摘要:

BLOXAM ON THE SOUBCE OF THE XI.-On the source. of the Arsenic in the Sulphuric Acid of Com-merce aid tibe preparation of that Acid free from Arsenic. By CHARLESL.BLOXAM. IN an account of some experiments upon the electrolytic test for arsenic published in the Society’s Journal for January 1861 it was stated that I had been unable to procure specimens of sul-phuiic or hydrochloric acid which did not ‘yield any indication of arsenic when examined by that test. Although tlie purest samples of these acids furnished by the operative chemist contain so minute a proportion of arsenic that it could not mislead an expe- rienced ztnalyst engaged in a judicial inquiry still it cannotbe denied that if these most important re-agents could be declared incapable of yielding the slightest indication of the poisoil under the most rigorous scrutiny greater confidence would be felt by the person eliciting and-which is perhaps more important-by those receiv- ing the cliemicul evidciicc in criuiiual cases.I therefore beg to submit to the Society the following account of experiments madc to ascertain firstly the possibility of preparing sulphuric acid which should yield no arsenical deposit in the electrolytic test and secondly the source of the arsenic in the bcst samples of the com- mercial acid. The sample of sulphuric acid selected for the experiments was taken from the ordinary laboratory supply aid contained so small a quantity of arsenic that no evidence could be obtained by Marsli’~ test when applied in the ordinary way though hy passing the gas through a narrow heated tube for abmt half an hour a slight deposit of arsenic was olitained and the elcctrolytic test gave a very decided result.Experiments were first niacle upon the niethod gcner:tlly rccom- mended for the removal of arscnic from sulpliuric acid Ljr convcrt-ing it into the volatile chloride. 1. Two measured ourices of tlie acid mere mixed with a solution of 100 grains of chloride of sodium in six draclirns of water ; the mixture was boiled in a flask the cvolved hydrochloric acid gay being passed into two drachms of water. As soon as the volume of the latter had increased to eight drachnis tlie sulphuric acid ARSENIC IN COMMERCIAL SULPHGRIC ACID. remaining in the flask and the hydrochloric acid which had dh-tilled over mere esamined for arsenic which was found in them distinctly both by the electrolytic and Marsh's test.2. Three measured ounces of sulphuric acid were distilled with 100 grains of fused chloride of sodium. *4fter the evolution of hydrochloric acid gas had ceased two drachms of aqueous hydro- chloric acid distilled over. containing enough arsenic to give a yellow tinge with hydrosulphuric acid. Two ounces 'of the sul-phuric acid mere tlicn distilled over each bcing reccived separately but they both contained arsenic as did also the last ouncc remain- ing in the retort. 3. Four ounces of sulpliiiric acid mere boiled in a flask and the carefully waslied hydrochloric acid gas from one ounce of salt arid two ounces of sulpliuric acid was pasgecl into thq boiling acid for half an hour after which arsenic could still be distinctly detected in it.Not having succccded in removing the last traccs of arsenic by the action of hydrocliloric acid I next endeavoured to effect it by continued electrolysis ; but even after a powerful current had acted driring five hours upon the acid enough arsenic Jwnaiued to coiiriuce me that this plan would be inapplicable. A process of fractional distillation was then tried. 4. Twenty measured ounces of the sulphuric acid were distilled and the following fractions collected :-(1) loz. (2) ~oz.,(3) 402. (4) ~oz.,(5) 4-02.,' (6) ~oz.,leaving about 202. in the retort. Each of these fractions contained arsenic and the residue in the retort was found to contain a larger proportion than the original acid.Half of the fifth fraction was distilled again but the first half ounce was still found to contain arsenic though in very minute proportion. The remainder of the fifth fraction was distilled with bichromate of potash in the hope of converting any arsenious into arsenic acid but the first portion of the distillate gave evidence of arsenie. Three ounces of the fourth fraction were rectified the first two drachms bcing rejected and 2ioz. distilled over. This still con-tained a trace of arsenic though more was found in the 402. left in .the retort. Two oiinces of the twice-distilled acid were subjected to a third distillation the first drachm being rejected. Ten drachms were BLOX-4M ON THE SOURCE OF THE distilled over,* and of this tlwice-distilled acid two drachms gave evidence of the presence of a trace of arsenic both by electrolysis and by Marsh’s test.No satisfactory result was obtained by distilling the sulphuric acid with permauganate of potash to oxidize the arsenious acid. My endeavours were next directed to the preparation of pure sulphuric acid from sulphurous acid gas when I anticipated not the least difficulty in obtaining an acid perfectly free from arsenic. 1. In thc first experiments the sulphurous acid was prepared from sulphuric acid and charcoal well washed and oxidized by moist air with the aid of heated pumice-stone coated with pla- tinum. This acid however contained more arsenic than the ordinary sample which was traceable to the hydrochloric acid used in preparing the bichloride of platinum for platinizing the pumice.Morcovcr the process was found very troublesome and furnished too little acid in a given time to answer my purpose. 2.The sulphurous acid prepared from sulpliuric acid ad copper,? was very well washed and oxidized by means of air steam and nitric oxide (prepared from nitric acid and copper) in a glass globe the sulphuric acid being afterwards boiled down in a platinum dish. A trace of arsenic was also found in this spccimen. 3. The copper employed in the preccding experiment having been found to Contain much arsenic mercury was next employed for evolving sulphurous acid but still a trace of arsenic was found in the sulphuric acid produced and acconipaiiging it mas a minute quantity of mercury.4. Believing it possible from the result of the last experiment that the high temperature employed in preparing the snlyhurous acid expelled arsenic from the acid in the generating flask cnd that washing was incapable of removing the last traces of arsenic from the gas I next evolved the sulphurous acid at a. far lower temperature from crystallized sulphite of soda by the action of sulphuric acid and in this case it was but just possible to demon- strate the presence of a trace of arsenic. Three trials of this * It may be worth notice that the residual acid in the retort contained a con- siderable quantity of platinum in several of these distillations a piece of platinum foil having bPen used to prevent bumping.f The formation of free sulphur and cf sulphide of copper was wcll observed in preparing the large volume of sulphurous acid required in these experimente. A HSENIC IN COMMERCIAL SDLPITURIC ACID. method having gircn tlic snmc result it mas tlmnght that tlie trncz of arscnic might be dcrivccl frorn thc coppcr cmploycd in cvolving tlic nitric osiclc. 5. 111 this cspcrimcnt tlic nitric osidc was prcparcd from nitre by the action of siilphatc of iron and dilutc sulphnric acid at a very modcrate hcat wlrilst thc srilpliiiro~is acid was disengaged as before from siilpliite of soda aid sulphnric acid.* The iesulting sulphiiric ?.cicl was found to yield not the lcast indication of arsenic mhcn tcstcd by clcctrolysis.Having satisfied myself that it mas possible to ohtnin sulphuric acd ~vliicli furnished no indication in the electrolytic test I pro-ceeded to look for tlie source of the arsenic in the purest speci- mens ef the commercial acid. By the kindness of the manufacturer I was supplied with a sample of the Sicilian sulphur employed in the manufacture of one of the purest sulpliiiric acids in which homerer the electro- lytic test as well as a prolonged application of 31arsh's test in- dicated the presence of a trace of arsenic. This Sicilian sdphur was burnt in air and the sulphurous acid obtained was converted into sulphuric acid in precisely the same manner as in the last of the experiments above described as giving an acid free from arsenic.The srilphuric acid thus prepared from the Sicilian sulphur gave distinct evidence oC the presence of arsenic. A repetition of the experiment with R fresh portion of the sulphur gave the same result. In order to be quite sure that the arsenic had been derived from thc sulphur T burnt 500 grains of the sulphnr when it left about a grain of a black residue consisting chiefly of sulphide of iron. This was dissolved in a very little nitro-hydrochloric acid ;the diluted solution was saturated with hydrosulphuric acid and boiled when a slight dirty yellow precipitate fell ;this was treated with ammonia which dissolved the yellow portion leaving a few black particles which proved to be sulpbide of lead. The ammo-niacal solution when evaporated left a yellow residue which was dissolved in nitric acid; on evaporating the acid and testing with nitrate of silwr the characteristic precipitate of arseniate of silver mas obtained.* I found it advisable for obvious reasons to dispense with the use of caoutchouc connectors in the tubes immediately leading to the globe in which the gases were mixed and to employ a perforated ghs plate instead.of a cork for closing the lpouth of the globe. BLOXAM ON ARRRKIC IN SULPIIURIC ACID. It ie evident therefore that the sulphur under examination contained a minute proportion of arseuic part of which passed off with tlic sulpliurous acid whcn the sulphur was burnt wliilst thc remainder was fouiid in thc piclue with the sulphides of iron and lead.Thoiigli it cannot bc infcrrcd from the esmiination of a siugle saniplc of the identity of which 1 ‘have no direct evidence that Siciliiui sdpliur Jn-ays contains arsenic such an infcrencc is greatly fitvourccl by tlic circumvtancc that tliia impnritg has been detcctecl iii the spccimcns of sulphuric acid manufactured with evcry l~rec(zution to iiisure its abscliicc. Tlic conclusions to ivhiclr I bavc been led bv the above =pi-meiits arc :-1. That snlplwiic acid cannot be completely purified from arsciric citlicr by Irylroclrloric acid or cliloriclc of sodium or by rcpcntcd distillatioii whctlicr donc or with bichroinatc or pcr- 111allgallatc of 1’0tash. 2. That tlic minute qiiantity of arscnic foiau4 even in the purest samplcs of commcrcial sulpliuric acid is derivcd from the natire sulphur cinploycd iii its maiiufacturc 3.That mhcn sulplruric acid is rcquircd \sliicIr shall yield no indication of arscnic to the clcctrolytic test t!ic sulplrurous acid and nitric osidc employed in its preparation must \)c cvolved at as low a temperature as possiblc sincc tlic funics which accompany thc gascs prepared by the ordinary methods arid are not corn-pletcly removed by washing bring ovcr small quantitics of arscnic. It is very probablc that experiments concluctccl upon a manu-facturing scale would lead to rm casicr proccss for obtaining the sulpliuric acid in a statc of &solute purity. Note.1n a forrncr commuiiicution I have stated that arsenic acid docs not respond to the electrolytic tcst.This is not strictly corrcct the result depending .upon the presence or absence of hgdrochloric acid,* crlthoirgh even when that acid is not prcsent arsenic acid as might bc expected does not yicld arscniurcttcd hrdrogen so rapidly as arseriious acid. Tlircc experiments were Since in tlic practical applic:htion of thc clcctroljtic tcst to Ue detection of arscnic ip organic niixtiires hgclroclrloric acid is alvap prescnt the addition of eul-phurous or h~drowlphuric wid as fornicrly recommended is etill necessary. It wae while endeavouring to discover by eloctrolgeis the etate of oxidation of thc amnic in sulphuric acid that the reduction of medic acid in thc absence of bvdrochloric SMITH ON A DOILINO RPRIIC’Q IN NEW ZEALAND. made with pure arseniate of magnesia and ammonia dissolved in dilute sulphuric acid. A quantity of this solution corresponding to 0-1 grain of arsenious acid gave an immediate deposit of me-tallic arsenic in the heatcd reduction tube; one-tenth of that quantity gave a deposit in seven minutes (though not 80 much as would have been furnished by arsenious acid) and a quantity representing 0.001 grain of arsenious acid gave a deposit in twenty-one minutes.

ISSN:0368-1769    

DOI:10.1039/JS8621500052

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

SMITH ON A DOILINO RPRIIC’Q IN NEW ZEALAND. XII.-.Xote on the Composition of a Boiling Spring in New Zealand. BYPROFESSOR S M IT H University of Sydney. STRETCHING in a north-easterly direction from Tarauaki in the north isiand of New Zealand is a line of volcanic action termi-nating in White Island in the Bay of Plenty. In this line are numerous solfataras boiling springs basins of seething mud and hot lakes presenting in some localities scenes of remarkable beauty and grandeur. Some of the boiling springs are intermit- tent jets of the same character though not of the same magni- tude as the geysirs of Iceland. The New Zealand springs have in many cases formed terraces and incrustations of siliceous matter probably unsurpassed in extent and magnificence by any similar deposits in the world.One of the most copious of the boiling pools is named ‘‘Te Tarata.” It is on the nhore of Roto-mahana ((‘ Hot Lake ”) at an elevation of some fifty feet. The water is of a beautiful pale blue colour. It descends to the lake in a series of cascades over the edgcs of extensive basins and ter- races of siliceous deposit. On the occasion of my visit the water was in violent ebullition the temperature being a little above that of pure watcr boiled at the same place. I carried a bottle of it with me to Sydncy and made an analysis of it about a month aftcr its collection. The specimen was then milky and had a slight smell of sulphuretted hydrogen. Taste soft and utipleasant. It was highly alkaline to test paper.Specific gravity 1.00205. A slight sediment had fallen which seemed to be chiefly vegetable mattcr. The qiiaritity of water in my possession was too small for a complete and unexceptionable analysis but the following Table gives -1holieve a tolerablv close approximation :- 58 SMITH ON A BOlLINQ GPRIRQ IN NEW ZEALAND. Grain8 per Gallon. Silica. . I . .. .. .. .. 42-40 eda (probably combiued with s ilica) .. 16-00 Chloride of sodium .. .. .. .. 113.57 Chloride of potassium .. .. .. 6.67 Sulphate of potash .. .. .. . . 528 Carbonate of lime .. .. .. .. 1.76 Alumina .. .. .. .. .. 0.32 Magnesia and iron .. .. .. . . traces 186.00 Total solid matter obtained by evaporation m. at 212"F. .. .. .. . 189.12 Matter volatilized by ignition ... . 4-00 Leaving for fixed salts .. .. . . 185.12 The arrangement of acids and bases is of course to a consi- derable extent matter of opinion. There being only a small amount of carbonic acid present (not directly estimated) 1assume that it is just sufficient to supply the lime. The sulphuric acid found' (2.42 grs.) is given to potash the remainder of the potassium being supplied with chlorine. The potassium (calculated from the precipitate by bichloride of platinum) amounted in all to 5.87 grns. The whole chlorine was 72grns. There is a residue of soda which I suppose may be combined with silicic acid. There could have been no sulphide of sodium present for the prccipitate with nitrate of silver was white and there was no escape of sulphuretted hydrogen on adding hydrochloric acid to the dry residue obtained by cvaporation.Boracic acid was tested for but none found. In a bottle of water that I afterwards obtained from the same locality though perhaps not from the same spring I found solid matter at the rate of 1'78%grns. per gallon. Of this the silica amounted to 57.08 grm. 30.08grns. being in a state of solution and' 27 grns. having separated as a yellowish-white gelatinous sediment. The chlorine amounted to $0 grns. per gallon. I examined the white incrustation upon reeds and other objects immersed in the spring. It was silica with traces of common salt lime and alumina. Dried at 212'F. it lost 2.26per cent. of its weight. On ignition there was a further loss of 5.05 per ILODIVELL ON THE BOLUBILITY OF BULPXATE OF LEAD 69 cent. making altogethcr a loss of 7-20 per cent. calculated on the air-dricd pomdcr.

