摘要:

VANSTONE : SODIUM AMALGAMS. 261’7CCXLV. -Sodium Amalgams : Specific Volumes andElect &a 1 Conductivities.By ERNEST VANSTONE.AN account has already been given of the investigation of thethermal diagram and the determination of the specific volumes ofsolid and liquid sodium amalgams (Tram. Faraday Soc., 1911, 7,42).It wzs shown that when specific volume was plotted againstconcentration of amalgam expressed in atomic percentages, smoothcurves were obtained, although the corresponding thermal diagramshowed many discontinuities.Since the publication of the first paper, the specific volumes havebeen plotted against concentrations expressed in percentages byweight. It was shown by Meey ( Z e i t s c h . p h p i l i d Cherti., 18992618 VANSTONE : SODIUM AMALGAMS :29, 119) that the specific volume of alloys is a linear function ofthe concentration expressed in percentages by weight, hence thenew volume-concentration diagram (Fig.1) consists of a numberof straight lines, having nearly the same obliquity, and confirms theexistence of inter-metallic compounds shown by the t'hermaldiagram.The concentrations (in atomic percentages of sodium) where theFIG. 1..O 5 10 15 20 25 30 35 40 5discontinuities occur ar0 given below; those obtained by the thermalmethod are given for comparison.Concentrations.Weight per cent. Atoms per cent.36.0 83-023.6 73-516.4 63.09.4 47.55.2 32.52-8 20-0Atoms per cent.(thermal).85-2 and 83.473.563.347.5 and 51.533.317.9When the comparative slope of the lines in Fig.1 is considered,and the fact that the concentrations have t o be read from thediagram in percentages by weight and then transformed intSPECIFIC VOLUMES AND ELECTRICAL CONDUCTIVITIES. 2619atomic percentages, the agreement becween columns (2) and (3) inthe above table is as satisfactory as can be expect,ed.The Constitution of Liquid Amalgams.Many reeearches have been carried out on liquid amalgams,having f o r their object tho determination of the molecular com-plexity of metals in amalgams rich in mercury.Measurements of (1) vapour pressure, (2) E.M.F., and (3) lower-ing of freezing point show that the metal is present as a singleatom, yet they cannot prove1 that that atom is not combined witha certain number of atoms of mercury.Two other researches may be mentioned.(1) The rat- of diffu-sion of metals in mercury have been found, and when atomicdiffusivities are plotted against atomic weights, two curves areobtained; metals which do not form compounds with mercuryhave higher diffusivities and lie on one curve, whereas metalswhich are known to form compounds lie on a second curve withlower diffusivities. It has been suggested that compounds MHg,are formed in which the attached mercury retards the process ofdiffusion.(2) Bornemann and Muller (Metallurgie, 1910, 7, 396) deter-mined the electrical conductivity of liquid sodium amalgams, andobtained a marked discontinuity a t a concentration of 33.3 atomsper cent. of sodium, showing the existence of the compound NaHg,in the liquid condition.The thermal diagram indicates the existence of a t least fiveother compounds of sodium and mercury, but their existence inthe liquid condition was not made manifest by the electricalconductivity experiments.We are led to inquire why this is so.Bornemann and Muller'sexperiments were carried out a t very high temperatures, and it ispossible that all the other intermetallic compounds were disso-ciated; the compound NaHg, was stable, since it has a muchhigher melting point, namely, 360°, than the other compounds;i t lies at the maximum point on the thermal diagram; other com-pounds, with the possible exception of Na,Hg, do not showmaxima.It was thought Ghat indications of the existence of the otherintermetallic sodium-mercury compounds might be obtained ifphysical properties were investigated a t temperatures not farremoved from the melting points of the alloys.The specific volumes of liquid alloys a t l l O o , 184O, and 237Ohave already been determined.The concentration-volume diagram for llOo is shown in Fig.2It, is seen t h a t the specific volume of the liquid alloys is a linearfunction of the concentration when expressed in percentages byweight.The absence of discontinuities shows t h a t the intermetallic com-pound Na,Hg does not exist a t l l O o .A consideration of Fig. 1 shows t h a t the property of volumedoes not suffer any profound change when combination takesplace between the metals sodium and mercury, so further investi-FIG.2.gations were made by means of electrical cor1ductivit.y rneasure-ments of liquid amalgams.The Electrical C o i i d i i c t i u i t i e s of Liquid A tnalgams.The method of experiment has already been described in a formerpaper. The amalgams were kept under paraffin, and drawn upinto a capillary spiral having platinum terminals sealed into theglass a t convenient pointsSPECIFIC VOLUMES AND ELECTRICAL CONDUCTIVITIES. 2621The spiral was open a t the lower end and fitted with a glasstap a t the top. It was connected t o a hydrogen apparatus, andbefore, allowing any amalgam t o enter, it was dried and filled withdry hydrogeri.The1 capillary was 1 mm. in diameter, and the distance betweenthe platinum terminals about a metre, when unwound.Itl wascalibrated by finding the resistance of me'rcury filling the spiral.3.52-51 ' 50 '565 70 80 90 100Temperatures of approximately l l O o and 1 3 5 O were obtained byjacketing with boiling toluene and xylene.The results are given in the table below; concentrations areexpressed in atomic percentages of sodium ; the resistances referto a spira in which the resistance of mercury at. 1 7 O is 1 ohm.It will be noticed that conductivity measurements have beenmade for each alloy a t two t-emperatures differing by 2 6 O . Thevalue for the temperature-coefficient has thus been obtained2622 VANSTONE : SODIUM AMALGAMS.Electm'cal Conductivities of Liquid Amalgams.Concentra- Resistance Conduct- Resistance Conduct- Ternperature-at 107".ivity. (133") ivity. coefficient. tion.10095-3693.6489.8885.6080.8077.8975-317 1-7470.0268-080.22850-42250.58350.77490.97961.15691.21241.25321.29211.2968-4.3972-3661.7141.29051.02080-86430.82480.79790.77390.7711-0.2455 { 0.24490.24770.43340-81391.01331.16271.22481-25841.30871.30961-3208-FIG. 4.4.0652.3071.22860.98680.86000.81640.79460.76410.76350-7571-0.0 12760.002260.002380.001300.000 160.000320.0001 30.000400.00054--60 70 80 60 100Atoms of sodium per 100.The conductivity-concentration curve for 1 0 7 O is shown in Fig. 3.It is a rectangular hyperbola possessing no discontinuity. Theresults for 1 .3 5 O form a similar curve, which would lie slightlybelow that in Fig. 3DUNNINGHAM: THE SYSTEM ETHYL ETHER, ETC. 2623It will be observed that the fall in conductivity is most markedfrom 100 to 85 atoms per cent. of sodium, the conductivity a t85 per cent. being less than onefourth the value for pure sodium.It may be pointed out that thO concentIration of 85 per cent. isthat of the eutectic point in the thermal diagram.The differences in conductivity for a temperature range of 2 6 Oare small, and become much smaller as the mercury content of thealloys increases.The temperature-coefficient falls with extreme rapidity as wepass from pure sodium to alloys containing 5 and 10 atoms percent. of mercury. The coefficient has an extremely small, almostconstant value for alloys containing more than 20 atoms per cent.of mercury. This is shown in Fig. 4. The curve does not give anyindication of the formation of compounds.The conclusion to be drawn from electrical conductivity measure-ments for liquid amalgams is thus the same as from specific volumedeterminations, namely, that the intermetallic compounds ofsodium and mercury are completely dissociated in the liquidcondition.It is possible also from the present and from previous work tocompare the relative values of the properties specific volume,electrical conductivity, and freezing point in determining theconstitution of alloys, and it is quite evident that the last is farsuperior in the certainty of its indications.THE TRAININU COLLEGE,CAERLEON,MONMOUTHSEIRE

ISSN:0368-1645    

DOI:10.1039/CT9140502617

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

DUNNINGHAM: THE SYSTEM ETHYL ETHER, ETC. 2623CCXLV1.- The System Ethyl Ether- Water-PotassiumIodide-Mercuric Iodide. Part I1 I. SolutionsUnsaturated with Respect to Solid Phases in theFo.rw-component System.By ALFRED CHARLES DUNNINGHAM.THE fact that the surfaces of saturation with respect t o solid phasesdivide the tetrahedron into two parts has been used as an arbitrarydivision in the consideration of the system. That part representingsupersaturated solutions, or complexes of solid and solution, hasalready been considered (this vol., p. 724, e t sep.). The otherrepresents liquid phases only, and extends from the surfaces o2624 DUNNINGHAM : THE SYSTEM ETHYL ETHER-WATER-saturation with respect t o solid to the edge B(7 of the tetrahedron(Fig. 11, Part 11).It is therefore bounded by the solid saturationsurfaces and portions of the side-planes, namely, HFGHJZ on L4 BD,Cabcfmgde on A4GD, BFFn’Md7 on .3BC, and BZQPrC on BDC. Ithas been found experimentally that liquid mixtures unsaturatedwith solid phases can exist as one, two, or three layers respectively.FIG. 13. Fra. 14.LThe above space representing liquids only is therefore divided intoat least three parts, corresponding with t,hese three cases.The Formition of Two Liquid Lciyers.It will be well t o consider first the conditions under which liquidmixtures, unsaturated with solid phases, can exist as two layers.I n a four-component system all such mixtures lie inside what maybe called a “two liquid volume,” whilst the layers themselves aregiven by points on the surface enclosing this volume.A “twoliquid volume.” if complete, is more or less egg-shaped, and iscircled by a critical curve, AX3BIC4, as shown in Fig. 13.* Thiscritical curve divides the binodal surface into two parts, such thatany solution u on one part is conjugate with a definite solution b* Fur Fig. 12, see this vol., 1’. 731POTASSIUM IODIDE:-11ERCURIC IODIDE. PART 111. 2625011 the other part. The line c t h , wliicli lies entirely inside the two-liquid space, represents all mixtures of cc and b .two-liquid volume " may be intersected by the side-planesof the tetrahedron, or by tlie solid saturation surfaces of t,lie system,so that part of it becoliies inetastable. I n Fig. 13 LA,IRN representssuch a curve of intersection, so that either the upper or lowerportion of tlie two-liquid space is rendered metastable.4 LU aridA XU are conjugate curves, that is, solutions given by points onALU are iii equilibrium with definite solutions given by points onAIiU. That this must be so will be seen at once from the followingconsiderations. When La1 h'B is the curve of int'ersection of a side-plane with the binodal surface, it lies entirely in that side-plane,which represents a three-component system. If solutions on d L.7)were not in equilibrium with solutions on ARB, they would there-fore be conjugate with solutions given by points somewhere elseon the right-hand side of ths binodal surface; that' is, either insideor outside) the tetrahedron.I n the former case a solution on ALBin a three-component system would be in equilibrium with asolution in a four-component system in the latter with a non-existent solution. I n a similarway it can be shown that when the binodal surface is intersectedby a solid saturation surface, ALB and BRB arel conjugate, for ifthey were not, a saturated solution would be in equilibrium witheither an unsaturated o r a supersaturated soiution. When,however, the binodal surface is intersecteld by a plane such as A LUin Fig. 11 (Part II), ALB and ARB are not' necessarily conjugate.I n Fig. 11 (Part 11) NRSK,TUiCf and &&-,P are curves of inter-section of a binodal surface, and thel solid saturation surfaces, whilstN X and MY, &S and PY are curves of intersection of the binodalsurface and the side-planes.XNRSK,T UiIlYPK,QZ thereforerepresents the boundary of the stable portion of the binodalsurface, K , and I!, being points on the critical curve, the stablepart, of which therefore extends from K , t o K,.The relation between the stable and metastable portions of thetwo-liquid space is shown in Fig, 14, which is lettered t o correspoiidwith Fig. 11. The critical curve KIKz divides the stable portion ofthe binodal surface into two parts, NRSK,K,QX andX U TK',X,PP,such that all solutions given by points on one part are conjugatewith solutions given by definite points on the other part. When,therefore, all pairs of conjugate points on NRSK,K,&X aiidMUTK,K,PY are joined, a space is formed, inside which lie allliquid mixtures existing as two layers.This space is bounded bythe stable portion or" the binodal surface, XNRSE,T TiillYPX,&Z,ANeither of these cases is possible2626 DUNNINGHAM : THE SYSTEM ETHYL ETHER-WATER-and the surfaces formed by joining all pairs of conjugate pointson the following pairs of lines: E2Q and K2P, &X and P P , X Nand Y M , NR and M U , RS and U T , SK, and TK,. Outside thisspace lis unsaturated homogenous liquids, so that the stablebinodal surface divides the unsaturated space into two parts, oneof which represents liquid mixtarss existing as two layers, the otherhomogeneous liquids. The latter is bounded by the followingsurfaces (see Fig. 11, Part 11):(1) The binodal surface XNRSK,T UMY PK,QZ.FIG.15.1 /(2) The saturation surfaces FNRG, MabU, GRSH, UbcfrnnpwT,HSK,TwJ, ZJzwpnmgdePKzQ.(3) The portions of the side-planes BFGHJZ on ABD,Cabcfmgde on ACD, BFNX and CaMP on ABC, and ZQXB andCYPe on BDC.The conjugatel curves cp and f r z , cd and f g , g n and d p appear tobe intersections of saturation surfaces and side-planes with a secondbinodal volume which extends into the tetrahedron, and, as willbe shown later, intersects the binodal volume, of whichNRSK,I'UMYPK,Q Xis the stable part of the surface.As in the case of solutions saturated with solid phases, the reacPOTASSIUM IODIDE-MERCU RIC IODIDE. PART III. 2627tions occurring in the system are best understood by studying theintersections of a series of planes with the binodal and saturationsurfaces. Fig.15 shows diagrammatically the curves of intersectionon such a plane ax ADL iu Fig. 11. As in Fig. 12 (Part II),puYxyhk is t.he curve of intersection of the solid saturation surfaces,x and h lying on the critical curves SKIT and QK,P respectively.The intersection of the plane with the stable binodal surface there-fore extends from x to h, as shown by the curve xdh in Fig. 15.I n this figure it is assumed that L represents a mixture of etherand water in which netither component is present in sufficientlylarge proportion to cause complete miscibility. puvxyhkL represents liquid mixtures. Those lying on xdhy are homogeneous; thoseon puvxdhkL exist as two layers. If L is joined to x and h, andLx and Lh are produced to meet ,40 in a and c respectively, theline AD, which represents mixtures of potassium and mercuriciodides, is divided into three parts.Points on A a and cD representmixtures which on addition to L cause saturation without homo-geneity. Mixtures on ac, however, on addition t o L cause theliquid to become homogeneous before saturation is reached; forexample, on adding the solid mixture b t o the liquid L, the mixturefollows the line Lb. From L t o d it exists as two layers; at d itbecomes hDmogeneous, and then follows df until saturation isreached a t f. The solid phase is necessarily potassium mercuri-iodide, mercuric iodide, or, if Lb passes through y, a mixture ofthe two.The position of L on BC (Fig. 11) determines the positions ofx and y on the curvM SKIT and QK,P respectively. In most casesthe plane A D L cuts the critical curve K J 2 in a point e ; xe and ehlie on opposite sides of this critical curve.When, therefore, Lbcuts xe, which represents upper or ethereal layers, the mixturebecomes homogeneous by the disappearance of the lower layer andpersistence of the upper. When it cuts eh (as in Fig. 15), whichrepresents lower o r aqueous layers, homogeneity ensues by thedisappearance of the upper layer and persistence of the lower.When Lb passes through e, the two layers become identical. Thecurve xdh can lie entirely on one or other of the binodal surfaceswithout intersecting the critical curve. When it lies entirely onthe part representing upper or ethereal layers, all mixtures becomehomogeneous by the disappearance of the lower layer ; similarly,when it lies entirely on the part representing lower or aqueouslayers, all mixtures become homogeneous by the disappearance ofthe upper layer2628 DUNXINGHAM : THE SYSTEM ETHYL ETHER- WATElt-The FormatiotL of Three Lipid Layers.I n a ternary system three liquid layers, unsaturated with respectt o solid phases, arise through the intersection of three binodalcurves (see Roozeboom, ‘I Die Heterogene Gleichgewichte,” 111,Part 2).I n a quaternary system the three layers arise throughtlie interseetion of three “ two-liquid volumes.” Fig. 16 shows thesimplest case o€ this, where three liquid layers occur in the twoternary systems ACB and ADB.Thus, in the system ACB, aK,b,bK,c, cK,n are the stable portions of three binodal curves inter-secting in 0, b, and c. These) points of intersection represent theFIG. 16.three conjugate liquids, the composition of which cannot vary in aternary system ; similarly, in the system ADB, afK2/bl, b l K l l c f ,cfK3fd’ are the stable portions of the binodal curves, a’, bl, and cIthe three conjugate liquids. We have already seen that a binodalcurve in a ternary system may be considered as arising from theintersection of the side-plane representing the ternary system, withthe surface of a “two-liquid volume” in the quaternary system.It therefore follows that between each pair of binodal curves in theternary systems AC‘B and ADB a binodal surface extends rightthrough tlie four-component system.There are thus three binodalsurfaces intersecting along the lines an’, bbl, and c c f . These linePOTSYYIUM IODIDE-ME RCURIC IODIDE. PART 111. 2629represent series of three conjugate liquids, such that a solutionrepresented by a point ul' on the line is in equilibrium withsolutions represented by definite points trlf and C" on the lines bbfand ccf respectively. allK 3 IfcIlK 1 IfbIlK,If is a section across thespace enclosed by the three binodal surfaces, such that all, blf, andclI are conjugate points. affK2ff bll, blf KllIcII, and cffK,riaff are thustwo-liquid areas, whilst alfbflcl~ is a three-liquid area. Any pointin this triangle represents a mixture of the three liquids aft, bfl, andell.The position of the point shows the relative amounh in whichthese are present.From the consideration of a series of such sections it is clearthat the volume enclosed by the three intersecting surfaces isdivided into four parts, namely, three two-liquid volumes and athree-liquid volume, lying inside the others, of which d b ~ f c ~ l is asection.In the system ander consideration three liquid layers do notFIG. 17.AB represents bottom layers. BC represents middle layers.CD repmsents top layers.occur in any of the ternary systems. The threeliquid volumetherefore lies entirely inside thO tetrahedron. The three curvesrepresenting a series of three conjugate liquids have been deter-mined experimentally, and their form is shown graphically inFig.17, the same projection being employed as in Fig. 11 (Part 11).The numbers obtained are given in table VI.** In connexion with the experimental work involved in tho three-liquiddeterminations, one point is of particular interest. It was found that three stableliquid layers could be obtained easily when freshly purified ether was used, but thatether which has been kept some time, and liberated traces of iodine frompotassium iodide solution, caused a curious form of metastability, which is bestillustrated by the following experiments. A liquid mixture was prepared contain-ing 6'035 gmms of potassium iodide, 11,067 grams of mercuric iodide, 9447 gramsof water, and 19.440 grams of freshly purified ether. This gave three liquid layerswhich were perfectly stable at 20".The same mixture, in the preparation of .whichordinary '' pure " ether was used, gave only two stable layers a t 20". It was foundpossible, however, to prepare three metastable layers by gradually warming themixture without agitation. Thus, the mixture existed as two stable layers at loo,VOL. cv. 8 9630 DUNNINGLIAM : THE SYSTEM ETHYL E'FHBK-WATEK-TL4BIAE VI.?'he Systern : h'tkyl Bther- Wnt er-Potassium Zodide-MercuricZodide at 20°.Three liquid layers witli no solid phase.Percentage composition Percentage composition Percentage compositionHgI,. EtlO.H,O.of t o p layer. of middle layer. of bottom layer.A A7-- No. KI. HgI,. Et,O. H,6. KI. HgI,. Et,O H,O. KT.*57 2.1 6.2 88.3 3.4 16.7 30.8 23.4 29-1 16.7 30.8 23.4 29-1t58 2.2 6.2 87.9 3.7 16.6 30.9 23.2 29.3 -- - --'59 2.2 6.8 87-0 4-0 15.8+SO 2.3 6.8 86.7 4.2 14.313.27.7 85.4 4-2 13.163 2.7 7.5 85.4 4.4 12.564 4.1 12.8 77-5 5.6 10.365 4.5 11.2 78.2 6-1 10.366 5.8 16.6 68.9 8.7 8.867 6.0 16.8 69.2 8.0 8.7$68 7.1 19-2 64.3 9.4 7.1- - - - 'ti 2.730.6 28.5 251 18.5 32.4 18.4 30.729.4 33.3 23.0 - - - --30.1 37.7 19.0 20.3 33.0 12.8 33.928.7 38.7 19.5 20-5 32-9 12.9 33.728.8 39.4 19.3 20.8 32.6 12.9 33.726.6 47.7 15.4 21.9 34.2 12.4 31.525.9 49.1 14.7 22.2 34.5 10.7 32-621.9 58-0 11.3 22.4 35.9 10.1 31.621.6 58.6 11.1 23.0 34.7 9.8 32.519-2 64.3 9.1 22.4 35.2 10.0 32.4* In No.57, the middle and bottom layers are identical, that is, they form acritical solution.t Nos. 58 and 60 give the solutions left when the bottom layer has justdisappeared.Z No.61 gives the solutions left when the top layer just disappeared.§ In No. 68, the top and middle layers are identical, that is, they form Rcritical solution.Any solution represented by a point on A B is equilibrium withsolutions represented by points on BG and CD respectively. A Brepresents bottom, BG middle, and CD top layers. Conjugatebut gave rise to three layrrs when placed in the thermostat a t 20" wi+houtagitation. On shaking, however, the three layers, which were clearly metastable,immediately gave only two stable layers. I t was further found that the relativeaiiiounts of tlic three metastable layers depended on the amount by which thetemperature was raised without agitation.The same phenomena were iuvariablyobserved whenever a three-liquid mixture u'as prepared with ether which had notbeen freshly purified.It has not been found possible to investigate the matter further, so that thenature of the action of impure ether 011 the equilibrium existing between the threelayers is still in doubt. The effects observed, however, were undoubtedly due totraces of impurity amounting to an almost negligible percentage of the totalmixture, and i t appears probable that these traces of impurity affected the surfacetenlion existing between two of the layers (the upper two in all cases investigated)to such an extent as to render equilibrium between them impossible.The ether used in the determinations was purified as follows : I t was first shakenwith dilnte permaiiganate solution, slightly acidified with sulphuric acid, until thepermanganate was no longer decolorised.It WAS then distilled and kept overanhydrous sodium carbonate for some days, when it was again distilled. Athird distillation over anhydrous sodium carbonate completed the purification, andthe final product never produced metastability between three liquid layersPOrASSIUM IODf Dk-MEItCURIC IODIDE. PART 111. 9631solutions are lettered alike; t h u s 16, 26, arid 3b are in equilibriuiiiwith one another. A and C represent two conjugate liquids, suchthat when A (the lower layer) moves along AB, C (the upper layer)gives rise t o two layers, which move along C'B and CD respectively,as indicated by the arrows.When the top layer (No. 3) reaches D,FIG. 18.h + 2the bottom (No. 1) and middle (No. 2) layers both reach B, wherethey become identical, thus leaving only two layers, B and D, inequilibrium. This reaction is reversible. Starting with B and D,when D, the upper layer, moves along DC, B, the lower layer, givesrise to tw9 layers which move along BA and BC respectively.8 1 autl01zly.s :Fig. 18 shows a type of equilibrium in which the intersection ofthree binodal surfaces gives rise to three-liquid curves similar tPOTASSIUM IODIDE-MERCURIC IODIDE. PART 111. 2633those shown in Fig. 17. The three surfaces, the critical curves ofwhich are lehtered Kl, K2, and K, respectively, intersect along AB,UC, and CD, which are lettered to correspond with Fig.17. Theequilibrium is best understood by studying a series of sectionsacross the figure, which are shown in det,ail in Figs. 19a, 19b, 19c,19d, 19e, 19f, and 199. With regard to these, the following pointsFIG. 20.may be mentioned. In Fig. 18 BIZ,+& is the curve of intersectionof two binodal surfaces, the critical curves of which meet a t K,fl.Fig. 19a is a section of the space enclosed by these two surfaces.Any point on ?zIl;,pK3 represents a mixture of two conjugateliquids. Points on nK,p represent mixtures of liquids on nKil andpR1 respectively, lying on binodal surface 1, whilst those on nKaprepresent mixtures of 'liquids o n 1111~ and pK3 respectively, lyin2634 DUNNINGHAM : THE SYSTEM ETHYL ETHER-WATER-on binodal surface 3, Section ( b ) differs from ( a ) in that B is acritical solution, from which arise liquids s and t of section ( c ) .Sections c, d, m d e show three-liquid areas, namely, $tTG, wyv, andxhm respectively. I n section (1) C is a critical solution formedF I G .21.from m and A of (e), which have become identical. (g) is the sameas (a), with the difference that binodal surface 3 has been replacedby binodal surface 2. The three-liquid volume terminates in thelines B7l aid AC, and its general forin is clear froin sections ( c ) ,(d), and (e)POTASSIUM IODIDE-MERCURIC IODIDE. PART III. 2635I n the system under consideration two of the intersecting “two-liquid ” volumes ” are also intersected by side-planes of the tetra-hedron o r by solid saturation surfaces.The curves formed bythese intersections have already been considered. There is no indi-cation that the third ‘‘ two-liquid volume ” intersects either side-planes o r solid saturation surfaces. Figs. 20 and 21 show modifica-tions of Figs. 18 and 19, which agree more closely with the fackjust mentioned. Only a portion of binodal surface 1 is shown, thiscorresponding with the surface XNRSK,TT/MPPE,& of Figs. 11and 14. The critical curve of this surface, lettered R,, terminatesin the points K , and X , of Fig. ’11. One of the other surfacesFIG. 22.gives rise to the curves cpd and fng of Fig. 11, which show that thesurface is not intersected across its critical curve. These inter-sections are not shown in Figs.20 and 21, the significance of whichwill be readily understood by reference t o Figs. 18 and 19, to whichthey bear a close resemblance.Fig. 22 shows the three binodsl surfaces in positions which giverise t o curves of intersection having the same relative positionsas those of Fig. 17, and siiice i t represents the actual equilibriummost nearly it will be well t o consider it in some detail. The letterscorrespond with those OF the preceding figures, AB, BC, and Cnagain representing the three curves of conjugate liquids. Surface 1,of which par!, only is shown, corresponds withXNRSK,T UMPPR2,2636 DUNNINGHAM : THE SYSTEM ETHYL ETHER-WATER-of Figs. 11 and 14, and c m be considered as lying in the planeof the paper. The stable portions of the two binodal surfaces inter-secting it are shown by AK,+,CB (No.2) and BCDH,+3 (No. 3 ) .A B is the curve of intersection of surfaces 1 and 2, BC that ofsurfaces 2 and 3, CFD that of surfacw 3 and 1. AB and CD there-fore lie on surface 1, that is, iri the plane of the paper, whilst BConly touches it a t its end-points, B and C. A.K1+& is the curvealong which only surfaces 1 and 2 intersect, BK,+3D that alongwhich only surfaces 1 and 3 intersect. They therefore lie onsurface 1, and are both critical curves.The parts into which the space enclosed by the binodal surfacesis divided are four in number, as follows :(1) Tho two-liquid space representing mixtures of two conjugateliquids lying on surface 1. This is bounded by the binodal surfaceitself, and the surface ABCD, formed by joining all pairs ofconjugate points on A B and DC.It has already been defined asthe space formed by joining all pairs of conjugate points on thebinodal surface.(2) The two-liquid space representing mixtures of two conjugateliquids lying on surface 2. This is bounded by the binodal surfaceitself, ABCK,+2, the surface AK,+&' formed by joining all pairsof conjugate points on -4K,+, and CKl+2, and the surface ARC,formed by joining all pairs of conjugate points on AB and CB.The space is thus formed by joining all pairs of conjugate pointson the binodal surface.(3) The two-liquid space representing mixtures of two conjugateliquids lying cjn surface 3. This again is formed by joining allpairs of conjugate points on the binodal surface.It is boundedby the binodal surface itself, together with the surface BK,+@,formed by joining all pairs of conjugate points on BE,+, andDKl+3, and the surface BCD formed by joining all pairs ofconjugate points on BC and DC.(4) The three-liquid space, representing mixtures of three coii-jugate liquids lying on ,4B, BC, and CD respectively. This isbounded by the surface ABCD, formed by joining all pairs ofconjugate points on A13 and DC; the surface BCD formed byjoining all pairs of coiijugate points on BC and DC; and thesurface ABC, formed by joining all pairs of conjugate points onA 3 and CB. The three-liquid space thus lies inside the surfacesformed by joining all sets of coiljugate points on AR, BC, andC'D.A consideration oE Fig.22 shows that the triangular planesformed by joining three conjugate points on AB, BC, and Cl,respectively are iiot parallel t o one another. If a plane is drawPOTASSIUM IODIDE-MERCURIC IODIDE. PART 111. 2637so as t o intersect tlie three-liquid space, i t may cut the threeconjugate curves in points which are either conjugate or not con-jugate with one another. The intersecting planes t o be consideredare those representing mixtures in which ether and water bear aconstant ratio t o one another, such a s ,40L in Fig. 11, and thosedrawn parallel to one side of the tetrahedron, representing mixtureswith a constant percentage of one particular component.Fig. 23 is a section formed by a plane such as ADL in Fig.11,cutting through the three-liquid space and across the three conju-F I G . 23.gate curves a t a, b, and c respectively. The sectioii of the threeliquid space is shou711 on a larger scale in Fig. 24.We will first consider the case in which a, b, and c are conjugatewith one another. The significance of the areas into whichRnK2bK3cG' is divided will be clear from what has already beensaid with regard to the sections in Figs. 19 and 21. When a definiteiiiixture of the two solid components is added little by little t o theliquid mixture L, the mixture so formed follows a straight line onthe plane ABL, such as rvsyw in Fig. 24. As it moves along rvtlie two layers into which it separates follow Rn and Gc respec-tively, SO that.when tlie mixture is represented by 2; the layers ar0represented by n and c. When the mixture nioves froin u alon2638 THE SYSTEM ETHYL ETHER, ETC.us it enters the three-liquid area, and a third liquid, by begins t oseparate, a and c remaining unchanged in composition. As s isapproached 6 increases in amount, whilst c decreases, until a t slayer c entirely disappears, leaving a and b. As the mixture thenfollows sy, the two layers follow aK, and bK2 respectively, untilonly solution y is left, the .other quite disappearing. The homo-geneous liquid then follows yw, eventually, of course, becomingsatnratcd. It is obvious that either the layer on a K , or that onbK, can disappear, or they can become identical, according t o theposition o€ t.he point y, a t which rvsyw cuts the curve aK&.Whenthe mixture follows the line efghlc the phenomena occurring aresimilar. Of the three-liquid layers, a, b, and c, however, n disap-pears, leaving only Z, and c when the mixture reaches g .When the mixture follows a line such as pmbp, passing throughb y a slightly different behaviour occurs. A t m, a and c representthe two layers, and as t'he mixture follows mb, the third layer bseparates, and increases in amount whilst a and c decrease. At6 , a and c disappear simultaneously, leaving only 6, which thentraverses t'he honiogeneous area along the line bp.When the plane intersects the three-liquid space in such a waythat a, 6 , a i d c are riot conjugate points, the section, althoughsimilar in form to that shown in Fig. 24, is no longer capable of aquantitative interpretation. Thus, a point inside the triangleabc represents a mixture of three layers, but these are not repreTRANS-CTCLOPENTANE-1 : 2-DICARBOXY1,IC ACID. 2639sented by the points a, b , and c. The plane cuts across a numberof cor;jugation triangles, so that as the mixture follows the line z'so r fg the three layers change, not, only in amount, but in composi-tion. Similarly, the compositions of the layers composing mixtureson the two-liquid areas are not given by points on the boundingcurves.A plane can intersect the three-liquid space in a variety of ways,giving rise to various special forms of sectional curves, such as thoseformed when the plane intersects the three-liquid space withoutcutting all three conjugate curves (AB, BC, and CD). The formsof these1 various sections can be readily determined, and wiIl notbe considered here.The author desires to acknowledge a grant from the ChemicalSociety towards the expenses of this research.SIR JOHN DEANE'S GRAMMAIL SCHOOL,NORTIIW I CH, CHESHI RI

