摘要:

368 DUNNINGHAM : THE SYSTEM : ETHYL ETHER-WATER-XL.-The System : Ethyl Ether- Water-PotassiumIodide-Mercuric Iodide. Part I. .The Under-lying Three- Component Systems.By ALFRED CHARLES DUNNINGHAM.THE formation of three partly miscible liquids in a four-componentsystem has been observed from time to time, but has never beenstudied quantitatively with a view to elucidate the conditions ofequilibrium underlying such a phenomenon.The most convenient system f o r the purposes of such a studyappeared to the author to be the system ethyl ether-water-potassium iodide-mercuric iodide, in which three liquid layers wereobserved by Marsh (T., 1910, 97, 2297), who, however, made noattempt to investigate the question from the point of view ofheterogeneous equilibrium.Sime ether has an appreciable vapour pressure a t 20°, it wasnecessary to devise a special form of apparatus in which to agitatethe mixture whilst equilibrium was being attained.This apparatusis shown in Figs. 1 and 2. It consisted of a glass tube c, that couldbe fixed into a metal clamp d, which was free t o revolve in thejaws ab. The top of this tube was connected to a short shaft gh,which was fixed eccentricaiiy to a pulley m, so that when thispulley revolved the tube was shaken violently backwards andforwards. This motion served to agitate the contenh of the tube,and stir the water in the thermostat, in which it was immersed.The temperature was maintained constant t o Oslo. The tube wi19closed by means of an ordinary cork tied firmly with string.The composition of the various solid phases was, where necessary,determined by the residue method described by Schreinemakers(Zeitsch. physikal.Chem., 1893, 11, 81; 1907, 59, 641). Theappearances of potassium iodide and mercuric iodide, however, areunmistakable, and i t is only possible for confusion to arise betweenpotassium mercuri-iodide and its hydrate, KHgI,,H@, which havea similar appearance.I n analysing solutions and residues, the ether was first expellePOTASSIUM IODIDE-MERCURIC IODlDE. PART I. 369by the passage of a current of air previously dried by means ofanhydrous calcium chloride. A special weighing bottle was there-fore used, as shown in Fig. 3. The air leaving the'bottle was thenpassed through a weighed tube containing anhydrous calciumchloride, in order to absorb any water-vapour carried over by theether.The water was then expelled at a temperature slightlyabove looo by the further passage of dried air. The potassiumiodide in the solid residue was then estimated by Bray and MacKay'smethod (J. Amer. Chem. SOC., 1910, 32, 1193), in which the iodineis liberated by the addition of potassium permanganate in slightFIG. 1. FIG. 2.aIApparatus.excess in the, presence of an acid, extracted with carbon tetra-chloride, and titrated with standard thimulphate. The mercuriciodide, which is not affected by permanganate, was then obtainedby difference.The System : Potassium Iodide-Mercuric Iodide-Water.This system has been studied a t 30° as well as 20° in order toconfirm the existence of potassium mercuri-iodide, KHgI,.Theresults obtained a t 20° and 30° ar0 given in tables I and 11, andshown graphically in Figs. 4 and 5 respectively, and since they arealike in type, a discussion of the isotherm a t 20° will also servefor that at 30°370 DUNNINGHAM : THE SYSTEM : ETHYL ETHER-WATER-TABLE I.The System : Potassium Zodide-Mercuric Zodide-Water at 20°.No.123466789101112131416Percentage composition Percentage compositionof solution. of residue. - - KI. HgI, KI. HgI,. - - - 59.250-9 19.3 86.2 5.647.5 25.4 85.3 7.644.4 32.5 82-4 10.241.3 39.6 76.2 16.439.0 48.0 82-7 13.638.2 51.2 83-6 13.537.4 63-6 42.6 50.937.8 52.6 35.1 67-436-1 62.2 32.1 60.036.6 51.2 30.3 61.126.7 60.3 17.6 74.326.6 49.4 10.2 82-423.7 40.2 - -14.9 22-5 4-1 83.4Solid phase.KIKIKIKIKIKIKITABLE 11.The System : Potassium IocEide-Mercuric Iodide-Water at 30°.1617181920213223242660.640.039.640.040.239.333.733.03 1.429.1-63.062.762.261.260.349.862-061.752.2-61.036.133-636-933.629.630.329.126.6-37.060.762.169.260.462.761.060.667.1KIA t 20° the following phases are stable in equilibrium with solu-tion : Potassium iodide, potassium mercuri-iodide, potassiummercuri-iodide hydrate (KHgI,,H,O), and mercuric iodide.It has been shown by Schreinemakers (Zeitsch. physikal.Chem.,1909, 65, 553) by means of the 3 function (thermo-dynamic poten-tial) that the type of an isotherm in a system of two solid and oneliquid components, the liquid component being regarded as solute,does not alter, provided that the solute does not combine with thetwo solids; thus he showed that in the system silver nitrate-ammonium nitrate-alcohol-water, in which the two solid com-ponents form two compounds, these compounds persist in both thethree-component systems, and right through the four-componentsystem. By an analogous process of reasoning, one may deducethat potassium and mercuric iodides do not form mixed crystalsat 20°, as there is no evidence of this in the threecomponentsystems.This is remarkable when the great tendency of mercuriPOTASSIUM IODIDE-MERCURIC IODIDE.PART r. 37 1iodide to form mixed crystals with other iodides is remembered;on the other hand, the heterogeneous area often widens rapidlybelow the eutectic point, and in this case may have done so to suchan extent that mutual miscibility has, for practical purposes,vanished.One may also deduce from the above that a compound, potassiummercuri-iodide, occurs in the two-component system potassiumiodid*mercuric iodide, probably a t all temperatures.The isotherm under discussion presents some remarkable featuresFIG. 4.20".for a system in which the components are two salts and water. Therestricted extent of the threephase areas, and the great extent ofthO unsaturated and two-phase areas, me very unusual.The following is' a resume of the more important features of thediagram (Fig.4):Point e represents water ; f , potassium iodide ; g, mercuric iodide;m, potassium mercuri-iodide ; and n, potassium mercuri-iodidehydrate (KHgI,,H,O).Line ab represents the range of saturated solutions co-existingwith solid potassium iodide; bc, with solid potassium mercuri-iodide372 DUNNINGHAM : THE SYSTEM : ETHYL ETHER-WATER-cd, with solid potassium mercuri-iodide hydrate (KHg13,H,0) ; andde, with solid mercuric iodide.Point b represents a saturated solution coexisting with solidpotassium iodide and potassium mercuri-iodide ; c, with solidpotassium mercuri-iodide and its hydrate; and d, with solidpotassium mercuri-iodide hydrate and mercuric iodide.Area fab represents mixtures of saturat.ed solutions on ab + solidpotassium iodide ; bcm, on bc + solid potassium mercuri-iodide ;end, on cd + solid potassium mercuri-iodide hydrate; edg, onFra.5.3 0".ede + solid mercuric iodide ; f bm represents mixtures of solutionb + solid potassium iodide -t solid potassium mercuri-iodide ; mcn, ofsolution c + solid potassium mercuri-iodide + solid potassium mercuri-iodide hydrate ; ndg, of solution d + solid potassium mercuri-iodidehydrate + solid mercuric iodide ; and m n g represents solid mixturesof potassium mercuri-iodide, its hydrate, and mercuric iodide.On attempting to prepare a saturated solution of either of thedouble salts, the following phenomena occur. If water is added topotassium mercuri-iodide the composition of the mixture followsthe line me.When 9b is reached, all the salt is converted intPOTASSIUM IODIDE-MERCURIC IODIDE. PART I. 3’73potassium mercuri-iodide hydrate. Further addition of watercauses the formation of kolution d, together with solid mercuriciodide, until a t p all the double salt is decomposed, and onlysolution CF and solid mercuric iodide exist. As the- mixture thenfollows the line pe, the solution follows the curve de, more mercuriciodide being formed as the proportion of water becomes greater,until at e the solution is almost pure water, since the solubilityof mexcuric iodide is negligible.When solid mercuric iodide is added to a saturated solution ofpotassium iodide represented by a, the composition of the mixturefollows the line “9.The first solid phase which separates is thuspotassium mercuri-iodide hydrate (KHgI,,H,O).The System : Potassium Iodide-Water-Ethyl Ether.The results obtained in the investigatio,n of this system a t 20°are given in table I11 and shown diagrammatrically in Fig. 6,where point qz represents potassium iodide, rn water, and r ether.TABLE 111.The System : Potassium Iodide-Ethyl Ether-Water at 20°.Percentage composition Percentage composition - - KI H,O Et,O KI H,O Et,O Solid phase.of upper layer. of lower layer.26 - None. - 59.2 40.8 - K127 0.0 3.9 96.1 0.0 93.0 7.0 None.28 0.4 0.4 99.2 55.6 40.7 3.7 KI29 0.1 2.2 97.7 25.0 72.1 2.9 None.The base line mr represents the heterogeneity which occurs in thesystem water-ether. On the addition of the third component, thelimits of miscibility are naturally altered.I n this case there issome indication of approaching homogeneity after saturation withpotassium iodide is reached. It is therefore conceivable that a t ahigher temperature there would be an uninterrupted solubilitycurve from the solubility of potassium iodide in water to the samein ether.The folIowing is a brief consideration of the system.The solubility of ether in water is represented by the point x,that of water in ether by the point 9.The solubility of potassium iodide in water is represented by thepoint d , that of potassium iodide in ether by the point c. This, inpractice, is negligible.The curve da represents the saturation curve of potassium iodidein water containing ether, ch that of potassium iodide in ethercontaining water. Further addition of ether to solution a i374 DUNNfNGHAM : THE SYSTEM : ETHYL ETHER-WATER-contact with solid potassium iodide causes the separation of asecond lighter layer, the composition of which is represented by h .Similarly, the addition of water to solution h in contact with solidpotassium iodide causes separation of a second, denser layer, thecomposition of which is represented by a ; a and h are thereforeinvariant solutions ; a is an aqueous solution saturated simultane-ously with solid potassium iodide and ethereal solution h, whilsth is an ethereal solution saturated simultaneously with solidpotassium iodide and aqueous solution a ; a and h are thereforeFIG. 6 .mconjugate solutions in equilibrium with one another and with solidpotassium iodide.In Fig.6 the curve ax represents aqueous solutions unsaturatedwith respect to solid potassium iodide, but in equilibrium withethereal solutions represented by points on gh, whilst gh representsethereal solutions unsaturated with respect to solid potassiumiodide, but in equilibrium with aqueous solutions represented bypoints on the curve ax; ax and hg are therefore conjugate curves.A solution represented by a point on one of these is in equilibriumwith a solution represented by a definite point on the other.These curves, ax and hg, naturally end in the points 5 and grespec tivel pPOTASSIUM IODIDE-MERCURIC IODIDE. PART I. 375We can now distinguish the portions into which the trianglew w is divided.Area dnu represents mixtures of aqueous solutions on da + solidpotassium iodide ; chm represents mixtures of ethereal solutions onc h +solid potassium iodide ; nah represents mixtures of the twoconjugate solutions a and h + solid potassium iodide; duxm repre-sents unsaturated aqueous solutions ; chgr represents unsaturatedethereal solutions ; and axgh represents mixtures of two conjugatesolutions (aqueous and ethereal) represented by conjugate pointson ax and gh respectively.The behaviour of a mixture of two components when the thirdis added to it is as follows:I f nu is drawn and produced to meet mr in p, whilst nh is drawnand produced to meet mr in q, the line mr is divided into threeparts, namely, mp, pp, and qr.We will first consider a mixture of ether and water representedby a point k; on mp.If, as in Fig. 6, k lies between m and x, thismixture is homogeneous, whilst if k lies between x and p , twolayers, of compositions represented by x and g respectively, areformed. I f now potassium iodide is added to this mixture, itscomposition follows the line kn. This line cuts the curve da, andenters the area dna. The addition of potassium iodide to themixture k therefore finally gives a homogeneous saturated solutionrepresented by a point on da. Similar considerations show thatany mixture represented by a point on q~ gives, on addition ofpotassium iodide, a saturated homogeneous solution repraented bya point on ch.It will further be observed that if k lies between m and x it ispossible for the line kn to cut the curve xa in two places, c and f.When thi8 is the case, the addition of potassium iodide causes theseparation of an ethereal layer at e, which disappears again a t f,where the mixture becomes homogeneous.This ethereal layer is,of course, very small in amount.Any mixture of ether and water represented by a point j betweenp and g exists throughout as two layers. These are first representedby x and g, and as potassium iodide is added, they follow thecurves xu and gh until, when the mixture reaches b , they havecompositions represented by a and h respectively. Further additionof potassium iodide leaves these layers unchanged.The phenomena occurring when potassium iodide is added to anether-water mixture lying between g and q can be seen at oncefrom the figure.When ether is added to an unsaturated solution of potassiumiodide in water, such as that represented by t , the composition o376 DUNNINGHAM : THE SYSTEM : ETHYL ETHER-WATER-the mixture follows the line tr.A t 21 an upper o r ethereal layercommences to separate. I f the line fr coincides with the conjuga-tion line through 27, as in Fig. 6, the composition of this upperlayer is represented by zu. As the mixture moves along vw thecompositions of the two layers remain unchanged, but the relativeamount of w increases. At any point y t.he ratio of the two liquidsis given by the relationship:amount of v - length of wyamount of w lengtt-1 ot vy’-When w is reached all the lower layer ZJ has disappeared.Thesolution then remains homogeneous on further addition of ether.I n most cases, however, tr does not coincide with a conjugationline, but cuts through a number of them. This means that thecomposition, as well as the ratio of the two liquids, changes asether is added. Since, however, in reality the curve h g is veryshort, the line tr always approximates to a conjugation line, andthe compositions of the two layers vary only slightly.The addition of water to a mixture of ether and potassium iodiderepresented by z almost immediately (at u) causes a separation intotwo layers, represented by a and h, in contact with solid potassiumiodide. A t b all the potassium iodide just dissolves, the solutionsstill being represented by a and h.As the mixture then movesfrom b to s, these solutions follow the curves ax and hg, whilst therelative amount of the ethereal solution decreases. A t s the etherealsolution just disappears, and the aqueous solution remains homo-geneous on further addition of water.The System : Ethyl Ether-Potassium Zodide-Xercuric Iodide.The equilibrium obtained in this system is of a remarkablecharacter. The results are) given in table I V and shown diagram-matically in Fig. 7, and the more important features of thisdiagram may first be briefly considered.Point a represents potassium iodide; s, ethyl ether; c, mercuriciodide ; and i potassium mercuri-iodide.TABLE IV.The System : Potassium 1od:ide-dlercur.ic Iodide-EthylEther at 20°.Percentage Percentage Percentagecomposition of composition of composition ofupper layer.lower layer. residue. -- - KI. HgI,. KI. HgI,. K; l332. Solid phase.30 1-1 2.8 None. KI + KHgI,31 1-1 2.4 17.6 53.2 25.6 67.4 KHd,HgI, 32 0.8 2.5 16.5 56.1 - -33 None. 17.0 58.2 18.3 71.6 KHgI,+HgIPOTASSIUM IODIDE- MERCIJRIC IODIDE. PART r. 377Line d e represents the range of saturated solutions co-existingwith solid potassium iodide; lines cf and hk represent the range ofsaturated solutions co-existing with solid potassium mercuri-iodide ;by/ and mk, with solid mercuric iodide; and f g and hm representthe ranges of two series of conjugate liquids in equilibrium withone another.Point e iepresents a saturated solution co-existing with solidpotassium iodide and solid potassium mercuri-iodide ; points f and ILrepresent two conjugate solutions co-existing with solid potassiummercuri-iodide; i~ and m, with solid mercuric iodide; point k repre-FIG.7.a, (KI)sents d saturated solution co-existing with solid potassium mercuri-iodide + solid mercuric iodide.Area defgb represents unsaturated solutions containing a smallproportion of dissolved salts ; h.km represents unsaturated solutionscontaining a, large proportion of dissolved salts; a d e representsmixtures . of solutions on de +solid potassium iodide; efj, onef + solid potassium mercuri-iodide; fhmg represents mixtures oftwo conjugate solutions on fg and hm respectively; bgc representsmixtures of solutions on b y + solid mercuric iodide; hjk, on hk +solid potassium mercuri-iodide ; kmc, on mk + solid mercuric iodide ;ae j represents mixtures of solution e + solid potassium iodide + solidVOL.cv. c 378 DUJSNINGHAM : THE SYSTEM : ETHYL ETHER-WATER-potassium mercuri-iodide ; fj?L, f and k + solid potassium mercuri-iodide; gmc, g and m +solid mercuric iodide; and jlcc, k+solidpotassium mercuri-iodide + solid mercuric iodide.It will be noticed at once that the saturation curve of potassiummercuri-iodide is divided into the two parts ef and hk, whilst thatof mercuric iodide is divided into the two parts b y and mk. Thesetwo saturation curves intersect at I%, which thus represents asolution saturated with both solids. Both these saturation curvesare divided into two portions by a binodal curve, E,xfgl~2m?L~,which cuts across them.Only the parts f g and hm, representingtwo series of conjugate solutions, are stable. The metastable parts,both of the binodal curve ar,d of tlie saturation curves, areindicated by dotted lines.Unfortunately, the actual range of all the curves is exceedinglysmall, but the form of the isotherm as shown in Fig. 7 is deducedfrom the experimental evidence given belo,w.There is no formation of two liquid layers in any of the threetwo-component systems from which the three-component system isbuilt up.Both potassium iodide and mercuric iodide are practicallyinsoluble in ether, so that in the ordinary way it might be expectedthat the addition of a small quantity of mercuric iodide to asolution already saturated with potassium iodide, and containinga considerable quantity of that salt as solid phase, would merelycause the solution t o become saturated with respect to potassiumiodide and potassium mercuri-iodide ; tlie formation of the doublesalt can be premissed on the law of corresponding isotherms.Theactual course of events, however, is different from the abovescheme.The experiment described above causes the separation of aheavy liquid rich in potassium iodide and mercuric iodide, which,on continued shaking, disappears, and leaves the solution saturatedwith respect to potassium iodide and potassium mercuri-iodide.The transitory formation of this heavy liquid may be readilyexplained by reference t o the diagram, in which the whole of thebinodal curve is shown, the stable part by complete lines, themetastable part by dotted lines. A consideration of the 3 surfacesshows us that if the metastable prolongation of the saturationcurve of potassium iodide cuts the metastable portion of thebinodal curve, we can obtain two liquid layers in equilibrium withsolid potassium iodide.The conditions for such a metastable equili-brium ar0 shown in the diagram by the area axy, in which z and yrepresent the two liquid layers. This area is divided up into twostaEle areas representing the following equilibria : (1) potassiuPOTASSIUM IODIDE-MERCURIC IODIDE. PART I. 3’19iodide + potassium rnercuri-iodide -t solution e , and (2) potassiummercuri-iodide + solutions on ef.Since we started with a solution containing a considerable excmsof solid potassium iodide, it is evident that the ultimate stableequilibrium will be potassium iodide + potassium mercuri-iodide +solution e.If we take some of solution e saturated with potassium iodideand potassium mercuri-iodide, but containing only potassiummercuri-iodide as solid phase, and add mercuric iodide to it, asecond liquid layer is formed almost at once, which does notdisappear on continued shaking.This means that we rapidlytraverse the small range of solutions on ef saturated with potassiummercuri-iodide, and arrive in the complex area, fjh, which repre-sents mixtures of potassium mercuri-iodide with solutions f and h.I f a complex consisting of it small quantity of solution f anda large quantity of solid potassium mercuri-iodide and solution his now taken, and solid mercuric iodide added to it, the solutionf disappears, and if sufficient mercuric iodide is added, we obtaina solution saturated with respect to two solid phases, namely,potassium mercuri-iodide and mercuric iodide.This means thatthe complex of solid and solution has entered the area jlic.I f , on the other hand, the two solutions f and h saturated withpotassium mercuri-iodide and containing this salt in slight excessare treated with small quantities of solid mercuric iodide, the solidphases disappear, and w0 enter a twoliquid region. This is shownin the diagram by fhmg.The addition of a large excess of mercuric iodide causes theformation of two liquid layers saturated, with respect to mercuriciodide. This equilibrium is also attained when potassium iodideis added to a saturated solution of mercuric iodide in ether, con-taining an excess of that salt. It is represented by the area gmc.The author is carrying out a further series of observations onthis system at, other temperatures.The System : Mercuric Iodide-Water-Ethyl Ether.Since mercuric iodide is practically insoluble in ethyl ether andwater, and in all mixtures of these two components, no pointshave been determined in this system, which is similar in type t o thesystem potassium iodidewater-ethyl ether.I n conclusion, the author wishes t o acknowledge with gratitude agrant from the Chemical Society, which has enabled him to carryout this research.SIR JOHN DEANE’S GRAMMAR SCHOOL,NORTHWICH, CHESHIRE

