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Proceedings of the Chemical Society, Vol. 22, No. 318 |
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Proceedings of the Chemical Society, London,
Volume 22,
Issue 318,
1906,
Page 311-326
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摘要:
Issued 4/1/07 PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 22. No. 318. Thursday, December 20th, 1906, at 8.30 p.m., Professor R. MELDOLA, F.K.S., President, in the Chair. The PRESIDENTannounced that the following congratulatory telegram had been sent this day to Prof. Adolph Lieben (Honorary and Foreign Member of the Society), on the occasion of his seventieth birthday and the fiftieth anniversarF of his Doctorate. ''Hearty congratulations to our Honorary and Foreign Member, Dr. Adolph Lieben, from the Chemical Society, London. '(MELDOLA, (( President." Messrs. W. R. S. Ladell, W. T. Lattey, and J. Mastin were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. : Alfred Frederick Allen, B.Sc., 35, Purrett Road, Plumstead, S.E.Henry Bassett, jun., B.Sc., Ph.D., 26, Belitha Villas,JBarnsbury, N. John Christie, B.A., Eton College, Windsor. Francis Davidson, Dover Place, Ashford, Kent. William Smith Denham, B.Sc., 2, Kelvinside Terrace North, Glasgow. George Fowles, 28, Weltje Road, Hammersmith, W. William Godden, B.Sc., Station Road (East), Canterbury. Charles Pask Matthews, B.Sc., 6, Fortress Road, N.W. Charles Schlienger, B.Sc., 273, Camdm Roa,d, N. William George Sewell, B.Sc., 27, Park Road, Wandsworth Common, S.W. Frederick George Shepheard, B.Sc., 9, Leinster Road, Rathmines, Co. Dublin. 312 Of the following papers, those marked * were read : *221. (‘A new laboratory method for the preparation of hydrogen sulphide.” By Frederick Robert Leyland Wilson.The common method for the preparation of hydrogen sulphide by the interaction of hydrochloric acid and ferrous sulphide is open to several objections, the most serious of which is the liability of the gas to contain the hydrides of arsenic and phosphorus, due to the con-tamination of the iron sulphide with phosphide and arsenide. The method here described ensures freedom from these impurities, as well as the absence of most of the unpleasant accompaniments of the ordinary process of preparation. If a current of hydrogen sulphide is passed over an alkali hydroxide, for example, sodium or calcium hydroxides, a hydrosulphide is formed, heat being evolved and a change in colour from white to yellow taking place.If a current of carbon dioxide is now passed over the hydro- sulphide, the compound is at once decomposed, a carbonate being formed and hydrogen sulphide set free. In the case of calcium hydroxide, the yellow substance has the com- position Ca(HS)(OH), and the action of carbon dioxide is given by t,he equation Ca(HS)(OH)+00,=CaCO, + H,O +H,S. A drying tower is filled either with granular soda-lime or an intimate mixture of calcium hydroxide and moist sawdust. A stream of hydrogen sulphide is passed into the tower until the contents are saturated with the gas, the course of the action being easily deter- mined by the change in colour and by the movement of a heated zone upwards through the tower. After the action has proceeded for some time the gas which escapes from the exit tube smells strongly of hydrogen phosphide and is inflammable, doubtless consisting of hydrogen mixed with all the other gaseous impurities evolved by the action of acid on the ferrous sulphide.When the hydroxide has reacted with as much hydrogen sulphide as possible, a carbon dioxide generator is substituted for that supplying hydrogen sulphide, and the apparatus is ready to yield as slow or rapid a supply of the latter gas as may be desired. The supply of hydrogen sulphide ceases at once when the stream of carbon dioxide is cut off, and if the exit tube from the tower is closed, a partial vacuum will soon be produced owing to combination of the gases in the tower with unaltered hydroxide.Owing to this absorption of the gas in the tower, it is only neces- sary to cut off the supply of carbon dioxide in order to prevent further escape of hydrogen sulphide. 