ISSN:0368-1645    

DOI:10.1039/CT9140502623

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

TRANS-CTCLOPENTANE-1 : 2-DICARBOXYJAIC ACID. 2639CCXLVI1.-Besolution of trans-cycloPentune-I : 2-di-carboxylic Acid.By LEONARD JAMES GOLDS WORTHY and WILLIAM HENRYPERKIN, jun.IN accordance with the theory of Le Be1 and van't Hoff, manyof the dicarboxylic acids of the cyclic hydrocarbons should becapable of resolution into optically active modifications. Hitherto,only two acids of this type have been investigated in this respect,and the first to be resolved was tmns-hexahydrophthalic acid :CO,H H\//\$!H,*CH2*YCH,*CH;CH CO,lfI n 1899, Werner and Conrad (Bey., 32, 3050) showed that thisexternally compensated acid may be resolved into its activemodifications by the fractional crystallisation of the quinine salts,and the active acids were found t o have a,, + 1 5 - 2 O and --18*5Orespectively.These invetigators also showed that, whilst the e s -ternally compensated acid is almost insoluble iii water and melt2640 GOLDSWORTHY AND PERKIN : RESOLUTION OFat 215O, the d- and I-modifications melt a t 179--183*, and axemuch more soluble; again, the anhydrides of the active acids melta t 164O, or considerably higher than that of the dl-acid, whichmelts at 140O. Furthermore, the conversion of the acids intotheir anhydrides is attended by a reversal and a t the same timeconsiderable increase of the rotation, since the 6-acid (a, + 18.2O)yields an anhydride with a, - 76-7O; the) dimethyl est'ers have thesame sign as their acids and the rotations a, + 28*6O and - 39*Gorespectively. At a later date (Ber., 1905, 38, 31121, Buchnerand von der Heide investigated tl.ans-cyclopropane-I : 2-dicarb-oxylic acid,and showed that this acid can be resolved into its active com-ponents by the fractional crystallisation of the salts with brucine,quinine, or cinchonidine.The active acids melt a t 175O, that is,a t the sme temperature as the &-acid, and have a, +84-5O; allattempts to prepare the anhydrides of these acids have been un-successful, since they distil unchanged and are not acted on byacetyl chloride.Some years ago, a series of experiments was commenced inthe Laboratories of ManChester University by one of us in con-junction with Mr. H. D. Gardner with the object of effectingthe resolution of tmns-cy dopentane-1: 2-dicarboxylic acid,(Perkin, T., 1887, 51, 244), but the investigation was notcompleted.We have now taken up the subject again and find that resolutionmay be readily and completely brought about with the aid ofbrucine.When the dl-acid is combined with bruciiie and the mixed saltsare recrystallised from water, the salt of the d-acid separates firstand is readily obtained pure by.repeated recrystallisation. TheZ-acid may then be recovered from the mother liquors in themanner described on p. 2643. The observed rotations of the d-and7-modifications were a,, + 87.6 and - 85.9 respectively, and thoseof the corresponding ethyl esters, a, 4- 70*31° and - G9.76O. Thed- and I-modifications of cyclopentane-1 : 2-dicarboxylic acid melta t 1 8 2 O or 2 1 O higher than the melting point of the dl-modifica-tion (m.p. 1 6 0 O ) . For the sake of ready comparison, the rotationsand melting points of the trma-cyclopropane-, -pentsane-, and-hexane-1 : 2-dicarboxylic acids are appeiiclecl in tabular form 'I'ltANS-CYCLOYENTANE-1 : 2-DICARROXPIJC ACID. 2641&I. p. of M. p. ofal,. a],. d- and I- inactive(1-acid. l-acid. ncids. acid.fr/c I LS -cycZoPropane -trL~rLs-cycloPentane-t mns -cycloHexane -Z : 2-dicarhoxylic acid . . . . . ... . + 84.9 ' 84.5" 175" 175"1 : 2-dicarboxylic acid .. . . . . . . . -t 87.6" -- 85.9" 181" 1 tic)"1 : 2-dicarboxylic acid ......... +18.2' -18.5" 178-183' 215'It would be interesting t o fill up the gap between trans-cyclo-propane-1 : 2-dicarboxylic acid and the corresponding cyclopentane-dicarboxylic acid by the resolution of t~a.ns-cyclobutane-1 : 2-di-carboxylic acid,?€I,* H*CO,HCH,*CH'CO,Hbut, unfortunately, the preparation of this acid (T., 1894, 65, 585)in quantity sufficient for resolution is most troublesome and,although experiments with this object have been commenced, wehave not yet been able to separate the active modifications in apure state.EXPERIMENTAL.d-t rans-cycloPen tan e- 1 : 2-dicar b o x ylic A cid.The dl-t~~ns-cyclopentane-1 : 2-dicarboxylic acid employed inthese experiments was prepared by the method described by Perkin(T., 1887, 51, 240; compare T., 1894, 75, 586).The pure acid,in quantities of 15 grams, dissolved in hot water, was mechanicallystirred, and brucine (90 grains) gradually added, when the alkaloidreadily dissolved.The excess of brucine was filtered off, wellwashed with hot water, and the filtrate and washings were con-centrated on the water-bath until crystals just commeiiced t o formon the surface. When the liquid was cooled and vigorously stirred,a copious crystallisation took place, and the whole became semi-solid ; the crystals were then collected and repeatedly recrystallisedfrom hot water. During this operation, the progress of the separa-tion of the brucine salt of the d-acid from that of the Z-modi-fication was followed with the polarimeter, and the table givenbelow shows that the separation is nearly complete after six crys-tallisations, since the difference between the rotation of this cropand of that obtained as the result of the twelfth crystallisationis very small.Weight ofNo.of subst,ance. 0 b served SpeciGccrystallisation. Gram. rotation. rotation.1st crop 0.8250 - l-Q!P -32.1'3rd 9 9 0.4566 - 1.14" - 25.0'6th ), 0.5050 - l*liiO - 22-8012th )) 0.2612 - 0.51" - 19.92642 GOLDSWOHTIIY AND PERKIN : RESOLUTION OPA specimen of tlie pure bruciiie salt was subsequently preparedby adding excess of bruciiie to the hot dilute aqueous solution ofthe pure d-acid (see below), and, after filtering, the solution wasallowed to crystallise slowly over sulphuric acid, when large,brilliant, tabular crystals separated. As these crystals efflorescein a vacuum desiccator, they were dried by exposure t o air, andthen analysed :0.1314 gavel 0.2782 CO, and 0.0859 H,O. C=57*7; H=7.3.0.5079 ,, 32.6 C.C.N, at 19.8O and 753 mm. N=5-1.2C23H2s0,hT,,C7H,,0~,9H,0 requires C = 57.4 ; H = 7.2 ; N = 5- 1per cent.That the salt has this composition was confirmed by the factthat 0.2316 gram, heated for one hour a t 125O, lost 0.0336 H,O,whereas the calculated loss for 9H,O is 0.0339 gram.I n order t o obtain the pure d-acid, the brucine salt from thetwelfth crystallisation was dissolved in hot water, the brucineprecipitated by ammonia and, after filtering and washing, thesolution of the ammonium salt was concentrated and acidifiedwith hydrochloric acid when, on cooling, the d-acid separatedin plates, and melted a t 178-180°. After completely decolorisingwith tlie aid of animal charcoal, and twice crystallising fromwater, the acid melted a t 18lo, and 0.1752 dissolved in water(20 c.c.) gave, in a 2-dcm.tube, a rotation of +1*535O, whencea, +87*6O. On titration, 0.1778 required 0.0898 NaOH forneutralisation, whereas this amount of an acid, C,H,(CO,H),,should neutralise 0.0900 NaOHThe d-ethyl ester, C,H,(CO,Et),, was prepared by boiling thed-acid with five times its weight of 10 per cent. alcoholic sulphuricacid for six hours; water was then added, the ester extracted withether, and, after washing with water and dilute sodium carbonate,the ethereal solution was dried, evaporated, and the ester distilledunder diminished pressure.It boiled constantly at 170°/100 mm., and 0.2596, dissolved inacetone (20 c.c.), gave, in a 2-dcm.tube, a rotation of + 1*825O,whence a, +70*3lo.The d-Anilide, C,H,(CO*NH.C,H,),.-In order to prepare thisderivative, the d-acid was heated with thionyl chloride in a sealedtube in boiling water for an hour, the clear liquid evaporated onthe water-bath, and the residual acid chloride dissolved in benzeneand mixed with excess of aniline. The benzene was removed byevaporation, the residue stirred with dilute hydrochloric acid, andthe crystalline precipitate collected and recrystallised twice froTRANS-CYCLOPENTANE-1 : 2-DICAKBOXYLIC ACID. 2643iuetihyl alcohol, in which itt is sparingly soluble, separating as avoluminous mass of needles melting a t 245-247O (uncorr.) :0.2756 gave 21.7 C.C. N, a t 18.4O and 762 mrn.N=9*1.C,,H,,02N, requires N= 9.1 per cent.0.1708, dissolved in acetone (20 c.c.), gave, in a 2-dcni. tube,the rotation + 1*880°, whence a, + 110*lo.Attempts which were made with the object of preparing theanhydride of the d-tram-acid were not successful and the resultsobtained seem t o throw some doubt on the existence of thisanhydride. Since, however, trans-cyclohexane-1 : 2-dicarboxylic acid(trans-hexahydrophthalic acid) yields an anhydride without diffi-culty (Baeyer, Annale?z, 1890, 258, 179), there is every reasonto suppose that the anhydride of tram-cyclopentane-1 : 2-dicarb-oxylic acid should also be capable of existence, but i t is doubtfulwhether the substance described by Haworth and Perkin (T., 1894,65. 985) can be accepted as this anhydride.I-trans-cycloPentane-1 : 2-dicarboxylic A cid.I n order to obtain this acid, the mother liquors from the firstsix crystallisations of the Srucine salt of the dl-acid (p. 2641) wereconcentrated until crystals began to appear on the surface of thebrown liquid. The salt, which separated in quantity on cooling,was dissolved in hot water, the solution decolorised with animalcharcoal, and the crude Z-acid isolated in the manner describedin the case of the d-acidThis acid is readily obtained pure simply by recrystallising fourtimes from water, i t then melted sharply at 180-181°, and 0.2363,dissolved in water (20 c.c.), gave, in a 2-dcm. tube, a rotatiqn of- 2*03O, whence a, - 85*9O, On titration, 0.3110 required 0.1568NaOH for neutralisation, whereas this amount of an acid,C,H,(CO,H),, should neutrslise 0.1575 NaOH.The 1-ethyl ester, C,H,(CO,Et),, obtained in the manner describedin detail in the case of the ester of the d-acid, distilled a t170°/100 mm., and 0.3326, dissolved in acetone (20 c.c.), gave,in a 2-dcm. tube, a rotation of -2.3Z0, whence u, -69-76O.THE UNIVERSITY MUSETJM,OXFORD

ISSN:0368-1645    

DOI:10.1039/CT9140502639

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

2644 KENYON AND PICKARD : IN VESTIGA‘PIONS ON DEPENDENCECCX LVI I I .--hvestigat ions on the Dependelice oJ’Rotatory Power on Chemical Constitution, PartI X . 2 %, e Rot a tory Powers of 1 -.ATup h t h y 1 - n - h ex y 1 -carbinol and its E s t e mBy JOSEPH KENYON and ROBERT HOWSON PICKARD.THIRTY-EIGHT optically active carbinols of the formulaR,*CH(OH)*R,have been described so far in this series of investigations, and withone exception have been shown to possess certain characteristics asregards dispersive power. Thus their rotatory powers for light ofwave-length ranging from that of sodium yellow to that of mercuryviolet not only increase continuously with decreasing wave-length(that is, the compounds exhibit what is commonly spoken of asi~ormal dispersive power), but also conform t o the law of simpledispersion expressed by Drude’s equation with one term,a = k/ h2 - h,2 (compare Lowry, Pickard, and Kenyon, this vol.,p.94). Further, a dispersion ratio, such as, for example,H g g z , is in the cases of many of the carbinols approximatelyconstant over a range of temperature extending up t o their boilingpoints, and even in the others varies only to a very slight extent,whilst the dispersion ratio is only affected to a very slight extentby solvents. It is probable, however, that this is a special propertyof this class of compounds, the rotatory powers of which are notaffected to any large extent by increase of temperature or solution.Indeed, on reference 60 the ‘‘ characteristic diagrams ” (for example,see P a r t V., this vol., p.847) for a homologous series of suchcarbinols these properties appear as an obvious arithmetical fact,since the violet and green lines of the diagrams intersect so closeto the zero. It should, however, be borne in mind that the methodof plotting rotation data known as “ Characteristic diagrams ” asdeveloped by the present authors for the correlation of the rota-tion data of many compounds of allied structure-whilst provingextremely useful in several directions-is, however, largely empiri-cal, having been devised originally on theoretical grounds byArmstrong and Walker (Proc. Roy. SOC., 1913, [ A ] , 88, 388) t oaid in the explanation of the at~ornalous dispersion of a compoundby assuming the presence in i t of two dynamic isomerides ofdifferent optical properties.It also seems desirable to suggest that inferences drawn from\ ioleOF ROTATORY POWER ON CHEMICAL CONSTITUTIOK.2645variations in the magnitude of a dispersion ratio are likely to provemisleading, whilst the use of negative and positive signs for suchratios in the region of what is commonly known as anomalousdispersion has apparently no meaning whatever.Among the carbinols referred to above the conspicuous excep-tion is E-1-naphthylmethylcarbinol (Part VI., this vol., p. 1116).The rotations of this compound appear to obey the law of simpledispersion only a t temperatures above 160°, whilst in the super-cooled state Lhe carhinol exhibits the phenomenon known as anoma-lous dispersion a t and below a t’emperature of about loo.Soextraordinary, then, are the optical properties of this carbinol thatit seemed desirable to investigate some of its homologues, but owingt o the many experimental difficulties only d-1-naphthylqz-hexyl-carbinol has been prepared.The properties of the new carbinol are quite analogous t o thoseof the corresponding methyl compound. Thus in the homogeneousstate (see Fig. 1 and table I) the dispersion is “anomalous” (foryellow to violet light) a t temperatures between about 2 2 O and 38O,but the rotations conform t o the law of simple dispersion a t aboutand above a temperature of 180°. The regular character of therotation curves seems to negative any suggestion that the anoma-lous dispersion is due specially t o polymerisation in the neighbour-hood of the melting point of the carbinol, although they show thatthe cause of the “anomaly” is gradually removed by increase oftemperatare.The majority of chemists appear t o favour the explanation ofanomalous dispersion in compounds of simple constitution by theassumption of the presence in what is otherwise the homogeneouscompound of two dynamic isomerides differing in optical sign anddispersive power.It has been suggested already (Part VI., Zoc. c i t . )that in the case of these naphthylcarbinols such isomerides arecaused by a difference in the disposition of the valencies in thenaphthyl radicle. An alternative suggestion made by Patterson(T., 1913, 103, 145) that this phenomenon is due to a successionof maxima and minima on the rotatJon curves occurring a t differenttemperatures for light of various refrangibilities, whilst very diffi-cult of direct experimental test, is nevertheless rendered verydoubtful in the authors’ opinion by the accumulation of datarecorded in these investigations.It has now been shown that the presence’ in an optically activecompound of a naphthyl group attached a t the “a”-position orof an esterified carboxylic group is associated very frequently withthe phenomenon of anomalous dispersion.I n each case tempera-VOL. cv. 8 2646 KENYON AND PICKARD : INVESTIGATIONS ON DEPENDENCEture has a great effect on the phenomenon, increase of temperaturedestroying it in the case of naphthyl compounds, but bringing itto view in the case of the esters.It is desirable, however, that theterm " anomalous '' dispersion should no longer be used. PortionsFIG. 1.61-Naphthyl-L&)*-40'Temperature.0' 1of the rotation curves on either side of the region of rcanomalous"dispersion have dispersion ratios which rapidly increase or decrease." Anomalous " dispersioc as commonly understood refers as a rulemerely to portions of the rotation curves artificially selecte,d accord-ing to the wave-lengths of light under consideration. In view oOF ROTATORY POWER ON CHEMICAL CONSTITUTION. 2647Lowry’s work (T., 1913, 103, 1067 et seq.) it is much better touse only the terms simple and compJex as applied to dispersivepower according as the rotations conform to Drude’s equation withone or more terms.Among the large number of compounds studied in these investi-gations the 1-naphthylcarbinols a t low temperatures and the estersdescribed in the authors’ previous communications a t high tem-peratures tend, then, to exhibit compIex dispersive power, thedispersive power becoming simpEe in each case if the conditions oftemperature are reversed.These generalisations ++ are confirmed by the optical properties ofthe esters of the two naphthyl carbinols with normal fatty acids,since it has been found that the acetate of I-1-naphthylmethyl-carbinol and a homologous series of esters (ranging from the acetateto the n-undecoate) of d-1-naphthyl-n-hexylcarbinol each exhibitscomplex dispersive power a t all temperatures from 20° to 200°, thelimits of the experimental conditions.The dispersion ratios forthese esters are not affected much by temperature, and are nearlyidentical throughout the series. This is noteworthy, not onlyfor the exceptions, but also as occurring in a series all membersof which have complex dispersions. The dispersion ratios of eachester, however, are about 5 per cent. greater in carbon disulphidesolutions than in the homogeneous state.The configurations ascribed to I-1-naphthylmethylcarbinol andd-1-naphthyl-n-hexylcarbinol, although these compounds and someof their derivatives are under certain conditions dextro- and laevo-rotatory respctively, are justified by drawing the characteristicdiagram for each carbinol, when i t will be found that the twodiagrams form exact mirror images of one another.As has beenalready mentioned, such diagrams are based on the assumptionof the presence in the carbinols of two dynamic isomerides differingin optical sign and dispersive power, but in the case of the estersof these cai-binols there may be assumed to be present four dynamicisomerides in each ester. It is therefore not surprising that therotation data f o r the esters recorded in the experimental partcannot be correlated on the characteristic diagrams of the carbinols,although these four dynamic isomerides would in pairs have thesame optical sign.* The authors arc aware that many of the generalisations stated in this andprevious papers of the series are open to the criticism that the same are based onpolarimetric readings of small magnitude.However, they feel that the concordantresults which have now been obtained for a very large number of compoundcl justifytheir generalisntions.8 K 2648 KENYON AND PICKARD : INVESTIGATIONS ON DEPENDENCEThe trend of the values of the molecular rotatory powers of themembers of this series of esters is dissimilar to those of the otherFIG. 2.4 5 6 7 4 q I0 tiNumbel. of cnrbna atoms in m y 1 grot6p.series of wters described in these investigations. Thus it will beseen from Fig. 2 that the curves connecting molecular weight andmolecular rotatory power determined under several conditions oOF ROTATORY POWER ON CHEMICAL CONSTITUTION. 2649temperature and solution show maxima a t the propionate andoctoate in additlion to the maximum so commonly exhibited at theFIa.3.hexoate (or valerate). This somewhat irregular result is perhapsnot surprising in a series of esters of such complexity, that is, ascompared to the esters previously described, which have been thos2650 KENYON AND PICKARD : INVESTIGATIONS ON DEPENDENCEof carbinols of simple structure (compare, however, Part III., T.,1912, 101, 1430). To explain this is difficult, but it is significantthat the maxima a t the propionate and octoate follow one anothera t points ic the series in the interval between which the chain hasgrown by five carbon atoms, that is to say, a t the octoate thegrowing chain may be assumed to have all but returned on theposition occupied by it in the propionate.It is, however, possiblethat the mass of the growi12g chain as it approachea (or just exceeds)that of one of the other groups (for example, the hexyl or naphthylgroup) may have an additional effect on the molecular rotatorypower and cause Dome special exaltation.I n Fig. 3 the effect of temperature on the rotatory powers of theesters is illustrated. I n general this effect (within the experimentallimits) is a common one on a11 the members of the series, althoughthere is a significant change of slope in the curve for the octoate.Temper-ature.loo20406080100120140160180200D:.1.03101.02321.00750.99110-97540-96000.94440.92850.91290-89700.8813TABLE I.d-1 -Naph t hyl-n- he3[a]:.