ISSN:0368-1645    

DOI:10.1039/CT9140500368

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

380 NEWBERY : UNSTARLE COMPOUNDS OFXLI.- Unstable Compounds of Cholesterol withBarium Methoxide.By EDGAR NEWBERY.A METHOD for extracting cholesterol and cerebrone from brain byboiling with a methyl-alcoholic solution of barium hydroxide,evaporaking ta ,dryness, and extracting the dry material with anorganic solvent, has long been in use in the Chemical and Patho-logical Departments of the Manchester Un.iversity (compare Smithand Mair, J . Path. Bacf., 1910, 15, 122, and Lapworth, ibid.,1911, 15, 254).Professor Lapworth, using this method, found that with excessof baryta the cholesterol was extracted by ether in a Soxhletapparatue only with great difficulty; but if the excess of baryta *had been destroyed by a stream of carbon dioxide, or by additionof acetic acid before removal of methyl alcohol in the first instance,then the cholesterol was extracted from the dry residue with greatfacility.The work described in the present paper was undertaken witha view to ascertain, if possible, the cause of this retention of thecholest er 01.Cholesterol was carefully purified by repeated crystallisationfrom methyl alcohol, acetone, and ether, dried thoroughly, and asolution in ether made up containing 0.01 gram of dry cholesterolin 1 C.C.Definite volumes of this solution were measured out foreach experibent, and the ether distilled off, thus ensuring thepresence of a, pure substance free from the hydrated compound.Experiments were first performed t o determine the conditionsunder which cholesterol is taken up by baryta.Series I.-All the evidence collected pointed to the conclusionthat solid barium oxide, hydroxide, or methoxide added t o asolution of cholesterol in ether does not absorb any appreciablequantity of cholesterol, and consequently that the solid baryta andcholesterol must previously have been in solution together beforethe influence of the former on the solubility of the latter becomesappreciable.Subsequent investigations were therefore confined tocases where this condition was fulfilled. Since methyl alcohol isthe only available liquid capable of dissolving both solids, it wasused in all the operations described hereafter.Series IZ.-In these experiments 1-25 grams of barium hydr-* Throughout this paper, the word ‘ I bnryta ” is used where i t is doubtful if theoxide, hydroxide, methoxide, or cholesterol compound is the active agentCHOLESTEROL WITH BARIUM METHOXIDE.381oxide, or its equivalent of barium oxide, dissolved in methyl alcoholwas added to 0.25 gram of cholesterol, and the solvent subse-quently evaporated. Consistency in the weights of solids used wassecured by employing standard solutions of both, dry ether beingused as a solvent for the cholmterol, and evaporated off beforeaddition of baryta.(i) I n the first experiment of this series the dried cholesterol-baryta mixture was covered with 60 C.C. of ether, the whole boiled formeasure$ periods of time, and cooled, when 10 C.C. of the clear,supernatant solution were removed with a pipette and evaporatedto dryness on the steam-bath, with the following results:(a) The solution attained a definite concentration of 1-95 gramsof cholesterol per litre after ten minutes a t the boiling point, andfurther boiling for two hours did not appreciably affect this.(b) On pouring off the bulk of the residual ether, and replacingit by 30 C.C.of fresh ether, a steady state was again attained, butthe concentration of cholesterol was higher than before, namely,2-30 grams per litre.( c ) On repeating the last process three times with successivequantities of 30 C.C. of ether, the steady concentrations attainedwere successively 1.7, 1.0, and 0.4 grams per litre.The results of this experiment are represented by curve A *(ii) An attempt was made to repeat experiment I1 (i), usingboiling benzene as solvent, but after ten minutes' boiling 0.24 gram,or roughly 96 per cent., of the cholesterol had been dissolved fromthe solid.(iii) Experiment I1 (i) was repeated with benzene at 25O anda.t 3 5 O , but it was found that extraction was very slow; twelvehours a t 3 5 O and at least a week a t 2 5 O elapsed before a stcadystate was attained.The results of the successive extractions areshown in Fig. 3.(iv) I n continuation of 11 (ii) above, experiments were made t oascertain whether the cholesterol removed at 80° was re-absorbeda t 25O. The results showed that no appreciable re-absorption tookplace.Series ZII.-Conditions under which Equilibrium is A ttained.Re-absorption of Cholesterol by the Ezhausted Residue.-(i) !Thefirst evidence of reverse action was obtained in the following way:A cholesterol-baryta mixture, prepared as before, was extractedfrom 60 C.C. of boiling ether, followed by five successive lots of* I n these curves, Figs. 1, 2, and 3, the abscise represent the combinedvolunies of the solvent used ; and the ordinates, the concentration of thecholesterol solution in grams per litre.Fig. 4 illustrates the influence of tempera-ture on the qllantity extracted hy 60 C.C. of ether382 NEWBERY: UNSTABLE COMPOUNDS 01'30 C.C. each, fifteen minutes being allowed for each extraction. Bythis means 0'226 gram out of 0.25 gram was extracted at constanttemperature 35O. This weight, 0-226 gram of cholesterol, wasthen dissolved in 60 C.C.of ether and the solution added to theresidue in the flask, thus giving a more concentrated solution thanhad previously been in contact with the baryta. After remaininga t 3 5 O for twenty-four hours, boiling twenty minutes, remaininganother eighteen hours, and again boiling twenty minutes, cooling,B2.01 *o0.0Volunze of ether w e d i ? ~ C.C.0 60 120 180 240 300 360I 2.0 j0 60 120 180 240 300 3609.3 *O'2.01 '00 60 120 180 240 300 360Yoltbmc of ether used in C.C.c u s 0.0 1 I0" 10" 20' 30" 40Volume of beiizene used in O.C. Temperature.and decanting, it was found that the 0.226 gram of cholesterol insolution had been reduced t o 0.205 gram. Boiling again underthe same conditions for twenty-five hours further reduced this to0.186 gram, indicating that 0.040 gram had been re-absorbed bythe solid.Further boiling for twenty-four hours produced noappreciable change of concentration.To test the accuracy of the observations, the solid residue wastreated with diluLe hydrochloric acid, and the liberated cholesteroCHOLES fEROL WITH BARIUM METHOXIDE. 383was recovered with ether and weighed. 0.064 Gram was present,showing an increase of 0*040 gram on that present a t the beginningof the reverse ” experiment.From this it appears that re-absorption does, in fact, take place,but very much more slowly than does the direct action.(ii) A similar experiment was conducted with benzene a t 3 5 Oin place of ether. Out. of a total of 0.162 gram of cholesterolextracted and then retizriied t o the mixture, with 60 C.C.ofbenzene, after remaining with frequent shaking f o r two days,0.024 gram was re-absorbed by the solid; after five days, 0.032graln; and after six weeks, 0.036 gram.Series IV.-Effect of Extent of Desiccation. of Solid.-In carry-ing out the above experiments, a solution of cholesterol with barytain methyl alcohol was in each case evaporated t o dryness beforeextracting with ether or benzene.This operation of drying the mixture was extremely difficult tocarry out efficiently without decomposing the cholesterol, andfurther experiment showed that the curves obtained were greatlymodified by more thorough drying.(i) When the methyl alcohol was boiled off in a flask on asteam-bath, and pure dry air passed over for five minutes, curve Awas obtained.(ii) When the mixture, after treating as in (i), was further driedin a vacuum for half-an-hour, curve B was obtained.(iii) On drying further a t looo in a stream of pure dry air,exhausting, and filling with pure dry air thirty times, and keepingin a vacuum for three hours, curve C was obtained.(iv) Still more careful drying led to curve D.It was also found that the more careful the drying the greaterwas the time necessary to attain constant concentration in theether solution, an hour’s boiling being needed in extreme casesin place of the ten minutes in the first experiments.From this i t is evident that the presence of water or methylalcohol profoundly affects the state of equilibrium attained in thesupernatant solution.(v) To determine the influence of water a solution was made ofanhydrous barium oxide in dry methyl alcohol, sodium-dried etherbeing used for extracting, and the same precautions taken to drythe baryta-cholesterol mixture as f o r experiment IV (iii).Theresults are illustrated by curve E.(vi) This was so different from what, had been expected that theexperiment was repeated, ab iizitio ; still more stringent precautionswere taken in drying and removing adherent alcohol, the dryingprocess being continued until no change in weight occurred, whe384 NEWBERY : C7SSTAHI.E COMPOUSDS OFthe mixture was kept in an exhausted desiccator €or twenty-fourhours. Curve F illustrates the result of this experiment.Morethan two-thirds of the cholesterol was extracted in the firstoperation.The weighings in this experiment, taken primarily with theobject of proving the mixture incapable of further drying, showedalso that 0.248 gram of methyl alcohol was firmly retained by1.111 gram of barium oxide present. Since 0.232 gram of methylalcohol is required t o form the compound HO*Ba-O*CH, with1.111 grams of barium oxide, only 0.016 gram of free methylalcohol could possibly have been present, and even this was possiblynot free, but combined in the form of barium dimethoxide.(vii) To determine the effect of excess of water on the curves,1 C.C. of water was added to a carefully dried baryta-cholesterolmixture, prepared as before, and the mixture again well dried.The whole of the cholesterol was extracted a t once by the first lotof ether.The flask containing the mixture was weighed before and afterthe addition of water, and it was found that a loss of weight hadoccurred, doubtless due t o the decomposition of methoxide bywater.From this it is evident that the barium methoxide or dimeth-oxide is in some way responsible for the retention of the chole5tero1,and the decomposition of this barium compound by water, orcarbon dioxide, as in Lapworth's experiments, sets free all thecholesterol.It would thus appear that the absen,a of water andthe presence of methyl alcohol are the two most important condi-tions for preventing extraction of the cholesterol.This conclusion was fully justiiied by the following experi-ments :Serzes Tr.-(i) A baryta-cholesterol mixture was prepared asbefore, using anhydrous barium oxide in dry methyl alcohol, butthis time was left visibly moist with methyl alcohol.The extraction curve G was obtained.On adding ether (60 c.c.)and boiling for five minutes, the concentration of the solutionbecame constant a t 0.4 gram per litre, and did not rise abovethis when boiled for three hours further, although the solubilityof cholesterol in ether a t this temperature is five'hundred times asgreat as this concentration suggests.I n the earlier stages of the work an unsuccessful attempt wasmade to absorb cholesterol from an ethereal solution by meansof baryta which had been diMolved in methyl alcohol and evapor-ated to dryness.I n the light of the last two experiments, thCHOLESTEROI, WITH BARIUM METHOXIDE. 385attempt would have succeeded i f water had been excluded andexcess of methyl alcohol had been present.This conclusion again was justified by experiment as follows:(ii) A solution of anhydrous barium oxide in dry methyl alcoholwas evaporated nearly to dryness, but left visibly moist with thealcohol. Sixty C.C. of ether containing 0.25 gram of cholesterolwere then added, and the solution was boiled gently for twelvehours. After remaining a t 1 5 O for a further twelve hours, it wasfound that more than half (0.138 gram) of the cholesterol had beenremoved from the solution by the solid. With further boiling theconcentration of the solution was again slightly diminished, show-ing that equilibrium was not fully attained in twenty-four hoursunder theae favourable conditions.From the foregoing data i t may confidently be inferred thatbarium methoxide forms a more or less definite solid compoundwith cholesterol, which is quite stable only in presence of excessof methyl alcohol.The horizontal sections of curves C, D, and Gsuggest the presence of a solid two-phase system, which probablyconsists of the solid compound, with its dissociation product,barium methoxide, above which there is a definite concentration ofcholesterol.The right-hand end of the horizontal section would thus corre-spond with the disappearance of the solid compound, whilst thegradually descending section of the curve is probably characteristicof an adsorption of cholesterol by barium oxide or methoxide orboth.The initial rising sections of €he cnrves are probably associatedwith the removal of the stabilising excess of methyl alcohol; theform of this section also suggests that adsorption of methyl alcoholoccurs, and may correspond with a three-phase solid system of solidcompound, barium methoxide, and a solid or solid solution whichcontains adsorbed or dissolved methyl alcohol.Summary and Conclusions.( a ) Under certain conditions, Smith and Mair’s original methodfor extracting cholesterol from brain matter may either fail toyield all the cholesterol or require an excessive time and quantityof solvent to remove it.The conditions are:(1) Presence of methyl alcohol in excess.(2) Low temperature of extraction (see Fig. 4).(3) Absence of water and other substances capable of decom-The reason for the difficulty of extraction appears t o be theposing barium methoxide386 DAWSON AND MARSHALL: THE REACTIONformation of a compound or possibly a series of compounds ofbarium methoxide with cholesterol.( b ) Cholesterol is not singular in the above respects, as hexadecylalcohol has been found to behave in a similar way.I n conclusion, thO author desires to express his thanks toProfessor Lapworth fcr suggesting this work, and for the interesthe has taken in its progress.THE CHEMICAL TARORATORIES,UNIVERSITY OF MANCHESTER

ISSN:0368-1645    

DOI:10.1039/CT9140500380

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

386 DAWSON AND MARSHALL: THE REACTIONX LIL-- The Reaction Bettoem Iodine and AliphaticAldehydes.By HARRY MEDFORTH DAWSON and JOSEPH MARSHALL.THE only account of experiments on the action of iodine in ali-phatic aldehydes was published in 1889 by P. Chautard (An?L.Chim. Phys., 1889, [vi], 16, 656), and a r6sum6 of Chautard’sresults is necessary to explain our re-investigation of this reaction.This observer obtained monoiodo-substituted aldehydes by allowingiodine and iodic acid to remain in contact with a dilute alcoholicsolution of an aldehyde for some time a t the ordinary temperature,and he was unable to obtain further substitution by increasing theproportion of iodine and iodic acid reacting with the aldehyde.The monoiodo-aldehydes were unstable substances, which could notbe distilled without decomposition, and of those which he described,the iodopropionaldehyde was the most stable.With regard t otheir constitutioiz, Chautard makes certain statements which seemto us to be of considerable interest. There can be 110 question ofthe constitution of a mono-substituted acetaldehyde, but the caseis, of course, different with the higher aldehydes. Chautard statesthat on boiling iodopropaldehyde with dilute nitric acid, it isconverted into @-iodopropionic acid, melting at 8Z0, and he con-cludes that the aldehyde is, therefore, the P-compound,CH,I*CH,*CHO.I n the case of iodoisobutyraldehyde, Chautard was unable to isolateany @-iodobutyric acid from the products of oxidation, but lieassumed that the iodobutyralhhyde is also a @-compound, namely,CH,-CH(CH,Ih *CHO.Further, Chautard obtained an iodovaler-aldehyde which, from analogy t o a chlorine derivative described byPopoff and Pavleski (Ber., 1576, 9, 1606), he assumes is theBETWEEN IODINE AND ALIPHATIC ALDEHYDES. 387a-derivative, CH(CH,),*CHI*CHO, and in the case of heptalde-hyde he assigns to the iodine derivative the formula(‘sous toutes r8serves.”Apart from the fact that Chautard assigns formulze to twoiodoaldehydes which show them to be a-derivatives, whilst intwo more cases he assigns formulae showing them to be 8-deriv-atives, it seemed of interest to us to re-investigate the question,since the production of 8-substituted derivatives would bedifficult to reconcile with a theory of substitution analogousto that adopted by one of the authors in the case of the actionof a halogen on an aliphatic ketone (T., 1909, 95, 1860). I nthis reaction, it is assumed that the ketone changes into itstautomeric enolic form, and that then a molecule of halogen isadded on a t the double linking.Finally, the elimination of amolecule of halogen acid results in the formation of the substitu-tion product, which must necessarily have the halogen atomattached to the a-carbon atom. A scheme showing this series ofreactions would be:CH,*[CH,],*CHI*CHOR-CO*CH, + R*C(OH):CH, -+ R*C(OH)X*CH,X +R*CO*CH,X(where X = halogen).Since Chautard described iodopropaldeliyde as the most stable ofthe iodo-aldehydes which he prepared, and was the only one inwhich he carried out experiments to determine the constitution ofthe substance, it was decided to investigate this aldshyde.Thirty grams of propaldehyde were mixed with 85 C.C.of 90 percent. alcohol, after which 41.5 grams of iodine were added, andfinally 16.5 grams of iodic acid. The mixture was allowed toremain, with frequent shaking, a t a temperature of from 1 8 O to20° for about fourteen days. After this period the solid iodineand iodic acid had disappeared, and the mixture was of a darkbrown colour. Water was added, and the heavy oil which was thusprecipitated was separated, washed with very dilute sodium car-bonate solution, and finally dehydrated over sodium sulphate.The iodo-aldehyde, contrary to Chautard’s statement, can bedistilled under diminished pressure, and was obtained as an almostcolourless liquid, boiling a t 83--84O/17 mm.I n one experimentthe yield was more than 30 grams, but in most cases only about15 grams of iodo-aldehyde were obtained from 30 grams of prop-aldehyde. The iodo-aldehyde was boiled with dilute nitric acid(1HNO3:4H,O) under reflux until iodine began to separabe, anda clear solution had been obtained. On cooling, the liquid wasfiltered and extracted with ether. The ethereal extract was washe388 REACTION BETWEEN IODINE AND ALIPHATIC ALDEHYDES.with dilute sodium carbonate solution in order to remove the acidfrom any unchanged aldehyde. After acidifying the alkalinesolution, it was extracted with ether, and subsequently, afterdehydration of the solution, the ether was removed by heating ina vacuum on a water-bath.The residual oil was allowed to remainfor several days in the ice-chest, but no crystallisation occurred,although a trace of /3-iodopropionic acid was added t o induce crys-tallisation. This oil was completely soluble in dilute ammonia ordilute sodium carbonate solution, but it was not very soluble inwater. After boiling the acid with dilute sodium carbonate solu-tion, cooling, and acidifying with dilute nitric acid, the additionof silver nitrate solution caused the precipitation of silver iodide.This reaction was used as a means of identifying the acid, whichwas boiled with sodium carbonate solution, acidified, and extractedwith ether.The liquid remaining after the removal of the etherwas identified as lactdc acid. It gave carbon monoxide when itwas heated with concentrated sulphuric acid, whilst boiling withthe dilute acid 1iberat.ed acetaldehyde and formic acid. The zincsalt was obtained and compared with zinc lactate, and was foundt o be identical.There can be no doubt, then, that the product of the action ofiodine on propionaldehyde is a-iodopropaldehyde.9 reaction which is described in Chautard’s memoir (Zoc. c i t . ) isthat of silver acetate on the iodo-aldehydes. Instead of obtainingthe acetyl derivatives of the hydroxy-aldehydes as would beexpected, Chautard claims t o have obtained the acetate of thealcohol corresponding with the aldehyde with which he was experi-menting; for instance, by allowing silver acetate to react withiodoacetaldehyde, he obtained ethyl acetate, whilst in a similarmanner from iodopropaldehyde, isopropyl acetate was produced.Chautard makes no attempt to explain the mechanism of thisreaction, and without attempting to do so, we think that theassumption is justified that the acetyl group would attach itselfto that carbon atom of the aldehyde t o which the iodine atom waspreviously linked.I n that case, accepting Chautard’s statementthat his iodopropaldehyde was the 8-derivative, he should haveobtained n-propyl acetate by the action of silver acetate, whereashe actually obtained isopropyl acetate.For thispurpose, iodoacetaldehyde was made according to Chautard’smethod.The reaction product was poured into water, andextracted with ether (free from alcohol). The ethereal solution wasdecolorised by washing with sodium thiosulphate solution, and,after dehydration, it was boiled under reflux on the water-bathIt seemed desirable, therefore, to repeat this reactionWATSON AND SEN: DYES DERIVED FROM QUERCETIN. 389with exces of silver acetate, until no appreciable amount of iodinewas left in the ethereal solution. The silver iodide was filtered off,the ether distilled off on a water-bath, and heating on the water-bath was continued until nothing further distilled. The tempera,ture of the yapour did not rise above 53*, so that no ethyl acetatecould have been present, a result which had been expected fromthe absence of the slightest odour of this substance. The residueleft after the evaporation of the ether was a yellow, viscous liquid,which distilled in a vacuum when heated on a water-bath, and i tdistilled a t the atmospheric pressure between 1 0 8 O and 1 1 2 O .The distillate was a colourless liquid with a pungent odour, butthis may have been due to the presence of a trace of unchangediodoacetaldehyde, as a little iodine was found in it. This liquidgave all the reactions of an aldehyde, and when heated with absolutealcohol and a little concentrated sulphuric acid, the odour of ethylacetate was observed.The phenylhydrazone was obtained as a faintly yellow substance,readily soluble in alcohol or ether, but not very soluble in lightpetroleum, and it melted a t 128O. Although no analysis was madeof the substance, there is every reason to assume, that the reactionbetween the iodo-aldehyde and silver acetate proceeds quitenormally, instead of abnormally, as stated by Chautard.THE UNIVERSITT, LEEDS