ISSN:0368-1769    

DOI:10.1039/JS8621500057

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

ILODIVELL ON THE BOLUBILITY OF BULPXATE OF LEAD 69 MIL-On the Solubility of Sulphate of Lead in Hydrochloric and Nitric Acids. BY GEORGE F. RODWELL. PERFECTLY pure and dry sulphate of lead was digested at ordinary spring and autumn temperature with the different strengths of hydrochloric and nitric acids given below iii well-stoppered Luttlcs the misturc being frequently shaken. The time of diges- tion viiried froin onc to ten days. Determinations of the amount of sulphatc of lcad dissolved were made on each intermediate day but it was found that tlie maximum amount was in every instance dissolved bcforc the fifth day of digestion. The sulphatc of' lead was allowcd a night to settle down; the required quantity of the solution was then filtered off weighed and transferred to a porcelain crucible; a few drops of dilute eul- yhuric acid were added ; the solution was evaporated to dryness over a water-lnth and heated in an air-bath to expel sulphuric acid with the lid on the Crucible; and the residue was ignited al-.lowed to starid in dry air just long enough to cool (previously determined) arid immediately weighed.It was found impossible to evaporate the more concentrated solutions of sulphate-of lead in hydrochloric acid over the water- bath for wlien the evaporation was about a third effected a scum of cliloridc of lead formed on the surface and the bubbles of hy- drochloric acid rising from tlie bottom burst at the surface of the liquid tliroming particles of the scum outside the crucible although it was riot half full.The evaporation of such solutions was there- fore completely effected in an air-bath the lid being placed on the crucible to prevent the possibility of a particle escaping. Twenty determinations of the amouut of sulphate of iead dis-solved by each difl'crcnt strength of hydrochloric and nitric acid were made tlie best four and their mem are given. The following results were obtained :-100 parts of dilute hydrochloric acid of the specific gravities given below dissolve severally of sulphate of lead,- 60 RODWELL ON THE SOLUBILITY OF SULPHATE OF I.EAh El’C. 1. Specific gravity 1.0519 = 10.602pcr cent. IIC1. -1468 ‘I-IGG *14G7 -14G5 RI~fill * l>J*G(i3. On dilnting tlic solution with watw no changr was apparent.2. Specific gravity 1.0800 = 1G-310pcr ccut IIC1. .I r-*3516 .3537 63558 3m7 Alean = .3;5-E05. On diluting the solution with water a fcw minute needlcs of chloridc of lead came down on standing. 3. Specific gravity 1.107 = 22.0100 per ccnt. IIC1. -9483 .Y 44.4 -94’76 9458 Ifcan = -946523. On dilutiiig the soliition with water npedles of chloride of lead came down. 4. Specific gravity 1.1339 = 2’7.5245 per cent. IIC1. 2.1169 2.1141 2-1121 2.1122 Mean = 2.113825. dn diluting the solution with water riecdles of chloride of lead at once came clown. 5. Specific gravity 1.1570 = 31.6013 per cent. HCI. 2.8549 2.8,j08 2.8553 2.8388 Mean = 2.85495. On diluting th;? solution with water an immediate and abundant precipitate of needlcs of chloride of lead was thrown down.If a solution of sulpliate of lead in hydrochloric acid be evapo- rated we get on cooling a number of crystalline platcs of pearly lustre. They consist of chloride of lead and are of the following forms :-I If these plates are dissolved in a small quantity of hot water needles of chlorirlc of lead are deposited on cooling. Whcn R concentrated solution of sulphate of lead in liydrochlo- ric acid is slowly evaporated at the rate of about a gramme in two hours we find that rlionibic plates of chloride of lead are fiwt formed. As thc evaporation proceeds howcver thc small quan-t ity of sulphuric acid presciit liecoming more concentrated slowly decompoyes these crptals and we get sulpl~ateof lead in rhombic platcs IN EYDI&OCHLOBIOAND NlTBIC AOIDS.100 parts of dilute nitric acid or the specific gravities given below dissolve severally of aulphate of lead,-1. Specific gravity 1.079 = 11.55 per cent. NO,. -3303 *3295' .3300 03299 Mean = *329925. 2. Specific gravity 1.323 = 17.5 per cent. NO,. -5748 ,5763 -5754 5756 Mean = 0575525. 3. Specific gravity 1-25= 34 per cent. NO,. 071532 ,7835 7854 -7855 Mean = -7844. If any of these solutions are evaporated we obtain on cooling octohedra of nitrate of lead. 4.Specific gravity 1.42 = 60 per cent. NO,. 9098 *0097 *0097 *0097 Mean = -009725. If this solution be evaporated to about *th of its bulk a small quantity of powder is deposited which is seen under the micro-scope to consist of octohedra of nitrate of lead.When sulphate of lead is digested with nitric acid containing 60 per cent. NO, it is found after three or four days to be almost entirely converted into octohedra of nitrate of lead. On continu-ing the digestion for twenty-one days a minute quantity of sd-phate still remained unconverted From the above results we see that 1 part of eulphate of lead is soluble at the ordinary temperature in- Dilute Hydrochloric Acid. Spec. Grav. Per Cent. HCl. 681.8956parts 1.0519 10.602 281.7298 , 1.08OO 16.310 105.6496 , lo107O 22.010 47-3076 , 1.1359 27.5246 350268 , 1.1570 31.6015 Dilute Nitric Acid. Spec. Grav. Per Cent. NO,. 303.0991 parts 1.079 11-55 173.7542 , 1.123 17-50 127-4859 , 10282.7763 , 1.250 1.420 34.0 m*Oo V0L.XV-3