- 11.26"- 1.51 + 12-4623.2931-2237.5041.0342-7143.8244.1342.62ra1;l..- 14.89"- 2.05 + 13.8526.8937.4744-3748-7851-3452-8663.6751-06[aICi.- 40.25"- 12-75 + 16.9240.4158.9572-9582.5887.2689.8290.8686.26qlcarbinol.[MIL.- 27.24"- 3.66+30.1556-3575.5490.7499-28103.4106.0106.8103.0[MI:,.- 36.03"- 4.97 + 33.5265.0790.67107.4118.0124.3127.9129-9123.6Dis-persion[M']ti. H g g .- 97.40" 2.704-30.85 6.213 + 40.96 1e.22297.79 1.503142.7 1-573176.5 1.644199.8 1.692211.2 1.700217.4 1.699219.9 1.693208.6 1.68Temper-ature.20'40608010012014016018020020'406080100120140160180200Dtp.1.02621.01100.99470.97850.96240.94600.93000.91390.89790.88161.01471.00020.98500.96920.95210.93390.91500.89610.87780.8595[a]:. + 23-85'28.1532.1235.1037.7539.6441.2042.3543.1043.3428.59'33-9336.6539.6242-0743.8245-1746.2447-0847-75[a]: e*+25.05O29.6633-5036.8939.5141.7843.4444.4244.8244.8430.18'34.4338.1341.2843.9645.7347.2048.3549.1249-71TABLE 11.A ce tat e of d-I-Naph t h yl-n-hex yl car binol.[a];,.+ 28.68'34-0738.7342.4845-5048.0951.3951.8451.40* 50.0334.69'39.9444.3947.9250-7652.9154.7056.1957.0357.51[.]ti*+53*16'63.1671-5879.1884-7889.4193.0795.4597-1297.90CMIt + 67.74'80.0591.2299-68107.2112-6117.0120.2122.4123.1Propionat e.64.36'74.0383.0189.7695.5499-40102.7105-1107.0108.185- 17'98-11109.2118-0125.4130-6134.6137.8140.3142.3CMlZe.+71.15'83.9595.13104.7112.2118.7123.4126.2127.3127-489.93'102.6113.8123.0131-0136.2140.6144.1146.4148.Tempera-ture.20'40608000204016018020020"406080100120140160180200D:.1.00500.98990,97440.95870.94310.92730.91160.89570.88000.86430.99740.98160.96600.95000.93480.91910.90350.88740.87170.8559[.I;, + 27.02'30.7133.7136.0237.8739.1340.1741.0441-6642.01-+ 22-23"25.4228.1930.4732.1833-4734.4535-1 135.5135.69[a];, '+28*16"32.1535-4437.8639.7741-2242.2743.1143.7544.10+ 23-30'26.6529.5331-8433.6735.1036.0836-7337.1537.33[ a d .+ 32-54'37-1641.0044- 1146-1547-6948.8449.8250.4650.71+ 26-73'30.7134-0936.7438.8940.5241.7342.4842-9443.04TABLE I1 (continued).n-Butyrate.[a]:i*69.3476.6881-9386.2489.0291-4993.4294.5894-99+ 60.22' .[MI:. +- 84.29'96.83105.2112.4118.1122.1125-3128.0130.0131.6n-?lal erat e.+ 49.45"57.6864.3069.0072-6975.8878.1 179.5080.5281.08+ 72.47"83.8591-8999.31104.9109.1112.3114.5115-8116.3" 7 e . + 87-100-110.6118.1124-128.6131.9134-136.6137.6+ 75.95"86-96-103-109.7114.4117.6119.8121.2121.TABLE I1 (continued).n-H exoate.Temper-ature.20°40608010012014016018020'406080100120140160180D:.0.98940.98630.96960.94330.92720,91120-89550.88000.86430.98300-96740.95180.93600.92000.90420.88860.87250.8570[a];. + 21-12'23.7926-3527.9429.3430.3731.2732.0232.62+ 19.63'21.9724-1125-7426.8327.5028.0228.5429.05~a14.e + 22.36'25.1027.7629-533 1.0632-1633.0533.7634.46+ 20.59"23.3125.3126.8528.0328.8229.3929.9630.51n-Heptoat e.+23-68"26.4628.7730.5631.9633.0333-7634-3935-50[MI$.+71-81'80.8789.6094.9999.74103.2106.4108.8110.9+ 69.50'77.7583.3591.1494-9997.3499.19101.0102.TABLE I1 (continued).n-Octoa t e.Tempera-ture.20'40608010012014016018020"406080100120140160180u:.0.97970.96500.95050.93570.92100.90600.89130.87660.86170.97260.95760.94250,92760.91260.89770.88300.86780.8529bit.f-21-13'23.4425.2326.4427.3628.0528.4928-7528.89+ 19-06'21.2522.8023.8224-5725.1525.6025-8826.03[a]:,. + 22.1 1'24.6726.5727-9328-8529-4729.8830.1430.34+ 19.68'21-8223.4524.6125-4626.2226-7727-0527.14[alir.+ 25-46'28.3930.6132-1533.1933.9134.4434.8135.03+ 22.88'25.2227-1628.5229.5830.4230-9931.3431.48ial:i*53.2757.4460.4962-3863.5764.6365.6966.70$47.56' -[MIL.f 77.75"86.2692.8597.29100.7103.2104.8105.8106.3n-Nonoate.+ 72.85'81.1987.1091-0193.8596.0797.7798.8899-45[MI&. + 81.36"90.7697.77102.8106.2108.4110.0110.9111.6+75.19'83.3789.5894.0197.27100.2102.3103.3103.Temper-ature.20°40608010012014016020Q406080100120D: .0.96930-95400.93890.92370.90860.89370.87880.86350.96140.94680.93250.91790.90310.8885[alt,. + 17-13'18.8920.4521.6522.6623.1823.6924.08+ 16-44'18.1719.6320.6521-3521.78[a1 :-e.+ 18.09"19-8221.2522.4523-4224.0824.5825-04TABLE I1 (continued).n-Decoate.[41;r.+ 20.80"22.8824.5525.9227-0227-8628.4428.95n- Undecoa t e.+ 17.08' + 19-76'18.79 21-9720.24 23.2821.29 24.2222.04 25.0222.48 25.55[MI:.t-67.82"74.8180.9885.7489.3591-8193.8295.39+ 67-39'744780.4884.6587.6489.3Temper-ture.20"406080100120140160180D:.1.10441.08981,07331.06521.03681.01851.00020.98200.9635[a]:.- 32-28'39.5144.5849- 1852.8555-2256.7858.1159-29TABLE 111.A ce tn t e of 1-1 -~TapIi t hylrne thylcarbinol.[aIL IaIfi. [MIX.- 38.90" - 73.79" - 69.07'47.47 88-02 84.5554.04 101.51 95.4359.39 113.02 105.264.21 121.57 113.167-07 126.02 118.168.68 129.82 121-570.33 132.62 124.471.83 135.39 126.OF ROTATORY POWER ON CHEMICAL CONSTITUTION.2657EXPERIMENTAL.dl-1-Naph t h y I-n- h ex yl curb inol,C,,H,*CH(O~)*CH,*CH,*CH,=CH2~CH,~CH,.The reaction between magnesium 1-naphthyl bromide, and mhept-aldehyde proceeds smoothly only under certain conditions. Thenaphthyl bromide should be' free from the dibromide commonlypresent in the commercial product, and the aldehyde should befreshly distilled. The aldehyde, dissolved in ten times its volumeof ether, should be added very slowly to an excess of a diluteethereal solutiozl of the bromide, which is a t the time reactingwith slightly less than the calculated amount of magnesium, thetemperaturd of the whole being kept a t that of a mixture of iceand salt. The products of the reaction should be poured on to amixture of ice and dilute sulphuric acid as soon as the additionof the aldehyde solution is complete, and then immediately extractedwith ether.Much naphthalene being formed in the reaction i t ispreferable to remove it along with the ether and unchangedaldehyde by distillation in a current of steam. The residue isagain dissolved in ether, carefully dried, and fractionally distilledunder a pressure of 3 mm. All the carbinol is in the portionboiling above 160°, whilst the lower fractions contain the corre-sponding unsaturated hydrocarbon and the unchanged naphthylbromide. I n one series of operations, working with 620 grams ofthe bromide and 228 grams of n-heptaldehyde, the yield of carbinolwas 370 grams.dl-l-i\7aphthyZ-n-?~ezylcarbilzol boils a t 184O/ 4 mm., and on keep-ing sets t o a crystalline mass, which crystanises from light petroleumin feathery needles melting a t 41-42O.When guarded from theaccidental access of crystal nuclei, i t will remain for some time inthe supercooled condition, but solidifies rapidly when seeded.!rhe hydrogerh pht ?/alate, prepared by the method described inPart IV. (7oc. cit., p. ll26), is only sparingly soluble in lightpetroleuin, and is best crystallised from a mixture of this andbenzene, from which it separates in slender needles melting a t0.2245 neutralised 0.0226 NaOH. M.W. = 397. Calc. M.W. = 390.102-104° :Resolution of Hydrogen Yhthalate.The fractional crystallisation from acetone of the brucine saltsof the (d+ 1) phthalic ester yields readily the salt of the d-ester,ths process being carried out in t,he manner previously describedin detail (see inter &a, T., 1912, 101, 634).The ester (514 grams2658 KENYON AND PICKARD : INVESTIGATIONS ON DEPENDENCEwas dissolved in warm acetone (18 litres), digested with brucine(614 grams), and set aside to cry&allise. The first crop weighed300 grams, and was then recrystallised six times. The seventhcrop weighed 160 grams, and was the pure EBdA salt, which meltsand decomposes a t 124-125O. Two successive series of operationswith the mother liquors comprising respectively eight and ninecrystallisations yielded further lots of the salt amounting to 54 and15 grams respectively. Samples of the salt from the fifth andseventh crops of the first series of crystallisations and from thefinal cIops of the second and third series yielded hydrogen phthal-ates which had respectively [a], - 23*01°, - 22.469 - 22'42O, and- 22'62O respectively in (approximately) 5 per cent.ethyl-alcoholicsolution.ci-l-Nuphthyl-n-hexylcarbinol boils a t 1 7 8 O / 3 mm., solidifies instellate nodules, and melts a t 41.5O.The corresponding d-hydrogen phthalate solidifies in crystallinenodules, melts a t 9l0, and is soluble in all the common organicmedia. The crystalline sodium salt, which was obtained by theneutralisation of a solution of the ester in methyl alcohol withsodium methoxide and subsequent removal of the solvent in a desic-cator, is decomposed by water.Normal Esters of the Carbino1.-Of the esters prepared (seetable IV) the acetate, propionate, and n-butyrate were obtained bythe interaction of the carbinol and the respective anhydrides, whilstthe others were prepared by the action of the respective acidchlorides on solutions of the carbinol in pyridine.They are allviscous liquids a t the ordinary temperature, and have no odour, butthe higher members of the series often develop a faint yellowbloom, which is difficult to remove by redistillation, thus render-ing uncertain any polarimetric readings in the green, and par-ticularly in the violet portions of the spectrum.TABLE IV.Esters of d-l-Napkthyl-n-hexylcarbinol.Acetate . . . . . . . . .Propionate . . .n-Butyrate ...n-Valerate . . .n-Hexoate .. .n-Heptoate . . .n-Octoate . . . . . .n-Nonoate.. . , . .n-Decoate . . .n-Undecoate . . .€3. P167'12.5169'12184'13187'12.5198'12.5207"/3214'13222'14224Oj2-5232'/2.5D:O.1-02621.01471.00500.99740.98940.98300.97970.97260.96930-96142. (n- 1)ld.M.1.6471 151.3 .1.6403 158.71-5365 166.61.5332 174.31-5289 181.81.5271 189.81.5249 197.11.5225 205-21.5208 213.01.5188 221.028.5927.0222-2321-1219-6321.1319.0617-1316.44+ 67.74'85.1784.2972-4771.8169.5077-7572-8567-8267.3Solvent.Benzene . . . . . . . . . . . .Acetone .... . .. . . . . . .Ethyl alcohol . . . .Chloroform . . . . . . .Carbondisulphide . . . . . .Ethylenedibromide . . .. . .P yridine . . . . . . . . . . . .Carbondisulphide . . . . . .Acetic acid .........Chloroform . . . . . . .Benzene . . . . . . . . . . , .Pyridine . . . . . . . . . . . .Ethyl alcohol . . .Ethyl alcohol.. . . . .Ethyl alcohol ... .cm221022222210202222222222222222TABLE V.d-1-Naph t hyl-n-h exylcarb inol.Length Weightof tube, of solute. ingrams. a=. agr- Chi. [.ID* [Q]p [a]1.05890.68871.06661,09520.96860.92191.03401.01060.99001,18461.09171.04541.03261.05951.0826+ 8-70' + 10.48O + 18.25" + 74-67' + 89.97" + 156.7'2-39 2.86 5-20 71.48 85.54 155.57-69 9-39 16.52 65.37 80.02 140.87.80 9.40 16.41 64-76 78.03 136.26-41 7.73 13.30 60.15 72.52 124.82.51 2-96 5-30 54.46 64.00 115.04.38 5.23 9-02 42-36 50.58Hydrogen Phthalate.8.37 10.09 18.90 75.26 90.72 170.02.75 3.23 5.22 25.25 29.662.28 2.71 4.22 17-50 20.800.60 0.57 0.12 5.00 4.74-0.15 -0.36 -1.28 -1.30 -3.13 -11.14-2.55 -3.25 -6.93 -22.46 -28.63 -61.02Sodium Salt of the Hydrogen Phthalate.Rrucine Salt of the Hydrogen Phthalate.+3*50 $4.14 f7.37 +29*35 +35*52 +63*-1.45 -2.07 -5.62 -12.81 -17.39 -47.21All solutions for the determinations of rotatory power recorded in this paper were preparedt o 20 C.O.with the solvent a t the tcmperature of the laboratory, a t which temperatdre all observationTABLE VI.DetermitLatioiL of the Rotatory I-loicers of the Esters in (approa.) 5Ester.Acetate . . . . . . . . . . . .Propionate . . . . . . . . .Butyrate .. . . . . . . . . . .Valerate . . . . . . . . . . . .Hexoate.. . . . . . . . . . . . . .Heptoate . . . . . . . . . . . .Octoate . . . . . . . . . . . .Nonoate . . . . . . . . . . . .Decoate. . . . . . . . . . . . . . .Undecoate . . . . . . . . .Length Weightof of solutetube,cm.20202220202020202220ingrams.1.13630.95031.10191.13920.97680.98870.90201.15891.00011.1233(ID. aye. ugr. a,i. [alp + + + + + 3-84" 4.02" 4.64' 8.62' 33-80'3.45 3.60 4.17 7.65 36.313.90 4.08 4.70 8.70 32.183.10 3.34 3.76 7.04 27.212.59 2.67 3.05 5-85 26.522.30 2.44 2.76 5-10 23.262-28 2-37 2.72 5-12 25.272-55 2.65 3.05 5.74 22.012.15 2.27 2.53 - 19.542-02 2.12 2.41 4.80 17.99[a],,. + 35.38'37.8833.6629-3227-3324-6826-2722.8720.6418.88r Qlzr.+ 40.84'43.8838.7733-0131.2327-9130.1626.3223-0021.4c0Pd c TABLE VII.Determination of the Rotatory Powers of the Esters in (approx.) 5 perLengthEster.Acetate . . . . . . . . . . . .Propionate ...... . ..Butyrate . . . . . . . . . . . .Valerat e . . . . . . . . . . . .Hexoate . . . . . . . . . . . .Heptoate . . . . . . . . . . . .Octoate , . . . . . . . . . . .Nonoate . . . . . . . . . . . .Decoate.. . . . . . . . . . . . . .. . . . . . . . . EUndecoat eFoftube,cm.22202020101010102022Weightof Isolutein grams. a,. aye. agr. a s r i . [a]o. + + + + + 1.1254 13.80" 14.51" 16.95" 33-19' 111-5"1.0157 12.48 13.12 15.31 29.83 122.81.0665 12.05 12.74 14.84 29.12 113.10.9541 9.79 10.32 12.07 23.58 102.70.9485 4.70 4.87 5.68 11.40 99.101.2190 5.47 5.79 6.72 13.25 89-741.0342 4.48 4-71 5.49 10.75 86.641.0209 4.29 4.52 5.34 10.40 84-061.0773 8-44 8.87 10.36 21.50 78.361.0180 8.31 8.74 10.19 20.50 74.22[alw + 117.3"129.1119.5108.1102.794.9991.0788-5482.3578.05[a]<,.137.0" +150.7139.3126.6119.8110.3106.2104.696.2090.92662 KEXYON -1NDIPICK.lE D 1 KVESTIGATIONS ON DEPENDENCEDeterminations of Density (I):) ond Rotalory Power (aloe mm.) ofthe G'crrbinol am? ES~PTS i 1 ~ t h e Ilomogerteous S t a t e .The procedure in the determinations of rotatory power anddensity was the same as described in Part VITI .(this vol., p .2270) .d-l .NapF, thyl-n-?A exylccrrb ino? .Temp ................ 31" 63" 91" 146"D, .................. 1.0147 0.9890 0.9668 0.9234Temp . 15" 24" 26.5" 28" 36" 38" 42.5" 44" 49"a, ...- 6.04" +3*26 3.88" 4.30" 10.12" 11.40" 13-60" 14-94" 17.50"53" 58" 64" 76" 98" 104" 119" 145" 169" 194" + 20.00" 22.00" 25.14' 29.10" 35-72' 36.52" 38.80" 39-60' 40.10" 38.20"Temp . 15" 24' 25" 26.5" 28" 32.5" 39" 43"a g l . ..... -8.12" +2*30" 2.48" 3.54" 4-78' 8.20" 12.90" 16-52'49" 55" 58" 69" 103.5" 125" 145" 168" 199"20.32" 23.70" 25.34" 31.86" 43.34" 46.80" 47.90" 48.30" 45.16"Temp . 15O 24" 25' 26.5" 28" 32" 39" 43" 50"ayi56" 58" 69" 73" 104" 125" 143" 169" 199"... - 24-82" - 6.00" - 5.06" - 3-34" - 0.76" + 5.10" 14.24" 21.48" 29.20"36-42" 37.48" 49.42" 50.90" 72.20" 79-20' 81.04" 81-90' 76.10"A cetat e of d-l-Naph t hyl.n.hexylcarbinol .Temp ................19.5" 54" 90" 132"D: ..................... 1.0266 1.0001 0.9699 0-9371Temp .......... 21" 47" 83" 104" 123" .. ............... +24.56. 29-90" 34-58' 36.68. 37-58"Temp .......... 21" 49" 83" 104" 123"Temp .......... 21" 49" 83" 104" 123"Temp .......... 21" 49.5" 83" 104" 123"a, i ............... +54.88" 67.42" 78.30" 82.18" 85-00"aYellow ......... + 25.96" 31-54' 36-50' 38-26' 39.68.ugr ............... 29.72" 36.50" 42.00" 44.10" 45.66"Temp .......... 20-5"D: ............. 1.0144Temp .......... 24"a,, ............... + 29-96"Temp .......... 24"Temp .......... 24"ayellow ......... + 31.42"agr ............... + 36.26"Temp ..........24"avi ............... + 67.80"56"0.988554"35.32"52"36-56'52"51"42-46"79-00"Y r o pio n a t e .94"0-957468"37.08"75"39-30'76"45-86'76"86-10"134"0-920897"39.88"96"41.80"96"48-04"96"90.30"154" 185"158" 195"38-64' 38-60"40.58" 39-70"153" 190"46.90" 46.00"158" 190"87.20" 86-70'123' 153"41.00" 41-40'123" 152"42-70" 43-34'123" 152"49-46' 50.24'123' 152'92-96" 94-16"190'41.22'190"42-94'190"49-80'190"93.48OF ROTATORY POWER ON CHEMlCAL CONSTITUTION . 2663u . B 11 t y?W t e .Temp .......... 18" 61" 07" 134-5"Temp .......... 20" 30" 60" 85" 105" 121" 163" 195"a,. ............... i-27.12" 28-94" 32-78O 34.86" 35.92" 36.28" 36-76' 36.42"D: ............ 1.0066 0.9739 0.9459 0.9156Temp ..........20" 57" 85" 105"uRr ............ +32-70" 39.54" 42.50" 43.60"~ ~ ~ l l ~ \ ~ ......... +28-30° 34.26" 36.60" 37.78"Temp .......... 20" 56" 84" 105"avi ............... + 60.50" 73.70" 79.20" 81.90"11- Vnlera t P .Temp .......... 20.5" 56.5" 93" 132"Temp .......... 23" 45" 65" 87"Temp .......... 23" 47" 87" 120"Temp .......... 23" 47" 87" 121"a+ ............... + 27.28" 31.22" 35.48" 37.26"Temp .......... 23" 47" 87" 122"a , , ............... + 50.70" 65-80" 66.42" 69.84"D: ............ 0.9956 0.9694 0.9410 0.9088a ,. ............... +22-58" 25-68" 27.68" 29.38"are]low ......... + 23.68" 27.01" 30.74" 32.26"121"38.18"44.34"121"82.78"119"30.72"138"32-56"138"37-66"138"70.58"163"38-56'44-60"163"83.66"138"31.10"182"32.33"182"37-38"182"70.08"195"38-18"44.02"195"82.46"182"30.90"170"n -1Z ex oa t e .Temp .......19" 570 97" 146"D: ......... 0-9897 0.9636 0.9285 0.8911Temp ....... 20" 48" 60" 72" 107" 130" 152" .. ............ +20.90. 24.36. 25.30" 25.90" 27.40" 27.80" 28-14" 28.16"Temp ....... 20" 49" 58" 76" 109" 129" 153" 170"u3-,,1,~..,, ...... +22*12" 25.80' 26.46" 27.68" 29.16" 29.35" 29.70" 29.74"n.Heptoate .Temp ................... 18" 53.5"Temp ................... 20" 56"Temp ................... 20" 53"ayellow .................. + 20.24" 23-66"D: ........................ 0.9825 0.9584a, ........................ +19*30" 22.66"Temp ...................20" 52"agr ..................... f23.28 26.76n-0 ctoa t e .Temp ................... 18" 55"D: ..................... 0.9806 0.954997"0.922082"24.18"87"25-40'86"28.88141"0-8874114' 148"24-84" 24-92"116" 148"26-04" 26.14"117" 148"29.82" 30*00"92" 144-5"0.9263 0.88808 T. 2664 TNVESTIGATIONS ON DEPEKDENCE O F ROTATORY POWER. E:TC .ri-Octoate (continued) .Temp . . . . . . . SO" 44" 58" 69' 88" 120" 143" 172"a. ............ -f-20.70" 22-94" 23-84" 24.36" 24.80" 25.50" 25.34' 25.04"Temp .......... 20" 45" 68" 91" 118" 143"agr ............ +24*94" 27.88" 29.84" 29.96" 30.74" 30.68"Temp .......... 20" 45" 67" 90" 117" 143"a).eli,,,r ......... +- 21.66" 24-24' 25-80' 26.00" 26.76" 26.62"a. i ...............+46-60° 52.28" 55.74" 56.48" 57-60" 57.60"n-Nonoa t e .Temp .... 17" 59" 95" 144-5"D: ......... 0.9731 0.9412 0.9157 0.8800Temp . . . . 18" 36" 77" 98"Temp .... 18' 58" 7 1" 101"Temp .... 18" 60" 74" 101"a,. ...... f18.30" 20.20" 21.92" 22.40"ayellow ... +l8*92" 22.00" 22.60" 23.24"aqr ......... 9".00" 25.60" 26.26" 27.00"n-I., e c oa t e .Temp . . . . . . . . 20.5" 58" 94"Temp . . . . . . . . 20" 56" 95"a.. ............ +16.60" 19.00" 20.40"Temp . . . . . . . . 20" 49" 95" . ........... -+ 17.54" 19.38" 21.18"as. ............ 20.16" 22.46" 24.44"DI ............ 0.9674 0.9410 0.9137n.Uizdecoate .Temp . . . . . . . . 20.5" 58" 94"Temp ........ 20" 61" 94"ayeii ............ + 16-42' 18.94" 19.84"D: ............ 0.9605 0.9341 0.9075a, ............ +15.80° 18.36" 19.22'agr ............... +19.00" 21.74" 22.54"136'22.60"136"23.64"136"27.38"132"0.8832133"133"20.78"21.60"35.00"133"0.8793172'26.26"30.36"163"22.44"164"23.40'164"27.10"A ce tn t e of l-l-Napht hylme t hylcarbit7ol .Temp ....... 16" 64" 99" 138"D: ............ 1.1071 1.0699 1.0380 1*0010Temp . . . . . . . 27" 36" 56" 100" 136" 160"a, ............ -38.66" 41.84" 46.90' 54.80" 56.70" 57.00"Temp ....... 19" 27" 36" 61" 78" 101" 136" 162"agT ............ -42.70" 47.02" 60.10" 58.32" 62.26" 66.84" 68.60" 69.00"Temp ....... 27" 34" 62" 76" 100" 136" 164"a\i ............ -887.30" 91.90" 110.30" 115.30" 126.00" 129.66' 130-30CSRROXYLIC AClDS DERIVED FlZOill CTCLOBUTANE, ETC. 26635In every case these esters were found to have undergone noracemisatioii during the heating i n the polariineter tube, whilst allof them when hydrolysed yielded samples of the carbinols ofrotatory power identical with hhat of the original, preparations.The authcrs have much pleasure in acknowledging the ableassistance given t o them by 1LI.r. John Ranson, and desire to expresstheir thanks t o the Government Grant Committee of the RoyalSociety for grants which have defrayed some of the expense of thisinvestigstion.MUKICIPAL TECIISICAL SCHOOL.B I, .\ C I i B U KS