ISSN:0368-1645    

DOI:10.1039/CT9140500386

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

WATSON AND SEN: DYES DERIVED FROM QUERCETIN. 389XLI11.-D!yes Derived from Quercetin.By EDWIN ROY WATSON and KUMUD BEHARI SEN.IN a previous paper by one of us (this vol., p. 338) there isdescribed the introduction of an amino-group into the quercetinmolecule, which was effected with the object of deepening thecolour of the dye. The arriino-group did not, however, p.roducemuch effect in this direction. The present paper contains anaccount of further work with the object of preparing quercetinderivatives which would dye deep shades. This object has now beensatisfactorily attained.The methods adopted with the object of deepening the colourmay be classified as follows:(1) The introduction of bathychrome groups.(2) The introduction of additional auxochrome groups.(3) The introduction of additional chromophores390 WATSON AND SEN : DYES DERIVED FHOX QUERCETIN.(4) Modification of the molecule so as t o satisfy the conditionsrequired by a theory proposed by one of us (P., 1913, 29, 348),namely, thah the molecule should be quinonoid in all possibletautomeric forms.(1) The bntroduction of Bnthychrome Groups.-As 6/-nitro-quercetinpentamethyl ether had already been prepared (Zoc.cit.),an attempt was made to demethylate it, and so obtain 6I-nitro-quercetin. Only partial demethylation has been satisfactorilyaccomplished with the production of 61-nitroquercetin dimethylether, which on acetylation gives the triacetate. The formersubstance dissolves in aqueous potassium hydroxide t o a reddish-brown solution, and consequently as a dye has no special interest.(2) The Introduction 0,’ Additionat Auxochrome Groups.-Nothing further in this direction has been accomplished.Nieren-stein and Wheldale (Ber., 1911, 44, 3487) have described thepreparation of 8-hydroxyquercetinY which, however, dyes practi-cally the same shades as quercetin. Quercetinsulphonic acid hasbeen prepared with the object of subsequently converting it intothiolquercetin, but this object has not been attained. Attemptsto replace the br0mic.e atoms in mono- and di-bromoquercetinpentamethyl ether by anilino-groups did not succeed.(3) The Ivitroduction of Additional Chromophores.-Naphthol-azoquercetin dimethyl ether has been obtained by the partialdemethylation of the corrwponding pentamethyl ether, previouslydescribed.It dyes maroon shades on alum-mordanted cotton.Triacetylpercetin, obtained by the action of anhydrous aluminiumchloride on quercetin penta-acetate, contains four chromnphoree(ketonic groups), but has no deeper colour than quercetin. Bysimilarly heating puercetin perhtachloroacetate with anhydrousaluminium chloride there is obtained a chlorine-free substance, ofwhich the acetyl derivative melts at 248-250°, and which isevidently a hydroxyfurano-derivative of quercetin. This has muchthe same colour as the original dye. From a similar treatment ofpuercetin tribenzoate no crystalline substance could be isolated,the amorphous product showing again no deeper colour.(4) It was thought that if the pyrone ketponic group could bereplaced by the group CR-OH, the resulting compound wouldbehave like the dyes of the triphenylcarbinol series, namely, losea molecule of water and become permanently quinmoid with nopossibility of tautomerising into a non-quinonoid form, and thatthis should result in a deepening of the colour.This anticipationhas been realised in several ways. 3 : 4 : 5 : 7-Tetrahyd~oxy-2-m-p-dihydroxyphemgl-1 : 4-benzopyran has been obtained by the reduc-tion of quercetin by sodium amalgam, preferably in alcoholiWATSON AND SEN: DYES DERIVED FROM QUERCETIN. 391hydrochloric acid solution. It had been already prepared byHlasiwetz and Pfaundler ( J . pr. Chem., 1864, 94, 85)) but theseinvestigators neither analysed it nor recognised its constitution.It dissolves in alcohol with a magenta colour, and in aqueouspotassium hydroxide t o a green solution, but is so readily oxidisedt o quercetin that it is useless as a dye.By the action of dimethyl-aniline on quercetin in the presence of phosphoryl chloride thereis obtained a substance which dyes slaty-blue shades, the analysisof which agrees with 3 : Ei-dihydroxy-7-keto-4-p-cEi~nethylamino-ph e ny l-2 -m- p-di h y drox y p h 4-b enzo pyran,0 OHExperiments have also been made to prepare the same substancethrough the methyl ether. The action of phosphorus pentachlorideon quercetin pentamethyl ether gives a white, crystalline substance,C,,H2,,0,C16, which must be regarded ils 4-chloro-4-hydroxy-3 : 5 : 7-trimethoxy-2Lm-p-~i~ethoxy~~~~e?~yZ-~ : 4-h enzopyi-an, but attemptst o replace the chlorine atom by the action of dimethylaniline andother reagents have been unsuccessful.With hydriodic acid(D 1.7) quercetin is produced. By the action of Grignard's reagent(magnesium ethyl iodide) on quercetin pentaethyl ether there isobtaified the crimson oxonium salt 3 : 5 : 7-triethoxy-2-m-p-diethozy-phenfyk-4-ethyl-l : 4-h enzopyran anhydroh.ydriodide (I), which on01 OEt 01 OHde-ethylatiori by hydriodic acid is converted into the crimson3 : 5 : 7-t?~h,~cFroxy-2-rn-p-cEihydroxy~henyI-4-etkyl-l: 4-benzopyram an-hydrohydriodide (11). The corresponding base, liberated by sodiumacetate, dissolves in alcohol with a magenta colour, in aqueouspotassium hydroxide to a, deep blue solution, and dyes wool violet(on alum and chrome) and crimson (on tin).By the preparationof this substance the object of the present investigation has beensatisfactorily attained. It indicates a general method, which maybe of very great value, for the preparation of dyes of deep colourby the action of metallo-organic compounds on the ethers ofhydroxy-ketonic dyes392 WATSON AND SEN : DYES DERIVED FROM QUERCE'I'IX.I n the course of this work the following compounds have alsobeen obtained :2-Iiydroxy-3 : 5 : 7-trimethoxy-l : 4-benzopyro.ne, by the action ofcliromic acid on 6'-nitroquercetin pentamethyl ether ; the oxoniumsidphate, chloride, and bromide of monobromoquercetin penta-methyl ether; and an oxonium compound of methyl sulphate andquercetin pentamethyl ether, C20H2007,( CH,),SO,, isolated insmall quantity during the preparation of quercetin pentamethylether.The latter compound seems of interest in connexion withthe question of the constitution of oxonium salts. It has the samebright yellow colour as the other oxonium salts of quercetin penta-methyl ether already described (Zoc. cit.), and therefore should beassigned a similar quinonoid structure. The possibilities wouldseem t o be:0,Rle0 OMe 0 OMeMe S0,Me\/0 OMebut the first two formulae would aesume complete splitting of themethyl sulphate molecule, and the attachment of the methyl andS0,Me groups at distant parts of the molecule-an assumptionwhich seems scarcely consistent with the ready regeneration ofmethyl sulphate on treatment of the oxonium compound withwater; whilst the last formula is similar to those assigned t o theoxonium salts of dimethyl-4-pyrone, which are colourless.EXPERIMENTAL,6/-.Xitropuerceti.n Dime th y l E t h e r , CI5H4O2( OH),(O*CH,),*N02.For the preparation of this substance nitroquercetin pentamethylether was quickly powdered with its own weight of anhydrousaluminium chloride, and heated for one hour a t 160° in a flaskfitted with a cork and delivery-tube, the latter dipping undermercury so that the mixture could not attract moisture from theair.The product ww added gradually to dilute hydrochloric acid,collected, washed, dried, and crystallised from glacial acetic acid. IWATSON AND SEN: DYES DERIVED FROM QUERCETIN.393was obtained in yellow, needle-shaped crystals, melting a t 240°,readily soluble in acetone, only very moderately so in alcohol orbenzene, and soluble in aqueous potassium hydroxide with areddish-brown colour. For the removal of a trace of alumina it wasconverted into i b acetyl derivative, which was subsequently hydro-lysed :0.1045 gave 0-2080 CO, and 0-0341 H20. C=54.28; H=3.61.Cl7IIl3O,N requires C = 54-40 ; H = 3-46 per cent.The triace ta t e, C15H402( OAC)~( 0 CH3),*N02, was prepared byboiling the above compound with acetic anhydride and a trace ofpyridine for half-an-hour, cooling the solution, and adding alcohol,when the acetyl derivative was gradually deposited in white, oralmost white, lozenge-shaped crystals, melting at 206O :0.1080 gave 0-2190 CO, and 0.0371 H20.C=55-30; H=3.81.C23€I,,012N requires C= 55.09 ; H = 3.79 per cent.Qwercetinsulphonic Acid, C,,H,O,*SO,H.One gram of finely-powdered quercetin was gradually added to4 C.C. of sulphuric acid, and the mixture heated on the water-bathfor one or two hours. The yuercetin dimolved almost completely,and the sulphonic acid was deposited in fine crystals. After themixture had remained for some time, the sulphonic acid wasseparated by an asbestos filter, dried on a porous tile, washed withglacial acetic acid (in which i t is insoluble), and recrystallisedfrom water. It was thus obtained in yellow, needle-shaped crystals,which redden on drying over soda-lime, and become browner onheating to 1 4 0 O .It is readily soluble in water :0.1158 *gave 0.1999 CO, and 0.0298 H20. C=47.07 ; H =2-84.0*2233-E ,, 0.1291 BaSO,. S-7.94.0.2721 t lost il.2282 at. 140O. H20 = 16.23.C,,H,,O,,S requires C = 47.13 ; H = 2-61 ; X=8*37 per cent.C,,H,,010S,4H,0 requires H20 = 15.85 per cent.The sodium salt, C,,H4O2(0H),(ONa)*SO3Na, wits obtained as abright yellow, amorphous precipitate on adding an alcoholicsolution of fused sodium acetate to the sulphonic acid in the samesolvent. On drying it became green:0.2520 * gave 0.0853 Na2S04.N a p h t h ola t o q uer c e tin, dime t h y 1 e the r,Na= 10.97.C",,H801,SN~ requires Na = 10.80 per cent.C,,H,O,(OH),( O*CH3)2*N2*C,&&*OH,was obtained by heating the corresponding pentamethyl ether withits own weight of anhydraus aluminium chloride at 200° for one* Dried a t 140". t Air-driecl.VOL.cv. D 394 WATSON AND SEN : DYRS IIER1VE:D FROM QWERCETIN.hour. The product was gradually added to dilute hydrochloricacid, and the mixture was afterwards boiled. I n order to removeall alumina, the substance, after collecting and drying, was dis-solved in cold sulphuric acid, and precipitated by pouring thesolution into water. It was purified by solution in acetic acid, butcould not be obtained crystalline. Several preparations, however,all melted sharply at 242O. The substance has dyeing properties,and gave a maroon shade on alum-mordanted wool. It dissolvm inalkali with a red colour, and in cold sulphuric acid to an indigo-blue solution :0.1028 gave 0.2435 GO, aiicl 0.0383 H%O.@=64*50; H=4*14.C,,H200,N, requires C= 64.80 ; H = 4.00 per cent.I'riacet~lty.irercet,irL, C,,H20,(0H),Ac,,Eight grams of quercetin penta-acetate were mixed with twicethe weight of anhydrous aluminium chloride, and heated for onehour a t 1 6 0 O . The product was carefully added to dilutehydrochloric acid, and the mixture boiled for five minutes. Theinsoluble substance was collected, washed, dried (5 grams wereobtained), and puri lied by acetylating, recrystallising the acetylderivative, and subsequently hydrolysing. The product thusobtained cons'sted of yellow, needle-shaped crystals, was verysimilar to quercetin in appearance, and melted at about 300O. Itdissolved in aqueous potassium hydroxide with a yellow colour, andwas only sparingly soluble in alcohol, It formed no oxoniumsulphate. With boiling alcoholic sodium acetate solution a sodiumsalt, C21H1,0,,Na, was produced, which separated on cooling as ayellow, gelatinous precipitate, subsequently changing to needle-shaped crystals :O * l l ' i O gave 0.2521 CO, and 0.0420 H20.C=58*70; H-3.98.C2,H16010 requires O= 58.90 ; H = 3.74 per cent.Trince tylpuerce tin Yenta-ace tat e, C,,H20,(0Ac),Ac,.The 5 grams of crude triacetylquercetin above mentioned wereacetylated by boiling with acetic anhydride and a few drops ofpyridine, and on adding alcohol to the solution the penta-acetatewas slowly deposited in minute crystals. After three weeks3-7 grams were obtained. It was purified by crystallisation froniglacial acetic acid, and obtained in pale yellow, needle-shapedcrystals, melting at 208-211° :0.1303 gave 0.2789 CO, and 0.0482 H,O.C=58-37; H=4*10.c31H26015 requires C = 58.30 ; H = 4-07 per centWATSON AND SEN: DYES DERIVED FROM QUERCETIN. 3950.4934, on hydrolysis, gave 0.3343 triacetylquercetin = 67.7 percent.C21Hl105(OAc), requires 67.1 per cent.Quercetin pentachloroacetate, C,,H50,(O~CO*CH,C1),, was ob-tained by heating a t 135-140° for fifteen minutea a mixture ofchloroacetic anhydride and quercetin in the presence of a trace ofpyridine. On adding alcohol to the mixture i t was deposited inwhite, needle-shaped crystals, melting a t 180° :0.2625 gave 0*2721 RgCl.C25H150&15 requires C1= 25.93 per cent.Previous attempts to prepare this substance by the action ofchloroacetyl chloride on quercetin were unsuccessful. I n the pre-paration described, it is very necessary not to let the temperaturerise too high.On heating with anhydrous aluminium chloride it is convertedinto a hydroxyfurano-derivative of quercetin, which has a yellowcolour, and dissolves in aqueous potassium hydroxide t o a brownish-yellow solution.This gives an acetyl derivative, crystallising inwhite needles from alcohol and acetic acid, which melts a t248-250°, and contains no chlorine.Quercetin tribenzoate, C,,H502(0H)2(0*CO-C,H5)3, was obtained(1) by the Schotten Baumann method, and (2) by heating quer-cetin with excess of benzoic anhydride at 190-200° for two hours.I n the latter case alcohol was added to the mixture after cooling,and the precipitated substance was recrystallised, first from itmixture of nitrobenzene and alcohol, and then from acetone. Thelat'ter solvent deposits it in almost white needles, melting a t 173O:0.1258 gave 0.3221 CO, and 0.0428 H,O.C=69*82; H=3-78.C3tiIT22010 requires C = 70.30 ; H = 3-58 per cent.The product obtained by heating this substance with anhydrousaluminium chloride (benzoylquercetin 1 ) was yellow, and dissolvedin aqueous potassium hydroxide to a brownish-yellow solution.Neither it nor its acetyl derivative hm been obtained crystalline.C1= 25.63.3 : 4 : 5 ; 7-I'ctrahydroxy-2-m-p-dihya?roxyphenyl-l; 4-benzopyran,One gram of quercetin was dissolved in 40 C.C. of warm alcoholand 2 C.C.of concentrated hydrochloric acid, and the theoreticalquantity of sodium amalgam added. The mixture was kept agitatedand warm, and the solution at once became deep magenta coloured.After a time similar quantities of hydrochloric acid and sodiumamalgam were again added. The solution now showed strongabsorption from the yellow right into the ultra-violet portion ofC15H1207.D D 396 WATSON AND SEN: DYES DERIVED FROM QUERCETIN.the spectrum. The substance was precipitated by pouring thesolution into water, and when collected and dried on a porous tilepossessed a curious, pale purplish-green colour. It qrystallised freelyfrom alcohol in needles, but owing to the readiness with which itwas re-oxidised to quercetin i t could not be satisfactorily recrystal-lised.It was first dried in a vacuum, and finally in the steam-oven :0.1012 gave 0.2200 CO, and 0.0385 H,O.C,,H,,O, requires C = 59-21 ; H = 3-94 per cent.The same substance can be obtained by reduction in cold aqueousalkaline solution, but excess of sodium amalgam must be avoidedand the solution must be kept cold. It dissolves in alcohol witha magenta colour, and in aqueous alkali to a deep green solution.I n either solvent it is readily oxidised to quercetin, and on boilingwith acetic anhydride and a trace of pyridine there is obtainedonly quercetin penta-acetate.C=59.28 ; H =4*22.3 : 5 -Dihydroxy-7-k e to-4-p-dim e t h ylamirzo p h e nyL2-m-p-dihydro xy-phenyl-l : 4-b eizzolzyrait, C23N,,06N.One gram of quercetin was added gradually to a mixture of12 C.C.o€ diinethylaniline and 3 C.C. of phosphoryl chloride, andthe mixture was heated t o 120° for one hour. It wi~s then pouredinto water, excess of sodium acetate was added, and the mixtureevaporated with water several times to remove excess of dimethyl-aniline. The dark blue, insoluble substance was collected, washed,and treated with hot dilute hydrochloric acid, in which itnearly all dissolved to a maroon-coloured solution. The filteredsolution was treated with excess of sodium acetat'e, the darkblue precipitate collected, very thoroughly washed, dried on aporous tile over soda-lime, and finally extracted with ether t oremove any traces of dimethylaniline. The product thus obtainedis of a dark blue colour, only sparingly soluble in alcohol, with aviolet colour, moderately so in glacial acetic acid, dissolving morereadily in the dilute acid to a deep blue solution, and in hydro-chloric acid (concentrated or dilute) with a deep maroon colour.It does not melt a t 300° It dyes wool either mordanted withalum, chrome, tin, or iron, or unmordanted, in slaty-blue shades.I n order t o make certain that the product was not a mixture con-taining a little methyl-violet, obtained by the oxidation of dimethyl-aniline, t o which its tinctorial propertries might be due, a blankexperiment was performed by heating a mixture of dimethylanilineand phosphoryl chloride only, which gave no methyl-violet.More-over, the colour reactions of the dye on the fibre are quite differentfrom those of methyl-violet, especially the reactions with aciWATSON AND SEN: DYES DERIVED FROM QUERCETIN. 397(cherry-coloured with hydrochloric acid, reddish-brown with sul-phuric acid, reddish-orange spot with nitric acid) :0.1301 gave 0.3238 CO, and 0.0607 H,O.C = 67-87 ; H = 5-18.0.3560 ,, 12 C.C. N, (moist) a t 28O and 758 mm. N=3*69.C23H,,0,N requires C’- 68.14 ; H =4.69 ; N = 3-46 per cent.4-Chloro-4- Ji ydiw xy-3 : 5 : ‘7-trim e t hoxy -2-m-p-di i n e t Ji oxy phenyl-1 : 4-&enzopyran, C,,132,0,C1.Two grams of quercetin pentamethyl ether were mixed withabout half t,he volume of phosphorus pentachloride, and heatedin a sealed tube a t 145O for three hours. The contents of the tubebecame crimt;on and partly liquid.They were mixed with ether,and poured into ice and water. The ether was allowed t o evaporate,and the insoluble matter was collected, dried, and extracted withbenzene. The portion extracted by benzene was crystallised fromalcohol, and obtained in white or cream-coloured needla(0.8 gram). This substance is only moderately soluble in alcohol,and melts a t 220--222O, and appears to give oxonium salts:0.1052 gave 0.2277 CO, and 0.0456 H,O.0.2906 ,, 0.1035 AgC1. C1=8*80.On boiling with hydriodic acid (D 1.7) it is converted intoquercetin. Attempk to replace the chlorine atom by the action ofdimethylaniline, aniline, alcoholic ammonia, tin, and hydrochloricacid, zinc dust, and acetic acid and potassium cyanide were notsuccessful.C = 59.03 ; H = 4.81.C2,H2,10,C1 requires C = 58.75 ; H = 5.14 ; Cl = 8.69 per cent.3 : 5 : 7 - T r i e t l ~ o x y - 2 - m - p - d ~ e ~ l ~ o x ~ ~ ~ h e r ~ .y l - 4 - ~ ~ ~ ~ y l - l : 4-benzomrunA nhydrohydriodide, C,,H,,O,I.1.5 Grams (I mol.) of quercetin pentamethyl ether were dissolvedin dry ether, and to this solution was added Grignard’s reagent,prepared by dissolving 0.24 gram (3 mols.) of magnesium in1.6 grams (a little more than 3 mols.) of ethyl iodide in the presenceof dry ether. A pale yellow precipitate was produced, and thereaction was completed by heating the mixture on a water-bathfor four hours. The product was poured into dilute hydrochloricacid (1 : 20), when the pale yellow substance became crimson, theether was evaporated, and the insoluble matter was collected,washed, and dried on a tile. It crystallised from alcohol in crimsonneedles, melting at 169O.The yield was 1.5 grams:0-1181 gave 0.2399 CO, and 0.0642 H,O.0.3050 ,, 0.1251 AgI. 1=22.16.C = 55-40; H = 6.04.C,,H,O,I requires C’=55.66; H=6.01; I=21.82 per cent398 WATSON AND SEN: DYES DERIVED FROM QUERCETIN.3 : 5 : 7-Trihydroxy-2-rn-p-dihydroxyphenyl-4-ethyl-1 : 4-benzopyranAnhydrohydriodide, C,,II,,061,H20.One gram of the above substance was boiled for two hours with20 C.C. of hydriodic acid (D 1.7) and 10 C.C. of acetic anhydride,and the mixture, after cooling, was poured into 60 C.C. of waterand decolorised by the addition of a small amount of sodiumhydrogen sulphite. The new substance was thus obtained incrimson, needle-shaped crystals, somewhat soluble in water.Onthe addition of a few drops of alkali either to the aqueous or thealcoholic solution a blue coloration is produced :0.1048 gave 0.1709 CO, and 0.0376 H,O. C -44.47 ; H = 3-98.0.1992 ,, 0.1008 AgI. I=27*34.C,,Hli0,I requires C = 44.34 ; H = 3-69 ; I = 27.60 per cent.The colour-base was obtained as a dark violet solid, with ametallic-green reflex, by adding sodium acetate to the aqueoussolutiori of the Eydriodide. It dissolves in alcohol with a magentacolour, and dyes wool violet (on alum and chrome), crimson (ontin), and magenta when unmordanted.2-Hydroxy-3 : 5 : 'I-tri?nethozy-l : 4-b enzopyrone,C,H20,(0*CH,),*OH.A solution of chromic acid (2 grams) in glacial acetic acid(10 c.c.) was gradually added to a well-cooled solution of nitro-quercetin pentamethyl ether (1 gram) in the same solvent '(5 c.c.),and the mixture was allowed t o remain overnight.On pouring intowater, a colourless substance was precipitated, which crystallisedin needles on boiling the mixture. It was recrystallised fromalcohol, and melted a t 155-156O:0.1135 gavc0.2402 CO, and 0.0481 H,O.0.2151 ,, 0.6134 A@. OMe=37*01.Mo n o b om o qu erc e t i n penta m e t h yl e t h e r sulp ha t e,C=57.70; H=4*70.C12H1206 requires (2-57-14; H=4.76; OMe=36*91 per cent,~20H,,0,Br>H2SO,,was prepared by adding a few drops of sulphuric acid to a solutionof monobromoquercetin pentamethyl ether in glacial acetic acid.It was obtained in bright yellow, needleshaped crystals, whichcould be dried in the steam-oven without decomposition. A weighedquantity was decomposed by boiling water, and the, acid liberatedwas determined by titration of the filtrate :0.5041 required lS.6 C.C. N/lO-H,SO,.The hydrochloride, C,,H,,O7Br,HC1, was similarly obtained inH,SO,= 18.07.C20H,90iBr,H2S0, requires H,SO, = 17-35 per centCONDENSATION OF KETONES WITH PHENOLS. PART I. 399bright yellow, needle-shaped crystals, and was dried in a vacuumdesiccator over sodaJime :0.2161 required 4.3 C.C. N / 10-HC1. HC1= 7-26.C2,H,90,Br,HCl requires RCl= 7-48 per cent.Quercetii~ I’entametlhyl .Ether Bimethyl Sulphate,C ‘ 2 - p .(,q 7 (CH,), s 0,.I n the preparation of quercetin pentamethyl ether alreadydescribed (Zoc. c i t . ) the mixture obtained by rubbing the drypotassium salt of quercetin trimethyl ether with methyl sulphatewas first washed with ether t o remove excess of methyl sulphate.On several occasions it wits noticed that the ethereal solutiondeposited bright yellow, needle-shaped crystals as it spontaneouslyevaporated. This substance appears to consist of an oxoniumcompound of the above composition, for on boiling with water thecolour disappears; an oil possessing the odour of methyl sulphateis produced, and, on cooling, the solution gradually depositsquercetin pentamethyl ether :0.2334 gave 0.1147 BaSO,. S=6*74.CWH,,O7,(CH3),SO, requires S = 6-42 per cent.CHEMICAL LABORATORY, DACCA COLLEGE,DACCA, E. BEXGAL, INDIA

