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Proceedings of the Chemical Society, Vol. 17, No. 244 |
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Proceedings of the Chemical Society, London,
Volume 17,
Issue 244,
1901,
Page 249-267
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issued 31/12/01 PROCEEDINGS CHEMICAL SOCIETY. BD?TED BY THE SECRETARIES. ~ -Vol. 17. No. 244. _--__ Extraordinary General Meeting, December 12th, 1901, Professor EMERSON Sc.D., F.R.S., President, in the Chair. REYNOLDS, The PRESIDENTstated that this meeting had been convened in accordance with a requisition signed by 128 Fellows of the Society and that the following motions would be proposed : (1) On line 7 of Bye-Law XI (page 21, fifth line from top) to delete the words “ the Council ” and insert in their place the words ‘‘ an Extraordinary General Meeting of the Society.” (2) To resolve that the Ordinary Meetings of the Society shall continue to t,ake place, as heretofore, on Thursdays, at S p.m. Motion (1)was proposed by Mr. HEHNERand seconded by Mr.PAKES. Professor FRANKLAND seconded, the proposed, and Professor RAMSAY following amendment : c‘ That this meeting desires to express its continued confidence in the Council as the Executive of the Society, as it has no reason to doubt that all the business of the Society, including the selection of days and hours of meeting, will be managed as heretofore in the interests of the Society as a whole and in accordance with the wishes of the majority of the Fellows.” After a discussion in which the following Fellows took part : Dr. Divers, B4r. A. H. Allen, MY. D. L. Howard, Professor Smithells, Dr. Lewkowitsch, Professor Dewar, Professor Warington, and 111Ir. Phipson Beale, K.C., the President asked for n shorn of hands and declared the amendment carried.A poll having been demanded, the President announced that it would be taken by means of cards having (‘For ” and ‘‘Against ” printed on them, with a space for the 250 signature of the Fellow voting, one of these words to be deleted. 111.. Heycock, Dr. Hewitt, Dr. Shield., and Dr. Tr<tvers, having been appointed scrutatot s, The PRESIDENTannounced that the votes were, for the amendment, '628 ; against, 120, The PRESIDEKTthen declare'J the follon ing carried : "That this Meeting desires tq expres9 its continued confidence in the Council as the Executive of the Society, as it has no reason to doubt that all the business of the Society, including the selection of days and hours of nieeting, mill be managed 3s heretofore in the interests of the Society as a whole arid in accordance with the wishes of the majority of the Fellows.REYNOLDS,F.R.S.,December 19th, 1901. Prof. J. EMERSON President, in the Chair. Messrs. Kiddell, Larter, Harding, and H. C. T. Gardner mere formally admitted Fellows of the Society. The SECRETARYread the following Address which was presented on November 24th to Professor Berthelot in the name of the Chemical Society by the President, who was accompanied by Dr. Gladstone and Professor Ramsay, as the representatives of' the Society. To &I. BERTHELOT,MARCELLIN Senator, Zccte Jlinisterfor Foreign Afuirs, Member of the Institute. SIR, On behalf of the President, OEcers, Council, and Fellows of the Chemical Society, we beg to offer you, the Senior Foreign Xember of our Society, our heartiest congratalations on the occasion of the Fiftieth Anniversary of your first scientific publication.The Chemical Society has recently received the first volumes of your monumental work, yet to be completed, including the great number of papers which you have contributed, during fifty years of scientific activity, to the Chemistry of the hydrocarbons and their methods of formation. There is, however, scarcely any department of Chemical Science in which you have not worked as a pioneer with distinguished results, whilst to you is largely clue the foundation of a new branch of the Science, namely, Thermo-Chemistry. Alike in the history of our Science, and in its applications to Agriculture and Industry, $011 have made brilliant contri butions. 251 We trust that for many years you may possess the health and strength to continue those investigations which have made your name famous throughout the Scientific world.Signed, on behalf of the Chemical Society, J. EMERSON REYNOLDS, President. TVILLIABI A. TILDEN, Freasurei-, WYNDHAM R. DUNSTAK, ALEXANDER SCOTT, RAPHAEL IUELDOLA, Foreign Secretary. November 22nd, 1901. DAY AND HOUR OF MEETING. The PRESIDENTannounced that at the Meeting of Council held this afternoon, the following resolution was unanimously adopted : “That having regard to the discussion which took place at the Extraordinary General Meeting on December 12tth, the Council re-solves to make the experiment of holding the Ordinary Meetings, as far as possible, alternately at 5.30 p.m.on Wednesdays, and at 8 p.m. on Thursdays, from January, 1902, until the end of the present ses- sion in June, instead of holding meetings on Wednesdays at 5.30 p.m. only during the period from January to March, 1902, as