ISSN:0368-1769    

DOI:10.1039/JS8621500059

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

62 XK.-On the Resin of Ficus rubiginosa anda new Homolbgue of Benzylic Alcohol. BY WARRENDE LA RUE,Ph.D. F.R.S.,Treasurcr of the Chemical Socicty Secretary of thc Royal Astronomical Society &.,and HUGOMULLEH,lJh.D. F.C.S. (Abetncted from the Philosophial Traneactione 1880 Part I.) AMONGthe interesting collcction of natural products contributed to the Paris Universal Exhibition of 1855 by the British Colonics waa a gum presenting some remarkablc qualities. This substance waa stated by the exhibitor to be a ncw species of gutta percha in consequence of its becoming plastic when masticated and on this account it attractcd considerable attention. It hul been contri- buted by Dr. Stephenson of Manning River N.S.W. who had obtained it from a specics of Ficus known as F.rubiyinosa. The tealous Commissioner for New South Wales Mr. (now SirWilliam) Macarthur brought this gum undcr our notice with the vicw of obtaining some information respecting its chemical properties. A few preliminary experiments which were made in Paris at once showed us that this substance had vcry little in common with gutta percha and moreovcr its chemical propcrties wcre found to be entirely diffcrent from those of that gum. Although our ex- periments did not allow us to hold out hopes to Mr. Macarthur of the gum becoming a valuablc articlc for cxportation from the colony they offered somc iriduccmcnt to us to make a more rigor-ous investigation of it on purely scictititic grounds. On communi-cating this view to Mr. Macartliur hc liberally placcd at our disposal the remainder of thc spccinien exhibitctl.In pursuing suliscqucntly the study of this subjcct we iliscovcred one of the proximate coristitucnts to bc a natural acctic ether of a new radical homologous to benzyl (C 11,). Thc peculiar in- tercst which attaches to this class of compounds induces us to bring under the notice of thc Socicty the results of our investigation. This gum or rcsiii exhibits on tlic first glance great similarity in its general appcarancc to ‘‘Gum Euphorbium,” occurring like that substance in irrcgular picccs generally pierced with holcs ; some specimens also exhibiting a stalactitic formatiou. The holes in the fragments of this rcsin are protluccd by a small beetle of the tribe ‘‘Curculio,” which apparcntly feeds upon and lives in ON THE BESIN OF FICU8 ILUBIGINOSA.this resin as it oozes in a semifluid state from the branch of the tree. We had no means of ascertaining whether or not this insect causes the secretion of the resin by puncturing the branches of the tree in the same manner as the Coccus~cusdoes for the pu'poe of depositing its ova. The colour of the gum varies from a dirty yellow or red almost to white. It is solid and brittle but some of the larger pieces exhibit especially in the interior a degree of toughness which renders it difficult to powder. It is opaque the fracture being dull and wax-like. At a temperature of about 30" C. (86' Fahr.) this resin becomes soft when it resembles gutta percha being plastic without.becoming sticky provided it has been previously wetted with water. In its natural condition it has neither taste nor odour ; but when heated it evolves a wax-like odour arid on being masticated evinces a characteristic taste. In hot or cold water it is perfectly insoluble; but warm alcohol ether oil of turpentine and other solvents of resioous substances dissolve it with facility. Solutions of caustic alkalies have DO effect on it even when aided by heat. When left for some time in contact with cold alcohol of ordinary strength the greater part of the resin is dissolved whilst a white flocculent substance remains undissolved. By employing this solvent we succeeded in separating several distinct classes of substances from the Ficus resin.,The constituent readily soluble in cold alcohol formed an amorphous resinous substance when separated from the solvent by distillation or precipitation with water. The white insoluble part when further treated with boil-ing alcohol is in part dissolved particles of bark sand and other accidental impurities remaining undissolved. The alcoholic solution of the white substance deposits on cooling a white crystalline mass which by repeated crystallization may be obtained in beautiful scaly crystals. From the residue insoluble in boiling alcohol bisulphide of carbon or chloroform extr'acts a small quantity of caout c houc. A quantitative experiment by the above method yielded the following approximate per-centage red t :-Resinous substance readily soluble in cold alcohol .73 White crystalline substances insoluble in cold alto-hol but soluble in warm alcohol 14 Caoutchouc fragments of bark sand and loss 13 DE LA RUE AND BIULLER ON The resinous substance readily soluhlc in cold alcohol which forms according to this analysis by far the principal constituent of our resin ofl’ered but little incluccment for chcmical investigation. However a number of experiments were made which although unproductire in their results may serve to characterize this sub-stance which possesses peculiarities distinguishing it from other bodies of like origin. In order to identify it hereafter we pro-pose to call this resiii Sy coret i 11. At the same time we must state that we were not succcssful for reasons hereinafter mentioned in obtaining this substance perfectly pure.Xycordin. Cold alcohol of moderate strength dissolves the principal part of the original resin forming a light brown solution which on precipitation with water or the separation of the alcohol by distillation yields the sycoretin. The alcoholic solution of this resin is perfectly neutral arid scarcely any precipitate is caused in it on the addition of an alcoholic solution of acetate of lead or acetate of copper. This behaviour indicated at orice that no acid compounds were present and that the resin is perfectly neutral. The minute precipitate which formed we ascertained to be tarmate of lend the source of the tannic acid being probably the bark which contaminated the resin.This resin was purified by redis-solving it in alcohol and in order to remove the small amount of colour the soliition 1%as treated with animal charcoal but this had no effect. No better result was obtained when a small quantity of acetate of lead was introduced into the solution and a basic lead- salt thrown down with ammonia. We afterwards found that the colour could be gradually removed by repeated precipitation of the resin from its dcoholic soliition by water. The decolorized resin was now redissolved in a just-suEcient quantity of alcohol and the solution left for some time in a cool place wheu a small amount of crystalline substance was deposited which was filtered off. By addition of a little water a small quantity of sycoretin was then thrown down in order to carry down the last traces of the less soluble crystalline compound in case ariy we1.E still present.After this treatment the solution was again allowed to stand for some time but no further precipitate was formed. The clear solution was now partly precipitated with water and the precipitate removed after it had subsided heat being used to facilitate the subsidence of the sycoretin by eausillg the THE 1tESIN OF FICUS RUBIGINUSA. precipitate to aggliitiiiate into one mass. That part of thc resin remaining in solution was aftcrwarils throwii doin1 with water and collcctetl separately. The two diff'crcrit lots of resin thus obtained had the sitme ap- pearance; both wcre brittle hut only the last bccaine sticky when masticated and tasted like the original resin.Both products were powclcrcd arid kept for some time in vacm over sulphuric acid in order to remove all traces of any adheriug water or alcohol. The analysis of the first prccipitatcd part (A) gavc the following per ceiitagcs :-Carbon . . 74-65 Hydrogen . . 10.11 The analysis of the portion last thrown down (B) gave the fol-lowing per-centages :-Carbon . . 77-89 Hydrogen . . 9.94 It will be observed from the preceding numbers that the resin wliich has the property of agglutinating on being masticated is richer in carbon than that first thrown down by water from the alcoholic solution. The peculiar characters of these substances did not however permit of any formulae being determined for them.Sycoretin is almost white ; it is very brittle. It melts in boiliiig water to a thick liquid floating on the surface and when powdered becomes so electric that it flies out of the mortar. In water dilute acids alkaline solutions or ammonia it is insoluble; but it is readily soluble in alcohol etlier chloroform oil of turpentine &c. In order to ascertain whether sjcoretin was allied to that class of bodies called glucosides (jalapin for example) the following experiments were made :-Action of Xu@huric Acid on kycoretin. A portion of the sycoretin prepared as stated above by frac- tional precipitation was added to conceritratcd sulphuric acid ; it was readily dissolved forming a fine deep red solution which gave off only a fairit odour of sulphurous .acid when kept for several days.By exposure to the air or on addition of water a brownish precipitate deposited which differed from the original solution by its lesser solubility; the aqueous liquid contained a trace of a 1)E LA RbE AND MULLEK OK sulpho-copulate acid but no snccliarinc snlntance could he dis-covered. Analogous results wcrc olitainctl l)y twatiiig it with a conccntratcd solution of potash. Tlicsc espcrinicnts sliow that sycoretin cannot he classec? with tlic glucosides ; iiiorcover dl at-tempts to placc this substarm in connciion nith sonic‘ of the clnssificd organic com1)ouiids wcrc unsucccssfiil and we arc tlicrc-forc constraincd to lcaw it for the przscitt anioiig tlic so callcd resins under which tcrm arc comprisctl all sorts of bodics wid and ncntrnl wliich haw notliing in comnion esccpt some physical 1’2sc113 bla11ce.Action of A\’&ic ~Icid on Sycoretin. It appears that the only products of tlic action of coiicentratcd nitric acid arc a peculiar :iitro-compounu arid a small quaiitity of odic acid no picric acid bcing formed. On submitting sycoretin to the action of nitric acid the pow- dered resin was iutroclueed in small quantities into tlie acid at tlie ordinary ternpcrature and whcn the action had somewhat subsided the acid was boiled for some time when every particle of resin disappeared. The resulting yellow liquid vns mixed with water when a copious precipitate of a pale yellow dour was formed. The precipitate was filtercd off and washed with water.The fil-trate when freed from nitric acid by evaporation gave an addi- tional precipitate of the nitro-compound on admixture with water. The nitro-compound has slightly acid pruperties and ip readily soluble in solutions of potash and ammonia. Carbonate of potash also dissolves it but there is no evolution of carbonic acid even when the solution is warmcd. All the solutions in alkalies are dark yellowish brown and leave on evaporation an amorphous re-sidue. Lead and other metallic salts give coloured precipitates with its solution but as might be expected no dcfinite compounds could be 2roduced in this way. Thc compound with potash when heated on platinum-foil melts takes fire pufls up and burns with the vivacity of other nitro-compounds.Action of Heat on Sycoretin. When heated in a retort spcoretin melts below looo C. and at a temperature of a few degrees higher froths considerably giving off water which retains the peculiar odour perceptible on heating the original resin. On raising the temperature much higher it becomes quiet and begins to decompose giving off at THE RESIN OF FICUS BUBIQLNOSA. first a mobile liquid and towards the end a dark yellow tar-like substance leaving only a small quantity of charcoal behind. The distillate so obtained has a disagreeable smell somewhat like burnt india-rubber acetic acid being also present in considerable quan- tity. By treating it with R solution of carbonate of aodium the acetic acid is removed a dark brown oily liquid remaining which pa-sesses now a less disagreeable odour.This oily liquid submitted to a new distillation gives at first a very mobile liquid possessing in every respect the properties of caoutchin and then a thick oily liquid which soon becomes dark brown when exposed to the air. Acetate of Sycoceryl. We assign this name for reasons hereafter to be mentioned to the crystallizable substance which as already mentioned is obtained when the residue left after the treatment of the original resin with cold alcohol is dissolved in boiling alcohol and the solution allowed to cool. For the preparation of this substance the original resin is coarsely powdered arid extracted with cold alcohol in order as far as possible to remove the sycoretin.The undissolped residue is then exhausted with boiling alcohol. The several solutions thus obtained are filtered and allowed to cool when a white deposit is formed which generally shows but little indication of crystallba-tion. This white deposit is again dissolved in a large quantity of boiling alcohol and left in a quiet place to cool slowly when a more perfect crystallization is obtained. Towards the latter part of the crystallization a substance is de-posited of different appearance being of a more flocculent nature and altogether different from the crystals first deposited. This substance is present only in very small quantity and its separation from the other crystallizable constituents of the resin is attended with great dificulties.Iu order to effect this separation the alco- holic solution is allowed to cool to about 40" C. (lO-ko Fahr.) and then the crystals which may have formed are separated by strain- ing off the liquor as quickly as possible through a piece of gauze. The mother-liquor on further cooling will now deposit the floc-culent substance contaminated however with the first substance. By repeating this operation a perfect separation of this second substance may be effected. By repeated solution in and recrystallization from hot alcohol the crystalline substance (acetate of sycoceryl) was obtained DE Id RUE AND MULLEI~ON perfectly white and transparent and apparently pare. h a&-nation with the microscope however proved tJmt another foreign body had deposited in smaller crystals on the faoe8 of the ~~pposed pure substance.This new body proved to be much less soluble in different vehicles than our acetate of sycoceqd but being present only in very small quantity its separation caused us at ht very greRt perplexity but finally we found the following method per-fectly efflcacions for that purpose. The dry crystals were placed in a flask,and a quantity of ether inaufficient to dissolve the whole substance was introduced the temperature being maintained at about 30' C. (86" Fahr.! ;more ether was cautiously added from time to time until the larger crystals had just disappeared leaving the smaller ones of the new eubstance undissolved. The separation of the two substances is not however perfect in a single operation; for when the flask iu allowed to cool a small part of this parasitical body depsita.After d$tilling the filtered etheric solution the acetate of sycoceryl is obtained in a state of perfect purity and by recrystallization from alcohol ether or chloroform it may be procured in beautifid crystals. Acetate of sycoceryl so obtained is perfectly colourless and crystallizes from ether in flat prisme which generally appear a~ six-sided plates. When crystallized from alcohol the crystals are thin and scaly like mica and have the greatest resemblance to cholesterin. Acetate of sycoceryl is brittle yet difficult to powder on account of its becoming highly electric when triturated. It melts at 118" -120" C. (244"4-248" Fahr.) and is still fluid when cooled down to 80"C.(176" Fahr.). It eolidifies at first to a transparent mass which however after a short time becomes opaque and crystalline especially if scratched with a hard body. Heated considerably above its melting-point it boils and distils almost without decomposition. The distillate is at first liquid but solidifies after 8ome time and becomes gradually crystalline. When not perfectly pure or if the heat is applied too rapidly it givea out a rancid odour in which that of acetic acid is recognisable. Hot alcohol ether chloroform benzel acetone oil of turpentine and concentrated acetic acid dissolve the acetate of sycoceryl with great facility. The alcoholic solution is perfectly neutral and gives no precipitate with alcoholic solutions of the acetates of lead or copper.Sulphuric acid dissolves it readily forming a viscid colourlem solution wliit~li gets grntlitnlly IJIWWII and tliw giws off trams of sulpliiiroiis atit1 acetic acids. \\Iwii tlic siilpliiiric soliit ion is miscd wit11 water n siibstnncc is thrown tlowi wliic4i is Iwrfcctly liartl at coniinon tcmp:mtiirCs hiit niclts bolow lo()?(:. (213"k'ithr.1 ant1 is very tliiliciiltly soltiblc iii alcoliol hut rc;ulily so in clilorofoi m ant1 I)ciizol. Nitric acid wlicii tlilutccl lias no cffcct nt ortlinary tcmpcra- turcs 011 acctittc of syc*occrFl ; hit if warm it cvolves nitrous fiimcw and prod iiccs a ycllow rcsiiious compoiiiitl. k'iitning nitrom acid Iio\vcvcr dissolves it rcadily at ordinary tcmpcraturcx giving n yellow soliition from wliicli water tlirows down a flocculent amorplious ycllow nit ro-coml)oiiiid.IIylrocliloric acid has no cflcct on acctatc of sycoccryl. Cliloritic bromiiic aiitl iotliiic iii coutact with this siihstancc act npoii it witli violcticc cspccinlly tlic two first-uamerl rcagcnts; the procliicts Jiowcvcr procurd in this matincr arc oiily rcsiti .like compounds iiot atlaptcd for aniilysis. If Iio\vcvcr a wiirni alcoliolic soliition of tlic acctatc of sycoccryl is cmployccl ant1 tlic 1)roiiiiiic or iociiiic also adtlccl iii solution and iii small qiiaiitititts at a tirnc the coloiir of tlicsc two rcagcnts tlisappcnrs and aftcr cooliiig a IICW hino-or iodo-compound as tlic cnsc niay be is tlepsitetl in small crpt:ds.Tlic iodine-corn-poiintl is y~llow,the 1)romiiic-coniponiitl colourlcss. l'lic purifica-catioii of tho two proiiiisiiig conipoiiiids ant1 tticir scpariition froiii t1ic 1111nl tcrcvl ()rigin;il siihi;tal iccs aid mi0t licr rcsi nou Y hodp f'ormctl at tlic samc tinic was imfortuiiatdy not possildc witti tlic liiiiitctl qiiniitity of nintcrial that coiiltl bc dcvotcd to their pl.cl):lratiOTi. Poliitioi~of potmli cvcn whcn boilcrl for a long time with the sitl)staiicc iiiitlcr coiisitlcrntioii tlocs riot act iipoii it. If hydrate of pot:i4i Iiowcwr is mcltcd with it a tlccomposition takes ~IRCC and if tlic tcwil)crritnrc is raised sonic liytlrogcii is given off. The protluct' of this reaction trcatcd wit11 water leaves bcliind a coloiii*lcss anioi.ptioiis I~otly,wliicli could not hc ohtaincd in a cryp t;dliiic stntc 01' siificiciitly pirc for aidysis.Thc alkaline mother- liqiior snturatcd with rliliitctl siilpliuric acid bccamc slig1itly turbi(J aid the prcscncc of ncctic acid was tlicii pcrccptible. Soda-tartrntc of coppcr gave no rcnction indicatiiig the presence of siigai*iii the solution. 