ISSN:0368-1645    

DOI:10.1039/CT9140502644

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

CSRROXYLIC AClDS DERIVED FlZOSI CTCLOBUTANE, ETC. 26635CCX LIX .-Curboxylic Acids Derived j+owb cycloButune,cyclopentane, cycloHexune, and cyclo [Reptune.By LEONARD JAMES GOLDSWORTIIY andWILLIAM HENRY PERKIN, jun.THE present investigation is one of a series which has been insti-tuted with the object of obtaining further evidence relating to thecomparative readiness of formation and stability of cyclic struc-tures containing varying numbers of carbon atoms. Judging by theyields produced in analogous reactions, experience is roughly inaccordance with Baeyer’s ‘‘ Spannungstheorie,” and seems t o indi-cate that, in the cyclopropase, cyclobutane, cyclopentane, andcyclohexanel series, derivatives of cyclopropane are produced withthe greatest difficulty, and t,hat, whilst derivatives of cyclobutaneand cyclohexane are much niore readily obtained, the tendency t oform cyclopentane derivatives is so pronounced that these areof ten produced in quantitative yields, and not infrequently duringreactions which might be expected t o lead t o the formation ofother ring complexes.The evidence on this point, however, is oftenconflicting, since it has frequently been observed that, althoughsome cyclic derivatives are obtained in very small yields, otherclerivatives of tho same ring seem to be produced under very similarconditions with great readiness. Thus the yield of ethyl (ydo-propane-l : 1-dicarboxylate (I) obtained when ethylene dihromitlereacts with t’lie sodium derivative of ethyl inaloiiate is very small,whereas ethyl cyclopropane-1 : 2-dicarboxylate (11) is readily pre2666 GOLDSWORTHY AND PEHKIN :pared in good yield when ethylene dibromide is replaced by ethyla@-dibrornopropionate in this interaction :Other similar cases have been observed, and one of the chiefdifficulties which arises is t o distinguish between the effect on theyield of tlie reactivity of the interacting substances on the onehand and of the readiness of formation of the closed ring on theother.It is clear that a useful generalisation cannot be formulateduntil a much larger number of cyclic carboxylic acids and otherderivatives have been prepared and investigated, and, in tlie presentcommunication, we describe some new carboxylic acids derivedfrom cycZo-butane, -pentane, -hexane, and -heptane.I n the firstplace, we have prepared the cis- and trans-modifications of cyclo-b utan e-l : 2 : 3-tricarboxylic acid,by causing ethyl ap-dibromopropionate t o react with the disodiuinderivative of ethyl ethanetetracarbosylate, when the reaction pro-ceeds t o the extenli. of about 50 per cent. in the required direction :The prod-uct, after hydrolysis and elimination of carbon dioxideby heating at 190°, yields cis-cyclobutane-1 : 2 : 3-t~iccrrbosy& acid(m. p. 141-143*), and this, when heated with hydrochloric acid at180°, is converted into the trans-acid, which melts at 168-170°.In the cyclopentane series the cis- and traiis-modifications of the1 : 2 : 4-tricarboxylic acid have $ready been prepared from thedisodiurn derivative of ethyl pentane-aay yeehexacarboxylate by theaction of iodine and subsequent liydrolysis and elimination ofcarbon dioxide :(Bottomley and Perkin, T., 1900, 77, 296).We have now suc-ceeded in obtaining t'he same acids much more conveniently and ina much better yield by the action of ethyl ap-dibromopropionate onthe disodium derivative of ethyl propane-aayy-tetracarboxylate(ethyl met,hylenedimalon ate) :CH,*$J(CO,Et),CH,Br*CHBr*CO,Et CH2.CH*C0,EtCARBOXYLIC ACIDS DEIi LVED FROM CYCCOBUTANE, ETC. 2667When the product of this interaction is hydrolysed, simultaneouselimination of one molecule of carbon dioxide takes place and acrystalline cyclopentanetetracarboxylic acid is formed. The crudeacid decomposes a t 180°, and yields a syrupy mass, from whichtrans-cyclopentane-1 : 2 : 4-tnricarboxylic acid is obtained by theaction of hydrochloric acid at 190°.It melts a t 127-130°, and isconverted, by heating with acetic anhydride and subsequent distil-lation, into the anhydro-cis-acid :a highly characteristic derivative, which melts at 215-21 To, andfurnishes the cis-acid (m. p. 146-148") on hydrolysis.We next, attempted the synthesis of cycloheznn e-1 : 2 : 4-tricarb.oxylic acid (hexahydrntrimellitic acid),an acid which does not appear t o have been previously described,and we ultimately succeeded in the following manner. The disodiumderivative of ethyl butanetetracarbaxylate was caused t o react, withethyl aP-dibromopropionate, when deconiposition takes place in thefollowing manner :The ester thus produced yields, on hydrolysis and elimination ofcarbon dioxide, a mixture of stereoisomeric acids, from which, byheating with hydrochloric ;rcid a t 190°, trans-cycloheznne-1 : 2 : 4-tricarboxylic acid was isolated, melting at 220-222O.When thisacid was digested with acetic anhydride and the product distilled,most of i t decomposed, but a sinall quantity of a distillate wasobtained, which, on hydrolysis, yielded the cis-acid as a crystallinecrust melting a t 225O. It is remarkable that the cis- and trans-modifications of this acid should have almost identical meltingpoints, and be so very similar in other properties that i t was a tfirst thought t h a t they were identical.However, a mixture of equal parts of the two preparations wasfound t o soften a t 198--30Clo, and to he alniost completely nielteda t 208O, so that they cannot be identical, and there can be littledoubt that they are the cis- and trcrm-modifications of cyclohexane-1 : 3 : 4-tricarboxylic acid2668 GOLDSWORTHY AND PERKIN :Finally, we have succeeded in synthesising trans-cyclokcpta~ze-1 2 : 4-t~i~c(rbox?/lic acidone of the few derivatives of cycZohept,ane which have, so far, bee11obtained.For the purpose of this synthesis, the disodium deriv-ztive of ethyl pentane-aaee-tetracarboxylate was digested with ethylup-dibroiiiopropionate when a coinplicated reaction took place, butan ester, evidently ethyl cyclopentane-1 : 1 : 2 : 4 : 4-pentacarboxylate,was produced in small quantity according t o the equation:CRTa(CO2Et),*CH2*CH2*C€J2*CNa(CC),Er), + CH,BI *CIIHBi *CO.,EtWiien the product of this interaction was hydrolysed, the syrupyacid mixture heated a t 200° and then esterified, i t yielded a smallquantity of ethyl cycloheptane-1 : 2 : 4-tricarboxylate (b.p.212-215O/30 mm.).On hydrolysis a syrupy mixture of stereoisomeric modificationswas obtained, from which, by heating with hydrochloric acid a t190°, trans-cycloheptane-1 : 2 : 4-tricnrboxylic acid was isolated, melt-ing a t 198--200°.Apparently there is little tendency in the direction of the forma-tion of the cycloheptane ring, since the yield of the above acid wasso small t h a t we were unable to examine it a t all completely.Further experiments, which are in progress, will show whether thisring and also the cyclo-octane and still larger rings are alwaysproduced with more difficulty than the simpler rings containingthree, four, five, and six carbon atoms.EXPERIMENTAL.Preparutio 1% of E t T~yl ap-Dib ro mopropionut e , CH,Br *CHBr *CO,Et.Dwing t h e course of this and other investigations, large quanti-ties of ethyl up-dibromopropionate were required, and, as the pricecharged for this ester is prohibitive, we have made a series ofcomparative experiments on the best conditions for its preparation,and find that the following process works well.Ally1 alcohol *(180 grains or 210 c.c.) is mixed with a n equal volume of chloro-forni (or carbon disulphide), the solutioii cooled in ice and salt,Crude coniuiercinl ally1 nlcoliol contains a large rtnioutit of water, and, if this isiiseil as tlio shrting-point, i t is shaken with l)otas5inni carbonate as long as thisdirsol~red, tlic aqueous layer r u n off and the nlcohol clehytfrnte 1 with a furtherquantity of potassinm carbonatc.It is tlicii fractionated nit11 ail ( ficient colunii~ ;the portion dirtilling a t 95-98' was collected for iise in the above preparationCAltUOXYLIC iiClDS DERIVED FROM CYULOBUTANE, ETC. 2669and tl.en bromine (496 grams or 156 c.c.) is gradually added, carebeing taken that the temperature remains below 5 O . The chloro-form is then removed by distillation from the water-bath underdiminished pressure, and the residual crude dibromopropyl alcoholneed not be fractionated, but can be directly oxidised t o up-dibromo-propionic acid.The crude dibromo-alcohol (150 grams) is mixedwith ordinary concentrated nitric acid (210 grams or 150 c.c.) andfuming nitric acid (90 grans or 60 C.C. of D 1.5) in a capaciousflask provided with a ground-in condenser and placed in water, andthe water is then very gradually heated. As soon as the initialviolent reaction has subsided, the water is raised t o the boilingpoint and maintained a t that for seven hours; the product is thenleft overnight in the ice-chest t o cool, when the dibroinopropionicacid usually crystallises, but, if not, the heating is continued andthe mass seeded. The acid is collected on a Bucliner funnel withoutfilter paper, drained on porous porcelain, and a further quantityniay be obtained by concentrating the mother liquors, so that thetotal yield is about 75 per cent.of that theoretically possible. I norder t o obtain the ethyl ester, the acid is dissolved in one anda-half tiixes its own weight of a 10 per cent. sorution of sulphuricacid in alcohol and heated on the water-bath for six hours. Wateris then added, the heavy ester extracted with ether, the etherealsolution washed first with dilute sodium carbonate, then withwater, dried, and the ether distilled off. The residual ethyl ap-di-bromopropionate distils almost completely a t 140-150°/ 100 mm.,and this was the material used in the following experiments.The cis- and trans-cycloRutnne-1 : 2 : 3-tricarboxylic Acids,CH(COP)>CH. CO,H.CH~<C€€(CO,H)I n order t o obtain these acids, the first, step was the synthesis ofethyl cyclobutane-1 : 1 : 2 : 2 : 3-pentacarboxylate (p.2666), and thiswas accomplished in the following way : Ethyl ethanetetracarboxylate (31 grams) was mixed with a little alcohol,* and then witha solution of sodium (4.6 grams) in alcohol (100 c.c.). and, afterkeeping for a few minutes until the whole of the ester had passedinto solution, ethyl up-dibrornopropionate (27 grams) was graduallyadded. I n a short time the mixture became warm, copious pre-cipitation of sodium broniide took place, and the process was coni-1)lstecl by lieating in a soda-water bottle in boiling water for fourhonrs. The product was mixed with water, extracted with ether,t h e ethereal solution washed well, dried, and the ether distilled off.* The alroliol u-etl i i i all these espcrinieiits was cdrefully dehydrated by distillationfirst over lirne a i d then over calciiiiil2670 GOLDSWORTHY AND PERKIN :The crude ester which appears to distil a t about 230°/20 mm.neednot be purified before conversion into cyclobutanetricarboxylic acid,but i3 a t once hydrolysed by boiling with 50 per cent. excess of25 per cent. methyl-alcoholic potassium hydroxide for four hours.Water is then added, the product evaporated until quite freefrom methyl alcohol, the solution is then acidified with excess ofconcentrated hydrochloric acid, evaporated to dryness, and theresidm extracted with ether in a Soxhlet apparatus.After distil-ling off tho ether, crude cyclobutanepentacarboxylic acid remains asa slightly brown, viscid syrup, and this is heated in an oil-bath a t190° for one hour. when the evolution of carbon dioxide will haveceased. The acid which remains does not readily crystallise, and istherefore purified by conversion into the ester which is obtained byboiling the acid with ten times its weight of 10 per cent. alcoholicsulphuric acid in a reflux apparatus for seven hours. The productis diluted with water, extracted with ether, the ethereal solutionwashed well with sodium carbonate, dried, and evaporated, and theresidue fractionated under 40 mm. pressure. A small quantity ofoil passes over below 1900, and probably contains ethyl succinate;then almost the whole of the remainder distils a t 190-205O, and onrefractionatioa, pure ethyl ciscyclobutane-1 : 2 : 3-tricarboxylate isobtained as a colourless oil boiling a t 195--197O/40 mm.:0'2246 gavo 0'4714 CO, and 0.1540 H20. C=57.2; H=7.6.C,,H,,,O, requires C = 57.3 ; H = 7.3 per cent.I n the preparation of the tricarboxylic acid, the ester distillinga t 190-205°/40 mm. was hydrolysed by boiling with excess of25 per cent,. methyl-alcoholic potassium hydroxide for four hours.Water was then added, the solution evaporated until quite freefrom methyl alcohol, mixed with excess of hydrochloric acid, eva-poreted, and the dry residue extracted with ether in a Soxhletapparatus. The ethereal solution deposited, after boiling off theether, a Eolicl acid, which was left in contact with porous porcelain,and then rwrystallised from concentrated hydrochloric acid :0,1410 gave 0'2332 CO, and 0.0592 H,O.C=45.1; H=4%.C,H,O, requires C = 44.7 ; H = 4.3 per cent.On titration, 0.1226 required 0-0772 NaOH for neutralisation,whereas this amount of a tribasic acid, C,H,O,, should neutralise0'0782 NaOH.cis-cycloButane-1 : 2 : 3-t~icarboxylic acid melts a t 141-143O, andis readily soluble in water or alcohol, but rather sparingly so incold concentrated hydrochloric acid.I n order to obtain the tmns-modification, the cis-acid (2 grams)was heated with concentrated hydrochloric acid (15 c.c.) in a sealedtube at 180° for two hours. After diluting with water and filterinciiImoxl’r,Ic ACIDS DERIVED FROM CYCLOBUTANE, ETC. 267 1from a trace of carbonaceous matter, the solution was concentrated,when, on standing over solid potassium hydroxide, a hard, glassy,crystalline mass, consisting of flat, glistening plates, graduallyseparated :0.1031 gave 0.1699 CO, and 0.0411 H,O.C=44*9; H=4*4.C,H,O, requires C= 44.7 ; H =4.2 per cent.On titrntion, 0.3500 neutralised 0.2236 NaOH, whereas thisamount of a tribasic acid, C7H,0,, should neutralise 0‘2234 NaOH.trans-cycloButrrne-1 : 2 : 3-tricarboxylic ncid melts a t 168-l7Oo,and is readily soluble in watler, but sparingly so in concentratedhydrochloric acid. The solution of the acid in excess of ammoniagives, when hoiled with barium chloride, a very sparingly solublebarium salt, and the cis-acid behaves in a similar manner. Bothacids are oxidised with difficulty, even when their alkaline solutionsare boiled with permanganate.The Trianilide of the trans-L4ccid.--In order to prepare this deriv-ative, the pure trans-acid was heated with thionyl chloride in asealed tube a t loOD for an hour; the product was then evaporated,and the residual syrup dissolved in benzene.Aniline was addedin excess, and, as soon as the vigorous action had subsided, thebenzene was evaporated, the mass treated with dilute hydrocliloricacid, and the precipitate collected and drained on porous porcelain.The trianilide of trans-cyclobutane-1 : 2 : 3-tricarboxylic acid meltsa t 252O, and separates from alcohol, in which i t is sparingly soluble,as a voluminous, almost gelatinous, mass of needles. For aaalysjsi t was recrystallised by dissolving in acetone and ;1 ddiiig benzene ;tlie acetone was then distilled off, and tlie solution set aside, whenthe substance separated as a crystalline crust of needles :0.2449 gave 21.5 C.C.N, a t 1 7 O and 763 inm.C2jH230XN3 requires N = 10.2 per cent.In order t o make sure that transformation of the trans-acid intothe cis-modification had not taken place during the heating withthionyl chloride, soiiie G f the syrupy product of this action wasdecomposed by boiliq with water and the acid recrystallised, w1iei-Li t melted a t 168-170O.hT==10*2.The cis- and trans-cycloPeutane-1 : 2 : 4-tricnrborylic ,-1 cids,The etliyl cyclopentane-1 : 1 : 2 : 4 : 4-pentacarhoxylate employed inthis synthesis of these acids was obtained nnder the followinqcmiidi tions.Ethyl inethylenedimalonate, (CO,Et),CH*CH,*CH(CO,Et), (33.2672 GOLDSWORTHY AND PERKIN :crams), dissolved in alcohol (50 c.c.) was added t o a cold solution ofsodium (4.6 grams) in alcohol (100 c.c.), and, after a few minutes,the disodium derivative was inixed with ethyl ab-dibromopropionate(26 grams), when gradual rise of temperature, followed by a vigor-ous action, set in, and sodium bromide separated. The actionwas completed by heating for three hours in a soda-water bottle,the product was diluted with water, extracted with ether, and afterwashing well, drying, and evaporating off the ether, the residual oilwas distilled, when almost the whole quantity passed over at226--240°/15 mm., and, on redistillation, the boiling point of theethyl cyclopentanepentacarboxylate was observed t o be about234--236O/15 min.The ester was hydrolysed in the' usual mannerby boiling with excess of 25 per cent. methyl-alcoholic potassiumhydroxide for four hours, the product was diluted with water,evaporated until free from methyl alcohol, acidified, again evapor-ated, and the mass extracted with ether in a Soxhlet apparatus.When the ethereal solution was evaporated, a syrupy massremained, which becams partly solid while still on the water-bath.This was stirred with concentrated hydrochloric acid, and the sandypowder which separated was collected, washed with hydrochloricacid, left in contact with porous porcelain in a vacuum desiccator,and then analysed:0.1670 gave 0.2768 CO, and 0.0644 H,O.C =43*7 ; H=4*3.C,H,,O, requires C = 43.9 ; H = 4.0 per cent.It is obvious that' during the hydrolysis under the above condi-tions one molecule of carbon dioxide had been eliminated, and thatthe above acid is cyclopentaite-l : 2 : 2 : 4-tetracarhoxylic acid,Ethyl cycloPentane-1 : 2 : 4-tricarboxylnte, C5Hi(C02H)3. - Inorder t o prepare this ester t'he crude' product of the hydrolysis ofethyl cyclopentaiiepentacarboxylate was heated a t 190° for half-an-hour, when a glassy mass remained, which did not crystallise. Thiswas converted into the ester by heating with alcohol and sulphuricacid in the usual manner (p. 2670), and the pure substance distilleda t 205-210°/40 mm.:0.1938 gave 0.4186 CO, and 0.1360 H,O.C,PH2206 requires C = 58.7 ; I$= 7.8 per cent.Tlie corresponding trimethyl ester, C,Hi(CO,Me),, liati beell pre-viously obtained (T., 1900, 77, 303), and distilled at 164-166*/12 mm.Tlie pure triethyl ester was hydrolysecl with niethyl-alcoholic potassium hydroxide in the usual manner, and, afterremoval of the metthyl alcohol, acidifying and evaporating t oC=58*9; H=7*8CAHBOSYLIC ACIDS DERlVED FROM CYCLOBUTANE, E'I'C. 26'73dryness, the mays was extracted with ether in a Soxlilet apparatus.Ou evaporation, the ethereal solution deposited a syrup, which,when rubbed with coiicentrated hydrochloric acid, crystallised, an(1the solid mass, after washing with hydrochloric acid and dryiiig 011porous porcelain, melted indefinitely a t 115-l25Oy and was appa-rently a mixture of the cis- and trans-modifications of cyclopentane-1 : 2 : 4-tricarboxylic acid.In order to demonst'rate this, half of thesubstance was heated with hydrochloric acid in a sealed tube at180° for four hours. The product was diluted with water, filteredfrom a small arnount of carbonaceous matter, and evaporated todryness; it was then dissolved in water, digested with animalcharcoal, and again evaporated. When the syrupy residue wasrubbed with concentrated hydrochloric acid, it crystallised withdifficulty (compare T., 1900, 77, 304), and the solid mass, aftercontact with porous porcelain and recrystallisation from hydro-chloric acid, melted a t 129-130°, and consisted of tmns-cyclo-pentane-1 : 2 : 4-tricarboxplic acid :0.1264 gave 0.2224 CO, and 0.0568 H,O.C = 417.9 ; H = 5.0.C,H,,O, requires C = 47.5 ; H = 4.9 per cent.On titration 0.1528 neutralised 0.0880 NaOH, whereas thisamount of a tribasic acid, C8Hl,,06, should neutralise 0.0907 NaOH.cis-cycloPentane-1 : 2 : 4-tricarboxylic Acid. - This modificationwas obtained by heating the crude mixture of acids melting a t115-125O (see above) with acetic anhydride for an hour, and thendistilling the product, when anhydro-cis-cyclopentanetricarboxylicacid solidified in the neck of the retort. After recrystallisation froma mixture of acetone and chloroform, this substance melted at215-217O, as stated by Bottomley and Perkin (Zoc.cit., p. 305).The solution of the anhydro-acid in water deposited, on concentra-tion, colourless crystals of cis-cy clopentane-1 : 2 : 4-tricarboxylic acid,melting at 146-148O.Y'he cis- aad trans-cycldexane-1 : 2 : 4-tm'carboxylic Acids(I~exahydrotrimellitic Acids),The ethyl butanetetracarboxylate,CH( C02E t)2*C15&= CH2=CH (C0,E t),,required for these experiments was prepared by the processdescribed by Perkin (T., 1894, 65, 578). This ester (34-6 grams),dissolved in an equal weight of alcohol, was mixed with a solutionof sodium (4.6 grams) in alcohol (100 c.c.) and then with ethylaS-dibromopropionate (26 grams), when, on setting aside, th2674 GOf,DSWOJtTHY AND PERKIN :mixture gradually becaaie quite liot. After heating for four 1iou.r~in a soda-water bottle in boiling water, water was added, the crudeester extracted with ether, and, since i t decomposed on distillation,it was a t once hydrolysed by boiling with excess of 25 per cent.methyl-alcoholic potassium hydroxide in the usual manner.Water was then added, the methyl alcohol carefully removed onth3 water-bath, the product acidified with excess of hydrochloricacid, evaporatled t o dryness, and extracted in a Soxhlet apparatuswith ether.On evaporation, the ethereal extxact deposited a syrup whichpartly solidified, and this was heated a t 190° for half-an-hour, thesyrupy residue being then esterified by boiling with alcoholicsulphuric acid and the ester fractionated (compare p.2670). Ethylcyclohezane-1 : 2 : 4-tricarboxylate was thus obtained as a colourlessoil, which distilled a t about 207O/30 mm.:0.1898 gave! 0.4142 CO, and 0.1374 H,O.C=59*5; H=8*0.This ester was hydrolysed by boiling with excess of 25 per cent.methyl-alcoholic potassium hydroxide for four hours, and, afterthe methyl alcohol had been completely removed, hydrochloric acidwas added, the whole evaporated to dryness, and extracted withether in a Soxhlet apparatus.The syrup which remained on distilling off the ether, only partlysolidified when it was rubbed with hydrochloric acid, and the solidhad an indefinite melting point, obviously consisting of two or morestereoisomeric modifications. I n order t o isolate one definite modi-fication (trans-), the whole was heated with concentrated hydro-chloric acid in a sealed tnbe a t 190° f o r four hours, the productwas dilute'd with water, filtered from a small amount of carbon-aceous matter, 6 ecolorised wfth animal charcoal, and evaporatedto dryness, during which the acid commenced to separate in colour-less crystals.Aftler remaining in the ice-chest for two days thecrystals were collected, dissolved in ether, filtered from a trace ofinorganic matter, and the ether removed, when a solid remainedwhich was crystallised from hydrochloric acid :0.1786 gave 0.3304 CO, and 0.0948 H20. C=50.4; H=5*9.C,H,,O, requires C=50.0; H=5-6 per cent.On titration 0.1526 required for neutralisation 0*0840 NaOH,whereas %his amount of a tribasic acid, C9H1206, neutralises 0.0847NaOH.tsans-cycloHexuae-1 : 2 : 4-tricurboxylic acid is rather sparinglysoluble in cold, but readily so in hot water, and has a markedtendency t o form supersaturated solutions, which only graduallyC,,H,,O, requires C = 60.0 ; H = 8.0 per centCARROXYLIC ACIDS DERIVED FROM CYCLORUTBNE, ETC.2675deposit, the acid as a hard, opaque, crystalline crust. It melts a tabout 220-222O t o a colourless, viscid syrup, but the exact' point, isdifficult to observe.cis-cycloHexane-1 : 2 : 4-tricarboxylic Acid.-In order t o obtainthis acid, the pure tram-acid (2 grams) was mixed with aceticanhydride (5 c.c.) in a test-tube, and gentlly boiled by means of asulphuric-acid bath for one hour; the temperature was then raised,and the excess of acetic anhydride distilled off.The test-tube wasdrawn out, and the whole heated as rapidly as pcssible over afree flame; when there was much decomposition and a voluminouscarbonaceous mass remained.The! small quantity of brown distillate, which partly solidifiedon keeping, was boiled with much water, filtered from a 1it;tls tar,decolorised with animal charcoal, and then evaporated to 'a smallbulk and mixed with an equal volume of concentrated hydrochloricacid. On remaining in the ice-chest a crystalline crust graduallyformed, and this was coilected and crystallised from water, inwhich it is rather sparingly soluble in the cold, and from whichthe cis-acid separated as a crust of colourless, warty masses, whichhad a quite different appearance from the crystals of the trans-acid :0.1432 gave 0.2630 CO, and 0.0752 H,O.C=50*2; H=5*8.C,HI20, requires C=50*0; H=5*6 per cent.On titration 0.1405 required 0.0764 NaOH f o r neutralisation,whereas this amount of a tribasic acid, C9Hl2O6, neutralises 0*0780NaOR.ciscycloHexnne-1 : 2 : 4-tricarboxylic acid softens a t 218O, meltsa t 225O, and, when it is mixed with an equal amount of thetrans-modification, the mixture softens very much a t 198-200°,and is almost completely melted a t 2 0 8 O (compare p. 2667).trans-cycloHeptaiae-1 : 2 : 4-tricarboxylic A cid,C0,H,CH<Cfl,--C'H2--C CH2*CH(C 02H) !1 2>CH*C02H.The investigation of this interesting acid has been rendered diffi-cult owing to the small yield which is produced by the followingprocess, and it has not been found possible to obtain bett'er resultsby varying these conditions.Ethyl cyczoheptane-1 : 1 : 2 : 4 : 4-penta-carboxylate (p. 2668) was first prepared by mixing 36 grams ofethyl pentanetetracarboxylate,CH(CO,Et),*CH,*CH,* CH,* CH( CO,Et),(Perkin, T., 1887, 41, 240), first with a solution of sodium ethoxidemade by dissolving sodium (4.6 grams) in alcohol (100 c.c.), an26'46 CARBOXYLIC A C I ~ S DERIVED FROM CYCLOHUTANE, ETC.t h e n with ethyl ap-t3il)l.ornopropioiiate (26 grams), and, after t l i pi iiitial somewhat vigorous action had subsided, the whole was heatedin a soda-water bottle in boiling water for four hours. Tlie productwas isolated by addiiig water arid extracting with ether, and wasliydrolysed in the usual irianner (p.2670), the crude, dark brown,syrupy polybasic acid being heated a t 200° f o r an hour, and theresidue esterified by boiling with alcohol and sulphuric acid. Ondistillation a considerable amount of ethyl pimelate,CO,Et*[CH,],*CO,Et,passed over a t about 190-195°/100 mm., and then crude ethylcycloheptanetricarboxylate distilled a t 200-230°/ 30 mm., leavinga considerable dark-coloured residue in the distilling flask. Thecr clde tricarboxylic ester was redistilled, and the fraction distillingatl 212--215°/30 mm. analysed, but the yield obtained was only7 grams, or 8 per cent. of that theoretically possible:0.1960 gave 0.4390 CO, and 0.1504 H@. C ' ' = G l - l ; H=8*5.Cl6HZ6O, requires C = 61.1 ; H = 8.3 per cent.This ester was hydrolysed by boiling with methyl-alcoholicpotassium hydroxide in the usual manner, and, after removal of thealcohol, excess of hydrochloric acid was added, the whole evaporatedto dryness, and extracted with ether in a Soxhlet apparatus. Theresidue from the ether was a syrup, which could not be induced tocrystallise, and was doubtless a mixture of stereoisomerides. Itwas heated with hydrochloric acid in a sealed tube a t 190° forfour hours, the product diluted with water, filtered from a smallamount of carbonaceous matter, and the hydrochloric acid removedby evaporation. The residue was dissolved in water, boiled withanimal charcoal, and again evaporated, when a viscid, colourlesssyrup was obtained, which, on rubbing, almost completely solidified.After contact with porous porcelain, the acid separated from hydro-chloric acid in hard, nodular masses:0*1100 gave 0.2106 CO, and 0.0623 H,O. C =52.2; H= 6.1.C,,H,,O, requires C= 52.2 ; H = 6.1 per cent.On titration 0.0488 required 0.0250 NaOH for neutralisation,whereas this amount of a tribasic acid, C10H1406, should neutralise0.0254 NaOH.trans-cycloHeptane-1 : 2 : 4-tricarboxylic acid melts a t 198-200°,and is readily soluble in water. Unfortunately the amount ofmaterial available was not sufficient for the preparation of thecis-acid.THE UNIVERSITY MUSEUM,OXFORD

ISSN:0368-1645    

DOI:10.1039/CT9140502665

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

INVESTlGATIONS ON DEPENDENCE OF ROTATORY POWER, ETC. 267 7CCL.-Investigations on the Dependence of RotatoryPower on Chemical Constitution. Part X . TheOptical Dispersive Power of Tetrahydro-%naphtholand its Esters.By JOSEPH KENYON and ROBERT HOWSON PICKARD.IT has been shown in Parts V I and IX (this vol., pp. 1117 and2644) that the opt'ically active 1-naphthylalkylcarbinols of thegeneral formula C,,H,*CH(OH)*R have complex dispersive powersat all temperatures up to those far removed from their meltingpoints. Thus the methyl member of the series has a complex dis-persive power at,all temperatures up to about 160° and the corre-sponding a-hexyl hoinologue up t o about 180°, above which limitingtemperatures the rotations of each obey the law of simple dispersivepower a3 expressed by the Drude equation with one term,a = k / h 2 - h $ .It is further of interest to note that in the super-cooled state a t a few degrees below the melting points of thesecom p ou nd s their temper a tu re-r ot a t i on curves for so di um- y ell o w t omercury-violet light, which are perfectly regular throughout, exhibita region of so-called anomalous dispersion.It has been suggested (Zoc. cit.) that below these limiting tem-peratures the apparently homogeneous carbinols are really mixturesof two isomerides having rotatory powers of opposite sign, anddiffering in dispersive power. The further suggestion that theisomerism is due to a different disposition of the valencies in theaaphthyl radicle (the two forms being of the nature of ar- andac-derivatives) makes it desirable t o consider the dispersive powerof other compounds containing either the naphthyl radicle or otherradicle closely related to it.Already in Part 111 (T., 1912, 101, 1427) the preparation andsome of the optical properties of both dextro- and kvo-rotatoryac-tetrahydro-%naphthol have been described, but unfortunatelythe optical measu.rements were confined t o light of one wave-lengthonly.Accordingly, the work described there has been partlyrepeated, and the results confirmed and extended. It has now beenfound that the temperature-rotation curves of ac-tetrahydro-2-naphthol in the fused state from a temperature of about 120° downto its melting point at 50°, and beyond in the supercooled state to(at least) 153, are perfectly regular and smooth.The rotationsobserved in the homogeneous state up to 120°, as also in varioussolvents, obey the law of simple dispersive power, but above 120°VOL. cv. 8 BKENYON AND PICKARD : INVESTIGATIOXS ON DEPENDENCEFIG. 1.160"140"120"100"80"60"40"20"0"CHARACTERISTIC DIAGRAMforac-Tetrahydro-2-naphthol and someof its derivatives.Points marked 1 to 4 correspond with the rotations of the hydrogen phthalatea t 5 per cent. concentration in ethyl alcohol, chloroform, pyridine and benzenerespectively, points 5 and 6 with ethgl-alcoholic solutions of the sodium andpotassium salts, points 7, 9 ar.d 10 with the rotations of the valerate in thehomogenecus state a t 200", 100" and 20" respectively, and points 8 and 11 withsolutions of the valerate in chloroform and carbon disulphide.Points marked 12to 17 refer t o the rotations of the tetrahydronaphthol in the homogeneous state a t2OO", a t 140., dissolved in carbon disulphide and in chloroform, and in thehomogeneous state a t 60" and 20" respectively. It will be noticed that pointsmarked 1, 3, 5, 6 , 7 and 12 do not fit on the lines of the diagmmOF ROTATORY POWER ON CHEMICAL CONSTITIJTION. 2679the dispersive power becomes complex. Of this phenomenon theredoes not seem to be any simple explanation, but the properties ofthe reduced compound are in marked contrast t o those of the1-naphthylalkylcarbinols. The n-valeric ester in the homogeneousstate a t ZOO and in solution and the hydrogen phthalate whendissolved in benzene or chlorof o m also exhibit rotations, whichappear to conform to the law of simple dispersive power.Thevalerate, however, in the homogeneous state at higher temperatures,solutions of hydrogen phthalate in alcohol o r pyridine, and aqueousor alcoholic solutions of the sodium or potassium salt of the latterester all show complex dispersive power.The alternative method of plotting such rotations by means of a" characteristic diagram " brings out these relations in a strikingmanner. Thus the diagram (Fig. l), which is constructed in theusual manner, using the rotations for mercury-green light as areference line, only correlates those rotations of the substances justmentioned, which conform to the law of simple dispersive power.It is not surprising that the diagram fails t o correlate the rotationsof the valerate in the homogeneous state a t higher temperatures,for not only has the ac-tetrahydro-2-naphthol then a complex dis-persive power, but.also, as has been repeatedly shown, an esterifiedcarboxylic group exhibits complex dispersive power a t high tem-peratures. Assuming that dynamic isomerism is the underlyingcause of the complex dispersive power exhibited by a colourlesscompound of simple chemical constitution (containing only oneasymmetric carbon atom), i t may be stated generally that in caseswhere complex dispersive power is exhibited a t all temperatures thecompound will contain more than one possible centre of dynamicisomerism.Illustrations of this general statement can be seen inthe esters of ihe naphthylalkylcarbinols and of ac-tetrahydro-2-naphthol, whilst each of the substances mentioned above as showingcomplex dispersive power when dissolved in certain solvents con-tains, when so dissolved, two possible centres of dynamic isomerism,and the observed rotations cannot be correlated on the characteristicdiagram (Fig. 1). However, the rotations shown by aqueous SOlU-tions at various concentrations of sodium ac-tetrahydro-2-naphthylphthalate can be correlated oli another diagram (Fig. 2) speciallydrawn for these, and permit the inference that there is some relationbetween them.Attention has already been drawn in this series of investigationst o the danger of basing conclusions on the values of any one disper-sion ratio.A good example of this danger is to be seen in thedispersion ratios of the1 substances named in tables I and 11. Itwill be noted that in the homogeneous state the ratio f o r mercury-8 M 2680 KENYON AND PICKARD : INVESTIGATIONS ON DEPENDENCEvioletlgreen remains constant, but that for mercury-violet/sodium-yellow tends constantly to increase. This is well brought out inthe diagram (Fig. l), where' the lines for violet, green and yellowFIG. 8.4"3"s 9 2"&$ 32&h0 1"0"- 1"- 29CHARACTERISTIC DIAGRAMforphthalate in aqueous solutions.(1) 2.0 per cent. solution(4) 8.0 .,Sodium 2-ae-tet ra hyd ro-2-napht hyl(594.2 ,)(3) 6 1 wintersect a t zero.When the green is used as a reference line therotation values for violet and green all lie approximately on thetwo lines, so that the dispersion ratio is constanti, but in the caseswhere complex dispersive power (see, for example, points markeTemp.20"40608010012014016018020020'406080100120140160180Density.D .1.09101.07501.05901.04311.02751.01210-99550.97900.96300-94701.02841.01400.99950-98530.97090.95650.94210,92760.9133[a]",-!- 75.68"71.8568.3565-3662-6659.9457-5055.2652.9650.86- 46.80"45.7744.7143.6242-4841-3040.0538-7937.43TABLE I.R o tat ory Powers u t Di ff ere n t Temperad-ac-Te tra hydro-2-vaapht hol.ial",.+ 90.26"86.7282.6279.1675.3972.3369.8267.3664.6662-47[a]:i.155.51148.98142.05135.65130.13125.88121.04116.10112.15$162.16' -+ [MIL.. 112.0"106.4101.296.792.688.785.181.878.475.3[MI:,.+ 133.6'128.3122-117.1111.6107.0103.499.795.792.51-ac-Te tra hydro-2-naphthyl n-Valerat-56.23" -55-3454.4353.5052.5251.5450.5649.5348.45.99-97" -98.4096.7495.1393.4091-6089.8087.9685.96108.6" -106.2103.7101.298.695.892.990.086.8130.5"128.3126.3124.1121.8119.6117.3114.9112.Length of Weightobserva-Solvent.Pyridine . . . . . .Ethyl alcoholChloroform . . .Carbondisulphide . .Benzene . . . . . .Chloroform . ..Ethyl alcoholEthyl alcoholChloroform . . .Pyridine . . . . . .Benzene . . . . . .Ethyl alcoholtiontube,cm.222022202022222222222222TABLE 11.d-ac-Tetra hydro-2-wpht hol.1.0163 + 8.49' + 10.23' + 18.40' +75.97" +91*54O + 164.6'1.0313 7.79 9.37 16.63 75-56 90.88 161.40.9968 7.38 8.85 15.70 67.32 80.71 143.21.0206 6.36 7.67 13.71 62.30 75.13 134.30.9653 5.95 7-14 12-70 61.50 73.98 131.6d-ac-Tetrahydro-2-mphthyl Hydrogen Phthalate.1.0718 +1*60 +1.89 +3.40 +13*67 +16.03 +28.84Brzscine Salt of the &Ester.1.0621 +@48 +0*25 -1.05 +4.11 f2.14 -8.99l-ac-Tetrahydro-2-6upht hyl H?/droyen Pht0.9830 -1.05 -1.22 -1.85 -9.72 -11.28 -17.1 11.0212 1.54 1.94 3.31 13.71 17-27 29-401.0597 1.85 2.33 3.99 15.87 19.99 34 2 30.4423 1.34 1.62 2.90 27.54 :{3.30 5 ~ 6Cinchonidine Salt of the I-F, / Y fi er.1.1052 -8.81 -11.03 -19.72 -72.46 -90.74 -102.20The solutions for the observations of rotatory power recorded in tables I1 and 111 were preparedsolute to 20 C.C.with the solvent a t the temperature of the laboratory, at whicLength ofobservationtube,Solvent. cm.Water .................. 22 ,, .................. 22,, .................. 22,, .................. 22Ethyl alcohol ...... 22Chloroform ......... 22Ethyl alcohol ...... 20Benzene ............. 20Carbondisulphide ......... 20TABLE 111.Sodium. 1-a c-Tetra.h ydro-2-napht hyl Phthalate.Weightofsolute,grams.0.51 171.03321.52801-96600.94230.98671.00670.82791.0292a,. agr.avi. [a]wf O o +0-04' +0.26' +O" ++_O +()a07 +0*45 +_O +-0.17 -0.14 +0*15 -1.24 --0.45 -0.48 -0.44 -2.54 --1.53 -1.83 -2.91 -18.05 -21.591-a-Tetrahydro-2-naphthyl n- Falerate.-4.45 -6.38 -9.48 -41.01 -49.57-4.15 -4.98 -8.91 -41.21 -49.45-4.44 -5.35 -9.53 -53.63 -64.63-6.57 -7.96 -14.40 -63.86 -77.3affords a much better method of purifying the' ac-compound thanthe older one.This sodium salt crystallises from water in long needles, or fromaqueous alcohol in large tablets, has the compositionCO,Na*C,H,*CO,* C,,H,,, 4H20,eflloresces a t about 60°, does not melt below 200°, and is verysoluble in ethyl alcohol :Na = 5-88.0.3218 lost 0.0582 H,O and gave 0.0584 Na,SO,. H20=18*23;C,8H,,0,Na,4H,0 requires H,O = 18.23 ; Na = 5-88 per cent'.The resolution of the 6Z-hydrogen phthalate was carried out inthe manner already described (Zoc.cit.), and the results were con-firmed. The d- and 1-est'ers form sodium salts, which have similarproperties to that of the' 61-ester.Determi?iations of Rotatory Power (u100mm.) of the Carbin02 awJl-ac-Tetrah ydro-2-izaphthyZ n-?'-alerate in the Homogeneous State.d-ac-l'e trahydro-2-naphthol.Temp. 28.5' 65"a,, ...... +80.50" 71.20" (see also Part III., loc. &.).Temp. 27" 59" 82" 126" 136" 156" 180'a,, ... +96*72' 88.54' 82.00" 71.72' 70.58' 66.88" 62.26'Temp. 26.5" 58' 84' 126' 137" 157' 180'a y t . . . . . . + 173.60" 158.80" 146.04" 129.64" 126.30' 119.70" 111.80'* When not otherwise stated, the experimental procedure is similar to thatpreviously described (Zoc. cit.)KENNER : THE HEDUCTlON PRODUCTS, ETC. 2685l-ac-Te t~niiydro-2-?iapJ~th y l n- Valeya t e.*Temp. 20" 44" 54" 110" 135" 161"a=...... -48.12" 46.24" 45.64" 40.16" 38-36' 35.80"Temp. 20" 43; 6 9 O 110" 138" 160"agr ... -557.80" 55.86" 54.44" 50.22" 47-84' -446.00"Temp. 20" 41" 59" 110" 136" 162"ari . . . - 102.78" - 99.90" - 96-52' - 89.60" - 85.00" - 81.20"The authors desire to express their thanks to the GovernmentGrant Committee of the Royal Society for a grant, which hasdefrayed some of ths expense of this investigation.MUNICIPAL TEOHNICAL SCHOOL,BLACKBURN

