摘要:

THE JOURNAL OF THE CHEMICAL SOCIETY OF LONDON. 4Larnmiiite MX "8$blimtiafi F A ABEL F.R.S THOHAS GRAHAM F.R.S. WARREN DE LA RUE,PH.D. F,R,S. I W A MILLER M.D. F.R.S. 6bibYk HENRY WATTS B.A. F.R.S. F.C.S NEW SERIES VOL. V. (Entire Series Vol. XX.) LONDON HTPPOLXTE BAILLIERE 219 REGENT STREET 18'6'7. L@iVDON HARRISON AND SONS PltlNTZRS 1s ORDlHAnY TO IIER MAJESTY ST. MARTIN'S LANE. CONTENTS OF THE TWENTIETH VOLUME. PAffE 1 On Ozone. By Charles Daubeny M.D. F.R.S. On the Synthesis of Butylene. By Xrnest Theophron Chapman .....a 28 The Relation between the Products of Oxidation and the Molecular Constitn- tion af the Bodics Oxidized. By E. T. Chapman and W. Thorp ... . 30 On a Chlorsulphide of Carbon.By Walter Noel Hartley ...... ........ 33 On a New Class of Compounds containing Nitrogen in which Hydrogen is 36 replaced by Nitrogen. Synthetical Researches on Ethers. No. 2. Action of Sodium and Isopropylic Iodide upon Etliylic Acetate. By E. Frankland F.R.S. and B. F. 102 Duppa Esq. On the Alloys of Magnesium. By James Parkinson ..,...... . . . ... . . . 117 On the Oxidation of Ethylic and MethylicBenzoates. By R. H. Smith F.C.S. 131 On a New Synthesis of Formic Acid. By Ernest Theophron Chapman.. 133 On the Basicity of Tartayic Acid By W. H. Perkin F.R.S. . ,.,,.. . . .... 138 On thedbsorption of Vapours by Charcoal. By John Hunter M.A. F.C.S. Chemical Assistant Queen’s College Belfast ,..., . ,. . .......,..... 160 On a New Form of Aspirator.By Herbert MCLeod .. ..... . .. .. . . .... 164 On some Reactions of Hydriodic Acid. By Ernest Theophro n Chapman 166 Titration of the Compound Ethers. By J. Alfred Wanklyn Professor of 170 Chemistry at the London Institution Quantitative Analysis by ‘‘Limited ” Oxidation. Examples Lactic Acid and Diethoxelic Acid. Ry Ernest T. Chapman and Miles H. Smith.. .. 173 On the Preparation of Berberine from Cosciniziin Fenestratum. By John Stenhouse LL.D. F.R.S Bc...,.. .. .. .......................... 187 On the Amount of Carbonic Acid contained in Sea Air. By T. E. Thorpe,Dalton Scholar in the Laboratory of Owens College Xanchester.. . . ... . 189 On the Amount of Carbonic Acid contained in the Atmosphere of Tropical Brazil during the Rainy Season.By T. E. Tho rpe. . .. ... . ..... . .... 199 On -4uoys. By A. hlatthiessen F.R.S. Lecturer on Chemistry in St. Mary’s Hospital 3Sedical School ,... .,. . .. ..,..,. . ,.....,,. . . . . .. 201 Xote on 8ome Varieties of Orchella Weed and products obtained from them. By John Stenhouse LL.D. F.R.S. &c. ,.....,..... .. .I... .. ,. .... 221 Limited Oxidation Determination of the Oxygen Consumed. By Ernest Theophron Chapman.. .. . . . . ......,..... .. .... .. ........ .... . . 221 On the Abcorption and Dialytic Sepzration of Gases by Colloid Septa. ByThomas Graham F.R.S. Mastcr of the Milit ,. ,.. . ....... . ........ 235 Oxidation of Formic Acid. BF Ernest Theophron Chnpnisii . . ..,... . . 289 Kotc on the Synthesis of Formic and Hyposulphurous Acid.By A. DKIPY~ Ph.D..,.. .. ..*... .. .. .. ,. .. .. .. .. .. .. .. .. .. ,..... ,. .. .. .. .... .. 291 CONTENTS. PAUE Experiments on Oxidation by mean's of Charcoal. By F. Crace Calvert Ph.D. F.R.S. ** * *. *a ** ** -* *. * ..a * 293 Oxidation of the Acids of the Lactic Series. By Ernest Theophron Chap- manand Miles H. Smith.. *. -...-....# .............. .. .......,. 296 On Limited Oxidation with Alkaline Permanganate. By Ernest 'J'heophron Chapman and Miles H. Smith -. . . . a 301 On tlie Presence of Soluble Phosphates in Cotton Fibres Seeds &c. By F. Crace Calvert F.R.S. .. . . .. . ... ........ . . ...... . .. . . . . . ..... .. 303 Observations on the Weathering of Copper Ores.By John Spiller F.C.S.. 306 On Phosphide of Magnesium. By James Parkinson ... . ....,.,,,. . 809 Researches on h-cotton. On the Manufacture and Composition of Gun-cotton. By F. A. Abel F.R.S. V.P.C.S. .* ..........,. ,...,. ..,. 310 On the Constitution of Phosphites. By C. Rammelsberg.. ...,..... . ..,. 358 On the Changes in the proportion of Acid and Sugar present in Grapes during the Progress of Ripening. By A.. D upr6 P1i.D. . . ... . ,,,. . . .. ... . . 378 Note on Crystallised Glycerin. By Dr. J. H. Gladstone . . ......,,.,.. ..' 384 Anniversary Meeting .......... . .. . ... . .. . . .......... ..............,. 385 On some of the effects produced by the addition of Plaster of Paris to Must. By A. DuprB Ph.D. ...... . ........ . .............. .............. 403 On the practical Loss of Soda in the Alkali Manufacture. By C. R. A. Wright B.Sc. Private Assistant in the Chemical Laboratory at St. Thomas's Hospital ...... . ...... . . . ..... . . . . . . ........... .... .. . . 407 Description of an Apparatus for preventing Escape of Sulphuretted Hydrogen. By theRev. B. W Gibsone M.A. B.Sc. .......................... 415 On some new Derivatives of the Hydride of Salicyl. By W. H. Perkin F.R.S. ........................s. ......*a .**. ....-* .....a .... 418 Action of Chloride of Iodine on Picric Acid. By John stenhouse LL.D. F.R.S. ....,.,. ,......... .. .................................. .. 433 On Pyrophosphoric Acid. By Dr. J. H. Gladstone Ph.D. F.R.S. ,.,,... 435 On Julin's Chloride of Carbon.By Henry Basset t ... . . ... . .....,.... 443 Water Analysis ; Determination of the Nitrogenous Organic Matter. J. Alfred Wanklyn E. T.Chapman and Miles H. Smith ......By 445 Analysis of a Biliaq Concretion ; and on a New Method of preparing Biliver- &n. By Dr. T. L. Phipson F.C.S. &c. Member of the Chemical Society of Paris .. 454 On the observation of tlie course of Chemical Change. By A. Vernon Harcourt Lee's Reader in Chemistry at Christ Church Oxford ..... . 459 011 tlle Estimation of Compound Ethers in Wine. By A. Dupr6 Ph.D .... . 493 Researches on Gmi-cotton.-Second Memoir. On the Stability of Gun-cotton. By F. A. Abel F.R.S. V.P.C.S. .... .. .. . ...............,. 505 Nitrous and Nitric Ethers ; their Decompositious and Reactions. By E. T. Chapman and M. H. Smith ,. ... ,.. ,......... ......... .... 576 On the Actioll of Acetic Anhydride upon the Hydrides of Salicyl Ethyl- saEcyl &c. By W. H. Perkin F.R.S.......................... . .. .. 586 Verification of Wanklyn Chapman and Smith's Water Analysis on a ~eyies ofktificial Waters. By J. Alfred Wanklyn Professor of Che-nlistry at the London Institution.. ..,... . ,,.. . . . . . . . . ,, ..,.,.,,,. 591

ISSN:0368-1769    

DOI:10.1039/JS86720FP001

出版商:RSC    

年代:1867

数据来源: RSC

摘要:

II.-On the Synthesis of Butydene. By ERNEST CHAPMAN. THEOPHRON IT is now some time since Kurtz succeeded iu synthetically forming amylene by the action of zinc-ethyl upon iodide of allyi. It is obvious that iodide of allyl C,H,I would be isomeric with mono-iodpropylene and this latter compound is homologous with monobromethylene. I therefore thought it worth while to treat this latter substance with zinc-ethyl with the idea of forming butylene. The ziuc-ethyl was contained in a tubulated retort surrounded by ice and salt. Monobromethylene was introduced into the CHAPMAN ON THE SYNTHESIS OF BUTYLESE. retort in the state of vapour. It was at once condensed. Care was taken not to add excess of it. The retort was then removed from the freezing mixture and gently warmed.The liberated vapours were conducted through a U-tube surrounded by ice and salt. In this manner about three c. c. of a colourless liquid were obtained. It mas introduced into a small distilling apparatus and the boiling point carefully taken. It was found to lie between 12 and 14'. The sp. gr. of the liquid was -739 at 0"C. A small portion of it was carefully tested for bromine by passing it over red-hot caustic lime. No bromine was detected. The remainder of the liquid was treated with bromine. The two bodies combined with con- siderable evolution of heat. The operation was conducted in a long test-tube immersed in ice-cold water. The resulting product was dried and distilled. It was found to boil between 158' and 160°C.thoilgh a small portion of it had a higher boiling point. It was distilled three times to remove this trace of liquid of higher boiling point By this time the total amount of liquid had been reduced to little more than 1c.c. It weighed 1.526 grammes. It mas then digested with solution of canstic potash in alcohol free from chlorine. TIie amount of bromine which it yielded to this agent corresponded with the amount required on the assumption that we were dealing with bibromide of butylene. This substance would of course give only up one equivalent cf bromine. There-fore on distilling off tlie alcohol and gently igniting the residue we should obtain a mixture of bromide of potassium and caustic potash. It was in this mixture that the bromine was determined as bromide of silver.1.526 of substance yielded 1.326 AgBr therefore 36-97 per cent. Br. Theoretical per centage 37.037. The alcohol distilled cjff was diluted with ice-cold water a few drops of an oily liquid rose to the surface. This liquid on treat- ment with bi-chromate of potash and concentrated sulphuric acid yielded bromine. The reaction to which the butylene owes its existence is as follows :-Zn(C,H,) + 2C,H,Br = ZnBr + 2C,H,. It appears to me that this reaction will enahle us to obtain the whole of the olefines normal as well as abnormal for it is almost certain that dibromethylene would act upon two equivalents of CHAPAMAX AND THOIZI’ ON THE RELATION zinc-ethyl prodnciug hesylene-a secondary hexylene no doubt ; aid iri a similar nianner any other required olefine could be obtaiued.

ISSN:0368-1769    

DOI:10.1039/JS8672000028

出版商:RSC    

年代:1867

数据来源: RSC

摘要:

CHAPAMAXAND THOIZI’ ON THE RELATION III.-The Reladioiz between the Products of Oxidabion and the Molecular Constitution of the Bodies Oxidized. By E. T. CHAPMAN and W. THORP. [Contribution from the Laboratory of the London Institution.] PART XI. GLYCERIN and mamxlite :-these two substances resemble each other in many particulars. They both yield iodides of secondary alcohol-radicals when treated with hydriodic acid. These iodides in both instances yield olefines when acted upon by alcoholic solution of potash. By oxidation these olefines yield acids of lower carbon-condensation than themselves. That obtained from mannite P-hexylene yields as we have already shewn propionic acetic and carbonic acids. The olefine from glycerin has been shewn by M.Truchot to yield acetic and formic acids ; we have oxidized it and obtained acetic and carbonic acids. It is well known that glycerin when heated with caustic potash yields acetic and formic acids. We have examined the reaction and can confirm this statement. These acids have the same carbon-condensation as those obtained from the corresponding olefine by oxidation. Mannite when treated mi th caustic potash yields propionic acetic and formic acids. The following experiments enable us to confirm this result. Thirty grammes of mannite were heated with caustic potash just moistened with water. The mixture melted turned yellow frothed up very much and gave off inflammable gas; the contents of the dish were theu dissolved in water and distilled with excess of sul-phuric acid.Formic acid was found in the distillate. A portion of the latter was converted into haryta-salt. Per centage of Bn from mixed salts 52.83. The remainder of the distillate was neutralized with potash evaporated to dryness and gently warmed I3ETWEEN THE PRODUCTS OF OXIL>.\TIOS ETC. with concentrated sulphuric acid. Carbonic oxide was evolved.* The mixture was then diluted and distilled and a portion of the distillate was converted into haryta-salts. Per cent. of Ba 50.11 showing the presence of acetic acid because the formic acid was destroyed and no other acid yields a barium-salt containing more than 48.41 per cent. of barium. q!he remainder of the distillate mas neutralized with standard solution of caustic potash and divided into four fractions the first three of one-fifth each and the last of two-fifths.These different fractions were as usual converted into baryta-saSts and the percentages of barium they contained were determined. 1 Theoretical Acid to which this Substance taken. Ba-SO4 Per cent. 1 found. Bs found. per cent. corresponds. i ~-First fraction 6 3962 -3249 Propionic Second fraction *3690 -3042 99 Third fraction 3 *4120 *3-140 Fourth fraction 5 -5382 -4902 53-55 Acetic Practions 1 and 2 correspond closely enough with propiouic acid. Fraction 3 corresponds to propionic acid contaminated with a trace of some lower acid acetic of course; and fraction 4 corre-sponds to pure acetic acid. Thus mannite also yields to this treatment acids corresponding with those obtained by the oxida-tion of the olefine obtained from itself.We now proceeded to oxidize glycerin and mannite with our ordinary oxidizing mixture bichromate of potash and sulphuric acid. In both instances a most violent reactioii occurs; carbonic acid is evolved abundantly and formic acid produced. No other acid appears to be fwmed. The absence of other acids was proved by our ordinary process of fractionation and by the fact that on converting a portion of the distillate in both instances into baryta-salts and determining the percentage of barium the numbers obtained agreed with those required by formic acid. The results of these two experiments the treatment with caustic potash ThiB treatment with concentrated sulphuric acid does not injure any acid of the acetic series from acetic to caproic inclusive.32 CHAPMAN AND THORPE 03 THE RELATION ETC and the process of direct oxidation appear to be to a certain extent antagonistic. The latter process would lead one to believe that these two substances contain each atom of their carbon directly attached to hydroxyl and hydrogen. We observed that mannite in acid solution decolorized perman- ganate of potash. It appeared therefore of interest to determine how much permanganate a given weight of mannite would de- colorize. But as formic acid would probably be among the pro- ducts of the action we previously experimented on some formic acid and found that perrnanganate can exist in the presence of formic acid for some hours without decomposition provided the fluid hq strongly acid with sulphuric acid.In neutral or alkaline solu- tions the permanganate is rapidly decolorized. If therefore formic acid be once produced it would not be at once decomposed by the further action of permanganic acid. Having ascertained the behaviour of formic acid we proceeded to operate upon a sample of mannite in precisely the manner ordinarily employed in determining oxalic acid. At first the solution decolorized somewhat slowly exactly as in the case of oxalic acid; then the process rapidly quickened and for some time the decolorization of the permanganate took place almost instantaneously ; afterwards longer and longer periods were re- quired for the decolorization.When after ten minutes' standing the colour had not perceptibly decreased the process was stopped. 0*36*of mannite dissolved in dilute sulphuric acid decolorized 214 c.c. of permanganate of potash. 100 c. c. of the perman- ganate solution contained 0.094504 of available oxygen therefore the mannite had required 0.20372 of oxygen. This corresponds to 92 per cent. of the amount of oxygen required to produce for-mic acid. As there was so much difficulty in marking the completion of the reaction and as the perrnanganate solution qas much more rapidly decomposed when concentrated than when dilute we devised a modification of the experiment. More than sufficient permanganate of potash was introduced into a flask along with dilute sulphuric acid and a weighed quantity of maiinite added.After ten miirutes oxalic acid was added in more than sufficient quantity to decolorize the excess of permanganate employed. Then the excess of oxalic acid was in its turn determined by per-* 1-08of msnnite was dissolved in 150 c. c. of water and + of the solution em-ployed in each experiment. IIARTLEY ON CRLORSULPITIDB OF ClARI3ON. msngmate. The result of this roundabout experiment ras that a little more oxygen was employed than would have been required if the whole of the mannite had been converted into formic acid. 0.36 of mannite dissolved in dilute sulphuric acid mas treated with 300 C.C. of the above-mentioned permanganate solution. It was allowed to stand ten minutes.A known excess of oxalic acid was then added which immediately caused the fluid to become colourless and clear. The amount of odic acid in the fluid was then determined by the addition of permanganate. It appeared that 238 c. c. of permanganate had been required by the rnannite. Another such experiment was made with the exception that the liquid mas allowed to stand fifteen minutes before the addition of oxalic acid instead of ten. In this case 241 c. c. of permanganate were required by the mannite. From the first experiment it appears that 102.26 per cent. of the amount of oxygen required to convert mannite into formic acid was actually consumed in the operation. In the second ex- periment in which the action had been allowed to continue half as long again 103.6 per cent.of the required amount of oxygen mas actually consumed. These differences between the numbers found and those calcu-lated are very trifling and are amply accounted for by the slow action of permanganate upon formic acid. In order that no doubt whatever might rest upon the subject the formic acid was actually distilled out of the mixture remaining after these opera- tions. From it were obtained the well-known actions of formic acid. A portion of it was converted into a baryta-salt and the percentage of barium determined. 0.3402of the salt yielded 0.3468 of sulphate of baryta; there- fore 59-93per cent. of barium. Theoretical percentage 60.30. Therefore mannite is decomposed by nascent oxygen thus :v C,H,,06 + 70 = 6CH,O + H20.

ISSN:0368-1769    

DOI:10.1039/JS8672000030

出版商:RSC    

年代:1867

数据来源: RSC

摘要:

IIARTLEY ON CRLORSULPITIDB OF &IRl3ON. 1V.-On a Chlorsulphide of Carbon By WALTER NOELHARTLEE-. INthe preparation of a large quantity of dichloride of carbon tlr tetrachlorethjlene a solution of hydropotassic sulphide was used VOL xx. D HARTLEP ON CHLORBULPMDE OF CARBON. for reducing the terchloride of carbon according to the following equation :-The mode of operation was as follows :-To a mixture of the di- and terchlorides which contained as an impurity the protochlo- ride of carbon was gradually added the reducing agent prepared by dissolving potash in absolute alcohol and passing sulphuretted hydrogen through to saturation ; after warming slightly the re- action ceased and the reduced chloride of carbon was precipitated by water from its solution in the alcohol separated and distilled.There was a residue in the retort after distillation which had a brown colour and a remarkable smell suggestive of a sulphur compound. For examinatioii a portion was heated in a test-tube and the result was a sublimate of sulphur and fine needle-shaped cl*ystals. On digestion in alcohol the substance proved to be soluble and left on evaporation a deposit of brownish crystals. TOpurify this substance it was boiled in a flask with much alcohol and animal charcoal an inverted condenser being attached to prevent the waste of alcohol; the liquid after about four hours was filtered hot and allowed to cool in a porcelain basin; the crys- tals sere separated; and the alcohol was used again to extract what yet remained in the flask; a fresh crop of crystals formed and the alcohol with a little added to it was used again and again until the solid residue was exhausted.The substance not yet quite pure was again treated with alcohol and charcoal and the filtrate was allowed to evaporate spontaneously. The resulting crystals slightly yellow in dour were dried under the air-pump and submitted to analysis. The specimen beiug only small a8 little as possible was used. 0.109 grms. burnt with chromate of lead gave 0.0519 grrns. of carbonic acid corresponding to 00141 grms. of carbon or 12-93per cent. 0.115 grms. were burnt in a small combustion-tube with pure quicklime and oxygen was passed through the tube ; it was then while hot dipped cautiously into water as in an ordinary chlorine determination and treated with nitric acid.The solution yielded with nitrate of baryta 0.424 grms. of sulphate corresponding to 0.058 grms. of sulphur or 50*43per cent. On treating with nitrate of silver thc filtrate yielded 0.17 SLARTLEY ON CHLORSULPHIDE OF CARBON. grms. of chloride of silver corresponding to 0.042 grms. of chlorine or 36.52 per cent. Calculated for the Found by snalysis. formula Q2CI,S.;. C= 12.93 per cent. 12.56 C1 36.52 , 37.1'7 s 50.43 )) 50.26 99.88 ) 99-99 The formula deducible from these data is then €2C12S3 the name applicable under these circumstances being chlors u lp h o-form a body of the composition G2H2S,,being already known and called sixlphoform it being chloroform in which sulphur re-places chlorine.Chlorsulphoform crystallises from solii tions and by sublimatiou in fine needles possessing a disagreeable and peculiar smell soluble in alcohol and ether with difficulty; easily soluble in chloroform the bisulphide and the liquid chlorides of carllon and in oil of turpentine. Its melting-point is not below 250° C. andit begins to sublime before it melts. 'When it is treated with moderately strong uitric acid in sealed tubes for three or four hours at 120° to 130" C. white crystalline scales are formed of which 1 had not enough for analysis but from their contRiriing sulphur which fact I provcd and the nitric acid containing snL phuric acid they may be regarded as a substance with perhaps this formula G,Cl,SB,.The formation of the chlorsulphoform can be in no way explained except by supposing that the sulihr pro-duced in the reducing process just as it gains its state of freedom combines with the protochloride of carbon (G2Cl2). Facts sup-port this idea for if there be no G2Cl2 in the mixture to be reduced none of the new compound is formed and unless much sulphur be separated in the reaction we find the G2C12unacted upon; a solution of the hydropotassic sulphide alone has no action on it. I do not know that any other substance has been obtained by the actioq of nascent sulphur; if not this may be the first in- stance of the formation of a compound being attributed to such an agent. The subject of this paper is part of an unfinished research upon which I mas working last year in the laboratory of Professor K ol be.

ISSN:0368-1769    

DOI:10.1039/JS8672000033

出版商:RSC    

年代:1867

数据来源: RSC

摘要:

3c V.-On a New Class of Compounds coniaining Nitrogen iiz zuliich Hydrogen is replaced by Nitrogen. By PETER GRIESS. {Abstracted by the Author from the Philosophical Transactionn for 1865.1 ALL the different nitrogen-substituted compounds that I have studied up to the present moment may according to their com- position and their chemical deportment be arranged in two different classes. If the composition of amido-compounds be expressed by the gerieral formula C,H,,,, (NH3)"0,*) the dif- ference in the mode of formation of the two classes may be illustrated by the following equations :-Whilst thus in the first case the substitution of three atoms of hydrogen by one atom of nitrogen takes place in two atoms of the amido-compound it is in the second case confined to one atom Hence it is obvious that for every amido-compound there must be two corresponding nitrogen-substituted bodies.The conditions which have to be observed in order to lead the reaction at will either in the one direction or the other differ occasionally according to the special character of the amido-corn- pound ;but in general it may be taken as a rule that the action of nitrous acid upon neutral solutions of the amido-compounds gives rise to compounds of the first class whilst those obtained by em-ploying an acid solution belong to the second class. I haveup to the present moment chiefly submitted to minute * Chemisb are not agreed upon the rational constitution of amido-compounds. They are frequently referred to the ammonia-type and almost as frequently to the same type to which the nitro-compounds from which they are derived belong.In the latter case the group NH2is considered a8 repIacing one atom or NH3as taking the place of two atoms of hydrogen. Aniline can thus be written in three different ways and expressed by the three formule Cs%HJN? CfjHdH2W CJ&(HJY)". Phenglamine. Amidobenzol. Ammoniabenzol. The two latter formule appear to me to be capable of explaining in the most natural manner the formation of bodies in which nilrogen i8 substituted for hydrogen. CONTAINING NITROGEN ETC. 37 examination members of the first series of compouuds for instance diazo-arnidsbenzoic acid and diazo-amidobenzol ; the latter substance in order to give a practical illustration being formed according to the following equation :-2C6H,N + NHO = C,,H,,N -I-2H,O.As a representative of the second class may be taken diazo-dinitrobensol the formation of which takes place thus :-C,~T,(_\.:0,),NM20 + NHO = C,H,(NO,!,N,O + 2T1,O. To this last group belong also a number of compounds formed from organic bases the existence of which up to the present time I have communicated only in short notes as for instance diazo- benzol (C6H,N,) diazonaphthd &c. I have now had the oppor-tunity of submitting these bodies also to a more minute examina- tion and I will endeavour to communicate the results which 1 have obtained in this and several following papers. Here already I will mention that all these bodies are particularly distinguished by the great variety of their forms of combinatioii and that iza this respect they exhibit peculiarities not to be found elsewhere in the domain of organic chemistry.In the free state they are remarkable for their extraordinary instability whilst in their com- binations on the other hand they are comparatively stable. The following examinations were conducted therefore chiefly with the latter. Very conspicuous also are the physical properties of these peculiar substances as well as the great number of their products of decomposition ; in consideration of all these proper- ties they may be viewed as one of the most interesting classes of chemical compounds. I have avoided as much as possible discussing their rational constitution and have abstained from theoretical speculation.I maintain however that the two atoms (or the molecule) of nitro-gen N, they contain must be considered as equivalent to two atoms of hydrogen as is the case with the bodies described in my preceding papers and it is in accordance with this view that the names of the new compounds have been framed. In the present paper I intend to confine myself solely to the description of diazobenzol and its derivatives. Nitrate of diazobenzol is of special importance as the etarting point for the preparation of all the other derivatives? and 1will therefore give its description the precedence GRIESS ON A NEW CLASS OF COMPOUNDS Nitrate of IXuxo benzol C6H4N,.NHO,. This substance can be prepared in various ways; most readily however by acting with nitrous acid upon a solution of nitrate of aniline.This salt of aniline is not very soluble in cold water; therefore in order to obtain a concentrated solution of the new compoundj it is best Eo make a thick paste by grinding up a por-tion of the nitrate with water and submitting it to the action of the gas when the undissolved portion of the aniline-salt rapidly disappears and thc whole is converted into the uew body. The reaction being accompanied by considerable increase of tempera-ture it is necessary to keep the solution cool and to guard against passing a too-rapid current of the gas. The temperature of the solu- tion should not rise much above 30" C. The operation is inter-rupted as soon as the whole of the aniline has disappeared.This can be ascertained by adding a little strong solution of potaesa to a portion of the liquid on a watch-glass when if no more aniline is liberated it may safely be inferred that the reaction is com-plete. The nitrate of diazobenzol is almost insoluble in ether and even in ether mixed with much dilute alcohol in consequence of which it may readily be obtained in a crystalline state thus :-the soiution is first filtered to remove traces of a brown resin then mixed with about three times its volume of strong alcohol and ether added until the precipitation is complete. The crystals are allowed to subside and then filtered from the mother-liquor. The small quantity of' the new body which remains in the mother- liqsor may be neglected altogether as its recovery is accompanied with great difficulty.To remove the last traces of colouring matter the crystals are taken up with eold dilnte alcohd and re-precipitated by the addition of ether when they are obtained as long white needles. Analysis as will be shown further proves that the new com-pound has the formula C6H4N,.NH0,. Its formation may be explained by the following equation :-CkH7N.NH0 + NHO = C6H4N2.NH0 -I-2H@. Nitrate of aniline. Nitrous acid. Nitrate of diazobenzol. Water. - Another method of preparing nitrate of diazobenzol is based Upon the action of nitrous acid upon diaao-amidobenzot a body CONTAINING NITROGEN ETC. 89 described in a previous communication. On dissolving this latter compound in cold ether and passing a current of nitrous acid gas through the solution long acicular crystals of the new substance soon appear.The action should be continued as long as crystals form. The compound so obtained is collected on a filter and washed with ether. The reaction is expressed by the folIowiag equation :-C12H,,N + NHO + ZNHO = 2(C6H,N,.NH0,) + 2H,O. Diazo-amido-Nitrate of diazobenzol. benzol. However elegant and simple this method of preparation of the nitrate of diazobenzol may appear it will scarcely ever be em-ployed since it involves the previous preparation of diazo-amido-benzol a body which it is rather troublesome to obtain in large quantities. Xitrate of diazobenzol can also be procured by the direct action of nitrous acid upon a mixture of aniline with about four times its volume of alcohol.The gas is passed into the alco- holic solution till on the addition of ether to a small portion of it a copious precipitation of white acicular crystals is produced. . When this point is reached the whole of the reddish-brown soh-tion is mixed with ether and the precipitate purified as already described. This method of preparing the nitrate however is not suitable when large quantities have to be prepared. It is similar in prin- ciple to the preparation by means of diazo-amidobenzol since to all appearance the aniline is first converted into this compound. The methods just described although simple will only give favourable results when strict attention is paid to the directions given above; for it happens sometimes and especially when the temperature of the solution is allowed to rise too high that a copious evolution of nitrogen gas ensues which cannot be stopped by any means before the whole of the substance has been de..stroyed. By employing the first of the above processes it is sometimes found that on' the addition of ether to the weak alcoholic solution of the crude compound no crystals separate but that an aqueous layer is deposited at the bottom of the vessel. This however happens only when an insufficient amount of alcohol has been originally added to the solution because in this case the ether not being able to mix with the liquor causes no separation of GlLIEM ON h NEW CLASS OF CO;1I[POUKDS crystals to take place.If this occurs it is best to remove the ethereal liquor and dilute the residuary aqueous solution with strong alcohol when on the addition of ether crystallisation invariably ensues. The nitrate of diazobenzol by whatever method it may have been prepared crystallises in long white needles which have been obtained several inches long and are very soluble in water less so in alcohol and almosl insoluble in ether and benzol. They can be dried over sulphuric acid without undergoing any change. Heated even below 100' C. they explode with unparallelled violence far surpassing that of fulminating mercury or iodide of nitrogen. About a gramme of this substance causes by its explosion a con-cussion like that produced by firing a pistol.The destructive action cf such an explosion is likewise extreme. Iron slabs of several lines in thickness were found smashed to atoms when 8 somewhat larger quantity was esploded upon them. Friction pressure and concussion also cause it to explode. The smallest particles of this substance accidentally dropped upon the floor of a room when trodden upon mhen dry gave rise to a series of explosions attended witti flashes of' light. The properties of the nitrate of diazobenzol render it absolutely necessary that the greatest precaution should be observed when manipulating it. The portion of the substance required for analysis having been well washed with ether,* was placed in a platinum crucible and dried over sulphuric acid.Concussion or pressure had to be care-fully avoided especially with the dry substance on account of its great explosiveness. * When it is intended to recover the ether employed in thc preparation of nitrate of diazobenzol it is advisable in order to avoid explosions to shake the ethereal mother-liquor first with a little water so as to dissolve any traces of the diazo-corn- pound suspended in it. I have had amost danger0us:explosion byneglecting this simple precaution. A large quantity of ether which had been employed for the precipita- tion of the new compound from it<salcoholic solution had accumulated. From thie liqllid a few crystals were observed to have separated. Their number seemed however to be SO small that it was deemed unnecessary to remove them from thevessel containing the ethereal liquid for distillation.As soon as the vessel became warm in the water-bath and before the boiling-point of the ether had been reached a fearful explosion took place shattering the whole of the distilling apparatus to pieces and setting fire to the ether the flame of which spread most alarmingly through the laboratory. The gas-flames which were burning at the time in the room were suddenly extinguished by the violent pressure upon the atmosphere and zd1 those working in the laboratory (who fortunately escaped unhurt) mere for a moment deprived of their breath. The explosive properties of the nitrate of diazo. benzol perhaps at a filtilr3 period find practical applicstiop CONTAISTNG NITROGER ETC.4L For the above mentioned reasons I abstained from analyzing this compound in the usual manner especially as I had opportu- nities of ascertaining the eompositior of analsgous but less dan- gerous compouiids by the ordinary analytical methods. I have however been enabled to arrive at a knowledge of the composition of nitrate of diazobenzol by the very interesting change which an aqueous solution uadeigoes by the action of heat. By ebullition the wmpound is transformed under the influence of the water into carbolic acid nitrogen and nitric acid; and by estimating the quantities CJf the two latter products I have arrived at thc trw cornposition of the explosive substance CGH,N,.NE-IO + fI,O = C6H60 f NHU fN,. Nitrate of diazobcnzol. Carbolic acid.The method employed for the determination of the quantity of nitrogen evolved by the ebullition of the aqueoiis solution of the explosive compound is as follows :-The solution was introduced into a flask and a stream of carbonic acid gas passed through it. When the air was expelled the delivery-tube was placed under a graduated cylinder containing solution of potassa and the contents of the flask heated to ebullition.* I. 0.605 grm. of the compound treated as above gave 80.4 cub. centims. of nitrogen at Oo and 760 millims. bar. pres-sure = 0.101 grm. of nitrogen or 16.70 per cent. Theory. Experiment. N = 17.77 16.70 11. *492grm. of substance dissolved in water and boiled required for neutralisation 29.5 cub. centims. of standard alkali solution corresponding to 0-185 gym.of nitric acid or 37-77 per cent. Calculated. Pound. (---h---7 C6114N .. 190 62.27 NHO,.. .. 63 37.73 37.77 L--253 100.00 Subhate of Diaxobenzol C,H,N,.SH,O,. Acid sulphate of aniline when treated with nitrous acid is f In all analyses mentioned herein the analyzed substance8 are understood ioh deaiccated by sulphuric acid previoudy unless the contrary is dktinctly ~tqted GRIESS ON A NEW CLASS OF COMPOUNDS converted into sulphate of diazobenzol according to the eqiia- tion-4 4 r A *C,H,N.SH,O + NIIO = C7H,N,.SH,04 -j-2E1,O. Acid sulphate of Sulphate of diazobenzol. aniline. On account of the slight solubility of sulphate of aniline aid in order to avoid employing a large quantity of liquid it becomes necessary to suspend the salt in water and to expose it in this state to the action of nitrous acid.The reaction however is very slow and the salt is only gradually converted into the diazo- compound I found it therefore more convenient to prepare thc sulphate from the nitrate of diazobenzol by treating a concen-trated aqueous solut'iont of the latter with a sufficient quantity of sulphuric acid previously diluted to avoid rise of temperature upon addition. Tbe solution thus obtained is then mixed with tliree times its volume of absolute alcohol and lastly with a sufficient amount of ether which causes the sulphate of diazobenzol together with some water to separate in a layer at the bottom of the vessel the liberated nitric acid together with the excess of sulphuric acid remaining mixed with the supernatant alcohol and ether.This latter is decanted and the solution of the snlphatc (with a yiew to the removal of a further quantity of water) is once more treated with absolute alcohol and reprecipitated by means of ether. The precipitated liquid is then placed in flat dishes over sulphuric acid when it soon solidifies to n magma of white crys- tals. In order to purify these crystals completely they are washed on a filter with a mixture of alcohol and ether which removes any trace of sulphuric and carbolic acids that may have been produced by a partial decomposition of the sulphate of diazo-benzol then dissolved in weak cold alcohol and precipitated by the addition of ether.The crystals are separated without delay from the mother-liquor and dried over sulphuric acid. Sdphate of diazobenzol cry stallises in prisms which readily dissolve in water but are soluble with difliculty in absolute alcohol and insoluble in ether. The aqueous as well as the alcoholic * Ordinary mlphate of aniline containing excem of free sulphuric acid is under-btood by this formula. .t-The crude solution obtained by the action of nitrous acid upon nitra:e of aniline may be employed. CONTAINING NITROGEN ETC. solution is decomposed on boiling with evolution of gas. Exposed to the air this compound attracts moisture very rapidly becomes liquid and gradually decomposes. Heated alone it deflagrates feebly at about 100"C. Hydrobronzute of Diazobenrol C6f14N,,HBr.This compound is prepared by the action of bromine upon diazo-amidobenzol. When an ethereal solution of bromine is gradually added to a rather concentrated solution of the diazo-amido-corn- pound each drop of the bromine-solution is seen to produce a precipitatioii of the hydrobromate of diazobenzol. When no more crystals are formed the precipitate is separated from the mother-liquor washed with ether till quite white and then dried over sulphuric acid. All these operations must be performed as speedily as possible since thenem compound is of a very unstable nature and rapidly decomposes. Should it be found necessary to recrystallise the precipitate it must be dissolved in the least possible quantity of cold alcohol and ether added to the solution till no more precipitation takes place.Hydrobrornate of diazobenzol crystallises in white nacreous scales which like the compound previously described are readily soluble in water less so in alcohol and insoluble in ether. The solution of this' compound is distinguished by a strong acid re-action. Heat friction and pressure cause the crystals of the hydrobromate to explode with the same violence as the nitrate of diazobenzol. Even when in a perfectly dry state this compound can only be kept for a short time without undergoing decomposi- tiou (which is accompanied by the production of a peculiar aromatic odour) the decomposition being complete in a few days. It is formed according to the equation CI,H,,N2 + 6Br = C&I,N,.HBr + C,H,Br,N -k 2HBr.Diazo-amido-Hydrobr0mat.e of Tribromaniline. beuzol. diazobenzol. Tribromanilint; rcmains in the ethereal mother-liquor from which it crystallises on evaporation. It is most likely that by the action of chlorine upon diazo-amidobenxol hydrochlorate of diazobenzol may be obtained. An aqueous solution of this latter cornpound however may also be prepared by treating a solution of the hydrobromate with moist chloride of silver Perbromide of Diaxobenzol C H,N, HBr.Br,. On adding a small quantity of bromine-water to an aqueous solution of the nitrate of diazobenzol a white crystalline precipi- tate of tribromophenylic acid is usually obtained owing to the presence of a small quantity of phenylic acid formed by the spon-taneous decomposition of the nitrate by water.On removing the tribromophenylic acid as quickly as possible by filtration slid on adding a large excess of bromine-water containing free liydrobromic acid to the filtrate the new bromine-compound separates as a brownish-red oil which solidifies to a crystalline mass soon after the supernatant liquor has been removed. The crystals are obtained pure for analysis by washing with a little ether. Perbromide of diazobenzol which crystallises in yellow plates is insoluble in water rather difficultly soluble in alcohol and in-soluble in ether. It is comparatively stable when dry. Its alcoholic solution on the other hand rapidly decomposes even in the cold with evolution of gas.For this reason it is irnpossi- ble to recrystallise it without loss. In order to purify this unstable perbromide it is most advantageous to dissolve it in cold alcohol and to allow the solvent to evaporate spontaneously in shallow vessels in the open air. Very fine crystals are usually obtained in this manner but contaminated with trifling quantities of an oily product of decomposition which however may be removed by mashing with a little cold ether. On application of heat this com- pound deflagrates at a comparatively low temperature. The con-stitution of the perbromide of diazobenzol appears to be the same as that of periodide of tetrethylammoaium and similar compounds of other bases. Platinum-salt of Hgdrochlorate of Diaxobenzol C,H,N,.HCl.PtCl, is obtained by the addition of bicliloride of platinum to a rather concentrated aqueous solution of the nitrate of diazobenzol.The fine yellow prisms which are precipitated are almost insoluble in alcohol and ether. They are rather stable; when kept for some time however they acquire a bromish colour and arc grndnal!y hut completely decomposed. Ou heating they deflagrate ;Iicnce it it is impossible to estimate the platinum by simple ignition. Gold-sali of Hydrochlorate of Diazobenxol C6H,N,HC1,AuCl3. By the addition of terchloride of gold to a dilute aqueous solu-tion of the nitrate of diazobenxol this compound is obtained in the form of a light-yellow crystalline precipitate insoluble in water but soluble in alcohol especially when warm from which on cooling it is deposited in the form of’ small golden-yellow plates.This salt cannot hom.ever be recrystallized without some loss especially when the alcoholic solution is heated to bciling. The decomposition is indicated invariably by an evolution of gas ; contirmed boiling with alcohol destroys it completely It is well known that when bromine chlorine or hyponitric acid is substituted in organic compounds for certain hydrogen atoms the product formed is distinguished from the original com- pound if the latter be an acid by stronger acid properties or if a base by less pronoixnced basic characters; and also that the con-trary is observed in the case of substitution of potassium NH, &c. for the same hydrogen-atoms. Nitrogen however exhibits in this respect a peculiar double nature since it is found only slightly (or not at all) to affect the basic properties of a compound whilst at the same time it exerts so decided an acidulating action as to impart to strong bases an acid nature.I have already clearly shown that diazobenzol has all the characters of an organic base capable like aniline of forming saline compounds with acids. It possesses at the same time the property of combining with metallic hydrates playing to a certain extent the part of an acid. These metallic derivatives are as a rule distinguished by the same instability as the corn- pounds of diazobenzol with acids. They are less affected horn-ever by heat. Their aqueous or alcoholic solutions can be heated to boiling for some time without suffering complete decomposition.Heated alone they explode although at a much higher tempera- ture and not with so great violence as the bodies previously rte-scribed. The compounds which are soluble in water are mostly well crystallised whilst the insoluble ones such as those formed with silver and lead are obtained as amorphous piwil)itates GRIESS ON A NEW CLASS OF COMPOUNDS Compound of Hydrate of Potassium with Diaxobenxol C,H,N,. KHO. By introducing a very concentrated solution of nitrate of diazo-benzol into an excess of an equally concentrated solution of caustic potash drop by drop a yellowish liquid is obtained possessing a peculiar aromatic odour and solidifying by evaporation in the water-bath to a crystalline mass.This is a mixture of the com-pound of hydrate of potassium with diazobenzol and nitre to-gether with a brownish-red amorphous body-the result of a secondary reaction which a portion of the original substance undergoes aud which is always indicated by the evolution of gas. In order to separate these bodies it is necessary to remove the excess of caustic potash. This is best done by putting the crys- talline mass into a strong linen cloth and squeezing it powerfully between porous stones. The dry cake is then treated with abso- lute alcohol which readily dissolves the compound of hydrate of potassium with diazobenzol leaving the nitrate of potassium in- soluble; it is then separated by filtration. The alcoholic filtrate (which on account of the above-mentioned secondary product of decomposition possesses an intense reddish-brown colour) is then evaporated on the*water-bath.The residue is once moTe pressed and washed with a mixture of alcohol and ether to remove the reddish-brown substance ;the compound is then obtained nearly white. By again pressing aad dissolving the dry cake in a small quantity of absolute alcohol filtering and adding a sufficient amount of ether the substance is obtained in white plates which must be dried at once over sulphuric acid. The compound of hydrate of potassium with diazobenzol crys-tallises in small white soft plates which become reddish by ex- posure to the air; they are very readily soluble in water and alcohol but insoluble in ether.The solution has a strong alkaline reaction. A freshly prepared aqueous solution is hut slightly coloured; but by keeping for a short time it rapidly acquires a yellow colour and ultimately a reddish-yellow substance is preci-pitated. Ebullition does not seem to accelerate this decomposition materially. The dry substance is very stable and cm be kept a long time unchanged Heated alone it explodes at n little above 130";the explosion is accompanied by a slight report. CONTAINING NITROGEN ETC Compound of Hydrate of Silver with Diasobenxol C,H,N,.AgHO. This is obtained as a white or slightly chocolate-coloured pre- cipitate by treating a freshly prepared solution of the previous compound with a solution of nitrate of silver. After removing the mother-liquor the precipitate is thoroughly washed with water dried by pressing between filter-paper and finally over sulphuric .-acid.The compound of hydrate of ailver with diazobenzol is insoluble in all the ordinary neutral solvents. Nitric acid even when cold dissolves it with great facility. It is distinguished by great sta- bility; for even after having been kept for weeks not the least sign of decomposition could be discovered. Exposed to a higher temperature it explodes with some violence. Compound of Hydrate of Barium with Diaxobenrol. This compound is obtained when a solution of a very soluble barium-salt is added to a rather concentrated solution of the potas- sium-compound. It is precipitated in the form of white rnicro- scopic indistinct needles or plates which become yellowish in consequence of a gradual decomposition.It is difficultly soluble in water. The compound of diazobenzol with hydrate of zinc is a white amorphous powder insoluble in water. The compound with hydrate of lead is also a white powder but acquiring rapidly a yellow colour. With sulphate of copper a brown precipitate changing to green is obtained. Mercuric chloride gives a white precipitate. Diaxobenxol C,H,N,. This remarkable substance is obtained when an aqueous mlu-tion of the compound of hydrate of potassium with diazobenzol is treated with a sufficient quantity of acetic acid. A thick yellow oil it liberated which possesses a peculiar odour and is remarkable for its extraordinary instability.Its existence is very ephemeral and after a short time nitrogen gas begins to be evolved and the oil is rapidly converted into a brownish-red substance. The heat which is produced when larger quantities of the oil undergo this spontaneous decomposition is sufficient to give rise to dangerous explosions The addition of ether to the oil dissolves it instantaneously producing a red solution a tumultuous evolution of gas taking place. It combines with nitric and sulphuric acids and vith hydrate of potassa terchloride of gold &c. forming the com-pounds previously described. COMPOUNDS WITH BASES, OF DIAZOBENZOL ORGANIC Diazo-amidobenzol as is well known is formed by the action of nitrous acid upon an alcoholic solution of aniline according to the equation f2CGHYN + NHO = C12H,,N3 + 2H,O.Aniline. Diazo-amid obenzol . By viewing this body as a double compound of diazobenzol and aniline I mas led to prepare it by the direct action of aniline upon COM-pounds of diazobenzol. This reaction proceeds readily on mixing an aqueous solution of nitrate of diazobenzol with aniline when a viscid yellow mass is speedily produced which becomes crystdline after a short time and can be obtained in a perfectly pure state by several recrystallisatioid from alcohol. The formation of the diazo-amidobcnzolmay be expressed as follows :-C6H,N2.NI-I0 -I 2C,H7N = Cl2H1,N3+ C,H,N.NH03. Nitrate of diazobenzol. Aniline. Diazo-amidobenzol. Nitrate of aniline. On referring to the equation given on page 39 for the formation of nitrate of diazobenzol from diazo-amidobenzol it is seen that these two bodies may be readily transformed into one another.LMauy other bases deport themselves with nitrate of diazobenzol exactly like aniline and we may therefore look forward to the dis--sF Any cxccs~of anilinc must be rcrnwcd Eg n?e;lns of acetic =id kefore crysk?A!-lisation. CONTAINING NlTROGEN~ ETC. covery of a large number of double compounds analogous to diazo-amidobenzol. It is not my intention to give a full history of these compounds as a few short statements will shorn clearly how closely they are allied to their prototype diazo-amidobenzol. Diaxobenzol-amidobronobe~~zol,C6H6BrN]. {c6H4N2 This compound is obtained by the action of hromaniline upon riitrate of diazobenzol.It crystallises in very fine small yellow plates or needles which are rather difficultly soluble in alcohol but readily soluble in ether. Its platinum-salt is obtained as a buff-coloured precipitate consisting of fine hair- like crystals. Nitrate of silver produces in an alcoholic solution a yellow precipitate similar to that of the compound previously described. In the formation of the above bodies two atoms of base enter into chemical action with one atom of nitrate of diazobenzol forming together with the diazo-amido-campound the nitrate of the base employed. Naphtalidine (amidonaphtol) however com- bines directly in equal numbers of atoms with nitrate of diaso-beuzol giving rise to a compound which has the formula and which as will be shown must be viewed as nitrate of diazo-benzol-amidonaphtol = This compound is ob-333)NHO,.10 9 tained in an impure state as a violet crystalline precipitate on adding an aqueous solution of nitrate of diazobenzol to an alco-holic solutiori of naphtalidine. It is purified by repeated washings with cold alcohol and recrystallisation from the same forming beautiful green prisms. Its formation takes place according to the equation C6H4N2NH03f C,,H,N = Cl6H14N403. Xitrate of diazo-Naphtalidine. Nitrate of diazo-henzol. benzol-amidonaphtol. YOL. ss €? GRIESB ON A NEW CLASS OF COMPOUKDS lt is one of the finest bodies of which chemistry can lionst. It crystallises in well-defined prisms which by reflected light are of a magnificent grass-green colour but ruby-red Lg transmitted light.The crystals are almost insoluble in water and ether Hot alcohol dissolves them freely and redeposits them almost entirely on cooling. DiaxobeikxoZ-amidonu~htoI 10 9 This compound is obtained from the previous substance by removing the nitric acid by means of ammonia or potnssa. It crystallises in very brilliant ruby-red prisms readily soluble in alcohol and ether forming yellow liquids. Acids impart a beauti-ful violet colour to these solutions. Bichloride of platinum pro-duces a purple-blue crystalline precipitate ; nitrate of dyer it yellow precipitate which consists of small fine needles. It is worth mentioning that these diazobenzol-arnido-compounds can also be obtained by acting with an aqueous solution of the salts of the respective bases upon the compound of hydrate of potassium with diaxobenzol.The reaction which takea place may be expteaaed by the following equation :-C6€I,N,KH0 + C,H,NHCl = C,,H,,N + KC1 + H,O. Hydrate of potasaitim Hydrochlorate Diazo-amido-with diazobenzol. of aniline. benzol. COMPOUNDS DIAZOBENZOL AMIDO-ACIDS. OF WITH Amido-acids are likewise capable of entering into combination with diazobenzol. One mould have expected that the compounds to which this reaction gives rise would deport themselves in an analogous manner to the sulphate or nitrate of diaeobenzd which like the salts of organic bases are capable of double decomposition. This however is not the case.The compounds of diazobenzol with amido-acids behave more like simple bodies exhibiting much similarity to the diazo-amidobenzol being capable like the latter of forming with bichloride of platinum double compourids of the nature of the potassio-biciiloride of platinum. They possess moreover the property of combining with metals giving rise to bodies which correspond entirely to the salts of simple acids. CONTATMING NITROGEN ETC. DicrxobenxoI-*ami dobenzoic acid c,II,NO,o This cornpoiind is obtained by simply aixing an aqueow solution of the nitrxte of diazobenzol (1 molecule) with a solution of amido-benzoic aciJ (2 molecules). It separates as a yellow crystalline precipitate vi:ich is readily freed from the mother-liquor rid when dry dissolved in ether and filtered.The ethereal solution deposits on evapomtion yellow crystals which are obtained piire for analysis by washii;g with cold alcohol. This body is fomcd according to the equation C6H,N2.NH0 -I-?,C,H,NO = C,,HllN,02 + C,H,NO,.NHO,. Nitrate of diazo- Amidobenzoic Diazobenzol-amido-Nitrate of amidoben-benzol. acid. benzoic acid. zoic acid. DiazQbenzol-.nmidobenzoic acid forms small indistinct plates or crystalline grains. It is almost; insoluble in wzter very difficultly sduble in alcohol and easily soluble in ether. Solutions of ammonia potash or cnrbonatc of potassiiiin dissolve the acid readily the solution acquiring a yclkm colonr. On heating a little of the substance on platinum-foil it fuses aid is rapidly decomposed tlic decomposition being accompanied by a violent evolution of gas.Cold dilute mineral acids act upon it but slowly; on heating howemr speedy dccomyosition ensues. Acetic acid even when highly concentrated has no action is the cold but the appli-cation of heat destroys it. Platinum-salt of the Hydrochlorate of D-iazoben~oZ-asnidob~nnoic Acid C 3H N,02.2HC1.2PtC1,. This ccmpound forms small yellowish-white indistinct; plates and is obtained by adding an alcoholic