摘要:

J 0U RN A 11 01 THE CHEMICAL SOCIETY 1;~E. J. MILLS. THEfmwiula of Sparccinc the vol;itile hisc discovcretl hy S tc n-house,* in Spartiurn sc(ipurium lias loiig hccu n matt cr of tloitl)t among chemists. 8tcnhouse assigns to this suhtnnce the ~111- position- c' 1,H 1:Pf which cxpression cannot bc reprcscntcrl if the carbon-cquiva- lent (C=l2) be adopted. To avoid this difficulty Gcr1iardt-f proposed the formula- cf 1,I 11p,$ which offcrcd a tolerable approximation to the analrticnl rcsults of St cnhouse witliout liowcvcr dccidirig the qiicstioii 1)y mi appeal to csperiincnt. Tlic opinioii of tl!is illustrioiis clicmist so oftcn tricd arid fouiid corrcct in similar cases has \-cry naturdly ?mnacccpted iii inost Mauuxls. Ncverthcless thc point rcmaiiictl iinsettlcd; and it aIiliearcd of some interest to gain additional cxpcritncntal civdcncc for thc final clucidntion iiot oiily of tlic formula but also of tlic coiistitution of spartciiic.Some results wliich I have obtaincd iii this direction are recordcd in the follow-ing paragraphs In preparing this substance I have essentially followed the pccss devised by Dr. S t ciilio use. Tlic plant was simply * Stcnliousc ,\nil. CI1. Pliarin. (1851) Ixxviii 15. *ICcrhardt. Cliim. org. iv 236. 7 ::((I 6,0= 8 &c.) MILLS ON SPARTETNE. exhausted with water faintly acidulatcd with sulphuric acid. The extract was then evaporated to a smaller bulk and distilled with caustic soda until the distillate ceased to exhibit a bitter taste or an dkalinc re-action.On evaporating the distillate mixed with hydro- chloric acid to dryness on the water-bath and distilling the mass with solid hydrate of potassium-the mixture being just moistened at thc commencement-the thick oily base passed over into the receiver,-long preccdcd of course by the ammonia inwriably present. The substancc vas then gently heated with sodium in a current of dry hydrogen gas hy which means all ihe water was removcd. (It deserves to bc noticed that no other mode of drying succcedcd ; even exposure in vucuo for tmcnty-four hours with metdlic sodium failed to dehydrate the base.) The s’parteinc was now freed from the sodium and again distilled the assistance of the curr,ent of hydrogen being this time dispensed with.1501hs. of the plant yielded about 22 cub. cent. of base. I need not recapitulate the propcrtics of this substance already so well described by Stcnhouse. If it3 high boiling point be considered the idea naturally suggests itself to attribute it dism-monic charnctcr to sparteine. This circumstsncc together with the odour the well-defined narcotic action and other properties tempted me to hope that it would prove homologous with nicotine. In fact if Gcrhardt’s formula be doubled the homology of the two suhstances which arc so closely dlied in their chemical cha- racters becomes at once apparent. Nicotine C,,H,,N,* Sparteine C,,H 2sN,. In this hope however I was disappointed as will be secn from the following numbers :-I; 032475 grm.substance burnt with oxide of copper gave 9.91525 grm. carbonic acid and 0.33375 grms. water. El. 0.4225grm. substance again distilled and similarly treated gave 1.18675 grm. carbonic acid and 0.43625 grm. water. I. H. Carbon . . 76.86 76.86 Hydrogen . 11.42 11.47 Nitrogen . , 9 These results are so closely coincident with those of Dr. Sten-* c = 12 &c. et seq. MILL8 ON SPARTETNE. house that they may be fairly assumed to represent the compo-sition of sparteine which mould thus become a diamine COU-hining-15 *'XiN a formula which is unequivocally eupportcd by its deportment with iodide of ethyl. Thc following table shows the theoretical ralrics of Gerhardt's and Stenhouse's formulz together with the means of tlic analy- tical results obtained by S tenhouse and myself respectively Qerhardt's Formula Stenhousc'a Formula Stcnhonee.Mills. (doubled). (doubled). (Ad*). c16 78.05 C, 76.92 76 69 76.86 11,6 10.57 11.11 1 I -09 11.44 N 11-38 N2 11.97 ,> 99 Sult.9 of Sparteine. Some of these salts am uncrystallizable while others are easily obtained in crystals. The chloride bromide and iodide are amorphobs of' a resinous character and tinfit for analysis. The oxalate T obtained by neutralizing the aqueous solution of the base with oxalic acid and cvaporating. The crystals mere of acicular form and difficult to obtain. For additional corroboration of the formula of sparteine I have examined scveral of its doublc-salts. Platinum-salt.-This salt is precipitated as a yellom crystallinc powder when a solution of dichloridc of platinum is added to a solution of sparteinc in h-jdrochloric acid.It may be rcadily purifictl by solution in hot h~drocl~loric acid fil tcring ant1 reqs-tallizing. With care large crystals having wry hrilliant fnces may be obtained. Analysis furnished thc following rinnibers :-I. 0.475 grm. &bstance dried in z'acuo gave on combustion 0.459 grm. carbonic acid and O-210t3 grin. w:itcr. 11. 0.613 grm. same substancc siniilarly clrictl gam on ignition 0.176 grm. platinum. TIT. 0.1.795grm. substance similarly dried garc on corn1)us-tion 0.47'35grm. carbonic acid arid 0.2280groi. water. IV. 0.45175 grm. substance dried at lo",gav? on ignition 0.1317 grm. pl at'UlUIU V.0.34750 grin. suhshnco clricd at loo” gave on ignition 0.10250grm. platiiiiirn. Thesc numbers lcacl to thc formiila- thc thcorctical values of which I placc in juxtaposition with the cxpcrimental percentagcs :-c, H, N = = = 180.00 32.00 28.00 25.38 4.69 4-11 C1 = 213.00 31.22 Pt2 = 107*40 28-91 0 = 32-00 4.69 682.40 100~00 The Gold-snlt tvns prcl”irc(1 but not analysecl by Stcnhousc. 1 have obtained this salt with all the propcrtics assigned to it by its discoverer. 0.188 grra; snbstmcc gaw ON iguition 0.0605 grm. gold = 32.18per ceirt This iiumbcr agrees with the formda- ~,5N,GN3.21€Cl.:~I~C1;J which reqnires 32.27 per cent. ; aid thus it is seen that the hydro- chloratca of the iliamines are capablc of combining cithcr iiith om or with two equivalents of a metallic cldoride.I have also prepared the zinc-iodide and ziric-chtoride of spar-tcinc. Tlicy arc readily olttainctl by gently heating a solrition of sprteinc with hydriodic acid aid iorliclc of zinc or with liydro- chloric acid and chloride of zinc Iodide of Zinc and Sparteine.-This salt crystallizes in fine needlcs which are apt to become brown 011 cxposure to air. have only determined the iodine in this salt. MILLS ON SPARTEINE. 0.366 grm. substance dried in vacuo and precipitated with nitrate of silver gave 0.4225 grm. of iodide of silver =62.39per cent. iodine. The formula- C,,H,6N2.2H I.ZZnI requires 62-78 per cent. Chloride of Zinc and Sparteine.-This salt crystallizes in niag-iiificent needles which I have obtained half an inch long.They are white somewhat hard and lustrous. The composition of this salt is probably C,,H,6N,.2HC1.2ZnCl. Actioit of Iodide of Ethyl on Sparteine. The process of ethylation unknown at the time when sparteine was first prepared has proved of the greatest service in establish- ing the constitution of this base. When equal volumes of sparteine ordinary methylated spirit and iodide of ethyl arc heated together for about an hour in sealed tubes at 100' C. the mixture assunies a dark colour arid deposits abunclance of crystals of an ethylated cornpound,- sparingly soluble in cold readily soluble in hot alcohol and excessively soluble in water. Well-waslied with cold and owe recrystallized from hot alcohol the substance mas obtained pure and gave the following analytical results :-I..0.5010grm. substance* gave on combustion with a mixture of chromate of lead and oxide of copper 0.7275 grm. car-bonic acid and 0.2895 grm. water. 11. 0.4550 grrn. substance similarly treated gave 0.6505 grrn. carbonic acid and 0.2635 grm. water. 111. 0.5135 grm. substance gave on precipitation with nitrate of silver 0.4656 grm.iodide of silver. IV. 031525 grm. substance gave on similar treatment 0.2861 grm. iodide of silver. These numbers represent the foimula * The substance was in each anaiysis dried in vwuo. MILLS ON SPARTEINE. as may be seen from the following comparison of the theoretical dries with tlie experimental percentages :-Theory.1. Experiment. 11. 111. Iv. C, = 204 39.38 39.60 38-99 , #I H, N2 I = = = 32 6.18 28 5-40 254 49*04 6-42 ¶ , 6.43 9 , , ,J 4940 ,,,)49.04 518 100.00 The formation of this compound proves most satisfactorily the diammonic nature of sparteine.* The iodide crystallizes in the form of long needles beautifully groupcd and radiating from a centre. Treated with a boiling solution of potash this salt remains unaltcred ; oxide of silver however rapidly transforms it when in aqueous solution into the powerfully alkaline hydrated oxide-the composition of which was confirmed by the analysis of its p2ati-num-salt. This was prepared by treating the iodide with chloride of dver and tho chloride thus produced with dichloride of platinum in the cold.In this manner a semi-crystallized precipitate was obtained soluble in water alcohol and more readily in hydro-chloric acid. Dried in vacuo over sulphiiric acid 0.227 grm. substance gave on ignition 0066 grm. platinum corresponding to 29.07 per cent. The formula requires 29.26 per cent. * Note. In the above reaction’between iodide of ethyl and eparteine,a secondary product is found in very small quantity in the dcholic wa,ahhgs from the mono-ethylated di-iodide. The substance ie wsite exceeeively mluhle in alcohol almoet insoluble in cold sparingly soluble in hot water. Crystallized from the latter solvent it apperm in the form of small well-defined almost s~uarerhombohedral crystals. I determined the iodine in this substance aa well as the platinum in the platinum-salt obtained from it ; tbe numbers were respectively 36-25 per cent.(I) and 27.95 per cent (Pt). It will be perceived that these numbera present ;.-discrepancy ; and I much regret that I wag unable t~ procure su5eientl ~*:bs+ance 4t.i a determination of the carbon and hydro- MILL8 ON SPARTEINE. The dichloride corresponding to the mono-ethylated di-iodide is less easy to obtain and crystallizes also in needles. It forms with chloride of zinc a beautiful acicular double salt easy to cryst dize. * Action of rod& of Ethyl on EthyESparteine. When the hydrate of this base obtained by the action of oxide of silver on the iodide is digested with alcohol and iodide of ethyl in sealed tubes at 100”C. for a short period there is obtaind on evaporation of the liquid a crystalline iodide always contaminated with free iodine which differs essentially from the iodide of the mono-ethylated base.If the evaporation be conducted in a stream of sulphuretted hydrogen gas the separation of much of the iodine is effected and the subtance rendered considerably purer. The ncw iodide crystallizes from alcohol in short minute crystals and is very soluble in water. Treated with oxide of silver it yields a powerfully alkaline solution Boiled with chloride of silver the iodide is converted into the corresponding chloride which is deli-quescent and not easy to obtain in crystals. The latter treated with dichloride of platinum furnishes a very voluminous platinum- salt of light yellow colour and crystallizing in radiated aggrega-tions from its solution in weak alcohol.It is very soluble in water ; a mixture of alcohol and ether fails to precipitate it entirely. On analysis 0.213 grm. substance gave by ignition 0.0610grm. platinum = 28-64 per cent. Want of material here prevented me from perf‘ormiug these expe- riments on a more extensive scale. The natural interpretation of the above observations would be to assume that the action of iodide of ethyl upon the mono-ethylated sparteine produces the di-ethylated iodide which with oxide of silver yields the caustic hydrate of the diammonium- Compare Dr. Hofmann’s ‘‘ Notes of Researches on the Poly-ammoniaa” No. XIV. ‘(Diagnosis of Diarnines.”-Proceedings of Royal Society vol.xi p. 978 BENCE JOXES ON CRYSTALLTBED PHOSPlIATE OF fiirniehing lastly by treatment with hydrochloric acid and dichlo-ride of platinum the platinurn-salt-This formula requires 28*10per cent. of platinum. The analysis above gives as much as 28-64 pcr cent. The salt was probably still contaminated with IL minute proportion of the mono-ethylated compound. The results of this inquiry prove unmistakably that sparteine is a tertiary diamine of the formula C,,H,,N = (ClSH2JViNZ. Further investigation is nccessary to afford some insight into the nature of the-complex atom (C151126)v1 which assumes the place of six equivalents of hydrogcn. The above experiments on sparteine were cnrried out in Dr H ofm ann' s laboratory.

