid, this sub-stance yielded bromomaleic acid and benzylamine hydrochloride(2 mols.), and i t appeared to be identical with a product obtainedby allowing an alcoholic solution of bromomaleic acid and benzyl-amine (2 mols.) t o crystallise in the cold.These facts render itimprobable that we are here dealing with a bromobenzylamino-acid.Investigations, as yet unpublished, by the author in conjunc-tion with H.Webb and C. Mowinclcel on the action of ammonia* The tcrnis ( T - ) and (meso-) applied to distinguish the two isomeric dibeuzyl-amino-acids are bascd on the apparent analogy between these acids and the r- andmeso-diaminosuccinic acids respectively. Incidentally it may be noted that thedibenzylamino-acids (r-) and (meso-) arc derived from the corresponding r- and meso-dibroniosiiccinic acids, although,lof course, this ielationship affords no direct indicationof the assumed configurations of the dibe?izylamiiio-acidsBENZYLAMlNE AND THE DIBRUMOSUCCINIC ACIDS. 2881on the two dibromosuccinic acids have not resulted in the isolationof bromoaminosuccinic acids,* only ammonium salts of bromo-maleic and broniofumaric acids being obtained.It has been found that when the dibenzylamine salt of bromo-maleic acid is heated in aqueous solution i t undergoes a reaction,yielding some (meso-)dibenzylaminosuccinic 'f- acid, together with amore soluble substance.When heated in alcoholic solution, thedibenzylmino-acid is accompanied by the monobenzylamine salt ofbromomaleic acid. Circumstances having compelled the author tointerrupt these and other investigations proceeding at the Uni-versity of Birmingham, Edgbmton, i t is hoped that in time afurther communication may be made in which some light will bethrown on the mechanism of the reaction whereby the bromo-unsaturated acid passes into the saturated dibenzylamino-acid.Reaction products other than the above have been noted in caseswhere r-dibromosuccinic acid has been treated in chloroform solu-tion ; these also await further investigation.EXPERI M E N T A L .Eight grams of r-dibromosuccinic acid (prepared by McKenzie'smethold) were treated with 12.4 grams of benzylamine (4 mols.) in25 C.C.of water, and the mixture was heated to looo for threehours. An orange-yellow precipitate appeared, which was collectedfrom the cooled mixture and washed with water. The filtrate, onbeing heated and kept for some time, yielded a further smallquantity of precipitate' (colourless).These precipitates contain (r-)dibenzylaminosuccinic acid, prob-ably together with some benzylamine salts of the same, also alittle dibenzylamide of racemic acid and brown, tarry matter.(r-) Dib enz ylaminosuccinic Acid.The precipitates were heated on the steam-bath with diluteaqueous ammonia; a tarry, semi-crystalline residue was separated,and the solu€ion concentrated to a small bulk.The r-dibenzyl-aminosuccinic acid crystallised in flakes and crusts on the surfaceof the liquid, the yield amounting t o 3.9 grams, including a smallamount extracted subsequently from the tarry residue. This pro-duct was purified by several recrystallisations from dilute ammonia,from which solvent it separated in small, acicular prisms, meltingand decomposing, on quick heating, a t 25OO.z Pure (meso-)dibenzyI-* Claus (Ber., 1832, 15, 1849) claims to havc isolated the silver salt of a bromo-aminosucciuic acid derived from the action of ammonia on meso-dibromosuccinic acid.t See foregoing note on the (r-)dibenzylamino-acid.$ All melting points uncorrected2882 FRANKLAND : THE REACTION BETWEENaminosuccinic acid, when similarly heated, decomposed a t 260°,and mixtures of the two acids a t 244-247O.(r-)Dibenzylamino-succinic acid is only sparingly soluble in hot water (although con-siderably more readily soluble than the meso-acid), and practicallyinsoluble in alcohol. It dissolves in ammonia o'n warming and inmoderately concentrahd hydrochloric acid. Unlike the meso-acid, it is not readily precipitated by diluting the acid 60111-tion, but separates out on the addition of sodium hydroxideor sodium carbonate solution.The ?--acid undergoes considerabledecomposition on long heating with potassium hydroxide solution,but is little affecbed by heating in sealed tubes with concentratedaqueous ammonia :0.2094 gave 0.0799 gave 97.66 C.C. (20, and 5.51 C.C. Nz.*14.32 C.C. N,. C=65*53; N=8*63, 8.56.CI8H2,O4N, requires C = 65-86 ; N = 8-54 per cent.Bibenzylamide of Racemic Acid.The tarry residue separated from the ammoniacal solution of thereaction product (see above) was extracted again with ammonia,and then warmed with a little methyl alcohol. The tar dissolved,and a crystalline precipitate remained. This was extracted againwith hot ammonia, and the residue weighed 0.18 gram and meltedat 207-210°. A further quantity of the same substancej0.05 gram) was obtained from alcoholic washings.Theaminoniacal extracts yielded some (r-)dibenzylaminosuccinic acid(see above).The dibenzylamide of racemic acid was purified by recrystallisa-tion from alcohol, from which solvent it separates in glistening,oblong, rectangular plates, so>me of which have truncated angles,forming pentagons and hexagons. It melts at 208-210° :0.0756 gave 92.73 C.C. CO, and 5-28 C.C. N,. C=65*70; N=8*74.C,,H,,04N2 requires C = 65-86 ; N = 8-54 per cent.The dibenzylamide of racemic acid was synthesised by warmingdimethyl racemate with benzylamine in methyl-alcoholic solution.The substance crystallised out on the addition of a few crystals ofthe product obtained from r-dibro,rnosuccinic acid. After recrystal-lisation from abso1ut.e ethyl alcohol, the substance presented thesame appearance under the microscope as the above-described pro-duct, and melted over the same range of temperature (208-210°),as did also a mixture of the two substances.(Found: N=8*63.Calc., N=8.54 per cent.)The yield of the dibenzylamide from ?-dibromosuccinic acid is++ Dry GO, a i d N, st N.T.P. ; C and N combustion in a vacuuInBENZYLAMINE ANI) THE DIBROMOSUCCINIC ACIDS. 2883smaller than that of the corresponding substance from ?neso-dibromosuccinic acid; 5 grams of the latter subst.ance, when heatedwith aqueous benzylamine (2 mols.), gave 0.6 gram, and with4 mo1s., 0.7 gram of the dibenzylamide of i-tartaric acid, a purifiedspecimen of which crystallised in rhomboidal plates, accompaniedby a few hexagons, and melted a t 203O.A mixture of raceniobenzylamide from r-dibromosuccinic acidwith synthetic i-tartarobenzylamide melted at 194O.,4 ctioit of Bemylamitie oi& r-Dib?*omosuccitbic d c i d in Noti-uqueous Solvents.The principal product of the reaction was apparently thedibenzylamine salt of bromofumaric acid.The amount ofdi benzylamino-acid was again very small.( a ) ChZoroform.-Five grams of freshly prepared r-dibromo-succinic acid (Fo'und, Br =57*11, 57-22. Calc., Br = 57-97 percent.) were h a t e d with a solution of 8 grams of benzylamine in60 C.C. of chloroform, and heated to boiling under reflux for twohours.The precipitate (7.1 grams) contained bemylamine hydro-bromide, together with.less soluble substances. These wereseparated by treating with water, and eventually by extractingany residual benzylamine hydrobromide with absolute alcohol.The less soluble products (2.8 grams) consisted of benzylamine saltsof bromof umaric and (r-)dibenzylaminosuccinic acids, together witha little dibenzylamide' of racemic acid.The chloroform mother liquor and washings were evaporated,and the rmidual tarry residue heated with water. A small amountof (r-)dibenzylaminosuccinic acid (0.66 gram, decomposing a t236-238O) was separated, and the solution contained a littlebenzylamine hydrobromide, together with about 0.3 gram of aproduct melting and decomposing a t 205-225O.( b ) Alcohol.-Five grams of r-dibromosuccinic acid were dis-solved in 20 c .~ . of warm absolute ethyl alcohol, and treated with8 grams of benzylamine. After keeping for about three hours, acrystalline precipitate began to form in the liquid. About sixteenhours later this precipitate was collected, washed with alcohol andwith ether, and dried. It weighed 2.6 grams, and melted anddecomposed a t 172O. An aqueous solution of this substance de-colorised cold alkaline perinanganate almost instantly, showing thepresence of bromofumaric acid. The aqueous solution was slightlycloudy, even on heating, perhaps owing to the presence of a littledibenzylamino-acid.On acidifying with dilute hydrochloric acid, a crystalline pre2884 FRANKLAND : THE REACTION BETWEENcipitate appeared, which was collected and recrystallised fromwater.The substance melted and decomposed a t 219O, and provedto be the monobenzylamine salt of bromofumaric acid (see below).The alcoholic mother liquor and washings on concentrationyielded about 1.3 grams of a substance melting at 205-211°,followed by a little (r-)dibenzylaminosuccinic acid (decomposinga t 248O).I n another experiment, 8 grams of the r-dibromo-acid weretreated with 16 grams of benzylamine (more than 5 mols.) in120 C.C. of alcohol, and the solution was heated t o boiling underreflux for four hours. On concentrating the solution, a crystallineprecipitate separated, which was collected and extracted with hotwater. The residue, which was soluble in boiling water, decom-posed a t 2 3 1 O . This substance is probably the nio?zobenzyZami?iesalt of (r-)dibenaylaminoszLccinic acid, but cannot readily be purifiedfrom possible admixtures of the free acid and its dibenzylaminesalt :0.1429 gave 10.98 C.C. N,.N:=9.61.C,8El&04N,,@,H,N req=xires N = 9.65 per cent.Action of Bemylamine o n Brornofurnnric Acid.The following experiments were carried out with a view toinvestigate more fully the intermediate products of the reactionbetween benzylamine and r-dibromosuccinic acid. The reaction isin this case simplified by the' non-appearance of the dibenzylamideof racemic acid, and by taking a smaller proportion of amine t othe acid, the' amount of dibenzylamino-acid produced becamealmost negligible.A chloroform solution (50 c.c.) of 4.4 grams of bromofumaricacid was treated with 6 grams of benzylamine (2g mols.) andheated to boiling under reflux for three hours.The resultingprecipitate weighed 9.3 grams, and a portion dissolved in watercontained only a trace of ionic bromine. Theory requires 9-2 gramsof the dibenzylamine salt of bromofumaric acid. When the pro-duct was dissolved in water, only a very small precipitate re-mained, but when a large proportion of amine was used (3 mols.)this precipitate appeared in greater quantity, and proved to be(r-)dibenzylaminosuccinic acid (decomposing a t 242O).The aqueous solution was treated with 3.7 grams of concentratedhydrochloric acid, whereupon a crystalline precipitate was de-posited, which was collected, washed with water, alcohol, and ether.The mother liquor was shown to contain benzylamine hydro-chloride. The substance, after recrystallisation from water, de-composed at 221°, and appeared on analysis to be the monobenzylBENZYLAMINE AND THE DIBROMOSUCCINIC ACIDS.2885amiue salt of bromofumayic acid. The yield was 5.75 grams, whilsttheory requires 6.8 grams. The substance is rather sparinglysoluble in hot water, and almost insoluble in cold water:0.1238 gave 96.84 C.C. CO, and 4.69 C.C. N,. C=43*93; N=4*74.C4H30,Br,C,H,N requires C =43-71; N=4-64 per cent.On the results of this analysis, the substance might equally wellbe the isomeric bromobenzylaminosuccinic acid, C,,H,,04NBr ;however, the aqueous solution rapidly decolorises cold alkaline per-manganate, and when treated with ethereal hydrochloric acid thesubstance yields benzylamine hydrochloride and bromof umaricacid.Two grams of the substance were shaken with dry ethereal hydro-chloric acid.The precipitate weighed 1 gram, and melted a t 258*,whilst theory requires 0.95 gram of benzylamine hydrochloride.The ethereal mother liquor yielded some bromofumaric acid. Bylong-continued heating with aqueous benzylamine, the monobe,nzyl-amine salt of bromofumaric acid passes into (r-)dibenzylamino-succinic acid.Thus 1.3 grams of the above-described product were heated a tlooo with 1.3 grams of benzylamine in 10 C.C. of water for fourhours. The substance gradually dissolved, and, on cooling, a pre-cipitate of small crystals appeared, which weighed 0.25 gram anddecomposed at about 233O (compare second experiment withalcoholic benzylamine on r-dibromosuccinic acid).After recrystal-lisation from dilute ammonia, the substance decomposed a t 242O[ (r-)dibenzylaminosuccinic acid].Experiments with meso-Bibromosuccinic Acid.These experiments were undertaken with the object of investi-gating the structure of the compound melting a t 156O described ina previous communication (T., 1911, 99, 1779). It was also thoughtpossible that an intermediate compoand might be found betweenthis substance and the final product, (meso-)d'ibenzylaminosuccinicacid.Seven grams of meso-dibromosuccinic acid were treated with11 grams of benzyiamine (4 mols.) in 100 C.C. of absolute ethylalcohol, and the mixture was heated to boiling for five minutesand then kept overnight'.The resulting precipitate weighed8.6 grams. After extraction with boiling alcohol 0.6 gram remained(crude benzylamine salt of (meso-)dibenzylaminosuccinio acid). Thealcoholic solution on cooling deposited 4.1 grams of the substancemelting a t 156O, which was investigated as follows: After shakingwith dry ethereal hydrochloric acid the resulting precipitat2886 THE REACTION BETWEEN gENZYLAMINE, ETC.weighed 2.85 grams, and proved t o be benzylamine hydrochloride,a specimen melting a t 257O after recrystallisation from a mixtureof alcohol and chloroform. Assuming the substance t o be the di-benzylamine salt of bromomaleic acid, theory requires 2.87 gramsof benzylamine hydrochloride, whereas if a bromobenzylamino-acid(benzylamine salt) had been present only half this quantity ofbenzylamine hydrochloride should be obtained.The ethereal mother liquor deposited colourless crystals of bromo-nialeic acid, melting a t 138-140° (Found, Br =4P15.Calc.,Br = 41.03 per cent.).A substance melting at 1 5 6 O and apparently identical with theabove, except for its more rapid reducing action on permanganate,was obtained by allowing an alcoholic solution of bromomaleic acidand benzylamine (2 mols.) to crystallise in the cold.The mother liquor from the 4.1 grams of substance mentionedabove deposited, on concentration, 0.25 gram of a substance decom-posing a t 239--242O, presumably crude (mesa-)dibenzylaminosuccinicacid, and then, on the addition of chloroform and further concen-tration, a precipitate of needle-shaped crystals, which melted at142--148O, and proved on analysis to be the monobenzylamine saltof bromomaleic acid (Found, Br = 26.06.Calc., Br= 26.01 percent.) (compare T., 1911, 99, 1779).It is suggested that, contrary to what was sta<ted in the previouscommunication, the substance melting a t 15 6 O is the dibenzylaminesalt of bromomaleic acid, and that on heating in alcoholic solutioni t is converted partly into the dibenzylamino-acid with simultane-ous formation of the monobenzylamine salt of bromomaleic acid :I3r.E C0,H,C,H7.X 11 Il C;( LCT H*C,H ,)*CO,H + -H*C*C02H,C7H7*NH2 HC(NH*C,H7)*CO,H 2+ C7H7*N H,, H B I-.BIS*CO,HHC* CO,H, C,H,*NH,I n a second experiment 7 grams of meso-dibromosuccinic acidwere treated with 8.2 grams of benzylamine (more than 3 mols.) in60 C.C. of absolute ethyl alcohol. The mixture was heated t o boilingfor five minutes, and then kept for about twp and a-half hours.The precipitate weighed 8.57 grams, and melted and decomposeda t 1 4 2 O . The mother liquor yielded 0.9 gram of coarse needlesmelting a t 156O (ciibenzylamine sa.lt of bromomaleic acid) and alittle nearly pure (meso-)dibenzylaminosuccinic acid (decomposingat 250-254O).The 8-57 grams of substance were dissolvetd in water, separatedfrom some undissolved dibenzylamino-acid, the solution acidifiedwith hydrochloric acid, and extracted with ether. The etherealextract yielded some meso-dibromosuccinic acid (decomposing a FIRTH AND MYERS: SOME I’ROYERl’IES OF SOLUTIONS. ETC. 2887284-285O; found, Br = 58.13. Thisshows t h a t the reaction product obtained under these conditionsstill contains unchanged nzeso-dibromosuccinic acid (as benzylaminesalt). A similar result was obtained by hesating the acid andamine together f o r two hours in boiling chloroform solution.Calc., Br = 57.97 per cent,.).CIIJCNTCAL I)RIBAI:TMEIW,BIRMINGHAM.THE UKIVERSIIT~, E D G I ~ \ S I O S