solution of bicldoride of platinum to the ethereal solution of the diazobenzol-Rmido’senzoic acid. Diazobeuzo~-arnidobenzoicacid in its behaviour with bases is similar to a bibasic acid sincr it combines with metallic bodies in two ways. All the salts formed at*ecomparatively stable ;tlmse for example which are solnble in water 2i.s t!ic potassium-salt will eve& bcar recrystallisation.Vith the oxide of silver and barium it GRTESB ON A NEW CLASS OF COMPOUXDS forms insoluble precipitates. A more minute description of t1:ese compounds I must defer to a future time. Compounds analogous to diazobenzol-arnidobenzoic acid arc formed when amido-dracjlic acid [isoamidobenzoic acid) amiclo -anisic acid &c. are made to react in the manner previously de-scribed upon nitrate of diazobenzol. It is my intention to investi- gate these compounds more specially and I therefore abstain from entering further upon their description only noticing that they possess a remarkable resemblance to diazobenzol-amidobenzoic acid.CONPOUNDS IMIDOGEN OF DLAZOBENZOL. By this name are designated a peculiar class of diazobenzol-compounds obtained by the action of ammonia ethylamine and analogous organic bases upon perbromide of diazobenzol (C4€14N2. HBr.Br2). All the compounds hitlierto described exist in the solid state and none of them can be volatilised without decomposition ; the new compounds to be described on the other hand are liquids which can be distilled and which possess the narcotic odour of some vegetable bases such as conidine and nicotine. Beyond this odour however they have nothing in commou with these natural bases. They are indifferent bodies combining with neither acids nor bases. Diazobenxolimide C,H,N = (C6H4:2)’’} N. On treating perbromide of diazobenzol with aqueous ammonia a speedy decomposition ensues with evolution of much heat.The products of the reaction are first bromide of ammonium mhicli passes into solution ; secondly diazobenzolimicle IVhich separates as a heavy oil rather highly coloured by n brown substance simul- taneously produced in small quantity. By repeatedly distilling the oil with water it is obtained perfectly pure and of a slightly yellowish colour ; the substance which imparts to it the intense brownish colour not being volatile is left behind in the retort. The purified oil is separated from the water by a separating filnnel placed over chloride of calcium and then distilled once more from a water-lath in vacuo. Its formation is explained by- the following eqiiation :- COKTAINIXG NITROGEN ETC.HI + 3911,~r. C6H,N,.HGr.Bi* + 4XH = C&',N,7 l'erbromide. Diazobenzolimide. Diazobenzolimide is remarkable for its narcotic aromatic-ammo- iiiacal odoui.. It is volatilised by distillation with water and also when heated in oacuo as shown above. TTlieu distilled at the orcli-nary atmospheric pressure it decomposes with explosive violeuce. Alcohol and ether dissolve it with soine difficulty. I could not sue- ceeci in solidifying the oil by using a frigorific mixture of nitre and sal-ammoniac. Hydrochloric acid even when concentrated and aqueous potassa have no effect upon it. Strong nitric and sul-phnric acids dissolve it with decomposition. This body is obtained in a manner exactly similar to the one employed for the preparation of diazobenzolimide viz.by acting with ethylamine upon the perbromide of diazobenaol It is like-wise a yellowish-coloured d having a deceptive resemblance to the previously described compound. PRODUCT^ OF DECOMPOSITION OF THE DIAZOBENZOL-COMPOUNDS. The transformations which the molecule of diazobeuzol under- goes through the influence of various reagents are numerous and there is probably no other body to be met with in the large field of organic chemistry that surpasses it in this respect. The pro- ducts of decomposition to which it gives rise frequently possess new and very distinctive features ;more frequently however they belong to the benzol or phenyl group in which latter case their formation depends upon the great inclination which the two nitrogen-atoms of the diaaobenzol exhibit to escape and to cedc their place to other atomic groups of the same value (HH).Deportment of Diaxobenxo2-cornpounds when boi Zed in aia aqueozts solution. The transformation of nitrate of diazobenzol under the in-fiiience of boiling water has already been noticed. A similar 5-11 GRIESS ON A NEW CLASS OF comoums change is observed with regard to its sulpliate and hydrobroinate as will be seen from thc following equations :-C6H,N,.SH,0 + H20 = C61160 + SH,O + N,. Sulphate of Phenylic diazobenxol. acid. c6H,N,.HBr + H,O = C6H60 + HBr + N,. Hydrobromate Plienylic of diazobenzol. acid. On the other hand the compounds of diazobeiizol with metallic hydrates exhibit a very different deportment with boiling water.B,V neutralizing the mctal however with a mineral acid the de- composition takes place in accordanee with the above equations. Action of Alcohol upon Nitrate of Diuxobenzol By gradually and cautiously introducing the nitrate of diwzo- benzol into a moderate quantity of alcohol (previously warmed to about 50" C. in order to accelerate tlie solution) and submit- ting the whole to distillation in a water-bath a yellow residue remains which solidifies to a crystalline mass on cooling and dis-solves readily in alkaline solutions whence it mas inferred that it had the character of an acid. There was in fact no difficulty in ascertaining that this body was ncthiiig else than dinitrophenylic acid possessing dl the well -pronounced properties of this com-pound; and to prove this most conclusively it nns converted into the characteristic amidonitrophenylic acid.Dinitrophenylic acid however is not the only product to which this reaction gives rise; for on mixing the distillate with water an oily body separates which collects upon the liquid especially when its specific gravity has been increascd by the addition of R solution of chloride of sodium. This oil may be remaved by means of a separating funnel and dried over chloride of calcium. It possesses when rectified by distillation all the properties of ordinary bcmzol. have converted it into dinitrobenzol by the action of fuming nitric acid and have found this latter identical with that prepared from coal-tarbenzol.The fusing-point of the dinitrobenzol was in both instances 89' C. The production of dinitrocarbolic acid and of benzol can be expressed by the following equation :-2(C6H4N2NH03) I-CZH60 = CGH4(NO,&O + C&&j + C,&O + hT4 + H-0. Nitrate of dineo-Alcohol. Dinitrophenylic Benzol. Aldehyde. benzol. acid. CONTAlNINO NITROGEN ETC. Sulphate of diazobenzol when distilled with alcohol is acted upon in a similar manner. The alcoholic distillate contains the benzol whilst the residue in the flask consists of sulphuric acid and a small quantity of an organic acid. Deportment of Nitric Acid und Nitrute of Dia.;obexol. Ordinary nitric acid as well as the fuming acid has no action upon this compouud in the cold.The diazo-compound was dissolved in the strongest fuming nitric acid allowed to stand for one hour and cautiously diluted with water so as to prevent any rise of temperature; solution of terchloride of gold was then added which gave au immediate precipitate. Analysis showed this precipitate to be identical with the gold-salt of hydrochlorate of diazobenzol. On boiling the solution of nitrate of diazobenzol in fuming nitric acid trinitrophenylic acid is produced. By employing a somewhat weaker acid an admixture of tri- and di-nitrophenylic acid is obtained. Action of Sutphzlric Acid tipon Sulphutt! of Diaxobennol. On dissolving the sulphate in a small quantity of concentrated sulphuric acid and heating in a water-bath a copious evolution of nitrogen gas ensues and a brownish-coloured liquid remains con-sisting of a mixture of the excess of acid employed and a new snlpho-acid.The separation of the two acids is readily accom-plished by preparing their barium-salts. After diluting the brownish liquid with a sufficient quantity of water and adding car- bonate of barium as long as the solution exhibits an acid reaction the insoluble sulphate of barium may be separated by filtration from the barium-salt of the new sulpho-acid. The filtrate is evaporated till a pellicle forms when on cooling a large quantity of crystals of t?ie barium-salt of the new sulpho-acid appears. After separating the crystals by filtration and then cvapornting the mother-liquor further and cooling a new quantity of crystals is obtained.A single recrystallisation from water renders them perfectly pure. This salt forms fine white well-developed prisms attaining frequently to the length of half an inch when the solu-tion is allowed to cool. very slowly. The crystals are readily so!uble in hot rather di6cdtly in coid water and almost insoluble GRIESS ON A NEW CLASS OF CO&lPOUNI)S iu alcohol and ether. The solutions have a neutral reaction. The substance was dried at 160' C.; and on analysis gave numbers which agree with the formula The salt dried over sulphuric acid contained 34 atoms of water of crystallisation which escaped entirely at 130"C. In accordance with 'the analysis of the barium-salt the free acid must be expressed by the formula C6H8S208,and I propose to call it disu@hophenyZenic acid since it may be viewed as a cornpound of two molecules of sulphuric acid with the hypothetical hydro- cnrbaii CcH (plieaylene) viz.C6H,S,H,0,. Its formation may be thus expressed :-C&I,N2.SH,O4 + SH20 = C6H4S2H,0 4-N,. Sulphate of diaaobenzol. Diaulphophenylenic acid. The free acid is easily prepared by dissolviiig the barium-salt in water carefully precipitating the barium with sulphuric acid and concentrating the filtrate on a water-bath till it acquires a syrupy consistency ; when placed over sulphuric acid it crystallises out in the form of warty crystals which are exceedingly soluble in water and alcohol and deliquesce in a moist atmosphere. Besides the compound just described there exists yet another barium-compound of disulphophenylenic acid of the composition C6H,S,Ba,H0, formed by the exchange of a third equivalent of the hydrogen for barium.It is obtained by digesting either the barium-compound with two atoms of barium or the free disulpho- phenylenic acid with baryta-water for some time. The excess of baryta is neutralized by carbonic acid and the filtrate evaporated till it begins to crystallise. The new salt forms very thin white plates which on being left for some time in contact with the mother-liquor are likewise comer t ed into well- formed prisms. This salt differs moreover from the salt containing only two equivalents of barium by its greater solubility in water,* and the strong alkalinity of its solutions which is not destroyed by the carbonic acid.When freshly prepared the crystals of this com-* On preparing the salt CSH4S1H3Ba308, a0 described above with excem of car-bonate of barium a certsin amount of the second barium-compound is formed which rcmains in the mother-liquor from \rhic!i tfic first salt liiis cr,ystaliised. CONTAINING NlTROGEN ETC. pound are clear and transparent; they soon however lose a portion of their water of crystallisation and are reduced to a white powder. It is possible that two more barium-salts of disulphophenyle-nic acid exist having the respective formulz C6H,S2BaH,0 and C6H4S,Ba,0,. Disulphophenylenic acid is likewise capable of combining in two proportions with other metals; with lead it seems to combine even more freely forming apparently no fewer than five distinct salts viz.C6H4S2H,Pb0, C6H,S,H,Pb20, C6H4S2HPb,0, C6g4S,Pb40, and C6H4S,Pb0,.Pb20. The description of the preparation and properties of these bodies will be reserved for a future communication. The silver- salt of disulphophenyleriic acid may however find a place here since it exhibits the peculiar chemical department of the new acid in a striking manner. Disulphophenylenate of Silver is obtained by treating an aqueous solution of the free acid with carbonate of silver evaporating the filtrate first on the water-bath and lastly over sulphuric acid It crystallises either in warty masses or in small plates. It is easily soluble in water difficultly so in alcohol and almost inso- luble in ether.It does not contain any water of crystallisation. After drying over siilphixric acid it does not lose weight even when heated to upwards of 160" C. To judge from the composition of the silver-salt of disulpho- phenylenic acid it appears to be bibasic (C6H4S2H20,),whilst the formula deduced from its barium arid lead salts establishes its tetrabasic character (C6H4S2H,0,). The new acid exhibits there- fore the rare property of varying basicity such a,s is possessed by phosphoric acid in the inorganic and by terebinic acid in organic chemistry as shown by Ekrnau.* Action of Sulphuretted Hydrogm upon the Gold-salt of Hydrochlorafeof Diazobenxol. By passing a current of sulphuretted hydrogen gas through cold water in which the gold-salt has been suspended all the gold is converted into the trisulphide whilst the diazobenzol is trans- formed into a volatile product.When the reaction is complete * Limpricht Lehrbuch der Chemie p. 1016. VOL. sx. F 58 GRIESS ON A NEW CLASS OF COMPOUXDS the liquid is submitted to distillation when a very nauseous heavy yellowish oil is found to pass over with the aqueous vapoar. 1 have not pursued its examination further than to convince myself that it is not the phenylmercaptan (C6H6S) described by Vogt which at first sight it appeared to be. Its mercaptanic odour and its derivation from the diazobenzol in the gold-compound (according to the equation rendered this view very probable. Neitheie basic acetate of lead however nor nitrate of silver even in presence of ammonia gave precipitates with the oil which proved convincingly that it differed entirely from phenylmercaptan.On examining the residue in the retort after the oil has been distilled off it was found to consist of tersulphide of gold and an aqueous liquid; the latter is found to contain chloride of ammonium together with a little free hydrochloric acid and a small quantity of the hydrochlorate of a base which is no other than anilinc. The occurrence of these bodies shows that a mall portion of the diazobenzol is decomposed as follows :-The same products of decomposition are met with when an alcoholic solution of the gold-salt is treated with sulphnretted hydrogen. On passing the latter however over the dry gold-compound it speedily causes an explosion.By employing only a very small quantity of the substance and by spreading it in a thin layer in a glass tube it is possible to avoid explosion and secure a quiet decomposition. The reaction is over when no more hydrochloric acid fumes escape with the current of sulphuretted hydrogen. The black residue which is left behind in the glass tube appears to contain besides tersulphide of gold free diazobenzol. I was not able to isolate the latter. The explosive nature of the residue and its deportment with ether which speedily produces a rapid evolution of gas leave however little doubt of its presence. Hydrochloric acid tersulphide of gold and diazohenzol are there- fore the products of decomposition of the gold-salt by means of sulphuretted hydrogen CONTAINING NITROGEN ETC* Action of Nascent Hydrogen upon DiaxobenzoZimide.If hydrogen is generated by means of zinc and sulphuric acid in an alcoholic solution of this body a point is reached in a com-paratively short time when on the addition of water no more turbidity occurs indicating that the diazobenzolirnide has COM-gletely disappeared. By removing the excess of zinc and evaporating the alcohol on a water-bath the residue when treated with potassa evolves much ammonia-an oily base simultaneously separates ; this is purified by distillation aud is found to be identical with ordinary aniline. The decomposition may be thus expressed :-C6H,N + 8H = C6H,N + 2NH,.Diazobenzolimide. Aniline. Action of Curbonate of Barium upon Nitrate of Diazobenzol. Bp treating a cold aqueous solution of this salt with levigated carbonate of barium a feeble evolution of gas is observed which lasts for several days. A reddish-brown mass is produced insoluble in water which remains with the excess of carbonate of barium when the reaction is over. The residue is a mixture of two dis- tinct bodies. By filtering off the solution containing nitrate of barium and removing the excess of carbonate by means of dilute hydrochloric acid these two products can be readily separated by treatment with cold alcohol in which they are very unequally soluble. In order to obtain the more soluble one in a pure state the alcohol is evaporated and the residue treated with ammonia.An intensely yellow-coloured solution is produced which must be filtered to remove a small quantity of a resinous substance and decomposed with hydrochloric acid when the new compound is precipitated in crystals. These are obtained perfectly pure for analysis by repeated crystallisation from weak alcohol. The formation of this compound may be expressed by the fol-lowing equation :-2(C6H,N,.NH0,) + N,O = C,,H,,N,O + 2NH0 + N,. Nitrate of diazobenzol Hew compound. FfL GRIESS ON A NEW CLASS OF COMPOUNDS It will be readily seen that this formula contains the elements of phenylic acid and diazobenzol* C6H4N2+ C,H,O = Cl2Hl0N2O. I mill therefore call it phenol-diasobenzol without prejudging its rational constitution.This body usually crpstallises from alcohol arid ether (in which it is very easily soluble) in brittle brownish-yellow warts. It is almost insoluble in cold water slightly so in boiling water from which on cooling it crystallises in small yet well-formed rhombic prisms of a fine yellow coIour with a tinge of violet. These crystals fuse at 148 -150' C. to n brownish-yellow oil which cannot be volatilised without decom- position and is destroyed at a higher temperature with formation of yellow vapour. A1 though phenol-diazobenzol has the properties of an acid forming with certain metals saline compounds its acid character is so slightly pronounced that it is not even capable of decomposing carbonates. On evaporating a solution of phenol-diazoberizol with aqueous carbonate of potassium to complete dryness the former mill he left behind unaltered.On evaporating it with aqueous ammonii the whole of the ammonia is driven off. Treated with nitrate of silver it yields a scarlet-red silver precipitate which appears specially snited for determining the atomic weight of this compound. It deserves mention that phenol-diazobenzol is isomeric with azoxybenzide. The pro- perties just described show conclusively however that it has nothing in common with the latter compound beyond the forM ula. The second product of the above-mentioned reaction may usually be obtained perfectly pure by recrystallising it once or twice from strong alcohol afterwards dissolving it in ether aad allowing the solution to evaporate spontaneously.Sometimes however the crystals are slightly contaminated with traces of a body which has to be removed by means of caustic potassa,? in Q Witrosoethyline recently described by Geuther and Kreutzhage will pro- bably come under the same class of compounds since its composition may be expressed by the addition of the hypothetical diazohydride of ethyl and alcohol vi z. C,HJ3" + CzHGO = CAHIJ!l,O. + Instead of treating the mixture of the crude products of decomposition and car-bonate of barium wilh hydrochloric acid in order to remove the Iatter the new compounds may be extracted with potassa then precipitated with hydrochloric acid and lastly separated a8 already described by means of alcohol. CONTAINING NITROGEN ETC.which the new compound is completely soluble whilst the foreign substance remains behind as a brown resin. Hydrochloric acid precipitates it from the alkaline solution and it can now be com- pletely purified by crystallisation from alcohol or ether. Its formation is explained by the equation 3(C6H,N,.NH0,) + H,O = C18H,,N40 + N + 3NH0,. Nitrate of diazobenzol. New compound. It may likewise be viewed as composed of phenol and diazo- benzol viz. and I Would therefore propose the name phenol-bidiaxobenzol. This new cornpound crystallises in brownish-red needles or plates; it is readily soluble in ether difficultly soluble in cold alcohol. Hot water dissolves it but very slightly. When heated it deports itself like the compound previously described.It melts at 131O C. Phenol-bidiazobenzol is an almost perfectly neutral body. Its deportment with potassa (in which it dissolves readily forming a ruby-red solution) reminds one however of the pro-perties of an acid. Ammonia-water dissolves it with difficulty and aqueous carbonate of potassa not at all. Dilute acids exert like- wise no solvent action ; concentrated acids however dissolve it with a blood-red colour. Decomposition ensues when the latter solutions are heated. Action of Potassa upon Nitrate of DiasoBenzol. On mixing diluted aqueous solutions of these two bodies," a yellow liquid is obtained which possesses a peculiar aromatic odour and soon begins to evolve nitrogen gas a reddish-brown neutral substance being simultaneously formed.At the common temperature this reaction is very slow and requires several weeks to be completed. If however heat is employed the decomposition proceeds rapidly and the reddish-brown substance is separated as a resinous semifluid mass quite insoluble in water and only very * The compound of hydrate of potassium and diazobenzol (page 46) does not seem to be furmed in this case as I was able to separate this substance only when very concentrated solutiona of the nitrate ol diazobenzol and potma had been em- ployed in its preparation. GRIESS ON A hfEW CLASS OF COMPOUNDS slightly soluble even in boiling alcohol. Ether dissolves it readily. I have not been able to obtain this substance in crystals. By allowing its ethereal solution to evaporate spontaneously it is left behind in a resinous state.As a powder it is very electric. Boiling with nitric acid produces a new yellowish crystalline body. In order to purify the amorphous product of decomposition I have first washed it thoroughly with water then boiled it with alcohol and finally dissolved it in ether ; the substance remaining after the evaporation of the ether was submitted to analysis. The numbers obtained agree best with the formula The formation of this substance may be expressed by the follow-ing equation :-4(C,H,N,.NHO,) + H20 = + 4-0 + N6. If instead of an aqueous an alcoholic solution of potassa be added to the nitrate of diazobenxol dissolved in water the reaction which takes place is much more complicated.In this case in addition to the reddish-brown body two volatile substances are formed viz. benzol and phenyl C12H10, the hydrocarbon recently discovered by Fittig.* When the reaction is conducted in a retort and heat is applied the benzol passes over with the alco- hol and may be separated from it bp the addition of water. The phenyl being less volatile is obtained after the whole of the alcohol has distilled over ; it condenses to a crystalline mass in the receiver Repeated recrystallisations from alcohol render it quite pure in white plates resembling naphthaline and fusible at 70°C. These properties leave no doubt as to its identity with the phenyl of Dr. Fit ti g to whoin I am indebted for a small portion of his substance which resembles in every respect the body obtained as mentioned above.The third product of the decomposition in question viz. the amorpbous brown substance is left behind in the retort as a resinous mass. From the foregoing observations it will be seen that potassa in the presence of alcohol causes simultaneously three different Jf Ann. Ch. Pharm. cxxi 363. CONTAINING XIT&OGEN ETC. decompositions of the diazobenzol-molecule which may he ex-pressed as follows :-T. CBH,N + C2H60 = C6H6 + C2H,0 + N,. Diazobenzol. Alcohol. Benzol. Aldehyde. 11. f2C6H4N2+ C,H60 = CI2H, + C,H40 + N,. Phenyl. 111. 4C6H4N + H20 = C,,H,,N,O + N,. Reddish-brown substance. Action of Ammonia upon Aqueous Nitrate of Diaxob.enxo1. On adding diluted ammonia to an aqueous solution of this diazo- compound a similar reaction takes place as when the potassa is employed.On treating the brown rnaFs however with alcohol it becomes evident that it consists of two bodies. The difficultly soluble porticn is identical with the nitrogenous body previously described as was proved by analysis. The body accompanying it which is readily soluble in alcohol is obtained by repeated crystallisation in the form of small light-yellow plates which detonate on heating and whose alcoholic solution gives precipitates with nitrate of silver and bichioride of platinum. This compound is in fact no other than the diazo-amidobenzol previously mentioned. The coincidence with this latter was so complete that it appeared to me loss of time to analyse it.With regard to the first of the two products of decomposition it is clear that its formation must be expressed by the same equation which illustrated the reaction with caustic potassa upon nitrate of diazobenzol whilst the formation of the latter (the diazo-amidobenzol) is explained by assuming that a portion of the original compound is decomposed in the following manner :-2(C6H,N,.NH0,) + 3NH = C12H,,N + N + 2NH,NO,. Nitrate of diazobenzol. Diazo-amidobenzol. Two atoms of nitrogen in two equivalents of diazobenzol have therefore been simply replaced by one of ammonia. d4 GRTESS ON A NEW CLASS OF COMPOUNDS Decomposition of the Platiwm-salt of Diaaobenzol and of the Per-bromide of Diaxobenzol by the action of heat.When speaking of the platinnm-salt I had occasion to mention that it detonates when heated. By mixing it however with a large excess of perfectly dry carbonate of sodium,* and heating the whole in a retort on a sand-bath it is quietly decomposed. The decomposition begins at a moderate heat and is marked at first by evolution of gas and subsequently by the distillation of an oily body. The residue in the retort consists of carbonate of sodium metallic platinum and chloride of sodium. The oily distillate contains chlorine. It is obtained perfectly pure by dis- tilling once with chloride of calcium and forms an almost colour- less oil which is heavier than water and has the odour of berizol. These properties as well as the chlorine determination prove that it is chlorobenzol C,H,Clt.The formation of chlorobenzol may be eapreased by the follow- ing equation :-C6fI,N2.Hc1.PtC12 = C6H,Cl + Pt +c1 + N,. Platinum-salt. Chlorobenzol. The platinum-salt of the bromide of diabenzolt is decomposed in an exactly similar manner. The resulting bromobenzol diEers in no way from the bromobenzol obtained by Couper by the action of bromine upon berizol as may easily be shown by converting it into nitrobromobenzol which possesses all the properties of nitro-bromobenzol prepared from coal-tar oil Bromobenzol can also be produced by the decomposition of per- bromide of diazobenzol by heat according to the equation C6H,N,.HBr.Br = C6H,Br + N + Br,. Perbromide of diazobenzol. Bromobenzol.In order to decompose larger quantities of the perbromide of diazobenzol in this manner it is likewise reqnisite to mix it first * It is mlf-evident that other carbon,ates such aa carbonate of barium calcium &c. max be used instead of carbonate of sodium. + In all probability it is identical with chlorobenzol obtained from benzol or phenol. 5 This compound is obtained as an insoluble reddish-yellow precipitate on mixing bibromide of platinum with an aqueous solution of nitrat,e of diazobenzol. CONTAINING NITROGEN ETC. with a sufficient quantity of carbonate of sodium to avoid a vio-lent explosion. By heating the mixture in a retort bromobenzol is obtained almost p"erfect1y pure. The perbromide when heated with alcohol likewise gives rise to a decomposition in accordance with the pre- vious equations.Bromobenzol separates as a heavy oil on the addition of water to the alcoholic solution. It deserves to be mentioned that all these reactions arevery well defined arid that the ammnt of the products of decomposi-tion corresponds allmost theoretically with the quantities em-ployed. APPENDIX. It may be of some interest to mention an experiment I made to obtain ethylated diazobenzo! compounds. For this purpose I submitted nitrate of ethylaniline to the same reaction which pro- duced from nitrate of adine the nitrate of diazobenzol. I ob-tained a body crystdlising like the latter in long needles. If this body had really been nitrate of ethgldiazobenzol I should have expected to obtain by boiling with water a reaction accord- ing to the equation- C,H,(C,H,)N,.NHO + H20 = C,H,(C,H,)O .+ NHO + N, Nitrate of ethyldazobenzol.Ethylyhenjlic acid. It soon became evident however that the oily body produced was nothing else than ordinary phenylic acid; and since no other organic product of decomposition could be traced I had to come to the conclusion that the above-mentioned crystals were nothing else than ordinary nitrate of diazobenzol. In order to decide this question the gold-salt was prepared and after purifying it by recrystallisation from alcohol the well-knowa golden brilliant crystals were obtained which gave on analysis numbers leading to the formula C6H9N2.HC1.AuCl, The action of nitrous acid upon nitrate of ethylaniline may therefore be expressed by the equation- CGH6(C,H,)N.NH0,+NH02 = C6H,N2.NHL),+ C2H60+ H,O.Nitrate of ethylaniline. Nitrate of diazobenzol. Alcohol. GRIESS ON A NEW CLASS OF COMPOUNDS PARTV. The peculiar and somewhat remarkable properties of the corn. pounds derived from aniline in the manner previously described have induced me to try whether bromaniline nitraniline &c. when similarly treated would be converted into the corresponding substituted diazobenzols. This I have succeeded in doing and the new substances thus obtained exhibited all the properties which I found so cliaracter-istic of the normal diazobenzol-compounds. They are if anything more stable owing if I may so express myself to the compara- tively larger amount of solid and stable materials combined with the extremely volatile and easily disturbed nitrogen.This pro-perty renders them better adapted for many experiments in which the non-substituted diazobenzol-compounds are liable to give rise to dangerous accidents. They are likewise remarkable for great beauty. 2\r;trate of Diazobrornobenzol C6H3BrN,.NH03. This compound may be prepared by the action of nitrous acid gas either upon nitrate of bromaniline or upon diazo-amidobromo- benzol and in an exactly similar manner to the nitrate of tliazo-benzol. If an aqueous solution of nitrateof bromaniline be em-ployed nitrous acid gas must be passed through very rapidly at first or else diazo-amidobromobenzol (even in the presence of much free nitric acid) begins to separate.This it is very difficult to convert into the desired compound in an aqueous solution. Nitrate of diazobromobenzol remaining comparatively constant in aqueous solutions it is possible to concentrate them without any great loss by spontaneous evaporation in the open air before precipitating with alcohol and ether. It can be obtained per- fectly pure by repeatedly dissolving in alcohol and precipitating vith ether when it is obtained in the form of purely white scales which mhep crystallising out rapidly present themselves in the form of regular rhombic plates. These crystals like those of nitrate of diazobenzol are exceedingly soluble in water difficultly so in strong alcohol and almost insoluble in ether. They explode when heated struck or compressed though not so readily nor with the same violence as the nitrate of diazobenzol and they CONTAININU NITROGEN ETC.1 can therefore be mixed without danger with oxide of copper and burnt in the usual mode of organic analysis. The formation of nitrate of diazobromobenzol may be repre-sented by the following equations :-I. C,H,BrN.NHO + HNO = C6H,BrN,.NH03 + 2H20. Nitrate of bromaniline. Nitrate of diazobromobenzol. 11. Cl,H9Br,N -k HNO +2NH0,=2(C6H3BrK2.NH0,) +2II,O. Diazoamidobromobenzol. Nitrate of diazobromobenzol. Sulphate of Diaxobromobmxot C6H3BrN2.SH,0,. The preparation of this compound from nitrate of diazobromo-benzol and sulphuric acid corresponds so closely with that of the non-substituted (abromous) sulphate that it may suffice simply to refer to the description already given of the preparation of the latter and I will therefore restrict myself to a few remarks on its properties.Sulphate of diazobromobenzol crystallises in very fine colourless prisms which are very soluble in water very difficultly soluble in alcohol and almost insoluble in ether. The new body is com-paratively stable and can be crystallised from water without suffering the least decomposition by alIowing its solution to evaporate over sulphuric acid. Boiling water decomposes the compound and heat causes it to explode. Hydrobrornate of Diarobromobenxol C,H,BrN,.HBr. This compound is prepared either Fy decomposing an aqueous solution of the previous salt.by means of a suficient quantity of bromide of bqriurn and spontaneous evaporation of the filtrate or by the action of an ethereal solution of bromine iipon an ethereal solution of diazo-amidobromobenzol. If prepared by this latter method the new compound speedily separates in crystals on account of its insolubility in ether and is obtained pure by filtering off from the mother-liquor and washing the crystals with ether. Its formation may be expressed by the following equation :-C12H9Br,N3 + 4Br = C,I13BrN2.HBr + C6H,Br3N + HBr. Diazoamidobromo-Hydrobromate of diazo-Tribromaniline. benzol. bromobenzol. 