ISSN:0368-1645    

DOI:10.1039/CT9140500389

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

CONDENSATION OF KETONES WITH PHENOLS. PART I. 399XL I V.-- Co”iLdensatioiz of Ketones with Phenols. Part I.Condensation with a- Naphthol. *By HEMENDRA KUMAR SEN-GUPTA,THE condensation of ketones with phenols has already been investi-gated in some cases (Wittenberg, J . p. Chern., 1882, [ii], 26, 76;Dianin, J . Buss. Phys. Chem. SOC., 1891, 23, 488; Fabinyi andSzBki, Ber., 1905, 38, 2307; Zincke and Gaebel, Annnlen, 1912,388, 299), but no special study appears to have been made withreference to the influence exerted by substitmnts in the phenolson this type of condensation; further, the position of the linkingof thO carbonyl carbon with the phenols, particularly naphthols,has not yet been ascertained. The idea of elucidating the latterpoint led to the present investigation, and i t was hoped that by* For abstract, see P., 1913, 29, 29400 SEN-GUPTA : CONDENSATIOS O Foxidising the cmdensation products obtained from ketones anda-naphthol(E>CO + ZC,,H,*O 1 I = 1' ,:>C<Eloz">O + 2H2010 0naphthaxanthones of known constitution could be prepared, whichwould, therefore, settle the question in view.Instead, however, ofyielding a iiaphthaxanthone, the oxidation of the anhydrides of1 : 1-dihydroxydinaphthyldialkylmethanes gave rise t o two seriesof coloured, crystalline substances (P., 1913, 29, 382). The workdirectly bearing on the constitution of these being still in progress,and as final conclusions must depend on cumulative evidence basedon a large number of experiments, i t is proposed t o describe in thefollowing pages some new condensation products of a-naphtholwith ketones that have come t o be studied in this connexion.The only case of condensation of a-naphthol with a ketone thathas hitherto been described, is that with acetone.Dianin (Zoc c i t . )employed fuming hydrochloric acid (D 1.19) as the condensingagent, but in course of the present investigation i t has been foundthat phosphoryl chloride serves the purpose decidedly better. Theyield is subetantially improved, whilst the duration of the experi-ment is very much shor€ened, and the reaction can be conductedin an open vessel. The condensation products are obtained in theform of anhydrides, having the general formulaexcept in the case of cyclohexanone, which, in addition t o theusual type of compound, yields one having probably the constitu-tion * :(compare Zincke and Gaebel, Zoc.c i t . , p. 300). The production of* Schmidlin and Lang (Bor., 1910, 43, 2806) incidentally describe thcpreparation of a compound, C,,H,O, which they obtained by the action of coiicen-trated sulphuric acid on a mixture of a-naphthol and cyclohexanonp, and to whichthey attribute the constitution C H /C10H6)0. Their compound has nearly theI0\C,,H,same tnclting point (232") as that of th9 above siibstnnce (Zoc. cit.), but that i t hasnot the constitutioo assigned by thcm will appear from their aiialysis : '' 0.1183 gaveC0,=0*3636 ; H,O=O.0769 ; C=83.82 ; H=7.22 per cent." The correct nnmhwsfor C,H,O, however, are c'=89*15 ; H=6 28 per cent.It should be noted hcrethat aIthough they found the carbon about 2 per cent. lower than what is requiredby the compound CY2H3202, the percentage of hydrogen obtaiiied by them is inagreementKETONES WITH PHENOLS. PART I. 401this evidently poinix to the intermediate formation of chlorohydrinsin this type of reaction.The readiness with which this condensation takes place depends,in the first place, on the molecular weight of the ketones generally-the smaller the molecular weight, the more c a d y is the con-densation brought about. Exception, however, is met with inthe case of fluorenone, which condenses with a-naphthol as readilyas does acetone, although benzophenone gives a yield of 7 percent. only. Secondly, the nature of the carbon atoms in directunion with the carbonyl group seems to influence the condensation.Thus i t is found t h a t tertiary carbon atoms greatly inhibit it, asis seen in the typical case of camphorquinone, which condensesfairly readily with two molecules of phenol, cresol, or catechol(compare P., 1913, 29, 155), whereas under the same conditionsof experiment camphor itself does not undergo condensation.Thisis probably due, as stated above, to the tertiary carbon atom indirect linking with the carbonyl group of camphor, which, althoughpresent in camphorquinone, is there associated with another car-bony1 group in direct union with a secondary carbon atom.EXPERIMENTAL.The Anhydride of 6-1 : l-D,iA.ydroxydinaphthylpropana,A mixture of 28.8 grams of a-naphthol, 5.8 grams of acetone,and 2-3 C.C.of phosphoryl chloride wm heated a t looo f o r fiveminutes, when a brisk action occurred, a t the end of which theliquid set to a crystalline mms. To ensure complete reactionabout. 1 C.C. of acetone was further added, and the flask heatedanother five minutes. The crystalline mass was digested withalcohol, which dissolved out any unchanged a-naphthol and decom-posed the unchanged phosphoryl chloride, leaving the condensationproduct in a white, crystalline stab. The yield at this stageamounts to about 65 per cent. of the theoretical, and, on recrystal-lisation from alcohol, about 58 per cent. By Dianin’s method,using fuming hydrochloric acid as the condensing reagent, theyield scarcely exceeds 50 per cent. The substance crystallises inlustrous, quadratic plates, melting at 186O (as stated by Dianin).It is sparingly soluble in alcohol, readily so in acetone, chloroform,carbon disulphide, pyridine, or benzene.(Found, C = 89.4 ;H=5.86.The picrate, prepared in benzene solution, crystallises in darkred prisms, melting at 164-165O. It is soluble in most solvents;almost insoluble in ether:Calc. C=89*03; H=5.8 per cent.402 SEN-GUPTA : CONDENSATION OF0.2500 gave 17.4 C.C. N, at 18’5O and 744 mm. N-7.88.C~3H,80,C,H30,N3 requires N = 7.79 per cent.The dichloro-derivative, CHB>C<U10H5C1>0, CH, C,,,H,Ci was prepared bysaturating with dry chlorine a solution of the anhydride in carbontetrachloride.The solid residue left after expelling the solventwas crystallised twice from pyridine diluted with a few drops ofwater. It is very sparingly soluble in alcohol, readily so in carbondisulphide, chloroform, pyridine or acetone, and melts a t 262O :0.2264 gave 0.1680 AgCl. Cl= 18-32.C,,H,,OCI, requires C1= 18-73 per. cent.The diibronio-derivative was prepared by adding the requisitequantity of bromine dissolved in carbon disulphide to the anhydridealso dissolved in the same solvent. When the evolution of hydrogenbromide ceased, the carbon disulphide was expelled, and the residuecrystallised from pyridine diluted with a few drops of water. Itis sparingly soluble in alcohol or acetic acid, but readily so inacetone, carbon disulphide or pyridine.It crystallises in rhombicprisms, melting a t 287--289O :0.3374 gave 0-2675 AgBr. Br = 33.73.C,,H,60Br2 requires Br= 34.1 per cent.grams of the anhydride were suspended in about? 50 C.C. of glacialacetic acid, and the temperature kept below 5O; 3 C.C. of fumingnitric acid were next added drop by drop with constant shaking;towards the latter part of the addition of nitric acid, most ofthe nitro-compound separated from the solution. After allowingthe mixture to remain a t the ordinary temperature for about aquarter of an hour, the yellow precipitate was collected, washedseveral times with alcohol or water, and crystallised from boilingglacial acetic acid, from which it separates in long, yellow needles,melting at 225O. It is sparingly solubIe in almost all solvents,but dissolves readily in hot nitrobenzene or pyridine.It can befurther brominated or chlorinated, whilst the dinitro-derivativedescribed below cannot be further brominated at the ordinarytemperature :0.2615 gave 9.25 C.C. N, a t 16.8O and 746 mm. N=4*1.The Dinitro-derivative.-One part of the anhydride was dissolvedin 12 parts of glacial acetic acid by boiling. The solution wasallowed to cool to 80-90°, and 8 par& of fuming nitric acid wereadded. The mixture was allowed to remain at looo for about anhour. and then poured into water. The dinitro-derivative separ-C,,H,,O,N requires N = 3.94 per centKETONES WITH PHENOLS. PART I. 403abed in an almost theoretical yield. When crystallised from hotnitrobenzene, it is obtained in golden-yellow, prismatic needles,which remain unmelted a t 327O.It is sparingly soluble in theordinary solvents, more readily so in boiling acetone, carbondisulphide or pyridine :0.2758 gave 16.4 C.C. N, at 20° and 763 mm. N = 6-84,C,,H,,O,N, requires N = 7.0 per cent.The Anhydride of j3-1: 1-Dihydroxydinaphthylbutane,Three grams of methyl ethyl ketone and 14.4 grams of a-naphtholwere heated with 2 C.C. of phosphoryl chloride in an open flask forabout half an hour, when the contents solidified to a, crystallinemass. If, however, the phosphoryl chloride is added in excem, themas8 is usually pasty, but, on boiling with alcohol, a white, crystal-line residue is left behind which is almost pure. On crystallisationfrom glacial acetic acid, the compound separates in lustrous,rhombic or prismatic plates, melting a t 154-155O.The yield isabout 65 per cent. The solubility of the compound is analogousto its previous homologue:0.1168 gave 0.3803 CO, and 0.0639 H,O.0.6839, in 10.1244 naphthalene, gave At = - 1.452O. M.W. =C=88*87; H=6.07.330.3.C2,H,0 requires C=88.88; H=6*17 per cent. M.W.=324.The dichtloro-derivative prepared by direct chlorination crystal-lises from pyridine, diluted with a few drops of water, in small,colourless needles, melting at 221O :0.1664 gave 0.1244 AgCl. C1= 18.49.C,,H,,OC1, requires c1= 18.06 per cent.The dibromo-derivative crystallises from pyridine in plates,0.1802 gave 0.1420 AgBr. Br=33.5.The dinitro-derivative crystallises from glacial acetic acid in0.1986 gave 12.0 C.C.N, a t 1 8 O and 742 mm.The p'crate is very soluble in benzene, and crystallises in redmelting a t 250O:C,,H,,OBr, requires Br = 33.2 per cent.golden-yellow, prismatic needles, melting a t 2 62-265O :N=6-93.C24H,805N2 requires N = 6-76 per cent.needles, melting at 142-143O404 YEN-GUPTA : CONDENSATION OFThe Anhydride of y-1 : 1-Di hydroxydinaph t hylpentutze,4.3 Grams of diethyl ketone and 14.4 grams of a-naphthol weredissolved in 35 C.C. of glacial acetic acid, and fuming hydrochIoricacid was added until the precipitation of a-naphthol just began.Tha bottle was heated for about 6 hours a t looo, when crystalsbegan t o appear. The heating was continued for two hours more,and the' product was crystalhed as usual from glacial acetic acid,from which it was obtained in colourless plates, melting a t166-167'.The yield is about 30 per cent. of the theoretical.The alternative preparation by the use of 2-3 C.C. of phosphorylchloride takes about an hour, with a yield amounting to about55 per cent.:0.1261 gave 0.4116 CO, and 0.0736 H,O.C25H22O requires C = 88.75 ; H = 6-58 per cent.The dibromo-derivative crystallises in plates, melting a t 258" :0.3140 gave 0.2333 AgBr. Br=31'6.Cz5H2,0Br, require8 Br = 32.22 per cent.The dichloro-derivative crystallises in prisms, melting a t0.3072 gave 0.2136 AgCl.C,,H,,OCl, requires C1= 17-44 per cent.The dinitro-derivative crystallises from glacial acetic acid or hotnitrobenzene in golden-yellow, prismatic needles, becoming dis-coloured a t 29U0, sintering at 298O, and decomposing and meltingat 301-302':C=88.89; H=6-48.238-239' :C1= 17.19.0-1590 gave 9.5 C.C.N, a t 23O and 769.2 mm. N=6.85.C,5€12005N2 requires N = 6.55 per cent.The ,4nhydride of p-1: 1-Dihydroxydinaphthtylpentane,This compound was prepared by using hydrochloric acid as thecondensing reagent, the yield amounting to 40 per cent. of thetheoretical. The alternative preparation with phosphoryl chloridegave a yield of 62 per cent. It crystallises in plates, melting atC=88.38; H=6*34.162-163' :0.1041 gave 0.3374 CO, and 0.0596 H20.C,,Hz,O requires C = 88.75 ; H = 6.58 per centKETONES WITH PHENOLS. PART I. 405The dichloro-derivative melting a t 178-179O was obtained in0.3134 gave 0.2146 AgCl.C1= 17.03.The dibromo-derivative melts a t 196O :Br = 31.93.The dimitro-deriva.tive crystallism from hot nitrobenzene inyellow, prismatic needles, melting at 260-263O :0.4321 gave 24 C.C. N, at 23O and 768 mm. N=6.32.colourless, rhombic plates :C,,H2,0C12 requires C1= 17-44 per cent.0.1566 gave 0.1175 AgBr.Ck,H,,0Br2 requires Br = 32.22 per cent.Ca5H2,0,N, requires N = 6.55 per cent.The ,-2 nhydride of j3-1 : 1-Dihydroxydinaphthyloctane,CH3>C<C,OH,>O. c, ' { I 3 C,,H,6.4 Grams of methyl hexyl ketone and 14.4 grams of a-naphtholwere heated with 2 C.C. of phosphoryl chloride at looo for one-halfto three-qumters of an hour. The resulting paste was boiled withsmall portions of alcohol to remove any unchanged a-naphthol, andthe residue was boiled with about 30 parts of alcohol and thesolution allowed to cool gradually.As the solution cools, a gummydeposit is observed on the sides of the beaker, when the solution iscarefully decanted into another dry beaker. After several minutes,if the sides of the second beaker are found coated with any gummydeposit, the solution is decanted into a third, and so on, until thefirst appearance of a crystalline solid is noticed. On allowing thesolution now to remain for two to three hours, pure crystals canbe collected, melting at 96-97O, which after recrystallisation fromglacial acetic acid or alcohol, melt a t 99O, Gppearing in well-definedprisms. The yield scarcely exceeds 25 per cent.of the theoretical.The substance is markedly more soluble in alcohol or acetic acidthan its homologues :0.1039 gave 0.3386 CO, and 0.0690 H20. C=88*89; H=7*37.The dichloro-derivative melts at 162O :0.2078 gave 0.1354 AgC1.The dibromo-derivative melh a t 193O and crystallises in rhombic0.1720 gave 0.1231 AgBr. Br = 30.46.C&H,,O requires C=88.42; H=7.36 per cent.C1= 16-12.C,,H2,0C1, requires (3 = 15.81 per cent.plates :C281€260Br, requires Br = 30.88 per cent406 SEN-GUPTA : CONDENSATION OFThe dimitro-derivative crystallises in golden-yellow, prismatic0.2160 gave 11.8 C.C. N, a t 1 8 . 5 O and 754 mm. N=6.28.needles, melting at 228-229O :C28H2605N2 requires N = 5.95 per cent.The Anhydride of a-1 : l-Dihydroxy~inaphthy~ethylb enzene,Four grams of acetophenone and 9 grams of a-naphthol weredissolved in about 4 C.C.of glacial acetic acid, and the liquid wassaturated with dry hydrogen chloride in the cold. The mixturewas then heated in a stoppered bottle f o r six hours at looo, whencrystals began t o appear, and the contents of the bottle soon solidi-fied. On recrystallisation from glacial acetic acid, the substance isobtained in rhombic plates, melting a t 167O. The yield amounts toabout 47 per cent. of the theoretical; using phosphoryl chloride a6the condensing reagent, it rose on on0 occasion t o 60 per cent.:0.1001 gave 0.3324 CO, and 0.05 H,O. C=90*8; €X=5*54.The dibromo-derivative melts a t 279-280° :0.1897 gave 0.1296 AgBr. Br=29*6.The dichloro-derivative crystallises in white needles, melting a t0.1407 gave 0.0919 AgCl.C1= 16.15.C,,H,,0C12 requires C1= 16.1 per cent.The dinitro-derivative becomes red above 250°, and melts at0.1457 gave 8.0 C.C. N, at 1 8 O and 765 mm.C2,H2,0 requires C = 90.32 ; H=5.38 per cent,Cz,H180Brz requires Br = 30.18 per cent.242O :308-309O :N=6*3.C2,H,,0,N2 requires N = 6.05 per cent.The Anhydride of Biphenyl-1 : l-dihydroxydinapht?~ylrnethane,C H >c'<cloII~>o. PhPI1 10 6The condensation between bemophenone and a-naphthol couldnot be appreciably brought about in glacial acetic acid solutionby means of hydrochloric acid, even after heating two days a t looo.With phosphoryl chloride, however, although the condensationproduct is easily obtained pure, the yield is only 7 per cent.of thatrequired by theory.Four grams of benzophenone and 6.3 grams of a-naphthol weremelted together on the water-bath, and 1-14 C.C. of phosphoryKETONES WITH PHENOLS. PART I. 407chloride added. Any excess of the condensing reagent must beavoided, or complicated products, difficult to purify, are produced.After heating for two hours, a dark-coloured, viscid mass isobtained, which is treated with alcohol t o remove the unchangeda-naphthol and benzophenone, leaving about 0.7 gram of thecondensation product. It is best crystallised from a hot solutionin pyridine diluted with a few drops of water, when snow-whiteneedles are obtained, melting at 274-275' (compare Clough, T.,1906, 89, 771) (Found, C=91*09; H=5*15.Calc., C=91*2;H=5*@7 per cent.). It is very sparingly soluble in boiling alcoholor acetic acid, but fairly so in benzene, chloroform, or acetone.The dichloro-derivative crystallises from pyridine in platesmelting a t 302-303O :0.1884 gave 0.1090 AgCl. C1= 14.37.The dibronmderivative sinters at about 309' and melts at0.2012 g.ive 0.1255 AgBr. Br=26'55.C,H,OCl, requires C1= 14.11 per cent.311-312':C33H200Br2 requires Br = 27.02 per cent.The A ?LA y dride of Biph eny 1 ene-1 : 1 -c€ihydroxydinaph th y Em e t hane,Two grams of the ketone and 3-22 grams of a-naphthol were heatedwith 1 C.C. of phoaphoryl chloride for about eight minutes a t 100°,when the liquid set to a mass of crystals. The product was washedwith hot alcohol, when the condensation product was left behindas a colourless, crystalline mass.The yield a t this stage amountedto 3h grams, corresponding with 70 per cent. of the theoretical.When crystallised from pyridine, it was obtained in colourless,prismatic needles, melting at 290' :0.1164 gave 0.3910 CO, and 0.0495 H,O.0.3354, in 10.6283 naphthalene, gave A t = - 0*660°.C=91*49; H=4.72.M.W. =400.1.C33H200 requires C = 91.66 ; H = 4.63 per cent. M.W. = 432.The dirtitro-derivative crystallises from hot nitrobenzene in0-3751 gave 15.8 C.C. N, a t 20' and 763 mm.golden-yellow, prismatic needles, which remain unmelted a t 340° :N=5*16.C33€I,,0,N2 requires N = 5.36 per cent.Condensation of cycloHezanone with a-n'aphthol.Cyclic ketones also condense readily with a-naphthol, althoughsecondary reactions seem considerably to diminish the yield (Bey.408 SEN-GUPTA CONDENSATION O F1896, 29, 1595), in the presence of fuming hydrochloric acid orother such condensing reagents. The purification of the condensa-tion product is therefore often attended with some difficulty.cycZoHexanone itself gives two products with a-naphthol, namely,(I) the normal product, CH,<c~~.U,,:>C<~lO::')O.CH .CH and (2) a10 6compound probably having a constitution represented by theformula :the mechanism of the formation of which has already been discussedI n order to obtain the latter compound, 3 grams of cyclohexanoneand 9 grams of a-naphthol were dissolved in about 25 C.C. of glacialacetic acid, and 15-18 C.C.of fuming hydrochloric acid added.The clear solution soon became turbid on heating a t looo, andminute drops of oil began to separate. The heating was continuedfor about one and a-half hours with frequent shaking, when theoil set almost completely to a crystalline cake. This was treatedwith boiling alcohol, when a snow-white, crystalline mass, weighingabout 24 grams, remained behind. It is best crystallised from asaturated solution in boiling glacial acetic acid, in which it issparingly soluble. On allowing to cool gradually, small, colourless,rectangular plates melting a t 236O are obtained :(loc. cit.).0.1103 gave 0.3454 CO, and 0-0708 H20. C=85*4; H=7'12."x0.2144, in l O * T 2 naphthalene, gave At = -0'336O. M.W. =422.7.C,,H,,O, requires C = 85.71 ; H = 7.14 per cent.M.W. = 448.A mononitro-derivative is obtained by suspending the anhydridein glacial acetic acid, heating to 80°, and adding a slight excess offuming nitric acid. The suspended solid dissolves, and on cooling,small, yellow, prismatic needles appear, melting a t 266-267O :0.2175 gave 5.5 C.C. N, a t 20° and 762 mm. N=2*93.C32'H310nN requires N = 2-84 per cent.The A nlzydr?;de of 1 : 1-Dihydrox ydinaph thylcyclohexane,If instead of heating the mixture of cyclohexanone and a-naphtholin an open vessel, as in the previous case, the same proportionsare heated in a sealed tube for eight to ten hours at 100-105°, a* A second analysis gave C = 85-99 ; H = 7 -15KETONES WITH PHENOLS. PART I. 409viscid, black oil is obtained.This is washed once with cold alcohol,and once or twice with small portions of hot alcohol, which removesa great part of the impurities, leaving the condensaticm productin the form of a brown paste. This is dissolved in a small quantityof ethyl acetate, and left for a day or two, when dark-coloured,prismatic needles appear. These are collected and washed with aminimum quantity of light petroleum, which leaves the crystalsmuch brighter. On crystallising twice from it hot solution inpyridine, diluted with alcohol, colourless, thin prisms or needlaare obtained, melting a t 146O. I n a subsequent preparation, thesolution of the brown paste in ethyl acetate wit9 eown with a fewcrystals from the first crop, when the condensation product separ-ated in the course of a few hours. The yield is extremely poor.From 3 grams of cyclohexanone about 0-3 gram of the condensationproduct was obtained :0.1089 gave 0.3570 CO, and 0.0612 H,O. C=89*39; H=6'24.0.1464, in 7.4984 naphthalene, gave At = - 0'390O. M.W. = 355.4.C,,H,O requires C = 89.15 ; H = 6.28 per cent. M.W. = 350.Condensation of 1-Methylcyclohexan-3-one with a-Naphthol.Two grams of 1-methylcyclohexan-3-one and 4 grams of a-naphtholwere heated with 1 C.C. of phosphoryl chloride for two hours in astoppered bottle a t looo. The paste so obtained was boiled severaltimes with frmh portions of alcohol, until it set into a solid. Itwas then repeatedly crystallised from small portions of acetoneuntil it melted at 164-165O:0.1394 gave 0-4531 CO, and 0.0826 H,O. C=88*66; H= 6.59.It is markedly more soluble in glacial acetic acid than the otherThe dinitro-derivative melts at 282O :0.1355 gave 7-45 C.C. N, a t 20° and 759 mm. N=6*25.Further investigation regarding the oxidation and hydrolyais ofC,,H,O requires C=89-01; H=6-59 per cent.members of the series.C,7H,20,N2 requires N = 6-16 per cent.the products described above is in progrees.I take this opportunity of expressing my thanks to Dre. M. A.Whiteley and M. 0. Forster for their kind encouragement in thiswork.ROYAL COLLRGE OF SCIENCE,S. KENSINGTON, S. W.VOL. cv. E

ISSN:0368-1645    

DOI:10.1039/CT9140500399

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

410 MELDOLA AND HOLLELY :XLV.-Acylation as InJEuenced by Xteric Hindrance :the Action of Acid Anhydrides orb 3 : 5-Dinitro-p-aminophenol.By RAPHAEL MELDOLA and WILLIAM FRANCIS HOLLELP.IN compounds of the type of isopicramic acid (I) the protection ”of the hydroxyl is so effective that methylation by methyl sulphateand alkali completely fails to attack this group, the aminqroupalone being attacked, with the final formation of those quinone-ammonium- derivatives whichpapers formerly communicatedOHN0,()N02\/N=2(1. )*have been described in a series ofto, and published by, the Society :OH/\NO,j,NO, INH2(11.)The isomeric 3 : 5-dinitro-paminophenol (I1 above : Reverdin,Arch. Sci phys. mt., 1904, [iv], 18, 342; 1905, 19, 353) shows anequally “ protected ” amino-group, so that methylating agents inthis case fail to attack this group.The corresponding dinitro-anisidine can be readily prepared by the action of methyl iodide onthe silver salt of the monoacetyl derivative and hydrolysis of theproduct (Meldola and Stephens, T., 1905, 87, 1206), but themethylation of the amino-group cannot be effected by methylsulphate alone, whilst alkaline methylating agents are inapplicableon account of the tendency of the free alkali to cause completedecomposition with removal of a nitregroup. I n these circumstancesit became of interest to study the influence of configuration on theintroduction of acid radicles, it being well known that underordinary conditions unprotected amino-groups are much morereadily acylated than similarly unprotected hydroxyl groups.Thusisopicramic acid quite readily gives a monoacetyl derivative (acetyl-amino-compound) when boiled for a few minutes in acetic acidsolution with acetic anhydride. The hydroxyl in this compound isonly attacked when the monoacetyl derivative is dissolved inundiluted acetic anhydride mixed with a little concentratedsulphuric acid. From this point of view, the action of aceticanhydride on 3 : 5-dinitro-paminophenol ha5 been studied under* This formula is assigned to the free compound; in solution it may have aquinonoid structure (Meldola and Hewitt, T., 1913, 103, 880)ACYLATION AS INFLUENCED BY STERIC HINDRANCE. 411various conditions, and with results which appear of importancefrom several unexpected points of view.In the first experiments the inertness of the compound towardsacetic anhydride was revealed by the fact that acetylation in aceticanhydride a t 1000 only takes place after heating for several hours.Under these conditions the product proved t o be mainly the knowndiacetyl derivative.The same diacetyl derivative is formed imme-diately on dissolving the dinitro-compound in acetic anhydride withthe addition of sulphuric acid. From this diacetyl derivative theknown monoacetyl derivative (m. p. 182-183O) can be most readilyprepared by dissolving the diacetyl compound as rapidly as possiblein cold dilute sodium hydroxide and precipitating by acid. Thephenolic character of the product indicates that the 0-acetyl isremoved by the alkali.These first experiments resulted, therefore,simply in the production of the diacetyl derivative, and from thelatter the N-monoacetyl derivative by quite normal methods,Acetylation in Acetic Acid Solutwn.In order to modify the action of the acetic anhydride, the latterwas diluted with glacial acetic acid, and the experiments continuedwith this mixture. Under these conditions it wit^ found that anon-phenolic substance wi~g formed, the further investigation ofwhich showed that the compound was. isomeric with the knownmonoacetyl derivative. After many experiments the followingmethod was found the most effective for the preparation of thenew compound :The dinitroaminophenol is dissolved in a small quantity of hotglacial acetic acid, and two to three times the theoretical quantityof acetic anhydride necessary for the introduction of one acetylgroup added to the solution.The latter is then boiled for half-an-hour, and when cold poured into water so as to precipitate theproduct. I f the heating is prolonged beyond the time specified, theyield is diminished; three or four hours' boiling appears t o destroythe compound completely. The crude product is collected, washed,and purified by first washing with a little dilute alkali, then withwater, and finally crystdlising from alcohol or acetic acid. Thepure compound crystallises in flat needles or scales of a golderi-yellow colour; the melting point is 185-186O. A mixture of thesubstance with the isomeric monoacetyl derivative (m. p.182-1 830)melted a t 151-156O:0-1026 gave 0-1500 CO, and 0.0282 H,O. C=39.87; H=3*05.0'0898 ,, 13.7 C.C. N, (moist) a t 21° and 762.8 mm. N=17.43.0.1090 ,, 0.1588 CO, a, 0.0284 HZO. C=39.73; H=2.89.C,H,O,N, requires C=39*82; H=2.93; N=17.43 per cent.E E 412 MELDOLA AND HOLLELY :Them results leave no doubt as to the isomerism between the twoacetyl derivatives.3 : 5-Dinitro-Oa;cetyI-pami~pl5.e?tot.I n discussing formuh for tho new compound, its properties ascompared with those of its isomeride had to be considered. TheN-acetyl derivative when pure crystallises in nearly white needles,extremely soluble in alcohol, and distinctly phenolic in character.The new compound is fairly stable towards alkali, and not veryreadily soluble in alcohol. It is very stable under the influence ofheat, and can be partly sublimed without decomposition whenheated in a dry tube.The most striking visible difference betweenthe isomerides is the intense yellow co'lour of the new compound.The chemical properties of the latter are at first sight quite inharmony with the view that it is the 0-acetyl derivative:On further acetylation with acetic anhydride in presence of alittle sulphuric acid it gives the known diacetyl derivative identicalwith that obtained by the direct acetylation of the dinitro-com-pound- When hydrolysed by sulphuric acid it gives 3 : 5-dinitrepaminophenol; it imparts a transitory violet colour to an alkalihydroxide solution, this colour being due to the dinitro-compoundliberated by hydrolysis.The free dinitro-compound has the sameproperty, the transient violet colour being due to the alkaline saltwhich is a t first formed, but decomposes in presence of excess ofalkali. Boiling with sodium carbonate solution also effects hydro-lysis, and the violet solution of the sodium salt on acidificationgives 3 : 5-dinitro-paminophenol. Attempts to methylate the amino-group by methyl sulphate under various conditions gave negativeresults. The compound dissolves much more freely in methylsulphate than the isomeric N-acetyl derivative, but the solutionafter being kept at looo for an hour wi18 found to contain only theoriginal dinitroaminophenol, the methyl sulphate acting simply asa hydrolysing agent.These properties all point to the conclusion that the new com-pound is the expected 0-acetyl derivative ; nevertheless, its d o u rhnd the extreme readiness with which it is formed seem to indicatethat the simple formula given above does not adequately representthe whole of the ascertained facts.The acetylation of a truephenolic hydroxyl group by simply boiling for a short time witACYLATION AS INFLUENCED BY STERIC HINDRANCE. 413acetic anhydride diluted with acetic acid is, as already stafed, mostunusual. Moreover, such phenolic acetatee, even when containingseveral nitro-groups, are never very highly coloured. The colour ofthe present compound suggested, theref ore, that the amino-groupwas implicated, and the formulz given below have been considered :0 OAc OAc/\ /\or cross-linking) I I:NO2H NO, I ‘No“\/NH,Ac g HA\/IN0\()N ’.Hf- /NO,\/NO, I 1 (..(1.1 (11.1 (111.)Of these formula?, I is disposed of by the fact that no evidenceof interconvertibility of the isomerides has been observed; allattempts to convert the N-acetyl derivative into the isomeride andvice versa, have-led to negative results. Between I1 and I11 it isnot so easy to decide, but the absence of acidic character andgeneral analogy to similarly constituted nitroamino-compoundsleads us to adopt the “inner salt” formula (111) as the mostprobable.It follows from these conclusions that the isomerides are ofdiff went types of benzenoid structure, the N-acetyl derivative beingincapable of forming an “inner nitrolic salt ” on account of theattachment of the acid radicle to the 4N-atom, whilst the 0-acetylderivative containing a nitregroup orthol to the 4NH2-group iscapable of (‘ inner salt ” formation, with consequent orthoquinonoidstructure.Specimens of the isomerides were kindly examined forus spectroscopically by Dr. J. T. Hewitt, by whom the accompany-ing curves represehting the absorption spectra have been prepared.It will be seen that the absorption spectrum of the 0-acetylcompound is quite different in type from that of the N-acetylderivative.We may add that in deciding in favour of the above formula(111) we have had also under consideration the results of certainexperiments devised with the express object of getting evidence asto paraquinonoid structure (I) and nitrolic acid structure (11) ;thus the non-phenolic acetyl derivative is not profoundly affectedby such reagents as hydroxylamine, hydrazine, or phenylhydrazine,all of which simply act as hydrolysing agents.An attempt to forma nitrolic salt by adding sodium ethoxide to the toluene solutionof the compound also led to a negative result. The whole of thecompound is precipitated by this means as a brown, amorphoussubstance, which is the same product as that which results fromthe decomposition of the origind dinitro-compound by the samemethod. Sodium ethoxide does not, therefore, form a nitrolic salt414 MELDOLA AND HOLLELY:but simply removes the 0-acetyl, and then decomposes the dinitro-compound with the formation of the usual indefinite products.The Colour of Nitroaminop?benols and their Derivatives inRelation to their Constitution.This conclusion concerning the constitution of the 0-acetyl deriv-ative warrants the extension of the same type of structure t o theSca Ze of oscillation frcqiscncics.-- Non-ph,enolic acctyl derivative in alcohol.- - - Phenolic acetyl derivative in alcohol..... .. ). f ? 9 ) ,, alcoholic KOH.original (unacetylated) compound, and, generally, to all the nitro-aminophenols and their derivatives which have been under investi-gation in our laboratory for many years. The condition essentialfor the production of highly-coloured compounds appears t o be theortho-position of a nitro-group with respect to an amino-group or ACYLATION AS INFLUENCED BY STERIC HINDRANCE.415substituted amino-group. The presence of additicmal nitro-groupsin the nucleus has generally the effect of increasing the intensityof the colour. From this point of view 3 : 5-dinitro-paminophenolwould have the formula (I) * :OH OH O*CH,(1.1 (11.1 (111.)O*CH, OH OoCH,/\ N02/\N0 /\NO, I Red l"(j\ / * \o \o .. /oNH2-- GH2--/ NH,---/NO,! Bed I* NO Bsd 1.~0NO;\/* \(IV.) (V. 1 (VI. 1The above compound is of a deep red colour, all analogouslyconstituted compounds being more or less red and far more highlycoloured than the mere presence of nitro- and amino-groups in thenucleus would account for unless some more profound change ofstructure is allowed; thus, isopicramic acid, in which there is nonitro-group cirtho to an amino-group, is very feebly coloured (inthe free state) as compared with the above isomeride.On theother hand, 2 : 3-dinitro-paminophenol (I1 above) is red (Meldolaand Hay, T., 1907, 91, 1482), and the corresponding 2:3-dinitro-panisidine deep orange (Meldola and Eyre, T., 1902, 81, 990).2 : 6-Dinitroanisidine (111) is ochreous (Meldola and Stephens, T.,1905, 87, 1204) and 3:5-dinitroanisidine (Tv) deep red (ibid.,p. 1206). 2:3:6-Trinitro-p-aminophenol (V) is also deep red(Meldola and Hay, T., 1909, 95, 1380), as is the correspondingtrinitroanisidine (Meldola and Kuntzen, T., 1910, 97, 456). Theisomeric 2 : 3 : 5-trinitro-p-anisidine (VI above) is also red (Reverdinand de Luc, Arch. sci.phys. nat., 1909, [iv], 27, 383). A detailedcomparative study of the absorption spectra will be necessary tocomplete the evidence from the optical side. So far as observationswith these compounds have hitherto been carried out, it is instruc-tive to compare the curves representing the absorption spectra of2 : 3 : 5-trinitrvanisidine and of its acetyl derivative (in whichno inner salt formation is possible) given in a former paper(Meldola and Hewitt., T., 1913, 103, 884) with those given in thepresent communication.* This structural formula may explain the inertness of the amino-group towardsacylating agents, although "steric hindrance " must also be allowed for, since the.5-nitro-group would act as a " protecting" group416 ACYLATION AS IEFLUENCED BY STERIC HINDRAKCE.Preparation of the 0-Propionyl Derivative.The extreme readiness with which the hydroxyl group of t'lredinitro-compound can be acetylated suggested the application of theforegoing method for the introduction of other acid radicles. Itwill no doubt be found possible to acylate the hydroxyl group of3 : 5-dinitro-paminophenol by means of the higher homologues ofacetic anhydride generally.A preliminary experiment with pro-pionic anhydride diluted with propionic acid carried out inprecisely the same way-as with acetic anhydride showed that the0-propionyl derivative could be prepared with equal readiness.This compound has all the properties of its lower homologue; itcrystallisee from alcohol in flat, golden-yellow needles, melting at172-173':0.1022 gave 0.1588 GO, and 0.0354 H20.0.1274 ,, 18.5 C.C. N, (moist) a t 23O and 760.5 mm. N=16*37.C,H,O,N, requires C= 42.34 ; H = 3-55 ; N = 16.47 per cent.The compound is therefore 3 : 5-dinitro-0-propionyl-p-amino-cT=42*38; H=3.85.phenol,NO,\ /:NO\KH*- /O'Attempt to Prepare the 0-Benzoyt Derivative.An attempt to introduce benzoyl by the same method led to aninteresting result. The dinitro-compound was boiled as before withbenzoic anhydride dissolved in glacial acetic acid. The productproved, however, to be the 0-acetyl derivative previously described.I n this case, therefore, the benzoic anhydride simply promotes theacetylation, or else the benzoyl derivative is first formed and thenconverted into the acetyl derivative by interchange of radicles.*Whether the protection of the amino-group by ortho-substituentsis exerted equally by radicles other than the nitro-group yet remainsto be investigated. The corresponding 3 : 5-dihaloid-p-aminophenols,so far as we have been able to ascertain, do not appear to be known,and their preparation will be attempted in order to throw furtherlight on this question.FXNSBURY TECHNICAL COLLEGE, E.C.* The dinitro-compound is not acetylated by boiling for many hours with aceticacid alone