ISSN:0368-1769    

DOI:10.1039/JS8621500001

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

BENCE JOXES ON CRYSTALLTEED PHOSPlIATE OF 11.-On the occurrence of deposits of Crystallised Phosphate of Lime in Human Urine. BY H. BENCE JONES,M.D. F.R.S. F.C.S. IN March 1861 Dr. William Roberts Physician to the Man- Chester Royal Infirmary published a paper in the British Medical Journal on the occurrence of deposits of crystallised phosphate of lime in human urine. Hesays :-“By adding a little chloride of calcium to healthy urine and reducing its acidity to near the neutral point with caustic soda I have often succeeded in obtaining an abundance of crystals,‘ closely resembling those occurring spontaneously in urine.” At this date .I had satisfied myself that healthy urine out of the body could be made to give crystals of phosphate of lime first by simply adding chloride of calcium to the urine; secondly by taking away some of the acidity of the urine; thirdly by totli means sininltaneously.When the fluid waa very acid much chloride of calcium was required to be added ; but if a portion of the acid was removed in LIME IN HUYAN URINE. any way then less cliloride of ca; cium was required to procliice crystals of phosphate of lime. These experiments made me believe that by ,oiling a lime-salt internally phosphate of lime crystals ought to be found in the urine even without adding anything to the water after it mas made. A long delay occurred before I could begin the observations in St. George’s Hospital and ultimately I was obliged to ask my friend Dr. Dickenson to undertake the microscopical examina-tion of the urine of those to whom the lime-salt was given.Although therefore these experiments mere ended long after Dr. Roberts’ publication set as the obserdions recorded in the first part of this paper were made without any Itnowledge that he was experimenting on the same subject our agreement must be considered as accidental and may therefore be taken as the better evidcnce of the truth of our facts PART 1. On the yroductio)h of crystcils. of Phsyhate of Lime ill the b?ine by the additioii of substames ufter it 7~asbeeu passed. IT appeared desirable to determine the circumstances and form in which crystallised phosphate of lime occurred when pure solutions of chloride of calcium arid common phosphate of soda or acid phosphate of soda were mixed together.When a solution of chloride of calcium in excess is precipi-tated by a solution of conimon phosphate of soda the precipitate when examined by the microscope is seen to be partly arnorplious and partly crystalline. The amorphous precipitate according to H eint z is 3Ca0. PO, and the crystalline 2Ca0.H0.P05. When a solution of common phosphate of soda in excess is precipitated by solution of chloride of calcium the precipitate examined by the microscope is amoyphous. If a little acetic acid is first added to the solution of common phosphate of soda and then the solution of chloride of calcium an amorphous precipitate is first seen and this more or less rapidly (in the course of half an hour) becomes entirely crystalline.When lactic acid butyric acid valeranic acid or yery meak hydrochloric acid was used instead of acetic acid the same crystals were observed after a ahoi*t time. if an excess of these acids was lxsed no crystals were formed. When a solution of chloride of calcitini in excess was added to a solution of acid phosphate of soda crystals of phosphate of lime were found by the microscope in from tell to fifteen minutes. 10 BENCE JONEB ON CRYBTALLISED PHOSPHATE OF Wheu there was much acid phosphate in proportion to the chloride of calcium the crystalline deposit was always found. It was clear then that crystalline phosphate of lime was formed if sufficient lime-salt was present and if the acid was not in such excess as to keep the salt dissolved.As the urine always contains common phosphate of soda or acid phosphate of soda with or without free acid and with variable quantities of lime-salt experiments were made to obtain crystalline phosphate of lime lst by increasing the lime-salt by adding chlo- ride of calcium; or 2ndly by diminishing the acidity of the urine by cautious additions of alkali so as to allow the lime-salt naturally present to crystallise out ; or 3rdly by increasing the lime-salt and diminishing the acidity of the urine at tbe same time. In each of these waya crystalv of phosphate of lime were obtained. 1st. By simply adding chloride of calcium to healthy urine. To 50 c. c. of urine a few drops of a strong solution of chloride of calcium were added until a slight precipitate waa obtained.The precipitate that formed was first amorphous but half an hour afterwards beautiful crystalv of phosphate of lime were seen by the microscope. If a great excess of chloride of calcium was added the preci pitatz was almost entirely amorphous. Thirteen different experiments were made with different healthy urines from two men chloride of calcium in solution was added and in each cke crystals of phosphate of lime were found in from half an hour to an hour. Bndlp. Crystalline phosphate of lime was obtained from healthy urine by diminishing the aciditj of the urine by the cautious addition of alkali. To 30c. c of healthy urine a quantity of ammonia was added not sufficient to produce QL precipitate. Aftcr standing 12 hours no crystala of phosphate of lime could be found with the microscope.To 80c. c. of urine ammonia was added SO that the urine had a feebly acid reaction. Tbe precipitate whioh formed appeared when examined by the microscope to consist chiefly of crgstallised phoephate of lime. TO30 c. c. of nrine 80 much ammonia was added as gave a neutral reaction. Besides crystals of phosphate of ammonia and magnesia crystals of phosphate of lime were formed. In another experiment the urine was made alkaline; the pre- cipitate then consisted of phosphate of ammonia and magnema and amorphous phoephate of lime. LIME IN HaMAN UBINE. Solution of common phosphate of soda and solution of potmsa also when added to healthy urine occasionally gave on standing for some time crystals of phosphate of lime.3rdly. By increasing the lime-salt and diminishing the acidity of the urine at the same time crystalline phosphate of lime was produced. Four specimens of healthy urine gave with chlosde of calcium no precipitate. Solution of potassa was then added in smallquantity till a slight precipitate was observed ;the urine still had a slightly acid reaction; on examination with the microscope from half an hour to an hour afterwards crystals of phosphate of lime were found. In two other cases some of the aciditywas removed by potassa and eolution of chloride of calcium was then added; the pre- cipitate when examined with the microscope contained crystals of phosphate of lime. In another case in which chioride of calcium gave no precipitate at all the urine wm mixed with a little ammonia to take away the greater part of the acid present and then a solution of chloride of calcium was added.The precipitate conthed crystals of phosphate of lime. That it is not necemary to lessen the acidity of the urine pro-vided the phosphate of lime ie in great excess is proved by the following experiments :-To 60 c. c. of healthy urine a few drops of lst dilute acetic or 2ndly lactic acid were added and then LW) much of a solution of chloride of dciuni as caused only a slight precipitate. After rtanding some hours the precipitate which was at first amorphous waa changed in both caw into beautiful crystals of phosphate of lime. Hence-The two chid conditio~~s, w3kh need not ceexist an which the formation of crystalline phosphate of lime in the urine depends we-1st.An excess of phoephate of lime; and 2ndly. A alight &&ty of the urine in which the phosphab of lime is dissolved. BKNCE JONES ON CRYSTALLISED PHOSPHATE 05’ PART 2.=Oit the production of Crystuls of Phosphate of Lime in the uriiie bg giving preparations of lime as medicine. THEease with which crystals of phosphate of lime were obtained after any urine was passed by adding substances to the urine led me to expect that by giving lime-salts as medicine phosphsttc of limc crystals would with equal rcadiness he detected in the urine. I soon found that it was not so easy to affcct the composition of thc urine bcfore it passed from the body and that careful collect- ing and watching for many hours afterwards was required to arrive at clear results.My friend Dr. Dickenson uridertook the microscopical es- amination of thc urinc in the wards of St. Gcoi*ge’sHospital where T ordcred the yrcparations and quantities of tlic mccliciiie which I wished to try. At first acetate of lime with lime-nratei; and. sometimes with carl)onate of potassa to reduce the acidity of the urine were tried. Then limc-water done or carbonate of lime was used; but ultimately a solution of acetate of lime containing about 15 grains to a draclini of solution gave the bcst results. As examples of our first experiments we give the following,- E.P. aet. 22 admitted Nay If 1861 for dyspepsia.He mas nearly leaving the hospital well mid the urine mas healthy and in all respects natural when lie was ordered June lst 2drachnis of solution of acetate of lime in water cvery six hours (each drachm contained 14.7 grains of acetate of lime). The urine which was passed at night and morning mas repeatedly examined after standing for various periods but nothing but a few crystals of oxalate of limc was observed. On the 4tb eight ounces of lime-water mere given in the day instead of the acetate. On the Gth still only oxalate was found. The lime-water was increased to a pi,nt. On the 8th n drachm of carbonate of potassa in addition mas given. On the Ilth no change haviug bemi observed tlie morning iirine mas faintly acid; and the surfacc mas covered with an iridcscent plate of phosphate of liiiic.The evening urine was faintly acid when passed and 110 crystals of phosphate of lime were found at first. It was again examined forty hours afterwards ; LIME IN HUMAN URINE. it was then alkaline and a white precipitate had fallen which consisted of a considerable quantity of amorphous phosphate with a great number of very characteristic crystals of phosphate of lime. The surface was covered with a phosphatic pellicle. 12th and 13th morning and evening. No crystals of phosphate. 14th. Morning urine alkaline with phosphatic pellicle and much deposit consisting chiefly of amorphous phosphate with a few stellate crystals of phosphate of lime. 14th evening nrine.Eighteen hours after it was passed no deposit was found; on the third day many stellate crystals of phosphate of lime were found. The experiment was continued until the 20th; phosphate of lime crystals occasionally but by no means constantly appearing ; ovzlatc of lime was always detected when the urine was acid. K. E,,aet. 30 admitted May 15th for dyspepsia. June 1st. The urine was in all respects natural; he drank a pint of lime-water during the day. June 2nd. A few crystals of phosphate of lime were found. , 3rd. No phosphate of lime; Rome oxalate. , 4th. No phosphate of lime crystals mere fonnd. Iu more than one case carbonate of lime was given in coil-siderable quantity but no crystals of phosphate of lime were detected in the urine; but the results with acetate of lime iu large doses were very decided and very uniform for example,- S.K. aet. 24. admitted with chronic rheumatism July 10. July 20. The urine mas perfectly natural except a small quantity of pus cells the result of a gonorrhoea. He was ordered two drachms of solution of acetate of lime equal to 29-4 grains in water three times daily. The urine was examined night and morning and no crystals except a few oxalate of lime octahedra were seen until- 23rd evening. The urine mas faintly acid with an iridescent pellicle on the surface aad a heavy white precipitate formed which consisted of amorphous phosphate oxalate of lime and very numerous characteristic crystals of phosphate of lime. Three drachma of the solution of acetate of lime were ordered thrice daily.24th morning. Urine faintly alkaline ; amorphous and laminar phosphate of lime were seen but no crystals of phosphate of lime. 18 BEROE JONEB ON OBYSTALLllllD PUOBPHATE OF Mth evening. Urine acid ; very large crrystals of oxalate were men; no phosphate. Four drachms of tbe.oolution of aoetate of limewere ordered. 26th morning. The urine waa acid and showed a few phorphate crJr8tslr. 25th evening. The urine was acid and showed a large depoeit of octahedra but no phoephate. 26th morning. The urine was acid but showed no crystale. 26th evening. The urine waa very faintly acid; numeroue fine crystals of phosphate of lime were found. July 27 morning. The urine was faintly acid; crystalline phoe- phata of lime wm seen and much oxalate.The acetate of lime was ordered to be stopped and only three doses were taken be-tween the 27th of July and the 3rd of Auguet; during which time crystds of phosphate of lime were only twice found by the microscope. August 2. Morning urine slightly acid; no phaepbate crystals. , Evening urine acid; much oxalate bat no phoaphate. Three drachms of the solution of acetate of lime were ordered in water. 3rd. Night water alkaline; few small phosphate of lime crystals were found. 4th. Morning urine alkaline and few phoephate of lime crystals were found. 9th. Evening urine alkaline ; abundant and splendid crystals ofphosphate of lime. 5th. Morning urine faintly acid. Phosphate of lime crystals were found; the experiment was stopped.L. B. aet. 26 admitted with slight rheumatism July 10. July 23. The urine was acid and perfectly natural except thbt it contained a quantity of pus cells the result of gonorrhoea. Two drachms of solution of acetate of lime equal to 29.4 grains were given thrice daily. The urine was examined night and morning no crystals were aeen until 24th evening. Urine faintly acid; a few needles of phosphate of lime wire found and much amorphous phosphate. 25th. Three drachms of the solution were ordered But no more crystals of phosphate of lime were seen until 27th morning. The urine after standing 48 hours gave many fine bundles of phosphate of lime crystals. 27th evening. Urine gave much oxalate but no phosphate.LIME IN HUMAN URINE. 28th morning. Urine faintly alkaline; gave many fine crystals of phosphate of lime. 28th evening and 29th morning. The urine was not kept. 29th evening to 31st. When the acetate of lime was omitted no crystalline phosphate was found. August 3. Three drachms of the solution were again given thrice daily. No crystals were found until the evening of the 7th when the urine was acid and many phosphate of lime crystals were seen. Four drachms of the solution were ordered but the patient dis- likicg the medicine the experiment was stopped. C. W. Eet. 30 was admitted with chronic rheumatism July 10. July 30. The urine was acid and perfectly natural excepting that occasionally a little bladder epithelium was seen.Three drachms of the solution of acetate of lime were ordered thrice daily in water. Nothing was observed until August 3. Morning urine faintly acid ; some decided aggrega- tions of phosphate of lime crystals were seen with microscope. August 3rd evening. Urine acid but no deposit. , 4kh morning. The urine was acid and showed huch oxalate of lime but no phosphate. The medicine had to be omitted in consequence of an increase of rheumatism Conclusion. From the experiments detailed in this paper it follows that the formation of phosphate of lime crystals in the urine does not depend upon the amount of phosphoric acid present but that it does depend firstly on the amount of lime in the urine ; and secondly on the acidity of the urine allowing the crystallization to occur. The increase of lime in the urine or the diminution of the acidity of the urine or the simultaneous' occurrence of both of these conditions does not indicate any diseased condition of the body but may be caused by medicines or by diet.