313 The rate of supply of the gas may be nicely regulated by introducing a short length of capillary glass tubing between the carbon dioxide apparatus and the generating tower. The danger of contamination of the hydrogen sulphide with carbon dioxide is very small, and may be entirely eliminated by making use of two towers. As goon as the first shows signs of exhaustion (indicated when calcium hydroxide is used, by the change in colour) it is replaced by the second tower; a new one is put in place of the latter, and the supply of gas taken from this.DISCUSSION. The PRESIDENTasked how the method compared with the known laboratory process of preparing hydrogen sulphide by heating sulphur with certain hydrocarbons such as solid paraffin. Mr. WILSONstated that he had not compared the two methods. *222. (6 The affinity constants of aminocarboxylic and amino-sulphonic acids as determined by the aid of methyl-orange.” By Victor Herbert Veley. The method of determining the affinity constants of acids by means Qf a very dilute methyl-orange solution and a tintometer described in a former paper (Zeit.physikal. Chena., 1906, 57, la”), as applied to the carboxglic acids and certain chloro- and hydroxy-derivatives, has been extended to the aminocarboxylic and aminosulphonic acids. It is shown that the same general mathematical expressions hold good, namely, those of straight lines y=kx or y=kx-6, or logarithmic curves logy =logk +zloga.Acids which show irregularities in the Ostwald electric conductivity expression +(A) =az/(1 -a)K(u =p/pm ) likewise show similar irre- gularities in the methyl-orange method. The aliphatic aminocarboxylic acids act as neutral substances, but their hydrochlorides as hydrochloric acid only, hydrolysis being nearly complete at the degree of dilution used. The special cases of asparaginic acid, as possessing a higher affinity factor than succinic acid, and of cacodylic acid, as allied to amphoteric electrolytes, have been investigated. The aminobenzoic acids show a distinct acid function, and the results obtained are in a similar arithmetical ratio to those deduced by Winkelblech (at a different degree of dilution) by the electric con- ductivity method.The two aminobenzenesulphonic acids studied, namely, sulphanilic (1:4) and metanilic (1:3) acids are remarkable in that the latter 314 conforms to the straight line, but the former to the logarithmic expression. The introduction of a second sulphonic grouping diminishes rather than increases the acid function. A study of the naphthylamine mono- and di-enlphonic acids (eighteen in number) affords examples of steric I‘ furtherance ” as regards the positions 2 and 7 relative to I, and of steric hindrance as regards the position 8 relative to all other positions. DISCUSSION.Dr. CAIN suggested that, as the 1-naphthylamine-8-sulphonicacid exhibited the phenomenon of “steric hindrance ” and the 1-nnphtbyl- amine-2-sulphonic acid that of “ steric furtherance,” it would be of interest to know the behaviour of the 1-naphthylamine-4-sulphonic acid, particularly as this underwent molecular change into the 1 :2-acid by the action of heat. Dr. HEWITTasked if there was any definite stage between the colour of methyl-orange in alkaline and in acid solution. He had himself compared the absorptions of methyl-orange and butter-yellow, and found that the solutions of dimethylaminoazobenzene and sodium dimethylaminoazobenzenesulphonateon the one hand, and the salts of butter-yellow and acidified solutions of methyl-orange on the other gave practically identical absorption spectra. Any intermediate coloration between that of the free sulphonic acid and its sodium salt might be explained by partial neutralisation, and this opinion is confirmed by the fact that dimethylaminoazobenzenesulphonicacid in solution gives practically the same absorption as solutions of methyl-orange with an excess of mineral acid.The supposed free acid of methyl-orange would thus appear to be an internal salt. The PRESIDENTasked whether special precautions had been taken to ensure the purity of the naphthylnminesulphonic acids used by the author, since the technical prepmations supplied were