68 GBIESS ON A NEW CLASS OF COMPOUNDS The hydrobromate of diazobromobenzol forms pearly white shining scales which dissolve very readily in water; like the hydro- bromate of diazohenzol they are more difficultly soluble in alcohol and quite insoluble in ether.In the dry state it can he preserved a long time without undergoing decomposition. On heating it explodes almost as violently as the corresponding nitrate. By treating an aqueous solution with freshly precipitated chloride of silver the hydrobromate is converted into the hydrochlorate of diazobenzol. Perbromide of Diaxobromobenzol C6H,BrN2.HBr.Br2. By treating an aqueous solution* of any one of the previously- described diazobromobenzol-compounds with excess of bromine-water a crystalline orange precipitate speedily falls increasing rapidly till all the diazobromobenzol has been precipitated. If too much bromine has been added the precipitate becomes gelrerally of an oily consistency solidifying however to a yellow crystalline mass as soon as the mother-liquor has been removed and the excess of bromine allowed to evaporate spontaneously.In order to obtain the perbromide thus prepared in fine crystals it is dissolved in the smallest possible quantity of warm not boiling alcohol from which it separates on cooling in yellow monoclinic prisms. A small portioii only remains in the alcoholic mother- liquor from which evaporation rarely recovers it since it usually undergoes decomposition. It will however be seldom necessary to run this risk of losing part of the substance by recrystallisation for the compound is almost perfectly pure from the very first and at all events quite fit to be employed for the experiments to be described further on.Under certain circumstances this perbromide is formed during the preparation of hydrobromate of diazobromobenzol from diazo-aniidobromobenzol in which case the two compounds are readily separated from one another by washing with cold water. Per-bromide of diazobromobenzol crystallises as already remarked in orange monoclinic prisms insoluble in water freely soluble in warm difficultly so in cold alcohol and very difficultly soluble in cold ether. On boiling an alcoholic solution decomposition ensues and on ii The cnide aqueous solution obtained by the action of nitrous acid npon the nitrate of bromaniline may conveniently be employed. CORTAININQ NITROGEN ETC.heating the crystals alone they explode feebly with disengagement of bromine vapour and nitrogen gas. Platinum-salt of the Hydrochlorafe of Diazobromobenrol C6H,Brllri ,.HCl.PtCI,. Bichloride of platinum even from a very dilute solution of the nitrate or sulphate of diazobromobenzol separates a mass of small yellow crystals which appear under the microscope as fractured plates and which are almost insoluh1.e in every neutral solvent. They are stable at 100"C. Gold-salt of the HydrochZorate of Diaxobromobenzol C6H3BrN,. HCl.AuC1,. This compound is precipitated from an aqueous solution of nitrate of diazobromobenzol on the addition of terchloride of gold at first as a yellow oil which however rapidly solidifies to a crys-talline mass.The crystals are insoluble in water but can be recrystallised from warm alcohol without much loss and are thus obtained in the form of splendid small golden-yellow shining plates. Compound of Hydrute of Potassium with Diazobromobenzol C6H3BrN,. KHO. On the addition of caustic potash to a concentrated solution of nitrate of diazobromobenzol a lemon-yellowish precipitate of diazo-bromobenzol separates at first but redissolves in excess of potash. On evaporation by means of a water-bath the solution solidifies when sufficiently concentrated to a reddish-coloured crystalliue paste of nitre and the new compound of hydrate of potassium and diazobromobenzol. The latter is separated and purified exactly in the same manner to the analogous compound of diazobenzol.It differs from this compound in being precipitated from its alcoholic solution by means of ether as a white gelatinous mass and not in the form of crystals. White plates are obtaiiied by allowing its aqueous solu-tion to evaporate on a watch-glass over sulphuric acid which however turn red on keeping owing to a partial decomposition. GRIESS ON A NEW CLASS OF COMPOUNDS Compound of Hydrate of Silver with Diazobromobenzol C6H,BrN,.AgH0. This body is obtained as an almost white insoluble precipitate very similar to the hydrate of silver with diazobenzol. I abstain from describing any more of the compounds of diazobromobenzol with metallic hydrates since they entirely resemble the correspond- ing diazobenzol-compounds in every respect Diazobromobenzol C6H,RrN, is obtained in slender bright-yellow needles by adding weak acetic acid to the compound of hydrate of potassium with diazobromo- benzol or as a bright yellow amorphous precipitate on the addition of dilute potassa to the aqueous solution of the nitrate of diazo-bromobenzol.In either case it is necessary to remove it speedily from the mother-liquor and dry it rapidly over sulphuric acid Diazobromobenzol is an exceedingly dangerous compound ; for the slightest pressure or even touch with a rough object causes it to go off in a fiery explosion almost exceeding in violence that of the nitrate of diazobenzol. Although much more stable than diazobenzol it can be kept only for a short time in a per-fectly unchanged condition.After being kept for some time a reddish-brown residue is left which no longer explodes even on heating and it seems that the nitrogen has been gradually elimi- nated. Ether dissolves diazobromobenzol and causes a violent evolution of gas frequently of such intensity as to give rise to ex-plosions. When freshly prepared this body is soluble in caustic potassa as well as in mineral acids with formation of the previously- described saline bodies. COMPOUNDS WITH AMIDO-COMPOUNDS. OF DLAZOBROMOBENZOL Diazobromobenzol like diazobenzol can enter into combination with amido-bases and amido-acids. Since however these new bodies possess absolutely no fresh chemical interest but resemble in every respect the amido-compounds of diazobenzol it may suffice to mention a few only as briefly as possible CONTAINING NITBOOEN ETC.separates in yellow needles or small plates when a concentrated aqueous solution of nitrate of diazobromobenzol is treated with an alcoholic solution of bromaniliue. This compound mas obtained by me on a former occasion* by the action of nitrous acid upon alcoholic aniline. It needs no further proof that both methods furnish a product of identical properties. The action of aniline upon nitrate of diazobromobenzol gives rise to diazobromo-amidobenzol which not only has the same empirical composition as the diazobenzol- amidobromobenzol (C,,H,,BrN,) (page 49) but resembles it in every other respect. It would no doubt be of interest to deter-mine whether the two compounds are identical or only isomeric.I must however defer answering this question till a future oppor- tunity Diazobromobenxol-amidobenzoic acid {“CiEfNO + BrN2} This body is obtained as a yellow crystalline precipitate ou mix-ing an aqueous solution of nitrate of diazohromobenzol and amido- benzoic acid according to the equation { %2:2} C6H3BrN2.NH03t 2CjH7N0 = -t C7H7N0,.NH0,. Nitrate of diazobromo- Amidobenzoic Diazobromo-Nitrate of amidoben-benzol. acid. benzol-amido zoic acid. benzol. Recrystallised from ether it forms roundish lumps of small needles or plates. 11 every other respect It is identical with diazobenzol-amidoberizoic acid. IMIDOGEN COMPOUNDS OF DL4ZOBROMOBENZoL. Diazobromobenzolimide (‘tiH,’ H rN2) ”}N. On mixing the yellow crystals of perbromide of diazobromo-benzol with solution of ammonia they are speedily converted into a yellowish oil which after a single distillation with water is ob-tained in an almost colourless condition.This oil is diazobrouio- benzalimide in a perfectly pure state. * Ann. Ch. Pharm. cuxi. 273. BRIESS ON A NEW CLASS OF COMPOUNDS If the temperature of the atmosphere be not too-high the oil usually solidifies after a short time. If this does not take place artificial cold must be resorted to The new compound is obtained for analysis by removing the water and drying over sulphuric acid. Its formation is expressed by the following equation :-C6H3BrNZHBr+ 4NI1 - 'GHSBr;2}N + 3NH,Br. Perbromide. Diazobromobenzolimide.Diazobromobenzolimide presents itself generally as a white or slightly yellowish mass of small crystalline plates which melt at about 20' C. to a heavy oil. It is insoluble in water rather diffi-cultly soluble in alcohol and easily soluble in ether and benzol. It distils readily in the presence of water ;heated alone it explodes feebly. Left exposed to the open air it appears gradually to volatilise giviag off the same aromatic ammoniacal odour which characterises diazobenzolimide. It resembles the latter moreover in its behaviour with various reagents ; caustic potassa hydro-chloric acid and bromine have no action upon it strong siilphuric and nitric acids decompose it readily. By the action of ethylamine aniline &c. upon perbromide of diazobromobeuzol corresponding substitution-compounds of diazo-bromobenzolimide are obtained.Ethyldiazohromobenzolimide (c6''3B6:iL} N forms a yel-lowish oil which does not solidify even when cooled much below oo c. PhenyIdiazobromobenxolimide (C6H3B>?$i} N is obtained in the form of orange crystals. REMARKS OF THE COMPOUNDS ON THE PRODUCTS OF DECOMPOSITION OF DIAZOBROMOBENZOL. The great similarity existing between the properties of the diazobromobenzol-compounds and those of the corresponding abromous bodies ia likewise encountered in their products of de-composition ohtained under similar circumstances ; and I have thercfore generally abstained from verifying the latter by analysis CONTAINING NITROGEN ETC. having restricted myself to bringing forward analytical numbers in a few cases only.On heating an aqueous solution of nitrate or hgdrobromate of diazobromobenzol an evolution of nitrogen gas takes place bromo- phenylic acid (which separates as a brownish oil of the odour of creosote) being simultaneously produced. C6H,BrN,.HBr + H,O = C6H,Br0 -t HBr + N,. Hydrobromate of diazo-Bromop henylic bromobenzol. acid. Ebullition of nitrate of diazsbromobenzol with alcohol gives rise to the formation of bromobenzol which distils over with the vapour of alcohol a yeliow acid (probably bromodinitrophenylic) being left behind. Ammonia forms a yellow body with simultaneous production of diazo-amidobromobenzol which owing to its greater solubility in alcohol can be readily separated from the former.The formation of diazo-amidobromobenzol takes place according to the formula 2C6H,BrN2 + NH = C,,H,Br2N3 + N,. Diazobromobenzol. Diazo-amidobromobenzol. Sulphate of diazobromobenzol when heated with sulphuric acid is converted into a sulpho-acid which is most probably di- sulphobromophenylenic acid C6H,Br.S,H408. Nascent hydrogen generated by the action of zinc upon sul-phuric acid in presence of an alcoholic solution of bromobenzo-limide converts the latter into bromaniline and ammonia. C6H4BrN3+ 8H = C,H,BrN + 2H,N. Diazobromoben-Bronianiline zolimide. When the addition of water no longer gives rise to a precipitate indicating that the whole of the imide has been decomposed the brornarriline is most easily isolated by evaporating the alcoholic solution on a water-bath and distilling with caustic potassa.Bromaniline then passes over in oily drops which quickly solidify and may be crystallised from alcohol in octahedra. These crys- tals as well as the properties of the platinum-salt prove it to be identical with the ordinary bromaniline. By heating the platinum-salt of diazobenzol with carbonate of VOL. xx 0 GEIESS ON A NEW CLASH OF COMPOUNDS sodium chlorobenzol was obtained; so in like manner by the action of heat ou the platinum-salt of hydrochlorate of diazo-bromobenzol chlorobromobenzol is produced according to the following equation :-C,H,BrN,,HCl,PtCI = C6H4BrC1+ Pt + C1 + N,. Platinum-salt of diazobrorno-Chlorobro-benzol.mobenzol. By pressing the crystals which condense in the neck of the re-tort between filter-paper distilling a second time and crystallising from alcohol they are obtained sufficiently pure for analysis. Chlorobromobenzol is rather difficultly soluble in alcohol readily so in ether and crystallises in white needles or plates from a hot saturated alcoholic solution on cooling or by evaporation of the ethereal solution. The crystals possess a peculiar odour resembling that of benzol. Tbe double salt of dibromide of platinum and hydrobromate of diazobromenzol is obtained in the form of' ruby-red crystals by mixing a tolerably concentrated aqueous solution of the diazo- salt with dibromide of platinum. This cornpound shows as might be expected a similar deportment.Like the preceding platinum- salt it breaks up according to the equation C6H,BrN,.HBr.PtBr = C6H4Br + Br + N + Pt. Platinum-salt of the hydro- Dibromo-bromate of diazobromobenzol. beozol. Dibromobenzol is readily prepared also from the perbromide of diazobromobenzol by heating the latter alone,* or with carbonate of sodium when it is decomposed according to the equation C6H,BrN,HBr = C6H,Br + Br + N,. Perbromide of diazo-Dibromobenzol. bromobenzol. A still more convenient method of' preparing dibromobenzol consists in the decomposition of the perbromide with alcohol which is completed after a few minutes' boiling; and if too much * Only small quantities must be employed in order to prevent riolent explosions. On heating the perbromide in a long-necked flask,the dibromobenzoi condenses in the cold part of the vessel.CONTAINING NITROGEN ETC. alcohol has not been employed a large portion of the dibromobenzol separates at once in the form of crystals The remaining portion is precipitated on the addition of water in the form of a thick oil which soon solidifies to a crystalline mass. After washing with a little alcohol and pressing between bibulous paper this mass together with the crystals first precipitated is subjected to distilla-tion. Dibromobenzol distils over as au almost colourless oil which speedily solidifies. Dibrornobenzol very much resembles chlorobromobenzol in its various physical properties. It ci-jstallises from ether in the form of rectangular prisms or small plates which are frequently very regular.and well formed sometimes however agglomerated in various ways. It melts at 89OC. The properties of the dibromobenzol prepared in the manner just described can leave no doubt that it is identical with the dibromobenzol described by Coil per and obtained by the action of bromine upon benzol. Although large quantities of dibromobenzol can be prepared by Couper's method with perhaps greater facility it is always difficult to obtain the dibromo-compound quite free from tribromo-benzol which is simultaneously formed. The above method might be preferred in all cases when abso-lutely pure dibromobenzd is required as for instance for certain physical purposes-the more so since it invariably yields theo- retical quantities.The same may be said of several other deri- vatives of benzol and its homologues which are obtained from diazo-compounds to be described hereafter. DJAZODIBROMOBENZOL COMPOUNDB. Nitrate of Diazodibromobenzol C6H,Br2N,.NH0,. This compound is readily obtained bf the action of a rapid current of nitrous acid upon an aqueaus solution of nitrate of bromaniline containing free nitric acid. The liquid is allowed to evaporate spontaneously the residue taken up with weak alcohol and the new cornpound precipitated by means of ether. It can be recrystallised without loss from water or alcohol by evaporating the respective solutions below their boiling-points. Its aqueous solution remains remarkably constant. Continued boiling even for hours frequently leaves some of the substance undecornposed.Nitrate of diazodibrornobenzol crystallises in fine white prisms UlL GRIESS ON A NEW CLASS OF COMPOUNDS or elongated hexagonal plates. 3 does not detonate with the same violence as the corresphding bodies proviously described. Perbromide of Biazodibrornobenzol C6H2Br,N2.HBr,. This compound is formed by the addition of bromine-water to an aqueous solution of the nitrate of tliazodibrornobenzol when it is precipitated in the form of fine long needles. On boiling with alcohol and subsequently adding water an oily substance is thrown down which soon solidifies and can be obtained perfectly pure by pressing the precipitate between bibulous paper then dis- tilling and finally crystallising from alcohol.Thus purified it presents itself in the form of fine long silky needles. This sub- stance is evidently tribromobenzol presenting all the properties of that compound obtained by the distillation of C,H6Br6 with alkalies by L ass ai gn e.* Platinum-salt of the Hydrochlorate of Diaxodibromobenzol. C,H,Br,N,.HCI.PtCI,. It separates in small orange oval plates which are difficultly soluble in water on adding dichloride of platinum to the hydro- chlorate. Diazodibromobenxolimide Is easily obtained iu crystals by mixing the perbromide with ammonia. Repeated recrystallisation from hot alcohol yields it in the form of white needles which melt at 62OC.,and deto- nate slightly at a higher temperature. It is very little soluble in water more soluble in hot alcohol and very readily so in ether.DIAZOCHLOROBENZOL COMPOUNDS Perfect analogy exists between these bodies as well as between the diazodichlorobenzol compounds and the compounds just described with regard not only to the modes of preparation from * Rev. Scient. vol. Y p. 360. CONTAINING NITROGEN ETC. chlorine and dichloroaniline but also in respect to their various physical properties. I therefore abstain from entering into a minute description and will simply enumerate some few experi-ments which I hope will satisfactorily prove their great similarity. Nitrate of Diazochlorobenzol C6H,C1N2.NH0, crystallises in small white plates which on boiling with water yield chlorophenylic acid in the form of a brownish oil possessing the odour of creosote.Perbromide of Bazochtorobsnzol C6H,ClN2.11Br3 forms yellow prisms which are decomposed ia boiling alcohol with formation of bromochlorobenzol the composition of which is thus expressed C6H,C1Br.* Platinum-salt of the Hydrochlorate of Diazochlorobenzol C6H3~1N,.HC1.PtC12 forms fine yellow needles. On heating with carbonate cf sodium it yields dichlorobenzol which is obtained according as it crystal-lises slowly or rapidly in long fine needles or in elongated four-sided plates possessing the same peculiar aromatic odour as the dibrornobenzol. Diu~ochlorobenzolimide,(C6H3CIN2)” N forms readily fusible HI crystals. Diaxochlorobewol, C6H,CIN2 is obtained as a highly explosive lemon-yellow precipitate.DIAZODICHLOROBENZOL COMPOUNDS. flitrate of Diazodichlorobenzol presents itself in the form of white plates. The perbromide C,H2C1,N2 HBr, which is formed by the action of bromine-water crystallises in yellow prisms ; the platinum-salt in small beautiful yellow very brilliant plates DIAZO-IODOBENZOL COMPOUNDS It will suffice to give likewise only a short outline of these * The bromochlorobenzol thug obtained is identical with the body described oq page 74 aa derived from C6H3BrN2.HCl.PtCl2. ORIES8 ON A NEW CLASS OF COMPOUNDS bodies owing to the great resemblance whicli usually exists between them and the cornpounda of diazobrornobenxol both in regard to their preparation and chemical deportment and also with respect to their physical properties Nitrate of Diazo-iodobenzol C,H,TSJ,.NHO, is prepared from nitrate of iodaniline precisely like the corres- ponding bromo-compound and crystallises in white needles or prisms which are exceedingly soluble in water.SUlphafe Of Diazo-iodobenzol C6H,IN2,SH,O,j crystallises in small plates which are easily soluble in wafer diffi-cultly so in alcohol. Pwbromide of Diazo-iodobenxol C6E-I,IN,.HBr, forms small lemonqellow slender plates. On boiling this compound with alcohol it yields bromoiodo-benzol C6H,BrT which crystdlises from ether or alcohol in large white plates volatile without decomposition. Platifiurn-saltof the Hydrochlorate of Diazoiodobenxol C,H,IN,. HCLPtCL, forms small bright yellow clusters of needles.forms yellowish-white crystals which are readily fusible and pass over on distilling with water as a yellowish oil soon solidifying. Thislikewise is of a peculiar aromatic ammoniacal odour. Diazo-iodobenzol C6H,IN2 is obtained as a yellow explosive precipitate. DIAZONITROB~NZOL COMPOUNDS. The remarkable isomerism observed between a and /3 nitraniline and hitherto left unexplained by any chemical theory likewise extends as I have shown upon a former occasion to the double compounds which I have described as 01 and fl diazo-amidonitro-benzol. This isomerism however is somewhat less striking since COXTAINING NITXOGEPU’ E’I’C. these bodies retain sue-half the nitraniline required for their for- mation in the original condition as will be clearly seen on ex-amining the rational formula which I assign to these bodies.The simple diazo-componnds derived from these isomeric nitranilines cannot however be viewed similarly and it was impossible therefore to decide h prz’ori the question of their isomerism. The experiments presently to be described nevertheless leave no doubt that a similar isomerism exists between the several member8 of both series and that although of identical compositiou they exhibit difl‘erences in their physical properties as striking as those observed between the original bases. a Diaxonitrobenzol compounds.* Nitrate of The preparation of this compound by the action of nitrous acid upon a nitraniline is exactly similar to that of the analogous bodies already referred to.By gradually adding ether to its alco- holic solution till crystallisation coLz;mences it is obtained in fine long needles which however do not exhibit any distinct form of crys tallisation. This compound like all the rest of the like bodies is very readily soluble in water more difficultly so in alcohcl insoluble in ether and explodes with the same violence on heating. Perbromde of a Diazonitrobenzol C,H,(NO,)N,.HBr,. On mixing an aqueous solution of the former compound with bromine-water this new body is speedily thrown down in slender orange prisms which are almost insoluble in water and scarcely soluble in ether. They dissolve however readily iu warm alco-hol from which they are deposited on cooling in well-defined crystals.* The a nitraniline employed for these experiments was obtained according to Arppe’s method by the action of alkaline liquids upon nitrated anilides. The /3 nitraniline wasprepared according to Hofmann and Muspratt’s method from dinitrobenzol by the reduction with sulphnretted hydrogen. 0,.NH,)N,0(NH,c 2 benzoDiazonitro GRIESS ON A NEW GUS OF COMPOUPU'DB Platinum-salt of the Hydrochlorale of tr. Diaxonitrobenzol C6H3(N02)N,.HCI.PtC12. On the addition of chloride of platinum to a hot aqueous soh-tion of the hydrochlorate of diazonitrobensol this double salt which crystallises in long yellow needles is precipitated. On recrystallising it from boiling water in which it is soluble (d-though with difficulty) the crystals are obtained as prisms fre- quently very well formed u Diazonitro benzo limide This compound is prepared by the action of ammonia upon Derbromide of a diazonitrobenzol.By repeated recrystallisation A from alcohol it may be obtained in a perfectly pure state in the form of very brilliaut yellow rounded plates which are so soluble in hot alcohol that a magma of crystals separates on cooling from a firaturafed solution. The crystals dissolve as readily in ether. In boiling water they fuse producing a yellow oil but slightly soluble in water ; the portion dissolved yields very fine almost white crystals on cooling. The melting point of the crystals obtained by recrystallisation from alcohol was found to be 71' C. The substance explodes when heated a little above the melting point.@ Diazonitrobenzol compqunds. Nitrate of p Diaxonitrobenaol C6H3(N02)N2.NH0, is obtained from the nitrate of ,l3 nitraniline. The /3 doee not differ much from the corresponding tr. compound in solubility; they however exhibit perceptible differences in the forms of their crystals which in the 18 compound are prisms frequently ap-proaching the cubical form whilst the crystals of the nitrate of a diazonitrobenzol are long needles of a somewhat unpronounced charactep Perbromide of /3 Diazonitrobenzol C6H,(N0,)N,,HBr3. On treating an aqueous solution of the nitrate of p diazonitro-benzol with bromine-water the new cornpourid is thrown down CONTAINING NITROGEN ETC. 8'' generally as an oil which soon solidifies.It forms small plates or prkms of an orange colour which seem to differ from tht. crystals of the a compound by their want of stability when treated with warm alcohol and which I have scarcely ever been able to recrystallize. The perbromide of ,S diazonitrobenzol is also obtained by the action of bromine upon diazo-amidonitro-benzol by suspending tile latter in water and adding bromine till the whole is converted into a heavy brownish-red oil. The suyer- natant aqueow mother-liquor is decanted and the excess of bro-mine allowed to evaporate spontaneously when the oil solidifies to a crystalline mass. Before however cornplete solidification occurs thick yellowish- red prisms are frequently seen to shoot out of about an inch in length which consist of almost pure perbromide containing mere traces of tribromonitranilipe a body which forms in the reaction to nearly the same extent as wit1 be seen from the following equa- tion :-C13H,(N02)pN3-t 8Br = C6H,{No2)N,.HBr3+ C6H,(N02)Br3N+ 2H8r.@ diazoamidotri-p Perbromide. Tribromonitraniline. benzol. The adhering tribromnitraniline* can be removed by washing the finely pulverized crystals with ether in which the perbromide is almost insoluble. If no crgstsls are formed after the bromine has evaporated in the mariner described but only a crystalline mass of perbromide and tribromaniline the latter is pressed betweeu bibulous paper and then washed with ether in order to separate the two com- pounds. This however cannot be done without incurring a con-siderable loss of perbromide since by the action of the ether it is partly coil ver ted into nitrobromobenzol.* In order to obtain the tribromnitraniline in a pure state the ethereal sqlution iq evaporated to dryness,and the residue dissolved by warm alcohol. Water is then added to the alcoholic solution till it hecomes milky and deposits crystals. These are thrown upon a filter and then pressed between sheets of filter paper in order to remove any adhering bromonitrobenxol and purified further by recrystallisation from weak alcohol. Tribromnitraniline crystallizes in small slightly yellowish plates yhich cannot be sublimed withoqt dqcqmposition. GRIESS ON A NEW CLABS OF COMPOUNDS Platinum-sa It of the €€ydrochEorateof p Diaxonitrobenxol C6H,(N0,)N2.HCl.PtC1,.This compound crystallises likewise in needles or prisms resem-bling much the crystals of the a compound. Diazonitrobenzolimide [C6H3(N02)N2g} N differs from the M compound by crystallising invariably in orange- coloured needles which melt at 5Y C. and consequently much below the melting point of the a compound It is likewise somewhat soluble in hot water from which it crystallises on coolingin whitish needles closely resemblirig those of the a diazonitrobenzolimide recrystallised also from hot water. It has sQmewhat of the odour of nitrobenxol. ON THE PRODUCTS OF THE RIAZONITROBEN-OF DECOMPOSITION ZOL COMPOUNDS. These so far as my observations go are decomposed unde'r the influence of reagents like the other diazobenzol compounds ; and their transformations may be expressed by corresponding equa- tions.The nature of their products of decomposition may in fact be safely predicted before-hand as the same isomerism which characterises the compounds already described is observable. It appeared of sufficient interest to trace them somewhat more fully. I could not have given the comparative history of the products of decomposition however without deviating too far from the main direction of this investigation and I must therefore reserve for a future opportunity a more intimate acquaintance with these in- teresting bodies. A few illustrations will show how promising a harvest of interesting results may be expected from such an in-vestigation.One peculiar fact deserves mention here. I had taken it for granted that the same relations would be exhibited between the isomeric diazonitrobenzol compounds and the isomeric acids of the formula C6H,(N0,)0 (the nitrocarbolic acid of Hofrnann and the isonitrocarbolic acid of Fritsche) as that ob-served between the compounds of diazobenzol and carbolic acid and that their deportment would be represented by the equation CONTAINING NITROGEN ETC. C6H3(N02)N2.NH03+ H,O = C6H,(N02)0 + NHO + N2. a-P Nitrate of diazonitro-a-fl Nitrocarbolic benzol. acid. The assumption has not been verified. On boiling these diazo- nitrobenzol compounds with water they are certainly decomposed after some time with evolution of nitrogen gas but neither the a nor 6 compound furnishes under these circumstances either of the well-known phenylic substitutes.In both cases a brownish and easily fusible substance is obtained which readily dissolves in alcohol and ether but can in no manner be made to crys- tallise. I have not ascertained whether this substance deports itself differently according to its origin (from the a or p cornpound) iior have I analysed it; but judging from the progress of its for- mation and also from the weak acid properties it exhibits (dis- solving in potassa and being reprecipitated by hydrochloric acid) I presume that its composition is probably represented by the formula C,H,(~O,)O* On heating an alcoholic solution of the perbromide of a-diazo-nitrobenzol it is readily decomposed according to the equation C6H3(N02)N,.HBr,= C6H4(N0,jBr + N2 + Br,.a perbromide. Bromonitrobenzol. A portion of the bromonitrobenzol formed in this manner sepa- rates in crystals on cooling provided the amount of alcohol em-ployed has not been too large; the rest is precipitated on the additiop of water. The crystals are purified by pressure between filter-paper and distillation when they pass over as a slightly yellowish oil which soon solidifies to a crystalline mass. The bromonitrobenzol thus prepared is diEicultly soluble in cold readily in hot alcohol and ether. It crystallises from these sol- vents in long almost white needles which melt at 126' C. and have the odour of nitrobenzol. If the perbromide of P-diazonitrobenzol is decomposed in a similar manner with boiling alcohol and the solid product of decom- position which forms is purified as described before a compound is obtained to which the formilla C6H4(N0,)Br must likewise be assigned but which differs greatly in its physical appearance and properties from the former bromonitrobenzol.It crystallises from alcohol and ether in which it seems to be more easily soluble $4 GRIESS ON A NEW CLASS OF COMPOUNDS in the form of well-made slightly yellowish or almost white rhombic prisms sometimes also in plates and melts at 56' C. or 70° below the melting point of the bromonitrobenzol derived from the a compound. The existence of these bromonitrobenzols suggests the question whether one of them be not identical with the bromonitrobenzol prepared by Couper by the action of fuming nitric acid upon bromobenzol.Couper's description of this body appeared to me scarcely conclusive of its nature; and in order to decide this question I have treated bromobenzol prepared from coal-tar naphtha with fur6ing nitric acid and have compared the perfectly pure product after repeated recrystallisations from alcohol with the bromonitrobenzolv prepared by my method. The striking co- incidence between the crystalline form of Coup er's compound and of the bromonitrobenzol corresponding to the a-nitraniline which I will now call a-bromonitrobenzol became at once per- ceptible ; and since both compounds crystallise in white needles that could by no means be distinguished from one another I felt justified in corning to the conclusion that both are identical.In order however to make quite sure I have also determined the melting point of the respective compounds and have found it uniformly at 120' C.* They are acted upon in like manner by various reagents. When reduced in alcoholic solutions by sulphide of ammonium they are both converted into bromaniline which crystallises in octahedrons and proves itself to be completely identical with that obtained from bromisatin or bromacetanilide by distillation with potash. Very different from this is the deportment of brornonitro- benzol (6 bromonitrobenzol) prepared from perbromide of 6 diazonitrobenzol. On treating this compound with sulphide of ammonium it is certainly also converted into bromaniline but this base differs greatly from the above-described bromaniline.Ordinary bromaniline (which I would now designate as a brom-aniline) crystallises as is well known in octahedra which melt at 57" C. The new base however (the /3 bromaniline) forms an oil which does not solidify even in winter. The chemical deport- ment of both compounds is the same; they form under like con- ditions a series of derivatives which are of the same composition and differ only in their physical properties. * C o u p e r states (Ann Ch. Phys. [3] lii 309) that his compound melted below 90" C. This is evidently erroneous. CONTAINING NITROGEN ETC. In order to establish the composition of the bromaniline experimentally I have analysed the hydrochlorate and .its pla- hum-salt.The hydrochlorate qf $ bromaniline forms white nacreous brilliant plates which are readily soluble in water and alcohol and are rapidly coloured red when exposed to the air. The Platinum-salt of the Hydrochlorute of $ Bromaniline C,H,HrN.HCl.PtCI, crpstdlises in yellow often well-formed prisms which are far more soluble in water than the slender highly lustrous plates of the platinum-salt of a bromaniline. I need scarcely state that nitrochlorobenzol compounds corres- ponding to CL and $ nitrobromobenzol can readily be obtained by submitting the platinum-salts of a! and @ diaeonitrobenxol to dis- tillation with carbonate of sodium. These two bodies differ like- wise most characteristically ; CI.nitrochlorobenzol crystallises inva- riably in long almost white needles which melt at 83' C. whilst nitrochlorobenzol crystallises from its ethereal solution in thick columns which fuse at 46'C. The former is converted by sulpliide of ammonium into the ordinary (a) chloraniline the latter into a new base (6 chloraniline) which is distinguished by its remaining an oil at the common temperature. The platinum- salt presents itself in the form of yellow crystals which differ like- wise considerably in form and solubility from the small slender plates of the platinurn-salt of 3~ bromaniline. It may I think be safely deduced from these facts that two distinctly different series of compounds are obtained by the substitution of two atoms of hydrogen in benzol by two different elements or groups of atoms according to the manner in which this substitution is accomplished and that these two series differ most distinctly in their physical properties although their chemical composition is the same The great differences between the melting-points form one of the most important means of distinction between the members of the two series.The melting points of series a lie considerably higher than tbose of the series; sometimes a difference of 70" C. is observable as will be seen by the accompanying Table. Bromouitrobenzol ..... . a Series. 