摘要:

JOURNAL OF THE CHEMICAL SOCIETY. CONTAINING THE PAPERS READ BEFORE THE SOCIETY AND ABSTRACTS OF CHEMICAL PAPERS PUBLISHED IN OTHER JOURNALS. F. A. ABEL F.R.S. E.E. ARMSTRONG,Ph.D. W. MARCET M.D. F.R.S. N. STORY-MASKELYNE,F.R.S. E. ATKINSON Ph.D. E. J. MILLS,D.Sc. c. L. BLOXAM F.C.S. HUGO M~~LLER Ph.D. F.R.S. H. DEBUS Ph.D. F.R.S. H. M. NOAD Ph.D. F.R.S. G. C. FOSTER,B.A.,F.R.S. W. ODLING M.B. F.R.S. MICHAELFOSTER,M.D. F.R.S. E. FRANKLAND,D.C.L.,F.R.S. . W. H. PERKIN,F.R.S. H. E. ROSCOE,Ph.D. F.R.S. J. H. GILBERT Ph.D. F.R.S. W. J. RUSSELL,Ph.D. F.R.S. J. H. GLADSTONE Ph.D. F.R.S. A. VOELCKER,Ph.D. F.R.S. A. VERNONHARCOURT,M.A. ,F.R.S. A. w. WILLTAMSON Ph.D. E'.R.S. @kitrattar# Ph.D. E. W. PR~VOST, H. E. ARMSTRONG Ph.D. Ph.D.G. T. ATKINSOR. W. RAMSAY ROBINSON. E.C. BABER. JOHN BOLAS. i R. ROUTLEDGE, THOMAS B.Sc. M.D.,D.Sc. MORTYN T. L. BRUNTON J. SALTER. CHILDS,B.A. a. SCHENK, CHRISTOPHER Ph.D. F.R.S. B. J. GROSJEAN. C. SCHORLEMMER SMITH. C. E. GROVES. WATSON H. J. HELM. i THOMAS M.D. STEVENSON EDWARD KINCH. W.A. TILDEN D.Sc. LICHTENSTEIN. WILLIAMVALENTIN. MAURICE MUIR. ROBERT M. M. PATTISON WARINGTON. 1 WATTS D.Sc. C. H. PIESSE. JOHN W. H. PIKE,Ph.D. 1 C. R. A. WRIGHT,D.Sc. NEW SERIES,Vol. XIII. (Entire Series Vol. XXVIII.) LONDON J. VAN VOORST 1 PATERNOSTER ROW. 1875. LONDON HARRISON ARD SONS PRINTERS IN ORDINARY TO HER MAJESTY ST. MARTIN’8 LAKE.

ISSN:0368-1769    

DOI:10.1039/JS87528FP001

出版商:RSC    

年代:1875

数据来源: RSC

摘要:

STEXHOUSE ON THE ACTION OF BROMINE ETC. 11.-Action of Bromiue on Protocatechuic Acid,Gallic Acid ad Tanwhz. By J. STENHOUSE, LL.D. F.R.S. A PRELIMINARY notice appeared some time ago (Chern. News xxix 95) on this subject of which the details are now given together with some additional matter. Action of Bromine on Protoeatechic Acid. Barth has shown (AWLChem. Phaym. cxlii 246) that when pro-tocatechuic acid is treated with excess of bromine in the cold one equivalent of the hydrogen in the acid is replaced by bromine giving rise to monobromoprotocatechuic acid C7H,BrOa. If however this bro-moprotocatechuic acid or protocatechuic acid itself be heated in sealed tubes to 100° with excess of bromine I find that the reaction which STENHOUSE ON THE ACTION OF BROMINE ON takes place is quite different-hydrobromic acid and carbonic anhy- dride are evolved and tetrabromopyrocatechin is produced.C7H,0a+ 4Br2= C,H2Br402+ GO2 + 4HBr. As is well known protocatechuic acid at a high temperature splits up into pyrocatechin and carbonic anhydride but this reaction does not take place at 100". The presence of bromine however deter- mines the decomposition of the acid with simultaneous production of the highly brominated tetrabromopyrocatechin. The latter substance produced in this way crystallises in long silky needles and possesses all the properties ascribed to it by Hlasiwetz (Ann. Chew%.Pharnz. cxlii 246). The best solvent from which to crystallise it is ordinary acetic acid of density 1.050. It melts at 187" and when submitted to analyses gave the following results :-I.-229 gram substance gave ,406 of silver bromide. 11. -329 9) 9 -580 9 9> 111. *267 ?> , -165 gram of carbonic anhydride arid -016gram of water. I. 11. 111. Cg = 72 .... 16.90 -16.86 Hz 2 .... 947 --66 Br4 = 320 .... 75.12 7544 75.01 -02 = 32 .... 7.51 --426 100-00 Although the action of bromine alone on protocatechuic acid when gently heated with it does not go further than the formation of bromo-protocatechuic agid iodine bromide under similar circumstances causes a more complete decomposition giving rise to bromopyrocatechin. Prepnration of Protocatechuic Acid. Ofthe numerous sources from which protocatechuic acid may be obtained East India kin0 is by far the best and that which yields it most readily.One part of the kin0 in fine powder is gradually added to three parts of fused sodic hydrate stirring the mixture constantly during the introduction of the kino the most convenient met'hod being to sift the fine powder over the surface of the hydrate which is kept fused at a gentle heat. When the mixture has acquired a bright orange-brown colour it is poured out on a stone or an iron plate and allowed to cool. The cake is then broken np and dissolved in about 20 parts of hot water to which dilute sulphuric acid is added from time to time so as to render the solution slightly acid. The dark PROTOCATECHUIC ACID GALLIC ACID AND TANXIN. brown solution is then allowed to stand for 24 honrs when it deposits a large quantity of sodic sulphate in the crystalline state ; the mother liquors which contain the protocatechuic acid after being filtered to remove a small quantity of tarry matter are agitated with ether.The ethereal solution is then separated and the ether recovered by distilla- tion in the water-bath the dark-coloured syrupy residue on standing deposits the protocatechuic acid in the crystalline state. The mother- liquors may be readily separated from the crystals by means of the vacuum pump and the acid is then easily purified by one or two crystal- lisations from a small quantity of hot water with the addition of some freshly precipitated lead sulphide which removes the brown colouring matter. If kin0 be dissolved in hot water and the solution boiled for an hour after being strongly acidified with sulphuric acid a bright red powder (kino red) is deposited which is insoluble in water.This when fused with about four times its weight of sodic hydrate yields a purer pro- tocatechuic acid than the original kino. A similar crimson powder (larch red) is obtained by boiling the extract of larch bark with dilute acid (Phil. Mag. xxiii 336) and this also when fused with an alkaline hydrate yields protocatechuic acid with facility. The extract itself does not yield such good results. The amount of protocatechuic acid obtained from catechu is but small and it is very difficult to purify. Pure catechin however is a much better source but not superior to ordinary East India kin0 or to larch red.Action of Bromine on Gallic Acid and on Tafinin. As gallic acid bears the same relation to pyrogallol that proto- catechuic acid does to pyrocatechin it seemed probable that when treated with bromine at 100" it might undergo a similar decomposition. On making the experiment this was found to be the case-hydrobromic acid and carbonic anhydride are evolved and tribromopyrogallol is formed-C7H605+ 3Br2= CsH3Br303 + C02+ 3HBr. Here also the action of bromine on gallic acid when the two are gently heated together is to convert it into dibromogallic acid C,H4Br20 (Grimaux BUZZ.SOC.Chirn. [2] vii 479) but at loo" in presence of excess of bromine this acid is decomposed carbonic anhydride being eliminated and tribromopyrogallol produced.When tannin is heated to 100' in a sealed tube with excess of com-mercial bromine large quantities of hydrobromic acid and carbonic anhydride are liberated and t,he product) a,fter the removal of the PERKIN ON PROPIONIC COUMARIN excess of bromine is found to consist of bromopyrogallol. If however both the tannin and the bromine be very carefully dried the reaction is quite diff erent-hydrobromic acid and some carbonic anhydride are evolved but the prodzlct consists of a dark-coloured amorphous sub- stance tot,ally different in appearance from the colourless crystals of the bromopyrogallol I have not as yet investigated the nature of the product obt'ained by the action of dry bromine on dry tannin but the result strongly confirms Sc hiff 's view (Awz.Chem. Phann. clxx 43) that tannin is merely digallic anhydride. In the experiment made with nndried tannin and commercial bro-mine the small amount of water naturally present in these substances was sufficient to convert the tannin into gallic acid which was then decomposed with formation of bromopyrogallol and elimination of carbonic anhydride. Action of Chlorirbe on Protocatechuic Acid and on Pyrogallol. When protocatechuic acid is heated to 100" with a saturaied solution of chlorine in carbon tetrachloride in sealed tubes a chlorinated com- pound is produced which after being purified by crgstallisation from carbon disulphide forms colourless needles. A similar reaction ta,kes place when pyrogallol is treated with a carbon tetrachloride solution of chlorine. I cannot conclude this paper without expressing my obligations to Mr. Charles E. Groves for the valuable assistance he has rendered me in conducting this investigation.

ISSN:0368-1769    

DOI:10.1039/JS8752800007

出版商:RSC    

年代:1875

数据来源: RSC

摘要:

PERKIN ON PROPIONIC COUMARIN III.-Om Propionic Cowmaria and some of its Derivatives. By W. H. PERKIN, F.R.S. OURknowledge of the coumarins extends at present to the valeric derivative; but to render the series complete as far as it goes the propionic coumarin has been wanting ; and it appeared to me that it would be desirable to prepare this substance not only to complete the series but also to compare its properties with ordinary or acetic coumarin to which it is so closely related. I have therefore made some experiments upon the subject the particulars of which I now beg leave to lay before the Society. Propionic Anhydride. Thc propionic anhydride employed in these experiments was obtained AND SOME OF ITS DERIVATIVES. by distilling propionic chloride with dry sodium propionate.The pro- pionic acid used was prepared from ethylic cyanide. The anhydride is a colourless liquid having an odour somewhat like that of butyric anhydride but more irritating. It boils at 168"-169" and has a specific gravity of 1.0169 at 15" C. Specimens burnt with oxide of copper gave the following numbers :-I. a198 of substance gave ,4035 of COz and -140of water. 11. ,293 of substance gave r5965 of COaand ,204 of water. These give the following percentages :-I. 11. C6H1003requires. Carbon .......... 55.55 55.45 55.38 Hydrogen ........ 7.89 7-73 '7.69 Propionic Cozlmariw. Propionic anhydride acts much more slowly on hydride of sodium-salicyl than acetic anhydride. If heat however be applied chemical action sets in and a fluid product is soon obtained.In my experiments I have always used a considerable excess of pro- pionic anhydride and boiled it with the sodium compound for an hour or more the excess of anhydride and the resulting propionic acid being afterwards distilled off. The crude coumarin remaining in the retort is freed from sodium propionate by pouring it into boiling water in which it sinks as a heavy oil but solidifies into a browuish crystalline mass on cooling. It is then collected and distilled to render it colourless and after being well pressed between bibulous paper twice crystallised from alcohol. In this way it is obtained in beautiful transparent slightly oblique prisms. It gave on analysis the following numbers :-I.-273 of substance gave *760of C02 and a126 of HzO. 11. -2675 of substance gave ,738 of CO and -1265 of water. These numbers give perceiitages agreeing closely with those required by the formula- PERICIN ON PROPIONIC GO UlliIBRIN -Theory. Experiment. /-I. 11. C, .......... 120 75.0 74-90 75-21 H .......... 8 5.0 5.12 5.25 02 .......... 32 20.0 - -160 100.0 Propionic coumarin possesses an odour difficult to distinguish from that of ordinary cournarin. At 90' it melts and on cooling solidifies to a beautifully crystalline mass. It can be distilled without decom- position. Boiling water dissolves it to a small extent the solution becoming milky as it cools and afterwards depositing fine hair-like crystals.It is moderately soluble in cold and easily soluble in boiling alcohol. Propionic coumarin is nearly insoluble in cold aqueous potassium hydrate and when gently heated melts and floats as an oil on the sur- face of this alkaline solution. If boiled however it dissolves forming a clear pale yellow liquid which becomes opaque when concentrated. On standing an oily liquid rises to the surface and solidifies on cooling to a tenacious mass. It is easily soluble in water and is decomposed with separation of the propionic coumarin upon the addition of an acid. When fused with potassium hydrate this coumarin yields a crystal-line acid probably a propionic coumaric acid but when it is more strongly heated with potassium hydrate salicylic acid is produced.P-Bromopropionic Coumarin. If the hydride of sodium-salicyl med in the preparation of propionic coumarin be replaced by the hydride of sodium-bromosalicyl a brominated product is obtained homologous with P-bromocoumarin or in other words a bromopropionic coumarin is produced the bromine being in the Csgroup. This product when crystallised from alcohol is obtained in long thin needles. When propionic coumarin is mixed with bromine in excess it dis- solves and on driving off the excess of bromine and hydrobromic acid by heating the mixture over the water-bath and then over the lamp a crystalline product is obtained which generally weighs nearly half as much again as the coumarin employed showing that about one atom of hrdrogen has been replaced.On recrystallising the product from alcohol long thin needles are obtained which are also /%bromopro-pionic coumarin. Analyses of specimens prepared by both the above processes gave the following numbers :- AND SOME OF ITS DERIVATIVES. I. ,236 grrbm of substance prepared from hy dride of sodium-bro-rnosalicyl gave *434gram of CO and -063 gram of water. 11. -297 grm of substance prepared from propionic coumarin and bromine gave ,5455 gram of C02and *077gram of H,O. 111. -2385 gram of substance Same as No. I1 gave -4385 gram of CO and -065 gram of H20. These give percentages agreeing closely with those required by the formula-Theory. Experiment. . -I F I. 11. 111.\ Cia ...... 120 50.20 50-15 50.08 50.1 H7 ......7 2.92 2.96 2.88 3.03 Br ...... 80 33.47 --02 ...... 32 13.41 --a-bromopropionic coumarin vhen heated melts at 146O and on cool-ing solidifies to a crystalline mass. It can be distilled with but little decomposition. It dissolves easily in boiling alcohol but is less soluble than propionic coumarin. It gradually dissolves in a boiling solution of potassium hydrate and may be precipitated unchanged by acids. When fused with potassium hydrate it gives an orange-red coloured product potassium bromide being formed. 6-Dibromopropionic Coumarh. When propionic coumarin is heated for a few hours in a sealed tube to about 150" with twice its weight of bromine dissolved in carbon disulphide large quantities of hydrobrornic acid are formed and on evaporating the carbon disulphide and twice crystallising the residue from benzol a crystalline product is obtained which gave on analysis the following numbers :-I.-296 of substance gave ~417of GO2 and -056 of H,O. 11. *3085of substance gave -436 of COz and ~053of I120. PERKTN ON PROPIONIC COUMARIN ETC. The formnla CloH6Brz02, requires the following percentages :--Theory. Experiment. / I. 11. c, ...... 120 37.73 38-41 38-6 H ...... 6 1.90 2-11 2.19 Brz ...... 160 50.31 -0 ...... 32 10-06 -318 100-00 These results are not so close to the theory as could be desired ; the excess of carbon however is probably owing to the presence of the trace of monobromopropionic coumarin . I believe that the bromine in this substance is all in the C group as it does not seem to be touched with caustic alkali until it is fused with it when the mixture changes to an orange-red colour in the same manner as the 6-monohromo-derivative.I therefore have called it 6-dihomopropiofiic cournarin. Dibromide of Propionic Coumnh. Propionic coumarin when exposed to the action of bromine-vapour in the cold changes to a viscid liquid and greatly increases in weight. The product appears to be the dibromide corresponding with dibromide of coumarin but I have not been able to get it sufficiently pure for analysis. With caustic alkali Fropionic coumarin is separated from it. It will be remembered that the dibromide of coumarin under these circumsfances yields a-bromocoumarin which if further treated with alkalies gives coumarilic acid.Xzclpphopropionic CozcrnarilicAcid. Propionic coumarin dissolves in fuming sulphuric acid without any change of colour and on gently heating the mixture in the water-bath it is entirely convei+ed into a sulpho-acid. This is easily converted into the barium salt by treatment with barium carbonate and filtering from the barium sulphate. On concentrating the filtrate and allowing it to stand small but brilliant crystals are obtained which contain a considerable quantity of water of crystallisation ; part of this is given off by drying irz vacuo and the rest at 150" C. It gave the following numbers on analysis :-I. -0855 of substance dried at 150" C. gave -0325 of barium sulphate = 22.26 p.c. barium.11. -297 of substance air-drird lost -068 of water at 150 = 22.9 p,c. BECKETT AND WRIGHT ON THE ACTION ETC. The formula C20H1P04BaS20S, requires 22.77 p,c. barium and CmH,,04BaS,06.10 aq. requires 22.9 of water. From the foregoing results we see that although this coumarin corresponds in most of its properties to those of ordinary coumarin yet it differs in some particulars especially in its tendency to produce @-derivatives with bromine whereas with ordinary coumarin the ten- dency is in the opposite direction.

ISSN:0368-1769    

DOI:10.1039/JS8752800010

出版商:RSC    

年代:1875

数据来源: RSC

摘要:

BECKETT AND WRIGHT ON THE ACTION ETC. IV.-Action of the Organic Acids aid their Anhydrides on the Natural Alkaloids. Part 11. Butyry 1 and Benzoyl derivatives of Morphine and Codeine. By G. H. BECKETT D.Sc. (Lond.) and C. R. ALDERWRIGHT Lecturer on Chemistry in St. Mary's Hospital Medical School. 8 1. Actioiz of Ezctyric Acid ow Codeirte. When anhydrous codeine and twice its weight of butyric acid are gently boiled together for five or six hours dihutyql-codeiize is formed in virtue of the reaction- C36H42N206 + 2( C&O.OH) = 2H20 + C36H,0(C&O)2N206. On evaporating off the excess of acid on the water-bath dissolving the residue in water and adding sodium carbonate a tarry mass is pre-cipitated which must be dissolved in dilute hydrochloric acid and repre- ciyitated by sodium carbonate to remove any traces of unaltered codeine mechanically carried down.The ethereal solution of the purified base does not crystallise by spontaneous evaporation even when a crystal of some analogously constituted body (e.g. diacetyl-codeine) is added to the saturated solution the dibutyryl-codeine only making its appearance as a varnish-like mass ; even when the base was regenerated from a speci- men of hydrochloride purified by several recryst,allisations it was found impracticable to obtain it in a crystalline condition by any means what- ever. On adding hydrochloric acid to the varnish-like base or to its ethereal solution a well-crystalliseil hydrochloride is produced ; of this 1.545 gram dried in blotting-paper lost at 100" 0.183 gram = 11-84? per cent.The formula C3sH,o(CaHTO) 2N206,2HC1,6H20,requires 11.75 per cent. 0.2730 gram of hydrochloride dried at 100" gpve 0.6535 CO and 0,177 H20. 0.4280 gram of hydrochloride dried at 100" gave 0.1510 Ag(311. 16 BECKETT AND WRIGHT ON THE ACTION OF THE Calculated. Found. C44 528 65.11 65.28 H56 56 6.91 7.20 c12 71 8.75 8.73 NZ 28 3.45 - 08 128 15.78 - - C36H43( C*H,O)JY2O,.2HCl 811 1OO.OO - The platinum salt gave the following numbers :-0.5370 gram gave 0.0920 Pt = 17.13 per cent. The formula C,SR~O( C,H,o)2N206.2HC1.Ptc14 requires 17-18 per cent,. Dibutyryl-codeine differs from diacetyl-codeine not only in being non-crystalline (the latter base being most readily crystallised from ether) but also in the amount of water of crystallisation taken up by the hydrochloride the former base yielding a salt containing six pro-portions of water while the latter contains only four.tj 2. Action of Butyric Amhydride OW Codeine. From the former results obtained with acetic acid and anhydride it would appear a priori probable th ' butyric anhydride would yield the same dibutyryl-codeine as that obtained by the action of butyric acid ; and in point of fact this is the case by heating codeine to 140" with excess of butyric anhydride the dibutyryl-codeine above described is produced. The hydrochloride obbained as above described gave the following numbers :-1.144 gram dried in blotting-paper lost at loo" 0.1480 gram = 12.94 per cent.The formula C3sH,o( C,H,o),N,o6.2HCt.6H,o requires 11-75 per cent. 0.3185 gram of platinum-salt gave 0.0550 Pt = 17.26 per cent. Calculated percentage = 17.18 per cent. All attempts to obtain the free base in the crystalline state proved fruitless. 5 3. Actioiz of Butyric Acid on Morphine. When anhydrous morphine is heated to 130" or higher for 5-43 hours with twice its weight of butyric acid a reaction occurs precisely similar to that produced by the action of acetic acid (Part I) viz. :-CaH3sN,Os + ~(C~HTO-OH) = 2HZO + C,H3s(C,H,O),NZO, *he only difference observable being that the hydrochloride of the resulting dibutyryl-morphine is far more soluble and crystallises less readily than that of the corresponding a-diacet,~l-rnorphirie.ORGANIC ACIDS AND THEIR ANHYDRIDES ETC. On treating the product of the reaction with ammonia or sodium carbonate and ether an ethereal solution is obtained which if evapo- rated quickly dries up to a variiish-like mass ; by slow spoiitaneous evaporation however crystals are sometimes formed and on bringing a crystal so produced into contact with the sticky resinous product formed in other cases the whole becomes crystalline. The crystals thus produced appear to be anhydrous when air-dry. They lose in weight slightly at loo" however apparently from decomposition. In three experiments 0.22 0.& and 0.51 per cent. was thus lost whilst the dried substances gave on aiialysis numbers slightlyin excess of the calculated values.After several recrystallisations from ether dibutyryl-morphine gives no coloration with ferric chloride ; it is however difficult to arrive at this state of purity as a small quantity either of some decomposition- product formed on standing or of some substance formed simultaneously with the dibutyryl morphine (P-dibutyryl morphine ?),pertinaciously adheres to the crystals and communicates to them the power of striking a faint blue with ferric chloride. The following numbers were obtained after drying at 100" :-Specimen A. 0.3030 gram gave 0.7935 CO and 0.2020 H,O. , 13. 0,3240 gram gave 0.8530 CO and 0.2230 HzO. Calculated. Found. (-4.) (BJ C42 504 71.00 71.43 71.80 He0 50 7-04 7.41 7.64 -I NZ 28 3.94 128 18.02 -08 __-_ -~ C34H36( C4H,0)2NzOs 710 100nOO When exactly neutralised with dilute hydrochloric acid this dibutyryl-morphine forms a syrupy liquid which sonietimes dries up to a gummy mass without crystallising and sometimes solidifies to a mass of radiating crystals very soluble in water.The same behaviour has also been noticed in the case of tetracetyl-morphine hydrochloride. After drying at 1000 the following numbers were obtained; the slight excess of carbon found denoting a minute amount of decomposi- tion just as with the free base :-0.6020 gram gave 0.2190 AgCI. 0.6390 , 0.2330 , 0.4490 , 1.0645 CO and 0.2725 K,O. Tor.. XXVTTI. C BECKETT AND WRIGHT ON THE ACTION OF THE Calculated. Found. C42 504 64.37 64.65 Ha2 52 6-64 6.74 CL 71 9.07 8.99 9-02 NZ 28 3.5 7 08 128 16-35 C3aH,,(CaH,0)zN,06.2HC1 783 100'00 The platinum salt gave the following numbers :-0.5970 gram gave 0.1055 Pt = 17.67 per cent.The formula c3,H3,(CaH,o),N,06.2HC1.PtCl requires 17.60 per cent. The ethereal mother-liquors from which the dibutyryl-morphine has separated contain a small quantity of a non-crystalline base which gives a blue coloration with ferric chloride probably this is the butyryl correlative of the analogous product formed together with a-diacetyl morphine by the action of acetic acid on morphine (Part I.). Separated as far as possible from the crystalline base by spontaneous evaporation almost to dryness rubbing up with a few drops of absolute alcohol (which only dissolves the crystalline base slowly) and quick filtration a viscid liquid was obtained which utterly refused to cry-stallise ; converted into platinum salt it gave the following num- bers :-0.6545 gram gave 0.1130 Pt = 17.27 per cent.Calculated for Cd3&(C4H,O),N2O6 2HC1 PtC14 = 17.60 , Hence it appears that this non-crystalline base is isomeric with the crystalline one in a,ll probability the two are the butyryl correlatives a-and P-diacetyl morphine respectively. § 4. Action of Bzctyric Aizhydride OTL Morphine. Anhydrous morphine was heated to 140"for three hours with twice its weight of butyric anhydride ; the product was dissolved in warm water filtered from a little tarry decomposition-product and precipi- tated by sodium carbonate the precipitate on treatment with ether yielded an ethereal solution from which no crystals could be obtained by evaporation a varnish-like mass only resiilting like dibutyryl codeine ; unlike this product however the base tetrabzctl/r~Z-morp7~~~ e refused to yield a crystalline hydrochloride ; the neutraZ solution of the hydrochloride drying up to a gummy mass differing from the hydro- chlorides of a-diacetyl-morphine only in that it gave no blue colora- tion with ferric chloride.The following numbers were obtained ORGANIC ACIDS AXD THEIR DERIVATIVES ETC. 0.3270 gram gave 0.7745 C02and 0.2120 H,O. 0.3340 gram treated volumetrically gave 0.0301 GI. 0.5430 grain of a different specimen treated volumctricdly pve 0.0422. Calculated. Fouiid. 600 65-01 64.60 c50 HGt 64 6.93 7.20 CI2 71 7.69 7-64 7-77' 28 3.03 -N2 010 160 17-34 --_--C34H34(CaH,O)J2OG.2HC1 3.33 100.00 Converted into platinum salt the following numbers were obtained :-0.7295 gram gave 0.1150 gram Pt = 15.76 per cent.The formula C,,H,,( C4H70),N2O6. 2HC1.PtCIA requires 15.65 per cent. 9 5. Action of Water0% I~tr~bzcty~~l-?nor~~~ne. It has been shown in Part I that tetracctyl-morphine on boiling with water breaks up tlius :-C~~HN(C~H~O)~NZO~ + 2H2O = 2(C&LO.OH) + C3aH34 C2H30)2N20 forming the same diacetyl morphine (the a-modification) that is produced by the action of acetic acid on morphine. Przcisely the same result is produced in the case of tetrabutyryl-morphine with this difference that the action is very much slower and that in order to facilitate it, it is necessary to use a mixture of alcohol and water (about equal bulks) so as to retain the base in solution.Even then 12 hours' or more incessant boiling (with an inverted condenser attached) is required before any considerable amount of dibutyryl-morphine is formed. On distilling off the alcohol an aqueous liquor is obtained containing the butyrates of dibutyryl-morphine and morphine (the lattei. generated by the further splitting up of the dibutyryl-morphine) and a tarry preci- pitate of unaltered tetrabutyryl-morphine this is filtered off and trreated over again. On treating the aqueous solution with Roctiurn carbonate and ether an ethereal solntion is obtained fi-om which dibutyryl-morphine may be obtained in crystals by slow spontaneous evaporation.This base appears to be in all respects identical with that formed by the action of butyric acid on morphine ; the base when suffi- ciently purified gives no coloration to ferric chloride. By spontaneous evaporation its ethereal solution deposits crystals which appear to be anhydrous but which lose a small amount on heating to loo" just as c2 BECKETT AND WRIGHT ON THE ACTION OF THE the product from the action of butyric acid on morphine probably from incipient decomposition after drying at 100'-0.5370 gram gave 0.8850 GOz and 0.2290 H?O. Calculated. Foulla. C4z 504 71.00 71-62 H60 50 7.04 7.55 N2 28 3.94 - 08 128 18.02 - - C34H36(C4H70) 2N2Os '710 100.00 The hydrochloride in one experiment dried up to a non-crystalline gum in another to a mass of radiating crystals very soluble in water ; the platinum salt gave these numbers- 0.7700 gram gave 0.1350 Pt = 17.53 per cent.The formula C~,H~(C4H70)zNzOs,2HC1.PtC1,,requires 17.60 per cent. 8 6. Acety1-bu(tyry1-morphirze. When anhydrous morphine is boiled for several hours with twice its weight of a mixture of equivalent quantities of acetic and butyric acids acetyl- bu tyryl-morphine is generated in virtue of the reaction- C34H38N206 + C2HSO.OH + CaH,O.OH = 2HzO + c34H36(C2H3O) (C4H7O)NzOs. On treating the product with sodium carbonate and ether and agitating the ethereal solution of the base with enough hydrochloric acid to form a neutral liquid a copious supply of crystals was obtained notably more soluble in water than a-diacetyl morphine hydrochloride ; after drying at llOo,they gave the following numbers :-0,5695 gram gave 0,2185 AgCl chlorine = 9-49per cent.The formula C34H,( C,H,O) (C4H70)NzO6.2HC1 requires 9.40 per cent. These crystals were recrystallised from boiling water ; but unfortu-nately it was found that they were decomposed by the treatment ; cry-stals were deposited on cooling consisting chiefly of a-diacetyl-morphine hydrochloride whilst the mother-liquors contained much of a very soluble butyrylated morphine after three successive recrystallisations from hot water the crystals finally obtained were nothing but a-diacetyl- morphine hydrochloride ; they lost at 120° 13.35 per cent.the ca1- culated amount (for 6H20) being 12.93; and on saponification by potash and distillation with enough sulphuric acid to liberate just half ORGANIC ACIDS AND THEIR DERIVATIVES ETC. the acid thus formed a distillate was obtained from which a barium salt was formed containing Barium . . . . . . . . . . . . . . . . 53.5 per cent. Calculated for acetate . . . 53.7 , Had any acetyl-butyryl-morphine been present in the crystals this barium salt would have contained all the butyric acid formed on saponification. In another experiment where a mixture of acids in which butyrio acid greatly predominated was employed a product was formed from which a crystalline hydrochloride was isolated as before ; this gave the following numbers after one recrystallisation from warm (not boiling) water :-0.9995 gram of air-dry salt lost at loo" 0.1590 = 15.91 per cent.The formula C34H,(C2H30) (C,H,0)Nz06.2HC1.8H20 requires 16.02 per cent. 0-314.5gram of dried substance gave 0.7280 COz and 0.1835 H,O. 77 3, 0.4615 , , 0.1765 AgCl. 9, 0.3775 , , , 0.1445 , 0.4730 , fiubstance dried at 120" gave 0.1795 AgC1. Calculated. Found. C40 480 63.58 -63.13 -His 48 6.36 -6.66 -C1 71 9.40 9.46 9-47 9.39 N 28 3.71 --08 128 16.95 --~ ---C34H3,( C2H30) (C,HyO)N,O+ZHCl 755 100eOO The neutral liquid from which these crystals separated in the first instance dried up to a gum-like mass wbioh gave a blue coloration with ferric chloride and contained- Carbon 63.75 ; chlorine 9.16 per cent.Dibutyryl morphine requires carbon 64.37 ; chlorine 9.07 per cent. from which it appears that as might be expected the excess of butyric acid present gave rise also to dibutyryl-morphine or a mixture of isomeric dibutyryl-morphine. 8 7. ActiorL of Bewzoic AdLydride otL Codeim. Codeine was heated to 130" for four hoiirs with rather more thaii its own weight of benzoic anhydride the product dissolved sparingly in hot water somewhat more readily in hot very dilute hydrochloric acid. The warm opalescent solution was precipitated by oarbonate of soda ; the precipitate was dissolved in warm diluie hydrochloric acid BECKETT AND WRIGHT Oh' THE ACTION OF THE and again precipitated with sodium carbonate ; and this precipitate was dissolved in ether.The ethereal solution gave on evaporation a copious crop of anhydrous crystals which yielded the following numbers on combustion :-0.3110 gram gave 0.8525 GO and 0.1780 H,O. Calculated. Foun& c50 600 74.44 74.76 H5o $0 620 6~36 NZ 28 3.48 -08 128 15.88 -C,6R,(C,H,O)~N20 806 100*00 This base dibenzoyz-codeiwe is very sparingly soluble in water both cold and hot ; from a large bulk of boiling water it can be cryshllised unchanged; when it is dissolved in very dilute warm hydrochloric acid a clear solution is obtained ; on cooling this salt does not deposit crystals but becomes an opalescent gelatinous mass much resembling starch- paste or gelatinous silica ; from it strong solution the hydrochloride separates as an amorphous tarry mass it is however possible to obtain the hydrochloride in crystalline form by dissolving it in dilute slightly warm alcohol and leaving the solution to cool slowly with con- stant stirring and kubbing the crystals thus produced gave rise to nothing but a gelatinous mass when dissolved in warm water and allowed to cool.Dried in blotting-paper and exposed to the air until a constant weight was attained they gave the following numbers :-1,027 gram of air-dried substance lost 0,043gram = 4.18 per cent The formula C36H40( C,H,o),N,06.2HCl.2H20 requires 3.93 per cent. The anhydrous salt gave the following numbers :-0.34-20gram gave 0.8530 C02 and 0.1990 H,O. 0.2800 gram estimated volumetrically gave 0,0225 C1. 0.2990 gram gave 0.0970 AgCl.Calculaked. Found. Go 600 68.26 68.02 -a2 52 5.92 6.47 -71 8.08 8.03 8.03 N2 28 3.18 -138 14-56 -08 C36H,(C,H,O),N2Os.2HCl 879 IOO*OO The platinum salt gave the following numbers :-0.3080 gram gave U*0500 Pt = 16-23 per cent. 1,c ORGAKIC ACIDS AND THEIR DERIVATIVES ETC. The formula C36H4,( C,H,o),N2o6.2HC1.PtCl4 requires 16.21 per cent. This platinum salt like the benzoylated morphine products described in the next sections differs from the acetylated platinum salts and most platinum salts of morphine and codeine derivatives in being much more readily soluble in alcohol than in water the converse being usually the case. 9 8. Action of Bensoic Anhydride on 2Cfoyphine. Morphine was heated to about 130"for three or four hours with twioe its weight of beneoic anhydride ; the product dissolved in hot dilute hydrochloric acid was precipitated by sodium carbonate and treated with ether ; on evaporation anhydrous crystals of tetrabenzoyl-morphine seprated these gave no colour reaction with ferric chlo- ride.0,2960 gram gave 0.8220 GO and 0.1530 H,O. Caloulated. Found. c 744 75.46 75-73 H54 54 5.47 5.74 NZ 28 2.84 -160 16.23 -010 CS*HsP( C7H,O)aN,06 986 100.00 The hydrochloride of this base is very sparingly soluble in oold water ; it possesses properties precisely similar to those of dibenzoyl-oodeine saving that no artifice has hitherto been successful in obtaining it in a ci-ystallised condition. 0.4775 gram gave 0.0312 gram C1 (volumetric).0,3810 , , 0.9845 COz and 0.2000 H20. Calculated. Found. C6-2 744 70.26 70-47 H5s 56 5-29 5.83 C12 71 6-70 6-53 N2 28 2.64 -010 160 15.11 -C34H34( C,H6O)JJaO6.2HCl 1059 IOO*OO The platinum salt made by adding platinic chloride to it warm aqueous solution of the salt gave these numbers :-0.2440 gram gave 0.0345 Pt.. . . . . . . . . . . . . . . . . . . = 14-14per.cent. The formula C3aH3i(C,H,0)4N,O,.2HCl.PtC14 requires 14.13 ~~ BECKETT AND WRIGHT ON THE ACTION OF THE § 9. Action of Water on TetraDeiLxoyl-?7aorp~ine. Tetrabenzoyl morphine is somewhat less readily acted on by boiling water than tetrabutyryl-morphine (which as above shown is less readily attacked than tetracetyl-morphine) ; when boiled with a mixture of about equal volumes of alcohol and water as described in § 5 for 48 hours consecuti-oely it partially undergoes the following reaction whereby dibeneoyl-morphine is generated apparently identical with that formed by the direct action of benzoic acid on morphine (§ 10).The production of benzoic acid in this way was verified by treating the resulting liquid (after distillation of alcohol) with hydrochloric acid and ether when benaoic acid was dissolved out giving the ordinary qualitative tests. Carbonate of soda threw down from the acidified solution a small amount of precipitate ; on agitating this with ether an ethereal solution was obtained which yielded a mixture of the hydrochlorides of te trabenzoyl- morphine and dibenzoyl- morphine ; the latter crystallised in minute crystals on cooling the slightsly warm aqueous solution ; it wag however found difficult to obtain this free from tetrabenzoyl-morphine hydrochloride which does not crystallise forming a tarry mass ; the platinum salt finally obtained gave the fol-lowing numbers showing that a small quantity of tetrabenzoyl-mor-phine platinochloride was also present.0.8805 gram gave 0.1400 gram Pt = 15.90 per cent. Dibenzoyl morphine platino-chloride rcquires i6.60 , 3, Tetrabenzoyl > 7 14-13 p7 0 10. Actiorb of Beiizoic Acid on dIoryliii$e. Anhydrous morphine was heated for seven hours to about 160" with twice its weight of benzoic acid ; the product was dissolved in warm dilute hydrochloric acid and precipitated by carbonate of soda (which only gave a very trifling precipitate morphine being not instantaneously thrown down by this reagent at any rate from solutioiis not too con-centrated).On treating the mass with ether a minute portion was dissolved ; the ethereal solution yielded a tarry mass on agitation with a few drops of hydrocliloric acid and this when dissolved in hot water gave white crystals on cooling yery sparingly soluble and apparently identical with those described in the previous section. The quantity of these being too small for experiment they were converted into platinum salt of which 0.4005 gram gave 0.0670 Pt = 16.73 per cent. The formula C3iH3F(C,H,0)2N206.2HC1.PtCla requires 16.60 , ORGANIC ACIDS AND THEIR DERIVATIVES ETC. The crystals of hydrochloride gave no blue colouration with ferric chloride whence it seems that benzoic acid acts to a minute extent like acetic acid giving rise to a-dl:be.naoyl-molplaine thus-C34H38NZO6 + 2(C,H&.OH) = 2HzO + C34H3,( C,H,O),N,Os.§ 11. Action of Benaoic Anhydride on a-Diacetyl-morphine. Anhydrous a-diacetyl-morphine was heated with rather more than its own weight of benzoic anhydride to 150" for about three hours. The product treated with sodium carbonate and ether gave an ethereal solution which refused to crystallise spontaneously by slow evaporation only forming a gummy varnish; by rubbing the side of the vessel,' however with a glass rod to which a minute fragment of crystalline tetrabenzoyl-morphine adhered crystallisation was set up and a copious supply of anhydrous crystals of a new base a-diacetlll-dibenxoy 1-nzor-phine separated.0.3300 gram gave 0.8770 CO and 0.1910 H20. Calculated. Found. C52 624 72.39 72.48 H50 50 5-80 6-43 N2 28 3-25 010 160 18.56 - - __I-p- C,aH,,( C2H3O),(C7H,O),N,O6 862 100.00 This base gives no colour reaction with ferric chloride ; when treated with dilute hydrochloric acid it forms a hydrochloride pretty readily soluble in pure water but precipitated therefrom as tarry flakes by addition of hydrochloric acid ; all attempts to crystallise this salt have hitherto proved fruitless. The following numbers were obtained :-0.4140 gram gave 0.1310 AgCl chlorine = 7.83 per ct. The formula C,H3,( CzH30)z(C7H,0)zNz0,.2HC1 requires 7.60 , The platinum salt gave the following numbers :-0.1435 gram gave 0.0225 Pt = 15.68 per ct.Calculated for C34Hs(CZH30),( C,H,O),NzO,.2HCl.PtC1 = 15.50 , § 12. Action of Benzoic and Acetic Adagddes on Illetl.a-nc~tyl-mor~hine a11 d TetrccbemoIJ 1-morphirk e respective1y . In order to see if it mere possible to displace benzoyl by awtyl or vice i~rsd,in these derivatives each base was heated to about 130" for four hours with 3 to 4 times its weight of the required anhydride. In neither case however was any marked amount of action noticeable. Bci BECKETT AND WRIGHT ON THE ACTlON ETC. The product of the action of benzoic anhydride on tetracetyl morphine was precipitated by carbonate of soda and treated with ether ; by syon-taneons evaporation crystals were formed.A portion of these crystals and the last few drops of mother-liquor (representing about one-twentieth of the whole) were converted into platinurn salts and examined with the following results :-0.3585 gram of salt from crystals gaye 0.0620 Pt = 17-29p.c. 0.5040 , , mother-liquors gave 0.0830 16.46 , Tetracetyl-morphine platinochloride requires 17.17 , Diacetyl-dibenzoyl-morphine , 15-50 ,? 79 Tetrabenzoyl-morphine 14.13 ,, 9 99 In the same way the product of the action of acetic anhydride on tetrabenzoyl morphine was converted into the free base ; the ethereal solution of this however did not crystallise spontaneously; it was therefore converted into hydrochloride by treatment with warm dilute hydrochloric acid.Most of the base became converted into an almost insoluble tarry hydrochloride resembling in all respects tetrabenzoyl morphine hydrochloride ; a minute portion however dissolved. These two portions were converted into platinum salts and examined with the following results :-0.6800 gram of salt from insoluble hydrochloride gave 0.1015 Pt = 14.92 per cent. 0.0760 gram of salt from soluble hydrochloride gave 0.0110 Pt = 14.47 per cent. Tetrabenzoyl-morphine requires platinum = 14.13 per cent. I? Diacetyl-dibenzoyl-morphine , 15.50 , 9 7, Tetracetyl-morphine 17.17 , The physical characters of the resulting hydrochloride show that only a very minute amount of the readily soluble tetracetyl morphine or diacetyl-dibenzoyl-morphine hydrochlorides could have been present.Hence it may be concluded that there is no marked tendency towards the replacement of benzoyl by acetyl or vice zfersd on heating benzoylated morphine with acetic anhydride or acetylated morphine with benzoic anhydride. In conclusion we beg to tender our sincere thanks to Messrs. Mac-farlan and Co. (Edinburgh) for further supplies of pure alkaloids presented for the purpose of making these experiments.

ISSN:0368-1769    

DOI:10.1039/JS8752800015

出版商:RSC    

年代:1875

数据来源: RSC

摘要:

27 V.-Observations on the Use of Pernzanynnate of Potash iiz.Volumetric Amalysis and or,.the Est,imatiosL of Iron in Iroqh Ores. By EDWARD F.C.S. A. PARNELL OF all chemical reagents applicable to volumetric analysis probably the most delicate is permanganate of potash. Hence its extensive application not only for the estimation directly of a reducing mate- rial but indirectly of an oxidising material by first mixing that material with a known weight of a reducing agent and determining the excess of the latter. Various circumstances however vitiate the results thus obtained. One of these is the production by the application of permanganate of a coloured material which obscures the exact point of peroxidation. An important case of this kind is iron when present as ferrous chloride.The yellow colour of the resulting ferric chloride so hinders the determination of the exact point of peroxidation that the use of permanganate in the analysis of iron ores has I believe been entirely superseded by that of bichromate of potash. If the iron is present as ferrous sulphate of course no such difficulty exists ; but in the analysis of almost every variety of iron ore hydrochloric acid has to be em-ployed as the solvent rather than sulphuric acid. This hindrance to the use of permangxnate with ferrous chloride may however be overcome by a very simple expedient namely the use of artificial light instead of daylight. Viewed hy the light of a candle as radiated from a white background the intensity of the yellow colour of ferric chloride is greatly reduced.A solution con- taining one part of metallic iron (or about three parts of ferric chlo- ride) in 400 parts of water is almost colourless. In such a solution when viewed by candle light an exceedingly miniite trace of perman- ganate produces a distinct coloration but in daylight a much larger quantity is necessary to produce a decided effect. By this method of manipulating iron present as chloride may be estimated with even greater accuracy than by bichromate and ferri- cyanide. The operation may also be conducted with greater facility and dispatch ; IL-circumstance of no small importance in the technical laboratory. Another advantage possessed by permanganate Over bichromate in the estimation of iron is that it allows of the use of zinc instead of sulphurous acid as the preliminary reducing agent.AS a solution of zinc produces a white precipitate with a very dilute solu- tion of ferricyanide of potassium the presence of a large quantity of zinc prevents the detection of a minute trace of ferrous oxide by that 28 PARNELL ON THE USE OF PERMANGFANATE OF POTASH ETC. reagent. Hence sulphurous acid has to be employed when bichromate is used although zinc is more effective and provided titanic acid is not present more convenient. Various methods have been recommended for standardising the solu- tion of permanganate. A recent experimenter M. B e r t he 1 o t con-siders oxalic acid preferable to iron or any ferrous preparation. The slowness of the action when approaching complete oxidation is an important objection to the use of oxalic acid I have no hesitation in giving the preference to arsenious acid ad the standardising material.In respect of the facility with which it may beobtained in a state of absolute purity and preserved without change arsenious acid is certainly preferable to any preparation of iron. But a difficulty presents itself in the tardiness of the action when near completion even although hydrochloric acid is present in considerable excess. The last traces of arsenious acid reduce perman- ganic acid not to manganous oxide but to a higher oxide commonly known as manganic oxide which gives a brownish tinge to the liquid. This difficulty however may be easily overcome.After adding enough permanganate to develope a faint pink colour (a proof that all arsenious acid is oxidised) I introduce a small quantity of standard solution of ferrous sulphate ; this immediately reduces the manganic oxide and causes the disappearance of the brownish colour. The excess of ferrous sulphate is then peroxidised by the permanganate. By this conjunction of arsenious acid with iron we have the advantage of combining the best material as regards purity with the best mate- rial as regards delicacy for the finishing touch. I may observe that for the estimation of iron I employ a solution of permanganate containing 2.21 grams per litre of which about 114 C.C. correspond with 0.5 gram metallic iron. Por standardising I use a solution of arsenious acid containing 4.42 grams per half litre ; the arsenious acid being first dissolved in caustic soda and this super- saturated with hydrochloric acid 50 C.C.of this solution correspond with 0.5 gram metallic iron. If the quantity of iron ore operated on is not less than 1.0 gram and the ore not of the worst quality then to the reduced solution filtered in an atmosphere of carbonic acid gas 100 c.c of the above permanganate solution may be freely introduced by means of a pipette which is itself used as a stirrer the remainder being applied from a burette in artificial light. The burette may also be used as a stirrer its extremity being elongated for that purpose to SL couple of inches below the glass stopper. With a moderate excess of hydrochloric acid at orGinary temperature riot the slightest odour of peroxide of chlo- rine or similar gas is porceptible.I€ a brownish colour appears on the first addition of permanganate more hydrochloric acid has to be PARNELL ON THE USE OF PERMANGASATE OF POTASH ETC 29 added. It is convenient to have at hand for comparison a beaker containing solution of ferric chloride of similar strength to that operated on ; also another to retain a portion of the liquid in case the perman- ganate is added in excess. When the peroxidation is complete half a drop of the permanganate produces in artificial light a decided change of colour. Application of heat is not only unnecessary but has to be avoided owing to the greater intensity of colour of ferric chloride when hot than when cold both in daylight and in artificial light. It may not be uninteresting to observe that if a solution of ferric chloride containing 1of iron in 100 of water is heated to near the boiling point the inten- sity of its colour is so much increased that '7 or 8 volumes of boiling water have to be added to reduce the colour to t'hat of the cold liquid.

ISSN:0368-1769    

DOI:10.1039/JS8752800027

出版商:RSC    

年代:1875

数据来源: RSC

摘要:

30 ABSTRACTS OF CHEMICAL PAPERS PUBLISHED IN BRITISH AND FOREIGN JOURNALS. General and Physical Chemistry. Action of differently Refrangible Rays on Iodide and Bromide of Silver. By E. B E CQUE RE L (Compt. rend. lxxix 185-190). WHENa sensitive photographic plate prepared in the ordinary manner with silver iodide and collodion is exposed for a short time to the solar spectrum the image when developed by pyrogallic acid is found to extend only from the violet to between F and G. But if a little chlorophyll is added to the collodion employed the plate under the same conditions shows also a feeble but well-defined action ex- tending from E to beyond B in the red with a remarkable and strongly marked band of maximum effect between c and B. The photographie action in this .band is however much weaker than that which Oakes place in the violet and attains the intensity of the latter only when the red end is exposed from five to ten times as long as the violet.Other much less st'rongly marked bands may be perceived between E and B. The author finds that the conspicuous band between c and D coincides in position and limits with the characteristic absorption-band of chlorophyll as he observed it in the collodion solutions made use of in preparing tlie plates. The colouring matter on the photographic plates obviously does not act as a screen cutting off the absorbed rays for in that case the contrary effect would be produced ; but we may explain the phenomenon by supposing that the silver salt is so con-nected with the chlorophyll that.an action set up in the latter by the rays it absorbs communicates an i~mpulse to the former by virtue of the intimate association of their particles. The author long ago showed that when sensitive plates are exposed for an instant to sunlight before submitting them to the spectrum the range of the chemical action is greatly extended towards the less re-frangible end. These earlier observations are rea,dily explained by the results above described. We may suppose the exposure to operate by producing a change of the colour or other physical condition of the upper film of the plate by which its absorptive power for the different rays is altered. R. R. The Electric Conductivity of Fused Salts. By F. BRAUN (Deut.Chem. Ges. Ber. vii 958-962.) THEauthor has determined the conductivity of the following salts at temperatures as little as possible above their fusing points in order t,o GENERAL AND PHYSICAL CHEJIISTRY. 31 ascertain whether any connection can be established between this and other physical constants. 3pecific con- Specific Constants of Molecular ductivity. gravity capillarity. Molecular volume at Hg = 100 ,tfusing weight. fusing millions. point. rl"" point. a2 -__ ---PbCI,. ............ 32200 5.802* -278 47 -9 NaNO ........... 114.75 1.878 8 *03 8.55 85 45 -3 AgNO ........... 8688 4 '355* -170 33.8 , just solidified. 4120 -KC1.. ............ -1.612 '7 *06 8.76 74*5 46 *2 NaCl ............. 8660 1.612 6 -78 8 '41 58 -5 36 -3 KNO ............6500 1*702 '7 *11 8 *35 101 59 .3 KI ............... -2 -497 6.04 4 '84 166 66 *5 NaaSOd-. ........... 3680 2 *lo4 18 55 L7 -64 119 56 *6 SrCl ............. 2260 2 mo 11.33 8.18 158 -5 57 '2 Na,CO .......... -2 *041 18.25 17.88 106 51 *9 K&O,. ........... 2150 2 .oo 16 *33 16.33 138 69 -0 -ZnC1 just fused. .. 85 .9 --136 *2 , just solidified. 8 -68 ---* Specific gravity at 0". a denotes the constant of capillarity OP the tangential force which in consequence of the opposite attraction of the liquid molecules is exerted on a line 1mm. long of the surface molecules. 2a a2denotes &uincke's specific cohesion = -,c being the specific gravity. a The numbers show that the expected connection cannot be traced.They show further that while the electric conductivity of fused salts is of the same order of magnitude as that of saline solutions it is gene-rally rather higher in the former case than in the latter. The case of zinc chloride is the most remarkable. Not only is it the widest removed from lead chloride to which fi-om the chemical resentblance between them it might be expected to approximate but in the fused state it has a lower conductivity than its own aqueous solution. The absence of any recopisable connection between the conductivity of fused salts and that of their solutions indicates that salts do not enter into solution with the same properties as they possess in the anhydrous state but that new molecules are formed possessing their own specific conductivity.M.J. S. The Heat of Formation of the Phosphorus Acids. By J. THOMSEN (Deut. Chem. Ges. Ber. vii 996-1002). THEfollowing results are given all of them refer to normal phos-phorus to 1gram-molecule of the respective acids and to reactions taking place at 18"-19" :- ABSTRACTS OF CHEMICAL PAPERS. Melting point. Heat of fusion. H3PO4 38.6' 2520 gram-degrees. H3PO3 70.1" 3070 9 ape 17.4O 2400 Heat of Solution &a ?Vder. Crystalline Acid. Liquid Acid. (H3PO4,Aq) + 2690 5210 (H3PO3,Ay) -130 2940 (H3PO2,Aq) -200 2200 Heat qf Formadiofi of the Acids from their E1eiiierzt.s. Crystalline Acids. Liquid Acids. (H3,F04) 302560 300040 (H3,P,O3) 227680 224610 (H3,P,02) 139950 137550 Aqzceozcs Solutions (H& O4,Aq) 305250 (H3,p,03,Aq) 227550 (H3,P,02 Aq) 139750 The steps in the determinations were (l),the oxidation of phos-phorus.This was performed by means of a solution of iodic acid of tlre strength HIo3+ 2400 H20. With a strong solution as used by Ditte Troost and Hautefeuille secondary reactions take place. In each experiment & molecule of HI03was completely reduced by the addit,ion of an excess of powdered normal phosphorus. It was found that each molecule of iodic acid oxidised 1.6 (1.602 to 1.63) atoms of phosphorus so that half of the iodic acid produced phosphorous acid and the other half phosphoric acid the two acids being formed in the ratio of 5 3. (2.) The oxidation of phosphorous and hypophosphorous acids to phosphoric which was best accomplished by the use of a large excess of bromine-water.Chlorine act,s more slowly. (3.) Determination of the heat of solution of the solid and liquid acids the difference between which gave the heat of fusion. M. J. S. The Heat of Formation of Arsenious and Arsenic Acids. By J. THOMSEN (Deut. Chem. Ges. Ber. vii 1002-1006). THEfollowing determinations made by processes differing from those employed by Favre in 1853,show nevertheless a very close agreement. The heat of solution of acnzorphows ASz03in water was ascertained by observing the difference in the heats evolved when powdered arsenious acid and its solution were respectively added to an excess of sodium hydrate The result (As203,Aq) = -7550 indicates that the anhy- dride dissolves as sz~chin water no hydrates being formed.The two GENERAL AND PHYSICAL CHEMJSTRY. hydrates of arsenic acid HlAs207and H3As04,were examined. The solution of the hydrate HiAs207,lowers the temperature from 18" to '2" but as it almost immediately begins to combine with water the temperature quickly rises again to 30" and if only the requisite ynan- tity of water has been used the whole solidifies to a mass of the hydrate H3As04. The oxidation of arsenious to arsenic acid was per- formed with iodine keeping the arsenious acid in excess. Metallic arsenic was oxidised with bromine-water. The following are the results for one molecule of the respective compounds at 18' :-(As20j,Aq) = -7550 gram-degrees. (hs205,Aq) = + GOO0 Heat of Solution... . *. (HjAsO4,Aq) = -400 7 , (HiAszO,,Aq) = + 1300 ? 77 Formation of Hydrates (As205,2H20) = 4.710 (As~O~,~H~O)6800 ,7 Formation of the Anhy- (As2,03) = 154590 f> drides { (As2,05) = 219400 9 (Asz,03,Aq) = 147040 9 99 Formation of the Acids (Ssz,05,Aq) = 225400 in Aqueous Solution (H3,As,04,Aq) = 215240 ?* (As,O,Aq 0,) = 78360 99 M. J. S. The Equivalence and Transformation of the Chemical Forces. (Compt. rend. Ixxix (CommissionReport.) By P. A. FAVRE 44244). FROM this memoir of If.Favre which embodies the substance of com- munications published during the last twenty years we learn that among other questions in connection with the correlation and equiva- lence of chemical and electro-dynamic work he has resolved the fol- lowing :-That the heat generated in the cell and that which results from the resistance of the metallic circuit are always complementary and furnish the total heat due to the sum of the chemical actions which take place; that the oxidation of the zinc alone is not sufficient to account for the thermic effects produced by tho current but that it is necessary to take into account also the heat of combination of the acid with zinc oxide or in other words that the reaction is correctly ex-pressed by the substitution of the hydrogen of the acid by metallic zinc.He explains the impossibility of effecting the decomposition of water wit<ha single zinc and platinum couple immersed in dilute sul-phuric acid; a result easily attained with a cell of Grove's arrange- ment.He also suggests an explanation of the apparent transfereiico of hydrogen in the electrolysis of sulpliuric acid. He shows that the chemical decompositions resulting from the passage of the elect-ric carrent always bring icto play the same quan-tities of heat as those which accompany similar decompositioiis effected by other influences and that he has t,hus been enabled to determino YOL. XSVIII 1) ABSTRACTS OF CHEMICAL PAPERS. the heat of combustion of a large iiiimber of metals unat,tackable by acids. Various experiments have induced him to conclude that the calorific movement and the electro-dynamic movement can be produced simul- taneously in the circuit without either movement necessarily involving the transformation of the other ; in fact that whatever be the tempe- rature of the circuit the quantity of heat which reverts to the pile is always equal to that which the pile throws off in the circnit in the electro-dynamic state.He also briefly touches the complex problem of the conductivity of liquids without electrolysis. J. W. On Gladstone's Experiments relating to Chemical Mass By EDMUND J. MILLS(Phil. Mag. [4],xlviii 241-24'7). INHarcourt and Esson's experiments on the time occupied in chemical reaction it was shown that when a substance undergoes chemical change the residue y of changing subsfance is connected with the unit-intervals x,of change by the equation y = a'~ -a'z & a"~-a"s where a represents the amount of suhstauce originally present and a the amount of it disappearing per unit of x.Many yeass previously Gladstone published the results of numerous experiments on " Cir-cumstances Modifying the action of Chemical Affinity," but did not succeed in deducing any relative mathematical expression from his observations. The author has applied Esson's equation to the re-actions previously observed by Gladstone and has obtained in this manner some very interesting results. Gladstone's experiments may be briefly summarised as follows :-For oiie " equivalent " of a ferric salt successive groups of equivalents of potassium sulphocyanate were added in presence of water and the amount of red salt thus produced was estimated by the colorimetric method.The total amount a of red salt produced represents therefore in special measure the original unexhausted energy of the ferric salt. Taking each unit of x (the value of which is seldom given in the original experiments) to represent 25 " equivalents " of sulphocyanate the equation becomes in the case of ferric nitrate y = 401 (*855)"+ 224 (~1516)". With ferric sulphate the equation is y = 438 (-8208)" + 132 (-140)") where the unit of x is 15 equivalents ; and with ferric chloride y = 406 (-89)" + 214 (.25)" the unit of t( representing 20 equivalents. The results calculated from the above equations are expressed in percentages of the initial value of y and the following are partial instances of the coincidences observed :- GENERAL AND PHYSICAL CHEMISTRY.~ ~ ~ ~~~~ Ferric Nitrate. Ferric Snlphate. Ferric chloride. 2. y calculated. y calculated. y found. y calculated. y found. ~---1 60 ’3 66.3 65 ‘3 66.9 65 ’0 2 47 ,7 52‘2 53 .9 54 *o 54 ‘0 i!i11 3 40.2 43 *6 44 -2 46 .7 46 *9 4 34 ‘3 34 ‘9 35.6 41 ‘2 41 *2 5 29.3 28 -5 28 ’6 28 *7 36 ‘6 36 ’8 6 25 *1 23 *7 32 *6 33 ‘2 24‘5 I 23 -5 Ferric citrate mixed with solutions of gallic acid or with potassium ferrocyanide gave similar results the number calculated from the equation coinciding with those obtained by experiment. The results show that while an ordinary equation such as + GKCNS = Fe,(CNS)G + 6KC1 may represent the result of dis-tributing weight it does not represent in any way the chemical energy of the reacting salts for in the present instance the energy of the quantity QFezC16 is not exhausted until about 400 units (KCNS) have been brought to bear upon it.It would be well therefore in making use of the word “ equivalent,” as in the expression “C is equivalent to Hp,” to bear in mind that H and C have never been com- pared as to the work they can do under certain circumstances and that the relations of their potential energies have yet to be determined. J. W. Researches on the Simultaneous Diffusion of Certain Salts. By C. MARIGNAC (Ann. Chim. Phys. [5],ii 546-581). INthis paper the author discusses the results and gives all the numeri- cal details of a very extensive series of experiments which he has conducted on exactly the same plan as Graham adopted in his cele- brated investigation.The present research is however directed to points only incidentally touched on by Graham and was undertaken with the design of throwing some light on the vexed question of thc existence in solution of double salts and with the hope also that rela- tions between the diffusibilities of salts might be deduced from their simultaneous diffusion out of one solution with greater precision than from direct experiments. The author confined his observations to pairs of salts incapable of acting chemically upon each other that is the two salts used had either both the same base or both the same acid In general equal weights of the two salts were employed. The time of the diffusion varied from four days to five weeks and no special precautions were taken to maintain the vessels at a uniform tempera- ture.It is pointed out that Graham’s figures merely express the relative weights of salts diffused in equal times from solutions of equal quan- tities and that no regard was paid to the change in the rate of diffusion which is constantly going on in consequence of the diffusion D2 ABSTRACTS OF CHEMICAL PAPERS. itself. For Graham showed that diffusion takes place in direct pro-portion to the quantity of salt contained in the liquid; the results observed by him must therefore be regarded as the integral effects of a constantly-diminishing rate of diffusion. Hence the ratio of the dif- fused quantities of the two salts is nearer unity than the figure which would express the ratio of their real diffusibilities.If the constantly diminishing quantity of the salts in the difhsing liquid were the only changing condition affecting the rate of the action it would be easy to determine the co-efficicnts of diffusion. But there are other modifying circumstances and in the absence of any means of estimating these a formula must be sought for empirically which will approximately satisfy the condition of giving a constant qumtity for the ratio of the co-eGcients of diffusion even when the duration of the experiment is made to vary within wide limits. The author has found such a formula in a logarithmic expression deduced from the assumption that the diffusion of each salt diminishes in proportion to twice the quantity diffused out.The ratio thus calculated of the co-efficient of diffusi- bility of the less diffusible salt to that of the more diffusible he terms the relative co-eficieid of simzsltsneous &fusion. The value of this co-efficient for some hundreds of cases' is given in tables contained in the paper but the author has not been able to elicit any general law except the abundant confirmation of Graham's observation that in all cases the mixture of two salts diminishes the diffusibility of the less diffusible. The nature of the results may be illustrated by the follow- ing figures which refer to the simultaneous diffusion of 4-67'grams of potassium chloride and an equal weight of barium chloride dissolved together in 31 grams of water :-Duration of the Experiment in Days.Quantities of the Salts Diffused. BaC12. 1 KC1. Direct Ratio of the Quantities Diffused. Relative Co-efficientof Simultaneous Diffusion. 4 0.2047 0 *4808 0.426 0 -398 5 0 '2712 0 *6165 0 *439 0 -403 7 0 -4260 0 '9116 0.467 0.407 10 0.408 By a special series of experiments made to determine these points it was found that the value of the relative co-efficient of simultaneous diffusion is not affected by variat'ions in the proportions of the two salts but that on the other hand the value does vary with the degree of concentration of the solution in a manner which cannot be referred to any general principle. In order to determine the influence of one salt in modifying by it's presence the diffusibility of another present in the same solution three diffusion-cells were prepared as much alike as possible.In two of these the salts compared were made to diffuse separately and in the third the same quantities of each salt were caused to diffuse simul- taneously. The effects of any slight disparities in the vessels were GENERAL AND PHYSICAL CHEiIIISTRY. eliminated by repeating each experiment. six times so that every Dossible combination of the solutions and the vessels came into play and the mean of the six determinations was taken. The results show that in the mixture of two salts the most marked and constant effect is a diminution of the diffusibility of t'he less diffusible salt while the diffusion of the other salt is in some cases increased and in others decreased in a smaller degree however than in the case of the less diffusible This mutual influence becomes less and less as the solu-tions are made more and more dilute and it might be supposed that the limit towards which dilution tends to bring the ratio of the co- efEcients in simultaneous diffusion woidd coincide with the ratio of the co-efficients in separate diffusion.So far is this from being the case that it was observed only in the following instances :-Potassium sodium and ammonium chlorides in presence of the corresponding nitrates ; sodium and ammonium chlorides ; potassium and ammonium nitrates ; sodium and potassium sulphates in presence of magnesium sulphate. Since when mixed in a dilute solution,.potassium sulphate and magnesium sulphate retain their own diffusibilities which have no relation to their equivalents it follows that there is no affinity between two salts in solution even when they are capable of forming a double salt hence such double salts are probably formed only at the moment of crystallisation from the solution. The author's conclusion is that although experiments on the simultaneous diffusion of salts may show us the relative order of their diffusibilities such experiments cannot in general give us the ratios of their real diffusibilities. The results obtained prove that acids and bases preserve a certain relative order of diffusibility in a11 their combinations and the radicals may be thus arranged in two series according to that order ; those among which the order has not been determined with certainty being grouped together in brackets :-Negative Tadicals.[Chlorine bromine iodine] ; nitric acid ; [chlo-ric perchloric and permanganic acids] ; fluorine ; chromic acid ; sulphuric acid ; carbonic acid. Positive radicaZs. Hydrogen ; [potassium ammonium] ; silver ; sodium ; [calcium strontium barium lead mercury] ; [man-ganese magnesium zinc ] ; copper ; aluminium. In no one case has the author been able to detect any traces of the separation of acids and bases by diffusion R.R. Suspension of Clay in Water. By W. DURHAM (Chemical News xxx 57). CLAYremains suspended in pure water for an indefinite time ; but if a few drops of acid be added to the water the power of suspension is destroyed.In solutions of sulphuric acid and sodium chloride the liquid clears in the order of the specific gravities of the solutions so that the densest liquid settles nnd clears last. Alkaline solutions hat-e the same power with the exception that the liquids clear in the inverse ABSTRACTS OF CHEXICAL PAPERS. order of the specific gravities. The suspension of the cIay is attributed by the author to electricity generated by the friction of the water against the solid particles. As water is a had conductor the differ- ence in potent,ial between the clay and the water continues for some time hence they are mutually attracted; but when acid or salt is added the liquid becomes a good conductor the potentials are equal-ised and the clay falls.With the alkali on the other hand although the liquid does become a better conductor it at the same time becomes a better generator of electricity and it is only when by adding a considerable quantity of alkali the conducting exceeds the generating power that the potentials are equalised and the clay falls. E. W. P. Determination of the Emissive Power of Black Bodies by means of the Ice-calorimeter. By A. LEHNEBACH (Pogg. Ann. cli 96). The Graphic Representation of Absorption-spectra. By K. VIERORDT (ibid. 119). Observations on Roiti’s paper u Is the Electric Current an Ether-current ? ” By E. EDLUND (ibid. 133). Determination of the Specific Heat of Air. By A. Kunz (ibid.,173). The Heat-conducting power of Mercury is independent of Tern-perature.By H. HERWIG (ibid. 177). On the Photography of the Diffraction-spectrum and the determination of the Wave-lengths of the Ultra-violet Rays. By H. DRAPER (ibid.,337). Preliminary Experiments to determine the relation between the variations of Density and Elasticity of Gas at Pressures less than one Atmosphere. By F. A. SILJESTROM (ibid. 451 573). Experimental Determination of the Dielectric Constants (ibid. 482 531). of Insulators. By F. KESSLER On a simple Euthyoptic Spectroscope. By F. KESSLER (ibid. 507). On the Hemimorphism pf Cane-sugar. By H. BAUMHAUER (ibid. 510). On the Heat of Mixtureand Specific Heat of Mixed Liquids. By A. WINKET~MANN (ibid. cl 592 ; cli 512j. On a Modification of Senarmont’s Method of determining the Isothermal Surfaces in Crystals.By At. C. RONTGEN (ibid. 603 ; clii 367). GENERAL AND PHYSICAL CHEMISTRY. 39 Apparatus for the safe Evolution and Combustion of Detonating Gas. By A. GAWALOVSKI (ibid. cli 628). KI Self-acting Washing Apparatus. By A. GAWALOVS(ibid., 630). Exsiccator for Drying in Rarefied Air without the use of the Air-pump. By A. GAWALOVSKI (ibid. 631). Filtration under Pressure. By A. GAWALOVSKJ (ibid.,632). On a Capillary Galvanoscope constructed by W. Siemens. (ibid.,639). A simple Law for the Development and Grouping of Crystal- zones. By G. JUNGHANN (Pogg. Ann. clii 68). On the Reflection of Light from the Surfaces of Isotropic Bodies. By G.LUNDQUIST (ibid.,177). Application of the Mechanical Equivalent of Heat to Molecular Forces Weight and Distance. By G. WEINBERG (Pogg. Ann. Erganzungsband,vi 586). On the Secondary Current. By K. W. KNOCHENHAUER (ibid. 302 607) Geometric Solution of some Electrical Problems. By E. PICKERING (ibid. 622). On Attraction and Repulsion accompanying Radiation. By W. CROOKES (Phil. Mag. [4],xlvjii 81). An Improvement in the Construction of the Spectroscope. By H. G. MADAN (ibid. 116). On Unilateral Conductivity. By A. SCHUSTER (ibid. 251). On an Absolute Galvanometer. By F. GUTHRIE (ibid.,296). On Electricity produced in Mechanical Actions. By L. JOULIN (Ann. Chim. Phys. [5] ii 5). Action of Electricity on Flames Solid Bodies and Gases. By V. NEPRENEUF (ibid.,433).

ISSN:0368-1769    

DOI:10.1039/JS8752800030

出版商:RSC    

年代:1875

数据来源: RSC

摘要:

ABSTRACTS OF CHEMICAL PAPERS. Inorganic C hem i s tr y. Behaviour of Ozone with Water and Nitrogen. By L. CARIUS(Ann. Chem. clxxiv 1-30). CONTRAD~CTORY statements on this subject having been put forth by various able investigators the author has carried out a new series of researches with the view of determining these questions. By prefer-ence he obtained the ozone for his experiments by Soret's method of electrolysing dilute sulphuric acid at a low temperature ; but for com- parison he also used Houzeau's and von Babo's apparatus for producing ozone by silent electric discharges in air or oxygen. Contrary to the generally received statement he has found that ozone is soluble in water that liquid quickly acquiring from its own bulk of a gas con- taining 2 per cent.of ozone its odour and characteristic properties. Even when the gas contained orjly 1 per cent. of ozone the solution produced a powerful effect on potassium iodide and starch but dimi- nution of the proportion of ozone leads very rapidly to an extreme weakening of the solution. Ozone mixed with oxygen gas obeys in fact that law of gaseous absorption which makes the quantity dissolved proportional to that fraotion only of the total pressure due to the quantity of the gas itself which may be present in t)he mixture. Taking this law into account the author has from a series of experi- ments obtained a set of numerical results which show a very satisfac- tory accordance and furnish a mean of 0.834 as the co-efficient ot absorption for ozone at 1"and under 760 mm.pressure. For certain reasons however he believes this somewhat below the true value. The strong aqueous solution of ozone has an odour easily distinguish- able from thak of chlorine chlorous acid &c. It bleaches litmus- paper decolorises indigo changes tinct3ure of guaiacum to deep blue and precipitates thallium oxide from its solutions. The formation of silver peroxide by the action of the solution does not take place with certainty. No trace of the production of hydrogen peroxide by the action of ozonised oxygen on water could be detected either when these bodies alone were in contact or when nitrogen was also present. Nor after leaving in contact for weeks oxygen containing 2 per cent. of ozone water and nitrogen could the author discover by the most delicate tests the presence of any acids of nitrogen.He therefore emphatically asserts that nitrogen is not oxidised by ozone in the presence of water at ordinary temperatures. But when the ozone was prepared by electric discharges in oxygen containing even a very small percentage of nitrogen tthe presence of nitric acid was easily recognised. The wid is here the result not of the oxidation of nitrogen by the ozone but of the oxidation by the ozone of the nitrous acid produced by the electric discharges. Hence while electrolytically prepared ozone admits of being accurately estimated by potassium iodide the formation of nitrous acid in the other process forbids the use of this reagent with the ozone so produced.The gradual conversion of ozone into ordinar,y IXORGANIC CHEMISTRY. oxygen in presence of water which was observed by Andrews has been found by the author to be greatly influenced by temperature and at 0" it takes place so slowly that its effect did not require to be taken into account in the puthor's experiments which were conducted at about this temperature. R. R. Preparation of Crystalline Hypophosphorous Acid. By J. THOMSEN (Deut. Chem. Ges. Ber. vii 994). HYPOPHOSPHOROUS acid is generally stated to be an uncrystallisable syrup. The author has obtained it as a snow-white crystalline mass fusible at 17.4". The dilute solution obtained by decomposing the barium salt with sulphuric acid is first boiled down rapidly in a porce-lain dish and the evaporation completed in a platinum dish without ebulition.The bulb of a thermometer is immersed in the liquid and the temperature allowed to rise gradually to 105" at which tempera- ture most of the water can be driven off. The liquid is then filtered hot and the heating continued gradually up to 130". After ten minutes at this temperature the acid is transferred to a bottle and cooled below 0". It exhibits strongly the phenomenon of superfusion but crystal- lises when touched with a glass rod or more readily by the addition of a crystal of the same acid. M. J. S. Formation and Decomposition of Metallic Sulphides. By K. HEUMANN (Ann. Chem. clxxiii 21-39>. CONSIDERING it probable that the formation of crystalline cuprous sul- phide when copper remains in contact with yellow ammonium sulphide is due to the action of copper on the red crystalline substance CU~(NH~)~S,, the author allowed copper to remain in contact with a solution of the above-mentioned red salt but no cuprous sulphide was produced the red salt remaining unaltered.The double salt CU,(NH~)~S,, can be obtained abundaiitcly but in a slight,ly impure stake by adding cupric sulphate to concentrated ammo- nium pentasulphide. It is as might be expected decomposed by heat or strong acids and it is insoluble in water but soluble in ammonium sulphide the addition of an acid to this solution causing the precipi- tation of a mixture of sulphur and cupric sulphide. Copper causes the evolution of hydrogen not only from yellow ammonium sulphide but also from the hydrosulphide and the piire sulphide crystalline cuprous sulphide being formed in each case.The reactions are probably as follows :-Nz) s + CUP= CUPS+ NH + €3,. The crystals of cuprous sulphide obtained by the above reactions consist of thin ihombic needles which slowly oxidise in moist air and ABSTRACTS OF CHEMICAL PAPERS. are gradually dissolved by hot hydrochloric acid but are not acted on by sulphuric acid. Strong nitric acid acts violently on the crystals oxidising half the sulphur and leaving pseudomorphs of cupric sulphide. Dilute nitric acid dissolves the crystals sulphur being separated ; while yellow sulphide of ammonium converts them into cupric sulphide and ammonium pentasulphide transforms them into the substance Cu2(NH&S7.Silver nitrate decomposes the crystalline cuprous sul- pliide with production of a crystalline mixture of silver sulphide and metallic silver. Cupric oxide acts energetically on ammonium sulphide a mixture of cupric sulphide and cuprous sulphide being formed while sulphur is liberated and remains in solution. Metallic silver simply removes the excess of sulphur from yellow ammonium sulphide no gas being evolved. Copper reacts on an ammoniacal solution of arsenic sulphide with production of a yellowish-brown precipitate containing copper arsenic and sulphur ; while the action of copper on an ammoniacal solution of antimony sulphide leads to the production of a brown-black precipitate containing copper sulphur and antimony.These products will be investigated and the action of copper on solutions of antimony sulphide and arsenic sulpbide in ammonium sulphide will also be studied. Action of Light on Cilznabcw.-men cinnabar which has been pre- pared either in the wet or dry way is suspended in an alkaline liquid such as ammonium sulphide potash or ammonia and exposed to sun- light the outer layers become dark brown. This change takes place most readily with cinnabar prepared in the moist way. It does not take place when the cinnabar is suspended in an acid solution and only with extreme slowness when pure water is employed. Cinnabar prepared in the wet way contains metallic mercury and treatment with nitric acid partly removes this but a portion is con- verted into a white substance which is doubtless a basic nitrate.Ammonia blackens cinnaba'r containing this basic nitrate but a second treatment with nitric acid restores the red colour and renders the cinnabar pure. A sample thus purified was blackened by exposure to light and after the change it yielded no mercury to nitric acid. Hence t'he author concludes that the blackening is a molecular change and is not due to a decomposition of the cinnabar. Zinc and copper partially reduce moist cinnabar with production of metallic mercury or of a black substance from which nitric acid extracts mercury cinnabar remaining. Zinc in presence of hydrochloric acid reduces cinnabar more readily hydrosulphuric acid being evolved and other sulphides may be reduced in a similar way.Copper sulphide when treated with zinc and an acid yields a black powder which is probably cuprous sulphide this latter sulphide being very difficult to decompose by zinc a8nd an acid. T. B. INORGANIC CHEMISTRY. New Sulphur-salts. By R. Sc H N E ID E R (Pogg. Ann. cli 437-450). Potassium-nickel S~~lpl~ide.-lpart of nickel sulphate is fused for 8 or 10 minutes at a red heat with 9 parts of pure potassium carbonate and 9 parts of sulphur and the fused mass is t'reated with cold water deprived of air whereby the excess of potassium sulphide and nickel sulphide is removed and the new conipound remains in the form of brilliant crystalline plates which are further washed with water and lastly with absolute alcohol.This salt is readily decomposed by contact with air and water; the analyses agree with the formula E;i 1NiS, which is analogous with the double palladium-potassium sulphide already described KS 1Pd&. Potassium-cobaZt Su 2p 7~ide.-By fusing cobalt or cobaltous chloride with potassium carbonate and sulphur a substance is formed which the author believes to be the cobalt double salt corresponding with the above-described nickel-compound but he has not been able to obtain it in the pure state. If 1part of cobaltous chloride be fused with 6 parts of soda and 6 parts of sulphur for ten minutes at a full red heat and the fused mass be treated with water light iron-grey crystals of cobalt sesquisulphide COZS~ remain. Sodium-naaizg~~zese Szdphide.-B y fusing manganous oxide with soda and sulphur the author has prepared the two salts NaZS.2MnS and Na2S.3MnS.In attempting to prepare the corresponding potassium salts he found that considerable quantities of minute green needles were produced consisting of manganous sulphide MnS. M. M. P. M. On the Constitution of the Lead-chamber Crystals. By A. MICHAELIS (Deut. Chem. Ges. Ber. vii, and 0. SCHUMANN 1075-1078). INorder to test the validity of the formula SO generally given Yo to the lead-chamber crystals the authors have prepared the compound by the action of sulphurous acid on concentrated nitric acid and sub-mitted it to the action of phosphorus pentachloride. The decompo- sition proceeds according to the equation Towards the end of the distillation a small quantity of a crystalline body boiling at about 360° passes over presenting the characters of the anhydride S205(N02)2.Some metaphosphoric acid remained in the retort. The anhydride thus produced is the result of the action of heat on the sulphate experiments described by the authors leading to the conclusion that this decomposition takes place in accordance with the equation 4i02{gz= 250 { gg + S,O,(NO,) + N,O,. W. A. T' ABSTRACTS OF CHEMICAL PAPERS. Sodio-ferrous Sulphate. By E. B I LTZ (Zeitschr. Anal. Chem. 1874 124-128). THEauthor draws attention to the salt Na2S0414H20 which is if FeS04 properly prepared very stable and of much use #in standardised per- manganate solutions &c.instead of iron wire. This salt is best pre- pared by dissolving pure crystallised ferrous sulphate in its own weight of warm water which contains 2 per cent. of dilute sulphuric acid ; an equivalent amonnt of sodium sulpha,te is added and the liquid evapo- rated by gently boiling it until a considerable quantity of crystals is formed. The liquid is now allowed to cool with gentle stirring the salt collected on a filter pressed between paper dried in a warm air chamber and finally brought into the water-bath where it quickly becomes thoroughly dry. M. M. P. M. Ultramarine. By E. Bu c H N E R (Deut. Chem. Ges. Ber. vii 989-993). IN order to ascertain whether the presence of silica was absolutely necessary to the formation of artificial ultramarine two mixtures were made as follows :-I.A12Na60,+ 6s + 3c 11. A1zNa606 f 6s + 3c + 2Sio2 and submitted to the ordinary process for preparing ultramarine. The second mixture gave a deep blue ; the first however also gave a pale blue which was accounted for by the presence of 10 per cent. of silica subsequently found in the aluminate. Silica appears therefore to be necessary. Contrary to the statements of Unger the author finds nitrogen absent from and sodium invariably present in ultramarine. The excess of sodium is removed by washing as sulphide not as sulphate. When a mixture of clay and soda is heated in a stream of hydrogen sulphide or carbon disulphide vapour a green mass is obtained which by heating in a current of air or with sulphur or ammonium chloride is converted into blue.A similar result is obtained by heating natrolite first in carbon disulphide then in sulphur dioxide. The author regards Scheffer’s red and yellow ultramarine as the products of partial decomposition since he finds that they are obtained when ultramarine is heated in oxygen before the action has been cayried far enough to yield a white residue. Finally he shows that R. Hoff-mann’s ultramarine crystals are only quartz. They are found both in the clay employed and in the residue of the decomposition of ultra-marine by acids. M. J. S.