professedly impure from the chemical point of view, and the difficulty of obtaining homogeneous products from mixtures of isomerides mas often very great. With respect to the question of the proximity of position 8 as compared with position 2 relatively to position 1 in the naphthalene ring, he did not think that enough was known about the actual configuration of the atoms in the molecule to enable any dogmatic: statement to be made.Dr. VELEY,in reply, said that it would be unwise to express any dogmatic views as to the relative contiguity of substituent groupings in the naphthalene nucleus. As regards the position 4, a difficulty had arisen on account of the sparing solubility of the 315 1-naphthylamine-4-sulphonicacid. The acids had been purified previous to use by recrystallisation or otherwise. He felt some hesitation in discussing the actual composition of the yellow, orange- red, and red shades of methyl-orange, but it was clear that, the last was the result of some more profound chemical change.In any case the hypothesis of migratory ions appeared to be too speculative. “223.“Contributions to the study of the calcium phosphates, I. The hydrates of the calcium hydrogen orthophosphates.” By Henry Bassett, jun. Although numerous hydrates of dicalcium phosphate have been mentioned in the chemical literature, the author’s experiments show that, in all probability, dicalcium phosphate can only form one hydrate, namely, the dihydrate. The experiments also allow of some conclusions being drawn as to the position of certain of the quintuple points on the space model of the three-component system, CaO-P,O,-H,O.There are indications that the point at which the phases present are CaHP0,,2H20 ; CaHPO, ; solid solution (see the papers by Cameron and Seidell in J.Amer. Chenz. Xoc., 1305, 27, 1503, and Cameron and Bell, J. Anzer. Cheaz. Xoc., 1905, 27, 1513); liquid solution and vapour lies at about 80” ;whilst the point at which the phases CaH,(PO,),,H,O ; CaHP04,2H,0 ; CaHPO, ;liquid solution and vapour can coexist lies at about 30”. The monocalcium phosphate has also been studied, and it has been found possible to prepare the crystallised anhydrous salt. This com- pound can be obtained in long, bright prisms by crystallisation at 160” of a solution of calcium carbonate in orthophosphoric acid if the ratio of P,O,/CaO in the solution is sufficiently large.The best value for this ratio was found to be 4.6. If it is less than 3.0, then, even at 160°, the monocalcium phosphate monohydrate crystallises out. *224. ‘‘ Contributions to the study of the calcium phosphates. 11. The action of ammonia gas on the calcium hydrogen ortho-phosphates.” By Henry Bassett, jun, It was found that under certain conditions when the acid calcium phosphates were treated with ammonia gas, absorption of the latter took place. The cause of this and the reactions occurring have been investigated with the following results : CaHPO, does not absorb ammonia either at the ordinary temperature 01’ at loo3. CaHP04,2H,0 does not absorb ammonia at the ordinary tempera- 31 6 ture, but if heated in the gas to 100°, vigorous absorption takes place with formation of a mixture of tricalcium- and ammonium phosphates according to the equation : 3CaHP0,,2H20 + ZNH, = Ca3(P04),+ (XH,),HPO4 + GH,O.When CaHP0,,2H20 is heated, it would seem that at a temperature of about SO’, one of the quintuple points of the system CaO -P,O, -H,O is reached. At this temperature the dihydrate breaks up into A mixture of CaHPO,,Ca,(PO,), and solution, and it is in this solution that the above reaction with ammonia takes place, CaH,(PO,), absorbs ammonia very slowly at the ordinary teni- perature, but rapidly at 100’ with formation of the compound Ca(NH,),H,(PO,),. This compound is not stable in presence of water, which at once decomposes it into CaHPO, and (NH4)2HP04.This explains why, when CaH4(P0,),H,0 reacts with ammonia gacp LZ mixture of CaHPO,, Ca3(P0,),, and (NH,),HPO, is formed. The commencement of the ammonia absorption by the CaH,(PO,),,H,O, is probably due to formation of the above calcium ammonium phosphate. This, however, liberates water of crystallisa-tion, which