摘要:

WOOD : THE AFFINITY CONSTANTS OF XAX‘THINE. 1839 By JOHN KERFOOT WOOD. IN a previous paper (Trans., 1903, 83, 568) the author gave the results of the determinations of the affinities of a number of feeble bases, including, amongst others, several members of the xanthine series. Some of the values obtained for these xanthino derivatives were not in agreement with those expected on constitutional grounds. It was therefore decided to repeat some of the earlier experiments, and to extend the investigation so as not only to include other methyl derivatives of xanthine, but also to determine the acidic dissociation constants as well as the basic constants. Particulars Begarding the Substances Employed. Xunthiiie.-A portion of the same sample as was used in the earlier Heteroxantl,h~e.-This substance was prepared by Fischer’s method l’heobromine.-The sample used was Gbtained from Merck.experiments (Zoc. cit.) was employed. (Ber., 1897, 30, 2,400).1840 WOOD: THE AFFIKITY CONSTANTS OF Y'heophyZZine.-This substance was also obtained from Merck. The Paraxanthine.-This compound was prepared by Fischer's method Cafleine.-The sample used was supplied by Kahlbaum. It melted sample was crystallised from water and then dried at 140'. (ZOC. cit.). at 2349 Determinations of Basic Constunts. The methods used were those basod on : (1) The catalysis of methyl acetate (see Walker and Wood, Trans., (2) The solubility in water and in hydrochloric acid of known The majority of the experiments, as previously, were conducted at XccGmthine.-The basic constant of this substance, as in the earlier The following 1903, 83, 484).concentration. 40.1°, but a few determinations were also made at 25'. experiments, was determined by the solubility method. results were obtained at 4 0 ~ 1 ~ . 1000 C.C. water dissolved 0*1823 gram xanthine. 1000 C.C. N/lO hydrochloric acid dissolved 0.2183 gram xanthine. These figures give a value for the basic dissociation constant (kb) of 1.933 x K, where K is the dissociation constant of water. The value of K at 40*1° is 3.15 x 10-14 (Kohlrausch and Heydweiller, Zed. physibal. Chew., 1894, 14, 317), and therefore kb = 6.09 x This figure is of the same dimensions, but of rather greater magnitude, than that previously determined, viz., 4.6 x 10-14. Hetermanthim.-Determinations of the solubility at 40.1' gave the following results : 1000 C.C.water dissolved 0.7325 gram heteroxanthine. 1000 c,c. N/10 hydrochloric acid dissolved 1.003 gram hetero- Therefore kb/K= 3.754 and k b = 11-82 x 10-14. Theohornine.-Repeated determinations of the solubility of theo- bromine in water gave a result greater than that previously obtained ; the value, however, for the solubility in hydrochloric acid was in close agreement with that already given. The following are the mean values obtained : xanthine. 1000 C.C. water dissolved, at 40*1°, 0.8125 gram theobromine. 1000 C.C. N/10 hydrochloric acid dissolved, a t 40*1°, 0.939 gram From these figures the following values are given : theobromine. kb/K= 1.47 ; kb = 4.63 X wi4. The greater value obtained for the solubility in water on the presentXANTHINE AND ITS METHYL DERIVATIVES.1841 occasion has caused the value of kb to fall to about one-quarter of the figure previously determined. 2'heophyZZine.- With this substance it was found possible to employ both the previously mentioned methods. Velocitg Comtants at 25". N/20 solution of theophylline hydrochloride + methyl acetate . . . . . . , . . . . . 0*0001276 N/20-C1 solution (90 per cent. HCl, 10 per cent. KCl)+methylacetate ... 0.0001225 N/2O-Cl solution (95 ,, ,, 5 ,, ,, )+methyl acetate.. . 0*0001328 Calculating from these results, a N/20 solution of theophylline hydrochloride is hydrolysed to the extent of 92.52 per cent. at 25". Velocity Constants at 40.1 ". X/20 solution of tlieophylline hydrochloride +methyl acetate .. , . . .. . . . . 0.0005333 N/20-C1 solution (90 per cent. HC1, 10 per cent. KCl) +methyl acetate ... 0*0005140 N/20-C1 solution (95 ,, ,, 5 ,, ,,)+methyl acetate ... 0.0005460 These results show a N/20 solution of theophylline hydrochloride t o be hydrolysed to the extent of 92.57 per cent. at 40.1". Results of Solubilitp Det erminutiom Grams of theophylline 25" 6.607 7 -43 40'1 14.23 15.70 It is interesting to observe how much more soluble is theophylline than most of the other members of this series; caffeine, in fact, is the only other member possessed of a solubility comparable with that of theophylline. The values of the ratio kb/K, calculated from the foregoing data, are given in the following table : Grams of theophylline per 1000 C.C. of Temperature.per 1000 C.C. of water. N/10-hydrochloric acid. 25". 40 '1 '. Methyl acetate catalysis uiethod ... 1.74 1.734 Solubility method.. . .. . . . . . . . . . . . . . . . . . . . 1'125 1 *305 The results, it will be observed, are all of the same dimensions. Probably most reliance can be placed on those arrived at by the methyl acetate method, in which errors are not as likely to occur as in the solubility method ; a slight error in the determination of one of the solubilities would cause a proportionately greater error in the value of kb/K. I n the case of the results obtained by the catalysis method, it will be noticed that the value of kb/K is unaffected by a change of temperature. Taking the value of kb/K found by the catalysis method, the basic dissociation constant of theophylline at 40*1° is calculated to be 5.46 x 10-l4.1842 WOOD: THE AFFINITY CONSTANTS OF Paraxanthine.-With this substance it was impossible to prepare a solution of sufficient concentration to permit of the methyl acetate method being employed.Determinations of the solubility at 40*1° gave the following results : 1000 C.C. water dissolved 1.06 grams paraxanthine. 1000 C.C. XI10 hydrochloric acid dissolved 1.17 grams paraxanthine. From these figures the following values are obtained : ka/K = 1.044; kb = 3.29 X Cuc$eine.-A determination by the methyl acetate catalysis method showed caffeine hydrochloride to be hydrolysed to the extent of 89 *7 per cent. in N/lO solution at 40.1". This figure is identical with that previously determined (Zoc.cit.). Therefore, as previously found, kb = 4.0 x 10 - 14. Determination of Acidic Constants. The method chiefly employed was that of the saponification of methyl acetate by the sodium salt of the substance (Shields, Zeit. physikal. Chem., 1893, 12, 167), the results being Calculated by means of the equation given in the preceding paper. The velocity of saponification of methyl acetate being much greater than that of the catalysis of the same substance, and the velocity increasing with the temperature, the determinations mere made at 25O, instead of at 40*1° as in the case of the determination of the basic constants. With one or two substances the acidic constant was calculated from the solu- bilities in water and in N/20 sodium hydroxide; these solubility experiments were conducted at 40.1'.Xanthine.-The solubility method was employed, and the following results obtained : 1000 C.C. water dissolved 0.1823 gram xanthine. 1000 C.C. N/20 sodium hydroxide dissolved 6.405 grams xanthine. From these data i t is found that ka/K=3767, and therefore at 2Zeteroxanthine.-With this substance also the solubility method 1000 C.C. water dissolved 0,7325 gram heteroxanthine. 1000 C.C. N/20 sodium hydroxide dissolved 7.781 grams hetero- Therefore ka/K=1276 and ka=4*019 x 2'heobrornine.-The determination of the velocity with which the sodium salt of this compound saponifies an equivalent quantity of 40.1' ka= 1.186 x lo-''. was employed. xant hine.XANTHINE AND ITS METHYL DERIVATIVES. 1843 methyl acetate is rendered more difficult by the slight solubility of the compound.After the action has proceeded to some extent, the theobromine, being no longer kept in solution as the sodium salt, begins to be precipitated. The conditions of equilibrium are thus changed, and it is impossible to obtain readings a t the most trust- worthy part of the change, namely, the middle portion. It is possible, however, to obtain a very good estimate of the velocity of saponification by comparing the readings during the initial period of the saponification of methyl acetate by solutions, of equal con- centration, of sodium theobromine and sodium phenoxide respectively. The figures for the two reactions are shown below; in both cases 25 C.C. of the solution of the alkali salt were mixed with an equal volume of the solution of methyl acetate.NjZ5 sodium theobromine + N/25 methyl acetate :- Time. 0 61 81 117 Titre. k. 7-92 - 5-72 0*00097 5 -39 0-00104 4'95 0'00111 N/25 sodium phenoxide + N/%5 methyl acetate : Time. 0 63 83 119 Titre. 7-92 5 '85 5.47 5 *lo k. 0*00080 0*00093 0-00094 - It will be observed that the values obtained for k are in both cases of gradually increasing magnitude. Such inconstancy is always noticed when results are calculated from observations made during the initial period of the reaction. The rate of increase of k: is almost the same in both series, the ratios between corresponding figures of the first and second series being respectively 1.21, 1.12, and 1.18. It is evident, therefore, that the saponification of the ester by the salt of theo- bromine is proceeding a t a rate which, on the average, is 1.17 times as great as that with which the saponification by sodium phenoxide proceeds.The velocity of saponification being inversely proportional to the acidic dissociation constant, and the dissociation constant of phenol at 25O being 1.3 x 10-1O (Walker and Cormack, Trans., 1900, 77, IS), it follows that the acidic dissociation constant of theobromine is approximately 1.1 1 x 10 - 10. Theodor Paul (Arch. Phurm., 1901, 239, 48j calculated the dis- sociation constant at 18' from the results of determinations of the solubility in water and in solutions of sodium hydroxide. The result obtained was 1.33 x but an error appears to have been made in1844 WOOD : THE AFFINITY CONSTANTS OF the calculation. A recalculation by the author from Paul's data gave a value for ka of 0.91 x 10-lo, which, allowing for the differ- ence in temperature, is in good agreement with the value given above.!Z'heophyllins.-No difticulty of the bind experienced with theo- bromine was met with in the case of theophylline, and it was there- fore possible to calculate the dissociation constant from the readings obtained during the middle period of the saponification. The results obtained were as follows : k = 0.0000845 ; ka = 1.62 x lo-'. Experiments on the solubility of theophylline in water and sodium hydroxide were made. It was found that the additional amount of theophylline which passed into solution because of the presence of the alkali was equivalent to the amount of the latter, thus showing that theophylline is a comparatively strong acid, the sodium salt of which is not appreciably hydrolysed in solution.Pumxanthine.-For this substance also, the saponification method was employed, giving as results : k = 0 ~ 0 0 0 0 6 1 6 and ka=2*22 x 10-9. Cafeine.-This compound is almost devoid of acidic properties. A solution of it in sodium hydroxide saponified methyl acetate with a velocity almost as great as that shown by the pure alkali. Moreover, the solubility in a solution of sodium hydroxide is only very slightly greater than that in pure water. The value of ka is evidently, there- fore, of dimensions less than 1 x Xurnrnary of Beszllts. NH*CO*C*NH, CO*NH-C-N~ Xanthine, I I ( CH ...... ... Heteroxanthine, 1 \ I \CH ... Theobromine, 1 11 \CH ... NH'CO'C'NMe CO-NH.C----N/ NH- CO-C -NMe CO-NM~*C----N~ NMe'CO'C'NH, Theophylline, I 11 'CH ...... CO*NMe*C-N/ NMe'CO 'C'NMe, Paraxauthine, 1 ( 1 \CH ...Caffeine, I 1 ) \CH ........ -NH-c---N/ NMe' CO 'C "Me CO'NMe'C---N/ kb x 1014. Temp 4.6 40'1" 11.82 40.1 4-63 40.1 5-46 40.1 3.29 40-1 4.0 40'1 ka x 11-86 4.019 11 -1 162.0 222.0 < 0 *OOl Temp. 40.1" 40 -1 25.0 25'0 25'0 25-0XANTHINE AND ITS METHYL DERIVATIVES. 1845 Before comparing in any way the results given in the above table, one or two points require to be specially mentioned. The methods used for the determination both of the basic and the acidic constants have not been the same for all the substances examined, and it might perhaps be urged that this difference i n method made any comparison of the results of uncertain value. This objection vanishes, however, when it is recalled that for each series of constants the results for one substance have been arrived a t by both methods. Thus, in the case of the basic constants, the constant of theophylline was determined both by the methyl acetate catalysis method and by the solubility method, the values obtained being of similar dimensions.I n the case of the acidic constants, the fact that, the dissociation constant of theo- bromine as found by the saponification method is in close agreement with that of the same substance calculated from Paul's solubility data shows that the results arrived at by the two methods are strictly comparable. The effect of temperature on the results must also be referred to, seeing that in the case of the acidic constants results are given at two temperatures.This difference in the working temperature was largely due to the desire to obtain results of the greatest possible accuracy. A comparatively low temperature was found to be the best in the case of the saponification method, whilst in the case of the solubility method it was considered that, the solubilities of some of the sub- stances being very small, more accurate results could be obtained by working at a higher temperature. For purposes of comparison, it will be sufficient to state that at 40.1' k, will have a value rather greater than twice the value which it has at 25'; this result was arrived at by experiments made with theophylline by the saponification method. Discussion of Results.It has been pointed out by Walker (Trans., 1903, 83, 182 ; Proc. Roy. Soc., 78, A , 140) that the value kb is a composite expression con- taining not only the real ionisation constant of the base, but also a hydration constant. If the hydration remained constant, it might be expected that the values of kb would gradually increase as the number of methyl groups in the xanthine nucleus increased. It seems reasonable to suppose that with substances of similar constitution such as those examined the degree of hydration will not vary t o any great extent, and on this assumption it will be evident that there can likewise be no great difference in the values of the true ionisation constants, since for all the substances kb has nearly the same magnitude.1846 WOOD : THE AFFINITY CONSTANTS OF XANTHINE. The matter becomes simpler when acids are under consideration, for in such cases the process of hydration does not as a rule form part of the operation of solution. The general effect of the substitution of a hydrogen atom by a methyl group might be expected to be a very slight diminution in the value of the acidic constant, and it will be observed that in the transition from xanthine to heteroxanthine such an effect on the value of k, is produced.But when we proceed further and replace a second hydrogen atom by a methyl group, it is observed that k,, instead of undergoing a further slight diminution, assumes in all cases a much greater value, the increase being most noticeable in the cascs of paraxanthine and theophylline.The imino-groups which are now strongly acidic were present in the parent substance xanthine, and yet that substance has an acidic dissociation constant which is only a small fraction of those possessed by the dirnethylxanthines. This great augmentation of the value of k, can only be explained by-tho assumption of some stereochemical change taking place on the intro- duction of the second methyl group, the change produced being least when substitution takes place at position 3 of the xanthine nucleus. The almost complete freedom from acid characteristics shown by caffeine is in accordance with what might be expected on constitutional grounds, since it contains no imino-group. A coaparison of the values of k, given by the isomeric dimethyl- xanthines is also of interest when taken in conjunction with their respective constitutions.From our general knowledge as to the negative character of the carbonyl group, it might have been reasonably expected that theobromine, in which the imino-group is attached to two carbonyl groups, would possess a value for k, greater than those given by paraxanthine and theophylline, in both of which substances the imino-group is only connected with one carbonyl group. This view is supported by some of the results described in the previous paper ; for example, those obtained with the dimethyluracils. The results obtained, however, with the dimethylxanthines show that the positions are entirely reversed, paraxanthine having the highest and theobromine the lowest value for k,. Were it not for the fact that the constitu- tion of these substances appear to have been fixed with certainty by Fischer and others, it might almost be believed that some confusion between the two had taken place, and that theobromine should really have the formula ascribed to paraxanthine, and vice versd. In the circumstances, however, this view cannot be entertained, and we must therefore conclude that in the case of the dimethylxanthines the ordinary influences of the carbonyl group are not seen because of the stereochemictil influence of the methyl groups being more powerful andRUHEMANN : XANTHOXALANIL AND ITS ANALOGUES. 1847 varying in magnitude according t o the positions in the xuiithirie nucleus occupied by the methyl groups. I n view of the interesting results obtained, the investigation is being extended to other purine derivatives. UNIVERSITY COLLEGE, DUNDEE.

ISSN:0368-1645    

DOI:10.1039/CT9068901839

出版商:RSC    

年代:1906

数据来源: RSC

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RUHEMANN : XANTHOXALANIL AND ITS ANALOGUES. 1847 CLXXVIII.-XccnthoxaZa.ilil and its A YL cc 1 og u es. By SIEGFRIED RUHEMANN. RECENTLY (Trans., 1906, 89, 1236) it has been shown that the yellow product which W. Wislicenus and Sattler (Bey., 1889, 24, 1245) obtained by the action of sodium ethoxide on a mixture of ethyl oxalate and acetanilide had the composition C2,,Hl2O,N2 ; it was found also that similar compounds could be prepared by using, instead of acetanilide, the acetyl derivatives of o-toluidine, p-toluidine, and a-naphthylamine. This reaction has now been applied t o the produc- tion of analogous substances from the acetyl derivatives of m-xylidine, pseudocumidine, P-naphthylamine, and p-aminophenetole. It was sug- gested (Zoc. cit.) that the formation of xanthoxalanil was preceded by the production of sodio-oxalacetanil, which, on treatment with a mineral acid, yielded the coloured condensa- tion product.Its constitution accordingly was represented by the formula This view concerning the mode of formation of xanthoxalanil induced me to examine whether the solution of sodio-oxalacetanil, when treated with pyruvic acid, instead of with a mineral acid, furnished the compound CO 7H2 PhN<CO*C:C(CH,)*CO,II’ just as indoxyl condenses with the ketonic acid to yield the correspond- ing indogenide; I found, however, that this reaction did not take place, but that in this case also xanthoxalanil was formed. I n my previous communication (Zoc. cit., p. 1239) I pointed out that1848 RUHEMANN : XANTHOXALANIL AXD ITS ANALOGUES. xanthoxalanil, on heating with an alkali, might be expected to undergo the following decomposition : PhN<co'FH2 ?o'co>NPh + 5H20 = 2C6H,*NH2 + (C02H), + co*c=c-co CO,H*CH,*C(CO,H): CH*CO,H, and furnish aconitic acid or its stereoisomeride. W.Wislicenus and Sattler (Zoc. cit.) had already studied this reaction; they stated that the compound was completely decomposed by caustic potash and yielded, besides aniline and oxalic acid, a mixture of volatile organic acids which reduced silver solutions, but they did not succeed in proving the presence of acetic acid which they expected to be formed. On repeat- ing this experiment I was able to prove that the alkaline solution, which wzts produced by the action of caustic potash on xanthoxalanil, contained oxalic acid and dianilaconitic acid.Their formation might be represented by the equation (C02H), + C,H,(CO,H)( CO*NHPh),. Similar to the decomposition of xanthoxalanil is the behaviour of alkalis towards its analogues ; thus from xanthoxalo-m-xylidil, m-dixylil- aconitic acid could be obtained. On hydrolysis of dianilaconitic acid with concentrated hydrochloric acid, aconitic acid is produced. These facts support the constitution of xanthoxalanil and its analogues which I put forward from the mode of their formation. These compounds when reduced with zinc dust and acetic acid, are transformed into colourless substances. Up t o the present I have isolated the reduction product which is formed from m-xanthoxalo- rn-xylidil. Its composition, C,,H,,O,N,, indicates that, under the influence of the reducing agent, the yellow condensation product has united with six atoms of hydrogen.There cannot be any doubt that two of them are rinited wibh the unsaturated group of the molecule of the yellow compound ; I hope to be able to ascertain the position of the other four hydrogen atoms in the reduced substance by examining the behaviour of this substance towards alkalis. The results of this examination, and of the further study of xanthoxalanil and its analogues, will be published shortly.RUHEMANN : XANTHOXALANIL AND ITS ANALOGUES. 18413 E X P E R I rd E N T AL. X c m thoxa lo -m-xylidi I , This substance is prepared in the same way as xanthoxalanil by adding ethyl oxalate to sodium ethoxide suspended in dry benzene, and mixing the solution which is thus produced with aceto-m-xylidide dissolved in benzene.The product, after standing for several days, is shaken with water, the aqueous layer filtered and treated with an excess of dilute hydrochloric acid, when a yellow solid is precipitated in the course of a few hours. This is readily soluble in hot nitrobenzene, sparingly, however, in boiling glacial acetic acid, and, on cooling, crystallises from either solution in yellow plates which melt and decompose at about 244' after having begun to darken a few degrees before : 0.2280 gave 13-6 C.C. moist nitrogen at 20' and 756 mm. N= 6.78. C,,H,,O,N, requires N = 6.73 per cent. Xanthoxulo-+-cumidil, Aceto-$-cumidide reacts with sodium ethoxide and ethyl oxalate under the same conditions as the former compound, and yields a yellow condensation product.This is very readily soluble in hot nitrobenzene, but sparingly so in boiling glacial acetic acid, and, on cooling, crystallises in yellow prisms which begin to darken a t 220' and melt at about 250' with decomposition : 0-2014 gave 0,5190 CO, and 0.0950 H,O. 0 2498 ,, 14 C.C. moist nitrogen at 18' and 757 mm. N = 6-44. C2,H2,O,N2 requires C = 70.27 ; H = 5.40 ; N = 6-30 per cent. C = 70% ; H = 5.46. Xanthoxa lo-/3-nuphth y Zuni I , This substance is formed from aceto-/3-naphthalide in the same way as its stereoisomeride. It differs from it inasmuch as it dissolves in boiling nitrobenzene with great difficulty, and, on cooling, crystallises in bronze-coloured, shining plates which decompose at about 290" :1850 RUHEMANN : XANTHOXALANIL AND ITS ANALOGUES.0.2013 gave 0.5375 CO, and 0.0635 H20. 0.2192 ,, 12.2 C.C. moist nitrogen a t 27" and 'i60 mm. N = 6.14. C= 72232 ; I3=3*53. C2SH1SOSN2 requires C = 73.0 ; H = 3.47 ; N = 6.08 per cent. Xanthoxa Eo- p-e thoxylanil, ( p)C2H,0*C,H,-N<co*~H2 co*c== ?o*Co>N*C,H,*OC2H,( c-co p). This compound is prepared in the same way as the former substances by the action of phenacetin on ethyl oxalate in the presence of sodium ethoxide. Owing to the fact that phenacetin is sparingly soluble in benzene, a large quantity of the solvent is required. The condensation product is sparingly soluble in glacial acetic acid, but readily so in hot nitrobenzene, and, on cooling, crysballises in orange plates which melt at about 260' with decomposition : N= 6.25.0.2493 gave 13.6 C.C. moist nitrogen a t 1s' and 755 mm. C,,H2,07N2 requires N = 6.25 per cent. Action of Alkalis o n Xanthoxakcnil and its Homologues. On digesting xanthoxalanil with dilute caustic potash on the water- bath, it dissolves and deposits an oil which was identified as aniline. The yellow alkaline solution, after removal of the aniline by ex- traction with ether, when treated with an excess of dilute hydro- chloric acid, yields a solid. This dissolves in sodium carbonate and is precipitated on adding an acid to the solution. This property has been made use of for purifying the compound. It is readily soluble in alcohol, and crystallises from this solution in bunches of colourless needles which melt at 199-ZOOo after having begun t o soften a few degrees before : 0.2048 gave 0,4992 CO, and 0.0913 H20.0.2116 ,, 16.4 C.C. moist nitrogen a t 25' and 769 mm. N=8*75. The behaviour of this substance, which is recorded below, charac- terises it as dianilaconitic acid. Michael (Amer. Chenz. J., 1887, 9, 192) obtained a compound with this formula by allowing an aqueous solution of the dianiline salt of aconitic acid to remain for some time at the ordinary temperature ; he stated that it crystallised from alcohol in long, prismatic needles, which had a faint pink shade and melted at 188-1 89". These properties of Michael's dianilaconitic acid hardly differ from the behaviour of the substance which I obtained from xanthoxalanil except in the melting point. Indeed, isomeric dianil derivatives would correspond to a compound having the C = 66-48 ; H = 4.95.C,,H,,O,N, requires C = 66-67 ; H = 4.94 ; N = 5-64 per cent.RUHEMANN : XANTHOXALANIL AND ITS ANALOGUES. 1851 same structure as aconitic acid, but a closer comparison of the two substances will be necessary before they can be regarded as different. The production of d ianilaconitic acid from xnnt hoxalanil is accom- panied by the formation of oxalic acid. This is contained in the acid filtrate from the derivative of aconitic acid ; it was characterised by a calcium determination of the salt which is precipitated from the solution by means of ammonia, calcium chloride, and acetic acid : 0.4410, on ignition, left 0.1695 CaO. CaC20,,H20 requires CaO = 38.35 per cent. That the compound which is formed from xanthoxalanil is indeed dianilaconitic acid follows from its behaviour on hydrolysis, when aconitic acid and aniline are produced. This decomposition may be effected by caustic potash, as is indicated already by the fact that aniline is formed on digesting xanthoxalanil with the alkali, but it is preferable to use concentrated hydrochloric acid for this purpose. The solid dissolves after two to three hours' boiling wiLh the acid.The solution, when cold, is extracted several times with ether and the ethereal solution decolorised with animal charcoal ; on evnpor- ating the ether, colourless crystals of an acid separate which was identified as aconitic acid by the melting point (186-187') and by the analysis of the silver salt : CaO = 38.43. 0.2520, on ignition, left 001642 Ag.Ag = 65-15, C,H,O,Ag, requires Ag = 65-45 per cent, Di-m-xyZidiZaconitic Acid, C,H,(C02H)[CO*NH6CBH3( CEt3)2],. On digesting xanthoxalo-mxylidil with dilute aqueous caustic potash, it turns red and then rapidly dissolves. The yellow solution, when treated with an excess of dilute hydrochloric acid, yields a solid which readily dissolves in boiling alcohol and, on cooling, crystallises in bunches of colourless needles ; these, after recrystallisation from the same solvent, melt at 196-197' with evolution of gas: N= 7.49. C2,H2,O,N2 requires N = 7.37 per cent 0.2193 gave 14.4 C.C. moist nitrogen a t 20' and 758 mm. Reduction of Xar~thoxalo-rn-xylidil. The boiling solution of xanthoxalo-m-xylidil i n glacial acetic acid is decolorised by zinc dust ; on adding water to the filtrate, a solid is precipitated which dissolves slowly in cold sodium carbonate solution with the exception of a small quantity of a resinous product. The filtrate, when treated with an excess of hydrochloric acid, yields a VOL. LXXXIX. 6 F1852 FRANKLAND AND TWISS: THE INFLUENCE OF VARIOUS white precipitate which crystallises from dilute alcohol in colourless plates melting at 160--161° : 0.2013 gave 0.5025 CO, and 0.1118 H20. 0.2116 ,, 12.2 C.C. moist nitrogen at 17" and 755 mm. N = 6.64. C24H2605N2 requires C = 68.24 ; H = 6-16 ; N = 6-63 per cent. C=68*13 ; H=6-17. 0.2020 ,, 0.5055 CO, ,, 0.1121 H20. C= 68.24 ; H= 6.16. The substance is fairly soluble in cold alcohol, readily so when hot; the alcoholic solution gives with ferric chloride a deep violet coloration which, on warming, changes to red. GONVILLE AND CAIUS COLLEGE, CAMBRIDGE.