ISSN:0368-1769    

DOI:10.1039/JS8621500008

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

I~I.-l~~l)i)ll~it~eI,fa,.?/ Note to (1 Memoir 0i1 the power ctscribcd to the Roots of Ph/s of q~’t(:hgpoisoriotis or (ib~iormabst& Ytuiices ymeiiteil to tAenz. By CHA~~LES DAUUESY,XU. F.R.S. M.R.S.B. Foreign Associate of tlic Koyal Academy of Munich and Professor of not ally Osfiml. IN a iiienioir rend heforc the Cliciiiical Society in May last and siiicc publishcd in the Society’s Journal,* I intiinatcd my intention of coiitiriuing the researches hcgun last year rc On tlic power ascribed to tlie roots of plants of rejecting poisonous or ahiormnl substances prcscnteil to tlictn ;”and as in the experiments thercin detailed tlic foreign iiigredients hail beeu applied to tlic plants after thy had sprung from the ground in the liquid form by watering them with the solution and it IVBS conceivable that some sniall portion might have adhcrcd to their external surfacc8 although none was actually absorbcd 1)y the roots,-I this year endeavoured to avoicl that sourcc of crror by introducing the salt into the soil before the secd \\a.’ 3 SOW11. The abnormal substanccs tried wre as bcfore the earths strontia and baryta ill combination with nitric acid,-aiid the metal nrseiik wliich however was applied not iii thc form of arsenious hut of arscnic acid which latter being isoinor-phous t;vith phosphoric acid might it mas coiiceived be substitutcd for it in tlic organism of a plant and thus bccornc assiimilatcd morc readily than arscnious acid. Thc crops tricd were as on the former occasion barley and tnr-nips aiid in neither of the two did any yery marked differcncc in the quantity of the crop olhined arise from the application of tlie salt.If ally thing the advantage seerncd to bc rather 011 the side of tliosc portions of tlic field which had been thus treated. Thc crops were scvcrally cxamined in the same manner as those of the year preceding had hen; but in no one of thc six caws three hcing the samples of tiirnips tried with arsenic baryta and strontia mid tlirce tliosc of barley treated with the same substances did any indications of the poisonous or abnormal ingredient which had been introduced into the soil manifest them- selves iii the resulting crop. * Vol. xiv 1’. 209. FOBTER ON PIPERIC AND HYDROPIYERIC ACIDS. I consider these results as rather more conclusive than those obtained in the preceding year because the substance experimented with being incorporated with the soil before the seed had been sown could hardly fail to get into contact with the roots at some part or other.The only question that can arise is whether the quantity ad- ministered was in each casc sufficient to become appreciable in the plants that had grown in contact with it. In the case of the arsenic I hardly know how this point could be determined more fully as a larger dose of the poison would be fatal to the vitality of the plant and thus the very conditions of the problem would be vitiated. With regard however to the strontia and baryta where this objection does not seem to exist it might be well to settle the point more conclusively by trying whether the earth would be taken up when quantities of either larger than were this year employed had been introduced into the soil.