at once forms some solution in which the reaction proceeds. Although this reaction first leads to the formation of CaHPO,, this can further react with ammonia as long as any solution is present. It is to this further reaction that the presence of Ca,(PO,), in the final product is due. DISCUSSION. Dr. VELEYasked if the author had dried the ammonia gas, and if the phosphates experimented upon were quite free from traces of adherent moisture.It appeared that the subsequeiit solution in water of the products obtained introduced a very essential disturbing factor. Dr. BASSETT,in reply, said that the ammonia used had been dried by passing over solid caustic soda and sodium wire, but, of course, such ammonia was not absolutely dry. The calcium phosphates used in the experiments were also as free from adherent moisture as was possible without extreme precautions. With regard to the examination of the reaction products by treatment with water, the author realised the dangers of the method and the possibility of reactions occurring during this treatment. The method had, however, been employed as being the only one which would enable one to distinguish between, for in- stance, a mixture of Ca3(P0,) and (NH,),HP04, and a compound Ca(NH,)PO,, and he considered that the difficulty caused by possible reactions during the extraction with water had been satisfactorily overcome in each particular case in the manner described in the paper.31’7 “225. ‘{ Relation betwzen chemical constitution and physiological action in the tropeines,” By Hooper Albert Dickinson Jowett and Frank Lee Pyman. Reference mas made to Ladenburg’s generalisation, according to which a tropeine in order to possess mydriatic action must contain a benzene nucleus and a fatty hydroxyl in the side chain containing the carboxyl group, and also to a recent paper by Jovett and Hann (Trunt?., 1906, 89, 357), in which it was stated that terebyl- and phthalidecarboxyl-tropeines,which are lactones, and do not contain fatty hydroxyl groups, produce, nevertheless, marked dilatation of the pupil, and lose their physiological activity when converted into the corre- sponding hydroxy-acids.The authors have prepared the Zactone of o-carboxyp?LenylgZyces.yZ~ tropeine, expecting to find it very active physiologically, since it is not only a lactone, but also conforms to Ladenburg’s generalisation, isocou~carincai*boxyttropei?~ewhich results on heating the above, and certain alkyl bromides of these tropeines and of homntropine. The physiological examination showed that these tropeines are only slightly mydriatic, and that their physiological activity is lost when they are converted into the corresponding hydroxy-acids.The authors conclude that Ladenburg’s generalisation cannot be maintained since it does not hold good either in the case of terebyltropeine or of the lactone of o-carboxyphenylglyceryltropeine,but that the difference in activity between a lactone and its corresponding hydroxy-acid possesses important physiological significance. 226. Some derivatives of salicylic acid.” By Hooper Albert Dickinson Jowett and Frank Lee Pyman. In the course of the production of some derivatives of salicylic acid which might possibly find application in medicine, cin?aamoyZsuZicyEic acid, its methyl and ethyl esters,and quinine salt, and also 3 ;5-dichloro-acetylscclicylic acid were prepared and characterised. Cinncimoylscdicylic Acid, CO,H*C,Fl,*O*CO*CH:CHPh.Ten grams of salicylic acid and 12 grams of cinnamoyl chloride were heated together on a water-bath during three-and-a-half hours. The end of the reaction was indicated by the mixture becoming quite solid. After two recrystallisations from benzene, cinnumaylsaZicyZic acid was obtained in a pure state, and in quantity amounting to 48 per cent. of the theoretical yield ; it crystallises from benzene in needles melting 318 at 155O:is very readily soluble in alcohol or ether, sparingly so in chloroform or benzene, and almost insoluble in water : 0.2409 gave 0.6316 CO, and 0.0981 H,O. C =71.5 ;H =4.5. C,,H,,O, requires C =71.6 ;H =4.5 per cent.The Quinine Salt, C,,H,,04,C20H,,0,NJ,,crystallises from alcohol in