ISSN:0368-1769    

DOI:10.1039/JS8752800040

出版商:RSC    

年代:1875

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRT M in e r a1o gi c a1 C h e rn i s t r y. Tungsten Minerals from Meymac (Corrbze). (Fourth Note.) By AD.CARNOT (Compt. rend. lxxix 637-640). WoZfmm.-Occurs in lamellated masses with an easy and brilliant cleavage ; no well-defined crystals have yet been noticed. Not mag- netic. Density 6.54. Average composition :-WO,. FeO. MnO. CaO. MgO. Td05. H20. 74.25 15.85 6.51 0.80 0.04 1-10 0.70 = 99-25. Some specimens contained about 5 per cent. of tantalic acid. 8cheeZife.-Tungstate of lime found in masses having a crystalline texture. Lustre vitreous to adamantine. Fracture lamellated often iridescent. The relative proportions of tungstic acid and lime lead to the formula Ca0.W03. The mineral sometimes contains a little tantalic acid.Hydrated Tzmgstic Acid.-Results from the decomposition of the Scheelite. Lustre resinous. Friable between the fingers. Colour yellow to brown. Ammonia partially dissolves out the tungstic acid. Analysis of three samples gave :-I and 11. Friable. Yellow or brownish-yellow. Powder yellow. Sp. gr. 3-80. 111. Hard. Fracture lamellated. Powder yellowish. Sp. gr., 4.54. I. 11. 111. Tungstic acid ............ 71.85 74.25 75.12 Tantalic , ............ 1.00 1.05 0.70 Lime .................... 2.50 4.65 7-00 Oxide iron.. .............. 6.00 6.10 6.25 , manganese.. ........ 0.75 0.65 0.32 Water. .................. 12.93 11.75 6.85 Gangue .................. 4.50 1-85 2.50 99.53 100.30 98.74 Deducting the calcium tungstate and ferric hydrate which may be regarded as merely admixed there remain for the proportion of tungstic acid and water numbers which may be repreaented by one of the formulee 2W03.5H20,or WO3.2H20.To decide between these two formulae new analyses will be required ; but the preceding numbers viewed in connection with the decided differences between the physical characters of this mineral and those of anhydrous tungstic acid (tungs-tite) are sufficient to show that the former is really a distinct species. The author designates it as Meynzncite. C. H. P. ABSTRACTS OF CHEMICAL PAPERS. Warwickite. By J. LAWEENCE SMITH (Compt. rend. lxxix 696-698). THEfollowing are the results of a new analysis of the mineral made by the author :- Found.Oxygen. Oxygen-ratios. Compositionassigned. Percentagetalculated. Boric.acid .. 27.80 19.06 9 3&03 30.57 Titanic acid.. 23.82 Magnesia. ... 36.80 Oxide of iron. 7.02 10.37 14.46 2.10 5 6 1 2Ti0 SMgOFeO 23-58 35.36 10.49 Silica . . . .. Alumina .... 2.21) Impurities. 100.00 He suggests the formula 5Mg0.3B,03 + (Mg0,Fe0)2Ti02 and remarks that warwickite is the only known boro-titanite in nature. R. R. Native Cuprous Sulpharsenate. By R. W. EM E xsoN MAc IY o K (Chemical News xsx 103). A SPECIMEN of Swiss dufrenoysite crystallised in small monometric crystals of a dark grey colour of sp. gr. 5.52 yielded on analysis (small percentages of lead and iron sulphidcs being neglected)- a;. 43. As. S. 46.05 2.43 18.79 32.46 = 99.73 If the 2.43 per cent.of Ag be replaced by Cu the composition agrees with t,hat required for cuprous sulpharsenate CuS(AsSp),tending to prove that tfhis mineral is dimorphous as enargite has also the formula CU,(ASS~). E W. P. Investigation of a New Fossil Resin. By K. HELBING (Ann. Chem. clxxii 297-303). THISmineral was found in a quarry at Engenau near Heilbrunn in a tertiary formation of the age of the gypsum of Montmartre. This formation usually contains no organic remains except marine alilgne ; but as both the fragments of resin and the iron pyrites which accompanies them have externally a smooth polished surface ; they are probably of organic origin. The resin is of a dark brown colour with resinous lustre and conchoidal fracture and is faintly transparent at tlre edges.It is easily reduced to a yellowish-grey powder. It remains solid up to 300" but melts when heated on platinum foil and burns with production of a large quantity of carbon while the burning pro- ducts give out a pleasant aromatic smell. It is mixed with iron pyrites in so fine a state of division that it becomes visible only on levigation. The percentage composition is- NINERALOQICAL CHEMISTRY. 47 I. 11. 111. C ............ 74.15 74.68 75.01 H ............ 9.53 9.60 9-51 0............ 1.91 1.11 1.37 FeS2.......... 1441 14-61 14-11 The resin is partly soluble in ether and in hot alcohol and can thus be divided inlo three parts. The part soluble in ether but not in alcohol amounts to about 19 per cent. ; that soluble in ether and hot alcohol to about 9 per cent.; and that insoluble in both to about 72 per cent.The soluble parts are also taken up by carbon bisulphide benzene and chloroform. The insoluble part after removal of the pyrites gave on analysis-I. 11. C.. ............ 88.21 88.46 H.... .......... 11-22 11.25 -I_ 99.43 99.71 This would indicate a hydrocarbon answering to the formula Cd0HKR2 which might be derived from a terpene CloH6, by the removal of two atoms of hydrogen. The part soluble in ether but not in alcohol melted at 19a0 and gave on analysis- I. 11. 111. C.. .......... 82.84 83.59 83-70 H ............ 11.53 11.28 11-17 o............ 5.63 5-13 5.20 These numbers point to the formula C40H6202, which would be de- rived from the hydrocarbon above mentioned by replacing two atoms of hydrogen with two of hydroxyl.The part soluble in hot alcohol and ether softens at 70° and on further warming becomes viscons and darker coloured. Analysis gave-I. 11. C ................ 81.35 81.55 H ................ 10.48 10.62 0 ............... 8-17 7.83 These numbers agree with a formula C40H6003 and this compound may be derived from the pyevious one by replacing two atoms of hydrogen with one of oxygen. The three constituents of the resin shorn a similar deportment towards reagents. The part soluble in ether and hot alcohol is alone attacked by melted pottash; the other two float on the potash as soft brown masses and are decom- posed with esca,pe of vapours of an aromatic odour.Concentrated sulphuric acid dissolves the three bodies on warming to brown liquids. A mixture of chromate of potash and sulphnric acid has no marked action upon any of them ; concentrated nitric acid has little action in the cold but when warmed with it on the water-batlh the three are converted into clew red liquids from which a part of tlie compounds ABSTRACTS OF CHEMICAL PAPERS. formed is precipitated on cooling and almost the whole on addition of water. These compounds are amorphous yellow masses containing nitrogen-probably nitro eompounds. This resin agrees in composition and properties with no other yet described. The one which comes nearest to it is from Settling Stones in Northumberland and con-sists according to Johnson of 85-29 C 11.03 H 3.68 0 and 3.25 ash.He assigned to it the formula C,H,,02 and supposed that it contained a hydrocarbon CIH,. The author is of opinion that it con-sisted of a mixture of different compounds. G. T.A. Petrified Wood of Lough Neagh. By Prof. HODGES (Chemical News xxx 102). AS the analyses of the petrified wood he had made did not satisfy Bischof that the wood had been petrified by t'he water of the lake but rather led to the inference that it resembled the silicified wood of the brown coal formations the author has made further analyses of the lake-water and finds that an imperial gallon of it cont,ains 12.95 grains of solid constituents consisting of 10.826 grains of mineral and saline matters of which 0.36 grains were silicic acid.The ash left after ignition of the wood was affected by the magnet as stated in the Phdosophical Transactions. The ash contained amongst other sub- stances 89.11 per cent. silicic acid and only *04 per cent. of iron oxide. The author therefore considers that the lapidifying material of the petrified wood is silicic acid and not oxide of iron. E. W. P. The Recent Eruption of Nisyros. By M. GORCEIX (Ann. Chim. Phys. [5] ii 333-354). PARTLY noticed already (see Journal 187'3 p. 1212 and 1874 pp. 347 562) but the complete paper contains a considerable amount of new matter and gives a connected view of the whole. The ''residue " obtained in the analysis of the gases from the fuma- roles b and c (p. 1212 of last volume) had the composition- Nitrogen.Marsh gas. Hydrogen ? 9S.2 5.9 0*9?= 100-0 The hot saline water discharged from the fissure which opened on June 8th 1873 collected in a small lake where as it evaporated it de-posited crusts of nearly pure sodium chloride. The water was slightly acid. It contained the following subst,aiices in 1litre :-Chlorine .......................... 113.00 Sulphuric acid .................... 1-06 Hydrogen sulphide ................ 0.01 Silica ............................ 0.07 Iodine ............................ traces Sodium .......................... 44.40 Calcium .......................... 16-60 0RGANIC CHEMISTRY. 49 Magnesium.. ...................... Potassium ........................ 2.73 1.72 Ferric oxide with a little alumina ....4.12 It is evidently sea-water highly concentrated and mixed with pro- ducts of the volcanic action. During the period of greatest activit,y the composition of the gases from the fumaroles was soniewhal altered the sulphuretted hydrogeii being diminished the total quantity of combuskible gases in the residue being increased and the hydrogen exceeding the marsh-gas in the pro- portion of 5.3 1. The immediate cause of the present eruption appears to have been the penetration of the sea-water into an ancient fissure which extends from Nisyros to the neighbouring island of Hyali its submarine course being indicated by an evolution of carbonic acid and sulphuretted hydrogen. The fumaroles which are all situated on thc line of this fracture usually afford sufficient vent for the vapour generated but for some time previous to 1871 a considerable diminution in their activity had been observed probably in consequence of accidental obstructions.The vapour thus acquiring a sufficient tension (which from the height of the column of water ejected the author calculates as at least 16 atmospheres) opened at first two small exits producing at the same time the phenomena of an incipient eruption. Succeeding upon this the sea-water penetrating with greater facility attained a greater depth and after some months produced a second eruption of still greater violence when part of the water was ejected in the liquid form still holding its salts in solution its organic matter decomposed by the high temperature appearing as marsh-gas and hydrogen. The author considers that the study of this eruption will throw light upon the causes of volcanic action in general X J. S.

ISSN:0368-1769    

DOI:10.1039/JS8752800045

出版商:RSC    

年代:1875

数据来源: RSC

摘要:

0RGANIC CHEMISTRY. Organic Chemistry. Investigation of the first Products obtained in the Manufac-ture of Benzene. By K. HELBING (Ann. Chem. clxxii 281-297). ERLENMEYER detected propione while searching for the hydrocarbon C4H4,among the volatile liquids which pass over at low temperatures during the distillation of light coal-tar oils in the preparation of benzene. The author endeavoured to obtain a large quantity of pro-pione from the same source but failing in this he divided the liquid by fractional distillation into a number of parts and examined each closely. The liquid contained still 51 per cent. of benzene and 16.28 per cent. of carbon bisulphide. The part boiling between 18" and 40" was treated with bromine and again distilled and by this means a liquid and a solid product were obtained.The liquid consisted of amylene bromide C5HloBr2, mixed with bromine substitution-pro- ducts ; the solid contained crotonjlene tetrabromide C,H,Rr,. VOL. XXVIII. E ABSTRACTS OF CHEMICAL PAPERS. The part boiling between 50" and 70" was also treated wit'h bromine and gave hexylene bromide C6HI2Br2, mixed with a small quantity of bromine substit,ution-products. G. T. A. Action of Nitric Acid on Paraffin. By A. G. POUCHET (Compt. rend. lxxix 320-324). BY the action of fuming nitric acid upon paraffin the author has obtained very complex products including soluble fatty and other acids and a substance which according to liis statement contains a new acid to which he gives the nameparqfiwic acid.He has not observed the cerotic acid which was observed by Gill and Meusel under similar circumstances. Paraffinic acid is described as a slightly yellowish solid rather lighter than water and combustible. It is soluble in alcohol giving a solution which is acid to test paper and from which it crystallises in pearly scales. It melts between 45" and 47'. The acid is monobasic and its formula deduced from the analysis of the barium lead and silver salts as well as of the acid itself is C24H4802. If this .formala is correct that of paraffin must be C21H,o.. W. A. T. Note on Tertiary Nitrobutane. By J. TSCHERNIAK (Deut. Chem. Ges. Ber. vii 962). THIS body prepared by treating the corresponding iodide with silver nitrite during which operation much isobutylene oxides of nitrogen water and nitrite of ethyl were also pr'oduced gave by reduction with iron and acetic acid much isobutylene ammonia aid a small quantity of butylamine.When treated by the usual methods it yielded neither bromine derivatives nor a nitro-acid. 31. J. S. Constitution of ordinary Bromo-Propylene. By E. REBOUL (Compt. rend. lxxix 317_32,0). THEauthor finds that ordinary bromo-propylene is a mixturc of two isomerides ; one which he distinguishes as a-bromo-propyleiic boils at 48" ;the other ,B-bromo-propgrlenc boils at 59"*5-G0" under a pressure of 740 mm. The latter has the formula CH,-CH=CHBr. These two bodies cannot be separated by fractional distillation but the second may be completely isolated by taking advantage of tlhe fact) that it unites with hydrobromic acid much less rapidly than the first.The new bromo-propylene ccim bines slowly at 100" with hydrobromic acid furnishing a mixture of two propylene bromides which distil bctween 132" and 143". It also combines with bromine yielding a liqiiicl bromide CH3,-CHBr-CHBr2 of specific gravity 2,356 at 18" and boiling at 200"-201" (corr.). The isomeric a-brorno-propylei:e gives with bromine a bromide CH,-CBr,-GHBr which boils at 190". W. A. T. ORGANIC CHERIISTRT. Note on the Etherification of Glycol. By A LORIN (Compt. rend. lxxix 387-389). OXALICacid reacts with glycol nearly in the same manner as with glycerin but some of the formina produced distil over unchanged uhcn the mixture is heated.The author also finds that potassium foimate may bc substituted and with some advantage for the acetate in the preparation of glycol. W. A. T. Action of Ally1 Bromide on Silver Nitrite. By R. SCHIFF (Deut. Chem. Ges. Ber. vii 1141-1145). BRACKEBUSCH states that by the action of allyl bromide on silver nitrite allyl nitrite and nitropropene are formed. On repeating this reaction the author could only obtain besides gaseous products and water an oily liquid still containing much undecomposed allyl bromide and only so small a quantity of nitrogenous products that by using 377 grams of the bromide no definite compound could be isolated. c. s. Diallyl Compounds. By L. HENRY (J. pr. Chem. [Z] ix 476 480). DiaZZyZcZicl~Zor7~y~~~~~, CsH,,(OH),CI,.-The author has formerly shown that ally1 compounds unite with hypochlorous acid to form deri-vatives of glycerin.Some recent experiments have shown that diallyl unites with hypochlorous acid to form diallyl- dichlorhydrin. The mercury used in the preparation of the hypochlorous acid must be removed with hydrogen sulphide taking care not to pass excess of the gas as it acts on diallyl. The chlorhydrin is extracted with et,her and the solution left. to evaporate over sulphuric acid. It forms a thick fluid with a pleasant odour resembling that of' glyceric chlor- hydrin and has a bitter acrid taste. At 7" its specific gravity is 1.4; it is sparingly soluble in water but dissolves with ease in alcohol and ether. It cannot be distilled for on heating it hydrochloric acid is evolved and a carbonaceous residue remains.This body may be regarded as two molecules of glyceric chlorhydrin connected together. The author hopes to be able to form diallyl erythrite C,H,,(OH) from this substance. The two hydroxyl groups and the two atoms of chlorine must as far as analogy shows be con- nected with four separate carbon-atoms ; he therefore supposes that the two allyl groups are united by a double affinity. The author offers a fern remarks on another alcoholic compound of dlyl-ncryZ pi?zccco?zc,CsH,,02. It is obtained by the action of nascent E2 ABSTRACTS OF CHEXICAL PAPERS. hydrogen on acrolein two molecules of ncrolein uniting with one mole-cule of hydrogen. Acrolein is an aldehyde and a,s such must contain the group CHO.Its formula may be expressed by C2H3.CH0. Acryl- pinakone may be regarded as a secondary tetratomic unsaturated glycol and its formula would accordingly be- C2HS-CH.OH I C,H,-CH.OH. If the constitution CH2=CH.CH0 be accorded to acrolein acryl- pinakone would have the formulab-CH2=CH.CH(OH)-CH( OH)-CH=CH,. Henninger's croton glycol derived from erythrite by the action of formic acid has the formula C4H6(OH),. If the formula ascribed to acryl-pinakone is correct it may be possible to transpose it into an octatomic hydrocarbon C6H6 different from propargyl . The products of addition of the halogens [C6H8(OH),X4] must be identical with the derivatives of a normal hexatomic alcohol CeH8( OH)6 probably mannite.It may be possible thus to prepare mannite synthetically. This the author proposes to attempt W. R. Researches on Mannite. By LEOVIGNON (Ann. Chim. Phys. [5],ii 433-473). THISpaper opens with an account of the discovery sources properties and composition of mannite. The work is then divided into three chapters the first,portions of each being devoted to a history of the questions brought under consideration. I. The Action of Mannite on Polarised Light.-Alone mannite exerts no perceptible action on polarised light but on saturating the solution with boric acid and examining its action on a polarised ray in a Soleil's apparatus with a column of liquid 200 millimeters long a comtant deviation of + 1.20" occurred. On noutralising the acid with pure sodium carbonate the deviation increased to + 5.04'.On dissolving borax in an aqueous solution of mannite the liquid becomes strongly dextrogyrate ; other borates show the rotatory power of mannite though in different degrees. A given weight of boric acid in the state of alkaline salt increases the rotatory power much more than the same weight of acid in the free state. A mannito-boric acid solution (satu- rated) gave with yellow light a deviation of a = + 1-38'; the same neutralised with sodium carbonate a = + 5.83"; neutralised with potassium carbonate a = + 6-63"; or with ammonium carbonate a = + 6-73". Borates insoluble in water but dissolved in hydrochloric acid gave the same deviations as boric acid ; diffi~ult~ly soluble borates such as that of lime with excess of boric acid gave intermediate devia- tions.The amounts of the deviations thus caused for all these bodies are immediate and permanent. Arsenates dissolved in solutions of mannite likewise develop rotatory ORGASIC CHEXISTRS. power and other bodies will probably be found to act in a similar manner. Arsenic acid in a solution of mannite causes a deviation which in- creases with time ; thus to a solution of mannite in which the propor- tion by weight of water to mannite was as 6.3589 exactly 10 per cent. by weight of arsenic acid was added. For the yellow ray with a thickness of 200 millimeters the deviation was after one hour a = + 0.3924"; after 24 hours a = + 1*1090°. The solution was then gradually neutralised by the addition of sodium carbonate in portions of 0.5 gram at a time.After the first addition a = + 0.1674" ; after the second a = -11*2059";after the third a = -11.7642". In 40 grams of the mannite solution made as before two grams of neu trxl sodium arsenate were dissolved. This examined for a thickness of 200 millimeters gave ccy = + 0.3574 and after some time only such trifling variation that with tri-sodic arsenate the mannite appears to effect a deviation which is immediate and permanent. Monopotassic arsenate increases with time and according to the quantity of the salt present the extent of the deviation in the mannite solution. Thus in four solutions of the original strength (weight of mannite to water 6.3589) increasing weights of monopotassic arsenato were added and examined after five days.The results were- 1. 61 == 0.036 ........ a = -4.22" 2. B2 = 0.049 ........ a = -8.46" 3. @3 = 0.060 ........ a = -11.59" 4./3& = 0.072 ........ a -16.30" P represents the weight of the salt in one part of the solution. A fifth solution in which /3 = 0.083 became in three days quite solid but without diminishing in transparency. This substance may readily be produced by saturating boiling water with mannite and monopotassic arsenate ; on cooling it solidifies and is as transparent as glass rather friable and it is strongly laevogyrate. It dissolves slowly in water yielding an acid solution. Hence it is inferred that mannite dissolved with arsenic acid or monopotassic arsenate suffers a commence- ment of etherification.Determination of the Molecular Rotatory Power of XurLnite.-Thtt method employed which was the same as that devised by Biot in the case of tartaric acid was based on a comparison of the deviations pro- duced by a series of mannito-boric solutions in which the proportion of water to mannite remained constant while the proportion of boric acid was continually increased. The result gave €or t,he rotatory power of mannite in aqueous solution with tJhe particular proportion of water used in the experiments- (a) = + 018255". 11. Ma,~mitan.-This compound was prepared from mannite by treat- ing it with half its weight of concentrated sulphuric acid at 125" (below this temperature the action is very slow ; above it the mass blackens and only a small quantiiy of impure mailnitan is obtained), the mixture being stirred from time to time.The mass browned 54 ABSTRACTS OF CHEUICAL PAPERS. slightly and became liquid. dfher two lioara it wa4 noutralised with barium carbonate without allo.ving the temp4rature to fall. The mass was then exhausted with absolute alcohol filtered evaporated and dried at 120". By this process mannitan is obtained as a very viscous slightly brown mass very soluble in water and in absolute alcohol having a sweet taste and an odour somewhat like that of caramel. 20 grams of mannite yielded 12 to 15 grains of mannitan. The formation of maiinitan in this process is due tl>the direct dehy- dration of the mannite by the sulphuric acid and not to the formation of sulphomannitic acid and its subsequent resolution into sulphuric acid and mannitan for when barium sulphomnnnitate prepared by neutrali- sing with barium carbonate the product of the action of sulphuric acid on mannitan is heated to 125" it quickly becomes acid and if after two or three hours it be saturated at the same temperature with barium carbonate the products obtained are barium sulphate and mannitan but if the sulphomannitate be previously mixed with excess of barium carbonate so that the mixture may always remain neutral the sul-phuric acid being neutralised as fast as it is set free nothing is obtained but barium snlphate and niannite without a trace of mannitan.It is clear then that the formation of mannitan in the former case is due to the dehydration of mannite by the sulphuric acid set free by the decom- position of the sulphomannitate. The molecular rotatory power of mannitan was found to be- (a>y= +36.5". Nit~oma?mitmzwas obtained by dissolving 1part of mannitan in cz mixture of 10 parts of sulphuric acid and Q parts nitric acid of sp. gr. 1.50. The materials having been left in contact for a quarter of an hour and kept cod the mixture is thrown into a large quantity of water. A white precipitate then falls which is washed with water and digested with ether which dissolves the nitro-mannitan. This ethereal solution is evaporated and concentrated in a vacuum. Nitromannitan wlieii gradually heated evolves nitrous vapouw swells up and burns rapidly leaving a carbonaceous residue.It ex-plodes when struck with a hammer. It is soluble in alcoliol and ether. Its rotatory power determined in an ethereo-alcoholic solu-tion is-(a) = + 53.26". No anal-j-sis of this compound could be effected on account of its physical condition and its proneness to detonation but from analogy the formula C6H7(N02)505 is suggested. Heated with caustic soda solution nitromanni tan yields a blackish gummy mass not explosive by percussion and not containing either mannite or mannitan. With ammonium sulphide it yields mannitan. 111. Actiox of Water OTL JIarzi~itein Xealecl Tubcs nt tlifererit Tenapso-tures.-l. By heating mannite with half its weight of water in a scaled tube for four hours to 280° a yellow translucent liquid is obtained cyntnining blonn flocks in saspension ; no gas is cvolvccl on opening tlie tube.ORGANIC CHEMISTRY. If tlie tube be heated to 295" maniiitan is obtained. 2. The aqueous solution obtained by heating to 280° evaporated on a water-bath and dried at lZOo,.yields a thick syrup containing crys- tals of mannite ; and on exhausting this syrup mit8h absolute alcohol evaporating the solution and drying the residue at 120" a yellowish viscid mass remains which is hvogyrate. If this viscid mass be exposed to air either moist or dry or dry hydrogen or oxygen it deposits crystals which are also hvogyrate and therefore do not con- sist of mannitan. The crystals are insoluble in absolute alcohol and appear to have pre-existed in the mass and to have been carried into solution in absolute alcohol by reason of the great excess of the viscous mass which was also soluble.In about a month the viscous mass ceases to deposit crystals ; and if from time to time they are removed the mass then taken up with absolute alcohol tbe solution evaporated the residue boiled for an instant with water the liquid filtered through animal charcoal arid evaporated to dryness the residue washed with ether again taken up with absolute alcohol the alcoholic solution filtered and evaporated and the residue finally dried at 120" till it no longer loses weight a yellowish substance of the consistence of turpen-tine is obtained having the composition of mannitic ether t,he mean of several analyses giving C =41-70 ; H = 7.6; while the formula of mannitic ether CIZH2G011, requires C 41.6 -H 7.5.Mannitiic ether is hvogyrate its molecular rotatory power being (a) = -5.59". It does not reduce Barreswill's liquid nor ferment in contact with yeast. By boiling with dilute snlphuric acid or baryts-water it does not yield either mannite or mannitan. That this substance is really mannitic ether is shown by the facts that when dissolved in concentrated sulphuric acid it yields a sulpho- conjugated acid identical with the one yielded by mannitan ;that when treated with a mixture of nitric and sulphuric acids it yields a nitro- derivative analogous to nitro-mannitan ; and that when heated with a little water to 295" in sealed tubes it is converted into mannitan.3. The Crystalline Xubstan,ce deposited by the Ct-ucle iklccnnitic Ether Xmz,nitone.-This substance is obtained pure by washing with cold absolute alcohol dissolving in water filtering through animal charcoal and then evaporating. It is chemically isomeric with mannitan. The two isomelides do not give two distinct series of derivatives. Mannitonc treated with a mixture of nitric and sulphuric acids yields the same nitro-derivative as mannitan and mannitic ether. Mannitone is lmogyratc (u) = -25". It has a sweet taste and does not reduce a cupro-potassic solution. Heated with water to 295" in sealed tubes for three hours it is completely converted into mannitan. C. H. P. Contributions to our Knowledge of the Starch-group.By W. NAGET~I (Ann. Chem. clxxiii 218-227). STARCH is a mixture of several modifications ; when it is treated with not too coilcentrated acids that portion which is coloured blue by iodine and preponderates in the softer parts of starch is dissolved and 5 6 ABSTRACTS OF CHEMICAL PAPERS. a portion is left to which iodine imparts a yellow coloar. This modi- fication is only slowly changed by acids or boiling water; it still possesses the structure of the granules and its hardest part seems to be identical with or nearly related to cellulose. The “ blue” and “yellow ” modification-meaning thereby the modifications which are respectively termed blue and yellow by iodine-change gradually into each other forming others which are coloured by iodine violet red or orange.Potato-starch contains little of the latter but much of the “blue,” and still more of the “yellow,” and in wheat-starch less yellow occurs and hardly any blue but much of the violet and reddish- violet. When starch is boiled with water the quantity of the “blue ” modification increases. On boiling “ yellow ” starch with water for a long time the greater part dissolves and the solution gives with iodine a violet colour. On evaporation or on allowing the liquid to freeze amylodextrim separakes out in discs having a diameter of 0.035 mm. and consisting of small needles which may be obtained singly by carefully precipitating the solution with alcohol. Under the polariscope the discs show crosses like starch but in a different position being turned about 45”.Amylo-dextrin when freshly precipitated by alcohol is soluble in cold water but it soon loses this property and then dissolves in water only at 6Oo-65O. On cooling no amylodextrin separates out at once but only slowly on standing quickly however when the liquid is frozen. The composition of the substance dried at loo” and after deducting 0.1 per cent. of ash containing phosphoric acid potassium sodium and calcium is C36H6,O:o + H20. Its solution turns the plane of polarisa-tion to the right; the rotatory power being about the mean of that of starch and dextrin. Alcohol does not precipitate it as readily as starch while tannin basic lead acetate and barpta-water do not precipitate it.The solid substance is coloured yellowish by iodine but the solu- tion turns first violet and then red because amylodextrin also exists in two modifications which can be separated by partially precipitating its solution with sodium acetate. The dextrin obtained from amylodextrin also exists in two modifications one being coloured red and the other yellow or brown by iodine. It is also readily converted into sugar even by potash-solution and therefore it reduces Fehling’s solution. c. s. On a mode of Decomposition of Chloral-hydrate. By M. TANRET (Compt. rend. Ixxix 662). IF a mixture of solutions of chloral-hydrate and potassium perman- ganate be made alkaline say with caustic’potash gas is evolved the liquid becomes discoloared and sesqnioxidc of manganese is precipi- tated.If several grams of chloral-hydrate be acted upon and the temperature not raised above 40° the reaction will last for some hours ; then on filtering the liquid the filtrate will be found to contain chloride carbonate and formate of potassium. The gas evolved is carbon monoxide. The reaction occurs equally with very dilute solu- tions and even if borax be substituted for potash. This decomposition ORQA.NIC CHXMISTRY. leads to a theory to account,for the action of chloral-hydrate upon the animal system. It is snggested that when this substance is taken into the circulation it is submitted to oxidizing agencies ; the alkalinity of the serum determines its decomposition ; the carbon monoxide dis- places the oxjgen from the arterial blood and produces an effect similar to that resulting from poisoning by carbon monoxide.The lowering of the temperature of the body and the prolonged action of the chloral-hydrate owing to slow decomposition tend to make this theory more tenable than the assnmption of its conversion into chloro- form. C. H. P. New Method of Preparing Ethylnitrolic Acid. By V. MEYERand J. LOCHER (Deut. Chem. Ges. Ber. vii 1137-1141). Tms acid is formed by allowing a mixture of an alcoholic solution of dibromonitroethane and an aqueous solution of hydroxylarnine to stand for 12 hours-NO2 NO2 CHa-C / + HZN-OH =CH3-C / + 2HBr. \\ N-OH Hydroxylamine gives no crystalline product with monobromonitro- ethane and does not act all on nitroethane.c. s. Ethylic Ethyl-sulphonate. BJ A. KURBATOW (Ann. Chem. Pharm. clxxiii 7-8). THIS substance originally obtained by Carins can be readily ob- tained by heating silver sulphite with ethyl iodide in the presence of ether. T.B. On Sulphocyanocarbonic Acid and its Derivatives. By L. HENRY (J. pr. Chem. [2] ix 464-468). Eulpkocy am-carboiaic etk el^ CO { was obtained by the action of chlorocarbonic ether on potassium or ammonium sulphocyanate dis- solved in alcohol. Potassium or ammonium chloride separates and is separated by filtration off. Most of the alcohol is then distilled off and on addition of water a heavy oil sinks to the bottom and after a short time crystallises. The ether when re-crystallised from alcohol or ether forms long prismatic transparent crystals tasteless and nearly without smell in the cold.It is insoluble in water but dissolves easily in alcohol ether and carbon sulphide. It melts at 41". When dis- tilled it begins to boil at go" with decomposition into carbonic anhj-dridc ethyl sulphide and cyanogen sulphide. The ethyl sulphide ABSTRACTS OF CHEMICAL PAPERS. distils over first. The sulphocyanocarbonic ether comes over heiwecn l60"-21O0. SzcZ~l~ocya~ocarbonntes,-The alcoholic solution of the ether gives a precipitate with alcoholic potash. The potassium salt is very slightly soluble in alcohol even when hot but dissolves easily in water. Other salts are with exception of those of the alkaline metals insoluble in water.The copper salt is blue and the lead and silver salts white ; the latter turns black with formation of silver sulphide. Szc7phocyanoca;rboric Acid.-If hydrochloric acid be added to the potash salt an oil separates out which rapidly crystallises. Af t'er cool- ing the liquid is interlaced with white qeedles. The acid is easily soluble in alcohol ether and moderately soluble in warm water. It may be sublimed with water-vapour. It melts at about 43",has a sharp taste and a slight odonr resembling that of its ether. In a foot-note the author adds that he has failed to form malonic acid bv the action of chlorocarbonic ether on acetic ether neither did the compound { result from its action 011 potassium sulphite. W. R. Structure of the Derivatives of Benzene.By E. WROGLEVSKI (Deut. Chem. Ges. Ber. 1060-1061). WHENin a para-compound a third atom of hydrogen is replaced a 1,3 4,or what is the same a I 2 4 compound is formed. But met&- and ortho-compounds yield also products of this structure. Thus Reilstein and Kuhlberg have found that common monochlorobciizoic acid yie1ds.a dichlorobenzoic acid which is identical with that formed by oxidising chlorinated parachlorotoluene and that orthonitrotoluene and paranitrotoluene yield the same dinitrotoluene. PurLhcr Fittig has shown that pseudocumene may be obtained from isoxylene and from paraxylene. The derivatives of benzene behave in the same way. On brorninating the three dibromobenzenes one and the same tribroinobciizcne is formed which melts at ao, and has also been obtained fi-om dibromo-phenol and dibromaniline.c. s. Electrolysis of Potassium Phenylacetate. By T. SL AJV I IC (Deut. Chem. Ges. Ber. vii 1051-1057). WHENpotassium phenylacetate is decomposed by the galvanic current it is resolved like other salts into the base and acid ; but by the action of the oxygen and ozone the latter is oxidised to benzaldehyde and berlzoic acid which however have only an ephemeral existence being quickly burnt to water and carboii dioxide. A solution of the free acid is but slowly decomposed the same products being formed which are also produced in an alkaline solution together with two neutral solids one melting at 90"-93" arid the other at 115". By the action of potassium pernianganate on an alkaline solution benzoic acid is formed while I)y pissing ozoiie into it the odour of ORGANIC CHEMISTRY.5 9 benzaldehyne is given off and benzyl phenylacetate CsH,.CH2.C0,.CH2. CsH5,is obtained as a light-yellow liquid having a faint aromatic smell the sp. gr. 1.101 and boiling at 317"-319". c. s. Cyrnenes. By F. FITT I c A (Ann. Chem. clxxii 303). THIOCTMENE was prepared by heating together four parts of thymol and one of phosphorus pentasulphide in fine powder in a flask with inverted condenser ; much sulphuretted hydrogen was evolved and thiocymene (b. p. 230") was simultaneonsly formed ; the hydrocarbon isolated from this by fractional distillation treatment with soda-ley and repeated distillation over sodium boiled at 175" (mercury-column wholly in the vapour) and dissolved in strong sulphuric acid without evolving sulphnrous acid ;this serves as a good test of purity.Ptychotis cxmene was prepared by fractional distillation of the expressed oil of Ptychotis Aj02u$n the portion boiling at 170"-210" being heated with sodinm and treated with diluted sulphuric and potassium dichromate or with dilute permnnganate of * potassium until it would bear the test of sulphuric acid. The purified product boiled at 175"-1 StiO (mercury-column wholly in the vapour) . Camphor cymene was prepared by acting on camphor with phosphoric anhydride in quantity sufficient to forin (theoretically) cymene and metaphosplioric acid ;the yield is thus GO-SO per cent. whereas Pott'rJ method with pentasulphide of phosphorus gives only 25 to 30 per cent.; after purification as before this specimen boiled at 175" (mercury-column wholly in the vapour). Beilstein and Kupffer found the same number. These three hydrocarbons were oxidised by dropping into gently boiling red nitric acid (sp. gr. 1.5) ;in each case 71itrotoZuic acid meltling at 189" was produced hence all these are methyl-propyl-benzenes. By acting on them with bromine in presence of iodine a bromocymenc wag produced boiling at 228"-229" in each case and by oxidising this with dilute nitric acid b~oi~zonit.rotoZrcicacid melting at 204"-205" was formed. Strong colourless nitric acid converts these cymenes into drocymmm of two kinds one fluid and incapable of distillation unaltered (save in vncuo) ; the other crystalline and melting after due purification at 125"; by oxidation the fluid varieties yielded a nitroto-luic acid different from the above-mentioned body melting at 189O ;the barium salt of this acid was readily soluble in water and crystallised therefrom in starlike needles ;the acid itself was soluble in 450 parts of water and was readily soluble in alcohol of 90 per cent.and sub-limed without melting ; the solid nitrocymene yielded on oxidation a third modification of nitrotoluic acid subliming without previous melting and practically insoluble in hot and in cold water and only slightly soluble in alcohol of 90 per cent.; it is not yet decided however whether this product is homogeneous or a mixture of jsomerides.The cymene-sulphonates of barium prepared from these three sub-stances contained (C,,H,,.S0,),Ba,3H20 in each case ; the author's fbniier result with only 2H20 was ixicorvwt tlie estimation linviiig GO ABSTRACTS OF CHEMICAL PAPERS. been made in the ordinary way in watch-glasses in the air-bath whereas the pregent determinations were made by sucking air dried by sulphuric acid over the substances in a Liebig's tube in a paraffin bath at 140"-150". Normal propyl-meth yl-benzene was prepared by acting with sodium on recrystallised bromotoluene melting at 29O together with pure normal propyl bromide dissolved in ether free from water and alcohol. It boiled at 175"-17Ci0 ; gave paratoluic acid melting at 177" and terephthalic acid on oxidation by nitric and chromic acids respectively ; with nitric acid it also yielded a fluid and a solid nitrocyrnene iden- tical with the modifications obtained from the above hydrocarbons the solid melting at 125" and the liquid body giving by oxidation a nitrotoluic acid identical with that obtained from the liquid nitrocy- menes above described.The author hence concludes firstly that Ptychotis thyrnol and camphor cyrnene are identical and secondly that the hydyocarboi$ thzcs obtained is normal propyhethy 1-benzene and not isopropyl-methyl-benzene ;the different results obtained by other experimenters being explicable by this imperfect purity of the materials worked with; thus Kekul6's normal propyl-methyl-benzene was impure on account of the method of preparation of pure bromotoluene (m.p.29') not having been discovered at the time of his experiments ; and the results of Landolph and others were erroneous on account of t'he presence of hydrocarbons richer in hydrogen in the cymenes used. The thymo-cymene mercaptan obtained from thymol together with nymene by the action of phosphorus pentasulphide was converted into mercury-compound and decomposed by sulphuretted hydrogen ; it then boiled at 230"-231' and did not solidify at -20". The mercury salt melts at a temperature near 78" is very sparingly soluble in alcohol and crystallises therefrom sZowly in greenish rhombohedrons. As the camphor thiocymene gives a mercury compound crystallising from alcohol quickly in stellar groups of needles and melting at log", the author regards the two as isomeric.In like manner the silver-salt of the thymo-compound is amorphous whilst that of the camphor body becomes a mass of silky plates on standing ; moreover by oxida- tion a toluene sulphonic acid is formed different in each case; the acid from thymol is anhydrous and sparingly soluble in water; that from camphor contains Walter and readily soluble in water ; the for-mer gives an anhydrous magnesium salt the latter one containing water of crystallisation. The isomerism of these two derivatives of normal propyl methyl benzene may be represented by the formuh- ORGANIC CHEMISTRY. tj1 Camphor thio-cymene Thymo-thiocyinei ie (cymophenol or thio-(thymo-cymene cymene of Flesch). mercaptan).CH3 CH3 I I C C / \\ /\ HC 'C-SH HC CH I1 I HC CH Note by Abstractor.-The abstractor's experiments on 16 different varieties of cymene obtained from various terpenes and substances allied thereto have led him to the conclusion that there is but one cymene obtainable from all these sources and that this cymene is identical with camphor cymene. The abstractor however has uni- formly found a slightly higher boiling point (when duly corrected) than that obtained by Fittica 176.5" being the mean result obtained with specimens purified by numerous treatments with sulphuric acid and distillation over sodium. C. R.A. W. Tetraterebenthene a Solid Polymeride of Essence of Turpen-tine. By J. RIBAN(Compt. rend. Ixxix 389-3933. THE new compound is produced by the action of antimonious chloride SbC13 on terebenthene.It is an amorphous brittle solid of slightly yellow colour almost insoluble in alcohol soluble in ether carbonic sulphide benzene petroleum and essence of turpentine which on evapo-ration leaves it as a colourless varnish. Tetraterebenthene rotates the plane of polorisation to the right [a],= + 20" whilst the hydrocarbon from which it is produced has a left-handed rotation. Its deiisitg is 977 at 0'. It melts below 100" but passes into a viscous condition which renders it impossible to de- termine the point precisely. Heated to 350" it is not volatilised but above that temperature it undergoes a transformation into hydro- carbons of the same composition but of less condensation.The pro- ducts of this metamorphosis are volatile and are soluble in alcohol. Tctraterebenthene furnishes amorphous compounds with hydrochloric and hydrobromic acids ; from their composition its formula is inferred to be C4,,He1. The author points out that the depolymerisation of tetraterebenthene under the influence of a high temperature suggests the explanation of the fact that certain natural resins copal and amber for example become soluble in the usual solvents only after exposure to 350" or 400". W. A. T. BBSTRACTS OF CI-IENICAL PAPERS. The Physical Properties of Isoterebenthene. By J. R I BA N (Compt. rend. lxxix 314-317). BOILING point 175". Two specimens prepared from lzevogyrate (-39.3j terebenthene from French turpentine gave a left-handed rotation of 9.17" and 9.72" respectively.Density at 0" = a8.586; at any higher temperatuye up to 10~'it is given by the formula- D = -8586 -*0007692t -*0000002375P. Index of refraction for line U at temperatare 25" = 1.4709. Specific refractire energy fn-1 = -5611. L__ a For corresponding characters of terebene and terebenthene see this Journal p. 580 last volume W. A. T. Constitution of Phenyl-bromethyl. By E. BAND n OW s K I (Dent. Chem. Ges. Ber. vii 1016). WHEXphenyl-bromethyl is treated with zinc-dust and toluene a hydrocarbon is produced which boils at 278"-280" and contains C15H16.When this is oxidised by chromic acid mixture parabenzoyl- benzoic acid is obtained together with another substance which was not obtained in sufficient quantity for examination.The above-mentioned liydrocarbon has probably the constitution C,H,-C,H,-C,H,-CCH, and its formation confirms Radzizewski's formula for phknyl-bromethyl. T.B. Action of Heat on Phenylxylene. By P. BARBTER (Compt rend. lxxix 660-462). BESIDES the hydrocarbons C14H14,derived from the double molecule of toluene there exists a whole series of isomeric hydrocarbons resulting from the association of 1 molecule of benzene with 1 molecule of xylene thus :-CsHio + CsH -H = C,,H,,. Each of the isomeric xylenes should furnish its own hydrocarbon C14H,,. In order to get a general idea of the possible reaction the action of heat on the hydrocarbon yielded by coal-tar xylene and hen-zene was investigated.The new hydrocarbon was prepared by the action of powdered ziiic On a mixture of benzene and tolyl-chloride in the proportions of 1to 3. On warming the mixture a lively reaction occurred accompanied by a copious evolution of hydrochloric acid. The product! after repeated fractional distillation gave a liquid boiling at 270"-280" which when kept boiling on sodium till it ceased to attack the latter then again fractionated yielded a liquid boiling at 283"-286" (corrected) of density 1.01 at 0" Laving a slight alliaceous odour and exhibiting 8 blue fluorescence. By analysis it yielded the following numbers :- ORGANIC CHEMIST&I7. C14H14 C ........... 91-8 92.1 92.3 H ......... 7.9 8-0 7.7 Heated in a tube to a dull red heat for tliree minutes phenylxylene solidifies without deposition of carbon to a yellowish-white mass of an thracene mixed with phenanthrene the secondary products being a mixt)ureof xylene and benzene volatile at 14@", and giving terephtalic acid by oxidation.A slight pressure occurs in the tube the gases being hydrogen and a trace of hydrocarbon vapour. The following equation exhibits the reaction :-Triphenylbenzene. By C. ENGLER and H. E. BERTHOLD (Deut. Chem. Ges. Ber. vii 1123-1125). THIS hydrocarbon which is formed but in small quantity only. by the action of phosphorus pentoxide and other dehydrating agents on ncetophenorie is conveniently prepared by saturating this ketone with dry hydrochloric acid. On standing yeliow needles separate out niore of which are obtained by treating the liquid portion repeatedly in the same way.By recrystallising the crude product from ether pure triphenylbenzene is obtained in well defined crystals of the rhom bic system. It melts at 169"-170" boils above the boiling point of sulphur is but sparingly soluble in dilute alcohol readily in absolute alcohol ether and carbon sulphide and very freely in benzene. ~o52obronzotr~hei~yZbeizzene, C2*H1,Br,is formed by leaving a solution of the hydrocarbon and bromine in carbon sulphide to stand. It crystal-lises from alcohol in small colourless needles melting at 104O. Concen-trated nitric acid converts the hydrocarbon into a mixture of nitro-con?pounds. The formation of triphenylbenzenc is perfectly analogous to that of mesitylene from acetone :-3(CH,.CO.CsHtlf,) = C6H,(C6?