ISSN:0368-1645    

DOI:10.1039/CT9140502677

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

KENNER : THE HEDUCTlON PRODUCTS, ETC. 2685CCLI.-- The Reduction Products of Ethyl Hydrindenc-2 2-dicarboxylate.By JAMES KENNER.IN a previous communication it was suggested that the ease withwhich cyclic condensation occurs should be modified by the presencein a chain of certain carbon atoms which, being already membersof a closed ring, have the directions of their valencies to'someextent determined (Kenner and Turner, T., 1911, 99, 2102). Theinvestigation now to be described was undertaken with the objectof studying ring-formation from compounds, the molecules ofwhich contain one carbon atom fulfilling this condition; in otherwords, the preparation of sp-ro-compounds was to be attempted.Since substituent groups are also known to be important factorsin determining the facility of formation, and stability, of cycliccompounds it appeared that, among spire-compounds, .the hydro-carbons would furnish the most decisive evidence of the influencesreferred to in the preceding paragraph.These and other considera-tions suggested the application t o ethyl hydrindene-2 : 2-dicarboxy-late of Bouveault and Blanc's method of reduction by means of* These rotations are somewhat lower than those previously published. It hasnot been thought necessary to investigate the cause of the discrepancy, as this paperdeals mainly with optical dispersive power, which is only very slightly affected bythe smsll discrepancy2686 KENNER : THE REDUCTION PRODUCTS OFsodium and ethyl alcohol, in the hope of preparing oo’-dzhydrozy-2 : 2-dimethylhydrindene (I), from which the hydrocarbon (11)C6H,<CHqC<FH, CH, CH,’w.1might subsequently be obtained.It had previously been shown by Bouveault and Blanc that ethyldiisobutylmalonate, whilst furnishing a certain amount of theexpected glycol, was t o a considerable extent decomposed in thefollowing way under the influence of sodium ethoxide formedduring the reaction :the ethyl isovalerate being then reduced in the normal manner(Bull.SCC, chim., 1904, [iii], 3 1, 1203). Ethyl hydrindenedicarb-oxylate had, however, been shown by Thole and Thorpe to bequite stable towards sodium ethoxide a t the ordinary temperature(T., 1911, 99, 2186), and the hope was therefore entertained thateven a t the higher temperature to be used in these experiments thetype of decomposition observed by Bouveault and Blanc might notassert itself in a marked degree.This expectation, however, wasnot realised, for the yield of the glycol (I) was disappointinglysmall, being less than 3 per cent. of the calculated. More than40 per cent. of tho ethyl hydrindenedicarboxylate was convertedinto 2-htydroxymethylhydr~n~ene (111), the remainder being re-covered in the form of a mixture of hydrindene-mono- and di-carb-oxylic acids, in which the former largely predominated :(C4H,),C(COzEt)z + CZH,*OH ++ (C4H,),CH*COzEt + CO(OEt),,Initially, therefore, the dicarboxylic ester was almost entirelyconverted into the monocarboxylic ester, and, in the author’sopinion, this reaction must be ascribed to spatial causes, whichwill bO discussed lahr.It is probable that such influences also playa part, although possibly a subordinate one, in promoting thedecompositions discussed by Thole and Thorpe (loc. cit .).2-Hydroxymethylhydrindene was readily converted by the usualmeans into 2-bromonzethylhydrindei~e (IV), the reactions of whicETHYL HYDRINDENE-2 8-DICARBOXYLATE. 2687invited investigation, because it has frequently been observed thatthe bromine atom in derivatives of this type is remarkably inert.Thus Perkin and Pope found that 1-methyl-4-bromomethylcyclo-hexane (V) was converbd into the cyanide only with considerabledifficulty (T., 1908, 93, 1079). SimiIar relationships were dis-covered in tha present instance. The bromo-compound was un-changed after prolonged boiling with amalgamated zinc and hydro-chloric acid, in spite of the efficiency of this reducing agent (Clem-mensen, Ber., 1913, 46, 1837; 1914, 47, 51, 681).Interaction ofthe bromo-compound and ethyl sodiomalonate in alcoholic solutionafter ten hours a t the boiling point resulted in the production ofonly about 65 per cent. of tlie calculated amount of ethyl 2-hydrin-dylrnethylmnlonate (VI) :*C 6 H 4 < ~ ~ 2 > C H - C H2-CH (CO,Et\,The formation of 2-phthalimi?zomethylhydrindene (VII) by heat-ing the bromo-derivative with potassium phthalimide at 180-200°for nine holm was similarly incomplete:2(VI.)C6H4<g: 2>CH*CH 2*N<Eg>C,H4(VII.)The contrast between the inertia of the bromine atom in suchcompounds and its activity in, f o r inst'ance, benzyl bromide, isworthy of some comment, and is obviously in some way connectedwith t,he difference between the saturated and the unsaturatedconditions of the cyclic structures present in the two types ofcompounds.If, however, benzyl bromide be represented by theformula (VIII), in Flurscheim's notation, it would appear to followas a striking consequence that Perkin and Pope's 1-methyl-4-bromo-methylcyclohexane is t o be represented by the formula I X :(VIII.) (IX).The similar inertia of the bromine atoms in tetrabromotetra-methylmethane (Perkin and Simonsen, T., 1905, 87, 161; Fecht,Ber., 1907, 40, 3884) would then find expression in the formula X :Br-CH CH --BrBr--CH;>C<C +I3 L'(X-2688 KENNER: THE REDUCTION PRODUCTS OFThe facts symbolised by these formuh are illustrative of theinfluences referred to a t t’he commencement of this paper, and, inthe author’s opinion, they are all explicable by a thorough appli-cation of Baeyer’s strain theory.For it is a t once clear that thenormal relative positions of substituents known to exert sterichindrance, such as methyl (or bromomethyl) and carboxyl groups,may, when they are attached to the same carbon atom, be compar-able, in regard to this atom, with those of the carbon atoms in,for instance, a cyclohexane or a cycloheptane ring. Then, adoptingWerne’r’s conception of the uniform spherical distribution of affinityround a carbon atom (“Beitrage zur Theorie der Affinitiit undValenz,” Zurich, 189l), we see that, if aal in XI represent insection the zones of affinity appropriated by two univalent group-ings in the plane of the paper when “the angle between theirvalencies is 109O281,” an increase in this angle will cause an altera-tion in the relative position of the zones, which will now be repre-sented by XII:(XI.) (XU.)I n this manner a certain amount of affinity, corresponding withthe region (b), will be left unsatisfied, and the extent of this regionis a measure of the “strain,” in Baeyer’s terminology.I f the othergroups attached to the carbon atoms be free t o move, they willprobably so adjust themselves as partly to engage the valency thusleft free because the change in position of the zones aa’ involvesan incursion into the zones of affinity previously available for them.I n the following paragraphs, the attempt is made to apply theseconsiderat,ions to the cases in which ( a ) two of the groups attachedto a carbon atom are components of the same) cyclic system, whilstthe other two are groups of large molecular volume.I n this case,the motion of the former groups is restricted, and the affinity repre-sented by b will then remain free and available t o a greater or lessextent as partial valency to an atom situated above or below theplane of the paper and, for example, coplanar with the groupsappropriating a d .Thus, in the case of ethyl hydrindenedicarboxylate there will beresidual affinity on the quaternary carbon atom, and, owing to theencroachment of the carbethoxy-groups on the zones of affinitETHYL HYDRINDENE-8 8-DICARBOXYLATE.2689normally available for the two carbon atoms of the hydrindene ring,one or more of these groups will obtain less than its proper shareof affinity. This deduction is in agreement with the experimentalevidence just advanced, according to which we may conclude thatthe ester is more adequately represented by the formula XIII:(XIV.)Similar considerations probably supply an explanation of anumber of reactions met with in the chemistry of cyclic compounds.I n illustration of this may be cited the change of carone intocarvenone by distillation (Baeyer, Ber., 1894, 27, 1917), and intobromo- and hydroxy-menthanone by absorption of the elementsof hydrogen bromide or water (ibid., p.1920); the isomerisationof carylamine hydrochloride into vestrylamine hydrochloride(Baeyer, Ber., 1894, 27, 3486); the disruption of the bridgein dimethyldicy clopentanonecarboxylic acid by reduction (Perkin,Thorpe, and Walker, T., 1901, 79, 729); the addition of theelements of hydrogen bromide t o a-camphylic acid (Perkin, T.,1903, 83, 842); and the various reactions by which the bridge inthe camphor molecule is broken between two quaternary carbonatoms (see Aschan, “ Konstitution des Kamphers,” Braunschweig,1903, p. 79).The reactions of certain other compounds are illustrative ofanother mode of relieving the stlress on the quaternary carbon atom,namely, the replacement of two single bonds by a double bond.This results in a smaller demand being made on the affinity of thecentral carbon atom.Thus Wallach has shown that ethyl cyclo-hexan-1-01-1-acetate on hydrolysis is partly converted into cyclo-hexanone, accompanied by some’ cyclohexanol (a hydrogen atomhaving displaced a group of large molecular volume). Further,dehydration of the ester or of the acid is easily carried out, andresults in the formation of Al-cyclohexeneacetic acid or of carboxy-methylenwyclohexane, according t o the agent employed. Indeed,the initial condensation product of 1 : 5-dimethyl-Al-cycZohexen-3-one cannot be isolated, but passes over at onoe into 1 : 5-dimethyl-A1:3-cyclohexadienyl-3-acetic acid (Annalen, 1900, 3 14, 147 ; 1902,323, 135; 1905, 343, 40, 347, 316; 1908, 360, 26).That thesereactions are not due t o the presence of the hydroxyl group assuch is shown by a remarkable instance of an analogous kind, com-municated to the author by Prof. J. F. Thorpe. Ethyl cyclo-hexane-4-dibromodiacetate (XIV) when boiled with dilute potass-ium hydroxide solution is converted into carboxymethylenecyclo2690 KENNER: THE REDUCTION PR0I)UcTS OFhexane (XV), although whe,n it is dropped into concentratedaqueous potassium hydroxide a t 130° hhe acid (XVI) is produced :It is obvious that similar conditions will prevail when, as in theinstances quoted above, three o r four separate groups of largemolecular volume are attached t o a single carbon atom.When, as in the molecule of cyclopropane-1 : l-dicarboxylic acid,the cyclic structure is such that the '' angle between two valencies "of the quaternary carbon atom is less than 109O28/, the effectsjust discussed will be intensified.Hence this acid and 1 :l-di-methylcyclopropane are almost comparable with unsaturatedcompounds in the readiness with which they take part in addi-tive reactions, and the general conclusions of Kotz ( J . p. Chem.,1903, [ii], 68, 174) in regard to the derivatives of cyclopropaneare in agreement with the statement just made. Further,Radulescu's observation that the acid (XVII) is stable towardshalogen hydrides (Be?., 1909, 42, 2771; 1911, 44, 1018)appears to be direct evidence in favour of the suggestion that itscarbonyl groups are differently situated with regard t o the centralcarbon atom from those in cyclopropane-1 : l-dicarboxylic acid :7H2 CC*YH=CO,H(XYII.)The rearrangement of derivatives of ethylene oxide into those ofacetaldehyde are instances of a similar nature among heterocycliccompounds (Fourneau and Tiffeneau, Compt.rend., 1905, 141,662; Klages, Ber., 1905, 38, 1969; Klages and Kessler, Ber., 1906,39, 1753):>c<co-cH.co,H CH2Both pairs of valencies attached t40 the carbon atom ( b ) areinclined to one another a t angles less than 109O28/, when similarinstability of the molecule may be expected. Thus the followingtable shows in tho case of the central carbon atom of the spiro-compound, (CH2)J2(CH2),, the angle between a valency of the(x + 1)-membered ring and one of the (y + 1)-membered ring :Y+1x + l 2 3 42 180' 150' 136"3 139 12ETHYL HYDRINDENE-2 : 2-DICARBOXYLATE.2691The magnitude of these angles indicates that, considerableamounts of unsatdsfied affinity will exist between the zones corre-sponding with the valencies in question. Consequently, compoundsof this type may be very difficult to isolate, and, when obtained,very liable to undergo change. Thus Dimroth and Feuchter wereunable to prepare an allene derivative from the compounds XVIIIand XIX (BeT., 1903, 36, 2238; compare Ipatiev, J . pr. Chem.,1899, [ii], 59, 517):C02Et cGH6>C: CCl*CH,* CH,(XVIII.)CC), CeH5>CH*CCI Et :CH*CH,(XIX.)Similarly, ethyl allenetet,racarboxylate (XX), which is onlyobtained by heating the initial product (XXI) of the action ofethyl sodiomalonate on carbon tetrachloride, absorbs two molecularproportions of water when exposed in a moist atmosphere (Zelinskiand Doroschevski, Ber., 1894, 27, 3376):(XX.j.-The action of alcoholic potassium hydroxide on iodomethylcyclo-propane leads to the production of erythrene, presumably owing tothe rearrangement of methylenecyclopropane (Dem janov, J . Buss.Phys. Che.m. SOC., 1903, 35, 375):Also, Favorski and Batalin have recently shbwn (Ber., 1914,47, 1648) that Gustavson was mistaken in attributing the consti-tution of an ethylidenecyclopropane to a compound he had preparedin an analogous manner (Compt. rend., 1896, 123, 242). Further,the sole product of dehydration of cyclopropyldimethylcarbinol isP-cyclopropylisopropylene (XXII), notwithstanding the fact thatOH.C(CB,)2*CH<yH2 + CH2:C(CH,)-CH<FH2C*2 CH2(xxIr.1dimethylisopropylcarbinol furnished the isomeric olefines (XXIIIand XXIV) in the proportion of three to one (Henry, Compt.rend.,1908, 147, 557) :OH*C(CH,),*CH(CH,), --+ C(CH,),:C(CH,), and(XXIII.)CH,:C(CH,)*CH(CH,),.(XXI v. 2692 KENNER: THE REDUCTION PRODUCTS OFThe production of methylenecycZobut*ane (XXV), in place ofspiropentane (XXVI) , from t2etrabromotetramethylmethane isdoubtless t o be ascribed to similar causes (Demjanov, Ber., 1908,41, 915; Favorski and Batalin, Zoc. cit.; compare Gustavsonand Bulatov, J . pr. Chem., 1896, [ii], 54, 97; 56, 93; Fecht,Zoc. c i t . ; Zelinski, Ber., 1913, 46, 170):(XXV.) (XXVI.)Neither this hydrocarbon nor cyclobutanone (Kishner, J . Buss.Phys. Chem. SOC., 1905, 37, 106; 1907, 39, 922) exhibits anytendency towards the breaking down of the f our-membered ring,but it is significant that cyclobutane-1 : 3-dione behaves as thoughit were represented by the formula XXPII (Chick and Wilsmore,T., 1910, 97, 1982):CH,*C<'I O:C*CH,----.(XXVII.)The illustrations thus brought forward are not intended to beexhaustive, but suffice to indicate the aspect from which, in theauthor's opinion, the study of spko-compounds should beapproached. The quaternary carbon atom is not per se a sourceof weakness, this being conditioned by the distortion of its valenciesfrom their normal positions.Finally, it may be mentioned that experiments have also beeninitiated with a view, on the one hand, to the synthesis of thecompound (XXVIII) by the condensation of the chloride of hydrin-den62 :%dicarboxylic acid with benzene, and, on the other, t o the(X XVIII.)preparation of reduction products of ethyl cyclohexanediacetate,' from which sp*ro-compounds might be prepared. The investigationin this direction has, however, only just been commenced, and thememure of success attained is indicated in the experimental portionof this paper.EXPERIMENTAL.Reduction of Ethyl Hydrindene-2 : 2-dicarboxylate.Sodium (30 grams), cut into pieces the size of a pea, was placedin a large flask, fitted with a long, upright condenser and a tap-funnel, and the flask was heated to 80° in an oil-bath.A solutioETHYL HY DRINDENE-8 : 2-DICARBOXYLA1 E. 2693in absolute alcohol of ethyl hydrindenedicarboxylate (23 grams),previously purified by distillation under diminished pressure(100 c.c.), was then run from the tap-funnel on to the sodium asrapidly as possible, consistent with efficient action of the condenser.Th0 temperature of the oil-bath was then raised t o 130°, and afurther quantity of alcohol (100 c.c.) gradually added in the courseof two hours. A t the end of five hours from the experiment anyunreduced ester was hydrolysed by the gradual addition of watert o the mixture. The product was then cooled, considerably diluted,and treated with sufficient sulphuric acid to leave the solutionweakly alkaline.By exhaustive extraction with ether the mixtureof reduction products was removed, whilst hydrindenemonocarb-oxylic acid (5.5 grams) could be recovered by subsequent acidificn-tion of the aqueous solution.The ethereal extracts, after treatment in the usual manner,furnished an oil, which was distilled under diminished pressure.I n this manner a large fraction (5.5 grams) was obtained, whichboiled a t about 140"/11 mm. and solidified a t the ordinary tem-perature.2-Hydroxymethyll~ydrindene (111), obtained in this way, has acharacteristic agreeable odour, and consists of prismatic crystals,which melt a t 3 3 O and boil a t 139-140°/11 mm. It is readilysoluble in niost organic solvents, but only sparingly so in lightpetroleum (b. p. 40-50°), and may be crystallised from thissolvent :0.1490 gave 0.4424 CO, and 0.1078 H,O.C = 80.98; H = 8.04.C,,Hl20 requires C = 81.07 ; H = 8.11 per cent.The phenylurethane, C,H,<CB2>CH*CH2*O*C0.NH.C,W,, CH was2prepared by heating a solution of molecular proportions of thecarbinol and phenylcarbimide in light petroleum (b. p. 90-110O).After crystallisation, it melted a t 99.5O :0.2188 gave 10.2 C.C. Nz a t 1l0 and 755 mm. N=5*59.CI7Hl7O2N requires N = 5-24 per cent.w wf-Dihydroxy-2 : 2-dimet~~lhtyd~~nde?ze (I) was obtained by dis-tilling the united residues from four of the above preparations of2-hydroxymethylhydrindene. A colourless oil passed over a t about200°/15 mm., and rapidly solidified. On the addition of lightpetroleum (b. p.90-110O) to its solution in ethyl alcohol, small,hexagonal prisms, melting a t 112.5O, separated. The yield was1.5 grams:0.1568 gave 0.4266 CO, and 0.1090 H20. C =74*20; H =7*73.C,,H,,O, requires C = 74.16 ; H = 7.86 per cent.VOL. cv. 8 8694 KENNER: THE REDUCTlON PRODUCTS OFR eductio 1% of Ethyl Hydrindene-2-car b oxylate.A solution of tha ester (20 grams) in alcohol (100 c.c.) was addedto sodium (18 grams> in precisely the same manner as alreadydescribed for fhe previous case, alcohol (20 c.c.) being subsequentlyadded. The yield of carbinol was 8.5 grams.2-Hydroxymethylhydrindene (10 grams), having been added toa solution of chromic acid (4.2 grams) in 10 per cent. sulphuricacid (75 grams), thp, mixture was heat'ed on the water-bath f o r twohours.The ?thereal extract of the cooled solution was washed withsodiuni carbonate solution, and then shaken with concentratedsodium hydrogen sulphite solution. The aldehyde, isolated in pooryield frcm this solution in the usual manner by decompositionwith sodium hydrogen carbonate, was a fairly mobile oil, boilinga t 122O/12 mm., which did not, solidify. It readily underwentoxidation on exposure, and its odour also characterised it as analiphatic aldehyde :0.1440 gave 0.4325 CO, and 0.0878 H,O. C=81*91; H=6*77.CloHloO requires C = 82.19 ; H = 6.85 per cent.The semicarbasone, prepared in the usual manner, readily dis-solved in alcohol, and separated from this solvent in radiate masseaof small needles melting at 174O:0.1120 gave 20.6 C.C.N, a t 17O and 730 mm. N=20*90.C,,H,,ON, requires N = 20.69 per cent.2-Bronzom e t h y l h ydrindene (IV) .This compound was easily prepared by heating a solution of2-hydroxymethylhydrindene (35 grams) in glacial acetic acid,saturated a t Oo with hydrogen bromide (50 c.c.), a t 100-1200 forthree and a-half hours.The compoulnd boiled a t 132O/11 mm., and solidified a t lowtemperatures t o rnassa of magnificent prisms, melting a t 210. Itsodour was characteristic and reminiscent of aniseeld :0.1742 gave 0.3646 CO, and 0'0812 H,O. C=57-08; H=5*19.It was recovered unchanged after being boiled for ten hours withC,,H,,Br requires C = 56.87 ; H = 5.21 per cent.amalgamated zinc and dilute hydrochloric acidETHYL HYDRINDENE-2 2-DICARBOXY LATE.2695Coitdensatiorh of 2-Bromomethylhydrindene with Ethyl Mrilonate.Ethyl malonab (6.4 grams) and the bromo-compound (8.4 grams)were successively added to a solution of sodium (0.9 gram) in alcohol(14 c.c.). A t the temperature of the water-bath a separation ofsodium bromide soon commenced, and after ten hours the productwas worked up in the usual manner By distillation underdiminished pressure, well-defined fractions of ethyl malonate,bromomethylhydrindene, and finally of the desired ester (7.5 grams)were obtained.Ethyl 2-hydrindylmethylmalonate (VI) is a colourless liquid,which boils a t 211°/15 mm., and does not solidify even when cooledin a freezing mixture:0.1594 gave 0.4092 CO, and 0.1074 H,O. C = 70.00; H = 7.48.C1,H2,04 requires C = 70.35 ; H= 7-59 per cent.The corresponding acid was prepared by hydrolysis with alcoholicpotassium hydroxide, and separated from its solution in alcohol inclusters of small, transparent plates, melting a t 174O :0.1746 gave 0.4285 CO, and 0.0965 H20.C = 66.93 ; H = 6.14.C13H1404 requires C = 66.66 ; H = 6.00 per cent.Its barium, calcium, lead, tin, and ferric salts are insoluble inh o t water, whilst its mag,zesiurn, copper, and cobalt salts are solublein cold water.ThO dihydrazide, C,H4<~~2>CH*CH,*CH(CO*NH*NH2)z, crys-0.1868 gave 35.6 C.C. N, at 2 3 O and 747 mm. N=21*6.2tallises from alcoholic solution in silky needles melting a t 177O :C13Hl,0,N4 requires N = 21.4 per cent.8-2-Hydrindylpropionic acid, C,H4<E::>CH=CH2*CHz*C02H,was prepared by heating the a'bovel acid a t 190° until the evolutionof carbon dioxide had ceased.It was readily soluble in benzene,but sparingly so in hot light petroleum (b. p. 90-llOo), andseparated from a mixture of these solvents in small plates meltinga t 120O:0.1758 gave' 0.4902 CO, and 0.1166 H20. C=76.05; H=7*37.0.2474 required 14.6 C.C. N / 10-NaOH. Equivalent = 189.7.C12H14O2 requires C = 75-79 ; H = 7-37 per cent. M.W. = 190.Its barium and magnesium salts are soluble in cold water, whilstits calcium salt is sparingly soluble, and separates from its solutionin hot water in needles. Its ferric, copper, and cobalt salts areinsoluble in hot water, its lead and tin salts sparingly so, and itsmercuric salt turns yellow when boiled with water2696 KENNER : THE REDUCTION PRODUCTS OF%Phthalimii? omethtyEltydriiideit e (VII) .An intimate mixture of 2-bromomethylhydrindene (10 grams)with potassium phthalimids (9 grams) was heated a t 180-200° fornine hours in an apparatus provided with a reflux tube.Themixtnre solidified on cooling, and required to be finely powderedbefore adherent oily matter could be removed by repeated diges-tion with hot light ptroleum (b. p. 90-110O). Potassium bromidehaving then been removed by extraction with hot water, the residuewas crystallised from glacis1 acetic acid. The compound separatedin small, slender prisms, which were usually somewhat discoloured,and melted a t 174O. The yield was 57 per cent. of the theoretical,and was not improved by carrying out the condensation in thepresence of sodium iodide:0.1984 gave 9.0 C.C.N, a t 16O and 752 mm. N=5*30.C18H1502N requires N = 5-05 per cent#.2-EEydrkdylrn e t h y la mk,e, C6H4<g2> CH*CH2*NH2.Phthaliminomethylhydrindene (8 grams) was heated with con-centrated hydrochloric acid" (35 c.c.) a t 180-200° for six hours,and the product was then heated in the usual manner. A largeproportion of the hthalimino-derivative remained unchanged, butfour such experiments furnished a sufficient quantity of the base,boiling a t 248O, t o perlr.it of its characterisation.The hydrochloride separated from its solution in dilute hydro-chloric acid & thin plates with a satiny-lustre, melting and decom-posing a t 258-260O:0.1890 gave 12.4 C.C.N, a t 15O and 751 mm.The platinichloride was obtained as a yellow powder, whichN=7*68.CloH13N,HCl requires N = 7.63 per cent.decomposed a t 233O:0.3614 gave 0.1008 Pt. Pt=27*89.(C,,H13N)2,H2PtC16 requires Pt = 27.70 per cent.The iodide, sulphate, oxalate, and phosphate are readily solublein water, whilst the carbonate (prismatic needles) and thedichromate (orange, prismatic needles) are soluble in hot water.2-Phenylthiocarbamidome t h ylhydrilbdene,c , H , < ~ ~ CH ;>CH-CH,-N H~S.NH*C,H,,crystallises from alcohol in hexagonal plates melting a t 145O:0.1760 gave 15.5 C.C. N, a t 16O and 745 mm. N=10-20.CI7Hl8N2S requires N = 9.93 per centETHYL HYDRINDENE-8 : 8-DICARBOXYLATE. 2697The Chloride of Bydrindene-2 : 2-dicarboxylic Acid,C,H,<gg2>C( COCI),.2This compound was prepared by the interaction of the calculatedamounts of hydrindenedicarboxylic acid and phosphorus penta-chloride. It boiled at 173-175°/20 mm., and solidified a t theordinary temperature. It crystallised from light petroleum (b. p.60--80°) in clusters of reckangular plates, which melted a t 45O,and did not exhibit any marked tendency towards decompositionin contact with the atlmosphere ;0.2516 gave 0,2952 AgC1. C1= 29.02.C,,H,O2C1, requires C1= 29.22 per cent..An attempt was made to condense this compound with benzeneunder the conditions employed by Freund (Annalen, 1910, 373,310) in the case of diethylmalonyl chloride. It was found that, asin the latter case, the liquor obtained by steam distillation of theproduct was coloured green, and a small quantity of golden-yellowcrystals was obt'ained by extraction with ether. There can, there-fore, be no doubt that the reaction took the desired course.Reduction, of Ethyl cycloHexnnediacetate.This operation was carried out in the manner already describedin the case of ethyl hpdrindenedjcarboxylate. The oil obtainedboiled indefinitely, but small quantities of solid matter separatedfrom the later fractions, boiiing a t 195-200°/21 mm. This productwas sparingly soluble in light petroleum (b. p. 60-80°), andmoderately so in benzene. By crystallisation from this solventlezflets, melting at 123O, were obtained:0.1106 gave 0.2848 CO, and 0.1046 H,O. C = 70.23 ; H = 10.51.C,,H,,O, requires C = 70.06 ; H = 10.06 per cent.The author hopes to prosecute his investigations in the directioxindicated a9 soon as circumstances permit a resumption of theexperiments.THE UNIVERSITY,f!i HEFFTELTI

