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Proceedings of the Chemical Society, Vol. 29, No. 421 |
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Proceedings of the Chemical Society, London,
Volume 29,
Issue 421,
1913,
Page 343-365
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[Issued 16/12/13 PROCEEDINGS OF THE CHEMICAL SOCIETY. Vol. 29 No. 421. Thursday, December 4th, 1913, at 8.30 p.m., Prof. W. H. PERKIN, LL.D., F.R.S., President, in the Chair. The PRESIDENTreferred to the loss sustained by the Society through the death of : Elected. Died. James Tudor Cuiidall (Edinburgh) ... .. March 17th, 1887. July 24th, 1913. Thomas Ebenezer Pye (Chichester) ....., July 5th, 1906. Oct. lSth, 1913. The PRESIDENTannounced that the Society had replenished its stock of apparatus and reagents for the use of Fellows making experiments at the meetings of the Society. Fellows can obtain a list of the apparatus and reagents by applying to the Assistant Secretary. Certificates were read for the first time in favour of Messrs.: Sydney George Clifford, 3 Norman Villas, East Dulwich, S.E.Thomas .Alexander Davidson, 57, Strathyre Avenue, Norbury. Thomas Eynon Davies, B.Sc., 25, Trevor Street, Aberdare. James Stanley Hale, Principe 4, Bilbao, Spain. Alfred John Leigh, B.Sc., Duff House, Banff. Archibald Macpherson, 51, Keir Street, Glasgow. Frederick Arthur Makin, The Nest, Taunton Road, Ashton-under-Lyne. Thomas Morris, 53, Poolstock, Wigan. Raymond William Nichols, Central Experimental Farm, Ottawa, Canada. 344 Parmanand Mewaram Advani, . &LA., George Alfred Hebden. B.Sc. Richard Pendarves Hodgcs. Richard Watson Askew, R.A. William Francis Hollely. Sankar Rao B. Badami, M.A. Charles Huxtable. Alan Milsom Bailey. Alexandrr Hynd, M.A., B.Sc.Stanley Charles Bate, B.Sc. William Johnson, B.Sc. Alan Hamilton Bateman. Harold Rranifield Jones. Charles Maurice Berlein, B. A. Ghulani Rasul Khan, KSc. Arthnr Bicknell, B.Sc. Sidney Oliver Leivesley. Angustus Pearce Llewellyn Blaxter, l3.A. William John Lewis. Adhor Krishna Bose. Percival James Lycett. Arthur Bramley, B. Sc. Frank Clifford Marcharit. Arthur Joseph Brearley, B. A. Kunerji Gosai Naik, M.A., B.Sc. George Bernard Butler. John Allen Nichols. Bertram Campbell, B.Sc. John Thomas Pattison. Norman Phillips Campbell, €3. A. ll~ilfricl Roberts Powell, B. A. Frederick George Carter. Henry Edward Findlatcr Pracy. Smti Pada Chowdry. Benedict Hugh Kolfe, M.A. Francis W7illiam Clark. Philip Howard Stott. Herbert Stoddard Coleman.John McArthnr Stuart. Thomas James Dralteley, B. Sc. John Algernon Lacy Sutcliffe. Mohamed Bhanis Eldin, B.Sc. Harold Frank Tayler. Cyril Duncan Fuller. Robert Tonnant. Charles John Dickenson Gair. Henry Walker. Stanton Gibson, B.Sc. Bertie Mandcl Welch. Richard Hargreaves, B.A. Henry Wood. Alexander Houghton Hay, *305. ‘(The action of sulphuric acid on copper.”By (the late) James Tudor Cundall. It is commonly supposed that the mutual action of copper and sulphuric acid may be represented by t.he production first of cupric sulphate and nascent hydrogen, which latter produces more sulphuric acid and from it sulphur dioxide. The present investigation shows that cuprous sulphate, rather than cupric sulphate, is one of the primary products, as may easily be tested by pouring off the sulphuric acid at any stage of the reaction through a Gooch filter into water, when a precipitate of 345 finely divided copper ;.s produced.This result is best obtained when the sulphuric acid is slightly diluted with water, for when hot or concentrated acid is used, the cuprous sulphate acts on the acid almost as soon as formed, giving cuprous sulphide and cupric sulphate. This last action also takes place, but more slowly, with cooler acid. The cuprous sulphide then, as Pickering found, becomes oxidised to cupric sulphide and cupric sulphate with evolution of sulphur dioxide, and thereafter the cupric sulphide gives the sulphate, with a further evolution of gas. "308. Synthesis of polypeptides from the higher fatty acids." By Arthur Hopwood.Although so many polypeptides have been prepared lately, only one has been obtained from the higher fatty acids. The author has therefore synthesised several dipeptides from palmitic and stearic acids, so that their properties could be ascertained and compared with those of the degradation products of the proteins. a-B7omopalmityl chloride, C,,H,Br.COCI, prepared from a-bromo- palmitic acid and thionyl chloride, is a colourless oil, which crystallises on cooling, and boils with decomposition at about 215O/20 mm. a-UromopaZmityZgZycine, C,,H,Br*CO*NH*CH2*C0,R, prepared by condensing a-bromopalmityl chloride with glycine, crystallises in colourless plates, melting at 118-121°.a-8minopaZmityZglyciiae, NH2*C,,H,,.C0.NH*CH,.C0,H, pre-pared by heating a-bromopalmitylglycine with ammonia, crystallises in colourless, hexagonal plates, melting and decomposing at 2 22-2240. Similar dipeptides have been prepared by coupling a-bromo-palmityl or a-bromostearyl chloride with alanine or leucine, and heating the products with ammonia. Isomerides of these dipeptides have also been prepared by the action of ammonia on the products obtained by condensing a-bromoacetyl, a-bromopropionyl, or a-bromo- isohexoyl chloride with a-aminopalmitic or a-aminostearic acid. The dipeptides derived from palmitic and stearic acids are taste- less, or slightly bitter, crystallino solids melting and decomposing at above 200O. They are insoluble in water, alcohol, ether, or benzene, but dissolve in hot dilute mineral acids or alkali hydroxides.They form characteristic crystzlline compounds with B-naphthalene- sulphonyl chloride, and, like the natural proteins, the dipeptides give white, amorphous precipitates with phosphotungstic acid. 346 *307. ('A new series of ring compounds." (Preliminary note.) By Richard Poore Beesley and Jocelyn Field Thorpe. The fact that the ethyl ester of labile P-methylglutaconic acid, which can be readily obtained from ethyl acetoacetate (T,, 1912, 101, 1565), condenses with the sodium compound of ethyl cyano- acetate, yielding the cyano-ester (I), and that from this ester an almost quantitative yield of the tricarboxylic acid (11) can be obtained on hydrolysis, has led to an investigation in which the CH,.CO,Et CH ;CO,II CH,.C/CH(CN).CO,EL cH,W'C H,. c O,H \CH,*CO,Et \CH,.CO,H (I.)