ISSN:0368-1645    

DOI:10.1039/CT9140500410

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

STUDIES OF THE CONSTITUTION OF SOAP SOLUTIONS. 41’7XLV1.-Studies of the Constitution of Soap Solutions.The Electrical Conductivity o j Potassium Salts o jFatty Acids?By HUGH MILLS BUNBURY and HERBERT ERNEST MARTIN.THE preseni; communication is a study of the conductivity ofsolutions of potassium salts of the saturated fatty acids, fromstearic acid down to acetic acid. For most of these aubstances nodata are in existence, and yet they present special points ofinterest. A number of these will be discussed in future communi-cations dealing with the boiling points and the degree of hydrolysisof soap solutions.The electrical conductivity of sodium soaps has already beenshown to be unexpectedly great, and the conductivity curves areanomalous in that they pass through a minimum in N/5- toN/10-solutions and a maximum in N- to N/2-solutions.It might have been expected that the potassium salts (soft soaps)would have exhibited a different behaviour, since they are lessviscous a t room temperature, and more nearly resemble ordinaryelectrolytes.It will be seen in the sequel that the contrary is thecase..EXPERIMENTAL.Preparation of Solutions of Pure Potassium Hydroxide.Potassium in the form of the commercial balls is thrown intoordinary ether in a wide-mouthed, loosely-stoppered bottle. Thestormy effervescence serve6 to keep the potassium cool enough toavoid explosion, and a t the same time its surface becomes cleanand highly polished. These balls are now thrown into moltenparaffin in a nickel crucible, where they unite, since their surfacesare clean.The large piece obtained is allowed to solidify, andremoved just before the paraffin solidifies. After it has beenf,hrown into clean ether and shaken, it is rapidly wiped with filter-paper and placed on nickel gauze above a nickel crucible in adesiccator containing alkaline water. To avoid explosion, thenickel gauze must be cleaned and thoroughly dried each time. A tfimt the absorption of oxygen is more rapid than the evolutionof hydrogen, and the potassium ultimately gets deeply coveredwith a slowly deliquescing layer of potassium hydroxide, so that* Previous communications from this laboratory : Ber., 1910, 43, 321 ; ztihch.physika2. Chem., 1911, 76, 1 7 9 ; T., 1911, 99, 191; 1912, 101, 2042; Trans.Faraday SOL, 1913, 9, 99 ; KolZoid-Zeitsch., 1913, 12, 256418 BUNBURY AND MARTIN:the desiccator and contents must be left undisturbed in a fire-proofroom.To obtain pure hydroxide, the desiccator should be of the vacuumtype, with ground-in glass stopper, and tap sealed to a U-tubehalf full of a concentrated solution of potassium or sodium hydr-oxide.It should be emphasised here that it has been foundnecessary to discard many months of work done in this laboratorywhere in dealing with solutions of alkali, acid, or soap the precau-tion had not been rigorously taken of quite thoroughly smearingwith vaselin all ground-in connexions and glass stoppers (rubberis worthless as a protection against carbon dioxide).Preparation of Soap Solutions.The solutions were made up in silver tubes, with the precautionsdescribed in previous papers, from Kahlbaum’s best acids,* andthe calculated amounts of potassium hydroxide solution.Thedensity of the potassium hydroxide solution was taken to be thatgiven in Landolt-Bornstein’s (‘ Tabellen ’’ (1913) a t 15O.f Theconcentrations are expressed in weight normalities (gram-moleculesof salt per 1000 grams water), which is not affected by the largetemperature interval involved.The time allowed for equilibrium to be attained varied from afew hours, in the case of the dilute solutions, to a’ day or twofor the more concentrated solutions of the higher homologues. Thesilver tubes were then taken from the shaking machine (80°),opened, and the solution transferred whilst hot and homogeneousto a tube of Jena-glass into which was inserted the dippingelectrode, also made of Jena-glass after the pattern already* Of these acids NMcBain and Taylor (Zoc.c i t . ) had shown that the conductivitywas unaltered, in the case of the special palmitic acid, by further purification;decoic and hexoic acids were synthetic acids, and the acetic acid has been shown tobe very pure. Less weight can be laid on the values for the myristates, laurates,and octoates as these were only froni Kahlbaum’s ordinary acids.j- I n practice the following simple calculation gives the correct amount of waterrequired to make the solutions exact within 0.1 per cent. in all cases. The weight(in air) of acid taken is divided by its molecular weight (which is diminished by0-11 per cent.in order t o give the apparent weight in air) and is multiplied by1000 and divided by the weight-normality desired. This is the weight of watertheoretically required, but it has to be corrected for two errors, both of which areproportional to the concentration, namely, the water introduced with thehydroxide solution and the amount of water formed by the union of the hydroxideand acid, the latter being 1-80 per cent. of the total water i n a N-solution. Forthis purpose the number obtained is converted from grams to c.c., and from it issubtracted for potassium salts, 1-14 per cent. (for sodium salts, 2’04 per cent.miiltiplied by the weight-normality desired ; finally, this volume of water miniisthe volume of alkali used is added to the solutionSTUDIES OF THE CONSTITUTION OF SOAP SOLUTIONS.419described. The cell constant is therefore found to be independentof the rwistance of the solution, and there are other obviousadvantages. The previous work of McBain, Cornish, and Bowdenhad shown that this use of Jena-glass would be permissible forthese comparatively mobile and homogeneous solutions. Themeasurements were carried out a t 90*OOo (con.).The conductivity data appear to be more accurate than thoseof McBain, Cornish, and Bowden (Zoc. cit.). Electrode XV wasused throughout; it had a cell constant in glass of 4.070 (H. M. B.)and 4.080 (H. E. M. eight months later).Duplicate determinations of the densities of N / 2- and moreconcentrated solutions were made, agreeing within 0.06 per cent.,using the special form of pyknometer (capacity about 10 c.c.)previously described.Previous work in this laboratory and else-where has shown that no error exceeding 0.1 per cent. is madeif the densities of solutions of intermediate concentrations areobtained graphically by linear interpolation from the densities ofthe O.5N-solutions and that of water (D:! 0*9653), using the concen-trations (not the dilutions) as abscissz. The densities obtainedby interpolation are enclosed in brackets in the tables.Jn all the tables the first column gives the weight-normality;the second the number of grams of potassium salt to 100 grams ofwater ; the third the specific conductivities observed ; the fourththe average specific conductivity; the fifth the density; and thelast the equivalent conductivity a t 90°.The equivalent conduc-tivity is derived by multiplying the weight of solution containing1000 grams of water by the specific conductivity, and dividing bythe weight-normality and the density. In each cam all the correc-tions previously enumerated have been applied. The duplicatedeterminations were carried out on entirely independent solutions,as usual.Po t assium Pdmit ate.Particular attention wm given to these solutions, since on theprevious careful study of the possible sources of error in theinvestigation of the conductivity of soaps, using sodium palmitate(McBain and Taylor, 1911, Zoc. cit.), is based the validity of allthe subsequent conductivity results. The 1.5N-solution proved tooviscous for introduction into electrode XV, although the momdilute solutions, of which eight concentrations were studied, seemmuch more mobile than the corresponding sodium soaps.Thefollowing data were obtained at 90'OOo420 RUNBURY AND MARTIN :TABLE I.Conductivity of Potassium Palmitate (C,,) at 90*OOo.I.1.007-N0.764-N0.6016-N0.2003-N0- 1001-N0.0500-N0.02000-N0~01000-N11.29-6422.1914-776-8962.9461.4720-58880.2944111.0.09320.093330.076280.076350.053650.053640.020270.020280.0 10060.0 10070.0052680.0052720.0025560.0025560.0016510.001650IV.0.09330.07630.053650.020280.010070.0052700.0025560.00165 1V.0.96790.96720.9668(0.9659)(0.9656)(0.9654)(0.9654)(0.9653)VI.124.2127.9127.011 1.0107.0110.8133.2171-6The results given in table I are shown graphically in Figs. 1 and2, where the ordinates are equivalent conductivities and theabscissze the dilutions in litres.As in the case of the sodium palmitate, an anomalous conduc-tivity curve is produced.The greater apparent solubility ofpotassium soaps, and the fact that they do not, like sodium soaps,form gels with alcohol, might have pointed to a more normalbehaviour as compared with the sodium soaps; the contrary isseen to be the case.The conductivity curve exhibits a maximum at 0.75N- and aminimum at 0-lrV-potassium palmitate. Sodium palmitate exhibitsits maximum at 0.5N and its minimum at 0.2-0.1N; thus theposition of the depression in the conductivity curve is the samefor potassium palmitate as in the case of the four sodium soapsalready described.The anomaly is accentuated in the case ofthe potassium salt as compared with sodium palmitate, for thedifference between the maximum and minimum conductivitiesamounts to 20.9 mhos in the former case and to only 7.1 in thelatter.The solutions from N / 2 downwards are quite fluid and clear at90°, but the l*OiV-solution was rather viscous, and it coagulated a t60-70°. A t room temperature the 0-01N- and 0*02N-aolutionsexhibit a large amount of fine, shiny sediment a t the bottom of anearly clear, slightly opalescent aolution.The separation is muchless complete in the case of the 0~05N-solution, where silky fibres orstriae fill the liquid even on long keeping. With increaae ofconcentration the viscosity rapidly increases, and the pearly appear-ance diminishes. A 0.5N-solution has the appearance of boileSTUDIES OF THE CONSTITUTION OF' SOAP SOLUTIONS. 42190 -80 *70 -60 -40 -30 -20 -10 ..!!? -starch, but the 1*5N-solution is nearly colourlese, and it is veryviscous, scarcely flowing a t room temperature, bubbles caught init never rising to the surface.These descriptions should be compared with similar data inprevious papers and with those of Zsigmondy and Bachmann(Rolloid-Zeitsch., 1912, 11, 145).FIG. 1.c l l 1 1 I I IPo tassiurn A ce tu t e.I n order to have a standard of comparison, measurements weremade of potassium acetate, which is always considered to be atypical electrolyte.Since this salt is very hygroscopic, the solutionswere made up from solutions of pure acetic acid and potassiumhydroxide, as in the case of the soaps proper. The resdtingsolutions were neutral to litmus, and did not affect phenol-phthalein. The conductivity data are given in table 11422 BUNBURY AND MARTIN:FIG. 2.260240220200180160140I2010080604020I.1.000-N0.500-A'0.2000-N1 I I 1 1 I1 2 5 10 20 litresEquil:alcnt concluctizilics of potassium salts of fatty acids at PO".TABLE 11.Conductivity of Potassiwm Acetate at 90.00°.0~1000-N0.0500-N0.0 1000-N11.9.8124-9061.9620.9810.49060.0981111.0.16280.16210.092680-092510.042280.0423 10-022710.022740.012030.012010.0026100.0026 14IV.0.16250,092600.042300.022730.012020.0026 12V.1.00900.98680,97400.96970.96750.9657VI.176.9196.6221.2236.5249-5270.4In order to evaluate these data it is necessary to know theconductivity a t infinite dilution at 90° of each of the ions conSTUDIES OF THE CONSTITUTION OF SOAP SOLUTIONS. 423cerned.This was done by a consideration of the following dataof Kohlrausch and of Noyes (Report of the Curnegie Zmstitute ofTVashington, 1907, 63, 1):A t 18O, KC1 = 130.1 ; NaCl= 109.0 ; NaC2H302= 78.1 ; NaOH =216.5; K'=64-7; C1/=65.4; Na'=43.6; C2H30,/=34*5; OH'=172.9; that is, the mobilities of the five ions named are as1 : 1.011 : 0.674 : 0.533 : 2.673.At looo, KC1 = 414 ; NaC1= 362 ; NaC,H30, = 285 ; NaOH = 594.I f the fairly reasonable assumption be made that the potassiumand chlorine ions have attained equal mobilities at this hightemperature (the very pronounced tendency of all ions a t hightemperatures), then K' = C1' = 207 a t looo, and Na' = 155 ;C2H,0,'=130, and OH/=439; that is, the mobilities at looo areas 1 : 1 : 0.749 : 0.628 : 2-120.If t,he further assumption be now made that these ratios betweenthe mobilities of the ions at infinite dilution change linearly withthe temperature, the magnitude of the effect is small between loooand 90°, being 2 per cent.for the acetate and 1 per cent.for thesodium ion, and even for the hydroxyl ion only 3 per cent; thusthe mobilities of the ions KO, Cl', Na', CaH302/, OH' become as1 : 1.001 : 0.740 : 0-616 : 2.187 a t 90°.Finally, if the value for potassium chloride at infinite dilutionbe interpolated graphically on the very flat curve obtained byplotting the values already cited together with KC1=321*5 a t 75O,232.5 a t 50°, and 152.1 a t 25O, the conductivity of potassiumchloride a t infinite dilution is fouhd to be 376.5 at 90° (compareBohi, Diss., Zurich, 1908, p. 37). From this we obtain the follow-ing final values for 90°:K. = 188 KCl = 376C1' = 188 NaCl = 327NaC2H,0, = 255KC2H,0, = 304C.,H,O,' = 116 NaOH =550Na* =139=411 KOH =599 0-H' -Utilising these data, we are now in a position to calculate thedegree of dissociation of the sodium acetate and hydroxide deter-minations of McBain and Taylor, as well as of the above solutionsof potassium acetate.Data for a fewintermediate concentrations have been obtained by interpolationon the graph of the molar conductivity plotted against the cube-rootof the concentrations; this graph deviates from a straight line onlyin the most concentrated solutions.This is done in table 111424 BUNBURY AND MARTIN:TABLE 111.Electrolytic Dissociation a.t 90°.Potassium Sodium sodiumacetate. acetate.* hydroxide. * - - - a. a. aPer cent. P. Per cent. p. Per cent.( 6 3 ) 50.3 - - - -71.6 176.9 58.2 129.7 51.1 392.8183.9 60.5 138-6 54.6 -196.6 64.8 154.0 60.6 427.3 77.822 1-2 72.8 178.9 70.4 458.4 83.5236.5 77.7 195.0 76.6 476.9 86.9249.5 82.1 207.8 81.7 491.1 89-5262.6 86.4 221.0 86.9 - -270-4 89.0 228.0 89.6 614.3 93.7304.0 100.0 254-5 100.0 648.9 100.0-* Measured a t 89.75" ; volume-normality at 18".2.0-N1.0-N0.75-N0.6-N0-2-N0.1-N0.05-N0.02-N0.01-N0The values obtained for sodium acetate fit in well with thosedetermined by Noyes (Zoe.eit.) at other temperatures. It will benoted that the dissociation of this sodium salt is very distinctlyless than that usually found for binary univalent electrolytes,although according to Noyes the dissociation of ammonium andsodium acetate are the same. The results in table I11 will proveuseful in estimating the significance of the data obtained for thevarious soap solutions.Other Potassium Salts.I n view of the interesting character of the conductivity data forpotassium palmitate, it appeared desirable to extend the measure-ments to the potassium salts of the other saturated fatty acids ofeven number of carbon atoms in the molecule, these being theonly saturated fatty acids occurring in soaps.I n each case thenormal acid was the one investigated. The data are given intables IV to IX.TABLE IV.Conductivity of Potassium Stearate (CIJ at 90*OOo.I, 11. 111. IV. V. VI.1.007-N 32-46 0.08301 0.0830 (0.9637) 113.4(0.9641) 112-6 0.754-N 24.30 0.065990.06567 0'065830.9645 113.9(0.9648) 100.016.17 0.047436-468 0.018200.04735 0.047390.01807 0.018140.5016-N0.2003-NE:EEi:;f 0.008980 (0.9652) 96.00.004839 0.004829 0.004834 (0.9652) 101.70-1001-N 3.2260.05001 -N 1.612~ : ~ ~ ~ $ $ ! 0-002397 (0.9653) 124-9 0*02000-N 0-64600.0014 18 0.001426 0.001421 (0.9663) 147.7 0.0 1000-N 0.322STUDIES OF THE CONSTITUTION OF SOAP SOLUTIONS.425At 90° 1.0N-potassium stearate is a clear, colourless liquid, buthighly viscous-at room temperature the white paste resulting isscarcely more viscous; it will hardly pour under the influence ofgravity. A t 90° the O’lN-potassium stearate is clear, but the0*05N-solution is distinctly cloudy, and the 0-02N- and O.02N-solu-tions are faintly opalescent.A t room temperatures the solutions from N/10 upwards arewhite pastes; the more dilute solutions are white and translucent,exhibiting very little shiny sediment, with the exception of the0~05N-solution, where the precipitate occupies about one-half ofthe volume.The silky appearance is not nearly so marked as inthe case of the palmitates.I n view of the fact that Kahlenberg and Schreiner (Zeitsch.physikal. Chem., 1898, 27, 552) have measured one concentrationof potassium stearate solution a t temperatures from 40° up to80°, and further t h a t their data for sodium oleate are twice a53great ils those of Dennhardt (Diss., Erlangen, 1898), it is interest-ing to note that the data for their .iV/4-stearate solution whenextrapolated for 90° (105-106 mhos) agree with ours within afew per cent.TOLE V.COl LductivityI. IL1.007-N 26.810.60 16- N 13.360-2003-N 5.3400.1001 -N 2.6650.0600-N 1.332of Potassium Myristate (C14) at 90.009111. IV.V. VI.0.1051 0.9718 136.20.10520.10510.9693 135.4 0*0.58030.05800 0.05801 !::if:: 0.02405 (0.9669) 130.8 8::::;: 0*01147 (0.9659) 121.80.006512 0.006506 0.006509 (0.9656) 136.6: : ~ ~ ~ ~ ~ ~ 0.003488 (0.9654) 181.60.0034860.002 15 10~02000-N 0.53260.002168 0.002159 (0.9654) 224.3 0*01000-N 0-2663On comparing the values in table VI for potassium laurate withthose of F. Goldschmidt (Zeitsch. Elektrochem., 1912, 18, 386) forthe potassium salt of the acids from palm kernel oil (“ chief consti-tuent potassium laurate ”*), his values are seen to vary somewhat* Oudemanns (J. pr. Che?n., 18’15, 11, 393) gives the following data for a palmkernel oil : oleic acid, 26.6 ; stearic, palmitic, aud myristic, 33 ; lauric, decoic,octoic, and hexoic acids, 44‘4 per cent.Lewkowitsch, however, in view ofValenta’s later data considered that lauric acid must be the chief constituent, andthat the oleic acid could not exceed 10 to 20 per cent.VOL. cv. F 426 BUNBURY AND MARTIK' :TABLE VI.Conductivity of Potassium LCHLTU~C (C,,) at 90.00'.I. 11. 111. IV. V. VT.0.1650 0.9835 123.5 2.028 - N 48.34 0.16530.16470.1134 0.9761 143.2 1-007-N 23.99 0.11350-11330.754-N 17-97 0.0888 0.0888 (0.9741) 142.60.9720 146.0 0.50 16-N 11.95 0.06363(0.9680) 144.2 0.2003-N 4.772 0.02665(0.9666) 159.7 0.1001 -N 2.384 0.01509: : ~ ~ " g ~ p 0.009341 (0.9660) 195.6 0.0500-N 1.1910.06357 o'063600.02671 0.026680.01508 0.015098::::::; 0.002245 (0.9654) 233.0 0.0 1000- N 0.2383irregularly between those here obtained for potassium laurate andmyristate.Some of his data are 137.3, 143.6, 141, 135, and 173.5for the 1.0, 0.74, 0.5, 0.2, and 0*05N-solutions respectively. Hisresult3 for 0.74N- and 0'5.N-solutions are relatively high, as ourresults show no such decided maximum. We have not yetmeasured mixtures of pure fatty acids.TABLE VII.Conductivity of Potassiam Decoate (Cl,,) at 90*OOo.I.1.007-N0.6016-N11. 111. IV.0.1185 21-17 0.11880.118210.54 0.069010.06927 0.06914V. VI.0.9827 145.90-9749 156.3(0.9691) 180.9 4.21 1 0.033682-104 0-01902 (0 9672) 200.6 0.01902 0.019020.03372 0*033700.2003-N0*1001-N0.0500-N 1.051 0*01014 0.01014 (0.9663) 211.90.002231 0.002239 (0.9655) 232.4 0.0 1000-N 0,2103 0.002241TABLE VIII.Conductivity of Potassium Octoate (C,) at 90*OOo.3.063 -N 55.82 0.2165 0.2165 (1.027) 107.3'I.11. 111. IV. V. VI.0.1251 0-9893 148.7 1.007-N 18.34 0-12510.12510.5016-N 9.14 0*07584 0.07672 0.9784 168.50.075 600.2003-N 3.746 0'03586 0.03578 (0,9706) 191.0*0.0357 10.1001 -N 1.823 o'ol 953 0.01 952 (0.9679) 206.20.019500.0505-N 0.91 1 o'01062 0.01061 (0*9666) 219-20.010600.0 1000-N o*1822 0*002310 0.002309 (0.9666) 239-6 0*002309* Dekrniinatiou by Miss CornishSTUDIES OF THE CONSTITUTION OF SOAP SOLUTIONS. 427TABLE IX.Conductivity of Potassium Hexoate (Cs) at 90.00°.I. 11. 111. IV. V. VI.1.007-N 15.62 0- 1300 0.1300 0.9974 149.50.9822 177.7 0.6016-N 7.74 0.081460.08098 o*08122(0.9721) 201.2 0.2003-N 3.088 0.037 740.03767 0.03771(0.9687) 216.5(0.9670) 227.70.1001 -N 1.643 0.020690.0600-N 0.771 0~010900.02064 0.020670.01095 0.010930~01000-N 0.1542 0.002368 0.002375 0.002371 (0.9656) 245.9At 90° all the potassium soaps from the myristate downwardsare clear liquids, below and including the l*ON-solutions.A t roomtemperature, to which the following notes refer, theae soaps exhibitnone of the silky appearance characteristic of the palmitates (andto a less extent of the stearates).The 1.0N- to 0'05N-myristate solutions are clear liquids (the1 *ON-solution being oily) with steadily increasing amounts of flakysediment, the O*OlN-solution containing most, and being alsoslightly opalescent.On long keeping large groups (2 cm.) offeathery crystals separate out from the 0*05N-solution.l*ON-Potassium laurate is clear except for a slight sediment.The 0.5N-solution contains much more of this flaky sediment, butthere is also a large amount of amorphous turbidity at the topof the liquid, which is clear in the middle layer. The 0-2N-solutionis similar with less sediment and less turbidity. The O*lN-solutionhas as much sediment as the 0'2N-solution, but there is only avery slight turbidity a t the top. The 0~05N-mlution has a slightsediment, is faintly opalescent, and shows no upper turbidity.With the decoates (Clo) the sediment is less than with the laurates( C Q , and it is a t a maximum in the 0.W-solution.The1'0N-decoate solution is very slightly viscous, and has only a veryslight sediment. Only in the 0.2, 0.1, and 0'05N-solutions is therea trace of the " upper turbidity"; the 0.01N-solution is almostclear, wikh a alight sediment.In the case of the octoates (Cs) no surface turbidity is observed;the maximum sediment is found in the 0*2N-solution, but there isonly a trace of sediment in the l'Ofl-solution. The 0*05fl-solutionis somewhat opalescent, the O'OIN-solution only faintly so.With the hexoates (Cs) the sediment is still less, being at amaximum in the 0-1N-solution ; the O*O5N-soluti~n is faintlyopalescent.It was impossible to measure the conductivity of l.5N-potassiumF F 428 BUNBURY AND MARTIN:palmitate, 2*ON-myristate, and 3.0N-laurate at 90°, as they areviscous jellies even a t looo, and conductivity electrodes could notbe filled with solution free from air-gaps even through severalhours' work.A t room temperatures the 2.ON-laurate and the3-ON-octoate solutions are oily liquids, with a distinct sediment ;the S*ON-solution, on the other hand, is a transparent jelly,preserving its form unaltered by the influence of gravity.Kashing Power."It is interesting and important to note the different washingpowers of the various hard and soft soaps. The potassium myristateand laurate are ideal soaps (for washing the hands), and the palmi-tate is almost as good, but the stearate is much less so. Sodiummyristate is good, but sodium palmitate and stearah are quiteuseless, feeling remarkably like greasy sawdust.Potassium hexoate (C,) is distinctly a soap in concentratedsolution, although this at om0 disappears on dilution.Potassiumoctoate (C,) is still more distinctly a soap, but this again disappearson dilution. The decoate (C,,) is the first to raise a typical lather,although this has not much body.Discussion of the Results.In order to facilitate comparison, the conductivity results aresummarised in table X. These molar conductivities are also showngraphically in Figs. 1 and 2, which should be compared with thecorresponding graphs (T., 1912, 101, 2049) of previous data forthe higher sodium salts.TABLE X.Molar Conductivity of Potassium Soaps a t 90*OOo.Concentration . . .Stearate, C,, ......Palmitate, C,, .. .Myristate, C,, . ...Laurate, C,, ......Decoate, C,, ......Octoate, C, .......Hexoate, C, .......Acetate, C, .......1.0113.4124.2136.2143-2145.9148.7149.6176.90.75 0.6112-6 113.9127.9 127.0 - 135.4142.6 146.0- 168.6 - 177.7183.9 196.6- 156.30.2100.011 1.0130.8144-2180-9191.0201.2221-20.196.0107.0121.8169.7200.6205.2216.6236.50.06101.7110.8136.6195-6211.9219.2227.7249.60.02 0.01124.9 147.7133.2 171.6181.6 224.3 - 233.0 - 232.4 - 239.6 - 246.9262-6 270.4It will be noticed at once how similar the behaviour of eachof these salts is to that of the corresponding sodium salts as far asThese notes are certainly not intended to be taken as a general discussion ofwashing power, which is known to be a complicated property, some of the factorsof which have received separate elucidation. On the contrary, the present remarksrefer only to the conditious stated (warm tap water ; pure, not mixed acids, etc.).STUDIES OF THE CONSTITUTION OF SOAP SOLUTIONS.429these have been measured. All these soap solutions conduct excel-lently. The nature of the constituents which exhibit this highconductivity will be elucidated in two further experimental com-munications from this laboratory now completed and awaitingpublication ; almost all authors have ascribed this conductivity(erroneously as will be seen) to free alkali hydroxide.The close similarity between the corresponding sodium andpotassium salts does not, however, amount to an identity, either inthe position or form of the conductivity curves; as is seen, forexample, in the following calculation : If the difference in theconductivity of the sodium and potassium soaps is essentially dueto the difference in mobility of the sodium and potassium ion, thisdifference might be allowed for by adding to the conductivity valuesfor sodium palmitate the excess in conductivity of potassium acetateover that of sodium acetate, taking the corresponding concentrationsin each case.(It so happens that the difference between the con-ductivity of potassium and sodium acetates is constant, within thelimits 41.2 and 42.6 mhos., over the whole range of concentrationfrom 0.5N to 0*01N.) The values thus predicted for potassiumpalmitate from the conductivity of sodium palmitate, and thedivergence between these calculated and the observed values are :Concentration .. . . . . 1.0 0.5 0-2 0.1 0.05 0.01KP Ob60I'Ved ......... 124.2 127.0 111.0 107.0 110.8 171.6-observed . ........ 7.7 5-1 13.7 17.0 19.5 8.5Difference per cent. 6-2 4.0 12.4 16.9 17.6 4.9NaP+(KAc-"eAc) 131.9 132.1 124.7 124.0 130.3 180.1Difference, theoryPotassium palmitate has thus an appreciably lower conductivitythan that predicted in this manner from the values for sodiumpalmitate; the difference being greatest in the N/ZO-solution,where it amounts t o over one-sixth of the total conductivity.Another mode of comparison, not a t all necessarily morelegitimate, is that to be shown graphically below (in Figs.3 and 4),which is mathematically equivalent to adding to the values forsodium palmitate only that fraction of the difference between thetwo acetates which the conductivity of sodium palmitate itselfbears to that of sodium acetate a t the same concentration.A second proof that the potassium ion as such is not entirelyresponsible for the differences between the conductivity of the hardand soft soaps is to be found in the fact that the differences betweenthe maximum and minimum conductivity values are much moremarked in the case of the potassium soaps. This is seen withparticular clearness in the case of the laurates, where the potassiumsalt exhibitg a well-marked maximum and minimum conductivity430 BUNBURY AND MARTIK:whilst these are entirely absent from the curve for the sodium salt,which exhibits merely a " step-out."Considering the molar conductivity values for the various potass-ium salts as a whole (if the specific conductivities were considered,the relationships would be similar), it is seen from the graphs inFigs.1 and 2, that in dilute solution, below N/20, the soaps fallinto two groups, the stearate and the palmitate, on the one hand,and from the laurate t o the hexoate (C,) on the other, with themyristate occupying an intermediate position.If solutions ranging between N/5 and N/20 be considered, theintermediate member is the laurate, the myristate here resemblingthe higher maps. I n X/2-solutions, the grouping is entirely lost,for the conductivity values are almost equidistant from each other.I n l'ON-solutions, however, the conductivities of potassium hexoate,octoate, decoate, and laurate are nearly identical, whilst the valuesfor myristate, palmitate, and stearate fall off regularly.It should be emphasised here that, in a sense, even the hexoates(C,) are soaps, for they precipitate quite appreciable amounts ofsediment( a t room temperature (of course, not silica, for it is ob-served just as well in solutions freshly taken from the silver tubesin which all our solutions are prepared), and, as was seen, theamount of this sediment is a t a maximum in O'lN-solution.Donnan and Potts (Rolloid-Zeitsch., 1910, 7, 208), on the basis ofsurf ace-tension experiments, conchded that sodium octoate (Cs)was the lowest soap, although Donnan, using diluh solutions(Zeitsch.physikd. Chem., 1899, 31, 42), found that sodium lauratewas the lowest member to give a great lowering of surface-tension.Krafft (Ber., 1896, 29, 1328), on the other hand, had found thatthe nonoate (C,), in very concentrated solution, was the first togive too high a molecular weight, whilst Mayer, Schaeffer, andTerroine (Compt. rend., 1908, 146, 484) state that the hexoate (Cs)is the lowest member showing ultramicroscopic particles.The data available are still quite inadequate to decide whethera gradual transition takes place from crystalloid to colloid onchange in concentration or change in the homologue, or whether,on the other hand, the transition may be completely accountedfor on the hypothesis that true electrolytes co-exist with colloidaland electrolytic colloidal (in the narrow sense) constituents, andthat these merely vary in relative amount.Perhaps the clearest insight into the complicated behaviour ofthese conductivity data may be obtained through a direct compari-son of all the other salts with the corresponding acetate.In thisway the effect of change in degree of dissociation (and also thedifferent influence of the two cations on the degree of dissociation)STUDIES OF THE CONSTITUTION OF SOAP SOLUTIONS. 431which mwt be, to some extent, superimposed upon the otherfeatures, is approximately eliminated. The further communicationsalready referred to will bring more justification for this mode ofcomparison, although owing to the difference in mobility of thevarious ions concerned a relative method (involving a ratio) suchas this can never be quite exact.An attempt will be made tocomplete this comparison by measurement of the concentrations ofthe potassium and sodium ions by a direct method.If the conductivity of potassium acetate be taken for the sakeof comparison to be unity at all concentrations, the conductivitiesof the potassium soaps may be expressed as fractions of thisstandard. Similarly, the conductivity of the sodium soaps so far1'000-900.800.700 *600.500'40FIG. 3.0.200 -10 0.10frl2 5 10 20 25 27 9899100Abnormality of conductivity of potassium soaps relative to potassiumacetate at 90".measured in this laboratory (Zoc.cit.) may be compared with thatof sodium acetate of the same concentration taken a.s unity. Theresults of thie comparison are best seen graphically in Figs. 3 and4, where the conductivities relative to the corresponding acetateare plotted against the dilution in litres.The effect on the appearance of the conductivity curves is reallystriking, and the graphs in Figs. 1 and 2 permanently lose muchof their appearance of irregularity.*The similarity in magnitude and form between the values forthe corresponding potassium and sodium salts is appreciably* The 1.0N-sodium stearate and the O-lN-potassium decoate now appear as ifa redetermination ought to give slightly lower values, although there is no otherreason t o suspect the accuracy of these particular solutions432 BUNBURY AND MARTIN:enhanced by this mode of comparison, although there is definitelyno identity in any case.The results for the potassium soaps nowlie a little higher than the curves for the corresponding sodiumsalts. The general remarks concerning the grouping of the resultsstill hold, but the regularities are much more distinct.Thus the curves, except for the hexoate (C,) and octoate (CJ,all exhibit minima. These minima are regularly graduated inposition and depth. The minimum for sodium stearate is a t N / 2 0 ,for potassium stearate between N / 2 0 and N/10; for sodium palmi-tate between N / 2 0 and N / l O , for potassium palmitate a t N/20;for the myristates ,V/lO in both cases; for the laurates N / 5 in bothcases; for potassium decoate (C,,) at N / 2 .ThO most concentratedFra. 4./Ih a i - - - - - - i0.90o .a00 *700.600 5 00.400.300.200.10I I I I I I 1 I ........ u 1 DL&&L in fmed43 1 2 3 4 5 10 20 25 27 9899Abnormality of conductivity of sodium soaps relative to soditcmacetate at 90".0'900 3 00 -700.600 -60P0.400'300.200.10100solutions of the lower homologues were not measured, so that itis not certain whether, for example, the decided dip of the curvefor l*ON-potassium hexoate (C,) leads to a minimum or not.*It was expected that the value for the 2*ON-potassium laurate(C,,) would be much higher, but it is, if anything, just less thanthe value for the 1-0N-solution.I n the graphs for the sodium soapsthe 1*5N-solutions are included in each case, with a very markedeffect on the appearance of the curves (compare, for example,sodium and potassium palmitates) ; the 1*5N-solutions have notbeen measured in the case of any potassium salt.If the hexoate had been taken as a standard of comparison in* The insertion. i r i thp proof of this paper, of the low value of the ratio forThe valueThus the relative conductivity of all the3*01\7-p btashiiim octoate (Cs), 0.79, practically excludrs this possibility.for 2-01\~-11otassiiirn laurate (C12) is 0.81.lower members rapidly falls off in concentrated solutionSTUDIES OF THE CONSTITUTION OF SOAP SOLUTIONS. 433place of the acetate, owing to the hexoate curve being horizontalbetween N / 2 and N/100, the resulh would have been uniformlyincreased by 0.10, except in the meet concentrated solutions, wherethe values would have been still further increased.Reference must here be made to the able arguments advancedby F.Goldschmidt (Zeitsch. Elektrochem., 1912, 18, 394) in favourof the view that the conductivity data are not wholly distorted bythe effects of the very considerable viscosities here met with insome of the solutions.It is indeed increasingly evident that one of the ultimate resultsof the study of colloidal electrolytes will be to throw new light oncome of the problems of the dissociation theory, both in aqueousand in non-aqueous solutions. Physical chemists were formerlyquite clear on the point that they did not know how to allow forthe effects of viscosity on the quantitative interpretation of conduc-tivity data, for this question has not 80 far received adequateexperimental treatment.In the last few years, however, it hasbecome customary to correct all conductivity data for the ratio ofthe viscosity of the solution compared with that of the solvent, orwith some power of this ratio, this being based on consideration ofStokes’s law, the temperature-coefficient of conductivity a t infinitedilution, or the effect of change of solvent on the conductivity a tinfinite dilution, or a few meagre data on the effect of an addednon-electrolyte on conductivity. This arbitrary procedure is but amake-shift until the effect of viscosity on diffusion has been experi-mentally elucidated, and even its empirical basis appears inad+quate until phenomena such as are met with here have beenreconciled with it.Densities.The densities observed promise to afford some help towards theelucidation of the soap problem.The results are collected in tableXI, and for convenience of comparison they are referred towater of the same temperature its unity; each result is, of course,the mean of several determinations differing by a few units in thefourth decimal place.TABLE XI.Densities D$ of Potassium Salts.Concentration ...............Stearate, C1, ...............Palmitate, C16 ...............Myristate, C,, ...............Laurate, (& ................Decoate, C,, ...............Octoate, C, ...............HeXO&t.e, C6 ...............Butyrate, C, ...............Acetate, C, ..................2.0-N.1.0-N - - - 1-0029 - 1,00671.0189 1.0112 - 1.0180 - 1.0249 - 1.0333 - 1-0398 - 1.04630.6-N. AI.0.0.9993 -1-0016 0.00381,0041 0-00451-0069 0-00681.0102 0.00691.0136 0-00841.0175 0.00651.0212 0.00551.0223 -2A0.,.0.00460.00500.00560-00660.00680.0078000.74000- 18 - -0.0003040160-00260.00240.00230.00170-0026.0.000434 STUDIES OF THE CONSTITUTION OF SOAP SOLUTIONS.The density values are analysed in the last three columns oftable XI; Al.,, is the amount which has to be added to the densityof a 1-ON-solution in order to bring it up to the value for the nextlower homologue, 2A0.5 is the corresponding difference for the0~5N-solutions, but doubled in order to compare them directlywith Al.o; and finally, A, is the difference between the density pre-dicted for the 1'0N-solution from that of the 0'5N-solution if theusual rule for electrolytes mere obeyed, that the divergence of thedensity of the solution from that of water is directly proportionalto the concentration. It will be noted that all the salts betweenthe acetate and the palmitate (for which it holds) depart decidedlyfrom this rule, for the density rises very much less rapidly thanproportional to the concentration.Thus the excess of density of2*0N-potassium laurate over that of water is only two-thirds of thatpredicted from the O.5N-solution.The effects are very regular and gradual, as may be seen from thetable, or still better from a graph.When plotted against theposition in the homologous series, the densities give quite smoothcurves (not straight lines), provided that the acetate is put intothe place of the butyrate, the latter being omitted. I n other words,there is a point of inflexion or a decided break in the curve betweenhexoate (C,) and acetate (C,). Thus again the hexoate betrays itsrelatedness to the higher soaps.The densities of the solutions of the corresponding sodium salts,as far as our data extend, lie on similar curves from 0.0060 to0-0070 units (for 1*0N and half that for 0.5X) below those intable XI, and, in this respect, again illustrate the parallel be-haviour of the potassium and sodium soaps.*Potassium and sodium stearates and sodium palmitate areexamples of the rare case that the density of a solution may be lessthan that of either coiistituent (compare A.L. Hyde, J . Amer.Chem. Soc., 1912, 34,1507).Summary.(1) The conductivities of the potassium salts (soft soaps) of thesaturated fatty acids of even number of ca.rbon atoms from thestearate down to the acetate have been measured a t 90° by thesomewhat laborious method previously described by McBain andTaylor.* The density of 1 'ON-sodium myristate appears to be about 0.15 per cent. toohigh, and the molar conductivity previously published should be increased by thisamount ; similarly, the 1*5N-sodinm myristate should be corrected by about0'34 per cent., whilst the conductivities from the 0'5N-solution downwards remainexactly as they standNON-AROMATIC DIAZONIUM SALTS. PART 111. 435(2) The conductivities of the potassium soaps are higher thanthose of the corresponding sodium soaps, but there it3 a generalresemblance between the form and position of correspondingcurves. Closer comparison shows an even greater tendency towardsabnormality on the part of the potassium salts, this not being dueto the potassium ion as such, well-developed maxima and minimain the conductivity curves being exhibited from the stearate asfar down as the laurate (CI2).(3) The appearance, washing power, density, and conductivitycurve of potassium hexoate (C,) distinctly mark the beginning ofthat deviation from the behaviour of the acetate, which rapidlyand regularly increasw through the otker members of the homo-logous series until it attains the typical character of the highersoaps.(4) In all cases where it is directly visible the depression in theconductivity curve occurs in the same region of concentration,independent of the nature of the acid or alkali taken. Furtherinvestigation might, however, show that the real abnormality isshifted in the case of the lowest homologues to regiogs of higherconcentration.In conclusion, w0 desire to express our thanks to the ResearchFund Committee of the Chemical Society, and especially to theColston Society of the University of Bristol, for grants towardsthe purchase of materials. and apparatus.Our thanks aro due to Dr. James W. McBain, a t whose sugges-tion this work was undertaken, for his constant interest and advice.THE CHEMICAL DEPARTMENT,THE UNIVERSITY, BKISTOL