ISSN:0368-1645    

DOI:10.1039/CT9140502685

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

2698 MORRELL: STUDIES IN THECCLIL-Studies in the Succinic Acid Swies. Part 11.Anilides and Anilic Acids, and t i l e h’fect ofSterG Hindrance o n the Formation of the Arnides.By GEORGE FRANCIS MORRELL.THE method of Bouve’ault and Blanc (Bull. Soc. china., 1905,[iii], 33, 879) for the conversion of acids into the correspondingalcohols by reduction of their esters in alcoholic solution withsodium frequently gives very unsatisfactory results with the di-basic acids of the aliphatic series (compare Harries, A n d e n , 1911,383, 167). The original intention of studying the reduction ofother open-chain derivatives of dibasic acids was hindered by thelack of suitable methods for preparing them in quantity. This isespecially the case with the derivatives of the succinic acids, wherering-formation takes place so readily, and the open-chain deriv-ative forms either a small fraction of the product, or is entirelyabBent.The prment communication deals with an investigation of themethods and conditions requisite for the production of a maximumyield of certain of the open-chain aniline and ammonia derivativesof succinic acid and its homologues.Whilst with substitutedsuccinic acids the neutral anilides were, under all conditions, pro-duced only in traces by the action of aniline on the acids, and theanil wzs generally the sole product, in the case of succinic acidthe aniline could, by repeated treatment of the succinanil obtainedas a by-product, be prepared in excellent yield by this methodunder specified conditions.The formation of the five-memberedring is, therefore, apparently facilitated by the presence of methylsubstituenta in the succinic acid. Where the direct ” methodof preparation failed, good results were obtained by the actionof aniline on the acid chlorides.The anilic acids are of importance on account of their use forthe characterisation of the dibasic acid by Auwers’ method, butthe investigation has here been limited to methylsuccinanilic acid,as the others have already been fully described by other workers.From an unsymmetrically substituted succinic acid, two isomericanilic acids can theoretically be derived, but although methyl-succinanilic acid has been prepared in different ways by manyinvestigators, only one of these possible isomerides has ever beenisolated.Arppe and Biffi (AnmaZen, 1854, 90, 141; 91, 106)obtained an anilic acid, melting a t 14‘i0, from the anil by openingthe ring with alkali. Anschutz (Annulen. 1888, 246, 122; 248SUCCINIC ACID SERIES. PART 11. 2699273) likewise prepared the anilic acid both by Arppe’s methodand by two methods of his own, namely, the reduction of mesacon-anilic acid, and the action of aniline on methylsuccinic anhydride.I n all cases the acid obtained melted a t 143O. Later, Bone andSprankling (T., 1899, 75, 860) give 148-149O as the meltingpoint, and specifically state that they were unable to isolate anyisomeric acid. Auwers (Annalen, 1896, 292, 195) ascribes theformation of only one anilic acid to the influence of the un-symmetric molecule, which thus determines the sense in whichthe aniline is added to the anhydride, or sodium hydroxide tothe anil.Thus, for example, reaction (1) might proceed to theentire exclusion of reaction (2):(1) CH,*YH--UO CH,*QH*CO,HCH,*CO<t CH,*CO*NH*C,H5(3) CH,*YH--CO> + CH,-F]H*CO*NH*C6H,C H,. CO CH,*CO,HIn. support of this idea, he states that in the case of methyl-ethylsuccinic acid, where the lack of symmetry is not so pronounced,two isomeric anilic acids were isolat,ed.I n preparing methylsuccinanilic acid, whether from the anil,or from the anhydride, two points of interest were noted whichseemed t o indicate the incorrectness of Auwers’ and Bone’s assump-tion, and the existence of two isomerides in the product.It wasobserved that the anilic acid was always precipitated as an oil,which solidified slowly on keeping, and that never more thanabout 40 per cent. of the theoretical yield of the acid, meltinga t 149O, could be isolated. Both of these observations w0re quiteat variance with those made in the otherwise perfectly analogouscase of succinanilic acid. It seemed scarcely possible that thepresence of an isomeric acid could have been overlooked by somany investigators, and, indeed, the evaporation of the aqueousmother liquors to dryness yielded only a very soluble, viscidresidue, which, however, was sufficient in amount to account forthe deficient yield. It was not until it Wac discovered that- boththe acids in question were, in aqueous solution, extremely sensitiveto heat, being converted into the above-mentioned viscid products,that an explanation was forthcoming.So quickly does this trans-formation occur tliat the acids cannot even be crystallised un-changed from hot aqueous solution, ax has hitherto been thecustom. On atbempting to recrystallise a quantity of the puresubstance from water, only 40 per cent. was recovered, and, more-over, its melting point was loo lower than when crystallised fromother solvents2700 MORRELT,: STUDIES IN THEBy carefully avoiding anything more than the slightest warmingwhen dealing with aqueous solutions of the acids, the two struc-tural isomerides were satisfactorily isolated. They were purifiedby taking advantage of their different solubilities in water andin chloroform. The less soluble methylsuccinanilic acid melts a t159O, and is the main constituent of Anschutz’s acid (m.p. 143O).Its isomeride is much more soluble both in water and in chloro-form, and melts a t 1 2 3 O . Both acids, on being heated above theirmelting points, lose water, and are converted into methylsuccinanil.No solution has been arrived a t of the problem as to which ofthe acids the constitutionCH3*CH(C?H2*CO2H)*CO.NR.C,H,must be assigned, and to which the alternativeC‘H,*CH (C0,H) *CH,*CO *NH C,H,.The matter is closely dependent on the constitution of the mes-aconanilic acid which, on reduction, yields the methylsuccinanilicacid melting a t 159O (Anschutz, Ber., 1890, 23, 891). Basing hisargument on an erroneous observation of Reissert (Ber., 1888, 21,1370) on the oxidation products of mesaconanilic acid, Anschutzascribed the constitution (I) to this acid, and, c-onsequently, theconstitution (11) to his methylsuccinanilic acid melting at 143O(Annulen, 1888, 246, 117) :C H3*g* CO N H*C,H,C H * C0,HCH,*FH*CO*NH*C,H5C H,* C0,H(1.1 (11.)Neverthelless, after revising Reissert’s work, he convinced him-self that no light whatever could be thrown on the constitutionof mesaconanilic acid, or of methylsuccinanilic acid, as the resultof oxidation expeziments (Ber., 1889, 22, 747; and Annalen, 1889,254, 137).It is noteworthy that during the whole of the controversy overthese anilic acids between Reissert and Anschutz, the melting point,143O, of methylsuccinanilic acid was not challenged by either ofthem, During this present investigation specimens of this sub-stance, crystallised from water, have been obtained, melting a t143--145O, and having all the appearance of individual substances.In the first place, many of Anschiitz’s melting points are some-what low, as has been pointed out by Auwers, owing to the slowmethod of heating which he employed, whereby an incipient d ecomposition of the anilic acid sets in at temperatures below thetrue melting point.Secondly, these anilic acids should not becrystallised from water, for although succinanilic acid &elf seemsto be but little affected, yet others are rapidly attacked. Methyl-succinanilic acid (m. p.159O), for example, has never been obtaineSUCCINIC ACID SERIES. PART 11. 2701after crystallisation from water with a melting point higher thanThe only way open for the preparation of the neutral amidesof succinic acid and its homologues is by the action of ammoniaon the esters. Other methods lead either to the formation of alarge preponderance of the unsymmetrical amide (this Vol., p. 1737)or of the imide. The rate of format4ion of the amides from theesters and the percentage yield obtained has been found to dependon the ester used and on the extent of substitution in the methylenegroups adjacent t o the carboxy!, on spatial influence in otherwords. 'The methyl esters react much more quickly than the ethylesters, although the yield is about the same in each case.Withunsubstituted methylene groups, that is, with succinic ester itself,the reaction proceeds the most rapidly, and the introduction ofmethyl groups produces a marked decrease, not only in the velocityof formation, but also in the yield. The reaction has been carriedout in a number of different ways for the sake of comparison,using the methyl and ethyl esters a t ordinary and a t elevatedtemperatures, and the most satisfactory results have invariablybeen obtained by allowing the met'hyl esters to react a t the ordinarytemperature with concentrated aqueous ammonia,, but insteadof allowing thb liquids to remain in two layers, or using a shakingmachine, just sufficient alcohol was added to bring the ester intosolution. I n the succinic series this method has given betterresults than E.Fischer's process, devised for the malonic series:in which the ethyl esters are heated with alcoholic ammonia ina sealed tube a t 130°, generally for twenty-six hours (Ber., 1902,35, 844). A comparison o t the results obtained in the variousexperiments, combined with Fischer's results in the malonic series,is interesting :14 9-1 50'.Percentage yield ofamide using alcoholicammonia in bomb.7*7Methyl EthylAcid. ester. ester.Malonic ......................... - 98 ............... 40 Methylmalonic -.................. 53 Ethylmalonic -Propylmalonic ................ - 61Dimethylmalonic -Diethylmalonic -Succinic ........................ 63 40Methylsuccinic ............... 33 -.tmrLs-u/3-Dimethylsuccinic .- -ch-aS-Dimethylsuccinic .... -............ 2.6 ............... 0.0__Percentage yield ofamide using aqueousammonia in cold.Methyl ester. Ethyl ester.--80 ( 12 days)-The yield of amide in the case of succinic acid is therefore com-parable with that obtained with metliylmalonic acid, and the sub2702 MORRELL: STUDIES IN THEstitution of one only of the four methylene hydrogen atoms by amethyl group produces a marked retardation in velocity anddiminut'ion in yield. Fischer suggested (Zoc. c i t . ) that the reactionwith tetramethylsuccinic acid would probably yield only a trace ofamide, but it is now evident that this is already the case with thedimethylsuccinic acids, the amides of which have now been preparedfor the first time.These results, whilst quite in harmony withFischer's hypothesis that the methylene hydrogen is involved in thereaction in the formation of a preliminary ammonia additiveproduct, or salt, of the type (111) which decomposes into theCO,Et*CMe:C(OEt).ONH, -+ C02Et.CHMe*CO*NH,(ITI.) PV.1amide (IV), yet show that steric hindrance must be accounted afactor in the case, for there are still in the dimethylsuccinic acidstwo methylene hydrogen atoms similar to the one in methylmalonicacid, yet the velocity of the amideformation and the yield of amideare enormously greater in the latter case, whereas if the presenceof an unsubstituted methylene hydrogen atom were the sole condi-tioning factor we should expect the acids to behave similarly, o r a tleast that more than mere traces of dimethylsuccinamide would beproduced.Moreover, the results with the constitutionally identicalcis- and trcr as-dimethylsuccinic acids are different, the cis- reactingmore slowly than the trans-acid, as one would expect from con-siderations of spatial interference. The conclusion is thereforedrawn that the accumulation of substituent groups round theesterified. carboxyl group hinders the reaction with ammonia, evenalthough some inethylene hydrogen is still unsubstituted.EXPERIMENTAL.Suc cina.nilide.Succinanilide was obtained by Menschutkin (AnnuZen, 1872,162, 187) in 25 per cent, yield by the direct action of aniline onsuccinic acid. It can be obtained in better yield by the actionof succinyl chloride on a solution of aniline in benzene (comparethis vol., p.1736, and Dunlop and Cummer, J . Amer. Clzem. SOC.,1903, 25, 612). Since this method involves the previous prepara-tion of succinyl chloride, which is itself obtained at most in 75 percent. yield, the following direct method of preparation from succinicacid is preferred.Twenty grams of succinic acid were heated f o r three to four hoursat 200° (thermometer in the liquid) with 40 grams of aniline. Avery short reflux air-condenser was used, so that only the anilinewas condensed, tlie water generated by the reaction being alloweSUCCIMIC ACID SERIES. PABT 11. 2793to escape, as it was found that if condensed and returned to theflask the temperature of the boiling mixture eventually sank aslow as 125O, and the unsatdsfactory yield described by Menschutkinwas obtained: The product was poured into dilute acid, and whencold the precipitate of anilide and anil was collected and warmedwith an excess of dilute aqueous sodium hydroxide, whereby theanil was dissolved as sodium succinanilate, but the anilide wasunattacked.The latter was collected, and after one crystallisationfrom alcohol was quite pure. From the aqueous solution of thesuccinanilats dilute hydrochloric acid precipitated succinanilic acidin an almost pur0 condition. The above amount of succinic acidgave 10 grams of anilide and 25 grams of anilic acid, an almosttheoretical yield.Succinanilide crystallises irom alcohol in short, stout needles,melting a t 230^ (Menschutkin gives 227O).It is quite insoluble inwater, and is not acted on by boiling dilute alkali hydroxide. It issoluble in about 35 parts of boiling alcohol, and-460 parts a t 16O,and almost insoluble in the other common organic solvents.Conversion. of Succinanilic Acid into Succinanilide.The anilic acid obtained as a by-product in the above preparationmay be readily converted into the anilide by heating with 75 percent. of ik weight of aniline in sealed tubes at 110-115° for forty-eight hours. The product is a mixture of anilide and anil withexcess of aniline, similar to that obtained in the direct preparation,and the arilide is separated by treatment with hydrochloric acidand then with sodium hydroxide exactly as there described.From25 grams of anilic acid 12 grams of anilide were obtained, and11 grams of anilic acid recovered (compare Tingle and Cram, Amer.Chem. J., 1907, 37, 597, who obtained only a 25 per cent. yieldafter five days' heating in an open vesse'l). By repeat'ing thisprocess with the recovered anilic acid it is eventually almostentirely transformed, giving a total yield of about 30 grams ofsuccinanilide from the 20 grams of succinic acid originally taken.Met hylsuccinanilide.This has been briefly described in a previous paper (this vol.,p. 1736). Unlike succinanilide, i t could be obtained only in tracesby the acti%n of aniline on either the free methylsuccinic acid orits anilic acid. Under all experimental conditions tried, ring-formation ensued with the almost exclusive production of the anil.I n contrast with succinanilide it is very re'adily soluble in alcohol.It is fairly soluble in ethyl acetate, sparingly so in chloroform, andinsoluble in wat.er or benzene2704 MORRELL: STUDlES IK THEMet hylsuccinanil.This was obtained in almost theoretical yield by an improvementof Kling’s process (Ber., 1897, 30, 3040).Ten grams of methyl-succinic acid were gently boiled for a few minutes with 9 gramsof aniline in an inverted retort. The retort was then reversed, andthe mixture distilled as rapidly as possible. No appreciablecarbonisation occurred, and the distillate solidified t o a hard massof the anil, which after one crystallisation from much boiling waterformed clusters of tiny needles melting a t 109-1 loo (Anschutzgives 104O, acd Kling 107O).Methylsuccinanil is very readily soluble in alcohol, ethyl acetate,chloroform, or benzene.It is soluble in about 40 parts of boilingwater, and t,o the extent of 0.28 per cent. in water a t 16O.Methylsuccinanilic Acids.,4n aqueous solution of the sodium salts of the two isomeric acidswas prepared either by dissolving the product of the action ofaniline on methylsuccinic anhydride in cold sodium hydroxidesolution, or rnethylsuccinanil in aqueous sodium hydroxide by theaid of gentle heat. The isolation of the two isomerides was accom-plished by fractional precipitation of the acids from this solution,combined with fractional crystallisation from chloroform.I n oneexperiment 7.7 grams of methylsuccinanil were dissolved in 30 C.C.of 2N-sodium hydroxide, and to the filtered solution hydrochloricacid was slowly added with constant agitation. No oil was precipi-tated, but a clear solution was obtained, from which in a fewmoments crystals of the anilic acid separated. The followingFractions were obtained: (1) After the addition of 20 C.C. of2N-hydrochloric acid 1.9 grams were deposited, melting a t 150°,which, when recrystallised twice from ethyl acetate, melted a t158-159O. (2) On adding a further 10 C.C. of 2147-hydrochloricacid, 2.8 grams were deposited, melting a t 95--135O, which wereextracted with cold chloroform. The residue (1.3 grams) consistedof the acid melting a t 159O, and after crystallisation from ethylacetate melted a t this temperature. The solution contained mainlythe isomeric acid, and it was added to the chloroform solution (seebelow).(3) On keeping overnight, 1.0 gram of material separated,melting a t 85-95O. This was the fairly pure isomeric acid, and wasalmost entirely soluble in cold chloroform.Tho united chloroform solutions were precipitated with lightpetroleum, and the precipitate (m. p. 105-108°) was purified bya process of alternate precipitation from the aqueous solution of itssodium salt, and recrystallisation from chloroform. This procesSUCCINIC ACID SERIES. PART IT. 2705was successful because the difference in the solubility of the iso-merides in water was not so great as in chloroform. Eventually aproduct was obtained melting a t 123O, which consisted of broad,clean-cut, microscopic needles, and further treatment produced noalteration in the melting point.The less soluble acid appeared to form from 40 to 45 per cent.of the total product, but, of course, the more soluble acid couldnever be isolated in a pure condition in quantity anywhereapproaching the amount (55-60 per cent.) in which it waspresent.I n order to remove all doubt as t o the chemical individualityof these two acids, the following data were obtained.Methylsuccinanilic acid, m.p. 159O, crystallises from ethylacetate in fairly broad, flat needles. It is very readily soluble inalcohol, moderately so in ethyl acetate, and very sparingly so inchloroform (about 0-05 per cent.at 18O) or water (0.09 per cent.a t 15.). When heated above its melting point it is converted intothe anil, melting a t logo:0.1011 gave 09361 CO, and 0.0597 H,O.0.1566 ,, 9.2 C.C. N, a t 153 and 749 mm. N=6*85.Methylsuccinanilic acid, m. p. 123O, crystallises from chloroformin clear, broad, microscopic needles. It is extremely readily solublein alcohol or ethyl acetate, very readily so in hot chloroform, anda chloroform solution contains 1.6 per cent. a t 16O. It is fairlyreadily soluble in hot benzene, insoluble in light petroleum, andmoderately soluble in watm (1.2 per cent. a t 15O). When heatedabove its melting point it is converted into the anil melting a t logo.A mixture with the anilic acid melting at 159. melted at 105-108°,and when this mixture was recrystallised fern-like clusters of theusual mixture type were obtained :C = 63.69 ; H = 6.56.CllH13O3N requires C = 63.76 ; H = 6-28 ; N = 6.76 per cent.0.0957 gave 0.2225 CO, and 0.0554 H,O.0.1204 ,, 7.1 C.C.Nz at 16O and 760 mm. N=6*94.C = 63-43 ; H = 6.43.C,,H,,O,N requires C = 63.76 ; H = 6.28 ; N = 6.76 per cent.Succinamide.This compound can be obtained only in minute quantity by theaction of ammonia on succinyl chloride. It was prepared, however,in a variety of ways indicated in the introductory portion, and in80 per cent. yield by the action of concentrated aqueous ammoniaon methyl swcinate, just sufficient alcohol being added to themixture to bring the ester into solution. After three days thereaction was complete, and the precipitated amide was found to b2706 STUDIES IN THE SUCCINIC ACID SERIES.PART 11.almost pure without further treatment. It crystallises from hotwater in short, stout ne’edles, melting and decomposing a t 260O.This is considerably higher than the melting point usually given,and if the temperature rises slowly a much lower value is actuallyobtained. One part of the amide dissolves in 15 parts of boilingwater, and in 300 parts of water a t 1 5 O . It is almost insoluble inalcohol and other organic solvents.Me t h y l s icccinamid e .This was prepared most readily in the same way as succinamideby the action of concentrated aqueous amniaiiia on a solution ofthe methyl ester of the acid. After remaining for five days a t theordinary temperature no more amide was deposited, and the totalyield then amounted t o 52 per cent.of the theoretical. Methyl-succinamide crystallises from water in short needles, melting anddecomposing a t 225O. It is almost insolublt in alcohol and organicsolvents, but soluble in about 50 parts of water a t 15O, and verysoluble in hot water.cis- and trans-Dimethylsuccinamide.[With SIDNEY. HENRY GROENEWOUD.]The only mention of a dimethylsuccinamide in the literature isby E. von Meyer ( J . pr. Chem., 1882, [ii], 26, 359), who states thathe prepared it by the action of ammonia on the oily productobtained by the bromination of cyanethine. The substance isdescribed as crystallising in fine, pyramidal, pointed prisms, whichdid not melt a t 260O. That it could really have possessed theconstitution assigned to it by von Meyer seems impossible sincethese properties agree in no way with those of either the cis- ortrans-amide obtained by a method which admits of no doubt,namely, from the respective esters by the action of ammonia.Itseems, moreover, improbable that the symmetrical amides could beobtiained in any appreciable quantity by the action of ammonia onthe acid bromides, even if such were present in the oil obtainedfrom cyanethine.cis-I)imet~yls-uccinamid.e was obtained by the action of concen-trated aqueous ammonia on dimethyl cis-diniethylsuccinate (b. p.200°), prepared according to Zslinski’s method (Bey., 1889, 22,646), sufficient alcohol being added to make the alcoholic strengthof tho resulting solution about 33 per cent.After being kept forone month a t the ordinary temperature 0.06 gram of amide hadseparated in well-formed, triclinic prisms from a solution containing3 grams of the ester. The mother liquors yielded on evaporatioA RiAGNETIC STUDY OF COMPOUNDS OF WATER, ETC. 2’70’7an oil consisting apparently in the main of unchanged ester, buton treating this a second time with ammonia no less than 0.6 gramof crystals separated in fourteen days. The crystals obtained byboth operations, after washing with alcohol, were quite pure withoutfurther treatment’. They melted and decomposed a t 244O, and werealmost insoluble in alcohol or cold water, but fairly readily solublein hot water:0.0951 gave 16 C.C. N, a t 22O and 767 mm. N=19.49.C,H,,O,N, requires N = 19.44 per cent.trans-Dimeth~lsuccinamide was obtained in a precisely analogousrnanr?er to the cis-amide by substituting the trmas- for the cis-dimethyl esber in the experiment described abcve. Under si iiiilarconditions 3 grams of the trans-ester yielded a larger amount ofamide in the first treatment, namely, 0.15 gram. It was depositedin triclinic prisms of similar appearance, and solubilities in alcoholand water, as the cis-isomeride. It melted and decomposed at 2 3 8 O :0.1098 gave 18.6 C.C. N, a t 20° and 760 mm. N=19*63.C,H,,O,N, requires N = 19-44 p0r cent.Both amides were decomposed extremely slowly by boiling hydro-chloric acid, more rapidly by boiling potassium hydroxide solution.Unfortunately the quantities a t our disposal were too- small for thesaponification products to be satisfactorily identified, but since theesters regenerated their corresponding acids on hydrolysis and itis remotely improbable: that the action of cold ammonia wouldprcduce any change of configuration, it may be confidently assumedthat the amides, also, yield on hydrolysis the respective acids fromwhich they were obtained.THE SIR JOHN CASS TECHNICAL INSTITUTE,LONDON, E.C

ISSN:0368-1645    

DOI:10.1039/CT9140502698

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

A RiAGNETIC STUDY OF COMPOUNDS OF WATER, ETC. 2’70’7CCLTI1.-A Magnetic Study of Compounds of Waterand of Aqueous Solutions.By FRANCIS WILLEAM GRAY and WILLIAM MILNE BIRSE.THE object of the work described in the present paper was toascertain whet her magnetic measurements can throw any light onthe state of ccrnbination of water in compounds of different types,and especially t o measure the magnetic properties of water in(1) aqueous salt solfitions, (2) hydrated crystals such as those ofcopper sulphate, and (3) organic acids, such as benzoic andphthalic acids, which may be regarded as compounds of theiranhydrides with water2708 GRAY AND BIRSE: A MAGNETIC STUDY OFI n all these classes instances were found in which tho law ofadditivity, in the molecular sense, is obeyed.Thus aqueous solu-tions of potassium ferricyanide obey the law of additivity through-out the whole range of concentration, and yield a more trustworthyvalue f o r the susceptibility of potassium ferricyanide than thatobtained from the solid.I n the case of copper sulphate, if it is assumed that the suscepti-bility of the water is not affected appreciably by the union, theni t is found that the paramagnetic susceptibility of the anhydrouscopper sulphate molecule is increased by about 11.5 per cent. whenit unites with one molecule of water. Further addition of watermolecules to form the higher hydrate has no marked influence onthe susceptibility.-%I n the case of organic acids it is found that additivity, in themolecular sense, holds for benzoic, phthalic, maleic, and fumaricacids, but not for succinic and camphoric acids.Aqueous solutions of potassium ferricyanide obey (see table I)X very nearly the equation -- - .2/ = 1, where z=the weight of10.0'7 0.72potassium f erricyanide in 100 grams of aqueous solution, andy x denotes the susceptibility of a solution of percentage x.It is not usual for an aque'ous solution to follow so closely the addi-tive law.Indeed, many of the older determinatJons of the sus-ceptibility of salts are quite valueless, since they were calculatedfrom determinations of solutions of single concentrations on thebasis of additivity, and the value obtained in this way variesusually according to the concentration of the solution. Cabreraand Moles (Arch, Sci.phys. m t . , 1913, [iv], 35, 425) have shownhow the atomic susceptibility of iron varies with the concentrationin solut'ions of ferric chloride, ferric nitrate, and sodium ferricp yrophospha t c.l n the magnetic study of solutions the following effects are to belooked f o r : (1) ionisation, (2) union of two or more molecularmagnets t o yield an astatic system not oriented in a magnetic field,(3) formation of hydrates and the stability of the same, (4) hydro-lysis. I n addition, care must be taken to ascertain whether or notthe susceptibility of a solution changes with time. Instances havebeen found of solutions originally additive which showed a gradualdeparture from additivity. Heydweiller (Ber. Deut. physikal.Ges.,1913, 15, 112) gives results for solutions of ferric chloride, man-ganese sulphate, and nitrate, nickel nitrabe, chromic sulphate,chromic nitrate, and cobalt nitrate. H e observed a maximum inthe curves for the relation between concentration and molecular* It is well known that similar differeuces have been observed in the specific heatsand heats of hydration for the different water molecules in polyhydratesCOMPOUNDS OF WATER AND OF AQUEOUS SOLUTIONS. 2'709susceptibility. This maximum may be produced by the joint actionof effect ( l ) , which causes increase of susceptibility, and effeet (a),which causes diminution of susceptibility. Oxley discusses effect (3)(Proc. Camb. Phil. SOC., 1912, 16, 421), and points out that thehydrate may be so unstable as not to affect the magnetic propertiesa t all.Wiedemann claims from magnetic measure'ments to be ablet o calculata the degree of hydrolysis of ferric chloride in aqueoussolutions. I n aqueous solutions of pchassiurn ferricyanide whichseem to obey the additive law none of the above effects can bedetected by the present method.X Using -- ' - 1 and putting x=lOO, we obtain for the sus-10.07 O--ceptibility of potassium ferricyanide t'he value + 6.43 x 10-6. Thisgives 10-97, or very nearly 11 magnetons per molecule. Weiss(Compt. rend., 1911, 152, 367) gives 10.41 magnetons.The susceptibility of solid potassium ferricyanide (powder) wefound to be + 6-77 x 10-6, the error-range being 50.16, or about-t2-2 per cent. (when calculated by the average deviation method).This figure, 6.77, gives 11-26 magnetons per molecule.Ihde (Ann.Physik, 1913, [iv], 41, 829) points out, in the caseof paramagnetic powders, that the molecules a t the surface of thegrains are most easily oriented in the magnetic field. An increasein the size of the particla causes a diminution in the total surface,and therefore in the number of surface molecules, and thus a fallin the susceptibility. This was found to hold f o r powdered potass-ium ferricyanide.On the other hand, the increased density which accompaniesincreased size of particles tends to an increased value for thesusceptibility.On the whole, therefore, with potassium ferricyanide, the sus-ceptIbility obtained from solutions is more trustworthy thal; thatfrom powders, because, with solutions the precision is much better,the law of additivity is obeyed throughout the whole range ofconcentrations, and, further, the result implies an integral numberof magnetons per molecule.I n order to account f o r the magnetic difference between coppersulphate monohydrate and copper sulphate pentahydrate, wesuggest the following hypothesis : that the water-molecules arearranged in space round the outside of the copper sulphate molecule,one in the vicinity of each oxygen atom and one in the vicinityof the copper atom.The last-mentioned water-molecule is the onlyone that causes deviation from the additivity of the magneticproperties. When two copper atoms of two anhydrous coppersulphate molecules are near one another they hamper one another'smovement in the magnetic field.Thus the orientation of the copperFOL. cv. 8 2710 GRAY AND BIRSE: A MAGNETIC STUDY OFatom is not so free in the a-nhydride as in the monohydrate o r inthe pentahydrate, in both of which water-molecules intervenebetween the copper atoms, keeping them apart and thus preventingthe mutual action above referred to. In other words, the para-magnetic susceptibility of the copper atom is less in the, anhydridethan in the monohydrate or in the pentahydrate.This theory receives support from the fact that similar hypotheseshave served to explain two observations recently made in the cryo-genic laboratory a t Leiden. Perrier and Onnes (Compt. rend.,1914, 158, 941) studied mixtures of liquid oxygen and liquidnitrogen, and found that the coefficient of magnetic susceptibilityof liquid oxygen increases as the concentration diminishes.Again,Onnes and Oosterhuis (Proc. IT. A Lad. Wetensch., Amsterdam,1913, 15, 969) in studying paramagnetism a t low temperaturesfound for hydrates of salts and anhydrous salts, in the case offerrous sulphate and manganese sulphate, that whilst the hydrateobeyed Curie’s law, xT=constant, down to the temperatares ofliquid nitrogen, the anhydrous salt followed the law, x(T+A)=constant, where x = specific susceptibility, T = absolute temperature,and A=a constant. Thus, a t any given temperature withiu acertain range the paramagnetism is increased by the union ofwater with the salt.Mlle, Feytis (Compt.rend., 1911, 153, 668) about the same timeas we made our observations obtained similar results f o r coppersulphate (see experimental part).Mlle. Feytis (Zoc. cit. and Compt. rend., 1913, 156, 886) foundfor the salts CuC12,2H20, CuC1,,2NH4C1,2B,0, CuC12,2KC1,2H20,and NiS04,6H20 departure from additivity in the same sense as incopper sulphate. On the other hand, she observed that additivityheld for the salta CoS0,,7H20, Cr,(S04),,16.74H20, andbut not for CrCl,,6H20, for which the departure was in a directionopposite to that for copper sulphate. This last case may be broughtinto line with our hypothesis by supposing that in anhydrouschromic chloride the chlorine atoms are arranged symmetricallyround the chromium atom, chlorine atoms keeping apart thechromium atoms of different salt molecules, and thus enhancing theparamagnetism.When water unites with the anhydrous moleculewe suppose that there is no longer the symmetry referred to, andthat chromium atoms can come nearer one another than before,and thus the atomic paramagnetism of the chromium is diminished.The hydrates of chromic chloride are represented thus :K2so,,cT2 (S04)&H@,[Cr(H20),]Cls (violet) and [CrC12(H20),]CI + 2H20 (green).Tha difference between these is not shown in m’agnetic measure-mentsCOMPOUNDS OF WATER AND OF AQUEOUS SOLUTIONS. 2'711We have observed departure from additivity in tlhe hydrates ofdiamagnetic salts also, and from our own results and those of otherswe have been led t o the general rule, that when there is departurefrom additivity a paramagnetic anhydride has its paramagnetismincreased and a diamagnetic anhydride has its diamagnetismdiminished by the union with water, on the assumption that thesusceptibility of the water is not affected appreciably by the union.I n a paramagnetic substance the always present diamagnetism ismasked by the larger paramagnetism.According to our generalrule, the diamagnetism in a paramagnetic substance might bediminished by union with water (when there is departure fromadditivity), and thus the apparent paramagnetism would beenhanced. We believe, however, that the departure from additivityin paramagnetic salts can be only partly explained by this cause,and that the hypothesis suggested under copper sulphate, or asubstitutle, is still required.For copper sulphate pentahydrate the theory might be broughtforward that the water of crystallisation is made up of two dihydrolmolecules and one monohydrol molecule, or one trihydrol moleculeand two monohydrol molecules, or on0 trihydrol molecule and onedihydrol molecule, or one dihydrol molecule and three monohydrolmolecules, or five monohydrol molecules.The first of these fivepossibilities is best suited for explaining how one water-moleculediffers from the other four. We think, however, that this wouldaccount for only a very small magnetic difference, judging fromthe results of Piccard (Compt. rend., 1912, 155, 1497), who studiedthe susceptibility o i water a t various temperatures from Oo t o looo.The susceptibility of water is only 0.75 per cent.greater a t looothan a t Oo; also the decreasa on solidification is 2.4 per cent., sothat variations in the proportions of trihydrol, dihydrol, and mono-hydro1 has very little eff ect-on the susceptibility.Similarly the results of Piccard do not encourage us to suppoaethat departure from additivity in a hydrate is due to any appre-ciable extent t o any change in the magnetic susceptibility of thewater, that is, to change caused by the union with the anhydride.The water which is present in a paramagnetic metallic hydroxideis usually regarded as a clear case of water of constitution, andwhen water unites with the oxide to form the hydroxide there isoften a considerable enhancing of the paramagnetic susceptibilityof the oxide molecule. Thus, there are hydrates and hydroxidesin which the magnetic r6le of water is identical, and it becomesan interesting question whether we can extend the hypothesis wegave for hydrates t o the case of metallic hydroxides.With regard to the organic acids (see tables I11 and IV) theparallelism between constitutional and magnetic similarities an2712 GRAY AND BIRSE: A MAGNETIC STUDY OFdifferences is interesting.In every case except the two acids whichshow decided depart.ure from additivity (succinic and camphoricacids), the anhydride is obtained from the interaction of twocarboxyl groups which are either near one another in the samemolecule or are in different molecules, so that interaction can takeplace without any great change in the configuration of the atomsand their electrons.On the other hand, with succinic acid there isa marked change in the relative position of the atoms when the twocarboxyl groups a t the ends of the open chain interact t’o form acyclic compound, and similarly with camphoric acid when twocarboxyl groups attached to two non-adjacent carbon atoms in thecamphoceanic ring interact to give the anhydride.In comparing our rwult8s with Pascal’s it should be noted thatwe use for the molecular susceptibility of water the experimentalvalue - 12.96 x 10-6, whilst the sum of Pascal’s atomic values is- 10.46 x In calculating the molecular susceptibility of anorganic compound, however, Pascal introduces corrections for con-stitution, so that the two methods are not necessarily inconsistent.A t any rate, our experimental figures and Pascal’s calculated valuesagree for furnaric acid and maleic acid and benzene; also, accord-ing to our method, additivity holds for these three substances.EXPERIMENTAL.The rezent concordant result;s of de Haas and Drapier (1913),of Wciss and Piccard (1913), and of S&ve (1912) yield for thespecific susceptibility of water reduced to a vacuum the value-0.72 x 10-6, which we u3e here in preference to the value-0.75 x 10-6.formerly used by Pascal, and the still older valueof Curie, namely, -0.79 x 10-0.All our results were obtained with a CurieChBneveau magneticbalance except number 8 of table 111, for which a Pascal balancewas used.The permanent magnet of the Curie-ChBneveau balancehad an average field of 232 gauss per sq. cm. over an area of5.6 sq. cm. round and a t right angles to the axis. Platinumtorsion wirea were used about 33 cm. long and of diameter 0.15mm., 0.10 mm., or 0.07 mm., according to the requirements. Thescale was placed a t a distance of more than 2 metres from themirror. The greatest precisian was obtained with a pure liquid, as,for example, with benzene, as shown in table 111. All the solidsin table I11 were in the form of powder, and the precision isusually not so great as with benzene. In some cases we improvedthe precision by heating the anhydride both before and after it wasin the tube, or by leaving the filled tube in a vacuum desiccator forsome time before the determination.With a glass tube the heatingmight cause volcme changes resulting in error, and it occurred t COMPOUNDS OF WATER AND OF AQUEOUS SOLUTIONS. 2'713us to t4ry a quartz tube, ?Ve found, however, that little, if any-thing, was gained by its use, as the susceptibility of the quartz wasmuch greater than that of the glass we used, so that a degree ofuncertainty was introduced which perhaps more than balancedany advantage obtained froni the constancy of volume of the quartz.I n the case of the substances in table IV we sometimes foundthat purification improved the precision, even when the method ofpurification produced no change in the melting point.Result number 8 in table I11 was obtained with a Pascal balance,the field of the electromagnet having an average of about 9000gauss per sq.cm. over an area of 2-21 sq. cm. a t right angles toand round the axis.The determinations were carried out at 1 5 O .I n the following numerical results we have given as many digitsas we obtained in our calculation. The precision of the estimationindicahs how many digits should be retained in each case.Magnetic Susceptibility of Aqueous Solutions of PotassiumFerricyanide.TABLE I .Numberletter or measure-Reference ofnumber. ments. z. Y- Y1. 4. yy d?.A 3 29.13 +1.394 3.1.362 +0-032 +1.354 +0*040B 2 26.22 +1*188 +1*155 +0.033 +1.148 +0*040C 3 23.53 +0.993 +0*962 +0*031 $0.956 +0-037S 2 20.35 +0.731 +0.735 -0.004 f0.731 0.0001 2 17-32 $0.513 SO.518 -0.005 +Om515 -0.0022 2 15.55 +0.391 +0.392 -0.001 +0.390 +0.0013 3 12.37 +0.162 +0.164 -0.002 +0*163 -0.0014 1 11.08 3.0'0675 +0.0722 -0.0047 +0*0718 -0*00435 2 8.27 -0.123 -0.129 +0.006 -0.128 +0*0056 1 7.416 -0.178 -0.189 $0.011 -0.188 +O.OlO7 4 6.005 -0.286 -0.291 +0.005 -0.289 +0.0038 4 4.594 -0.383 -0.392 +0.009 -0.390 +0*0079 6 2.976 -0.506 -0.507 $0-001 -0.504 -0*002In table I, x denotes the weight of potassium ferricyanide in100 grams of aqueous solution, y x 1 0 - 6 denotes the susceptibilityfound by experiment for a solution of percentage x.y1 is thez Y value of y as obtainsd from 1m - o% = 1 . d, denotes the distancein the direction of y that the: experimental point is above or belowthis straight line; + means above, - means below.Under ys andX d2 are given corresponding values obtained from ~- -!!--- -lO.07-O*716 - ''Neglecting the three solutions A , B, and C , we note that the firststraight line fits the experimental points very closely, and that thesecond fine fits still closer, but does not pass through the water-point. However, taking into account the degree of uncertainty o2714 OKAY AND BIRSE: A MAGNETIC STUDY OFthe measurements and seeing how near the lines lie tot one another,we need not push the refinement of the calculation so far, and maybe content nrith the first and simpler equation.Of the solutions, A was the most concentrated we could con-veniently use, and its composition was found by chemical analysis.By adding a weighed amount of ,4 t o a weighed amount of water,B and C were obtained.S was.prepared by adding a weighedamount of water to a weighed amount of pure potassium ferri-cyanide. A stock of S was prepared, froin which, by the weighingmethod, the series of solutions 1 . . . . 9 were obtained. Thusany error in the determination of the composition of A will affectB and G, and any error in the preparation of S will affect the set1 t o . . . . 9. The two sets are, of course, independent of oneanother.This explains why the three points obtained with A , B, and Cdeviate further from the straight line than any of the points of theset 8, 1, . . . . 9. It is probable that the analysis of A bychemical means is not so accurate' as the preparation of 8 by theweighing method.The degree of the uncertainty of the magnetic measurementsof the solutions will be seen from solution 9, for which the averagedeviation from the mean was 0.0038 or 0.76 per cent.TABLE 11.AverageSpecific Susceptibility deviation x 106.from mean, Molecular NumberSubstance. values. values. lute. cent. x 10'). ments.,-- suscepti- ofCUSO, ............... 3-8-6 8.39 0.02 0.2 -+ 1339 3CUSO,,H,O ......... +8.6 8.32 0.04 0.5 +1479 3CuS0,,5HL0 ...... +5*9 5-81 0.03 0.5 3.1450 4Mlle. Feytis' Our Abso- Per bility measure-Molecular susceptibility of CuSO,,&O= + 1479 XCorrection for water= - 13 x lo-"Susceptibility of the molecule CuSO, in CuSO,,H,O = + 1492 X lo-"Molecular susceptibility of anhydrous CuSO,= + 1339 X lo-';Difference= 153 x lo-"Thus, the union with one molecule of water has increased theparamagnetic susceptibility of the anhydrous copper sulphate rnole-cule by + 153 x 10-6 or by about 11.5 per cent.Further additionof water molecules to form the higher hydrate has no marked influ-ence on the susceptibility.Otherwise :Deviation fromMolecular susceptibility x 10';. additivity. -- -- Substance. 4 x emmental. Calculated. Absolute. Per cent.CuSO,,H,O ... 4- 1479 + 1326 153 11(from CuSO, and -0)CuSO,, 5X20 ... + 1450 + 1427 23 1.5(from CuSO,,H,O and S O COMPOUNDS OF WATER AND OF AQUEOUS SOLUTIONS. 2715Oopper Nitropusside.Average deviationSpecific from mean Number Molecular Deviatiorisuscep- & of suscep- fromtibility Abso- Per measure- tibility additivityx lW.lute. cent. ments. x106. per cent.Cu(NO)Fe(CN),,2H20 +4.54 0.05 1.0 5 +1432 8.4Cu(NO)Fe(CN), ...... +5-73 0.03 0.5 5 +1593 -This would indicate that the deviation is opposite in direction t othat for copper sulphate. However, any slight decomposition inthe preparation would make the anhydride too highly paramag-netic. A general study of nitroprusiides, on which we are a tpresent engaged, may throw more light on this question.Some Diamagnetic Salts.Potassium ferrocyanide :Molecular susceptibility of K,Fe(CN),,3H90 = - 172.0 x 10 riCorrection for 3H2O = - 38.9Susceptibility of the molecule K,Fe(CN), in K4Fe(CN),,3&0= - 133.1Molecular susceptibility of anhydrous K,Fe(CN),= - 145.1Difference= 12.By union with water thc diamagnetism of the moleculeK,Fe(CN), is diminished by about: 9 per cent.The following figures were calculated from the results of St.Meyer.Loss per cent. means the percentage by which the diamag-netic susceptibility of the anhydrous salt molecule is reduced byunion with water to form the given hydrate.Hydrate .................. MgCL,,6&0. CaCL,, 6H,O. BaCh, 2H20.Loss per cent ............ over 100 over 100 25Loss per cent ............. over 100 24 over 100masked by the diamagnetisni of the water.Hydrate .................. MgS0,,7H20. Li2S0,,H,0. Na,CO,,lOH,OThis would imply that in these salts we have paramagnetismTABLE 111.Organic Acids.SpecificReference susceptibilitynumber.Substance. x 106.1. [Benzene] ...... -0.70862. Benzoic acid ... -0.55603. Benzoicanhydride ... -0.55224. Phthalic acid ... -0.48786. Phthalicanhydride ... -0.44606. Maleic acid ...... -0.42697. Fumario wid ... -0.41588. Fummic acid ... -0.42699. Maleiotdlydride ... -0.3656Average deviationfrom mean.\Absolute. Per cent.0.0049 0.70.0123 2.20.0060 1.10.0054 1.10.0048 1 e.10.0182 4.00.0043 1.00.0096 2.20.0056 1.5Numberofmeasure-ments.566768452716 A MAGNETIC STUDY OF COMPOUNDS OF WATER, ETC.T.~BLE TJT. (continued).SpecificReference susceptibility10. Succinic acid ... -0-46151 1. Succinicanhydride ... -0.475312. Camphoricacid ............ -0.748113. Camphoricanhydride ... - 0.6204number. Substance. x loc.Average deviationfrom mean.Absolute. Per cent.0.0016 0.30.01 11 5.30.0054 0-s0.0172 2.7,TABLE IV.Molecular susceptibility x loq. Deviation *\ fromReferencenumber. Substance.2. Benzoic acid ...:I. Benzoicanhydride ...4. Phthalic acid ...5. Phthalicanhydride ...G. Maleic acid ...7. Fumaric acid ...8. Fumaric acid . .9. Maleicanhydride ...10. Succinic acid ...11. Succinicanhydride ...12. Camphoric13. Carnphoricanhydride ...acid ............Experi-mental.- 67.78- 62.37 x 2- 81.36- 66.01-48.23-49.62- 36.81- 64.46- 47.63- 149.3- 112.3- 49-62Forndditivity.- 68-85-- 78.97--48.77 - 48.77-#8*77-- 60.49-- 126.3-additivity.Per cent,.1.5-2.6-1.61.01.5-9.9-19.0-Nunilwrofmeasure -in~nts.554c,Pascal.70.63-86-0349-8749.6749.67--57.48--IMolecularsusceptibility Pas4 givesBenzene ......................... - 56.27 - 55.1 (Expt.) -- 55-03 (Calc.)Phthalic acid .................. - 81.36Mean ................... - 68.31ncnzoic acid .................. - 67.78Thus when t h molecular susceptibility of benzoic acid is calcu-lated from benzene and phthalic acid on the basis of additivity,then the experimental result differs from this calculated value byless than 1 per cent.Under the heading ‘‘ Pascal ” we give the molecular suscepti5li-ties as calculated from Pascal’s atomic values and his correctiohs forconstitution.~’HYSICAL CZIICMISTRT DEPARTMENT,ABERDEEN UNIVERSITY