needles which melt at 169’. It is almost insoluble in water or cold alcohol : 0,2151 gave 0.5729 GO, and 0.1208 H,O. C =72.5 ;H =6-2. C1,H,,0,,C,,EC,,02N2 requires C =72.9 ;H =6.1 per cent. The Methyl Xster was prepared by the condensation of molecular quantities of cinnamoyl chloride and methyl salicylate by means of anhydrous potassium carbonate. The product was purified by first treating with hot water, dissolving in chloroform, drying this solution, and mixing the oil which resulted after the removal of the solvent with light petroleum. On theu recrystallking froin alcohol, the pure ester was obtained in large, tabular crystals melting at 71° and in an amount equal to 63 per cent.of the theoretical yield : 0.2320 gave 0.6144 CO, and 0*1049H20. C=73.2; H=5*0. C17H1404requires C =72.3 ;H =5.0 per cent. The Ethyl Ester, obtained in an analogous manner, crystallises from alcohol in fine needles melting at 66-67’ : 02433 gave 0.6476 CO, and 0.1182 H,O. C =72.6 ;H=5*4. C18H1604requires C =72.9 ;H =5.4 per cent. 3 :5-DichZo~oacet~Z~cclicyZicAcid, C9H,04C12. This substance was prepared by the acetylation of 3 :B-dichloro-salicylic acid with acetic anhydride and sodium acetate. It cryshllises from benzene in needles melting at 159’ : 0.3350 gave 0,5328 CO, and 0.0732 H,O. C =43.4 ;H =2.4. 0.2060 ,, 0.2358 AgC1. C1= 28.3. C,H,O,CI, requires C =43.4 ;H =2.4 ;C1= 28.5 per cent. 4b227. The addition of bromine to cinnamic acid and its esters.Preliminary notice.” By John Joseph Sudborough and John Thomas. The appearance of ,a communication from W. Herz and Bruno Mylius in the last number of the Berichte (1906, 39,3816) on the velocityof the addition of bromine to cinnamic acid induces us to give 319 a preliminary account of experiments made by us on the same subject. All oizr experiments were conducted in pure dry carbon tetra-chloride at 15O. The bromine used was the commercial product dried with sulphuric acid. We find that the velocity varies enormously according as the reaction proceeds in the dark or in daylight. The following numbers calculated by means of the equation for a bimolecular reaction, when molecular proportions of bromine and of cinnamic acid, namely, some 0.0333 mol.per litre, are used, show’ this clearly. Cinnccmic Acid.-K (in dark). Series 1 : 0.0054, 0.0044, 0.0066, 0.010, 0.013. Series 2 : 0.0072, 0.0074, 0.0066, 0.012. K (in diffused daylight). Series 1 : 0.28, 0.33, 0.36, 0.33. Series 2 : 0.41, 0.37, 0.31, 0.34, 0.30, 0.31. Similar results have been obtained when the methyl and ethyl esters are used. Methyl ester.-K (in dark). Series.1 : 0.0058, 0*0060,0.0058, 0.0089, 0.0089, 0.0081. Series 2 : 0.0047, 0.0047,‘ 0.0039, 0.0062, 0*0089, 09071. Series 3 : 0.0049, 0.0091, 0.0071, 0.0079, 0.0095. Ethyl ester.-K (in dark). Series 1 : 0.0085, 0.0074, 0°0077,0*010, 0.011, 0.012. Series 2 : 0.0071, 0*0074,0.0053, 0.0076, 0.012, 0.010 Series 3 : 0.0044, 0.0048, 0.0050, 0.0050, 0.0049.(In diffused daylight) 0.29, 0.25, 0.25, 0.30. (In sunlight) 1.85, 1-70, 1-60, 1.29, 1.62, 1.49. The velocity constant with crotonic acid is smaller than with cinnamic acid. Crotonic acid (in dark) K =0.00096, 0.00094, 0.00069, 0.00101. All the experiments were made in glass-stoppered bottles, not in sealed tubes ;those conducted in the dark were in amber-brown coloured, the others in colourless bottles. We wish to extend the work in the direction of studying the effect of the introduction of various substituents into the crotonic and cinnamic acid molecules. 228. ‘‘The optical and magneto-optical influence of ethenoid linkings attachedto contiguous carbon atoms.” By Julius Wilhelm Briihl.It has been found by Sir W. H. Perkin that limonene and dipentene (l), and A3:s~g)-p-menthadiene(11). (1.1 (11.) exhibit a remarkable difference in magnetic rotation, the values of (11) being much higher than those of (I). The author showed that this is 320 clue to the presence of two double linkings in the position -C:C*C:C-in the molecule of A3:-e(J)-p-menthadiene. 