126" C. p Series. 56' C. Chloronitrobenzol ...... 83"C. 46" C. Nitraniline . . ....... . 141°C. 108' C. GRIESS ON A NEW CLA.58 OF COMPOUNDS a Series.Seriea. Bromaniline.. .......... 57' C. Liquid at the ordinary temperature. Chloraniline.. .................... Liquid at the ordinary Diazo-amidonitrobenzol .. 245"C. temp erat ur e. 195' C. Diazonitrobenzolirnide .. 71° C. 53O c. The compounds to which the experiments just described gave rise belonged exclusively to the aniline group. Now there could be little doubt that the homologues of aniline and the similarly constituted bases might be also converted into diazo-compounds. This I have confirmed by experiment the more readily since it was to be foreseen that the decomposition of some of these com-pounds would give rise to the formation of certain bodies which could not have been obtained by the ordinary methods e.g. naphtylic alcohol the existence of which however could not be doubted for a moment.DIAZOTOLUOL COMPOUNDS. These compounds exhibit considerable analogy with regard to preparation solubility and many other properties to the corres- ponding aniline derivatives. They seem however to be somewhat more constant and to crystallise more readily. Nitrate of Diaxotoluol C,H6N,.NH0,. This substance is best prepared by the action of nitrous acid upon an aqueous solution of nitrate of toluidine but it can also be obtained from diazo-amidotoluol. It forms long white needles which are decomposed on boiling with water according to the following equation :-C,H6N,.NH0 + H,O = C,H,O + NHO + N,. Nitrate of diazotoluol. Cresyl-alcohol The otlrer compounds are readily obtained from the nitrate in the ordinary manner.&@hate of Diaxotohol C,H6N,.SH,0, is obtained in brilliant needles plates or prisms according to the CONTAINING NITROGEN ETC. circumstances under which it crystallises. On heating; it with sulphuric acid in the manner described when speaking of the sulphate of diaeobenzol it is converted into a sulpho-acid. The barium-salt of this acid crystallises in long white needles and consists of disulphotoluylenate of barium which has the fOPmUla C7H6S,Ba,07. Perbromide of Diaxotoluol C,H 6N2.HBr.Br2 is thrown down as a yellow oil which after evaporation of the excess of bromine solidifies to a crystalline mass. Piatinurn-salt of the Wydrochlorate of Diazotoluot, c,z6N,.HCI.PtCI, is precipitated from a dilute solution of the hydrochlorate of diazo- ioluol by means of bichloride of platinum and forms fine yellow prisms.When ignited with soda it yields an aromatic oil chloro-toluol (C,H,Cl). It remains to be seen whether this oil is iden-tical or only isomeric with the chlorobenzyl discovered by C anizzaro. DiazotoluoI-amidoben~ol,{C7H6N2 ‘GH5 (H,N) is obtained by the action of aniline upon nitrate of diazotoluol. It crystallises in beautiful long yellow needles. DIAZONITRANISOL COMPOUNDS. These compounds are nearly related to the diazonitrobenzol- compounds both with regard to physical properties and their deportment with reagents. They are prepared also in a similar manner and it is only necessary therefore to refer respecting their preparation to these analogous bodies.Nitrate of Diaxonitranisol C,H,(N02)N,0.NH0, is obtained from nitrate of nitranisol. It separates from an alcoholic solution on addition of ether forming small white plates which are dowlg decomposed on heating with water giving rise to the formation of a brownish-red substance. GRIESS ON A NEW CLASS OF COMPOUNDS Perbromide of Diaxonitranisol C,H,(NO,)N,O.HBr, forms small yellow plates Which on boiling with alcobol,. furnish bromonitranisol (C,H,(NO,)Br) crystallising in light-yellow opaque needles which may be sublimed and possesses the odour of nitrobenzol. crystallises in light-yellow needles and has the odour of bitter almonds. Platinum-salt of the Hydrochlorata of Diarmitranisol C7H,QN02)N,O.HCI.PtC1,. When precipitated from a moderately concentrated solution it forms a yellow powder which under the microscope is found to consist of fine needles. Recrystallised from boiling water it is obtained in orange-red well-formed prisms. On heating it with carbonate of sodium chloronitranisol (C H 6( N0,)ClO) distils over which crystallises in fine almost white needles. DIAZONAPHTOL COMPOUNDS. Nitrate of Diazonaphtol C,,H6N2.NH0, is prepared by the action of nitrous acid on moist nitrate of nap-thalidine (amidonapb tol) an amorphous reddish-brown substance* being formed at the same time which must be separated by filtration when the reaction is over. As nitrate of diazonaphtol is not pre- cipitated from its aqueous solution by alcohol and ether it is not so easily obtained in the solid state as the corresponding bodies previously described ; if however its aqueous solution be allowed to evaporate spontaneously in 8 shallow vessel long white needles are formed which are very soluble in water and alcohol and like- wise very explosive.Perbromide of Diazonaphtol C,,H6N,,HBr, is obtained in the form of orange-coloured crystals by the action of bromine-water upon the crude solutioii of the nitrate. # Probably impure nitrate of diazonaphtol-amidonaphtol. COXTAIKING NITROGEN ETC. Platinunz-salt of the Hydrochlorate of Diazonaphtol C,,H6N,.H C.lPtCl, forms truncated yellowish crystals which are almost insoluble in water alcohol and ether Diazonaphtolimide,(C10H6%)''} N passes over as a yellowish-coloured oil (which becomes brown when exposed to the air) by distilling with water the substance obtained by the action of ammonia upon the perbromide.It possesses somewhat the odour of naphtaline. Ol3SERVATIONS ON THE PRODUCTS OF DECOMPOSITION OF THE DIAZONAPHTOL COMPOUNDS. After it had been shown that the products of decomposition of the diazouaphtol compounds so milch resembled those of the other diazo-bodies the intention of pursuing their study in all directions could not be entertained especially since known bodies would frequently have formed the subject of such study. The decomposition of the perbromide for instance by means of alcohol gives rise to the formation of bromonaphtaIine that of the plati- num-salt when ignited with carbonate of sodium to the formation of chlornaphtaline.It was thought however of sufficient im-portance to ascertain whether nitrate of diazonaphtol would split up according to the equation- C,,H6N2"0 + H20 = C,,H,O + N + NHO, since the possibility of obtaining the long-sought-for naphtyl-alcohol presented itself. On boiling the solution of the nitrate of diazonaphtol an immediate evolution of gas takes place and a viscid violet-brown mass separates which remains on the filter when the solution is filtered hot. The filtrate deposits generally small white plates retaining however a portion of the substance dissolved which can be re- covered by shaking the aqueous solution with ether. On evapo-rating the ether it remains behind as a violet-coloured oil which quickly solidifies.This latter as well as the plates first deposited is in fact almost pure naphtyl-alcohol whilst the violet-brown VUL. xx. H GRIESS ON A NEW €?.LAM OF COMPOUNDS mass on the filter contains besides naphtyl-alcohol a considerable quantity of a reddish-brown body. In order to purify the naph- tpl-alcohol the united portions are treated with a cold solution of potassa the residuary brown-red body* is filtered off and the filtrate treated with acetic acid as long as precipitation ensues. Naphtyl-alcohol separates first as an oil soon solidifying to a net- work of small plates which are still somewhat violet-coloured. They are thrown on a filter wasbed with cold water (which re- moves the mother-liquor) and then submitted to distillation.This process must be repeated until the maas of crystals which is invariably found deposited in the condensing-tube is quite white and fuses on heating to a limpid oil. Naphtyl-alcohol crystallises in small white shining plates melting at 91' C. to T. colourless highly refractive oil which may be vola- tilised without decomposition. It is but slightly soluble in water readily soluble in alcohol ether and benzol. When inflamed it burns with a thick smoky flame. Its formation and its physical properties prove its relationship with phenylic alcohol ; it pos-sesses a similar burning taste and a creosote-like odoar some- what resembling that of naphtaline. The relation betwezn it and phenylic alcohol is likewise indicated by its chemical de- portment.It stands on the same narrow boundary line between acid and alcohol; and naphtyl-alcohol may like phenol be classified with alcohols or with acids The strong bases form with the new alcohol (acid) a series of salts which are as unstable as those of phenylic acid and are mostly decomposed even by the cslrbonicacid of the air. The potassium- or sodinm-salt may also be obtained by the action of the respective metals upon the fused naphtylic acid with evolution of hydrogen. In both cases a crys- talline saline mass is obtained which dissolves in water and alco- hol. Basic acetate of lead produces in a solution of naphtyl- alcohol a white voluminous precipitate. An ammoniacal silver solution is decomposed metallic silver being deposited.Nitric acid of sp. gr. 1.4 dissolves naphtyl-alcohol in the cold with evo-lution of red fumes. If the solution be boiled for some time and water added a sparingly soluble yellow acid precipitates whilst a second readily soluble acid is deposited in yellow crystals on evaporating the mother-liquor. The latter appears to he the picric * This body is soluble in alcohol to which it imparts a blood-red colour. On concentrating the alcoholic solution reddish-brown indistinct crystals are deposjted which on rubbing acquire a green metallic lustre. CONTAINING NITBOGEN ETC. acid of the naphtyl group. By treating the aqueous solution of naphtyl-alcohol with bromine-water it deposits bromonaphtylic acid in the form of an oil which speedily crystallises.Many of the experiments described here and in the previous part of this investigation were made in the laboratories of the Royal College of Chemistry London and of the IJniversity of Marburg ; and it gives me great pleasure to express my sincere thanks to Professors Hofmann and Kol be for the kind manuer in which the laboratories of these institutions have been placed at my disposal. PARTVL All the diazo-compounds which have formed the subject of Parts IV. and V. of this inquiry are derived from monoamido-compounds. If the composition of the latter be again expressed by the general formula C,H(+,,(NH,)”O (see page 361 it is at once perceived that the process of formation of the diazo-compounds is similar to the reaction which takes place by the action of nitrous acid on ammonia 11.(NH,)” + NHO = (N2)ft+ 2H,O. Ammonia Nitrogen. By viewing the diamido-compounds in like manner as repre- sented by the general formula C,H(,-4)(NH,),”,0z it is evident that the action of nitrous acid may give rise to two decomposi- tions The hydrogen contained in one atom of ammonia can thus be replaced by nitrogen or both atoms of ammonia present in the * It must be borne in mind that nitrous acid acts upon the nitrate8 of t,he amido-compounds ;if otherwise the reactions would frequentlygive rise to the formation of diazoamido-compoundsformerly described by me. a2 GR,IESS ON A NEW CLASS OF COMPOUNDS original compound may be replaced by nitrogen giving rise to a tetrazo-compouhd.Although this theory has not been fully confirmed by the action (presently to be described) that nitrous acid exerts on benzidine since an intermediate compound according to equation I could not be obtained it is nevertheless highly probable that nitrogc- nous compounds in accordance with equation I exist and that further experiments with other diarnido-compounds will confirm this view. Action of Nitrows Acid upon Benziclisze. Benzidine which Zinin its original discoverer expressed by the formula C,H,N has been found on further investigation by P. W. Bofmann to have double the atomic weight first assigned to it and to be a base capable of coabining with two moleculev of acid.Very recently Fittig has shown that it must be viewed as the diamido-com- pound of his newly discovered hydrocarbon phenyl and that it ought to be expressed by the rational formula C12H8(NHJ2,or C12H6(NH,)”,. I entirely agree with Fittig’s view but find it necessary to select for both compounds a somewhat modified no-menclatnre in order to avoid the use of the same names for some derivatives of these bodies (which I shall have occasion to de-scribe) already employed for several long known derivatives of phenylic acid. I propose therefore to designate Fit t ig’s hpdro- carbon C12H10,as diphenyl and to call benzidine diarnidodi-phenyl. Nitrate of Tetrakodiphenyl C,,H6N,.2NH0,. This compound is most readily and copiously obtained by pass- ing nitrous acid through a cold concentrated aqueous solution of nitrate of diamidobenzidol when only traces of a brown amor-phous body are formed whilst from an alcoholic solution the latter is deposited in considerable quantities When a sufficient current of gas has heen passed through the solution the brown body is separated by filtration the filtrate mixed with twice its volume of strong alcohol and ether added as long as any white crystals are deposited.By once more dissolving the crystals in a very smalk COSTAININB XITROGEN ETC. quantity of water and reprecipitating with alcohol and ether they are obtained perfeotly pure ; it will be readily perceived that this mode of preparation closely resembles that for the prepara- tion of nitrate of diazobenzol which body presents a striking analogy to the nitrate of tetrazodiphenyl.‘Yhc latter crystal- lises in white or slightly yellowish needlee which are readily soluble in water more difficultly so in alcohol and insoluble in ether. On heating they explode with the same violence as the analogous diazo-compound After mixing a cancentrated aqueous solution of the nitrate of tetrazodiphenyl with a sufficient quantity of cold sulphuric acid diluted previously with its own bulk of water this new body separates on the addition of strong alcohol either in the form of a white crystalline powder or in white needles. If alcohol does not completely precipitate it ether must be added to complete its separation. It is very soluble in water.On heating it in the dry state an explosion ensues. Flatinurnsalt of the Hydrochlorate of Tetraxodiphcynl C1,H6N,.2 H Cl.fLPtC1,. This salt is precipitated from a moderately dilute solution of the nitrate or sulphate by means of bicliloride of platinum. It forms light-yellow very small narrow plates. By employing a very dilute solution it is slowly deposited in small elongated well- formed hexagonal plates. These crystals are almost insoluble in water alcohol and ether. Exposure to light during drying causes them to assume a slightly brown colour. Perbromide of Tetrazodiphenyl C1,H6N,.SHBr.Br,. This compound is formed on the addition of bromine-water to an aqueous solution of nitrate of tetrazodiphenyl being precipi- tated in the form of round reddish crystals which are collected on a filter thoroughly washed with water and dried without delay over sulphuric acid and caustic lime.They are thus obtained sufficiently pure for analysis. FurtheP purification indeed is im-possible since this body is decomposed by dissolving in alcohol GRlESS ON 11 NEW CLASS OF COMPOUNDS with evolution of gas. Even at the ordinary temperature it under-goes a gradual decomposition and evolves bromine recognizable by its odour. Tetrarodiphenyl-amidobenzol C H7N {::::} . By adding aniline to an aqueous solution of nitrate of tetrazo-diphenyl this cornplex substance corresponding to the diazo- amidobenzol in the diazobeuzol series is at once separated as a yellow crystalline mass; by repeatedly washing with alcohol it is easily obtained in a pure state for analysis.The formation of this new substance may be expressed as follows :-C,,H6N4.2NH0 -I-4C6H7N =Z C,H,,N6 4-2(C6r17N.NH03). Nitrate of tetrazo-Aniline. Tetrazodiphenyl-Nitrate of aniline. diphenyl. amidobenzol.. Tetrazodiphenyl-amidobenzol is insoluble in water and although very little soluble even in boiling alcohol and ether can be recrystallised from them. By this means lance-shaped crystals are obtained which are generally grouped together in a star-like form. When heated they explode ; boiled with mineral acids they are decomposed with evolution of nitrogen gas This body is obtained in crystds when the perbromide ig acted upon by solution of ammonia. The crystals are purified by re-peated recrystallisation from strong alcohol when they are obtained in small very brilliant white or slightly yellowish plates insoluble in water very difficultly soluble in cold alcohol and only moderately soluble in ether.Boiling alcohol however dissolves them very readily and yields on coolirig a mass of crystals. The compound melts at 127' C. to a yellow oil whioh is decomposed at a higher temperature giving rise to slight explosions. It does not combine with acids or alkalies and is perfectly neutral to test- paper. No change is produced even by boiling with concentrated hydrochloric acid or with aqueona or alcoholic potash. It is decomposed however by nitric or strong sulphuric acid. CONTAINING NITROGEN ETC. The formation of this compound may be expressed by the fol-lowing equation :-cl,H6N,.f2HRr.Br4* + 8NH = C,,H,N,? + GNH,Br.Perhromide. Tetrqodiphenylimide. It has been niy endeavour to study somewhat more closely the compounds whiah tetrazodiphenyl forms with metallic hydrates but all attempts to obtain them more definitely have failed; their preparation seems indeed to be beset with insurmount-able difficulties. I omit a lengthened dtwription of the unsuc-cessful attempts and will merely show by me instance how tetra-zoiliphenyl oan play the part of an acid. An aqueous solution of nitrate of tetrazadiphenyl when mixed with caustic potash yields a yellow liqnid exhibiting such properties as might be looked for in a solution of the compound of hydrate of potassa with tetra-zodiphenyl.On treating it with chloride of platinum it gives rise to the formation of the platinum-compound above described a proof that the tetrazodiphenpl remains unchanged in the alka-line solution. It is invariably decomposed on the application of heat with evolution of gas and separation af a reddish-brown amorphous substawe. PRODUCTS OF THE COMPOUNDS OF DECOMPOSITION OF TETRAZODIPHENYL. By applying the laws of classification now accepted by chemists t o the tetrssotised derivatives of benzidiue specially taking into accopnt their manner of formation and combination these bodies must be classified with the diatomic compounds whilst the respective diazo-compounds belong to the monatomic bodies It has been of late a favourite subject of chemical research to trace the analogies which monatomic bodies exhibit under the influence of certain agents with poljatomic bodies.In illustration of this I may refer to the reaulta obtained in the comparative study of the products of decomposition of the ethyl-and ethylene-alcohols in order to shorn how simple are the laws which regulate these chemical transformations. The experimental results which I am able to adduce pave likewise * Leaving aside the hydrobromic acid this compound may he looked upon the bromide of a tetratomic radical (C19HSNdyBr4. S6 GRIESS ON A NEW 6LAS& OF COMPCIUSDS that the decomposition of the tetrazo-compound gives rise to derivatives which differ in nothing from those obtained under similar circumstances from diazo-compounds beyond the distinc- tive features imparted to them by the polyatomic nature of the compound from which they are derived.Action of Water upon Nitrate of Tetrazod@henyl. An aqueous solution of this body when left in a cold place gradually undergoes spontaneous decomposition. When heated it gives rise to a copious evolution of nitrogen gas with separation of two substances-one an amorphous brown and the other a white crystalline body. An additional quantity of the latter is obtained when the liquid has become quite cold. It is easy to aeparate these two bodies by filtering off the acid mother-liquor pressing the residue between bibulous paper and repeatedly ex-tracting with dilute alcohol which takes up the crystalline sub- stance and leaves the brown body undissolved; this latter being very probably identical with the brown compound obtained as a by-product in the formation of nitrate of tetrazobenzidol and being moreover of a very unpromising nature I have not pursued its study any further.The crystalline product of decoaposition dissolved by the alcohol is obtained on evaporation as a yellowish crystalline mass from which the last traces of’ the brown body are removed by repehtedly dissolving in ether and recrystallising from dilute alcohol. The formation of this compound for which I propose the name of diphenyl-alcohol or diphenyliic acid takes place according to the equation C,,H6N,.2NH03 + 2H20s C,,H,,O + 2NH0 -I-4”. Nitrate of tetmzodiphenyl.Diphenyl-alcohol. Diphenyl-alcohol (diphenylic acid) crystallises in small white or slightly tinged plates or needles which possess slight solubility in water but are soluble to any extent in alcohol and ether. It melts when heated and can be sublimed in small quantities by heating it cautiously in a test-tube. It is thus obtained in the form of soft white very lustrous plates. The chemical deportment of diphenyl- alcohol shows it to be most closely allied to the class of compounds the best-kuown representative of which is phenylic alcohol. It may in fact be considered as the- first biatomic representative of CONTAINIRG NITROGEN ETC. this peculiar group of chemical componnds. The new alcohol is readily soluble in potash and can be reprecipitated by the addition of an acid.Concentrated ammonia also dissolves it. On treating an ammoniacal solution with basic acetate of lead a white volumi- nous precipitate ensues. Heated with ordinary strong nitric acid it is changed into EL nitro-acid which crystallises out in yellow roundish crystals ; the ammonium-salt of this acid crystallises in beautiful long needles. Action of Alcohol upon Sulphate of Tetrazodiphenyl. On heating a mixture of alcohol and sulphate of tetrazodiphenyl violent decomposition takes place. The products formed are nitro- gen sulphuric acid and a solid substance which separates in small indistinct plates on mixing the alcoholic liquid (after the reaction is entirely over) with a large quantity of water. In order to free the precipitate from a trace of a brown substance which likewise forms in the reaction it is filtered off from the mother-liquor dried and then sublimed through paper according to the method proposed by Gorup-Besanez.The snbstance is thus obtained in the form of perfectly white plates which dissolve easily in ether and hot alcohol and crystallise from the latter very much like naphtaline. At 7OoC. it melts yielding an oil which distils at a higher temperature without decomposition. It possesses a peculiar aromatic odour like that of cinnamol and benzol combined. Its chemical composition combined with the before-mentioned physical properties prove that the hydrocarbon is identical with the diphenyl described by Fittig.* Its formation may be de-scribed by the followit~g equation :-2(CizH,N4.3SH20J + 4CpHb0 = 2C12Hi0 + 4CLH*O + N8 + 6SHp04-Sulphate of t,etrazo-Alcohol.Diphenyl. Aldehyde. dipheny1. Nitrate of tetrazodiphenyl is decomposed in a similar manncr by boiling alcohol but simultaneously the formation of a yellow * If the diphenyl prepared according to my method has not been previously sublimed through paper as described it crystallises only in small indistinct silvery- white plates which gre SO different from the large naphtaline-like plates de- scribed by Fittig that they appear at first sight to be crystals of quite a different compound. GRIESS ON A NEW CLASS OF COMPOUND8 nitro-acid takes place which stands probably to diphenylenic alcohol in the same relation as the nitrophenyl to phenylic alcohol (compare also the corresponding decomposition of nitrate of diazo- benzol p.54). Action of Sulphuric Acid upon Sulphate of Tetrazod@henyt. On heating sulphate of tetrazodiphenyl dissolved in a small quantity of oil of vitriol a violent evolution of nitrogen gas is observed The brown liquid which remains after the reaction has ceased contains besides the excess of snlphuric acid employed two new sulpho-acids which can be separated by means of their barium-salts. For this purpose the brown liquid is diluted with at least thirty times its volume of water boiled and saturated with carbonate of barium. The precipitated sulphate of barium is then filtered off the saline solution evaporated to dryness on the water-bath and the residue several 'times extracted with hot water.The portion remaining undissolved is the barium-salt of a new acid which I will call tetrasulphodiphenylenic acid ;the soluble portion contains another new acid for whioh the name trisulpho-diphenylenic acid may be adopted. I mill first erideavour to give a brief description of the former. The barium-salt of this acid obtained as before mentioned being only very slightly soluble in water could not well be pufified by recrystallisation ; I preferred therefore to convert it into the ammonium-salt which served me as a starting-point for the pre- paration of all the saline compounds presently to be described. The ammonium-salt is readily obtained by decomposing the barium-salt with a solution of carbonate of ammonium.The mixture is heated for a short time the insoluble carbonate of barium filtered off and the filtrate concentrated on a water-bath till the ammonium-salt crystallises out on cooling. One recrystal- lisation from alcohol yields it in the form of perfectly pure white prisms Barium-salt of Tefrasulphod@henyleenic Acid C,,HG. S,H,Ba*O 6 On adding chloride of barium to a rather concentrated boiling solution of the ammonium-salt this salt is precipitated in white needles or prisms; the crystals are allowed to subside and after COXTTAINING sITROBEN ETC. the mother-liquor has been separated by filtration repeatedly washed with cold water ; in this manner they are obtained quite pure. Dried over sulphuric acid the salt retains four molecules of water of crystallisation.If the ammonium-salt of tetrasulphophenylenic acid be treated with baryta-water instead of chloride of barium another barium- salt is formed which according to the subjoined barium-determi- nation has the composition C12H6.S4Ba6015. It is precipitated as a white amorphous powder which on washing with water is con- verted into small prisms. Silver-salt C,,H6.S,H3Ag3O1,. On mixing a concentrated solution of the ammonium-salt with an equally concentrated solution af nitrate of silver separation of warty crystals of this salt takes place after some time. They may be purified by recrystallisation from water in which they are easily soluble. The concentratiqn of their soIution must be con- ducted in vacuo.When dried over sulphuric acid it retains three molecules of water of crystallisation which are givcn off at 100' C. When describing disulphophenglenic acid (page 96) it was shown that it is capable of forming two series of salts exhibiting to each other a relationship analogous to that of the metaphosphates and ordinary phosphates. Tetrasulphodiphenylenic acid behaves in a similar manner. Thus the salts previously described point most naturally to the conclusion that it is hexabasic while the salts which will be presently mentioned indicate its capability of assuaing also an octabasic character Lead-saZt Cl,H6.S4Pb,016. When a boiling solution of tetrazodiphenylenate of ammonium is mixed with a solution of neutral acetate of lead this salt is pre-cipitated in the form of white needles.Repeated washings with water render it quite pure. Basic Leadsalt C,,Ei6.S4Pb,016 3. Pb,02. This salt is obtained by treating the hot solution of the ammo- nium-salt with basic acetate of lead. It is a white amorphous precipitate. 100 GRIESS ON A NEW CLASS OF CONPOUNDS Tetrasulphodiphenylenic acid is easily obtained in the free state either by decomposing the lead- or silver-salt with sulphu- retted hydrogen or by treating the barium-salt with an equivalent quantity of sulphuric acid. The filtered aqueous solution is eva- porated on a water-bath to a syrupy consistence and placed over sulphuric acid; after some time white needles or plates are ob-tained which are very soluble in water and alcohol but not deli- quescent in the air.I have not yet analysed this acid; but accord- ing to the above-mentioned salts it seems very probable that it can exist in two different states as expressed by the formulz C,,H~.SSH~O~, and C12136. S$&016. The second compound (trisulphodiphenglenic acid) to which the reaction of sulphuric acid on sulphate of tetrazobenzidol gives rise deserves likewise a few passing remarks. The separation of its barium-salt from the barium-salt of tetrasulphodiphenylic acid by means of hot water has already been described. The aqueous extracts thus obtained when sufficiently evaporated and allowed to cool will generally solidifv to a gelatinous mass from which no dis- tinct crystals can be obtained even hy repeated solution and evapo- ration.Crystallisation may however be eil'ected thus The gela-tiaous salt is converted into the ammonia-compound by boiling with an aqueous solution of carbonate of ammonium. The excess of ammonia is removed by evaporation and ttie crystalline residue dissolved in a little hot water and treated with a solution of chlo- ride of barium. On cooling warty crystals or globular groups of small plates of the barium-salt are obtained which can be freed from the difficultly-soluble tetrasulphodiphenylate of barinm with which it may still be contaminated and also from the mother- liquor by repeated crystallisation from water. White amorphous precipitate obtained by treating a hot solution of the barium-salt with a solution of neutral acetate of lead.Precipitated from a solution of the ammonium- or barium-salt with basic acetate of lead. It scarcely differs in its properties from the previous salt. CONTAINIRQ NITROGEN ETC. Trisulphodiphenylenic Acid. is obtained in the free state in exactly the same manner as tetra- sulphodiphenyle'niciic acid which it resembles in every other retipect. It is evident at aglance that its cornposition may also be expressed in two different ways viz. C,,H6.S,II,0,, or C,,H6.S3H6012. In accordance with the experiment jiist described the decom- position which tetrazodiphenyl undergoes by the action of sul-phuric acid may be expressed by the following equations :-I. Cl,H6N -I-S,H,O, = C12H6S4H8016 4-N4.Tetrmodiphenyl. Tetrasulphodiphen ylenic acid. 11. C1,H6N4 + S,H60, = C,,H6.S3H,01 + N,. Tetrazodiph enyl Trisulphodiphenylenic acid. Decomposition of the Platinum-salt of Tetrazodipphenyl and of the Perbromide. On mixing the platinum-salt of tetraaodiphenyl with from four to six times its weight of carbonate of sodium and heating tlie mixture Cn a retort a copious evolution of gas speedily ensues; and on increasing the heat an oily body distils which solidifies in the neck of the retort to a white mass. By pressing this body between bibulous paper and repeated recrystallisation from boiling alcohol it is obtained perfectly pure. Its composition is C,,H,Cl, and its formation takes place thus t-C,,H6N4.2HC1.2PtCl = C,,H,CI2 + el + Pt + N4.Platinum-salt. New body. This new body which I will call dichlorodipheny! crystallises in white usually wellAformed prisms ; it is difficult of solution even in boiling alcohol but readily soluble in ether and quite insoluble in water. It melts at 148"C. to a yellowish oil which can be dia-tilled without decomposition. On heating in like manner the perbromide of tetrazodiphenyl with carbonate of sodium a mixture of bromine and nitrogen gas is evolved and on heating more strongly an oily substance distils over which quickly solidifies It is obtained pure for analysis by repeated recry sta11isation from ether. FRANKLAND AND DUPPA'S This compound which may be called dibromodiphenyl resem-bles the previously described chlorine-corn pound ; it crystallises likewise in a-ell-formed prisms which appear to be even more in-soluble in alcohol and ether than the above and melt at 164' C.This substance is obtained moreover by boiling the perbromide with alcohol a13in the following equation :-C,,H6N,.H,Br,.Br = CI2H,Rr + N4+ Br,. Perbromide. Dibromodiphenyl. The substance separates from the alcoholic solution on cooling in crystals; it is best purified by distillation. Dr. Fittig informs me that he obtained a cornpmnd of like composition by acting with bromine upon diphenpl. The descrip-tion of this new componnd given by him applies so entirely to the dibromodiphenyl prepared by me thnt no doubt remains of the identity of the bodies obtained by the two methods.