ISSN:0368-1645    

DOI:10.1039/CT9140502707

出版商:RSC    

年代:1914

数据来源: RSC

摘要:

KENNER : THE INFLUENCE OF NITRO-GROUPS, ETC. 2717CCLIV.-The InJuence of Nitro-groups on the Re-activity of Xubstituents in the Benzene N.zm?eus.By JAMES KENNER.ALTHOUGH the enhanced reactivity of substituents in the ortho-or para-position relatively t o a nitro-group has been a familiarfact since i t was first observed by Pisani in the case of picrylchloride (L4~znaZen, 1854, 92, 326), little insight appears to havebeen gained into the nature of the processes which result in thedisplacement of such substitaents by others.The ‘‘ activating ” influence of the nitro-group is in direct con-trast, with its retarding, and at times inhibitive, effect on otherreactions. Whilst, however, the nitro-group shares its power ofsteric hindrance with other substituents of large molecular volume,quite irrespective of whether they are meta- o r ortho- and para-directive, this is not the case where the opposite effect is concerned.I n general, only meta-directive groupings can render substituentsin the ortho-position mobile; for instance, Schopff and his pupilsshowed that the carboxy-, aldehydo-, sulphonic, and cyano-groupseach conferred mobility on a bromine atom in the ortho- o r para-position (Bey., 1889, 22, 900, 3281; 1890, 23, 3440, 3445, 3450;1891, 24, 3771, 3785, 3808).The presence of a nitro-group wasnot essential, but its influence was much more powerful than thatof the other groups named, and a t least two of these, as comparedwith a single nitro-group in the ortho- or para-position (compareLobry de Bruyn, Rec.trav. chim., 1894, 13, lOl), were requiredt o render a substituent mobile. Ortho-para-directive substituentsappear, however, to increase the mobility of substituents in themeta-position in some1 cases, Thus Laubenheimer showed that,whilst the conversion of o-dinitrobenzene into o-nitroaniline bymeans of alcoholic ammonia requires ten weeks a t the ordinarytemperature for its completion, the corresponding reaction in thecase of 5-chloro-1 : 2-dinitrobenzene is complete within five days, andleads to the formation of 5-chloro-2-nitroaniline (Ber., 1876, 9,1826; 1878, 11, 1156).Similarly, Tiemann found that o-chloro-pnitrobenzaldehyde iseasily converted into o-chloro-p-anisaldehyde by the action ofsodium methoxide, pnitrobenzaldehyde being stable in these, circum-stances (Ber.., 1891, 24, 709).Attention has apparently not beenpreviously directed to this phase of the problem, and i t is thereforea t present not possible to indicate how far this influence of thechlorine atom is general, or shared by other ortho-para-directivesubstituents.VOL. cv. 8 2718 BENNER: TEtE INFLUENCE Ol? NITRO-GfiOUPS ON TBEThe evidence as it stands, however, suggests a close connexionbetween the phenomena a t present under discussion and those ofdirective substitution ; and, indeed, the various facts just enumer-ated find a ready explanation in terms of the views advocated byFliirscheim (,I. p. Chem., 1902, [ii], 66, 321; 1905, 71, 497; 1907,76, 165, 185; T., 1909, 95, 718; 1910, 97, 84).Thus it is clearfrom the diagram that a nitro-group in the ortho- or para-position,and a chlorine atom in the meta-position, each weaken the attach-ment of tho substitaent X t o the nucleus, rendering it moremobile :X xand that their influence is cumulative. Conversely, i t may beexpected that the effect of, for instance, a nitro-group in the nieta-position, or a chlorine atom in the ortho- or para-position, wouldbe a detrimental one. Quantitative experiments on the velocitiesof such reactions are therefore desirable, in order to discoverwhether these influences exist, and, if so, whether they are parallelwith Lhose observed, for example, by Staudinger and Kon ( A ~ ~ n a l e ? ~ ,1912, 384, 38), which are also capable of interpretation in thelight of Flurscheim’s views.It must be remarked, however, that the attachment of thenitregroup to the benzene nucleus has been frequently assumed t obe a comparatively strong one.Thus Kaufmann (“Die Auxo-chrome,” Stuttgart, 1909, p. 76) refers t o the aliphatic nature ofthe nitro-compounds, as illustrated by the reactivity of the chloro-nitro-compounds, and later (p. 93) attributes the formula I tonitrobenzene :Aux NH21) 1)__.._ O=N=O. ..../\It II /\ . ...-\J1-*-1 I\/(1.1 (11.) (111.)I)\/(‘Ii iThe adoption of this formula, preceded as it is (pp. 80,85) by theformihe I1 and I11 for benzene with the “ ideal auxochrome ” asa substituent, and for aniline, involves certain difficulties. ThusKaufmann is a t once driven to attribute something in the natureof nu amphoteric character to the phenyl residue, and to assume“ dass die Absiittigung der Partialvalenzen bei Antiauxochromenpolar zu der bei Auxochromen stratthat.” Further, it is probablREACTIVITY OF SUBSTITUENTS IN THE BENZENE NUCLEUS.2719that the presence of raidual affinity on the ortho- and para-carbonatoms, as represented by Kaufmann, would tend to promote thesubstitution in the ortho- and para-positions which actually takesplace. I€, then, Kaufmann’s formula for nitrobenzene be accepted,substitution might be expected to take the same course in this case,but this is not so. The strongest evidence in favour of Kaufmann’sview is probably supplied by the work of Meisenheimer (Annalen,1902, 323, 222; 1907, 3155, 249), who examined very thoroughlythe action of potassium methoxide on various nitro-compounds, andexplained his results in terms of Thiele’s theory of partial valencies,making the same assumption in regard to the nitlro-group a8 thatmade by Kaufmann.It will, however, be suggested that theseresult3 are not; irreconcilable with the opposite point of view. Noris Kaufmann’s formula, in the author’s opinion, a necessary conse-quence of Thiele’s theory, which is based on a conception of thenature of the double bond uniting two atoms of the same element.Where a double bond connects two different elements, i t is conceiv-able that one of these, that of greater residual affinity, may claimthe whole of the available affinity of the other.This is especially soas regards the nitro-group, where the single nitrogen atom isattached to two oxygen atoms, and if such were actually the case,Fliirscheim’s formula would represent nitrobenzene more accurately.Further, Werner’s explanation of the activity and inertia of therespective halogen atoms in triphenylmethyl bromide and tribenzoyl-bromoinethane (Ber., 1906, 39, 1282), symbolised by ttlie formulae :(C,H,),~C---Br, (C,H,--CO),ZE-C--Br,appears to lend support to the following formula for bromotrinitro-methane, the bromine atom of which is also inert (Meisenheimerand Schwarz, (Ber., 1906, 39, 2544):( N0,)3EC-Br.The evidence supplied by these considerations is therefore also infavour of Fliirscheim’s views.The following instance appears to show that the activating influ-ence of nitro-groups may act through a chain of atoms, which donot all form part of an aromatic nucleus.Whilst o-hydrazino-benzoic acid only passes over into 3-keto-l : 3-dihydroindazole whenit is heated alone to 220-230° o r with boiling phosphoryl chloride(E. Fischer, Ber., 1880, 13, 681; E. Fischer and Seuffert,, ibid.,1901, 34, 795), methyl 3 : 5-dinitro-2-hydrazinobenzoate cannot beisolated as a product of the interaction of methyl 1-chloro-3 : 5-di-nitrobenzoate and hydrazine hydrate, but is immediately convertedinto 5 : 7-dinitro-3-Leto-1 : 3-dihyd~oindazole. The following schemeshows that this reaction is also in accordance with the views justdiscussed :8 P 2720 KENNER: THE INFLUENCE OF NITRO-GROUPS ON THE.HNH-N'\H--+N/\0 0NH-NHI IO,Nf\ -eoIt might, however, be objected that, whereas Flurscheim hasapplied his views to explain the replacement of a hydrogen atom inthe meta-position with respect to a nitro-group, they are hereemployed to explain the replacement of substituents in the ortho-or para-positions. This consideration is of great importancebecause it shows that, whatever the nature of the substitutiveprocesses involved in the two cases may be, they must be essent!iallydifferent in character.Such a conclusion is supported by the factsthat the steric hindrance of the negative groups in the ortho-posi-tion is to a large extent, although not completeIy, overcome, andthat the nitro-group, which is the substituent most effective inexerting this hindrance, is also the most effective in promoting thecondensations of the type under consideration.It seems clear thatthe activating group is itself concerned in the reaction. I n viewof the increasing favour with which the addition theory of chemicalreaction is now received, and of the fact that the nitro-group isespecially prone to take part in the production of molecular com-pounds, it seems natural to assume t,hat the formation of sucha compound is the first, step in the process a t present under dis-cussion: and, indeed, when an aromatic amine, for example, reactswith an active chloronitro-compound in alcoholic solution, an intensecoloration is a t once produced which differs from that imparted toalcohol by t'he final condensation product, and is probably to beatltributed to the formatdon of an additive compound.This sug-gestion is not a novel one, and appears to have been originallymade by Bamberger (Ber., 1900, 33, l02), who, however, expressedno opinion as to the nature of the process by which the intermediateproduct passed over into the final condensation product. Bam-berger actually isolated a molecular compound of picryl chlorideand a-naphthylamine, from which picryl-a-naphthylamine was easilyformed ; whilst Sudborough and Picton isolated similar additivecompounds of 4 : 6-dichloro-1 : 3-dinitrobenzene and of 2 : 4-dichloro-1 : 3 : 5-trinitrobenzene, each with one' molecular proportion of a- or8-naphthylamine (T., 1906, 89, 583).Sudborough and PictoREACTIVITY OF SUBSTITUENTS IN THE BENZENE NUCLEUS. 2721suggested the following scheme to explain the mechanism of thereaction (compare also Richter, Ber., 1875, 8, 1419):C1 NH*C,,H7N H*C,,H:,02Nf‘,N02c1\/ \/NO2 NO2 NO2whilst Borsche has recently (Annalen, 1911, 386, 356; 1913, 402,81 ; compare also Meisenheimer, ibid., 1902, 323, 218) advocatedthe following expression of the reaction between 4-chloro-1 : 3-di-nitrobenzene and ethyl sodiomalonate * :Lapworth (P., 1903, 19, 123; compare Meisenheimer and Patzig,Ber., 1906, 39, 253; Lobry de Bruyn, Rec. trav. chinz., 1904, 23,60) suggested the formation of the same type of intermediateproduct’, as a result of the passage of the substituting radicle froman u- t o a y-position (T., 1898, 73, 445):Br OHBr \ / n T r O HIt is obvious that the whole question depends on that of the con-stit’ution of the molecular compounds first formed.The fact that* 4 : 6.Dichloro-1 : 3-dinitrobenzene furnishes first ethyl 5-chloro-2 : 4-dinitro-phenylmalonate, only reacting with a further molecular proportion of cthyl sodio-malonate with much greater difficulty, and this unequal reactivity is considered tobe “an experimental proof” of Kekul6’s beazene formula, as against Thiele’s or thecentric formula. I t appears exceedingly doubtful whether this evidence is asvaluable as that afforded by the work of Marckwald (Anncclesi, 1894, 279, 5 ) , for i tis hardly convincing that evidence, which is interpreted with the assistance ofThiele’s theory of partial valencies, should be used to disprove a formula whichfollows from an application of this theory to KekulB’s formula.Further, it may be remarked that the formula of ethyl sodiomalonate used byBorsche is not the one generally adopted, and to this extent his choice of anillustration for his theory is not a happy one,Also, according to Borsche, the chlorine atom in the compound nnder discussionis not loosely held.In this case i t is difficult to account for the fact that Ullmann’ssynthesis of diphenyl derivatives by heating the haloid benzenes with copper powderis only applicable to chloro-compounds mhcn they contain nitro-groups in theortho- or para-position to the halogen atom (Ullmann and Bielecki, B&. , 1907, 34,2177)2722 KENNER: THE INFLUENCE OF NITRO-GROUPS ON THEtetranitromethane and other aliphatic nitro-derivatives may formsuch compounds (Werner, Ber., 1909, 42, 4328) appears to bedecisive evidence against a formula of the type postulated bySudborough and Picton, and by Borsche, whilst Lapworth’s formulasupplies no explanation of the intense colour phenomena observed.The formula (IV) suggested by Werner (Zoc.c i t . ) is seen to be(IV.) (V.)closely related to that (V) adopted by Hantzsch for the nitro-anilines (Ber., 1910, 43, 1669), and is in harmony with theobservations of Sudborough and Beard (T., 1910, 97, 779), thatsubstituents which tend to increase the auxochromic effect of theamino-group always tend to increase the depth of colour of theadditive compounds of trinitrobenzene with amines (compare alsoGreen and Rowe, T., 1912, 101, 2446; Meldola and Hewitt, T.,1913, 103, 884; Meldola and Hollely, this vol., p.413). No attemptappears to have been made to institute a quantitative comparisonby an examination of the absorption spectra of the two series ofcompounds, but i t seems to the present author that this point needsattention before tho alternative formula (VI), hinted a t by Pfeiffer(Ammlen, 1914, 404, 13), is accepted:R-NO, C,H,NH,.Meanwhile, Werner’s formula has been reta’ined in the followingattempt to depict in outline the course of the reaction by whichan arylamino-radicle displaces a mobile substituent X :VI.)NHRAs a consequence of the formation of the molecular compound, acertain amount of unsatisfied valency may be expected momentarilyto exist, as shown, on the carbon atom to which X is attached, anREACTIVITY o ~ ’ SUBSTITUENTS IN THE BENZENE NUCLEUS.2723may either be absorbed by X or engage a portion of the residualaffinity of the spatially proximate nitrogen atom. Of the twoalternatives, the latter, represented by the third formula in thescheme, seems the more probable because it enables the system, bya subsequent rearrangement in the manner indicated, to attain acondition of smaller potential energy.The process by which the nitro-group facilitates the condensationis thus considered to consist in rendering i t intra- rather thaninter-molecular by bringing the amine molecule into a positionfavourable to the formation of a fivemembered ring (or, if Pfeiffer’sformula were adopted, of a six-membered ring).It is this featurethat differentiates the views now put forward from those ofLapworth ; whilst, in the author’s opinion, the supporters of theremaining theory are confronted with the dilemma that the sterichindrance of groups is probably explicable in a manner substan-tially similar to that by which they seek to explain the oppositeeffect. Thus Henry’s theory, that esterification depends on theformation of the intermediate compound (VII), has been extendedHO OR/OH RC-OH\OEt(VII.)by Wegscheider to the case of tho phenols, i t being assumed thatthe sterically active group X prevents the formation of the inter-mediate additive compound (VIII) (Monatslt., 1895, 16, 140 ; com-pare also Davies, T., 1900, 77, 33).The theory, that this is theusual mode of formation of substitution derivatives of phenol, hasbeen current for a considerable time, and is strongly supportedby experimental evidence recently adduced (Meyer and Lenhardt,A?c?tnle?t, 1913, 398, 51 ; Meyer, Irschich and Schlosser, Ber., 1914,47, 1741 ; compare Auwers and Michaelis, ibid., p. 1275).I n this connexion attention may be drawn to the behaviour ofpicramide. This aniine furnishes a reddish-brown explosive potass-ium salt (Green and Rowe, T., 1913, 103, 513), but is attacked byacetic anhydride only in the presence of sulphuric acid * (Witt andWitte, Ber., 1908, 41, 3092; compare Paal and Benker, Ber., 1899,32, 1251; Paal and Hartel, ibid., p.2051; Meldola and Hollely,this vol., p. 410). Similarly, 5 : 7-dinitro-3-keto-1 : 3-dihydroindazole* It is noteworthy that sulphuric acid has also been found to be effective infacilitating the esterificdtion of acids which remain unaffected under the nsualconditions (Wegscheider, Ber,, 1895, 28, 3128 ; Kenner and Mathews, this POI.,p. 2474)2724 RENNER: THE INFLUENCE OF NITRO-GROUPS ON THEfurnished a rnoiioacetyl derivative (IX), and a deep brown explo-sive disodium salt (X), whereas its 2-phenyl derivative could not beacetylated, and only yielded a rnoimsodium salt% (XI). It thusappears that the hydrogen atom in position (1) cannot' be acetylatedunder ordinary conditions, but can take part in salbformation.Since a diacetyl derivative and a monosodium salt are obtainedfrom 3-keto-1 : 3-dihydroindazole itself, it is clear that its relation-ship in these respects t o its dinitro-derivative corresponds exactlywith t h a t of aniline to picramide :(IX ) (X.) (XI.)These examples illustrate the fact t,hat a nitro-group can protectan amino-group by steric hindrance, and yet render its hydrogenatoms active towards alkali.I n other words, the two processesinvolved, of which one is a particular example of those with whichthis paper is concerned, are fundamentally different.A group of large molecular volume occupying the second ortho-position to the substituent X may, of course, be expected toexercise the steric hindrance usually observed in such cases of ring-formation, and we therefore ficd that 2-chloro-1 : 3-dinitrobenzenereacts much less rapidly than 4-chloro-1 : 3-dinitrobenzene (Borscheand Rantscheff, AnnuZen, 1911, 379, 152).Steric influencesmust further be considered in regard t o their effect on theformation of the primary additive compound. Thus Sudboroughand Picton (Zoc. cit.) showed that the introduction of three methylo r two methoxyl groups, or three bromine atoms into the moleculeof trinitrobenzenei completely inhibited the formation of molecularcompounds with a- or j3-naphthylamine, whilst Hofmann and Kirm-reuther found that alcoholic solutions of trinitromesitylene and oftrinitro-m-xylene, in contrast with trinitrobenzene, developed nocolour when hydrazine hydrate was added (Ber., 1910, 33, 1765).Similarly, Jackson and Boos showed that di- and tri-nitromesi-tylenes did not give coloured additive products with metallic alkyl-oxides (Amer.Chem. J., 1898, 20, 444). The importance of thisfactor is illustrated by the case of 4 : 6-dibromo-l : 2-dinitrobenzene,from which the 1-nitro-group is displaced by the amino-group(Blanksma, Rec. trav. ckirn., 1908, 27, 50):* The formulae given to these salts in the text are of course alternative to para-quinoiioid ones, or t o Hantzsch's nci-formul?REACTIVITY OF SUBSTITUEN'TS IN THE BENZENE NUCLEUS. 2725NO2 NH2Brf)N02ESr\/ \/BrA comparison with the behaviour, already quoted, of 4-chloro-(or bromo-)-1 : 2-dinitrobenzene a t once suggests that the nitro-group in position 2 would be the more easily displaced were itnot that the other nitro-group is sterically prevented from formingthe necessary additive compound.Thus,the reaction between potassium methoxide and trinitrophenetole(Meisenheimer, Zoc.c i t . ) may be represented in the followingmanner ;The above considerations are applicable in other cases.MeOK MeOKOEt EtO i I E tO ,**"'*-,.\ /''\/ \/'NO2&feO __._- I.-.-NO, NO2&!+.U--KEtO ,*,' EtO / ,,/'\,/" O.....- \/ (j02pJ / \z?s //I I No -+\NO,\/NO,Me()----- I<The formation of coloured salts of nitrophenols, to which Hantzschhas assigned the formula (XII) (Ber., 1912, 45, go), can beexpressed in the same manner:I< (-J-- - -_------I I1I I - \\//L/(XII.)and it is no longer remarkable that "echte Nitrokorper mit einerzweiten negativen Gruppe isomerieren sich als Pseudosauren (durchWasser oder Alkalien) niemals nur zur ersten Stufe der einfache2726 KENNER: THE INFLUENCE OF NITRO-GROUPS ON THEaci-Nitrokorper, sondern stets sofort zu der zweiten Stufe der kon-jugierten aci-Nitrokorper, so dass in dem f olgenden Umwandlungs-schema das Mittelglied nicht existiat " (Hantzsch, Zoc.cit.) :The course of the condensation of 2 : 4-dinitrotoluene with benz-aldehyde in presence of secondary bases (Thiele and Escales, Ber.,1901, 34, 2842) may perhaps be considered to take place in asimilar manner. This suggestion a t once accounts for certainobservations inade by Borsche (AnnaZen, 1911, 386, 351), whichhe was unable to explain. Whilst 4 : 6-dinitro-(XIII)- and2 : 4 : 6-trinitro-(XIV)-m-xylenes respectively give yields of 35 and43 per cent.of the corresponding dist,yrylbenzenes when condensedwith benzaldehyde, 2 : 4-dinitro-(XV) and 2 : 4 : 6-trinitro-(XVI)-mesitylenes are unchanged.Me Me Me Me()Me0 2 7 \/Me (NO2 Me(,!Me Me(,)Me/\ /\NO, 02N/\N0, O,N/'\NO2(XVI.)NO2(XIII.) (XIV.) (XV. 1NO, NO2I n the last two cases the nitro-groups are sterically preventedfrom forming the required additive compound, but in the first twocases both the 4- and the 6-nitro-groups are free to do so. If, how-ever, the condensation took place by direct interaction of the methylgroups with the aldehydes, tsinitro-m-xylene should be unchanged,as trinitromesitylene is, whilst dinitromesitylene should react withease.Also, a comparison of the behaviour of the two reactive com-pounds is interesting as illustrating the resultant influence of, onOMeOMREACTIVITY OF SUBSTITUENTS IN THE BENZENE NUCLEUS. 2727tho one hand the activating influence, and on the other the sterichindrance to the later stages of the reaction, of the 2-nitro-group.Further, i t may be observed that Hope and Robinson, when con-sidering the mechanism of the condensation of nitromeconine withcotarnine (shown on p. 2726), attributed two functions t o theimino-group : (‘ first, in attracting the nitro-compound and informing a l’oose combination of the type of the compounds obtainedfrom amines and trinitrobenzene, and secondly, in effecting theCondensation between the aldehyde and methylene groups ” (T.,1911, 99, 1153, 2114).The views thus expressed approximate veryclosely to those cdvocated above.The reactivity induced by other meta-directive groups maypossibly be explained in a similar manner. Thus there is abundantevidence that the carbonyl group is able to take part in the forma-tion of molecular compounds (compare, for example, Pfeiff er,Annnlen, 1910, 376, 285; 1911, 383, 92; Ber., 1914, 47, ISSO),and i t is probable that the same will be found to be true of thesulphonyl and the cyanogen groups.It is possible that similar considerations might lead to anexplanation of the activity of the chlorine atom and the methylgroup in 2-chloro- and 2-methyl-pyridines.At any rate, theseexamples serve to expose the inaccuracy of Vorliindes’s statement(Annaleih, 1910, 320, 66), according to which the ‘( reactive ” un-saturated group, *X:Y*, causes mobility of the hydrogen atom insystem XVII, but not in XVIII or XIX:H*A*X:Y* H*X:Y* H*A*B*X:Y*(XVII.) (XVII 1.) (XIX.)Whilst, however, the views just developed suffice to explain anumber of observed facts, they do not embrace another reaction,which was observed during the course of the experiments aboutto be described. Thus i t was found that 3-chloro-5 : 7dinitroindazoZe(XX), formed when 5 : 7-dinitro-3-keto-1 : 3-dihydroindazole isheated under pressure with phosphoryl chloride a t 140°, is convertedinto 3 : 5 : 7-trichloroindaso7e (XXI) if the reaction is carried outa t 1 8 0 O ; and the 2-phenyl derivative showed a similar behaviour :NH--NH N-JSH N-NHI \NO21 A /--uo 1 -+ NO,(\i>CCl I‘ I -+ Cl()dCl\/C1(XXI.)