229. “A difficulty in the theory of valency of W,Barlow and W.J. Pope.” By David Leonard Chapman. In the last number of the Transactions (p. 1675), W. Barlow and W. J. Pope claim to have demonstrated that the doctrine of valency follows as a necessary consequence of certain simple assumptions as to the nature and mode of packing of the atoms. The consequences of the theory have not as yet been fully worked out ; for the present, therefore, it mill be best to restrict any remarks to an examination of the premisses.An analysis of these has disclosed a difficulty which appears to be of importance and to necessitate some modification of the fundamental assumptions, In the paper in question the following is laid down as the first geometrical property of spheres : “ If in a close-packed assemblage of spheres, single spheres or groups of two or more, selected homogeneously, are replaced homogeneously by other groups of spheres in such a way that the resulting assemblage is close-packed without resorting to remarshalling, the replacing group is of practically the same relative magnitude as: the group replaced, and possesses the same fundamental valency ’’ (?‘rams., p.1724). A second geometrical property is stated thus: “If a sphere of volume 91% (an atom of valency m) is replaced by one of volume UE + n (valency m + n) one or more additional spheres (atoms) having the total volume n (valency n) must be simultaneously inserted in order that the close-packing may be re-established without remarshalling ” (Trans., p. 1729-1730). It is declared that from these propositions the law of the equivalence of elements and compound radicles can be immediately deduced, and the fact that an element of fundamental valency m can function as one of valency m + 2n is said to receive by means of them a rational explanation. It mill now be shown that different results can be deduced from the propositions in question.Consider a close-packed homogeneous assemblage, the similar parts of which are built up of spheres of the relative volumes 2n1, 2n, ............2~~~,2 ; where nlrqh2, &c., are whole numbers. Replace the sphere of volume 2 by two spheres each of volume 1. According to the geometrical property of spheres formulated first above, this can be done without remarshalling being involved. Now replace one of the spheres of volume 1 by two spheres of respective volumes 2 and I, and finally replace the two spheres of unit volume by a single sphere of volume 2. The original system has now been converted into one composed of spheres of volumes represented by the numbers 2n,, 331a............2nlL,2,_2 without remarshalling, and by three substitutions in two of which the first geometrical property and in one of which the second geometrical property have been assumed to hold. Now we are not concerned with the absolute dimensions of t,he system, and therefore the initial group of spheres can be regarded as consisting of spheres of the volumes ?a,, w2............n,&,1, and the final group of spheres can be regarded as consisting of spheres of the volumes n1’ n2............n,,,1, 1, the marshalling being the same in both cases. Therefore two spheres of volume 1 can function as one sphere of volume 1. By similar reasoning it can be shown that a sphere of volume 2 can function as a sphere of volume 1, and in general that a sphere of any size can replace any other without any resort to re- marshalling being necessary. From the foregoing argument it mould appear that the two proposi- tions quoted above cannot be used alone (in their present unqualified form at any rate) to demonstrate that valency is a simple volume relation.A formal statement, from the authors, of the restrictions to he put upon their use would be of value. 230. ‘‘ On the more exact determination of the densities of crystals.” By the Earl of Berkeley. A conical pyknometer with thermometer stopper and graduated side tube is used, and instead of filling to a mark, the author relies on the evaporation of the liquid (round the neck) to bring the level in the capillary side-tube within the graduations.The liquid used is carbon tetrachloride, and care is taken that the temperature of the balance case varies but little while the pyknometer is being weighed. The air adhering to the crystals is expelled by causing a current of carbon tetrachloride vapour to pass over them when in an exhausted vessel, and the pyknometer is filled while still in this vacuous space. A desiccator was described whereby hygroscopic salts may be dried in 322 a current of hot air, and the pyknometer filled in a vacuuni. Results for the density of quartz, barytes, and potassium carbonate were given. The maximum difference between any two observations out of eleven on quartz, and out of nine on barytes, is 0.02 per cent.The experiments on potassium carbonate do not agree so closely. 