stated in the resolution of July 4th, 1901, which is hereby rescinded,” and that a Committee had been appointed consisting of the President, the Treasurer, the Senior Secretary, Dr. Armstrong, Professor Dobbie, and Dr. Forster to arrange the exact dates on which future meetings during the session should be held. The next Ordinary Meeting of the Society will be held on Thursday, January 16th, at 8 p.m.It was also announced that Sir Henry Roscoe had presented a plaster cast of the bronze portrait on Bunsen’s tomb in Heidelberg, and that a photograph of a bas-relief of Professor Julius Thomsen had been presented to the Society by Mr, Harald Faber. Certificates were read for the first time in favour of Messrs. Evelyn Andros de la Rue, 52, Cadogan Sq., S.W. ; Keith Benham Benham, Deans Hall, Stafford ; William Dennis, Ocean Road Pharmacy, South Shields, Paul Haas, 11, Westbourne Park Rd., W. ;Eugene Edwin Henhesey, Bigods, Dunmow, Essex ; William Holdsworth Hurtley, St. Bartholomew’s Hospital, E.C. ;David Smith Jardin, Rathgar House, Rathgar ;Harry Lucas, 1,St. Agnes’ Place, Kennington Park, S.E.; John Koss MacKenzie, 31, Bailey St., Ton-Pentre, Glam.; William Maitland, 236, Brookhill, Sheffield ;Francis Martin, 64, 252 Samuel St ., Woolmich ; Francis Hylton Molesmorth, Turramurra, Sydney, N.S.W. ;Alfred Holley Mundey, 17, St. Margaret's Rd., Plumstead; Robert Eley Blake Smith, 93, Upper Richmond Rd., Putney, S.W. ; William Southworth, County Council Farm, Hutton, Preston, Lanes. Of the following papers those marked * mere read : *171. '(Corydaline. Part VII. The constitution of corydaline." By J. J. Dobbie, D,Sc., M.A.,and A. Lauder, B.Sc. The decomposition products of corydaline have been studied by the authors in greater detail with the following results. The acid, C6H,N(C0,H),, obtained by oxidising corydaline (Trans., 1897, 71 657), is, by long-contiuued heating with potassium permanganate in alkaline solution, converted into 2 :3 : 4: 6-pyridinetetracarboxylicacid. The acid, C6H,N(C0,H),, must therefore either be g-CH, 3 :4 :6-pyridinetricarboxylic acid or 2-CH, 4 :5 :6-pyridinetricarboxylic acid.From what follows, the former formula is probably the correct one. Corydilic acid, C,,H,N(OCH,),(CO,H), (Tg*a.ns.,1897, 71, 657), is sol- uble in hydrochloric acid and under certain conditions forms an unstable hydrochloride. When boiled with potassium permanganate, it is split up into a mixture of meta-hemipinic acid and the acid C,H,N(C02H)3. When corydic acid (Tmns., 1S97, 71, 657), C,,H,N(OCH,),(CO,H),, is oxidised with permanganate at the ordinary tomperature, it yields a yellow, dibasic acid, C,,H,N(OCH3),(C0,H),, which contains the two rnethoxyl groups of corydic acid.Mild oxidising agents remove four atoms of hydrogen from cory- daline and convert it into dehydrocorydaline, an intensely yellow coloured base (Z'mns., 1897, 71, 657). Berberine is also a yellow coloured base, but readily takes up four atoms of hydrogen, forming colourless tetrahydroberberine, Corydaline therefore corresponds to tetrahydroberberine and dehydrocorydaline to berberine. Corydaline Tetrahydroberberine (colourless). (colourless). C2,H27NO,* C20H21N04' Dehydrocorydaline Berberine (yellow) (yellow). C22323NO4* C20H17N04' The four oxygen atoms of corydaline are all present in methoxyl groups (Trans., 1892, 61,605). When oxidised with potassium per- manganate at looo, corydaline yields a mixture of hemipinic and meta- hemipinic acids, together with corydaldine, CllHl,NO,, a neutral substance of which the yield is larger when the oxidation takes place 253 at the ordinary temperature, This substance has been shown to be an isoquinoline derivative.When oxidised with dilute nitric acid, corydaline, C,2H,7N04, is first converted into dehydrocorydaline, C2,Hz3N0,;further oxidation splits off one of the benzene rings and yields corydic acid, a yellow, crystalline substance (Trcms., 189'7, 71, 657). Corydic acid in turn, when oxidised at 1OOo with permanganate, yields meta-hemipinic acid, the acid C,H,N( CO,H),, and the highly insoluble, colourless corydilic acid, C,2H6N(OCH3),(C0,H),, which, on further oxidation with per- manganate, is entirely resolved into meta-hemipinic acid and the acid C6H4N(C0Z H)3' As the acid C,H,N(C02H)3 contains six atoms of carbonin addition to the carbon atoms of the carboxyl groups, it cannot be derived from the isoquinoline nucleus which has no methyl group attached to it, but must represent a fourth ring, and the nitrogen atom must, as in the case of berberine, be common to two rings.There are thus four rings in corydaline. The following formula satisfactorily explains the formation of all the derivatives of corydaline which have been examined. CH Corydaline. 