ISSN:0368-1645    

DOI:10.1039/CT9068901847

出版商:RSC    

年代:1906

数据来源: RSC

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1852 FRANKLAND AND TWISS: THE INFLUENCE OF VARIOUS CLXX1X.-The Influence of Various Substituents on the By PERCY FARADAY FRANKLAND and DOUGLAS FRANK TWISS, M.Sc. IN a previous communication on the same subject, the optical activity of seventeen derivatives of tartramide has been described by one of us (P. F. Frankland and Slator, Trans., 1903, 83, 1349), but amongst these only the methylamide and ethylamide were derivatives of tartaric acid with aliphatic amines. I n the present communication we have confined our attention to the latter, having prepared and examined the normal and isopropylamides, the allylamide, the normal and iso- butylamides, and the normal heptylamide. The rotation of these compounds has, as before, been determined in pyridine, and, when possible, also in methyl alcohol, and in water solution.The amides described i n the present paper were prepared by the interaction in the cold of the amine with an alcoholic solution of methyl tartrate, and all were obtained as crystalline bodies of high melting point (183-216'). Excepting in the case of the isopropyl- amide, of which only 23 per cent, of the theoretical quantity was obtained, the yields were excellent, and in the case of the isopro- pylamide also a better yield would no doubt have resulted if the alcohol had been evaporated off after completion of the reaction. The results of our investigation are summarised in the following table : Optical Activity o f Tartramide. Part 11.SURSTITUEKTS ON THE OPTICAL ACTIVITY OF TARTHAMIDE. 1853 Tartaric di- Amide.................. Methylamide ......... n-Propylamide ...... isoPropylamide ...... E th ylamide ......... Allylamide .......... n-Butylamide.. ....... n-Heptj lamide ...... isoButylamide ...... Sunzrnary of Results : Py ridinc. Mc thy1 alcohol. Water. Melting b F-, point. p . p. [hl]?'. p. [w:oO. 195" - - 0.0807 -t208" 0'077 +160" - - 0-1797 213 1-305 158 189 0.684 +274" 4'998 266 0-994 255 7-679 279 4-986 262 10.350 242 210-211 1.049 277 4,997 282 1'390 262 5.030 2 i 9 5.001 281 i-468 256 216 2.196 289 2.019 290 1.808 264 4'741 287 4.857 290 2.717 260 189 1'654 272 1'910 273 1.398 247 4.665 272 4.867 272 4.682 247 183 2.528 251 2900 273 2.392 247 4.735 252 5.914 270 4.697 246 193 1.899 286 0.907 298 0.258 280 4.801 288 4'416 291 - - 183.5 1.753 295 1.007 306 0.549 275 5'064 294 5'432 305 - - 183 1'621 304 0.9951 303 - - 3.579 305 - - - - With the above may be compared the previously-determined rotations of the following substitution derivatives of tartramide : Tartaric di- Pyridine.Methyl alcohol. Piperidide * ................................ 0" - Phenylhydrazide .......................... < + 80 - Diacrtj lltartaricl-o-toluidide ............ + 80 - H ydrazide -- - nc-Tetrahydro-/3-naphth~lamide * ...... + 240 - Tartranil. ..................................... + 2 i 2 + 268" Benzylamide ................................ + 300 Furfurylaniide .............................. + 307 _- Tartaric-p-toluil ........................... + 366 + 280 Acetophenone- hydrazone .................. + 397 - a-Naphthylamide ...........................+ 400 - Benzylidene-hydrazide ..................... + 554 - o-Toluididc - ............................... + 667 ni-Toluidide - ................................. -t 730 Furfurylidene-hydrazidc ................ t 736 - Anilide + 739 - p.Toluidide ................................... + i 9 3 - nr-Tctrahydro-/3-naphthylamide * ...... + 840 - B-Naphthylamide .......................... + 1160 - Methyltartrimide t ...................... c - Ethyl tax t rimide t - - .................................... - ..................................... ........................... * Frankland and Ormerod, Trans., 1903, 83, 1342. t Ladenburg, Ber., 1896, 29, 2710. Water. + 281 *6 f 264 -3 The foregoing figures show that all the substituted tartramidcs, excepting the phenylhydrazide and piperidide, have a higher dext ro- 6 F 21854 FRANKLANn ANT) TWISS : TT-TE INFT,UENCE OF VARIOIJS rotation than tartramide itself, and that substitution by aromatic radicles leads to a dextrorotation of a much higher order than that resulting from substitution by aliphatic groups.The piperidide is inactive, at any rate in pyridine and in aniline solutions, which were the only ones in which it was examined, The benzylamide and fur- furylamide have about the same rotation in pyridine as the n-heptyl- amide, whilst the ac-tetrahydro-/I-naphthylamide has even a lower dextrorotation in pyridine than any of the alkyl-substituted tar- tramides. Taking the derivatives with the aliphatic amines of the normal series, it appears that the value of [MI, does not show any evidence of having reached a maximum within the range of the series of com- pounds prepared, for the n-heptylamide has a higher molecular rota- tion than any of the lower homologues.The isopropylamide has a lower rotation than the n-propylamide, whilst the rotation of the iso- butylamide is greater (excepting in water solution) than that of the 91-bntylamide. The rotatioh of the allylamide as compared with that of the n-pro- pylamide is particularly interesting, for it is now generally believed that the presence of a double bond in a carbon-chain leads to an increase in the optical activity (see P. Frankland and Slator, Trans., 1903, 83, 1351, where numerous references to this relationship are given). In the present case, however, the substitution of n-propyl by ally1 is attended by a marked diminution in the rotation, and the same exceptional relationship will be shown by one of us (P.Frankland and Done) to be exhibited in the case of the n-propylamide and allylamide of malic acid. The piperidide ig the only secondary amide hitherto examined, and, as indicated in the above table, it was found to be practically inactive ; this result naturally suggests that racemisation of the tartaric acid had taken place in the process of preparation, but it may also be due to the dextrorotation being depressed to about zero by the introduction of the piperidine group, and that this is perhaps the case is rendered less remotely possible since it has been found by one of us that in the malic series the piperidide has a much lower rotation than the un- substituted malamide in pyridine and methyl alcohol solutions, whilst in glacial acetic acid solution the sign of the rotation is actually reversed.EXPERIMENTAL. Tartaric Di-n-propylarnide. An excess of n-propylamine was added to a concentrated solution of methyl tartrate in absolute ethyl alcohol in the cold. The separation of amide commenced in the course of a few minutes j the crystalsSUBYTITUENTS ON THE OPTICAL ACTIVITY OF TARTRAMIDE. 1855 formed, after standing for two days, were filtered off, and a further crop was obtained by evaporating part of the alcohol. The yield was about 80 per cent. The product was purified by recrystallising from a mixture of equal parts of ethyl alcohol and ethyl acetate. 0,0946 gave 10.0 C.C.moist nitrogen at 16.5Oand 761 mm. N = 12.30. Tartaric di-n-propylcmi& crystallises in colourless, flat, elongated plates, or fiat needles, melting at 216' with slight decomposition. It is easily soluble in pyridine, or hot alcohol, less so in ethyl acetate, whilst in cold water the strongest obtainable solution was about 2.4 per cent. C,oH,,04N, requires N = 12-07 per cent. Rotation of l'ccrturic Di-n-popyEanLide. 2). cl 20"/4". 4.741 0-9867 2.196 0.9817 4.857 0.8083 2'019 0-7991 2'717 1.0029 1 '808 1'0014 1. ay. [a]?. " 1 5 Ppaidine Solution. 0.999 +5.79" +123'9" +287'4" 1 *998 5 *37 124'7 289'2 Methyl Alcol~ol Solution. 1 '998 + 9 -79" -I- 124 '8" + 289 *5" 1.998 4-03 124'9 289.7 TVater Solution. 0.999 + 3.05' + 112.1" + 260.0" 1 -998 4-11 113'6 263-6 Turta ric Diisoprop y la~nide.The theoretical quantity of i8opropylamine was added to ' a solution of methyl tartrate in absolute ethyl alcohol. After standing two days the liquid became viscid and yellow ; the amide separated from this on cooling with ice or adding a crystal as nucleus. After standing two more days the crystals were filtered off, but only a 23 per cent. yield was obtained. The product was recrystallised from ethyl acetate to which a little alcohol had been added. N = 12.03. 0.1130 gave 12.1 C.C. moist nitrogen at 17Oand 737 mm. Tartaric di-isopropylamide crystallises in slightly flattened needles, I t s solubility in the ordinary C,,H,o04N, requires N = 12-07 per cent. melting at 189' without decomposition. solvents is rather greater than that of the normal propylamide.1856 FRANKLAND AND TWISS: THE INFLUENCE OF VARIOUS Pa 1.654 4-665 1910 4-867 1 '398 4 -682 Rotation of Tartaric Diisopropylamide.d 20"/43 0.9806 0.9858 0.79iO 0 8058 1 '0003 1 -0059 1. Qpidine Solution. 1.998 +3$Oo 3-117.3" 0.999 5 -38 117.1 Jlethpl Alcolml Solutiow. 1'998 + 3-59O + 117%" 0'999 4 -60 117'4 Water Solution. 1 '998 4- 2.98" + 106.7" 0.999 5 -00 106-3 Taqstaric Diallylantide. This was similarly prepared by mixture of theoretical of allylamine and methyl tartrate in alcoholic solution. [M]",". + 272 *Oa 271 *7 1- 273'3" 272'4 + 247-4" 246.6 proportions The amide already began to separate after an hour, and by filtering off the crystals after twenty-four hours' contact, a yield of 62 per cent. was obtained. The product was purified by recrystallisation from a mixture of equal parts of ethyl alcohol and ethyl acetate.0,0997 gave 10.84 C.C. moist nitrogen at 15Oand 745 mm. N= 12.48. CloH160,N, requires N = 12.28 per cent. Tartaric diaZZyZamide crystallises in flat, thin, colourless plates Its solubility in the common melting at 1 8 3 O to a pale yellow liquid. solvents is about the same as that of the n-propylamide. IZotatio~t of Tartayic Diallylamide. P. d 20"/4". 2.528 0'9838 4.735 0'9896 8'900 0'8023 5'914 0'8092 2'392 1'0036 4-697 1 'ooa6 I?. U","". [4y. [MI?. Pyridine Solution. 1 -998 +5*48" 4-110-3" +%51'4" 0'999 5 -18 110.7 252.3 Methyl A lcohol Solution. 1.998 + 5 -5i" +119%" + 2 7 3 Y 0.999 5 -66 118'4 269.9 FVate?. Solutiooh. 1 -99a + 5-19' 3- 1082" + 246.7" 0'999 5-10 107'8 245-7SUBSTITVENTS ON THE OPTICAL ACTIVITY OF TARTRAMIDE 1857 Tartaric Di-n-butylamide.Butylamine was added in theoretical quantity to a cooled solution of methyl tartrate in ethyl alcohol. The separated amide was filtered off after themixture had stood f o r about thirteen hours, a 75 per cent. yield being obtained. The product mas purified by recrystallisation from a mixture of two parts of ethyl acetate to one of ethyl alcohol. 0,1482 gave 14.0 C.C. moist nitrogen at 17" and 737 mm. N = 10.84. Tartaric di-n-butylamide crystallises in beautiful, long, flat, needles melting at 193' without decomposition. Like the other amides described above, it is very soluble in pyridine or alcohol ; its solubility in water is, however, very small (only 0.3 per cent.).C12H2404N2 requires N = 10.77 per cent. Rotation of Turtcevic Di-n-butylamide. . d 20"/4". 1. a","", [a]ioo. Pyridine Soiution. 1'899 o-gaog 1-998 i- 4.10" + 110.2" + 286.4" 4.801 0.9849 0.999 5-23 110.7 287.8 Methyl Alcohol Solution. 0.907 0.7949 3.893 + 3.22" + 114-6" + 297.8" 4.416 0 *a033 0'999 3-97 112-0 291.3 Wuter Solution. 0.258 0.9989 3'899 + 1.08" + 107 '5" + 279 -5" Tartaric Diisobutylamide. i8oButylamine was added in theoretical quantity to a cooled solution of methyl tartrate in ethyl alcohol. After standing twelve hours, the amide which had separated was filtered off, the yield being about 70 per cent., whilst more was obtainable by evaporating the mother liquor. 0.1227 gave 11.8 C.C. moist nitrogen at 19"and 756.5 mm. N= 11.01. l'urturic diisobutylamide crystallises in small rhombic pJates melting at 183.5".It is more soluble in the ordinary organic solvents than the normal butyl- and propyl-amides, resembling the isopropylamide in this respect, but it is only very slightly so in water (0.8 per cent.). C!l,H,,O,N, requires N = 10.77 per cent.1858 P. 1 *753 5 '064 1 -007 5'432 0.549 OPTICAL ACTIVITY OF TARTRAMIDE. Rotation of Tuifuric Diisobutylamide. d 20"/4". I?. a:". [a]?. Pyridine So lution. 0.9805 1 '998 + 3.90" + 113.6" 0.9853 0'999 5.64 113.2 Methyl Alcohol Solution. 0-7949 3.899 + 3-67' + 117%" 0'8065 0 '999 5.13 117 -2 Wuter Solution. 0'9991 3.899 4- 2'26" d- 105.6" Tartaria Bi-n-hept ylumide. [ M]y. + 295.3" 894.3 + 305.7" 304.8 + 274.6" A theoretical quantity of n-heptylamine (Kahl baum) was added to a cold solution of methyl tartrate in absolute alcohol, The mixture became a solid mass i n the course of a few hours, and a theoretical yield of the amide was obtained.It was recrystallised from methylated spirit until of constant rotation. It forms elongated, flat plates melting at 183' without decomposition, and is much less soluble in most solvents than are the lower amides above mentioned. I t is insoluble in water, slightly soluble in cold alcohol, and at the ordinary temperature gives only about a 4 per cent. solution in pyridine. 0.2680 gave 19.4 C.C. moist nitrogen at 12' and 728 mm. ; N = 8.22. C,,H,,O,N, requires N = 8.14 per cent. Rotution of Taytaric Bi-n-?Leptylumide. P* d 20°/4". 1. a"," . [a]',"". [MIY. 1.621 0.9789 2.993 + 4.190 + 88-24" + 303.5" Pyridine Solution. 3.579 0'9805 0.999 3.11 88-72 305-2 Methyl Alcohol Solution. 0.9951 0.7955 3.899 + 2'72" t 88.14" + 303.2" Rotation of Tartayic BiphenyEhydrasiJe. Glacial Acetic Acid Solution. 0'5672 1.052 3.899 + 1'88" + 80'55" + 266.80'OPTICAL ACTIVITY OF MALAMIDE. 1859 Rotation of Tarturic Dinzethykamide. P. d 20"/4". 1. a:*'. [a]ioo. [ M]ioe. Nethyl Alcohol Xolution. 4.998 0.8147 3'899 + 23-97' + 151.0" + 265.8" 4.986 0.8147 1.998 12-08 148 *8 261.9 Rotation of Tartaric Diethylamide. MetAp 2 A Zcohol Xolution. 4'997 0'8117 1.998 $11'20" -1-138'1" +281'7" 5 '001 0-8127 1'998 11-21 137'9 251'3 CHEMICAL DEPARTMENT, UNIVERSITY OF BIRMINGHAM.

ISSN:0368-1645    

DOI:10.1039/CT9068901852

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

OPTICAL ACTIVITY OF MALAMIDE. 1859 CLXXX.- The InJEuerLcc of various Xubstituents on the Optical Activity o f Malarnide. By PERCY FARADAY FRANKLAND and EDWARD DONE, M.Sc. THE results recorded in this paper form part of a systematic investigation which is being made by one of us on the rotation of the amides of optically active acids, in connexion with which papers have already appeared on some substitution derivatives of glyceramide (P. Frankland, Wharton, and H. Aston, Trans., 1901, 79, 266), and of tartramide (P. Frankland and Slator, Trans., 1903,83,1349 ; Ormerod, Trans., 1903, 83, 1342 ; and Twiss, preceding paper). The present communication deals with the methylamide, ethylamide, normal- and bo-propylanaide, allylamide, normal- and iso-butylamide, and normal heptylamide of ordinary I-malic acid, as well as with the piperidide, and phenylhydrazide of the same acid, Of these derivatives, only the m-propylamide has been previously prepared (McCrae, Trans., 1903, 83, 1324), whilst the anilide and the three toluidides have been described by Guye and Babel (Arch.Xc". phya. nat., 1899 [iv], 7, 23), and by Walden (Zeit. physiknl. Chern., 1895, 17, 264). The alkylamides were all prepared by the interaction of the amine with diethylmalate, either alone or in alcoholic solution, and either in the cold or at a temperature not exceeding 100'. The yields were in most cases, and especially in the case of the higher amines in which no alcohol was used, very satisfactory. As in the corresponding1860 FRANKLAND AND DONE: THE INFLUENCE OF VARIOUS derivatives of tartramide, the poorest yield was obtained in the case of the isopropylamide.The piperidide was prepared by the prolonged heating of diethyl- malate with piperidine at 130", whilst the phenylhydrazide was prepared, on the one hand by Bulow's method, in which malic acid and phenylhydrazine are heated together at 120-1 40°, and, on the other, by Fischer and Passmore's method, in which an aqueous solution of malic acid is heated on the water-bath with a solution of phenylhydrazine in acetic acid. The products obtained by each of these methods had substantially the same rotation, showing that no racemisation occurs at the higher temperature to which the mixture is heated in the case of Biilow's method. The rotation was in all cases, excepting that of the phenylhydrazide, determined in pyridine, in methyl alcohol, and in glacial acetic acid solution.The rotation of the phenylhydrazide was determined in pyridine and in glacial acetic acid only, in consequence of its insolubility in methyl alcohol. The results of the polarimetric determinations are summarised in the following table :- Glacial Pyridine. Methyl alcohol. acetic acid. Melting * point." p. [MI?. p. Maldi-amide * . . . . . . . . . 157" c= 1.998 - 76.2" - ,, rnethylamide ... 99 4'634 89.6 6.250 10'080 90.0 9.982 ,, ethylamidc ...... 122 4.319 90.6 4.984 10.250 89.1 9.177 ,, n-propylamide . 126 4,530 90.5 5.020 7'896 88.8 11.340 ,, ivopropylamide. 150-151 2'548 69.1 3.803 3.986 69-0 6.039 ,, allylamide ...... 117.5 4.639 72.7 4.804 10-390 74'0 9.095 ,, n-butylamide ...125 3.776 87-1 5.633 10-850 86'3 10.540 ,, isobutylamide.. 121 5.394 86.9 5.316 7.984 89'4 9'128 ,, n-heptylamide.. 131 5.166 88.6 6'001 ,, benzylamide*.. 155.5 c=4*855 101.1 - ,, piperidide ...... 157.5 0'5981 55.2 4.975 ,, phenylhydrazide 214 5'119 54.1 - - - - 11'010 88.8 - - 8.845 - 7'175 55.0 - [bI]r. p. [M]zoo. - c=4'678 - 59.7" 107.9 8'185 117.2 110.3 4.170 116.0 111.8 7.995 117.2 114.3 4-278 115.4 114.7 5.040 114-8 - 9'048 112.8 92.0 3.710 92'1 90.3 6-284 92.5 1025 4.492 86.9 103.3 10.780 87.4 116'5 5.455 106.4 112.0 9.718 104.9 117.4 5.492 106.2 118.4 7.563 105.3 116.1 4'497 103.2 - 9.334 102.3 - e=4*654 63'0 73-7 3.575 +38'5 73.6 6.531 4-40-5 -109.6" 4'267 120.9 - 0.735 - 129'8 - - - * McCrae (Zoc. cit.). In the case of the n-propylamide prepared by McCrae, our results corroborate those obtained by this author with pyridine solution, but our values, given in this table, for the glacial acetic acid solution of thc n-propylamide are substantially higher than his, [M]igo - 101'3", c=4'798.The temperatures a t which McCrae's determinations were made were 20" for maldiamide in glacial acetic acid, 17" in yyridilie ; 22" for the dibenzylamide in glacial acetic acid, and 15" in pyridine solution.SUBSTITUENTS ON THE OPTICAL ACTIVITY OF MALAMIDE. 1861 From the above table it will be seen how greatly the rotation is influenced by the solvent, Thus the alkylamides have a lower lsvo- rotation in pyridine than in methyl alcohol or glacial acetic acid; on the other hand, the benzylamide and the aromatic amides have a higher lsvorotation in pyridine than in glacial acetic acid solution.Again, whilst in the normal series of alkylamides in pyridine solution the laevorotation is almost unaffected in passing from the methylamide to the n-heptylamide, in methyl alcohol there is a slight rise, and in glacial acetic acid solution a distinct decline in the molecular rotation. The derivatives of malamide in this respect exhibit much less regularity than those of tartramide (compare Frankland and Twiss), for in the latter series there is a continuous rise in the molecular rotation from the methyl to the heptyl term in the normal series in pyridine, and probably also in methyl alcohol and in water solution. In both the malic and the tartaric series the rotation of the normal- is greater than that of the iso-propylamide, whilst the relative magni- tudes of the rotation of the normal- and iso-butylamides in both series is dependent on the solvents, but in pyridine solution the isobutylamide, both malic and tartaric, has a higher rotation than the normal butyl- amide.I n both the malic and the tartaric series, the allylamide has a markedly lower molecular rotation, in all solvents, than the normal propylamide, thus showing that the presence of a double bond has not the invariable effect of increasing the optical activity as is often supposed. Malic benzylamide, in pyridine solution, has a higher molecular rotation than the n-heptylamide in the same solvent, whilst in glacial acetic acid the relations are reversed. On the other hand, in pyridine solution, the molecular rotation of tartaric benzylamide is slightly inferior to that of the n-heptylamide. The tartaric piperidide in pyridine solution is practically inactive, and therefore enormously less active than the n-heptylamide ; simi- larly, the malic piperidide, in pyridine and in the methyl alcohol, is much less active than the n-heptylamide, although still strongly lsvo- rotatory; in glacial acetic acid the difference is greatly further em- phasised inasmuch as the piperidide is strongly dextrorotatory.The phenylhjdrazide, again, in both malic and tartaric series, has in pyridine solution a much lower molecular rotation than the n-heptyl- amide, but in glacial acetic acid solution malic diphenylhydrazide has a higher rotation than the heptylamide.We have also found that the rotation of tartaric diphenylhydrazide is much greater in glacial acetic acid than in pyridine solution (see Frankland and Twiss). I n both malic and tartaric series, again, the aromatic amides have a much higher molecular rotation than the alkylamides.1862 FRANKLAND AND DONE: THE INFLUENCE OF VARIOUS EX P E R I M E N T A L. Ma ldirnethy Zamide. Twelve grams of diethyl malate and 21 grams of absolute alcohol were placed in a tall cylindrical bottle immersed in ice. Methylamine was liberated from Kahlbaum's 33 per cent. aqueous solution by heat, passed through a lime drying-tube, and then into the above mixture. When 6 grams of methylamine had been thus passed in, the bottle was stoppered and allowed to stand for three days.On evaporating the alcohol a yield of 50 per cent. was obtained. The methylamide is very soluble in hot or cold water, methyl alcohol, glacial acetic acid, methylated spirit, ethyl acetate, or pyridine, sparingly so in chloroform, benzene, or ether, and insoluble in carbon disulphide or light petroleum. From acetone it was obtained in acicular prisms and plates melting at 99'. 0.1047 gave 15.4 C.C. moist nitrogen at 11' and 762 mm. N = 17.60. C,H,,O,N, requires N = 17.50 per cent. Rotation of Maldimethylamide. P* cl 20"/4". I?. sip. [Wy- Pyridine 8ohthn. 4.634 0.987 1.9984 - 5'12" - 56.01" - 89.6" 10.080 1-001 1.9984 11 *35 56-27 90'0 Met]$ Alcohol XoZution. 6.250 0.8143 1.9984 - 6.97" - 68.50" - 109.6" 9 -982 0.8280 1'9984 11.14 67-42 107.9 Glacial Acetic Acid Solution.4.267 1.060 1.9984 - 6 . w - 75-54" - 120'9" 8.185 1.070 1.9984 12-83 73'26 117.2 Haldiethy Zamide. Seven grams of ethylamine (Kahlbaum) in the form of vapour were passed into a mixture of 11 grams of diethyl malate and 13 grams of absolute alcohol cooled with a freezing mixture. On standing for some days in a stoppered bottle, the whole set into a solid mass of fine white, silky needles. The ethylamide is very soluble in hot or cold water, methylated spirit, chloroform, pyridine, methyl alcohol, ethyl acetate, light petroleum, or Yield 90 per cent.SUBSTITUENTS ON THE OPTICAL ACTIVITY OF MALAMIDE. 1863 carbon disulphide. plates and needles melting at 122'. From benzene it was obtained as white, shining 0,1067 gave 14.0 C.C. moist nitrogen at 1 2 O and 735-1 mm.N = 15.05. C,H,,O,N, requires N = 14.89 per cent. Rotation of Ma Zdieth y lawaide. P. d 20"/4". 1. a20 D * [a]2,0'. Pyyidine Solutioia. 4.31 9 0.9854 1.9984 - 4.10" - 48.19" 10-250 0.9947 19984 9'66 47 *41 Methyl AZcoltol Solution. 4.984 0.8054 1-9984 - 4'71" - 58-69" 9.177 0-8185 1.9984 8-93 59.47 Glacial Acetic Acid Xolution. 4.170 1.056 1.9984 - 5.43" - 61.70" 7.995 1.060 1.9984 10.56 62-34 [MI?. - 90.6" 89'1 - 110'3' 111'8 - 116*0" 117-2 Maldi-n-propylarnide. Twelve grams of diethylmalate were added to 8 grams of n-propyl- amine (Kahlbaum), heat being evolved on mixing. On standing over- night the mixture had become almost solid. Yield 75 per cent. I n order to obtain a theoretical yield, it is necessary to allow the mixture t o stand for several days, or to heat on a warm water-bath for some hours.The propylamide (m. p. 126') is very soluble in water, benzene, alcohol, ethyl acetate, chloroform, pyridine, methyl alcohol, or glacial acetic acid, but insoluble in light petroleum or ether. It was purified by crystallisation from a mixture of benzene and light petroleum. Rotation of Baldi-n-propyhmide. 2). d 20"/4". 1. a","". [a]?. [ M]2,0". Pyridine Solution. 4.530 0.9833 1'9984 - 3.73" - 41.90" - 90.5" 7.896 0.9895 1.9984 6'42 41'11 88.8 Methyl AZcohol Solution. 11.340 093260 1.9984 9'94 53.10 114.7 5-020 0.8061 1'9984 - 4 '28" - 52-91" - 114.3" Gluciul Acetic Acid Solution. 5.040 1.052 1'9984 5.63 53'14 114.8 4.278 1.053 1.9984 - 4 . w - 53'430 - 115.4" 9.048 1.055 1.9984 9.96 52-20 112'81864 FRANKLAND AND DONE: THE INFLUENCE OF VARIOUS MccldiisopropyZamide.10.7 grams of diethylmalate were added to a solution of 5.8 grams of isopropylamine (Kahlbaum) in 8.4 grams of absolute alcohol, but the reaction takes place so slowly in the cold that even after five weeks only a small quantity of the amide bad crystallised out. The mixture was therefore heated in a stoppered bottle in a steam oven for six days. The yield was only 20 per cent. The substance is very soluble in hot water, alcohol, ether, acetic acid, pyridine, methyl alcohol, benzene, ethyl acetate, or acetone, but crystallises from each of these solutions on cooling. It is insoluble in light petroleum, and only very slightly soluble in carbon disulphide. It crystallises from acetone in long, slender needles melting a t 150-1 5 lo.0.1355 gave 15.7 C.C. moist nitrogen a t 15O and 738.4 mm. N= 13.17. CloH2008N2 requires N = 12.96 per cent. Rotation, of Ma ldiisopopykamide. P. d 20"/4". 1. UIp". [a]:O'. [ Pyridine Solution. 3'986 0.9828 0.999 1'25 31'93 69 '0 Aiethyl Alcohol Xolution. 6-039 0.8091 0'999 2-04 41'79 90.3 Glacial Acetic Acid Solution. 2.548 0.9813 1 *998P - 1'80" - 32.01" - 69.1" 3.803 0.8035 i w a 4 - 2-60" - 42.57" - 92.0" 3.710 1.050 0'999 - 1-66' - 42'65" - 92.1" 6-284 1 *056 0.999 2'84 42'83 92-5 Mu ldially lccmide. 11.1 grams of diethylmalate were mixed with 6.4 grams of allylamine (Kahlbaum) and 8.4 grams of absolute alcohol. Heat was developed on mixing, and, after standing for two days, a nucleus was obtained by placing a little of the mixture in a vacuum desiccator.On adding this nucleus t o the remainder, and allowing to stand for a few days longer, a crop of pure white needles separated out from which the alcohol was evaporated. The allylamide is very soluble in hot or cold water, methyl alcohol, methylated spirit, ethyl acetate, chloro- form, glacial acetic acid, or benzene. It is almost insoluble in light petroleum. From a mixture of benzene and light petroleum it was obtained in needles melting a t 11 7-54 Yield 90 per cent. 0.1438 gave 16.3 C.C. moist nitrogenat 12' and '752.8 mm. N = 13.32. C,,H,,03N, requires N = 13.21 per cent.SUBSTITUENTS ON THE OPTICAL ACTIVITY OF MALAMlDE. 1865 Rotation of Muldiallylamide. 2). d 20"/4". 1. a:p. [a]z,o'. [MI::. Pyridine Xolution.4.639 0.9837 1.9984 - 3.13" - 34.31" - 72 9" 10-390 0.9936 1.9984 7-20 34.89 74.0 MethpZ AZcohol Solution. 4.804 0.8056 1.9984 - 3'74" - 48-35" - 102.5" 9.095 o c m 4 1-9984 7'24 48.72 103-3 Glacial Acetic Acid Solution. 10.780 1.064 1'9984 9.45 41'22 87'4 4.492 1.060 1'9984 - 3.90" - 40.99" - 86.9" Maldi-n-but y lamide. 10.2 grams of diethyl malate were mixed with 7.8 grams of normal butylamine (Kahlbaum). Heat was developed on mixing, and, after standing overnight the whole had set solid. The mixture was allowed to stand for a few days longer. The n-butylamide is very soluble in alcohol, ethyl acetate, benzene, or chloroform, insoluble in light petroleum or cold water, but soluble in hot water. It was obtained from dilute alcohol in shining, silver- white plates melting a t 125O.Yield 100 per cent. 0,2278 gave 22.8 C.C. moist nitrogen at 12' and 746.7 mm. N = 11-67. C,,H,,O,N, requires N = 11 *48 per cent. Rotation of Maldi-n-butylamide. P. d 20"/4". I?. aiW. bly. [M]2,0". Pyridina Solution. 10'850 0.9860 1'9984 7'56 35'35 86.3 3,776 o m 0 4 1-9984 - 2.64" - 35-68" - 87.1" Methyl Alcohol Solution. 5'633 0.8037 1.99811 - 4.32" - 47 '74" - 116.5" 10540 0.8160 1'9984 7%9 4 5' 90 112.0 Glacial Acetic Acid Solution. 9-718 1 '052 1'9984 8 -79 43'01 104.9 5 *455 1-052 1-9984 - 5.00" - 43-59" - 106.4"1866 FRANKT~AND ANT) DONE: THE INFLUENCE OF VARIOUS Alaldiisobzltylninide. Ten grams of ethyl malate were added to 10 grams of isobutylamine (Kahlbaum), a little heat being evolved on mixing. After standing for a day and then warming on a water-bath for two hours, the mixture became solid, and a theoretical yield was obtained.The pro- duct is very soluble in hot water, ethyl or methyl alcohols, acetone, ethyl acetate, benzene, chloroform, ether, glacial acetic acid, or pyridine. It was crystallised from R mixture of benzene and light petroleum. Melting point 121'. 0.1456 gave 14.5 C.C. moist nitrogen at 14-5' and 755.8 mm. N = 11.63. C1,H2,0,N, requires N = 11.48 per cent. Rotation of Maldiisobut y lumide. P. d 20"/4". 1. a',". [a]?. [M12,0". Pyridine Solution. 5'394 0.9813 1.9984 - 3.77" - 35.63' - 86.9" 7.9134 0-9a37 1 w a 4 5.75 36'64 89.4 Methyl Alcohol Solution. 5.316 o.ao39 1.9984 - 4.11" - 48.11" - 117'4" 9.128 0.8153 ~"XM 7.22 48-53 118.4 Glaciul Acetic Acid Solution.7 5 6 3 1.051 1 -9984 6-87 43-25 105.3 5'492 1'051 1.9984 - 5-02" - 43.51" - 106.2" MaJdi-n-hptylumide. Sixteen grams of It-heptylamine (Kahlbaum) were added to 10 grams of diethyl malate, the mixture being accompanied by heat evolution. On standing overnight the whole had set to a solid mass. Yield 100 per cent. The n-heptylamide is very soluble in hot alcohol, chloroform, pyridine, glacial acetic acid, or methyl alcohol, readily so in hot benzene or ethyl acetate. It is sparingly soluble in carbon disulphide, acetone, ether, or hot water. From methylated spirit it was obtained in beautiful white, shining plates melting at 1 30*5-131°. 0.2083 gave 15.6 C.C. moist nitrogen a t 12.5' and 746.5 mm. N = 8.71. CI8Hs6O,N2 requires N = 8.54 per cent.SUHSTITUEKTS ON THE OPTICAL ACTIVITY OF MALAMIDE 1867 Rotation of ~~alcli-n-heiutylamicle. P.c.? 20"/4". 1. aton. [a]ioo. [qO Yyridine Xolut ion. 11'010 0.9804 1.9984 5.84 27'08 88.8 Methyl AZcohoE 8olution. A 10 per cent. solution crystallised. Glacial Acetic Acid Solution. 9.334 1'053 1.9984 6-13 31 *20 102.3 5.166 0'9792 1'9984 - 2-73" - 27.01" - 88%" 6.001 0.8035 1-9984 - 3.41" - 35.38' - 116'1" 4'497 1.050 1.9984 - 2.97" - 31'47" - 103.2" Ma Zdipiperidide. Twelve grams of piperidine (Kahlbaum) were added to 10 grams of diethyl malate, and, although heat was evolved on mixing, only a 20 per cent. yield was obtained, even after keeping the mixture at 130° in an oil-bath for three days. A 50 per cent. yield was obtained by heating a similar mixture t o the same temperature for ten days.The progress of the reaction is indicated by the contents of the flask becoming more and more solid on cooling. An attempt to prepare the piperidide by heating piperidine and malic acid together for several days proved unsuccessful. The piperidide is very soluble in methylated spirit, but sparingly so in water, benzene, ethyl acetate, or pyridine. From a mixture of alcohol and acetone it was obtained in flat plate8 melting at 157.5O. 0.126 gave 11.2 C.C. moist nitrogen at 13' and 749.5 mm. N = 10.35. C,,H,,0,N2 requires N = 10.45 per cent, Rotation of illaldipiperidide. Y. i2 2Q0/4'. 1. a',"". [a]?. [ M y . Pyridine Solution. 0-5981 o w 9 4 3.899 - 0.47" - 20.58" - 65'2' Methyl Alcohol Solution. 8.845 o m o o 0-999 1.99 27'47 73'6 Glacial Acetic Acid Solution.3 a575 1.061 1.9984 + 1 *09" + 14-37" + 38'50 6.531 1.067 0.999 1 -05 16 -08 40 -5 4*975 0.8078 1.9984 - 2'21" - 27.41" - 7367" VOL. LXXXIX. 6~1868 OPTICAL ACTIVITY OF MA1,AhlI DE. This compound was prepared, firstly, by Bulow’s method (Annalen, 1886, 236, 194), which involves the use of a high temperature ( 120-140°), and secondly, by Fischer and Passmore’s method (Ber., 1889, 22, 2734), in which the reaction is carried out on the water-bath. As mill be seen below, however, the products obtained by both methods were of substantially the same rotatory power, thus showing that the higher temperature does not lead to any racemisation. Bulow’s Method.-T wenty-eight grams of phenyl hydrazine (Kahlbaum) were added to 20 grams of finely powdered malic acid ; the mixture which solidified with evolution of much heat mas further heated to 120-140O for eight hours until no more steam was evolved.The heating must be begun with caution as there is a sudden evolution of a large amount of steam. The resulting mass, which was of a light brown colour, was first well washed with dilute acetic acid, and then with a solution of ammonium carbonate. The yield was 55 per cent. The substance is almost insoluble in water, methyl alcohol, or light petroleum, sparingly soluble in methylated spirit, and only slightly so in acetone, chloroform, carbon disulphide, ethyl acetate, ether, glacial acetic acid, or pyridine. It was obtained from alcohol in white shining plates melting at 214O with slight decomposition. 0.1232 gave 18.4 C.C. moist nitrogen at ll’and 764.2 mm. N = 17.91. C,,H,,O,N, requires N = 17.83 per cent. Fischer and Passmore’s Method.-Twenty grams of dried malic acid were dissolved in 180 grams of water, and to this were added a solution of 22 grams of glacial acetic acid in 22 grams of water with 40 grams of phenylhydrazine, the whole being then heated on the water-bath in a flask provided with an air-condenser. The reaction took place suddenly after heating for 4 hours, much of the liquid being violently projected into the condenser. The light brown produd was washed successively with water, dilute acetic acid, and ammonium carbonate solution. The product had to be crystallised three times from glacial acetic acid before being obtained in a state of chemical and optical purity. Melting point 214’. The yield was only 20 per cent.THE ACTION OF POTASSIUM CPANIDE ON PULEGONE. 1869 Rotation of ,~~ldip~en~~l~ycE./.azide. p . ti 20"/4". 1. D . [a]r. [MI:, Pyridine Solution. Prepration by 0,9929 1-9984 - 1-75' - 17-22" - 54.1" Ifiilow's method. { !:;:! 0.9987 1.9984 2.51 17.53 55.0 6-390 0.9960 1.9984 2.17 17'06 53-6 Preparation by 4'809 0'9914 1.9984 - 1-65" - 17-28" -54.3" Glacial Acetic Acid Solution. P. d 20°/4". 1. a~o'. [ a l y . [ M]zoo. CHEMICAL DEPARTMENT, 0.7350 1.054 0.999 - 0.32" - 41 '35" - 129'8" UNIVERSITY OF BIRMINGHAM.