\/ \/NO2 NO2(XX.)Analogous observations have been made by Lobry de Bruyn(Rec.trav, chirn., 1896, 15, 84), who found that, among others2728 KENNER: THE INFJAUENCE OF NITRO-GROUPS ON THEs-trinitxobenzene and the three dinitrobenzenes were converted intothe corresponding chloro-derivatives when heated with saturatedhydrogen chloride solution at 200-300°. Similarly Zincke andKuchenbecker (AnizaZeiz, 1904, 330, 50) showed that 2 : 2’-dinitro-azobenzene-4 : 4/-disulphonic acid, when heated with concentratedhydrochloric acid a t 160°, furnished tetrachloroazobenzene :NO, NO, c1 c1\-/ \-/ \-/ \-/ *HO,S/-\N : N/-\SO,H --+ CI/-\N :N/-\CIThe facts that all the nitro-groups are displaced, and that in thecases of the dinitrobenzenes the reaction is independent of theirorientation, would appear t o indicate that the cause of the reactionis t o be sought in the relationship of the’ nitro-groups to thebenzene nucleus rather than in any direct mutual influence of thesegroups.Since, however, nitrobenzene itself does not undergo thisreaction (Lobry de Bruyn and van Leent, Zoc. cit.), i t is evidentthat the second nitro-group does play some part, probably bysuitably modifying t-he condition of the benzene nucleus. Thissurmise receives some measure of support from the fact that) thedisplacement of nitro-groups by chlorine atoms takes place muchmore readily in the case of naphthalene derivatives (Atterberg,Ber., 1876, 9, 1187, 1732; 1877, 10, 1843), in which the conditionof the nuclei is generally acknowledged t o be somewhat differentfrom that of the ordinary benzene nucleus.This idea is not novel,f o r it is implied in the term “negativity,” by which the chapterof organic chemistry dealing with such cases of mobility is gome-times designated. It is therefore also probable that this effect ofnitro-groups on the benzene nucleus must bel taken into accountin connexion with the reactions to which the main part of thepresent discussion has been devoted. Similarly, the nature of thesubstlituent t o be replaced also requires consideration, Thus Sud-borough and Picton were unable t’o prepare picryl-a-naphthylaminefrom picrylaniline, although the necessary additive compound wasisolated (Zoc.cit., p. 587). The fact that s-Lrinitrobenzene is con-verted into 3 : 5-dinitroanisole by the action of sodium methoxide,but is not affected by ammonia (Lobry de Bruyn, Rec. trav. chim.,1890, 9, 214, 218; 1894, 13, 148), shows that the nature of theentrant group is also of importance. It must, however, be observedthat these factors operate by predisposing the system to reactionrather than by playing any active part’ in the change.Thus thedisplacement of a nitro-group in the course of the synthesis of3 : 5-dinitro-oxazine from 2 : 4 : 6-trinitro-2~-hydroxydiphenylamine,Still other influences are noticeable in certain casesREACTIVITY OF SUBSTITUENTS IN THE BENZENE NUCLEUS.2729observed by Turpin (T., 1891, 59, 722; see also Kehrmann, Ber.,1899, 32, 2605):NH /\/ \Ais comparable with the conversion, just cited, of s-trinitrobenzeneinto 3 : 5-dinitroaniso1e7 and is probably a result of the negativity ofthe benzene nucleus. This, however, affords no explanation of thefact, observed by Ullmann, that whilst Turpin’s reaction is applic-able to 2 : 6-dinitro-2’-hydroxydiphenylamine, i t fails in the case ofthe 2 : 4-isomeride (Awnalen, 1909, 366, 79).Further, the result of the action of potassium cyanide on alcoholicsolutions of the bromonitrobenzenes and similar compounds a t 180°,first studied by Richter, is remarkable.Para- and meta-bromo-nitrobenzenes are respectively converted into meta- and ortho-bromobenzoic acids, but the ortho-isomeride is recovered un-changed (Ber., 1871, 4, 21, 461, 553; 1874, 7, 1145; 1875, 8,1418 ; compare Zincke, Ber., 1874, 7 , 1503). Whilst these reactionsare normal in the sense that the hydrogen atom in the ortho-posi-tion to the nitro-group is atbacked in each case, they disclose astrong tendency, not observed in any of the cases previouslyreferred to, on the past of the substitut’ing group (in this casecyanogen, which is subsequently hydrolysed), t o enter the nucleusas close to the other negative group as possible. So strong is thistendency that i t prevents the conversion of o-bromonitrobenzeneinto m-bromobenzoic acid, although both the bromine atom and thenitro-group in this case conduce to the mobility of the meta-hydro-gen atom; whilst in the second case quoted above the reaction takesplace irrespective of considerations of steric hindrance, which wouldsuggest the para-hydrogen atom as more likely to be attacked.* Ifdue allowance is made for this factor, the action of potassiumcyanide on various nitro-compounds, apparently so bewildering inthe variety of results observed (collated by Lobry de Bruyn, Rec.trau.chim., 1904, 23, 47), affords an excellent illustration of theeffect of the influences previously discussed, namely :(a) the loosening influeace of meta-directive groupings on ortho-and para-substituents ;( b ) the corresponding effect of ortho-para-directive groups onmeta-substituents ;* Probably bromonitrobenzonitriles are first prodwed in this reaction. Forevidence of the mobility of the nitro-group in such compounds, compare the cases ofo-nitrobenzonitrile, m-dinitrobenzene, and other compounds referred to later2730 KZNNER: THE INFLUENCE OF NITRO-GROUPS ON THE( c ) steric hindrance to the formation of the initial additive(d) the, negative condition of the benzene nucleus:( e ) the nature of the substituent to be replaced and of theentrant group.It will be observed that, in the following instances,nitro-groups attached to a negative nucleus and hydrogen atomsalone suffer displacement. Halogen atoms are not affected bypotassium cyanide.The following table shows the more notable of the resultsobtained in this direction, accompanied by references to the abovecompound and to the attack of otherwise mobile groups;summary :Nitro-compound.o - Dinitro -benzene.p - Dinitro -benzene.in - Dinitro -benzene.Dinitrated6 - nitro-2-ethoxy-b e n z o -nitrile.1 : 2 : 4-Tri-nitrobeii-zene.4 - C h l o r o -1 : 3 - d i -n i t r o -beuzene.Conditionsemployed.Alcoholic so-lution a t170".Boiling alco-ho!ic solu-tion.Boiling alco-holic solu-tion.Warm alco-holic solu-tion.Roiling alco-tion.Boiling alco-holic solu-tion.holic solu-Product.~ No change.p-Nitroanisole.12 - 6; Dinitro -benzonitrile]-+ 6-nitro-2 - niethoxy -benzonitrile.A d i n i t r i l e ,the 6-nitro-group beingdisplaced.2 :4- Dinitroani-sole.5 - C h 1 o r o- 6 -n i t r o - 2 -m e t h o x y-benzonitrilc.Referencest o literature.Bruyn and van Geuns,Xec.trav. chim., 1904,23, 32.Bruyn and van Geuns,Eoc. c i l .Rruyn and van Geuns,Eoc. cit. ; other refer-ences in this paper.van Geuns, quoted byBruyn, REC. trau.chim., 1904, 23, 52.Bruyn, Xec. trav. chinz.,1890, 9, 193.van Heteren, Ihc. trav.chim., 1901, 20, 107 ;Blanksma, ibid., 1902,21, 424.* The cyanogen group renders a nitro-group i n the ortho-position mobile(influences (a) + ( d ) ) . Thus o- and p-nitrobenzonitriles, when boiled with a solutionof sodium methoxide, are converted into o- and p-methoxybenzonitrileel (Ringer,Rec. trav.chim., 1899, 18, 330 ; Reinders and Ringer, ibid., 326). Lulofs showedthat some o-nitroanisole is also produced in the former case (Rec. trav. chim., 1901,20, 321). Further, Lobry de Bruyn showed that 2-methoxy-6-nitrobenzonitrile wasconverted into 2 : 6-dimethoxpbenzonitrile by ruethyl-alcoholic potassium hydIoxide(Rec. trav. chim., 1883, 2, 205). t The l-nitro-group diminishes the mobility of the 3-hydrogen atom, and thusprevents the reaction from following a similar coiirse to that observed in the case ofm-dinitrobenzene. The influence of the chlorine atom and the amino-group in thecases next quoted is, however, in favour of such a result. This influence of thechlorine atoni is clearly responsible for the partial conversion of 5-chloroREAC'fIViTlf OF SUBSTITUENTS IN THE BENZZNE NUCLEUS.2731Lippniann and Fleiss-ner, Nonatsh., 1885,6, 807 ; 1886, 7, 95.Nietzki and Petri, Ber.,1900, 33, 1788;Rorsche, Ber., 1900,33, 2718, 2995;Horsche and Locatelli,Ber., 1902, 35, 569 ;Horsche and Biicker,Ber., 1903,36, 4357 ;Bruyn, Bec. trav.chirn., 1904, 23, 56.Blanksmn, Rec. trav.c7~ina., 1901, 20, 411,423.Nitro-compound.Alcoholic so-lution a t60".Aqueous solu-tion at 35"( N i e t z k iand Petii).2:4-Dinitro-aniline.2: 6 - Dinitro-3- (a) i (b) + ( d )Potassium iso- ( a ) + ( b ) + (c)aminophenol. + (c).purpurate.* + ( e ) .2 : 4 :6-Tri-nitrophe-nol.Di- and tri-n i trome-sity lenes.Referencesto literature.Product. 1 Influences. I employed.1 : 3-dinitrobenzene into 3-chloro-5-nitroanisole by the action of sodium methoxide,whilst 1 : 3-dinitrobenzene is simply reduced (Kock, Bee. trav. chim., 1901, 20, 111 ;Steger, ibid., 1899, 18, 13).* The authoritics quoted agree that isopurpuric acid contains cyanogen groups inthe 3- and 5-positions, but differ in regard to the fate of the 2- aud 6-uitro-groups.According to Nietzki and Petri, one of them is converted into an amiuo-group, whilstBorsche suggests that the rcduction only reaches the stage of a hydroxylamino-group. Lobry de Bruyn considers that the colour of the compound would bebetter explaiued by the presence of a nitroso- and a hydroxylamino-group in placeof the two nitro-groups.The question as to the extent t o which the nitro-groupssuffer reduction has, however, no bearing on the present discussion.Two points in connexion with the above table call for explana-tion. No attempt is made to explain the introduction a t one timeof a cyanogen group, a t another of an alkyloxy-group, as a resultof the action of potassium cyanide. This problem, which lies out?sido the scope of the present discussion, was considered by Lobryde Bruyn, who, however, was unable t o arrive a t any very definiteconclusion (Rec. trav. chirn., 1904, 23, 47). Also, the term" influences " a t the head of one column of the table is only meantto comprehend those which would appear t o play a decisive partin determining the final result2932 KENNER: THE INFLUENCE OF NITRO-GROUPS ON THEEXPERIMENTAL.[With RAYMOND CURTIS.]5 : 7-Dinitro-3-keto-1 : 3-dihydroiizdnzole,NH*NHOpN(\;--bO\/NO2An alcoholic solution of hydrazine hydrate (6 grams) wascautiously added to a Golution of methyl 2-chloro-3 : 5-dinitro-benzoate (10 grams) in warm alcohol (100 c.c.).Each additioncaused a vigorous reaction, which became violent if the initialtemperature was too high, and a dark red hydrazine salt wasimmediately precipitated. After dilute hydrochloric acid had beenadded t o the mixture, the free indazole derivative was collected,and purified by crystallisation from glacial acetic acid. Itseparated from the solution in yellow, hexagonal plates, melting anddecomposing a t about 300O:0.1900 gave 0.2596 CO, and 0.0368 H20.0.1736 ,, 38.2 C.C.N, at 17O and 734 m p N=25*06.C7H40,N4 requires C = 37.50 ; H = 1.78 ; N = 25.00 per cent.The compound was not appreciably soluble in cold alcohol, water,benzene, or chloroform; i t was fairly soluble in boiling alcohol, andreadily 80 in glacial acetic acid or acetic anhydride.The1 d’isodium salt was prepared by triturating 5 : 7;dinitro-3-keto-1 : 3-dihydroindazole (2 grams) with 5N-sodium hydroxidesolution (7 c.c.). After the addition of absolute alcohol (5-10 c.c.)t o the resulting deep brown paste, the salt was collected andwashed with absolute alcohol until the washings were free fromalkali. For analysis two different. specimens were prepared, thesecond by the use of a considerable excess of sodium hydroxidesolution; although the products were dried a t 130°, the salt stillretained two molecular proportions of water :0.1288 gave 0.0603 Na2S0,.Na = 15.17.0.2938 ,, 0.1380 Na2S0,. Na = 15.22.0.134 required 9.2 C.C. N/lO-H,SO,.C,H20,NENa,,2H,0 requires Na = 15.13 per cent. ; M.W. = 304.The salt exploded when heated, and this prevented determina-tions of its other elements being made. It was readily soluble inOwing to the difficulty indetermining the exact end-point, no claim can be made for great accuracy in theresult.C=37.26; H=2*15.M.W. =291.** The salt itself served as indicator in the titrationREACTIVITY Ol? SUBSTITUENTS IN THE BENZENE NUCLEUS. 2733water, soluble in alcohol or acetone, but insoluble in benzene o rclilorof orin.By treating its aqueous solution with suitable re-agents, a reddish ferric salt, an insoluble dark brown silver salt,and a moderately soluble dark brown copper salt were obtained.The’ monoctcetyl derivative separated in greenish-yellow crystalson cooling the solution obtained by boiling the compound (2 grams)with acetic anhydride (5 grams) for eight hours. It crystallisedfrom glacial acetic acid in rectangular prisms, melting a t195-200° :0.1701 gave 0.2548 CO, and 0.0340 H,O.0.1548 ,, 28.6 C.C. N, a t 1 8 O and 741 mm. N=21*2.The solubility relationships of the acetyl derivative correspondedIt was soluble in alkali, form-All attempts to prepare a diacetyl derivative were fruitless, theC=40*85; H=2*22.C,H,O,N, requires C = 40.60 ; H = 2.25 ; N = 21.05 per cent.with those of the parent substance.ing a deep red solution.monoacetyl derivative being produced in every case.5 : 7-Dicsrnino-3-keto-l : 3-dihydroindazole.N H*KHBH,The dinitro-derivative (4 grams) was added to a solution ofstannous chloride in glacial acetic acid (80 grams), saturated withhydrogen chloride.After twelve hours, the reduction product wasisolated from the precipitate by treatment with hydrogen sulphidein the csual manner. It was analysed in the form of its oxalate,which was precipitated when ammonium oxalate was added t o anaqueous solution of the hydrochloride of the base :0.1062 gave 20.8 C.C. N, at 1 8 O and 740 mm. N=21*95.C,H,ON,,C,H,O, requires N = 22-20 per cent.5 : 7-Didro-3-ke to-2-phenyl-l : 3-dih ydroiir dazol e,N H NPhO,N/j-&O\/NO2An alcoholic solution of plienylhydrazine (12 grams) was slowlyadded to a warm solution of methyl 2-chloro-3 : 5-dinitrobenzoate(10 grams) in alcohol (100 c.c.).After the mixture had beenheated on the water-bath for fifteen minutes, it was worked up asVOL. cv. 8 2734 KENNER: THE INFLUENCE OF NITRO-GROUPS ON THEin the previous case. The product consisted of two compounds,one of which was extracted by boiling alcohol. The residue(90-95 per cent. of €he yield) crystallised from glacial acetic acidin flat needles, which melted and decomposed between 220° and250° :0.1814 gave 0.3464 CO, and 0-0477 H,O.0.1552 ,, 25.2 C.C. N, a t 16.5O and 740 mm. N = 15-72.CI3H8O,N4 requires C =52.00 ; H = 2.66 ; N = 18.66 per eent.The compound was therefore either the 1- or the 2-phenyl deriv-ative of 5 : 7-dinitro-3-keto-1 : 3-dihydroindazole.It was onlysparingly soluble in boiling alcohol, benzene, or chloroform. Itwas moderately soluble in glacial acetic acid and in epichlorohydrin.Tho monosodium salt was obtained as an amorphous powder inthe manner already described in the case of dinitroketodihydro-indazole, and exhibited a similar tendency t o explode when heated.It was readily soluble in water, soluble in alcohol or acetone, butinsoluble in chloroform or benzene :C=52.08; H=2*91.0.2162 gave 0.0491 Na2S04.0.161 0 required 5.0 C.C. N/lO-H,SO,.Na = 7-35,M.W. = 322.C,,H70,N4Na requires Na = 7.1 per cent.; M.W. = 322.By double deconiposition with its aqueous solution, an insoluble,deep red silver salt, and a moderately soluble, brown coppw saltwere obtained. The compound is insufficiently acidic to permit ofthe formation of a ferric salt.Attempts to prepare) an acetyl derivative by various methodswere unsuccessful, the original compound being recovered in eachcase. A colourless substance separated from the solution obtainedby adding sulphuric acid to- a mixture of the compound with aceticanhydride, but it decomposed and turned yellow immediately itcame in contact with the moisture of the atmosphere.As explained in the introduction, these reactions agree with thebehaviour of picramide, and i t is therefore considered that thecompound is a 2-phenyl derivative.This conclusion is in harmonywith the results of E. Fischer (Aiz~inleiz, 1878, 190, 67), whoshowed that the condensation of picryl chloride with phenyl-hydrazine results in thel formation of trinitrohydrazobenzene. Itappears that other products may result under slightly different con-ditions (Willgerodt and Ferko, J. p. Chem., 1888, lii], 37, 346;Fischcr, AIznaleu, 1889, 253, l), and Fischer himself showed thata i-nixture of symmetrical and unsymmetrical derivatives is pro-duced by the action of alkyl bromides on phenylhydrazine (com-pare also lticliaelis and Schmidti Ber., 1887, 20, 43). These factsmay throw some light on the formation in the present case of REACTIVITY OF SUBSTITUENTS IN THE BENZENE NUCLEUS. 2735second compound, which was deposited from the above-mentionedalcoholic solution in yellow, rhomboidal plates.After repeatedcrystallisation from alcohol, the compound melted a t 175O :0.1420 gave 0.2897 CO, and 0.0502 H20.0.1450 ,, 25.6 C.C. N, a t 1 6 O and 737 mm. N=20*51.ClSH,,0,N6 requires C= 55.89 ; H = 3.92 ; N = 20.60 per cent.C=55*64; H=3*93.The compound therefore resulted from the condensation of onemolecular proportion of the ester with two of phenylhydrazine :CGH,(N0,)2C1*C0,Me + 2C,H3*NH-NH, +We were unable to oxidise i t with mercuric oxide, to condense i twith aldehydes, to convert it into the indazole derivative producedsimultaneoixsly with it4, o r to prepare it from 2 : 4-dinitro-6-carbo-methoxyhydrazobenzene. Unless steric influences be assumed, thisevidmce is a t variance with the possible formulae XXII andXXIII, whilst forniula XXIV, representing the product of thesemidined inversion of XXIIC, is rendered improbable by the factthat the compound in question may be isolated without the aid ofacid by removing the phenylhydrazine salt of dinitroketophenyl-dihydroindazole by solution in cold alcohol :NPh-NH, NH*NHPhHCl + MeOH + CGH,(N02)2*C',,H,40N4./\CO*NH*NHPhO,N{)CO*NKNHPh 02Nl I\/ \/NO2(XXII I.NO2(XXII.)N H*C,H,*NH,O,N(\CO*N H ON H Ph(XXI v.)2 : 4-Dir~itro-6-car bomethoxyhydrazobenzene,C0,Me/ - \NH*NH-C,H,.02N\- -/NO2After plienylhydrazine (8 grams) had been added to a solutionof methyl ' 2-chloro-3 : 5-dinitrobenzoata (10 grams) in alcohol(100 c.c.), the mixture was heated to the boiling point, and thencooled.The precipitate thus obtained was warmed with alcohol,and, after filtration, the solut8ion deposited orange crystals of thehydrazo-derivative. After further crystallisation from warmalcohol, it melted a t 144-145O:S Q 2'736 KENNER: THE INFLUENCE OF NITRO-GROUPS ON THE0.1634 gave 0.3016 CO, and 0.0523 H,O.0.1430 ,, 21.7 C.C. N, a t 20° and 732 mm. N=17.11.Cl4I6CI3O6N4 requires C = 50.60 ; H = 3.61 ; N = 16.87 per cent.When its alcoholic solution was boiled f o r a few minutes, internalcondensation took place, and the corresponding dihydroindazolederivative was precipitated. The same product was obtained wiienattempts were' made t o condense the hydrazo-derivative withphenylhydrazine or benzaldehyde.C=50*45; H=3.55.s-2 : 4 : 2f : 4f-Tetrai~itro-6 : 6 ~ - d i c a r b o m e t h o x y t e t r a ~ h e ~ ~ ~ ~ -NO2 NO9h ydrasiize, O,N/-\N Ph* N P b <-)NO2.\-/C0,Me C0,McAn alcoholic solution of hydrazobenzene (2 grams) was heatedwith a solution of methyl 2-chloro-3 : 5-dinitrobenzoate (6 grams)in alcohol (60 ex.) on the water-bath for one hour. The brick-redprecipitate, after filtration and crystallisation from nitrobenzene,melted a t above 340O:0.1777 gave 0.3480 CO, and 0.0526 H,O.0.1918 ,, 21.6 C.C. N, a t 20° and 747 mm. N=12.94.C2,H2,012N, requires C = 53-16 ; H = 3.1 6 ; N = 13-29 per cent.It was insoluble in alkalis, and in most organic solvents exceptnitrobenzene and epichlorohydrin. Attempts t'o hydrolyse the com-pound with acid or with alkali were unsuccessful.I f the coiistitution assigned to the phenylindazole derivative,already described, is accepted, it is remarkable that the secondphenylamho-group of hydrazobenzene reacts with a second mole-cule of ester rather than with the carbomethoxyl group of the firstmolecule, and it, might be suggested that this is evidence in favourof the alternative constitution.On the other hand, however, itmay bO argued that the velocity of reaction in the present case ismuch slower than when phenylhydrazine is used, and that this isdue to the greater facility with which the ester condenses with theamino-group of phenylhydrazine.C=53*40; H=3.29.N-NHO,N()-CCI "\I3-Chlo Fo-5 : 7-dirtit roindaaol e,5 : '7-Dinitro-3-keto-1 : 3-dihydroindazole (5 grams) was heatedwith phosphoryl chloride (35 grams) for four hours unde'r pressureat 120-140O.After the excess of phosphoryl chloride had beenremoved by warming t.he product under diminished pressure, thREACTIVITY OF SUBSTI'I'UENTS IN THE BENZENE NUCLEUS. 2737residue was stirred with water, collected, and repeatedly crystal-lised from glacial acetic acid. I n this way, yellow needles(3 grams) were obtained, which melted a t 179-180°:0.1994 gave 0.250s CO, and 0.0197 H,O.0.2020 ,, 40.6 C.C. N, a t 18O and 752 mm. N=23*39.0.3615 ,, 0.2112 AgCl. C1=14.46.C7H30,N,C1 requires C = 34.66 ; H = 1.19 ; N= 23.09 ; C1= 14.64.per cent.C=34.30; H=1*09.N-NH5 : 7-Dinitro-3-keto-1 : 3-dihydroindazole was heated underpressure with 10 parts by weight of pliosphoryl chloride for tenhours a t 160-180°.The product was isolated in the same manneras in the previous preparation, and separated from glacial aceticacid in microscopic, white twinned needles, which melted a t190-190*5O :0.1085 gave 11.8 C.C. N, at 18O and 740 mm. N=12*47.C,H,N,C13 requires N = 12.64 per cent.N-NPhAfter a sealed tabe containing a mixture of 5 : 7-dinitro-3-keto-2-phenyl-l : 3-dihydroindazole (3 grams) and phosphoryl chloride(24 grams) had been heated for four hours a t 120-140°, andcooled, it; was found that the above chloroindazole derivative hadcrystallised. After separation from the liquor, and recrystallisa-tion from glacial acetic acid, somewhat indefinite small, greenish-yellow needles were obtained :0*2000 gave 30.7 C.C. N, at 17O and 725 mm. N=17.3.C,,H70,N,Cl requires N = 17.6 per cent.N-NPh ' \\I3 : 5 : 7-Trichloro-2-p~eizylilzdaaole,\Cl5 : 7-Dinitro-3-keto-1-phenyl-1 : 3-dihydroindazole (5 grams) washeated with phosphoryl chloride (40 grams) for fourteen hour2738 EWINS: THE ALKALOIDS OF QUEBRACHO BARK. PART I.under prwsure a t 160-170°. The product, isolated in the Bamemanner as in the previous cases, separated from glacial acetic acidin silky, yellow needles, which melted a t 208-210° :0.1779 gave 13.8 C.C. N2 a t 18.5O and 754 mm.0'3783 ,, 0.5429 AgCl. C1=35*53.N=9*06.C1,€I,N,CI, requires N = 9-41 ; C1= 35.79 per cent.Action of Phosphoryl Chtoride on $2 : 4 : 21 : 4'-Tetranitro-6 : 61-dicarbomethoxytetraphenylhydrazine.A mixture of the hydrazine derivative (3 grams) with phosphorylchloride (40 grams) was heat'ed for ten hours under pressure a t170-180°. The product of the reaction could not be crystallisedfrom the ordinary solvents, and was therefore purified by digestionwibh sodium hydroxide solution and reprecipitation from thefiltered solution :0.1815 gave 0.3572 CO, and 0.0436 H,O.0.1672 ,, 11.0 C.C. N, a t 20° and 731 mm. N=7.4.C,,H,,0,N4C1, requires C = 53.51 ; H = 2.74 ; N = 9.90 per cent.C,,H,,O,N,Cl, ,, C=55*51; H=2*84; N=4-99 ,, ,,The product was therefore a mixture! of two acids, derived fromthe original est4er by hydrolysis and replacement of respectivelytwo and four of its nitro-groups by chlorine. The incompletenature of the relaction was probably due to the high molecularweight and sparing solubility of the hydrazine derivative.This resulb is of value, since it shows that the pyrazole ring wasnot the predisposing cause' of the mobility of the nitro-groups inthe previous instances, although this mobility is specially notice-able in t'he naphthalene series (see the introduction), and Frieshas shown (Amtalen, 1912, 389, 313) that 6-hydroxyindazole iscomparable in its reactions with &naphthol.C=53*67; H=2*66.THE UNIVERSITY,SHEFFIELD

ISSN:0368-1645    

DOI:10.1039/CT9140502717

出版商:RSC    

年代:1914

数据来源: RSC