ISSN:0368-1645    

DOI:10.1039/CT9140500417

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

NON-AROMATIC DIAZONIUM SALTS. PART 111. 435XLVIL-Non-aromatic Diazonium Salts. Part III3 : 5-Dimethyl23yrazole-4-diazunium Salts and thebA xo-derivcxt ives.By GILBERT T. MORGAN and JOSEPH REILLY.IN an earlier communication (T., 1913, 103, 808) it was shownthat the diazotisation of 4-amino-1-phenyl-2 : 3-dimethylpyrazolone(4-aminoantipyrine) hydrochloride leads to the production of adiazonium chloride comparable with the diazonium salts of benz-enoid and naphthalenoid A ~ I I I ~ F . The investigation has now bee436 MORGAN AND REILLY:extended to the simpler case of 4-amino-3 : 5-dimethtyZpyrazoZe, abase containing no aromatic substituent. Diazotisation withalkali or alkgl nitrites in aqueous or alcoholic hydrochloric acidgives rise to a remarkably stable, colourless diazonium chloride,crystallising with great facility, and permanent under ordinaryatmospheric conditions.I n connexion with the relationship, which undoubtedly exists,between the unsaturated character of a cyclic system and its pro-perty of giving rise to diazotisable primary amines, it is noteworthythat although 4-amino-3 : 5-dimethylpyrazole behaves as a diacidicbase, yielding a dihydrochloride (formula I), yet the product ofdiazotisation, in the presence of excess of acid, separates with onlyone equivalent of the chlorine anion.There are evidently twosalbforming centres in the parent base, but in 3 : 5-dimethylpyraz-ole-4-diazonium chloride (formula 11) one of these centres has beenstrengthened a t the expense of the other, the residual affinity ofwhich is probably involved in the production of the diazoniumcomplex.(1.1 (11.1The remarkable stability of this diazonium salt may be due t othe circumstance that the residual affinity of the pyrazole ring,as indicated by its two double linkings and the higher valenciesof the two cyclic nitrogen atoms, is rather more than sufficient tosaturate the residual affinity of the diazonium complex.The aurichloride (111) and pZatinichZoride (IV) indicate a similardegree of salbf orming power for the diazonium base.[ rH N==C c(cH3)>C (C H 3)*N2] Au ClTH*C(CH,)(111.) (1V.IThe replacement of the diazonium complex by an azide radicledestroys the stronger salt-forming group, with the result that theweaker salt-forming centre again becomes operative as manifestedby the fact that the product, 4-triaao-3 : 5-dimethylpyrazole (V),is a basic substance dissolving readily in dilute acids.w.1In spite of its simpler structure and the absence of any aromaticsubstituent, 3 : 5-dimethylpyrazole-4-diazonium chloride is distinctlymore stable t.han antipyrine-4-diazonium chloride ; its couplingpower with phenols, aromatic amines, and &diketon- is not imNON-AROMATIC DIAZONIUM SALTS.PART 111. 437mediately destroyed bg’ solutions of alkali carbonates, hydroxides,cyanides, and thiocyanates, nor is it decomposed by warming withdilute hydriodic acid (T., Zoc. cit.).Striking differences are noticeable between the mixed azo-deriv-atives containing the pyrazole ring and those containing the anti-pyrine nucleus.Antipyrine-4-a.zo-@-naphthylamine and ita mono-alkyl derivative yield dark purple salts with dilute mineral ororganic acids, and this property is retained even when the naphtha-lene nucleus is sulphonated (T., 1913, 103, 1501) or when theamino-radicle is replaced by hydroxyl as in antipyrine4-azo-&naphthol. The formation of thme intensely coloured salts must bedue either to the phenyl substituent or to the carbonyl group ofthe antipyrine nucleus, for no marked colour change is producedon adding aqueous mineral acids to 3 : 5-dimethyZpyrazoZe-4-azo-B-naphthylamine (VI) :p 2K*C(CH,) >C*N:N -r\ \ ,,,N= C( CH,)/-- \\-/VI.)4-Amino-3 : 5-dimethylpyrazole has the remarkable property ofdeveloping characteristic colorations with the phenols in alkalinesolution; the reaction is one of oxidation, progressing slowly inpresence of air, and more rapidly on adding a small amount ofhydrogen peroxide.The development of colour takes place, how-ever, immediately, and much more intensely when this base isreplaced by 4-triazo-3 : 5-dimethylpyrazole. A fragment of thelatter substance added to a very dilute alkaline solution of phenolproduces an intense purplish-blue coloration. The relationshipbetween the nature of the phenol and the coloration is indicatedin the following synopsis:Phenol, its honaologues and derivatives : blue to bluish-purpleshades.Metadihydric phenols, remrcinol, etc. : lilac shades.a-Naphthol and its derivatives : purple shades.&Naphthol and its derivatives : green shades.EXPERIMENTAL.Dimethylpyrazole (1 mol.) prepared from acetylacetone andhydrazine sulphate by Rosengarten’s method (AnnaZen, 1894, 279,237) was added slowly to fuming nitric acid (1.4 mols., D 1-49),cooled by ice to moderate the ensuing vigorous reaction, afte438 MORGAN AND REILLY:which the solution was warmed for two ho'urs on the water-bath.The colourless product, 4-nitro-3 : 5-dimethylpyrazole, obtained bypouring the nitration on to ice, was washed with cold water, inwhich it was sparingly soluble, and dried in a vacuum desiccatorover solid potassium hydroxide.When crystallised from hot water,the nitro-compound melted a t 126O, and was identical with thesubstance (m.p. 124-126O) obtained by Wolff on oxidking4-nitroso-3 : 5-dimethylpyrazole (Annalen, 1902, 325, 193).4-Amino-3 : 5-cEimethylpyrazole.The foregoing nitro-compound (10 grams) dissolved in 12 C.C. ofwater and 40 C.C. of concentrated hydrochloric acid was reducedwith 15 granis of tin gradually added a t the ordinary temperature;the solution wtts cooled at first, then heated for two hours a t looo,afterwards diluted considerably with water, and the tin precipitatedas sulphide. The filtrate, when concentrated considerably, yieldedyellowish-white, well-defined prismatic crystals of 4-arnino-3 : 5-di-methylpyrazole dihydrochloride. This salt, which was extremelysoluble in water, dissolved fairly readily in methyl alcohol, spar-ingly in ethyl alcohol, and was practically insoluble in the non-h y droxylic solvents.The crystals from methyl alcohol were distinctly yellow, butshowed no change in crystalline form or chlorine content (secondestimation below), and gave the same benzoyl derivative as thesnow-white product obtained by recrystallisation from wa.ter :0.2257 gave45.2 C.C. N, a t 22O and 765 mm.N=23*13.0.3496 ,, 0.5440 AgCl. C1=38.51.C,H,N3,2HC1 requires N = 22-85 ; C1= 38.55 per cent.4-Amino-3 : 5-dimethylpyrazole, liberated from itrs dihydrochlorideby aqueous sodium hydroxide, was freely soluble in water, alcohol,and ether ; its acetyl derivative and platinichloride also dissolvedreadily in water.4-23 enz o y lamiit o-3 : 5-dim e th ylpyrae ole,This acyl derivative, which was insoluble in water, was preparedfrom the preceding hydrochloride by the Schotten-Baumannreaction; it dissolved readily in methyl or ethyl alcohol, and moresparingly in ethyl acetate, ether, and benzene.It separated fromalcohol in lath-shaped crystals, melting and decomposing a t290-292' :0.1309 gave 22.0 C.C. Ne a t 18-5O and 765.5 mm. N=19*72.C,H130N3 requires N = 19.54 per centNON-AROYATIC DIAZONIUM SALTS. PART 111. 4393 : Ei-Dirme thylpyrazole-4-diazonium Chloride (Formula 11).To 4-amino-3 : 5-dimethylpyrazole dihydrochloride, concentratedhydrochloric acid (1 mol.), alcohol (5 parts), and sufficient water tobring the salt into solution was added freshly prepared ethyl nitrite(14 mols.), and the liquid concentrated a t the ordinary temperaturein a vacuum desiccator.Lustrous, colourlees, transparent, acicularprisms of the diazonium chloride separated, the crystals beingfrequently more than an inch in length:0-1811 gave 55.0 C.C. N, at 18'5O and 760.5 mm.0.2780 ,, 0*2508 AgC1. C1=22.32.3 : 5-Dimethylpyrazole-4-diazonium chloride was quite stableunder the ordinary atmospheric conditions. A t 150-160° it begant o decompose, showing red patches, and exploded feebly at 175O,b r t the residue ha.d not completely melted at 200O. This salt wasextremely soluble in water, fairly so in methyl or ethyl alcohol; itdissolved sparingly in ethyl acetate or chloroform, but not in etheror benzene.The diazonium chloride coupled readily with phenols andaromatic amines.With phenol and dimethylaniline it gave yellowazo-derivatives, and red, soluble azo-dyes with &naphthol-6+ml-phonic acid, 8-naphthol-3 : 6-disulphonic acid, and a-naphthol-4-sul-phonic acid. ThO coupling power of this diazo-derivative wasretained after treatment with alkali carbonates, hydroxides,cyanides, and thiocyanah under conditions which determined theimmediate decomposition of th0 antipyrine4diazonium salts.3 : 5-Dimethylpyrazole-4-diazonium chloride coupled readily withacetylacetone, benzoylacetone, and ethyl acetoacetate, giving bulky,yellow precipitates with those P-diketo-derivatives containing the-CO*CH,*CU>- group with two mobile hydrogen atoms. Withacetylmethylacetone, which contains only one reactive hydrogenatom, there was no appreciable condensation until after a solutionof the diazonium salt and $he &diketone had been warmed for onehour on the water-bath.N=35.39.C,H,N,Cl requira N = 35.34 ; C1= 22.38 per cent.3 : 5-Dime t h ~ l p ~ r a z o l e - 4 ~ ~ z o n i ~ r n Auricldoride (Formula III).Preliminary experiments having shown that this double salt wasonly sparingly soluble in water, 4-amino-3 : 5-dimethylpyrazoledihydrochloride was diazotised with sodium nitrite in dilute hydrechloric acid, and the colourless solution mixed with aqueous sodiumaurichloride, when a quantitative precipitation of the diazoniumaurichloride was obtained, the compound separating in well-defined440 MORGAN AND REILLYgolden-yellow, rectangular plates, melting and decomposing a t90--95O :0.2875 gave29.4 C.C.N, at 17O and 762 mm. N=11*99.0.2282 ,, 0.2773 AgC1. C1=30.07.0.2142 ,, 0'0909 Au. Au=42*44.C6H7N4C1,AuCl, requires N = 12-12 ; C1= 30.70 ; Au = 42-68per cent.The aurichloride, which was sparingly soluble in ether or alcohol,gave a red precipitate with aqueous sodium hydroxide. Thediazonium complex remained unchanged in the double salt f o rseveral months, for subsequently, after removing the gold assulphide, the filtrate gave a copious, red precipitate with alkaline&naphthol.3 : 5 -Dime thy l pj raz o l el-dia z onium Plat inic h 1 or ide .As this double salt was somewhat soluble in water, but dissolvedonly sparingly in alcohol, it was prepared by diazotising 4-amino-3 : 5-dimethylpyrazole dihydrochloride with ethyl nitrite in aquo-alcoholic solution, any excess of this reagent being removed byevaporation in a vacuum desiccator.The concentrated solutionwas added to chloroplatinic acid dissolved in alcohol, when thediazonium platinichloride separated in yellow, prismatic needles,which were washed with alcohol and dried at the ordinary tem-perature :0.1495 gave 21.0 C.C. N, a t 17O and 754 mm.0.1570 ,, 0.2077 AgC1. C1=32*74.0.2362 ,, 0.0708 Pt. Pt=29-97.N'=16.35.(C?5H,N4Cl),PtC1, requires N = 17.13 ; C1= 32.55 ;Pt = 29.83 per cent.The platinichloride decomposed a t 226-228O with a brisk evolu-tion of gas, the residue swelling up into a very voluminous ash.Four concordant analyses of the nitrogen in this double salt showedthat there was a marked tendency for the substance to losenitrogen, the oldest specimen giving the lowest result (15.54).3 : 5-Dime t hglpyrazole-4-azo-&naph t hot,C6N,H7*N,*C,,,H,*OH.This azo-derivative, which witg obtained in almost quantitativeyield from any of the foregoing diazonium salts, wits insoluble inwatar: but gave a turbid solution with strong aqueous solutions ofthe alkali hydroxides.It was very soluble in chloroform or glacialacetic acid, and fairly so in the alcohols, ethyl acetate, a.nd theother volatile organic solvents, excepting light petroleum or dilutNON-AROMATIC DIAZONIUM SALTS. PART 111. 441acetic acid. From ethyl alcohol it separated in bright red, hair-likecrystals, darkening at 250' and melting and decomposing a t251-252';0.1549 gave 27.9 C.C.N, a t 19O and 760.5 mm.C,,Hl,ONq requires N = 21.05 per cent.Concentrated sulphuric acid dissolved the compound to a cherry-red solution, but concentrated hydrochloric acid had no appreciableaction. In this respect the azo-&naphthol differed from the corre-sponding azo-derivative of antipyrinediazonium chloride (T., 1913,N=20*96.loc. cit.).3 : 5-Dimethylpyrazole-4-azo-P-naphthylamine (Formula VI).An aqueous solution of 3 : 5-dimethylpyrazole-4-diazonium chlor-ide, treated with carbamide to remove excess of nitrous acid, wasadded to P-naphthylamine (1 mol.) dissolved in alcohol. The mixedsolution gradually darkened, and a bright orange-red precipitatewas produced on adding sodium acetate.The product was verysoluble in pyridine or glacial acetic acid, less so in benzene oralcohol, and sparingly soluble in ether, chloroform, o r light petrol-eum. It separated from alcohol in light orange-yellow crystals,showing rhombohedra1 outlines, and melting a t 255-257O, withbrisk evolution of gas:0.1565 gave 35.5 C.C. N, a t 19O and 765 mm.Cl5HI5N, requires N = 26-41 per cent.Concentrated sulphuric acid dissolved this azo-derivative to acherry-red solution, but concentrated hydrochloric acid producedno appreciable change. I n this respect, 3 : 5-dimethylpyrazole-4-azo-P-naphthylamine is remarkably unlike the azo-j3-naphthylaminecompounds containing the antipyridinediazo-complex which gaverise t o a series of stable, dark purple salts with the stronger acids(T., 1913, Eoc.cit.).N=26.54.4-Triazo-3 : 5-dimethylpyrazole (Formula V).The addition of sodium azide (1 mol.) to an acid solution of3 : 5-~imethylpyrazole-4-diazonium chloride led to a brisk evolutionof nitrogen, but owing to the basic nature of 4-triazo-3:5-dimethyZ-pyrazole there was no permanent precipitation of this substanceuntil the mineral acid present was neutralised with sodium carbon-ate or exceB of sodium azide, when the solution became almostsolid from the separation of the triazo-derivative. The colourlessprecipitate was collected rapidly, washed with cold water, dried atthe ordinary temperature, dissolved in benzene, and the solutionmixed with iight petroleum (b. p. 60--8OO). Lustrous, colourlessVOL.cv. G 442 MORGAN AND REILLY :flakes with rhombohedra1 outline separated on concentration. Thissubstance reddened at 75O, and melted sharply a t 81° to a cherry-red, frothing liquid :0.0531 gave 23 C.C. N, at 16O and 763 mm.C,H7N, requires N = 51.10 per cent.Concentrated sulphuric acid decomposed the triazo-derivativeexplosively, evolving fumes and leaving a tarry residue; theproducts had an odour of acetamide. Diluted sulphuric acid(50 per cent.) produced a less violent reaction without tar, andon gently warming with 30 per cent. acid, two-thirds of the azidicnitrogen were evolved quantitatively :N=51*20.0.0905 gave 15.9 C.C. N, a t 20° and 763 mm.C,H7N, requires 2/5ths N = 20.44 per cent,.4-Triazo-3 : 5-dimethylpyrazole, which had a characteristic odourresembling that of iodoform, was very soluble in all the volatileorganic media with the exception of light petroleum,N=20.70.Colour Reactions of 4-Triazo-3 : 5-dimethylpyrazole with AromaticH ydroxy-derivatives.The addition of small quantities of 4-triazo-3 : 5-dimethylpyrazoleto dilute alkaline solutions of phenolic compounds determined inevery case examined but that of the nitro-phenols the developmentof an intense coloration which faded more or less rapidly.Thetest, which was usually found to be extremely delicate, was appliedto 36 phenolic substances with the following results:Aromatic hydroxy-derivative.Phenol ........................o-Cresol ........................m-Cresol ........................p-Cresol ........................m-4-Xglenol ..................o-Xy lenol .....................+- C umenol .....................Thymol .......................Carvacrol ....................mz-Chlorophenol ............pChloropheno1 ...............Salicylaldehyde ...............p-Hydroxybenzaldehyde ...Salicylic acid ..................m-Hydroxybenzoic acid ...p-Hydroxybenzoic acid ...Catechol ........................Coloration.Bright reddish-blue, changing slowly to purple andBluish-violet, redder than the preceding coloration,Intense blue (a greener shade than that due to phenol),Pale blne, disappearing in twelve hours.Faint bluish-violet, changing to light red.Intense reddish-blue, changing to light purple.Reddish-purple, changing to light brown.Deep reddish-violct, fairly permanent, but changingslody to dichroic shades of lighter blue and red.Greyish-blue, changing to bluish-black.Greenish-blue, changing to light red.Intense bright blue, reddened on exposure to air.Reddish-grey, changing to dark olive.Intenhe purple, changing to redder shades.Intense blue, changing t o light red.Intense blue, changing to brown.Reddish-blue, changing to palc purple.Red to reddish-lilac, oxidising to black.finally to brown tints.changing to dark red.changing slowly to brownNON-AROMATIC DIAZONIUM SALTS, PART 111.443Aromatic hydroxy-derivative.Resorcinol .....................Quinol.. .........................Pyrogallol .....................Hydroxyquinol ...............Phloroglucinol ...............Orcinol .......................a-Naphthol ..................a - Naphthol - 4 - sulphonicacid ..........................a-Naphthol- 4 : 8 - disulph-onic acid .....................1 : 3-Dihydroxynaphthalene1 : 5-Dihydroxynaphthalene&Naphthol ..................3 - Hydroxy - B - naphthoicacid ...........................8 - Naphthol - 6 - sulphonicacid ...........................&Naphthol- 3 : 6 - disulph-onic acid .....................8-Naphthol-6 : 8 - disulph-onic acid .....................2 : 3 - Ilihydroxynaphth -alene ........................2 : 7 - Dihydroxynaphth -alene .......................1 : 8 - Dihydroxynaphth -alene - 3 : 6 - disulphonicacid ...........................8-Ammo-a- naphthol-3 : 6 -disulphonic acid .........Coloration.Clear red, changing to dark cherry-red.Coloration masked by brown oxidation tints.Coloration masked by brown oxidation tints.Bluish-lilac, changing to brown.Bluish-red (like the resorcinol colour), changing toReddish-lilac, changing to brown.Reddish-blue, changing t o brownish-violet.Purple (redder than the a-naphthol colour), changingbrown.to brownish-red.Purple, permanent after twelve hours.Brownish-red, masked t o some extent By oxidationPurple, changing t o brownish-black oxidation tints.Bright green, changing to red and then to brown.Bright green, changing slowly to brown.Emerald-green, changing quickly to reddish-brown.Olive-green, changing quickly to claret.Leek-green, changing quickly to claret.Bluiah-green, changing to dark orange.Sage-green, changing to brovnish-red.tints.Olive, changing to brownish-black.Olive-green, changing to brownish-red.Similar but much less intense colorations were slowly developedon adding 4-amino-3 : 5-dimethylpyrazole to alkaline solutions of thephenolic substances.The colour change evidently needed the inter-vention of atmospheric oxygen. Addition of a small' amount ofdilute hydrogen peroxide accelerated the development of colour,but excess of this reagent destroyed the characteristic tints, givingrise only t o light red and brown shades.The authors desire to express their thanks to the Research GrantCommittee of the Royal Society for a grant which has partlydefrayed the expenses of this investigation.ROYAL COLLEGE of SCIENCE FOR IRELAND,DUBLIN.G G

ISSN:0368-1645    

DOI:10.1039/CT9140500435

出版商:RSC    

年代:1914

数据来源: RSC