254 By oxidation, rings I and IV would yield hemipinic and meta-hemi- pinic acids respectively; ring 11,the acid C,H,N(CO,H),.Corydaldine, cH30>c6H,<"-YH ,contains rings I11 and IT,and would result CH,O CH,*CH, from the oxidation- of corydaline, just as o-amidoethylpiperonylcarb-oxylic anhydride results from the oxidation of berberine. Corydic acid would be formed by the destruction of ring I, and corydilic acid from corydic acid by the oxidation of ring 111. The formula of the last-mentioned acids are therefore : C*CO,H 3H Corydilic acid. A comparison between the formuls of corydaline and tetrahydro- berberine explains the resemblance between the two substances and their oxidation products. By oxidation, ring I, both in berberine and corydaline, yields hemipinic acid ;ring IV in berberirie yields hydrastic acid, corresponding to meta-hemipinic acid from corydaline.w-Amidoetbylpiperonylcarboxylic anhydride, corresponding to cory-daldine, is derived from rings I11 and IV, and berberonic acid, C,H,N(CO,H), [(CO,H), =3 : 4 : 61, corresponding to the acid C6H,N(C02H)3,from ring I1 in corydaline. Berberonic acid is derived from ring 11, and not from ring 111, which would yield carbocinchomeronic acid. This point is not dealt with by Perkin, but incidentally affords confirmation of the correct- ness of his formula. The ease with which corydaline is oxidised to dehydrocorydaline is explained in the same way as in the case of the oxidation of tetra-hydroberberine to berberine, the hydrogen atoms attached to the 255 carbon atoms 2, 5, and 6 of ring I1 being removed on oxidation, and a link established between the atoms 2 and 5, and a second link be- tween 5 and 6.The above formula for corydaline, which accounts for its decompo-sition products and explains the analogies with berberine, involves the adoption of the constitution 2-CH3 :3 : 4 :6 for the acid CGH,N(CO,H), ; the alternative formula would leave the resemblance to berberine unexplained. *172. “The relation of corydaline to berberine; the oxidation of berberine with nitric acid.” By J. J. Dobbie, D.Sc., M.A., and A. Lauder, B.Sc. In the pravious abstract it is shown that the constitution of corydaline can be expressed by a formula similar to one of the formula proposed by Perkin for berberine. Assuming the correctness of the formula for corydaline, the absence of compounds corresponding to berberal and berberilic acid (Perkin, Trans.,lS90, 57, 992) from amongst the decomposition products of corydaline is explained, since all these substances contain an atom of oxygen united to the carbon atom 2 in ring I1 (see previous abstract), where owing to the presence of the methyl group it is impossible to introduce an oxygen atom into corydaline derivatives.If the view of the relation of the two substances expressed in the formulae is correct, the first of Perkin’s alternative formuls (Perkin, T~ans.,1890,57,992) must be adopt,ed. In his second formula, a double bond is shown between the carbon atoms 2 and 5 of ring 11. No double bond in this position is possible in dehydrocorydaline on account of the presence of the methyl group, and the analogy between the two substances breaks down if we suppose the double bond in ring I1 to occupy different positions.Whilst the absence of certain decomposition products is thus satisfactorily accounted for, the formation of corydic acid from corydaline suggests the possible formation of a similar acid from berberine. By oxidising berberine with dilute nitric acid in exactly the same way as was followed in the preparation of corydic acid (Trams.,‘1897,71, 657), an acid, C,GH11NO, (m. p. 9S5O), was obtained closely resembling corydic acid in properties and obviously bearing to berberine the same relation as corydic acid to corydaline. This acid is very difficultly soluble in hot water; it dissolves in sodium hydroxide, forming a blood-red solution.It is dibasic, almost all its salts are soluble, a notable exception being the acid silver salt. It contains no methoxyl groups, hence (as in the case of corydaline) it is formed by the destruction of ring I. By oxidation with potassium 256 permanganate, it yields berberonic acid, C,H,N(C0,H)3 [(CO,H), = 3 :4 :61, and o-amidoethylpiperonylcarboxylicanhydride. The name berberidic is proposed for this new acid. *173.‘6 The magnetic rotation of some polyhydric alcohols, hexoses and disaccharoses.” By W.K. Perkin, sen., Ph.D., F.R.S. The object of this investigation was to see if any clue could be obtained from the magnetic rotation of the sugars as to the cause of their bi- or multi-rotation. Some of the polyhydric alcohols were also examined in order that data might be obtained from which to cal- culate the probable values for the various sugars.From the rotations obtained for glucose and for fructose, it was found that the suggestion that bi-rotation was due to hydration was untenable. The magnetic rotations are too low for substances possessing the aldehydic and ketonic constitutions usually assigned to these sugars, but they correspond with substances containing an oxygen atom linked as in ethylene oxide or the lactones, all of which give low numbers. This agrees with the suggestion of Lowry (Tmns., 1899, 75, 215), that when in solution and having undergone the largest amount of change, glucose exists chiefly in an isomeric form for which he gave two formulae, of which the more probable one, judging from the magnetic rotation, may be represented thus, CH,OH*CH-OH*QH*CH*OH*CH*OH*vHOH. I 0 I This is the formula originally proposed by Tollens for dry glucose (Ber., 1883, 16, 92).When slightly modified it can also be used to represent Eructose in an isomeric condition, equally consistent with the magnetic rotation of this substance in solution. Saccharose may be regarded as built up from glucose and fructose, both being in their isomeric forms, with elimination of water, its con- stitution being that proposed by E. Fischer (Be?