'l'lius far vc did not siicccctl in producing any derivative which would tlirow light upon tlic tlicoretical composition of our substance ant1 fiirnisli us with the nieans of ascertaining its rational formula. DE LA RUE AND MULLER ON Analysis gave numbers which agree with the empirical for-mula C, H,60,* our substance bcing accordingly isomeric with camphor to which howcver it has no further resemblance.This composition varics also widely from that of the crystalline snbstanccs procured from analogous sources and which have a great rescmblancc to OUT sabstaiicc,-for instance the crystalline resins on the one hand Chinese wax and waxes generally on the other. We have mentioned above in spcaking of the action of various reagcnts on our new substance the occurrence of acetic acid under two different circumstances; we did not attach much importance to this fact at the time because this acid occurs so frequently among the products resulting from the breaking up of organic substances ;nevertheless we subsequently repeated these experiments on a somewhat larger scale chiefly however with the view of stndying the other products of decomposition which are formed.In order to eliminate as much as possible the effect of temperature we made use of that powerful reagent the so-called ('sodium-alcohol,'' which is ohtained by dissolving sodium in absolute alcohol. Sodium-alcohol and potassium-alcohol at ordi- nary temperatures are for the most part equivalent in their reac- tions to the hydrates of those alkalies when in a state of fusion and hence present the advaiitage of etfecting decompositions in a more simple manner the effect of a high temperature not inter- fering with the final result as is somctimes the case when the fusing hydrated alkalies are employed. Some experiments of this kind performed with great care convinced us that the occurrence of acetic acid could not be attributed to the effect of empyreumatic decomposition but that it actually existed as an integral proximate coiistituent of our crystallizable substance.This led us at once to suspect that our substance was in reality an ether-like compound. This supposition was confirmed hy the separation of a body which might be con-sidered as the hydrated oxide of a radical; moreover we were ultimately enabled to give the fullest coiifirniation to this theoreti- cal speculation by actually producing the original substance in a manner suggested by this view. It should be stated that sodium-alcohol dissolves our substance with the greatest facility and even at a temperature of 30" C. * Carbon = 12 Oxygen = 16. TIlE RESIN OF FICUS RURIQINOSA. (86" Fahr.) decomposition takcs placc the reaction being unac-collll)ii~li(d by the cvolution of gas.On cooling the solution coritiiiucs liquid altliough il largc qnantity of the substance mfiy have Imn emyloycd; hut on addition of watcr a white flocculent substance scpimatcs from the colourless alkaline mother-liquor. The flocculciit substaricc is insoluble in water but readily soluble evcn in cold alcohol. IVlicn it is dissolvd in a quantity of boiling alcoliol just sufficient to tnkc it up tlic solution on cooling solidi-fies complctely to a mass of beautiful silky crystals quite different from those of the origiiial substancc this new derivative proved to bc the nmv alcokol which we proposc to call Sycocerylic A1 c o 1101. Thc aqueous liquor from wliieli the flocculent precipitate was separated rcmains almost pcrfcctly clear on saturation with a mine-ral acid ; 011 examination no othcr product bcsidcs a volatile organic acid coiilcl be found in it.Thc existence of a volatile acid with tlie odour of acctic acid was rendered evidcnt by saturating the alkaline rnothcr-liquor with phosphoric acid and distilling ;the distillatc was saturated with carbonate of barium and evaporatcd to the crystallizatioii poirit wlien prismatic crystals of the charac-teristic form of acetatc of barium were obtained. A barium determination gave riumbers which agree with the formula c I€ BaO,. Alcohol of Sycocmyt. The preparation of this substaiwe has been already detailed. In order to render it prc it is orily necessary after it has been pre- cipitatcd from the solution of sodium-alcoliol to wash it well with watcr in order to rcniove dl traces of fixcd alkali ;then to crystal- lizc it a few timcs from warm alcohol.The crystals usually occur aggrcgatctl iii splicrical inasses like the miricral Wavellite ; they are vcry tliin aid have a great rcsernblancc to caffcine. In sevcral iiistiuices (luring the earlier stages of its purification or wllcii dilute alcoliol is employccl for its solution it was noticed that tlic suhstaiicc did iiot dcposit in crystals but the transparent liqitid coiigcalccl to a jelly. Tliis jelly however after some time became crystalliiic the crystallization commcncing in several points of the inass and cstending gradually throughout the whole ; ulti-mately a crystallization was obtaincd of the same appearance as occurs undcr othcr circumstances.In the dctcrminatioii of the rational formula of this substance DE LA BUE AND MULISB ON we took cognizance of the fact that beside acetic acid it waaJ the only other product obtained in the decompoeition of the origid compound which we have deuominated acetate of sycoceryl and the analysis of which led to the empirical formula C, H,60. From the nature of this compound we inferred that it contained the radical of acetic acid in a state similar to that in which it exieta in acetic ether; that in fact we had to deal with a compound containing acetic wid miniia one atom of hydrogen and a radical. According to this view the empirical formula C, H160 would have to be doubled whereby we obtain Cm Hm Oa and if we now deduct the elementst of acetic acid minus hydrogen .) = C H 0 we have c, H,, for the radical of our new alcohol whose formula would come- quently be C, H,,O.The analysis of the supposed alcohol obtained from acetate of sycocerpl gave results which support this view. Accordirig to the formula C,,H, 0 the new alcohol would be homologous with benzylic alcohol obtained from ''oil of bitter aimonds." Alcohol of sycoceryl is perfectly insoluble in water the fixed alkalies aud ammonia ; but alcohol especially when warm ale0 ether benzol chloroform and naphtha are good solvents for it. At a temperature of about 90"C. (194"Fahr.) sycocerylic alco- hol melts to a liquid heavier than water and solidifies on cooling to a crystalline mass especially if any fragments of crystals have remained unfnsed because they hecome the foci of a new crystal- lization.When however the heat is increased only a little beyond the fusion point it remains perfectly transparent and amorphous. By contact with alcohol this glassy condition is changed to the normal crystalline structure. When it is heated considerably above its melting-point a portion distils unchanged and a hrownish residue is left in the retort. Potassium brought in contact with this substance when in a state of fusion disengages hydrogen and hecorncs covered with a white crust; but when heat is applied in order to fuse tbe so-formed potassium-compound of the sycocerylic alcohol the reaction becomes so violent that the mass blackens and even catches fire.THE RESIN OF FICUS RCBTGTN0S.l. Heated with hydrate of potash above the melting-point of the latter it evolves hydrogen and decomposes; it appears that this reaction does not stop with the probable formation of an acid which unites with the potash but goes further; for in the product of this reaction me did not find the expected acid; but it is our intention to pursue this subject if ever we are so fortunate as to procure a larger supply of material. Concentrated sul phuric acid easily dissolves sycocerylic alcohol with evolution of heat forming a brown liquid which remains un- altered for some time. The liquid yields c?n addition of water 8 resinous viscid substance which melts at the temperature of boil- ing water and is but very sparingly soluble in alcohol.Ether and chloroform dissolve it with facility and on evaporating merely leave the resinous product in its original amorphous state. The aqueous liquor saturated with carbonate of barium gave no indi- cations of the presence of a conjugated sulphuric acid. Chlorine bromine and iodine act readily on sycocerFlic alcohol if solutions of these reagents are used crystalline compounds are formed. The iodine-compound is of a yellow colour. Action of Chloride of Phosphorus on Sycocerylk Alcohol. For the purpose of preparing the chloride of sycoceryl me em- ployed pentachloride of phosphorus and a solution of sycocer-ylic alcohol in benzol.At common temperatures no reaction took place but when the temperature mas raised to about 60" C. (140" Fahr.) hydrochloric acid mas given off and the pentachloride gradually di3appeared. After the disengagement of' hydrochloric acid had ceased the liquid was removed from the remaining penta- chloride and washed with water aud afterwards with an alkaline solution. After tlie benzol had been got rid of by keeping the liquid for some time in a warm place a viscid residue was obtained which was soluble with great difficulty in alcohol but easily soluble in ether or chloroform. These solutions after evaporation depo-sited this substance again in its original sticky state. In the first experiments which were carried out only on a very small scale a crystalline substance mas formed besides the amorphous greenish compound.This crystalline substance differed in its properties from the original alcohol. It therefore seems probable that a slight excess of pentachloride (or the phosphoric acid formed during the reaction) destroys to a great extent the chloride of sycoceryl formed during the reaction ; or at all events phosphate 74 DE LA RUE AND MULLER ON of sycoceryl which is produced simultaneously and predominates cannot be separated from the chloride. We are therefore at pre- sent unable to give a description of the chloride of sycoceryl in its pure state. Benzoate of Sycoceryl. Chloride of benzoyl dissolves with the greatest facility a large quantity of sycocerylic alcohol at common temperatures but no hydrochloric acid is disengaged j probably therefore no reaction takes place at ordinary temperatures but if heat is applied the liquid soon commences to give off hydrochloric acid.When the evolution of hydrochloric acid has ceased the mixture is allowed to ~001 when it solidifies to a fibrous crystalline mass. Any excess of chloride of benzoyl is removed after the reaction by throwing the mixture into a solution of bicarbonate of potassium whereby a resinous mass separatcs. The whole being kept warm for several hours all the chloride of benzoyl is decomposed. During this process a slight smell somewhat like benzoate of ethyl is percep-tible. The resinous mass after removal from the saline liquors is washed several times with warm water ;it is now free from ben- zoic acid and chloride of benzoyl.On boiling the resinous mass with absolute alcohul a trace of a yellowish secondary product dissolves leaving the principal quantity undissolved which then appears as a white crystalline mass. When the product thus obtained is boiled with a large quantity of ether and the solution allowed to cool small crystals are. depo- sited which are soluble with difficulty in ether. Absolute alcohol dissolves only a trace of this substance and when boiled with it deposits the dissolved part on cooling in minute spherical aggre- gations of crystals which under the microscope are seen to be prismatic. The best solvent for this cotnpound is banzol it being soluble in all proportions in this liquid.On evaporating the solution the substancc is left behind in fine prismakic crystals. Chloroform behaves like benzol but the crystals obtained from this solvent are much finer and can be obtained of considerable size. In order to ascertain the nature of the compound produced by the action of chloride of benzoyl on sycocerylic alcohol we decom- posed it by means of sodium-alcohol which we found to be pre- ferable to any other form of caustic alkali. Even with this reagent the decomposition is effected only with dificulty possibly 011 account of the new substance being only sparingly soluble and THE RESIN OF FICUS BUBIGlNOdh. also 011 account of the resulting bnzoate of sodiuin not being much more soluble in the alcohol.IIowcver after boiling for some timc the bcitzoate of sycoceryl disappcaru. On additiou of water a bulky su1)staiice was sepmtltcd which provcd to hc tlic rcgcncratcd alcohol of sycoceryl. Thc aqueous liquid saturatctl with an acid sooii formed a crystal-liiic yrcciyitate which 0x1 removal with ether proved to be benzoic acid. Tlic foregoiug experimciits bear couclusive evidciice that thc alcohol of sycoccry1 behaves towarch chloride of berizoyl iii a manner perfectly analogous to that of other members of the alco- holic group producing that is to say a bcrizoatc of the ether- radicle. After haviiig sliown that the substancc separated li,~sodium-alcoliol may bc rcgardcd as the alcohol of the ncw radiclc sycoccryl it became dcsiralile to have a syntlietic proof of this tlicory; and it occurred to us tliat if we could succecd iu combiriitig the spco-ccrylic alcoliol again with tlie racliclc of acetic acid ad thus repro- ducc tlic origiiial substancc wliicli wc haw cnllcd acctate of syco-ccryl it would be the licst possihlc coiifirinatioii of our views.1x1 ordcr to test this we accordiiigly brought chloride of acetyl in contact with sycoccrylic alcoliol. At ordinary temperatures no action took placc ; but wlicii a littlc llciit was applied tlic alcoliol was dissolved arid the liquid coilirnciicctl to boil giving off copious fumes of hgdrocliloric acid. Aftcr tlic rciictioti liad ccascd heat was agaiu applied aiid tlic wliolc subjectctl to tlic boiling tcmpcra- tiire for soine time iu ordcr to gct rid of tlic excess of cliloridc cf acetyl.After cooliiig the resiil ting protluct was lioilctl with water alicn a heavy oily hody scpnratcd. The boiling with wtitcr was continucd for sonic timc uiitil at last thc oily liyiiid hcciinle per-fectly solid arid bcautifully crystalliiic iiidictitiitg at once that a siil~tance had been forni(v1 diffcriiig fi*oni t lic origi~ial alcollo] I\ liich it will IIC rcnicmbcrcd is fluid at thc tcnipcrnturc of boiliiig \vater. This white crystullinc substancc wits now tlissoliwl iii boilirig nl- cohol of wliicli it rcqiiirccl a considcrahle quantity rwl su1)scquciltly allowcd to cool. TVlicn almost tlic wl~olc1i:id clissolvecl a srnzlll quantity of a compouid was left beliiiid wliicli at last nicltctl being evidently a I~CWsubsta~icc tlic pro1)al)Ie protlilct of the actiori of a small quantity of os~cliloridc or pliosyliorus wliicli contanii- riated the chloridc of acetgl.1113 LA HUE AND MULLEU ON On cooling tlic filtcrcd liqnid bcpn to crystallize yielding bcautiful iridcscciit flat 1)risniiLtic crystals wliicli sparklad with the colours of tlic rainbow in tlic solution likc cliloratc of potash in the act of crptalliziiig. The crpcidlizcd suhtaiicc lwohccd iu tliiu cxpcrimcnt proved to bc in cvcry rcspcct identical with tlic iiatural acetatc of sycoccryl aid thiis pvc tlic most dircct confir- mation to our tlieorctical yicws. Haviug tiins cstilbli~licd tlic iiatiirc of the sycoccrylic :dcoliol it becamc dcsirnble to prodiice also tlic acid wliich moiild be homo-logous with benzoic acid ;ind woiilrl bcar to this acid a rclatioii similar to that wliich pahitic acid bcars to tlic lowcr mcmbcra of tlic series to 17-hicli it liclongs.A sniall quaiitity of tlic alcohol was tlicreforc boiled fbr ilhtit six lioiirs with dilutc nitric acid. A fccble rcrrctioii was iiidicrrtccl by tlic diglit evolution of nitrous fwncs aud aftcr SOXIIC tinic tlic sycoccrylic alcohol becamc.of a dark ycllow coloiw niid prcsciitcd a rcsiiious aspcct. At'tcr digest- iug for sin hours t-lic rcsiiious procliict was rcmoved waslicd with watcr and tiricd. This substuiicc was rcadily soluble in warm al-~01101 and oii cooling a white crrstalliiie substaucc was depositcd. This crystalliiie sul)stil11ce had all the cliamctcrs of an acid; it wiis perfectly soluhle in ail nqucoiis solatioii of potash or ammonia aud gave with an alcoholic solution of acetatc of lead a copious prc- cipitnte.Altlioiigli this rcactioii sliowcd that ivc had olitaiiicd aii acid wliich posscsscs all tlic propcrties that niiglit be anticipated of an acid corresyoiiding to oiir alcohol we could not with the wry siiiall quantity of substance at our disposal get ciiough of it in a pure state for analysis on accoiiiit of the ycllow nitro-conipound (iil)l)arc11tly the iiitro-acid of the ncw acid) arlhcriiig wiili great obstinacy to it md acconipaiiyiiig it in all its compouiids and solu-tions. ln ordcr to exclude tlic formation of this sccoudary product we tried tlie action of chromic acid ofi sgcoccrrlic alcahol; n smid1 quantity of tlie alcohol was boilcd with a moderatcly concentrated soiution of cliromic acid for about eight hours.The product so obtoiiicd was washed aid boiled with a clilute solution of potash but aftcr saturating this alkaline solution with an acid 110 prccipi.. tate was foriucd mid it was altogetlicr inipossiblc to clctcct any acid tliercforc wc must conclude that this acid was not formed by this treatment. On oiie occaaioii on repcating this experimciit we accidcntally ob-served among the products of tlie action of chromic acid on syco-cerylic alcohol a crystalline body j on trcating tlic mass with dilute THE REBIN OF FICUS EUBIOINOSA. alcohol this product was procured in large flat priiains resembling somcwhat in appcarance the acetate of sycocerpl but differing in its melting-point arid was perfectly ncntral.From the mode of formation it might I3c inferred that we had obtairicd the aldehyde (C18 H2RO) corresponding to our alcohol hut the minuteness of the quantity procmd rendered it impossible to decide this point; For the prcsetit we must contcrit ourselves with the foregoing account of tlie compounds of thc radiclc sycocoryl the very emall amount of the substatice at our disposal bcing barely sufficient for the performance of tliose exppiments which we have described. The grcat ititcrcst wliich naturally attaches to this new homo-lope of thc bciizyl-alcohol scrics will be a sufficient inducement for us to take up this suhjcct again for the purpose of studying its tlerivativcs should we be so fortuuate as,to obtain a further supply of raw material.On rcvicwing tlic members of which Cannizzaro's benzylic alcohol is the type arid with which our ~icwalcohol must be classed it will bc perccivcd that -tlierc are still niaiiy gq)s to be tilled up in their series. Bciizylic alcohol . c71r8 o Cumiiiylic alcoliol > uuknown. Sycoccrylic alcohol . Oil comparing tlie properties of our sycocerylic alcohol with those of benzylic alcoliol wry little rcscnihlaricc will at first be traceable between them ; but whi it is rcmcxntcred that thcre are not fewer than teri stcps bctwceii bcnzglic auil sycoccrylic alcohol this dif-fereiicc of piwpertics is easily accounted for ; more particularly if we takc into consideration a siniilar case in aiiotlier iiomologms wries the liiiks uf wliich are murc fully kiiowri.The change in thc properties of tlie acetic acid scries for examplc by each in-crcmeut of increase of C €I2 is quite as remarkable; and when we BENCE JONES ON CBYSTALLIZED XANTXIN compare acetic acid on the one hand with palmitic acid on the other the dissimilarity is not leas remarkable than if we compare sycocerylic alcohol C18H, 0 with benzylic alcohol C H 0. In conclusion we may mention that benzylic alcohol aud cow-quently also cuminylic alcohol are generally considered to be homologues of phenyl-alcohol (carbolic acid) ; cresyl-alcohol would be ivomeric with benzyl-alcohol and carvacrol and thymol with cuminylic alcohol.On comparing these substances we find that this view is not tenable and that there exist in reality at least two distinct series of isomeric compounds the types of which are ben-cylic alcohol on the one haud and phenylic alcohol on the other. The crystalline substance which adhered to the acetate of syco-ceryl and which it will be recollected was left in part undissolved when the acetate was dissolved out with ether can be obtained in only very small crystals. It is perfectly neutral and we did not succeed in obtaining any derivative from it calculated to throw light on its true nature. The quantity was indeed extremely small and we therefore content ourselves with giving the results of the ultimate analysis of this substance which was found to contain 75.56 per cent.carbon and 12.30per cent. hydrogen.