ISSN:0368-1645    

DOI:10.1039/CT9140502879

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

FIRTH AND MYERS: SOME I’ROPERTIES OF SOLUTIONS. ETC. 2887CCLXX.-Xome Pmpey&ies of Solutions of the B o ~ i cAcids in AZcohol. A Modz$cd Boiling-poii2 tAppayatus.By JAMES BRIERLEY FIRTH and JAMES ECKERSLEY MYERS.THE well-known property of orthoboric acid of imparting a greencolour to the alcohol Rame has usually been ascribed, a t any ratein text-books, t o the formation of some organic derivative of boricacid such as triethyl borate.This idea seems to present considerable theoretical difficulties,and i t was with the object of obtaining information on this point,and mom particularly of examining the physical properties ofalcoholic solutions of the boric acids, that the present work wasundertaken.The first part of the investigation as described in the presentcommunicati‘on is devoted t o the determination of the boilingpoints of the solutions and of the composition of the variousdistillates.Preliminary experiments indicated that it was extremely prob-able that the additions of very small proportions of orthoboric acidproduced a very slight lowering of the boiling point of ethylalcohol.This lowering appeared t o be of a similar magnitude t othat observed by the addition of small quantities of water toalcohol. It was therefore essential that the materials used shouldbe as free from water as possible, and that the experiments shouldbe carried out with the exclusion of water-vapour from the atmo-sphere.The alcohd was therefore purified, and then dried thoroughly bytreatment with metallic calcium or with lime prepared by calciningmarble.Both methods were used, and as there appeared t o be no differ-ence in the results obtained, alcohol dried over calcium wasemployed for the experiments described below.It may be men-tioned in passing that in addition to the usual precautions observe2888 FIRTH AND MYERS: SOME PROPERTIES OFin drying alcohol, the hydrocarbons sometimes found in the alcoholafter treatment with calcium were readily and completely removedby distillation from animal charcoal.The orthoboric acid was purified by several recrystallisationsfrom water; the metaboric acid was prepared by heating the ortho-acid to about 130° until decomposition was complete, and the borontrioxide was obtained by 'fusing the ortho-acid. I n the last caseP I G .1.UAthe glass was ground to a fine powderin an agate mortar. Precautionswere taken to exclude moisture fromthe meta-acid and the anhydride.The three materials were found byanalysis to be tolerably pure.As it was a question of measuringvery small differences in boilingpoint, several kinds of apparatuswere tried, and the one describedbelow was eventually used, owing tothe unsuitability of the existingtypes.The general characteristics of theapparatus, which can be thoroughlyrecommended for this kind of work,will be clear from the sketch (Fig. 1).The ordinary Beckmann boiling-point tube is used, and is enclosedin a Dewar vessel. All exposedglass surfaces are covered with alayer of cotton-lint so as t o shieldthe heated liquid and vapour fromdraughts.This precautlion is foundto be very necessary. The heatingis by an electric current of from2.5 t o 3.0 amperes, and is keptsteady by means of a rheostat withan ammeter in the circuit.The current is carried by stout platinum wires, sealed throughgIass tubes, in contact with the leads by means of mercury, untili t reaches the liquid. The wire is now very much thinner, and iscarried through a glass coil made of tubing about 2 mni. indiameter and open a t both ends, so that the wire is in contactwith the liquid. The glass coil is broken half-way along its length,so that it is really t,wo small coils with a gap ( A ) between them.The two arO bound together with platinum wire for conveniencSOLUTIONS O F THE BORIC ACIDS IN ALCOHOL.2889of handling and suspending. The gap between the coils shouldbe about 4 mm. The efficiency of the apparatus is largely dueto this gap. As the wire becomes heated the liquid inside thenarrow tube expands, and rushes out, and is replaced by otherliquid, thus causing circulation. This process goes on until boilingpoint is reached inside the coil, when the circulation becomes morerapid until the whole liquid is at the boiling point and streamsof bubbles issue from the various openings in the tube. It willbe seen that the enclosure of the wire prevents local superheatingcommon with a bare' wire, and the openings in the coil cause rapidand continuous circulation and ebullition.'rt is essential that bubbles should appear from the middle andlower opcmirlgs in the coil.It happens on rare occasions thatbubbles issue from the top and middle openings, and then super-hezting often takes place. I n such cases a slight tap will startbubbling from all three points.With a pure liquid the boiling point, as registered by a Beck-mann thermometer, remains steady to 0 ' 0 1 O or even t o 0.005°, solong as the barometric pressure remains steady.I n all experiments a control apparatus was employed containingpure alcohol, so that variations in the boiling point due to baro-metric changes could be determined and the boiling point of thesolution corrected. I n the values given below this correction hasbeen included, and all temperatures are expressed in degrees centi-grade of an arbitrary Beckmanii scale.TABLE I.Solute, H,BO,,.Solute, HBO,. Solute, B,O,.v- \ 7- ,--B. p. B. p. B. p.Gram- of Change Gram- of Change Gram- of Changemols. solu- in mols. solu- in mols. solu- inH,,BO,,. tion. b. p. HBO,. tion. b. p. B,O,. tion. b. p.A\O.OC33 1.49' -0-07' 0.0036 1-52" -0.04' 0.0049 1.52' -0.04'0.0084 1.44 -0.12 0.0074 1.48 -0.08 0.0111 1.36 -0.200.0136 1.42 -0.14 0.0140 1.43 -0.13 0.0180 1.36 -0.200.0180 1.41 -0.15 0.0200 1.41 -0.15 0.0277 1.38 -0.180.0227 1.40 -0.16 0.0261 1.40 -0.16 0.0348 1.46 -0.100.0270 1.40 -0.16 0.0311 1.40 -0.16 0.0435 1.61 +0*050.0320 1.42 -0.14 0.0375 1.41 -0.15 0.0639 1.98 +0*420.0384 1.45 -bll 0.0457 1.43 -0-13 0.0773 2-25 +0*690.0438 1.49 -0.07 0.0520 1.51 -0.05 - - -0.0500 1.52 -0.04.0.0610 1-66 - - - -0.0548 1.57 +0.01 0.0690 1.61 +0*05 - - -0.0628 1.67 +0*11 0.0800 1.69 3-0-13 - - -0,0675 1.75 +Om19 0.1334 2.30 +0*70 - - -0.0740 1.83 +Om27 0.1482 2.62 +1.06 - - -Boiling point of pure, alcohol 1.56O; volume of alcohol 75 C.C.It will be clear from the table' that there is a 'lowering of the- - - - 0.0840 1.97 f0.41 2890 FIRTH AND MYERS SOilIE PROPERTIES OF'boiling point of alcohol on adding either of the three solutes. Thislowering reaches a maximum in the case of orthoboric acid when0.0227 grain-molecule lics been added, and then amounts to 0.16' ;in the case of metaboric acid it' is 0 . 1 6 O for 0.0261 gram-molecule,and for the anhydride it is 0*20° for 0.018 gram-molecule.Thevalues given in the table are shown on the graph (Fig. 2) for thesake of comparison.No further bend or change in the curve was observed up to thepoint of saturation at boiling point.The question of the composition of the distillate was nextFIG. 2. Frc. 3.examined. The method of distilling is shown in the sketch ofthe apparatus.When sufficient time had been allowed for the solute to dissolvecompletely and the boiling point had become steady, two fractionsof the distillate each of 5 C.C. were, analysed. The distillate wastreated with water, and thus in all cases orthoboric acid wasformed, which was titrated with alkali in the presence, of glycerol.The1 assumption was made that the distillat,e contained, before theaddition of wat?r, the original solute.I n this connexion it may beremarked that it was frequently observed that after distillatioSOLUTlONS OF THE BORIC ACIDS IN ALCOHOL. 2891a small quantity of solid substance appeared in the tubes, etc., ofthe apparatus after the alcohol had evaporated. This was assumedto be the original solute.The following table gives the results obtained, the strength ofeach distillate being expremed in values of the particular soluteemployed.A separate experiment was carried out for each strength ofsolution, not as in the case of the boiling points, where the experi-rneiits in each series were inade continuous by adding successiveamounts of the solute.TABLE 11.Original volume of alcohol, 75 C.C.H,BO,. HRO,. R,O,.A h *Weight Weight i; Weight Weight i; Weight Weight in 'of 1st 2nd of 1st 2nd of 1st 2ndH,,BO, +A HBO, -7' B,O,added.fraction. added. fraction. added. fraction.0.25300.48600.63480.81701.19501.37001-58802.06002.72003-56300,03550.05940.08200-09030.10330.11150.12570.12760-14510.15800-03220-05420.07090.087 10.10250.10710.11990.12700.14120.15530.3300 0.0498 0-0435 0.5230 0.0527 0.04880.6430 0.0691 0.0673 0.9355 0.0823 0.07350.9810 0.0906 0.0892 1.2770 0.0898 0.08761.4510 0.1172 0.1103 1.8020 0.1055 0.10392.3890 0.1341 0.1305 2.3730 0.1183 0.11603-2830 0.1387 0.1400 3.1140 0.1314 0-1289- - - - - -These values are shown in the graph (Fig. 3) for comparison, allweights being expressed in grams of solute per C.C.of solution. I nthe curve for orthoboric acid the dotted line shows the coursewhich it is considered the curve should take as no reasons can beassigned for the values producing the break. They are probablydue to' experimental error.On considering the two sets of curves, the first f o r the change inboiling point and the second for the volatility of the solutes, itwill be noticed that the maximum effect on the boiling point isproduced by t,he solute of minimum volatility, boron trioxide andvice versa with orthoboric acid. I n both cases the metaboric acidoccupies a middle position in a general way.Experiments are a t present in progress t o examine whether theeffect of the solute on the vapour pressure is dependent on thetemperature, by means of surf ace-tension measurements andmeasurements of the heats of solution are being made.The conclusions drawn from the work described above are asfollow 2892 WILSON, HEILBRON, AND SUTHERLAN D : CONTRIBUTIONS(1) With certain small concentrations of orthoboric and meta-boric acids and boron trioxide, ths boiling points of ethyl alcoholsolutions are lower than the boiling point of the pure solvent.(2) Tho maximum lowering of the boiling point is produced byth3 least volatile solute, which also has the greatest subsequenteffect on the boiling point.(3) The distillate contains the original solute.n f E UWEWWY,MAKCHES~TR