(M.p. 30".) (11.) (BI. p. 1720.) possibility of the existence of '' enclosed " or "caged '' carbon rings has been studied. It is evident that the simplest type of such a series would be the enclosed four-carbon ring, in which the carbon atoms occupy the four points of a tetrahedron, as in formula (111), whilst another type would be the caged '' cube, a6 in formula (IV) : I C--C C C-C Lb -cNc-C I I (111.) (IV.1 It is well known that the esters of the bromoglutaric acids eliminate hydrogen bromide and pass into derivatives of cyclo-propane, and it therefore follows that if this reaction could be applied to the tribromo-ester (V), which can be prepared by the bromination of the acid (11),that ring-formation would ensue in accordance with the following scheme : p3 7% C C CH Ur*CO,Et 1 1 I '1 CH,*CLCHBr-CO,Et or \ \OHEr*CO,Et !I 1' '1 C0,Et.Y Br H*$!*CO,Et C0,Et.C \I/ 7 C.CozEtH Hr Br*F.t1 CO,EtCO,Nt (V.1 (VI.) N any difficulties were experienced in attempting to accomplish this change, because it was found that all the usual reagents, eniployed for the purpose of eliminating hydrogen bromide, led to the production of the corresponding lactones. Ultimately a reaction was discovered, which has since been found to succeed in a number of other cases, and seeins to favour the formation of the carbon ring from compounds of this character.The reactioii is carried out by adding the bromo-ester to a very concentrated aqueous solution of potassium hydroxide at 130O. The reaction is very violent, but the more violent it is the better is the yield of the ring ccmpound. By the aid of this reaction, the tribromo-ester (V) has been converted into a tricarboxylic acid having the formula C,H,O,, which has all the properties of the "caged " ring tricarboxyllc acid : C'0,H.C I/ C.c'C),~ I' c*(:c by I I (11. 11. lSi".) The acid is a remarkably stable substance, and does not decolorise alkaline permanganate in the cold ;it is not attacked by bromine at the ordinary temperature. It yields methylsuccinic acid when oxidised by hot alkaline permanganate.DIsCUS SION. In reply to Prof. Armstrong, Dr. THORPEsaid that so soon as larger quantities of material had been prepared it was his intention to study the action of hydrogen bromide, but it was necessary in order thoroughly to investigate the products of this reaction that considerable quantities of material should be available. In reply to Sir V. Ramsay, he said that the formula of the "caged " ring compound could only be expressed in the plane of the paper by: ICO,H representing the compound as a derivative of cyclobutane, which it certainly was not. 348 ‘I*308. Organic derivatives of silicon. Part XX. Some condensa- tion products of dibenzylsilicanediol.” By Robert Robison and Frederic Stanley Xipping.The two condensation products of dibenzylsilicanediol, namely, anhydrobisdibenzylsilicanediol and trianhydrotrisdibenzylsilicane-diol (Robison and Kipping, T., 1912, 101,2142), have been further studied in order to ascertain the conditions under which they are formed. A further condensation proauct, namely, dia?ahydro trisdibenz yl-silicanediol, HO~Si(CH,Ph)2~O~S~(CHzPh)2~O*Si(CHzPh)2~OH,has also been obtained by the partial hydrolysis of trianhydrotrisdi-benzylsilicanediol with potassium hydroxide, and with hydrochloric acid, in a suitable solvent. This compound crystallises in massive prisms, melting at 82O, and is analogous to dianhydrotrisdiphenyl- silicanediol;it is readily transformed into trianhydrotrisdiphenyl- silicanediol when it is treated with hydrogen chloride in alcoholic solution, the following reversible reaction taking place : +309.1t The rotatory dispersive power of organic compounds. Part V. A comparison of the optical and magnetic rotatory disper- sions in some ;optically active liquids.” By Thomas Martin Lowrg, Robert Howson Picked, and Joseph Kenyon. After examicing thirty-f our optkally active liquids, only two cases have been found in which the optical and magnetic rotatory dispersions are approximately equal ;even this equality is fortuitous, as it does not appear ir. the next homologues. Wiedemann’s law, which applies exactly in the case of quartz, does not therefore hold good for optically active liquids. 310. (L A relation b5tween ,chemical constitiition and depth of colour of dyes.” By Edwin Roy Watson.The theory is pat forward that those dyes which are quinonoid in all possible tautomeric forms exhibit a deep colour, however simple the molecule may Le. On the other hand, if there is the possibility of the molecule existing in a non-quinonoid form, it may not attain a deep colour, although the inolecular complexity may be very considerable. A survey of all the better known dye-stuffs 349 fully bears out this theory, and it explains remarkable differences in depths of colour between dyes of very similar constitution. A permanent quinonoid structure alone is not sufficient, for example, dihydroxy-p-benzoquinone ; the substance must be capable of tautomerising from one quinonoid arrangement to another.The theory has been fully borne out by the preparation of dyes of deep colour from quercetiri 311. ii Dyes derived from quercetin.” By Edwin Roy Watson and Kumud Behari Sen By the action of magnesium ethyl iodide on quercetin pentaethyl ether, there is obtained 3 : 5 : 7~trzethoxy-2-m-p-dietho~yphe~zyZ-4-rthyl-1: 4-benzopyran anhydrohydriodide, which, on de-ethylation, yields 3 : 5 : 7-trihydroxy-2-m-p-dlihydroxyphenyZ-4-ethyl-1 : 8-benzo-1,yiuti anhydrohydriodide : 01 011 €lo/\/\&-C.OH\-/I /-\oH,H,o 9 \/\/HO 9 CP, this dyes wool violet (on alum and chrome) and crimson (on tin). 