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444 ANDREW : THE WATER-GASXLVIII.-TheBYIT has been foundWuter-Gas Equilibrium in Hydro-cmebon Flames.GEORGE WILLIAM ANDREW.that when such hydrocarbons as methane,ethylene, acetylene, etc., are fired with certain proportions ofoxygen, the cooled products from the reaction may consist largelyof water, hydrogen, carbon monoxide, and carbon dioxide.The experiments described herein were made at ManchesterUniversity during 1905-6 at the suggestion of Professor Bone, asan extension o l his researches on hydrocarbon combustion, toascertain how the relative proportions of such constituents, con-sidered more especially from the equilibrium point of view, variedwith variation in the composition and pressure of the gaseoasmixture fired, it being considered possible that thereby some addi-tional light might be obtained on the subject of hydrocarboncombustion.The reversible water--gas reaction :CO + H,O S CO, + Hz,giving a t any temperature to the relation between the concentra-tions of the constituents :has been investigated by many workers, and the results obtainedfrom the interaction of these constituents, either alone or associatedwith inert gases, cover a wide range of temperature.The early experiments of Bunsen (Annaleri, 1853, 85, 137) onthe partition of oxygen between carbon monoxide and hydrogen,when mixtures containing an excess of the combustible gas areexploded, were vitiated by several inaccuracies, particularly thosedue t o the use of a wet eudiometer in the experiments.The sourca of error in Bunsen's experimenh were pointed outby H.B. Dixon (Phil. Trans., 1884, 175, 617), who systematicallyre-investigated the question, and established two essential condi-tions necessary f o r a correct determination of the final equilibriumcondition, either in presence or absence of an inert gas, namely, theuse of a heated eudiometer in order to prevent condensation ofsteam during the initial cooling of the exploded gases, and theattainment of a certain minimum flame temperature. When theseconditions are complied with, Dixon demonstrated that the finalequilibrium is defined by the expression EQUILIBRIUM I N HYDROCARBON FLAMES. 44 5The experimental results of Horstmann (Annulen, 1877, 190,228; Bey., 1877, 10, 1626; 1879, 12, 64) subjected to thermo-chemical analysis by Hoitsema (Zeitsch.physikal. Chem., 1898, 25,695) are untrustworthy, since the above-mentioned conditions werenot complied with.I n 1892 Smithells and Ingle (T., 1892, 61, 214) mentioned thatin their experiments on the composition of the interconal gasesof hydrocarbon flames, the ratio ”’ H90 calculated from theirmost trustworthy analyses, did not differ greatly from 4.0.Later investigations on the water-gas equilibrium have been madeby Hahn (Zeitsch. physikal. Chtem., 1903, 44, 510; 1904, 48, 735),who passed mixtures of steam with carbon monoxide, and hydrogenwith carbon dioxide respectively, over platinum as contactsubstance, a t temperatures below 1400°, whilst Haber, Richardt,and Allner (Haber, Thermodynamics of Technical Gas Reactions,”pp.142, 299, e t Sep.) have obtained figures for the equilibriumconstant Rt in open flames a t temperatures as high as 1500O.Hahn also subjected the reaction to thermodynamic treatment,and has deduced the equation:where F= t + 273.t 0 x H,O’log Kt= - 2232/ T - 0.08463 . log T - 0.0002203T + 2.5084,From such an equation the following values of Kt are derived :to ............... 1006 1205 1405 1600Kt ............. 1.65 2.54 3.43 4-24which are in general agreement with the experimental resultsobtained by Haber, Richardt, and Allner.All attempts experimentally to determine the value of the equili-brium constant at high temperatures are liable t o inaccuracy owingto further interaction in the gaseous system during the coolingperiod.This is accentuated when the gases are in contact withheated surface, but it has also been found that such re-adjustmentmay take place even in free gas space, with considerable rapidityat temperatures above 1600O.EXPERIMENTAL.Mixtures of the individual hydrocarbons, methane, ethane, andethylene with oxygen, were prepared in proportions such as wereknown to give on ignition practically only the constituents of thewater-gas reaction, the actual mixtures employed correspondingapproximately with Clr, + O,, 2CH, + 30,, 2C2HR, + 30,, 2C2H, +Every care was exercised in the preparation of the hydrocarbons,502, CaH, + 202446 ANDREW : THE WATER-GASwhich were finally subjected to rigid purification by low tempera-ture fractionation prior to use, the purity of the hydrocarbon beingproved by explosion analysis.The oxygen was prepared from recrystallised potassium perman-ganate, and the desired gaseous mixture of ascertained composi-tion was dried by passage over calcium chloride, and filled into dry,cylindrical, boro-silicate glass bulbs of 60 C.C.capacity, fitted withplatinum firing wires, similar t o those used by Bone and Drugmanin their experiments on the explosive combustion of hydrocarbons(T., 1906, 89, 662). The pressure and temperature of the gaseousmixture in the bulbs was noted, and the capillary connexionssealed. The bulbs were then heated to 130° in an air-bath, main-tained a t this temperature for thirty minutes, and the contentsthen fired by a spark.The dimensions of the bulbs were such asto permit of ordinary inflammation only; detonation was, of course,impossible. Pinally, the bulbs were cooled, opened in connexionwith a vacuous, capillary manometer, and the pressure and tem-perature of the gaseous constituents ascertained (suitable correc-tions being applied for the dead space of the manometer and thetension of aqueous vapour), and a sample of the gaseous productswithdrawn for analysis.From such data it was possible, by preparing a balance sheetof carbon, hydrogen, and oxygen in the original mixture andproducts respectively, to deduce the amount of water present inthe products within the limits of an experimental error subsequentlynoted, and the reaction constant X t was obtained therefrom.I n general, with a given gaseous mixture, experiments werecarried out a t more than one pressure in order that the effectof a variation in flame temperature might be investigated.I n no way was any deposition of carbon noticed, a point whichis confirmed by the carbon balance sheet.I n some bulbs a faint aldehydic reaction was detected, but thequantity of aldehyde present was not sufficient to materially affectthe results of the investigation.The quantity of water finally present is deduced by the fore-going method and checked by the H2 : 0, ratio in the condensedproducts was probably, in most cases, accurate to within 3 per cent.from the mean value accepted.Tubulat ed Results.The tabulated results refer t o experiments with the six hydro-I n the tables are carbon-oxygen mixtures previously mentioned.noted EQUILIBRIUM I N HYDROCARBON FLAMES.447(1) The percentage composition of the dry nitrogen-free mixtureand products respectively.(2) The absolute pressures reduced to Oo in mm. of mercuryof the dry, nitrogen-free mixture and products noted as P, andP2 respectively.(3) The ratio P, : Pz.(4) The balance sheet of carbon, hydrogen, and oxygen in drymixture and dry products respectively, from which the waterfinally present is deduced.(5) The absolute pressures in mm. of mercury reduced to Oo ofthe carbon monoxide, carbon dioxide, steam, and hydrogen in thefinal products.CHzo deduced from the above data. (6) The constant Kt= ccocvcoz x Gl,TABLE I.Experiments with Mixture CH, -I- 0,.Analysis ofEx-- original mixture Analysis of productspen- (percentage). (percentage).No.CH,. 0,. CO,. CO. &. CH,. mm. mm. P,/P,.ment - PI. P,. /1. 49-5 50.5 8-70 39-65 51-10 0.55 396 400 0.9902. 49.5 50.5 8.60 39.60 51.25 0.55 396 400 0.9903. 49.5 50.5 8.80 39.70 50.85 0.65 532 535 0.994TABLE Ia.Experiments with Mixture CH, -I- 02.Absolute pressure water-vapour in mm. reduced to 0'EX.-peri- Calcu-ment lated UnitoNo: from carbon.Originalmixture... 1961. Producta . 196Deficit . . . .Originalmixture ... 1962. Products . 1951i Deficit . . . .0 riginalmixture.. . 263Deficit . . . .Calcu- Calcu-Units lated latedhydro- Units from fromgen.oxygen. hydrogen. oxygen. Mean.784 400418 228 183 172 277.8366 172784 400419 227 183 173 178.0365 1731051 538558 307 246 231 238.0493 23448 ANDREW : THE WATER-GASTABLE I b .Experiments with &fixture CH, + 0,.Absolute pressures of constituent gases in mm. reduced to Oo.1. 159 177-5 34-8 204 3.982. 158 178.0 34.4 205 4.003. 212 238.0 47.1 272 3.95Mean... . . . . .. K = 3.98.TABLE 11.Ezperiments with Mixture 2CH4 + 30,.Analysis ofEx- original mixtureperi- (percentage). (percentage).ment <-J-, I A \Analysis of productsNo. CH,. 0,. CO,. CO. H,. CH,. P, PY PI lPB'4. 39.70 60.30 35-46 35.45 28.60 0.50 310.0 mm. 172 mm. 1-805. 39.45 60-55 33.90 35-90 29-70 0.50 437.0 mm. 243 mm. 1-806. 39.45 60.55 34.50 35.30 29.70 0.50 437-Omm.243 mm. 1.807. 39-45 60-55 33.90 35.90 29.65 0.55 264.5 mm. 146 mm. 1.818. 39.45 60.55 33.90 35.86 29.70 0.55 264-5 mm. 146 mm. 1-81TABLE IIa.Experiments with Mixture 2CH4 + 30,.EX.-peri- Calcu-ment lated UnitsNo. from Carbon.Originalmixture.. . 1234. Products . 123Deficit . . . .Originalmixture ... 172-55. Products . 271-0i I Deficit . . . .Originalmixture ... 172.5Products . 171.0Deficit .Absolute pressure water-vapour in mm. reduced to 0".h/ \ Calcu-lated Calcu-Units from latedHydro- Units Hydro- fromgen. Oxygen. gen. Oxygen. Mean.492 374102 183 195 191 193390 191690 529149 252 270 277 274541 277690 529149 253 2 70 276 273541 27EQUILIBRIUM IN HYDROCARBON FLAMES.449TABLE IIa (continued).Experiments with Nixture 2CH4 + 30,.Absolute pressure water-vapour in mm. reduced to 0".EX-peri- Calcu-ment lated UnitsNo. from Carbon.Originalmixture... 1047. Products . 103Deficit .Originalmixture.. . 1041Deficit . . . .<Calcu-lated Calcu-Units from latedHydro- Units Hydro- fromgen. Oxygen. gen. Oxygen. Mean.418 32090 151 164 169 166328 169418 32090 151 164 169 166328 169TABLE 116.Experiments with Mixture 2CH4 + 30,.Absolute pressures of constituent gases in mm. reduced to 0".ment K=Experi- cco x CH20,No. c o . s o . co,. H,. CC02 X cH24. 60.9 193.0 60.9 49.2 3.925. 87-2 274.0 82.4 72-2 4.026. 85.8 273.0 83.8 72-2 3.877. 52-4 166.0 49.5 43.3 4-068. 52.3 166-5 49-5 43-4 4.05Mean .........K=3.98.TABLE 111.EX:pen-mentNo.9.10.11.12.Experiments with Mixture 2C2H6 + 30,.Analysis oforiginal mixture Andy& of products(percentage). (percentage).C&& 0,. COP CO. C,H,. H,. CH,. mm. mm. P,/P239.0 61-0 5.35 44.60 nil. 49.00 1.05 272 417 0.65138.9 61.1 5.40 44-50 nil. 49.35 0.75 339 518 0.65538.9 61.1 5.70 44-40 nil. 49.30 0.60 339 519 0.654* & / \ P,. P*.39.0 61.0 5.50 44-15 0.30 49.35 0.70 272 413 0.65450 ANDREW THE WATER-GASTABLE IIIa.Experiments with Mixture 2C2H6+ 30,.Absolute pressure watervapour in mm. reduced to 0'.EX.-peri- Calcu- Unitsment lated Units Hydro- UnitsNo. from Carbon.Originalmixture. , , 2 129. Products . 213Deficit . . . .Originalmixture ...21210. Products . 210Deficit . . . .OriginalI1 mixture ... 264Deficit . . . .Originalmixture.. . 264Deficit . . . .gen. Oxygen.636 331425 230Calcu-lated Cdcu-from latedHydro- fromgen. Oxygen. Mean.105 101 103.0211 101636 331424 227 106 104 105.0212 104792 414527 286 132 128 130.0265 128792 415524 290 134 125 129.5268 125TABLE IIIb.Experiments with Mixture 2CzH6 + 30,.Experi-ment cco x cJ&oNo. co. H,O. co, . =2. K = - cco2 -~ x CR,9. 186.0 103.0 22- 3 205 4.2010. 182-0 105.0 22.7 204 4-1411. 230-5 130.0 28.0 256 4.1912. 230.0 129.5 29.6 256 3.94Mean ......... K=4-12.TABLE IV.Experiments with Mixture ,2C2H6 + 50,.Analysis ofEx: original mixtureperi- (percentage).ment /-A--No. C2q,.0,.13. 27-20 72.8014. 27.15 72.8515. 27.15 72.8516. 27.15 72.85Analysis of products(percentage).A/ ~ P,. P,.CO,. CO. C,H,. H,. CH,. mm. mm. P,/P,.40.35 36.40 0.30 22-65 0.30 454 320 1.42041.85 35.25 0.75 21.85 0.30 293 201 1.46042.25 35.50 0-35 21.75 0.15 293 200 1.46542-05 35.55 0-40 21.70 0.30 346 239 1.45EQUILTRRIUM IN HYDROCARBON FLAMES. 451TABLE IVa.Experiments with Mixture 2C;H, + 50,.EX.-pen- Calcu-ment lated UnitsNo: from Carbon.Originalmixture.. . 247Deficit . ...Originalmixture.. . 15914. Products . 158Deficit . ...Originalmixture.. . 15915. Products . 157Deficit . . . .Original{i mixture.. . 188Deficit . . . .Absolute pressure tvater-vapour in mm. reduced to 0".*/ \ Calcu-lated Calcu-Units from latedHydro- Units Hydro- fromgen.Oxygen. gen. Oxygen. Mean.742 661153 375 294 286 290589 286477 42796 239 190 188381 188477 42791 240 193 187386 187564 505110 286 227 219454 219189190223TABLE IVb.Experiments with Mixture 2CT,H,+ 50,.Absolute pressures of confitituent gases in mm. reduced to Oo.Experi- CCO XQHgOCCOzXCH, 'ment K=NO. co. H,O. GO,. =213. 116.5 290 129.0 72.50 3-6114. 70.8 190 84.1 43.90 3.6215. 71.0 190 84.4 43.50 3-6616. 85.0 223 100.5 51.85 3-64Mean ......... K=3*63.EX-peri-mentNO.17.18.18.20.TABLE V.Experiments with Mixture 2C,H4 -I- 50,.Analysis oforiginal mixture Analysis of products(peroen tap). (percentage).- A PI. pz.c,H,. 0,. CO,. CO. H ~ . CH~.' mm. mm. PJP,30.05 69.95 47-80 36-90 15-00 0-30 738 520 1.42030.05 69.95 47.60 37.30 14.80 0.30 738 518 1.42030.05 69-95 47.55 36.95 15-25 0.25 375 265 1-41530.05 69.95 47.75 36.75 15.20 0-30 375 267 1.40452 ANDREW : THE WATER-GASTABLE Va.Experiments with Mixture 2C,H4 +- 50,.Absolute pressure water-vapoir in mm. reduced to 0'EX-peri- Calcu-ment lated UnitsNo. from Carbon.Originalmixture ... 44417. Products . 442Deficit . . . .Originalmixture.. . 444 ii Deficit . , . .Originalmixture.. . 22519. Products . 225Deficit . . . .Original i Deficit . . . .mixture.. . 22520. Products . 226r Calcu-lated Calcu-Units from latedHydro- Units Hydro- fromgen. Oxygen. gen.Oxygen. Mean.887 1032162 689 362 343 353725 343887 1032159 686 364 345 354728 345451 52484 350 184 174367 174451 52485 353 183 171366 171179177TABLE Vb.Experiments with Mixture 2C2H4 + 50,.Absolute pressures of constituent gases in mm. reduced to (lo.Experi- cco x Ctf.20 K =CCO? X CH2 'mentNO. co. H'2.0. cop H2.17. 192.0 353 249.0 78.0 3.4918. 193.0 354 247.0 76.7 3.6219. 97.9 179 126.0 40-4 3-4420. 98.1 177 127-5 40.6 3.35Mean ......... K=3*47.General Conclwsions.(1) The ratio Kt="O CHzo is almost constant for the mixturesused within limits of experimental error, the value, as thus deter-mined, being to a considerable extent independent of the natureof the hydrocarbon-oxygen mixture fired or the pressure of thegas before ignition.Hence this ratio is apparently independent ofthe maximum flame temperature; the average value is practicallyG o 2 x GIEQUILIBRIUM IN HYDROCARBON FLAMES. 4534, a figure previously found by Dixon (Zoc. cit.) in the inflamma-tion of mixtures containing carbon monoxide, hydrogen, andoxygen.(2) Since under the stated conditions the maximum flame tem-perature would vary with the composition and pressure of themixture ignited, the experimentally-determined constant mostprobably does not correspond with the maximum flame temperature,but is characteristic of some hypothetical temperature, the equili-brium condition a t which corresponds with the integration of thechemical changes which occur in a rapidly cooling mixture fromhigher to atmospheric temperatures.This purely hypotheticaltemperature, which may be referred to as “ t h e temperature offinal reaction” (since it may be supposed that the gases are inequilibrium, and cease to further react at this temperature), isidentified both on thermodynamic and experimental groundsbetween the limits 1500O and 1600O.(3) No calculation is attempted of the flame temperature, sincethere is no accurate information available relative to the increasedspecific heat of the gases, the radiation from the flame, or thenature of any reversible reactions having thermal effects character-istic of high temperatures. In all cases, however, the flame tem-perature would, no doubt, be higher than 1600°, and, assumingequilibrium to be attained in the flame, subsequent readjustmentduring cooling is thus found to take place.(4) The results, thus interpreted, prove the rapidity with whichthe secondary reaction, GO + H,O Z CO, + H,, proceeds during thecooling period of such hydrocarbon flames, and the ready adjustiment of equilibrium in such systems down to a comparatively lowtemperature.(5) Since in the author’s experiments there was no carbondeposited, and the amount of methane in the final gases neverexceeded 1.05 per cent.(being usually 0-3 to 0.6 per cent. only), noconclusion can be drawn therefrom as to the possible influence ofsuch factors on the water-gm equilibrium. Fortunately, however,the previous experiments of Bone, Drugman, and Andrew (T.,1906, 89, 1614) on the explosive combustion of mixtures C,H6+0,and 3C2H4 + 20, under varying conditions, in all cases carbon beingdeposited and larger quantities of methane formed, provide amplematerial for deciding this point.Although in these experiments the temperature of the enclosingvessel was below the saturation temperature of the ultimateproducts, the results, according to the author’s calculations (whichare summarised in the following paragraphs), approximately con-form, so far its the proportions of carbon dioxide, carbon monoxide454 ANDREW : THE WATER-GAShydrogen and water in the final gases are concerned, to the requirements of the water-gas equilibrium at about 1600O.This fact points to the conclusion that in hydrocarbon explosionsthe adjustment of the ‘‘ water-gas” equilibrium during the coolingperiod is not greatly influenced even when relatively large quanti-ties of methane and carbon are found in the final products.(a) Experiments with Ethane.The results obtained with the mixture C,H,+ 0, are reproducedin tabular form, showing the products obtained when this mixturewas fired in a tube, in a spherical vessel, and detonated in a coilrespectively, the yields of deposited carbon and aldehyde producedshowing wide variation, according to the type of vessel.From thecomposition of the gases, the volume of steam as a percentage onthe dry gas, calculated for a thermodynamic constant .ZKt=4, isderived, and the figures are also quoted showing the actual steamequivalent of the condensed hydrogen and condensed oxygenrespectively.It is seen that the proportion of steam thus calcu-lated is in general agreement with that required to account f o r thecondensed products, when it is recalled that in the case of the tubeexperiment these products contained considerable quantities ofaldehydes.MixtureCylindrical vessel.Percentage com- ‘0-position of dry C~HJgaseous products.Calculated steam per-centage on dry pro-ducts from &=a.Steam deducedcondensed hydrogzm}Steam deducedcondensed oxygen.from}Percentage original car- \bon deposited. 1C2HG + 0 2 .Sphericalvessel.3.4036.10 34.800.157.2544.50 53-05E}8.8521.5 20.029.8 17.826.3 15.37.6 18.0Detonation incoil.1.8039.10{ :::: 7.7050.009.213.211-73.0( b ) Experiments with Mixture 3C,H4 + 20,.Three experiments were made with the same mixture, correspond-ing with 3C2H, + ZO,, fired in three vessels of different shape anddimensions.The .following summarised calculations point, ae inthe case of the mixture C,H, + O,, to the general agreement, withinthe limits of experimental error, between the quantity of wateEQUILIBRIUM IN HYDROCARBON FLAMES. 455actually formed and the calculated amount required for a thermo-dynamic constant Ht = 4.Descriptionof vessel.cop co.Percentage com- C2Hpposition of dry C,H,.gaseous products. CH,.Steam per cent. on dryproducts calculated fromSteam deducedcondensed hydrogeFm}Steam deducedcondensed oxygen.from}Percentage original car-bon deposited.I Ha.Kt = 4.Shortnarrowcylinder.2.6537-3510.002.904-1542-200.7512.016.614-716.0Longerand widercylinder.2.5040-101.255.2047.20nil11.718.012.329.03-75 \Sphericalveseel.0.5041.450.402.9054.75nil2.64.83.931.0( c ) Experiments with Mixture 2C2H2 + 0,.A similar deduction might perhaps also be made from the resultsobtained on ignition of a mixture 2C,H2+0,, which has beenshown by Bone and Andrew (T., 1905, 87, 1241) to give rise to aseparation of carbon without any visible condensation of moisture.From the results obtained from the final products i t is found thatthe value Kt = 4 would only require the presence in a bulb originallyfilled at 727 mm.of an amount of water-vapour having a partialpressure of 12 mm. Such an amount might readily escape con-densation a t room temperature.(6) It is thus apparent that the explosive combustion of numer-ous hydrocsrbon-oxygen mixtures, under widely differing condi-tions of incomplete combustion, gives rise to products which atleast approximately conform to the requirements of the water-gasequilibrium with a value of 4 for the thermodynamic constant, andthat this value is not greatly altered even when large quantitiesof carbon are separated or a considerable percentage of methanefound in the ultimate products; it is possible that other secondaryreactions also play an important r61e,' and the author believes thata fuller knowledge of t h s e possibilities, together with moreaccurate data relative to the thermal decomposition of hydro-carbons a t the very high temperature of flames and their possibleinteraction during cooling with primary decomposition and combus-tion products, would throw additional light on the subject ofhydrocarbon combustion. Professor Bone has, in his publishedlectures, emphasised the important r61e which secondary reaction456 FRANKLAND AND TURNBULL: THE ACTION OF PHOSPHORUSmust play in explosive combustion; thus in comparing the condi-tion of slow and explosive combustion of hydrocarbons, he expressedthe opinion (lecture at the Royal Institution, February 28th, 1908,p. 6 ) that whereas the mechanism of combustion is essentially thesame above as below the ignition-point in so far as the result of theinitial molecular encounter between the hydrocarbon and oxygenis concerned, yet “ a t the higher temperatures of flames secondarythermal decompositioiis undoubtedly come into operation at anearlier stage, and play a more important r61e than in slow combus-tion, but they do not precede the onslaught of the oxygen on thehydrocarbon, but arise in consequence of it.”The author desires to express his thanks to Professor Bone forsuggesting the research, and for advice during its progress.RUTIiwuL R.S. O.,DUMFRIESSH IRE