ISSN:0368-1645    

DOI:10.1039/CT9140502887

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

2892 WILSON, HEILBRON, AND SUTHERLAN D : CONTRIBUTIONSCCLXXT.-Cont~.i~utiorLs to Our Knowledge of Semi-carbaxorm. Part IV. Action of HydrogenChloride.By FORSYTH JAMES WILSO&, ISIDOR MORRIS REILBRON, andMAGGIE MILLEN JEFFS SUTHERLAND.IN the course of our investigations on tho preparation and proper-ties of some semicarbazones it was found that the presence of hydro-chloric acid produced colorations in solutions of some of thesesubstances. As the semicarbazones are, in part, basic compounds’it occurred to us that this development of colour might be dueto the formation of salts, and in fact experiments instituted toelucidate this point showed that some of these substances do formsalts with acids.The following experiments were carried out to determine underwhat conditions salts are formed, and to what extent their forma-tion is influenced by the constitution of the semicarbazone.Forthe most part the investigations have been made on the hydro-chlorides oE the semicarbazones. Various methods were tried forthe preparation of these salts, and it was found that special pre-cautions had t o be taken against the presence of moisture, as thistended, in the presence of hydrochloric acid, to hydrolyse the semi-carbazone and give only the aldehyde o r ketone and semicarbazidehydrochloride.I n many cases the salt may be prepared by dissolving the semi-carbazone in dry chloroform and passing dry hydrogen chlorideinto the solution. The difficulty in this case is that, if the salt isunstable, exposure t o air while filtering brings about decomposi-tion, so that correct results are not obtained.The most satisfactoryresults were obtained by passing dry hydrogen chloride over tmhedry substance contained in a U-tube and estimating the quantityof acid addedTO OUR KSOWLEDOE OF SEMICARB.\ZONES. PART 1V. 2893Two ~iperoitylidenencetolzesemic~rbazolzes were prepared, an a-and a P-modification. These isomerides have different meltingpoints and different properties. a-Piperonylideneacetonesemi-carbazone was exposed to the action of dry hydrogen chloride, andan unstable, crystalline, vermilion salt containing 2.5 molecularproportions of hydrogen chloride was obtained. This salt onexposure to air loses hydrogen chloride, and finally gives a stable,orange mono hydrochloride.kl - Piperonylideneacetonesemicarbaaone gives with hydrogenchloride a stable, yellow mo~Lohydrochloride, and no further addi-tion can be made to this compound even on continued passage ofhydrogen chloride over the dry salt.A slight change in colour isobserved, but no addition of acid.This semi-carbazone exhibits interesting phototropic properties after exposureto bright light. On treating this substance with hydrogen chlorideit coinbiiies with 2 molecular proportions of hydrogen chloride, andgives an exceedingly unstable, deep orange compound. A sulphateof this semicarbazons was also prepared, which contained onemolecular proportion of sulphuric acid. The sulphate is brightyellow, and stable in ordinary air.Cinnamaldehydesemicarbazone, an unsaturated compound, might,be expected to combine with hydrogen chloride a t the double bond,or, at least, that the unsaturated nature of the substance wouldinfluence the formation of an additive compound.The presence of a phenyl group in the semicarbazide radicle evi-dently influences the absorption of hydrogen chloride, for it wasfound that cinna~aldehydepheitylsemicarbazo~~e unites with onlyone -nolecular proportion of hydrogen chloride, the monohydro-chloride thus obtained being yellow.On saturating cinnamalde-hydeplienylsemicarbazone with bromine a dibromide, @16H150N3Br2,is formed, and this substance does not combine with hydrogenchloride. The addition of bromine therefore prevents salt-forma-tion.A n~onobromo-derivative was prepared from this dibromide byboiling with alcohol, when hydrogen bromide was evolved and mot2 0-h Torti ocin 7tn nialdehydephen ylsemicarbazo n e , C16H,,0N3Br, obtained.This compound combines rapidly with hydrogen chloride, giving abright yellow salt containing one molecular proportion of hydrogenchloride.On preparing monobromocinnamaldehyde, and then for m-ing the phenylsemicarbazone and passing hydrogen chloride overthe compound, a d i h ydrochlwide is obtained, which is exceedinglyunstable, all the hydrogen chloride being liberated on exposureto air.Cinnamaldehydesemicarbazone was next prepared.VOL. cv. 9 2894 WILSON, HEILERON: AND SUTHERT,AND : CONTRIBUTIONSSimple semicarbazones, such as acetonesemicarbazone and acetone-phenylsemicarbazone, also absorb hydrogen chloride, but no colouris developed ; the substances remain white, but lose their crystallinestructure and fall to powder.Acetonesemicarbazone forms a com-parat'ively sts~ blo monohydrochloride, whereas the addition ofhydrogen chloride to acetonephenylsemicarbazone reaches a maxi-mum when one and a-half molecular proportions have been takenup. This salt loses hydrogen chioride very rapidly, becoming mcrestable when half a molecular proportion of hydrogen chloride hasbeen lost, that is, the monohydrochloride is comparatively stable.Acetophenonesemicarbazone and acetophenonephenylsemicarbazonewere also examined, as these contain more phenyl groups in themolecule, and might be expected to react differently.These sub-stances combined very readily with hydrogen chloride, giving, ineach case, a yellow dihydrochzoride, which is exceedingly unstable.A simple aromatic aldehydesemicarbazone, such as benzaldehyde-semicarbazcne, reacts also with hydrogen chloride, giving a mono-hydrochloride, which is comparatively stable and only slightlycoloured. Benzaldehydephenylsemicarbazone gives a yellow di-hydrochloride, which is very unst'able.From the results obtained it would seem, first, that the mono-hydrochlorides are f o r the most part more stable than the dihydro-chlorides, and, secondly, that the introduction of a phenyl groupinto tho basic partl of the molecule of unsaturated semicarbazonesdiminishes their capacity for addition of hydrogen chloride, whereasin the case of the saturated semicarbazones it increases this capacity.This is shown by a comparison of cinnamaldehydesemicarbazonedihydrochloride and cinnamaldehydephenylsemicarbazone mono-hydrochloride with benzaldehydesemicarbazone monohydrochlorideand benzaldehydephenylsemicarbazone dihydrochloride.We intend t o extend these investigations to a larger number ofsemicarbazones before giving our views on the possible change ofstructure during addition of acids t o semicarbazones, but as cir-cumstances have arisen which render the continuation of the workimpossible for the present and as i t is uncertain when it can becompleted i t was thought advisable to record these results.E XPE R I MEN T AL.Piperoi&den eacetonesemicarbazones.Yellow piperonylidereacetone was prepared according t o Haber'smethod (Ber., 1891, 24, 618).Haber recrystallised his productfrom alcohol, in which the substance is sparingly soluble, but itwas found more convenient, to use benzene as the solvent. ThTO OUR KNOWLEDGE OF SEMICARBAZOKES. PART IV. 2895white, stereoisomeric piperoiiylideneacetone was also prepared byHaber’s method.A semicarbazone was prepared from each ketone in the usualmanner, and crystallised first from alcohol and finally from chloro-form. It was found that the two stereoisomeric ketones gave oneand the same semicarbazone, melting a t 217O, and a mixture ofthe products showed no depression of the melting point:0,2020 gave 29-15 C.C.N, a t 16O and 766.5 mm. N=16*85.The semicarbazone forms white crystals, which are insoluble inWe designate this semicarbazone as the a-modification.On hydrolysis with hydrochloric o r acetic acid the semicarbazoneyielded the yellow modification of piperonylideneacetone.A solution of this a-semicarbazone in alcohol was exposed t oultra-violet light for thirty hours. The alcohol was then evaporatedand the residue fractionally crystallised, first from water andfinally from benzene and Gglit petroleum. Besides unaltered sub-stance there was obtained a fairly large quantity of a crystallinesubstance melting a t 168O. The substance crystallises in creamyneedles, which are more readily soluble in chloroform or alcoholthan the a-semicarbazone. We designate this product the P-modi-fication, since analysis showed it t o have the same composition asthe a-modification :C1,H&,N, requires N,= 17.0 per cent.water, and fairly soluble in hot alcohol or chloroform.0.1400 gave 20.5 C.C.N, a t 12O and 746 mm. N=1-6.94.C,,H,,O,N, requires N = 17.0 per cent.Addition of Hydrogen Chloride t o t h e a-Modification.The reaction was first carried out by passing dry hydrogenchloride into a solution of the substance in dry chloroform. Areddish-orange precipitate’ separated, which was collected and driedon a porous tile, This substance was very unstable, and easilydecomposed by moisture. To determine the amount of hydrogenchloride with which the semicarbazone had combined the substancewas warmed with excess of standard alkali, and the residual alkalititrated with standard acid.The results varied with each prepara-tion, but approximated to a compound of the formulaC,,H,,03N3,2HCl.Owing to the unsatisfactory nature of the results obtained by thismethod the following procedure was finally adopted.ThisU-tube was specially constructed so that the substance can beexposed to the action of the gas in thin layers. For this purposeinstead of the ordinary tube of long limb and narrow bend theA U-tube closed by means of glass stop-cocks was used.VOL. cv. 9 2896 WILSON, HEILBRON, AND SUTHERLAND : CONTRIBUTIONSlimbs of the U-tubel were 8 cm. apart and the limbs only 5 cm. inlength.The tube was first filled with dry air and weighed (weight=a).Dry hydrogen chloride was then led into the tube until the weightwas constant (weight=b).The hydrogen chloride was then dis-placed by a current of dry air, and a quantity of the a-semi-carbazone introduced into the tube (weight of tube + semicarbazone+air=c). Dry hydrogen chloride was then passed through thetube until the weight was constant; this was obtained only afterseveral days. As therewas a possibility that the hydrochloride might be unstable in airthe atmosphere of hydrogen chloride was not displaced, but* a cor-rection was made for weighing in such an atmosphere.The tube was then closed and weighed.Thus : Weight of tube + hydrochloride +hydrogen chloride = d.- Weight of semicarbazone ---a.Weight of hydrogen chloride1 added = d - { c + (71 - a ) }.Weight of hydrochloride = d - b .0.3040 semicarbazone gave 0.4198 ‘hydrochloride.HCl added =27.58.C12H,303N3,2$HCl requires HCl = 26-93 per cent.This salt forms bright, vermilion-coloured crystals. The meltingpoint was indefinite, since decomposition takes place on heating ;this occurs a t about 125-140O.I f this salt is exposed to light for some days in the tube in whichit was weighed the colour changes from vermilion t o deep orangewithout change in weight. In order to prove that the change ofcolour was not due to slight loss of hydrogen chloride, hydrogenchloride was again passed over the substance, but the orange colourremained unchanged, and the weight was not altered. On pro-longed exposure to light the orange-coloured salt acquired a greentint without change in weight.The vermilion colour was notrestored either on warming or cooling the substance, or on keepingi t in the dark. The experiment was repeated, the semicarbazonethis time being subjected to the action of hydrogen chloride in thedark. The same absorption took place, and the vermilion-colouredsalt was again obtained :HCI added = 0.2254 semicarbazone gave 0.3114 hydrochloride.27.61.C,2H,30,N,,2$HC1 requires HC1= 26.93 per cent.This salt on exposure to air a t the ordinary temperature rapidlyevolves hydrogen chloride. A sample of the salt was exposed t othe air a t room temperature until, after drying in a desiccator,the weight was constant. For this several weeks were requiredTO OUR KNOWLEDGE OF SEMICARBAZONES.PART IV. 2897The substance so obtained was orange, but not so deep in colouras the orange salt, Cl,H130,N,,2~HCl, just mentioned. Analysisshowed the product to be a monohydrochloride.The substance was warmed gently with excess of N/20-alkali, andthe residual alkali, after filtration, titrated with N / 20-sulphuricacid :0.1534 required 11.4 C.C. NI20-NaOH. HC1= 13.52.This orange monohydrochloride is only partly decomposed bywater, but is completely decomposed by dilute alkalis. It is appa-rently quite stable in ordinary air, and in a closed tube it meltsand decomposes at 173-175O.The residue obtained by treatment of the monohydrochloridewith alkali was recrystallised from alcohol, and proved to be thea-semicarbazone.C12H130,N,,HC1 requires HC1= 12.83 per cent.Addition of Hydrogen ChZoride to the P-Semicarbazone.A solution of the #3-semicarbazone in dry chloroform was satur-ated with dry hydrogen chloride.A yellow, crystalline precipitateseparated almost immediately, which was collected, washed withchloroform and light petroleum, dried on a porous tile, and finallyin a desiccator. This substance was analysed in the way alreadydescribed, and proved to be a moimhydrochtoride :0.3249 required 10.8 C.C. iV/ 10-NaOH. HC1= 13.3.The monohydrochloride is canary-yellow, melts and decomposesa t 169O, is stable in air, and fairly stable towards water. Ondecomposition with alkali a white substance was obtained, whichon crystallisation from alcohol yielded the a-modification only, andnot the #3-modification.Hence in this way transformation from theP- into the a-modification can be effected. Thus:Piperonylideneacetone (white) \,Piperonylideneacetone (yellow) /Cl,Hl,O,N,,HC1 requires HC1= 12.9 per cent.4 a-Piperonylideneacetone-7( semicarbazoneI.t.1J.&Piperon ylideneace t o ne-semicarbazoneP-Piperonylideneacetone-semicarbazone + 1HCla-Piperonylideneacetone-semicarbazone..143.a-piper on ylideneacetonesemicarbazone+ 24HCla-Piper onylideneacetoneseniicarbazone+ lHCla-Piperonylideneacetonesemicarbazone.9 ~ 2898 WILSON, HEILBRON, AND SUTHERLAND : CONTRIBUTIONSI n order to determine whether this moiiohydroclrloride couldcombine with more hydrogen chloride a weighed quantity wasplaced in a U-tube and dry hydrogen chloride passed over it.Noincrease in weight took place, but the substance acquired a greentinge.C'in n a rn n lde h ydes e rn ica r b az o n e.This compound was prepared according t o Young and Witliam'smethod (T., 1900, 77, 230). It is white, and, if freshly prepared,undergoes no change of colour in the dark. I f , however, it is firstexposed to bright light', which produces no visible effect, and thenplaced in the dark, a yellow colour is developed. This yellowcolour disappears on reexposure of the substance t o light. Evi-dently the freshly prepared substance' must first be made active byexposure to intense light before phototropic properties are deve-veloped.Further, if either of the active! forms is recrysta~lised, theactivity disappears, and exposure t o bright light is again necessaryto develop phototropic properties. These three modifications allpossess the same melting point, namely, 217O, which is slightlyliiglier than that recorded in the literature. An alcoholic solutionof the semicarbazone was exposed to ultra-violet light for thirtyhours. The solution was then concentrated, and the residue frac-tionally crystallised, but unaltered substance only was obtained.Addition of Hydrogeta Chloride to the Semicarbazone.Owing t o the sparing solubility of the substance in all coldsolvents the reaction could not be carried out in solution. Accord-ingly a weighed quantity was placed in a stoppered U-tube of theform already described, and dry hydrogen chloride passed over thesemicarbazone until the weight became constant.The same pre-cautions were taken as in the previous experiments, the substancebeing weighed in an atmosphere of dry hydrogen chloride and acorrection made for the difference in weight of hydrochlorideweighed in hydrogen chloride and hydrochloride weighed in air :HCl added = 0.4148 semicar bazone gave 0.5820 hydrochloride.28.11.C,,H,,ON,,BRCl requires HCl = 27.86 per cent.This salt of cinnamaldehydesemicarbazone, which is evidently adihydrochloride, is deep orange, and very unstable. Moist airimmediately decomposes it, with the formation of a viscid com-pound. During the preparation of the salt the semicarbazone, onfirst passing hydrogen chloride over it, partly fuses, changes colourto yellowish-orange, and finally the substance becomes powderysnd assumes a deep orange colourTO OUR KNOWLEDGE OF SEMICARBAZONES.PART IV. 2899As the dihydrochloride is unstable in ordinary moist air i t wastransferred from the U-tuba to a weighing bottle in dry air inwhich the salt is comparatively stable. A melting-point' tube wasfilled a t the same time, sealed, and the melting point found t o be80--83O, decomposition also occurring. The apparatus used was asimple but very efficient arrangement, which enabled us t o work indry air with comparative ease.Addition of Szclphuuric Acid to CiPznumalcFeh,?/dcsemicarbcrzo?~e.A quantity of the semicarbazone was rubbed into a paste withconcentrated sulphuric acid, when the mixture became oily andyellow.Dry ether was added, the mixture being kept cool, thenjust sufficient absolute alcohol to bring the whole into solution, andthe mixture placed in ice. On keeping for some time yellow needlescrystallised from the solution, which were collected, washed withdry light petroleum, and dried first on a porous tile and finallyin a desiccator. Analysis showed the compound t o be a salt ofsulphuric acid. The analysis was conducted in the same way asin the case of the hydrochlorides, namely, the salt was warmedwith excess of N/10-alkali and the residual alkali titrated withN / 10-acid :0.109 required 7.325 C.C. N/lO-alkali. H,SO, = 32-92.C,,H,,ON,,H,SO,~ requires H,SO, = 34.1 per cent.P r e p r a tion of Cinicamalde hydephe nylsemicurbazo tz e.Molecular quantities of cinnamaldehyde in alcohol and of phenyl-semicarbazide hydrochloride in water were mixed.The solutionbecame deep orange, and a precipitate immediately formed, whichwas collecte'd, washed with water, and crystallised first from alcoholand finally from a mixture of chloroform and light petroleum.The pheiL~lsemicarbazoIzc: crystallises in white, felted needles,melting a t 205O. It is readily soluble in chloroform or hot alcohol,and practically insoluble in light petroleum :0.200 gave 27.2 C.C. N, a t 1 2 O and 751 mm. N=15*93.The behaviour of the phenylsemicarbazone towards light isexactly the same a s that of cinnamaldehydesemicarbazone. Thefreshly prepared subst,snce is not affected by light or darkness, but,if i t is exposed t o bright light and then placed in the dark a deepyellow colou=.is developed, which disappears on again exposing t olight. Rise of temperature accelerates the conversion of the whiteinto the yellow^ modification. Thus on exposing a sample of thecolourless, inactive modification to light and then placing in aCI6H,,ON, requirc3s N = 15.84 per cent2900 WILSON, HEILURON, AND SUTHERLAND : CONTRIBTJTIONSclosed steam-oven the yellow colour becomes apparent almost imme-diately. I f , however, the preliminary exposure to light is omittedno change of colour is developed by heating the substance in thedark. The melting points of the three modifications were thesame, namely, 205O.A chloroform solution of the phenylsemicarbazone was exposedfor thirty hours t o ultra-violet light.The solution was carefullyexamined, but only unchanged substance was obt'ained.Addition of Hydrogen Chloride to Cinnamaldehydephenyl-semicar b azone.A concentrated solution of the phenylsemicarbazone in drychloroform was saturated with dry hydrogen chloride. A yellow,crystalline precipitate soon separated, which was collected, washedwith chloroform, and dried on a porous tile. It was analysed inthe usual way, and found t o be a monohydrochloride:0.6465 required 20-9 C.C. N / 10-NaOH. HC1= 11.8.C16H150N3,HCl requires HCl = 12.11 per cent.The hydrochloride is canary-yellow, stable in air, and fairlystable towards water.It melts and decomposes a t 161-162O. Asthe semicarbazone of cinnamaldehyde formed a dihydrochloride onpassing dry hydrogen chloride over the dry substance it wasthought that the phenylsemicarbazone might react with anothermolecule of hydrogen chloride if exposed to the1 action of dryhydrogen chloride in the dry state. Accordingly, a quantity of themonohydrochloride was placed in a U-tube and treated as alreadydescribed in the preparation of other hydrochlorides. After thegas had been passed over the monohydrochloride for several daysit was found that no increase in weight had taken place, thesubstance remaining a monohydrochloride. No change in colourwas observed. Starting, however, with cinnamaldehydephenylsemi-carbazone (white variety) and passing hydrogen chloride over thedry substance, the gas is rapidly taken up, and the colour becomesdeep yellow.After passage of the gas for one week the percentageof hydrogen chloride absorbed was found to be 19.72; thereafterweighing a t intervals the hydrogen chloride content appeared t odiminish, and after passage of the gas for thirty-eight days thepercentage was found to be 17.4. After this the compound con-tinued t o lose hydrogen chloride, but a t a very slow rate, and withcontinued passage of the gas would probably approximate t o 12.11per cent. or 1 molecular proportion of hydrogen chloride.On exposure to air this hydrochloride again gives the stablemonohydrochloride TO OUR KNOWLEDGE OF SEMICARBAZOKES. PART IV. 29010.2014 required 6.5 C.C.N / 10-alkali. HCl= 11.79.C,,H150N3,HCI requires HC1= 12.11 per cent.I n the same way tjhe yellow modification of cinnamaldehyde-phenylsemicarbazone was exposed to the action of dry hydrogenchloride in the dark. The yellow compound formed was slightlydar;ker in shade than that from the white modification, and it alsoreached a maximum addition of hydrogen chloride. The maximumafter ten days in this case was 19-46 per cent.. The hydrogenchloride content diminished much more rapidly, and in thirty-eight days fell to 15.15 per cent., again an approximation t o1 molecular proportion. On exposure to air this hydrochloridegives, like that of the white modification, a stable monohydro-chloride :0'232 required 7.4 C.C. N / 10-NaOH.HC1= 11.59.C16H,,0N3,HCI requires HC1= 12.11 per cent.Addition of Sulphuric Acid to Cinnamddehydephenyl-semicarbazone.The phenylsemicarbazone was mixed with a small quantity ofconcentrated sulphuric acid, alcohol added until the substance dis-solved, and the mixture cooled in ice. After a time yellow crystalsseparated, which were collected and recrystallised from glacialacetic acid. The sulphate was analysed in the usual way by heat-ing gently with excess of standard alkali and titrating the residualalkali :0*100 required 11.1 C.C. rV/ 10-NaOH.C,,H,,ON,,H,SO, requires H,SO, = 26.99 per cent.The sulphate is a brilliant, yellow-coloured powder, stable in air,but easily decomposed by COT& water and dilute alkali with theformation of the phenylsemicarbazone and sulphuric acid.H,SO, = 27.2.Yreparatiom of a Dibiornide of CiiznamalclPI~ydepherzyl-semicarbazoize.The theoretical quantity of dry bromine in dry chloroform wasadded to the phenylsemicai-bazone dissolved in dry chloroform,and the mixture was allowed to remain for half-an-hour, whenyellow crystals began t o appear. When all t,he substance hadcrystallised out the crystals were collected, dried, and recrystallisedfrom chloroform.The substance crystallises in canary-yellowneedles, which are very sparingly soluble in chloroform, and melta t 187O. Analysis showed it t o be the &bromide of cinnamalde-hydephenylsemicnrbazone :0.200 gave 17.1 C.C. N, at 10" and 754 mm. N=10*14.C,6H,,0N3Br, requires N = 9.91 per cent2902 WILSON, HEILBRON, AND SUTHERLAND : CONTBIRUTIONSThis dibromide was subject,ed to the action of dry hydrogenchloride, but no addition took place.Evidently the dibromidedoes not form a hydrochloride. Also on treating cinnamaldehyde-phenylsemicarbazone monohydrochloride with bromine in chloro-form solution and adding light petroleum a yellow precipitate isobtained, which consists of the dibromide of cinnamaldehydephenyl-semicarbazone.Prepmatioil. of a Mo?zobrorno-derivative of Ciimamaldehyde-p h enyl se micar b azo n e from the U i b roinid e.It was found that on recrystallisation from alcohol the dibromidewas decomposed, hydrogen bromide being liberated and a whitesubstance melting a t 1 6 8 O crystallising out. Some of the cinnam-aldehydeplienylsemicarbazone dibromide was theref ore boiled inalcohol until dissolved, then diluted with water, and the productallowed t o crystallise :0'200 gava 21.05 C.C.N, a t 1 2 O and 739 mm. N=12*15.C,,H,,ON,Br requires N = 12.20 per cent.The substance obtained is therefore a monobromo-derivative ofcinnamaldehydephenylsemicarbazone. It crystallises in small,colourless, glistening needles, which after several crystallisationsmelt a t 195O. It is readily soluble in chloroform, benzene, or boil-ing alcohol, but practically insoluble in light petroleum.Additioih of Hydroget8 Chloride to the Monobromo-derivntive ofCimzanzalde hydephe?zylsemicarbazone.A weighed quantity of the monobromo-derivative was placed ina U-tube and subjected t o the action of hydrogen chloride in t.hemanner already described. Reaction took place immediately, anda yellow salt was produced.Passage of the gas was continued untilthe weightj became constant:HCl 0.6624 monobromo-derivative gave 0.7458 hydrochloride.added = 11.18.C,,H&N,Br,HCl requires HC1= 9-59 per cent.The hydrochloride is bright canary-yellow, and fairly stable inIt is part'ly decomposed air, gradually losing hydrogen chloride.by water and completely by dilute alkaIi.Yre para t io i b of Mo ILO b ro m o cin na muld e h yde p h e tcy 1 s e NL icar b a z o ii, e .Cinnamaldehyde was first brominated according to the methoddescribed by Zinckel and Hagen (Ber., 1884, 17, 1815). Thebrominated product separated at once, and was crystallised froTO OUR KNOWLEDGE OF SEMICARIUZONES.PART IV. 2903alcohol. It was mixed with the necessary quantity of phenylsemi-carbazide in alcoholic solution, when the phenylsemicarrbazo,ze sepa-rated immediately and was crystallised from alcohol :0.250 gave 26.2 C.C. N, a t 12O and 745 mm. N=12*13.The substance crystallises in flat', colourless prisms, melting a t197O. It is soluble in alcohol or chloroform, but more readilysoluble in the latter than is the monobronio-compound derived fromthe dibromide. It is not identical with the latter substance, as isshown by crystalline structure, solubility, and melting point.C,,13,,0N3Br requires N = 12-22 per cent.d dditiotb of HydrogeTL Chloride to t h e above n-ioizobrornocititiar6r)i-alde hydephenylsemicarbaso ne.Hydrogen chloride was passed over a weighed quantity of thesubstance until the weight became constant.The addition ofhydrogen chloride took place a t once, but several days elapsedbefore the weight became constant :0.5922 phenylsemicarbazone gave 0.713 hydrochloride. HCladded = 16-94.C,,H,,0N3Br,2HCl requires HC1= 17.50 per cent.This di/Lydrochloride of monobromocinnamaldehydephenylsemi-carbazone is bright yellow, of a slightly deeper shade than themono hydrochloride of the monobromo-compound obtained fromcinnamaldehydephenylsemicarbazone dibromide. It is, however,much more unstable, and on keeping even in a stoppered weighingbottle loses hydrogen chloride, the colour at the same time dis-appearing. A portion of the salt was exposed t o the air for sometime, then dried in a desiccator, and weighed. This treatmentwas repeated until the weight was constant, which condition wasreached a t the end of three weeks, and the yellow colour hadentirely disappeared.On titrating a weighed quantity of thesubstance with standard alkali it was found that the hydrochloridehad lost the whole of tho hydrogen chloride on exposure to the air.Addition of Hydrogen Chloride to Acetonesemicarbazotie.Dry hydrogen chloride was passed over a weighed quantity ofacetonesemicarbazone (m. p. 187O) in the manner previouslyadopted. Hydrogen chloride was absorbed a t once, and the sub-stance fused slightly, although no change in colour occurred. Aftersome time the substance became powdery, the U-tube was weighed,and increase in weight found t'o have taken place.Hydrogenchloride was then passed over the substance until the weightbecame constant 2904 WILSON, HEILBRON, BND SUTHERLAND : CONTRIBUTIONS1.1 984 acetonesemicarbazone gave 1.5820 hydrochloride. HC1added = 24.24.C,H,ON,,HCl requires HCl = 24.09 per cent.The hydrochloride is evidently a monohydrochloride, and isobtained as a white powder, melting in a closed tube a t 150-151O.It is unstable in ordinary air, and hydrogen chloride is graduallyevolved from it. I n dry air i t is comparatively stable.Addition of Hydrogen C hl om'de to A c e t oneph enylsemicar bazoize.Dry hydrogen chloride was passed over a weighed quantity ofacetonephenylsemicarbazone (m.p. 1 5 7 O ) as before until the weightwas constant. The substance caked slightly on the first addition ofhydrogen chloride, but ultimately became powdery. No colour wasproduced, but an addition in weight occurred, showing the forma-tion of a salt:HCl 1.1088 phenylsemicarbazone gave 1.4180 hydrochloride.added = 21.80.Cl,H130N3,HC1 requires HCl -- 16-05 per cent.Cl~H130N3,1~HCl ,, HC1= 22.26 , , ,,On exposure t o air it rapidly loses hydrogen chloride.Addition of Hydrogen Chloride to Acetophenonesemicarbazone.Dry hydrogen chloride was passed over a weighed quantity ofthe semicarbazone (m. p. 202O) as before. The substance fusedalmost immediately and a yellow colour was developed. The weightincreased gradually, but did not become constant, and the substanceremained semi-solid, and appeared to decompose.The amount ofhydrogen chloride taken up approximated to two molecular propor-tions, but the results could not be trusted owing to the semi-fusedcondition of the substance.AdditioiL of Hydrogen Chloride to Acetop~~enoiEephenylsemi-carbaaone.This compound behaved in much the same way as the semi-carbazone. Addition of hydrogen chloride takes place with fusion,and a deep yellow colour is developed. The effect of strong coolingwas tried in this case, the tube being surrounded by carbondioxide snow. Even under these conditions the substance fusedalthough the colour developed was very much less. I n the caseof this phenylsemicarbazone the hydrochlorkle solidified t o a hardmass adhering t o the tube.Two experiments were tried: (1) Addition of dry hydrogenchloride a t room temperature TO OUR KNOWLEDGE OF SEMICARBAZONES.PART IV. 29050.5932 phenylsemicarbazone gave 0.7808 hydrochloride. HCladded = 24-02.C1,H,,0N3,2HC1 requires HCl = 22.36 per cent.(2) Addition of hydrogen chloride at the temperature of solid0.3272 phenylsemicarbazone gave 0.4094 hydrochloride. HClcarbon dioxide :added = 20.05.Addition of Hydrogen Chloride t o Benzaldehydesemicarbazone.Hydrogen chloride was passed over the semicarbazone (m. p.222O) in the manner already described. The colour changed fromwhite to greyish-white, and slight fusion took place on the firstformation of the nionohydrochloride :HC1 added = 0.8548 semicarbazone gave 1.061 3 hydrochloride.19-45.C8H,0N,,HCl requires HCI = 18-29 per cent.The hydrochloride is greyish-white, melts a t 199O, and is fairlystable in air.Addition of Hydrogen Chloride to Be?zzaldehydephee.nylsemi-carbazone.The phenylsemicarbazone was dissolved in dry chloroform, anddry hydrogen chloride passed through the solution.The solutionbecame yellow, and a white precipitate formed, which was collectedin an atmosphere of dry air, washed with chloroform, and driedon a porous tile. A quantity of this was placed in a dry, previ-ously weighed weighing-bottle, the bottle weighed, and the contentswere shaken into excess of standard alkali; the excess of alkaliafter warming the mixture was titrated with standard acid:0.2598 required 13.3 C.C.N/10-NaOH.The hydrochloride evidently loses hydrogen chloride too rapidlyeven in dry air to allow of accurate estimation.The substance was therefore exposed to the action of dry hydro-gen chloride until the weight became constant. The substancebecame yellow immediately on the passage of the gas, and a t thesame time partly liquefied. The final product was deep yellow andsemi-solid in appearance.Owing to fusion having taken place a satisfactory result was notobtained :0.3264 phenylsemicarbazone gave 0.4196 hydrochloride. HClCl4Hl30N3,2HC1 requires HCl = 23-4 per cent.HC1= 18.68.Gl,H,,ON3,2HC1 requires HC1= 23-4 per cent.added = 22.212906 CONTRIBUTIONS TO OUR KNOWLEDGE OF SEMICABBAZONES.This dihydrochloride is yellow and exceedingly unstable ; itAnnexed is a summary of the compounds examined.decomposes immediately on exposure t o air.Substances investigated,a-Piperonylideneacetone-semicarbazone8-Piperonylideneacetone-semicarbazoneCinna m a1 d e h y de s e m i -carbazoneChnamaldehydepheny 1 -semicarbazoneCinnamaldehydephen y 1 -semicarbezone di-bromideMonobromo-d e r i v a t i v efrom cinnamaldehyde-phenylsemicarbazonedibromideMonobromocinnamal de -hydesemicarbazoneAcetonesemicarbazoneAcetonephenylsemic r b-azoneAcetophenonese mi c a rb-Ace t op hen o n ep h e n y 1-Benzaldehydesemicarb-Henz a1 de h y d ep h en y 1-azonesemicarbazoneazonesemicarbazoneMols. HCladded.2121Noadditioii121221(indefinite)2Colour of ad-ditive product,VermilionCanary- yellowDeep orangeCanary -yellow-YellowEright ycllowNo colourNo colourYellowYellowGreyishYellowStability of additiveproduct.Very unstable, af-fected by light,stable a t 1 mol.HCl.Stable.Unstable.Stable.Fairly stable ; gradu-ally loses HCl.Unstable.C o m p a r a t i v e l ystable in dry air.HC1 evolvedslcmly in ordinaryair.Unstable. Tends tostability a t 1 mol.HC1.Unstable.[Jnstable.Fairly stable.Exceedingly un-stable.I n conclusion, we desire t o express our thanks to the CarnegieTrust for the Universities of Scotland for a grant which defrayedthe expenses of the work. We also desire to record our thanks t oProfessor G. G. Henderson for the interest he has taken in theseinvestigations.CIIEMISTRY DEPARL'MENT,ROYAL TECHNICAL COLLEGE, GLUGOW

ISSN:0368-1645    

DOI:10.1039/CT9140502892

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

ABSORPTION SPECTRA OF SULPHUROUS ACID AND SULPHITES. 2907CCLXXI1.-The AbsoqAon SpectraAcid and Suiphites.By ROBERT WRIGHT.of SulphwousIN a fcrmer paper (this vol., p. 669) dealing with the relationbetween the absorption spectra of various acids and their alkalisalts, the absorption curves of sulphurous acid and sodium sulphitewere shown. I n view of the doubtful constitution of these sub-stances, and as their light absorptive powers are so fundamentallydifferent, the acid showing selective, and the salt only generalabsorption ; i t was considered of importance t o investigate theirspecial case more closely.Potassium sodium sulphite, prepared either from sodium hydro-gen sulphitel and potassium hydroxide o r from potassium hydrogensulphite and sodium hydroxide, gave a spectrum identical with thatof sodium sulphite.Most sulphites of the bivalent metals are too insoluble to admitof investigation ; magnesinm sulphite is, however, sparinglysoluble, and on photographing its M/lOO-solution it was found t ogive the same spectrum as the alkali sulphites.It seemed possible that sulphurous acid might have a structuresimilar to that of the sulphonic acids, for it will be seen on refer-ence to the paper already mentioned that benzenesulphonic acidand its salt both give a band in the same region of the spectrum,but at a greater dilution than sulphurous acid.On examination,however, the sodium salt of ethylsulphonic acid was found to bequite diactinic, so that the occurrence of the band in the aromaticcompound must be attributed t o the phenyl nucleus, which, as iswell known, almost invariably causes selective absorption.Ethyl sulphite, from thionyl chloride, was also examined inalcoholic solution, and was found t o be practically diactinic atM / 10-dilutionStewart and Macbeth, in an unpublished research, observed thatgaseous sulphur dioxide gave a band in the ultra-violet. It wastherefore thought advisable to compare this band with that ofaqueous sulphurous acid.The investigation was carried out by means of the followingapparatus. A tube of about 2 cm.in diameter and exactly 10 cm.long has its ends closed with quartz windows. This observationcell has two side-tubes, one connected with a source of the gas andthe other with a manometer and pump.The apparatus is fittedwith three taps, one between the source of the gas and the cell2908 WRIGHT: THE ARSORPTION SPECTRA OFone between the cell and the manometer, and the third betweenthe manometer and pump. .All connexions in the apparatus wereof glass.i n using the apparatus, all the taps are opened and the air isswept out by a stream of sulphur dioxide; the taps are now closed,the apparatus is connected with the pump, and a series of photo-graphs taken through the cell a t different pressures, which areobserved by means of the manometer. Taking 2.9266 grams as theweight of a litre of sulphur dioxide a t N.T.P., the normality of thegas under these standard conditJons is 2*9266/ 64 = 0.04572N. Athickness of 100 imn.of a gas the normality of which is 044572corresponds with 4.57 mm. of N-concentration. By a similar cnlcu-Frequeiicies.30 32 34 36 38 40 42 44Full curve = Sulphur dioxide iir, aqueous solution.Dotted ,, = Gaseous Sulphw dioxide.Dash ,, = Alkali sulphites.lation the 10 cm. thicknesses a t different pressures can be reducedto the corresponding thicknesses of N-gas. The curve drawn fromthese results is shown in comparison with that of aqueous sulphur-ous acid, and it will be seen that they strongly resemble oneanother : for although differing slightly in persistence, they corre-spond in their positions in the spectrum and in the thicknesses a twhich they occur.A few comparison photographs were also made, using air as adiluent. For this purpose the tube was filled with gas as before,the pressure reduced, and a photograph taken; air was nowadmitted t o the cell by raising a tap out of its seat, and a secondexposure made.Since the gas in the cell is under less than atmo-spheric pressure, it cannot escape during this process, and so thSULPRUROUS ACID AND SULPHITES. 2909second exposure is made through the same amount of sulphurdioxide as the first; only, in the latter case it3 is diluted with airinstead of being under diminished pressure. I n the half-dozencomparisons made no difference could be detected between the twosets of photographs.The result seems t o indicate that aqueous sulphurous acid consistslargely of uncombined sulphur dioxide molecules. The solution wasalso examined a t zero, by surrounding the cell with ice, in orderto see if the solution of the crystalline compound which separatesat that temperature gave the same spectrum as the solutlion underordinary conditions. No difference in the two spectra could bedetected.From this work the conclusion may be drawn that an aqueoussolution of sulphur dioxide consists to a large extent of uncombinedgas molecules.Q U I ~ N ’ S UNIVERSITY,B 14: LFASTPRINTED IN GREAT BRITAIN BYRICHARD CLAY AND SONS, I,IMITED,HRUNSWICK STREET, STAMFORD S'CKEET, S.E.,AND BUNGAY SUFFO1.