3 : 3 -Dihydroxy-7-keto -4 -dimethylaminophenyl-2-m-p-dihydroxy-ph~riyl-1: 4-benzopyran, obtained from quercetin by the action of dimethylaniline in the presence of phosphoryl chloride, dyes wool in slaty-blue shades on all mordants.3: 4 : 5 : 7-Tefrahydroxy-2-m-p-dihydroxyphe?~yl-l: 4-benzopyran, prepared by the reduction of quercetin by sodium amalgam in alcoholic hydrochloric acid solution, dissolves in alcohol with a magenta colour, and in potassium hydroxide to a green solution, but is very readily oxidised to quercetin. Several other derivatives of quercetin and 2-phenyl-1 : 4-benzo-pyraii were also prepared. 312. i‘ An improved apparatus for the determination of molecular weight by the Landsberger-Sakurai method.” By William Ernest Stephen Turner and Cornelius Theodore Pollard. The great convenience of the Landsberger-Sakurai method of determining molecular weights, especially as a time-saver,* has led * Besides saving time, the mpidity of the process perntits the investigation of substances which wonld deconi1,usc during tlie prolonged boiling involved in the ordinary Beckmami metl:oll.S1:c’i substances are tricthylsul~lioniiiin salts (see 350 to its adoption in principle in a number of pieces of apparatus devised by subsequent investigators. Most of these forms, liowever. are unsuitable for accurate work, and in a paper which discussed the various sources of error in the Landsberger-Sakurai method (Turner, T., 1910, 97,1184) an apparatus was described which enabled rapid and accurate measurements to be uiidertakell. During the course of some three years' work with this apparatus, several improvements have suggested themselves, and have been collected in the new form figured below.The most important alteration of the original is the use of the boiler as the constant temperature jacket." For one of the disacl- vantages of the Landsberger and Sakurai forms of apparatus is that the molecular-weight tube fills so readily as to make it difficult, with easily condensable vapours. to obtain more than three or four readings iii a series. By using the boiler as outer jacket T and making the entrance for the vapour stream high up in the molecular-weight tube, the cooler solvent or solution in the tube is heated considerably before the eii-trance of vapour, and the amount of con-densation thus diminished.The molecular-weight tube dB, 17.5 cm.1 in length, 2.8cm. diameter in the main Y portion, and 3.5 cm. at the mouth, carries a ground-glass stopper with two tubulures, fitting flush with the mouth of the tube at cl. TOthe solvent or solution under measure- ment, vapour is admitted through two per- forations at the bottom of the tube EF,the entrance E being 12 cm. from the lower end .-of the molecular-weight tube. The outer jacket CD, of approxi-mately 5 cm. diameter in the cylindrical portion, fits the moleculai- weight tube at a second ground joint at h, and carries a safety-tube GH, provided with a tap TI. Although shown in one piece, the tube sealed into the boiler reached only the level of the tubulated stopper, and the tap was connected by rubber tubing, the ends of the tubes being in contact.Whilst a determination is in progress, T, is usually closed in order to drive a steady stream of vapour through E, but when the molecular-weight tube has been removed Turner, T., 1911, 99, 880) and amylamine l~ydrochlo~ide (Turner, Zoc. cit. ; compu Hantzsch and Hoftnann, Bw.,1911, 44,1776). t In much the same way as used by McCoy (Amcr. Chem. J.,1900, 23, 353) and Ludlani (T.,1902, 81, 1193). 35 I for weighing, a cork is inserted in the mouth of the boiler, and T, is opened to admit dry air, drawn in through drying tubes connected at G'. Hygroscopic solvents are thus protected. Vapour escapes by the tube I<,of length as short as possible, coiinexion with the condenser being made at a third ground joint, so that the molecular-weight tube, together with the therinometer and escape tube, can be lifted away bodily for weighing, during which process the tap T, is closed.A small cork may be inserted at E if desirable, and complete protection from moist air thus secured. Of other points it may be remarked that the molecular-weight tube is graduated with marks 2 mm. apart to assist in determining the correction for the use of boiling point due to increasing head of liquid (alternatively the graduation may be in c.c.); that the thermometer used is one of the Beckmann type specially made by Eaumbach, of Manchester ; and that it is advantageous to protect the cylindrical portior, of the outer jacket by two or three thick- nesses of asbestos paper, and so diminish the loss of heat by radia-tion.The following results were obtained during the course of little more than an hour from the time of setting up the apparatus: Pyrogn!lol in Ethyl Alcohol. C,H,(OH),= 12G.0. Weight of Solute, 0,8090 gram. Weight of solvent. Grams. AD. 3I.W. 9 69 O.ii3 124.9 I 1'90 0 625 125 7 14.31 0,530 123.'i 16.71 0.444 126.1 19'17 0'399 124'0 21 92 0,352 128.3 2.3 96 0 2i7 128.4 ~ bIeaii ,, ...... 