ISSN:0368-1769    

DOI:10.1039/JS8621500062

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

BENCE JONES ON CBYSTALLIZED XANTXIN XV.-Vn a Deporit of Crystallized Xanthin in Human Urine. By H. BENCE JONES,M.D. F.R.S. INJuly 1861 I was consulted regarding a schoolboy nine yean and a half of age. The following history was given to me. He had good health until seven years old when he was seized one night with violent sickness and pain in the stomach which con- tinued incessantly for three days. Neither mustard poultices blisters nor leeches relieved the pain or stopped the sickness. The third day his water gradually became of the colour of blood ; it then stopped altogether and nothing was passed for four days; then delirium and convulsions came on and these lasted for twenty-four hours when he was relieved by a most violent per- spiration.No stone was seen to pass. In a few days he was perfectly well and continued SO for nearly three years when in IN RUMAN IJRISE. June 1861 hecaught a slight cold and mas delirious one night. A medical man saw him and found some albumen in the urine which then was generally thick and the quantity of deposit was increased by excitement or temper ; cold produced the same eff'ect in a less degree. He never complained of pain in the back and was able to take more exercise than other bops of his age without fatipie. He always had a good appetite and was allowed to eat everything. On examination I found a very small quantity of albumen in the water made at night and none in that made in the morning. There were no blood cells no tubular casts and the specific gravity was high.T examined many specimens without finding anything remarkable. About the end of July when he was leaving London a small vial of urine was sent to me which was quite thick and deep- coloured. A drop was placed under the microscope and a crys-talline deposit was found resembling one form of uric acid. From the form I considered the deposit was uric acid. On examining the unfiltered urine for albumen by heat I was surprised to see the Crystalline deposit entirely dissolve. A fresh portion of sediment showed the same crystalline appearance aud the same solubility by heat. This was so utterly unlike any uric acid deposit that a closer examination of the sediment was made but so little substance was left that no satisfactory conclusion could be arrived at except that it was not uric acid.A day or two afterwards another specimen was brought to me containing the same crystalline deposit soluble by heat. The RERCE JONES ON XANTHlN IN URINE. sediment formed about an eighth of the bulk of the fluid. It waa collected on a filter mashcd with alcohol and it gave the follcw- ing reactions. It dissolved in water and in hydrochloric acid; when treated with nitric acid it dissolvcd without efferves-cence and when evaporated to dryness it left a yellow residue. When the solution in hydrochloric acid was evaporated to dry- ness it left beautiful minute crystals of this form :-These crystals were soluble in water. The sediment ma3 easily dissolved by alkalies.The watery solution of the sediment had a feebly acid reaction and when evaporated to dryness left an amorphous residue which was again easily dissolved in water. These reactions agree only witti the latest and best observations of the reactions of xanthin. Hoping to get more of the substance I wrote to the country for the sediment of the urine. It was collected on many occa- sions but I could only find urates and uric acid and none of the crystalline deposit soluble by heat. In January 1862 the same boy was brought to me with two specimens of urine and four different dried deposits; and at different times for three weeks I examined the urine. It was generally of high specific gravity 1025 1026 1027 1030; once a8 low as 1013. It sometimes contained a trace of albumen. Usually it contained urates and sometimes uric acid and oxalate of lime but never the crystalline deposit soluble by heat. The dried deposits consisted of urates and uric acid mid one of them consisted of phosphate of lime with a little phosphate of ammonia and magnesia without a trace of uric acid or xanthin.

ISSN:0368-1769    

DOI:10.1039/JS8621500078

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

81 XVI.-Ou llae Simultaneous Variationsof Hippuric and Uric A& in Hellthy Urine. By 11. BENCE JONEEI M.D. F.R.S. INI1mtL"sZeitschrij't fur rutionelk Medicin 1858 ii. 331 Dr. A. Wcismann gives the results of his experiments on the amount of hippuric acid in healthy urine These results were obtained by evaporating very small qnantities (20 cc.) of urine and they show so largc an amowit of liippuric acid excrctcd daily that a different method of analysis scemed most desirable. The average amount cscreted duriug fow days of mixed diet he gives as 406 grs. daily. 3%.Wreden in the Bulletin de St. Petershury Classe Phys.-med. xvii. 500 states that heiletermined the amount of hippuric acid in licalthy urine by means of a standard solution of chloride of iron; the amount he obtained was also immense.He gives as the mean of twenty-nine determinations 47.4 grs. of hippuric acid to n litre (1000 cc.) of wine = 1'7'pint. The miiiimum amount found was 32.3 grs. and the maximum 87.8 grs. to a litrc. 111 the followiiig expel iments the method of determining hip- pwic acid described by Professor 11ic b i g in the Annalen der C'lcmie ztnd Phurmucie vol. 50 p. 170 mas followed as being the most accurate provided a sufficient quantity of urine is taken for analysis and sufficient cther is used. Usually 400 cc. of wine were cvaporated to a syrupy consistence in a water-bath ; hydro-chloric acid was ailtlcd and the hippuric acid was extracted by trcating the precipitate with eihcr four or five times.That by this method results arc obtained which agree very well together tlic following experiments show 840 cc. of urine were divided into two equal parts and the amount of hippuric acid in each part was determined. Weight of hippuric acid 1st experiment 3.53 grs. ; 2nd esperi-nicnt 3-42 grs. 700 cc \vc~c divided iuto two equal parts and the hippuric acid was determined in each. IVeight of hiypuric acid 1st cxpcrimciit 1-49619. ; 2~cIexperi-IllCLlt 1-42 gr. l3HNCl3 JONES ON IIIPPURIC AND Tlic dctcrininatioii of the amouiit of uric acid iii a11 the follow-ing cxpcrimciits (exccpt in experiments 13 I-+ 15 IG) was madc after tlic liippuric :lcid 1iml heen cxtractcd by ctlicr. Tllc syrupy rcsidnc was then dilutctl with a littlc water riiicl filtcrcd 2L hoitrs nftcrwartls.‘l’hc uric acid was dissolved in soda prccipitated by hydrocliloric acid atid collcctccl 24 lioiirs afterwards. In cxpcrimciits 13 1#11, 15 and 16 a srq)amtc qiiaiitity of urine was takcti to which Iiydrochloric acid was nddccl and aftcr stand-ing 218 hours tlic uric acid was collected on cz filter. Two hc;iltliy mcn wcrc tlic subjccts of the cspcrimcnts. Thc dict of A wlio wcigliccl lost. 121l)s. was breakfast (84a.m.) tea brcntl and huttcr; luiiclicon (1 pm.)bred aiid httcr ;tlinncr (54 pm.) (z pound mil a-’half of mcat bred and tca; supper (9p.m.) bread and clicesc and pint of beer. Modcrate cscrcisc was taken. Thc dict of 13 weighing 14st. Blbs. was lircakfmt (9am.) about 8 poiuitl of mcat lircad buttcr and tea; tliiincr (7 pm.) :illout onc poiin(1of nicat aiid somc vcgitaMcs witli Imiicly and watcr or tea.Vcry littlc cscrcise was taken. Firstly cxpcrimcnts mrc madc on the total quantity of hip-puric acid cscrctccl in 24 hours. A. The total ainount of nrine passcd in 24 hours was 930 cc.; sp. gr. 1022. 4.00 cc. wcrc takeii for tlic rletcrmiiiation of tlic liippuric acid. Tlic uric acid WH lost by nccitlent. TVciglit of liippiiric acid 2-64 grs. Heiice 930 cc. coiitaiiicd liippuric acid 6.1 grs. A. The total anionat of urinc )mwcd in 2 1t lioui*swas 980 cc. ; sp. gr. 1020. it00 cc. wcrc tiilccii far thc clctcr~iiirintionof thc liippuric acid. Wciglit of liippric nciil 1-68gr. ; wciglit of tlic uric acid 3.44grs. fleucc the 080 C. contain liippiiric acid 8L-1grs.; uric acid 8.L grs.A. Thc total amount of uriiic passed in 2 4 hours wns 790 cc. ; sp. gr. 1022. Weight of liippuric acid 2-12 grs. ;wcight of uric acid 3-60 gr.;. TIcncc tlic 700 cc. contain hippuric acid 4.7 grs. ; uric acid 7.1 grs. Ilcncc tlic claily cscrctioii of A iii thc tlircc cspcrimcnts mas 1cl. 2ud. 3rd. 3lcan. IIippnric acid . 6.1 grs. 4.1 grs. 4.7 grs. 4.9grs. Uric acid . . -3.4 p.7.1 grs. 7*7grs. UrLIC ACIDS IN I?EALTnY URINE. 13. Thc totd nmount of iujnc pnwxl by 13 ill 24 1lolil-s was 1160 cc. ; sp. gr. 1017. 400 cc. wcrc talicii for tlic clctcmiiiiatioii of thc 1iipI)uric scitl. Weight of hippnric acid 2.00grs. ; weight of uric acid ,l*G0grs. Ilcncc the 1 160cc. contain hippiiric acid 7.3grs.;uric acid 1.E.Ggrs. B. Tlic total amount of urine passcd in 2 L hours was 1103 cc. ; sp. gr. 1Oi9. Wcight of hippiirk acid 1st cspcrimcnt 2.00grs. ; 2nd cspcri- incnt 2-12 grs. TVciglit of uric acid 1st cspcriment 3% grs. ; 2nd csperimcnt 4.00grs. IIencc tlic 1103 cc. contain- 1st csp. 2nd exp. Mcan. IIippuric acid . 5.5 grs. 5.8 gra. 5-65 grs. IJric acid . . 10.8 grs. 11.0 grs. 10.9 grs. l3. Thc total amount of urinc passcd in 21 hours was 1510 cc. ; sp. gr. 1017. 400 cc. wcre taken for the dcterminatioii of tlic hippuric wid. Weight of hippuric acid 1st cxpcriment 1-98gr. ; 2nd csperi- rnent 2.08 grs. Weight of uric acid 1st cxperimcnt 3-43 grs.; 2nd expcrimcnt 3-54 grs. IIcncc tlic 1510 cc. contain- 1st exp. 2nd cxp.Mcan. I-Iippwic acid . 7,405 grs. 7.8 grs. 7.6 grs. Uric acid . . 13.0 grs. 13.3 grs. 13.1 grs. C. Tlic total amount of urinc passed in 2& hours mas 1326 cc. ; sp. gr. 1019. 400 cc. were taken for thc determination of thc hippuric acid. Weight of hippuric acid 1% gr.; weight of uric acid 3.80 grs. IIcnce thc 1326 cc. contain hippuric acid 5-8 grs.; uric acid 12.5 grs. EIcnce the daily excretion of B in the four cxperiments was-1Bt. 2nd. 3rd. 4th. Mean. IIippuric acid 7.3 grs. 5.6 grs. 7.6 grs. 5.8 pa. 6.5 grs. Uric acid 14%grs. 10.9grs. 13.1 grs. 12.5 grs. 12% grs. Secondly to determine the variations in the amount of hipiuric and uric acids in the urine passcd before and after food a long scrics of expcriments mere niadc with the urine of B.In the following €our experimeuts 400 CC. of' urinc passcd bcfore and aftcr food were taken Experimeiit 1.-Bcforc fod sp. gr 1016;wiglit of liippuric acid 1.52 gr. ; wciglit of uric acid 2.70 grs. After food sp. gr. 1018; wiglit of liippuric acid 2.70 grs. ; weight of uric acid 444 grs. Experiment 2.-13cfore food sp. gr. 1013 ;weight of hippiiric acid 1-10gr. ; wight of uric acid 2-80grs. After food sp. gi.. 1019; weight of liippuric acid 1.94 gr.; weight of uric acid 4.78 grs. Experimcnt 3.-Bcfore food sp. gr. 1016; wcight of hippuric acid 1-12 gr.; weight of uric acid 3-46grs. After food sp. gr. 1019;’ weight of liippuric acid 3.88 grs. ; weight of uric acid 5-32grs. Esperiment J.-Bcforc food sp. gr. 1013;weight of hippwic acid 1-38gr.;n.eiglit of uric acid 1.92 gr. After food sp. gr. 1018; weight of hippuric acid 3-60grs. ; weight of uric acid 3-00grs. In the next six experiments 350 cc. of uriiic were taken Experiment 5.-Before food sp. gr. 1014; wcight of liippuric acid 1.46 gr.; wciglit of uric acid 2%2 grs. After food sp. gr. 1016 ; weight of hippuric acid 1.94 grs.; weight of uric acid 3-80grs. . Experiment 6.-Before food sp. gr. 1013,; wcight of hippuric acid 2-02grs.; weight of uric acid 0.68 gr. After food sp. gr. 1012; weight of hippuric acid 1.20 gr. ; weight of uric acid 2.08grs. Experimcnt 7.-Beforc food sp. gr. 1019; weight of hippnric acid 3*0f grs.; weight of uric acid 3.43 grs. After food sp. gr. 1014; weight of hippuric acid 2.84 grs.; weight of uric acid 2-84grs.Experiment &-Before food sp. gr. 1012; weight of hippuric acid 1*12 gr.; weiglit of uric acid 1014gr.. After food sp. p. 1013; weight of hippuric acid 1.62 gr.; weight of uric acid 2.24 grs. Experiment O.-Before food sp. gr. 1019;weight of hippuric acid 1*4%gr.; weight of uric acid 3:90 gr. After food sp. gr. 1.017; weight of hippuric acid 1.97 gr.; weight of uric acid 2-30grs. Experiment lO.-Dcforc food sp. gr. 1012;weight of hippuric acid 1.01gr.; nciglit of uric acid 0.10 gr. After food sp. gr. 1016;wcigtit of hippuric acid 1.01 gr. ;weight of uric acid 1.88gr. Experiment 11.-376 cc. of urine pasveil before and after food wcrc taken. Heforc food sp. gr. 1020; wciglit of Lippric acid 1.-41 gr.; \wight of uric acid 2-92grs. lifter fd sp. gr. lOlG wcight of hippuric acid 1-18gr.; wcight of uric acid 2-94grs. Experiment 12.-Before food sp. gr. 1022;~eightof hippuric acid 1.36 gr.; weight of uric acid 2.56 grs. After fcrd sp. gr. gr,; wcight of uric acid 102% ; wciglit of hippuric acid 1*9& 4-92grs. Experiment 13.-570 cc. of urine passed bcforc and after food were taken for the determination of the hippuric acid ; arid 190CC. of urine passed before and after food were taken for thc determi- nation of the uric acid. Before food sp. gr. 1014; wight of hip-puric acid 1.20 gr. ;weight of uric acid in 190 cc. 0.61 gr. ;ditto in 570 cc. 1-83gr. After food sp. gr. 1015; weight of hippuric acid 2-02grs. weight of uric acid in 190 cc.1.32gr.; ditto in 570 cc. 3-96 grs. Experiment 14.-380 cc,. of urine passed before food were taken for the determination of the hippuric acid and 240 cc. for uric acid. 380 cc. of urine passed after focil were taken for the deter- mination of both. Before food weight of hippuric acid 3.80 grs. ; weight of uric acid in 2pO cc. 2-26 grs ; ditto in 380 cc. 3.50grs. After food weight of hippuric -acid 2.26 grs. ; weight of uric acid in 380 cc. 4060grs. Experiment 15.-300 cc. of uriue passed before food mere taken for the determination of the hippuric acid and 200 cc. for uric acid ;300cc. of urine passed after food were taken for the deter- mination of both. Before food weight of hippuric acid 2-00grs. ; weight of uric acid in 200 cc. 1-20 gr. ;ditto in 300 cc.1-80gr. After food weight of hippuric acid 1.18gr.; weight of uric acid in 300 cc. 2-30grs. Experiment 16.-127 cc. of urine were taken before food for the determination of the hippuric and uric acids and 150 cc. of urine were taken after food for the determination of the hippuric and uric acids. Before food weight of hippuric acid in 127 cc. 1-01gr.; weight of uric acid in 127 cc. 1.24 gr. After food weight of hippuric acid in 150 cc. 1-10gr.; ditto in 127 cc. 0.93 gr.; weight of uric acid in 160 cc. 1.68 gr.; ditto 127 cc. 1-42gr. Experiment 17.40~~. of urine were taken before food far the determination of the hippuric and uric acids and .244 cc. of urine mere taken after food for the determination of the hippuric and uric acids.Before food sp. ‘gr. 1013; weight of hippuric acid in 400 cc. 1.80gr. ; weight of uric acid in 400.c~. 2.5%grs. After (SG DENCE JONEFI ON IfIPPPURIC AND food sp. gr. 1023 ; weight of hippuric acid in 244 cc. 3.00 grs. ; ditto in 400 cc. 4.90 grs. j weight of uric acid in 244 cc. 3.78 grs. ; ditto in 400 cc. 6-19 grs. Hence there were in 1000 cc. of urine before food and in 1000cc. of urinc after food,-BEFORE FOOD. AFTERFOOD. Exp. Sp. Gr. Grs. Sp. Or. Grs. 1. Hippuric acid 1016 3.8 .. 1018 6.7 hippuric acid Uric 9 9) 6% . . , 11.6 uric J7 2. Hippuric , 1013 2.7 .. 1019 48 hippuric , 97 Uric ,> 79 7.0 .. 9 11.9 uric 3. Hippuric ) 1016 2.8 .. 1019 9.7 hippuric J Uric 9 >J 8-6 .. JJ 13.3 uric ,9 4. IIippuric , 1013 3.3 ..1018 9.0 hippuric , >I Uric 7 99 4.8 .. 9 7.5 uric 5. Hippuric , 1014 4.1 .. 1016 5.5 hippuric , Uric >> 9 7.4 .. , 19% uric 99 6. IJippuric , 1012 5.7 .. 1012 3.4 hippiiric ) Uric J ,Y 1.9 .. , 6.7 uric 97 7. Hipywic , 1019 5-8 .. 1014 8-1 hippuric J Uric ,J ,> 9.8 .. , 8.1 uric J? 8. Hippuric , 1012 3.2 .. 1013 4.5 hippuric , Uric , ,J 3.2 . . 6.4 uric ,> JI 9. Hippuric , 1019 4.1 .. 1017 5.6 hippuric , 3, Uric 9 > 4.2 . . JJ 6.5 uric 10. Hippuric , 1012 2.8 .. 1016 2.8 hippuric , Uric ,> 9 0.2 . . , 5.3 uric >I 11. Hippuric ,J 1020 3.7 .. 1016 3.1 hippuric , Uric 7.7 .. , 7.8 uric ,> JJ 99 12. Hippuric , 1022 3.6 .. 1025 5.1 hippuric , 11 uric 9 , 6.8 .. , 13.1 uric 13.Hippuric , 1014 2.1 .. 1015 3.5 hippuric , 1) Uric 9 J 3.2 .. J 6.9 uric 3> 14. Hippuric ,# 10.0 .. , 5.9 hippuric , uric 1 , 9.4 .. )) 12.1 uric 9 15. Hippuric , 9 6.6 .. ? 3.9 hippuric , 99 uric , 9 6.0 .. , 7.6 uric 16. Hippuric , 7.9 .-, 7.3 hippuric ,, ,J J, Uric , YY 9.7 . . ,Y 11.2 uric 17. Hippuric , 1013 4.5 .. 1028 12.2 hippuric , Uric J7 URIC ACIDS IN HEALTHY URINE. Hciicc the average in 1000cc. of urine bcfore food is-sp. gr of urine 1015*3-hippnric acid 4.51 grs; uric acid 6-05grs. After food sp. gr. 1017.2; Eiippuric acid 5-94!grs. ; uric acid 9.48 grs. It follows from these two series of experiments on the quantity of liippiwic and uric acid excreted in twenty-four hours and on the increase or diminution of the hippuric and uric acids in the urine after food that in 24 hours :-1.The lighter nian gave 496 grs. of hippuric acid and 4.714 grs. of uric acid; thc mean quantity of urine being 1.25 pints. The heavier man gave 6.5 grs. of hippuric acid and 11.6 grs. of uric acid ; tlic mean quantity of urine king 2.37 pints. 2. The hippuric acid was increased on froni 4.51 grs. per 1000cc. urinc hcforc food an average in the to 5-94grs. , , after food heavier man Whilst the uric acid ,> , before food increased after food was on to 9.45 grs. an average ,, ,, Licbig states,” that all the urinc that hc examined of persons living on mixed diet contained about equal quantities of hippuric and uric acid. Parkes in his work c‘ On the Composition of the Urine,” p.12 gives the amount of uric acid found by fourteen observers in the urine secreted in 24 hours. The lowest quantity was 4.32grs. and thc highest 14*40grs. The mean of all the observations together was 8.5 grs. of uric acid in 24 hours. As yet I have made only a very few experiments on the amount of hippuric acid present in the urine in diseased states of tbc body. Souchar dat in the ‘:Annuaire de Th6rspeutique” for 18442 p.285 speaks of a disease which he calls “hippurie.” A case resembling his description was met with in St. George’s Hospital. The urine was vcry dilute of ycllowish colour and fcebly alkaline reaction. 4420cc. of urine contained only traces of hippuric acid. fn a case of acute rheumatic fever thc sp.gr. of the urine was Ann. Ch. Plinrm. 50 p. 1’33. ADIE ON GROUKD ICE. 1010 ; it had a brown yellow colour and acid reaction. 350 cc. of this urine contained a vcry small quantity of liippuric acid. In a case of diabetes (sp. gr. of the urine 1040) 4.00 cc. of urine were examined for hippuric acid but only traces were fdund. These experiments only show that a far more extended inquiry is requisite to find the variations of liippuric acid in discasc. In conclusion I must express my obligation to Dr. Ulricli for the care lic took to make these results as accurate as possiblc.