ISSN:0368-1645    

DOI:10.1039/CT9140502907

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

INDEX OF AUTHORS' NAMES.TRANSACTIONS AND PROCEEDINGS. 1814.(Marked T. and P. respectively.)A.bcree, Solomon Farley. See John Ean-ston Shroder.Adams, Matthew Algernon, obituarynotice of, T., 1189. .Adhicary, Bircndra Bhusan. SeePanchcinon Neogi.Bllmand, Arthur John. See FrederickQeorge Donnan,All ress, Charles Frederick, SeeJfTederick Challenger.Andrew, George William, the water-gasequilibrium in hydrocarbon flames, T.,Applebey, Malcolm Percival, and DazidLeonard Chapman, a new formula forthe latent heat of vapours, T., 734;P., 27.Ark, Harry. See Earry MedforthDawson.Arrhenins, SvanAe, Faraday lecture, thetheory of electrolytic dissociation, T.,1414 ; P., 165.Atkinson, Harford Montgomery, somederivatives of as-dipropyl- and -diamyl-oxamic acids, T., 1290 ; P., 81.444 ; P., 22.B.Bain, (Miss) Alice Mary.See WilliamHobson Mills.BaF, David, William Henry Perkin,jun., and Robert Robinson, some de-rivatives of isocoumarin and isocarbo-styril, T., 2392 ; P., 234.Bainbridge, Ernest Graham, experi-ments on the conversion of certaindibromides of the type of ethyleliedihromide into the corresponding gly-cols, T., 2391 ; P., 232.Baker, Herbert Brereton, the spitting ofsilver, P., 56.CV,Baker, Herbert Brereton, and WalterHenry Watson, the atomic weight ofmercury, T., 2530 ; P., 243.Baker, Julian Lcvett, and Henry FrancisEverard Hulton, the action of diastaseon starch granules. Part I . , T., 1529 ;P., 133.Barendrecht, Hendrik Pieter, alcohol-ometry and rational fractionation, P.,160.Barger, George, and Walter WilliamStarling, crystals of organic com-pounds coloured blue by iodine,P., 2.blue adsorption compounds of iodine.Parts 11.and 111. Derivatives of 2-and 4-pyrone, P., 303.Barker, Thomas Vipond, attempts toresolve inetallic salts of amino-acidsand other co-ordinated compounds ;preliminary note, P., 295.Barrow, Fred. See Percy FaradayFrankland.Bassett, Henmy, jun., and Bugh StottTaylor, calcium nitrate. Part 111.The three-component system : calciumnitrate-lime-water ; T., 1926 ; P.,204.Beesley, Bichurd Moore, experiments onthe rate of nitrification, T., 1014 ; P.,67.Bell, Joseph Carter, obituary notice of,T., 1193.Bell, Normaiz illurray. See AlfredHolt.Bennett, George Macdonald, and EzsataceEbenezer Turner, the action of chromicchloride on the Grignard reagent, T.,1057 ; P., 79.Benson, Percy.See Albert Ernest Dnn-stan.Birse, William Milne. See FrancisWilliam Gray.9 2912 INDEX OF AUTHORS.Bissett, Crellyn Colgraw, the system :silver-silver sulphide, T., 1223 ; P.,82.the removal of sulphur from silver,T., 2829 ; P., 269.Bissett, CrelZyn Colyraoe. See alsoWilliam Ernest Stopheit Turner.Bloxam, Willaamn Popplewell, obituarynotice of, T., 1195.Bone, William Arthur, and BamiltonDavies, the thermal decompositionof methyl alcohol, T., 1691 ; P.,178.Boon, Alfred Archibald, Kenneth JohnMcKenzie, and John Trotter, somearylidenedimethylpyrones and theirsalts, P., 205.Boon, Awred Archibald, Forsyth JamesWilson, and lsidor Aforris Heilbron,the constitution of the arylidene-niethylpyrones and their salts, T.,2176 ; P., 209.Bousfield, William Robert, ionisationand the law of mass action. Part11. The osmotic data in relation toconibined water, T., 600.ionisation and the law of mass action,Part 111. Utilisation of the osmoticdata and a new dilution law, T.,1809 ; P., 156.Boyd, David Runciman, and ErnestRobert Marle, the velocities of com-bination of sodium derivatives ofpheiiols with olefine oxides, T., 2117 ;P., 199.Boyle, (M;ss) M a y , molecular conduc-tivities of iodoanilinesulphonic acids,P., 161.Bradbury, Hurry, and Charles Weiz-mann, some homologues of alizarin,T., 2748 ; P., 259.Bradshaw, Lawrence. See Harold BailyDixon.Brady, Oscar Lisle, the isomerism of theoximes. Part IV.The constitutionot N-methyl ethers of the aldoximesand the absorption spectra of oximcs,their sodium salts, and methyl ethers,T., 2104 ; P., 198.Brady, Oscar Lisle, and Frederick PercyDunn, the isomerism of the oximes.Part I1 I. The h ydroxy benzal d-oximes, T., 821 ; P., 65.the i3omerism of the oxiriies. Part V.?n-.Mt.thnxyheczaldoxinie, vanillin-oxitlie, and veratraldoxime, T.,2409 ; P. , 240.the isomerism of the oximes. Part VI.p-Dimethylaminobet,zaldoxime, T.,2872; P., 292.Brinsley, Frank. See Eubert FrankCoward.Briscoe, Henry Vincent Aird, a redeter-mination of the atomic weight of tin,P., 290.Briscoe, Henry Vincent Aird, and HarryPrank Victor Little, the atomic weightof vanadium, T., 1310 ; P., 64.Browning, Henry, jun.See FrederickBeZding Power.Bunbury, Hugh Mills, and HerbertErnest Martin, studies of the consti-tution of soap solutions ; the electricalconductivity of potassium salts off t t t y acids, T., 417 ; P., 8.Bnrgen, Peter. See George FrancisMorrell.Burgese, Maurice John, and XichardVernon Wheeler, the distillation ofcoal in a vncuum, T., 131.the limits of inflammability of mix-tures of methane and air, T., 2591 ;P., 245.the propagation of flame in “limit ”mixtiires of methane, oxygen andnitrogen, T., 2596 ; P., 245.Burrows, George Joseph, the inversion ofsucrose by acids in water-alcohol s o h -tions, T., 1260 ; P., 9.Burrows, George Joseph, and CharlesEdward Faweitt, the decompositionof carbamide, T., 609.Burrows, Harry, obituary notice of, T.,1200.Burton, Donald.See Harry MedforthDawson.C,Cain, John Cannell, and (Aiiss) FrancesMary Gore Micklethwait, studies inthe diplieiiyl series. P.lrt VI. Theconfiguration of diphenyl and itsderivatives, T., 1437 ; P., 146.studies in the diphenyl series. PartVII. Isonieric 0- and m-dinitro-o-tolidines, T., 1442 ; Y., 147.Cain, John Cannell, and John LionelSimonsen, nitro-acids derived from2:3-dimethoxybeuzoic acid and 4-methoxyphthalic acid, T., 156.Cain, John Cannell, John Lionel Simon-sen, and Clarence Smith, researches onsatitdin. Part II., T., 1335 ; P., 132.Campbell, Colin.See Harold BailyDixon.Cardwell, David. See Wililliam HenryPerkin, jun.Carr, Francis Howard, and Frank LeePyman, the alkaloids of ipecacuanha,T., 1591 ; P., 157.Caspari, William Awgustiis, the osmoticproperties and physical constitution ofcaoutchouc solutions, T., 2139 ; P.,226.INDEX OF AUTHORS. 2913Canwood, John Douglas. See FViEliamErnest Stephen Turner.Caven, Robert Martin, and Henry JzcliscsSulonton Sand, the dissoriation pres-sures of the alkali bicarbonates. Part11. Potassium, rubidium aud cmiumhydrogen carbonates, T., 2752 ; P.,268.Challenger, Frederick, organo-derivativesof bismuth. Part I. The prepara-tion and properties of sonie tertiaryaromatic bismuthines and their halo-gen derivatives, T., 2310 ; P., 229.Challenger, Frederick, and CharlesFrederick Allpress, organo-derivativesof bismuth.Part 11. The stability ofderivatives of quinquevalent bismuth,P., 292.Chapman, Alfred CJiaston, the nitro-genous constituents of hops, T., 1895 ;P., 196.Chapman, David Leonard. See MalcolmPercival Applebey.Chattaway, Frederick Daniel, interactionof glycerol and oxalic acid, T., 151.Chattaway, Frederick Daniel, and AlfredBertie Constable, derivatives of p-iodo-aniline, T., 124.Chattaway, Frederick: Dawiel, and CharlesFrederick Byrde Pearce, 2:4-dichloro-phenylhydrazine, P., 308.Chou, Tsan Quo. See William HenryPerkin, jun.Chowdhuri, Tayini Charan. See Panch-a n o n Neogi.Clarke, George, phytin and phytic acid,T., 535 ; P., 32.Clarke, (Miss) Rosalind.See AlfredSenier.Clewer, Hubert William Bentley. SeeFrank Tntin.Clough, George William, the opticalrotatory power of derivatives of suc-cinic acid i n aqueous solutions of in-organic salts. Parts I. and II., T.,4 9 ; P., 307.Coates, Joseph Edward, and (Miss) AdaFinney, the rate of combination ofgaseous nitric oxide and chlorine.Part I., T., 2444 ; P., 211.Cohen, Julius Berend, position-isomerismand optical activity, T., 1892 ; P.,221.Cohen, Julius Berend, and PavitraKzrmar Dutt, the progressive bromina-tion of toluene, T., 501 ; P., 15, 271.Cohen, Julius Berend, and Colin JamesSmithells, the chlorination and bro-mination of substituted toluenes, 1’. ,1907 ; P., 224.Coleman, Frederick Charlcs.See JamesWilliam YcBain.Constable, Alfred Bertie. See FrederickDaniel Chattaway.Cooke, John Harbourne. See GilbertThomas Morgan.Cooper, Charles. See Hubert FTankCoward.Cooper, William Francis, and WalterHarold Nuttall, the condensation offuran-2:5-dialdehyde with maloiiicester and malonic acid, T., 2218 ; P.,227.Copisarow, &!aurice, note on the forma-tion of triphenylcarbinol, P., 111.Coppin, Noel Guilbert Stevenson, andArthur Falsh Titherley, the con-densation of chloral hydrate and carb-amide, T., 32.Coppin, Noel Guilbert Stexenson. See alsoArthur Walsh Titherley.Coward, Hubert Frank, and FrankBrinsley, the dilution-limits of in-flammability of gaseous mixtures.Part I. The determination of dilution-limits. Part 11.The lower limits forhydroeen, methane, and carbon mon-oxide ?n air, T., 1859 ; P., 176.Coward, Hubert Frank, Charles Cooper,and Julius Jacobs, the ignition ofsome gaseous mixtures by the electricdischarge, T., 1069 ; P., 78.Cramer, William, the reduction of cupricsalts by sugars, P., 292.Crofts, James Murray. See HaroldBaily Dixon.Crommelin, C. A., the capillary constantsfor liquid carbon monoxide and liquidargon ; a correctioo, P., 248.Crossley, Arthur William, and WalterRyley Pratt, hydroaromatic ketones.Part 111. l-isoPropylcycZohexan-3-one,Crossley, Arthur Williant, and (Miss)A-ora Renouf, aromatic compoundsob!ained fro111 the hydroaromaticseries. Part 111. Bromoxylenols fromdimethyldihydroresorcin, T., 165.Crowther, Horace Leslie, BarniltonMcCombie, and Thomas Harold Reade,condensations of cyanohydrins.Part11. The condellsation of chloralcyano-hydrin with chloral hydrate andwith bromal hydrate, T., 933 ; P.,57.Cruikshanks, George Xheoas. See ThomasGray.Crymble, Cecil Reginald, the absorptionspectra of some mercury compounds,T., 658 ; P., 16.a comparative study of the absorptionspectra of some compounds of phos-phorus, arsenic, antimony and bis-muth ; preliminary note, P., 179.P., 552914 INDEX OF AUTHORS.Cullis, Hedert Edwin. See BertramLambert .Cundall, James Tudor, obituary noticeof, T., 1201.Cundall, James Tudor, and MuagoMecallurn Fairgrieve, the action ofsulphuric acid on copper, T., 60.Curtis, Raymond, and James Kenner,the condensation of' ethyl glutaconate,T., 282 ; P., 3.Curtis, Raymond. See also JamesKenner.Cutts, Hubert Cyril, the action of phos-phoric oxide on dibenzylmalonic acid,P., 39.D.Daish, Arthur John, the action of coldconcentrated hydrochloric acid onstarch and maltose, T., 2053; P.,225.the velocity of hydrolysis of- starchand maltose by cold concentratedand fuming hydrochloric acid, T.,2065; E., 226.Dakin, Wenry Drysdale, and HaroldWard Dudley, a general method forthe prefaration of glyorals and theiracetals, T., 2453 ; P., 108.Davies, Hamilton.See Wil2iam ArthurBone.Dawkins, Alfred Ernest. See EdwardHenry Rennie.Dawson, Harry Medforth, the ioiiisationof acids and their activity as catalysts,Dawson, Harry Medforth, Donald Burton,and Harry Ark, the dynamics of theaction of halogens on aliphatic alde-hydes.Keto-en01 isomcrism of thealdehydes, T., 1275 ; P., 117.Dawson, Harry Medforth, and JosephMarshall, the reaction between iodineand aliphatic aldehydes, T., 386 ; P.,24.Dawson, Harry ,Wedforth, and FrankPowis, the catalytic activity of acidsin ethyl-alcoholic solution, T., 1093 ;P., 60.Denham, William Smith, and (Miss)Hilda Woodhouse, the methylationof cellulose. Part 11. Hydrolysis ofmetliylated cellulose, T., 2357 ; P.,238.Dey, Biman Bihari, hydrazoximes ofmethyl- aiid phenyl-glyoxals, T.,1039 ; P., 79.condensation of ethyl a-chloroaceto-acetate with pheiiols, P., 38.See Herbert HenryHodgson.P., 112.Dix, AEbert CTilbert.Dixon, Harold Baily, Lawrence Brad-shaw, and Colin Campbell, the firingof gnses by adiabatic compression.Part I.Photogruphic analysis of theflame, T., 2027 ; P., 222.Dixon, Harold Baily, and James MurrayCrofts, the firing of gases by adiabaticcompression. Part 11. The ignition-points of mixtures containing electrcj-lytic gas, T., 2036 ; P., 223.Dobbie, James Johnston, and John JacobFox, the composition of somemedisval wax seals, T., 795 ; P., 67.the relation between the absorptionspectra and the constitution ofcertain isoquinoline alkaloids andof the alkaloids of ipecacuanha, T.,1639; P., 184.Dodgson, John Wallis, the reaction ofp-benzo uinone with sulphurous acidand wi& alkali. Part I., T., 2435;P., 239.Donnan, Frederick George, and ArthurJohn Allmand, ionic equilibria acrosssemi-permeable membranes, T., 1941 ;P., 180.Drew, Hurry Dugald Keith.See Alex-ander McKenzie.Dudley, Harold Ward. See HenryDrysdale Dakin.Duff, James Cooper, p-toluoylacetic acid,o-nitro-p-toluoylacetic acid, and 65'-dimethylindigotin, T., 2182 ; P., 230.Duncan, Robert Kennedy, obituary noticeof, T., 1203.Dunlop, John Gunning Moore, the actionof sulphuric acid on paraformaldehyde,T., 1155 ; P., 108.Dunn, Frederick Percy. See Oscar LisleBrady.Dunningham, Alfred Charles, the system :ethyl ether-water-potassium iodide-mercuric iodide. Part I. The un-derlying three component systems,T., 368 ; P.: 8.the system : ethyl ether-water-potas-sium iodide-mercuric iodide.Part11. Solutions saturated with respectto solid phases in the four-com-ponent system, T., 724 ; P., 58.the system : ethyl ether-water-potas-sium iodide-mercuric iodide. Part111. Solutions unsaturated with re-spect to solid phases in the four-component system, T. ,2623 ; P., 107.Dunstan, Albert Ernest, the viscosity ofsulphuric acid, P., 104.Dunstan, AZbeA Ernest, FerdinandBernard Thole, and Percy Benson, therelation between viscosity and chemicalconstitution. Part VIII. Some homol-ogous series, T., 782INDEX OF AUTHORS. 2915Berend Cohen.E.Earl, John CamPbell- See ~YrnestGoulding.Egerton, AIf?.ed Charles GlZln, a studyof the VaPour Pressure of nitr@@nperoxide, T., 647 ; P., 5 .Elliott, J. Canipbtll.See Gilbert ThomasMorgan.English, Solomon, and William ErnestStephen Turner, the ViScoSities ofley Myers, some properties of solutionsof the boric acids in alcohol ; a modi-fied boiling-point apparatus, T., 2887 ;P., 293.Fleck, A Zexander, the relation of uranoussalts to thorium, T., 247.Fletcher, James, and William JacobJones, equilibrium in the system :ethyl alcohol, acetic acid, ethyl acetatealld water, and its apparent displace-nieiit by mineral chlorides, T., 1542 ;p., 118.Forster, Martin Onslow, and Ernst Kunz,F.Fairgrieve. Jfungo AfcCaZlum. SeeJames Tudor Cundall.Fargher, Robert George, and Wilh'amHenry Perkin, jun., the actioii ofay-dibromobutane on the sodiumderivatives of ethyl acetoacetate andhenzoylacetate, T., 1353.Farmer, Walter.See Andrew JaiiziesonWalker.Fawsitt, Charles Edward. See GeorgeJoseph Burrows.Fernandes, Francis Vito. See PrafullaChandra ROy.Findlay, Alexander, and Owen RhysHowell, the influence of colloids andfine suspensions on the solubility ofgmes in water. Part IV. Solubilityof nitrous oxide a t pressures lowerthan atmospheric, T., 291 ; P., 13.Findlay, A lexander, and George King,rate of evolution of gases from super-saturated solutions. Part 11. Carbondioxide in solutions of gelatin and ofstarch, T., 1297 ; P., 114.Findlay, Alexander, IdwaZ Morgan, andIvor Prys Morris, the solubility of thenitrates of potassium, barium, andstrontium, and the stability of thedouble nitrate of potassium andbarium,T., 779 ; P., 73.Finney, (Miss) Ada.See Joseph EdwardCoates.bility of formic acid and benzene,and the system : benzene-formicacid-water, T., 350 ; P., 3.the alkaloids of quebracho bark. PartFox,' John .Jacob. See James JohnsfoitDobbie.Frankland, Edward Percy, the reactionbetween benzylamine and the dibronio-succinic acids, T., 2879 ; P., 260.Frankland, Percy Faraday, and FTedBarrow, incnthyl esters of chloroacetic,menthoxyacetic, and met hylanilino-acetic acids, T., 990 ; P. 84.Frankland, Percy Faraday, and WilliamEdward Garner, the action of thionylchloride on lactic acid and on ethyllactate, T., 1101 ; P., 84.Frankland, Percy Faraday, and AndrewTurnbull, the action of phosphoruspentachloride on the esters of glycericacid ; optically active as-dichloro-propionates, T., 456 ; P., 29.Friend, John A lbert Newton, and CharlesWilliam Marshall, the corrosion ofiron and its application to determinethe relative strengths of acids, T.,2776; Y., 263.Furness, Reginald, IZobcrt TaylorHardman, and Edgar Newbery, electro-motive forces i n alcohol.Part IV.Combinations of the hydrogen andcalomel electrodes, T., 2302 ; P.,233.Furness, Reginald, and William HenryPerkin, jun., d- and dl-epicamphor,T., 2024.Fyfe, Alexander Walker. See WalterNorman Haworth, and JamesColquhoun. Irvine.nminocamphor, T., 2770 ; p., 268.Senier.Forster, Robert Benjamin. See AlfredFoulds, Robinson Percy, and Robert1. 