ISSN:0368-1645    

DOI:10.1039/CT9068901859

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

THE ACTION OF POTASSIUM CPANIDE ON PULEGONE. 1869 CLXXXI. -Reactions Iiwolving the Addition o f Hydro- gen Cyanide to Carbon Compounds. Part VI. The Action of Potassium Cyanide on Pulegone. By REGINALD w. L. CLARKE and ARTHUR LAPWORTH. THE action of hydrogen cyanide in presence of bases or of potassium cyanide on up-unsaturated ketones leads in all instances hitherto examined to the formation of a p-cyanoketone : CK,:CR’*CO:R + HCN = CNCR,*CHR*CO*R”. I n the case of pulegone, reaction occurs somewhat slowly at the ordinary temperature, but if the ketone is heated on the water-bath with alcoholic potassium cyanide, a product is obtained which has the composition of the expected addition compound, the change being represented by the equation : C,,H1,O -I* HCN = CI1Hl~ON. The substance, which was first referred to in a note by Hann and Lapworth (Proc., 1904, 20, 54), behaves in some respects as would the normal addition product, namely, cyaaodihydropulegone (cyano- menthone), and was for a long time supposed to be that compound.I n accordance with this supposition, it could be hydrolysed by acids 6 a 21870 CLARKE AND LAPWORTH : REACTIONS TNVOLVING ADDITION or alkalis, being converted into a saturated ketonic acid, namely, ment honecarboxylic acid, UHMe<LYH2*CH2>CH*C3/Ie,*C0,H. CH,--CO Nevertheless, the supposed cyanoketone exhibited many characters mainly negative in type, which distinguished it from the others previously examined. Thus i t did not react with hydrazines, semi- carbazide, or hydroxylamine, and could not be made to yield a cyano- hydrin.When boiled with alkalis, even in presence of ferrous hydroxide, no decomposition into pulegone and hydrogen cyanide cmld be detected, although p-cyanoketones as a rule are easily decom- posed in this manner. The inactivity of the compound was suspected to be due to a manifestation of steric hindrance, although later a difficulty arose in applying this assumption, for the ketonic acid, to which it gave rise, reacted readily enough with the hydrazines and with hydrogen cyanide. The clue to the character of the substance was finally obtained in the following manner. Menthonecarboxylic acid is converted with great readiness into an unsaturated lactone, UH,*CH, CHMe/ \C*CMe,\ \CH,--CH /CO, \O-- when warmed with mineral acids or when treated with acetyl chloride.This compound is precisely analogous in type to the anhydride obtained by VorlPnder (Annulen, 1906, 345, 188) from ‘ I pulegoneacetic acid,” of which the present substance is the next lower homologue. When the anhydro-derivative of menthonecarboxylic acid is shaken with ammonia, it yields a mixture of substances from which, by frac- tional crystallisation, a compound having the formula C,,H,,ON, and identical in all respects with the nitrogenous compound obtained by the action of potassium cyanide on pulegone, is obtained. To this sub- stance, therefore, must be assigned the constitution and is referred to in the paper as an “anhydramide,” as it may be regarded as formed by the dehydration of menthonecarboxylic amide.OF HYDROGEN CYANIDE TO C!ARBON COMPOUNDS.PART VI. 1871 The foregoing formula is adopted instead of the altern a t' ive one, CHMe/ '\CH*CMe,\ CH,*CH '\CH,--C/ /co, "-- for several reasons. In the first place, the substance behaves as if it contains an ethylenic linking, being capable of decolorising a dilute solution of bromine in acetic acid even when excess of sodium acetate is present, and also of reducing an ice-cold solution of potassium permangsnate. Secondly, the exceptional tondency of these menthone compounds, as well as those described by Vorliinder (Zoc. cit.), to form anhydro-derivatives, is shared by the menthonecarboxylic acid, and therefore is probably to be attributed to the disposition of the carbon ring to assume the cyclohexene form. The corresponding configuration is used by Vorliinder for the anhydramide of '' pulegoneacetic acid." Menthonecarboxylic anhydramide is not the only product obtained by the action of potassium cyanide on pulegone.Menthonecrtrboxylic acid is also produced in considerable quantity when the reaction is carried out at the water-bath temperature, and results from the action of potassium hydroxide on the anhydramide. A third substance formed has the composition C,,H,,O,N, and is a monobasic acid which must be analogous in constitution to mesitylic acid. It is therefore to be formulated as CHMe / \CH*Clrie,, and is a \CH,*C(CO,H)/ I CH,-CH2 \NH*CO hydroly tic product of the intermediate cyanomenthonecyanohydrin, CH,*CH, CHMJ >CH*CMe,* CN. The latter compound mas a t last isolated from the products obtained by leaving pulegone in contact with a solution of potassium cyanide containing free hydrogen cyanide at the ordinary temperature for a considerable period.Since the cyanohydrin can only have been formed from cyanomenthone itself in the first instance, its production indicates that the ketonitrile must have at least a transient existence, and many attempts were made t o isolate the latter, but without success. On leaving pulegone with potassium cyanide solution in the cold, the only product was the cyanohydrin, in spite of the fact that much free alkali was present. Attempts to remove a molecule of the hydrogen cyanide from the molecule of the cyanohydrin were therefore made. At the ordinary temperature, alkali, even in the presence of ferrous \CH,-C(OH)*CN1872 CLAliKE AND I,BP\VOEI'H : 1tEBCTIONS INVOLVlNG ADDITION hydroxide, was without action ; a t higher temperatures hydrogen cyanide could be removed, b u t the product mas always the an- hydramide.By heating the cyanohydrin alone at its melting point, hydrogen cyanide is eliminated, but, again, the cyanomenthone at first produced at once undergoes isomeric change, and the anhydramide is the only substance which can be isolated. I n the latter instance, i t seems clear that the change must be represented as the result of the conversion of the cyanomenthone into its enolic form, in which the new ring formation then trkes place, CH,*CH, CHMe/ \ C CIC31e2 C N \OH \ca,---c// CH,* CH, CHMe/ \C*CMe \NH- \CH,---& ,)Co. Although menthonecarboxylic acid could not be reduced by z i m and acetic acid, sodium amalgam, or sodium and ethyl or amyl alcohol, it exhibits most of the usual characters of a y-ketonic acid, and reacts readily with phenylhydrazine, yielding the ring compound CHMe/ \C--CMe, CH;CH, \CH,-C/ \CO or \NH*NPh/ CH , CH, CHM~/ \CH*CMe, \CH,,--C/ \co, " NN--NPh/ which is the most characteristic derivative of the acid yet obtained ; the oxime and semicarbazide are difficult to obtain in a pure state.I n presence of potassium cyanide, it is converted into a mixture of isomeric cyanolactones : E x P E H. I M E N T A L. When piilegone is left in a cold solution of potassium cyanide in dilute alcohol it slowly absorbs hydrogen cyanide, and at the end of a week at the summer temperature is partially converted into cyano- menthonecyanobydrin.A t 80-100' a mixture of this compoundOF HYDROGEN CYANIDE TO CARBON COMPOUNDS. PART VI. 1873 with menthonecarboxylic acid, the anhydride of menthonecarboxylic amide, and the lactame of aminomenthanedicarboxylic acid is formed. The relative proportion of the products obtained varies very greatly with the conditions used, and directions are given in the following pages for the preparation of each of the four compounds directly from pulegone. Menthonecai.box@ Anlydmmide, CH Me /CH,'CH2 \C*CMe,\ \CH,--C/ / C O . -A solution of pulegone (45 grams) in 96 per cent. alcohol (75 c.c.) is mixed with a solution of potassium cyanide (25 grams) in water (30 c.c.) and the whole heated on the water-bath under a reflux condenser; at the end of about half an hour one molecular proportion of acetic acid, or, better, ethyl acetate, is slowly introduced beneath the surface of the liquid.The liquid, which at first forms two layers, gradually becomes homogeneous, and a t the end of a further half hour is cooled and poured into a large bulk of water, when an oil is deposited which slowly becomes semi-solid. The average yield of the dried solid obtained from the above quantities was 45 grams. The product may be purified by fusing it in a round bottomed flask for ten minutes, a process which serves t o convert any cyanomenthonecyanohydrin present into anhydramide, after which crystallisation from alcohol yields the pure anhydramide without difficulty. With large quantities of crude material, it is probably simpler to decompose the cyanohydrin present by boiling the material with a little alcoholic potash instead of fusing it.\NH- 0.2052 gave 0.5521 CO, and 0.1726 H20. 0.1703 ,, 11.8 C.C. of moist nitrogen at 19O and 757 mm. N = 7.9. C = 73.4 ; H = 9.3. C,,HI7ON requires C = 73.7 ; H = 9.5 ; N = 7.8 per cent. Menthonecarboxylic anhydramide is readily soluble in cold ethyl acetate, ethyl or methyl alcohols, chloroform, benzene, or acetic acid, and also in hot carbon disulphide, acetone, or ether, but is only sparingly dissolved by hot light petroleum or water, 'l'he crystals are translucent needles which have straight extinction in polarised light, their directions of greatest length and elasticity being a t right angles. The fused substance sets on cooling somewhat rapidly in long needles separated by air spaces, and when these are examined in convergent polarised light the acute bisectrix of a biaxial figure of narrow axial angle is sometimes seen to emerge nearly perpendicularly to the field.The dispersion is weak and the double refraction strong and negative in sign. For the determination of its optical activity, 0-25 15 gram dissolved1874 CLAliKE AND LAPWORTH : REACTIONS INVOLVING ADDITION and made up to 25 C.C. with absolute alcohol was examined in a 2-dcm. tube at 1 7 O ; the observed rotation was + 1-34', whence [a]D +66.6. This compound, which was for a long time thought to be cyano- menthone itself, is quite different in character from all the other /3-cyanoketones. Thus, when it is heated with alcoholic potassium or sodium hydroxide containing ferrous hydroxide, it does not yield a trace of ferrocyanide, and pulegone is not obtained from it by this process.Further, i t does not evince any tendency t o react with hydrazines, with semicarbazide, or hydroxylamine ; it does not yield a cyanohydrin with hydrogen and potassium cyanides, and is hardly affected by amyl nitrite or ethyl oxalate and cold sodium ethoxide. The anhydramide behaves as an unsaturated compound, and when shaken with a cold solution of potassium permanganate, decolorises the liquid a t once ; its solution in acetic acid readily absorbs bromine even in presence of excess of sodium acetate (compare Trans., 1904, 85, 38). By the action of phosphorus pentachloride a t 100' it is slowly converted with evolution of hydrogen chloride into a dark red sub- stance.This gave a small quantity of oil when distilled, but it was not chlorocyanomenthene as was anticip:ited, for it was found to contain much phosphorus. The anhydramide dissolves in cold, strong sulphuric acid without change, is slowly hydrolysed by hot, strong hydrochloric or hydrobromic acid, and somewhat rapidly by alcoholic potassium hydroxide, in each case menthonecarboxylic acid being the main organic product, illent?~oizecarboxy& acid, CHMe<CH,--cu CH2'CH2>CH*CMe2*C02H, may be obtained from the anhydramide by the methods already mentioned, but it is more convenient to. prepare it directly from pulegone by the same method as was recommended for preparing the anhydramide, but no acetic acid or ethyl acetate is added, and the heating is continued for four to five hours, after which the bulk of the alcohol is removed by distillation.The residue is diluted with water and poured into excess of dilute hydrochloric acid. After standing for twenty-four hours, the insoluble matter which has separated is collected, washed with water, then extracted with benzene, which leaves undissolved the nitrogenous acid (p. 1879) formed at the same time, and the filtered benzene solution is extracted with dilute caustic soda solution, from which the ketonic acid is subsequently recovered by acidification. The compound is crystallised, first from dilute acetic acid, and, finally, from ethyl acetate. On analysis : 0.2002 gave 0.4864 CO, and 0.1636 H,O. C = 66.5 ; H = 9.0.C,,H,,O, requires C = 66.7 ; €I = 9.1 per cent.OF HYDROGEN CYANIDE TO CARBON COMPOUNDS. PAKT VI. 1875 On titration with sodium hydroxide, 0.1962 of the acid required 10.0 C.C. of N/IO alkali for neutralisation, whence the equivalent of the compound was 196.2, whilst the number calculated for a monobasic acid, CllH1,O,, is 198. Menthonecarboxylic acid dissolves readily in methyl or ethyl alcohols, acetone, benzene, chloroform, ether, acetic acid, or ethyl acetate, and sparingly in water and light petroleum. It separates from ethyl acetate in rosettes of small needles, which melt at 120-12lo. Under the microscope, the needles are seen to be flat- tened, and in polarised light show straight extinction, and the relative directions of greatest length and elasticity vary according to the orienta- tion of the crystal examined.After fusion, it solidifies slowly CO opaque masses of very small quadrangular plates or elongated needles. For the determination of its oFtical activity, 0.2500 gram dissolved and made up to 23 C.C. with absdute alcohol was examined in a 2-dcm. tube. The rotation observed was - 0.46', whence [a], - 23-0. The compound behaves as a saturated ketonic acid, and when dissolved in sodium carbonate solution does not a t once decolorise a cold solution of potassium permanganate ; its solution in acetic acid does not decolorist: bromine if sodium acetate is present. J t is very stable towards reducing agents, and all attempts to convert i t into the corresponding hydroxy -acid were unsuccessful.It did not appear to be affected by sodium amalgam, zinc dust, and acetic acid, stannous chloride in hot alkalis or colcl acids, and even after attempted reduction with sodium and boiling ethyl or amyl alcohols was recovered almost unchanged. Attempts to reduce it by any agent in the presence of mineral acid resulted in the production of the anhydride mentioned later. The sernicccrbaxone, Cl,Hl,02:N,H*CO*NH,, was prepared by the usual method and purified by crystallisation from hot methyl alcohol, employing a Soxhlet extractor. 0.1049 gave 15 C.C. moist nitrogen at 18" and 759 mm. C12H210,N, requires N = 16.5 per cent. It is sparingly soluble in methyl or ethyl alcohol, chloroform, acetone, ethy 1 acetate, benzene, carbon disulphide, or carbon tetra- chloride.It separates from boiling methyl alcohol in small needles melting at 1 8 8 O with evolution of gas, but without darkening. N = 16.4. CH2*UH, PzcEegenyZpyridcczinone, CHMe/ \C--CAEe, \CH,-C/ 'co (I), \NH*NPh/ is formed when the ketonic acid is heated with phenylhydrazine acetate, and usually crystallises when the product is washed with acid, It is purified by crystallisation from alcohol.1876 CLARKE AND LAPWORTH : XEACTIOSS INVOLVING ADDITION 0.1785 gave 16.0 C.C. of moist nitrogen at 1 3 O and 743 mm. N = 10.3 C17H,,0N, requires N = 10.4 per cent. The substance is neutral in character and is not affected when boiled with dilute alkalis. It is soluble in most of the usual organic solvents with the exception of light petroleum, and forms crystals melting at 93'.The crystals under the microscope present the appearance of opaque or translucent needles, which in polarised light have extinction directions inclined a t about 45' to their length. The substance, after fusion betwesn glass slips, sets very slowly to patches of transparent needles, through which the axis of a biaxial figure of wide angle may occasionally be seen i n convergent polarised light. /CH, CH, Pulegenylisooxaxolone, CHMe \CH*CMe, \CH,--C/ \GO (f), "-o/ is the subtance obtained when menthonecnrboxylic acid is heated on the water-bath with hydroxylamine in alcoholic solution, and is purified by crystallisation from alcohol. 0.2076 gave 12.4 C.C. of moist nitrogen at 15' and 762 mm. Cl,Hl,O,N requires N = 7.2. Cl,H170,N ,, N = 6.6 per cent. N = 7.0.The compound is not soluble in alkalis, but is more readily so in dilute mineral acids than in water. It separates from alcohol in glistening crystals melting at 113-1 14'. Under the microscope, the crystals are seen as brilliant, well-formed, quadrangular plates, having straight extinction in polarised light. These in convergent light show a bisectrix emergent at right angles to the field, the axial angle being large, the double refraction positive in sign and strong, whilst the axial dispersion is weak. The fused substance solidifies between glass slips to areas of parallel, transparent needles, separated by air spaces, and most of these have a bisectrix emerging at varying inclinations to the field, ,CH,-OH, The anhydvide, CHMe \C*CMe, \CH2-CH \()---/ \GO, is obtained in small quantities when menthonecarboxylic acid is warmed with mineral acids; it is best prepared, however, by heating the ketonic acid with excess of acetyl chloride for some hours, at the end of which time the acetyl chloride is removed by distillation, and the cooled residue agitated with a di1ut.e mlution of sodium bicarbonate,OF HYDROGEN CYANIDE TO CARBOS COMPOUNDS.PART VI. 187 the neutral substance being extracted with ether. The dried ethereal extract is then fractionated at the ordinary pressure and the portion boiling at 245-247' cooled in a freezing mixture, The crystals which separated were drained on cold, porous earthenware and analysed : 0,2124 gave 0.5661 CO, and 0.1702 H,O. The anhydride forms massive transparent rhombs, often approaching a centimetre in length.It is readily soluble in the usual organic solvents, but is only recrystallised from them with much difficulty; it melts a t 17.5-18'. 0.8500 gram dissolved and made up to 25.2 C.C. with absolute alcohol, was examined in a 2-dcm. tube a t 18'; the observed rotation was + 1*46", whence [a ID + 73.6. When shaken with cold, dilute alkalis, even in the fused stabe, it does not at once dissolve, but disappears a t the end of some hours or days, according to the temperature of the air. It is also reconverted into the ketonic acid by long-continued contact with water. The substance, which is somewhat volatile in steam, has a marked odour of cocoa-nuts, and this renders it easy to detect small quantities of the ketonic acid. as it is merely necessary to boil it with 20 per cent.sulphuric acid when the odour of the anhydride soon becomes noticeable. It has the properties of an unsaturated compound, a t once absorbing bromine even in presence of sodium acetate and acetic acid. When it is shaken with a cold solution of potassium permanganate, the colour of the latter is almost instantaneously discharged. I n the expectation that the snhydro-compound would readily be con- verted into the amide of menthonecarboxylic acid, a portion of the former was shaken with aqueous ammonia (sp. gr. = 0*880)* until it was converted into a mass of white needles. These were collected, washed, and crystallised from alcohol. Analysis of a specimen dried at 100" gave the following result : 0.2034 gave 14.25 C.C. of moist nitrogen at 19' and 762 mm.N = 8.1. C = 72.7 ; H = 8.9. CllH1602 requires C = 73.3 ; H = 8-8 per cent. C,,H,,O,N requires N = 7.1, C,,H170N ,, N = 7.8 per cent. The compound was therefore an anhydride of the amide, and was finally identified with the substance previously regarded as cyano- menthone, obtained by the action of potassium cyanide on pulegone. It melts a t 165', alone or when mixed with the supposed cyano- menthone. When 0.2518 gram was dissolved and made up to 25.1 C.C. with absolute alcohol, and examined in a 2-dcm. tube a t 22", a rotation of + 1-34' mas observed, whence [aID + 67.0.1878 CLARKE AND LAPWORTH : REACTIONS INVOLVING Al)l)ITION -This compound was obtained on attempting to prepare cyanomenthone by the action of potassium cyanide on pulegone in the cold.The ketone, dissolved in a large bulk of alcohol, was mixed with an aqueous solution of potassium cyanide, the amount of water and alcohol being so regu- lated that the whole was a homogeneous liquid. The mixture was allowed to remain at the ordinary temperature for about a week, and afterwards worked up by diluting i t with water, when the oil which separated gradually became semi-solid. The solid matter was freed from adherent pulegone either by spreading it on porous porcelain or removing the pulegone with a current of steam. It was found that the same product was obtained whatever proportions of potassium cyanide were used i n the first instance. 11 certain quantity of the anhydramide already described was usually formed a t the same time, but cyano- menthone itself was never detected.The cyanohydrin was purified by crystallisation from ethyl alcohol. On analysis : 0.1438 gave 16.7 C.C. of moist nitrogen a t 17'and 771 mm. N = 13 6 . C,,H,,ON, requires N = 13.6 per cent. Cyanomenthonecyanohydrin is fairly soluble in cold ethyl or methyl alcohol, acetone, ethyl acetate, chloroform, or ether, readily so in the hot solvents, sparingly so in carbon disulphide or carbon tetrdchloride, and is almost insoluble in light petroleum or water. It melts somewhat indefinitely a t 195-197', and decomposes if heated to its melting point for a short time without blackening, hydrogen cyanide being evolved. 0.2606 gram dissolved in absolute alcohol and made up to 25-1 c.c., was examined in a 2-dcm. tube at 16'; a rotation of - 0.63O was observed, whence [a], - 3 0 3.The crystals from alcohol are six- sided plates or elongated flat needles, having straight extinction in polarised light. The axial plane is identical with the plane of the larger faces of the crystals, but crushed fragments of the substance, examined in convergent polarised light, occasionally show the bisectrix of a figure of moderate axial angle. The double refraction is strong and positive in sign; the dispersion is weak. The compound loses hydrogen cyanide readily and quantitatively at its melting point, and the residue sets to a mass of needles which, after recrystallisation, melted at 164-1 65', and were identical with men thonecarboxylic anh y dramide. A t the ordinary tern perat ure, however, the cyanohydrin exhibits a remarkable degree of stability, and is not decomposed by cold alcoholic potassium hydroxide even in presence of ferrous hydroxide, an agent which decomposes most cyano- hydrins with great rapidity.No precipitate is formed when silver nitrate is added to the alcoholic solution, although cyanohydrins, asOF HYDROGEK CYANIDE TO CARRON COMPOUN~S. PART -VI. 1879 a rule, are quantitatively decomposed by such treatment. When warmed with alcoholic alkalis in presence of ferrous hydroxide, the substance is decomposed and the ferrous hydroxide dissolves, but the product in all instances is the anhydramide and not cyanomenthone ; the latter compound must be regarded as a very unstable one, being quickly converted into the anhydramide by heat or by the action of warm dilute alkalis.The cyanohydrin is slowly converted by hydrochloric acid at 100' into the nitrogenous acid described below, but when heated with strong hydrobromic acid on the water-bath, it suffers more profound decomposition, and yields little but ammonium bromide and menthone- carboxylic acid after prolonged treatment. The Zuctame qf aminomenthanedicurboxylic acid, CHMe<CH2--C H2\ CH*CMe CH,*C(CO,H)/ 2>co, \NH-- is produced in considerable quantities when pulegone is heated with potassium cyanide in dilute alcohol for several hours, and was therefore obtained in considerable quantities as a by-product in the preparation of menthonecarboxylic acid from pulegone. It was freed from attend- ant impurities by extracting it repeatedly with warm benzene and then recrystallising it from glacial acetic acid : 0.2454 gave 0.5751 CO, and 0.1860 H,O.0.1346 ,, 7.7 C.C. moist nitrogen a t 20' and 757 mm. N = 6.5. C,,H,,O,N requires C = 64.0 ; H = S.4 ; N = 6.2 per cent. C = 63.9 ; H = 8.4. On titration with standard alkali, 0.3034 gram required 13.7 C.C. N/10 NaOH for complete neutralisation, the equivalent was therefore 222, whilst the number calculated for a monobasic acid of the above formula is 225. This compound is very sparingly soluble in water, light petroleum, benzene, or chlorofcrm, somewhat more readily so in alcohol, acetone, or ethyl acetate, but is freely dissolved only by glacial acetic acid. It separates from a hot solution in the latter solvent in small crystals melting a t 237-239" after some preliminary sintering.Under the microscope, the substance presents the appearance of nodular aggregates of small needles, of which the optical characters could not be directly determined. The crystals obtained by fusing the substance between glass slips are transparent, well-formed needles, which slowly become opaque owing to contraction and consequent cracking ; a part of the material often sublimes when heated, and the deposit consists of brilliant, well-formed, but minute plates, faceted in a complicated manner.1880 CLARKE ASD LAPWOR'l'li : ItEAC'I'IOKS INVOLVING ADDITIOS The substance is extreniely stable and many attempts were made to convert i t into hydroxynienthanedicarboxylic acid or its lactone, but without success. It was not appreciably affected by strong boiling potassium hydroxide, hydrochloric mid, or dilute sulphuric acid.When dissolved in strong sulphuric acid to which sodium nitrite or amyl nitrite had been added, a slight change occurred on warming, but the greater portion of the material was recovered unchanged. Hypobromites or hypochlorites also had little o r no effect at the temperature of the water-bath. When heated in a closed tube with fuming hydrochloric acid, no change was noticed a t 120°, but after being heated to 1'70-180" for ten hours, the liquid separated into two layers, the upper one a dark brown oil. The whole was diluted with water and extracted with ether, and the ethereal solution shaken repeatedly with sodium hydroxide solution. On evaporation of the ether, a neutral oil remained.An attempt was made to distil this, but a t 280" it evolved hjdrogen chloride and the distillate had an odour of paraffin and peppermint, so that the original oil was probably a mixture of hydrochlorides of unsaturated ketones or of a hydro- carbon. The alkaline extract when acidified deposited an oil, which slowly solidified. After being drained on porous porcelain and crystal- lised from ethyl acetate it was obtained in needles melting at 122' and having all the characters of menthonecarboxylic acid. Addition of Hydrogen Cyanide to Menthonecarboxylic Acid. tion of Isomeric Qyanohydrina (Cyanon~entholcarboxylactones), Forma- -Menthonecarboxylic acid (1 mol.) dissolved in the requisite quantity of dilute sodium carbonate solution, mas mixed with an aqueous solution of potassium cyanide (14 mols.) in a flask which was afterwards closed with an india-rubber stopper, through which passed a dropping-funnel containing dilute sulphuric acid (1 mol.).A few C.C. of the sulphuric acid were allowed to run very slowly into the flask, which was then closed, and the addition of the remainder of the acid allowed to occur automatically (compare Trans., 1906,89,964). A t the end of twenty- four hours, the alkaline liquid was rendered slightly acid with sul- phuric acid, the dark brown oil which separated being washed first with water, then with warm hydrochloric acid and finally extracted with petroleum. The petroleum solution was shaken with dilute sodium carbonate solution to remove acids, a process which caused theseparation of needles, but theso dissolved on the addition of a little benzene. On evaporating the dried benzene-petroleum solution, a substance separated, which WLLS purified by recrystallisation from light petroleum.On analysis : 0.1952 gave 0.4969 CO, and 0,1952 H,O. C,,H170,N requires C = 69.6 ; H = S.2 per cent. a-CyanomentlzoZcas~boxylactolze is readily soluble in all the usual organic media, and crystallises from light petroleum in slender needles melting at 48-49'. The crystals are opaque needles, of which the optical properties are difficult to determine. When fused between glass slips, the substance sets to a mass of needles, through most of which a bisectrix of a narrow angled axial figure emerges obliquely. The double refraction is weak and positive in sign. The compound is not acted on by cold aqueous alkali, but when boiled with aqueous sodium hydroxide dissolves, being converted into menthonecarboxylic acid and hydrogen cyanide.It is somewhat stable towards mineral acids, but when warmed with fuming hydro- bromic acid yields ammonium bromide and ment honecarboxylic acid, ~-C~anornentholc~rborcylactone was obtained from that portion of the original oil which did not dissolve in light petroleum. It was isolated by dissolving the residue in benzene, shaking the resulting solution with sodium carbonate, and evaporating, the crystals which separated being purified by recrystallisation from a mixture of benzene and light petroleum. On analysis : C = 69.9 ; H= 8.4. 0.1845 gave 0.4683 CO, and 0.1371 H,O. C,,H170,N requires C = 69.6 ; H = 8.2 per cent. The substance is very readily dissolved by chloroform, benzene, or alcohol, somewhat readily also by ether or ethyl acetate, but is very sparingly soluble in light petroleum. It separates from a mixture of benzene and light petroleum in large, transparent crystals melting a t 126-127". The prisms are well formed, and in convergent polnrised light some of these show the bisectrix of an axial figure of moderate angle. The double refraction is strong and negative in sign; the dispersion is also fairly strong, the angle for blue light being greater than that for red. The axial plane is perpendicular to the direction of greatest length in the crystal. After fusion on a glass slide beneath a cover-slip, the lactone rapidly sets to patches of radiating or parallel needles, the optical properties of which were identical with those of the prisms just described, C = 69.2 ; H = S.3.1882 DEHN AND THORPE: XO'I'E ON THE In cheulicd properties the compound closely resembles the isomeric cyanolactone. The authors desire to express their thanks to the Research Fund Committee of the Chemical Society for a grant which defrayed part of the cost of the investigation. CHEMICAL DEPARTMENT, GOLDSMITHS' COLLEGE, NEW CROSS, S.E.