*.,1893, 26, 2405), which is a slight modification of that suggested by Tollens (Ber., 1883, 16, 923).Maltose and lactose, which possess both birotation and reducing power, appear to have analogous structures, the formula proposed by Fischer for lactose (Zoc. cit.) being practically applicable to both, but their constitution is different from that of saccharose. Hence maltose and lactose are formed from a molecule of glucose or of galactose in the isomeric condition, plus a molecule of glucose in the ordinary or aldehydic form, minus water, the aldehydic part under- going isomeric change to a greater or less extent when these disaccharoses are dissolved in water ; in this may the possession of birotation by these substances may be explained. 257 *174. Stereoisomeric halogen derivatives of a-beneoylcamphor." By M.0. Forster and Miss F. M. G.Micklethwait. Ia'-Bencoyl-a-bromocccmphor,C,H, 4< CBr'C0'CGH5, prepared by dis-co solving 1-hydroxy-2-benzoylcamphene in glacial acetic acid containing sodium acetate (18 mols.) and adding a solution of bromine (1 mol.) in acetic acid, crystallises from light petroleum in large, transparent, six-sided prisms and melts at 114"; dissolved in benzene it has [a]D = -10.Oo, and in chloroform [aID= + 10.3". a-BencoyZ-a'-bromoca?nphos.is formed in preponderating amount when potassium hypobromite acts on hydroxybenzoylcamphene dissolved in potash ;it crystallises from hot alcohol in transparent, rectangular plates melting at 214O, and has [a]D= -53.2' in benzene and [a],= -19.3' in chloroform. Hydrogen bromide converts the lorn melting isomeride into the less readily fusible modification.a'-Benxoyl-a-chlorocarnphor, C,H,,<&., CC1*Co*cGH5,obtained by the action of sodium hypochlorite on hydroxyhenzoylcamphene, melts at 88O, and has [ a]D = -27.9" in chloroform. a-BenxoyLa'-chZorocan~phor is produced in the same way and separ- ated by means of its sparing solubility in alcohol; it melts at 219' and has [a], = + 269O in chloroform. "175. Brasilin and haematoxylin. Part VI. The constitution of brasilic acid, of brasilin and of haematoxylin." By W. H. Perkin, jun. In part I of this research (A. 'CV. Gilbody, W.H. Perkin, jun., and J. Yates, Pram., 1901, 79, 1401), it was argued that since trimethyl- brasilin on oxidation with permanganate yields 2-carboxy-5-methoxy- phenoxyacetic acid and meta-hemipinic acid, the constitution of brasilin must be represented by one of the following formulre: I.11. In order to decide between these two formulre, the author has sub- mitted brasilic acid to a detailed examination and has obtained re- sults which show clearly that formula I must be accepted as represent- ing the constitution of brasilin. 2.38 BYasiZic acid, C1,H,,O,, is produced by the oxidation of trimethyl-brasilin with permanganate, but the yield is only 0.7 per cent. ; it is a monobasic acid, the silver salt having the formula C,,HllAgOd. The sodium salt, C,,H,,NaO,, is comparatively sparingly soluble and crystallises in glistening plates. Since brasilic acid contains one methoxyl group, its formula may be written MeO*Cl,H,O,*CO,H, and as on fusion with potash it yields a substance which with ferric chloride gives a violet coloration, it is evidently derived from the resorcyl nucleus of brasilin.Furthermore, it yields an oily oxime, RleO*C,H80,(C:NOH)C0,H, and when reduced with sodium amalgam it is convert,ed into the Znctone of dihydro-bras& acid, C,,H,,O,, which melts at 144O and is very sparingly soluble in ether. From this behaviour, it follows that brasilic acid contains a car-bony1 group, and that this is probably in the y-position in relation to the carboxyl group. When warmed with sulphuric acid, brasilic acid loses one molecule of water and is converted into delqddwasilic acid, C12H,,0,, a mono-basic acid, which is very sparingly soluble in water, melts at 197", and when treated with permanganate in the cold is oxiclised with formation of p-methoxysalicylic acid, MeO*C,H,( OR)*CO,H.Hydroxylamine converts dehydrobrasilic acid into an oxime, C,,H,,NO,, which melts at 172". The acid, therefore, still contains a carbonyl group, When digested with baryta water, it is readily decomposed with formation of formic acid and a new acid, C,,H,,O,. C,,H,,O, +2H20=HgCO,H + CllH1,05. This new acid crystallises from water in colourless needles, melts at 155O and gives, in aqueous solution, an intense violet coloration with ferric chloride ;when heated with sodium methoxide and methyl iodide it yields a methyl derivative, Cl2H1,O5, which melts at 147'.In