ISSN:0368-1769    

DOI:10.1039/JS8621500016

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

FOBTER ON PIPERIC AND HYDROPIYERIC ACIDS. IV.-On Piperic and Hydrcpiperic Acids. By G. C. FOSTER,B.A. PIPERIC acid was first described in 1857 byv. Babo and Keller.+ Their analyses led them to represent its composition by the for-mula C26H1208 C50H240,6 or C,,H2,016 the last formula they considered the most probable. The analysis of the acid and of its silver-salt was soon afterwards repeated by St 1:ecker t who gave the formula C24H,,08 for piperic acid and the formula C,,H,MO for the piperates and showed that many of Babo and Keller’s own analyses agreed with these expressions. If the accuracy of Strecker’s formula be admitted it seems to indicate that piperic acid is a triatomic acid analogous to glyceric acid C3H604f; otherwise it is difficult to reconcile its monobasic character with the high proportion of oxygen it contains.These considerations induced me to make a few experiments on piperic acid in the hope of obtaining some knowledge of the relation in which it stands to bo-dies whose constitution is better understood. * J. pr. Chem. lxxii 53; Jebresber. 1867,p. 413. + Ann. Ch. Pharm. cv 317; Jahreaber. 1857 p. 414. $ Here and hereafter in this paper C=12 H =1 0=16. VOL. xv. C 18 FOSTER ON PIPERIC AND HYDROPIPEHIC ACIDS. The piperic acid cmployed wa.s obtained by decomposing piperino with alcoholic potash according to 13abo and Keller’s proccss; but I foulid that by employing a closed vessel in which thc matcrials could bc heated above the boiling point of alcohol much time might be saved 100 grms.piperine mixed with an equal weight of solid potash and as much strong alcohol aa will dissolve both is completely decomposed when heated for five or six hours to 100°C; The ailalpis of pipcric acid and of its potassium- and barium- salts gavc me numbers which agree with Strecker’s formula m is shown by the following statement of results. Piperic acid C12Hl,0,. 0.517 grm. acid gave 1.248 grm. carbonic acid and -229 grm. water. 0443 grm. acid gave 1.074 grm. carbonic acid and *197 grm. water. Calculated. Found. ... \ / -14% 66.05 65-83 66.12 c12 10 4.59 4-92 4.94 % 04 6% 29.36 , ,> C12H1004 218 100.00 Piperate of potassium C,2H9K04. 0.4371 grm. salt gave ,147 grm. sulphate of potassium.425 grm. salt gave ,144 grm. sulyhate of potassium. -7325grm. salt gave 1.502 grm. carbouic acid and -232grm. water. Calculntcd. Found. -7-C12 144 5625 > , 55-92 9 3.52 3-52 2 39 15-23 15’bS 16’19 , 04 64 25-00 ,f 9 >> C,,H-,KO 256 100.00 Piperate of barium C,,H,FaO,.-This salt wi1s prepared by adding chloride of barium to a solutiou of yiperate of potassium arid purified by crystallizatim from boiliug water in which it is somevliat more soluble than in cold water and subsequent wwh- POBTER ON PIPEBIC AND UYDBOPIPERIC ACIDS. ing with boiling alcohol. A current of carbonic acid passea through a solution of this salt in hot water decomposes it into carbonate of barium and piperic acid. Air-dry it does not lose weight at looo 03082 grm.salt gave *I251grm.aulphate of barium. ,3406p.salt gave 01388grm. eulphate of barium. Mculated. Found. Barium per cent. 23.99 23-86 23.98 My first experiment with piperic acid was an attempt to reduce it by means of hydriodic acid in the hope of obtaining a mona-tomic acid (C12Hl,-,0,$ which should bear the same relation to'it as propionic acid (C,H,O,) bears to glyceric acid (C,H,O,). In this attempt I was unsuccessful. At 100°C. and even below piperic acid is converted by hydriodic acid into a black uncrystal- lizable substance carbonic acid being formed at the same time but no iodine set free. The only crystalline .substance which I SUC-ceeded in separating from the black carbonaceous product of this reaction was a small quantity of what appeared to be unaltered piperic acid.Having failed to reduce piperic acid by hydriodic acid I hoped to be more successful iik employing uascent hydrogen. This re- agent however instead of giving a product containing less oxygen gives rise to a new acid containing two atoms of hydrogen more than yiperic acid which I have named hydropiperic acid. This substance is best obtained by allowing sodium-amalgam to act for some hours upou a solution of piperate of potassium kept at a gentle heat and frequently stirred. The piperate of potassium which is obtained as a direct product of the action of alcoholic potash on piperiue may be employed for this preparation after hav-ing been once recrystallized. The hydropiperic acid is separated from the alkaline solution by the addition of hydrochloric acid in the form of oily drops which gradually solidify when allowed to stand.It may be purified by solution in a large quantity of boiling water which deposits it ou cooling in exceedingly thin silky needles sometimes as much as an inch long; or by solution in alcohol and treatment af the solution with animal charccal. Pure hydropiperic acid is colourless; it melts at 63" or 64"C. and solidifies at about 56'; it may sometimes be cooled still lower FOSTGIL ON PIPERIC AND FIYDROPIPEIIIC ACIDS. without solidifying but then solidi fics suddenly when touchetl with a glass rod ; it docs riot appcar to bc volatile without dccom- position but wlicii hcatcd in a tcst-tiih it creeps up thc sides of the tulle lcaviiig only a very alight residue at the bottom.It is very slightly solulde in cold watcr biit sufficicntly so ta give a faint acid rcwtion to the solution and to cause it to give a preci-pitate with acetate of lead; it is somewhat more but still only sparingly soluhle in hot watcr and givcs a solution having a strong acid rcnction. It separatcs on cooling partly as an oil partly in very fine crystals. Alcohol dissolvcs hyclropiperic acid in all proportions ;in cthcr also it is wry soluhlc and it crystnl- lizes hy the spontaricous evaporation of its cthcrcal solution in largc but confusedly formcd hard crystals apparently belonging to thc iiionoclinic system and many of them hemitropic (2.1724grm. acid gave 4124 grm.carbonic acid arid ,0877 gym. water. *4883grin. acid ;saw 1,1715 grm. carhonic acid and 02495 grm. water. 4GG grm. acid xavc 1.116 grin. carbonic acid and .235 grni. water. Calculntctl. Found. 7'-. Cl2H12 144 12 (i;i*4fi 5-43 r G 5 5.65 - 4 4 547 G5-31 5.60 04 6 l! 29-09- .>> ,> 99 C,2Hl,0 220 100.00 The first mid sccoiid analyses werc made witli the products of two diffcrciit preparations ; tlic third analysis is of the product obtaiiicct by trcntirig sonic of tlic satlie siil)stwcc ns scrvcti for thc sccoiid analysis a second time with sodium-amdgani. Stroiig sulpliuric acicl givcs il 1h)cl-rerl colour with hydro-pipcric wid ; filming nitric acid acts in tlic snmc way; nitric acid ilililtcrl witli its owti bulk of water acts viol(tnt1y 011 1iydrol)il)cric acid WIACI~ sliglitly licntcd giving a soltitioil f'rorn whicli wntcr prccil)itatcs a scmi-fluid nitro-acid.IVhcn hytlropiperic acid is licntctl with cxyccss of' alkali a good deal of gas is givcii off and the rcsitluc csliihits thc rcactioiis of tlic acid Cj€I6O4,obtairicd by Ur. X at tliiesseii aid myself* by distilling hemipixiic acid with * I'ro:.. Coy. SOC.,xi 58. FOSTER ON PIPERIC AND EYDROPIPEBIC ACXD8. 2& hydriodic acid and sul~scqucntly obtained by S trecker* by heating pipcric acid with excess of potash. With hydriodic acid it behaves in the same way as piperic acid. Hydropir,erct!e of nrn~~io)iiu~n, C12H (NIX,)O,.-This salt ww prepared by nciltralizi~~g tlic acid with ammonia.It crystallizee easily from hot watcr iii small shining scales For analysis a portion was dissolved in :ilittlc waster ; the acid was precipitated by hydrochloric acid collcctcd on a wcighed filter and washed with as small a quantity of water as possible; the filtrate was evapo-rated ; the residue dissolyccl in very little water; the small additional quantity of acid thus separated was collected on the same filter as before and the whole quantity *eighed after being dried in vacuo; the second filtrate arid wash-waters were then again evaporated and the ammonia was determined in the residue aa chloro-platinate. 0.4813 grm. aalt gave .4469 grm. hydropiperic acid and 04126 grm. chloroplatinate of ammoaium. 05147grm. salt gave -4787 grm. hydropiperic acid and *2146 grm.platinum. Calculated. Found. 0-F /-,-, c1211,,0 220 92.83 92-85 93.01 H3 N 17 7.1 7 6.55 7.16 C12€11204113N 237 100.00 99.40 100.17 A strong solution of hydropipcrate of ammonium can dissolve a considerable quantity of hydropiycric acid the addition of strong aqueous ammonia to such a solution saturated with acid gives an almost solid maw of hydropiperate of ammonium ; by the addition of water it is decomposed into hydropiperate of ammonium which dissolves arid hydropipcric acid which is prccipitatcd. HydropQi&ate of potassium with excess of 'ucid Cl,HllKO + C,,H,,O,.-Tllis salt mas obtained by boiling it soliltion of hydro-piperic acid in nearly absolute alcohol with excess of dry carbonate of potassium filtering the solutiori while still hot and allowing it to cool the salt was thus obtaiiicd crystallized in hemispherical clunips of radiating needles.It was analysecl after being once recrystallized from alcohol and dried at 100°C. Ann. Ch. Pharm. cviii 280. FOSTER ON ?IPEBIC AND RYDROPIPERIC ACIDS. 0.316 grm. salt gave -688 grm. carbonic acid and *1455grm. water. 0.261 grm. salt gave -050 grm. sulphate of potassium. Calculated. Fonnd. C, / 288 h 4/-60.125 h 5938 7 >) H23 23 4.81 5.1 1 K 39 8.16 9 8'59 08 128 26.78 9 99 C,,H=KO 478 100.00 The deficiency of carbon and excess of potassium shown by the analysis were no doubt caused by the presence of a small quan- tity of neutral hydropiperate of potassium (cnlc. carbon 55.81 per cent.;potassium 15.12 per cent.) ;indeed the acid salt appears to he decomposed by repeated crystallization from alcohol into hydro- piperic acid and the neutral potassium-salt at least a portion which 'had been recrystallized three times from alcohol gave on analysis 12-63 per cent. potassium. The acid salt is imme-diately decomposed by water with precipitation of hgdropiperic acid. HIidropiperate of calcium C,,H ,CaO,( +H,O ?).-Obtained by boiling the acid with milk of lime filtering hot and separating the excess of lime by carbonic acid; or by precipitating a rather strong solution of hydropiperate of ammonium with chloride of cal.. cium. Tbis salt is partially decomposed by solution in hot water but may be purified by crystallization from a mixture of about 2 parts water and 1 part alcohol which deposits it in bunches of tine needle-shaped crystals.It is only slightly soluble in cold water. The crystals effloresce in the air but do not lose all their water below about 100"C.; they melt together to a sticky mass at lo", which may be powdered when quite dry pnd then docs not again become soft on heating. Hydropiperate of calcium dried at loo",does not further diminish iu weight at 120".* Hydropiperate of calcium appear8 to cqstallizc with one atom of water. A calciumdetermination in the airdry salt gave 7.53per cent. calciitm (the formula CI,HIICa04+ H,O requires 7.78 per cent. calciam) ; after the =me salt had stood two days longer over sulphiiric acid it contained 4.2 per cent.water ; in other prepa- rations of tbc salt (airdry) I found 4 94 4.88. and 4.87 pcr cent. water ; niimbere which do not agree with any simple atomic proportion. The percentage of water calculated for the above formula is 7.00 I can only explain the results oldnincd by ascribing them to the rapidity with which the salt effloresces. After drying very quickly by pressure between paper and exposure to the air the crystals were found te have partially effloreeced when examined under the microscope. FOSTER ON PtPERIC AND HYDROPIPERIC ACIDS. 0.595 grm. kalt (dried at 105') gave -170 grm. sulphate of calcium. -3348grm. salt (dried at 100") gave *095 grm. sulphate of calcium. Calculated. Found. -CI 1 144 60.25 99 9 11 4-60 9 ¶, HI1 Ca 20 8.37 8.30 8.35 64 26.78 , 9, 04 Cl,HllCaO 239 -100.00 Hydropiperate of barium C12HllBaO+,resembles the calcium- salt and may be obtained in a similar way.(Found 23.2 per cent. barium; calculdted 23.8 per cent.) Hydropiperate of silver Cl,H Ago,.-A crystalline precipitate almost insoluble in cold water; it dissolves in hot water but is partially decomposed at the same time. It can hardly be dried without undergoing slight decomposition. 0.2933grm.gave -0985 grm. metallic silver'. Calculated. Found. Silver per cent. . . 33.03 -33-58 A solution of hydropiperate of ammooium gives a whitish brown precipitate with perchloride of iron and white precipitates with corrosive sublimate mercurow nitrate and acetate of lead all of them soluble in hot water.Hydropiperate of ethyl.-A solution of hydropiperic acid in absolute alcohol was saturated with hydrochloric acid gas and heated to 130' for four or five hours; the product was then evaporated on a water-bath and the residue washed with dilute potash. In this may a neutral brown liquid was obtained which was heavier than and insoluble in water. By solution in ether treatment of the ethereal solution with animal charcoal and sub- sequent evaporation it mas obtained as a brownish yellow liquid. It was not altered by dilute potash or ammonia but gave a half-solid mass probably hydropiperamide when saturated with gaseous ammonia. Hydropiperic acid heated with an excess of monohydrated acetic - A. OPPENHEIM ON THE acid to 160OC.during 30 houre appears to be unaltered. The product of this experiment was poured into water which caused a precipitate of a solid acid; this precipitate was washed to remove acetic acid ; about two-third3 of it were then neutrdizcd by lime the other third added and the whole evaporated to dryness on a water-bath. The residhe was well washed with strong alcohol the remaining salt crystalhd from very dilute alcohol and then decomposed by hydrochloric acid. The acid thus separated was dried over sulphuric acid and analysed. 0.3394grm.acid gave 810 grm. carbonic acid and -1724 grm. water. These numbers show that the substance was nearly pure hydropiperk acid of which it had all the external properties. Found. Hydropiperic acid.Carbon . . 6512 6546 Hydrogen . . 5-64 5.45 The deficiency of carbon may perhaps indicate that a small quantity of aceto-hydropiperic acid C,,H, (C,H,O)O, (carbon 69-12per cent.) had been formed. Hydropiperic acid heated to 150"C. with chloride of acetyl gives a neutral oil insoluble in water and dilute alkalis ;probably accto- hydropipcric anhydride ; I do not know whether aceto-hydro- piperic acid was formed at the same time or not.