231. “A relation between the volumes of the atoms of certain compounds at the melting points and their valencies. Interpretation by means of the Barlow-Pope theory.” By Qervaise Le Bas. The molecular volumes of complex paraffins and alcohols can be calculated very exactly by means of the formula : M. V. of CnHqniq=(6%+ 2)s=61~s+ 2S, where S is a constant which has an average value of 2.970 and is called the unit-stere. It is a measure of the volume of hydrogen. Carbon, in accordance with its valency, is equal to 4s. The value of S is also obtained by dividing the difference for CH, by 6. The numbers obtained in this may confirm the previous values. Certain alcohols up to heptadecyl carbinol, C13H370H,have also been studied and their volumes are calculated by means of the expression M.V. of C,LH2n+10H=(6n+ 4)s=6,s + 4S, S having the same value RS in the former series. Oxygen is thus found to have a volume equal to 2s in accordance with its valency-number. These results were discussed in the light of the Barlow-Pope theory (Trans.,1906, 89, 1675). 232. “The action of acid chlorides on thioureas.” By Augustus Edward Dixon and John Hawthorne. In former communications it has been shown that alkyl and aryl chlorocarbonates unite with thiourea, forming the hydrochlorides of basic derivatives, or pseudo-thioureas, NH,*C(NH)*S*CO,*R; it is now established that Claus’ compound of thiourea and acetyl chloride (Ber., 1875, 8,42) is similarly constituted.Acetyl chloride unites spontaneously with monosubstituted aryl-thioureas, yielding compounds of ths form ArNH C(NH)*S=CONe,HC1; from these the corresponding picrates may be prepared. On with-drawing the combined hydrochloric acid by calcium carbonate OF sodium ethoxide, the odour of thioncetic acid becomes perceptible ; 323 hence the base is probably liberated and then hydrolysed to a slight extent. Nevertheless, the product left on evaporation of the solution is not the free base, but an isomeride, the acetyl group having migrated from the sulphur to a nitrogen-atom, so as to yield AcArN*CS*NH,. The latter compound is known to change readily, by migration of its acyl group, into another isomeride, namely, the symmetrical AcNH*CS*NHAr: it appears, therefore, that by this series of transfers the acetyl group may be passed, in a given thiourea molecule, from point to point, until it has occupied, in succession, every position of attachment which a substituting group can assume.If the hydrogen chloride is eliminated by heat alone, the symmetrical or nb-thiocarbamide is produced ; in like manner, Claus’ compound yields acetylthiourea. Benzoyl chloride. behaves with thiourea and its aryl monosubsti- tution derivatives similarly to acetyl chloride ; both chlorides unite with ab-aryl disubstituted thiocarbamides to form molecular additive products, the constitution of which has not yet been determined. Disubstituted carbamic chlorides unite with thiourea, forming haloid salts ; the corresponding nitrates and picrates are sparingly soluble in water.Organic acid chlorides do not appear to combine with thioureas which already contain an acidic group. 233. ‘‘3-Hydroxyphthalic and 3-methoxyphthalic acids and their derivatives.” By William Henry Bentley, Rona Robinson, and Charles Weizmann. An account was given of the preparation of 3-methoxyphthalic acid by the oxidation of 1 :5-methoxynaphthol with alkaline permanganab, and of 3-hydroxyphthalic acid by fusion of 3-methoxyphthalic acid with caustic potash. A number of derivatives of each acid were described. 234. 