conjunction with Illlr. E. Ormerod, the author has succeeded in synthesising this latter by treating dimethylresorcinol in the presence of aluminium chloride with the ester of the half-chloride of succinic lacid, COCl*CH,*CH,*CO,Et, the methyl derivative, C12H1405,must there-fore be 2 :4-dimethoxybenzoylbutyric acid, MeO/\O>leI\//CO.CH,*CH,GO,H 9 and the acid, C,,H,,O,, from which it is derived by methylation, is 2-hydroxy-4-methoxybenzoylbutyricacid, 1SleO/\OH1\/ICO*CH,*CH,*CO,H ' 259 The constitutions of the other acids mentioned above are now estab- lished, and are as follows : 0 0 MeO(y\FH, MeOf\(\FH,\/\,/C(OH)*CH,*CO,H \/\/C(OH)CH *CH2I co \O-- co Brasilic acid. Lactone of dihgdrobrasilic acid. 0 &leO(\l/\EH \/\/C*CH,*C 0,H co Dehydrobrasilic acid. Since, of the two formulae for brasilin given above, formula I alone accounts, in a simple manner, for the formation of brasilic acid, it appears to the author that this must be accepted as representing the constitution of brasilin. It hasalready been shown (PYoc.,1900, 16, 107) that tetramethyl- haematoxylin, on oxidation with permanganate, gives products which are exactly similar to those obtained from trimethylbrasilin, and there can, therefore, scarcely be a doubt that the constitutional formula of hzematoxylin is HO 0 OH CH, 176.'(Is argon an elementary substance '1 " By G.Martin. Some eighty distinct elementary substances are now recognised.These are assumed to be composed of different kinds of matter because each one has chemical properties peculiar to itself alone. Physical properties are of little value in deciding whether different substances are merely allotropic modifications of one kind of elementary matter, or whether they are distinct elements. The only certain test lies in the chemical natuye of the compounds produced when the elements unite with other elements. Elements often resemble each other so strongly in their physical nature that it is almost impossible to distinguish between them. For example, the new radio-active elements are so similar to bismuth, 260 barium and titanium, that many chemists still hesitate to believe them elementary.The rare earths are composed of elements so much alike that it is with the utmost difficulty they can be distinguished from one another. But all these substances have one characteristic which stamps them as elements-each produces its own peculiar set of compounds. This characteristic is absent from argon and its companions ;therefore, in order to demonstrate their elementary nature, Ramsay had to fall back on their physicai properties-the most untrustworthy of all methods. These properties stamp the new gases as a distinct class of elements ; but they do not, and cannot, prove that each ‘‘ element ” is a single substance and not a group of closely related elements. For inst,ance, were argon a mixture of 3 monatomic gases of like nature, and of which the atomic weights differed from each other by a fraction of a unit-as do those of nickel and cobalt-it would be impossible to dis- tinguish the mixture from an element.It would answer to exactly the same physical tests and could not be resolved into its compounds by any physical methods except with the utmost difficulty. It takes many thousands of fractionations to distinguish between two rare earths, which not only give different chemical compounds, but are far more unlike chemically than mould be 3 moncctonzic inwt gases. We are peculiarlyliable in the eighth group to meet with neighbouring elements of almost identical atomic weight and properties. For instance, in series 4 of the periodic table, as we advance with increasing atomic weight from potassium to nickel, the resemblance between SUC-cessive elements steadily increases ;potassium and calcium, for example, are quite unlike each other, but vanadium, chromium, manganese, and iron are all strikingly analogous, while the two last elements of the series, cobalt and nickel, have almost identical atomic weights and resemble each other in a most remarkable degree.In many of the other series, also, wa end up in the eighth group with elements so very similar that they are classed as ‘‘triads,” for example, ruthenium, rhodium, and palladium ; osmium, iridium, and platinum ; the atomic weights of these triads are in every case very close together. If each of the ‘‘ elements ” of Ramsay really consists of three allied substances, the eighth group of the periodic table would lose altogether its peculiar “ triad ” character and split up into three distinct groups-a possibility which of late years has been running through many minds.177. (‘The action of phosphorus trithiocyanate on alcohol.” By Augustus Edward Dixon, M.D. Lossner states in a brief preliminary note (J.prakt. Chein,., 1873, ii, 7, 474) that phosphorus trichloride, acting upon an alcoholic solution of 262 potassium thiocyanate, produces a substance crystallising in fin needles, and having the formula C8H,,N,S,0. From results obtained by the author in his study of phosphorous and phosphoryl ‘ thiocyanates,’ recently commenced (Tvam., 