ISSN:0368-1769    

DOI:10.1039/JS8621500017

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

A. OPPENHEIM ON THE V.-On the Camphor of Peppermint. By A. OPPENEEIM, Ph.D. THEcamphor of peppermint known as constituting the stearop- tene of the essential oil <Jf Mentha piperita has lately been obtained in larger quantities so as to allow of tl closer examination being instituted than has hitherto been possible. It arrives from Japan in coarse earthenware jars merely protected by paper covcrs and consists of a mass of small white fragrant prismatic crystals resembling sulphate of magnesia which salt in fact seem to be constantly used for the purpose of adulterating the Japanese peppermiut-camphor rn from ten to twenty per cent. of that salt may be scparatcd from the camphor by washing it with water. When washed with warm water the peppermint-camphor melts and CAMPHOB OF PEPPERMLNT.on congealing forms itself into a hard crystalline mass. It melts at 36 (1 and distils without decomposition at 210’. These pro- perties very nearly coincide with those established by Dumas,* for the stcreoptene of Americah oil of pcpperrnint. The compo- sition of thcse two substances is exactly the same viz. 0.260 grru. of Japanese camphor of peppermint dried at looo gave 0.732grm. of carbonic acid and 0.315 grm. of water or in 100 parts. Japan camphor Dumae of peppcrmint. American camphor. Calculated. C i6.93 76-5 76.92 H 13-40 13.1 12.82 0 , 9 10.26 This corrcsponds with the formula established by Dumas C,,€I,,O.t Walter verified this formula in 1830 by determining the vapour-density of the corresponding hydrocarbon Cl,HIB.The nature of this body which on many grounds claims our attcntion has not been determined by either of these chemists. Whether it be an alcohol an aldehyde a ketone or of a nature less distinct (like the hydrates of oil of turpentine) it possesses particular interest from the fact of its bordering on’the two great groups of organic chemistry the group of fatty and that of aromatic bodies. To the former it is related by being isomeric with capric aldehyde and to the latter by diff’ering from a number of aromatic bodies merely in tlie number of its hydrogen-equi- valcnts. The camphol of Berthelot C,,H,,O differs from it by two equivalents of hydrogen ; common camphor Cl,H,60 by four ; the cuminic alcohol of Rossi C,,H,,O also thymol and carvacrol by six; and cutninol C1,Hl20 by eight equivalents of hydro-gen.The relation of camphol and camphor being that of an alcobol and its aldehyde,$ the position which the camphor of peppermint holds towards them mill call for our particular attention from their being related not only as regards their composition but also with respect to their physical properties. The peppermintcam- phor turns the plane of polarization to the left. Gerhardt Trait6 de Chimie Organique vol. ir. p. 357. + C = 12; H = 1; 0 = 16. Berthelot “La Chimie Organique fondue sur la Synthbee.” A. OPPENHEIM ON TH.E A preliminary determination of its rotatory power has been arrived at by the aid of Dubosc's saccharometer.A tube 23mm. in length waa filled with a'10 per cent. solution of peppermint-cam-phor in alcohol when it was found to deflect the plane of polariza-tion as much aa a plate of quartz QUmm. thick. This corrc-sponds to an angle of 10*56'=a and to a molecular rotatory power,-a [a] = -= 59.6. 1€6 Peppermint-camphor is but slightly soluble in water although it imparts to the liquid 8 strong odour and taste. It is very soluble in alcohol ether sulphide of carbon and in fatty and essential oils ; insoluble in aqueous solutions of alkalies. From an alcoholic solution of soda it crystallizes in long needles. A current of sul- phurous acid or of hydrochloric aoid gas dissolves it. By evapo-ration the acids pass off leaving the peppermint-camphor unaltered.Concentrated acids especially nitric sulphuric hydrochloric formic acetic and butyric acid dissolve it very freely. From these solutions it is separated by water as well as' by alkalies as an oil which soon solidifies and then exhibits the original properties of the camphor. When concentrated acetic acid is heated with peppermint- camphor in a scaled tube for ten or twelve hours at about 120°C. these two bodies combine into a light oil no longer decom- posible by water or by cold solutions of alkalies. After washing with carbonate of soda and drying over chloride of calcium it boils between 222' and 224" C. without decomposition. I. 0.303 grm. of this distillate yielded hy analysis 0314 grm. of water and 0.827 grm. of carbonic acid. The same body is obtained by the action of anhydrous acetic acid on peppermint-camphor.11. 0.330 grm. thus prepared gave 0.303grm. of water and grm. of carbonic acid. T. n. Calcnlnted. C 73-06 72-58 72-73 H 1~04 11.18 11-11 This agrees with the formula,- Tlirit is pcppcrmiiit-cnrnl)lio~ i ii which onc cquivalcnt of liyilrogcn his hccn siibstitutctl by acctyl so ;~sto form ;Icompoitnd cthcr. Tliis Iiotly is Iiiglily rcfractivc mid tlcflccts the planc of polari- zntioii to thc lcft nioi-c stroiigly tli;iii tlic camphor from which it is dcri\*cd. By 1)rcliniiii:iry ol)scr\liLtiori with tlic sacclinrom(:tcr its molcculrrr rotal.ox-y power [a]1111sIiccii fouiid = 1I,laO. 1Iydratc of harytn. docs not sc'citi to tlccomposc it ; hut 1)y licntiiig it with mi alcoliolic solution of sotla to 1%" C.for tlircc Iioiirs it is pcrfcctly dccompoeccl iiito acctntc of so[l;i mid an oil wliicli soon coiigcals iiito n crystnlliiic mass not iiiilikc conimoii camphor. Aftcr \icing iircsscd 1)ctwccn blottiiig-l)apcr it distils at 210' C. fuscs at 3.10 mid cxliiliits othcrwisc tlic original propcrtics of pc~q)cnnint-cnniplior. I1ntyric acid comhics with pcppcrmint-camphor on bcing hcatcd with it to 200°C.for about thirty hours. The product mas scpnratcd into two parts distilling from 230' to 240" and from 210 to 250' respectiwly. Tlic fornicr of tlicsc portions gavc thc following analytical rcsults :-0.287grm. of thc liquid gnvc 0.303 grm. watcr and O'i92 grru. of carbonic acid corrcsponding to tlic forniuln which is that of butyratc of InciitIiFl; in 100 parts,-Foiind.Calculatcd. c 74.84 $4.33 H 1174 11.50 A prcliminary dctcrniinntioii of its rotatory ponw gnyc [a] = 88-8(:'. A coriccntrntcd solutioii of liydrochloric acid acts on pcppcr- mint-camphor at 100° C. But it is neccssary to licnt thcm together for a wcck iii ortlcr to olitaiii n coiisitlcrablc qiiantity of chloridc of mcntlipl. lit a tc.mpmtiirc of 1%' C. twcnty-four Iioiirs siifficcl to coiiiplctc tliis rcartioii. Tlic elilorirlc of mc-iitllj*lmay I)c \vaslicd witli carlionatc of soda hiit it rlocs not 1)c:ir tlistillatioii. Tlic followjng analyscs mcie m;itlc with non-distillcil portions of tlic liquid dricd ovcr chloridc of cn1ciii.m :- A. OPPENHEISI ON TEE I.0.323grm. gave 0.332 grm. of water and 0-794 grm. of car- bonic acid. 11. 0.382 grm. gave 0.296 of chloride of silver. 111. 0.310 grm. gave 0.206 grm. of chloride of silver. This corresponds to the formula C1,HlSC1 or in 100 parts 1. n. 1x1. Calculated. C 67.06 > * 68.62 H 11-32 , >> 10-89 c1 , 19.16 19-67 20.34 The same body was obtained by Walter by the action of perchloride of phosphorus on peppermint-camphor. Iodide and bromide of phosphorus react very strongly on this body; but as the resulting bodies bear distillation aa-little as the chloride of menthyl these methods are not advisable for obtaining them. Hydriodic acid combines with peppermint-camphor at about 120° C. Sodium acts very strongly on peppermint-camphm It dis-solves therein when fused; and disengages hydrogen.By raising the temperature about one equivalent of sodium map be made to unite with the fused camphor forming a vitreous transparent mass white originally but becoming brown and moist when exposed to the air. It is decomposed by water but soluble in absolute alcohol and in iodide of ethyl. The reaction of this body on the sodium-compound is not so simple as might be expected. When heated to loo" the transparent liquid solidifies but continues to be soluble in a mixture of ether and alcohol. From this solution deliquescent crystals may be obtained which contain iodine sodium carbon and hydrogen ; but continued evaporation decomposes these crystals into iodide of sodium and an oily sub-stance which does not appear to be the mixed ether expected to be formed by such reaction.The products of this and of similar reactions form the subject of the continuation of these researches. From the compound ethers and the sodium-compound hitherto obtained it is already evident that the caniphor of peppermint is a monatomic alcohol having the formula- C10H191 H O* It belongs to the general type and is therefore homo- logous with the allylic alcohol of IIofman and CiLhours and with tlic acctylic alcoliol of 13t:rtliclot. 11s it is isologous with cam-pllolic alcohol the iiatnc w~u!/idicufco/id or menthol may perhap bc advantageously substituted for that of camphor of pcppcrmint. Tfic corrcspontling hydrocarbon menthene C,,H, which Waltcr obtained by the action of phosphoric acid may likcwise bc protluccd in various other ways.It has been found among the products of tlic reaction of chloride of menthyl on ethylate of sodium. The most advntitagcous may of preparing it scems to he to react on mcritliol with chloride of zinc. Prepared in this way the meutlmic has no action 011 polarized light. It boils at 163' C. 0.227 gm. yielded by analysis 0-282grm. of water and 0.733grm. carboiiic acid ; in 100 parts-Found. Caldated c SG.39 86-94 I1 13-65 13-05 Bromine docs not combine directly with this hydrocarbon. It reacts on it wry violently disengaging currents of Pydrobromic acid and forming various products of substitution of no stability whatever even at ordinary tcmpcratures.By adding drop by drop two eqiiivalents of bromine to one of mcntheue monobroniiiiatcd menthene ClOI~,,Brmust be formed which by the action of oxide of silver or of hydrate of sod:i might he traiisformcrl into camphol. But this reaction gives risc to a hydrocarbon CioH16 boiling between 170" and 175' C. C,,H17Br + =' -I-14I 0 + C,,H,G. The acid corresponding to mcnthol is identical or isomeric with the campliolic acid of Delalande Cl,Hl,O,. The ordinary oxidizing agcnts such as nitric acid chromic acid &c. do not protliicc this acid. They at once attack the carbon of thc meritholic alcohol. I hopc howevcr to be able to produce it by a less direct method of osidation.

ISSN:0368-1769    

DOI:10.1039/JS8621500024

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

30 VI.-On mme Physical Properties of the Alloys of Tin and Lead. By PROFESSOR Bo L LEY. At the Conference of the Chemico-Technical Scction of the Swiss Polytechnic School at the end of the session 1858-9 the following prize problem was offered for solution the award to bc made in May 1861 :-1. A survey of all researches hitherto published on the physical propertie~-especially the hardness fusibility and specific gravity of the alloys of tin and lead. 2. Preparation of nine alloys containing definite equivalent quantities of these elements viz. :-1 equivalent of tin to a 4 4 % 1 l+ 2,3,and 4 eq. lead. 3. Determination of the specific gravities and melting points of these alloys ; also of their relations as elements of a simple voltaic circuit in connection with tin lead and ziuc and in presence of acids alkaline liquids and dilute saline solutions.The prize was .awarded to G. Pillichody of Bern from whose Essay we here extract the most interesting results. The experiments were made in the Technological Laboratory of the Institute. a. Specific Gravity.-From a comparison of the researches of Kup ffer Long and Tho rn p son it appears that the specificgravities of the alloys of tin and lead exhibit considerable variation. The author'^ determinations agree most nearly with those of Long. He found in accordance with Kupffer that the specific gravities of these alloys as determined by experiment are smaller than the mean values calculated from the quantities and specific gravities of the component metals; but that (contrary to Kupffer's statements) the expansion-that is to say the difference between the observed and calculated densities-is greatest in the alloy SnPb so that with an increase in the proportion of either metal the specific gravities as determined by experimeut and by calculation approach more nearly to each other.IIOLLEY OX ALLOYS OF TIS Axil) LEAD. TIicsc rclutiom wc cx1iil)itcd in t'iic fdhviiig tablc :-Pillichodj. . 01,s. Cult. Sa Pb .. Sn 1% .. Sn 1% .. Sn l'b .. Sll PI1 ..... Sn .. Sn PI) . SI1 1'5 . su 1'). . The author's results atford bn additional proof that very little deixmdcnce is to be placcd 011 the hydrostatic mctliod for the determination of the composition of lcad and tin alloys.b. Melting points.-'Phc statcments of difl'crciit authors respcct- ing the melting points of the alloys of tin and lead cshibit even grcatcr discordance thn thosc which relate to the specific gravities. Most of thosc who occupicd themsclves with thc subject prior to tlie investigations of ltudbcrg or without knowledge of those investigations neglccted to obscrvc a very important circum- stance perhaps the most jritcresting of all corinectcd with it. This circumstance is casily overlooked if only the melting point be obscrvcd instcad of tlic solidifying point which givcs much morc trustworthy rcsults. Whcii the lattcr method is followed the tbcrmomctcr immcrsed in thc melted alloy usually exhibits during the passagc of the mass from the liquid to the solid state two stationary points.This effect is due to the separation of ouc or other of the compouent metals while an alloy of constant composition still remains liquid. This alloy has thc coxnpositioii Sn,l'b. An alloy 'richer in lead would first dcposit lcad and an alloy containing il larger proportion of tin would first dcpsit tin-the alloy Sn,Ph. remaining liquid for a longcr or shorter timc and ultimatcly solidifying at about 181' C. Tliis tcini)eratnrc thc-refore corrcsponda to the lowest melting BOLLEY ON ALLOYS OF TIN AND LEAD. point that can be exhibited by an alloy of tin and lead a largcr proportion of either metal caiiscs the melting poiiit to rise. Rudberg determined oiily the intervals of time which elapsed during the fall of temperature through each 10°C.He also employed a thermometer the zcro of which according to his own statement hail not been exactly determined. Pilli ch ody’s experiments on the other hand were made with an exact ther- mometer arid with all the precawtions reqiiired in observations of this kind. In all these detern1inations the constant solidifying point was found to be exactly 181°C. Tuble of the Melting Poi)ils of Allop of Tin and Lead. Pillichody. Rudberg. Thomson. Kupfler. Parkes for Sn4 Pb ........ 187 190-180 190 189 (9 Sn+4 Pb)Ii3 Sn3 Pb ........ 181 190- 180 182.8 186 16893(6 +4) Sn2 Pb Sn3 Pb2 ........ ........ 197 210 210-200 - 182.8 - 196 - (;A42 Sn Pb Sn2 Pha Sn Pbz ........ ........ ....... 235 246 270 250-240 -280 -290 182.2 - 24 1 -289 (47 7)215.7 243.3 (4 +14) (4 +10) Sn Pb3 Sn Pb ....... ........ 283 292 290 -280 - - 254.4 269.4 (4 i-28) (4 f 22) 275 This Table shows that Thorn son who probably also sought for the solidifying point overlooked the variable and observed the thermometer in the neighbourhood of the constant solidifying temperature. Of this constant point no notice is taken either by Prtrkes or by Kupffer.