ISSN:0368-1769    

DOI:10.1039/JS8621500081

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

ADIE ON GROUKD ICE. XVII.-Un Ground Ice. By RICHARD ADIE,Liverpool. INa note to the paper on this subject which I last year submitted to the Chemical Society Dr. Franklaud has referred to the phenomenon of ground ice as well known to take place in rapidly flowiug streams and as having for its origin a source which I imagine to be similar to that adduced by -M. Arago in his paper on this question in the (c Annuairc ’’ for 1833 namely ‘‘ the aptitude to the formation of crystals of ice on stones and asperities of the bottom cooled to 32O F.” I wish to return to the subject to state that the district where ground ice is to be found very much more frequently than in any other place with which I am acquainted is called “Altcar,” about 11 miles north of Liverpool.Here I have found it twice during two moderate frosts of the present month of January 1862. The country there is flat with wide slow-flowing ditches separat- ing the fields and no hedge-rows or fences. Here two nights’ moderate frost appear to be sufficient to cool down the water on the surface of these ditches to near 3R0F. When this occurs therc is a supply of ice-crystals derived chiefly from a fringe of them along the edges which are seen to be continually detached and floated down with the current. Now it is to these crystals that I attribute the lodgments of ice for they are found in the places most suited to their detention without any reference to the expo- sure of the surface-for example where a stream sweeps round a turn or corner the weeds or plants there are sure to be the first to contain submerged ice.Oii tlic surfacc tlwc is a supply of aspcritics for tlic fcwniation of crystals at thc cdgcs nibrc thi at any 0th part of tlic stream; and as tlic temperature is often tcii tlcgrccs lo\vci* at tlic surfrtcc thfii it call hc'uiider water this vicw of the question is in accordance witli all the observcd facts. On tlic 1st of January I csaniiiicil a strcam lccally kno~rnby tlic name of The Brook," a tri1;utnry of tlic rivcr Alt aid found ice on thc plants in the bed of thc stream at places favourable to its detention; somc of it had a soiled aspect and contained many air- bubbles giving cvidencc of two or three days age. The frost was of a mild character but of scveral claps' duration.Surface ice on stagnant pools was trustworthy to walk on only where thc water was sliallow. On the 22nd of January I again visited the Altcar district after a second frost of a few days' duration had been established. At this time the thermometer had ranged six to eight dcgrees below 32" on thc Fahrenheit sale accompanied by a brisk piercing wind. Therc was abutidance of ground ice in the tributary and also in tlk river Alt where I had not before .found it Iii some parts where on former occasions ground ice had been plentiful at the present time surface ice covered everything; but it showcd that) while forming it had received large supplies of the ground ice. This I particularly remarked around and undcr the arch of cl narrow bridge where a quantity of spherical-shaped masses such as collect on the plants that twist and turn in the bed of a stream had bcen floated into a mass stretching across the surface and tlierc frozen iut.0 strong ice.I remember having seen a remark that in somc districts ground ice is a characteristic of the beginning of a frost of which the above observation gives a confirmatioxt; and I have no doubt that a quick sharp frost would cover the waters in Altcar with surface ice to the exclusion of the formation of ground ice but I have not been in the neighbourhood on such an occasion to examine them. The early period of the winter at which it has been recorded that ground icc was abundant is another proof that it belongs to thc beginning of a frost.A friend of mine wrote from Hawick under date 17th Novevber 1841 that he had seen ground ice m abundancc in the river Teviot. This fact of ground ice making its appearancc at the early part of a frost strongly favours the view that it is dcrivecl from edge-formed crystals for this is the place u~licrcon cvcry occasion the ice will first form. Dr. Farquhzrson wlio described the groimcl ice in tlic ditchcs of Lincolnshire in the c( Transactions of the Royal Society,” all-pears to have hail a district as favourable for showing it as A1tc:ir. The reason why streams of a flat country are so much more quickly cooled to near the freezing point than those of a more uneven surface is that they are free from underground supply either from natural or artificial sources.I can remember examin- ing a slow-flowing stream which received the water of many tilc drains; this during a severe frost ran in the centre as clear as in a midsummer day with only a light fringe of ice crystals along the edges. I In the valley of the Tay and some of the northerii rivers of tlic island the people resident say that a frozen fog is a freqent prc- cursor of ground ice. While examining the Altcar ground on tlic 1st of January I had a palpable proof of the immense quantity of ice-crystals a mooded district mould supply to a str*-nni running undernertth the branches of the trees. The weather at the close of the year was foggy the night frosts covering vooded districts with beautiful displays of ice-foliagc.For two or three successive days the sun’s rays had pover so far torelas the frost that the ice fcll from the branches to the frozen ground. When on the ground thc ice did not melt much. The branches were thus daily pre- pared to receive a fresh supply from the frosty and foggy night air. In this manner n large quantity of ice-crystals had collected in the shade of every tree aud these be it obscrved were more available for ground ice in a stream than if they had been supplied by snow for in the latter case the surrounding cowtry is covered and the streams reccivc water as if from drains. Some ycars ago when I first examined ice in the beds of strcams I held the opinion ihtthe temperature of 3.2’ was indis-pcnsnble for its appearance and prescrvatiou. Prom mow recent experiments I am of opinion that thc ground ice may h: preserved and be lodged with the water oi the strcam from tlircc to five-tenths of a dcgrce of Fahrenheit abovc thc freezing point when the temperature of the external atmosphere is low enough to form ice-crystals at the surface along the edgcs.