1901, 79, 541), it seemed probable ttat LGssner’s compound, if really formed, must have originated through some decomposition of the phosphorus trithiotri- urethane, P(NH*CS.OEt),, which might be expected to result from the union of phosphorus trithiocyanate, P(SCN),, or P(NCS),, with tho alcohol used as solvent ; to ascertain if this was the case, the two latter substances were caused to interact directly, in presence of dry benzene.Phosphorus trithiotriurethane could not be identified ; neither could Lossner’s compound : thiocyanic acid was expelled, and the residual liquid mas eventually resolved into (1) an acid oil, containing phos- phorus, and (2) isopersulphocyanic acid. Phosphorus trichloride interacted violently with alcoholic potassium thiocyanate : potassium chloride was precipitated,lthiocyanic acid is given off, and from the residual oily liquid, after concentration, isopersulpho- cyanic acid was deposited : no sign could be got of the presence of the compound C,H,,N,S,O.The author supposes the isopersulphocyanic acid, which is formed in small relative amount in either process, to be produced through the interaction of the mineral acid with the thiocyanic acid simultaneously liberated. Benzyl alcohol interacts spontaneously with phosphorus trithiocyan- ate, but, as in the case of ethyl alcohol, no evidence could be obtained of the existeiice of a salt of phosphorus trithiotricarbamic acid, P(NH*CS*OH),; if such compounds are formed at all iu these inter- actions, it is probable that, like their congeners of the thiocarbamidic class, they very readily undergo hydrolysis.178, “The influence of salts and other substances on the vapour pressure of aqueous ammonia solution.” By E. P. Perman. The author has investigated the effect produced by urea, mannite, potassium sulphate, ammonium chloride, and copper sulphate respec- tively on the vapour pressure of aqueous ammonia solution by a method similar to that described for sodium sulphate (Duns., 1901, ’79, 725). The objects of the research were to find (1) the effect upon the pressure of substances which have no direct chemical action on the ammonia, (2) the effect of rise of temperature on copper sulphate ammonia solution, (3) evidence for or against the existence of hydrates in solution. The conclusions arrived at by the author are : (1) that salts of the alkalis have a, greateffect in raising the pressure, but that the effect of 262 other substances which might be expected to have no direct chemical action on the ammonia is either small or nothing.(2) That copper sulphate forms complexes with ammonia in solution which tend to decompose on heating, especially when the proportion of copper sulphate is small. (3) The effect of potassium sulphate is similar to that ofisodium sulphate in raising the pressure. There is but little reason to suspect the existence of a hydrate of potassium sulphate, as it lcrystallises without water ; consequently it mould appear that neither sulphate exists in solution as a hydrate. 179.The action of sodium hypochlorite on benzenesulphonanilide. 'I Preliminary notice." By J. B. Cohen and J. T. Thompson. In the preparation of the different isomeric dichlorotoluenes (Cohen and Dakin, Trccns., 1901, 79, llll),the authors had frequent recourse to the method of chlorination recently studied by Chattaway and Orton (Trccns., 1899, 75, 1046 ; 1900, 77, 134 and 759, and Be?.., 1899, 32, 3573). The authors have found that a very similar reaction occurs with the aromatic sulphonanilides, of which, with Dr. Cliattaway's friendly acquiescence, the authors now give a brief notice. Twenty grams of benzenesulphonanilide were dissolved in 500 C.C. of a solution of sodium hypochlorite (1 C.C.= 0.03 gram Cl) in the cold and allowed to stand 12 hours, The brown solution was acidified with acetic acid until the buff precipitate redissolved, when it was extracted with chloro- form.After rapidly evaporating off the solvent, the residual red liquid was digested for an hour with two volumes of glacial acetic acid containing a few drops of concentrated sulphuric acid, until, on pour- ing into water, a solid substance separated. The new compound mas recrystallised from acetic acid and then from alcohol, when it melted at 129-130O. The yield amounted to 18 gram of crude or 11 grams of purified substance. The mother liquor contained a small quantity of a semi-solid sub- stance, which became crystalline on standing and after recrystallisation from benzene and petraleum melted at 116".This substance is pro- bably the benzenesulphonyl-p-chloranilide (m. p. 12lo),but it is difficult to free it from oily impurity. The substance melting at 129-130' was analysed, with the following result : 0.292 gave 14.15 C.C. moist nitrogen at 15.5' and 758 mm. N=5*66. 0.3185 ,, 0.1764 AgC1. C1= 13.57. 0.2097 ,, 0.1820 BaS04. S=11-93. C,,H,,O,NSCl requires N = 5.23 ; C1= 13.27 ; S= 11.90. 