ISSN:0368-1769    

DOI:10.1039/JS8621500030

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

BOLLEY ON ALLOYS OF TIN AND LEAD. VIT.-New experiments on the Dangers arising from the use of Certain Wutersfer feeding Steam Boilers. BY PROFESSOR EOLLEY. IT has hitherto been received as a kind of dogma in chemico- technical literature that waters which when evaporated. denosit nOLLEY ON WATERS FOR FEEDING STEAM BOILER% 33 only the carbonates of lime and magnesia are bettcr adapted for feeding stcam-boilcrs than those which likcwisc yield sulyhate of lime because the latter salt even in amdl quantity imparts to the deposit a stony cohcrcnce whererrs the carbonatcs arc deposited in the form of a soft mud. That serious mischief may arise from the formation of a stony incrustation on the srirface of a boiler is well known whereas the dcposition of mcrcly pul- verulerk mattcr has not hitherto been observed to crcatc much inconvenience.Most of the remedies proposed far thcse evils havc likewise for their object the convcrsion of thc sulphatc of limc into carbonate ; that is to say ; the production of a muddy in placc of a stony deposit; such for example is the action of carbonatc of soda. Since the practice of heating steam boilcrs vith cod has hen introduced into Switzerland many serious disturbanccs liavc hcen observed in the functions of boilers wliich wcre qnitc iinl<nown so long as they were heated with mood. Both old arid ncw boilcrs heated from within (the Cornish or Fairbairn construction) have become red-hot at the uppcr part of the flue ncar the firc-place while the water-gauge showed that tlie lcvel of tlic watcr was several iuahts above the heating surface.The boilcr-platcs started and had to he taken out and rcplaccd by ncw oiics but without any dimiiiution of the evil. The first of these cascs in which as well as in thc sccond I was consulted by thc well-known cnginccring firm of Esch er Wyss arid Co. happcncd in the Canton Zurich. The water used for feeding thc boiler vas taken from the Jcnal~acli on the southcrn declit ity of the Bachtel. Samples from tliff'crcnt parts of the strcam mcrc scnt to mc for csaminntion. Thrcc samples wcre analysetl and yicldcd thc following proportions of sokd mattcr and carbonate of limc In 1 litre. Total solid residue. Car\cnntc of limc. Samplc a. . . 0*2i2 grm. O.22X gi'iri., b. . . 0.232.E , I> '' . . O*.%l..'!G , 0.2010 , The water contained very little organic mattcr ; szdphates wtre entirely absent ; silica alummn magmsia axid allinline salts were present in small quantity only as compared with the carbonate of BOLLEY ON IVA'L'EliS FOR lime.. The water may be dcscribcd as pirc but rathcr liard-thc harducss beiiig of tlic kiiicl callctl twipor';try. It was sugg;cstcd that tlic niiscliict' d~ovoiiiciitioiicd might arisc from tlic circuiiistancc that above tlic 1)liicc at which tlic wtitcr was drawn for fccdiug tlic boilcr tlic rcfiisc water of n bloacli-work was rliscliargcd iiito thc strcain. A lwttlc of' tlic mastc lhicliiiig liqui(i was tlicrcforc 1ilicwi sc sciit fo c csiiiii ii i;it ic iI.It coi i t ai iicd in solntioii quick lime clilorictc of ~id~i~iii aiid a small quantity of decomposcd cliloridc of limc. 011 mixing it with thc water of the stream a stroiigly milky turldity was prodiiccd. So far there was notliing that +lit iiot liavc bccn cspcctcd but at tlic top of tlic liquid in tlic llottlc tlicrc was a laycr of futty mutter; wliich aftcr mising with water soiutioii iii ctlier and cv:y)orntioii remaiiicd in tlic form of n thickish oil. IIow this coinlwativcly largc quaiitity of fatty imttcr got iiito the hlcaching liquid conld not be asccrtained. The boilcr contained a coiisidcrahlc qiiaiitity of a whitish grey pulverulent deposit coiisisting cssciitially of carbonate of limc. By careful searckiug however certain substances were found in it mcchaiiically mixed; viz.black scaly particles of iron ferric oxide aiid adhcring organic matter which became perceptible on hcatiiig and rcd granules which were fonnd to consist of the remains of a red lead cement. The powder separated from the water eshiliitcd a furtlicr peculiarity. When thrown on water it swam on the surface did iiot become wet hut remained in ids place and drg evm cfter prolonged boiling. A portion of this powdcr was well dried on the matcr bath and then treated with ether wliicli extracted a small quantity of fatty matter. The cause of the plienonienon above-mentioncd was now apparent. Tlie pulverulcut dcposit in the boiler completely covercd the licatcd siirfacc of the flue so that this surface did not come in coiitnct with the water.The qiimtity of powder in the 5oilcr was so largc tliat it must have formed a layer several inches t1I i ck . Tlle ftlttp su1,stsnce which had found its way iiito the water sur-rounded the particles of the precipitated carboilate of lime with a lRper zol~icl~ cozslcl not Be wetted by the water; and in consequence of this Ivant of adhesion the powder mas kept floating on the surface. The powder after being treated with ether ad dried FEEDIXG STEAM ESGIKES. sank easily under water and in its original state was easily wetted by alcohol. The preccding investigations did not however afford any precise iiiformntion as to the nature of the fitttp substance. But shortly aftern-ards I was made ncquaintcd with mother accident of exactly the same kirrd wliich happened to a boiler in the Canton Tllurg:Iu.'Hie watcr with whicli this boiler was supplied n-as found to con- tain as a means of two espcriments 0.2417 grm. solid matter per litre 0.045 of which consisted of orgauic matter containing traces of nitrogen. The residue from four or fire litres of this water was 'distilled lyith a slight exccss of clilute sulpliu~~ic acid tlic distillate had a distiiict odour of butyrlc acid. In this boiler also a considerable quantity of whitish pul\-erulent matter mas deposited mliicli so far as I-could ascertain was free from mechanical impurities. This powder also was not wetted by water. On boiling half a pound of it with distilled water and gradually adding carbonate of soda the powder was at length thrown dowr to the bottom and an alkaline liquid was formed; containing the fatty substance in solution.After filtration and concentration it was mixed with a small quantity of hydrochloric acid ;the odour of hutyric acid then became perceptible and small drops of fat mere separated which did not disappear on dilution with water but hy agitation with ether and subsequent evaporation yielded a small quantitv of a nearly odourless oily body. I was at first of opinion tliat the butyric acid might have existed naturally in the water inasmuch as this acid has been found in many waters deriyed from peat-bogs; but on discovering tlie fat insoluble in water I abandoned this view and subsequently learnt from Mr.Jackson Dircctor of the factory of Esclier Wyss and C o. that the water supplied to the boiler was taken from the condenser of another steam-engine and consequently might have derived the fat from that source. It showed however scarcely any turbidity; arid all the results obtained with it led to the conclusion that the quantity of fat contained in it was very small. Practically the origin of the fatty niatter is of little consequence. By my recommendation a small quantity of solution of carbonate of soda was added to the water supplied to the boiler and by this means the inconvenience above described was completely obviated. It likewise ceased when the water was no longer taken from the condenser of the otlier ena. O'ine. J.Xi. NEWLANJM ON-THE CONSTRUCTION OF I regard these experiments as well worthy of attention. That observations of such cases and enquiries into their causes have been previously published I have not been able to iind. Never-theless though various conditions must conspire to produce the result in question it is very probable that such concurrence fre- quently takes place. The results of this investigation may be summed up as follows :-1. When a boiler is fed with water which deposits only carbonates unmixed with sulphates the preseucs of very small quantities of fatty.mattw may cause the deposit to assume a dusty instead of a muddy consistence. Under such circumstances rubbing the inside of the boiler with grease can only do mischief. 2.This pulverulent character of the deposit may cause those portions of the boiler-surface which are strongly heated and. directly covered by the ' powder to become red-hot thereby giving rise to explosions and all their attendant consequences. 3. In such cases as wdl as when the water contains sulphates the addition of a small quantity of carbonate of soda will be found very usefbl. 4. The effect so far as regards the form of the deposit is probably independent of the kind of fuel employed it appears however from the observations hitherto made that the heating of the boiler plates to redness takes place only when the fires are fed with cod this kind of fuel producing a more intense heat in the immediate neighbourhood of the burning mass.

ISSN:0368-1769    

DOI:10.1039/JS8621500032

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

J. Xi. NEWLANJM ON-THE CONSTRUCTION OF V111.-Qva the C~nstructionof Table8 exhibiting the Cornpition and Mutual Relations of Oryunic Substances. By JOHN A. R.NEWLANDS, F.C.S. THESE Tables may be formed hy arranging all homologous series (whether kuomn or otherwise) in tvro directions vertically accord-ing to the difference in the number of equivaleiits of C and H and horizontally according to the number of cquivalents of 0 con-tained in the general formula of each wries or vice versii. TABLEH BELATIlW TO OBGAAIC SUBSTANCES. The accompanying Table map ierve as a Bpecimen of those of a more complete character it is divided into a number of types uder each sf which are placed all eubstances homologous or isomeric with each other. The following are the principal relations observed on contrasting bodies belonging to these various types :-I.Vkrtically. 1. Bodieb differing by H as C,HI10,“ amyl-glycol ;C5H?,01 vderianic acid; CSHBO angelic acid ;and C,H6O picro-toxin. 2. Bodies differing by C as C,H,O” ethyl-glycol ; c3H60 propylic acid ;C,H60 crotonic acid ;C,H60 picrotoxin ; C,H60 oxpphenic acid; C,H,O benzoic acid; and C,H60 cumarin. 3. Bodics in which C and H replace each other as C,H,O1 biityric acid ; C,H60 picrotoxin ; and C,H,O kinone. 4. Bodics in which C arid H replace each other as butyl- glycol C,H,,0/ ; aid picrotoxin C,H,O,. 5. Bodics differing by CH as C,H,O benzoic acid; C,H,OO tcrebeutiiic acid; C,,H,,O eampholic acid; and C,,H,O margarit ic acid.TI. Horizontally. Bodies differing by 0 as C,H,” propylene C,l160 propyl-aldehyde or allylic-alcohol ; C,H60 propylic acid ; C,H60 lactic acid; and C,H,O glyceric acid. III. Diagonally from lcft to right. 1. Bodies in which 0and H replace each other as C,H60 alcohol ; C2H,02 acetic acid; and C,H,O glyoxylic acid. 2. Bodies differing by CO as CH,O methylic alcohol C2H,0 acetic acid; C H 0 pyruvic acid; C41J404” fu-maric acid; and C,H,&,” meconic acid. *3. Bodies differing by CO,. A few of these are here given from which it may be seen that monobasic bibasic and tribasic acids and also hydrocarbons and alcohols mtty be formed from each other‘by the addition or subtractim of co,. * The diagonal line exhibitiig thie relation ie drawn from the epsce immediately to thc right of a substance ; ane in the case marked thus f from the apace hme-diately to the left.In the remaining instances the diagonal lines are’drawn directly from Lhc sulatancc itsslf. Hydrocarbons alcohols &c. Monobasic acids. H2hydride of hg drogen CH20 formic acid CHI , methyl C,H,02 acetic acid CzH ) ethyl C3H,02 propylic acid C”H602ethyl-glycol CSHGO glyceric acid -CHIO methylic alcohol C2H403glycolic acid C2H60 ethylic ) C3HGOs lactic acid C3Hs0 propylic , CAHS03 CSH1002 CSH1004everninic acid C2H4“ethylene C3H402acrylic acid C3H6“propylene C4Hs02crotonic acid CfiHfibenzol C;H& benzoic acid CTH toluol CSH,O2 toluylic acid [acid C,H,O pyrocomenic CGHG03 pyrogallic acid Bibasic acids.Tribasic acids. C2H204“oxalic acid C:J1404fi C,li~O,“succinic acid C4H80611 tartaric acid C3H405tartronic acid CJHGOs‘‘malic acid cjC4€I 1-4;Oi”~Oi/” CjHyOjrr C,jHJji”’ citric acid C 2 CloHloOG“ hemipinic acid fumaric acid CjHAOG”’ [acic C4€I4O4“ citraconic acid CtjHgOG”’ aconitic C5HG04” CsHr,O,” phthalic acid C,Hs04” insolirric acid CGHdOj” comenic acid C;H,O,” gallic acid TABLES REI.ATINO TO ORGANIC SUBSTANCES. A tnble of this sort constitutes a8 it were a map of Organic Clicniisty wilicrciii riicli substarice is surroundcd by its derivatives and thoac from wliicli it is dcrivable. Thus rclations between the forinulz of botlics cannot fail to bc dctccted by the moat casual obscrver niany of which might otherwise escape the view of those wcll acqunititctl M ith tlic scicnce.For instance the formula of kiuic acid C,II 120G” is lioniologous with that of tartaric acid C,I-IGOfi”,-n rclation which is confirmed by the similarity of their crystals. This suggests the possibility of pimclic acid C,H,,O,” Iicirig forrnctl hy tlic rcduction of kinic acid just as succinic acid (’,II&“’ is formcd from tartaric or vice vers8. An unknown I~ol~loIogucof mdic acid C411605” having the compositian (‘i1~l,2(~s’‘,niiglit also be prutlucetl and would serve as a connect-ing liiik lxtivccw piinclic arid kiiiic acids. Otlicr Iioni0logous forniulx arc,- Extract from (I Tabkc mhililing the Composition and Mutual Relations of Organic Subatancecr.By John A. R.NEWLANDS, F.C.S. GH2ll+20 CH,0 methylic alcohol C21I,;Oethylic alcohol C,Il,O propylic alcohol CnH?,O CH20 C,1I4O aldehyde C:{IL,;O allylic alcohol CnH:n +202 CH40," C2HG0," ethpl-glycol C,H,O," propyl-glycol ~ ~ ~~ CnH21102 CH20 formic acid C,H,02 acetic , C:,HGO propylic ,) C,, H?,,-202 CI.H,O glyoxal C,11 ,O acrylic acid C,€I,;O crotonic , CIIZInn -902 CjH,Oz Cl,H.,02 kinone C;H,02 benzoic acid I I CnHrnOt CH,03" carbonic acid C2H403 glycolic ), C3HB03 lactic , CnH2n-603 0 3 [acid C5H40 pyrocomenic CbH60 pyrogallic acid