ISSN:0368-1645    

DOI:10.1039/CT9068901869

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年代:1906

数据来源: RSC

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1882 DEHN AND THORPE: XO'I'E ON THE CLXXXI1.-Note on the Anhydride of Phenylsuccinic Acid. By FRANK BERNHARD DERN and JOCELYN FIELD THORPE. THE anhydride of phenylsuccinic acid has been described as melting a t 40-50' (Spiegel, Anqtalen, 1883, 219, 32), 53-54' (Alexander, An~zalen, 1890,268, 75), 150' (Bredt and Kallen, Annnten, 1896, 293, 347),and as existing in two forms, one melting at 53-54',the other at 150' (Wegscheider and Hecht, Monatsh., 1903, 24, 418). I n spite of the fact that the compound melting at 150° mas analysed and titrated by Bredt and Kallen, we are of the opinion that it is an impure form of the acid, and that phenylsuccinic anhydride exists in only one form, which melts at 53-54', The errors concerning the properties of this compound have evidently arisen owing to its remarkable instability in the presence of moisture.Thus it is apparently impossible to prepare the pure anhy- dride by distilling phenylsuccinic acid under diminished pressure, and although the distillate boils constantly, yet a considerable quantity of unchanged acid is always carried over by the anhydride vapour. The use of this method, both by Bredt and Kallen and by Wegscheider and Hecht, for the preparation of the anhydride accounts for the presence of unchanged acid in the products with which they worked. I n the following experiments the experimental details given by these investigators have been closely followed. Distillation of Phenylsuccinic Acid under Di,minished Pressure. The distillation of phenylsuccinic acid was conducted according to the directions given by Wegscheider and Hecht, about 50 grams of the acid being slowly distilled under a pressure of 16 mm.The distillate, which passed over constantly at 196O, solidified after standingANHYDRlDE OF PHENYLSUCCINIC ACID. 1883 some hours and then melted at Yrom 53-1159 product gave the following figuros on analysis : 0.2012 gave 0.4892 CO, and 0.0856 H,O. A specimen of this C = 66.31 ; H = 4-72. C,,H,08 requires C = 68.1 ; H = 4.5 per cent. CloHlo04 ,, C=61*8; H=5.2 ,, The solidified distillate was dissolved in dry ether and allowed to stand, when the characteristic crystals of phenylsuccinic anhydride slowly separated. The product melted sharply at 53-54O. Another portion of the same distillate was dissolved in hot xylene, wbich had previously been purified by distillation over sodium and the solution placed in a steam-heated oven for some days, when the solid which had then separated was isolated by filtration and washed with a little xylene.It melted at 150-153', and gave the following result on analysis : 0.1984 gave 0.4500 CO, and 0.0991 H,O ; C = 61.86 ; H = 5.55. The compound dissolved instantly in cold aqueous sodium carbonate with effervescence. Another portion of the distillate was placed in a test-tube, which after being sealed was placed in a steam-heated oven for several days. Crystals slowly separated, which, after the deposition had ceased, were isolated and found to melt at 150 -156O. The compound was instantly soluble in sodium carbonate solution with effervescence. The products melting at 150-153' and 150-156' were recrystal- lised from hot, pure xylene, and in each case small needles melting a t 168O separated from the solutions on cooling : Cl0HZ0O4 requires C = 61 43 ; H = 5.2 per cent.0.2083 gave 0.4722 CO, and 0.1037 H,O; C=61.82; H=5*53. CloHl,04 requires C = 61.8 ; H = 5.2 per cent. This was evidently, therefore, pure phenylsuccinic acid. Another portion of the solidified distillate melting at 53-115O was treated according to the method employed by Bredt and Kallen. It was thoroughly ground with cold light petroleum (b.p. 110-1 20°), and the solid residue, after being collected by filtration and washed with light petroleum, recrystallised from this solvent. The crystals which separated melted a t 150-152' : 0.2078 gave 0.4713 CO, and 0*1015 II,O.C,,Hlo04 requires C = 61.8 ; H = 5.2 per cent. The compound dissolved in dilute aqueous sodium carbonate solution with effervescence, and, when recrystallised from xylene, yielded t h e pure acid melting at 168'. C = 61.85 ; H = 5-42, VOL. LXXXIX. 6 H1884 PATTERSON AND KAYE : Formation of Phenylsuccinic Anhydride from Phenylsuccinic Acid on Treatment with Acetic Anhydride und Subsequent Distillation. Fifty grams of the acid were mixed with a large excess of fresbly distilled acetic anhydride and heated on the sand-bath for five to six hours, when the acetic acid and unchanged acetic anhydride were distilled off, as far as possible, under the ordinary pressure and the residue distilled under a pressure of 16 mm. The anhydride passed over constantly at 196-197' as a colourless oil, which instantly solidified on cooling to a hard crystalline cake melting at 53-54' : C = 67.94 ; H = 4.62.0.19'76 gave 0,4923 CO, and 0.0821 H,O. C,,H,O, requires C = 68.1 ; H = 4.5 per cent. This anhydride, when dissolved in a little dried xylene and the solution placed in a steam-heated oven, deposited no solid even after three months. A portion sealed in a dried tube and also heated at 100' for the same period of time deposited no crystals, and another portion when sealed remained unchanged after standing three months at the ordinary temperature. Some of the anhydride was recrystal- lised from dry ether, and the large monoclinic crystals obtained in this way sealed in a tube which had been evacuated by the aid of the mercury pump. After three montbs, the surfaces of the crystals remained bright, and the melting point was found to be the same as before sealing. The anhydride also remained unaltered when kept either in an evacuated desiccator or in a sealed tube filled with dry air, but on exposure to the air of the laboratory it gradually passed into the acid, a change which was almost complete after three weeks (compare Hann and Lapworth, Trans., 1904, 85, 1367). UNIVERSITY OF MANCHESTBR.