263 In order to determine the constitution of the substance, it was hydrolysed. Two grams were heated wit,h about eight grams of con-centrated hydrochloric acid in a sealed tube to 190' for 4-5 hours. On opening the tube, there was a strong smell of benzene, the presence of which was confirmed by extracting with light petroleum, nitrating the extract with a mixture of concentrated sulphuric and nitric acids, washing, and evaporating off the light petroleum. On re- ducing the residue with zinc dust and acetic acid, aniline was formed and gave an intense violet coloration with sodium hypochlorite solu- tion. The appearance of benzene in the decomposition of the sulphon- anilide compound is readily accounted for, seeing that Armstrong and Field (Bey., 1874, '7, 406) and Jacobsen (Ber., 1876, 9, 258) have shown that sulphonic acids are converted into the hydrocarbons by strong hydrochloric acid under pressure. The acid solution, after ex- tracting with light petroleum, was made alkaline with sodium carbonate and distilled in steam.The distillate was extracted with ether, the ether removed, and the residue dehydrated in vacuo. A yellow oil weighing 0.S gram remained, The substance did not solidify on introducing a crystal of 11-chloraniline, even when cooled in ice; it yielded an acetyl derivative melting at 85-S6' and a benzoyl derivative melting at 102'.This corresponds to o-chloraniline which was prepared from o-nitraniline, and then converted into the acetyl and benzoyl derivatives having the above melting points. In further confirmation, the o-chloraniline was heated with benzenesulphonic chloride and converted into the sulphonanilide melting at 129-130', which agrees with the melting point of the product obtained by the action of sodium hypochlorite on benzenesulphonanilide. The re- action, therefore, probably occurs in two steps, as in the chlorination of the acetyl derivatives studied by Chattaway and Orton, C,H5S02NHC,H5-I-C1, = C,H5S02*NC11*C6H,+ HC1, C,H5S02*NCl*C,H5= C6H5S02*NH*C,H,Cl, with the formation mainly of benzenesulphonyl-o-chloranilideand a small quantity of the p-chloranilide. Wallach (Bey., 18'77, 9, 424) found that benzenesulphonanilide, when heated to 100' with phosphorus pentachloride, yields benzene- sulphonylp-chloranilide,m. p.121'; but no reference is made to an o-compound. The authors have repeated Wallach's work, which they can confirm. The product is difficult to purify and only a small yield of pure substance could be obtained. From y-chloraniline and benzene sulphonic chloride the authors have also synthesised this substance, which melts at 121' as stated by Wallach.To complete the series, the authors have synthesised the benzene sulphonyl-m-chloranilide from m-chloraniline, which has not been pre- 264 viously described; like the p-compound, it melts at 121'. It gave the following result on analysis : 0.2576 gave 12.85 C.C. moist nitrogen at 13" and 741 mm. N =5.76. C,,HloO,NSCl requires N =5.23 per cent. The authors intend to continue the investigation. 180. ('The relationship between the substitution and the constitu- tion of benzeneazo-a-naphthol." By J. T. Hewitt and S. J. M. Auld. Nohlau and Kegel (Be?..,1900, 33, 2S5S) have shown that benzene- azo-a-naphthol reacts with Michler's hydrol (tetramethyldiaminobenz-hydrol) to form a condensation product in the same manner as para-quinones and their derivatives.Moreover, the substance obtained acetylates in such a manner that the entering acetyl group attaches itself to a nitrogen atom, The authors mentioned draw the conclusion that benzeneazo-a-naphthol and its derivatives are of quinone-hydrazone type.The results obtained by the authors of the present communication are in favour of an oxyazo-formula. Benzeneazo-a-naphthyl acetate yields aniline on complete fission and no acetanilide. By partial reduction, a hydrazo-compound is obtained melting about 160-1 65" ; the formula C,H,*NH*NHOC,~H,*O*COCH,is confirmed by the in- solubility of the substance in dilute alkalis. Nitric acid is not a satisfactory substitnting agent to use with benzeneazo-a-naphthol, but bromine reacts with the azonaphthol in presence of acetic acid and sodium acetate, forming a monobromo-deriva-tive of m.p. 196". This substance yields aniline on fission, the bromine therefore enters the naphthol nucleus. From this benzeneazobromo- naphthol the ethyl etl~e79, m. p. 220" (uncorr.), and acetyl derivative, m. p. 146", have been prepared. The following substances containing bromine in the benzene nucleus have been prepared for purposes of comparison. o-Bromobenxenenao-a-naphthoI, m. p. I 83". o-B~onao6enaeneccxo-a-naph-thyl ncetate, m. p. 123'. m-Bromobenxeneaxo-a-nccpht~~ol,m. p. 21l3 (uncorr.). m-13?.omobe~xeneaxo-a-~ap~~t?~~~metate, m. p. 112'. p-Bromo-benzeneazo-a-naphthol, m. p.237-23s" (Bamberger, Ber., 1895, 28, 1896). p-Bromobenxeneaxo-a-.rzccp~~thylacetccte, rn. p. 141'. The bromination of benzeneazo-P-naphthol is now being studied. 