&)3 + 3H-20.c. s. Mesitylene. By A. LADENBURG (Deut. Chem. Ges. Ber. vii 1133-1137). WHEN amidonitromesitylene (nitromesidine) ,which is fornicd by the action of ammonium sulphide on dinitromesitylene is treated with acetyl chloride &ro-ncetyluzesidine is obtained crystal lisin g from alcohol in silky needles which melt at 188". By act'ing on it with a mixture of nitric and sulphuric acids the dinitro-compound, C6(CH3),(NH.C2H,0)(N0,)z,is formed crystallising from hot alcohol in glisteniiig white needles melting at 275". On heatling this com- pound with fuming hydrochloric mid to 160° it is converted into the same dinitromesidine that Fittig obtained by the reduction of trinitro-mesit-j-lene.It is violently acted upon by A solution of nitrogen ABSTRACTS OF CHEMICAL PAPERS. trioxide in absolute alcohol the same dinitromesitylene being formed that is obtained directly from the hydrocarbon. Mononitromesitylene was obtained as a bye-product in tlhe formation of the dinitro-compound and by means of the diazo-reaction from nitro-mesidine. The two pro- ducts are identical; they crystallise exceedingly well melt at 42" and boil at 255". By the action of tin and hydrochlorlc acid amido-mesitylene was obtained as a liquid boiling at 226"-227" and not solidifying at -15'. Acetyl chloride converts it into the acetyl-compound crystal- lising from alcohol in glistening thin prisms melting at 213"-214" and subliming in needles.The same body is obtained by heating the base with glacial acetic acid. Fuming nitric acid converts it into the same nitro-compound that was obtained from nitromesidine and acetyl chloride. These facts show that the three hydrogen-atoms of mesity-lene have the same value and therefore confirm Baeyer's hypothesis of the formation of mesitylene from acetone. c. 5. Orthocresol and other Ortho-Compounds. By A. KEKUL~ (Deut. Chem. Ges. Ber. vii 1006-1007). THE cresol which the author and Fleischer obtained by treating cary;t- crol with phosphoric anhydride has now been proved to be identical with orthocresol but previous descriptions of this substance are erro- neous as it melts at 31"-31*5" and boils at 185"-186". Ortho-cresotic acid melts at 163"-164".As statements regarding the ortho-iodo-toluene obtained from tolui- dine do not agree this subject was investigated with the following results. This iodotoluene boils at 205"-205.5" (211" with stem in vapour) and when oxidised it yieids an orthoiodobenzoic acid which melts at 156"-157" and yields salicylic acid on fusion with potash. Orthoiodotoluene can be made to yield orthotoluic acid melting at 102*5". T. B. Nitrophenol and Dioxybenzene. By H. SA L K ow s K I (Deut. Chem. Ges. Ber. vii 1008-1013). THE methyl-ether of nitrophenol melting at 114" was reduced by tin and hydrochloric acid the paranisidine thus obtained being then converted into paradiazanisol by nitrous acid. When the sulphate of this compound is heated with water hydroquinone is produced thus confirming Petersen's view that hydroquinone is a para compound.The paranisidine mentioned above forms colourless rhombic tables which have a peculiar smell resernhling that of honey Paranisidine acquires a dark colour on exposure to light boils at 245"-246" solidifies at 51°-52" and is but slightly volatile with water-vapour. The suZphate and rzitrate of para-diazanisol form colourless crystals which become brown on keeping and these salts are acted on very slowly by water unless a temperature of 140" is employed the hydro- quinone which is formed under these circumstarices being nlwa~s ORGANIC CHEMISTRY. 65 accompanied by a brown viscid substance which is probably a methyl- ether of hydroquinone.In order to prove the relation between paranisidine and anisic acid experiments were made the result of which is as follows. Para-nisidine unites with carbon disulphide and when an alcoholic solution of the product is treated with iodine nnkoZ-suZplzurea [c6H4(OCH,) NHzCS] is precipitated. This substance forms silky leaflets which are slightly soluble in alcohol and melt at 18.5". The addition of water to the alcoholic mother-liquor which has yielded anisol-sulphurea causes the separation of a dark coloured oil containing iodine. When this was distilled with water-vapour a small proportion of a light-coloured slightly volatile oil was obtained which boiled at about 270" and appeared to contain C6H,(OCH3)NcS. When the original dark oil is heated with copper-powder the odour of the iso- nitril becomes apparent but soon gives place to that of bitter almond oil.Although the nitril was obtained only in an impure state by rectification its treatment with alcoholic potash led to the production of a brownish product which in one case was found to yield crystals of anisic acid. Attempts were made to convert the bromanisol which is obtained by the action of alkalis on bromanisic acid into a methyl-benzoic acid but the results were not satisfactory. The bromanisic acid obtained by brominating anisic acid under water melts at 213"-214" and yields only a small proportion of bromanisol. T.B. Derivatives of Secondary Phenyl-ethyl Alcohol (Acetophe- nonic Alcohol) and other Ketonic Alcohols.By C. E NGL E R. and H. BETHGE (Deut. Chem. Ges. Ber. Vii 1125-1129). WHENhydrobromic acid gas is passed into cold secondary phenyl- ethyl alcohol CsH5.CH(OH) CH3,obtained from acetophcnone a bro- mide is formed which is identical with that produced by the direct action of bromine on ethyl-benzene. Radziszewsky found that when liquid bromine is added to the hydrocarbon at 140"-150" a large quantity of styrolene dibromide is always formed. This can be almost entirely avoided by following Berthelot's method and passing bromine vapour into the boiling hydrocarbon. The secondary chloride is ob-tained by passing hydrochloric acid into the alcollol as a liquid boiling with some decomposition at about 194". By acting with sodium on one of these compounds a mixture of products is formed containing dipheny Z-dinzethy Zet72 aize C,H ( CH3) ( C6H5),.It clay s tallise8 from ether in needles melting at 123.5". When the secondary phenyZ-buty Z alcohol C6H,.CH( OH). C3H, is treated with hydrochloric acid the chloride is obtained as a liquid which is decomposed by heatiug. ; and Linnemann's benzhydrol (C6H5),CH.OH yields a chloride which sometimes solidifies at 140",and sometimes remains liquid. On heating it hydrochloric acid is given off and tctraphenyl-ethene is formed. c. s. VOL. XXVIII. F ABSTRACTS OF CHEMTCAL PAPERS. Derivatives of Phloretin. By H. SCHIFF (Ann. Chem. 356-360). PURE phloretin is readily obtained by heating a solution of 20 grams of phloriain in 140 grams of water nearly to the boiling point adding an almost boiling mixture of 10 grams of sulphuric acid and 40 grams of water and keeping the liquid ,at this temperature.After a few minutes a white magma of phloretin separates out which has only to be mashed with water on the filter-pump. To resolve it into phloro- glucin and phloretic acid 20 grams are boiled with 1.50 grams of potash solution of sp. gr. 1.20 for three hours. The solution is then exactly neutralised; then a very slight excess of acid sodium carbonate is added and the phloroglucin extracted by shaking four times with ether. After acidifying with sulphuric acid the phloretic acid is isolated in tihe same way. The ph€oroglncin thus obtained is quite pure but the phloretic acid always contains a little phloroglucin.When phloroglucin is heated with phosphorus oxychloride for some hours it is converted into yldoroglucide C12HloOs, which after distilling off t'he excess of oxychloride and washing the residue with water alcohol and ether is obtained in fine greasy scales. On heating yhlo- retic acid with the oxychloride to 60" no compound resembling a tannin is formed but triphloretide C27H2607! which is insoluble in water and hot alcohol and crystallises from glacial acetic acid in small thin white plates. Quinic acid gives with phosphorus oxychloride an amorphous anhy- dride and meconic acid yields carbon dioxide and a derivative of comenic acid. By the same reagent paraoxybenzoic acid is converted into an isorneride of tetrasalicylide but citric acid yields a compound having the properties of a tannic acid.This body is not directly derived from citric acid but is perhaps a product of condensation of acetone. c. s. Synthesis of Anthraquinone Derivatives from Benzene De- rivatives. By A. BAEYER and H. CAR@(Deut. Chem. Ges. Ber. vii 968-976). THEaction of phthalic acid (1mol.) on the phenols is to form either (with 2 mols.) a phthalein or (with 1 mol.) an antlwaquinone deriva-tive. The reactions occur at an elevated temperature with or without the aid of dehydrating substances. If a moderate use be made of these agents phthaleins are produced whilst if they are more largely resorted to anthraquinones result. The phenols are to be divided however according to their behaviour into two classes thus resorcin and pyro- gallol yield phthaleins even without the aid of sulphuric acid but it has not hitherto been possible to prepare anthraquinone from them.Phenol hydroquinone and pyrocatechin on the other hand do not act upon phthalic acid unless sulphuric acid is present but these yield according to circumstances either phtlialeins or anthraquinones. Phenol and Phthalic Acid.-When phenol is gentiy warmed with phthalic anhydride and sulphuric acid the mixture assumes a brownish ORGANIC CHEMISTRY. 67 yellow colour from the formation of phe~Lol-~7LthnZeirt. On adding more sulphuric acid phenolphthalein-sulphonic acid is produced and if the heating be continued and the temperature raised the colour changes finally fo brownish-yellow.The addition of water at this stage causes the precipitation of yellow or brownish flocculi of ozyantl~ra~?~inone. The formation of the phthalein does not appear to be essential to the production of oxyanthraquinone since if phenol bc added to a suffi-ciently hot mixture of phthalic acid with sulphuric acid the anthra- quinone is obtained without the coloration due to the phthalein being observed ; and as phenolsulphonic acid phenol-disulphonic acid and oxysulphobenzide give a similar result there is reason to suppose that the phenol-phthaiein is converted by heating into phthalic acid and a sulpho-acid of pheiiol which substances at a higher temperakuro gradually react to form oxyanthraquinone CBH4O3 + 2CGHGO C21jH1404+ OH,; C2IjH1404 + 4S04HZ = C8H4O3 + 'LCGHGSZO + SOH ; CBH403 + CGHGS207 + OH = CI~H~O~ + 2SOaHZ.Salicylic acid anisol and even anisic acid behave like phenol ; with salicylic acid particularly when small quantities are employed the reaction takes place with greater regularity than with phenol. The oxyanthraquinone from phenol is a mixture of two isomerides- oxya.i~thmpui~~one, identical with that obtained by Grmbe and Lieber- mann and a new body erytlLroxZlniztl~rapuin,one.They may be separated by taking advantage of the fact that when the former is boiled with water and barium carbonate it forms a soluble barium derivative whereas the latter is without action on the carbonate. Erythroxyanthraquinone crystallises from alcohol in groups of pome-granate-yellow needles which are more soluble in hot than in cold alcohol.It melts at 173"-180" but sublimes already at 150" con-densing in long reddish-yellow needles of the colour of alizarin ; when sublimed it crystallises in very fine needles. Oxyanthraquinone crystallises from alcohol in single sulphur-y ellow needles or plates which aye scarcely more soluble in hot than in cold alcohol. It melts at 268"-271" and sublimes more difficultly in yellow plates. Erythroxyanthraquinone is almost insoluble in dilute ammonia and only slightly soluble in concentrated ammonia oxyanthraquinone being easily soluble in ammonia. The former yields with baryta or lime-water a dark red almost insoluble lake which is decomposed by car-bonic acid ; the latter is easily soluble in barytn and lime-water for&- in= a reddish-yellow solution.The absorption-spectrum of a solution of erythroxy anthraquinone in concentrated sulphuric acid exhibits a narrow band in the green which does not appear in that of the isomeric body. Both yield ordinary alizarin when fused with pot'assium hydrate ; the erythroxyanthraquinone is however less readily acted upon. Pyrocafechirt and Plzthnlic Acid. -When pyrocatechin is gently heated with phthalic anhydride and sulphuric acid the corresponding phthalein is apparently produced ; but if the temperature be raised to 140° the colour changes from rose-red to brown and after a time water precipitates ;t brownish-black mass. The residue from the alcoholic F'd ABSTRACTS OF CHEMICAL PAPERS.extract of this mass yields alizarin on sublimation. Guajncol behaves similarly. Protocatechuic acid also yields traces of alizarin but is in great part decomposed in other ways. Hydropinone awd Phthalic Acid.-The formation of quinizarin takes place not only with these materials (this Journal [2] xi l234) but according to the authors with all substances which when heated with sulphuric acid yield either hydroquinone or its sulpho-derivatives. Thus it is formed from quinic acid which is converted into a-hydro- quinone-disulphonic acid on heating with sulphuric acid ; and from potassium thiochronate which on heating with sulphuric acid fur-nishes 6-hydroquinonedisulphonicacid (Gmbe) . With regard to the constitution of the four anthraquinone derivatives oxyanthraquinone erythroxyanthraquinone alizarin and quinizarin which can thus be formed from phthalic acid and phenols since all of them correspond with the same anthracene it necessarily follows that the “ entry of the phthalic acid into the benzene group” takes place in the same manner in every case and t.he difference in constitution can therefore be due only to a difference in the relative posit,ion of the hydroxyl groups.It may be regarded as certain that in the dioxy- derivatives the hydroxyls are in the same relative position as in the phenols from which they are derived so that the two hydroxyls in alizarin are in the same relative position as in pyrocatechin and those in quinizarin in the same relative position as in hydroquinone.More-over the. two hydroxyls must be in the same benzene group. Two questions remain however to be settled concerning the constitution of anthraquinone namely the nature of the group C,O which unites the two benzene groups and the position of the two carbon atoms of this group in the one benzene group their position in the other being suffi-ciently determined by the formation of phthalic acid from alizarin and the synthesis of alizarin from phthalic acid. The former question need not here enter into consideration ; with regard to the latter Behr and van Dorp (this JourmaZ [2] xii 470) have shown that the pair of carbon atoms which unite the two groups cannot be joined in the para-position and the formation of two isomeric oxyanthraquinones confirms this conclusion.Whether however the position of the CzO group is 1 2 or 1 3 must remain at present undecided although the easy and perfect resolution of anthraquinone into benzoic acid on heating with potassium hydrate solution is in favour of the assumption of the 1 2 position. In the former case the forrnulze to be assigned to alizarin and quinizarin are ORGANIC CHEMISTRY. In the latter OH H c-c -c-c C,H,. C2040nc// 'c=c )COH. TT H a H. E. A. Synthesis of Purpurin. By F. DE LALANDE (Compt. rend. lxxix 669). ATJZARIN, perfectly free from purpurin was submitted to the action of oxidising agents whereby purpurin was obtained. 1 part of dry pulverised alizarin was mixed with 8 or 10 of sul-phuric acid and 1 part of arsenic acid or manganese peroxide added the whole heated to 15O0-16Oo till one drop of the mixture thrown into dilute caustic soda gave the red coloration of purpurin.The whole was then poured into a large bulk of water the precipitate exhaust,ed with cold water dissolved in a saturated solution of alum and then treated with an acid. The solution thus obtained deposits a>bundant ffocculi of purpurin. The yield is pretty large the chief cause of loss being the production (especially with arsenic acid) of a colouring matter soluble in water to a yellowish-brown and in alkalis to a red solution. The opinion which the author held that purpurin was not as generally supposed trioxyanthraquinone and that the atom of oxygen by which it differs from alizarin not belonging t.0 a hydroxyl group might be added by direct oxidation is thus substantiated.C. H. P. Derivatives of Benzyl-toluene and Tolyl-phenyl Ketone. By H. PLASCUDA (Deut. Chem. Ges. Ber. vii 982-and ZINCKE 986). ZINCKE'S benzyl-toluene is believed to cont,ain two modifications a-and 6- the former yielding a-tolyl-phenyl-ketone melting at 54"'together with benzoyl-benzoic acid melting at 194"; while the latter yields B-ben- zoyl-benzoic acid which melts at 85"-87" when hydrated or at 12'7'-128" when anhydrous. Treatment of a-tolyl-phenyl ketone with fuming nitric acid led to the production of a substancc containing C,4Hll(N0,)0 and identical with the similarly constituted substance which Milne obtained from benzyl-toluene.The further nitration of this or the direct nitration of a-tolyl-phenyl ketone with nitro-sul- phuric acid led to the formation of a trinitrotolyl-phenyl ketone which separates from alcohol or acetic acid in small yellowish pris-matic crystals melting at 165" and which do not undergo sublimation without change. When dinitro-bcnzyl-toluene is oxidised a corre-sponding ketone is obtained the nitration of wliicli gives rise to a diizitro-tolyl-pher~lketone C1PHIO(N02)20, melting at 126"-127" and ABSTRACTS OF CHEilIICAL PAPERS. forming thick yellowish needles which cannot be sublimed without decomposition. A tririitrotolyl-pheriyl ketone identical with that described above is obtained by the further nitration of the dinitro- ketone last described.These results indicate that mononitrotolyl-phenyl ketone contains its nitro-group in the CGHj,whereas the trinitrotolyl-phenyl ketone contains two nitro-groups in the CsH5,and one in the CsH4,while it is at the same time probable that dinitro-tolyl-phenyl ketone contains one nitro group united with each benzene nucleus. This view is con- firmed by the fact that the slow oxidation of dinitro-tolyl-phenyl ketone gives rise to para-nitrobenzoic acid and dinitrobenzoyl- benzoic acid. This latter acid separates from water in silky leaflets or from alcohol in yellowish needles melting at 211"-212". The oxidation of the mononitro-ketone was less satisfactory bcnzoic acid being produced together with a mono-nitrobenzoic acid melting at 140° and yielding a barium salt containing four molecules of water ; and this result pro- bably indicates that the nitro-ketone in question contains its NOz in the meta-position.When the potassium salt of the crystalline sulpho-acid which Milne obtained by treating benzyl-toluene with sulphuric acid is fused with potash a mixture of phenols is obtained together with paroxybenzoic acid and a small proportion of a higher acid perhaps containing C14H8( OH),Os. Probably Milne's crystalline sulpho-acid is derived from a-benzyl-toluene the amorphous sulpho-acid being most likely a mixture. All endeavours to obtain derivatives which are certainly produced from P-benzyl-toluene have failed although during the nitration of benzyl-toluene a second dinitro-derivative C14H,,(N0,)2,is produced in a small proportion.It melts at 100° and forms radial tufts of needles. This substance is probably derived from a-benzyl-toluene as its oxida-tion yields resinous products similar to those obtained by the oxida- tion of the ,@-ketone. T.3. Amido-Derivatives of Benzene. By H. SA J K o w sK I (Ann. Chem. clxxiii 39-71}. THEresearch on chryanisic acid has shown that the ethers of nitrated phenols behave towards ammonia like true saline ethers being readily converted into amido-compounds. This is the case even if they contain the carboxyl-group or are oxy-acids for when in such a compound the hydrogen of the hydroxyl as well as that of the carboxyl is replaced by an alcohol-radical that which is combined wit8h the pheiiol- oxygen is much more readily eliminated than the other.Further proofs of this are found in the following reactions. While dinitranisic acid is readily obtained by nitrating the mono- nitro-compound the corresponding dinitrometliylsalicylic acid is 110t produced in that way. When mononitromethylsalicylic acid pre-pared by boiling methylsalicylic acid with five times its weight of nitric acid of specific gravity 1.4 for a fcw minut'es is heated longcr with the acid oiily a little dinitrosalicylic acid ad picric acid are ORGANIC CHEMISTRY. formed while on boiling the mononitro-acid with three parts of fuming nitric acia for half an hour itl is hardly changed only a very small quantity of a more highly nitrated product being formed.To obtain hhe dinitro-compound oil of winter-green is dissolved in a mixture of five parts of fuming nitric and five parts of fuming sulphuric acids. The methyZ-di:nitrosaZicyZate C6Hz(N02)2(OH)C02.CHs, which by this method was first prepared by Cahours crystallises from alcohol in slightly colouyed plates melting at 127"-128". On heating its silver- salt with ethyl iodide the methyl-ethyl ether C6H2(N0,)z(OC,H5)C0,. CH, is formed which crystallises from a dilute alcoholic solution in thick and very brilliant monoclinic prisms with terminal faces con- sisting of two different augite-pairs and melting at 80". a b c = 0.3517 1 0.2535. Angle a c = 71" 13'. When this compound is heated with aqueous ammonia on a water-bath it first melts and then solidifies again being chiefly converted into methyl dinitranthranilate while the ammoiiiacal solution contains dinitranthranilic acid which on the addition of hydrochloric acid is obtained as a deep yellow precipitate crystallising from alcohol in scales resembling chrysanisic acid and melting at 256".The forma- tion of this compound is explained by the following equation :-C,H,( NO,),( OC2HS)C02CHz +2(NH,-OH) =C,H,( NOz),(NHz)COPH, + CH40 + CZH60 + HZO. Ammonium diuitramtlwad ate C,H (NOz),(NH,) .CO,NJ& + HZO forms yellow or brownish long needles. The methyl-ether which as already mentioned forms the chief product crystallises from hot alcohol in narrow yellow plates or feathery needles melting at 165". It is hardly attacked by boiling sodium carbonate but on boiling it with soda-lye ammonia is evolved and the dark-red solution changes into orange.When now hydrochloric acid is added a precipitate of di4rosaZicylie acid is obtained crystallising from hot water in colour- less slender needles melting at 165" ; its aqueous solution gives with ferric,chloride a red colour. When hydrochloric acid is passed into an alcoholic solution of dini- tranthranilic acid the ethyl-ether C6HZ(NOz),(NHz) CO,C,H is formed which is sparingly soluble in boiling alcohol and crystallises in small yellow plates melting at 135". Dimethy Z cli~itroscd icy1ate C6HZ (NO,) (0CH,) C0zCH3,which was obtained by t,he action of methyl iodide on the above silver-salt is isomorphons with the corresponding ethyl-compound and melts at Ammonia decomposes it like the ethyl-ether.6CLO. J C6H2(N02)z( ZtliyZ ~Ziizitrosnlic~late OH) CO2.CzH5,-which was pre-pared by the action of hydroclzloric acid on an alcoholic solution of thc acid forms small colourless plates melting at 98"-99". The ammo- nium-salt C6Hz(N0z)z(ONHI,).C02.C2H5,crystallises in long golden needles. By decomposing it with a silver-solution the corresponding silver-salt cannot be obtained in a pui*e state. To prcpare it silver oxide :nid tlie ct hgl-ether both ver~finely divictc~l,are lieated with t~ ABSTRACTS OF CHEMICAL PAPERS. large quantity of water first very gently and then gradually nearly to the boiling point. On cooling the salt crystallises in slender orange needles or yellow spherules but only if the solution be not too dilute or else the liquid.solidifies into a gelatinous mass. When this salt is treated with methyl iodide the compound C,Hz(NOz)2( OCH,) C02CzH5 is formed crystallising from alcohol in large thin six-sided plates melting at 47". The corresponding diethyl ether C6Hz(NOs)z(0CzH~) C02C2H5,separates like the preceding compound from a concentrat'ed solution as an oil and from a more dilute one in flat prismatic crystals. The results show that the group OCH3or OCzH5,which is linked to the benzene-nucleus is much more easily attacked than if combined with GO and further if the latter be acted on no amido-compound is formed but an ammonium-salt. When mononitranisic acid is treated with ammonia a complete reaction takes place only at 140"-160".The n~tropnrn7~aidobenzoic acid thus formed is identical with Griess' nitramidodracrylic acid. On heating it with tin and hydrochloric acid it is converted into @-dianzido-beaaoic acid yielding by dry distillation orthocZia~~idobep~zene, melting at 99". By treating nitroparamidobenzoic acid with a hot alcoholic solution of nitrous acid a mixture of compounds was formed containing monocldorobenzoic acid the chlorine being derived from the calcium chloride which was used for drying the nitrous fumes. But when nitroparamidobenzoic acid is introduced into a cold solution of nitrous acid in absolute alcohol it is gradually changed into small light-yellow plates of nitrodiaxobenzoic acid C,H,(NO,),N,CO,.On boiling this compound with alcohol common or metanitrobenzoic acid is formed. If the meta-compounds belong really to the I. 3 series it follows from the above facts that the diamidobenzene melting at 99" is an ortho- or 1.2 compound. Further it is easily seen that in this case the three diamidobenzoic acids of Griess possess the following constitution :-C02H COzH COzH Besides these three three others can exist :-NH C0,H Of these the first and second are known the former being obtained from the common dinitrobenzoic acid the other from the dinitrobenzoic acid produced by oxidising dinitrotoluene. Both yield the diamido- benzene melting at 63" which must also be obtained from the last yet unknown acid. ORGANIC CHEMISTRY.Aqueous ammonia acts but slowly on anisic acid even at 250"-285" some phenol being formed and a small quantity of an acid which appears to be paraoxybenzoic. Methylosybenzoic acid yields under the same conditions some oxybenzoic acid and methylsalicylic acid is principally converted into salicylic acid. Decomposition of some Diazo-compounds by Water. By E. WROBLEVSKI (Deut. Chem. Ges. Rer. vii 1061-1062). THEauthor has formerly shown that by decomposing the diazo-com- pounds of several substituted toluenes no cresols are formed but sub-stituted hydrocarbons. The same is the case with some other deri- vatives of benzene. Thus the dibromaniline which is obtained by brominating acetanilide yields a dibrornobenzene identical with that which Meyer and Stuber obtained while the dibromaniline from the solid dibromobenzene yields dibromophenol and chlorinated para-tohidine is converted into metachlorotoluene.The relative position of the side-chains appears to be the cause of this difference in the reaction. c. s. Synthesis of Aromatic Acids. By V. v. BICHTER (Deut. Chem. Ges. Ber. 1145-1147). WHENnitrodibromobenzene is heated with potassium cyanide and alcohol to 120'-140" and the product boiled with alcoholic potash a new dibromobemzoic acid is obtained crystnllising from hot water in pearly flat needles melting at 151". (C,H,Br,.CO,),Ba + 6Hz0 is readily soluble in water and forms warty crystals consisting of microscopic needles ; (C6H3Br. C02),Ca, -+ 3H,O forms indistinct crystals.c. s. Oxidation of Orthotoluic Acid to Phthalic Acid. By W. WE~TH (Deut. Chem. Ges. Ber. vii 1051-1060). WHILEin an acid solution orthotoluic acid is completely burnt to carbon dioxide and wafer it is oxidised to phthalic acid by adding potassium permanganate to an alkaline solution. c. s. Dibenzylacetic Acid and a New Synthesis of Homotoluic Acid. By LY D IA SE s E M A N N (Inaugural- Dissertation. Zurich 1874). WHEN the yellow solid product which is obt,ained by heating acetic ether with sodium gradually to 160° is mixed with benzyl chloyide and then heated to 200" in a flask which is connect'ed with a reversed condenser the ethyl ethers of bew:yZncetic (hydrocinnamic) acid and c7;beuzylacetic acid are formed according to the following formulae :- 74 ABSTRACTS OF CHEMICAL PAPERS.CH,Na CH,.CH,.C,H, I + ClCHpCtjH = I + NaCl C0.0C,H CO.OC2H CHNa CH( (332. CsH,), I + 2( ClCH,.C6H,) = I + 2NaCl. C0.0C2H5 co.0C,H Ethyl benzylacetate is a limpid liquid boiling at 245"-250" and having a fruity smell. The acid contained in it is identical with that described under the names homotoluic hydrocinnamic and phenyl- propionic acid. Ethyl dibenzylacetate forms a golden-yellow fragrant oil which boils above 300". On saponifying it and decomposing the salt with hydro- chloric acid the free acid was obtained which crystallises from petro- leum-naphtha in quadratic prisms melting at 85"; it is insoluble in water but dissolves readily in alcohol and ether. T'he barium salt [(CsH5.CH2)2CH.C02]zBa is a dense white precipitate which is in- soluble in cold water sparingly in boiling water and crystallises from it in fine white needles.The calcium salt is a similar precipitate con- taining one molecule of water and the 'silver-salt forms a flocculent and perfectly insoluble precipitate. An aqueous solution of the am-monium-salt containing 10 per cent. gave the following characteristic precipitates :-In the cold. On heating. Ferric chloride. ...... Pale-yellow Ochre- yello w. Cobalt nitrate. ...,.. . Reddish-violet Dark-violet. Manganese chloride .. White Bro wnish-yellow. Nickel sulphate ...... White Apple-green ; on cool-ing fine needles sepa- rated out. Copper nitrate. .... . .. Light- blue Dark-green. By the action of phosphorus pentachloride on the acid no chloride but apparently a substitution-product was obtained.When barium dibenzylacetate is heated with soda-lime some benzene is formed and dibenzyZnzelhane CH2( CH2.CsH5), an oily liquid boiling above 300". On adding it in small quantities to warm fuming nitric acid LZiiLitro-dibenzyZmethane CH2( CHzC6KN02)2 is formed separating from a solution in petroleum-naphtha as a pasty mass which by washing with carbon sulphide is converted into an amorphous powder melting at 186". The formation of the above two acids is quite analogous to Frank-land and Duppa's synthesis of butyric and diethylacetic acid &c. But while these chemists observed at the same time the formation of earbacetonc-carbonic ethers bcnzyl chloride does not forni similar com- pounds.This shows that the latter compound which belongs at the same time to the aromatic and to the fatty group does not behave exactly as the haloid ethers of the ethyl-series. c. s. ORGANIC CHEMISTRY. a-and P-Benzoyl-benzoic Acid. By H. PLA s c u D A (Deut. Chem. Ges. Ber. vii 986-988). THEmost characteristic properties of the 8-benzoyl-benzoic acid origin- ally described by the author and Zincke are detailed this being followed by a similar account of some derivat'ives of a-benzoyl-benzoic acid. p-Benzoyl-benzoic acid C,1H,o03+ H20melts at 85O-87' when air- dried or at 127"-128" when dried at loo" and it cannot be sublimed without change. The zinc sdt (C,4H90,)zZn+ 2Hz0 melts under hot water or if dry it melts at 140".The methyZ-ether forms rhombic prisms melting at 52" while the ethykether melts at 58" and forms rhombohedrons which gradually grow into long prisms. P-benzoyl benzoic acid yields amorphous product,s on nitration. Derivatives of a-berzzoyl-bewzoic acid. The potassium salt forms tufts of fine needles which are less soluble than the corresponding /%salt. The nrnrnoriiuin salt forms long thick needles which are not very soluble in water. The solution easily loses ammonia and becomes acid. The copper snlf was obtained as a green crystalline precipitate soluble in hot water. The methyZ-ether forms large shining leaflets which melt at 107" and are less soluble than the a-ether. The etlyZ-otlhev forms tabular monoclinic cr stals melting at 52".Water sepa- rates it in shining scales from its $coliolic solution. The nitration of a-benzoyl-benzoic acid led to the formation of a dini- trobenzoyl-benzoic acid which is isomeric with that obtained by the oxida- tion of dinitro- benzyl-toluene. It separates from water in shining leaf- lets which melt at 240" and are easily soluble in alcohol or acetic acid but less soluble in water. The unzrnowium salt forms shining easily soluble scales while the copper snZt separates fi-om hot water in shin- ing bluish needles. The xir~csalt is amorphous and the barium saZt [C14Hi03(N02)2]2Ba + H,O forms nodular tuft's of needles which are very slightly soluble in water. The cccZciuna saZt cr-j-stallises in shining white leaflets containing two molecules of water this being driven off at 120".T.B. Catechuic and Catechutannic Acids. By J. L~WE (Zeitschr. Anal. Chem. 1874 113-124). THE author assigns the formula C,,H,iO7 to pure catechuic acid ; this acid he has also obtained by less prolonged drying in combination with one molecule of water forming the substance C,,H,,O,. If either of these acids be slowly heated until it rneIts (160°-165") it undergoes partial decomposition producing a substance which dis- solves in water with a yellow colour arid shows the characteristic react,ionof catechutannic acid. By comparing this acid and its lcad salt with the acid and its lead salt obtained directly from catechu the author shows that this lattey is really catcdiutnnnic acid and he assigns to it the formula C,,H,,O,,.M. M. P. 31. ABSTRACTS OF CHEMICAL PAPERS. Isomeric Sulphocinnamie Acids. By W. RUDNET (Ann. Chem. clxxii 8-20). ONE part of cinnamic acid purified by crystallisatiom from ligroi'n was gradually added to 3.5 parts of fuming sulphuric acid (containing 20 per cent. of SO,) the products being then diluted and treated with sufficient barium carbonate to remove the free sulphuric acid. The mixed sulpho-acids thus obtained were separated by a fractional crystallisation of their acid barium salts the para-salt forming long needles and the meta-salt forming nodules. Para-su~~oci?zi~anic acid C6H4(S0,H) CH.COOH + 5H20 forms colourless monoclinic prisms which effloresce over sulphuric acid with loss of 4H20 a temperature of 100" being required for the removal of the-last molecule.The- crystals undergo aqueous fusion at looo and are readily soluble in alcohol but less soluble in ether. Para-sulpho-cinnamic acid readily converts alcohol into the acid ether which forms long needles but in presence of water a neutral ether is formed. The neutraZ barium saZt C9H6BaS05+ H20 forms crystalline crusts which are but slightly soiuble in water. The acid barium salt (C9E17S05)2Ba+ 3H20 separates from water in long colourless needles. The neutral calcium salt C~H~SO&L+ aH20 forms small crystals very slightly soluble in water. When its solution is treated with hydrochloric acid and alcohol the acid salt separates in needles. The nezctrab potassiwm salt CgH6K2S05 + 12H20 is not hygroscopic and was obtained in nodules.When treated with hydrochloric acid it yields needles of the acid salt. The acid copper sa& (C,H7S05)PC~ + 6H20 forms greenish prisms easily soluble in hot water. The Yzeutral silver salt was obtained in large anhydrous prisms and the lead salt in long hydrated needles. When para-sulphocinnamic acid is fused with potash paroxybenzoic acid is produced and when it is oxidised by chromic acid mixture para-sulphobenzoic acid is formed. MetnsuZphocin7zamic acid crystallises with 3H,O forming nodules consisting of small prisms which effloresce easily over sulphuric acid and decompose at 80" The .rzeutyal barium saZt C,H,BaSO + 1+H,O is more soluble than the para-salt and requires a temperature of 180' for perfect dehydration.Acid 71ariun2 salt (CgH7S05),Ba+ 3H,O. Nodules which are tolerably soluble in boiling water. NezctraZ caZciurn saZt C9H6CaSo5+ 1$H20. Crystalline and easily soluble in water. SiZver salt C9H6Ag2S05.Amorphous and slightly soluble in water. The potassium salt is very soluble in water or alcohol and separates in the crystalline form from the concentrated alcoholic solution. The fusion of meta-sulphocinnamic acid with potash leads to the formation of metoxybenxoic acid but its oxidation by chromic acid led to unsatis- factory results. Aldehyde and acetic acid were among the products in this case. T.R. ORGANIC CHEMISTRY. ParamidorthotoluenesulphonicAcid. By F. JE N s sEN (Ann. Chem. clxxii 230-239).WHENsulphur trioxide is passed into a mixture of paranitrotoluene and pure sulphuric acid until the mass dissolves completely in water paraizitrorthotol uenesdprphorh acid is formed crystallising from water in yellow well defined rhombic prisms which begin to soften at 130" and melt at 133.5" ; on cooling the anhydrous acid solidifies to fine needles melting at 130". It is readily soluble in water alcohol ether and chloroform.-[ C7H6(NOa)S03],Ba + 3H20,is sparingly soluble in water and crystallises in long needles. [C7H6(NO2)SO3]2Pb+ 3H20 forms yellowish needles and the potassium and ammonium salts crys- tallise in long slender needles which may be heated to 190" without loss of weight. C7H,(N0,)S0,C1 crystallises from ether in rhombic plates melting between 43" and 44.5".C7H,(N02) SO,.NH is sparin@y soluble in alcohol and ether readily in hot water and very freely in concentrated ammonia it forms yellowish long and very brittle needles melting at 186". By passing hydrogen sulphide into an am- moniacal solution of the nitro-acid paranaidorthotoluenesu~/1onicacid C7H6(NH,)S03H + H,O is produced crystallising in hard colourless rhombohedrons and not in yellowish flat prisms as Beilstein and Kuhl- berg have stated. It dissolves but sparingly in hot water and is in- soluble in alcohol and ether. Its salts are very soluble and do not crystallise well. By adding bromine to the boiling soldtion of the acid only the monobrominated acid is formed even if the bromine is in excess. Brornop~ramidorthotoluerzesu~ho.lzic acid C7H5Br(NH,)SO3H is insoluble in alcohol and ether sparingly soluble in hot water but more freely in hydrochloric and hydrobromic acids.C7H3Br(NH2)S03K + H,O forms compact hard prisms. [C7H3BrNH,S0,]2Ba + ~HzO crystallises from water in compact prisms and from alcohol in needles. The lead-salt forms very soluble plates and the silver-salt long white needles which dissolve sparingly in cold and more freely in hot water. The diazo-compound of the amido-acid forms yellow or brown needles and yields when boiled with absolute alcohol under pressure ortho-tolueneszclphonic acid which forms a syrupy mass while Terry (Ann. Chem. Pharm. clxix 27) describes it as a laminated crystalline mass. (C7H7S03)2Ba+ H,O is readily soluble in alcohol and water and form small glistening plates.