ISSN:0368-1645    

DOI:10.1039/CT9068901882

出版商:RSC    

年代:1906

数据来源: RSC

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1884 PATTERSON AND KAYE : CLXXXII1.-Studies in Optical Superposition. Part II: By THOMAS STEWART PATTER~ON and JOHN KAYE. IN the first part of this investigation (Patterson and Taylor, Trans., 1905, 87, 33, 122), di-Z-menthyl d-tartrate and its diacetyl derivative were described and data were given for their rotations, as well as for that of menthol, both in the homogeneous state and in solution. The present communication deals with the corresponding I-menthyl deriv- atives of Ltartaric acid.STUDIES IN OPTICAL SUPERPOSITION. PART 11. 1885 I n the first part, however, the chief problem for the elucidation of which the investigation was undertaken was not discussed, because the data secured were insufficient to supply a definite answer. The data which we now publish, whilst having, as in the former case, an interest of their own, are still insufficient to decide the main question at issue, but in consequence of the appearance of a paper by Rosanoff (J.dmer. Chent. Xoc., 1906, 28, 525) we will state briefly here the ideas which we wish ultimately to test. The rotation of a compound built up of two active radicles, for example, d-amyl Z-lactate, may be regarded as the sum of two rotations, say ao and p", one contributed by each radicle. van't Hoff is responsible for the assumption, very reasonable at the time it was made, that the rotation of Z-amyl Z-lactate may be represented as equal to -a'+pO, a quantity obtained by merely reversing the sign of rotation of the amyl radicle. This assumption is known as the principle of optical superposition, and a considerable amount of experi- mental work has been undertaken by Guye and by Walden with the object of proving it.A consideration of this work convinced us, firstly, that the experi- ments of Guye and Walden have in reality no bearing on the matter in hand, and, secondly, that the validity of van't Hoff's assumption is distinctly open to doubt.. According to a reference in Meyer and Jacobson's Lehrbuch (vol. i, 2nd edition, p. l04), Urban (Arch. Pharrn., 1904, 242, 51) has arrived at a similar conclusion, but unfortunately we have not been able to consult the original memoir. Lowry in a recent paper (Trans., 1906, 89, 1039) also calls attention to a case in which van't Hoff's assump- tion is contradicted. We may examine briefly an example of Walden's results.He prepared, for instance, three amyl lactates, and determined their rotations with the following results : C.Iw [MID. I. +Amy1 1-lactate .................. - 6-38" - 10.21" 11. 2-Amy1 i-lactate.. ................ +2-64 +4*22 111. 2-Amy1 Z-lactate .................. - 3.93 - 6.29 Since the sum of the molecular rotations of I and I1 ( - 5-99') is nearly the same as the rotation of I11 ( - 6 * 2 9 O ) , andfrom a number of other similar series of figures, Walden concludes that "die lande- siibliche Auffassung von der algebraischen Superposition der optischen Eigenschaf ten verschiedener asymmetrischen Kohlenstoffatome in einer Molekul findet ihre Bestatigung " (Zeit. physikal. Chern., 1895, 17, 724). That is, the experiment quoted above is taken as proving that the rotation of the active lactyl radicle in I is the same as in 111, the * The paper has recently been republished in Zeit.phpsikad. Chent. 1906, 56, 566. 6 ~ 21886 PATTERSON AND KAYE: rotation of the active amyl radicle in I1 is the same as in 111, and that therefore the rotat.ion due to the lactyl radicle is the same whether it be combined with a laevo- or a dextro-amyl radicle. It may be said at once that the mistake made here lies in regarding i-amyl and i-lactyl as simple radicles. The substances I and I1 above are not homogeneous compounds.* When Z-lactic acid acts on i-amyl alcohol, two substances are formed-we may assume for the moment that they are formed in equal proportions-so that if small letters represent amyl radicles and capital letters represent lactyl radicles, we have Therefore, in supposing the rotation of I to be that of i-amyl Z-lactate, Walden makes the tacit assumption that Z-amyl and d-amyl have the same effect on the rotation of Z-lactgl, the very point which was under investigation.Further, of the four compounds composing I and 11, d - L forming half of I and Z-D forming half of I1 are enantiomorphs, so that their rotations would be equal and opposite, say, p” and - p”, whilst the other half of I is the same as the other half of 11. If, then, the pure compound Z - L has a rotation equal to a’ for a given length of tube, it is obvious that the rotation of I for the Same length of tube will be equal to $ao+ ip”, whilst that of I1 will be equal to &ao - 8p9 their sum being, of course, a’, the rotation of the pure compound Z -L.What Walden has done in these cases, therefore, is merely to measure the rotation of Z- L in two different ways, and it is not surprising that the results agree fairly closely. The experiments have been carried out in such a manner as to eliminate in each case the influence they were intended to discover. There is, indeed, so far as we are aware, only one recorded instance in which this question can be directly tested, and, curiously enough, thedata are supplied by Walden himself, who, however, makes no reference to their bearing on this particular subject. I n a paper, “Ueber die optiache Drehung stereoisomerer Verbindungen ” (Zeit. p h y s i k d . Chem., 1896, 20, 377), he gives values for the rotations of the di-Z-umyl esters of racemic and i-tartaric acid, comparing them with the values for the rotations of the di-Z-amyl esters of maleic and fumaric acid, Now the Z-amyl ester of racemic acid will, of course, connist of two non-enantiomorphic substances, and if we assume definite rotation * This was clearlyseen by Frankland and Price in the analogous case of the amyl glycerates (Trans., 1897, 71, 267).These authors, however, were not thereby led to doubt the validity of van’t Hoff’s assumption. On the contrary, they accept it as the basis of some of their arguments.STUDIES IN OPTICAL SUPERPOSITION. PART 11. 1887 values for the different active carbon atoms in these compounds according to the idea of van't Hoff, Guye, and Walden, we shall have, if R = C,H,,*O*CO- Di-2-amyl i-tartaric ester.Di-Z-amyl racemic ester. / I. (deztro-acid? 11. (kevo-ac?d). 111. (2u" + 28"). (2u" - 28"). (2a"). Obviously the rotation of the racemic ester, since it is supposed to consist of equal parts of I and 11, should be - - 2ao+ 2PO - 2 + 2 2ao - 2PO = 2ao, that is, should be the same as the rotation of the i-tartaric ester. Walden's figures are : [MI?. Di-Z-amyl i-tartrate ..................... + 13.83" Di-2-amyl &-tartrate .................. + 9 77 Between these numbers there is a difference of 4.06°, almost half the rotation of the racemic ester, and much greater than the difference (0.3") i n the case of the amyl lactic esters already mentioned. These data of Guye and Walden are not, however, experimentally sound.I n all cases, as has been pointed out, the active compounds the rotations of which have been determined were mixtures, and herein lies a possible source of error. To take the last example quoted, Wben pure Z-amyl alcohol acts on racemic acid, it is probable that the d- and Z-acids do not esterify a t the same rate, and since in the preparation of an ester the esterification is seldom or never complete, it is by no means unlikely that after distiIIation the resultant ester does not contain equal proportions of the d- and Z-acid radicles. Further, the amyl alcohol used by Walde; was itself also a mixture, which renders the experiment still more complicated and unreliable. The esterification of the i-acid would, of course, only be affected by the latter cause. These considerations apply, however, to all the experiments with Z-amyl alcohol and &acids, and therefore it might be expected that the experimental error in each series would be much the same.This is the case in all except the experiments with i-tartaric and racemic acid. The difference in the rotations of the esters of these acids can hardly be ascribed entirely to experimental error, and that1888 PATTERSON AND KAYE: t h i s difference has been found goes, we think, some way towards dispioving van’t Hoff’s assumption. In Rosanoff’s paper, already referred to, the line of argument is exactly similar to ours,* and he arrives at the same conclusion, namely, that the principle ” of optical superposition is, at least, very doubtful. He also suggests that in the experiments of Walden and of Guye solvent influence may exercise a disturbing effect.That this may be so is possible, but we are inclined to think that any solvent action which may come into play is likely to be of much less consequence than the possibility of selective esterification, mentioned above, which Rosanoff has overlooked. Rosanoff, in his paper (p. 529), in discussing a case of supposed optical superposition, says, “ On the other hand, cases like Landolt’s, if general instead of exceptional, would lead, not to the principle of optical superposition, but to the theorem that the rotabory power of an active radicle is independent of the chemical composition of the rest of the molecule,” and to this passage he adds a footnote in the words: ‘‘ Patterson and Taylor (Trans., 1905, 87, 33) seem t o think that this is really what is meant by optical superposition.” It is difficult to understand how Rosanoff could have fallen into this error, since in the second paragraph of the paper to which he refers there occurs the passage, “ When in a simple active molecule, such as that of lactic acid, the replaceable hydrogen atoms are substituted by radicles like methyl and ethyl or scetyl and benzoyl, the change in rotation which occurs with each substitution is probably due, not merely to the addition of a new group, but also to a modification, a slight molecular rearrangement of the active radicle itself.That is, tbe lacfyl radicle, supposing it could be detached from a molecule of methyl lactate without suffering any other change, would show, when examined polarimetrically, a rotation differing from that of a lactyl radiclo separated, in the same manner, from a molecule of some other lactate.” The idea suggested here is surely the antithesis of the conception that the rotatory power of an active radicle is independent of the chemical composition of the rest of the molecule ! Rosanoff‘s paper contains no new experimental work, but some is promised, and, therefore, to prevent any possible overlapping we may state that the next part of this investigation will deal with the menthyl esters of i-tartaric acid, and we hope then to obtain data * The foregoing, except for the references to more recent work, was written, in a more extended form, more than three years ago, and was intended to serve as an introduction to Part I of this investigation.For the reason given on p. 1885, however, it was omitted from that paper. One other point we may refer to.STUDIES IN OPTICAL SWPERPOSITION. PART 11. 1889 which shall supply a satisfactory solution to the problem of opticaI superposition. EX PER I M E NTA L. The sodium ammonium I-tartrate used in this investigation was That the salt was pure is shown by the following figures : 2.5 grams made up to 50 C.C. with water gave in a 2-dcm. tube the prepared by us from racemic acid. rotations : t. a,. t. OD. 16.3" -4.650" I 20'1" - 4.670" from which cty - 4,669. from the dextro-acid, gave at the same concentration the figures : A recrystallised specimen of sodium ammonium d-tartrate, prepared t . a,. 13-9" + 4-62' 16 '9 4-634 t.%I. 17'2' + 4-640" 22 *5 4.669 from which ar +4.655. Ri-1-menthyl-1-tartrate. -For the preparation of this substance it is not necessary to isolate I-tartaric acid from the sodium ammonium salt. The process used was as follows : some sodium ammonium tartrate was thoroughly dehydrated by heating in the steam bath for three to four hours. Fifty grams of the salt were placed in a round-bottomed flask with 158 grams of menthol, and dry hydrogen chloride was passed into the mixture, first in the cold and then at 110-130' for about twelve hours. The liquid mixture in the Bask was then separated from the chlorides of sodium and ammonium formed, by pouring off while hot into a distilling flask. Most of the menthol was then distilled off under diminished pressure and steam blown through the viscid residue to remove the last traces.The ester in the flask was extracted with ether in which it did not seem very soluble, heating being necessary. A viscid brown solution was thus obtained, and on adding a small quantity of sodium carbonate solution (a few drops) a copious white precipitate separated. This, which proved to be sodium Z-menthyl- Z-tartrate, was filtered off and examined later. The ethereal extract was washed with sodium carbonate solution, then with water, and dried over anhydrous sodium sulphate. After removing the ether an attempt was made to distil the menthyl tartrate, but without success, as decomposition occurred. Attempts were also made to crystallise the ester after it had been purified by boiling, in ethyl alcoholic solution, with animal charcoal and then precipitating with water, but these were for a long time unsuccessful.Finally, we found that if the ester was dissolved in pyridirie and water added, a crystalline substance1890 PATTERSON AND KAYE: Eepsrated out. This compound, which contains pyridine, was re- crystallised twice from light petroleum, when it melted at 69--70°.* We then found that if the menthyl tartrate was dissolved in light petroleum and a crystal of the above substance added, menthyl tartrate crystallised in fine needles melting at 42'. It was recrystallised from light petroleum, when i t melted a t the same temperature as before, and on analysis 0.1900 gave 0.4719 CO, and 0.1711 H20. C2,H,,0, requires H = 9.86 ; C = 67.61 per cent.We made two attempts to determine the rotation of this ester, one with a specimen prepared before we had obtained any in the crystalline condition, and therefore purified by precipitation with water from ethyl alcoholic solution, and another with the crystallised substance. Since in both cases we observed the same behaviour we need quote only from the latter. The substance was melted and poured into a 30 mm. tube. It did not crystallise on cooling, so the first rotation was taken at t : 16*3', when uD - 23.86'. On raising the tempemture the rotation increised, and at 134.9' had the value uD - 24.12'. On the following morning, however, the rotation had not returned to the original value, but a t 18*4', uD - 24-31', and a day or two later a t 130°, uD - 24.51'.On cooling again to 9*5', aD had become -24.69', and when heated to 98.2', uD -24.83'. The last observation made at 9.3' gave uD - 24*77', and at 99.3' uD had the value - 24-84'. These observations extended over about a fortnight ; they show no constancy, but to what this is due we cannot explain. The density of the menthyl tartrate was also determined twice. The results agreed closely, as is shown by the following figures: Seriee I was carried out with an oil purified by precipitation, Series I1 with the crystallised substance. C= 6'7.73 ; H = 10.00. Series I. Series 11. t. t. Density. - 71.5" 1*0028 79 0'9968 94" - 0.9866 112 0'9725 8eries I. Series 11. t 1. Density. - 136" 0'9536 - 0'9541 - 154 0'9396 137" Obviously, specific and molecular rotations deduced from the above values are of little importance, but the following numbers for the extremes at low and at high temperatures may be given :- to.a: (30 mm.). Density. [a15 w1;. - 23.86" 1 -0450 - 76.11" - 324 '2" { l;:: 24.77 1 -0505 78.60 334-8 24-13 0.9547 84'22 358'8 { I;:; 24'84 0'9816 84.36 859.4 * This substance will be more fully investigated later.STUDIES IN OPTICAL SUPERPOSITION. PART XI. 1891 Sodium 1-Menthyl 1-Tartrate.-As already mentioned (p. 1889), a sub- stance was precipitated in rather a curious manner from the ethereal extract of crude menthyl tartrate on the addition of a drop or two of sodium carbonate solution. This compound was not very soluble in hot water. On cooling, the solution became turbid, and, on standing, clusters of needle-shaped crystals separated and the solution became quite clear.The substance was recrystallised from water. It did not melt when heated to 200O. On igniting with sulphuric acid : 1.0091 gave 0.208 Na2S04. Na = 6.68. 0.7013 ,, 0.147 Na2S04. Na = 6.79. 0.3480, dried at loo', lost 0.0191 H20. The rotation of the compound was determined in aqueous solution H20=5*48. C,,H2,0,Na,H20 requires Na = 7.01 ; H,O = 5.48 per cent. with the following result : P. to. a: (170 mm.). Density. [a]:. [MI:* 0.3623 48.6" - 0.466" 0.9896 - 76-46" - 250'8" Menthyl diacetyl-1-tartrate was prepared by boiling menthyl tartrate with excess of acetyl chloride for several ho;xrs. The residue, after the acetyl chloride had been distilled off, was washed with water and sodium carbonate Bolution, when it became solid.The compound, when dry, mas dissolved in hot methyl alcohol and boiled under a reflux condenser with animal charcoal, the solution filtered and allowed to cool. The crystals which separated were recrystallised from aqueous methyl alcohol, when they melted at 102.5'. On analysis : 0.1947 gave 0.4705 CO, and 0.1558 H,O. C = 65.90 ; H = S.89. 02136 ,, 0.5164 CO, ,, 0.1711 H,O. C=65.93; H=8.90. C,,H,,O, requires C = 65 a88 ; H = 9.02 per cent. The molecular weight of the compound was determined cryoscopically in beuzene solution (K=60), the following data being obtained: Theoretical M. W. = 510. Grams or substance per Weight of Weight of 100 grams of substance. solvent. solvent. A. M. W. 0.1903 gram 16-65 grams 1'14 0~11" 519.5 0.2863 ,, 16-65 ,, 1.72 0.17 505.7 0.4466 ,, 16.65 ,, 2-68 0 -28 478'9 1-0580 ,, 17'15 ,, 6.17 0.67 460'4 I n this case, therefore, as was also found for the corresponding derivative of d-tartaric acid (Patterson and Taylor, Trans., 1905, 87, 40), the molecular weight diminishes with increasing con- centration, but the substance seems to be unimolecular i n very dilute solution.1892 PATTERSON AND KAYE: The rotation of the substance in the homogeneous condition was then determined with the following result.The ester remained super- cooled for a long time, and therefore the observations could be extended over a wide range of temperature. The numbers are recorded in the order in which they were obtained. Rotation of Di-l-rnmtlbyl Diacet yl-l-tmtrate. to. 122%" 129.0 146-5 1045 15.0 49 -3 103.0 150.0 16.0 uz (30 rum.).- 22.135" 22.080 22.020 22'195 22.237 22,204 22.166 22.042 22'242 Densities determined : to ......... 98" d . . .......... 0'9894 Density. 0.9697 - 0.9646 0'9505 0'9842 1-0558 1.0283 0,9853 0.9477 1'0550 blk". * 76.10" 76.31 77.23 75.18 70.21 71-98 75-00 77'54 70'28 122" 142" 0'9701 0.9541 [MI:. - 388.1" 389'2 393.9 383.4 358'1 367.2 382.5 395-4 358.4 There is no sign here that any permanent alteration of rotation had occurred. The rotations of Z-menthyl Z-tartrate, and Z-menthyl diacetyl l-tartrate were then determined in ethyl alcohol, benzene, and nitrobenzene with the following results : 1- MenthyZ LTartmte. Solvent : Ethyl Alcohol. 2 3 9 to. Density. a: (170 mm.). I. 2.41729 14.25" 0'8009 - 2.490" 27.6 07893 2.491 38'9 0.7779 2,493 20'0 * - - 11.7.05393 18.0" 0.8055 - 7 '29" 24 -6 0.8000 7-30 48'0 0-7800 7 -30 20.0 * - - Deneities determined : to. d. 1". I. 19.56" 0'79615 11. 18.25" 23-22 0*79305 22-95 29 '8 0 78741 38 -6 Interpolated. [a]:. 75-64' 76.77 77.90 76.06 * 7548" 76.10 78.05 75.60 [ M I 5 - 321 '7" 327-0 331.8 324-0 * 324'2 332.5 322.2 * - 321.5" d. 0-8051 6 0*80136 0.78766STUDIES IN OPTICAL SUPERPOSITION. PART 11. 1893 I-Menthyl 1- Tartrate (continued). Solvent : Benzene. P. to. Density. I. 2.73118 18.3" 0'8826 31.0 0.8690 38.0 0.861 5 20.0 I 11. 5-39447 15.1" 0.8890 24.5 0'8790 35.9 0.8670 20.0 * - Densities determined : t". d. I. 18-5" 0.88196 21 *5 0 *87 9 10 27 -0 0.87342 as (170 mm.). [a]:. [MI$ - 3'001" - 73.22" - 311.9" 3'000 74.35 316.5 3-000 75-00 319.5 - 73-33 * 312.4 - 6.083" - 74.57" - 317'7" 6-071 75.30 320'8 6,065 76.34 325 *2 - 74.94 * 319.2 ' to.d. 11. 17.75" 0.88591 21 -60 0 -88202 30.15 0.87303 Solvent : Nitrobenzene. 1. P. to. Density. a: (170 mm.). [a]:. [MI:. 1.98411 13-8" 1.2047 - 3.610" - 88'84" - 378.5" 20 -2 1 *1983 3.600 41 -0 1.1775 3.528 51 5 1.1667 3'483 13.6 1 '2049 3.619 20'0 * - - 25 *3 1.1857 9.610 31 -3 1-1797 9-529 42.0 1'1692 9,482 20.0 * - - 11. 5.34773 13-5" 1 *1975 - 9 -727" Densities determined : to. a. to. I. 17-85" 1 *20083 11. 17.50" 20.80 1.19783 29.75 29 *30 1 *la933 43'50 l-MentA yl Diacet yl-l- tartrate. Solvent : Ethyl Alcohol. I. 11. P* to. Density. a: (1 70 mm. ). 89-06 379.4 a8-87 378.5 88'43 376.7 89.08 379.5 89-02 * 379.2 * 89-15 379.7 88-86 378.5 89.19 379.9 89.32 * 380.5 * 89-37' - 380.70 d.1.19337 1.18149 1.1679 3.9479 20.2" 32.6 42.0 20.0 * 5.80053 16.7" 24 -8 38 -0 20'0 * 0.7985 - 3-a7i0 - 72.210 o w 9 3.874 73-18 0.7795 3.874 73.97 0.8053 -5.675" -71.52" 0.7953 5.675 72.29 0.7854 5,680 73-34 * Interpolated. - - 72-20 * - 71.77 * - - 368'3" 373.3 375.2 368'2 * 368.7 374.0 366.0 * - 364'7"1894 PATTERSON AND KAYE: l-Menthyl DiacetyZ-1-tartrate (continued). Densities determined : to. d. to. d. I. 21.0" 0.79799 11. 19'1" 0.80333 25.5 0'79407 24 -0 0.79895 39.4 0-78200 37.2 0'78784 Solvent : Benzene. P. to. I. 2.06209 2lmO" 31-5 15.0 20.0 11. 5.21901 15.3" 27 -5 20.0 i t Density. a$ (170 mm.). [u]:. 0.8795 - 1.885" - 60-97" 0.8685 1.895 62-08 0.8860 1'895 60.85 - 61-17 * I 0.8905 - 4.822" - 61~01" 0.8775 4-827 62'01 - - 61'37 * [MI:. - 310'9" 316'6 310.3 312.0 * 316.2 313.0 * - 311.1" Dmitiss determined : to. d .to. d. I. 17.75" 0 -883 1 9 11. 17.85" 0.88763 21.25 0.87941 20.87 0:8a450 30.50 0.86930 30.10 0.87483 Solvent : Nitrobenzene. P. to. I. 2.59034 16.8" 28 -8 58 -1 20.0 .!+ 11. 5'35741 15 -3' 29.8 44.0 20-0 * Density. af (170 mm.). [u];. 1.2016 - 3'710" - 70.09" 1.1898 3.698 70.56 1.1610 3'666 71.68 - - 70.06 * 1.1985 - 7.570" - 69.36" 1'1842 7,568 70.18 1'1704 7.546 70.80 - c 69-54 * m1:* - 357'5" 359-8 365.5 357.3 * - 353 -7 357.9 361 -0 354.7 * Dernsities determirzecl: to. d. to. d. I. 16.66" 1.20187 11. 17.75" 1 '19594 22.80 1.19579 21 -42 1.19231 32.80 1.18594 30.65 1.1833 48.4 1-1661 * Interpolated. The table below is a synopsis of these data. I n it are given the rotation values (by interpolation) of the rarioiis active compounds examined in 5 per cent.solutions in ethyl alcohol, benzene, and nitro- benzene. We think it better to give these values rather than numbers for infinitely dilute solution, since, perhaps, for purposes of comparisonSTUDIES IN OPTICAL SUPERPOSITION. PART IT. 1895 it is preferable to deal with concentrations which can be practically realised. Z-Menthyl d-tartrate. I-Menthyl I-tartrate. Condition. w1y. CMI-20". A. Homogeneous ..................... - 284.0" - 325 -0" ( 1 ) 41 '0" In ethyl alcohol (5 per cent.) ... 305 '1 323-0 17-9 , , benzene J Y 293.6 318-4 24'8 , , nitrobenzene , , ... 246.0 380.4 134'4 I- Men t h y 1 diace tyl- &Men t h yl diace tgl- Homogeneous .....................-256 4" - 359.6" 103.2" In ethyl alcohol (5 per cent.) ... 268-2 367-0 98'8 , , benzene ,, * * a 285.0 312-9 27 '9 ,, nitrobenzene ), ... 238.0 355.1 117.1 d-tartrate. E-tartrate. The chief point of interest which we find in these data is that the differences between the rotations of the corresponding d- and I-com- pounds, under these different conditions or in solution, are not constant. Thus, for example, solution in benzene increases the negative rotation of I-menthyl diacetyl-&tartrate by 2 8 * 6 O , whilst it diminishes that of I-menthyl diacetyl-I-tartrate by 46*7", so that whereas the difference in the rotations of the homogeneous compounds as given in the &column is 103*2O, in benzene solution it is orily 27.9'. I n ethyl alcohol solution the rotations of both acetyl tartrates are increased, but that of the dextro- to a greater extent than that of the laevo-compound. I n nitrobenzene the opposite is the case: both rotations are diminished, that of the dextro-compound to the greater extent.The behaviour in each of these three cases is different, and the fourth possibility is found in the behaviour of I-menthyl d- and I-tartrates in nitrobenzene, the rotation of the former being diminished by 3 8 O and that of the latter increased by about 5 5 O . It is not difficult to understand this if we assume that the solvent exerts its influence separately on each of the three active groups of which the molecule is composed, and that our measurements represent the sum of these effects. Thus the influence of a solvent on the menthyl part of I-menthyl diacetjl-d-tartrate will probably be the same, or much the same, as its action on the menthyl radicle of I-menthyl diacetyl-I-tartrate, whilst its influences on the tartary 1 parts of the molecules will probably be equal, or almost equal, but in opposite senses.If, then, the solvent influence is represented by a+P in one case, it will be represented by a - p (or nearly) in the other, and it will depend on the relative magnitudes of a and 6 for different solvents which of the four possible casos exemplified above shall occur. It is also possible to trace other approximately additive phenomena somewhat similar to those discussed in Part I. (pp. 38, 39) when we consider the change of rotation of these compounds with variation of1896 PATTERSON AND KAYE: temperature.at 100" and 0" are the following : The numbers for menthyl diacetyl d- and Z-tartrates Z-Menthyl I - Menth yl diacetyl-&tartrate. diacetyl-Z-tartrate. - -- to. [MI;. A. [MI;. A. - 381 '8" - 27 .a0 354.0 39 - 2 O 100" - 227 '6" 0 266'8 The rotation of the d-tartrate is diminished (that is, becomes less negative) by 39.2' on heating from 0' to 100'. This corresponds with the behaviour of ethyl diacetyl-d-tartrate the positive rotation of which increases on heating (Patterson and McCrae, Trans., 1900, 77, 1098). The rotation of the 2-menthyl diacetyl-&tartrate, on the other hand, increases by 27.8' (that is, becomes more negative). Since these changes are in opposite directions it seems reasonable to suppose that they are chiefly due to those parts of the molecules which are of opposite configurations, namely, the acetyl-tartaryl radicles, and that tho numerical difference between them, 11*4', represents twice the change of rotation of two menthyl radicles attached to an acetyl- tartarpl radicle on heating from 0' to 100'.Thus, of the total change in rotation (39.2O) of the dextro-compound, +33*5' are due to the acetyl-d-tartaryl part of the molecule, and +2*85' to each of the menthyl radicles, all these changes being in the same direction, whilst in the laevo-compound the total changeof rotation ( - 27.8) is made up of - 33.5, due to the acetyl-Z-tartaryl group, and + 5.7', due to the two menthyl groups. The independent effect of each active group in the molecule seems, therefore, to be, at least roughly, traceable, although, of course, the above argtiment ignores the possibility that the change in rotation of, say, a menthyl radicle might be different according to whether it were combined with a d- or Z-acetyl-tartaryl group.It is likely, however, that such an influence would be slight, which is borne out to some extent by the fact that the change deduced above for a menthyl radicle attached to an acetyl-tartaryl group (2.85') is in fair agree- ment with that actually observed in Z-menthyl acetate (2.3') which was discussed in Part I. (Trans., 1905, 87, 38). We arrive at a somewhat similar conclusion from an examination of the variation of density of these compounds with change of tempera- ture which the following data exhibit.STUDIES IN OPTICAL SUPERPOSITION.PART 11. 1897 Z-Menth yl d- tartrate. I-Men thyl 2-tartrate. 1 *0040 i::::; 0.0617 0'9430 - to. bensity. A. Density. A. 0*0610 70" 150 I-Menthyl I-Men thyl diacetyl-d-tartrate. diacetyl-1-tartrate. 0.0641 1*0118 Q.0640 0 '9477 70" 1'0202 - 150 0-9562 It will be seen from these numbers that the change of density due to rise of temperature from '70° to 150' has almost the same value for the two simple tartrates, namely, 0.0610 and 0,0617, and that the same holds for the acetyl derivatives for which the changes are 0.0641 and 0.0640, but the change for either of the simple tartrates is quite different from that for an acetyl derivative, compare for example 0.0610 and 0.0641. From this we may conclude that the I-menthyl group expands to the same extent on heating, whether it be combined with a d- or a Etartaryl radicle, and that the latter groups also expand to the same extent when combined with an I-menthyl radicle.All these changes must of course be in the same sense, and differ in this respect from the corresponding rotation changes. So far we have dealt with variation of density; we may now con- sider the actual densities of the substances examined. Taking values at looo we have 2-Menthyl d-tartrate 0.9922 I-Menthyl &tartrate 0'9811 o'olll I-Menthyl diaoetyl-1-tartrate 0.9877 0'0085 Between the densities of the simple esters there is a difference of 0.0111, and between those of the acetyl derivatives a difference of 0.0086. On the other hand, the difference in density between I-menthyl d-tar- trate and I-menthyl diacetyl-d-tartrate is only 0-0040, whilst the difference in density between the corresponding laevo-compounds is 0.0066.Thus there is a greater difermce in denaity between the two simple tartrates than exists between one of these and its acetyl derivative. The difference in density caused by mere spatial change of the groups composing the molecules is distinctly greater in both cases than that due t o a considerable difference of chemical composition. This difference between two compounds which differ only spatially is perhaps shown more clearly in their molecular volumes. Substance. M.V.1OO'. A* Substance. Density. A. Substance. Density. A. Z-Menthyl diacetyl-d-tartrate 0.9962 4.9 C.C. 4'4 0.c I-Menthyl d-tartrate ... .. . . . . . . . . . . 429'3 C.C. I-Menthyl 2-tartrate ... , , . . . , . . . . . , 434'2 , , E-Menthyl diacetyl-d-tartrate ... ... 512.0 C.C. 1-Menthyl diacetyl-2-tartrate ...... 516'4 ,,1898 PATTERSON AND KAYE: The volume change due to re-arrangement is greater in the smaller than in the larger molecule. We have also calculated, from our density determinations, valued for the solution volumes of these two compounds in the various solvents used. We should mention, however, that owing to scarcity of material the data were obtained (except in the case of Z-menthyl diacetyl- I-tartrate in nitrobenzene) with a pyknometer having a capacity of only 7 C.C. The values for M.S.V. are therefore probably not so accurate as those formerly given for the corresponding derivatives of d-tartaric acid.The values, a t both concentrations examined, for the diacetyl-Z-tartrate in ethyl alcohol and benzene agree fairly closely and therefore confirm each other. The values for the same substance in nitrobenzene are the most reliable of all, having been obtained with a larger pyknometer. Moleczctar Solution VoZumes. 1-Menthyl Ltartrate, [ M F = 325O (?). M.V.20" = 426/1*042 = 408.9 C.C. Ethyl alcohol (6 20"/4"=0'79045) ... 2'41729 0.79577 389*8* C.C. - 324.0" 7'05393 0.80393 410.8 ), 322.2 Benzene (6 20"/4"=0'87784) ......... 2.73118 0.88053 431.0 C.C. -312'4" 5'39447 0.88364 426.2 ,, 319'2 Nitrobenzene (6 20"/4"-1'20319) ... 1.98411 1.19864 380.6" C.C. - 379.2" 5.34773 1.19095 422'1 ,, 3805 Solvent. P. d. M.8.V.200. * These values are doubtful.Z-Menthyl diacetyl-Etartrate, [M]r = - 359.6'. M.V.20"= 510/1*O518 = 484.9 C.C. Pa d. M.S.V.20. Ethyl alcohol ...... 3.9479 0.79887 472.9 C.C. 5230053 0.80252 477.9 ,, Benzene ... ... .. . ... .. , 2'06209 0.88076 487.5 C.C. 5'21901 0'88542 485.7 )) Nitrobenzene ...... 2.59034 1.19856 487'1 C.C. 5 *35741 1.19371 486.7 ,, [MITO", - 368 '2' 366'0 - 312*0' 313.0 - 357.3" 354'7 These numbers do not exhibit any simple relationship between solu- tion volume and rotation, but from the table below it will be observed that in all cases except one the volume of the Z-tartrate in solution is greater than that of the d-tartrate, which is, as has already been remarked, also the case for the compounds in the homogeneous state.STUDIES IN OPl'lCAL ST;PERPOSITIOS.PART 11. 1899 1- Jienthyl I- tar tratc. Z- 3it.n thy1 tl- tar tra te. -' 7<7 7- Solve11t. $I. Ji.S.V."O". 21. i r . s . v ~ . A. Ethyl alcohol ...... 7.1 410.8 C.C. 7.9 398'3 C.C. 4-12.5 C.C. Eenzene ............ 5 . 4 426'2 ,, 7.4 409.5 ,} + l S * 7 ,, Nitrobenzene ...... 5.3 422.1 , , 6'5 408.2 ,, +13*9 ,, I-Menthyl I-Menthy 1 diacetyl-I-tartrate. diacetyl-&tartrate. Ethyl alcohol ..... 5.8 477.9 C.C. 7 - 3 480.0 C.C. -2.1 C . C . Eenzeiic ............ 5.2 485.7 7 7 7.8 482 5 ,, +3'2 5 , Nitrobenzene ..... 5.4 48ti.7 ,, 6 ' 3 483'0 ), 4-3'7 ,) That the molecular volumes or molecular solution-volumes of partial enantiomorphs, like those we have been dealing with, should be different is by no means remarkable. It is merely in agreement with the very well-known fact t h a t the solubility of compounds such, for instance, as cinchonine-d- and I-tartrate or mannose, glucose and galactose is different, and it is further in agreement with the fact that such substances differ also in melting point. The melting points of the substances examined in this investigation, for example, are as follows :- 84.5" * + Trdus., 1905, 87, 124-126. I-llenthyl d-tartrate ...... 74--75" I-Menthyl diacetyl-&tartrate ... { I-Meathyl I-tartrate ...... 42 I-Menthyl cliacetyl-Z-tartrate . . , 102 5 Prom the fact that when an active group AE combines respectively with two other enantiomorphic groups, B d and Bl, the changes in the reacting groups, which accompany combination, are not the same in the two cases, since the melting points, solubility and density of the resulting substances are different, and, in spite of the fact that, on the other hand, the variation of volume and, 60 far a3 we can judge, the variation of rotation of the group Al, with change of temperature seem to be independent of the configuration of the other group with which it is combined, it is scarcely to be expected that the rotation of such partially enantiomorphic substances should be a purely additive property. As has been said, however, there exist no unimpeachable data to settle the question, but we hope with the next part of this investigation t o produce some evidence of a decisive character. -"- The substance is climorplious. It gives us pleasure, in conclusion, to acknowledge our indebtedness to the Research Fund Committees of the Chemical Society and of t h e Royal Society investigation. THE UNIVERSITY, G LASGOW. for grants which defrayed the expenses of this VOL. LXXXIX. G I

ISSN:0368-1645    

DOI:10.1039/CT9068901884

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

1900 RAY AND NEOGI : INTERACTION OF THE ALKTLSULPHATES CLXXXIV.-The hteq-action of the AlkylsulpJmtes with the Nibites of the AlIcali Metals arid Metals of the A 1 ha 1 i~z e Eur t h s . By PRAFULLA CHANDRA RAY and PARCHANAN NEOGI, AKA. AS silver nitrite by its interaction with the alkyl iodides yields a nitro-compound as well as an ester, i t has often been taken for granted that this nitrite has a twofold constitution, namely, nitronic and oxylic. Evidence has already been adduced in favour of the latter structure (RQy and Gaiiguli, Proc., 1905, 21, 273), which Dr. Divers is inclined to accept as fairly conclusive (ibid., p. 281). It seemed t o us that further light would be thrown on the question by studying the reaction between the alkylsulphates and the alkali nitrites, as the latter have always been supposed to have the oxylic constitution. E x PER I BI EN T A L.I. Potassium Etlqlsulphate mid Sodium Nit9.de. Lauterhch has published a brief note on the subject (Be?.., 1878, 11, 1225), but a systematic investigation seemed desirable, especially as this chemist contented himself with demonstrating the formation of ethyl nitrite by its odour and inflammability, and also in view of the additional interest lent to the subject by Wade's fruitful research on the interaction between the alkylsulphates and potassium cyanide (Trans., 1902, 81, 1596). Dried and powdered potassium ethylsnlphate and sodium nitrite were mixed in molecular proportions in a glass retort, to the neck of which was attached an inverted condenser. The upper end of the condenser was connected with a bulb provided with stop-cocks at both ends and three absorption bottles containing 90 per cent.alcohol. As the temperature of the laboratory was about 30°, the entire condensation and absorption apparatus was immersed in ice- cold water. It will be seen below that even this arrangement failed to condense the whole of the ethyl nitrite, as during the reaction a constant stream of nitric oxide was evolved, which carried off a considerable amount of it. For the same reason the air was expelled by a slow stream of carbon dioxide. The retort was heated in a glycerol bath. The reaction, which commences a t 145O, is indicated by frothing, which slowly extends towards the centre from the peripheral regions. When the reaction once begins i t proceeds continually, even when the temperature sinks so low as 110'.After a certain interval, the action becomes very violent and aWITH THE NITHI‘I‘ES OF THE ALKALI METALS. 1901 sudden and vigorous evolution of wliite vapours takes place. The reaction then moderates, effervescence ceases, and the mass has the appearance of tranquil fusion. The digestion lasts from two arid a half t o three hours. (a) Bt?uJ Nitrite. Although i t is “ dry ” ethylsulphate which is heated, much alcohol is given off at the temperature at which the reaction takes place (compare Wade, Zoc. cit.). A portion of this alcohol is carried off and condensed with ethyl nitrite in the bulb. The alcoholic solution of the ethyl nitrite in the bulb, as also in the absorption bottles, was estimated according t o the method prescribed in the British Pharmacopceia.- As will be shown below, the result is somewhat too low owing t o the fact t h a t a part of the nitrite escapes condensation, being carried off with the stream of nitric oxide and carbon dioxide.(b) Nitroethane. The nitroethane was now distilled off, using a small condenser, the distillation baing continued as long as oily drops appeared. The dis- tillate was shaken up with brine and the oily layer separated, washed with wa.ler, and dried over calcium chloride. Considerable difficulty was experienced here, as it was found that calcium chloride forms with the “ oil ’’ a kind of emulsion. When our work mas at this stage, Wade’s paper on “ The Influence of Water and Alcohds on the Boiling Point of Esters ” (Trans,, 1905, 8’7, 1656) appeared, which materially helped us.Fused sodium sulpliate was used as the dehydrating agent, as potassinrn carbonate acts on nitroethane. When the “oil ’’ was subjected t o distillation, curious and anomalous behaviour was noticed. A considerable amount passed over below 100” ; only a small fraction could be collected a t a constant boiling point between 110” and 118O, whilst a minute quantity came over between 150’ and 160° and the residue charred. As pointed out by Wade (Zoc. cit., 1668), an ethereal liquid containing alcohol, when shaken u p with brine, does not give up i t s alcohol, but, on the contrary, “ shares its alcohol with it.” The fraction below 100” answered to all the well-known tests of nitroethane, namely, i t solidified completely on the addition of alcoholic sodium hydroxide, and the aqueous solution of the sodium compound gave with ferric chloride a red coloration, and with copper sulphate a green precipitate.Obviously the quantity of nitroethane formed cannot be determined by fractionation.” Known mixtures of * A mixture made np of 5 C.C. of alcohol and 5 C.C. of nitroethane, when shaken up with biinc and dried over fused sodium sulphate, gave 6.1 C.C. of “ o i l ” which, on fractionation, gave 4 5 C.C. distilling between 75” and 100” and only 1.3 C . C . between 100‘ and 115”. t i 1 21902 RAY AND KEOGI : INTEKA4CT10S O F THE ALKYLSULPHATES nitroethane and alcohol were treated with alcoholic sodium hydroxide, the precipitate washed with absolute alcohol and ultimately converted into sodium sulphate and weighed as such ; but the results turned out to be too low.Consequently the nitrogen in an aliquot portion of the liquid was estimated according to Diimas' method, and from it the amount of nitroethane in the mixture deduced. The fraction between 110" and 118' was nearly pure nitroethane. The results of 3 experiments out of 27 are given below, 32.8 grams of potassium ethylsulphate and 14 grams of sodium nitrite being taken in each case. Weight of ethyl nitrite Weight of nitroethane No. of experiment. in grams. in grams. 1 2-3 1.3 2 3.2 1.0 3 2.0 1.3 As has been already explained, some of the ethyl nitrite is invariably lost, and the figures for nitroethane are also a little too low, as quite an appreciable quantity of it remains mixed with the liquid of higher boiling point (see below).The yield of nitroethane is 6 to 8 per cent. of that which is theoretically possible. (c) Liquid of Higher Boiling Point. The fraction which distilled a t 150-160" mas very small, and not more than 0.15 gram could be recovered in each experiment. I n order to study its nature and properties, the distillates from several preparations were mixed, and the crude '' oil," afker being treated with brine and fused sodium sulphate as above, was subjected to fractional distillation under diminished pi essure in Bruhl's apparatus. Four fractions were collected, namely, 40-60', 60-65', 65-1 25', and 125-130°, the distillation taking place under a pressure of 130 mm. The ranges of temperatiire recorded above are only approximate ; in fact, the liquid gave evidence of the properties of a homogeneous ternary mixture (compare Wade, Zoc a t .) . Blank experiments showed that piwe nitroethane distilled at 63-65' under the above pressure, so that the second fraction was nearly pure nitroethane. The fraction 125-130' proved to be a-nitro-rz-butane with traces of a compound of a still higher boiling point. The analyses of two typical samples of different preparations are given below : I. C = 47.06 ; H = 8.23 ; N = 14.10. II.* C = 46.06 ; H = 6.60 ; N = 13.85. C,H,O,N requires C = 46.60 ; 11 = 8.73 ; N = 13.60 per cent. * This represents a fraction which distilled at 150-160" wider the ordinary pressure.WITH THE SITRITES OF THE ALKALI METALS.1903 The vapour density of the liquid mas found by Hofmann's method to be 50.4, that required by nitrobutane being 51.50. That it has this constitution is evident from the fact that its boiling point was about 150', and it gave with alcoholic sodium hydroxide the characteristic precipitate and with potassium hydroxide, on standing, a yellow deposit. I t also responded to the nitrolic acid test. IT. Potccssiunz E'thylsulpliate and Potassiunz Nitrite. The conditions of the experiment mere similar to those previously described. The mass fused a t a much higher temperature, namely, a t about 165', and the reaction proceeded without the aid of heat ; white fumes and nitric oxide were evolved. The yield of nitroethane was much less than in the former experiment. Expt.1.--32.8 grams of potassium ethylsulphate and 17 grams of potassium nitrite gave 1.5 grams of ethyl nitrite and 0.S gram of nitroethane. In this case also nitrobutane was formed, as will be seen below. Expt. 2.-164 grams of potassium ethylsulphate and 85 grams of potassium nitrite yielded 8.5 C.C. of " oil " which on distillation under the ordinary pressure gave 70-loo", 5.0 C.C. ; lO0-l5O0, 1.5 c.c.; and 150-160°, 0.5 C.C. I I I . Bwiunz EthylsuZphte ccnd Bai'iunz Nitvite. Barium ethylsulphate crystallises with 2 molecules of water, and is completely dehydrated when kept for a few days over sulphuric acid under diminished pressure (see analysis given below), whilst t h e nitrite still retains some water (RAY, Trans., 1905, 87, 177). The anhydrous alkylsulphate and the nitrite were mixed in equimolecular proportions.The mass did not fuse and froth up, even when the temperature of the bath was raised to 190'. A distillate passed over which was mainly alcohol. With the hydrated salts, however, fusion commenced at 1204 but the action suddenly became violent at about 130°, and white fumes were evolved with violence. The yield of nitroethane was very poor, and only a few drops could be collected, which, however, answered to all the tests of this compound. IV. Calcium EthyEsu@?bcite and Calcium Nitrite. Calcium ethylsulphate, which also crystallises with 2 molecules of water, is completely dehydrated, like the barium salt, when kept over sulphuric acid under diminished pressure. The anhydrous salt mixed with dehydrated calcium nitrite in equimolecular proportions does not fuse on heating, but simply decomposes when the temperature is1904 R.kY AND NEOGI : IN'I'ERACTTON OF THE ALKYLSULPHATES sufficiently raised.The hydrated salts were therefore used. The mixture fused a t 2 1 6 O , but at about 125' torrents of white fumes were evolved. The yield of nitroethane was again very poor, the last drops of the distillate responding to the reactions for this substance. V. Sodium Etlqlsulphate and Sodium Nitrite. In the hope of obtaining better yields of nitroethane, the sodium salt was next tried. It crystallises with 1 molecule of water, which may be removed when kept under diminished pressure over sulphuric acid (see analysis given below). The anhydrous salt did not fuse with sodium nitrite, even when the temperature was raised to 195".The hydrated salt, however, when similarly treated, began t o fuse at so low a temperature as 80°, and the action, once begun, proceeded of itself as in the case of the potassium salt. The temperature of the bath was not allowed to rise above 180O. The sudden evolution of white fumes mas never noticed. As the reaction takes place at a much lower temperature, it gave a better yield of nitroethane, and, moreover, the liquid having a higher boiling point was not formed. The results of the two experiments are given below, 33.2 grams of sodium ethyl- sulphate and 13.8 grams of sodium nitrite being taken in each case. Expt. 1 gave 0.6 gram of ethyl nitrite and 2.2 grams of nitro- ethane. Expt. 2 gave 0.9 gram of ethyl nitrite and 2.0 grams of nitroethane.The yield of nitroethane is tbus as much as 13 per cent. of the theoretical, whilst i t is only about 6 to 8 per cent. when the potassium salt is used. VI. Sodium Eti~ylsulphate and Potassium Nitrite. This reaction began with frothing a t a higher temperature than that in V, namely, at 120° when the hydrated salt was used, there beiDg no fusion with the anhydrous salt. There was, again, no evolution of white fumes, and the reaction proceeded of itself when once started, nitrobutane not being formed. The yield of nitroethane is, how- ever, much less, being almost equal to that obtained from potassium ethylsulphate and sodium nitrite. 33-2 grams of sodium ethylsulphate and 17 grams of potassium nitrite gave 0.9 gram of ethyl nitrite and I *3 grams of nitroethane.Conclusiom. The formation of nitrobutane, as noticed in I and 11, is remarkable, and it is always associated with vigorous evolution of white fumes. Moreover, the interaction of sodium ethylsulphate and sodium nitrite,WlTH THE NI'I'Rl'L'ES OF THE ALKALI METALS, 1905 which takes place at a much lower temperature, does not give rise t o this compound. This mode of ascent in the homologous series does not admit of an easy explanation. The alcohol which was used in the present investigation was proved to be free from impurities. It was rectified over quicklime and had a constant boiling point (78'). The analyses of the various alkylsulphates are given below.* The argument in favour of the twofold constitution of silver nitrite simply because it yields with ethyl iodide both ethyl nitrite and nitro- ethane is scarcely tenable.The alkali nitrites have the constitution MO-NO, where M represents the'atom of the metal, in other words, the nitrogen is not directly attached to it. Hence we should have only expected the production of ethyl nitritein the present series of experi- ments, but its formation is always accompanied with that of its isomeride. The more correct view would seem to be that it is only during the substitution of the atom of the metal by the alkyl radicle that a tautomeric change takes place.? Summary. From the foregoing investigation, it would appear that by the inter- action of the sodium, potassium, barium, and calcium salts of ethyl- sulphuric acid and t,he nitrites of the alkali metals and metals of the alkaline earths, both ethyl nitrite and nitroethane are formed. In the case of the potassium ethylsulphate and potassium or sodium nitrite small quantities of nitrobutane are also obtained. PRESIDENCY COLLEGE, CALCUTTA. * (C2H,S0,),Ba,2H,0. (C,H,BO,),Ba. C,H,NaSO,,H,O. C,H,NaSO+ Ba, found 32.79 ; calculated 32.70. Ba, found 36-01 and 35.88 ; calculated 35.77. Na, found 13-70 ; calculated 13'85. Na, found 15.72 ; calculated 15.54 per cent. t Whether the hypothesis of tautomerism is adequate or not, there is evidently much force in what Wade urges : "It does not follow, for example, that because silver cyanate and nitrite yield alkylisocyanates and nitro-compounds respectively, the metal is necessarily linked to nitrogen ; it may equally be linked to oxygen " (Zoc. cit., p. 1612).