2G5 ADDENDUM TO DISCUSSION On Messrs. Hall and Plymen’s paper, No. 162, on ‘‘ The determination of available plant food in soils by the use of dilute solvents.” DR.DYERpointed out that any process must necessarily be empirical. The actions of the root sap of plants could not be exactly imitated and much must always depend, not only upon the composition of the solu- tion used, but also upon its volume and the duration of contact. He was very glad that the 1 per cent. citric acid solution had on the whole given more reliable indications of the degree of comparative fertility as regarded both phosphoric acid and potash than did the other acid solu- tions tried, When he was in America a year ago, he found in use for the determination of “available ” phosphoric acid a one-fifth normal solution of hydrochloric acid, but this did not give satisfactory results for potash and he understood that at that time they had not decided in America what was the best solution to use for potash.As to the limits which he had laid down as indicating need of manurial phosphoric acid or potash, both in his original paper on the Hoos Field soils and in a paper on the Broadbalk soils (I‘M. Truns., 1901, 194B.,235), he had pointed out that the limits which he gave related to cereal crops and might probably have to be modified with reference to root and other crops.In this direction, much more work was required. Dr. Dyer called attention to some experiments recently carried out by I@. Ingle of the Yorkshire College, Leeds, in which he had extracted a large quantity of soil with 1 per cent. citric acid solution, and after washing out had grown various crops in it in pot-culture, with and without total or partial replacement of the constituents removed. Some of Mr. Ingle’s photographs were exhibited, which showed that the soil when exhausted of its available ” constituents by 1 per cent. citric acid solution, was hardly able to support the life of bean plants, but that when the con- stituents thus dissolved out were replaced the plants flourished abund- antly. Mr. Ingle’s experiments were not yet completed, but so far they appeared to confirm the practical value of 1 per cent.citric acid solution as a reagent in soil analysis. Dr. J. A. VOELCKEBremarked that the experiments of the authors had shown very clearly the influence of one constituent of the soil upon another. Mr. Hall had himself pointed out the variations caused by the presence or absence of lime, and Dr. Dyer had shown how the action of citric acid was influenced by the presence of sodium and magnesium salts, and how irregular were the results when farm-yard manure had been applied to the land, He did not think it was right to take one particular solvent and of one particular strength, and to apply it indiscriminately to all classes of soils alike, nor did he think that the use of hydrochloric acid should be abandoned on the grounds given.That a 1 per cent. solution showecl, with certain soils, results not consistent with those of certain other solvents or with those of a strong solution of the acid afforded no proof that the acid was an unsuitable solvent,. In work on which he had lately been engaged, he had found a 1 per cent. citric acid solution useful in many cases, and it was certainly an advance on the older methods, but he was not alto- gether satisfied with it as yet, and had not found the results to be in all cases consistent with the conclusions arrived at from practical ex-perience of the land. It was not improbable that a distinction mould have to be drawn between the two different classes of phosphoric acid present in the soil, the one the phosphoric acid naturally belonging to the soil, the other the phosphoric acid accumulated by repeated manurial applications.ADDITIONS TO THE LIBRARY. I. By DoncLtio?a. Digest of criticisms on the United States Pharmacopceia, lS90. Part 111. Pp 180. Philadelphia. 1901. From the Committee of Revision. Duprd, A,, and H. Wilson Hake. X short manual of inorganic chemistry. Third edition. Pp. 392. London, 1901. From Dr. Hake, Ryn, J. L. van. The Composition of Dutch Butter. Pp. 55. London. 1908. From the Publishers. 11. By Purchuse. Vaubel, Wilhelm, Die physikalischen u. chemischen Methoden der quantitativen Bestimmung organischer Verbindungen.I Band. Die physikalischen Nethoden, mit 74 in den Text gedruckten Figuren. I1 Band. Die chemischen Methoden, mit 21 in den Text gedruckten Figuren. 2 vols. 8v0, pp. 593, 530. Berlin. 1902. Wallacb, 0. Briefwechsel zwischen J. Berzelius u. F. Wohler im Auftrage der K. Gessell. d. Wissen. zu. Gottingen, mit einem Corn-mentar von J. von Braun. Erster Band, mit Berzelius’ Bildnis. Zweiter Band, mit Wohlers Bildnis. Svo, pp. 717, 744. Leipzig 1901. 267 111. Pcunphlet,o. Batschinski, Xlexius. Studien zur Kenntnis der Abhangigkeit der Viscositat der flussigen Kijrper von der Temperatur 11. von ihrer cheniischen Constitution. Abt. 1. Illloscow. 1901. From the Author. Haas, P. Zur Kenntnis einiger Derivate des Acenaphtens. Freiburg i. Br. 1901 From the Author. Stoclclart, F. Wallis. The continuous sewage filter. Bristol. 1901, From the Author. The next Ordinary Meeting of the Society mill be held on Thursday, January 16th, at 8 p.m.
ISSN:0369-8718
DOI:10.1039/PL9011700249
出版商:RSC
年代:1901
数据来源: RSC
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