ISSN:0368-1769    

DOI:10.1039/JS8672000036

出版商:RSC    

年代:1867

数据来源: RSC

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FRANKLAND AND DUPPA’S TI.-Synthetical Researches on Ethers. No. 2. Action of Sodium and Isopropylic Iodide upon Ethy lic Acetate. By E. FRANKLAND, F.R.S. and B. F. DUPPA,Esq. IN a former memob* we described the consecutive action of sodium and the methylic ethylic and arnylic iodides upon ethylic acetate. Two distinct classes of bodies resulted from these reactions viz. lst bodies derived from the duplication of the molecule of ethylic acetate ; and 2nd bodies resulting from the substitution of one or more atoms of hydrogen in the methyl of acetic acid. The general formula of the first of these classes of compounds may be thus written :-{ ::;;; In this formula R may be either hydrogen or a monad organic radical. These bodies to which we gave the name carboketonic * Phil.Trans. vol. clvi p. 37 and Chem. SOC. J. vol. xix p. 396. SYNTKETICAL RESEARCHES ON ETHEES. etl2ers are derived from corresponding compounds in which sodium occupies the place either of one or of both atoms of R the latter compounds being themselves obtained by the action of sodium upon ethylic acetate according to the following equations :- 4{:$hto + Na = 2 + H, Ethylic acetate. Ethylic sodacetone carbonate. Alcohol. 2{z&to + ~a,= COiSle + H,. COEto Ethyiic acetate. Ethylic disodacetone Alcohol. carbonate. The second class of bodies have the general formulae :-COEto' They are obtained by the action of the iodides of the poslitive compound radicals represented by R upon corresponding sodium compounds viz.:-{:;E; {%E CCNa, COEto' Ethylic sodacetate. Ethylic disodacetate. Ethylic trisodacetate. These sodium compounds are produced simultaneously with those belonging to the first class by the action of sodium upon ethylic acetate. Thus ethylic disodacetate arises from t,he following reaction :-Ethylic acetate. Eth3ic disodacetate. By contact with the iodide of any radical C,R,,+, these cornpounds exchange their sodium for an equivalent amount of C*'H,,+ 1 ttllus:-Ethyiic disodtlcetate. EthFlie salt. 104 FRANKLAND AND DUPPA'S If in these formule n = 0 ethylic acetate ({-coj&o) isre-CH produced but if n be a positive integer an ethereal salt is obtained of the molecular weight of ethylic acetate increased by one two or three times C,H,,.We have now extended these reactions to isopropylic iodide for an ample sqply of which we are indebted to Professor Wankl y n. The sodium compounds derived from ethylic acetate and prepared as described in our former communica- tion,* were treated with excess of isopropylic iodide aiid digested for 24 hours in a water-bath an upright Liebig's condenser being attached to the flask containing the materials. At the end of this time the products volatile at 100" were dis- tilled off. They consisted chiefly of ethylic acetate isopropylic iodide and isopropylic ethylic ether ({Y::). Water acidu- lated with sulphuric was now added until the contents of tlu? flask exhibited a decidedly acid reaction. They were then submitted to distillation.A sweet-smelling oily liquid passed over along with water; it mas separated dried over calcic chloride and distilled. It began to boil at about 70" C. and the thermometer rose eventually to 300' 0. Below 100" the dis- tillate which consisted chiefly of ethylic acetate isopropylic iodide and alcohol contained an abundance of two products one boiling at about 135"C. and the other at about 200°C. The latter gave with baric hydrate the characteristic reaction of a carboketonic ether whilst the former possesned in a high degree the peculiar odour of ethylic valerate. ETEYLIC &3OPROPACETONE CA4RBONATE. The section of the above distillate boiling at about 200° yielded on careful rectification a liquid boiling constantly at 201' C.Submitbed to analysis this liquid gave the following results :-I. -3402 grm. gave -7826 grm. carbonic anhydride and -2896 grin. witter. 11. -1861 grm gave a4274 grm.ca'rbonic anhydride and el594 grm. water. * Chem. SOC. J. vol. xix p. 396. SYNTHETICAL RESEARCHES ON ETHERS. These numbers lead to the formula as seen in the annexed comparison of caIculated and experi- mental numbers :-Calculated. Found. -/ A I. 11. Mean. C9. .. 108 62-79 62-73 62.63 62.68 . 16 9.30 9.45 9.51 9.48 0,.... 48 27-91 .. .. 27.84 100*00 This product of the action of sodium and isopropylic iodide upon ethylic acetate is therefore homologous with ethylic methacetone carbonate and ethylic ethacetone carbonate ob-tained in the corresponding reactions with ethylic and methylic iodides as is evident on inspection of their respective for-mulae :-COMe COhSe COMe CMeH ; CEIH; CPPrH*.COEto COEto COEto Ethylic methacetone Ethjlic e thacetone Ethylic isopropacetone c irbonnte. carLonate. carbonate. Ethylic isopropacetone carbonate results from the action of isopropylic iodide upon ethylic sodacetone carbonate according to the following equation :- COXe COMe CNnH + PPrI = {CdPrH + NaI. COEto COEto Echylic soda- Isopropylic Ethylic isoprop-acetone iodide. acetone carbonate. carbonate. Ethylic isopropacetone carbonate is a colourlesa and somewhat oily liquid of an odour resembling damp &raw and a pungent. taste. It is insoluble in water but miscible in all proportions with alcohol and ether.Its specific gravity at 0" C. is -98046. It boils at 201" (barometer -7584 metre) and distils without decom- position. A determination of its vapour-density by Gay LIISS~C'S niet>hod gave the following results :-VOL. xs. FRANELAND AN3 DUPPA'S Weight of ethylic isopropacetone carbonate .. -1248gna Observed volume of vapour .. .. . . 34.9 c. c. Tempemture of bath .. .. .. .. 225'C. Height of barometer .. .. .. .. 767 m.ni. Difference of heights of mercury inside and out-side of tube ,. .. .. .. *-136 9? ?? Height of spermaceti column reduced to milli-metres of mercury . . .. .. .. 16-6 , , From these data the weight of one litre of ethylic isoprop acetone carbonate is calculated to be 85-6 criths or its Bpecific gravity compared with air taken as unity is 5.92.Theoretically the vapour of a body of this composition and occupying 2 vols. ought to give the numbers 86 criths and 5.94. Ethylic isoprop- acetone carbonate has no action upon polarized light. Boiling aqueous solutions of potash and soda rapidly decompose ethylic isopropacetone carbonate which also suffers a similar decompo- sition when boiled with baryts-water. Baric carbonate is in the latter case precipitated and a volatile liquid possessing a campboric odour produced. This liquid washed with salt and water and dried over quicklime boiled constantly at 114OC. and yielded on analysis the following numbers :-I. *2032 grm. gave *5338 grm. carbonic anhydride and -2250 em.water. 11. ,1722 grm. gave -4550 grm. carbonic anhydride and -1890 grm. water. The following comparison shows that these numbers agree closely with the formula :-Found. Calculated. I. 11. Mean. b. c6.4 -. 72 71-64 72-06 '71.85 H, .... 12 12-30 12-19 12-24 O...... 16 .. .. 15.91 I-100 100~00 Thia result is exactly homologous with those obtained in the corresponding reactions which we have previously described. For reasons given in the memoir above cited we regird SSXTKETICAL RESl&~CHESON ETHERS. this body as acetone in which one atom of hydrogen haB been displaced by isopropyl {%be# {%2 Acetone. Isopropacetone. and we propose for it the name isopropacetone. Isopropacetone is produced by the action of baryta-water upon ethylic isopropacetone carbonate according to the follow- ing equation :-CBPrH + BaHo = COBao" + EtHo + (COMe CBPrH,.COEto Baric Baric Alcohol. Ethylic isopropacetone hydrate. arbpnate. Isopropacetone. -rMe carbonate. Isopropacetone is a colourless transparent and very rnobiie liquid possessing a powerful camphoric odour and a burning taste. It is very sparingly soluble in water but miscible in all proportions with alcohol and ether. Its specific gravity is -81892at 0" C. It boils at 114' C. with the barometer at T584 meter. A determination of its vapour-density gave the follom-hgnumbers :-Weight of isopropacetone ............ *1160p. Observed vol. of vapour .............. 43.9 c. c. Temperature of bath ................137" C. Height of barometer ................ 764 m.m. Difference of heights of mercury inside and outside of tube ................ 112 mm. Height of spemaceti column reduced to millimetres of mercury. ............. 16.8 m.m. Hence one litre of the vapour weigha 50.1 criths and its ~p. gr. is 3.48. A two-volume vapour of the above formula requirw the numbers 50 criths and 3.455 Isopropacetone doea not reduce boiling aolution of argentic nitrate. Agitated with a concentrated solution of hydric sodic aulphite it solidifies to a Bplendid mass of white crystals. A ketone of the same composition (methyl valeral) has been obtained by Williamson in distilling a mixture of potassic acetate and valerate. This body which for reasons mentioned below we regard a8 isomeric with isopropacetone boils at FELA\NKLhXD AND DUTPA'S 120' C.Isopropacetone is also isomeric with ethyl-but,yral boiling at about 128' C. Amongst the products of the action of sodium and isopro- pylic iodide upon ethylic acetate there ought to be a carbo-ketonic ether containing two atoms of isopropyl and having a constitution analogous to that of ethylic diethacetone car bonate. COMe {:::r0 cm, {%to Ethylic diethaaetone Ethylic di-isopropacetone carbonate. carbonate. Unmistakeable indications of the existence of this body were noticed hut we have not attempted to isolate it. Isopropacetic Acid. The section of ebhereal product described above a8 boiling at about 135' C. yielded on further distillation a considerable quantity of a liquid boiling constantly at 134' to 135' C.Thk liquid was submitted to analysis and gave the following numbers :-I. m1836 grm. gave -4361 grm. carbonic anhydride and -1832 grm. water. 11 *2786 grm. gave -6602 gm. carbonic anhydride and -2722 grm. water. These results lead to the formula as will be evident from the following comparison of analytical and calculated numbers :- Calculated. I. Ir. Mean. C .... 84 64.62 64.78 64.63 64-70 H, .... 14 10.77 11-08 10.86 10.97 0 .... 32 24.61 .. 24-33 130 100*00 100~00 The formula and reactions of this body prove itfto be ethylic isopropcacetate; that is ethylic acetate in which one 1 atom of aon-ethylic hydrogen has been displaced by isopropyl - SYNTHETICAL RESEARCHES ON ETHERS.Ethylic isopropacetate is produced from ethylic sodacetate by the following reaction :-Etbylic Isopropylic Etbylic isoprop sodmetate. iodide. acetate. Ethylic isopropacet,ate is a colourless transparent and oily liquid nearly insoluble in water soluble in alcohol and ether and undistinguishable in odour from ethylic valerate (ethylic propacetate) with which as we have proved below ethylic isopropacetate is isomeric. Its specific gravity is 8882 at 0' C. and -87166 at 18' C. It boils at 134' to 135' C. (barom. 7584 metre). A determination of its vapourdensity gave the following number8 :-Weight of ethylic isopropacetate ...... -1396 grm. Observed volume of vapour .......... 41.56 cbcx. Temperature of bath ................147' C. Height of barometer ................ 751.4 m.m. Difference of heights of mercury inside and outside of tube.. .............. 110.5 m.m. Height of spermaceti column reduced to millimetres of mercury .......... 17.9 m.m. Hence the sp. gr. of the vapour is 4-64 or one litre weighs 67.1 criths. A two-volume vapour of the above formula re- quires the numbers 4.49 and 65 criths. Ethylic isopropacetate is readily decomposed by alcoholic potash potassic isopropacetate being formed. The alcoholic liquid so produced being mixed with water and evaporated to dryness left a saline residue which was treated with dilute sul- phuric acid and submitted to distillation. An oily liquid passed over which strongly reddened litmus paper.This liquid sepa- rated from the aqueous.layer below waB dried and then boiled constantly at 175' C. Submitted to analysis it gave the follow-ing results :-I. -1858 grm. gave -3991 grm. carbonic anhydride and -1663 grm. water. 11. .3322 grm. gave -7152 grm. carbonic anhydride and -2886grm. water. FRANKLAND AM) DUPPA'S These numbers agree with the formula aB shown by the following comparison :-Found. Calculated. 1 I. n 11. % Mean. C .... 60 58.82 58.58 58.72 58.65 H, .... 10 9.80 9-94 9.65 9-80 0 .... 32- 81-38 .. .. 31-55 7- 7- 102 100.00 100~00 Isopropacetic acid is a colourless transparent oily liquid somewhat soluble in water to which it imparts both its odour and strong acid reaction. Its odour cannot be distinguished &om that of valeric acid prepared &om amylic alcohol.Its specific gravity is -95337at 0' C. It boils at 175' C. and a de termhiation of ita vapour-density gave the following num-bers :-Weight of bopropacetic acid ........ ,1163grm. Observed volume of vapour.. ........ 50.77 c. c. Temperature of bath.. .............. 215' C. Height of barometer.. .............. 755-5 m.m. Difference of heights of mercury inside and outside of tube .............. 80.0 m.m. Height of spermaceti column reduced to millimetres of mercury.. ........ 16.9 mm. Hence the specific gravity of the vapour is 3'479 or one litre weighs 50.4criths. A two-volume vapour of' the above formula requires the numbers 3.52 and 51 criths.Isopropacetic acid diisolved in water boiled with argentic carbonate and filtered gives on evaporation in vacuo beautiful and very light pearly scales which are tolerably permanent in light and exhale an odour of the acid 100 parts of water at 10"C,. dissolve *187 parts of this salt. Dried over sulphuric acid this salt yielded on analysis the following numbers :-I *MOOgrm. gave *1876grm. carbonic anhydride 00700grm. water and *093P grm. silver. 11. *2194grm. gave -2312 grm. carbonic anhydride *OM3grm. water and -1136 grm. silver. SYNTHETICAL RESEARCHES ON ETHERS. These numbers agree closely with the formula as the subjoined comparison shows :-Calculated. I. 11. MfSL C .... 60 28.70 28.42 28.74 28.58 H .... 9 4.31 4.32 4.47 4.40 Ag ....108 51.67 0 .... 32 15.32- 51.88 .. 51-77 .. 51-82 15-20 209 100*00 100~00 In our formermemoir* we have entered fully into the chemical relations of the products derived fiom the duplication of the molecule of ethylic acetate; when the latter is acted upon first by sodium and afterwards by methylic or ethylic iodide. The corresponding reaction with isopropylic iodide described in the foregoing pages is so completely homologous with those ex- hibited by methylic and ethylic iodides as to render it super-fluous to enter into any theoretical considerations relating to the production of ethylic isopropacetone carbonate or of the ketone derived from it; but in order to prevent any misappre- hension of our views concerning the constitution of these bodies we here subjoin their graphic formule :-COEto Ethjiic isopropacetone carbonate.L@ I @-P * Phil. Trans. chi p. 37 and Jour. Chem. Soc ,vol. xix. 419. FRANKLAND AND DUPPA'S We have already mentioned that isopropacetone is isomeric with the ketone methyl-valeral obtained by Williamson in distilling a mixture of potassic acetate and valerate and also with etbyl-butyral. The origin of methyl-valeral indicates the probable constitution of that body whilst the cause of ita isomerism with isopropacetone is evident from the following constitutional formulae :-Isopropacetone differs from methyl-valeral in its boiling point which is 6" C. lower as might be anticipated from the boiling points of isopropylic and propylic alcohols which differ by 9" C.in the same direction. This difference of boiling point is doubt-less due to the difference in the constitution of the radicals propyl and isopropyl t.he former being a normal an$ the latter a secondary radical and as has been shown by Kolbe and our- selves normal compounds always boil at a higher temperature than their secondary iaomers. The temperatures of ebullition of the two radicals doubtless differ much more widely than those of their respective compounds ; and aB the atomic weight of the compound becomes proportionally greater with regard to that SYNTHETICAL RESEARCHES ON ETHERS. of the radical this difference becomes less and less appreciable. Unfortunately we are not acquainted with the specific gravity of methyl-valeral nor with its deportment towards hydric sodic sulphite.The production of ethyl butyral by the destructive distillation of calcic butyrate permits of no conclusions being drawn as to its rational constitution. Its behaviour with hydric sodic sulphite is not known but its boiling point 14' C. higher than that of isopropacetone proclaims its non-identity with the lnt ter substance. Two acids having the composition and atomic weight of valeric acid are now known viz. valeric acid or propacetic acid obtained by the oxidation of normal amylic alcohol and isopro- pacetic acid produced as above described. To these may be added a third which we have had for some time under investi- gation and the history of which we hope soon to be able to lay before the Society.This last acid is produced by the substitu- tion of the three atoms of hydrogen in the methyl of acetic acid by three atoms of methyl. These acids are represented by the following constitutional formulae :- FRANKLAND AND DUPPA'S Isopropketic acid. I Trimethacet,ic acid. I One other acid not yet obtained would complete this isome& group and would be produced by the aubstitution of two atoms of hydrogen in the methyl of acetic acid the one by ethyl and the other by methyl. Thils acid which might be appropriately liamed ethomethacetic acid would have the following constitu-tional formula :-m Y SYXTHETICAL RESEARCHES ON ETITERS. 115 In normal butyric and propionic acids we see the first step in the formation of this missing acid realised and the introduction of methyl into the first or of ethyl into ihe second in the place of cne of the remaining atoms of original methylic hydrogen would infallibly give rise to the acid in question.It will be observed on inspecting the above formulae that both valeric and isopropacetic acids are normal acids that is they both contain two atoms of undisplaced methylic hydrogen. The missing ethomethacetic acid would be a secondary acid because itwould contain only one atom of undisplaced methylic hydrogen whilst trimethacetic acid is a tertia.ry acid containing no undis-placed meth y lic hydrogen . The remarkable circumstance that both valeric and isoprop- acetic acid are normal acids led us to expect a very close resemblance between them and this anticipation has been com-pletely verified by a rigid comparison of the properties of the two bodies.In odour taste and general appearance they are quite undistinguishable from each other and the following table of comparison reveals no tangible difference between them :-Isopropacetic Valeric Acid. Acid. --Sp. gravity of liquid at 0" C. .............. -95357 -9555 (H. Kopp) Boiling point ........................... 175" C. 175" C. Specitic gravity of ether at 18" C. .......... *37166 -866 Boiling point of ether.. .................. 134°-136" C. 133.5' C. Silver-salt.............................. Nacreous Fcales Nacreous scales Solubility of silver-Ealt in water at 10" C..... 100 parts of water 100 parts of water dissolve '187 dissolve '1 80 Pad Pa* Had these acids been examined a few years ago no chemist would hsve hesitated to pronounce them identical on the fore- going evidence but the present state of our knowledge regad- ing the constitution of carbon compounds renders such an opinion utterly unt,enable. Nevertheless we were unwilling to leave the evidence of their difference upon a theoretical basis only and we have had the satisfaction of discovering a sharply defined physical difference between them. This difference is exhibited in their behavioiir towards circularly polarised light. The synthesized acid is inactive whilst valeric acid prepared 116 FRANELAXD AND DIJPPA'S .SYNTHETICAL RESEARCHES.from amylic alcohol powerfully rotates the plane of polarization to the right. We have also ascertained that the same differ- ence extends to their respective ethers. Professor Wanklyn has kindly titrated the ethylic valerate used for this experiment and has proved it to be of a purity almost absolute and free from amylic alcohol which moreover rotates the plane of polarization to the left Two experiments gave 30.17 parts and 30.15 parts as the amount of potassium necessary to displace the ethyl in I00 parts of this valeric ether. Theory requires 30.08 parts. Wurtz* states that valeric acid is inactive towards the polarized ray whilst we find that this acid possessea a tolerably powerful right-handed rotation. Our valeric acid was prepared fiom a sample of amylic alcohol which possessed a left-handed rotation.Past eur has shown? that ordinary amylic alcohol contains two varieties capable of being separated from each other; one of these is inactive whilst i~ stratum of the other 50 centimetres thick exhibits a lefbhanded rotation of 20°. It is highly probable that the active amylic alcohol gives active valeric acid and the inactive alcohol an inactive acid in which case the inactivity of Wurtz's sample of valeric acid would be explained on the supposition that it waa prepared from a sample of amylic alcohol containing only the inactive variety. We are at present engaged in the elucidation of this question with the view of ascertaining more especially whether or not the inactive amylic alcohol contains isopropyl and there-fore possesses the constitutional formula * Ann.Ch.Phys. xliv 275. t Compt. rend. xli 296 and Ann. Uh. Yharm. xcvi 265.

ISSN:0368-1769    

DOI:10.1039/JS8672000102

出版商:RSC    

年代:1867

数据来源: RSC

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LTII.-On the Alloys of Nagnesium. By JAMESPARKINSON. MAGSESIUM when heated to redness has a most powerful affinity for oxygen and in order to alloy this metal with others it is necessary to avoid bringing substances containing oxygen into contact with it. The fluxes used must therefore be free from oxygen and in order to prevent athe reduction of silicium &om free and combined silica and the loss of magnesium by volatilization it is necessary to avoid heating the fused mass too long. Easily fusible metals such as tin bismuth cadmium lead zinc and antimony may be fused in small quantitywith an equal bulk or less of magnesium in an atmos-Fig. 1. phere of hydrogen in a hard German glass test-tube over the coal-gas flame of a good air-burner.The less fusible metals are with the exception of silver gold and copper with difficulty alloyed in a flux or in brasqued crucibles; but silver gold and copper may be fused and alloyed either in a flux composed of equal parts of fluor spar and cryolite or of fluor spar and common salt- andwith the exception of zmc and cadmium-the easily fusible metals may be fused in like manner. The flux should be fused in a stout Cornish crucible before the metal is added and the magne- sium secured to an iron rod by a piece of clean iron wire as shown in Fig. 1,in order to keep it under the surface of the flux. An iron rod about one-quarter of an inch diameter and three feet long is well suited for this purpose bent and VOL. xs.118 PARKINSON ON THE ALLOYS OF MAGNESIUM. twisted at one end into the shape of a letter 0,of about me inch diameter in the manlier shown. The small piece of iron wire should be tightly wound round the piece of magnesium in one coil then the two ends twisted spirally for about half an inch to an inch (equal to the depth of the flux in which the metals are to be alloyed) and the remaining length wound round the iron rod tightly so as to secure the magnesium with as little wire as possible so that should the end of the rod be required to press down the magnesium the temperature of the flux may riot be too greatly reduced on plunging it into the fused mass. In the event of the displacement of the magnesium the bent end of the rod enables the operator to keep it under and thereby prevent loss by spirting and oxidation.Magnesium being highly volatile at high temperatures and very light and consequently occupying a large space it con-siderably diminishes the temperature of the fused mass when first plunged into it so that the flux thickens and adheres to the rod but in a few seconds the temperature rises and it becomes again tranquil and liquid; the rod may then be re-moved without contaminating the alloy with iron and without any adhering metal. The rod is readily cleaned by a few taps of a haminer both before and after cooling it in water. There is always a loss of magnesium by volatilization if the heat be continued after the fusion and after the metals are alloyed. The alloy should therefore be removed as soon as possible and quickly cooled either by pouring out into an ingot-mould or by cooling the crucible in water taking care not to let any water come in contact with the alloy otherwise a strong galvanic action will in most cases be set up and the button will become much corroded.Plashes of light due to the oxidation of t,he magnesium are emitted with all magnesium-alloys on pas-sage of the metal from the crucible to the ingobmould. The magnesium may be oxidised out of some (if not all) of these alloys simply by fusion with a flux of carbonate of soda and carbon. With the exception of some of the alloys of tin silver and lead with magnesium in notable quantity the colour of the white metalrs is not materially altered but the physical proper- ties are remarkably changed; and without exception the mag- nesium renders all alloys very brittle; even “triple alloys” of mag- nesium with gold and silver and also with nickel and copper are most remarkably brittle.The fracture is more or less crys- PARKINSON ON THE ALLOYS OF RIAQXESIUM. 119 talline and the hardness is slightly increased above that of' magnesium or that of the metal or metals with which it is alloyed. Exposed to the action of the atmosphere they tarnish inore or less rapidly ; those alloys with mercury bismuth lead phosphorus and also arsenic are very rapidly tarnished arid decompose water most readily. None of these alloys of mag- nesium promise to be of any practicaZ importance in the arts but the powerful deoxidizing properties of magnesium may ultimately be found useful.In employing brasqued crucibles m-uch time nncl trouble we required to arrange the metals and plug lute and pack tightly so as to exclude the air and prevent oxidation. With equal parts of fluor-spar and cryolite as a flux a fusioii may be readily effected in a stout Cornish crucible and with more satisfactory results where applicable. When cryolite call-riot be had a mixture of 3rd fluor-spar and +rds common salt will answer most purposes more espeeially for copper silver and gold. The alloys should be cleaned without 'lrushing them in water or else the surface will rapidly tarnish and alloys of tin bismuth lead and antimony will even set up a slow oxidation througli.out so that the fresh fracture will in iL very short time become dull and coated with an oxide.It is remarkable that tlie alloy of tin and magnesium prepared in a flux of fluor-spar and common salt has the gyq colour and lustre of steel and afine granzihr fracture which soon become8 dull and coated with a greyish oxide on exposure to the air; while the same alloy prepared by fusing the metals together in un atmo-511lwe of hydrogen or in a braspied crucible with more than 2 per cent. of magnesium tarnishes less when exposed to the air and has a lavende7.-tinted fracture and prismatic crystalline structure hut when polished a steel-grey colour and lustre. The results of alloys prepared by heating the metals together in hydrogen and also in the following fluxes! may be briefly summed up in a tabular form in the order of the fusibility of the rnetals with which magnesium alloys :- TABLEI.-ALLoYS OF MAGNESIUM prepared in an atmosphere of pure dry Hyd?.ogen in a ?hard Gemm gluss test-tube over the Gas-Jlameof a good Air-burner.Metals. Nature of Combination. Lustre and Colour. ffardness and Fracture. Remarks. Tenacity. -.----Mercuryaith Combination begins below Silver-white colour ; With the 7 per Finely granular ; Oxidized rapidly in the air and 1per cent. boilingpoint of mercm highly lustrous. cent. magnesium white fracture. also by water. The oxidized to 7 per without combustion The lustre not soft and brittle ; amalgam is a brownish black cent. mag- and without corrosion permanent.easily crumbled powder. nesium. dtube. between the fin-gers. Sodium with Combination begins with- Silver-white colour Soft and rather Finely granular. Water is rapidly decomposed by it. magnesi-out combustion at a and lustre. brittle. The sodium oxidizes and is dis-um. dull red heat and cor- solved by the water and magne- rodes and bIackens sium separates in small globules tube. nearly free from sodium. Tin with 2 Combination takes place Steel-grey lustre Rwder than tin Withmore than 2 The alloy prepared in brasqued cru- pcr cent. at a JuIi red heat. which tarnishes but softer than per cent. mag-cible also has a lavender tint but tu 10 per rapidly. magnesium and nesium givesa when re-fused in fluor-spar and cent. mag- far more brittle. lavender- t int- common salt it gives a steel-grey nesium.ed prismatic dour. (See Table 11.) crystalline fracture. Cadmium Combination begins at a Silver-white colour About as brittle Coarsely crystal- Tarnishes slowly. Within a period with lOper dull red heat and the and brilliant and as. hard as line and high- of six months it brokeup into small cent. mag- mass boils if the heat is lus t,re. magnerlium. ly lustrous. tarnished fragments though kept nesium. increased suddenly to loosely corked in a tube. redness. Bismii thwith 10 per cent. mag- nesium. Lead with 10 per cent. magnesiu II Zinc with 10 per cent. magnesium Antimony with 10 per cent. mag- nesium. Silverwith 10 per cent. magnesiurr Platinum with mag- nesium.Energetic combination and vivid combustion at a red heat. Combination takes place at B dull red heat ; tube blackened. Combination takes place at a red heat tube blackened. Combination takes place at a much higher degree of heat than any of the above metals. Combination take8 place at a red heat about the fusing point of Ag. Combination begins at a red heat with vivid combustion. Vhenpolished steel- grey lustre and colour. Crjstds laminated and colour of specu-lar iron ore. Very brittle. Steel- grey colour and lustre when po- lished. Tin-white colour and highly lus- trous. Steel-grey colour and lustre. When polished, silver-whi te co-lour and lustre ; tarnishes yellow.Tin-white colour and lustre. Very soft and brittle ; easily crumbled be-tween the fin-gers. Abfut as hard as zinc and very brittle. Very hard and veiy brittle. Some with 20 per cent. magnesium. Harder than anti- mony andequally brittle. Harder t,han mag- nesium and about aa brittle. White colour. Coarsely crystal- line ; lami-nated ; sub-metallic and lustrous Finely granular and lavender- tinted frac-ture. Like tin and magne-sium alloy. Smooth fracture and highly lua- trous. Dull lustre and finely granu-lar Deep straw-yel- low,and finely granular. Coarsely gra- nular with 20 per cent. magnesium. Finely granular. Oxidizes and deliquesces in the air veiy rapidly readily decomposes water and partly diasolved.by water. Fresh fracture becomes suddenly dull and coated with a black oxide. Exposed to the air disin- tegrates and gives a black oxide mixed with some metal. This alloy appears to tarnish the least of any alloy of magnesium. Next to this the alloy of copper and magnesium tarnishes least. Decomposes water and rapidly oxi-dizes in the air. Yellowish fracture with 10 per cent. magnesium whether prepared in hydrogen in a brasqued crucible or in a flux of fluor-apar and cryolite but a bluish-white colour with 20 per cent. magnesium. Partly soluble in hydrochloric acid. TABLEII.-ALLOYS OF UGXESIUM ucitli the easily fusible Metals pepred in a jux of 2 parts Chloride of Sodium and 1part Fluor-spar (freefrom Zinc OP Lead).Time and Degree of Heat Met a1 s. of Fusion on plunging mag Lustre and Colour. Hardness and Fracture. Remarks. nesium into the Fusion. Tenacity. I Tin with 10 450grs tin with 50 gra. Steel-grey colour Very brittle; hard- Finely granular; Tin Equates througb the fracture of per cent. magnesium were .fused and lustre. er than tin but steel-grey co-slag while cooling. Sp. gr. 5.2 ; magnesium and alloyed at a dull red softer than mag- lour and luatre decomposed water slowly. heat in five minutes nesinm and far but not theleast with 3 per cent. loss. more brittle. like that pre-pared in hydrG- gen or in bras-qued crucible. Bismuth with 450 gm.bismuth with 50 Colour and lwtre Very brittle; softer Coarsely cryatal- Deliquesces when expowd to the air 1 0per cent grs.magnesium gave thst of bismuth than bismuth and line and lami- and immediately becomes dull on but more brittle; crumbles under nated resem-the fresh fractured surface. The and alloyed & about five instantly tar-the blow of s bles micaceous actiou of the air and moisture is minutes at a dull red nishes in the air. hammer. specular iron so great that it hisses distinctly heat; a large loss and ore. when held in the hand. dark-coloured slag. Lead with 10 Fused andalloyed in about Steel-grey colour Harder than mag- Finely granular The crust of oxide formed is thick per cent. three minutea at a dull and lustre soon nesium and ex-with steel-grey and greyish white and gives dull magnesium red heat.Tranquil fu-blackens in the ceedingly brittle. colour and fracture when ingot is broken up sion and 6 per cent. loss. air thenwhitens Very brittle even quickly black- after surface has oxidized. and in a few with 4 per cent. ens in the air. weeks breaks up. magnesium. Zinc with Failed to obtain an alloy at a dull red heat in three experiments. The reac:.ion was violept and explosive in each experiment. magnesium Obtained an alloy by heating the metals together in an atmosphere of hydrogen. See Table I. Ant i mony Combination took place at Steel-grey colour Very brittle and Coarsely crystal- Decomposes water rapidly and like Kith 10per a red heat with about and lustre. about a! hard as line ; finely the alloy bismuth and magnesium cent.mag- 6 per cent. loss. magnesium. granular; re-gives a strong galvanic action -..-t.l-m m-t -LA-hrrrn+t.rrrl ..nnm nnrl Cnm:ahna nesium. TABLEIII.-ALLoYs OF &~GNESIU%~ with the less fusible Metals prepared in a jhx of Fluorspar and Cryolite (Silver with Ma9nesiurn and Cupper with Magnesium,ftwd in epual purts of Fluor-spar and Common Salt). Metals. * Time and Degree Of Lustre and Colour. Hardness and Fracture. Remarks. I-Ieat of Fusion. Tenacity. -,c--- ------.---.-Aluminum Failed to ohtain an alloy of aluminum and magnesium. The product waa found on analysis to contain aluminum and with mag-silicium (about 25 per cent. Si). The fusion was about five minutes in one and nearly ten minutes in another experiment. nesium. The product weighed less than the amount of aluminum taken in both experiments.Obtained aQ alloy of aluminum and magnesium in a crucible brasquecl with fresh and pure calcined magnesia. Si!ver with 200 grs. silver fused and Bluish-white co-Harder than mag-Coarsely crystalline Tarnishes slowly. 10percent. alloyed in about four lour with 20 per nesium. and bluish-wbite, magnesium minutes at a red heat cent.magnesium like zinc with 20 inclusive of time occu- and yellowish-per cent, but finely pied to fuse 50 grs. of white with 10 granular and yel- magnesium. per cent. mag-lowish with 10 per nesium. cent. mrcgnesinm. Copper with 200 grs. copper fused and Reddish-yellow or Very brit<tle ; 1per Smooth vitreous frac- With 15 per cent. magnesium magnesium alloyed with 50 mag-yellowish or cent.magnesium ture and tarnishes the alloy has a sp. gr. 5-95 nesium in about seven golden colour,ac- renders the cop-only slowly. and nearly as brittle as glasa. minutes at a bright red cording to per- per brittle; and heat. Loss 19 per cent. centage of mag with 15per cent. nesium. the alloy may be powdered in an iron mortar. Gold with Time of fdsion aboiit Golden colour and Hard and brittle. Finely granular Bme magnesium 15 minutes at a bright lustre. specks of white me- red heat. tal as if the magne-sium wasnot chemi-cally intermixed * The metals were not added until the flux was thoroughly fused and tranquil the metal with which the magnersium WIB alloved was fused before plunging the ma:wQiaminto the melted maw.TABLE111-continued Iron with Failed to obtain an alloy iron and magnesium. Fused 167 grs wrought iron in the state of fine wire (coiled up) in about 13 magnesium. hour then plunged a lump of magnesium into the fused metal. The button however contained only a trace of rnagne6lum, and its physical character remained unchanged in one experiment only. Cobalt with Failed to obtain an alloy cobalt and magnesium ; first fusing cobalt then plunging magnesium into it in like manner but magnesium. no magnesium wm present in the button. Niche1 with Failed to obtain an alloy nickel and magnesium by fiieing the metals together in brasqued crucible a trace only of magnesium magnesium. being found present on analysis of button. 0 2 TABLE IV.-TRIPLE ALLOYSOF &~AGNESIUM prepared by fusing in equalparts of fluor-spar and Cmmqn Salt.Metals. -.---Bismuth with copper and magnesium. Gold with Copper and magnesium. Nickel with Cop- per and 6 per cent.magnesium. Colour and Lustre. Brasa-yenow polish ; soon becomes dull. Steel-grey colour tinted yellow. Silver-white colour and high lustre. Hardness and Tenacity. Very brittle and about as hard as copper coin. Very hard and very brittle. Exceedingly brittle,and very hard. Fracture Dull and granular frac-ture,with specks of white metal intermixed. Coarsely crysta!Iine with steel-grey colour Finely granular and silver- white. Remarks. r F Bismuth liquates out and coats siirface Q of button with a thin coating while eooling.When freshly fractured resembles the finest specimens of white cast iron. Composed of copper 65-63 ; nickel 28-24 ; magnesium 6.84. 125 PARKINSON ON THE ALLOTS OF MAGNESIUM. BEHAVIOUR ELEMENTS. OF MAGNESIUMWITH NON-METALLIC Magnesium combines very energetically at high temperatures with phosphorus arsenic and sukhur with which it forms remarkably unstable compounds. The coherent and difficultly fusible alloys of magnesium with phosphorus and with arsenic oxidise rapidly and fall to powder when exposed for a short time only to the air at common temperatures the alloy of sulphide of magnesium only slowly. The apparatus used for the experiments with phosphorus and arsenic was made from a stout half-inch diameter glass tube of difficultly fusible glass such as is used in organic analysis.The two ends of a piece of a combustion-tube (eight inches long) were drawn out to about a quarter of an inch in diameter and four or five inches long and the middle part blown out into two bulba of about three-quarters of an inch in diameter (Fig. 2). The two ends were bent upwards at an angle of about 30 degrees and the larger orifice of one of the ends was connected to a Fig. 2. hydrogen apparatus by an india-rubber connecter after placing the substances in the bulbs ; and then after displacing the atmospheric air in the tube by arapid and dry current of hydro- gen the bulbs were heated by means of the gas flame of two or more good air-burners.The current of hydrogen was con- 126 PARKINSON ON THE ALLOYS OF MAGNESIUM. tinued after withdrawing the flame of the burners until cold and the product was weighed immediately. Pltosphorus and Magnesium. Pieces of phosphorus were placed in one bulb and magnesium filings in the other. The experiment was conducted as above described and the melted phosphorus was allowed to flow slowly by inclining the tube over the magnesium filings heated to dull redness. Then the flame of another burner was used with a view of maintaining uniformity of temperature and for volatilizing the excess of phosphorus from the tube. The com-bustion which took place at a dull red heat was highly lumi-iiou~and vivid and the tube was corroded and fractured in several cases from the sudden increase of heat during combus- tion With 3 grs.magnesium filings the increased weight was in the fist experiment 2.45 grs. in the second 1.98 grs. and in the third 2.08 grs. The product is a hard brittle coherent semi-metallic and difficultly fusible mass of a dark-brown colour with a fibrous crystalline fracture; it is immediately tarnished on exposure to the air and within a few hours falls to a floccu- lent powder at the same time undergoing several changes of colour. It first becomes brownish-black then brown yellowish straw-yellow and finally yields a permanent greyish-white powder emitting non-inflammable phosphoretted hydrogen during its oxidation as well as when thrown into water or into dilute hydrochloric acid.The freshly oxidized product when heated to dull redness in an open tube undergoes combus- tion and becomes whiter in colour. It is completely dissolved by dilute hydrochloric acid. A paper on phosphide of magnesium by Mr. Blunt is pub-lished in the Chemical Journal for 1865 [2] iii 106 the results of which do not coincide with the above. The black powder said to be a phosphide of magnesium and described as a very stable compound is probably carbon mixed with some phos- phide of magnesium the carbon to which it owes its blackness being probably deposited by the reaction of magnesium upon the carbonic acid used in the experiment. In all cases magne- sium decomposes the glass in which the experiments are con- ducted and is stained black by the reduction of the silicium of the glass with which it combines and forms a silicide.Oxygen PARKIKSON ON THE ALLOYS OF MAGNESIUX. 127 is also liberated at the same time which combines with the magnesium and probably with the phosphorus also. See the reaction of magnesium upon carbonic acid and also upon car- bonates further on. Su2phur and Magnesium. In combining sulphur with magnesium a single bulb-tube con- structed as before described was connected with a small flask containing sulphur used for generating sulphur-vapour ; the magnesium filings mixed with a little sulphur gave better results than sulphur-vapour alone. The heat was slowly raised to dull redness by means of the gas-flame of a good air burner. The product was a brownish-black scoriaceous coherent coke- like mass hard and brittle and mixed with a little oxide of magnesium and some undecomposed filings.On exposure for some time to the air the difficultly fusible sulphide slowly tarnishes and evolves sulphuretted hydrogen and the finely granular and bright steel-grey fracture becomes dull and coated with a greyish oxide ; it is partly soluble with straw-yellow coloration in water with evolution of sulphide of hydrogen but on exposure to light it deposits sulphur and becomes colourless. Arsenic and Magnesium. 1 The single bulbtube wa8 connected with a hydrogen appa- ratus through which a rapid current of pure dry hydrogen was passed ;and when all the atmospheric air was displaced thereby the magnesium filings mixed with arsenic placed in the bulb part were heated slowly to redness.In one experiment 3 grs. magnesium filings mixed with 15 grs. arsenic gave violent and vivid combustion with evolution of much heat. The heat was continued until the hydrogen flame at the orifice of tube ceased to be luminous; the current of hydrogen was passed through until the ignition tube was cold and then the product was im-mediately weighed. The loss was found to be 8.8 gss.,showing that about 6.2 grs. arsenic were fixed and combined with 3 gm. magnesium. 3 grs. magnesium heated in like manner for ten minutes lost only 0.05 grs. hence the 8.8 grs. lost were almost entirely due to the volatilization of arsenic. The pro- duct was a hard brittle and difficultly fusible mass of a choco- 128 PARKINSON ON THE ALLOYS OF MAGNESIUM.late-brown colour and dull lustre with finely grained fracture and a brown sub-metallic lustre; it crumbled up in a few hours into a dark-brown powder. The same quantity of magnesium filings and arsenic sud- denly heated in a glass test-tube over the flame of a good air- burner gave .a vivid and violent action slightly explosive. Another experiment with 3 grs. magnesium and 20 grs. arsenic gave an explosion with loud report and shattered the bottom of the test-tube into fine fragments. Behaviour of Magnesium with Oxides and Carbonates. The de-oxidizing action of magnesium at high temperatures is less violent than its combination with the non-metallic elements but sufficient to give a vivid combustion which occurs at a slightly higher temperature.Pure lime is decomposed at a red heat by magnesium flings with only a slow and dull combustion and yields a straw-yellow powder which has a fetid smell and decomposes water slowly. Pure alumina heated to redness with magnesium filings gives a vivid combustion and a blackish-brown powder which rapidly decomposes water and gives a violent action with moderate dilute hydrochloric acid sufficient in one experiment to ignite the hydrogen evolved in the reaction. Sespuioxide of chromium heated to redness with magnesium- filings gives a vivid combustion and a black powder which de- composes water. The inside of a glass tube in which some small fragments of magnesium were heated with chromic oxide was coated with a thin white metallic coat which when washed and scraped clean gave a silver-white lustre and on ignition in the air burnt with evolution of much light and gave a greenish- yellow oxide-indicating the reduction of the oxide to the metallic state-and combined with the magnesium and pro- bably also with silicium derived from the tube.Titanic acid heated to redness with magnesium-filings gives a vivid combustion and a bluish-black gritty powder partly if not wholly insoluble in cold dilute hydrochloric acid which when dried and heated in the open tube burps like tinder and when thrown into the flame emits bright-red scintillations. PARKIKSON ON TKE ALLOYS OF RIAGNEXIUM. Mugiiesia (pure and fiee fi-om carbonic acid) heated with magnesium-filings at a red heat is not acted upon lout the car- bonate gives a slow combustion with deposition of carbon and a brownisldlack powder ; so also do other carbonates.Silica heated to redness with magnesium-filings gives a vivid reaction and a brown to bluish-black powder according to the degree of heat and vividness of reaction ; if the siliciuin is in excess and the combustion slow the product is browfz; but if the magnesium is in excess and the combustion vivid the product is a black gvitty powder ;which in the latter case gives a much stronger reaction when thrown into hydrochloric acid and evolves more silicide of hydrogen and with louder detonation as the gas spontaneously ignites in the air-hence a " silicide of mag-nesium '' is formed in greater quantity in one case than in the other.The black powder contains the most silicide. The lighter coloured product probably contains more of anhydrous silicate of magnesia. 1part magnesium-filings to 2 parts silica heated in a current of hydrogen (in fine powder) give a brown gritty powder. Equal parts magnesium and silica give a more cemented and brownish-black powder ; and with 3 parts mag-nesium and 1part of silica the product was a bluisldlackpowder with sub-metallic lustre hard and brittle. When the darkest coloured products are thrown into concentrated sulphuric acid no spontaneously inflammable gas is evolved until the substance is rubbed with a glass rod against the sides of the tube and then 110 detonation takes place but luniinosity only is emitted.Similar results are obtained when the blackened part of the glass tube in which magnesium has been heated either alone or with other substances is broken up into fine fragments and thrown into either dilute or strong hydrochloric acid evidencing the presence of silicide of magnesium from the reaction of mag- nesium upon the glass. The same powerful deoxidization and production of silicide of magnesium takes place also with sili- cates when heated to redness with magnesium. Behuviour of Magnesium with Oxides of Curbon. Curbonic oxide and carbonic acid like the carbonates are deconi-posed when heated to redness with magneeium-filings. The magnesium is oxidised and the carbon ifir deposited in admixture ..! 130 PARKINSON ON THE ALLOYS OF MAGNESIUM.with the oxide so that the product resembles lampblack. The combustion is vivid and highly luminous Behaviour of Magnesium with Carbides of Hydrogen. 1. With Coal-yas.-Whether or not the coal-gas be washed and dried before heating with magnesium-filings a slow com-bustion takes place and the product resembles that obtained by heating magnesiixm in carbonic acid but with this difference that it decomposes water slowly with evolution of fetid hydro- gen while the product formed by heating magnesium with carbonic acid does not decompose water. 2 grs. magnesium-filings heated to redness in a bulbignition tube in a current of coal-gas unwashed absorbed 1.67 gr.carbon and oxygen. When 3 grs. magnesium-filings were heated to redness in a current of coal-gas washed by passing it through milk of lime ferric hydrate and acetate of lead and dried with oil of vitriol the increase of weight by ignition in like manner was only 1.43 gr. Marsh-gas was found to have little or no effect on magnesium-filings hence it would appear that the combustion in these experiments was due to the carbonic oxide; and pro- bably also to the beneol present .in the coal-gas. 2. With Marsh-gas.-This gas generated fiom a mixture of acetate of soda quick-lime and caustic potash was washed and dried by passing it through oil of vitriol and after expelling all the air in the apparatus and tube 3 grains of magnesium-filiflgs were heated in it as before to redness for five or ten minutes then cooled and weighed.The increase of weight was only 0.03 gr. ; the filings were merely tarnished and a little carbon deposited derived probably from carbonic acid not ab-sorbed by the lime and potash. Another experiment also with 3 grs. magnesium-filings heated to a higlzer temperature for ten or twelve minutes gave an increase in weight of 0.08 gr. The filings were only slightly tarnished as in the first experiment. 3. With BeizsoZ.-3 grs. magnesium-filings heated in pure benzol-vapour gave no combustion but the filings were ren- dered very brittle and coloared black and decomposed water. On dissolving them in dilute hydrochloric acid a separation of carbon took place. The increase of weight was 0.73 gr.SMITH ON THE OXIDATION OF ETHYLIC ETC. XuZphurous acid (SO,) prepared from copper and sulyhuric acid washed with concentrated sulphuric acid and passed over magnesium-filings heated to redness in a bulb ignition-tube by the gas flame of a good air-burner gave a vivid luminous com- bustion. Sulphur condensed on the cool part of the tube which was expelled by aid of another flame. The current of dry sulphur-ous acid was passed through the ignition-tube for some time after withdrawing the flame until the tube was cold when the pro- duct was removed and re-weighed. The combustion of 3 grains magnesium-filings (after expelling all the sulphur fiom the tube) gave a product which weighed 4-86 grs. and when treated with nitric acid evolved fumes of nitrous acid and gave with chlo- ride of barium a precipitate insoluble in hydrochloric acid thus showing that the sulphurous acid was not completely reduced.Before closing this paper it is desirable to draw attention to the erroneous statements on alloys of magnesium which have gone uncontradicted up to the present time. It has been said that magnesium would give a somewhat tenacious and malleable and useful alloy with copper. It is however much to be re-gretted that none of the alloys of magnesium arid copper possess the least tenacity or malleability. Magnesium alloys with copper as with most (if not all) metals in different proportions and the larger the proportion of magnesium the more brittle is the alloy. With copper the colour becomes paler according to the increased proportion of magnesium.