ISSN:0368-1645    

DOI:10.1039/CT9068901900

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

1906 ATRINSOX’ ASD THORPE: THE FORJIATIOS ASD By ERKEST FRAXCIS JOSEPH ATKINSOX and JOCELYN FIELD THORPE. The Condensation of Benxyl Cyanide with the Soc2izcm Derivcctive OJ Ethgl Cyanoiccetate. IN Part I. of this series it was pointed out by Baron, Remfi-y, and Thorpe (Trans., 1904, 85, 1726) that ethyl cyanoscetate readily reacted with its sodium derivative, forming ethyl p-imino-a-cyano- glutarate, and that tlhe reaction evidently proceeded according to the equation * Co2Et*~HNn + HCH(CN)-C0,Et -+ CN CO,Et*yHNa C( :NH)*CH(CN)*CO,Et* It was also pointed out that, on treatment with concentrated sulphuric acid, ethyl P-imino-a-cynnoglutarate (1) is quantitatively converted into ethyl glutazinecarboxylate (2). C:NH C:NH C:NH JYH bEt I OH (1.) (2.1 (3.) The tendency for the straight chain compound to pass into the if Subsequent experimeiits have shown that this view of the course of the conden- sation, which was based on the position of the sodium atom in the condensation product, is not quite correct, and that it is the reactive hydrogen atom of the sodium derivative which forms the imino-group.The course of the action is therefore best represented by the equation : CO,Et*CH CO,E t*CH, 1 t- HCNn(CN)CO,Et -+ I CN C(:NH)*CN~(CN)CO,E~‘ The change in the position of the sodium atom must be attribnted t o the mom strongly acidic character of the hydrogen of the methyleiie ~ T O I I ~ .11EACTIOSS OF IXISO-COMl'OUh'DS. PART 11. 1907 pyridine ring, which is indicated by this reaction, was still more strongly shown by the behaviour of ethyl hydrogen P-imino-a-cyano- glutarate (3), which was found to undergo conversion into ethyl gliitazinecarboxylate (2) on being heated a few degrees above i t s melting point (Zoc.cit., 1746). There seemed to be, therefore, a con- siderable tendency for a nitrile group in the y-position to a carboxyl group in n compound such as ethyl hydrogen p-imino-a-cyanoglutarate to pass, by intermolecular change with that group, into a six- membered ring, and that this tendency is also shown by the cor- responding p-ketonic derivatives mas demonstrated by the conversion of ethyl hydrogen cyanoacetonedicarboxylate (4) into ethyl 2 : 4 : 6- trioxypyridine-3-cnrboxylate (5), on heating a few degrees above its melting point. CO co CH,/\CH*CO,Et c Whilst desiring to continue the investigation of the conditions of formation of these irnino-compounds, we wished at the same time to ascertain whether the tendency of the nitrile group to enter into ring formation inigbt not be applied to the formation of carbon rings as well as those containing nitrogen, and with this object in view and for other reasons which will be given later, we have investigated the condensation of benzyl cyanide with the sodium com- pound of ethyl cyanoacetate and also with its own sodium derivative.It is apparent that the most probable course of the first reaction mould be represented by the equation (I), and that the product on. acidifying would be ethyl p-imino- a-cyano-y-phenyl-n-butyrate (6). (I) Ph'gt2 + HCNa(CN)*CO,Et -+ Ph*$!H, -+ C:(NH)C]H(CN)S P1i*$!H2 C0,Et C (NH) C Na( CN) CO,E t But it is also possible that the sodium derivative of ethyl cyano- acetate might react with benzyl cyanide, forming the sodium derivative of the latter, in which case the course of the condensation would be represented by equation (11), and on acidifying ethyl p-imino- yy-cyanophenyl-n-butyrate (7) would be the chief product.1908 ATKINSON AND THORPE: THE FORMATION AND CO,Et*$lH, CO,Et*$!H, C: ( N H)* CH( CN)Ph -+ C: (N Hj*CNa( CN)Ph (7.) Under conditions given in the experimental portion of this paper, a good yield of a well-defined crystalline compound (m.p. 125O) is formed on condensing benzyl cyanide with ethyl sodiocyanoacetate, and there can be no doubt that its constitution is represented by formula (6), although, under certain experimental conditions, there is evidence t h a t a compound of formula (7) also occurs as an intermediate product.I n Part I. of this series (p. 1728), it was shown that P-imino-ethyl salts are decomposed on treatment with alkaline hydrolytic agents and that the products formed, which are the same as those derived by the alkaline hydrolysis of the corresponding P-keto-ethyl salts, often afford valuable evidence as to the formula of tho compound hydro- lysed. It is apparent, however, that this method fails when applied t o two compounds of formulze (6) and (7), since these two substances would yield the same products, namely, a mixture of malonic and phenylacetic acids, on complete hydrolysis, thus : CH2Ph*C: (NH). CH(CN)CO,Et CO,Et*CH,* C:(NH) CH( CN)Ph (6.1 (7.) CH,Ph*CO,H CH,(CO,H), CH,(CO,H), CH,Ph*CO,H.The compound melting at 125" is readily hydrolysed by means of an alcoholic solution of potash, and the product consists of about equal proportions of malonic and phenylacetic acids. Although by this means, therefore, i t is not possible to distinguish between the two formuh ( 6 ) and (7), yet the evidence is valuable, since, taken i n conjunction with the boiling point of the compound (235'/20 mm.) and its percentage composition, it shows t h a t it has been formed by the condensation of one molecule of benzyl cyanide with one molecule of ethyl cysnoacetate. It was necessary, therefore, to adopt some other means of dis- tinguishing between the two compounds of formula: (6) and (7), and since me were unable t o isolate any inkermediate products during the alkaline hydrolysis, the formation of which might throw some light on the problem, we were led to study the action of concentrated sulphuric acid on the cornpound melting a t 125'.If the two formuh are examined, it will be seen- that the action of this reagent must give rise t o different compounds.REACTIONS OF 3MINO-COMPOUNDS. PARr 11. 1909 A substance of formula (7) is closely allied to ethyl p-imino-a- qanoglutarate (see page 1906) in constitution, and therefore should readily give phenylglutazine (8) on treatment with concentrated sulphuric acid, thus : C:NH CXH /\ A YH2 YHPh -+ VHP YHPh co CN co co ' I OEt (7.) \/ NH (8.) whereas a compound of formula (6), in which the nitrile group and the carboxyl group are united with the same carbon atom, cannot yield a derivative of glutazine under the same conditions.The compound melting at 125' does not give phenylglutazine on treatment with concentrated sulphuric acid, and there can therefore be no doubt that it possesses a constitution represented by formula (6), a view which is confirmed by a close study of the compound which is actually formed with this reagent. It has already been mentioned that one of our objects in investigat- ing t h e interaction of benzyl cyanide and ethyl sodiocyanoacetate was to prepare a compound in which the nitrile group could by reason of its position pass into a six-membered carbon ring instead of the pyridine ring formed from the other compounds which have already been investigated.This object will be more clearly understood when the formula of ethyl p-imino-a-cyano-y-phenylbutyrate is written thus (9) : CH, CHo (9.) (10.1 (11.1 It was thought possible that the nitrile group might react with the ortho-hydrogen atom of the benzene ring, forming a di-imino-compound (lo), which in its amino-form would be ethyl 1-3-diaminonaphthalene- 2-carboxylate (ll), and that by this means an interesting synthesis of the naphthalene ring might be effected. Since the original imino-compound (9) was formed in the presence of sodium ethoxide, we intended to attempt to obtain the di-imino- derivative (1 0) by treating ethyl P-imino-a-cyano- y-phenylbutyrate with excess of this reagent. We mere therefore considerably astonished to find that, on treating this ethyl salt with concentrated1910 A'l'KIXSOK' AND THORTE: THE FORMATIOX ASD sulphuric acid, in the attempt already mentioned to determine its constitution, it was quantitatively converted into the sulphate of ethyl 1 : 3-diaminonaphthalene-2-cnrboxylate (1 1).This result was all the more surprising because it has been shown by Metzner (Annalen, 1901, 298, 3S6) that a similarly constituted com- pound, namely, ethyl phenylacetylmalonate (1 a), on treatment with cold, concentrated eulphuric acid, is converted with loss of alcohol into ethyl 1 : 3-dihydroxynaphthalene-2-carboxylate (13), the reaction taking place a t the ordinary temperature, CH, (13.) and i t mas therefore to be expected that ethyl P-imino-a-cyano-y- phenylbutyrate (9) would behave in the same w ~ y , yielding 3-amino-2- cyano-1 -naphthol (14) : CH, CH, ., .I " co OH (14.) The yield, however, of ethyl 1 : 3-diaminonaphtbalene-2-carboxylate (1 1) from ethyl P-imino-a-cyano-y-phenylbutyrate (9), on treatment with sulphuric acid, is quantitative, and the reaction takes place with remarkable ease. Thus it is only necessary to add n quantity of well- ground ethyl salt t o three times its weight of concentrated acid and allow the mixture t o stand for one minute in order to complete the change.On first adding the ethyl salt it dissolves, forming a yellow solution which rapidly changes in colour in the course of a few seconds to deep malachite-green, heat a t the same time being generated.REACTIONS OF ININO-COMPOUNDS. PART 11. 1911 When this green solution is poured on ice the colour is discharged and a clear yellow solution is formed from which the sulphate of ethyl 1 : 3-diaminonaphthalene-2-carboxylate separates on standing as a pale yellow, crystalline precipitate.The sulphate is readily soluble in water, and if the aqueous solution is rendered alkaline the base is precipitated as an intense yellow crystalline compound, which, when purified by recrystallisation from alcohol, is obtained in deep yellow plates. There can be no doubt that this yellow compound represents the di-imino-form of ethyl 1 : 3-diarninonaphthalene-2-carboxyl;~te (10). The salts, especially the hydrochloride, can be obtained in almost colourless crystals, and they are therefore probably the salts of the amino-form (11). It is interesting to note, however, that although the solutions of these salts are colourless when cold, they become intensely coloured on boiiing, the colour being again discharged on cooling, The green colour which is formed when ethyl p-imino-a-cyano- y-phenylbutyrate is treated with concentrated sulphuric acid is difficult to explain, since ethyl 1 : 3-diaminonaphthalene-2-carboxylate dis*olves i n the concentrated acid, forming a yellow solution which does not change on warming. That this coloration is not necessary for the production of the naphthalene ring is shown by the fact that i f the solution of ethyl P-imino-a-cyano-y-phenylbutyrate in concentrated sulphuric acid is brought about a t Oo, and the temperature is not allowed t o rise above this point, no green colour appears, the solution remaining a light brown.Whether the green colour is formed or not, the yield of the naphtlialeue is not apparently affected. The corresponding carboxylic acid (15) can be readily prepared from ethyl 1 : 3-diaminonaphthalene-2-carboxylate (I 1) on treating it with a n alc+oholic solution of potash. The free acid, which is colourless, is unstable a t temperatures above its melting point (85"), being then transformed with evolution of carbon dioxide into 1 : S-naphthylene- diamine (16). 1 : 3-Naphthylenediamine prepared in this way is identical with the compound obtained by Urban(Ber., 1887, 20, 973) by the reduction of 1 : 3-dinitronaphthalene, and by Friedlander (Ber., 1895, 28, 1953) by the action of ammonia on 4-amino-2-naphthol. It was pointed out in Part I.of this series that ethyl p-imino- a-cyanoglutnrate (1 7) reacted with sodium ethoxide, forming a sodium1912 ATKINSON AND THORPE: THE FORMATION AND derivative, and that tlie metal entered in the po'ition (l), that after the sodium atom in this had been replaced by a n alkyl radicle, the hydrogen marked (2) could be replaced by sodium, and that finally, after this sodium had been treated with a n alkyl iodide, the third hydrogen atom marked (3) could be replaced. CO,Et* CHH*C:(NH)*CH(CN)*CO,Et (17.) (1) (4 (2 ) Ph.CHH*C(:NH)*CH(CN)*C02Et (18.) It is interesting to note that, although the hydrogen atom marked (2) is attached to the same carbon atom as a nitrile- and a carbethoxyl- group, yet the first hydrogen atom replaced is that marked (l), which is attached to the same carbon atom as the carbethoxyl- and the carb- imino-group.I n the case of ethyl p-imino-a-cyano- 7-phenylbutyrate (1 S), the influence of the phenyl group is at once apparent, and we have only succeeded in introducing one alkyl group into this compound after repeatedly treating it with sodium ethoxide and the nlkyl iodide. The hydrogen atom replaced is that marked (*), and apparently the hydrogen atom of the cyanoacetic residue is not replaceable under ordinary conditions. We have carefully studied both the methyl and ethyl derivatives of ethyl P-imino-a-cyano-y-phenylbutyrate, and have found that it is necessary to treat the ethyl salt four successive times with the calculated quantity of sodium ethoxide and excess of methyl (or ethyl) iodide in order to convert the whole of i t into its mono-alkyl derivative.The positions of the alkyl groups in the alkylated compounds can be readily shown by the products they give on complete hydrolysis with alcoholic potash. Thus the ethyl salt which is prepared by the action of sodium ethoxide and methyl iodide on ethyl P-imino-a-cyano- 7-phenylbutyrate gives phenylscetic and malonic acids under these uonditiony, thus : Ph*CHR.l[e* C: (NH). CH (CN)*CO, E t +% \ 4 CH,: (CO,H), i' Ph*UHILIe CO,H It is therefore ethyl P-imino-a-cyano-y-phenyl-n-valerate, Ph*CHMe-C:(NH)*CH(CN)*CO,Et. In the same way, the corresponding ethyl derivative gives a mixture of a-phenyl-n-butyric and malonic acids on complete alkaline hydrolysis. Its formula is therefore Ph*CHEt*C(:NH)*CH(CN)*CO,Et.REACTIONS OF IMINO-COMPOUNDS.PART 11. 1913 Both these ethyl salts behave in the same way as ethyl /3-imino- a-cyano-y phenylbutyrate on treatment with concentrated sulphuric acid. I n each case a similar green to blue coloration is produced if the solution is allowed t o become warm, but is not formed if the temperature is kept below O", and in each case, also, on pouring the mixture on ice a clear solution is obtained from which the sulphats of the base separates on standing. Ethyl 2 : 4-diamino-1-methyl- naphthalene-3-carboxylate (1 9) and ethyl 2 : 4-diamino-1-ethyl- naphthalene-3-carboxylate (22) are in each case precipitated from the solutions of their sulphates on the addition of ammonia as yellow oils which on extraction by means of ether are obtained as syrups rapidly solidifying to yellow, crystalline solids.Me Me 31 e Et (21.1 (22.1 Ethj.1 2 : 4-diamino-1-methylnaphthalene-3-carboxylate passes on hydrolysis with alcoholic potash into the corresponding carboxylic acid (20), which, like the unalkylated derivative, is a colourless, crystalline compound, decomposing with evolution of carbon dioxide on being heated above its melting point and passing into 2 : 4-diamino- 1-methylnaphthalene (21). Et Et (23.1 (24.) I n the same way, ethyl 2 : 4-diamino-1-ethylrraphthalene-3-carboxylate (22) yields 2 : 4-diamino-1-ethylnaphthalene-3-carboxylic acid ( 2 3 ) and 2 : 4-diamino-1-ethylnaphthalene (24). I%e Condensation of Benxyl Cyanide wit?^ its Sodizcm Devivative. The interaction of benzyl cyanide with its sodium derivative was first studied by Wache (J.pr. Chem., 1889, ii, 39, 251), who investi-gated the action of finely divided sodium on an ethereal solution of the nitrile. Although this chemist was unable to isolate the bimolecular nitrile, CH,Ph*C(:NH)*CH(CN)Ph, he found that, on heating the precipitate formed in the above reaction with excess of benzyl cyanide i n a sealed tube a t 180' for several hours, i t was transformed into a white, crystalline, basic substunce of the empirical formula C,,H,,N,, t o which he gave the name of cyanbenzyline (G-amino-5-phenyl-2 : 4- N---C(NH,)' ' dibenzylpyrimidine), and the formula CH,Ph*C< on account of the similarity between its mode of formation and properties and those of cyanethine and cyanmethine, which E.v. Meyer (J. pr. C~WH,., lS89, ii, 39, 156) had previously shown to be derivatives of pyrimidine. Wache subsequently found that the best way t o prepare cyanbenzyline was t o heat a mixture of the nitrile and dry sodium ethoxide in a sealed tube a t 170-180° for many hours. E. v. Meyer (J. pr. Chenz., 1895, ii, 52, 114), in conjunction with 0. Probst (Inaug. Diss. Leipzig, 1894), repeated the work of Wache, and found that if the precipitate which was formed by the action of finely divided sodium on a n ethereal solution of benzyl cyanide was washed with light petroleum and then added to dilute acetic acid, a viscid oil was obtained which could not be distilled without under- going decomposition, but which evidently consisted of @-imino-a-cyano- ay-ciiphenylpropane, CH,€'h*C( :NH)*CH(CN)Ph, since on treatment with hydroxylaruine i t gave the same oxime as that derived from cyanodibenzyl ketone, CI-I,Ph*CO*CH( CN)Ph.Later, v. Walther and Schickler (J. pr. Chem., 1897, ii, 55, 350) prepared the same compound by the action of ammonia on the cyanoketone, CH,Ph-CO-CH(CN)Ph, but also failed to obtain i t in the solid condition. The termolecular nitrile cyanbenzyline was thoroughly investigated by Herfeldt ( J . pr. Chem., 1896, ii, 53, 246), who prepared many of its derivatives, and still more recently v. Walthor (J. p. Chem., 1903, ii, 87, 447) has found that i t can be prepared by the action of finely divided sodium on an ethereal solution of berizyl cyanide containing dimethylaniline. Owing to the similarity in constitution between benzyl cyanide and ethyl cyanoacetate, we decided, in order to prepare P-imino-a-cyano-ay-diphenyl propane, CH,Ph* C( :NH)*CH(CN)Ph, to in- vestigate the interaction of benzyl cyanide with its sodium derivative in alcoholic solution, since in the case of ethyl cyanoacetate a good yield of ethyl /3-iminocyanoglut arate, CO, E t C H 2- C( N H) - CH( CN )CO,E t, had been obtained by Baron, Remfry, and Thorpe by this means (Trans., 1904, 85, 1726).We found that the products formed in this condensation varied with the leogth of time during which the heating was continued a t lobo. Thus, when two molecular equivalents of benzyl cyanide and one of N:C'(C H,Ph)>(jphREACTIONS OF IJIINO-CORLPOU,I'DS. P-iRT [I. 1915 sodium ethoxide dissolved in alcohol mere heated on the water- bath for half a n hour, the product consisted of about 70 per ceilt.of p-imino- a-cyano-ay-diphenylpropane, CH2P:i C( :NH) C H(CN)Ph, mixed with unchanged benzyl cyanide. When the heating was prolonged, an odour resembling amnionia became apparent at the mouth of the condenser and O K ~ working up the product at the end of two hours i t was found t o consist of ahoat equal proportions of P-iinino-u-cyano- ay-diphenylpropane, CH2Ph*C( :NH)*C H( CN)Ph, P-keto-a-cymo- ay-diphenylpropane, CH2Ph.CO*CH(CN)Pli, aucl cyanbenzyline, some benzyl cyanide being at the same time recovered unchanged. On prolonging the heating uiitil the oclour reseinbling ammonia ceased t o be perceptible, an operation which usually required twenty- four hours to accoiiiplish, the product was found to consist entirely of P-keto-a-cyano-ay-diplienylpropaue and cyanbeuzy h e .Subsequently i t was found by experiment that the odour resembling ammonia was riot due to this substance itself, but to ethylamine, which was probably foriltecl by the action of the alkaline alcoholic solution on P-imino-a-cyano-uy-dipheny 1 propme, the react ion eviden tl y proceedi ri g uccording to equation (111) : (111). CH,rh*C(:NH)'CH(CIU)Ph + ILOEt -+ CH,PLi*C!O.CH(ON)Ph + EtNW,. It is apparent, therefore, that the first action of benzyl cyanide ou its sodium derivative in alcoholic solution a t 100" is to form p-imino- a-cpno-ay-diphenylpropane according to equation (LV) : (IV). Ph*CH:Na.CN + H*CH(C")Ph -+ P h C HNa C ( : N H) C H ((2 N) P 11, and that if the reaction is stopped at the end of about half an hour n good yield of this compound can be obtained.After this time, the initial product is slowly clecornposed in accordance R. ith equation (111) and P-keto-a-cyano-ay-diphenylpropane is formed ; at the same time, the sodium derivative of P-imino-a-cyano-ay-tliphenylpropane reacts with the unchanged benzyl r.j.:xnide, forming cjanbenzyline in accord- ance with the observation of Watche. Like all previous investigators, we have beeu unable to obtain /3-imino-a-cyano-ay-diphenylpropane (33) in n crystalline condition, although we fiud that it can be distilled without decomposition under a presswe of 20 mm. if the operation is conducted rapidly and only small quantities are used. When treated with cold concentrated sulphuric acid, it behaves in just the same may as ethyl P-imino-a-cy ano-y-phenylbutyrate, being converted into 1 : 3-dinmino-2-phenylnaphthnlene (24) thus : VOL.LXXXIX. 6 li1916 ATKINSON AND THORPE: THE FORMATION AND (23) (24) It is worthy of note that, whereas ethyl 1 : 3-diaminonaphthaIene-2- carboxylate is intense yellow in colour, 1 : 3-diamino-2-phenylnaphthalene is colourless, and a comparison of the three following formuke is of interest as showing the influence of the carbethoxyl, carboxyl, and phenyl groups respectively on the stable forms of similar compounds : CHn Y (Yellow). (Colourless). (Colourless). It is also of interest to note that the same phenomenon occurs in the corresponding hydroxy-compounds, thus : Metzner (Annalen, 1901, 298, 386) finds that ethyl 1 : 3-dihydroxynaphthalene-2-carboxylate ( 2 5 ) is yellow, whereas the corresponding acid (26) is colourless.1 : 3-Di- bydroxy-2-phenylnaphthalene (27), which has been prepared by Volhard (Annulen, 1900, 296, 16) by the action of concentrated sulphuric acid on ethyl diphenylacetoacetate, CH,Ph* CO *CH(Ph)* CO,Et, is also colourless. CH, /\/\GO / V \ O H /\(\OH I I bH*CO,Et I I bO,H I \/\/Ph GO (25) (26) (2'1) OH \/\/ OH \/\/ Yellow (Metzner). Colourless (Metzner). Colonrless (Volhard). The salts of 1 : 3-diamino-2-phenylnaphthalene are colourless, but become intensely coloured on exposure to the air. A full investigation of its properties are in progress. EXPERIMENTAL. Formation of Ethyl p-1Tmino-a-cyano-r-p~~~n~lbutyrate, CH,Ph* C( :NH) CH( CN) CO,E t.This ester mas produced by the condensation of the sodium derivative of ethyl cyanoacetnte with benzgl cyanide in alcoholic solution. Twenty-three grams of sodium were dissolved in 275 grams of alcohol arid mixed with 113 grams of ethyl cyanoacetate. ToREACTIONS OF IMINO-COMPOUNDS. PART 11. 1917 the well-cooled solution 11 7 grams of benzyl cyanide were added and the whole heated on the water-bath. It was found that the yield of the condensation product varied considerably with the length of time during which the mixture was heated and that much care had to be exercised in order t o obtain the above compound in yields sufficiently large for the purposes of the research. This was necessary owing to the fact t h a t soon after being formed, the con- densation product was found to pass rapidly into another compound (see below) which has not yet been identified.This difficulty will be realised when i t is pointed out t h a t after the above mixture had been heated for twelve hours a t 100' only about 10 per cent. of ethyl p-imino-a-cyano-y-phenylbutyrate could be isolated, the majority of the benzyl cyanide being recovered unchanged, whereas if the heating was prolonged at the same temperature for twenty- four hours the product, whilst containing 25 per cent. of the ester, was found to be mixed with as much as 40-45 per cent. of another compound of high molecular weight, and only a relatively small proportion of the benzyl cyanide was recovered uuchanged. On heating for a still longer time the quantity of the complex substance increased and the amount of ethyl P-imino-a-cyano-y-phenylbutyrate formed and of unchanged benzyl cyanide diminished.After numerous experiments carried out under different conditions in which yields of the ethyl ester varying from 10-50 per cent. of the theoi etical amount were obtained, the following method was ultimately adopted as being the most convenient. The molecular mixture described above was heated on the steam- bath for fifteen hours, the flask being vigorously shaken from time to time. It was observed that the white insoluble sodium derivative of ethyl cyanoacetate gradually dissolved and that the solution became deep red in colour and very viscous. After being heated for the specified time the product was cooled, when it set to a thick jelly.Dilute hydrochloric acid was then added and the heavy oil which separated extracted by means of ether, the ether solution being washed with water and then with dilute sodium carbonate solution. During the washing with sodium carbonate a considerable quantity of acid oil was extracted, a description of which will be found below. The ether solution, without being dried, was evaporated free from ether, and the residue subjected to distillation in a current of steam, whereby the whole of the unchanged benzyl cyanide was recovered in the distillate. The residue, which consisted of a viscid brown oil solidifying on cooling, was then separated by filtration, dried on a porous plate, and recrgstallised from absolute alcohol.Ethyl p-imino-a-cyano-y-pheizyZbzLtyrute, purified in this way, was obtained in long, colourless needles, which melted at 125' : 6 K 21918 ATKINSON AND THORPE : THE FORRIATION AND 0 . 1 877 gave 0.4659 CO, and 0.1068 H20. C = 67.69 ; H = 6.32. C1,H,,O,N, requires C = 67.81 ; H = 6.1 per cent. The ethyl ester is insoluble in solutions of alkali carbonates and in aqueous caustic alkalis and is not acted on, even on prolonged boiling, by concentrated hydrochloric acid. It can be recrystallised from either methyl or ethyl alcohol or from benzene, but is almost insoluble in light petrole urn. The sodium carbonate washings from the ether solution were acidified, when a heavy oil separated, which partially solidified, This was filtered by the aid of the pump and the mixture of oil and solid washed with ether, in which solvent the solid was found to be quite insoluble.The residue was dried on a porous plate and found t o consist of a light brown amorphous substance apparently insoluble in all the usual organic solvents with the exception of hot glacial acetic acid in which it was only very sparingly soluble. It was insoluble in concentrated hytlrochloric acid, but dissolved in concentrated sul- yhuric acid apparently uiichanged, since i t was reprecipitated on the addition of water. It is, liowever, readily soluble in dilute solutions of alkali mrbonates and in caustic alkalis aud in the latter case on tlie addition of excess of the alkali :L crystalline alkali salt slowly separates. This salt is, however, difiicult to purify since it is dissociated by water, rind therefore cannot be freed from the excess of alkali.For the purpose of analysis the compound was purified by conversion into the potassium salt, which was effected by first washing the crude product thoroughly with ether and then dissolving it in a moderately dilute solution of caustic potash. On standing a crystal- line yotussiuni salt slowly separated which mas filtered and recon- verted into the higinal acid by treatment with dilute hydrochloric acid. The white amorphous precipitate thus obtained was then re- cryst:illisecl from a laiage quantity of glacial acetic acid, from which solvent it separated in colourless, microscopic needles which me1 ted t o a brown liquid a t 335' : * I. 0.3036 gave 0.5346 CU, arid 0.1416 H,O. C = 73.76 ; H = 5.14.11. 0.2072 ,, 0.5610 CO, ,, 0.0940 H,O. C=73.84 ; H=5*08. 111. 0.2508 ,, 35.0 C.C. nitrogen at 18" arid 767 mm. N = 15.95. C2,Hl,0N, requires C = 73.7 ; H = 5.2 ; N = 16.4 per cent. These figures furnish no clue as to the identity of the substance. Considerable quantities of this compound having accumulated during the course of this research, it is our intention further to investigate its properties. TlJe ethereal layer which floated on the filtrate from the above * This melting p i n t mas taken in cyaiibenzyliiie (see p. 1932).RE-4CTIONS OF ININO-COMPOUNDS. PART 11. 1919 compound after washing it free from oil was separilted in the funnel, washed with water, dried and the ether evaporated. The residue, which consisted of a viscid, dark oil readily soluble in dilute sodium carbonate solution, was, without further purification, mixed with three times its volume of absolute alcohol and an equal volume of con- centrated sulphuric acid and after being allowed to stand for twelve hours, heated on the water-bath for three hours.The mixture mas then poured into water, the oil which separated extracted with ether, and after any unchanged acid had been extracted by means of dilute sodium carbonate solution, the ethereal solution was dried and evaporated free from ether. The brown liquid which remained deposited a considerable quantity of crystals on standing, and these were collected and purified by recrystallisation from hot alcohol, being obtained in silky needles melting a t 178" : 1. 0.1868 gave 0.5262 CO, and 0.0882 H,O.C = 76-65 ; H = 5.28. 111. 0.2284 ,, 24.6 C.C. nitrogen a t 13' and 756 mm. N = 12.78. IV. 0.2264 ,, 24% C.C. ,, ,, 13" ,, 752 mm. N=12*Sl. IT. 0.1950 ,, 0.5472 C02 ,, 0.0908 H20. C = 76.52 ; H= 5.17. C2,HI7ON, requires C == 77.0 ; H = 5-2 ; N = 12.9 per cent. The compound is insoluble in alkalis and in concentrated hydro- Jts constitution has not yet been determined. chloric acid. The Constitution of Ethyl p-lni ino -a - cy ano- y - ph e 2 ~y l b u t yrnte. Formation of Phenylacetic and Malonic Acids bg the Action of illetlryl Alcoholic Potash. The proof o€ the constitution of ethyl /I-imino-a-cyano-y-phenyl- butyrate was derived from a study of the products which mere formed when it was completely hydrolysed by means of an alcoholic solution of potash. As already mentioned in the introduction, this proof is not in itself conclusive, since ethyl P-imino-y-cyano-y-phenylbutyrate, CHPh(CN)*C( :NH)*CH,*CO,Et, which might conceivably be formed in the same reaction would also give the same products on alkaline hydrolysis, but that, taken in conjunction with the other reactions of this ethyl salt, places its constitution beyond question.When ethyl /3-imino-a-cyano-y-phznylbutyrate was mixed with a solution of 1; times the calculated quantity of potash dissolved in methyl alcohol, considerable heat was generated and much ammonia was evolved on heating the solution on the water-bath. After heating for six hours the evolution of ammonia had ceased and a clear solution was obtained on pouring the hydrolysed product into water. The excess of methyl aIcohol was then evaporated and the residue acidified by means of hydrochloric acid, when a white, crystalline substance1920 ATKINSON AND THORPE: THE FORMATION AND separated.This was collected and recrystallised from dilute alcohol, being t.hus obtained in glistening plates melting a t 76". An analysis proved, as its appearance and odour indicated, that it was phenyl- acetic acid : 0.2107 gave 0.5222 CO, and 0.1232 H,O. C7E,0, requires C r= 67.8 ; H = 6-4 per cent. The filtrate from the phenylacetic acid was evaporated to dryness, acidified with concentrated hydrochloric acid and again evaporated, being finally placed in a Soxhlet apparatus and extracted with ether. The ethereal solution on drying and evaporating deposited a quantity of oil which rapidly solidified and then melted a t 132' with decomposi- tion.The analysis, together with the fact that on distillation it yielded acetic acid, showed it to be malonic acid : C = 67-61 ; H= 6 49. 0.2217 gave 0.2796 CO, and 0.0778 H20. C = 34.39 ; H = 3.89. C,H,O, requires C=34*6; 11=3-8 per cent. Formation of Ethyl 1 : 3- Diaminonaphthc~ Zene-2-car box ylute, When dry ethyl /3-imino-a-cyano-y-phenylbutyrate ground to a fine powder is added to three times its weight of cold, concentrated sulphuric acid it dissolves rapidly forming a yellow solution. If the mixture is allowed to becouie warm this solution becomes deep malachite-green in colour, but i t remains yellow if placed in a mixture of ice and salt. If, as soon as the ethyl salt has all dissolved, an operation which usually takes abont one minute, the strong d p h u i i c acid solution is poured on ice, a clear yellow solution is pro- duced from which an almost white crystalline substance separates on standing.This compound is the sulphccte, C,3H140,N,,H,S0,, of the above base and can be obtained in almost colourless plates by recrystallisation from water : 0.1539 gave 0,2706 CO, and 0.0705 H,O. Cl,H,40,N2,H2S0, requires C: = 47.6 ; H = 4.9. The sulphate gradually becomes yellow on exposure to the air, and when dissolved in water forms, in the cold, an almost colourless solution, which on warming becomes bright yellow; this yellow colour is discharged on cooling. Ethyl-1 : 3-diaminonapiithalene-2-carboxylate is precipitated as a yellow, crystalline solid on adding aqueous ammonia to a solution of tbe sulphate aissolved in water.It was collected by filtration and C = 47.95 ; H = 5.12.REACTIONS OF ININO-COMPOUNDS. PART 11. 1921 recrystallised from ether, being obtained in this way in golden yellow plates melting a t 108' : 002244 gave 0.5568 GO, and 0.1262 H,O. 0.3238 ,, 32.4 C.C. of nitrogen at 12" and 769 mm. N = 12-13, C1,H140,N, requires C = 67.8 ; H = 6.1 ; N = 12.2 per cent. C = 67.65 ; H = 6.24. The hydrochloride, C1,H1,O2N2,2HCI, is best prepared by dissolving the base in dilute hydrochloric acid and then adding excess of con- centrated hydrochloric acid to the almost colourless solution. On standing, colourless needles of the above salt separate : 0.2911 gave 0.2734 AgCI.C1= 23.30. Cl,H,40,N2,2HCl requires C1= 23.4 per cent. Ethyl 1 : 3-diaminonaphthalene-2-carboxylate is very readily oxidised by the mildest oxidising agents, being even slowly altered on exposure to the air. The compounds produced in these circumstances as well as the products formed by the action of nitrous acid on this ethyl salt are still under investigation, 1 : 3-DiaminonaphthaZene-2-cccrboxylic acid, I /\/\NH, I Jc02H \A/ NH2 This acid was prepared from the ethyl salt by hydrolysing it with methyl alcoholic potash. 