1'he constitution of aspidosperm-h e , l'., 2738 ; P., 258.Robinson, some derivatives of safrole,T., 1963 : P., 2212916 INDEX OF AUTHORS.G.Garner, William Edward.See PercyGarrett, Walter Reginald. See WilliamGhosh, Brojendranath, and XamuclSmiles, the interaction of nal’htha-sulphoninm-quinone and substancescontaining the thiol group, T., 1396 ;P., 148.dinaphthathioxoninm salts, T., 1739 ;P., 213.Gibbs, Izan Bichard, and Philip FViZfredRobertson, experiments on the migra-tion of para-halogen atoms in phenols,T., 1885 ; P., 221.Qibson, Charlev Stanley, sulyhonyl andcarbonyl derivatives of alanine, resolu-tion of externally conipensated p-tolu-enesulphonylalanine into its opticallyactive components ; preliminary note,P., 32.Gibson, John, obituary notice of, T., 1204.Qilmour, Robert, R contribution t o thestudy of the constitution of the methylpentoses.Part I. Synthesis of ani-methyl tetrose and an i-methyltetritol, T . , 73.Goldsworthy, Leonard James, andWilliam Henry Perkin, jzm., resolu-tion of trans-cyclopentane-l:2-di-carboxylic acid, T., 2639 ; P., 261.carboxylic acids derived from cyclo-butane, cyclopentane, cyclohexane,and cycloheptane, T., 2665 ; P., 261.Goulding, Ernest, and John CampbellEarl, the volatile oil of Cymbopogoncoloratz6s from Fiji, P., 10.Goulding, Ernest, and Oswald DigbyRoberts, volatile oil from the leaves ofHarosma venmta, T., 2613 ; P., 244.Graham, Joseph Ivon, and Thomas FieldWinmill, the estimatioii of carbonmonoxide, T., 3996 ; P., 160.Gray, Francis William, an adiabaticcalorimeter, T., 1010.Gray, Francis WilZiam, and Witliam. Milne Birse, a magnetic stndy ofcompounds of water and of aqueoussolutions, T., 2707 ; P., 211.Gray, Thomas, and Georgc ShevasCruikshanke, a method of separatingthe dihydroxgbenzenes, P., 305.Green, Heber, the viscosity of sugarsolutions, P., 158.Grey, Egerton CharZes, the volumetricestimation of carbon in alilbhatic sub-stances in the wet way, T., 2204;P., 231.Glroenewoud, Sidney Henry.See GeorgeFramis Morrell.Faraday Frankland.Ernest Stephen Turner.H.Hadfield, John Renry, and James Kenner,the preparation of 3-nitro-o-toluidine,P., 253.Hall, Norman, James Edward Hynes,and Arthur Lapworth, a-hydroxy-8-phenylcrotonolartone, P., 305.Haller, Percy. See William ErnestStephen Turner.Harden, Arthzw, and Xobert Robison,a new phosphoric ester obtained bythe aid of yeast-juice ; preliminarynote, P., 16.Harding, Yxtor John, substitution inaromatic hydroxy-compounds. Part 11.Acetyl-nitro-substitutbn, T., 2790 ;P., 299.Hardman, Ilobert Taylor. See ReginaldFurness.Harper.Erncct Mflgozuan, and .4 lexanderKillen Macbeth, the colours pro-duced on mixing the alkyl nitriteswith substances containing centresof residual affinity, P., 15.colorations produced by some organicnitro-compounds with special refer-ence to t e t m 11 it rom e th ane, P.,263.Hartley, Ernald George Justininn, a-and 8-trimethyl cobalticyanide, T,,521 ; P., 37.Hartley, Harold Brewer, and JohnAfcArthw Stuart, the miscibility ofazobenzene and azorybenzene in thesolid state and the supposed existenceof a stereoisomeride of azobenzene,T., 309 ; P., 13.Hartley, (Sir) lb’alter AToel, obituarynotice of, T., 1207.Haworth, Walter Normnn, a new methodof preparing alkylated sugars, P.,293.Haworth, Walter Norman, and A1l.x-mder Walker Fyfe, synthetic hydro-carbons allied to the terpcnes, T.,Haworth, Walter Norman, and AlbertTheodore King, the roiistitution ofcamphene.Part 11. Experiments onthe synthesis of several degradationrodncts of camphene, T., 1342 ; $., 143.Heilbron, Isidor Morris. See AlfredArchibald Boon, George Gerald Hender-son, and Forsyth James Wilson.Renderson, George Gerald, Isidor MorrisReilbron, and Matthew Howie, contri-butions to thechemistry of the terpenes.Part XVII.The action ofhypochlorousacid on camphene, T., 1367; P.,136.1659; r., 182INDEX OF AUTHORS. 2917Henderson, George Gerald, and (Miss)Maggie Millen Jefs Sutherland, con-tributions to the chemistry of theterpenes. Part XVIII. Campheiianicacid and its isomerides, T., 1710;P., 203.Heron, John, obituary notice of, T.,1216.Eewitt, John Theodore, (Miss) RlbodaMarianne Johnson, and Frank GeorgePope, the absorption spectra of nitratedphyylliydrazoues, T., 364 ; P., 4.Hewitt, John Theodora, (Miss) GladysRuby l a m , and Frank George Pope,colour and constitution of azo-corn-pounds. Part VI., T., 2193; P., 202.Hodgson, Herbert Henry, and AlbertGilbert Dix, the action of sulphur onatnines. Part 11.Aniline, T., 952 ;P., 82.Hogg, Thoma9 Percival. See JamesColquhoun Irvine.Hollely, William Francis. See RaphaelMeldola.Holmyard, Eric John, the destructivedistillation of soil ; preliminary note,P., 109.Holt, A Ifred, and Norman Murray Bell,the system : m-xylene-ethyl alcohol-water, T., 633.Eope, Edward, and IGobert Robinson,synthetical experiments in the grnupof the Goquinoline alkaloids. Part IV.The synthesis of 8-gnoscopine, T.,2085; P., 228.Howell, Owen Rhys. See AleznnderFindlay,Howie, Matthew. See George GeraldHenderson.Hulme, William, the mechanism ofdenitrification, T., 623.Hnlton, Henry Francis Everard. SeeJulian Levett Baker.Eutchison, Charles Graham, and SantuelSmiles, the interaction of nitric acidand the sulphides of &naphthol, T.,1744 ; P., 213.Hyman, Henry. See Frederick Soddy.Eyna, Alexander.See James ColquhounIrvine.Hynes, J a m s Edward. See NormanHall.I.Innes, (Miss) Helen Reid. See JosephKnox.Irvine, James Colquhozln, and AlemnderWalker Fyfe, the reactions of a-amino-8-hydroxy-compounds as cyclic struc-tures,.T., 1642; P., 179.Irvine, James Colquhoun, and ThomasPercival Hogg, partially methylatedglucoses. Part 111. Monomethylglucose, T., 1386 ; P., 145.Irvine, James Colquhoun, a113 AlexanderHynd, the conversion of d-glucosamiiieinto d-mnnnose, T., 698 ; P., 60.Irvine, James Colquhoun, and (Miss)Bina Mary Paterson, the influenceof configuration on the cond nsa-tion reactions of polyhydroxy-corn-pounds. Part I.The constitutionof mannitoltriacetone, T., 898 ;P., 68.the formation of ethers from mannitol,an example of steric hindrance,T., 915; P., 69.J.Jacobs, Julius. See Hubert’ lil’ankCoward.James, Thomas Campbell, arid Cli’ordWillinm Judd, the ad(litinn of 111 ga-tive radicles to Schifs bases. T., 1427.Jaques, Arthur. See Thonms XlaterPrice.Johnson, (Jfiss) Ehoda Mariame. SeeJohn I’hf*odore Hewitt.Jones, Bernard Mount, the dissociationof gaseous nitrogen trioxide, T., 2310 ;P., 230.Jones, David Trevor, and Richard Ver-non Wheeler, the composition of coal,T., 140, 2562; P., 243.Jones, (Miss) Marian, and ArthurLapworth, a-bromonaphthalene : itsphysicd properties and its applica-tion to the determination of waterin moist alcohol, T., 1804 ; P., 202.kinetics of the decomposition of acylderivatives of phenols by means ofalcohol in presence of acids aridalkalis ; preliiniirary note, P., 141.Jones, Wzlliam Jacob.the mechanismof cyanidion catalyses, T., 1547 ;P., 118.the interaction between hydrogencyanide and aldehydes and ketonesin dilutesolution, T., 1560 ; P., 118.Jones, William Jacob, and James RiddickPartington, ideal refractivities of gases,P., 201.Jones, William Jacob. See also JamesFletcher.Joseph, Alfred Francis, solutions ofbromine in water, nitrobenzene, andcarbon tetrachloride, P., 244.note on a gas-pressure regulator, P.,254.Judd, Cliford William. See ThomasCanybeEl Jamee2918 INDEX OF AUTHORS.K.Kay, Francis Willinni, and AlZanMorton, experiments on the syiithrsisof the beitzltterlienes.Part I. I)e-rivntives of beirzonor-p-meuthane, T.,1565 ; P., 162.Kenner, James, the reduction productsof e thy1 h ydrindenr -2 :2-dicarboxylate,T., 2685 ; P., 244.Kenner, ,James [with Raymond Curtis],the infliiciice of nitro-groups on thereactivity of substituerits in the benzenenucleus, T., 2717 ; P., 174.Kenner, James, and (Miss) Annie MooreMathews, 2-hytlrindamine, T., 745 ;diphenyl-2:3:2’:3’- and -3:4:3‘:4’-tetra-carboxylic acids, T., 2471 ; P.,242.Kenner, Jnmes. See also RaymondCurtis, and John Henry Hadfield.Kenyon, Joseph, iilvrstigtions on thedependence of rotatory power onchemical constitution.Part VII.Soriie esters of the carbinols of theformula C,H;CH(OH).R, T., 2226 ;P., 231.Kenyon, Joseph, and Robert WouxonPickard, investigations on the de-pendence of rotatory power onchemical constitution. Part VIII.The optical rotatory powers of thenormal esters of benzylmethylcarb-inol, T., 2262 ; P., 232.investigations on the dependence ofrotatory power on chemical constitu-tion. Part IX. The rotatory powersof l-naphthyl-n-hexylcarbinol andits esters, T., 2644 ; P., 243.inveatigations on the dependence ofrotatory power on chemical consti-tution. Part X. The optical dis-persive power of tetrahydro-2-naphthol and its esters, T., 2677;P., 262.investigations on the dependence ofrotxtoiy power on chemical consti-tution.Part XI. The co-ordina-tion of the rotatory powers (a) ofmenthyl compounds, (b) of thementhones, and (c) of the borneols,P., 273.investigations on the dependence ofrotatory power on chemical consti-tution. Part XII. The rotatorypowers of some esters of benzoic andof 1- and 2-naphthoic acids withoptically active secondary alcohols,P., 307.Kenyon, Joseph. See also Thomas Martin1’. , 4.Lowry, and Robert Howson Pickard.King, A lbert Theodore. See ll’alterKing, George. See Alexander Findlay.King, Harold, the possibility of a newinstance of nptical activity without anasymmetric carbon atom, P., 249.King, Harold, and Frank Lee Pyman,the constitution of the glyccrylphos-phates, T., 1238 ; P., 103.Kipping, Fmderic Stanley, and RobertRobison, organic derivatives of silicon.Part XXI.The condensation productsof diphrnylsilicanediol, ‘I?., 484.Kipping, Frederic Stanley. See alsoJohn Arthur Meads, and RobertRobison.Knapp, Arthur William. See JohnFrancis Liverseege.Knight, Willinm Arthur, the ageing ofalloys of silver and tin, T., 639;Knox, Joseph, and (Miss) Helen ReidInnes, compounds of pheuanthra-quinone with metallic salts, T., 1451 ;P., 159.Xunz, Brnst. See Martin Onslow Forster.Norman Haworth.P., 28.L.Lambert, Bertram, and Herbert EdwinCullis, the wet oxidation of metals.Part 111. The corrosion of lead,P., 198.Lamble, AIfred, and William Cz~dmoreMcCuZlagh Lewis, studies in catalysis.Part I. Hydrolysis of inethyl acetate,with a theory of homogeneous catalysis,T., 2330 ; P., 222.Lapworth, Arthur.See Norman Hall,and (Miss) Marian Jonea.Lattey, Robert Tabor, the azeotropicmixtures of ethyl acetate and water,P., 33.Le Bas, Gervaise, a formula by means ofwhich the molecular volume a t theboiling point may be calculated,P., 86.a study of the constitution of nitrogenand phosphorus oxides and some oftheir derivatives by means of mole-cular volumes, P., 87.Lefebure, Victor, absorption of gases bycelluloid, T., 328.Le Sueur, Henry Rondel, and JohnCharles Withers, the niechnnism ofthe action of fused alkalis. Part I.The action of fused potassium hydr-oxide on dihydroxystearic acid ariddihydroxybehenic acid, T., 2800 ;P., 257INDEX OF AUTHORS.2919Letts, Edmund AZbert, and (Miss)Florence Williamson Bea, an extremelydelicate colorimetric method for detect-ing and estimating nitrates and nitrites,T., 1157 ; P., 72.Levy, S'tanley Isaac, the action of amino-acid esters on ethvl dicarboxvplutacon- d n ate, T., 27.Le wi e, Wi Eliuam Cudmore MCCCC llacrh .See &frcd Lamble.Lewkowitsch, Julius, obituary noticeof, T., 1217.Little, Harry Frank Victor. See %enryVincent Aird Briacoe.Liverseege, John Francis, and ArthurWilliam Knapp, the erosion of lead,Lowry, Thomas Martin, the rotatorydispersive power of organic com-pounds. Part IV. Magnetic rota-tion and dispersion in some slimpleorganic liquids, T. , 81.tautomerism,desmotropy, and dynamicisomerism, P., 105.Lowry, Thomas Martin, Robert BowsonPickard, and Joseph Kenyon, therotatory dispersive power of organiccompounds. Part V.A comparisonof the optical and magnetic rotatorydispersions in some optically activeliquids, T., 94.Lowry, Thomas Martin, and VictorSteele, a new chlorocamphor; pre-liminary note, p., 201.P., 25.1.McBain, James WiZliam, and FrederickChades Coleman, a criticism of thehypothesis that neutral salts increasethe dissociation of weak acids andbases, T., 1517 ; P., 135.McB-ain, James William, and RerbertErnest Martin, studies o f the constitu-tion of soap solutions : the alkalinityand degree of hydrolysis of soap solu-tions, T., 957 ; P., 68.Xacbeth, Alexander Eillen. See EwicsCMagowan Harper.IldcCombie, Hamilton, and John WilfridParkes, the interaction of benzoin andthe chlorides of dibasic acids, T., 1687 ;P., 185.McCombie, Hamilton, aad HaroldArchibald Scarborough, the velocityof saponification of the acyl deriva-tives of the substituted phenols.Part I.Phenyl benzoate, T., 1304 ;P., 107.the rate of saponification of derivativesof ethyl benzoate, P., 294.McCombie, Hamilton. See also BoraeeLeslie Crowther.McKenzie, Alexander, Harry DugaldKeith Drew, and Gerald HargravcMartin, conversion of l-yhenylchloro-acetic acid into d-diphenylsuccinicacid, P., 304.McKenzie, Alexander, Geofrey Martin,and Harold Gordon Rule, action ofGrignard reagents on acid amides,T., 1583 ; P., 182.McKenzie, Kenneth John. See AIfredArchibald Boon,MacLean, ( M r s .) Ida Snaedley, and(Miss) Sibyl Taite Widdows, the actionof magnesium pheiiyl bromide onderivatives of phrnyl styryl ketone,T., 2169 ; P., 222.Mann, (Miss) Gladys Ruby. See JohnTheodore Xewitt.Marle, Ernest Robert. See David Runci-man Boyd.Marsh, James Ernest, a class o f saltswhich contain two solvents of crystal-lisation, T., 2368 ; P., 83.Marshall, Charles William. See JohnAZbert Newton Friend.Marshall, Hugh, obituary notice of, T.,1219.Marshall, Joseph, the action of alde-hydes on the Grignard reagent, T.,527 ; P., 13.Marehall, Joseph. See also Harry Med-forth Dawaon.Martin, Geofrey, researches on siliconcompounds. Part VI. Preparationof silicon tetrachloride, disiliconhexachloride, and the higher chlor-ides of silicon by the action ofchlorine on 50 per cent.ferrosilicon,together with a discussion on theirmode of formation, T., 2836; P.,251.researches on silicon compounds. PartVII. The actioii of ethyl alcohol ondisilicon hexachloride, T., 2860 ;P., 272.Martin, Oeofrey. See also AlexanderMcKenzie.Martin, Gerald Hargrave. See Alex-ander McKenrie.Martin, Herbert Ernest. See Hugh MillsBunbury, and James William I c -Bain.Mason, Frederick Ayred, and WilliamHenry Perkin, jun., oxidation ofpapaveraldine methosulphate, T.,20x3.Mathews, (Miss) Annie Moore. SeeJames Kenner.Matthey, Gsorge, obituary notice of, T.,12222920 INDEX OF AUTHORS.Xeads, John Arthur, and FredeericStanley Kipping, organic derivativesof silicon.Part XXII. The so-calledsiliconic acids, T., 679 ; P., 6.Xeldola, Raphael, and William FTancisHollely, acylation as influenced bysteric hindrance : the action of acidanhydrides on 3:5-dinitro-p-aniino-phenol, T., 410 ; P., 25.syntheses with phenol derivatives con-taining a mobile i>itro-group. PartVI. Substituted alkyl- and aryl-phenylaminw : coloar in relation totautomerism, T., 977 ; P., 85.quinone- ammonium derivati vcs. Part111. Dihaloid, nionoazo-, hisazo-,nitrotriazo-, and bistriazo-com-pounds : attempts to prcpare deriv-atives containing an asymmetricquinquevalent nitrogen atom, T.,1469 ; P.: 159.quinone-ammonium derivatives. Part1V. Products of the extreme alkyla-tion of alkylatetl isopicramic acid,T., 2073 ; P., 229.Merriman, Richard William, the azeo-tropic mixtures of ethyl acetate andwater, P., 73.Xerry, Ernest Wyndham, and JVilliamErnest Stephen Turner, the viscositiesof some binary liquid mixtures con-taining formamide, T., 748 ; P., 60.Merton, Thomas Ralgh, the absorptionof light by uranous chloride in dif-ferent solvents, T., 23.the production of high vacua bymeans of finely divided copper, T.,645 ; P., 55.Xicklethwait, (Miss) Frances Mamj Gore.See John CanmZl Cain.Mills, William RobSon, and (Miss) AliceMary Bain, the configuration of thedoubly linked nitrogen atom.Optic-ally active salts of the semicarbazoneand benzoylphenylhydrazone of cyclo-hexanone-4-carboxylic acid, T., 64.Mills, FVilZiam Hobson, Xoyace VictorParker, and Robert William Prowse,the resolution of 5-nitrohydtindene-2-carhoxylic acid, T., 1537 ; P., 161.Moore, Tom Sidney, asymmetric ter-valent nitrogen ; preliminary note, P.,182.Horgan, Gilbert Thomas, and John Har-bourne Cooke, benzmesulphonyl de-rivatives of o-aminonzo-compounds ;preliminary note, P., 249.Morgan, Qilbert Thomas, and J.Camp-bell Elliott, mercuration of aromaticamines, P., 186.p-chlorophenylselenious acid ; pre-liminary note, p., 248.Xorgan, Gilbert Thomas, and EenryWebster Moss, researches on residualaBnity and co-ordination. Part I.Metallic acetylacetones and their ab-sorption spectra, T., 189.Morgan, Gilbert Thomas, and JosephReilly, noii -aromatic diazoniumsalts. Part 111.3:5-Dimethylpyr-azole-4-diazonium salts sud theirazo-derivatives, T., 435.diazotisation of aminomesitylenes ;preliminary note, P., 74.Morgan, Gilbert Thow~as, and GodfreyEdward Scharff, con4tution of theo-diazoimines. Part IV. Isomeric ben-zenesulphon~1-3:4-tolyleneditizo-imides, T , 117.Morgan, Idwal. See Alexander Findlay.Morrell, George Francis, studies in thesiiccinic acid series. Part I. Thechlorides of succinic and niethyl-succinic acids, and thrir constitution,T., 1733 ; P., 175.Morrell, George Francis, and PeterBurgen, the polymerisation of cyan-atnide, T., 576.Morrell, George Francis [with SidneyHenry Groenewoud], studies in thesuccinic acid series. Part 11. Anilidesand anilic acids, and the effect ofsteric hindrance on the formation ofthe amides, T , 2098 ; P., 257.Morris, Ivov Prys. See AlexanderFindlay.Morton, AZZnn.See Francis WilliumKay.Moss, Henry Webster. See Gilbert ThomasMorgan.Mumford, Ernest Moore, the mechanismof nitrification ; preliminary note, P.,36.Myers, James Eckersley. See JamesBrierley Firth.N.Neogi, PanchEnon, direct combinationof nitrousacid with primary, secondary,and tertiary amines, T., I270 ; P., 35.Neogi, Panch6non [with Birendra Bhu-san Adhicary, and Tarini CharanChowdhuri], interaction of alkali alkylsulphates and alkali nitrites : theoriesof the formation of aliphatic nitro-componnds, T., 2371 ; P., 220.Newbery, Edgar, unstable compoundsof cholesterol with bnrium meth-oxide, ‘l’., 380 ; P., 5.overvoltage, T., 2419 ; P., 235.electromotive forces in alcohol.PartV. The dropping electrode in alco-holic solutions, T., 2563 ; P., 241INDEX OFNewbery, Edgar. See also ReginaldNuttall, Walter Harold. See WilliamFurness.Francis Cooper.0.Oesch, Josef, and Arthur George Perkin,the colouring matters of 22hammscatharticus, T., 2350 ; P., 236.alizarin a-methyl ether, P., 213.P.Parker, Albert, the lower limits of in-Atinmation of methane with mixtui esof' oxygen and nitrogen, T., 1002 ; P.,75.Parker, Albrrt, and AEan Victor ahead,the velocities of flame in mixtures ofmethane, T., 2150 ; P., 220.Parker, Horace Victor. See WillianzHobson Mills.Parker, Leslie Ilenry, reactions by tri-turation, T., 1504 ; p., 137.Parkes, John Wilfrid.See HamiltonMcCombie.Parry, William, synthesis of pinacones.Part II., P., 298.Partington, James Riddick, heats o fevaporation ; association in liquidsand mixtures of liquids, P., 61.note on the dilution law, P., 251.Partington, James Riddick. See alsoWilliam Jacob Jones.Paterson, (Miss) Bina Mary. See JamesColquhouit Irvine.Patterson, Thomas Stewart, and ErnestFerpson Pollock, the influence ofsolvents on the rotation of opticallyactive compounds. Part XX. Isomericsolvents, T., 2322 ; P., 23-1.Peacock, David Henry, rotatory powerand refractivity. Part I. Therotatory powers, refractivities andmolecular solution-volumes of cin-chonicine and borneol in certainsolvents, T., 2782 ; P., 264.the preparation of plienyl benzyl ether,P., 247.the rotatory powers, refractivities, andmolecular solution-volumes of cin-chonicine and some derivatives ;preliminary note, P., 274.Pearce, Charles Frederick Byrde.SeeFrederick Danir l Chattaway.Peddle, Cyril James, deliquescence.Part I. Tho deliquescence of salts ofammonium b a w , T., 1025 ; P., 81.Perkin, Arthur George, thujin, T., 1408 ;P., 150.note on quercitrin, P., 201.LUTHORS. 