125'9 Seven readings did not mark the limit of the capabilities of the apparatus with this solvent, and as no more than five could, as a rule, be obtained with the earlier form, the efficiency of the new apparatus is considerably greater.Ethyl ether, carbon disulphide, and water are easier to handle than alcohol, and with them quite e long series of readings is obtainable. When, however, the boiling point of the solvent exceeds looo, the number of readings becomes less, so that with amyl alcohol, for example, only four readings were obtained. Above 150° the apparatus may conveniently be employed only in measurements where it is sufficiently accurate to assume that the volume of the solution is the volume of the solvent ; 352 for in such a case it is unnecessary to detach t-he molecular-weight tube, thus avoiding the inconvenience of handling it at a high temperature. For a discussion of the details requiring attention and the correc- tions to be applied in accurate work, reference should be made to the previous paper on the subject.313. “The optical rotatory powzr of derivatives of succinic acid in aqueous solutions of inorganic salts. Part I.” By George William Clough. The specific rotations of d-tartaric acid, methyl d-tartrate, ethyl &tartrate, and d-tartramide respectively have been measured at various temperatures in aqueous solutions of sodium and barium haloids. The values obtained are in all cases lower than those for the corresponding aqueous solutions. The results were discussed from the point of view of Armstrong and Walker’s hypothesis (PTOC.Roy. SOC.,1913, A, 88, 388). 314. ‘‘ Derivatives of o-xylene. Part VI. 5-Bromo-o-3-~ylenol.” By Arthur William Crossley.5-Bromo-o-3-xylenol has been synthesised by a series of reactions indicated by the following formula: : C H3 cH, CH, CH, /\CH, /\CH, /\CH, /\C H,N”’j,NH, NO,,/OH XH,\JOH BA,,,/oH * It crystallises from light petroleum (b. p. 40-60°) in radiating clusters of glistening needles, melting at 84O, and is identical with the bromoxylenol, of similar melting point, obtained by the action of phosphorus pentabromide on diinethyldihydroresorcin (T., 1903, 83,1%). The benzoyl derivative crystallises in rhombic plates, melting at 98O, and the o-nitrobensoyl derivative separates from alcohol in transparent needles, melting at 128O. 316. ‘‘ The condensation of chloral hydrate and carbamide.” By Noel Guilbert Stevenson Coppin and Arthur Walsh Titherley The two derivatives obtained by Jacobsen (Annulen, 1871, 157, 246) in the condensation between chloral hydrate and carbamide are /3 -trichZoro-a-hydroayethylcarhanzide, CCl,.CH( OH).NH*CO-KH, (I), and di(/3-trichZoro-u-hyd~o~yet~yZ)cnrbamidr, CCl,~CH(OH)~NH*CO*NH.CH(OH).CCI,(11). They ar0 formed by a reversible change whenever the reactants are present in equimolecular proportion in aqueous solution ; with concentrated solutions the compound (I) greatly predominates unless a mineral acid catalyst is present, which favours the pro- duction of (11).When one molecular proportion of chloral hydrate acts on two of carbamide, however, the formation of the compound (11) is prevented, unless a mineral acid is present.Both sub- stances are slowly hydrolysed into chloral hydrate and carbamide on heating with water. Thus, in 50 per cent. aqueous solution at 70°, P-trichlorea-hydroxyethylcarbamide suffers decomposition to the extent of about 50 per cent. in an hour. The mixture which separates on cooling contains about 70 per cent. of cornpound (I), and 30 per cent. of compound (11). In the reversible system : water + /3-trichloro-a-hy droxyethylcarbamide chloral hydrate + carbamide, the true equilibrium is virtually never reached, owing to continual formation of di@-trichloro-a-hydroxyethyl)carbamide, which, being nearly insoluble, separates out. P-T,.ichloroethyZidenecnrbamide, CCl,*CH:N*CO*NH, (m. p. 234O), is readily obtained from 8-trichloro-a-hydroxyethylcarbamideby the action of acetic anhydride on its solution in alkali.Trichloroethylidenedicarbamide, previously obtained by Pinner and Lifschiitz (Ber., 1887, 20, 2346) from chloralcyanohydrin and carbamide, is produced slowly when 8-trichloro-a-hydroxyethy1-carbamide is heated at looo with carbamide and acetic anhydride. 316. The action of amino-acid esters on ethyl dicarboxgglutaconate.” By Stanley Isaac Levy. The reaction between ethyl dicarboxyglutaconate and organic derivatives of ammonia, which has been investigated by Ruheniann and his pupils, has now been extended to a-amino-acid esters. It has been found to apply generally to compounds of this class, and derivatives have been prepared from the esters of glycine, alanine, aminobutyric and aminoisobutyric acids, and leucine.With the exception of the first member of the series, ethyl glycylmethyleite- malonate, CO,Et*CH,-NH*CH:C(CO,Et),, which is a colourless solid, these compounds are yellow, viscous oils; in chemical behaviour they closely resemble ethyl aminomethylenemalonate. Thus they are easily decomposed by acids or alkalis, and are not reduced by the zinc-copper couple; when heated with aniline, they yield the monoanilide of ethyl anilinomethylenemalonate. 317. (‘The relationship between the absorption spectra and the constitution of ketones and their derivatives.” Part I. By George Gerald Henderson, James Alexander Russell Henderson, and Isidor Morris Heilbron. The authors have re-examined the absorytion spectra of a series of carefully purified aliphatic kctones, and have found that the characteristic absorption band cf acetone is shown by all these compounds, and that the persistence of the band is in each case fully equal to that of the acetone bani In order to account for these and other facts the authors suggest that the selective absorption of ketones is due to intramolecular vibrations caused by the momentary formation of unstable Ting systems through the agency of free .