5 grams were added to a solution of 18 times the calculated quantity of caustic potash dissolved in meth3 1 alcohol and the solution warmed on the water-bath. On cooling a crystalline potassium salt, CI1H,O,N2K, separated, which was collected by filtration, purified by washing with a little methyl alcohol, and dried on a porous plate.It is a yellow, crystalline solid readily soluble in water : 0.2195 gave 0.0788 K,SO,. K = 16-09. C,1H,0,N2K requires K = 16.25 per cent. The free acid is precipitated as a white, crystalline solid on adding dilute hydrochloric acid to a solution of the potassium salt in water. It was collected by filtration, dried on a porous plate and recrystallised from warm water. Since the acid rapidly loses carbon dioxide at 80°, it is necessary that the aqueous solution should be considerably below this temperature. Since, however, the acid is readily soluble in warm water and separates again on cooling, it can easily be recrystallised in quantities without raising the temperature of the solution above 60" 1 : 3-Diaminonaphthalene-2-carboxylic acid can be obtained in thisway in colourless needles melting at 8 5 O with immediate elimination of carbon dioxide : 0.2258 gave 0.5374 CO, and 0.1064 H,O.The carboxylic acid does not form salts with acids. C = 64.90 ; H = 5-27, Cl,Hlo0,N2 requires C = 65.3 ; H = 4.9 per cent. 1 ; 3 -AT~6~l~t?~ylenediallzi12e. This base was prepared from the above carboxylic acid by heating i t at 100' until the evolntion of c:trbon dioxide had ceased. The opera- tion was carried out in n small flask which was placed in n bath of sulphuric acid and heated to the requisite temperature. When the evolution of gas had ceased, the product was dissolved in dilute hydro- chloric acid and the deep red solution, after filtering, rendered alkaline with caustic potash.The base, which was then precipitated, was recrystallised from water and obtained in small plates, usually slightly red in colour, which melted at 96": 0.1628 gave 0.4520 CO, and 0.0910 H20. CloHloN2 requires C = 76.0 ; H = 6.3 per cent. The diacetyl derivative, CloH,N,(CO*CH,), mas prepared by dissolving the base in acetic anhydride and heating the solution on the sand-bath for one hour. The excess of the anhydride was then evaporated by placing the solution in an evacuated desiccator over potash until solid. Recrystallised from acetic acid, i t was obtained in fine needles melting at 263-265" (Friedlander, Ber., 1895, 28, 1953) : C = 76.00 ; 13 = 6%. 0.1693 gave 0.3826 CO, and 0.1112 H,O. C = 61-64 ; H= 7.29.C,oH,,O,N, requires C = 6 1.9 ; H = 7.2 per cent. Pornintion of Etlq,! /3-Imiizo-a-cyano- y p l m yl vnlernte, P h C HMe C( : N H) C 13 (CN) CO,F,t. As stated in the introduction, tho methylation of ethyl p-imino- a-cyano-y-phenylbutyriite by means of sodium ethoxide and methyl iodide in alcoholic solution is not easily :~ccompIished. The difficulty is probably due to the fact that the unrenctive char,tcter of the methylene hydrogen atom causes a state of eqnilibrium to be set up between the sodium ethoxide, the ethyl salt and its sodium derivative, i n which only about one-third of the last-named is formed. Thus, by the action of methyl iodide on a cold mixture of equimolecular proportions of sodium ethoxide and ethyl /3-imino-a-cj ano-y-phenyl- butyrate, only about one-third of the ethyl salt is converted into its nietliyl derivative.Therefore, in order t o complete the conversion,REACTIONS OF IMIKO-COMPOUNDS. PART 11. 1923 the process of methylation was repeated four times in the following manner : Ten grams of the ethyl salt were added to a solution containing 1 gram of sodium dissolved i n 1 2 grams of alcohol, and the whole, after being well cooled, treated with 12 grams of methyl iodide. After standing for some time in the cold the mixture was heated on the wat'er-bath until a test portion diluted with water gave a neutral reaction with litmu., when, after the excess of alcohol and unchanged methyl iodide had been distilled off as completely as possible on the water-bath, a further quantity of sodium ethoxicle made by dissolving 1 gram of sodium in 13 grains of alcohol was added, and the solution treated with methyl iodide and again heated until neutral.After this process had been repeated four times, water was added arid the oil, which then separated and which almost immediately solidified, was filtered by the aid of the pump and purified by recrystallisation from nlcohol. Ethyl p-im iiao-a-c~uno-y-pl~enylvcLlernte is obtained in this way in large needles melting at 93' : 0.1596 gave 0.4052 CO, and 0.0959 H,O. C=69.24; H=6*72. C,,H,,U,N, requires C = 68% ; H = % a 6 per cent. Forniation of a-Pheny'propionic Acid and NaZonic Acid j r o n z RthJ ~-1nii~~o-a-cyc~no-y-p~~~nylvnlernte. The proof of the constitution of ethyl P-imino-a-cjano-y-phenyl- y-methylbutymte was derived from the s t d y of the prodiicts formed from i t on alkaline hydrolysis.The operation was carried out as follows : Five grams of the ethyl salt wero mixed with a solution containing one-and-a-half times the cnlculated qiiantity of caustic potash dissolved in methyl alcohol and heated on the water-bath until the odour of ammonia, which was apparen t a t the commencement of the hydrolysis, had entirely disappeared. The prodrict was then diluted with water and evaporated on the water-bath u n t i l free from methyl alcohol, when it was acidified with concentrated hydrochloric acid and allowed to stand, Since the oil which separated on the addition of the acid showed no tendency to crystallise, the solution WIS extracted by means of ether and the ethereal solution,afler drying, evaporated free from ether.The oil which remained was then distilled under the ordinary pressure and was found to boil constantly at 264-265", at which temperature a-phenylpropionic acid, which does not appear to be a solid at the ordinary temperature, boils (Fittig and Wurster, Annalen, 1 S79, 195, 165) : 0.2100 gave 0.5332 CO, and 0.1295 H,O. C = 7134 ; I€ = 6.85. C9Hl,0, requires C = 72.0 ; H = 6-7 per cent.1924 ATKINSON AND THORPE: THE FORMATION AND The aqueous solution after the extraction of the above acid wao evaporated to dryness and extracted in a Soxhlet apparatus with ether. The ethereal solution after drying was evaporated free from ether yielding a solid residue which melted at 132" and gave acetic acid on distillation, evidently therefore consisting of malonic acid : 0.1774 gave 0.2237 CO, and 0.0622 H,O.C,H,O, requires C = 34.6 ; H = 3.8 per cent. The above analysis indicates that the substance is mslonic acid and not methylmnlonic acid, and therefore shows that only one methyl group had entered into the molecule of ethyl P-irnino-a-cyano-y-phenyl- butyrate on its being completely methylated in the manner already described. Owing to there being only a slight difference between the percentage corn positions of ethyl /3-imino-a-cyano- y-phen y 1 bu tyrat e and its met hg 1 derivative, this fact could not be definitely settled on the results of their analysis alone. C = 34.41 ; H = 3.90. Formation of Ethyl 2 ; 4-Diamino- lrnethyhaphthaZene-3-carboxyZate, Me The conversion of ethyl p-imino-a-cyano-y-phenylvalerate into the above derivative of naphthaleno takes place with the same ease as that already described in the case of the unmethylated derivative.Five grams of the finely-ground ethyl salt were added slowly to three times its weight of concentrated sulphuric acid cooled in ice. On each addition, the salt instantly dissolved, and in spite of the low tempera- ture the sulphuric acid solution became deep bluish-green. When all had been added, the solution was allowed to stand for two or three minutes and then poured on ice. The deep bluish-green colour of the solution was instantly discharged on mixing with the ice, forming a clear yellow solution from which the sulphate, C,,H160,N2,H,S0,, of the base slowly separated on standing as a pale yellow, crystalline precipitate : 0.1708 gave 0.3064 CO, and 0.0828 H,O.The sulphate is readily soluble in hot water, but separates from its concentrated solutions in this solvent on cooling. An aqueous solution of the salt at 0" is nearly colourless, but becomes a deep yellow on being heated to the boiling point. On being again cooled, the colour C = 48.92 ; H = 5.42. C1,Hl,O,N,,H,SO, requires C = 49.1 ; H = 5.3 per cent.REACTIONS OF LMINO-COMPOUNDS. PART 11. 1925 is discharged. The sulphate is insoluble in alcohol and this fact can be utilised in its formation, since on pouring the bluish-green sulphuric acid solution into three times its volume of well-cooled absolute alcohol, the salt is completely precipitated and can be isolated by filtration.The free base was prepared by dissolving the sulphate in water and adding ammonia until strongly alkaline. The deep yellow oil which was then precipitated did not8 show any signs OF crystallising, and mas therefore extracted by means of ether, the ethereal solution being washed with a little water, dried with calcium chloride, and evaporated. The yellow syrup which remained instantly solidified on scratching, forming a deep yellow solid, which was recrystallised from methyl alcohol and thus obtained in orange-yellow prisms melting a t 75" : 0.1676 gave 0,4245 CO, and 0.1017 H20. C14H1602N2 requires C = 6 8 3 ; H = 6.6 per cent. Ethyl 2 : 4-dinmino- 1 -methylnaphthalene-3-carboxylate is readily soluble in cold ether and can in this way be distinguished from the lower homologue.It is also soluble in all the usual organic solvents excepting light petroleum, and is readily oxidised, but is not altered on exposure t o the air so rapidly as ethyl 1 : 3-diaminonaphthalene-2- carboxylate. C = 69.08 ; H = 6.74. Formation of 2 : 4-Diamino-l-methyZnaphthalene-3-carboxyZic Acid, Me This acid was prepared from the ethyl salt by the action of alcoholic potash. Ethyl 2 : 4-diamino-l-methylnaphthalene-3-carboxylate was added to a solution containing one and n half times the calculated quantity of potash dissolved in metbyl alcohol and the mixture heated on the water-bath until a test portion diluted with water remained clear, Water was then added and the solution evaporated on the water-bath until free from methyl alcohol, when i t was acidified, and the colourless, glistening leaflets of the acid which then separated collected by filtration.The acid, which is slowly decomposed by boiling water, was recrystallised rapidly from hot water, and obtained in this way in colourless needles which decomposed with evolution of carbon dioxide at 155-160O apparently without melting : C1,H,,O,N, requires C = 66q7 ; H = 5.6 per cent. 0.1697 gave 0.41 39 CO, and 0.0875 H,O. C = 66.52 ; H = 5.73.1926 ATKINSON AND THORPE: THE FORMATION AND Me /\,A I I JNH2 Formation of 2 : $-Dinrnino-l-methylnaphtilalene, I \/\/ NH2 This base was prepared from the carboxylic acid by heating it for some time a t lS0". The finely-ground and purified acid was placed in a small flask and heated in n bath of sulphuric acid at the required temperature until carbonic acid ceased t o be evolved, when the residue was treated with dilute hydrochloric acid, and the deep red solution thus formed boiled with animal charcoal and filtered.On adding dilute aqueous caustic soda to the filtrate, the base was precipitated as a resin, which did not crystallise on standing. It was therefore dissolved in concentrated hydrochloric acid and the solution allowed to stand, when the hydrochloride, CllH12N,,2HCl, slowly separated in white, silky needles : 0.2117 gave 0.2467 AgC1. C1= 28.91. C11H,,N2,2HC1 requires C1= 29.0 per cent. The hydrochloride readily dissolved in water, and the solution on being made alkaline with caustic soda solution deposited the base as a white solid, which, when recrystallised from dilute methyl alcohol, was obtained in fine, white needles melting a t 65' : 0.1912 gave 0.5358 CO, and 0,1245 H,O.The base becomes slowly coloured on exposure to air and light. The platinichloyide, C11HlzN2,H,PtCI,, is precipitated as a yellow, crystalline powder on adding excess of platinic chloride to a solution of the hydrochloride of the base in water : C=76*43 ; H=7*23. C,,H,,N, requires C = 76.7 ; H = 7.0 per cent, 0 2513 gave 0.0834 Pt. Pt =133.38. C,,H,,N,,H2PtCI, requires Pt = 33.5 per cent. Poi-mution of Ztl,,yZ ~-Inaino-a-c~ccno-y-phenyZ-n-he~oc~te, Ph*CHEt-C( 3 H ) CH( QN) C0,Pt. The preparation of the ethyl derivative of ethyl P-imino-a-cyano-y- phenylbutyrate was undertaken in order to show conclusively that only one alkyl group could be introduced into this compound by the action of sodium ethoxide and an alkyl iodide.The process adopted was the same as that already described in the case of the methyl derivative, only in the present instance even greater difficulty was experienced in introducing the alkyl group, and, after the process of ethylationREACTIONS OF IMINO-COMPOUNDS. PART 11. 1927 had been repeated four times, considerable quantities o€ unchanged ethyl salt were recovered. The actual operation mas carried out as follows : 10 grams of ethyl p-imino-a-cyano-y-phenylbutyrate were added to a solution containing 2 grams of sodium in 30 grams of alcohol, which, after being well cooled, was mixed with 24 grams of ethyl iodide and warmed on the water-bath until ;L test portion diluted with water showed a neutral reaction to litmus.The excess of alcohol and ethyl iodide was then distilled off as far as possible on tile waler- bath and the above process again repeated. When the treatment had been carried out four times, water was added, and the oil, which was then precipitated and which solidified on standing, separated by filtration. I n the first place, the solid was recrystallised from dilute methyl alcohol, from which solvent it separated in needles having a melting point of 60-80". These were then ground with cold benzene, in which a considerable quantity dissolved, leaving a residue which melted a t 124-1 25'. The following analysis showed this substance to be unchanged ethyl P-imino-a-cyano-y-phenylbutyrafe : 0,1554 gave 0.3888 CO, and 0.0903 H,O.C,,H1,O,N, requires C = 67.8 ; H = 6.1 per cent. The benzene filtrate on evaporation left a residue which melted atJ 60-65', which was again ground with cold benzene yielding :L further small quantity of unchanged ethyl P-imino-a-cyano-y-pheayl- butyrate. The benzene solution from this second separation gave a product which melted at 60-6 lo. This was fioally recrystallised from methq 1 alcohol, pure ethgl p-imino-a-cytsno-y-phen$-n-?iexoate being thus obtained in small prisms melting a t 60" : C = 63-23 ; I€ = 6.50. 0.1564 gave 0.3990 CO, and 0,0996 H,O. C = 69-58 ; H = 7.12. C1,Hl,O2N2 requires C = 69% ; H = '7.0 per cent. Fornicction oj' a-Phenylbutyric Acid, Ph*CH(Et)*CO,H, and Halonic Acid froiri Ethyl ,8-l~~aino-a-cyc~no-y-phen~Z-n-I~exoate. The position of the ethyl group in ethyl P-imino-a-cyano-y -phenyl- ethylbutyrate was determined by the products formed on its com- plete hydrolysis with methyl alcoholic potash.Five grams of the ethyl salt were heated on the water-bath with a solution containing one-and-a-half times the calculated quantity of caustic pot ash dissolved in methyl alcohol until the odour of ammonia has ceased to he apparent. Water was then added and the solution evaporated on the water-bath until free from methyl alcohol, when it was acidified with hydrochloric acid and the product allowed to stand. The oil which was first pre-1928 ATKINSON AND THORPE: THE FORMATION AND cipitated on the addition of the acid became solid on standing and was isolated by filtration. Recrystallised from dilute alcohol it was obtained in crystals melting at 43' which is the correct melting point of a-phenylbutyric acid (Neure, Annalen, 1889, 250, 154) : 0.2001 gave 0-5358 CO, and 0.1333 H,O.CloH,,O, requires C = 73-2 ; H = 7.3 per cent. The aqueous filtrate after extraction with ether was evaporated to dryness on the water-bath, and the residue extracted in a Soxhlet apparatus with ether. The ether solution, after being dried with calcium chloride, was evaporated free from ether, yielding a white solid melting at 132O, which was converted on distillation into acetic acid. It was evidently, therefore, malonic acid, and its formation together with that of a-phenplbutyric acid indicates clearly that the ethyl group in ethyl P-imino-a-cyano-y-phenyl-y-ethylbutyrate is at- tached to the same carbon atom as is the benzene nucleus.C= 73.03 ; H = 7.40. Formation of Ethyl 2 : 4- Diunaino- l-ethyZ.lzapiLtiLnlelze- 3 - carboxylate, Et The conversion of ethyl /3-imino-a-cyano-y-phenyl-n-hexoate into the above derivative of naphthalene was accomplished in the following manner. The finely-ground ethyl salt was added gradually to three times its weight of concentrated sulphuric acid, the acid being kept well cooled in ice through the addition. When all had been added, the sulphuric acid solution, which had become deep indigo blue in colour, was allowed to stand at the ordinary temperature for about two minutes, when it was poured on to ice. On coming in contact with the ice the blue colour of the solution instantly disappeared, forming a light yellow solution from which, however, no separation of the sulphate of the base took place on standing.The clear solution was therefore made alkaline with ammonia and the yellow oil, which was then precipitated, extracted by means of ether. I n order further to purify the base, this ethereal solution was extracted twice with diluto sulphuric acid, and the sulphuric acid extract made alkaline with ammonia. The yellow oil precipitated in this way, and which became solid on standing, was collected by filtration and recrystallised from dilute methyl alcohol, being obtained in small yellow prisms melting a t 63O : 0.1282 gave 0.3298 CO, and 0.0832 H20. C J 70.16 ; H - 7-21, C15H1802N2 requires C = 69.8 ; H = 7.0 per cent.REACTIONS OF IMINO-COMPOUNDS.PART 11. 1929 The hydrochloride, C,,Hl,0,N2,2HC1, is prepared by dissolving the base in concentrated hydrochloric acid, and allowing the solution to stand. C1= 21.67. C1,H,80,N,,2HCl requires C1= 21.5 per cent. It consists of almost colourless needles : 0.2102 gave 0.1838 AgCl. Formation of 2 : 4- Diamino-1 -eth ylnaphtha lene- 3-ca~boxylic Acid, Et I n order to prepare this acid, 4 grams oE the ethyl salt were mixed with a methyl alcoholic solution of one-and-a-half times the calculated quantity of potash, and heated on the water-bath until a test portion was completely soluble in water. The product was then diluted with water and evaporated on the water-bath until free from methyl alcohol, when dilute hydrochloric acid was added and the precipitate, which then separated, isolated by filtration.The acid, like those already described, is rapidly decomposed by boiling water. It was therefore crystallised by dissolving it in water at 60" and allowing the solution to cool, when the acid separated in small leaflets which melted and decomposed a t about 130", the observed melting point, however, varied from 128-133O with the same specimen, depending on the rapidity with which the temperature was raised : 0.1729 gave 0.4281 CO, and 0.0969 H20. C = 67.52 ; H = 6.22. C,,H,,O,N, requires C = 67-8 ; H = 6.1 per cent. Formation of 2 ; 4-Diamino- l-ethylnaphth4zlene. Et This base was prepared by heating the carboxylic acid a few degrees above its melting point. The acid was placed in a small flask and heated in a bath of sulphuric acid at 150' until the evolut,ion of carbon dioxide ceased.The residue, which consisted of a viscid red gum, was dissolved in dilute hydrochloric acid and the solution, after being filtered, made alkaline with dilute aqueous caustic soda. The precipitated base, which solidified on stmding, was then collected by filtration arid recrystallised from dilute metbyl alcohol, being obtained in glistening plates melting a t 74' :1930 ATKINSON AND T'HORPE: THE FOHMATION AND 0.1812 gave 0.5127 GO, and 0.1256 H20. C,,H,,N, requires C = 77.4 ; H = 7.5 per cent. The hydrocldo~ide, C,2H,,N,,2HC1, is precipitated as a white, crystal- line powder on dissolving the base in concentrated hydrochloric acid and allowing the solution t o stand for some time : c! = 77-17 ; H = 7-70. 0.2207 gave 0-2429 AgCl.C1= 27.31. C,,H,,N2,2HC1 requires C1= 27.4 per cent. The plutinicldoyide, C,,H,,N,,H,PtCI,, is formed when a solution of the hydrochloride is mixed with an aqueous solution of plstinic chloride. It is a yellow, crystalline powder : 0,2401 gave 0*078l Pt. Pt =32.53. C,,H1,N2,H,PtCI, requires P t = 32.7 per cent. Codensat i o n of Benxpl Cyanide with its Sodium DerivcLtive, As mentioned in tlie introduction, this condensation was carried out i n three different ways, the nitrile being heated with its sodium deriv- ative in alcoholic solution a t 100" for (1) half an hour, (2) two hours, (3) twenty-four hours. ( 1 ) Forn~cttion of p- t n ~ i n o - a - c y c ~ ~ ~ o - a y ~ i ~ ~ ? ~ e n ~ t ~ ~ r o ~ u ~ CH,Ph* C(: N H)* CH(CN)P h.After a number of preliminary experiments it was ascertained t h a t this substance was produced in t>he greatest yields in the following way. 11.5 grams of sodium were dissolved in 130 grams of alcohol and mixed with 117 grams of benzyl cyanide, the whole being heated on the water-bath for half an hour. After this time the contents of the flask, which had a slight odour resembling ammonia, were mixed with water and the oil which then separated extracted with ether. The ethereal solution after being freed from alcohol by washing with water was, without drying, evaporated free from ether, and then aft'er being mixed with water distilled in a current of steam until all unchanged benzyl cyanide had passed over. The residue, which consisted of a viscid oil, was then extracted by means of ether, and the ethereal solution, after being dried with calcium chloride, evaporated free from ether.The oil which remained mas rapidly distilled under reduced pressure and was found to boil at 274'/20 mm., passing over as a colourless syrup : 0.2016 gave 0.6070 CO, and 0.1111 H,O. C,,H,,N, requires C = SB.0 ; N = 6.0 per cent. The identity of this compound with that prepared by E. v. Meyer was shown by the fact that with hydroxylamine it gavo an oxime melting C=82.12; H=6.17.HEACTIONS OF IMINO-COMPOUNDS. PART 11. 1931 at 107O, identical with that formed by the action of this reagent on the ketone, C!H,Ph*CO*CH(CN)Ph. Even when carefully purified by dis- tillation /3-imino-a-cjano-ay-diphenylpropane is a viscid liquid and shows no tendency to become crystalline. (2) Formation of /3-Irnino-a-cyano-ay-diphnylpropane, /I-&to-a-cyctno-ay-diphenylpropane, CH,Ph-CO*CH(CN)Ph.Cyan- benzyline (6- Amino-5-phenyl-2 : 4-dibenxylpyrimidine) and Ethylamine. In this experiment the reacting substances were mixed in the same proportions as in experiment (1) but were heated on the water-bath for two hours. The odour resembling ammonia which was apparent a t the end of the first half hour, became very marked on further heating, the contents of the flask becoming a t the same time dark red. At the end of the specified time a small quantity of alcohol was distilled over and collected in dilute hydrochloric acid, the solution evaporated on the water-bath to a small bulk and mixed with excess of a solution of platinic chloride.On adding a little alcohol to the mixture a yellow precipitate separated out which was collected by filtration and recrystallised from a little hot water, being thus obtained in yellow cubes. The following analysis showed it to be the platinichloride of ethylamine : CH,Ph*C( :NH)*WH(CN)Ph. 0.2713 gave 0.1054 Pt. (C,H,NH,),,H,PtCl, requires Pt = 39 .O per cent. As soon as the small quantity of alcohol necessary for the above experiment had been distilled over, the alcohol solution without further evaporation was mixed with water, acidified with dilute hydrochloric acid and extracted with ether. The ethereal solution after being washed with water to remom alcohol was thoroughly shaken with a solution of three volumes of concentrated hydrochloric acid to one of water.It was found that by shaking the ethereal solution with this mixture the cyanbenzyline could be completely extracted in the form of its hydrochloride, This hydrochloride, which is a viscid liquid under ordinary conditions, is quite insoluble in both dilute hydrochloric acid and in ether. Therefore on shaking the ethereal solution with the dilute acid three layers are formed, an upper layer consisting of ethereal solution from which the hydrochloride has been extracted, a middle layer consisting of this hydrochloride in the form of a viscid oil and a lower aqueous layer of dilute hydrochloric acid. The three layers were completely separated in the separating funnel, and it was found that on repeating the process three times the whole of the cyan- Pt = 38.85.VOL. LXXXIX. C i L1932 ATKINSOX AND THORPE: THE FORMATION AND benayline present was extracted from the solution. The oily hydro- chloride on warming on the water-bath with excess of sodium carbonate solution yielded cyanbenzyline as a crystalline mass which when recrystallised from absolute alcohol or from light petroleum (b. p. 90-100') was obtained in slender needles melting at 107" : C,,H,,N, requires C = 82.0 ; H = 6.0 per cent. 0.2076 gave 0.6250 GO, and 0.1160 H,O. The properties of cyanbenzyline have already been described by the investigators mentioned in the introduction. In addition to the published data concerning this substance, we find that it can be distilled under diminished pressure without undergoing any decom- position, passing over at 307O (20 mm.) as a colourless oil which sets to a highly refractive colourless glass on cooling.On dissolving this glass in hot alcohol the solution deposits the original cyanbenzyline on cooling.* The hydrochloride, C,,H,,N,,HCl, was obtained as a crystalline solid in the following way : cyanbenzyline was dissolved in absolute alcohol containing a small quantity of concentrated hydrochloric acid in which mixture it is readily soluble. Water was then added until a clear solution just remained, when, on standing, the hydrochloride separated in small, colourless needles : C= 82.11 ; H = 6%. 0.1690 gave 0.0640 AgCl. C1= 9.39. C,,H2,N,,HC1 requires C1= 9.2 per cent. Cyanbenzyline is converted into 6-hydroxy-5-phenyl-2 : 4-dibenzyl- pyrimidine on heating it with a 10 per cent,.sulphuric acid for twenty- four hours. This substance, which was originally prepared by Wache (J. pi-. Chem., 1889, [ii], 39, 251), crystallises from alcohol in small needles and melts a t 187' : 0,1540 gave 0.4646 CO, and 0.0816 H20, 0.2710 ,, 18.8 C.C. nitrogen a t 20' and 752 mm. N=7*88. C,,H,,ON, requires C = 81.8 ; H = 5.7 ; N = 7.9 per cent. The ethereal solution after the extraction of cyanbenzyline was, without drying, evaporated free from ether and the residue distilled in a current of steam until free from the small quantity of unchanged C = 82.28 ; H = 6-93. .Ic The stability of cyanbenzyline is such that it can be distilled a t the ordinary pressure without undergoing decomposition boiling under these conditions above 400" When once melted, it cools to a clear glass, which does not become crystalline except on long standing.We have found this substance extremely useful for determining the melting point8 of compounds between 230" and 380", for which purpose it is well adapted since it does not fume and does not become coloured unless kept near its boiling point for some considerable time.REACTIONS OF IMINO-COMPOUNDS. PART 11. 1933 benzyl cyanide, when it was again extracted with ether, the ethereal solution dried by means of caloium chloride and the ether evaporated. The residue, which consisted of a viscid oil, yielded two chief fractions on distillation under diminished pressure. The lower fraction which boiled at 225-230" (20 mm.) solidified on cooling and was purified by recrystallisation from a mixture of benzene and light petroleum (b.p. 70-80") being obtained in needle clusters, melting a t 86' : 0.1566 gave 0.4712 CO, and 0.0800 H,O. 0.2406 ,, 12 C.C. nitrogen at 20" and 756.5 mm. N = 5.70. CI6H,,ON requires C = 81.7 ; H = 5.5 ; N = 6.0 per cent. The analysis and melting point show this substance to be P-keto- a-cyano-ay-diphen ylpropane, originally prepared by v. Meyer (J. p. Chenz., 1895, [ii], 52, 115), by the action of sodium ethoxide on a mixture of ethyl phenylacetate and benzyl cyanide, a view which was confirmed by its conversion into the oxime (m. p. 107O) by the action of hydroxylamine. The higher fraction which boiled constantly at 274' (20 mm.) did not solidify on standing, but from the following analysis evidently consisted of /3-imino-a-cyano-ay-dipheny lpropane : C = 82.06 ; H =5*71.0.2013 gave 0.6042 CO, and 0.1110 H,O. C=81*86; H=6*12. Cl6HI4N2 requires C = 82.0 ; H = 6.0 per cent. ( 3) Format ion of P- Ke to - a - c y ano - a y -d iphen yZpropane and C y anbenz yline. I n this experiment the mixture of benzyl cyanide and sodium ethoxide in alcoholic solution was heated for twenty-four hours at looo, when the odour of ethylamine was hardly apparent. The product was mixed with water and the oil, which then separated, extracted with ether. The ethereal solution, after being washed with water to remove alcohol, was thoroughly washed with a mixture of three parts of concentfated hydrochloric acid to one of water, when the hydrochloride of cyanbenzyline separated as a middle layer in the manner already described.From this oily hydro- chloride the free base was isolated by means of sodium carbonate the yield of cyanbenzyline obtained in this way being about 60 per cent. of that theoretically possible. The ethereal solution, after being dried by means of calcium chloride, was evaporated free from ether and distilled under diminished pressure. It was found to boil con- stantly at 225-230° (20 mm.), and on cooling solidified to a crystal- line cake which when recrystallised from a mixture of benzene and light petroleum (b. p. 70-80O) yielded P-keto-a-cyano-ay-diphenyl- propane, melting at 86O. There is, therefore, apparently no p-irnino-a- cyano-ay-diphenylpropane formed under these oxperirnental conditious, c i L 21934 FORMATION OF IMINO-COMPOUNDS. PART 11.the amount produced in the first instance having either condensed with unchanged benzyl cyanide to form cyanbenzyline, or having passed into P-keto-a-cyano-ay-diphenylpropane through the '' hydrolysis " of the imino-group. The transformation of p-imino-a-cyano-ay-diphenylpropane into 1 : 3-diamino-2-phenyloaphthalene was effected in the following manner: five grams of the liquid nitrile were added gradually to 15 grams of concentrated sulphuric acid, the solution being kept well cooled throughout the addition, since the liquid, which dissolved rapidly in the concentrated acid, caused a considerable rise in temperature. When all had dissolved, the solution, which was dark brown, was allowed to stand at the ordinary temperature for from three to four minutes and then poured into a large volume of water. The solution thus obtained, after being filtered to remove any impurities, was made alkaline with ammonia, and the base, which was then precipitated, collected by filtration and purified by recrystallisation from methyl alcohol or benzene. 1 : 3-Diamino-2-phenylnaphthaZene crystallises in colourless, glistening plates melting at 116O : 0.1564 gave 0.4699 CO, and 0.0853 H,O. 0.3238 ,, 32.6 C.C. nitrogen at 15.8' and 758.4 mm. N= 11.73. C16H14N2 requires C = 82-0 ; H = 6.0 ; N = 12.0 per cent. The base becomes slowly coloured red on exposure to the air. It is easily soluble in alcohol or benzene, sparingly so in cold ether, and insoluble in light petroleum, Its solutions exhibit a marked blue fluorescence. The hydrochloride is precipitated in fine feather-like needles on dis- solving the base in a little dilute hydrochloric acid, and, after adding an equal volume of concentrated hydrochloric acid, allowing the solu- tion to stand : C = 81.94 ; H = 6.10. 0.2211 gave 0.2043 AgC1. C1= 22-92. CI6H,,N,,2HC1 requires C1= 23-1 per cent. The hydrochloride is rapidly coloured red on exposure to light. The dicccetyl derivative, 0, ,H,,N,(Ac),, is best prepared by boiling the base with excess of acetyl chloride until all has passed into solu- tion. A considerable quantity of acetyl chloride is necessary for this purpose, since the acetyl derivative is only sparingly soluble in this reagent. When all had dissolved the solution was cooled and allowedA NEW TRINITROACETAMINOPHENOL. 1935 to atand, the crystalline precipitate which then separated being isolated by filtration and ptirified by dissolving in alcohol and diluting the solution with water. On standing, the wcetyl derivative separated in small needles, melting at 367' : 0.1743 gave 0.4805 CO, and 0.0928 H,O. C = 75-18 ; H = 5.96. C,,H,,0,N2 requires C = 75.5 ; H = 5.7 per cent. The acetyl acetate, C,,H,,N,Ac,CH,*CO,H, was formed in an attempt to prepare the diacetyl derivatim by the action of acetic anhydride on the base. 1 : 3-Diamino-2-phenylnaphthalene was boiled with excess of acetic anhydride for two hours and the solution evaporated in an evacuated desiccator over caustic potash. The gummy residue became completely solid on scratching, and when recrystallised from absolute alcohol was obtained in small prisms melting at 185' : I. 0.1847 gave 0.4864 CO, and 0.0969 H20. C = 71.82 ; H = 5-87 11. 0.1872 ,, 0.4931 CO, ,, 0.0988 H,O. C=71*84; H=5*90. C,,H,,O,N, requires C = 7 1-4 ; H = 5-9 per cent. Other derivatives of this base are still under investigation. Much of the expense entailed by this research has been met by a grant from the Government Grant Committee of the Royal Society, for which we desire to express our indebtedness. MANCHESTER UNIVERSITY.