2921Perkin, Arthur George, carajura and chicared ; pteliniinary note, Y., 212.Perkin, Arthur George, and Isaac Shul-man, colouriiig matters contained asglucoside in the flowers of some Indianplants, P., 200.See also Josef Perkin, Arthur George.Oesch.tial address. T.. 1176 : P.. 101.Perkin, William Henry, jun., presiden-I , Perkin, WiZkam' Henry, jzcn., WalterMorreZZ Roberts, and Robert Robinson,1 :2-diketo-5:6-diniethoxyhydrindene,T., 2405 ; P., 235.Perkin, William Henry, jun., andRobert Robinson [with David Cardwell,Tsnn Quo Chon, and Walter MorreZZRoberts], some derivatives of 0-vanillin, T., 2376 ; P., 234.Perkin, William Henry, jun.See alsoRobert George Fargher, Reginald Fur-ness, Leonard James Goldsworthy, andFrederick Alfred Mason,Perkins, William Hughes, the porosityof iron, T., 102.Pickard, Robert Howson, and JosephKenyon, investigations on the de-pendence of rotatory power onchemical constitution. Part V.The simpler esters of the carbiiiolsCH;CH(OH).R, T., 830.investigations on the dependence ofrotatory power on chemical consti-tution. Part VI.The optical ro-tatory power of methyl-tert.-butyl-,benzylmethyl-, phenylethylmethyl-and a-naphthylmethyl-carbinols,T., 1115 ; P., 83.Pickard, Robert Homon. See alsoJoseph Xenyon, and Thomas MartinPickering, Spencer Percival U.mfrevilb,the colour intensity of iron and coppercompounds, T., 464.Pollard, Cornelius Theodore. See Wil-liam Ernest Stephen Turner.Pollock, Ernest Ferguson. See ThomasStewart Patterson.Pope, Frank George, fluorene derivatives.Part 11. Resorcinol-benzein, T., 251.Pope, Frank George. See also JohnTheodore Hewitt.Pope, William Jackson, and John Read,the identity of the supposed 8-2:5-dimethylpiperazine, T., 219.the variable rotatory powers of thed-a-bromocamphor-B-sulphonates,T., 800 ; P., 74.the optical activity of compounds ofsimple molecular constitution ; am-monium d- and 1-chloroiodomethane-sulphonates, T., 811 ; P., 75.Lowry2922 INDEX OF AUTHORS.Powell, Chmles Wi2frid Iloberts, thePower, Frederick Beldiqzg, and HenryBrowning, jun., the constituents ofthe flowers of Anthemis nobilis, T.,1829 ; P., 210.the constituents of the flowers of Matri-caria chamomilln, T., 2280 ; Y., 237.Power, Frederick Belding, aud ArthurHenry Salway, chemical examina-tion of sarsaparilla root, T., '201.the constituents of the leaves andstems of Davicsia Iatifolia, T., 767 ;P., 66.dibenzoylqlucoxylo~e : a natural benz-oyl derivative of a new disaccharide,T., 1062 ; P., 109.Powis, Frank.See Harry MedforthDawson.Pratt, Walter Eyley. See Arthur WiZ-lium Crossley.Prescott, James Arthur, the reaction-between dilute acid solvents and soilphosphates, P., 137.Price, Thomas Xlater, and ArthurJaqnes, the reaction between sodiumbenzylthiosulphate and iodine, T.,1140 ; P., 117.Price, Tudor Williams, osmotic pressureof alcoholic solutions, P., 269.Pring, John Norman, and Urlyn CliftonTainton, the electro-deposition of zinca t high current densities,l'.,710; P.,27.Procter, Renry Richardson, the equili-brium of dilute hydrochloric acid andgelatin, T., 313.Prowse, Robert William. See WilliamHobson Mills,Purvis, Johftt Edward, the absorptionspectra of the vaponrs and solutionsof various substances containing twobenzene nuclei, T., 590 ; P., 23.the absorption spectra of various sub-stances containing two, three, andfour benzenenuclei, T., 1372; 1'.,141.the absorption spectra of the vapoursand solutions of various derivativesof benzaldehyde, T., 2482 ; P., 240.Pyman, Frank Lee, the alkaloids ofDaphnandra micruntha, T., 1679 ;P., 184.aromatic selenium compounds ; pre-liminary note, p., 302.See also FrancisHoward Carr, and Harold King.viscosity of sugar solutions, T., 1.Pyman, Frank Lee.R.Ray, Praftdla Chandra, additive andsubstitutive compounds of mercuricnitiite with organic thioderivatives.Part I., P., 140.Ray, Prafulla Chandra, action of nitrousacid on dimethylpiperazine, P.,143.the actioii of mercuric, cupric andplatinic chlorides on 01 ganic sulphurcompounds, P., 304.RQy, PrafiiIZa Chandra, and FrancisYito Fernandes, action of monochloro-acetic acid on thiocarbamide andmononlkylated thiocarbamides, T.,2159 ; P., 181.Ray, Rmnes Chandra, maanesium borideand aniorphons boron, OT., 2162 ; P.,242.Rea, (Miss) Florcizce 7Vil'illiamson.SeeEdmund Albert Letts.Read, John. See William Jackson Pope.Reade, Thomas Harold. See HoraceLeslie Crowther.Reeve, William, and Samuel Smiles,thio-derivatives of ~-iiaphthylamine,P., 147.Reilly: Joscph. See Gilbert ThomasMorgan.Rennie, Edward Henry, and AvredXrnest Dawkins, the interaction be-tween nitric acid and briicine in thepresence of metallic nitrates, T.,1487; P., 71.Renouf, (Miss) Xora. See Arthur Wil-liam Crossley.Report of the Council, T., 1163 ; P., 90.Report of the International CommitteeonAtomic Weights, T., 2257 ; P., 216.Rhead, A Inn Victor.See A lbert Parker.Roberts, Charles Edward, the alloys ofaluminium and silicon, T., 1383 ; P.,143.Roberts, Oswald Digby. See ErnestGoulding.Roberts, Wulter 2llorrell. See WilliamHenry Perkin, jun.Robertson, Philip Wilfred. See IvanRichard Gibbs.Robinson, (Mrs.) Gertrude Ilfaud, areaction of homopiperonyl and ofhomoverstryl alcohol ; preliminarynote ; P., 252.Robinson, (Mrs. ) Gertrude Maud, andBobert Robinson, researches on pseudo-bases. Part 1. Some condensationreactions of cotarnine, hydrastiuine,and isoquinoline methyl hydroxide,T., 1456 ; P., 161.Robinson, Bobeyt.See David Bain,Robinson Percy Fonlds, Edward Hope,William Henry Perkin, jun., and(Illrs. ) Gcrtrude Maud Robinson.Robison, Xobert, and Prederic StanleyKipping, organic derivatives of silicon.Part XX. Some condensation 1wo-ducts of dibenzylsilicanediol, T., 40INDEX OFBobison, Robert. See also ArthurHarden, and Frederic Stanley Upping.Ross, John David McBeath, the rate oftransformation of ammonium cyanatein absolute alcohol, T., 690 ; P., 5.Rule, Alexander, and John SmeathThomas, the polysulphides of alkalimetals. Part I. The polysulphidesof sodium, T., 177.the polysulphides of the alkali metals.Part 11. The polysulphides ofpotassium, T., 2819 ; P., 270.Rule, Harold Gordon. See AlexanderS.Salway, Arthur Henry.See FrederickBelding Power.Sand, Henry Julius Satomon. SeeRobert Martin Caven.Sanders, James McCmznell, the fractionaldistillation of petroleum, T., 1697 ;P., 185.Scarborough, Harold Archibald, pre-paration of ethyl nialonate andethyl cyauoacetate, P., 306.Scarborough, Harold Archibald. Seealso Hamilton McCombie.Scharff, Godfrey Edward. See GilbertThomas Xorgan.Schlaepfer, Hax. See Martin OmlowForster.SegaIler, David, the relative activitiesof certain organic iodo-compoundswith sodium phenoxide in alcoholicsolution. Part 111. The tempera-ture-coefficients, T., 106.the relative activities of certain organiciodo-compounds with sodium yhen-oxide. Part IV. The influence ofthe solvent, T., 112.Sen, Kumud Behari. See Edwin RoySen-Gupta, Henzendra Kumar, condensa-tion of ketones with phenols.Part I . Condensation with a-naphthol, T., 399.the forniation of heterocyclic com-pounds from hydroxymethyleneketones and cyanoacetamide ; pre-liminary note, p., 148.Senier, Avred, aiid (Miss) RosalindClarke, studies in phototropy andtherinotropy.Part IV. o-Nitro-benzylidenearylaniines and their photo-isomeric change, T., 1917 ; P., 203.Senier, Awred, and Xobert BenjaminForster, studies in phototropy andthermotropy. Part V. Polymorphic4-hydroxybenzylideneamines producedby trituration and by the influence ofsunlight, T., 2462 ; P., 227.McXenzie.Watson.AUTHORS. 2923Shroder, John Hanston, and SolomonParleg Acree, catalysiu. Part XVIII.The reactions of both the ions andthe molecules of acids, bases andsalts: the reactions of alkyl haloidswith phenoxides and ethoxides, T.,2582 ; P., 228.Shulman, Isaac.See Arthur GeorgePerkin.Simonsen, John Lionel. See John CannellCain.Singh, Bazoa Kartar, studies in substi-tuted quaternary azonium compoundscontaining an asymmetric nitrogenatom. Part 11. Resolution of phenyl-benzylmethylazoniuni iodide into opti-cally active components, T., 1972 ; P.,136.Slade, Xoland Edgar, studies of ammo-nium solutions: a correction, T.,1351 ; P., 150.Smiles, Samuel. See BrojendranathGhosh, Charles Graham Hutchison, andWil liam Reeve.Smith, Clarence, existence of racemiccompounds in the liquid state. PartII., T., 1703 ; P., 22.Smith, Clarence.See also John CanwllCain.Smithells, Colin James. See JuliusBerend Cohen.Smyth, (Miss) Wilhelminu Rebecca, theuse of sulphuryl chloride in the alkyl-ation of phenols, P., 14.Smythe, John Armstrong, the oxidationof some benzyl compounds of sulphur.Part 11. Benzyl tctrasulphoxide, T.,546 ; P., 24.Snape, Benry Lloyd, the reactions ofisoamarine, P., 6.the rotatory powers of d-and 1-Go-aniarine and of their respective tar-trates, P., 151.Soddy, Frederick, and Henry Hyman,the atomic weight of lead from Ceylonthorite, T., 1402 ; P., 134.Spencer, Leo, photokinetics of sodiumhypochlorite solutions. Part II., T.,2565 ; P., 240.Starling, Walter William. See GeorgeBarger.Steele, Victor. See Thmnas MartinLowry.Stephen, Henry, and Charles Weizmann,derivatives of 3:4-dimethoxyaceto-phen one and 4: 5-dimethoxy-o- tolylmethyl ketone, and the synthesis ofphenylglyoxalines con taiiiing suh-stituents in the benzene ring, T.,1046; P., 71.synthesis of dl-tvrosine and dl-3:4-" dihydroxyphenilalanine, T., 11 52 ;P., 1142924 INDEX OFStuart, John McArthur.See HaroldBrewer Hartley.Itubbs, Leonard. See Arthur WalshTitherley.Sntherland, (Miss) Maggie Millen Jefs.See George Gerakd Henderson, andForsyth James Wilson.T.Tainton, Urlyn Clifton. See John. NormanPring.Taylor, Hugh Stott. See Benry Bassett,3 un.Thole, Ferdinand Bernard, the effect ofring-formation on viscosity, T., 2004 ;P., 181.Thole, Ferdinand Bernard. See alsoAlbert Ernest Dunstan.Thomas, John Srneath.See AlexanderBule.Thompson, Fmnk C7~arles, the metallo-graphy of German silver, T., 2342;P., 233.Tinkler, Charles Kenneth, the relativestrengths of ammonium and the sub-stituted animonium hydroxides, asmeasured by their action on a pseudo-base. Part I., T., 995 ; P., 70.Titherley, Arthur Walsh, and NoelGuilbert Stevenson Coppin, allanturicacid, P., 115.Titherley, Arthur Walsh, and LeonardStubbs, the hydrolysis of mixedsecondary amides by alkalis, T., 299 ;P., 12.Titherley, Arthur Walsh. See also NoelGuilbert Stevenson Coppin.Trotter, John. See Alfred ArchibaldBoon.Tschngaev, Leo Alexandrovitsch, thechemical constitution of dioximines,T., 2187; P., 224.Turnbull, Andrew. See Percy FaradayFrankland.Turner, Eustace Ebenezer, an attempt toprepare organometallic derivatives oftungsten, P., 4.Turner, Eustace Ebenezer.See alsoGeorge Macdonald Bennett.Turner, William Ernest Xtephen, a criti-cism of Holmes’ method of determin-ing the molecular complexity ofliquids, P., 29.consistent molecular formulie, Y., 110.Turner, William Ernest Stephen, andCrellyn CoZgrave Bissett, the con-nexioii between the dielectric con-stant and the solvent power of aliquid, T., 947 ; P., 59.AUTHORS.Turner, ?Villiam Ernest Stephen, andCrellyn Colgrave Bissett, the mole-cular weights of some salts of thealkali metals and an account of thecompounds of these salts with thealeoliois, T., 1777 ; P., 110.Turner, TVilliam Ernest Stephen, andSolonzon English, the nature of mole-cular association ; its relation tochemical combination, T., 1786 ; P.,132.Turner, TVilliam Ernest Stephen, andCornelius Theodore Pollard, [withJohn Douglas Cauwood, Walter Regi-nald Garrett, and Percy Haller], theinfluence of solvents on molecular.weights.Part I. Salts, T., 1751 ;P., 79.Turner, William Ernest Stephen. Seealso Solomon English, and ErnestWyndham Merry.Tutin, Frunk, isodibenzoylglucoxylose,P., 302.Tutin, Frank, and Hubert WilliamBentley Clewer, the constituents ofSolanurn angzutifdium : isolationof a new gluco-alkaloid, solan-gustine, T., 559; P., 7.the constitnents of Clematis vitalba,T., 1845 ; P., 210.Twiss, Douglas Frank, the action ofhydrogen peroxide on the sodiumalkyl thiosulphatcs, T., 36.the action of nitro-substituted arylhaloids on alkali thiosulphates andselenosulphates, T., 1672 ; P., 187.Tyrer, DanieZ, adiabatic aud isothermalcompressibilities of liquids betweenone and two atmospheres’ pressure,T., 2534 ; P., 236.V.Vanstone, Ernest, the reactivity of anti-mony haloids with certain aromaticcompounds. Part I., T., 1491 ; P.,140.sodium amalgams : specific volumesand electrical conductivities, T.,2617 ; P., 241.W.Walker, Andrew Jamieson, and WalterFarmer, influence of the dilution ofhydrogen peroxide on the velocity ofprecipitation of maiigaiiese from am-moniacal solutions in presence of zinc,P., 139INDEX OFWalker, (Miss) Nellie.See John Ker-Walpole, George Stanley, hydrogenpotentials of mixtures of acetic acidand sodium acetate, T., 2501 ; P.,237.the effect of dilution on the hydrogenpotentials of acetic acid and“ standard acetate ” solutions, T.,2521 ; P., 238.Watson, Edwin Roy, 6’-aminoquercetin,T., 338.a relation between chemical constitu-tion and depth of colour of dyes,T., 759.Watson, Edwin Roy, and Kumud BehuriSen, dyes derived from quercetin, T.,389.Wataon, ?Valter Henry.See HerbertBrereton Baker.Weiamann, Charles. See Harry Brad-bury, and Henry Stephen.Werner, Emil Alphme, the constitutionof carbamides. Part I. The pre-paration of isocarbamides by theaction of methyl sulphate on carb-amides, T., 923 ; P., 26.the isomeric transformation of am-monium methyl sulphate and ofsubstituted ammonium methyl sul-phates ; the interaction of atninesand methyl snlphate, T., 2762;P., 260.a simple demonstration of the forma-tion of biuret from the interactionof carbamide and cyanic acid, P.,262.Wheeler, Richard Vernon, the propaga-tion of flame in mixtures of methaneand air ; the “ uniform movement,”T., 2606 ; P., 246.Wheeler, Richard Vernon. See alsoMaurice John Burgess, and DavidTrevor Jones.White, Gerald Noel, the preparation ofdithiobenzoic acid, P., 37.Widdows, (Miss) Sibyl Taite. See(Mrs.) Ida Smedley MacLean.foot Wood.AUTHORS. 2925Wilson, Forsylh Jam.es, Isidor MorrisXeilbron, and (Miw) Maggie MillenJefs Sutherland, contributions to ourknowledge of semicarbazones. PartIV. Action of hydrogen chloride, T.,2892 ; P., 295.Wilson, E’orsyth James. See also AlfrodArchibald Boon.Winmill, Thomas Field. See JosephIvon Graham.Withers, John Charles. See HenryRondd Le Suenr.Wood, John Kerfoot, the influence ofacids and alkalis on the optical activityof some amino-acids, T., 1988 ; P.,220.Wood, John Kerfoot, and (Miss) NellieWalker, the oxidation of carbohpdr-ates and related substances by meansof potassium persulphate, T., 1131 ;P., 115.Woodhouse, (Miss) Hilda. See WilliamSmith Denham.Worley, Ra@h Palliser, the surfacetension of mixtures. Part I.Mixtures of partly miscible liquidsand the influence of solubility, T.,260.Part11. Mixtures of perfectly miscibleliquids niid the relation betweentheir surface tensions and vapourpressures, T., 273.Wright, Robert, the relation betweenthe absorption spectra of acids andtheir salts. Part II., T., 669 ; P., 39.the absorption spectra of sulphurousacid and sulphites, T., 2907 ; P.,264.Wgnne, William Palmer, 2~3-dibromo-naphthalene j preliminary note, P.,204.the surface tension of mixtures.Y.Young, Charles Robert, optically activederivatives of cl-dimethoxy- and d-diethoxy-succinic acids, T., 1228 ; F.,114