‘partial valencies,” which, under certain conditions, make their appearance on the atanis of the carbonyl group.318. Note on pnrpurogallin.” By Arthur George Perkin. In view of the fact that the author has been engaged for a long time with the study of purpurogallin (Perkin and Steven, T., 1903, 83, 192; 1906, 89, 802; A.G. and F. M. Perkin, ibid., 1904, 85, 243; 1908, 97,1186; A. G.Perkin, P., 1905, 21,211; T.,1912, 101, 803; 1913, 103,661), the recent paper of Nierenstein and Spiers (Be?., 1913, 46, 3151) requires comment. These authors, who have repeated the earlier work of Perkin and Steven (loc. cit.), already partly confirmed by Herzig (itfonntsh., 1910, 31,799), with identical result, claim to have established the presence of four hydroxyls in this compound, notwithstanding the fact that tetra- acetylpurpurogallin, moiioacetylpurpurogallin trimethyl ether (loc. elf., 1903), and purpurogallin tetramethyl ether (Zoc. cit., 1905) have been prepared. Although tzcetylpurpurogallin was described as yellow by Nietzki and Sheinnlsnn (Ber., 1887, 20, 1277) and Perkin and Steven (Zoc.cit.), Rerzig isolated this compound in the colourless condition, whereas Nierenstein and Spiers can only prepsre an orange-yellow product. A colourless substance can, however, easily be obtained by crystallising from benzene with animal charcoal, although in the author’s experience this purifi- cation is much more difficult to effect with acetic acid or alcohol. It is interesting to note that no distinccion in melting point can be observed between the yell3w and colourless preparations, from which it appears possible that the pure acetyl compounds exists in two forms. Thus purpurogsl!in, regenerated from the latter 35.5 variety, on reacetylatioii with acetic anhydride and pyridine yields the usual yellow product, which shows the same behaviour with solvents.Nierensteiii and Spiers refer also to tlie compound C,H,O,( II), first prepared by the oxidation of pyrogallol by means of isoaniyl nitrite (Toc. c~f.,1906), but more recently by means of pbenzo-quinone (7oc. cif., 1913), which yields purpurogallin among other products when digested with boiling water. By the pbenzoquinone method (20 grains of pyrogallol, 6 grams of p-benzoquinone and 15 C.C. of absolute alcohol), thc yield of 0.51 gram, although larger tlian that given by isoamyl nitrite (0'27 gram), is so small that in the hope of tlie discovery of a Setter process which, however, has not been forthcoming, the author until recently hesitated to prepare a quantity oi the material by these expensive methods.Although it suggested itself as possible that the production of this compound froin pyrogallol vas in reality due to the presence of traces of a second compound in this substance, this seems not to be the case, hecause pyrogallol, when submitted to the action of zinc dust and dilute acid, still reacts in tlie same way with p-benzoquinone. Whereas the constitution at first preferred for tlie compound C,H,02( 1) was that of a hydroxy-o-benzoquinone, Willstatter and I\liilier-(Be?.., 1911, 44, 2180) consider this to be unlikely, and further work now in progress favours the secoiid or peroxide fonnula : OH OH already alluded to in the earlier communication.Nierenstein and Spiers have again examined the product of tlie distillation of purpurogallin with zinc dust, although Kietzki and Steinmanil and also Perkin and Steven obtained naphthalene thereby, and it has been very receiitly shown that by tlie reduction of purpurogallone both ,&naphthol and 2 : 3-dihydroxynaphthalene can be produced. If purpurogallin, as now seems probable, is in reality a napht,lialene derivative, the simple expression C',,,H,(OH),CO is only available for it. In such a case it has suggested itself to the author among other considerations that the ,$!:CH.OHo-quinonoid grouping, c:c1 is present, because the isomeric /purpurogallone derived from it by tlie action of alkali at a high temperature, which has the properties of a trihydroxynaphthalene-carboxylic acid, can t,lius be regarded as a product of simultaneous 356 oxidation and reduction.Such a grouping would also account for the comparative resistance of the fourth hydroxyl in purpurogallin to methylation, and again, the fornation of the colourless acetyl and tetramethyl derivatives could be explained on the assumption that these exist in the tautomeric hydroxy-aldehydic condition. A \ $XCH, also suggests itself, andformula involving the grouping C:O / these points are mentioned here in that the work on which the author is now engaged, and which consists mainly of a study of the oxidation of the purpurogallin methyl ethers, involving as it does the preparation of large quantities of material will occupy a con- siderable time. 319.‘‘ I-Epicamphor (I-P-camphor).” By Julius Bredt and William Henry Perkin, jun A detailed description of work of which a preliminary account has already appeared (P., 1912, 28, 56). 320. iiThe action of hydrogen peroxide on the sodium alkyl thio- sulphates.” By Douglas Frank Twiss. Dibenzyl diselenide has been submitted to oxidation (both electro- lytic and by hydrogen peroxide) in the hope of producing com-pounds of the selenoxide, selenone, or selenonium salt class (compare Fichter and Sjostedt, Ber., 1910, 43, 3422), but the result of such treatment was to eliminate the selenium from the molecule either in the free state or as selenious acid. In consequence of the lack of success attendant on experiments in this direction, the effect of oxidation of sodium or potassium alkyl selenosulphates was considered as a possible process for the achievement of the desired end.The action of hydrogen peroxide was therefore first tried with sodium alkyl thiosulphates, when it was found that in acid soluticn this process gives rise to excellent yields of the corresponding disulphides even at the ordinary tem- perature. Dibenzyl, di-o-nitrobenzyl, di-p-nitrobenzyl, and diallyI disulphides were prepared in this manner. Under similar treat- ment, potassium o-nitrobenzyl selenosulphate produced di-o-nitro-benzyl diselenide. 321. Synthesis of d-and 2-sylveetrene.” By Walter Norman Howarth and William Henry Perkin, jun.A detailed description of work of which a preliminary account has appeared (P., 1910, 26, 97; 1913, 29, 223). 