(C7H,S0,),Pb $. H,O crystallises in warty groups consisting of small needles. The chloride of the acid is an oil yielding with ammonia the amide crystallising from water in needles melting at 148O and from ether-alcohol in compact monoclinic prisms melting at 155" which agrees with the melting points found by Wolkow and by Hiibner and Terry. On heating the diazo-corn- pound with water pilrac~esoZ0i~t7zo~z~~hoi~ic acid C7H6(OH) X03H -I-5H20 is obtained crystallising from water in long white needles melting at 98.5" ; over sulphuric acid they lose all the water and melt then at 187"-188". None of its salts could be obtained in the crystal- line state ; the solution of the barium salts gives with ferric chloride a violet colour which disappears on addins alcohol.When the diazo- compound is decomposed with hydrobromic acid parab.1.ornorthotoZue~ze-sulphonic acid is obtained crystallising in fine needles. ABSTRACTS OF CHEMICAL PAPERS. (C7H6RrSO2),Ba+ H20is sparingly soluble in cold more freelyk boiling water and forms either small plates or crusts which look quite amorphous. (C5H6BrS03),Pb+ 3H,O is readily soluble in alcohol and water and crystallises in needles. The eldoride crystallises from ether in plates or prisms melting at 30"-35". The arnide crystallises fkom water in needles melting at 165-5" and from ether-alcohol in compact prisms melting at 167"-168". This acid is identical witlh the P-parabromotoluenesulphonic acid of Hiibner and Post.By the action of hydrochloric acid on the diazo-compound parncldorortho-loluenssulpl~onicacid was obtained which appears to be crystalline and yields a barium salt. (C,H,ClSO,),Ba + H20 crystallising in small plates. This acid is probably identical with Hiibner and Post's B-para- chiortoluenesulphonic acid. c. s. Paramido-metatoluenesulphonicAcid. By H. TON PECHMANN (Ann. Chem. clxxiii 195-218). THISacid is formed together with ihe ortho-acid and a disulpho-acid, by heating paratoluidine with twice its weight of fuming sulphuric acid to 180" until sulphur dioxide is given off the chief product being then the meta-acid ; but if the heat be continued the quantity of the others increases. Thus on heating 5 grams of the pure meta-acid with 10 grams of fuming sulphuric acid for twenty minutes to 180"-200" 3 grams of the ortho-acid and about 1gram of the disulpho-acid werc formed.On the other hand on treating pure ortho-acid in the samc way only 1gram was changed int'o meta-acid the latter being less stable than the other. The acids are separated by diluting the product with twice its weight of water and distilling with an excess of baryta-water to remove free toluidine. From the residue the barium is removed by sulphuric acid and the free sulpho-acids are separated by crystallisa-tion the ortho-acid being the least soluble in vater and alcohol and the disulpho-acid being very soluble. Pfl,ram,~do-rnetatoZLe~~~~~~~~orLz'c acid 2[C611,(CH3)(NH,)S0,H]+H20 forms sulphur-yellow needles but on decomposing its lead-salt with hFdrogen sulphide the yellow colour disappears.It dissolves in 10 parts of water at the common temperature much more freely in boiling water scarcely in absolute alcohol and not at all in ether. Its solutions and those of its salts assume a reddish colour in the light. The aqueous solution gives with ferric chloride a red colour wliich becomes deeper on heating. When the dry crystals are heated to 130" they lose their water but in presence of more water they decompose at this temperature into paratoluidine and sulphuric acid. (C7H8NSOJ)2Ba+ 3H20is readily soluble in water not in alcohol and forms transparent six-sided plates. (C,H8NSOJ2Pb + 2K20 crystallises in long needles less soluble than the barium-salt.C,H,NSO,Ag is a precipitate consisting of shining crystals and dis-solves but sparingly in boiling water. When the acid is distilled with potash R little paratoluidine is formed while by fusing it with potash ORGANIC CHEMISTRY. until the mass becomes thick paraoxy benzoic acid is formed together with a trace of protocatechuic acid CsH SO,H + {: 3KOH = CsH3 COZK H + SOsK2 + NH3 + 4H. {OH When the finely divided acid is suspended in alcohol or better still in water at 30"-40" and nitrogen trioxide is passed into the liquid { Sp the diazo-compound C,H3(CH,) is obtained as a red crystal- line powdcr. Water at 60" dissolves it and on cooling the compound crystal-lises either in pale red or if a little nitric acid is present in colourless plates.On boiling with alcohol under pressure m eta-toZicei~csr.cll~l~oilic acid is obtained as a crystalline deliquesceiit mass. (C7H7S03),Ba-+ 2H,O is readily soluble in water less in alcohol and forms warty crystals. ( C7H7S03)ZPb+ H,O crystallises from water in nodules. According to Miiller this salt crystallises from alcohol in long needles with 2 mol. of water; this the author could not obtain. The chloride is a yellowish oil. The amide crystallises from dilute solutions in rhombic plates and from a concentrated solu-tion in small glistening plates or needles melting a little below 100". PnracresoZnzetasu~hoiiicacid C,H3(CH3)( OH)SOJH is formed by boiling the diazo-compound with water. It is a reddish-brown syrupy mass giving with ferric chloride a beautiful blue colour.With basic lead acetate it yields a white precipitate. The composition and pro- perties of the salts of this acid agree with those which Engelhardt and Latschinoff have described. When the acid is heated with nitric acid a ciinitmcresoZ is formed identical with that which Martius and Wichel- haus obtained by decomposing paratoluidine with nitric trioxide. By decomposing the diazo-compound with hyarobromic acid? parabrorn,o-metatolzceraesui~Lo~z~c acid is produced which is identical with the acid described by Post and Retschy (Ann. Chem. clxix 7). When paramidometatoluenesulphonic acid is treated with 2 molecules of bromine it is converted into dibromotoluidine which seems to be identical with that obtained by Wroblevsky and is also formed togc- ther with brorno~Cr,rami~o~netntoZue~tesu~lLonic acid 3[C6H2Br(CH,) (NH,) SO,H] + 2H,O which crystallises from a concentrated aqueous solution in yellowish nodules consisting of short needles and from a dilut8e alcoholic solution in slender sulphur-yellow soft needles.On distilling it with potash iizo;12ob1.o.motoZzLidi?Leis obtained as a colourless oil form- ing crystalline salts. C7H7BrNS03Kforms thick colourless prisms. ( C7H7BrNS03),Ba+ 2H20crystallises in small hard g!istening rhombic plates. (C7H7BrNS03),Pbis very sparingly soluble in cold water and crystallises from hot water in colourless soft glistening needles. C,H7BrNS03Agis a crystalline precipitate separating from a hot solu- tion in long dolourless needles.The diazo-compound- ABSTRACTS OF CHEMICAL PAPERS. is a brownish-red crystalline powder which when boiled with alcohol under pressure yields bromometatoluenesdp honic acid a colourless crystalline mass which dissolves readily in water. C,H,BrSO,K crysta,llises in transparent prisms. 2[ (C,H,BrSO,),Ba] + 7H,O is sparingly soluble in cold water and forms compact needles. (C7H6BrSO3),Pb3-3H,O crystallises from hot water in groups of needles. The chloride crystallises from ether in long needles melting at 53". The amide is readily soluble in alcohol and ether sparingly in cold water and crystallises from hot water in shining plates or needles melting at 134'. The free acid is converted by fuming nitric acid intooytho~zit.1.o-dinxo-.Inetato luenesulphonic acid C,H2(CH,) NO {">N c- crystallising on slow evaporation in dark-violet brittle needles.When boiled with absolute alcohol under pressure it yields an orthowibonzetn-toluenesulphowk acid. [C7H6(N0,)S0,],Ba + 2H20 is sparingly soluble in cold water and crystallises from a hot solution in glistening yellow plates. By the action of hydrogen sulphide on the ammonium-salt orthamidonzeta-toZuenesulphonic acid is formed crystallising from hot water in micro- scopic needles and giving with ferric chloride an intense reddish- yellow colour. On distilling it with potash pseudotoZuidirze is formed. PnranzidotoZueemedisu~72onac acid [C6H2(CH,) (NH,) (SO,H),] + H,O remains in the mother-liquors of the ortho- and meta-acid and sepa- rates from a very concentrated solution in soft warty crystals.C7H7N(S0,)2Ba+ 3H,O separates when alcohol is added to a hot con- centrated solution in fine glistening plates. The lead salt is still more soluble than the barium salt and forms warty crystals. The two sulpho-groups in t,his acid have most probably the position 2 3. c. s. Metatoluidine. By LORENZ (Ann. Chem. clxxii 177-190). THE author has followed Beilstein and Kuhlberg's (Ann. Chem. clvi 83) method for the preparation of metatoluidine (called by them orthotoluidine) and confirms their results. Acetoparatoluide is converted into metanitroparacetotoluide and then with alcoholic potash into metanitropuratoluidine which with nitrous acid and subse- quent boiling with absolute alcohol gives metanitrotoluene.This body is then reduced with tin and hydrochloric acid to metatoluidine boiling at 197". The following table contains a comparison of the reactions of the three toluidines with the reagents which according to Rosenstiehl are characteristic for the ortho- and paratoluidine. 1. The base dissolved in SH,04.H20 is treated with a solution of chromic acid in sulphuric acid of the same concentration. The mix-ture is coloured ORGANIC CHEEJ1ISTR.T. Orthotoluidine (pseudotoluidine). Metatoluidine Paratoluidine Blue changing on dilu-Yellow -brown which Yellow. tion to a permanent red- becomes greenish-yellow on violet. addition of a small quantity of water and on further dilution colourless.2. Nitric acid is added to a solution of the base in SH,Oa.H,O. An orange-colour is pro- The mixture becomes at Blue streaks are pro-duced and with very con- once red changing quickly duced which soon tinge centrated solutions a to intense blood-red then the whole liquid ;after one brown becoming yellow to a dirty dark red and on minu tc the colour becomes on dilution. dilution to ormge. violet then red and after some hours brown. 3. To a solution of the base in equal volumes of water and ethcr n few drops of a clear solut'ion of bleaching powder are added. The layer of muter be- The layer of water be- No reaction. comes first yellow and then conies a thick brownish-br>wn. The ether sepa-yellow; the ether asaumes a rated from the water and reddish colour.When sepa- when treated with dilute rated and shaken with a sulphuric acid is perma-few drops of dilute sul. nently coloured a red phuric acid the under sur-violet. face of the ether is coloured violet. The author has prepared and aiialysed the following salts of met a-toluidine. The solbbiiities of each in water alcohol ind ether have been observed :-Acid metatoluidine oxalate C7HgN.C2H20,. An oxalate of the formula (C711gN),.(C2H,0,),. An unstable neutral metatoluidinc oxalate (C7HgN),.C2H204. Metatoluidine sulphate (C7HgN) 2. SH204. Metatoluidine nitrate C7HgN.NH03. Metatoluidine hydrochloride C7H,N.HC1. NH To prepare this body one part of metatolu'idine is heated to 160"-175" with 8 parts of fuming sulphuric acid.After purification the acid crystallises in thick white rhombic tables insoluble in alcohol and nearly so in water. Heated above 275" the acid is carbonised. without melting. The barium and lead metamidotoluene-orthosulphonates have the formulae (C7H8NS03)nBa.9H20, and ( C7H8NS03)2Pb,3~H20. The barium salt crystallises in thin tables or long prisms like urea tthe lead salt in yellowish-grey nodules. If bromine-water be added to a cold saturated solution of metamido-toluene-orthosulphonic acid microscopic needles of tribromometatolui-dine are precipitated which after recrystallisation from alcohol melt at 95" after sublimation at 101". This body is insoluble in concentrated soda-solution and in hydrochloric acid but is dissolved by concentrated sulphuric acid and precipitated malt ered by water.VOL. XSVIII. G ABSTRACTS OF CHEMICAL PAPERS. To decide what position the sulpho-group occupies in metamido- toluenesnlphoiiic acid the powdered substance suspended in alcohol of 60 per cent. was treated with nitrous acid until a sample was entirely dissolved on warming with strong alcohol. The diazo-compound thus obtained was heated with absolute alcohol forming a toluenesulphonic acid. The acid was then converted into the potassium salt and this by phosphorus chloride into a liquid chloride which with concentrated ammonia gave toluenesulphonamide. This body crystdlised from water melted at 1.54!"-155" crystallised from alcohol at 161" and is therefore the amide of tolueneorthosulphonic acid whilst the original acid must have the formula- Metamidotoluenedisulphonic acid is contained in the mother-liquors and washings from the crude metamidotoluene-orthosulphonic acid.After removing the sulphuric acid with barium carbonate and unat-tacked nietatoluidine with excess of baryta and this in turn with carbonic acid a salt is obtained on concentration crystallising in white felted needles which have the formula [C7€17N( S03),],Ba.12-$H20(2). Lead metamidotoluenedisulphonate C,H,N( SO3),Pb,2K,0 crystallises in hard yellowish-white crusts. The author did not succeed in obtaining the acid itself in the pure state. The author in a separate notice (pp. 190-191) states that Rosen- stiel-11's method for the estimation of orthotolnidine in presence of paratoluidine by oxalic acid is improved if a piece of blue litmus be thrown into the solution of the substance in ether.The colour changes as soon as all the paratoluidine is converted into oxalate. A still more accurate method is to add more oxalic acid than is required to combine with the whole of the bases present and after filtering off the insoluble paratoluidine oxalate to estimate the oxalic acid in the filtrate with decinormal soda-solution. W. H. P. A new Nitrotoluidine. By 0. CUNERTH(Ann. Chem. Pharm. clxxii 221-229). THE liquid dinitrotoluene which is formed together with the solid on nitrating orthonitrotoluene was prepared by adding toluene to well- cooled fuming nitric acid as long as any action was perceptible and then heating the solution gently.On adding water a precipitate con- sisting of a mixture of the two dinitrotoluenes and a little paranitro- benzoic acid was formed which after being washed with water and sodium carbonate was dissolved in strong alcohol from which first the solid compound crystallised out and then an oil separated consisting chiefly of the liquid compound. By the action of alcoholic ammonium sulphide it was converted into nitrotoluidine which in order to free it ORGANIC CHEMISTRY 83 from that derived from solid nitrotoluene was converted into the benzopl-compound by heating it gently with benzoyl chloride. By fractional crystallisation from alcohol a separation was easily effected the benzoyl-compound of ort honitroparatoluidine being much less soluhle than that of the new nitrotoluidine.Benxoy Ztoluirline is very readily soluble in alcohol and forms short yeiloaish needles or warty crystals melting at 145"-146". By the action of boiling alcoholic potash or better still by heating it with concentrated hydrocbloric acid to 150" it yields the new nitrotohidine crystallising from hot water in long light yellow needles melting at 94.5". It is sparingly soluble in water readily soluble in alcohol and strong acids forming with them very unstable salts. By the diazo reaction it was converted into orthonitrotoluene .-consequently the nitroxyl occupies the position 2 and the amido-group must be either in 5 or 6 because the two other orthonitrotoluidines in which the amido-group occupies the positions 3 or 4 are known.When the new nitrotoluidine is heated with acetic anhydride for four hours to 150" acety ZnitrotoZzci~iIze is obtained crystallising from hot water in glistening colourless prisms melting at 155.5". By reducing the liquid dinitrotoluene with tin and hydrochloric acid some orthctparstoluenedianiiue was obtained together with a new diamins which on accouiit of its small quantity could not be examined more closely. Benzoyl-orthonitrotoluidine which has already been mentioned is very sparingly soluble in a1coho1 and forms long glistening needles melting at 168". It forms an acetyl-compound crystallising in long silky needles which melt at 160". When the ortho-compound is dis-solved in cold fuming nitric acid a benzoyl dinitrotoluidine is obtained crystallising from alcohol in flat rhombic prisms melting at 203'.c. s. Action of Nitrous Acid on Dimethylaniline. By A. BAEYER and H. CAEO (Deut. Chem. Ges. Ber. vii 809-811 963-968). ITis known of the action of nitrous acid on the amines:- 1. That the primary amines of the fatty series yield the correspond- ing hydroxyl derivatives whilst those of the aromatic series yieId diazo-compounds or derivatives of the same. 2. That the secondary aniiies 01the fatty series yield nitroso-deriva- tives in which the nitroso-group is united with the nitrogen; and Griess has recently shown that in a similar manner a secondary arnine of the benzene series ethylaniline furnishes nitrosoeiliyl-aniline.3. That the terliary amine tripthylamine is not acted upon when its hydrochloride and potassium nitrite am simply brought togethcr but that on warming nitrosodiethylamine is produced. It was therefore to be expected that nitrous acid would either be without action on dimetlhylsniline or would convert it into nitroso-metZ-LyZnrdiqLe. The aut,hors find however that it is converted into nitrosodinzethylanili?ze .thus CGH~N(CJiI-T,),HCl+ NOZH = CsHa(NO)N(CH,)2HCl + OHz. G2 ABSTRACTS OF CHEMICAL PAPERS To prepare nitrosodimethylaniline 100 parts of amyl nitrite is added to a mixture of 50 parts of dimethylaniline with 100 parts of con-centrated hydrochloric acid and 750 parts of a mixture of 1volume of hydrochloric acid with 2.volumes of alcohol which is well cooled with ice.After a short time yellow needles separate ;as soon as these no longer increase in quantity the mass is thrown on a vacuum-filter and washed with ether-alcohol. An almost quantitative yield of pure nitrosodimethylaniline hydrochloride is thus obtained in the form of small sulphur-yellow needles ;these melt at 177" but are apparently decomposed ;they dissolve in water forming an intensely yellow solu- tion. On adding potassium carbonate to the hydrochloride suspended in water the pure base separates in green flakes ;it may be extracted with ether and on evaporating the solution is obtained in large green plates which melt at 92" and are slightly volatile in a current of steam. The sulphahe and nitrate of the base are obtained in fine yellow needles on adding sulphuric or nitric acid to an e€hereal solu- tion of nitrosodimethylaniline.Nitrosodimethylaniline is easily re-duced by tin and hydrochloric acid a base different from dimethyl- aniline being produced. When boiled with an alkali it is resolved into dimethylamine and nitrosophenot C6Ha(NO)N(CH,)z +OH2 =NH(CHa)2 +CsH,(NO)OH. NitrosophenoL-A mixture of 90 parts of water with 10 parts of sodium hydrate solution (sp. gr. 1.25) is heated to boiling in a flask connected with a reversed condenser and 2 parts of nitrosodimethyl-aniline hydrochloride is gradually added care being taken each time to await the dkappearance of the oily drops of the base before a fresh quantity of the salt is added. The boiling is continued until the dark greenish-yellow coloui has entirely disappeared and changed to reddish-yellow.The greater part of the dimethylamine passes over during the boiling and is collected in hydrochloric acid ;in this way it may be prepared in a state of purity in any desired quantity. To obtain the nitrophenol the alkaline solution is well cooled rendered slightly acid with sulphuric acid and extracted with ether ; on dis-tilling off the ether it remains in the form of a brown crystalline mass or if the ethereal solution be slowly evaporated it separates in large brown rhombic plates measureinents of which by Dr. Hintze are given. Nitrosophenol melts when heated and between 120"-130" decom-poses with a slight explosion. It is moderately soluble in water very soluble in a dilute sodium hydrate solution ;dilute acids separate it from t,he latter solution as a pale-brown precipitate whilst concentrated sodium-hydrate solution precipitates its sodium derivative in red-brown needles.On oxidation by nitric acid or by an alkaline solution of potassium ferricyanide it is converted into nitrophenol (m.p. 114"). By reduction with tin and hydrochloric acid it is converted into amido- phenol. If it be dissolved in an excess of phenol and a small qitantity of sulphuric acid be then added the mass assumes a dark cherry-red colonr and on the addition of potassium hydrate and water yields a magnificent blue solution. This reaction probably furnishes the clue ORGANIC CHEMISTRY. to Liebermann’s recent observations (last volume p.692j on the colouring matters formed from the phenols by the action of’ nitrous acid. The first stage is in all probability the following N/C6H,0H /C,H4.OH* + C6H5.0H= N-C6HbOH. \O \OH The coIoured body thus produced is it is to be supposed then con- verted into the colouring matter either by oxidation or by condensa- tion. Weselsky’s diazoresorcin is evidently formed in a similar manner from nitrosoresorcin and resorcin :-2CcHs(NO)(OH) + CsH,(OH)z = C,sH,,N,06 + 20HZ. The formation of amidazobenzenc from diazoamidobenzene can also be easily explained if it be assumed that the diazobenzene undergoes conversion into the isomeric nitrosaniline which then acts upon t,he aniline present ; thus C,H,N.N( OH) =CsHd(NH2)(NO) ; (NO) + CsH,(NHg) =C~H~(NHZ)N.NC~H, CGH~(NH~) + OH,.From the foregoing it is evident that nitrophenol cannot co-exist either with nitric acid or with phenol in presence of a strong acid ; and in order to prepare it directly from phenol it is necessary to bear this in mind. The authors find that it is possible to obtain an almost quantitative yield in the following manner :-5 parts of phenol and 20 of potassium nitrite are dissolved in 1000 parts of water and the solution is cooled as well as possible with ice-water ; 10-12 parts of ordinary acetic acid diluted with 10 volumes of water is then added little by little and with constant shaking. After 12-16 hours t,he brown liquid is filtered from a small quantity of resin and extracted with ether ; in order to avoid the action of any excess of phenol and of the nitrous acid present on the nitrosophenol which would occur on distilling off the ether concentrated sodium hydrate solution is added and the mass of sodium-nitrosophenol which separates is spread upon porous plates.The dry sodium derivative is dissolved t,he nitro-phenol is separated by sulphuric acid and slightly washed then rapidly dissolved in hot water and the solution is filtered and extmcted with ether on distilling off’ the ether pure nitrosophenol remains. H. E. A. Diphenylgugnidine. By W. WEITHand B. SCHROEDER (Deut. Chem. Ges. Ber. vii 937-947). THE authors have compared the a-and 6-diphenylguanidines dis- covered by Hofmann and pronounced by him to be isomeric and find that the P-diphenylguanidine (melaniline) prepared by the action of chloride of cyanogen on aniline possesses the same properties as the * Liebermann has since shown that nitrosophenol is indeed 6rst produced but that it reacts with 2 mols.of phenol 1nzol. of water being sepmated,-the colouring matter having the composition C,,H,,NO,.-H.E.A. ABSTRACTS OF CHEMICAL PAPERS. a-diphenylguanidine from diphenyl-sulphocarbamide ammonia and oxide of lead. Both bodies melt at 147" (Hofrnanii found the melting point of 6-diphenylguanidine to be 131") and both possess the same solubility in water and alcohol. No difference could be observed between the two substances which the authors therefore regard as identical. Of the three possible formulae for diphenylguanidine-I.11. 111. Ct3H5.N.H CGH5.N.H C6H5.N.C6H5 I I I C=N.H C=N.CGR~ C=N.H I I 1 CeH5.N.H H,N.H H.N.H No. I11is the least probable since in none of the decomposition-pro- ducts of this compound do bodies appear containing two phenyl groups attached to one nitrogen-atom. Further evidence against this formula is afforded by the fact that no diphenylamine is produced by heating either a-or P-diphenylguanidine with hydrochloric acid to 250". Hofmann has shown that the reaction of melaniline with carbon disulphide may be expressed by the equation :-C,,H13??,(HN) + CS(S) = C13Hu(CS) + CSHN. Melaniline. Sulplzocarbanilide. a-diphenylguanidine also undergoes the same change. Two bye- products were observed in this reaction a small quantity of phenyl sulphocarbimide and a body not yet further examined containing sulphur and crystallising iu colourless needles (melting point 152"-153") ;no rnonophenylsulphocarbamide could be observed.Thus with carbon disulphide both guanidines belisve alike and both give as prin- cipal products siilphocyanic acid and dipbenylsulphocarbamide. In case formula I1represented the constitution of dipheny lguanidine phenyl-sulphocarbimide and monophenylsulphocarbamide should be formed by the action of carbon disulphide thus :-c6H5.N.H C6H5.N.H I I C=N.C6H5 4-C8.s = CS=N.CsH5 + c=s I I N.Hz N.H,. Formula I therefore most probably represents the structure of diphenyl-guanidine and the action of carbon disulphide must be represented thus :-C,H,.N.H C,H5.N.H I I C=N.H + CS.S = CSNH + cs 1 I C,H,.N.H C6H,.N.H .w. H. Y. ORGANIC CHEMISTRY. Diphenylguanidine. By A. W. HOFMANN (Deut. Chem. Ges. Ber. vii 947-950). THE author confirms the results of Weith and Schroeder and finds with them that a-and 6-diphenylguanidine have the same melting point 147". He remarks that it is however not impossible that under certain conditions an isomeric diphenylguanidine may be pro-duced from chloride of cyanogen and aniline ; since a small quantity of mclaniline still in his possession retained its melting point 131"after recrjstallisation from alcohol as well as after conversion into platinum salt and reconversion into the base. The platinum salt gave satis- factory numbers on analysis.The author corrects the statement made in a former communication (Deut. Chem. Ges. Ber. i 147) that a-diphenylguanidine is produced by heating guanidine hydrochloride with aniline. The body mistaken for a-diphenylguanidine was subsequently found to be diphenyl-urea. The guanidine salt was probably converted by some water present into urea which by its action on aniline gave diphenyl-urea. W. H. P. Cinchonine. By H. WEIDEL (Ann. Chem. Pharm. clxxiii 76). BY treating cinchonine with nitric acid of sp. gr. 1.4 a mixture of acids results the relative proportions of which vary with the strength of the acid and the duration of the action ; these acids are formed by the following reactions :-Cinchonine. Cinchoninic acid.C20HaN20 + 402 = 5HzO + CzoHl4N204. Cinchomeronic Cinchoninic acid. acid. C2oH14NZO4 + NHO2 + 5NHOs = 3HzO + 4NO2 + C1,H,NzO,. Quinolic acid. + C,H,N,Oa. 0xycinchomeronic Cinchomeronic acid. acid. Ci1HeN,Os + 02 = CiiH8N20.9 Cinchonine in half kilograms at a time is heated with ten parts of nitric acid in a capzcious retort; in an hour the mixture begins to boil and an energetic reaction sets in the liquid becoming dark orange- yellow ; the source of heat shoiild be removed till this stage is over ; finally the whole is boiled for 70 to 80 hours until a sample diluted with water and supersaturated with ammonia gives a clear solution the precipitate first thrown down being re-dissolved by the excess of ammonia. The excess of acid is then distilled off and the residue evaporated to a syrup diluted with a little water and then dissemi- nated through 4to 5 litres of water.After 24 hours a clear liquid A and a yellow precipitate B are obtained; the aqueous solution A (together with the washwaters of B) is treated with ether whereby a ABSTRACTS OF CHENICAL PAPERS. solution is obtained which leaves on evaporation an indistinctly crystal- line slightly coloured mass C. The aqueous liquor thus exhausted by ether deposits crystals on standing for several days D ;and the mother- liquors of these when evaporated give another crop oi needles E whilst the last mother-liquors F are uncrystallisable. B and C consist chiefly of quinolic acid ; the mixed substances are dissolved in hot strong hydrochloric acid and filtered from a little resin ; on cooling crystals form consisting of a hydrochloride of quinolic acid stable only in presence of strong hydrochloric acid and completely decomposed by water ; these are dissolved in dilute hydrochloric acid ; the solut-ion after treatment with animal char- coal and filtering deposits fine needles of pure quinolic acid.D is purified by dissolving it in hot dilute nitric acid filtering after boiling with animal charcoal whereby resin is removed and leaving the solution to crystallise; the crystals are dissolved in a large bulk of boiling water and treated with milk of chalk until the liquor is only feebly acid. The precipitate contains much calcium oxycinchomeronate some of which salt also crystallises from the filtrate on cooling ; the calcium salts are dissolved in hot dilute hydrochloric acid from which solution oxycinchomeronic acid crystallises in transparent tables.The filtrate from the crystals of calcium salt is evaporated and treated with hydrochloric acid when cinchomeronic acid separates in crystals ; this is the least soluble of all the cinchonine oxidation-products. By crystallisation this first product is purified ; finally it is transformed into copper-salt by addition of copper acetate to the hot aqueous solu-tion and decomposed by sulphuretted hydrogen. E consists chiefly of cinchoninic acid and is purified by recrystal-lisation from water and treatment with animal charcoal. F contains cinchoninic and cinchomeronic acids separable by satura- tion with ammonia filtration from resin treatment of the filtrate with silver oxide and of the silver salt thus formed with hydrochloric acid whereby a solution is obtained which gives a crystalline mass on eva-poration ;of this part is left undissolved on boiling with not too large a bulk of water ;this is cinchomeronic acid.Cinchoninic acid crystallises usually with 4molecules of water and is very difficultly soluble in alcohol and insoluble in ether; when anhydrous it is far more soluble in water than when hydrated; the calcium salt is C20H,2CaN20,. 1&H,O; the copper salt C20H12CuH20~ (anhydrous) ; the silver salt C2,H,,Ag2H204 ; the potassium salt C~oH~2K2N204.H20 ; ; it forms a platinum salt CzoH,4N20a.2HC1.PtC14 heated with nitric acid it forms quinolic and cinchomeronic acids ; but no carbonic or oxalic acid.Quinolic acid forms light woolly crystals resembling quinine sul-phate; it tastes sour at first then bitter and is but little soluble in alcohol and insoluble in ether and water save when a mineral acid is present. It crystallises anhydrous forms a silver salt CgH,AgN204, and unites with hydrochloric acid to form a hydrochloride CgH5AgN204. HC1 ; it also forms a platinum salt (CgH,L%gN20J3C1)2PtC14.By the action of bromine it furnishes a body melting at 88"-990" and of composition C9HBr,N ; by the action of sodium amalgam this seems to give rise to quinoline. ORGANIC CH.EII1ISTRY. Cimhomeronic acid crystallises anhydrous ; its calcium salt is (CllH,Nz06)zCa,.10H,0 ; the barium salt is ( CllH5N20,)2Ba3.4H20, and the silver salt Cl1H,Ag,N,O6 ; unlike cinchoninic and quinolic acids it does not form a platinum salt.The calcium salt formspyridirte on dis-tillation with excess of caustic soda; heating with nitric acid forms oxycinchomeronic acid. Oxycinchomeronic acid crystallises with water (amount not stated) which is lost at 120"; it is readily soluble in hot water and dilute alcohol but not in ether ; with ferrous sulphate it gives a blood-red colour like ferric sulphocyanate ; the calcium copper silver and potassium salts are respectively (~ll~5~z~8)z~a3, (c11&N203) cu, ClIH&,N2O8 and CIlH4&N208 ; when treated with sodium amalgam it evolves all its nitrogen as ammonia forming CilzcAolzic acid CllH1409.This acid does not precipitate silver nor copper salts or those of the irm group mef,als ; lead acetate gives a white precipitate. It does not reduce Trommer's copper-solution ; the silver copper and calcium salts are respectively CllHllAg309,( C11Hl10g)2Cu3, and ( CllH1109)2Ca3.Its formation is expressed by the equation CiIHeN206 + 3HzO + 3H2 = 2NH3 + CI1HlaOg. When submitted to dry distillation cinchonic acid yields a crystalline acid melting at 95" and of composition CloHlo05, the silver salt being CloH7Ags05; the formation of this is represented by the equation :-Cl,I-I1409 = 23320 + c02 + ClOH1005. Hence this substance is termed pyrocinchonic acid. [It seems to be isomeric with opianic acid.obtainable from narcotine by oxidation.-C. R. A. W.] Acetyl chloride has no action on it; melting caustic potash oxidizes it to oxalic acid and lower fatty acids ; when boiled in alkaline solution with sodium amalgam it forms hydropyrocinciio& acid C10H1607, the silver salt of which is CloH13Ag30,.This acid is apparently formed by the reaction :-CioHioO5 + Hz + 2H2O = CioHi60,. The author attributes to cinchonine the formula- This would readily give by oxidation C9Hl6N.CO2H this formula being half that attributed above to cinchoninic acid. OH Quinolic acid is probably dih ydroxyl-nitro-quinoline CgH4N OH , {NO2 as it yields nitrite of potassium on fusion with caust,ic potash and is converted by tin and hydrochloric acid into a resinous easily decom- posed amido-product.ICO.OH Cinchomeronic acid is probably C8HsN2 CO.OH. tCO.OH ABSTRACTS OF CHEMICAL PAPERS. OH OH Oxycinchomeronic acid C8H,Nz CO.OH. C0.OH CO.OH Cinchonic acid being c8H8{ [CO3H),' 013-whilst pyro-cinchonic acid is C8H8{ (CO.OH), bearing to cinchonic acid the same relationship as itaco& \acid to dihic acid. The author discusses the results of Stahlschmidt Schutxenberger Caventou Willm and Zorn and considers that the isomerism of cin- chonine and cinchonidine may be due to the conversion of the ethylene radical into ethylidene possibly the formule may express the composition of cinchonine ; it explains its power of taking up H2and even H (Zorn). The author dissents from Zorn's view that cinchonine contaius hydroxyl viewing the "cLlorocinchonide " of that chemist as not being truly indicated by the relationships- C,H2,NZ.OH cinchonine. CmH23N2 . C1 chlorocinchonide. C. R.A. W. Noh by Bbstractor.-In reference to the last paragraph Schutzen- bcrger obtained some years ago by the action of acetyl chloride on cinchonine a syrupy non-crystalline base apparently an acetyl-ch-cholaine; and from experiments now in progress by the abstractor it seems probable that the same or an analogous product is obtained by the action of acetic anhydride on cinchonine the hydroxylic character of this alkaloid would therefore seem probable. C. RV. A. W. Essential Oils. By A. KURBATOW (Ann. Chem. Pharm. clxxiii 1-5). OiZ of OZibawum.-A specimen of the gum yielded 7 per cent of oil boiling between 160°-1700.A fraction of this which boiled at 156"-158" was found to contain CloH16, and is called olibene. This hydrocarbon has a specific gravity of 0.863 at 12" is resinified by nitric acid and unites with hydrochloric acid to form a compound melting at 127" and containing CIoH,6.HC1. Another fraction of the crude oil boiled above 175" and contained 83.55 per cent of carbon mith 5.57 per cent. of hydrogen. When the resin of olibanum is distilled traces of acid products are ORGANIC CHEMISTRY. 91 formed together with solid semisolid and fluid substances which a'ppear to be condensation-products of the hydrocarbon CloH16. Calamus 0iZ.-The principal tei-pene of this oil boils at; 158"-159" and unites with hydrocliloric acid a compound melting at 63" being formed.When the blue portion of calamus oil which passes over between 250" and 255" is treated with soda it is decolorised and a terpene is obtained which boilsat 255"-258" has a specific gravity of 0.942 at 0" and does not unite with hydrochloric acid. Calamus oil contains portions of more volatile terpenes (158"-159"). rn~ 1. u. On a Substance called Myrlsticin. By I?. A. FL~~CEIGER (Pharm. J. Trans. [S] iv 136). THE published statements concerning myristicin being very con-tradictory the author was induced to submit the substance to further examination. A large quantity of ordinary nutmegs (Jfiipis-tica fragrans) was distilled as were also some " long nutmegs" (M.fatua). After three days' distillation the crystals which had collected on the water with the oil were analysed. They smelt strongly of nutmegs which smell it was found impossible to remove even after repeated purifications from alcohol ; the odour was however lost after the crystals had been kept for some months. They are readily soluble in warm alcohol which was used as a medium for their purification. In water the crystals are insoluble. The alcoholic solution is devoid of rotary power but reddens litmus slowly. The crystals are doubly refractive melt at 54.5",evolve offen- sive vapours but cannot be sublimed. The crystals from Myristica fatua are found by analysis to be iden-tical with those obtained from Jf.fragrans. They yield a soap with alkalis and when this soap is warmed with absolute alcohol and anhydrous sodium carbonate for some time a neutral solution is obtained from which on the addition of an acid the original "myristicin" separates.The formula of this substance is found to be ClaHzsOz,which is that of myristic acid. The author supposes that in the older investigations impure substances had been worked upon. Several salts of myristic acid have been formed. It is monobasic and is present in nutmegs as glyceryl trimyristicate or myristicim. E. W. P. On Chrysenin. By T. L.PHIPSON (Chem. News XXX 69). IFchrysene be treated with twice its volume of boiling water so as to render it fluid and the water be acidulated with hydrochloric acid cooled and filtered a liquid of a bright yellow colour is produced from which chrysenin separates on addition of ammonia as a brick-red precipitate mixed with quinoleine and other bases.It may be purified by forming and decomposing the sulphate several times and finally exposing the dark orange-coloured liquid to sunlight for a few weeks. Ammonia then throws down the base as a bright yellow flocculent precipitate. Its vapour is irritating to the eyes and forms 92 ABSTRACTS OF CHEMICAL PAPERS. dense fumes with vapour of hydrochloric acid; it has a hot acrid pungent taste is strongly alkaline and forms a nitro-compound with hyponitric acid &c. E. W. P. On the Albumins of White of Egg. By A. B~CHAMP (Compt. rend. lxxix 393-396). THE author infers from his experiments that white of egg cont,ains three soluble albumins the rotatory powers of which as determined by Soleil's saccharimeter are -33" -54" and -71" respectively.Normal white of egg rotates 42"to the left W. A. T.