ISSN:0368-1645    

DOI:10.1039/CT9140502911

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

INDEX OF SUBJECTS.TRANSACTIONS A N D PROCEEDINGS. 1914.(Marked T. and P. respectively.)Single organic compounds of known empirical formula mill be found in theFormula Index, p. 2937.A.Acetylacetones, C,H&&.Acids, relation between ahsorptionspectra of, and their salts (WRIGHT),T., 669 ; P., 39.catalytic activity of (DAWSON andPowrs), T., 1093 ; P., 60.ionisation and catalytic activity of( DAWSON), P. , 112.aliphatic, electrical conductivity of thepotassium salts of ( BUNBURY andMARTIN), T., 417 ; P., 8.rotation of esters of optically activecarbinols and (PICKARD and KEN:YON), T., 830.dibasic, action of benzoin with thechlorides of (MCCOMBIE andPARKES), T., 1687 ; P., 185.weak, iiiflnence of neutral salts on thedissociation of (MCBAIN and COLE-MAN), T., 1517; P., 135.Acylation, influence of steric hindranceon (MELDOLA and HOLLELY), T., 410 ;Address, presidential (PERKIN), T.,1176 ; P., 101.AfBnity, residual, and co-ordination(MORGAN and Moss), T., 189.Alcoholometry (BARENDRECHT), P.,160.Alcohols, viscosities of mixtures of form-amide with ( ENGLISH and TURNER),T., 1656 ; P., 187.Aldehydes,action of, on Grignard reagents(MARSHALL), T., 527 ; P., 13.action of hydrocyanic acid on (JONES),T., 1560 ; P., 118.aliphatic, dynamics of the action ofhalogens on (DAWSON, *B~RTON,and ARK), T., 1275; P., 117.action of iodine on (DAWSONand MARSHALL), T., 386 ; P.,24.Alkali alkyl sulphates, interaction ofalkali nitrites arid (NEQGI), 7‘. ,2371 ; Y., 220.P., 25.cv,Alkali hydrogen carbonates, dissocia-tion pressures of (CAVEN and SAND),T., 2752 ; P., 268.metals, molecular weights of salts of,and their compounds with alcohols(TURNER and BISSETT), T., 1777 ;P..110.polysnlphides of (RULE andTHOMAS), T., 177,2819 ; P. 270.nitiites, interaction of, and alkali alkylsulphates (NEOGI), T., 2371 ; P.,220.selenosnlphates and thiosulphates,action of nitro-substituted arylhaloids on (TWISS), T., 1672 ; P.,187.Alkalis, fused, mechanism of thc actionof (LE SUEUR and WITHERS), T.,2800 ; P., 257.Alkaloids from ipecacuanha. See Ipeca-cum ha.of quebracho bark. See Quebrachohark.Alkyl haloids, reactions of, with phen-oxides and ethoxides (SHRODER andACREE), T., 2582 ; P., 228.iodides, ielative activities of, withsodium phenoxide (SEGALLER), T.,106, 112.nitrites, colour reactions of (HARPERand MACBETH), P., 15.sodiuin thiosnlphates, action ofhydrogen peroxide on (Twxss),T., 36.Allanturic acid, nature of (TITHEKLEYant1 COWIN), P., 115.Aluminium alloys with SiliCon(ROBERTs),‘I’., 1383 ; P., 143.isoAmarine, C,,H,,N,.Amides, acid, action of Grignard re-agents on (MCKENZIE, MARTIN, andRULE), T., 1583 ; P., 182.Amines, action of sulphur on (HODGSONand DIX), T., 952 ; P., 82.mixed secondary, hydrolys’s of, byalkalis (TITHEKLEY and STUBBS),T., 299; P., 12.9 2928 INDEX OF SUBJECTS.Amines, preparation of nitrites of(NEOGI), T., 12iO; P., 35.interaction of nieT hyl sulpliate and(WERNER), T., 2762 ; P., 260.aromatic, mt rcurxtiam of' (MORGANaiid ELLIOTI'), P., 186.Amino-acids, influence of acids andalkalis on the optical activity of(WOOI)), T., 1988 ; Y , 220.resolution of metallic salts of(BARKER), P., 295.a-Amino-B-hydroxy-compounds, re-actions of, as cyclic strut tores ( IKVINEand FYFF,), T., 1642 ; P., 179.Ammonium bases, de iqiirwence of saltsorganic, influence of solvviits on themolecular weights of salts of('J?lJRNEIt and POLLARD), T., 1751 ;Ammonium salts, studies of solutioiis of(SLADI.:), T., 1351 , P., 150Ammonium hydrox de, relative strengthsof, aiid substituted aiiirnonium hydr-oxides, nieasuied by their action o na pseudo-base (TINKLEH), T., 995 ; P .,70Annual General Meeting, T., 11 62 ;P., 89.Adhemis nobilis, constituents of theflowers of (POWER and BI~OWKXXG),T..1829 ; P., 210.Antimony compouiids, absorption spectraof ( C'RYMBLE), P., 179.haloids, conipouiid5 of, with aromaticconipounds ( VANSTONE), T., 1491 ;P., 140.Argon, liquid, capillary constants of(CXOMMELIN), P., 248.Aromatic compounds, preparation of,frorii the hydrt laroriiatic aeries (CROSS-LEY aiid RENOUF), T., 165.Arsenic compounds, absorption spectraof (C'EYMKLE), P., 1i9.Aryl h lnilis, uitro-substituted actionof, on alkali thiosulpliates and seleiio-sulpliates (TWISS), T., 1672 ; P.,187.Arylidenedimethylpyrones, constitutionof, arld their salts (}SOON, WILSON,and HEILBRON), T., 2176 ; P.,209.Atmospheric air, velocity of ignition ofmethane and (PARKER and RHEAL;),T., 2150; P., 220 ; (BURGESS andWHEELER), T., 2591 ; P., 245;(WHEELEN), T , 2606; P., 246.of (PED~~LE), 'r., 1025 ; P., 81.P., 79.Aspidosine, ( leH260N2.Aspidospermine, C,, H3oOZNz.Atomic weight ot lead from Ceylonthorite (Y(JDDY and HYMAN), T.,1402; P., 134.Atomic weight of mercury (BAKERand WATSON), T., 2530 ; P.,243.of tin (BRISCOE), P., 290.of vanadium (BRISCOE arid LITTLE),T., 1310 ; P., 64.Atomic weights, reports of the Interna-tional Gomulittee on, T., 2577 ; P.,216.table of, T., 2581 ; P., 219.Azo-compounds, ccilour and constitutionof ( ~ ~ K w I ~ I ' T , MANN, and POPE), T.,2193; P., 202.Azonium compounds, substituted qua-ternary, coiltaitiing an asymmetricnitrogen atom (SrXGH), T., 1972 ;P., 136.B.Balance Sheets of the Chcmical Societyaiiti of the Research Fund.SeeRunual General Meeting, T., 1162 ;P., 89.Barium nitrate, solubility of, and of itsmixtures w i t h potassium nitrate(FINDLAY, MOKGAN, and MORRIS),T., 779; P., 73.Barosmn wenusta, oil from the leaves of(GOULDING and ROBERN), T., 2613 ;P., 244.Bases, weak, influence of neiitral salts onthr dissociatioii of (MCBAIN and COLE-MAN), T., 1517 ; P., 135.$-Bases, researches on ( G . M. andTi. Ronrr;soN), T., 1456 ; P.,161.Benzoterpenes, synthesis of (KAY andMOKWN), T., 1565 ; P., 162.Bismuth conipoiiitds, absorption spectraBismuth organic compounds (CHAL-LENGER), T., 2210 ; P., 229 ;(CHALLENGER and ALLPRESS), P.,292.Bismuthines, tertiary aromatic (CHAL-LEKGEH), T., 2210 ; P., 229.Biuret, C,f1,0,N3.Boiling point aptlaratus for determina-tiou of' (FIRTH and MYERS), T., 2887 ;P., 293.Borneol, C,oHl,O.Boron :--01 (CltYMBLE), P., 179.Boric acid, properties of solutions of,iii alcoliol (FIRTH and MYERS), T.,2887 ; P., 293.Bromine, solutions of, in water, nitro-beiizene and carbon tetrachloride(JOSEPH), P., 244.Brucine, C,,H,,O,N,INDEX OF SUBJECTS.2929C.Caesium bydrogen carlmnate, dissocia-tion pressure of (CAVEN and SAND),T., 2752 ; P., 268.Calcium hydroxide, equilibrium of cal-cium nitrate, water, and ( BASSETTand TAYLOR), T., 1926 ; P., 204.nitrate, equilibrium of cdciuin Iydr-oxide, water and (BASSETr andTAYLOR), T., 1926 ; P., 204.Calorimeter, adiabatic (GRAY), T., 1010.Camphane series, btiidies iu the (FOB-STER and KUNZ), T., 1718 ; P., 198 ;(FORSI-ER and SCHLAEPFER), T., 2770 ;P., 268.Camphene, C,,H,,.Caoutchouc, osmotic properties andphysical constitution of solutioiis of(CASPARI), T., 2139 ; P., 226.Carajuretin, C~($H~ZO.Carajurin, Clelil@5.Carbamides, con s t 1 tu tion of (WE RN E R) ,T., 926 ; P., 26.&oCarbamides, preparation of ( WEBNISR),T., 923 ; P., 26.Carbinole, preparation and rotation ofesters of (KENYON), T., 2226 ; P.,231.optically active, rotation of esters ofaliphatic acids and (PICKARD andKENYON), T., 830.Carbohydrates, oxitlation of, with potas-sium persulphate(WooDand WALKER),T., 1131 ; l'., 115.Carbon monoxide, liqnid, capillary con-stants of (CROMMELIN), P., 248.inflammability of mixtures of airand (COWARD and BHINSLET),T., 1859 ; P., 176.estimation of (GRAHAM and WIN-MILL), T., 1996 ; P., 160.dioxide, evolution of, fi om solutionsof gelatin and starch (FINDLAY andKING), T., 1297 ; P., 114.Carbon, estimation of, in organic com-ponnds (GREY), T., 2204 ; P., 231.isoCarbostyri1, C, H,ON.Catalysis (LAMBLE and LEWIS), T.,2330 ; P., 222 ; (SHRODER and ACXEE),T., 2582 ; P., 228.Catalytic activity of acids (DAWSON andPOWIY), T., 1093 ; P., 60.Caulosapogenin, CaZ H,,O,.Celluloid, absorption of gases by (LEFE-Cellulose, methylation of (DESHAJI andCephaeline, Cz,H.~~O+Nz.Chemical combinatloti aid molecularBURE), T., 328.WOOI)HOUSE), T., 2357 ; P., 238.association (TURNER and EXGLISH),T., 1786; P., 132.Chemical constitution and rotatorypower (PICKARD and KENYON),T., 830,1115 ; P., 83 ; (KENYON),T., 2226 ; P., 231 ; (KENYON aiidP., 232, 243, 262, 273, 307.relatioil hetween viscosity and (DUN-sTAh', THOLE, and BENSON), 'l'.,782.Chlorine, rate of combination of nitricoxidc and (C'OATE~ and FINNEY),T., 2444 ; P., 211.Hydrochloric acid, dilute, action of,on gelatin (PROCTEK), T., 313.PIC'KARD), T., 2262, 2644, 2677 ;Cholesterol, CZ,H4,O.Chromium : --Chromic chloride, action of, on Grignard reagents ( H E N N E ~ and TUK-NER), T., 1057 ; P., 79.Cinchonicine, CI,Hz20Nz.CZenaatis vitalba, constituents of (TUTINand CLEWER), T., 1845; P., 210.Coal, composition of (JONES andWHEELER), T., 140, 3562; P., 243.distillation of, in a vacuum (BURGESSand WHEELER), T., 131.Colloids, inlinence of, on the solubilityof gases in water (FINDLAY andHOWELL), T., 291 ; P., 13.Colour and tautomerism (MELDOLA andHOLLBLY), T., 977 ; P., 85.Colouring matters, relation betweenchemical constitution and depth ofcolour of (WATSOX), T., 759.from lndiitll plants (PERKIN andSHULMAS), Y., 200.derived froin quercetin (WATSON andSEN), T., 389.Co-ordination sod residual affinity(MORGAN and Moss), T., 189.Copper, finely divided, absorption ofgases anti ptoduct.ion of high vacwI y (MERTON), T., 645 ; P., 55.action of sulphnric acid on (CUNDALCand FAIRGRIEVE), T., 60.compounds, colour intensity of(PICKERING), T., 464.Cupric salts, reduction of, by sugars(CRAMER), P., 293.chloromcrcaptitles (RAY), P., 304.isocoumarin, C,H,OB.Cyanidion catalyses, mechanism of(JOSES), T., 1547 ; P., 118.Cyanogen : -Hydrocyanic acid, action of, on alde-Irycles aiid ketones (JONES), T.,1560; P., 118.Cyanohydrins, constittitioil of (CROW-THEK, bfCCIOMBIE, and READE), l'.,Cymbupogou eoloyatus, volatile oil of933; P., 57.(GOULDING and EARL), P., 102930 INDEX OF SUBJECTS.D.Daphnandra micmntha, alkaloids ofDaphnandrine, C3&3,06Nz.Daphnoline, C,,H,,O,N,.Dnviesia.latifolia, coristituents of theleaves and stems of (POWER and SAL-WAY), T., 767 ; P., 66.Deliquescence (PEDDLE), T., 1025 ; P.,81.Denitrification, mecliauism of (HULME),T., 623.Desmotropy (LOWRY), P., 105.Diastase, action of, 011 starch granules(RAKER and HULTON), T., 1529 ; P.,133.o - Diaz oimines, con st i tu t io n of ( M 0 11 G A Nand SCHARFF), T., 117.Diazonium salts, non-aromatic ( MOI:GAI\’and REILLP), ‘l’., 435.Dibenzoylglucoxylose, C25H28012.Dilution law (PAILTINGTON), l’., 251 ;(BOUSFIELD), T., 1809 ; P., 156.Dioximines, chemical constitn tion of(TSCHUGAEV), T., 2187 ; P., 224.Diphenyl series, studies in the (CAI;\’and MICKLETIIWAIT), T., 1437, 1442 ;P., 146, 147.Dispersion, rotatory, of orgaiiic com-pounds (LOWRY), T., 81 ; (LOWI:Y,PICKARD, and KENYON), T., 94.Distillation, apparatus for (13 ~ I ~ N D -RECHT), P., 160.(PYMAN), T., 1679 ; P., 181.E.Electrode, dropping, in alcoholic sola-tion (NEWREHY), T., 2553 ; 1’.,241.hydrogen, potentials of the, in niix-tures of acetic acid and sodiumacetate (WALPOLE), T., 2501, 2521;P., 237, 238.Electrodes, combiiiation of the hydrogel!aiid calomel (F[JRNESS, HAKI)IMAN,aiid NIWBERY), T., 2302 ; 1’. , 233.Electrolytic diasocia tioa (A R RH EN I us),T., 1414 ; P., 165.Electromotive forces, measurclnellt of,in alcohol (FURXESS, HARDMAN,and NEWBERY), T., 2302; Y., 233 ;(NEWREKY), T., 2553 ; P., 241.Emetine, C2,H400,N2.Epicamphor, C,,H,,O.Equilibria, ionic. See Ionic equilibria.Ethoxides, reactions of alkyl haloidswith (SHRO~ER and ACREE), T.,2582 ; P., 228.Ethylenic &bromides, conversion of,into the corresponding glycols (BAIN-BRIDGE), T., 2291 ; P., 232.F.Faraday lecture ( ARR HENIUS), T.,1414 ; P., 165.Flames, water-gas equilibrium in hydro-carbori (ANDREW), T., 444 ; P., 22.Fluorone derivatives (POPE), T., 251.G.Gases, refractivity of (JONES and PART-INGTON), P., 201.ignition of mixtures of (COWARD andBRINSLEY), T., 1859 ; P., 176.by adiabatic compression ( DIXON,I ~ R A U ~ H A W , and CAMPBELL), T.,2027; P..222; (DIXON andCROFTS), T., 2036 ; P., 223.by the e1ect:ic discharge (COWARD,COOPER, and JACOBS), T., 1069 ;velocity of evolution of, from snper-saturated solutions (FLNDLAY andKING), T., 1297 ; P., 114.irifluence of colloids and fine sus-pen5ions on the solubility of, inwater (FINDLAY and HOWELL), T.,291 ; P., 13.absorption of, by celluloid (LEFE-absorption of, by copper (MERTON),T., 645 ; P., 55.Gas-pressure regulator (JOSEPH), P.,254.Gelatin, action of dilute acids on(PROCTER), T., 1313.German silver, inetallography of(THOMPSON), T., 2342 ; P., 233.Glucoses, inethylated ( IRVIXE andHOGG), T., 1386 ; P., 145.Glucosides.See Sarsasaponin.Glucoxylose, C1lH,oOlo.Glycol nryl ethers ( I ~ O Y U and MA~LLE),‘l‘., 2133.Glycols, preparation of, from the corre-spondii~g ditiromicles ( BAINBKIDGE),T., 2291 ; P., 232.Glyoxals, preparation of, and theiracetals (DAKIN and DUDLEY), T.,2453 ; P., 108.Grignard reagvnts, action of, on acidarnitlrs (MCKENZIE, MATLI-IN, aridRULE), T., 1583 ; P. 182.action of alilehydes on (MARSHALL),T., 527 ; P., 13.action of clirorriic chloride on (BENNE’I-Tand TURNER), T., 1057 ; P., 79.r., 78.BUHE), T., 328.Thujin.H.Halogens, dynamics of the action of, onaliphatic aldehydes (DAWSON, BUR-TON, and ARK), T., 1275 ; P., 117INDEX OF SUBJECTS.2931Heat of vaporisation, latent ( AWLEBEYHops, nitrogenous constituents of (CHAP-2-Rydrindamine) C,HIIN.Hydrocarbons, water-gas eqnjlibriuin inflames of (ANDREW), T., 444; P.,22.aromatic, compounds of antimonyhaloids and (VANSTONE), T., 1491 ;P., 140.synthetic, allied to terprnes ( HAWORTHand FYPE), T., 1659 ; Y., 182.Hydrochloric acid. See unrl er Chlorine.Hydrocyanic acid. See under Cyanogen.Hydrogen, inflaniiriability of mixtures ofair and (COWARD and BRINSLEY),T., 1859; P., 176.electr de. See Electrode.peroxide, action of, on sodium dkylthiosulphates (TWW), T., 36.Hydroxy-compounds, influence of con-figuration on the condensations of(IRVINE and PATERSON), T., 898 ;P., 68.aromatic, substitution in (HARDING),T., 2790 ; P., 299.Hydrox ymethylene ketones, c ond en s-ation of cyaiioacetamide mith (SEN-GUPTA), T., 148.and CHAPMAN), T., 734 ; P., 27.MAN), T., 1895 ; P., 196.I.Ignition of gases (COWARD and BRIXB-LEY), T., 1859 ; P., 176.by the electric discharge (COWAED,CoomR, and JACOBS), T., 1069 ;l’., 78.by adiabatic compression (DIXON,BRADSIIAW, and CAMPBELL), T.,2027 ; P., 222 ; (DIXON andCROFTS), T., 2036 ; P., 223.Iodine, action of, on aliphatic aldehydes(DAWSON and MARSHALL), T., 386 ;P., 24.reaction of, with sodium benzylthio-snlplinte (PRICE and JAQUES), T.,1140; P., 117.conipounds of, with organic substances(BARGER and STARLING), P., 2, 303.Iodo-compounds, organic, relative activi-ties of, with sodium phenoxide (SEG-ALLER), T., 106, 112.Ionic equilibria between semipermeablemembranes (DONNAN and ALLMAND),T., 1941 ; P., 180.Ionisation and the law of mass action(BOUSF~ELD), T., 600, 1809 ; P., 156.lpecacnanha alkaloids (CARR and PY-MAX), T., 1591 ; P., 157.Ipecacuanha alkaloids, relation betweenthe ahsorption spectra and constitutionof (DOBBIE and Pox), T., 1639 ; P.,184.Isomerism, dynamic (LOWRY), P., 105.position-, and optical activity (COHEK),T., 1893 ; P., 221.Iron, corrosion of, and its application indetermining the relative strengths ofacids (FRIEND and MARSHALL), T.,2776 ; P., 263.porosity of (PERKINS), T., 102.compounds, colour intensity of( PICKERING), l’., 466.K.Ketones, action of hydrocyanic acid oncondensation of phenols and (SEN-hydroaromatic (CROSSLEY and PaAw),(JONES), T., 1560 ; P., 118.GUPTA), T., 399.P., 65.L.Lead froin Cejlon thorite, atomic weightof (SODDY and HYMAN), T., 1402;P., 134.corrosion of (LAMBERT and CULLIS),erosion of (LIVERSEEGE and KNAYP),P., 25.Liquids, optically active, rotatory disper-sion of (LOWRY, PICKARD, andKENYON), T., 94.relation between the solvent power of,and their dielectric constairts (TvR-KER and BISSETT), T., 947 ; P., 59.molecular complexity of (TURNEI~),P., 29.adiabatic and isothermal, compressi-biiities of (TYRER), T., 2534 ; P.,236,viscosity of binary mixtures of, con-taining formamide (MERRY andmixed, thermal properties of (PART-surface tension of (WORLEY), T.,organic, magnetic rotation and disper-P., 198.TURNER), r r . , 748 ; P., 60.INGTON), P., 61.260, 273.sion of (LOWRY), T., 81.M.Magnesium borides (RAY): T., 2162 ;P., 242.Manganese, velocity of precipitation of,in presence of zinc (WALKER andFARMER), P., 1392932 INDEX OF SUBJECTS.Xannitol, C6H&Mass action, law of, and ionisatioii(BOUSFIELD), T., 600, 1809; P., 156.Natricaria chaino,tjiilla, constituents ofthe flowers of (POWER aud BROWNING),T., 2280 ; P., 237.Membranes, semipermeable, ionic equili-bria between (DUNNAN and ALLMAND),T., 1941 ; P., 180.Menthyl derivatives, rotation of (KEN-YON and PICKARD), P., 273.Mercury, atomic weight of (BAKER andWATSON), T., 2530 ; P., 243.alloys with sodium, specific volumesand conductivities of (VANSTOKE),T., 2617 ; P., 241.compounds, absorption spectra of(CRYMBLE), T., 658; P., 16.Mercuric iodide, equilibrium i n thesystem, potassium iodide, ethylether and water (DUNKINGHAM),T., 368, 724, 2623 ; P., 8, 58,107.nitrite, compouiids of, w i d organicthio-derivatives (MAY), P., 140.Mercurous chloride (calomel) electrode.See Electrode:Mesitylenee, amino-, diazotisation of(MORGAN and RICILLY), P., 74.Metallic salts, trituratioii of mixtui es of(PARKER), T., 1504 ; P., 137.compounds of yheriaiithraquiiionewith (KNOX and INNES), T.,1451 ; P., 159.Metals, wet oxidation of (LAMBENT andMethyl pentoses, constitution of (GIL-Zldicranthine, C,,H,,O,N,.Molecular associatioit and chemicalcoinbination (TWNEIL and ENG-LISH), T., 1786 ; P., 132.forinulz, consistent (TUICNER), P.,110.CULLIS), P., 198.MOUR), T., 73.N.Nitrification, mechanism of (MUMFORD),P., 36.experiments on the rate of ( EEESLEY),T., 1014 ; P., 67.Nitro-compounds, colour reactions of(HARPER and MACBETH), P., 263.aliphatic, theories of formation of(NEOGI), T., 2371 ; P., 220.Nitrogen, i~iflanimability of methanewith mixtures of oxygeii and(PARKER), T., 1002; P., 75 ;( RURGESS and WHEELER), T.,2596 ; P., 245.oxides, constitution and molecularvolumes of (LE BAS), P., 87.Nitrogen inonoxide (nitrous oxide), solu-bility of, a t low pressures (FINDLAYand HOWELL), T., 291 ; I>., 13.dioxide (nilric oxide), rate of comhina-tion of chloriire and (COATES andFINNEY), T., 2444 ; P., 211.peroxide or tekroxide, vapoiir pressureof (EGERTOX), T., 647 ; I>., 5.trioxide, dissociation of gaseousNitric acid, actioti of, on brncinein presence of metallic nitrates(RENNIE and DAWKIKS), T., 1487 ;Nitratea, detection and estimstion of,colorilt~etrically (LETTS and REA),T., 1157 ; P., 72.Nitrous acid, action of, on ainiiiesNitrites, detection and estimation of,coloriinetrically (LETTS and PLEA),T., 1157 ; P., 72.Nitrogen atom, asymmetric tervnleiit,compounds of (MOORE), P., 182.asymmetric quinqnevalent,attemptsto prepare t lerivatives con taiiiing(MELDOLA arid HOLLELY), T.,1469; P., 159.doubly-linked, configuration of(MILLS and BAIN), T., 64.(JONES), T., 2310; P., 230.P., 71.rr., 1270 ; P., 35.0.Obituary notices :-Matthew Algernon Adams, T., 1189.Joseph Carter Bell, T., 1193.William Popplewell Bloxam, T., 1195.Harry Burrows, T., 1200.James Tudor Cundall, T., 1201.Robert Kennedy Duncan, T., 1203.John Gibson, T., 1204.Sir Walter Noel Hartley, T., 1207.John Heron, T., 1216.Julius Lawkowitsch, T., 1217.Hugh Marshall, T., 1219.George blatthey, T., 1222.Ole5ne oxides, velocity of combinationof sodium derivatives of phenols with(BOYD and MARLE), T , 2117 ; P.,199.Optical activity and position-isomerism(GOHEN), T., 1892 ; P., 221.without an asymiiietric carbon atom(KING), P., 249.of compounds of simple molecularcoirstitutiori (Poi>E and READ),T., 811 ; P., 75.influence of acids and alkalis on the,of amino-acids (WOOD), T., 1988 ;P., 220INDEX OF SUBJECTS.2933Optically active compounds, influence ofsolvents on the rotation of ( PATTERSOXand POLLOCK), T., 2322 ; P., 234.Organic compounds, rotatory disllersionof (LOWRY), T., 81; (LOWKY, PICK-ARD, and KENYON), T., 94.blue compounds of, with iodinealiphatic, estimation of‘ carboii in(GHEY), T., 2204 ; P., 231.aromatic, absorption spectra of(PURVIS), T., 1372 ; P., 141.compoiinds of antimony haloids and(VANSTONE), T., 1491 ; P., 140.Overvoltage (NEWBERY), T., 2419 ; P.,235.Oximes, isomerism of (BRADY and DUNN),T., 821, 2409, 2872 ; P., 65, 240, 291 ;(BRADY), T., 2104 ; P ., 198.Oxygen, iiiflamniability of niistures ofmetliane, nitrogwn, and (PAIU~ER),T., 1002; P., 7 5 ; (BURGESS andWHEELER), T., 2596 ; P., 245.(BARGER and STARLING), P., 2, 303.P.Petroleum, fractional distillation of(SANDERS), T., 1697 ; P., 185.Phenol derivatives containing a mobilenitro-group, syntheses with (MetiioLAand HOLLELY), T., 977 ; P , 85.Phenole, alkj lation of, by nieans ofsulphntyl chloride (SMYTH), P., 14.condenhation of krtones with (SEN-GUprA), T., 399.inigretion of p-hitlopen atoms in (GIBBsand KOBEKTSON), T., 1885 ; P., 221.velocity of drcorntiusitioii of acyl de-rivatives 0 1 (JONES and LAPWOIL r ~ ) ,P., 141.velocity of saponification of the scylderivatives of (hlCCoMBIs and SCAR-BOROUGH), T., 1304 ; P., 107.velocity of combixl’dtion r f sodiumderivatives of, with olefine oxides(BOYD and MAILLE), T., 2117 ; P.,199.consleiis:rt.im of ethyl a-chloroaceto-acetate with (DEY), P., 38.Phenoxides, reactions of a1 kyl haloidswith (SHRODER and ACREE), T., 2552 ;P., 228.9-Phenylfluorene. 3-hydroxy-.See Re-sorcinol- be11 win.Phenylglyoxalines, subs ti tutcd, prepma-tion of (STEPHEN and WEIZXAKN),T., 1046 ; P . , 71.Phenylhydrazones. nitrated, absorptionspvctra ot (HEWITT, JOHNSON, andPOPE), T., 354 ; P., 4.Phenylsiliconic acid and its sodiiinl salt(MEADS and KIPPING), T., 685.Phosphorus compounds, absorption spec-tra of (CRYMULE), P., 179.pentac.hloride, action of, on estersof glyceric: acid (FKANKLAND audTURNBULL), T., 456 ; P., 29.oxides, constitution and molecularvolumes of (LE BAS), P ., 87.Phototropy, studies in (SENIER andCLARKE), T., 1917 ; P., 203 ; (SENIERand FORSTER). T., 2462 ; P., 227.Phytic acid. C6Hl0O~,P2.Phytin, C12H,,0,,P,,Ca, Mg.Pinacones, synthesis of (PARHY), P.,Plants, Indian, colourinq matters fromPlatinic chloromercaptides (RAY), P.,Potassium hydrogen carbonate, disaocia-tioil pressure of (CAVEN and SAND),T., 2752 ; P., 268.ioditle, equilibrium in the system :ethyl ether, mercuric iodide andwater (DUNNIRGHAM), T., 36S, 724,2623 ; P., 8, 58, 107.nitrate, solnhility of, and of its mix-tures with strootium, and bariumnitrates ( FINDLAY, Mo KGAN, andMORRIS), T., 779 ; P., 73.pcrsril phate, oxidation of carho-hydrates bj* iileans of (WOOD andWALKEI:), T., 1131 ; P., 115.polysullihides (RULE aud TIIOMAS),T., 2819 ; P., 270.Psychotrine, C,,H,60,N,.2- aild 4-Pyrones, cowpounds of iodinewith (BARGER and STARLING), P.,303.298.(PERKIN and SHULMAN), P., 200304.Q.Quebracho bark, alkaloids of ( E ~ I N s ) , ‘r., 2738 ; P., 258.Quercetin, CI5Hl0( ),.Quercitrin, C,, H,,Oll.is1 Quinoline alkaloids (HOPE and ROB-INSON).T., 2OS35 ; P., 228.relatioii between the ahsorjltion spectraand consritutiou of (DOBBIE andFox), T., 1639 ; P., 184.Quinone-ammonium derivatives (MEL-n0I.A anGI HOLLELY), T., 1469, 2073 ;P., 159, 229.R.Racemic compounds, existcnce of, in theliquid state (SMITH), T., 1703 .P.,22.Refractivity and rotatory power (PEA-COCK), T., 2782 ; P., 2642934 INDEX OF SUBJECTS.Resorcinol-benzein, Cl9Hl2O3.Rhawmus catharticws, colo u ring mattersof (OESCH and PEKPIN), 'l'., 2350;P., 236.Ring-formation, effect of, on viscosity(THOLE), T., 2004 ; P., 181.Rotation of optically active compounds,influence of solvents on the (PATTEE-SON and POLLOCK), T., 2322; P., 234.Rotatory dispersion. See Dispersion.power and chemical constitution(PICKARD and KENYON), '1'. , 830,1115; P., 8 3 ; (KEXYON), T.,2226; P., 231 ; (KEPU'YON andPICKARD), T., 2262, 2644, 2677 ;P., 232, 243, 262, 273, 307.and refractivity (PEACOCK), T.,2782 ; P., 264.Rubidium hydrogen carbonate, dihsocia-tion pressure of (CAVEX and SANr)),T., 2752; P., 268.S.Salts containing two solvents of crystal-lisation (MARSH), T., 2368 ; P., 83.neutral, induence of, on the dis-sociation of weak acids and bases(MCBAIN and COLEMAN), T., 1517 ;P., 135.Santalin, C3oH2,Olo.Sarsaparilla root, constituents ofSarsapic acid, C,H406.Sarsasapogenin, C2,H4,0,.Sarsasaponin, C44H,2020.SchiPs bases, addition of negativeradicles to (JAMES and JUDD), T.,1427.Selenium organic compounds, aromatic(PYMAN), P., 302.Semicarbazonee, investigations on ( WIL-T., 2892 ; P., 295.Silicon alloys with aluminium(.ROBERTS), T., 1383 ; P., 143.Silicon compounds, researches on (MAR-TIN), T., 2836, 2860; P., 271, 272.Silicon chlorides, preparation of (MAR-TIN), T., 2836 ; P., 271.Disilicon hemchloride, action of ethylalcohol on (MARTIN), T., 2860 ;P., 272.Silicon organic compounds (ROBISONand KIPPING), T., 40 ; (KIPPING andROBISON), T., 484 ; (MEADS andKIPPING), T., 679 ; P., 6.Siliconic acids, so-called (hlEADs andKIPPING), T., 679 ; P., 6.Silver, equilibrium of, with silversulyhide (BISSETT), T., 1223 ; P., 82.(POWER and SALWAY), T., 201.SON, HEILBRON, and SUTHERLAND),Silver, spitting of (BAKER), P., 56.Silver alloys with tin, ageing of(KNIGKL'), T., 639; P., 28.Silver sullbhide, equilibrium of, withsilver (BISSETT), T., 12'23 ; P., 82.removal of sulphur from (BISSETT),T., 2829 ; P., 269.Soap solutions, constitution of (BUN-BURY and MARTIN), T., 417 ; P., 8 ;(MUBAIN and MARTIN), T., 957 ; P.,68.Sodium alloys with mercury, specificvolumes and conductivities of (VAN-STONE), T., 2617 ; P., 241.Sodium chloride, action of steam on(ENGLISH and T~'RNEB\, P., 162.hypochloi,ite, photokinetics of solu-tions of (SPENCER), T., 2565; P.,240.polysnlphides (RULE and THOMAS),T., 177.alkyl thiosulphates, action of hydro-gen peroxide 011 ( TWISS), T., 36.Soils, destructive distillation of (HOLM-YARD), P., 109.action of acid solvents on the phos-phates of (PKESCOTT), P., 137.Solanguetidine, 02,H4,02N.Solangustine, C33H5307N.Solanum angustifdlium, constituents of(TITTIN and CLEWEB), T., 559 ; P., 7.Solutions, aqueous, magnetic propertiesof (GRAY and BIRSE), T., 2707 ; P.,211.Solvents, influence of, on rotation ofoptically active compounds (PATTER-SON and POLLOCK), T., 2322 ; P., 234.Spectra, absorl)tion, of acids and theirsalts, relation between (WRIGHT),T., 669 ; P., 39.of mercury coinpounds (CRYMBLE),T., 658 ; P., 16.of nitrated phenylhydrazones( HEWITT, JOHNSON, and POPE),T., 364 ; P., 4.of aromatic organic coniponnds(PURVIS), T., 1372 ; P., 141.of substances containing two benz-etie nuclei (PURVIS), T., 590 ; P.,23.Starch, action of hydrochloric acid on(DAIRH), T., 2053, 2065; P., 225,226.granules, action of diastase on (BAKERand HULTON), T., 1529 ; P., 133.Steric hindrance, influence of, OH acyla-tion (MELDOLA and HOLLELY), T.,410 ; P., 25.Stigmasterol, C30H5,O.Strontium uitrate, solubility of, and ofits mixtures with potassium nitrate(FINDLAY, MORGAN, and MORRIS),T., 779 ; P., 73INDEX OF SUBJECTS.2835Succinic add aeries, studies in the(MORKELL), T., 1733, 2698 ; P., 175,257.Sugars, viscosity of solutions of(POWELL), T., 1 ; (GREEN), P.,158.alkylation of (HAWORTH), P., 293.reduction of cupric salts by (CBAMEK),P., 293.Sulphur, action of, on amines (HODGSONand Drx), T., 952 ; P., 82.Sulphuric acid, viscosity of (DUN-actioii of, on copper (CUNDALL andSulphurous acid, absorption spectraof, and its stilts (WRIGHT), T.,2907 ; P., 264.Sulphuryl chloride, alkylation ofphenols by means of (SMYTH), P.,14.Thionyl chloride, action of, on lacticacid and ethyl lactate (FRANKLANDand GAKKER), T., 1101 ; P., 84:with mercuric nitrite (RAY), P., 140.with cupric, mercuric, and platinicoxidation of benzgl compounds ofSulphur, removal of, from silver (BIs-SEW), T., 2829 ; P., 269.Sulphuric and Sulphurous acids.Seeunder Sulphur.Surface tension of mixtures (WORLEY),T., 260, 273.STAN), P., 104.FAIRGKIEVE), T., 60.Sulphur organic compounds :-chlorides (RAY), P., 304.(SMYTHE), T., 546 ; P., 24.T.Tautomerism (PERKIN), T., 1176 ; P.,and colour (MELDOLA and HOLLELY),Terpene6, chemistry of the (HENDERSON,HEILBRON, and HOWIE), T., 1367 ;P., 136; (HENDERSON and SUTHER-LAND), T., 1710 ; P., 203.Thermotropy, studies in (SENIER andCLARKE), T., 191 7; 1’. , 203; (SENIERand FORSTER), T., 2462 ; P., 227.Thionyl chloride.See under Sulphur.Thorium, relation of uranous salts to(FLECK), T., 247Thujin, constitution of (PERKIN), T.,1408 ; P., 150.Tin, atomic weight of (BRISCOE), €’.,290.Tin alloys with silver, ageing of(KNIGHT), T., 639 ; P., 28.Toluenes, substituted, brorniuation aiidchloriijation of (COHEN and SMITH-ELLS), T., 1907 ; P., 224.101 ; (LOWRY), P., 105.T., 977 ; P., 85.Trituration, reactions by (PARKER), T.,Tungsten organic compounds, prepara-U.Uranous salts, relation of, to thoriumchloride, absorption of light by1504 ; l’., 137.tiun of (TURNER), P., 4.(FLECK), T., 247.(MERTON), T., 23.V.Vacua, high, production of, by means offinely divided copper (MEHTON), T.,645; P., 55.Vanadium, atomic weight of (BRISCOEaiid LITTLE), T., 1310; P., 64.Vanillin, C,H,O,.Vaponrs, lateiit heat of (APPLEBEY andCHAPMAN), T., 734 ; P., 27.Velocity of evolution of gases from super-saturated solutions (FINDLAY andKING), T., 1297 ; P., 114.Velocity of ignition of mixtures of airand methane (PARKER and RHEAD),T., 2150 ; P., 220.Velocity of saponification of the acylderivatives of phenols (MCCOMBIEand SCARBOROUGH), T., 1304 ; P., 107.Viscosity, relation between chemicalconstitution and (DUNSTAN, THOLE,and BENSON), T., 782.effect of ring-formation on (THOLE),T., 2004; P., 181.of binary niixtures of liquids contaiuingformainide (MERRY and TURNER),T., 748 ; P., 60.Volumes, molecular, a t the boiling point,W.Water, magnetic properties of, in com-bination and in solutions (GRAY andBIRSE), T., 2707 ; P., 211.estimation of, in alcohol (JOKES andLAPWORTH), T., 1804 ; P., 202.Wax seals, medieval, composition of (DOBBIE and Fox), T., 795 ; P., 67.Weights, molecular, influence of solveiitson (TURNER arid POLLAHD), T.,1751 ; P., 79.of salts of the alkali metals (TURNERand BISYETT), T., 1777 ; P., 110.calculation of (LE BAS), P., 86.. X.Xylenols, bromo- ( CROSSLEY andREKOUF), T., 165.z .Zinc, electro-deposition of (PRING andTAINTON), T., 710 ; P., 27

ISSN:0368-1645    

DOI:10.1039/CT9140502927

出版商:RSC    

年代:1914

数据来源: RSC