357 322. “Note on the configurations of the optically active normal secondary alcohols.” By George William Clough. Pickard and Kenyon have prepared ten optically active carbinols of the series CH,-CH(OH)-R (the “methyl ” series), eight of the series CH(CH,),*CH(OH)*R (the ‘‘ isopropyl ” series), and thirteen ‘Iof the series C,H,.CH(OH)*R (the ethyl ” series). The simplest carbinol of the methyl ” series and of the ‘‘ ethyl ” series is methyl-ethylcarbinol. Pickard and Kenyon have made a comparison of the molecular rotatory powers of the dextrorotatory carbinols of the “methyl” and of the “ethyl” series, and have selected the dextrorotatory form of methylethylcdrbinol for comparison with the dextrorotatory carbinols of hot); series (T., 1911, 99, 45; 1912, 101,620; 1913, 103, 1923).Although it is impossible to staLe with certainty that the carbinols possessing the same sign of rotation are configuratively similar, it appears highly probable that in thv case of the higher members of a series similarity of sign does indicate similarity of configuration. The assumption may therefore be made (and the course of the curves for the molecular rotations strongly supports this view) that in the “methyl” series where R>CH, (that is, in all cases), and in the ‘I ethyl ” series where R>C,H,, similarity of sign of rotation accompanies similarity of configuration.Moreover, if the two series of carbinols, CH,.CH(OH).R and C,H,.CH(OH)*R, are compared, it appears exceedingly probable from a consideration of the curves representing the molecular rotations in the homogeneous state, in benzene solution and in ethyl-alcoholic solution respec-tively, that the higher dextrorotatory carbinols of the ‘.methyl “ series are configuratively similar to the dextrorotatory carbinols of the ‘‘ ethyl” series. Thus, if R>C,H,, the corresponding dextro- rotatory carbinols of the two series may be configuratively repre- sented by the formulz: 9Hs QAHY*OH HQ-OH I3 R J.“ bIethyl ” series. d-l‘ Ethyl ” series. The simplest optically active members of the d-“ methyl ” and d-“ ethyl ” series may therefore be represented by the formulae : Q“3 YzH5 Hy.0 H CH,&“Methyl ” series.d-“ Ethyl” series. 358 In other words, the simplest member of the d-’,methyl ’’ series is t’he optical antipode of the simpleei; member of the cl-”ethyl” series. The assumpt’ion which has already been made that similarity of sign in the methyl ’‘ series always indicates similarity of configuration leads to the view that. d-methylethylcarbinol is the simplest optically active member of the d-“ methyl ’’ series. Con-sequently, I-methylethylcarbinol is t’he first optically active member of the &“ethyl” series. We therefore arrive at the apparent paradox that the simplest members of the two configuratively similar series are enantiomorphic fornis of the same substance.The earlier members of the (7-“ methyl ’’ and d-,‘ethyl ’’ series illay be represented thus : p3 7‘437IT, 7% HC’OH Hy.0” H$!*OH I1y*OH CH, CP, C,H; c4A,Iiiactive. d-. d-. d-. d-“ Xtthyl” series. ?z& $H, 7i*5 7P5 HC;*OH €€$!*OH HY-OH HY-OH (333 C,H, (33% c4H, 2.. Itiactive. cl-. rl-. d-“ Ethyl” series. In the ”ethyl ~’ series, for the first inember R<C,H,, for the second R=C,H,, whilst. for the other members R>C,H,. It is therefore not surprising that there sliould be a change of sign in the passage from the first to the third member of this series. The view here advanced is confirmed by reference to the curves of Pickard and Kenyon (T., 1913, 103, 1924, 1926, 1929). The curves in Figs.1 and 2 fw the molecular rotations of the cl-” ethyl ’’ series show a marked abnormality in the case of t’he first member. If the value for I-methylethylcarbinol is substituted for that of the d-carbinol, the curves exhibit much greater regu- larity. The curve (Fig. 4) for the d-“metliy1”series shows no abiiorinalit,y in the first member, for d-methylethylcarbinol has the same configuration as the other d-carbinols of this series. Attention may also be drawn to the values for the molecular rctation of the hydrogen phtlialic esters of the dextrorotatory carbinols, C,H,*CH(OH).R, in ethyl-alcoholic solution. The value for t8he rotation of the ester with R=CH, is [MID +86.5O, with R =C,H,, [XID +9.42O,whilst with R =C,H,, [MI, + 52.3O.It is evident that the value for the ester of I-methyletliylcarbinol should be compared with those for the esters of the dextrorotatory carbinols Gf the ‘‘ ethyl” series (compare Fig. 1, lor. rit.). 3.59 The temperature-coefficients for the rotations of the two series of d-carbinols are also of interest in this connexion. The specific rotations of the dextrorotafory alcohols of the methyl series (including d-methylethylcarbinol) diminish with rise of temperature (T., 1911, 99, 50), whereas the values for the dextrorotatory carbinols (up to ethyl-71-nonylcarbinol) increase with rise of tem-perature, with the exception of d-methylethylcarbinol. If the view is accepted that Z-methylethylcarbinol is the first member of th6 d-(‘ethyl ’’ series the temperature-rotation curves for the earlier members of this series are similar in character.These considerations show the impossibility of expressing the relative configurations of a series of optically active compounds by the designations d and 1. 323. “The surface tension of mixtures. Part I. Mixtures of partly miscible liquids and the influence of solubility.” By Ralph Palliser Worley. Experiments were made with the object of throwing light 011 peculiarities noticed in the surface tensions of weak solutions c,i some liquids which are only partly miscible with water. The surface tension was measured by means of the capillary rise method, the liquids examined being aniline, phenol, and iso-butyl alcohol, The decrease of the solubility of aniline in water produced by the addition of common salt had the effect of greatly lowering the surface te-mion, the final value being not far above that of pure aniline.In tlie case of aniline and phenol t!ie surface tensions of some of t:ie more concentrated solutions rose with increasing temperature, whilst the surface tensions of ncne of th,n solutions, not even the weakest, fell normally, that is, similarly to that of a pure liquid. On the other hand, the surface tension of all solutions of isobutyl alcohol fell regularly. This difference of behaviour has been accounted for by the different behaviour exhibited towards water with increase of tem- perature. Whereas the solubility of aniline and phenol increases with rise of temperature, the solubility of isobutgl alcohol decreases up to 75O, and then increases rapidly until the critical solution temperature is reached.These results point to the fact, therefore, that the low sur:ace tension of solutions of partly miscible liquids is due to the lack of solubility of the solute. The reason of this is that liquids when near their limit of solubility form solutions which are rather of the nature of colloidal than of true solutions. 