ISSN:0368-1769    

DOI:10.1039/JS8672000117

出版商:RSC    

年代:1867

数据来源: RSC

摘要:

SMITH ON THE OXIDATION OF ETHYLIC ETC. VIII.-On the Oxidation of Ethy lie and Methylie Benzoates. By R. H. SMITH,F.C.S. AT the suggestion of Mr. Chapman I wag induced to under-take the following investigation :- 132 SJIITH ON THE OXIDATI@K OF ETI-ITLIC ETC. Pure ethylic benzoate was digested with excess of a 12 per cent. solution of potassic dichromate and dilute sulphuric acid at the temperature of 100" C. for 9 or 10 hours. The tube was then removed from the water-bath and left to stand all night. In the morning beautiful white crystals were observed and the tube on opening gave little or no carbonic acid but there was a strong smell of acetic acid. The white crystals thus produced were dissolved in a large quantity of hot water and a solution of argentic nitrate added.The whole was then hent'ed and set aside to crystallise. After another crystallisation the sdt was submitted to analysis. 0.1355 grm. of the silver-salt was precipitated with hydro- chloric acid and the resulting argentic chloride washed dried and ignited. The argentic chloride weighed 0-085 grm. whence the percentage of silver is 47.15 agreeing closely with the theo- retical percenta,ge of silver in argentic berizoate- C,H,AgO, which is 47.16. The liquid also found in the tube was carefully distilled until it no longer retained sulphuric acid. A portion of this was heated with alcohol and sulphuric acid when the well known smell of ethylic acetate was obtained. The remaining portion was then treated with baric carbonate which dissolved freely ; an excess was added and the liquid boiled and filtered.The resulting clear solution was evaporated to dryness in the water- bath and the residue dried at 11O*C. I. 0*0970 grm. of the barium-salt was precipitated with dilute sulphuric acid and the baric mlphate ignited. It weighed 0.0885 grm. Percentage of barium 53-60 11. 0.1140 grm. gave 0.1040 grm. of bark sulphate. Per-centage of barium 53-59. These numbers agree very nearly with the theoretical per- centage of barium in baric acetate Ba''(C2H3Q2)2, viz. 53.72. In one experiment the carbonic acid was determined with the following result :-1.7990 grm. of etliylic benzoate gave 0*0020grm. of carbonic acid. This is only a trace. It is quite possible therefore to produce benzoic and acetic acids from ethylic benzoate without carbonic acid a result which is in harmony with theory.CHrlPilUN OK h NEW SYXTHESZS OF FORillIC ACID. 133 After having tried the action of potassic dichrornate of ethylic benzoate I was induced to try it on the methyl-compound. Methylic benzoate is decomposed by potassic dichromate in a eimilar manner. A quantity of this compound (prepared by the distillation of benzoic acid wit>h woad-spirit and sulphuric acid) was introduced into a tube with an 8 % solution of the potassir dichromate and the tube after being sealed was digested in the water-bath for several hours. It was then allowed to cool when the benzoic acid made its appearance entirely filling the tube with white crystals On opening the tube carbonic acid escaped; the contents of the tube were thrown upon a filter by which most of the benzoic acid was separated from the liquid.The liquid was then distilled the distillate converted into barium salt and the barium determined which gave a percentage agreeing very closely to that required by formate of bariuni. The benzoic acid was converted into the silver-salt and the percentage of silver determined which also agreed with that required by argentic benzoate. Methylic benzoate is therefore resolved as might be expected into benzoic acid carbonic acid and more or less formic acid. It will be seen from the foregoing results that benzoic acid and probably the acids of the benzoic series will resist the power of oxidising agents as well as those of the acetic series as shown by Messrs Chapman and Thorp. These experiments were performed in the laboratory of the East London Soap Works.

ISSN:0368-1769    

DOI:10.1039/JS8672000131

出版商:RSC    

年代:1867

数据来源: RSC

摘要:

CHrlPilUN OK h NEW SYXTHESZS OF FORillIC ACID. 133 1X.-On a new Synthesis of Formic Acid. By ERNESTTHEOPHRON CHAPMAN. [Contribution from the Laboratory of the London Institution.] FROMa careful consideration of the results obtained by Mr. Thorp and myself in our investigation of the action of VOL. xx. I4 CHAPMAN ON A NEW SYNTHESIS oxidizing agents on organic bodies it appeared to me difficult to account for many of the reactions on the assumption that nascent oxygen was the sole agent in effecting the change. Thus to take a very simple case acetate of ethyl yields by oxidation two equivalents of acetic acid. In this case we have the same amount of hydrogen in the products obtained as in the substances operated upon. There are only two hypotheses possible in this case ; either the ethyl has given up a portion of its hydrogen to the residue of the acetic acid and has then itself appropriated two equivalents of' oxygen or the acetic ether has been decomposed by the assimilation of water and the substitution of' oxygen for hydrogen which amounts in point of fact to the action of hydroxyl.The assumption of the existence of hydroxyl in the oxidizing mixtures described in the paper before alluded to is of course an impossibility for hydroxyl is immediately decomposed by these liquids. It is we know difficult to convert water into peroxide of hydrogen but I am at a loss to understand t,he decomposition of bichromate of potash by concentrated sulphuric acid and heat uidess upon the assumption that hydroxyl is formed and at once decomposed by the excess of chromic acid present.This may appear a somewhat strained hypothesis. In order to give it weight it was necessary to find some instance in which an unequivocal addition of hydrogen actually took place in such an oxidizing mixture. The following synthesis of formic acid furnishes such an instance ; and I may remark that it was not undertaken with any idea of proving the truth of the foregoing hypothesis though had it not been for that hypothesis I should in all probability neither have carried out the investigation nor have put a correct interpretation on the results obtained. I wished to know whet'licr an acid solution of permangsnate had any action upon carbon in the &ee state ie.charcoal lamp- black &c I found that it did act upon it though but slowly unless the solution were very concentrated and contained much acid. Still there was no question but that action and very considerable action too took place provided sufficient time were allowed. Crystallized permanganate of potash was dissolved hi dis-.tilled water and a8 much sulphuric acid added as would Serve to liberate the permanganic acid. Lamp-black which had been intenrJely igsited waB then added *and the mixture boiled. OF FORNIC ACID. After some hours’ boiling the solution had changed to a brownish-black colour. On standing it became clear. The colour of the clear liquid was then seen to be very faintly pink. A few drops more sulphuric acid were added and the mixture distilled.The distillate was tasteless or nearly so and quite colourless but on adding a drop of ammonia and a little nitrate of silver and boiling a brown coloration was obtained. This constitutes the well-known test for formic acid. Now as even after the most intense ignition lampblack is said to retain traces of hydrogen-a statement which I am utterly unable to verify-I thought it advisable to employ some form of carbon which should be free from this objection. I tried pasBing car- bonic acid over ignited sodium but the yield of carbon froill this experiment is deplorably small. The mixture of oxide of sodium and carbon was dissolved in distilled water. [N.B.-The distilled water employed in this and all the fol- lowing experiments had been re-distilled slowly from perman- ganate.The vessel in which the distillation was conducted as well as the interior tube of the condenser and every other piece of glass apparatus used had actually been made red-hot so that it was free from all suspicion of organic matter No cork india-rubber nor any form of organic matter was allowed to touch the interior of any of the vessels.] The carbon gradually settled to the bottom the alkaline solu- tion above it was poured off and the carbon washed by decanta- tion with hot distilled water. It was then operated upon in the manner already described very minute quantities of per- mailgallate and sulphuric acid being employed. The operation was conducted in a digestion tube in the oil-bath.The tube was opened a little sulphuric acid added and a small portion of the liquid distilled off. But little of the carbon had disap-peared. The liquid in the tube was poured 06more distilled water added this again poured off permangauate of potash and sulphuric acidagain added and the process repeated. This was done six times. The distillate obtained in this manner was rendered alkaline by a drop of solution of potagh evaporated down to n uery small bulk and the silver test for formic acid applied. It gave a very considerable precipitate. The carbon used in the next experiments wa~ obtained fisonz hi-sulphide of carbon by the action of sodium. These two sub-stances when gently heated together yield aulyhide of sodium L.2 CHAPMAN ON A NEW SYNTHESIS and a substance which I take to be pure carbon.It was washed in the manner previously described and ignited in a covered platinum crucible. There wad something more than a gramme of it. It was treated in precisely the same manner as the carbon obtained from carbonic acid had been and the distillate obtained from it also gave the characteristic reaction with ammonio- nitrate of silver. Still no quantity of formic acid had been collected. Reactions had been obtained which rendered it highly probable that formic acid was a product of the gradual oxidation of carbon but the proof was still far from complete. The question in fact resolved itself into this apparently simpler one where can we obtain pure cazbon not in the state of graphite but in the amorphous condition? I believe that it may be obtained by simply igniting lamp black; but I fear most chemists would regard this as a delusion.I therefore mixed finely divided lamp-black with a small quantity of nitrate of potash insufficient to burn more than half of it. This mixture was heated in a platinum crucible. It deflagrated. A portion of the carbon of course remained unconsumed. This carbon I hope may be regarded as free from organic matter; if not I despair of finding any. The carbon was washed out of the accompanying potash-salts with distilled water and dilute sulphuric acid and then treated in the manner previously described. By several operations nearly twenty grammes of it were obtained. These were di- vided amongst five digestion tubes ; great care is necessary in these experiments in apportioning the acid to the permanganate.The solution must be perceptibly but not LIiore than perceptibly alkaline at the close of the operation. If too much or too little acid is employed no formic acid whatsoever is produced. This I have repeatedly verified to my cost. It is better that the liquid should be a little too alkaline than too acid. No advan-tage Whatsoever is gained by using large quantities of perman- ganate. For instance to four grammes of carbon two deci- grammes of permanganate of potash and a corresponding quantity of sulphiiric acid may be added apparently with exactly the same yield of formic acid as if only half the quantity were employed; in fact three of my tubes were always charged with about twice a.s much permanganate as the other two.Ths same number of operations were performed with each lot of carbon viz. eight and as will be seen below the amount of formic acid OF FORMIC ACID. obtained from the two tubes was almost exactly two-thirds of that obtained &om the other three. These operations extended over a considerable time-in fact I was about six days engaged in charging these tubes and dis- tilling from them. The product of two days’ work was employed in obtaining satisfactory qualitative tests with oxide of mercury and amrnonio-nitrate of silver. I obtained the reduction of both these substances. The products of the other four days’ work were devoted to analysis.About three-fifths of the total product (less than a decigramme) was employed in making a combustion that is to say the barium-salt obtained from the distillate was so employed The remaining two-fifths also converted into a barium-salt were employed in determining the saturating capacity of the acid. Combustion was performed with chromate of lead. From the barium determination the following numbers were ob-tained :-Substance taken.. 0-1402 Ba,SO found.. 0.1428 Therefore.. ...... 59-89 % Ba. By combustion the following numbers were obtained :-Substance taken. 0.2052 barium-salt. Found .......... 0.0784 CO and 0-0165 H,O ; Therefore ...... 10.44 % C. and *89%H. Theory. CHBa02. Found C 12 10.57 10.42 H 1 0.88 89 Ba 68.5 60.35 59.89 0 32 28.20 - - -I 113.5 100~00 It appears therefore beyond all doubt that formic acid may actually be obtained by the action of permangnnic acid upon carbon.The process is difficult in the extreme and little more than traces of the acid are obtained. It is only under the cir- cumstances here specified that it is obtainable. We require free permanganic acid to act upon carbon but a trace of potash or some alkali and not more than a trace must be present. imagine that a comparatively large quantity of formic acid k~ formed and destroyed dnring the process.

ISSN:0368-1769    

DOI:10.1039/JS8672000133

出版商:RSC    

年代:1867

数据来源: RSC

摘要:

138 X.-On the Basicity of Tartaric Acid. By MT. H. PERKIN, F.R.S. TEEtetratomic character of tartaric acid has been fully shown by its artificial formation &om auccinic acid. Reasoning upon this fact several chemists have been induced to regard it also as tetrabasic and in confirmation of their hypothesis have ob-tained several metallic combinations having the formula of tetra-basic tartrates. Thus Hugo 8chiff found that by heating the basic tartrate of lead to 130"C. it lost an equivalent of water yielding a body which he regards a8 the tetrabasic lead-salt* thus :-C4R4Pb",0,.Pb",0 = H,O + c4H,Pb",06. Fr isc h also obtained a remarkable zinc-compound by boiling metallic zinc with potash and tartaric acid and t,hen carefully neutraliskg the solution with dilute nitric acid.The product has the composition C,H,Zn",06 + +H,O; but if we consider the curious methods by which these sub-stances have been produced and the high temperatures at which Home of them have been dried and also the fact that tartaric acid will easily lose and again take up an equivalent of water it becomes very difficult to judge of the true constitution of these bodies especially as they are insoluble and cannot be crystallised. I have therefore thought it worth while to study the replaceable hydrogen in a different manner and for this purpose have examined principally new derivatives obtained by the action of the chlorides of the acid radicals on tartaric ether. Action of CJiloride of Benzoyl on Taratarie and Paratartaric Bthers.Chloride of benzoyl when mixed with tartaric ether does not react in the cold but upon. the application of heat hydrochloric * Ann. Ch. Pharm. lxix 2'12 PERKIN ON THE BASICITY OF TARTARIC ACID. 139 acid is abundantly given OE A mixture of these two bodies in about equivalent proportions (with however a slight excess of the ether) was heated in a water-bath for two or three hours. The product was well agitated at intervals with a solution of carbonate of sodium for the purpose of decomposing and re-moving any chloride of benzoyl or tartaric ether that might still be unacted upon. The alkaline solution was then separated fkom the new compound which presented itself as a very viscid oil This oil was then washed with water dissolved in ether and agitated with dry carbonate of sodium to remove any water or acid that might still be remaining.The ethereal solution was then filtered and evaporated over the water-bath. By this means the new body was left as a very viscid but transparent oil. Two combustions of this substance in oxygen gave the following numbers :-I.-.2270 of substance gave 4799 of C02and -1205 of H,O. 11.-2315 of substance gave -4913 of CO and *1217 of R,O. These numbers show the new product to be tartaric ether with one equivalent of hydrogen replaced by benzoyl as the following comparison will show :-Experiment. Theory. I. IT.\ -c, ...... 180 58-06 57.64 57.86 H, ...... 18 5.80 5.90 5.83 ~-0 ........ 112 36-14 .... 310 100.00 This product after standing especially under water for two or three weeks is almost entirely converted into a maas of colourless prismatic crystals which on being well pressed between bibulous paper under a very powerful screw-press until perfectly fkee from oil appears like a cake of white was. 140 PERKIN ON THE BASICITY OF TARTARIC ACID. This on being heated easily fuses and on cooling gradually solidifies into a beautifully radiated orystalline mass. A por-tion of this substance burnt in oxygen gave the following numbers :--2470 of substance gave -5256 of GO, and -1330 of H,O. These furnish the following percentages :-Experiment. Theory. Carbon ...... .... 58-03 58-06 Hydrogen ,.... . 5-98 5-80 These numbers it will be observed correspond to those ob-tained on burning the non-crystalline product.When I first obtained this solid body I was inclined to believe that it was isomeric with the oily product ;but on further consideration I am induced to regard it simply as a purer substance and this n70uld appear to be the case from the analysis of the solid body yielding the best numbers. I have had an oily product stand- ing for nearly three months perfectly clear but on rubbing the sides of the bottle with a glass rod it gradually began to crys tallise. This body I propose to call benxotartaric ether. When pure it is a white inodorous solid and may easily be powdered. It melts at 64O C. and cools to a viscid oil which does not solidify until it has stood for some considerable time but the introduction of a minute piece of the solid product im-mediately causes it to commence crystallising ; and this takes place with a very considerable elevation of temperature.It crystallises in transparent prisms. If strongly heated it distils with decomposition. It is soluble in all proportions in alcohol and ether; slightly soluble in boiling water the solution becoming milky and depositing oily drops on cooling ; after-warda beautiful but small prismakic crystals separate. Its aqueous solution has a slightly bitter taste. Its solutions do not change the colour of litmus paper. Aqueous potash ap- pears to be without action upon it. With sodium it liberates hydrogen and appears to form a sodium-compound.It is heavier than water Benzotnrtaric ether when heated in a sealed tube to 100" C. with alcoholic ammonia slowly decomposes and becomes of a PERKIN ON THE BASICITY OF TARTARIC ACID. 141 pale brownish. yellow colour. On evaporating the product to dryness and then adding water a few oily drops of the un-changed ether appear; these may be separated by filtering through wet paper. The filtrate on the addition of hydrochloric acid becomes filled with crystals of benzoic acid and upon re- moving these and evaporating the solution to dryness the residue presents a gummy appearance and is very soluble in water. After boiling this with strong potash (which causes the evolution of a considerable quantity of ammonia) the addition of hydrochloric acid again causes a very large quantity of benzoic acid to separate showing that in this reaction an amide is produced containing benzoyl ; no benzumide however is formed.The products of this reaction are probably benzoic acid tartramide benzotartramide and alcohol. I have made several attempts to replace a second equivalent of hydrogen in tartaric ether by benzoyl but at present have not succeeded. The result of heating tartaric ether with two equivalents of chloride of benzoyl or of heating benzo-tartaric ether with one equivalent of the reagent is the production of an oil the ethereal solution of which becomes gelatinous when evaporated. I have made several combustions of diEerent pre- parations of this product which were purified in various manners the last one having been heated aa high as 180"C.with the chloride of benzoyl. I have not however obtained any useful results. The carbon determinations gave numbers varying from 60.24 p. c. to 61 the hydrogen being about 5-4p. c. This increase of carbon I do not tlxink is due to the introduction of benzoyl as even at a temperature as high as 240"C. a mix-ture of benzotartaric acid and chloride of benzoyl evolves scarcely any hydrochloric acid gas. Chloride of benzoyl acts on paratartaric ether in precisely the same manner as upon tartaric ether one equivalent of hydrogen being replaced. The product I propose to call henzoparutartaric ether as it is isomeric and not identical with the preceding body. It melts at a considerably lower temperature viz.,57" C.and does not crystallise so easily as that substance. Action of Alcoholic Potash on Benzotarturic Ether. Eenzotartaric ether is easily decomposed by alcoholic potaah yielding if in excess benzoic and tartaric acids; but the de- 142 PERKIN ON THE BASICITY OF TARTARIC ACID. composition may be moderated and intermediate products obtained if a dilute alcoholic solution of this ether and a weak aolution of alcoholic potash are employed the potash solution containing an insufficient quantity of alkali to decompose all the ether. A quantity of benzotartaric ether treated in this manner was gently heated until the excess of alcohol had eva- porated; water was then added to cause the separation of any oily products.After filtration through a wet filter the solution was acidified with hydrochloric acid ; this caused the separation of an oil which was again separated and the clear liquid placed over sulphuric acid under the bell-jar of the air-pump. After evaporating in this manner for a few days beautiful tufts of crystals separated which on being well washed with water were found to be pure. A specimen dried at 100°C. and burnt in oxygen gave the follawing numbers :-,1474 of substance gave 02964of CO, and -0675of H,O. These numbers agree with the formula as will be seen by the following comparison :-Theory. Experiment. 4 A \ C, ........ 156 55.32 5484 HI,. ....... 14 4.9 G 5-08 0,........ 112 39-72 .. 282 100*00 This iB therefore ethylbenzotartaric acid or the benmtartrate of ethyl and hydrogen.This acid is a beautiful product crys- tallising in tufts of hard needles difficultly soluble in water but excessively soluble in alcohol and ether. On evaporating its alcoholic or ethereal solution it is deposited in fan-shaped masses of crystals. Its aqiieous solution reddens litmus paper. It is easily decomposed by potash and its salts appear to be rather unstable. Owing to the small quantity I have obtained of this acid I have been unable to examine it more fully. The mother-liquors from ethylbenzotartaric acid contain con- PERKIN ON THE BASICITY OF TARTARIC ACID. 143 aiderable quantities of Dessaigne’s benzotartaric acid.* The oily liquid previously mentioned as being thrown down on acidi-fying the crude product consists of a mixture of benzoic and ethylbenzoic acids with a little neutral oil having the odour of benzoic ether.Therefore by hydrating benzotartaric ether with alcoholic potash the following reactions take place :-I. c2H5} C4H3(CrH50)06 + HzO = C~Htio1. gH5} C4H3(C7H5O)Ofj-C2H5 Benzotartaric ether. Alcohol. Ethylbenzotartaric acid. 11. zz}C4H3(C;B,0)06 + 2H20= 2C2H60 +-i} C4H3(C7H50)Os. Benzotartaric acid. 111. ~$}C4H3(CiH50)06 + 3H20 = 2C2H60 + C4H406+ C,H,O,. 3 Tartaric acid. Benzoic acid. Action of Chloride of Strccinyl on Tartaric Ether. Chloride of succinyl and tartaric ether when heated together evolve hydrochloric gas in considerable quantity and produce a neutral oily body. In preparing this substance I have gene- rally employed the tartaric ether and chloride of succinyl in the proportions of two equivalents of the former to one equivalent of the latter.These bodies were heated together in a large test-tube in the water-bath until hydrochloric acid ceased to be evolved. The product after having been frequently agitated with water for several hours for the purpose of decomposing any free chloride of succinyl and removing any tartaric ether that might not have been acted upon was purified in the same manner as benzotartaric ether. Two combustions in oxygeii gave the following numbers :-I. -2564 of substance gave -4487 of CO, and 01343of H,O. 11. -2723 of substance gave -4772 of CO, and -1426 of H,O. # J. Pharm.[3] xxxii 47. 144 PERKIN ON THE BASICITY OF TARTARIC ACID. Theae numbers give percentages which nearly agree With those required by the formula This represents two equivalents of tartaric ether bound together by*the replacement of two equivalents of hydrogen by diatomic succinyl. The following is a comparison of the theoretical and experi- mental numbers :-Experiment. /. Theory. /- I. 11. ‘ c2,....... 7-240 48-58 47.72 47-79 HSw....... 30 6-07 5-81 5-81 O, ........ 224 45-35 8. .. 494 100*00 The carbon and hydrogen in these analyses are rather low. This originates I believe &om the presence of a small quantity of a neutral chloriuated oil which is generally found in the chloride of succinyl; and on account of the nature of the new product I was unable to purify it further.A compound repre senting one equivalent of tartaric ether with two equivalents of hydrogen replaced by succinyl would require a very much higher percentage of carbon viz. 53.7. This product I propose to call succinotartaric ether. It is an extremely thick oil generally of a pale yellow colour but I believe would be colourless if perfectly pure. It is soluble In alcohol and ether in all proportions producing solutions which are neutral to litmus paper. If heated with alcoholic potash it is decomposed. It cannot be distilled without undergoing decom- position. Action of Chloride of Acetyl on Benzotartaric Ether. Not succeeding in replacing a second equivalent of hydrogen In tartaric ether by treating it with chloride of benzoyl I thought it well to employ a more active chloride and selected the chloride of acetyl.PERKIN ON THE BASICITY OF TARTARlC ACID. 145 A mixture of benzotartaric ether and chloride of acetyl in about equivalent proportions using a slight excess of the chlo-ride was heated in a sealed tube to 140' or 150"C. for three or four hours. On opening the tube large quantities of hydrochloric acid escaped. The oily product was well agitated with water and dissolved in ether. The ethereal solution was then agitated with dry carbonate of sodium filtered and evaporated to dryness over the water-bath. A specimen of this product burnt in oxygen gave the following numbers :--2332 of substance gave -4965 of CO and *1219of H,O.These numbers give percentages which agree very closely with those required by the formula which represents benzo-tartaric ether in which one equivalent of hydrogen is replaced by acetyl. Theory. Experiment. n C, ........ '204 57.93 38.02 H2,........ 20 5.68 5.80 0 ........ 128 36-37 .. 352 100*00 This product which I propose to call Acetobenzo-tartaric ether is an extremely thick colourless oil heavier than water. It does not show any tendency to solidify as specimens which have been kept for months remain perfectly clear. It is very soluble in alcohol and ether and is quite neutral to test-paper. Heated with alcoholic potash it is entirely decomposed into alcohol acetic benzoic and tartaric acids thus ~c2H~~~c~H2~c~H~0~~c2H~0~06= + 4H'20 Acetobenzotnrtaric ether.2C,H,O -l-C2H4O + C,H,O + C4H,O6* Alcohol. Acegic acid. Benzoic acid. . Tartaric acid Action of Chloride of Acetyl on Tartaric Ether. Tartaric ether is freely attacked by chloride of acetyl even at 146 PERKTN ON THE BASICITY OF TARTARIC ACID. the ordinary temperature large volumes of hydrochloric acid gas being evolved and the mixture becoming quite hot. If equivalent proportions of these two substances are employed an oily body is produced. This product may be purified in the game manner as the aceto-benzo-tartaric ether. Combustion of this oil in oxygen gave the following numbers :--2639 of substance gave -4662 of CO and *1574of H,O these numbers give percentages agreeing with the formula which represents tartaric ether with one equivalent of hydrogen replaced by acetyl as the following comparison will show :-Theory.ExDeriment. I?,, ........ -120 48-38-48-17 HI6........ 16 6-45 6.62 0 ........ 112 45-17 - 248 100.00 Thissubstance which I propose to call Aceto-tartaric ether is n colourless oil not nearly so viscid as those already described being of about the consistency of olive oil. On heating it in a retort placed in an oil-bath it begins to decompose after the temperature has been considerably raised acetic acid condensing in the neck of the retort ; and at about 287O.C. an oil distils over leaving a residue of carbon. Aceto-tartaric ether is heavier than water and slightly soluble in that menstruum.It may be separated from its aqueous solu- tion by the addition of saline solutions as that of common salt. It is perfectly neutral to test-paper and has a rather bitter taste. With boiling aqueous ammonia aceto-tartaric ether decom- poses and on evaporating the solution it yellowish syrupy product is obtained having a bitter and slightly burning taste. Aceto-tartaric ether when heated with chloride of benzoyl evolves hydrochloric acid forming a thick colourless oil probably benzoacetotartaric ether. Sodium acts rapidly upon this ether with evolution of hydro- PERKIN ON THE BASICITY OF TARTARIC ACLD. 147 gen gas. The reaction is facilitated by the addition of benzole which renders the ether more fluid. The 'resulting product of this reaction is a transparent gum-like substance.This is pro- bably Sodacetotartaric etl~er. On treating tartaric ether with two equivalents of chloride of acetyl arid after the reaction has abated heating the product in a sealed tube to 100" for a short time a second derivative is obtained which on being purified like the preceding solidifies after standing into a beautiful crystalline mass wlkh may be separated from a small quantity of oily aceto-tartaric ether by pressure between bibulous paper under a powerM press and then crystallised from water. Specimens dried by fusion and burnt in oxygen gave the following numbers :-I. 02606of substance gave 04763of GO and -1500of H,O. fL 02604of substance gave *4763of C02 and 01507of H,O.These numbers give percentages which agree closely with those required by the formula- which represents tartaric ether in which two equivalents of hydrogen are replaced by acetyl. The following is a comparison of the theoretical and experi- mental numbers :-Theory. Experiment. 1. 11. C,2.. ...... 144 49.65 49.84 49-88 HI*........ 18 6.20 8-39 6-43 I 0 ........ 128 44-15 .- 290 100.00 This substance is therefore Diacetoturtaric ether. It is mluble in alcohol and ether in all proportions but crystallises from its alcoholic solution on dilution with water. If boiled with water B considerable quantity dissolves and the solution on cooling deposits it in splendid prismakic crystals more than an inch and 148 PERKIN ON THE BASICITY OF TARTARIC ACID.a half in length. It is slightly soluble in cold water but on the addition of a strong solution of chloride of sodium this solution becomes cloudy and the diacetotartaric ether crystallises out on standing. Diacetotartaric ether melts to a colourless oil at 67' C. and cools without resolidifying but as soon as a small particle of the solid product is thrown into it it begins to crystallise in tufts of needles and in a few moments becomes perfectly solid. During its crystallisation it evolves heat sufficient to become quite hot to the hand. If strongly heated this ether distils with only slight decom- position. Its boiling point is between 294" and 298' C. The second combustion was made with a product which had been distilled.I believe this to be the only derivative of tartaric acid which is known to bear distillation without being entirely or at any rate very much decomposed. Diacetotartaric ether is not quickly decomposed with aqueous potash and if it be dissolved in cold alcoholic ammonia the rsolution after having been kept for several days will be found to contain a very large quantity of unchanged product. Fused diacetotartaric ether evolves only a very small quantity of hydrogen when brought in contact with sodium-very much less than the monoacetotartaric ether-in fact its solution in benzole scarcely evolves a trace of hydrogen and on the evaporation of the benzole t'he product is found unchanged. This would tend to show that all the typical hydrogen in tartaric ether is substituted in this compound.Paratartaric ether yields two new bodies when treated with chloride of acetyl viz. acetoparntar.taric and diacetoparatar-taric ether. They are prepared precisely in the same manner as the two preceding bodies. The monacetoparat'artaric ether I have not closely examined. It is a colourless oil. The diaceto-paratartaric ether is a solid body melting at 5005~ C. It boils at about 298' C. and distils with slight decomposition. It is soluble in alcohol or ether in all proportions. It is deposited from its boiling aqueous solution on cooling in small tufts of needles and after long standing sometimes forms short but very brilliant prisms on the sides of the vessel. It differs from the ordinary tartaric derivative in its melting point which is 16.5 degrees lover and alao in the different PERKIN OF THE BASICITY OF TARTARIC ACID.149 manner in which it crystallises from iks aqueous solutions. It appears to be rather more soluble in water but does not cry+ tallise pearly so freely as its isomer. arid when fused it takee much longer to aolidify and then does not produce so well crystallised a mass. A portion of this product gave the follow- ing numbers :-*2063of substance gave 03769of CO and 01169 of H,O. Percentagu composition. Theory Carbon.. ,..... 49-82 49-65 Hydrogen ... 6-29 6-20 These results show it to possess exactly the same composition as diacetotartaric ether. I was anxious to take the vapour-densities of these two diaceto-ethers because if paratartaric acid be composed of right- and left-handed tartaric acids its formula should be doubled and this diffsreiice a vapour-density would show directly; but although these bodies are volatile they would decompose too much at the temperature required by such ex- periments to give trustworthy results ; but the boiling points being nearly identical affords strong eyidence that the formula must not be altered because if it were double it is certain that the boiling.point would be immensely raised. I may here meu- tion that diacetoparatartaric ether after having been distilled has exactly its arigirial characters arid fusing point. It is very curious to find that paratartaric acid which yields right- and left-handed tartaric acids and is also formed agair when their solutions are mixed even with evolution of heat does not possess a formula equal to two equivalents of tartaric acid.It would appear therefore not to consist of these two acids but to change into them when converted into certain salts. Action of Chloride of Acetyl on Tartaric Acid. If dry powdered tartaric acid be digested with about three times its weight of chloride of acetyl very little change ap- pears to take place at first but after continuing the heat for several hours it gadually disappears leaving a syrupy liquid VOL. xx. M 150 PERKIN ON THE BASICITY OF TARTARIC ACID. which on cooling generally solidifies to a crystalline mase; should this not take place more chloride of acetyl must be added.The crystalline product after being strongly pressed between dry thick bibulous paper may be rendered perfectly pixre by hsion in an open dish so as to volatilize adhering chloride of acetyl &c. On cooling it solidifies to a splendid white crystalline body. Specimens of this substance burnt in oxygen gave the fol- lowing numbers :-I. *2539 of substance gave *4122 of CO, and *0907 of H,O. TI. a2438 of substance gave 93974 of CO, aad *0862 of H,O. These numbers give percentages which agree with those required by the formula- representing diacetotartaric anhydride. The following is a comparison of the numbers :-Theory. Experiment. r ,. 1 --1. 11. C8 ........ 96 44-44 44-27 44.45 H ........8 3.70 3.96 3.93 0 ........ I12 51-86 - 216 100.00 Diacetotartaric anhydride is a tough orystalline solid melting att 126O-127" C. When distilled it undergoes a considerable amount of decomposition especially if the distillation be carried anslowly. It boils above 250" C. but no fixed point can be ob-tained acetic anhydride coming over during the distillation as well as other products some of which affect the eyes like acrdene; a residue of carbon is left in the retort. If heated gently it sublimes in beautiful but small prisms. It is slightly soluble in benzole and crystallises fkom this solvent in slender white needles. It also crystallises from acetic anhydride. Dried paratartaric acid when submitted to the action of PERKIN ON TIW BASICITY OF TARTARIC ACID.151 chloiide of acetyl undergoes precisely the ~amechange as ordinary tartaric acid but the reaction goes on rather more slowly. The diacetoparatartaric anhydride is a beautiful crystal- line body resembling its isomer in its characters. Its melting-point is also the same viz. 126O C. The following is a combustion of a specimen of diacetotar-taric anhydride prepared from paratartaric acid :--3012 of substance gave -4873of CO, and *lo56of H20. Percentage composition- Theory. Carbon . . . . . . . . 44.12 46.44 Hydrogen .. . . 3-89 3-70 Action of Water on Diacetotartaric Anhydride. If exposed to the air this anhydride quickly absorbs moisture or if placed in contact with warm water it gradually dissolves producing a powerfully acid solution.This contains an acid which I propose to call diacetotartaric acid. Its formation may be explained thus :-C,H,(C,H,%O + H,O = C4H,(C,H,Q),OB* Diacetotar taric anhydride. Diacetotartaric acid. Diacetotartaric acid obtained by evaporating its aqueous solution under the bell-jar of an air-pump generally presents itself as a transparent gum-like substance. It is very deli- quescent and possesses a powerfully acid taste. If strongly heated it decomposes without formation bf its anhydride. When heated with a solution of potash or soda it is decom-posed according to the followhg equation :-C,H,(C,H,O),O + 2H,O = C4H606+ 2C2H,0,. Diacetotartaric acid. Tartaric acid. Acetic acid. A quastity of diacetotartaric acid which had been prepared from ordinary tartaric acid was decomposed by potash and after neutralising with an acid the tartaric acid was precipitated as a calcium-salt which after being well washed was decomposed with dilute sulghuric acid and filtered.The filtrate on being con- 31 2 152 PFAlCIJY ON THE BASICITY OF TARTARIC ACID. centrated deposited large crystals of tartaric acid which were washed and recrystallised. The acid thus obtained does not contain water of crystallisa-tion nor does it precipitate solutions of chloride or nitrate of calcium; it would therefore appear to be ordinary tartaric acid but it appears to crystallise in a somewhat different manner. As I have obtained it in square tables about a quarter of an inch in diameter I hope to again examine this product.A portion of the acid was converted into the acid potasaium- salt. A potassium determination gave the following num-bers :-*1219 of substance gave 00357of sulphate of potassium = 20.4'7 p. c. of potassium. Theory requires 20.74 p. c. Diacet0tartrates.-With bases diacetotartaric acid forms salts containing one and two equivalents of metal,-it is therefore bibasic. These compounds are rather difficult to obtain pure and are remarkable for their great solubility. Sodiurn-salt.-This is obtained by carefully neutralising a solution of the acid with carbonate of sodium concentrating at a very gentle heat and then finally evaporating in vacuo. Thus obtained it is a crystalline solid remarkably soluble in water and very deliquescent.Tlzepotassium-salt is obtained in the same manner as the above substituting carbonate of potassium for carbonitte of sodium. It is a crystalline salt very soluble in water and deliquescent. Aeid potassium-saIt C,H,O,.-To prepare this salt two J equal quautities of an aqueous solution of the acid are taken one portion is neutralised with carbonate of potassium and then mixed with the other. The new salt crystallises out on concentrating the solution at a gentle heat or in vacuo; it is then separated from the mother-liquor by being strongly pressed between bibulous paper and purified by a second crystallisation. Thus obtained it forms a crystalline powder very soluble in water but not deliquescent.It reddens litmus powerfully and poswsses an acid taste. A specimen dried at 100" C. gave the following numbers :-0-3415 of mbstance gave 091080 of aulphate of potash ps= 14-17 p. c of potassium. Theory requires 14.34 p. c. PERKIN ON THE BASICITY OF TARTARIC ACID. 153 Calcium-salt Ca”C,H,O,.-T2lis salt is obtained by neutralis- ing a solution of the acid with carbonate of calcium filtering and concentrating first at a low heat and then in vacuo. I have not succeeded in obtaining it in a crystalline condition. Its solution concentrates to a syrup and then dries up to an opaque friable mass. It is deliquescent. A specimen dried at 100”C. gave the following numbers :--1871 of substance gave -0951 of sulphate of calcium = 14.94 p.c. of calcium. Theory requires 14-70p. c. of calcium. Barium-salt Ba”C,H,O,.-This is obtained in the same manner as the calcium-salt. Its solution after being concen- trated to a syrup on standing for a day or two deposits fine needles of this nev salt sometimes half an inch in length. It is excessively soluble in water and deliquescent. Specimem dried at 100”C. gave the following numbers :-I. -2065 of substance gave -1297 of sulphate of barium. 11. -1377 of substance gave *1307of CO,,. and -0300 of H,O. The following is a comparison of the theoretical and experi- mental numbers :-Experiment. A Theory. I. IT. -c8 ..* ..... 96 26.01 25.88 L H ........ 8 2.17 -2-34 ..... 137 37-12 36-93 -Ba”. .. 0 ........ 128 34-70 -369 100*00 Copper-salt Cu”C,H80B.-~Obtained by saturating a solution of the acid with carbonate of copper and concentrating the solu- tion at a low temperature.It is a blue crystalline salt very hble in water. Specimens dried at 100”C. gave the following numbers :-I. -3527 of substance gave 00945 of Cu”0 = 21-40 p. c. of copper. 154 PERKIN ON THE BASICITY OF TARTARIC ACID. 11. ,2268 of substance gave 00603of CuO = 21.22 p.c. of copper. Theory requires 21.48 p. c. of copper. Silvel-sa zt gac8H,08.-Diace t0tartaric acid is difficult to saturate with carbonate of silver. To obtain this salt it is best to agitate a solution of the acid with freshly precipitated car-bonate of silver filter and concentrate. After a time the silver- salt will then separate in the form of an albuminous magma of very minute silky needles which must be separated fiom the mother-liquor by pressure between bibulous paper and then recrystalliaed.Thus obtained it dries to a white crystalline mass extremely soluble in water and very slowly acted upon by light. Mercuq/-saZt.-A solution of mercurous nitrate when added to a solution of a salt of diacetotartaric acid produces a,gela- tinous precipitate soluble in acetic acid.* Diacetoparatartaric anhydride when brought in contact with water yields an acid viz. diaeetoparatarinric acid. So far as I have examined this body it appears to resemble diacetotartaric acid but when decomposed with potash it yields acetic and paratap taric acids. This at once proves that it and its anhydride are isomers of the ordinary tartaric derivatives a fact which it was important to prove on account of diacetotartaric and dia- cetoparatartaric anhydrides having the same melting point.A portion of diacetoparatartaric acid wm converted into a calcium-salt which was dried at 100"; a calcium determination gave the following numbers :-*2240of substance gave *lo92of sulphate of calcium = 14.33 per cent. Theory requiring 14.7 per cent. This salt was uncrystallisable. Action of Sodium on Tartaric Ether. On bringing sodium in contact with tartaric ether hydrogen * Since making the foregeing experiments I find fhat M. Ro chl eder ha0 also studied the behaviour of chloride of acetyl to tartaric acid and evidently obtained Borne of the bodies described above.He did not however make any analysis of his products. He states that he succeeded in obtaining the acid I have described aa diacetotartaric acid in the crystalline state (Chemical Gazette vol. xvii. (1 859) page 61). PERKIN ON THE BASICITY OF TARTARIC ACID 155 is evolved ; but owing to the viscidity of the ether the reaction takes place very slowly. If however it be rendered more fluid by admixture with five or six times its volume of anhydrous benzole the reaction goes on very rapidly the liquid becomhg quike hot and of a pale yellow colour. On separating the excess of sodium and evaporating the liquid a pale yellowish-brown uncrystalline but friable residue is obtained which quickly be- comes sticky fkom absorption of moisture ; mixed With water it produces a strongly aIkaline solution.A weighed quantity of tartaric ether was treated as above in an apparatus so arranged that the hydrogen could be collected. It was found that the reaction went on rapidly for about half an hour until nearly one equivalent of hydrogen was evolved ; it then slackened the solution remaining clear and the sodium quite bright The action then became still less,and a geIatinous product gradually formed on the sodium entirely stopping the reaction. Reasoning from these facts it would appear that the fist and principal product of this reaction is a tartaric ether with one equivalent of hydrogen replaced by sodium or wdiotartaTic ether the gelatinous product being disodiotartaric ether.By heating the &st sodium-product with iodide of ethyl an oil is produced probabIy ethyltartaric ether. The history of the foregoing substances has I think a con- siderable amount of theoretical interest especially with refer- ence to that somewhat difficult question of basicity and atomicity. Tartaric acid is known to be tetratomic; now if it be Iikew&e tetrabasic it is evident that tartaric ether must be a bibasic acid diethyltartaric acid because only two equivalents of hydrogen out of four are replaced by ethyl thus- H4,C4H20G. H,,E,,C,H,qy Tartaric acid Diethyltartaric acid. If this be true then most of the products 1have described would be diethyltartrates. For example the substance I have called diacetotartaric ether would be diethyltartrate of acetyl ; thut+-.H,,E,,C,H,OG. Ac,,E,,C,H,O,. DicthjItartaric acid. Diethyitartrate of acetyl If this be the case it is obvious that this body would be an 156 PERXIN ON THE BASICITY OF TARTARIC ACID. anhydride because anhydrides cohtaining monatomic acid radi- cals are but the salts of acid radicals; acetobenzoic anhydride for example is the acetate of benEoy1. But this substance has not in any respect the characterietics of this class of bodies. Were it an anhydride or salt of acetyl it would eady decom- pose with water and still more so if treated with ammonia; whereas it may be boiled in water and recrystallised without undergoing any change and its alcoholic solution may also be saturated with ammonia and left for days without any appre- ciable amount of decomposition taking place The same facts also hold true with benzotartaric ether ; and moreover when we decompose this product with a limited quantity of alcoholic potash we find that the ethyl is removed much more readily than the benzoyl ethylbenzotartaric acid and then benzotartaric acid being formed.Had it been a diethyl- tartrate of benzoj71 it would immediately have split up into tartaric ether and benzoate of potassium. Benzotartaric ether also if heated with ammonia does not produce beirzamide. The properties of diacetotartaric anhydride are also again& this view. This anhydride rapidly absorbs water forming diacetotartaric acid and this %id containing two equivalents of acetyl a radical so very easily hydrated when replacing basic hydrogen may be heated up to 100"C.with water with- out undergoing any appreciable amount of decomposition ; moreover it forrns salts which may be dried at 100" C,. without change. The properties of tartaric ether itself are also against this view as it is perfectly neutral to test-paper and does not form compouiids with bases. We have therefore I think strong evidence that although tartaric acid is tetratomic yet the two pair of hydrogen equiva- lents possess very different functions. The nature of this difference may I think be well understood by examining into the particulars of the artificial formation of this acid from succinic acid. Alaxwell Simpson* has lately shown that succinic acid is a derivative of ethylene and may be produced by hcating the cpnide of that hydrocarbon with p0tash.t * Chem.SOC.J. XY 134. 3 The formation of malonic acid from cyanacetic acid is analogsiis to this PEREAT ON THE BASICITY OF TARTAR10 ACID. 157 Cyanide of Succinic acid. ethylene. On treating succinic acid with bromine two equivalents of hydrogen are replaced. This replacement must evidently take place in the ethylene because the resulting acid retains its two original basic hydrogens ; Succinic acid. Bibromosuccinic acid. By boiling the bibromosuccinate of silver with water the two equivalents of bromine are removed and HO substituted. Bibromosuccinic acid. Tartaric acid. From this it will be seen that tartaric acid is succhic acid in which ethylene C,H[ is replaced by C2H2}f/02 repre sents the hydrate of acetylene or acetylene-glycol which in this case has all its atomicity active and holds together the two groups of (COHO).This shows tartaric acid to be a bibasic acid and diatomic alcohol. Therefore the hydrogen which I have yeplaced in tartaric ether by acid radicals is not basic hydrogen but alcoholic hy- drogen. Each of the tarta,ric ether derivatives will then have the double character of an ether and the hydrin of a glycol and those from tartaric a,cid the double character of an anhydride or reactton a8 will be seen if we start with the cyanide of methylene and stop the reaction at an intermediate stage. CHZCYCJ + 2H20 = C2(H,Cy)04 + NH3.Cyanacetic acid. C2(H,Cy)04 + 2HP0 = C3H104+ NH3. Chem. SOC.J. [2i ii 109. 158 PERKIN ON TKE BASICITY OF TARTARIC ACID. an acid and hydrin of a glycol. This will be best Been if I write out their formdae in the following manner* :-Benzotartaric ether ...... COHO COEO ) Ethylbenzotartaric acid . . (C2€€:)" H 0,. * It is worth remarking that tartaric bears to snccinic acid a relation simila~to that of glycollic acid to acetic acid. It is in fact a bibasic glycollic acid. CqH606 -02 = CqRg04. Tartario Succinic aeid. acid. C2H403 -0 z= C&4O2. Olycollic Acetic acid. acid. And 88 glycollic scid represents glycol half oxidized 80 tartaric acid repmsenta a tetratomic alcohol half oxidized.C2H602+ 03 = G2H403+ R20. Qlycol. Qlycollic acid. C4H100j i-04 = C4H6O6 i2H20. Tartaric acid. Thin alcohol would be the =me body as that termed tartaric alcohol in Xolbe's paper on the prognosis of new alcohols and aldehydes (Chern. SOC.J. [2] iv 56). It will be observed that tartaric acid has the composition of oralic acid + aeety-Eem-glycol thus :-Tartaric Oxalic acid. Acetylene acid. glycol. I have Itlready made several experimenta with the view of causing the two groups of COHO to combine and liberate the glycol but as yet have not succeeded. PERKIN ON TFIE BASICITY OF TARTARIC ACID. 159 (COW?/ Acetobenzotartaric ether ..(,'$!}*,) Acetotartaric ether ......(cp2j Diacetotartaric ether.. .... Succinotartaric ether...... Diacetotartaric anhydride.. ( Diacetotartaric acid ...... According to the foregoing reasoning the metallic compounds yepresenting tartaric acid as tetrabasic (if definite bodies) must 'be both salts and alcoholates. The lead-salt might be thus written :- HUNTER ON THE ABSORPTION OF Seeing then the great difference in the properties between the compounds in which basic hydrogen is replaced by acid radicals from those in which alcoholic hydrogen is replaced it appears to me that this points out a very useful method of de-termining the true basicity of an acid as well as its alcoholic nature if it possesses any,-and this is important because the alcohols of some series i. e. the aromatic series are capable of combining with bases ; therefore an acid of such a series if pos- fiessing alcoholic characters would produce saline compounds making its basicity appear greater than it actually is thereby preventing us from classifying it with analogous bodies of other series.I believe this to be the ca,se with salicylic acid and I am now engaged with experiments in this direction which I hope ahortlp to lay before the Society.

ISSN:0368-1769    

DOI:10.1039/JS8672000138

出版商:RSC    

年代:1867

数据来源: RSC