4Hydroxyphthalic and 4-methoxyphthalic acids. ” By William Henry Bentley and Charles Weizmann.The preparation of pure 4-hydroxyphthalic acid (m.p. 205’) from sulphophthalic acid by fusion with caustic potash was described, together with a number of derivatives of this acid. 235. Derivatives of Naphthacenequinone.” By William Henry Bentley, Arthur Friedl, Frederick Thomas, and Charles Weizmann. This paper is a fifth contribution to the Chemistry of naphthacene-.quinone (compare Diechler and Weizmnnn, Orchardson and Weizmann, Ber., 1903, 36, 547, 719, 2326; I’rccns., 1906, 89, 116), and contains a description of the preparation and properties of a large nuinher of pew hydroxy- and aminohydroxy-derivativesof this series. 236. ‘‘Dithioxant hoxalanil (Preliminary note).’’ By Siegfried Ruhemann. Thioacetanilide reacts with ethyl oxalate in the presence of sodium ethoxide to yield a compound similar to those which are formed from acetanilide and its homologues (Ruhernann, Ft*ans., 1906, 89, 1236 ; Proc., 1906, 22, 284).Dith~oxanthoxcc~nni~,PhN<CS’~~-~o’Co>NPh, crystallisesco*c--c-0s from glacial acetic acid in brown needles which decompose at about 2359 It differs from xanthoxalanil inasmuch as it is more stable towards caustic potash. The dilute alkali, or sodium carbonate, dissolves it on warming and transforms it into its tccutonzeride, C(SH):CH-CO*CO PhK<Co-&-&-CS>NPh, which crystallises from alcohol in red needles decomposing at 195O, and is soluble in cold sodium carbonate. On boiling with caustic potash (10 to 15 per cent.) one atom of sulphur is removed as hydrogen sulphide, and replaced by oxygen ; the compound, thioxanthoxcdanil, which is thus formed, crystallises from alcohol in shiny, orange plates which decompose at 216-218’, and are soluble in sodium carbonate.The constitution of this substance is either it is only decomposed by being heated with concentrated caustic potash (60 to 70 per cent.), when oxalic acid and aniline are formed. ADDITIONS TO THE LIBRARY. I. Donations. Roscoe, Sir Henrg Enjeld. The life and experiences of Sir Henry Enfield Roscoe, D.C.L., LL.D., F.R.S. Written by himself. pp. xii+ 420. ill. London 1906. (Recd. 17/12/06.) From the Author. Titherley, Arthur F. A laboratory course of organic chemistry, including qualitative organic analysis.pp. viii + 235. ill. London 1906. (Red. 19/12/06.> From the Author. Tschirch, Alexamder. Die Harze und die Harzbehalter mit Einschluss der Milchsafte. Historisch-kritische und experimentelle, in Gemeinschaft mit zahlreichen Mitarbeitern ausgefuhrte Unter-suchungen. 2 Auflage. 2 vols. pp. xxii+ 1268. ill. Leipzig 1906. (Recd. 28/11/09.) From the Publishers : Gebriider Borntraeger. II. By Purchase. Groth, Paul Beinrich. Chemische Krystallographie. Teil I. Elemente. Anorganische Verbindungen ohne Snlzcharakter. Einf ache und complexe Halogenide, Cyanide und Azide der Metalle, nebst den zugehorigen Alkylverbindungen. pp. viii + 626. Leipzig 1906. (Recd. 19/12/06.) Post, Julius. Chemisch-technische Analyse. Handbuch der analy- tischen Untersuchungen zur Beaufsichtigung chemischer Betriebe.3 Auflage. Bande I. i. und 11.i. pp. 180, 208. ill. Braunschweig 1906. (Recd. 19/12/06.) Procter, Hmrg Richardson. The principles of leather manulacture pp. xvi+512. ill. London 1903. (h'ecd. 6/12/06.) 111. PanaphEets. Blonnt, Bertram. Recent progress in the cement industry. A paper read before the Society of Chemical Industry on June llth, 1906. pp. 48. White, Ammicus Fvederic. Composition of the waters of Rockbridge County, Virginia, and their relation to the geological formations. pp. 38. Winchester, Va. 1906. 826 At the next Ordinary Meeting, on Thursday, January 17th, 1907, the following papers will be communicated : I‘ The relation between absorption spectra and optical rotatory power. Part I. The effect of unsaturation and stereo-isomerism.” B) A. W. Stewart. “Organic derivatives of silicon, Part 11. The synthesis of dl-benzylethylpropylsilicol, its sulphonation, and the resolution of the sulphonic derivatives into optically active components.” By F. S. Ripping. R. CLAY AND SONS, LTD., BREAD ST. HILL, E.C., AND BLWGAY, SUFFOLIi.
ISSN:0369-8718
DOI:10.1039/PL9062200311
出版商:RSC
年代:1906
数据来源: RSC
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