360 324. “The surface tension of mixtures. Part 11. Mixtures of perfectly miscible liquids and the relation between their surface tensions and vapour pressures,” By Ralph Palliser Worley. A relation exists between the surface tension and the vapour pressure of a liquid.The object of the presenJ research was to find out whether in mixtures of liquids deviatiods from a general law governing vapour pressures were accompanied by corresponding deviations in the case of surface tensions. The following mixtures were examined : (1) Benzene and Ethylene Dichlo~ide.-The surface tensions were found to agree with those calculated from the admixture rule. So also do the vapour pressures agree with those calculated (Zawidski). (2) Carboii Dzsulphide and Bcetone.-The surface tensions were found to be below the calculated values, and the curve to tend towards a minimum. The vapour pressures are much greater than those calculated, and the curve passes through a maximum. (3) Acetzc d czd ad Pyridine.-The surface tensions were much greater than those calculated, and the curve tended towards a maximum value.The vapour pressures are much below those calculated, and the curve forms a minimum. It seems therefore that when a mixture obeys one admixture rule it obeys the other also; when the surface tensions are greater than those calculated the vapour pressures are less, and vice versa. Additional proof was given by mixtures of benzene and carbon tetrachloride, and the homologous series of alcohols and water. From experiments with sulphur and carbon disulphide, it appears that the relations hold good for all mixtures. 325. The tautomerism of thioanilides.”‘I By Percy May. Although the thioanilides are usually represented as thioketones, R-NH-CS-R’, yet in many respects they react as iminomercaptans, R.N:C(SH).R’.The methyl derivatives corresponding with both forms were prepared in the case of thiobenzanilide and thioacet- anilide, and their absorption spectra were compared with those of the parent substances in the light of Thiele’s theory of “con-jugated ” unsaturated linkings. When thiobenzanilide was sub-jected to the action of methylating agents in neutral solvents, the sulphur was eliminated as methyl sulphide. N-,l~ethylthiobei~zaltilidewas obtained by the action of phos-phorus sulpliide on methylbenzanilide, and crystallises from alcohol in small, yellow cubes, melting at 90-91’. 361 S-~~et~yEthiobe?taa~~l~dewas obtained by the action of methyl sulphate on thiobenzanilide in alkaline solution, and crystallises from aqueous alcohol in colourless needles, melting at 63-64O.326. (‘The determination of viscosity.” By Malcolm Percival Applebey. In reply to the criticism of Bingham (T., 1913, 103,959), the author discussed the phenomena of flow in the Ostwald viscometer and the experimental conditions requisite for obtaining accurate determinations. 327. Lead cyanide.” ‘3 By Nalini Mohan Gupta. According to Rammelsberg (D.R.-P. 139456), the compound Pb(CN), is formed by precipitating a solution of a lead salt with aqueous hydrocyanic acid or a soluble cyanide, whereas Kugler (L4nnnlen,1848, 66, 63) states that a basic salt, Pb(CN),,2PbO,H2O, is formed by precipitation from an ammoniacal solution. It appears, however, to be generally recognised that the precipitate formed by the interaction of cyanides and lead salts in aqueous solution varies in composition with the concentration of the solutions employed, a fact which the author has confirmed.Lead cyanide was decomposed by hydrogen sulphide, and the hydrogen cyanide was led into water through a U-tube containing lead cyanide. To remove any traces of hydrogen sulphide from the aqueous hydrocyanic acid, some lead cyanide was added to it, and the solution shaken. As no €race of hydrogen sulphide was present no lead sulphide was formed; but after filtering this solution it was found that it contained a considerable quantity of lead. It was evident that lead cyanide, which is not appreciably soluble in cold water, is soluble in aqueous hydrocyanic acid, and it was expected that this solution would, on evaporation, deposit pure lead cyanide free from oxide.About 250 C.C. of a 5 per cent. solution of hydrocyanic acid were heated to boiling with a small quantity of precipitated lead cyanide under reflcx. After about half an hour the solution was filtered and allowed to evaporste slowly in a desiccator. The deep yellow, needle-shaped crystals which separated were collected and dried in a vacuum. Lead cyanide, even when powdered, appears to be unattacked by concentrated nitric and sulphuric acids in the cold. On adding water to a crystal, the insoluble oxycyanide is formed, and the water becomes cloudy. 362 A weighed quantity of tlic substance was heated for Some hours to 120O; there was no loss in weight.For the estimation of cyanogen and lead a weighed quantity of the substance was heated in a water-bath in a sealed tube with a weighed excess of silver nitrate and a fittle nitric acid. Thp silver cyanide was collected and weighed. The silver remaining in solution was precipitated and weighed as silver chloride, ~vhicli served as a check on the weight of the silver cyanide. Finally the filtrate was evaporated with sulphuric acid, and the lead sulpliate weighed. Two different samples were analysed : I. 0.1838 gave 0,1883 AgCN and 0'2137 PbSO,. CK"l9.90; Pb =79'42. 