ISSN:0368-1769    

DOI:10.1039/JS8621500036

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

44 1 IX.-Note on n Method of cfecting the substitution of Chlorine for I$ydroyeri irz. Organic C’orrzpounds BYHUGO MULLER. INthe investigation of Burmese naphtha madc a few years ago by Mr. Warren De La Rue and myself we eiideavourcd to obtain some definite iodine-compounds of thc hydrocarbons coritaincd in it by acting upon them with mono-and ter- cliloridc of iodine hoping that this reagent would act in this case in a similar \vily to that observed a short time hcfore by Brow 11 in tlie case of pyrome-conic acid. These experiments did not however givc tlie expected result but nierely the same chlorine-compounds that were already 0bt;iilictl by using chlorine only. Tlic result was the same when iodine was dissolved in tlie hydro-carbon mil chlorine passed into the deep violet-colonrcd solution.The oiily difference observable bctween the action of chloritic in prcsciicc of iodine and that of chlorine only was that in the forincr case thc action took place much more quickly tliari in the latter. Having some time ago commenced a scries of expcrimcnts with the vicw of obtaining from benzole the corresponding alcohol and acid I had occasion to invcstigatc the action of chlorine on this hydrocarbon. Chlorine is absorbed to some extent by bcnzole but if light be excluded no pcrceptiblc action takes place until the benzole is heated to the boiling point ;hydrochloric acid Is then liberated and chlorine-derivatives are formed but very slowly. In this reaction two series of compounds are formed namely CGH6C12 C6H,Cl, C61-16Clq and C,H,Cl C6W,C12 C6H3C13 The experience gained in the above-mentioned .experiments with Burmese naphtha induced me to try upon a large scale the action of chlorine upon benzole in the presence of iodine.When chlorine is passed into a saturated solution of iodine in benzole it is completely absorbed evcn when the current is mode-rately rapid and after the violet solution has become brownish red owing to the formation of monochloride of iodine hydrochloric MULLER ON THE SUBSTITUTlON OF CHLORIXE acid is liberatcd and chlorine-derivatives arc rapidly formed. In this may 1 hare 0-btained the compounds C6H,Cl C6H,C1, C6H ,C1, and wheu an excess of chlorine was used a beautiful crystalline compound which was previously obtained in small quan- tities 011 trcatiiig the hydrocarbons of Burmese naphtha in the same manner.It deserves to be noticed that whereas when chlorine acts alone upon bcnzole the chief products of the reactioii are formed by its dircct union mitli tlie hydrocarbon the action of chlorine in presence of iodine gives rise to substitution-products and the evolution of Iij+lrocliloric acid. I rcseri-e the dctailed description of tlie products of this re-action ‘and the method of obtaining tlicm in a pure state for a future conirriunication ;what I wish especially to draw attention to upon this occasion is the remarkable cffcct of iodine in facilitating the action of chlorine upon organic compounds. I have already ascertained tlint many substanccs which are actcd upon with great difficulty by cliloriiic donc and some of them only with the aid of direct sunliglit yield cliloriuc-products with great ease when acted upon in the maiiiwr dcscribed by chloririe in tlie presecce of iodine 1 have found for instancc that benzoic acid dissolved together with some iodinc in chloroform is acted upon by chlorine very readily with evolution of hyrlrochloric acid.Bisulpliide of carbon in which iodine is dissolved is acted upon by cliloriiic rciy frccly at its boiling point giving chloride of carbon cliloride of sulpliur and a highly volatile substance having a very irritating and puiigent cdour mliich is perhaps the chloro- sulpliicle of carlmxi which Kolbc believer1 he ltad obtained by exposing sulp!iicle of‘ carbon to the action of chlorine in dircct sunlight.The proccss I hare described promises to give this substance in sufficient quantity to admit of ascertaining its true nature. Wlicn cliloriiie is passcd into a solution of iodine in glacial acetic acid in thc cold tcrcliloridc of iodine is fornicd but the acid is not acted upon. If liowcvcr the acid is kcpt boiling whilst the clilorixie is being passed into it liydrocliloric 2cid is given off and cliloracctic acid is fornicd even in tlic dark. This affords a ready means of obtaiiiing .cliloracetic acid a substance whose preparation according to the usual method requires the aid of strong sunlight and is commonly very tedions. If the action of chlorine be continued a higher chlorinated acid is obtainkd which FOR HYDROGEN IN ORGANIC COMPOUNDS.43 does not solidify cven at O3 C. and which appears to he bi-chlor- acetic acid.* It seems likely that in this reaction the iodine acts merely as a carrier arid condcnser of the chlorine; the effect is very similar to that of some perclllorides like pentachloride of antimwip and in some cases pentachloride of phospliorus which nct upon many organic substances as if they were mixtures of terchlorides with free chlorine. I may illstance hcre the formation of Dutch liquid from olefiant gas and pentachloride of antimony according to WG hler aud the case of the transformation of bisulplde of carbon into chloride of carboii and chluride of sulphur by means of pentachloride of antimony mentioned by Hofmann.On comparing the action of pentachloride of aqtimony with that of chlorine in presencs of iodine upon the substances above mctitioncd I find that the fornier agent is rather more energetic and posscsscs a teridency to produce the higher chlorinated dcri- vatives. Bciizole adclcd in small qiiantitics to pentachloride of antimony is acted upon with great violence and there is at once formed a clilorinatecl derivative which crystallises in beautiful white prisms nearly insoluble in alcohol and not acted upon by alcohoiic potash. Succinic acid when brought in contact with pentachloride of antimony soon evolves hydrochloric acid and if the reaction is supprted by application of heat clilorosuccinic acid is formed.If however the mixture of succinic acid with pentachloride of airtinioiiy be kept warm whilst a current of chlorine is passing into it th succiriic acid is gradually decomposcd into volatile products. I am still engaged with the examination of some new products of these rcactions a full account of which I hope shortly to lay before the Society. Since tlie abovc was written I have found that together with the chloracetic acid there is invarialAj* some iodacetic acid formed and it appears that the for- mation of the latter is favoured by an exccs of iodine used in the proces. I have not ascertained wvhcthcr the remarkable compounds lately obtained by Schu tzen- bcrger by thc action of chloride of iodine upon acetate and benzoate of sodium are formed when clilorine acts ripon acetic and beozoic acid in the presence of iodine; but as thhe compounds are already decomposed at 100" C.their formation can hardly be expected under the circumstances.

ISSN:0368-1769    

DOI:10.1039/JS8621500041

出版商:RSC    

年代:1862

数据来源: RSC

摘要:

ANDERSON ON THE CONSTITUTION OF X.-Ot&the Con.ditution of Anthracene or Paranaphthalira ad some of its Products of Decomposition By THolrrAs ANDERSON, M.D. F.R.S.E. Profcssor of Chemistry iu the Univcrsity of 01asg:ow. [Abstracted from the Tmnwtions of the Royal Socicty of Edinburgh,vol. xxii part iii.] THEsolid cornpounds of carbon and hydrogen 'form a class of substances to which cliemists have scarcely as yet paid that attention which their importance and interest appear to merit. With tlic exception of naphthahi very little is known regarding them and it is remarkable that the numerous and wried products of decomposition obtained from that singular substnncc sliould not have induced a morc minute examination of the kiridred com- pounds whose existence has \,cell indicated by differcut cliemists.The intcrcst ,attaching to thcsc compouiidu is all the grcatcr because according to their cliscowrcrs several of them are isomeric or at Icast polymeric with iiaplitliiiliti ; and r?. niore careful examination of them might be espectcd to throw some light on their intimate constitiitiou and tlicir relatioils to that body. No fewer than five substances said to be yolyineric with naph-tliah have been described. The arc paranuphthalin or antiwa-ceHe rnetannphthalin or retistcrene pyrene and two substances not yet nztmcd which occur together with benzene and benkopheiione among the products of the destructive distillation of benzoate of lime aid arc apparently quite distinct from one aiiotlm and the other three.All of these substances; except naphttialin have hitherto been obtained in small and some of them in very minute quantity so that. their ccnstitution has been in most instaims fixed by analysis alone ;and the difficulties atteriding the analysis of highly carbonaceous compounds at the time they were made as well as the absence of any control derived from the examination of their products of ciecomposition have naturally occasioned some doubts as to the accuracy of the formulae assigned to them. Paranaphthalin or antlirilcenc which was discovered ly Durn as ANTHRACENE OK PARANAPHTHALIN. and Laurent in the year 1832,* is the only one of these sub-stances whose examination has extended beyond the mere analysis ; and the determination of its vapour-density by the former chemist gave for it the formula C&H12 which the examination of some of its dccomposition-products by the latter was supposed to confirm.A critical examination of Laurent's experiments by no means bcars out this opinion. They are in many respects extremely imperfect were obviously rnade.on a very small quantity of mate-rial and the formulz (mostly deduced from a single analysis) are so improbable that there can be but one opinion as to the neces-sity for submitting the subject to a further investigation. Anthr:iccnc as is well known from the observatious of Dumas and Laurcnt is met with only among the latter portions of the distillation of coal-tar. It has hen little seen by chemists because hitlicrto the distillation has not generally been pushed so far as to yield it in quantity ;but during the last fcm pears thc demand for thc asphalt and the highcr oils having increascd the distillation lias been carried further aiid it has bcen found abundantly in sonic of thc products and even been used in the manufacture of macliiiiery grcilse.I have arciiled myself of the opportunity which ;Lla1ge supply afi'orcled of cxtciiditig the esaminatiori of aiithra-ccnc arid with the result of showing that its constitution diflers from that attrihutcd to it by its discoverers and that it is not ply mcric with naph thalin. Bcforc eiitcriiig 011 the details of my own experiments it mag be advisa1,lc to recapitulate shortly the history of tlic substance. As alrculy atatccl it mas discowred by Dunias arid Laurent worliiiig in coiiccrt in 1832 aiid dcscrilml by the former chemist wllo attributed to it the formula C3()H12,with which his results corrcsporitlccl very closcly.111 1835 Laurcn tt descrilicd under tlic 11;1111c ofyaru,iui,ltf/iuk.se il compound to wliicli hc giws the formixla (&1l8O4 mid lie nppcars to have regarded it as a direct product of' the action of nitl-ic acid on anthraccne. In a subse-quciit pa.pcr$ lie cxtciids his investigation in this direction and descrilm iia~f'cwcr than fivc ilifYcrciit iiitro-compounds and assigns to tlicni wry prohlemntical forniulz. In this-paper he agaiu refer3 to i';~r'"'i.2l)litli:tlesc, Init uiidcr the rinmc of antjiraceizuse giving it tllc f'orriiula C,H,O, aid stating that it is not it pro-* Allll.CI1. l'!lJS. 1 137. I.Ann. Cli. I'iiyj. Ix. 2%. $ Thill. Ixxii. 415. ANDERSON ON THE CONSTITUTION OF duct of the direct action of nitric acid on antbracene but formed by the decomposition of a nitro-compound in a manner precisely similar to that in which naphthase is obtained from nitronaph-thalin. He mentions that a substance of similar properties is obtained from several of the nitro-compounds he prepared but leaves it an open question whether it is in all cases the same or whether it differs in constitution according to the nitro-compound from which it is produced. He also describes a chlorine substitu- tion-product and adopts the name of aathracene-a change even then advisable and which the results of my investigation show to be quite indispensable Crude anthracene is in the form of a soft yellow mass not unlike palm oil but with a greenish tinge and harder consistence; in this state it contains a little naphthalin and a considerable quantity of oil of high boiling point which 'causes it to leave a greasy stain on paper and to melt easily when rubbed between the fingers.It has a decided though not strong smell due partly to the naphthaiin but still more to the oil with which it is con-. taminated aid which it loses ou purification. It is soluble though not abundantly in alcohol but dissolves with tolerable facility in ether turpentine and still better in benzole. Methy-lated spirit was in the first instance used for its purification.The first solution on cooling deposited thick oily globules with a small quantity of crystals ;but after several successive quantities of apirit had been used crystals were deposited free from oil but still retaining the yellow colour of the original substance and- apparently owing to the removal of the oil-were much less soluble in new quantities of spirit. By repeated crystallisations it was found possible to obtain t'he anthracene quite colourless ; but the process was too tedious to be employed for preparing it on the larger scale. Other solvents and more particularly benzole were likewise tried ; but though preferable the complete removal of the colouring matter is difficult with them also and it was found necessary to begin by distilling the crude substance in a small iron still.The first portions which passed over during the process contained much naphthalin and oil but were quite free from colour. As the distillation proceeded however the colour gradually increased and at the end a small quantity of' a dark green substance remained in the retort. The first portions of the distillate were pressed to remove the oil and the last portions redistilled so as to get rid of thc colour as completely as possible ANTHBACENE OB PABANAPETHALIN. and the purification finished by repcated crystallisation from benzole and sometimes by sublimation. Antliracene is depositcd from its solution in perfectly colourlesa scales gencrally of very small size even when large solutions have been allowed to cool.Those obtained from spirit are generally the best and wheo suspended in the solution have a fine satiny lustre which they lose to some cxtent when dried. From benzole the crystais are somewhat granular and less brilliant in appear- ance. By sublimation it is obtained in thin plates resembling those of naphthalin but smaller and of inferior lustre. When quite pure it has no smell but it is apt to retain a trace of oil which communicates to it a faint ernpyreumatic odour. It ie entirely devoid of taste It is not volatile at ordinary tempera- tures but is slowly volatilised in the water-bath. At higher tem- peratures it sublinies freely. It melts at 416" F. into a trapspa- rent colourless liquid which on cooling solidifies into a foliated crystalline mass and aic a higher temperature distils unchanged.It is insoluble in water sparingly soluble in alcohol but more so in ether benzole and the volatile oils. The alkalies are without action upon it but sulphuric acid dissolves it and acquires a green colour with formation of a sulpho-acid; and nitric\ acid even when moderately dilute acts rapidly upon it. Chlorine and bromine form substitution-products. The analysis of anthracene at ' first prcscnted some difficulties. When oxide of copper was employed in the usual way the carbon was always deficient while chromate of lead gave an accurate result with that element but a marked excess on the hydrogen.* Oxide of copper and clilorate of potash were therefore resorted to and with success.The results correspond exactly with the formiila C,,H,,. This is precisely the constitution of a substance described some years since by Fri t zsch et as a new carlm-hydrogen obtaiiictl from coal-tar with which also its properties closcly agree. A careful comparison of the two substances made by Professor Fritz sclie arid myself during I have had freqlient occafiion to obAerVe that in the analjsia of carbo-hydrogene with chron~:~te of Ic.id a considerable CXCPSH of hydrogen is oftcn olitnined. I at first attributed this to impurities in the chromate btit analyees made with a pure material ~peciallymade for the piirpo~e,showed the game cxcees. I have not examined into the cause of ttik phenomenon. t J. pr. Chern. Ixxiii. 282.ANDERBON ON THE CONSTITUTION OF I) visit b paid to Glaagow some time since satisfied us that hi8 substance really ie anthracene. The picric acid compounds of the two are completely identical and have 8 fine ruby-red colour which distinguishes the compounds in question from those ob-tained from the other carbo-hydrogens. An analysis of the com- pound obtained from anthracene gave the formula C&HIO.CJX (NO,),O, which is that given by Fritzsche for his compound. ACTION ACIDON ANTlIRACENE. OF NITRIC Anthracene is but little acted on by cold nitric acid hut the boiling acid even when moderately dilute attacks it with con-sideFable rapidity the products depending upon the strength of the acid and the length of time during which the action is continued.Vxantlrracene C,,H,O,.-When anthracene is boiled for some day8 with nitric acid of sp. gr. 1.2,red fumes are evolved and a resinova mass is obtained which becomes hard and gritty ou cool-ing. The same change may be more rapidly effected with acid of ap. gr. 1*4 but the product is then liable to be contaminated with aome other compounds. The substance was washed with water and purified by crystallisation from alcohol or bexizole. It is theu obtained in crystals which when deposited from alcohol are long silky needles but from benzole are shorter and more compact. They are of a light buff colour and have neither taste nor smell ; they are insoluble in water sparingly soluble in alcohol and more so in benzole. They arc completely soluble in boilirig nitric acid of sp.gr. 1.4,and are deposited unchanged on cooling. Concen-trate& sulphuric acid in the cold dissolves them with orange colour which becomes deep red on heating and on dilution with watcr the oxanthraccne is deposited unchanged. Oxanthrwenc aiiblimcs when heated and is deposited unaltered in fine needles of conei-derable length. It may be distilled without decomposition over quick-lime. Its volatility may be taken advantage of as a mcans of preparing it as it is only necessary to boil anthracene in a retort with nitric acid and to continue the heat until the acid has distilled over and the oxnntliracene sublimes any other compounds formed at the same time hcing decomposed. Oxanthracene is derived from arithraccne by tlie removal of -two equivalents of h$lrogeii and tlie addition of four of oxygen.It belongs to a class of substaiiccs of which thcre are very few ANTHRACENE OB PABANAPATHALIN. examples and for which we have no satisfactory system of nomen-clature. I have given it the provisional name of oxanthracene as recalling its mode of formation. Binitr0xanthracene.-Whe6 anthracene mas boiled for a long time with nitric acid with occasional addition of -fuming acid red fumes continued to be given off and a resinous eubstance waa gradually produced. The substance was washed with water and dried. It appeared to be a mixture of some of the laat substance with R new compound which was obtained by heating it wiih a small quantity of alcohol aud cooling.It is deposited as a red powder which shows but little disposition to crystalbe. Analysb gave results affording a distant approximation to the formula C,,H6 (N0J204, which probably represents its constitution ;but as itu properties showed nothing of interest I did not prosecute its purification further. Anthracenic Acid.-When the nitric acid and the washingsof the preceding compound are carefully evaporated over the water- bath a pellow crystalline acid is obtained. It is very soluble ir water arid gives crystallisable salts with ammonia and potash and precipitates the salts of lead and baryta. The further invest@ tion of this substance is reseired for a future communication. ACTION ON ANTHRACENE. OF BROMINE Bromine acts rather slowly upon anthracene in the cold.The two substances when mixed together concrete into a resinous- looking mass the interior of which is not comp!etely siturated with bromine and it was found most convenient to expose the aiithracene in a thin layer under a bell glass along with a capsule containing bromine. After a day or two’s exposure the anthracene agglutinates into a mass which must be removed reduced to powder and reintroduced ; and this treatment is repeated as long as bromine is absorbed. This mass which has a brown colour dissolves in benzole and on cooling deposits hexbromide of anthracene in crys-tals which are purified by solution in benzole or ether. It is thus obtained in small hard white granular crystals apparently rhom- boidal. They are sparingly soluble in alcohol ether and benzole.Nitric acid acts upon them but slightly. When heated with strong sulphuric acid they fuse and bromine and hydrobromic acid are expelled. On digestion with alcoholic potash they imme- diately becoinc ycllow and arc converted into another compound. ANDEBBOX ON THE CONBTITUTIOI OF When heated to 348' F. they become brown and at 3610 fuse and give off bromine. Analysis gave the results &peeing nearly with the formula C,,H,,Br6. The substance is produced hy the direct absorption of six equivalents of bromine. Tetrdrominated Anthracene.-When the preceding compound is treated with an alcoholic solution of potash it swells up con-siderably and acquires a bright sulphur-yellow colour the solutiou containing bromide of potassium.This change occurs in the cold but it is more couvenient to heat the solution. The yellow powder is collected on a filter wmhed dried and crystallized from boiling benzole; It is thus obtained in long yellow needleu having a fine silky lustre. It is very sparingly soluble in cold alcohol ether and beuzole-more so when hot. Boiling benzole is its best solvent but evem of this it requires above a hundred times its weight. It melts at 460" F. and gives a dark-coloured mass which has undergone partial decomposition. The portions used for analysis were crystallieed from benzole and then washed with ether. Analysis gives for the constitution of the compound C2RHSBr4 a somewhat unusual formula differing from that of most similar compounds.In general when a bromide or chloride of an organic compound is treated with potash one half of the haloid is removed in combination with hydrogen the remainder passing into the radical. In this case howcver only two equivalcnts of hydrogen are removed and the formula of the cpmpouiicl ought in all pro- bability to be written C28€1813r2. Br,. ACTION ON ANTHRACEXE. OF CIILORINE The examination of thc compounds produced by the action of chlorine on anthracene is attended with some difficulty the changes occurring being of a somewhat complicated kind ; more than one substance being gcncrally obtained and thc nature and proporbion of the products depending very greatly on the circumstances of the experinleiit. Chlorine is rcatlily absorbed by anthracene in the cold and if the current is rapid it becomes warm gives off hydro-chloric acid in abundance atid is cventually converted into a hard cake.If the clilorine be passed through it in a slow current the evolution of hydrochloric acid is greatly diminished although it cannot he altogether avoided; and when this is done and the stream of chlorine is not continued too long the principal product is ANTHBACENE OR PABANAPRTHALIN. Bichloride of qnthracene C,,H,oCl,.-The mass obtained by the action of chlorine dissolves readily in benzole and on cooling groups of radiating needles often of considerable length are depo- sited. The bichloride is readily soluble in alcohol but only very sparingly in ether.When crystallised from alcohol it is very liable to lose hydrochloric acid and this change always takes place to some extent which causes a slight excess of carbon and defi-ciency of chlorine in the analysis. Chloranthracene C,,H&l.-W hen anthracene is treated with a rapid current of chlorine continued for a short time only this compound is produced. Jt may also be obtained by decomposing the preceding substance with alcoholic potash. It is soluble in alcohol ether and benzole from the last of which solutions it ie deposited in small hard scaly crystals When chlorine is passed over anthracene kept hot it is absorbed in much larger quantity and hydrochloric acid is abundantly evolved. The compounds thus obtained depend entirely on the length of time during which the current is continued and products analysed at different periods were found to contain very different quantities of carbon an6 chlorine; and as the substances produced differ little in solubility it was found difficult to effect their sepa- ration.When the passage of chlorine is continued for about eight days the product is semisolid and the greater part dissolves easily in cold ether ; and when this solution is evaporated first an oily chloride and then crystals are deposited. The crystals are soluble in benzole alcohol and ether and were found to have a composition agreeing with the somewhat improbable formula C,,H,Cl ; but it is-quite possible that the substance may be a mixture. The oi!y chloride gives more than one crystalline substance when treated with alcoholic potash.The facts now detailed are sufficient to fix the constitution of mthracene and to show that its chemical relations are of con& derable interest. Its formula connects it,with certain substances derived from oil of bitter almonds and more especially with stilbece the carbo-hydrogen discovered by Laurent from which it differs by two equivalents of hydrogen. A similar relation exists between oxanthracene and benzil as is seen by the following corn-parison of their formulae :-Anthracene . . C-8H,o Stilbene . . . CPHIZ Oxanthracene . . CL8H,04 iI Benzil . . . . CzeHloOc

ISSN:0368-1769    

DOI:10.1039/JS8621500044

出版商:RSC    

年代:1862

数据来源: RSC