ISSN:0368-1645    

DOI:10.1039/CT9068901906

出版商:RSC    

年代:1906

数据来源: RSC

摘要:

A NEW TRINITROACETAMINOPHENOL. 1935 CLXXXV1:-A New Trinitroacetaminophenol and its use as a Synthetical Agent. By RAPHAEL MELDOLA, F.R.S. IN the course of some experiments having for their object the preparation of Reverdin's dinitroaminophenol of m. p. 230-231°, referred to in a former paper by one of the authors and F. G. C. Stephens (Trans., 1905, 87, 1206), it was found that the nitration of diacetyl-p-aminophenol (p-acetaminophenyl acetate) gave rise under most conditions to the mononitro-derivative, OAc : NO, : NHAc = 1 : 3 : 4, corresponding to the m-nitro-p-aminophenol of Hiihle (J. p r . Chem., 1891, [ii], 43, 63; see also the recent paper by Reverdin and Bucky, Ber., 1906, 39, 2687). I n attempting to nitrate this mono-1936 MET,DOI,A : A NEW TRTNITROACETAMINOPHENOT, nitrodiacetyl-p-aminophenol so as to obtain the required dinitro- compound, it was found that under certain conditions a trinitro- derivative was produced, and as this compound was found to possess remarkably active properties as a synthetical agent, it has been and is being made the subject of a special investigation.Some of the results so far obtained are made known in the present paper. I n order to prepare the new trinitro-compound, fuming nitric acid is mixed with an equal volume of strong sulphuric acid and the mixture cooled by immersion of the beaker in melting ice. The mono- nitrodiacetyl compound is introduced into the mixed acids in small portions until the solution is nearly saturated, and the trinitro- compound is then precipitated by pouring the acid solution on to ice.The product, after being collected and washed, is best purified by crystallisation from glacial acetic acid. It cry stallises in yellow needles melting with decomposition a t 178-179O." The compound is soluble in boiling alcohol or acetone, and dissolves slightly in boiling water, from which it separates on cooling in slender, yellow needles : 0.0887 gave 14.9 C.C. moist nitrogen a t 15' and 753.8 mm. N= 19.51. 0,1037 ,, 16.9 C.C. 9 1 12' ,, 759.8 mm. N=19-34. C8H,08N, requires N = 19.63 per cent. l t is not absolutely necessary in preparing this compound t o divide the process of nitration into two stages. The trinitro-derivative can also be prepared directly by dissolving diacetyl-paminophenol in the mixture of acids as above.Under these conditions, however, a considerable excess of the acid mixture must be used in order to obtain a good yield. Tho constitution of the trinitro-compound is determined by the following considerations. A mononitro-derivative of the constitution stated can only give rise theoretically t o two possible trinitro-derivatives : OAc OAc OAc (1.1 The first of these formulae represents the compound as the introduction of a third nitro-group into Reverdin's arising from 3 : 5-dinitro- compound and the second (11) as arising by a similar process from 2 : 6-dinitro-pacetaminophenol, that is, as a derivative of isopicramic acid. Experiments have shown that the acetyl derivative of isopicramic acid cannot be further nitrated, whereas the 3 : 5-dinitrodiacetyl com- * All melting points given in this paper were corrected by reference t o standard short-stemmed thermometers having the certificate of the Reichsanstalt, Berlin.AND ITS USE AS A SYNTHETICAL AGENT.1937 pound is quite readily converted by a mixture of nitric and sulphuIic acids into the new trinitro-compound. The orienting influence of the acetoxy-group is paramount in deter- mining the entry of the first nitro-group into position 3, and the joint influence of the nitro- and acetoxy-groups determines the entry of the second nitro-group into position 5 , giving Reverdin’s compound, from which the new trinitro-compound arises. That the acetoxy-group is all important is shown by the now well-known fact that pacetaminophenol itself always gives rise toisopicramicacidonnitration,and the most recent observation by Reverdin and Bucky confirms this in a very striking manner. I n the description of the practical details of nitration given above, it will be noted that the diacetyl-p-aminophenol or its 3-nitro- derivative is introduced directly into the cooled mixture of acids.I n Reverdin and Bucky’s process, the diacetyl compound is first dissolved in strong sulphuric acid, and the solution thus obtained is then treated with the nitric acid mixture, I n these circumstances, as the authors point out, the diacetyl compound undergoes hydrolysis by the sulphuric acid a t the first stage, so that the nitric acid is really acting on p-acet- aminophenol, and the resulting compound is accordingly isopicramic acid (Ber., 1906, 39, 2687).The entry of the third nitro-group in the process now made known appears also to loosen the attachment of the acetyl group as hydrolysis simultaneously takes place and the new compound is accordingly : OH NO,( ’)NO, ,NO, a X H A ~ 2 : 3 : 5-Trinitro-4-acetaminophenol. Properties of the Trinitro-compound.-As might be inferred from its formula, the new compound is strongly phenolic in character. It forms highly-coloured salts of an orange-red colour, but owing to the readiness with which the substance is decomposed by bases, none of these salts could be isolated, nor has it been possible to alkylate or acylate the hydroxyl group. Attempts to remove the acetyl group so as to obtain the trinitroaminophenol also gave only resinous products of decomposition. When sulphuric acid was used as a hydrolysing agent, a small quantity of a crystalline compound was obtained, which on examination proved to be a highly explosive diazo-oxide, resulting no doubt from the simultaneous hydrolybis and diazotisation of the product by one of the nitro-groups removed by the hydrolysing agent, so that in this caw also decomposition takes place.1935 MELDOLA : A NEW TRINITROACETAMINOPHENOL Synthesis of Anhydro-bases.Previous experience with compounds containing a displaceable nitro- group led to the conclusion that in the new trinitroacetaminophenol one of the nitro-groups 2 or 3 would be easily eliminated. It might, for instance, be predicted with certainty that if the corresponding trinitro- p-anisidine could be obtained this compound on diazotisation would lose the 3-nitro-group. The instability of the salts and the ready decomposability of the trinitro-(*ompound in the presence of basic substances distinctly pointed to the conclusion that these properties were due to t b e mobile character of one of the nitro.groups, since polynitro-derivatives of phenols as a rule form stable salts with bases.It therefore seemed probable that under regulated conditions the mobile nitro-group might be replaceable by amine residues giving rise t o compounds of the following types : If, moreover, as seemed most probable, it WRS the 3-nitro-group which was the mobile group, decompositions taking place according to the first of the above schemes might be expected t o give rise to anhydro-bases by the interaction of the ortho-groups.Such com- pounds would be derivatives of substituted benzimiuazole and might be thus formulated * : NO, NR’ Experiments with various amines showed that the new trinitro- compound most readily interacted with primary amines both fatty and aromtttic, but that no action took place under similar conditions with secondary or tertiary bases. The products consisted of anhydro-bases mixed in some instances with the non-anhydridised compound, thus proving that i t is the 3-nitro-group which is replaced. Of the amines thus far tried, positive results have been obtained with ammonia, ethylamine, aniline, a- and /I-napht hylamine, benzy lamine, and piperidine. Negative results were given by dimethylaniline, di- phenylamine, and pyridine. As these iminazoles promise t o be of * I have adopted the numbxing of the atoms in the ring system given in Richter’s ‘‘ Lexikon.”AND ITS USE AS A SYNTHETICAL AOENT.1939 special interest from several points of view, it is proposed to continue their investigation in detail, and the present results are made known as a preliminary contribution to the subject. The compound formed by the action of ammonia, although theoretically the simplest member of the group of substituted iminazoles herein dealt with, will reqiiire further investigation before its constitution can be established. I n all the reactions the nitro-group is probably eliminated in the form of nitrous acid which reacts with the excess of amine with the production of an azo-compound, an alcohol, or simply a salt, according to the nature of the amine.As the compounds described in this paper are all formed by the substitution of various radicles for R' in the N R group in the iminazole ring in the foregoing formula, the constitution will be sufficiently expressed by the systematic name without repeating the formula for each componnd. 4 ; 7 -Din,itro-6-hydroxy-l -phen yl-2-rnethyZbenximinnzole.-The trini tro- compound reacts readily with aniline under all conditions. I n con- centrated alcoholic solution the action is so energetic that spontaneous ebullition takes place, I n order to prepare the above phenpl deriv- ative in quantity the trinitro-compound is dissolved in a considerable excess of alcohol and to the hot solution an excess of aniline is gradually added, A deep orange colour is at once developed, and on cooling the solution deposits the imioazole in ochreous needles After being collected and washed with alcohol and purified by crystallisation from glacial aretic acid, the pure substance crystallises i n transparent, yellow prisms, which become opaque on being washed with alcohol.From alcohol it crystallises in flat, yellow needles. The compound is soluble in all the ordinary organic solvents and is phenolic in character, dissolving in aqueous alkali with an orange colour and being precipitated unchanged by acids. It possesses a feebly basic character, its salts being readily dissociated by water. The melting point is 188-189' : 0.1053 gave 16 C.C. moist nitrogen a t 15O and 753.2 mm. N = 17.63. 0.1007 ,, 15.3 C.C. ,, ?, ,, 16O ,, 765.9 mm.N=17*85. C,,H,o0,N4 requires N = 17.87 per cent. The same compound is also obtained when glacial acetic acid is used as a solvent or when the trinitro-derivative is dissolved in excess of aniline and allowed to stand for some days a t the ordinary temperature. In both these cases aminoazobenzene wits found among the products and was easily separated from the iminazole by taking advantage of the phenolic character of the latter. When aniline acts on the trinitro- compound in alcoholic solution, as in the method oE preparation found most advantageous, there is also formed with the iminazole, which is the main product, a small quantity of another substance which is partly1940 MELDOLA : A NEW TRINITROACETAMINOPHENOL contained in the mother liquor, from which on standing it separates in the form of deep orange prisms.Some of the same compound is easily seen in admixture with the crude iminazole but is removed in the course of purification by crystallisation from acetic acid. This secondary pro- duct is no doubt the non-anhydridised compound, namely, 3 : 6-Dinit~o-2-acetamino-5-hydroxydiplmayZamine : OH This substance is also phenolic and dissolves in alkali with an orange colour. It crystallises from acetic acid in red, prismatic needles melting at 1 7 9 O : N = 16.82. 0.0968 gave 14 C.C. moist nitrogen at 12Oand 744.9 mm. Orily a small quantity of this compound has as yet been isolated and it is proposed to obtain a larger supply for further investigation. 4 : 7-Dinitro-6-hydro~y-1 -benxyZ-8-methylbenximin~zole.-A concen- trated alcoholic solution of the trinitro-compound is mixed with an alcoholic solution of benzylamine containing the latter base in excess, when a reaction at once takes place with the development of sufficient heat to cause ebullition.The solution when cold solidifies to a crystal- line pulp of orange needles. I n order to purify the crude product the crystals were collected, washed with dilute hydrochloric acid and crystallised from alcohol. The orange colour of the deposited crystals immediately disappears on washing with acid, thus indicating that the compound is a benzylamine salt. After treatment with acid and crystal- lisation from alcohol, the pure compound presents the appedrance of flat, silky needles of a greenish-yellow colour.The melting point is 207'. Analysis indicated that in this case the first product is the dinitroacetaminohydroxyphenylbenzylamine : CI,H1206N, requires N = 16.86 per cent. OH /\NO2 N oJ, )NH*CH,C,H~ NH-CO-CH, 0*0886 gave 13.2 C.C. moist nitrogen a t 14" and '763.3 mm. N= 16.29. C,,H1,06N, requires N = 16.22 per cent. This substance is sufficiently basic to dissolve in strong mineral acids, but the salts formed with such acids are dissociated by an excess of water. Ttie compound is also phenolic, dissolving in alkalis with anAND ITS USE AS A SYKTHETICAL AGENT. 1941 orange colour. An attempt to eliminate the acetyl group by boiling the solution of the sodium salt showed that some more complex decom- position takes place with the formation of benzaldehyde.A beautiful, crystalline, ammonium salt consisting of bright orange, prismatic needles is formed by the action of ammonia. When this salt is crystallised from boiling water and then decomposed by treatment with an acid the recovered substance is not the original phenylbenzylamine deriv- ative but the iminazole, so that anhydridisation takes place on boiling the ammonium salt with water. The iminazole is also formed by dissolving the phenylbenzylamine compound in strong sulphuric acid, heating the solution for a few minutes to 100' and then pouring into water. The compound thus obtained crystallises from alcohol in yellow needles melting a t 156' : 0.1048 gave 15.2 C.C. moist nitrogen at 15' and 770.6 mm. N = 17.22. 0.1195 ,, 17.3 C.C. ,, ,, 14' ,, 762 mm. N=17*07.This iminazole is both phenolic and basic. The alkali salts are orange in colour; the ammonium salt is much more soluble than the ammonium salt of the original phenylbenzylamine derivative. The substance dissolves in hydrochloric acid and the solution on the addition of strong acid deposits white needles of the hydrochloride, which are stable only in the presence of excess of acid. 4 : 7-Dinitro-6-hy~roxy-2-methyl-l-ethylbenziminaxoZe.-On adding an alcoholic solution of ethylamiue to the trinitro-compound suspended in alcohol an orange solution is a t once obtained, and this soon solidifies to a crystalline pulp of the ethylamine salt of the trinitroacetamino- phenol. I n order to bring about the iminazole formation, the solution must be heated on the water-bath for some hours.The product is best isolated by collecting the crystalline deposit which separates on cooling, and which consists of the ethylamine salts of the iminazole with some of the ethplamine salt of the phenylethylamine derivative, washing with alcohol, then with dilute hydrochloric acid and finally with water. At this stage the product consists of a mixture of the imin- azole with the non-anhydridised compound and, if the former is required, it is better to ensure complete anhydridisation by dissolving the dry product in a little strong sulphuric acid, heating for a few minutes on the water-bath and then pouring into water. After crystallisation from alcohol the compound consists of orange, nodular crystals melting with decomposition at 2 1 5 O : C15H1205N4 requires N = 17.1 1 per cent.C,,H,2O,N,,HC4 0.1335 gave 23 C.C. moist nitrogen at 13' and 776 mm. This iminazole forms orange salts with alkalis, the ammonium salt N = 20-79. CI,HIoO,N, requires N = 2 1 -09 per cent.1942 MELDOLA : A NEW TRINTTROACETAMINOPHENOL crystallising readily from hot water in bright orange-red needles. The compound is also basic, dissolving in mineral acids with the formation of colourless salts which are stable onlyio presence of excess of acid. 4 : 7-Dinitro-6-hydroxy-1 -a-nup?~thyZ-2-methyl6enximir~azole.--The tri- nitro-compound and a-naphthylamine in excess are heated together in alcoholic solution for some hours on the water-bath, the reaction in this case being less energetic and the yield of iminazole smaller than in the case of the other amines.The whole solation after completion of the reaction is poured into very dilute hydrochloric acid, filtered to remove excess of naphthylamine, the precipitate washed with water, and then extracted with dilute sodium hydroxide and again filtered. The latter treatment separates the iminazole from the a-aminoazo- naphthalene with which it is mixed, the orange alkaline filtrate giving the required compound on acidifying. After crystallisation from alcohol the iminazole was obtained in ochreous, hexagonal tablets melt- ing with decomposition at 241O : 0.0873 gave 11.2 C.C. moist nitrogen a t looand 766.9 mm. N = 15.50. C,,H,,O,N, requires N = 15.42 per cent. No formation of the intermediate a-naphthylphenylamine derivative was observed in this case.4 7-Dinitro- 6-h ydroxy-l -P-naphtA yl-2-methyZ6en ximinaxole.-The re- action in this case is also sluggish and the mode of procedure, both with respect t o the formation of the iminazole and its isolation, was similar to that adopted for the a-naphthylamine compound. I n this case /3-aminoazonaphthalene is also formed together with a certain quantity of the P-naphthylphenylamine derivative. The latter can ba removed by crystallisation of the mixed product from glacial acetic acid after having previously separated the aminoazo-compound by alkaline extraction. From acetic acid the iminazole separates slowly in two forms, brown nodules and ochreous prisms, both forms melting with decomposition at 242' : N = 15.29. 0.1088 gave 13.9 C.C. moist nitrogen at 11' and 763 mm.C,,H,,O,N, requires N = 15.43 per cent. 4 : 7-Dinitro-6-hydroxy -1-rn-nitrophenyl- 2 - methylber~ximinaxole. -In order to prepare this compound the trinitroacetaminophenol is boiled in alcoholic solution with an excess of ni-nitroaniline for a few minutes and the solution then kept gently heated on the water-bath for some hours. The product separates out in yellow needles, which are col- lected, washed with alcohol, and purified by extraction with aqueous alkali and, after filtration of the solution, precipitation by acid. The substance is only sparingly soluble in boiling alcohol and is best purified by repeated crystallisation from glacial acetic acid from whichAND ITS USE AS A SYNTHETICAL AGENT. 1943 it separates in two forms, light, o(*hreous, nodular aggregates of short, Blender needles and brown, nodular aggregates of stumpy needles.Both forms have the same melting point, 242-243O with decomposition : 0*1181 gave 19.3 C.C. moist nitrogen at 13'and 752.6 mm. N = 19.40. The compound is slightly basic and distinctly phenolic in character, the alkali salts dissolving in water with a yellow colour. The silver salt was obtained as an ochreous powder by adding a solution of silver nitrate to a solution of the ammonium salt : C14H,07N, requires N = 19.54 per cent. 0.1369, on ignition, gave 0.0319. Ag = 23.3. C1,H,O7N5Ag requires Ag = 23 15 per cent. Synthesis of Am-conapounds. The trinitro-compound reacts readily with hydrazines, with the formation of hydrazo-compounds which pass by oxidation into azo- compounds. As a typical case the action of phenylhydrazine has been studied and the resulting compound isolated. Its composition and properties indicate that i t is a derivative of hydroxyazobenzene : OH /\NO, NO,~/N,*C,H,. N H* CO*CH, In order to prepare this substance the trinitro-compound is heated with an alcoholic solution containing an excess of phenylhy drazine as long as nitrogen is evolved. On cooling, a crystalline pulp of red needles is obtained. After being collected and washed with alcohol, the substance can be purified by crystallisation from alcohol, from which solvent it separates in red needles decomposing at about 188' : 0*1091 gave 19.4 C.C. moist nitrogen at 14Oand 750 mm. N = 20.33. C14Hl106N5 requires N = 20.63 per cent. This azo-compound is of interest on account of its instability; it is decomposed on boiling with glacial acetic acid and also by alkalis. The compound itself and the products of its decomposition are under- going investigation. During the first part of this research I had the assistance of Nr. F. G. C. Stephens, and during the latter part that of Mr. J. G . Hay, to both of whom I desire to express my thanks. CITY AND GUILDS TECUNICAL COLLEGE, PINSBURY.

ISSN:0368-1645    

DOI:10.1039/CT9068901935

出版商:RSC    

年代:1906

数据来源: RSC