ISSN:0368-1769    

DOI:10.1039/JS8752800049

出版商:RSC    

年代:1875

数据来源: RSC

摘要:

92 ABSTRACTS OF CHEMICAL PAPERS. Physiological Chemistry. Chemical Researches on the Brain. By M. GOBL E Y (J. Pharm. Chim. [4] xx 161-16G). THEbrain contains two albumino'id matters one of which is sduble in water and does not differ from albumin ; for the other which is inso-luble in that liquid the author proposes the name of eephalin. The fatty matter of the brain is formed principally of cholesterin lecithin and cerebrin besides which there are traces of olein and margarin. The brain contains the ordinary sdts of the human system together with extractive matters of yvhich some are soluble in water and alcohol others solubIe in water and insoluble in alcohol. During putrefaction the cerebral pulp furnishes acid products amongst which are oleic margaric phosghogly ceric and phosphoric acids.The following may be considered as tile meari percent,age composition of the brain :-Water ........................................ 80*00 Albumin.. ................................... 1.00 Cephalin.. ............................:....... 7-00 Cholesterin.. .................................. 1.00 Cerebrin ...................................... 3.00 Lecithin ...................................... 5.50 Olein and margarin .......................... .. Inosite creatine xanthine &c. &c. .............. Extractive matters (aqueous and alcoholic) ........ 1:iO Chlorides of potassium and sodium.. ............} 1.00 Phosphates of potassium calcium magnesium &c. 100~00 H. J. H. On the Source of the Acid of the Gastric Juice.By B. MALY(Ann. Chem. clxxiii 227-273). THEfree hydrochloric acid of the gastric juice may be derived either from the dissociation of neutral chlorides or from their decomposition PHYSIOLOQICAL CHEMISTRY. 93 by an organic acid (lactic acid) formed from carbohydrates. Bence Jones found that the acidity of the urine is diminished during the secretion of the gastric juice and reached its minimum when digestion is at its height ; this is explained on the first supposition by the alkali formed by the dissociation being removed by the kidneys ; and on the second by the lactates formed by the decomposition being oxidised to carbonates and then entering the urine. The author has performed numerous experiments with dogs ;causing a flow of gastric juice by irritation he at the same time injected into their stomachs an insoluble substance which would neut'ralise the free acid and afterwards drew off tAhe urine and tested it.The substances employed were calcium carbonate bone-meal ferric hydrate calcium phosphate and aluminium hydrate ; in all cases the urine after the injection was alkaline whatever its reaction before. Also in an experiment without the use of a neutralising substance with a dog into whose stomach food was introduced and then with- drawn with the gastric juice through a fistula the urine was after- wards strongly alkaline. Experiments of a like nature with men though the conditions were more complicated tended to a like result. Quinck (Correspondemz-blatt f.Schweizerische Aerzte 1874 No. l) gives a case of a woman with abscess in the stomach whose urine was always alkaline subsequently to the removal of the contents of the stomach after food. A solution of lactic acid and sodium chloride when distilled yielded traces of hydrochloric acid only in the last distillate; but diffusion experiments with lactic acid and ferrous sodium calcium and magne- sium chlorides showed that all these were decomposed in dilute solutions by lactic acid with formation of free hydrochloric acid. A series of experiments on the lactic fermentation were then made with the mucous membrane of the stomach of pigs digested at 40" with 2 per cent. solutions of grape-sugar cane-sugar milk-sugsil. and dextrin.Lactic acid was formed from each of these carbohydrates but the formation was generally prevented by exposing the membrane to a temperature of loo" and always by a temperature of 110",though there still appears a tendency to renew the action after a time The same experiments tried with the fresh gast'ric juicerof a dog in place of the membrme developed no acid in any case. The watery infusion of the mucous membrane with the sugar-solutions developed acid as also did the residue though to a less extent than the fresh membrane. Blood serum from an ox was also digested at 40" with a piece of the stomach and its alkalinity found to decrease. Bacteria were developed in abundance at the same time as the acid was formed rendering it doubtful that the formation of lactic acid is a function of the living membrane.The addition of small percentages of phenol and arsenious acid prevented the fermentation this and the behaviour after heating are indications that the lactic ferment is an organised body and* not a soluble chemical ferment. The stomach taken from a dog immediately after killing digested with a 2 per cent. sugar solution produced scarcely any acid at first but much more after two days. ABSTRACTS OF CHENICAL PAPERS. The stomach of a dog with fistula was exhausted and milk of mag-nesia introduced ; after an hour the stomach was again emptied and the stmount of magnesia dissolved was eshimated. The same operation was afterwards repeated except that grape-sugar was introduced with the magnesia on again emptying the stomach the same amount of magnesia was found in solution showing that no acid had been formed from the sugar.All these results tend to the conclusion that the forma-tion of lactic acid from carbohydrates is not a function of the living membrane of the stomach. Though Lehmann and others have found lactic acid in the gastric juice Schmidt and the author have failed to identify it and maintain that it is absent in pure gastric juice. The source of the free hydro- chloric acid in gastric juice is to be sought in the dissociation of chlo- rides without the aid of an acid. E. K. Value of Gelatigenous Tissues in Nutrition. By CARLVOIT(Zeitechrift f. Biologie x 202-245). THEauthor gives details of a feeding experiment with ossein on a dog.The results like those with pelatin show that it effects a saving of albumin and of fat but cannot be substituted for albumin 10.71 grams of ossein per diem reduced the daily loss of nitrogen from 10.17 grams whilst fastiq to 8.4. Unlike gelatin it does not produce diarrhea. The author recapitulates the differences of opinion between himself and Hoppe-Seyler (compare this Jownal xxvi 284 and xxvii 487). The latter thinks that the consumption of albuminous matters in the system is due to the decay of the cells and tissues ; whilst Voit believes that by far the greater part is due to the oxidation of the circulating albumin of the lymph when this srnbstance enters the cells and tissues and not to the decay of the tissues themselves.E. K. Digestibility of the Gelatigenous Tissues. By JOHANN (Zeitschrift f. Biologie x,84-110). ETZINGER AFTERgiving a long historical review of the published experiments made and views held on the subject of the digestibility and nutritive value of gelatin and the gelatigenous tissues Etzinger proceeds to describe his own experiments made to determine the points in dispute. In experiments made with gelatin he found that at the temperature of the body no change took place in gelatin when this substance was treated with dilute acids even after prolonged digestion ; but that the. addition of pepsin to the acid solution debormined the gelatinization of the solution within forty-eight hours and that it subsequently under- went important changes.The gelatigenous tissues underwent rapid solution when treated with pepsin and mere dissolved to a fluid which did not gelatinise on cooling. On experimenting upon animaIs by feeding them with bones tendons cartilage and other gelatigenous tissues it was found that the gelati- PHYSIOLOGICAL CHEMISTRY. genous material of these tissues plays an important part in nutrition ; and since they contain no albumin those tissues furnish nitrogenous material for oxidation in the body and thus effect a saving in the oxidation of the albuminojid tissues. The inorganic insoluble material of bones did not appear to undergo absorption. T. S. Peptones and their Function in Nutrition. By P. P ~6 sz (Pfluger’s Archiv. f. Physiologie ix 323-329).THEauthor finds from his own experiments that dogs may be nourished and even gain weight when fed on a diet rich in peptones but froin which all the unchanged albumins are absent. It is hence evident that albumins may be formed in the animal organism from peptones. Plosz concludes that the real elements of nutrition are not the albu- mins but the products of decomposition of these-in fact their smallest nitrogenous molecules. T. S. The Absorption of Mucilage and Gum from the Intestinal Canal. (Zeitschr. f. Biologie x 58-68.) A MEMOIR mainly of physiological interest. It was found that in the intestinal canal gum is partly changed into glucose or it is converted by fermentation into acid products which are then absorbed. Quince mucilage is either absorbed unchanged or it undergoes an acid fermentation like starch.A conversion of mucilage into glucose can scarcely be said to occur. T. S. Replacement of Lime in the Bones. By J. E~~NIG (Zeitschr. f. Biologie x 65-72). H. WEISKE having asserted and Papillon denied that animals fed on food containing strontium phosphate have this salt deposited in their bones Konig has repeated the observations with certain modifica- tions in the method. His experiments support Weiske’s conclusions and show that strontium phosphate may yeplace calcium phosphate in part. Aluminium phosphate when administered in food was not detected in the bones. The experiments were made on Guinea pigs. T. s. Bile Pigments. By J. I?. T A 12 c HA N o F F (Pfluger’s Archiv.f. Physiologie ix 329-334). TARCHANOFF shows that the injection of a solution of haxnoglobin into the jugular veins produces a large flow of bile-pigment from the liver. This organ has indeed the power of absorbing bile-pigment from the blood slid secreting it in Lhc bile whilst the pigment simply filters through the renal cells into the urine. T. S. ABSTRACTS OF CHEMICAL PAPERS. Fermation of the Colouring Matter of Urine from Blood. By F. HOPPE-SEYLER (Deut. Chem. Ges. Ber. vii 1065). BYthe action of reducing agents especially tin and hydrochloric acid on an alcoholic solution of hErnatin? the author has obtained a yellow colouring matter which agrees in properties with the urobilin of JaEe or the hydrobilirubin of Maly.W A. T. Behaviour of some Aromatic Compounds in the Animal Body, By L. TON NENCKI(Chem. Centr. 1874 182). THEauthor experimented with benzamide terpene ( CloH,,),and mesi- tylene. According ta earlier researches of the author and Schultzen acetamide is excreted unchanged. Benzamide produced hippuric acid in the urine and therefore by combination with a molecule of water had split up into ammonia and benzoic acid. The experiments m4.h ter- pene led to no result. When mesitylene was administered mesitylenic acid was found in the urine together with small quantities of an acid which was probably ;t compound of mesitylenic acid with glycocine. Mesitylene is therefore allied in its behaviour to toluene and xylene. G. T.A. Connection between Isomorphism Molecular Weight and Physiological Action.By JAMES BLAKE(Am. J. Sci. [3] vii 193-197). A ‘rABLE is given showing the physiological action of compounds of metals and metallo’ids when introduced directly into the blood. The compounds are arrariged in isomorphous groups each group appearing to differ in physiological action from the other groups. In the case of the metallic elements it appears that the physiological activity in the same group increases with the atomic weight. A few exceptions are found as in czesium which differs from the other mem- bers of the group in its action on the nervous system. The author considers that in living matter we possess a reagent capable of aiding us in investigations on the molecular properties of substances. x.w. P. Intestinal Concretion containing Lithium. By DELACHANAL (Compt. rend. lxxviii 1859). and MERMET THIS concretion weighing 150 grams was taken from a sturgeon caught near Astrakan. The phosphate of lithium amounted to ha of the concreticn. 3.J. G.

ISSN:0368-1769    

DOI:10.1039/JS8752800092

出版商:RSC    

年代:1875

数据来源: RSC