ISSN:0368-1769    

DOI:10.1039/JS8621500088

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

91 XYIII.-On the occurrence of comiderable Deposits of Crystallirecl Phosphate of Lime in Teak-wood. By F. A LIBEL, F.R.S. THEwood of thc Tectona gratzdis which is imported from the south of India and a few other tropical countrics has becn \-cry cstensively employed within the last few years in connexion ivith military equipmcnts (for example in the construction of gun-carriages packing cases kc.) required for use in tropical climatcs as it is greatly supcrior to other descriptions of mood in its polver of rcsisting the destructive effects of extreme changes of tempera- t11re. In the reduction of the large hlocks of teak-wood to planks and small timber deposits of a white substance sometimes soft and pulverulent at other times so hard as quickly to blunt thc cutting edges of the saws cmploycd are constantly met with intersecting tlie mood in the forni of layers converging towards the centrc OF Iicart of the tree from which point they usually start.Thesc layers or deposits are often several feet in leiigtli (some havc been found to estciid more than six feet) and measure six or eight inches in breadth the thickness of the layers varying from one-eighth to three-eighths of an inch. Where thcse layers occur they have evidently been pdually deposited in flaws or cracks (so called shakes) which hare formed in the living tree. Cavities occasioned by knots in the wood are frequently lined or filled with the same white deposit; as are also the perforations of considerable size and length which are constantly met with in the teak-wood and which owe their existence to the labours of a large caterpillar.The remains of huge moths into which these insects have become transformed are occasionally found in tlie mood; the bodies of these consist of a ceraceous substance which on examination was found to exhibit the general properties of the product of the long-continued action of moisture upon fatty matters known as adipocerc. The white dcposit the occurrence of wliicli has just bcen described exhibits occasionally a very distinct striated crystalline structure and sometimes consists of conglomerates of small nciculilr crystals easily distinguished by the aid of a microscope of low power. It is readily soluble in dilute acids with separation of a very small quantity of organic colouring rnattcr.Effer- vescencc is not gcnerdly obscrvablc on dissolving tlic suhtancc but on the application of a very gentle hcat to the solution zt minute quantity of carbonic acid gas is disengaged. The analysis of an average specimen of this deposit dricd in VUCZIO yicldecl the following per-centage results :-Limc 34.04per ccnt. 3kgnesia . 1.86 , Ammonia . 1.12 , Phosphoric acid . . 43.35 f) Carbonic acid . trace Water and EL minutc pro-portion of organic matter 19.54 , From thc relations which the small proportions of magnesia and ammonia included in the above results hcar to each other they evidently exist in the substance in the form of ordinary am-monio-phosphate of magnesia 2Mg0 .NI3,O . PO + I2 Aq :-1.86 per cent. of magnesia in this form mould require 1.20 per cent. of ammonia; the per-centage obtained was 1-12. By calcu-lating from the per-centage of magnesia the proportion of the above double-salt existing in admixture with the phosphate of lime thc folIowing numbers are obtained :-Magnesia . . 1-86per cent. Ammonia . 1-20 , Phosphoric acid 3.35 J 'Water . . 5.02 )) The amount of ammonio-phosphate of magnesia present in the specimen analysed would therefore be 11.43 per cent. De-ducting the above numbers from the analytical results obtained the following proportions of phosphoric acid lime and water remain :-Lime . . 34-04 Phosphoric acid . . 40.00 Water . 14.52 which calculated upon one hundred parts yield the following numbers :-Lime .b . 38.44 b Phosphoric acid . . 45.17 Watcr . . 16.39 100~00 Tlic proportions wliicli the acid and base bcnr to each other in these numbcrs admit the conclusion that the form in which they are coni1)incd is in the proportioii of two equivalents of lime to onc of phosphoric acid the lime being about tlirce per cent. in cxcess of the amount required to form a salt coiitcliiiing two equi- valents of the base while it is more than twelve per cent. below what would be required to form a tri-phosphate. I was at first disposed to regard tliis phosphate of lime which as above statcd frequently exists in the form of distinct crystals as the crystallized ili-phosphate which may be produccd by adding lime-water to the acid phosphate of lime CaO .2HO .PO, by dis-solving lime in a slight excess of phosphoric acid or by digesting the amorphous tri-phosphate of lime with a proportion of ail acid such as hydrochloric acid insufficient for its solution. But the com- position of this salt which Bodeker describes as containing four equivalents of water of crystallization (2CaO . HO . PO +4 Aq.) does not accord with the numbers obtained." On comparing them however with the per-centage proportions required for a di- phosphate of lime of the formula 2 CaO . HO . PO,+2 Aq. con-taining therefore two equivalents less of water of crystallization than the salt described by Biidek er they correspond pretty closely particularly when it is remembered that a small proportion of the lime discovered in the deposit existed in the form of carbonate.TIie following is a comparison of the per-centage results with the numbers demanded by the above formula 2 CaO . HO . PO +2 Aq. :-2 CaO .. 56 .. 36.13 .. 38-44 PO5 . . 72 . . 46-45 . . 45-17 3 HO . . 27 . . 17.42 .. . 16.39 -155 1or3.00 It is however also not improbable that the deposits of phos-phate of lime which have been described and which vary con-siderably in the degree of crystalline structure exhibited may consist of variable mixtures of amorphous and crystallized di-phosphate of lime. In Gmelin's Handbook vol. iii. p. 195 the theoretical numbers given for comparison with the results of Bodeker's analysis of this salt are calculated upon four instcad of jive equivalents of water ; hence the results of that chemiat do not appear to agree well with the formula given whereas they accord closely with thoee demanded by the formula 2 CaO. HO PO5 + 4 Aq. VOL. xv-4