ISSN:0368-1645    

DOI:10.1039/CT9140500444

出版商:RSC    

年代:1914

数据来源: RSC

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456 FRANKLAND AND TURNBULL: THE ACTION OF PHOSPHORUSXLIX.-The Action o f Phosphorus Pentuchloride on theOptically Active &Di- Esters o f G'lyceric Acid. -chloropopionates.By PERCY FARADAY FRANKLAND and ANDREW TURNBULL.THE experiments recorded in this communication were made somefifteen years ago, soon after the discovery of the "Walden In-version," and were undertaken with the view of furnishing furtherexamples of that transformation. Owing to circumstances we wereunable to complete the investigation, and the results have hithertoremained unpublished, although they have been referrid to inoutline by one of us (P. F. Frankland, Presidential Address, T.,1913, 103, 718).By acting on the methyl, ethyl, isobutyl, and heptyl esters of theactive glyceric acid of Frankland and Frew (T., 1891, 59, 96),which are all lzvorotatory, opticaITy active ap-dichloropropionateswere obtained, of which the methyl compound alone was dextro-rotatory, whilst the others were laevorotatory. The relationshipbetween the optical activity of the glycerates and the ap-dichloro-propionates to which they give rise, is seen from the followingtable :[ M y [MI:".Methyl glycerate - 5.76' -+ Methyl aB .dichloropropionate + 2.67'Ethyl 1 9 - 12.30 -+ Ethyl 7, - 3.06isoButyl ,, -23.05 -+ isoButyl 9 9 - 7.20Hepty1 9 9 -23.05 -+ Heptyl Y9 - 4.1PENTACHLORIDE ON TRE ESTERS OF GLYCERIC ACID.457That the difference in sign between the rotation of the methyl,on the one hand, and of the other afl-dichloropropionates on theother, indicates a difference in configuration between them respec-tively is prima facie highly improbable, whilst the identity of theirconfiguration is rendered alqiost certzin by the uniformity in thef 4=$ 20 & x- 2- 4- 6-8INFLUENCE .j T€MP€RATUREon theMOLECULAR ROTATION ofa( 8-D I C H LOR 0-PR OPI 0 N I CI I I L0" 20" 40" 60" 80" 101influence of temperature on their optical activity.Thus, from theaccompanying diagram, i t will be seen that, whilst rise of tempera-ture increases the dextrorotation of the methyl aS-dichloropro-pionate, it diminishes the 1;evorotation of the higher esters. If thelatter were of enantiomorphous configuration to the methyl ester,their laevorotation would doubtless be increased by rise of tempera-VOL. cv.H 458 FRANKLAND AND TURNBULL: THE ACTION OF PHOSPHORUSture. I n this connexion it may be mentioned that rise of tem-perature increases the lmmrotation of all the esters of glyceric acid(P. Frankland and MacGregor, T., 1894, 65, 760).On the other hand, i t is still a matter of uncertainty as t owhether the uj3-dichloropropionates have the same or the oppositeconfiguration t~ the glycerates from which they are obtained(P. Frankland, T., 1913, 103, 738).The actual figures given for the rotation of the ap-dichloropro-pionates must necessarily be accepted with reserve as we have noknowledge as t o whether, and if so, to what extent, racemisationhad taken place in the action of the phosphorus pentachloride onthe glyceric esters, which were themselves all employed in anoptically pure condition.I n preparing the afl-dichloropropionates there was alwaysobtained also a fraction of higher boiling point, which in the caseof the methyl and ethyl compounds deposited a white solid, melt-ing, after purification, a t 7 1 O and 3 6 O respectively. Analysis andmolecular-weight determination show that these producta aredoubtless of the type CH,C1*CC12*CC12*OR orCHCl,* CHCI*CCl,*OR,in which R is methyl, ethyl, isobutyl, and heptyl respectively.I n the case of the methyl compound the solid had the samemelting point, 71°, irrespectively of whether it wae obtained fromactive or inactive methyl glycerate.Both the solid methyl andethyl compounds were inactive; the liquid isobutyl and heptyicompounds were not examined for activity, being presumablyinactive also.The fact that these highly chlorinated compounds were inactivesuggests that the following may be the mechanism of their forma-tion from the afl-dichloropropionates :$!H,CII P'$!H,Cl R H2 vH,Ci CCI, -+ YHCl --+ $El -+C0,R C0,R C'C1 x:& \ORor or nrYHCI,SHCI VHCI, CHCl%HCO,Rp c 1CO,RI /CIc,-CI\ORThese compounds are obviously pentachloropropyl ethers.Com-pounds of a somewhat similar nature are already known; thusdichloro-oxalic ester, CCI,(OEt)-CO,Et, is obtained by the action ofphosphorus pentachloride on ethyl oxalate (Anschutz and StiepelPENTACHLORIDE ON THE ESTERS OF GLYCERIC ACID. 459Bey., 1895, 28, 61). Again, ethyl dichloro-oxalyl chloride,CCl,(OEt)~COCl, is obtained by the addition of oxygen to trichloro-vinyl ethyl ether, CC1,:CCl-OEt (AfinaLen, 1899, 308, 324 ;L.Henry, Rev. truv. cham., 1899, 18, 215).EXPERIMENTAL.Methyl ap-Dichloropropiomt e.Eighty-four grams of methyl glycerate (a, - 12*53O, I = 198-4mm.) were dissolved in 240 grams of chloroform, and slowlydropped through an inverted condenser into a flask containing200 grams of phosphorus pentachloride (292 grams are theoreticallyrequired) and 80 grams of chloroform. Some four hours wereoccupied in the addition of the ester to the phosphorus penta-chloride, aqd the mixture was then heated to boiling until thephosphorus pentachloride had dissolved, when a further quantityof 50 grams was added.On cooling, phosphorus pentachloridecrystallised out, and the liquid was poured off and the crystalswashed with chloroform, the washings being added to the liquid.The latter was now distilled free from chloroform under the ordin-ary pressure on the water-bath; the distillation was then continuedunder diminished pressure (100 mm.), the phosphoryl chloridepassing over at 55--60°. The residue was dissolved in chloroform,and returned to the flask containing the phosphorus pentachloridepreviously unacted on, together with a further quantity, themixture being again heated until evolution of hydrogen chlorideceased. The phosphoryl chloride was then again removed asdescribed above. This alternate treatment with phosphorus pent&chloride and removal of the phosphoryl chloride formed wasrepeated in all nine times, the total quantity of phosphorus penta-chloride used being 400 grams, of which 98 instead of the 108 gramsrequired by theory were recovered.The chloroform solution of the product, free from phosphorylchloride, was shaken with water and then with a solution of sodiumhydrogen carbonate, separated, dried with calcium chloride, freedfrom chloroform under normal, and then fractionated underdiminished, pressure until a product of constant rotation wasobtained.I n this manner 10 graxns of a colourless liquid, distillinga t 9Z0/50 mm. with the oil-bath a t 140°, were collected. I n thefractionation a white solid, described below, was also obtained.The liquid gave the following results in the Carius determina-tions of the chlorine :I.0.3969 required 0-8627 AgNO,. Cl= 45-39,0.3969 gave 0.7245 AgC1. C1= 45.13.H H 460 FRANKLAND AND TURNBULL: THE ACTION O F PHOSPHORUS11. 0.1897 required 0.4112 AgNO,. C1=45.26.0.1897 gave 0.3461 AgCl. C1=45*11.C,H,O,Cl, requires Cl= 45.22 per cent.The following density determinations were made :d 12°/40=1a3382; d 2Oo/4O= 1.3282; d 45'/4O=1*2947;a? 68'/4O= 1'2648.Rotation of Methyl ap-Dichloropropionate(obtained from lzvorotatory methyl glycerate).t. tlt0/4". a,. [a]". [MID.1=99-9 mm. :3.5O 1.3500 + 1.28O + 0.95" + 1-49'13.5 1.3365 1.96 1-47 2.3120.0 1.3282 2.26 1-70 2-6743.5 1.2975 3.04 2.35 3.6954.5 1.2825 3.26 2.54 3.99I n the first fractionation of the crude product obtained by theaction of phosphorus pen tachloride on methyl glycerate, the secondfraction, which had passed over a t 115-120°/20 mm.and theoil-bath a t 165O, was a white solid amounting to 14 grams. Thefraction before solidification exhibited a rotation of :a:'' -2'47O in a 99.9 mm. tube.On redistillation, 6 grams were obtained between 115O and 125O/15 mm. and bath a t 1 6 5 O . After spreading on a porous plate, thesolid melted a t 70-70'5O. It had a slightly acid reaction, so itwas dissolved in light petroleum and shaken with a solution ofsodium hydrogen carbonate, separated, and dried with calciumchloride. After allowing the petroleum to evaporate, the crystalsmelted at 71O. The light petroleum solution was inactive.This solid was in every respect identical with a solid similarlyobtained by the action of phosphorus pentachloride on inactivemethyl glycerate, which melted a t 71°, had a pleasant, camphor-likeodour, and separated from light petroleum in colourless plates.Itis also very soluble in alcohol, ether, chloroform, benzene, or glacialacetic acid. It is insoluble in water, and on adding silver nitrateto the mixture there is no change, but, on boiling, a white precipi-tate insduble in nitric acid at once separates:I. 0-2141 required 0.7370 AgNO,.11. 0.4419 required 1.5240 AgNO,.Lead chromate and silver foil were used in the following com-C1= 71-88.C1= 72-02.0.2141 gave 0.6179 AgCl. C1= 71.36.0.4419 gave 1.2801 AgC1. C1=71.63.bustions PENTACHLORIDE ON THE ESTERS OF GLYCERIC ACID.461I. 0.1578 gave 0.1115 CO, and 0.0320 H,O. C= 19.27; H=2*25.11. 0.1638 ,, 0.1167 CO, ,, 0.0360 H,O. C=19*43; H=2*44.C4H,0Cl, requires C = 19.47 ; H = 2.03 ; C1= 72.01 per cent.The following cryoscopic determinations of the molecular weightI. 0.5017, in 10.0 of benzene, gave A t = - 1.039'. M.W. = 236.6.were made in benzene solution:11. 0.7020, ,, 10.0 99 ,, At = - 1.453'. M.W. = 236.7.C4H,0Cl, requires M.W. = 246.5.The compound has, therefore, the formula :CH,Cl*CCI,*CCl,*O*CH, or CHCl,*CHCl*CCl,*O*CH,.Ethyl a fl-Dichloropopionat e.The preparation was carried out on essentially similar lines t othose above described for the methyl compound.Seventy-six grams of ethyl glycerate (a: - 22-73', I = 198.4 mm.)were exhaustively treated with phosphorus pentachloride.Sixteengrams of final product were obtained, boiling a t 110°/75 mm., batha t 150'I. 0.2825 required 0.5655 AgNO,.11. 0.2784 required 0.5579 AgNO,.C1=41*80.0.2825 gave 0.4754 AgC1. C1=41.62.C1= 41-86.0.2784 gave 0.4693 AgCI. C1= 41.69.The following density determinations were made :C,R,O,Cl, requires C1= 41-52 per cent.d 16'/4'=1'2554; d 20°/40=1.2505; d 42°/40=1.2228;d 57'14' = 1.2048.Rotation of Ethyl a fl-Dichloroprop'onat e(obtained from lzvorotatory ethyl glycerate).f. dt0/4". a,. [a]=* [ b11D.I =99-9 mm.1 2*0° 1.2600 - 2.47" - 1.96O - 3.35020.0 1.2500 - 2.23 - 1-79 - 3.0639.5 1.2260 - 1.71 - 1.40 - 2.3956.5 1.2050 - 1.17 - 0.97 - 1.66In the original fractionation of this ester the higher fractionswere dissolved in chloroform; the solution was shaken for fourhours with an aqueous solution of sodium hydrogen carbonate,separated, and dried with calcium chloride.On evaporating thechloroform 6 grams of a liquid, which crystallised on keeping, wereobtained. This was redistilled (boiling point 112-114O/ 12 mm.,bath a t 155O), and the distillate (4 grams) found to be inactive462 FRANKLAND AND TURNBULL: THE ACTION OF PHOSPHORUSAfter repeated crystallisation from light petroleum the constantmelting point, 36O, was obtained.I. 0.2028 required 0.6668 AgNO,.11. 0'2142 required 0.7002 AgNO,.C1= 68.66.C1= 68.26.0.2028 gave 0.5594 AgCI. C1= 68.21.0.2142 gave 0.5886 AgCl. C1= 67.95.H = 2.91.111.0.2263 ,, 0.1930 CO, and 0.0592 H20. C=23*26;IV. 0-2745 gave 0.2316 CO, and 0.0665 H,O. C=23.01;H = 2-69.C,H,OCl, requires C = 23.03 ; H = 2.69 ; C1= 68.14 per cent.CH2C1*CC1,*CC1,~O*C,H, or CHC1,*CHC1*CC1,*O*C2H,.The compound has therefore the formula :isoButyl ap-Dichloropropionate.Seventy-eight grams of isobutyl glycerate (a, - 16-58O,1 = 99.2 mm.) were similarly treated with an excess of phosphoruspentachloride in chloroform solution. By repeated fractionationof the product, 14 grams were ultimstely obtained (b. p. 127O/62mm., bath 182*), exhibiting a constant rotation:0.2246 gave 0.3299 AgC1. C1= 36.32.0.2727 gave 0.3981 AgC1. C1= 36.10.I. 0.2246 required 0.3928 AgN03.11. 0.2727 required 0.4731 AgNO,.C1= 36.52.C1= 36.23.111.0.2479 ,, 0.3789 CO, and 0-1342 H20. C=41*68;C7Hl2O,Cl2 requires C = 42-21 ; H = 6-03 ; C1= 35.68 per cent.The following density determinations were made :H = 6.01.d 16O/4O= 1.1619 ; d 2lo/4O= 1.1565 ; d 37*5'/4* = 1.1378 ;d 65O/4O= 1.1076.Rotation of isoButyl ap-Dichloropropionate(obtained from lzevorotatory isobutyl glycerate).t. dt"I4". a D. [QID. I If ID.1 =99*9 mm. :14.5' 1.1640 - 4.34" - 3.73" - 7-42'20.0 1.1580 -4.19 - 3.62 - 7.2040-5 1.1350 - 3-75 - 3.31 - 6.5968.0 1.1050 - 3.21 -2.91 - 5-79I n the preparation of this ester, again, a fraction of high boilingpoint was obtained (10 grams, 136-14Z0/19 mm., bath 1 8 5 O ) ; byfurther fractionation this was reduced t o 5 grams (b. p. 140°/20 mm., bath 191O). It was a viscid, colourless liquid with anodour resembling t h a t of aniseedPENTACHLORIDE ON THE ESTERS OF GLYCERIC AClD.463I. 0.2196 required 0.6431 AgNO,.11. 0.2258 required 0.6603 AgNO,.Cl= 61.16.C1= 61.06.0.2196 gave 0-5463 AgCI. C1= 61-52.0.2258 gave 0.5585 AgCl. C1=61.16.111. 0.2352 ,, 02531 CO, and 0.0820 H,O. C=29*34;C7H,,0C1, requires C = 29.12 ; H = 3.81 ; C1= 61.52 per cent.CH,C1*CC1,*CCl2*O*C,H, o r CHC1,-CHCI*CCl2*O*C4H,.H = 3.87.The compound has, therefore, the formula :Heptyl afl-Dichloropropionate.Seventy grams of heptylglycerate (aD - 11.75O, I = 100.45 mm.,t = 22O) were similarly treated with excess of phosphorus penta-chloride in chloroform solution. On subsequent distillation underdiminished pressure, a high and a low boiling fraction were ob-tained. The latter was refracjionated until of constant rotation,and 18 grams were obtained, boiling a t 144--148°/18 mm.,bath 186O:I. 0.2002 required 0'2790 AgNO,.11. 0.2102 required 0,2933 AgNO,.C1= 29.10.C1= 29-14,0.2002 gave 0.2379 AgCI. C1= 29.38.0-2102 gave 0.2480 AgCl. C1= 29.17.The following density determinations were made :CloH1,O,Cl2 requires C1= 29-46 per cent.d 13*5°/40=1*0960; d21°/40=1'0894; d 50°/40=1*0607;d 79'/4O= 1.0321.Rotation of Heptyl aS-Dichloropropionate(obtained from lzvorotatory heptyl glycerate).t. dt /4". an. [ale. [ 1 I I D .12.0° 1.0980 - 2.02O - 1-84' - 4.43OI = 99.9 mm. :20.0 1.0900 - 1.88 - 1.73 -4.1740.0 1.0710 - 1-73 - 1.62 - 3.9053.0 1-0580 - 1.63 - 1.54 - 3.7199.0 1.0230 - 1.29 - 1-26 - 3.04The fraction of high boiling point, on redistillation, passed overa t 153-154°/20 mm., bath 1 8 8 O ; it doubtless consisted of thecompound CH2C1*CCl,*CC1,*O*C7Hl, o r CHCl2*CRC1*CCl2*O*C7Hl5,but was not further examined.CHEMICAL LABORATORIES,UNIVERSITY, EDGBASTON, BIKMIKGHAY

ISSN:0368-1645    

DOI:10.1039/CT9140500456

出版商:RSC    

年代:1914

数据来源: RSC