11. 0.2272 gave 0,2340 SgCN and 0'2638 PbSO*. CN=20,00; Pb =79'32. Pb(CN), requires CN =20.07 ;Pb =79'92 per cent.The crystals consisted therefore of lead cyanide having the formula Pb(Ch'),. 328. ('Contributions to the theory of solutions. The intermiscibility of liquids. By John Qolmes. The relative solubilities of liquids have been correlated with their molecular volumes as ascertained by a method (previously described) based on the deviations observed in the additive relations of mis-tures of liquids. On the assumption that a pure Lquid consists of a collection of like spherical molecules, it is deduceu that any liquids, the inolecular spheres of which have equal radii, should be miscible in all proportions. In binary m;xtures this mutual miscibility con-tinues until the ratio qf the respe,tive radii reaches 1.618, when the border line of partial miscibility is reached.When the ratio is greater than this value, the mixture separates into layers, in each of which the distribution of molecules is dependent on the further change in this raLio until it reaches 2 414, beyond which the liquids should be immiscible. The curves of volume chang2 calcuiated from densities available for various mixtures of liquids h-ve been drawn, and the molecular volumes deduced from the ascertained complexities are compared with those required theoretically, on the above hypothesis, for their relative Eolubilities. The molecular complexities found for these liquids differ from those generally accepted, but the corresponding molecular volumes approximate closely to solubility requirements, and render it probable that the intermiscibility of liquids is a 363 function of molecular volume and independent of chemical con-stitution.The experimental data include densities at 15’ of mixtures of isobutyric acid with water, ethyl tartrate with water, and ethyl tartrate with glycerol; also densities at 25O of mixtures of chloro- form with n-amyl alcohol and acetone. The critical temperatures of solution were determined for nicotine and water, and for carbon disulpliide and ethyl tartrate when mixed in the proportion of one to two molecules (liquid) respectively. Volume changes in aqueous ethyl alcohol inixtures are compared with the corresponding differ- ences from tha theoretical values for refractive indices. 329.(‘A contribution to the study of the constitution of the methyl pentoses. Part I. The synthesis of an i-methyl tetrose and an i-methyl tetritol.” By Robert Gilmour. An account was given of the isolation of an inactive methyl tetrose by reducing dihydroxyvalerolactone with sodium amalgam in acid solution. The free sugar has been prepared, and found to be a strongly reducing pale yellow syrup. Methyl tetrosazone forms pale yellow needles, melting at 140-142O. Methyl tetrosephenylbenzylhydrazone forms colour-less needles, melting at 99-100’. It was shown that the reduction of dihydroxyvalerolactone yields as the main product a methyl tetritol, along with only a small amount of the tetrose. The tetra-benzoyl derivative of methyl tetritol melts at 136-137’.In addition the methyl tetritol has been oxidised by Fenton’s method to the methyl tetrose, which was isolated in the !arm of the phenyl- benzylhydr azone. A racemic brucine salt of the methyltetronic acid was also described (m. p. 180-181°) as well as a dimethoeyvuleroluctone (m. p. 59-60’), which was obtained by methylating dihydroxy- valerolactone. Further, an account was given of a method which it is proposed to adopt for the preparation of other methyl tetroses, and their importance as a means of determining the constitution of naturally occurring methyl pentoses was indicated. ADDITIONS TO THE LIBRARY. I. Donations. Moureu, Chades. Notions foudamentales de chimie organique. 4th edition, Paris 1913.pp. vif383. 9. Fr. (Recd. 26/11/13.) From the Publishers : Messrs. Gauthier-Villars. Tilden, Sir WiUian~Auguatus. The progress of scientific chemistry in our own times. With biographical notes. 2nd edition. London 1913. pp. xii+366. 78. 6d. net. (Rscd. 24/11/13.) From the Author. 11. By Purchase. Rambousek, J. Industrial poisoning from fumes, gases and poisons of manufacturing processes. Translated and edited by Z’homas Y. Legge. London 1913. pp. xiv+360. 1%. 6d. net. (Red 29/11/13.) The next Ordinary Scientific Meeting will be held on Thursday, December 18th, 1913, at 8.30 p.m., when the following papers will be communicated : ‘‘ Chemical examination of Sarsaparilla root.” By F. B. Power and A. H. Salway. (‘Aromatic compounds obtained from the hydroaromatic series.Part 111. Bromoxylenols from dimethyldihydrorworcin.” By A. W. Crossley and N. Renouf. ‘I The equilibrium of dilute hydrochloric acid and gelatin.” By H. R. Procter. ‘I Metallic derivatives of acetylacetone and acetyl mesityl oxide.” (Preliminary note.) By G. T.Morgan and H. W. Moss. Constitution of the ortho-diazoimines. Part IV. Isomeric benzenesulphonyl-3 :4-tolylenediazoimides.” By G. T. Morgan and G. E. Scharff. Organic derivatives of silicon. Part XXI. The condensation products of diphenylsilicanediol.” By R. Robison and F. S. Kipping. “Sorption of gases by celluloid.” By V. Lefebure. “A study of the constitution of the nitrogen and phosphorus oxides and some of their derivatives by means of molecular volumes.” By G.Le Bas. 365 ‘‘ The absorption spectra of sulphurous acid and sulphites.” (Preliminary note.) By R. Wright. An adiabatic calorimeter.” By F. W. Gray. ‘‘ The distillation of coal in a vacuum.” By M. J. Burgess and R. V. Wheeler. (‘The composition of coal.” By D. T. Jones and R. V. Wheeler. isoMelamine.” (Preliminary note.) By H. Krall. ’. Fluorone derivatives. Part 11. Resorcinol-benzein.” By F. G. Pope.
ISSN:0369-8718
DOI:10.1039/PL9132900343
出版商:RSC
年代:1913
数据来源: RSC
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