ISSN:0368-1769    

DOI:10.1039/JS8621500091

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

94 XIX-On the Chemical Constitution and Artijcial Formation of Taurine. By HERMANN KOLBE,of Marburg. Som years ago Streck er* made the interesting observation that isethionate of ammonia when heated to 210" C. gives off water and is converted into taurine. By this discovcry as well as by the mpre recent observation of Gib bs,t that taurine treated with nitrous acid is reconverted into isethionic acid the existence of intimate relations between taurine and isethionic acid was placed beyond doubt; but the question relating to the chemical constitution of taurine with which that of isethionic acid is closely connected still remained undecided. That taurine is not the amide of isethionic acid is sufficiently shown by its behaviour with hydratesf potash which doe$ not cliniinate ammonia from it till heated to the melting point and then completely decom- poses it.I believe that I have found the key to the solution of this problem by an experimental confirmation of the conjecturc which I threw out a short time ago,t that taurine is related to isethionic acid in the same manner a alanine to lactic acid. In the same sense that the two last-mentioned bodies may be regarded as derivatives of ethyl-carbonic (propionic) acid that is to say alanine as amido-ethyl-carbonic acid and lactic acid as oxy-ethyl- carbonic acid,-so likewise may taurine and isethionic acid be viewed as derivatives of ethyl-sulphuric acid namely taurine as amido-ethyl-sulphuric acid and isethionic acid as oxy-ethyl-sul- phuric acid these relations are exhibited by the following formulae HO*C4H5[c,p,Io HO*C,H5[S,O+I 0 Propionic acid.Ethyl-sulphuric acid. * Ann. Ch. Pharm. xci 101. I. Jnhresbericht dcr Chemie xi 650. Ann. Ch. Pharm. cxii 241. KOLB15 ON TACTRlNE. I'o tlic assumption that taurinc and Rlaninc arc so nearly related to cacll othcr as tlicsc formulac indieatc it may be objected that taurinc docs not posscss thc power which is common to glycocinc alanine lcucine aspartic acid,. amidobenzoic acid and amido-acids in gencral of forming salinc compounds both with bases and yith acids. nut indcpcndcntly of the fact that the organic deri-vatives of sulphuric acid diffcr in many points from those of carbonic acid thc following consideration is of especial importance in conncction with thc present inquiry.It must in the first place be presumed that by tlic introduction of amidogcn into the ethyl-molccule the acid propcrties of ethyl- sulphuric acid will be wcakenccl in the samc degree asin alanine the body dcrivcd in likc manner from ethyl-carbonic (propionic) acid. But inasmuch as ethyl-siilphuric acid is a stronger acid than propionic acid it is not surprising that even the weak basic pro-perties of amidatcd propionic acid should be wanting in the amichted ethyl-sulphuric acid.* On the othcr hand this latter acid might 1)c expectcd to exhibit properties which have not hitherto heen actually observed in taurine. Guided by these considerations I liavc made several experiments with pure taurine prepared from ox-bilc the results of which I will here briefly communicate.Taurinc dissolwd in fuming hydrochloric or strong nitric acid crystallizes unalterccl from the solution on evaporation ; moreover it docs not increase in weight when exposed to an atmosphere of dry hydrochloric acid gas either at ordinary temperatures or when heatcd. In order to determine whether taurine like alanine is capable of forming crystalline compounds with salts I mixed thc concentrated aqueous solutions of equivaIent quantities of taurine and chloride of potassium and abandoned the solution to spontancous evaporation purc taurine then crystallized out first aid afterwards chloridc of potassium. Neither does thc hydro- chloric acid solution of taurine yield any compound with bichloride of platinum alcohol added to the solution producing a precipitate of pure taurine.It appears therefore that taurinc does not exhibit the basic properties possessed by other amido-acids; but on the other hand it is by no means destitute of the power of uniting with * 3Icthyl-sulphuric acid tlic analogue of acctic acid does not yield marsh-ps when treatcd with soda-lime ; ncither does benzyl-solphuric acid the analogue of ljenzoic wid yicld 1)enzolc whcn thus trcated. Other examples of thcse differences of charnctcr arc stTurtled by the obscrvations lately communicated by Vogt (;inn. Ch. Pharm. cxix 143) and Kellcr (ibid 153). KOLUE ON TIlE CONBTITUTlON AND bases; ad dthaugh I have not succecded in preparing salts of taurinc in tlic solid form the followitig expcrimeiits show that it is really capable of forming such compounds.A saturated aqueous solution of tatirine in which absolute alcohol immediately prduccs a copious precipitate is iict’ precipi- tated or even clouded by a mixture of absolute alcohol and ammonia; but if the solution be then exposed to the air till the ammonia is volatilized the taurinc separates in beautiful crystals. Ncither is a concentrated aqueous solution of taurine containing frcc potash precipitated by absolute alcohol-a property which may hc successfully applied to thc separation of taurine from oklier compounds iusolublc in alcohol. Carbonic acid passcd into thc solution separatcs thc taurinc iii its original state.Hydrated oxide of lead is taken up in considcrable quantity by a hot aqueous solutioq of taurinc the clcar filtcrcd liquid becoming only slightly turbid on cooling. On exposurc to thc air it dcposits a considerable quantity of carbonatc of lcad. An aqu,cous solution of taurine does not dccomposc carbonate of lcail cvcri at tlic boiling hat. These rcsults show that taiirinc is by no mcnns an iiidiffercnt body as it bas hitherto bccn considcred but rstlicr a wcak acid the acid propertics of thc primary compound cthyl-sulphiiric acid being wcakciicd in it by thc substitution of amidogcn for hydrogcn to nearly the sainc extent as in trichloraniliiic tlie basic properties of anilinc are wedtencd by tlic introduction of chlorinc. The consideration of taurinc as anlido-ctliyl-sulphuric acid is further supported by its formation from isctliionic acid by a process analogous to that of alariine from lactic acid.CHLORIDE OF CIILORETIIYL-SULPIIU~I~ACID,AND CIILORETIIYL-SULPIIURIC ACID. If isethionic acid be really constitutcd similarly to lactic acid as above suggcstcil it may bc cspcctcd to exhibit under the iiifluencc of pcntachloridc of phosphorus a hiisformation similar to that of lactic acid yiclding in fact thc chloride of clilorethyl- sulphuric acid thus :-hctatc of potash. Chloride of Chloro-propionic acid. ARTIFICIAL FORMATIOX OF TAURINE. Ieethionate of potash. Chloride of Chlorethyl-eulphuric acid. It may further be expected that the chlorethyl-sulylmric acid resulting from the actiou of water on this chloride will be con- verted by appropriate treatment with ammonia into taurine just as the analogously constituted compound chloropropionic acid in thereby converted iuto alaniue HO.C,(Ff} [C,O,] 0+ 2H,N= H0.C4{&} [C,02] 0 + NH,Cl.Chloropropionic acid. Allmine. HO.C4 1"cfj ' [SQO,]0+ 2HjN=HO.C4 cf [S20,] O+ NH4Cl. (" 1 Chlorethjl-sulphuric acid. Taurine. These expectations have been completely fulfilled by the results of the following experiments :-To prepare chloride of chlorethyl-sulphuric acid 60 grammea (1 at.) of finely pulverized isethionate of potash dried at 100" C. were introduced together with 150 grms. (2 ats.) of pilverulent pentachloride of phosphorus iuto a capacious tubulated retort the two substances being mixed together as completely as possible with a bent glass rod.The mixture after a whilc begins to get warm and to liquefy and at length boils with copious evolution of hydrochloric acid fumes a large quantity of oxy-chloride of phosphorus distilling over at the same time into the receiver. If after this violent action is over the retort be gently herrted nearly pure oxgchloride of phosphorus distils over at first; afterwards when the heat is raised a much heavier mobile oily liquid having a strong pungent odour passes over in sotnewhat considerable quantity. This liquid consists mainiy of the chloride of chlorethyl-sulphuric acid while in the retort there ultimately remains a dry blackish saline mass. The chloride of chlorethyl-sulphuric acid which boils at about 200' C.may be easily and completely separated from the oxy-chloride of phosphorus by fractional distillation ; neverthelem I have not succeeded in preparing this compound quite pure apparently because a quantity of chloride of iscthionic acid C (zb,) [S,O,]Cl is formed at the same time which EOLBE ON TIIE CONSTITUTION AKD chloride boils at nearly the same temperature as the chloride of chlorethyl-sulphuric acid. A precisely similar obscrvation was made by myself and Dr. Lautemann with rcgard’to tlie distilla- tion of salicylic acid or salicplate of soda with pcntacliloride of phosphorus tlie cliloridc of salylic acid thereby produced bcing always more or less accompanied by chloride of salicylic acid.The distillate which passes ovcr in the rectification of the crude product at 200’ C.-at which the boiling temperature remains to a certain dcgrec statioiifirp-is a ncarly colourless heavy liquid wliicli fumes in thc air does not mix with water and has an intense and vei‘y persistcnt odour strongly recalling that of volatilc oil of mustard. Analysis gave the folloiving numbers 0.6% grm. buimt with oxidc of copper gave 0.346 grin. carbonic acid and 0.150 grm. water corrcsponding to 15.0p. c. carbon and 2.6 p. c. hydrogen. 0.5055 grm. passcd in thc statc of vapour over red-hot lime gave 0.7825 grm. chloridc of silver = 38.3 p. c. chlorine. 0.604 grm. passed over red-hot carbonate of soda whicli was finally heated in a streani of oxygen yielded 0-905grm.sulphate of baryta corresponding to 20.8 p. c. sulphur. The formula C {:fi [s,o,J CI requires Calculated. Found. -F c* 24 1.4-7 15.0 H4 4 25 2.6 s2 32 19.6 20.5 04 32 19-6 >9 71 425.6 38.8 Cl -163 100.0 The somewhat too large amounts of- carbon and sulphur shown by the analysis on the one hand and the great deficiency of chlorine on the .other (a product obtained in another preparation yielded 39.2p. c. chlorine) corroborate the suppositioii that the compound analysed contained R small quantity of chloride of isethionic acid. Chloride of chlorethyl-sulpliuric acid is but very slowly decom- posed by water at ordinary tcmperatures. A drop of it covercd with a large quantity of watw did iiot &appear completcly in ABTIFICIAL FOEMATION OP TAURIPE.the come of a week. Heated with watcr to 100"C. in a her-metically sealed tube it dissolves somewhat readily yielding hyErochloric and chlorethyl-sufphuric acid and losing its odow at the same time. It dissdves easily in potash with great evolution of heat ; also .in aqueous ammonia with abundant formation of sal-arnmoniac. Taurine is not produced in this last reaction but probably the amide of amido-ethyl-sulphuric acid. The solution of chloride of chlorethyl-sulphuric acid in absolute alcohol even after being heated in a hermetically sealed tube to 100" C. docs not yield any chlorethyl-sulphate of ethyl on addition of water. If the strongly acid solution obtained by heating the chloride of chlorethyl-sulphuric acid with water in sealed tubes for several days be completely freed from admixed hydrochloric acid by evapora- tion first over the open fire afterwards over the water-bath a thickish acid liquid is obtained consisting chiefly of chlorethyl-sulphuric acid.This acid forms crystallizable salts with oxide of lead oxide of silver and other bases. For the preparation of the pure acid I have used the silver-salt which crystallizes easily and in beautiful forms. The solution of the crude acid diluted with a moderate quantity of water dissolves carbonate of silver with effervescence. After it has been treated for a while with a slight excess of the carbonate of silver without heating but with frequent agitation the clear filtered saline solution which is very sensitive to the action of light and still more to that of heat is evaporated nearly to dryness in vacuo over sulphuric acid being at the same time protected from the light.The crystalline mass separated Gom the mother-liquor and' washed with a little cold water is well comminuted and re-dissolved in the smallest possible quantity of cold water and on again leaving the filtered solution to evaporate in vacuo the pure chlorethyl-sulphate of silver crystallizes out in large transparent rhombic prisms the mother-liquor yielding an additional quantity on further concentration. Analysis gave the following numbers 1.256 grm. of the silver-salt burnt with oxide of copper yielded 0.440 grm. carbonic acid and 0.182 grm.water = 9.5 p. C. carhon and 1.G p. c. hydrogen 1.015 grm. ignited with carbonate of soda in a strealn of 100 ROLRE ON TRI* CONSTITUTION AND oxygen yielded 0.987 grm. sulphate of haryta = 13.3 p. c. sulphur. 1*257 grm. precipitated with tiydrocliloric acid yiclded 0703 cldoride of silver = 45.1 pc. silver. The forinula AgO.C {:!t) [S,O,] 0 reyuircs Culcul3tcd. Found. 24.0w9.5 cJ*3 c4 H4 4.0 1.6 1.6 C1 35.5 14.1 -32.0 12.7 13.3 s2 0 48.0 19.1 -Ag 108.0 43.0 43.1 251.5 100.0 The aqueous solution of this salt is rapidly dccomposcd hy heat especially at the hoilirig temperaturc with separatio,n of chloride of silver isetliionic acid being doubtless reproduced ; but tllc decomposition is never coinplcte evcn aftcr the heating has been continued for several days.The aqueous solution of chlorctliyl-snlpli~iI1.icacid obtained by pracipitatirig the sil\-cr-saltwith sulpllurettctl hydi ogcn has a strong acid recction and sustains a boiling heat without altcration. IVhcn coiiccntratcd by cvalwration finally in vacuo over oil of vitriol; it crystallizes in long colourless prisms which are highly deli- quescent and niclt at a moclcratc Iicat. The salts of chlorctliyl-snlpliuric acid' arc easily and to all appearaiice conipletclp decomposed by boiling with free .alkali yielding a nietallic ciiloridc and probably an iset hionate. Car-bonate of potash produccs tlie same decomposition at thc boiling hat. Attempts to replace tlic chlorinc of chlorcthyl- sulp?iiiric acid by Iiydrogcn h;ivc; to ii ccrtain extent given negativc rcsults.The frcc aqueous acid hoiled with zinc gives off n large quantity of hydrpgcri witliout forming a trace of' hydrochloric acid. Addition of sulpliriric acid incrcnses the evolution of gas but even in this cnsc tlic Iijdrogen docs not remove ally chlorine from the acid. Xci thcr is iiiiy dccoml)osition produced iii tlic acid solutioii Ly the hydropi c~olvcdI)? il poncrfiil voltaic current \\ ith two anial- ARTIFICIAL FORMATION OF TAURINE. gamatetl zinc plates as the electrodes. Tlie replacenlent of the cliloriric by hydrogen is ho~vevc~ easily effected by the electrolysis of n weak alkalilie solution of an alkaline chlorethyl- sulphate or by treating the soh-salt in the cold with sodium- aiiialgain.In this respect chlorethyl-sulphuric acid exhibits considerable resemblance to the homologous compound chlormethyl-sulphuric acid which I obtained in 1845 from trichlormethyl-sulphnlic wid arid to which I then gave the name of chlorelayl-byposulphuric wid.* TAURINE It has already been observed that chlorethyl-sulphuric acid is conwrted into taurine by the action of ammonia. The trhas-formation is easily effected as follows Dry chlorethyl-sulphate of silver is sealed up in a strong ghsa tube with a large exceee of the strongest aqueous ammonia,* and the clear saline solution which is immediately formed on agitation is heated to 100" C. for several hours. The liquid remains unclouded but if subsequently evaporated over the water-bath deposits a considerable quantity of chloride of silver.The dry residue &solves in water with the exception of the chloride of silver ; the solution still retains a very small quantity of silver which is best removed by adding a drop of hjdrochloric acid immediately after the residue is dissolved. The clear sliglitly acid filtrate is evaporated to a small bulk and mixed with strong alcohol which precipitates a bnsiderable quantity of taurine. The crystalline precipitate thus formed always contains besides taurine a- variable quantity of another substance which when the whole ie recrystallized from water mixea with the beautiful crystals of taurine in small white opaque crystalline nodules ;this substance also gives off ammonia when boiled with potash-ley.I think it probable that this compound is the amide of taiwine mixed perhaps with the amide of isethionic acid '4 {262)-s204] N. H2 Ann. Ch. Pharm. liv 168 ff. t With alcoholic ammonia the product obtained irs not trurine but roother crystalline compound not yet investigated. KOLBE ON THE CONBTITUTION AND TOremove this adventitious snbstancc the impurc tnirrinc pe-cipitatcd by alcoliol wslioilcd with pot:isIi-lep (iii aiiotller lwep ration tlic s:Ac trcatmclit vas iiiixiicc~iatc~y :Ippliec\ to tlre c:riitle solution of taurkc filtcrcd from the cltloridc of silver nf'tcr addition of liyilrocliloiic acid) till thc odour of ainnioiiin was 110 longer perceptihlc and the liiglily coiicentrntcd alkaliiie soliitioii was then mixed with about twenty timcs its volunic of a1)solutc alcohol which as already rcmnrked does not prccipitatc tniiritic from its alkaline solutioiis.Tlic clear filtrate diluted with watcr evaporated slightly rrcidulatcd with liydrochloric acid and again evaporated to a small bulk yiclds on ndditioii of a lnrgc qlliliitity of strong alcohol a copious crystallinc precipitate of taurinc coii-taminated only with a small quaiitity of cliloriclc of potassium. A better method of precipitating tlic t aurine from its nlkaliiic alcoholic solution might perhaps be to pass carbonic acid iiito it. By recrystallization from water it is iiltimatelp obtaiiicd in large hard crystals and perfectly purc. .I have subsequently found that the crude clilorc~liyl-sulplilu.ic acid obtained by treating the chloride of clilorethyl-sulpliuric acid with water may be used instend of tlic silwr-salt for the prcparn- tion of taurine.The liquid after being frced by cv:il)oration froin admixed hydrochloric acid is to bc iicntralizctl wit11 aii~Ii1~1~ii1 aid the ammonia-salt evaporated to dryiiess aiid licntcd for some tinic to 100' C. in a liermctically senlcd tiillc with ~SCCSSof sntilriitccT aqueous ammonia. The resulting solution is thcn to be treated in the manner above described excepting that the larqcr quantity of sal-ammoniac which it contains must be rcmoved by hoiling with hydrated oxide of lead. Taur-ine prepared by either of these processes agrees iii every respect with that which is obtained from ox-bile as I hnvc con-vinced myself by comparative esperirueuts.Aualpis gave the followiiig numbers 0.3855 grm. taurine burnt with oxide of copper iii a tube containing chromate of lead and metallic copper at its OFCI~ ciid finally in a stream of oxygen gave 0.2715grm. carbonic acid and 0-199 water =19.3 p. c. carbon and 5.7 p. c. hydrogen. 0.3955 grm. ignited with carboiiate of soda in a stream of oxygen vieldsd 0.743 grm. sulphate of 'baryta =25.8 p. c. of sulphur. ARTIFICIAL FORMATION OF TAURINE. The formula I10.C4 I&[ [S20,]0 requires Calculatcd. Found. - c4 2-L 19.2 19.3 H 7 5.6 5-7 N 14 11-2 -32 25.6 25.8 s2 48 384 -06 125 100*0 Glycocinc C4H5N04,and taurine C4H,NS20, which exist in bilc togethcr with cholalic acid-doubtless in the same state of combination 11s glycocine and berizoic acid in the hippuric acid of urine-appcar like heterogeneous compounds mlien regarded merely according to their empirical formula ; nevertheless they arc nearly related to one another as shown by the simple mode of formation of taurine just described.If glycocine be regarded as amido-acetic acid that is as carbonic acid in which one of the extra-radical oxygen-atoms ie replaced by amido-methyl then taurine must be regarded as an analogous derivative of sulphuric acid excepting that one of the extra-radical oxygen-atoms is replaced by amido-ethyl instead of by amido-methyl as shown by the following formulze Ctlycocine. Taurine.Since it is known that bcsidcs glycocine many similarly con-stituted homologous dcrivatives of the fatty acids-especialiy leucine (amido-propionic acid)-are widely diffused in the auirnal body the observation that tlie functions 'of taurine in the bile- compounds is precisely similar to that of glycocine lends some degree of probability to the supposition that the animal body coiitaixis besides tatwine other similarly constituted liomologoue dcrivatives of sulphuric acid especially amido-methyl-sulphuric acid tiic direct aiialogue of glycocine and amido-arnyl-sulyhuric acid analogous to leucine both of which compounds perhaps enter into the composition of many animal substances rich in sulphur such as horn hair &c. 104 GORE ON TRE DETERMINATION Ok’ N0.C2 [C,O,]O 1( [S,0,10 IIO.C iII,K Amido-methyl-carbonic acid.Am ido-methjI-sulpliuric acid. (Glgcocine). HO-C.4 {J&)cc20*10 HOG &) [S,O,IO Amido-ethyl-carbonic acid. Amido-cthgl-sulphuric acid. (itlanine). (Taurine). HO-C, g;&! HW g$j![S20*30 [C*0*10 Amido-amyl-carbonic acid. Amido-amyl-eulphuric acid. (Leucine). I regard it as by no means a thankless problem to search for these and other compounds homologous and analogous to taurine in the animal body and especially in the secretions which are peculiarly rich in sulphur. From the above-described mode of formation of taurine we might also expect that the artificial preparation of these other compounds moulcl not be difficult. I am at present engaged with the attempt to convert chlormethyl- auiphuric acid-a compound very closely resembling chlorethyl- sdphuric acid-by the action of ammonia into amido-methyl- sulphuric acid an acid which may be expected to exhibit con-siderable resemblance to taurine.

ISSN:0368-1769    

DOI:10.1039/JS8621500094

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

GORE ON TRE DETERMINATION Ok’ XX,-On the Determination of Alkalies in Fire-clays and Fire-bricks. By G. GORE. As the process of bringing pulverized fire-clay or fire-brick into solution by digestion with aqueous (or treatment with gaseous) hydrofluoric acid for the determination of the alkalies contained in it is very tedious,-and as the other process employed for the same purpose viz. mixing the substance with nitrate of baryta and subjecting it to an intense white heat does not produce a perfectly fused and fluid mixture but only agglutinates the materials into a semi-fused mms,-I have adopted the following method which has proved in my experience more effectual and satisfactory. ALICAT,IES IN FIRE-CLAYS AND FIRE-I%RICKS. 105 TIircc parts of pcrfrctly dry nitratc of hnryta very finely pulveikd to prcveut ticcrepitatiun wcrc mixed with three parts of eqwilly dry and fincly powdered fluoride of hnriiini and one part of the finely pulvcrized clay or brick.‘l’hc mixture was projected in successive portions,. into a red-hot platinnm crucible a little of the nitrate and fluoride unmixed with the clay being reserved and spread upon the top and the mixture then heated as highly as possible over a Bunsen’s burner. The crucible was then transfcrrcd to ;IGriffin’s ana1ptic;il gas furnace and heated during fiftceii minutes to il still higher degrec then removed and cooled. Any particles of the mixture which now adhered to the edge of the crucible were scrupulously removed and added to the general contents.The crucible was placed in a Griffin’s gas blast furnace and covered with a stout sheet of platinum and heated to the maximum power of that furnace duriug twenty minutes ;tlie lid waa then removed ; tlie contents of the crucible (which were perfectly liquid) werc poured into a shallow massive vessel of cast-iron and a cold block of cast-iron at once placed upon the heated mass. It quickly decrepitated into numerous small pieces which were collected and carefully crushed still smaller in a steel crushing mortar; and thc resulticg coarse powder together with the crucible and any portions adhering to it was placed in a platinum dish and covered with pure sulphuric acid. A very moderate heat wm now applied the decomposition proceeded rapidly and the resulting sulphate of baryta floated upon the acid as a bulky scum ; as soon as the action declined further heat was applied and the contents of the vessel were evaporated to perfect dryness to remove excess of sulphuric acid; the residue was now digested with abundance of hot water and the liquid part containing the whols of the alkalies in solution was then treated in the usual manner. The portion of the process here described occupied about four bours. The results obtained in three different analyser agreed very closely with each other and with three analyses of tbe mama substance made with aqueoua hydrofluoric acid.

ISSN:0368-1769    

DOI:10.1039/JS8621500104

出版商:RSC    

年代:1862

数据来源: RSC