DR. E. FRANKLAND ON THE VIII.-Researches 0% the Organic Radicals ;Part 11 AMMYL. By E. FRANKLAND, PH.D. F.C.S. PROFESSOR OF METALLURGY IN THE COLLEGE FOR CIVIL ENGINEERS PUTNEY. In studying the decomposition of iodide of ethyl by zinc7* I obtained in addition to ethyl and zinc-ethyl two bodies as secondary products having the empirical formulz C H and C H,; the furmer agreeing exactly so far as its reactions were followed out with olefiant gas and the latter having the same composition and specific gravity as methyl; but as both these bodies are permanent gases it was difficult to prove their complete identity with olefiant gas and with the methyl procured in the decomposition of cyanide of ethyl by potassium,+ and by the electrolysis of acetic acid;$ owing however to the much higher atomic weight and vapour-density of the amyl compounds it appeared highly probable that if the iodide of this radical be similarly decomposed by zinc the secondary products of decomposition corresponding to the two bodies above- named will exist at ordinary temperatures as liquids the re-actions and physical character of which would lead to the discovery of their rational constitution as well as that of the two gaseous bodies before alluded to.These considerations induced me to attempt next the isolation of the hitherto hypothetical radical arnyl in preference to any of the other members of ihe same series. For the preparation of the iodide of amyl which served for the experiments detailed in the following pages a modification of the process described by Cahourst was employed.Four parts of iodine were dissolved at intervals in seven parts of pure ftisel-oil and between each addition of iodine a stick of phosphorus was suspended in the liquid until the latter became nearly colourless. The fluid thus obtained had an oily consistence and emitted copious fumes of hydriodic acid when exposed to the air ;on being submitted to distillation in an oil-bath a colourless liquid containing much free hydriodic acid and unchanged fusel-oil passed over into the receiver whilst a non-volatile thick oily fluid insoluble in water * Chem. Soc. Qu. Journ. II. 265. t Chem. Soc. Qu. Journ. I 60. $ Chem. Soc. Qu. Journ. 11 173. Ann. Ch. Phys. LXX 95. ORGANIC RADTCALS.and re-acting strongly acid remained in the retort.* The distillate was washed with a small quantity of water to remove the hydriodic acid and after standing twenty-four hours over chloride of calcium was redistilled it began to boil at 120° C. (the boiling-point of iodide of amyl as given by Cahours) ;but the thermometer gradually rose to 146O C. at which teniperature the last 8 of the fluid distilled over and was collected in a separate receiver. If the whole of the hydriodic acid had not been removed by the previous washing with water the liquid generally became coloured violet by free iodine during this second distillation ;but the coloration was easily removed by a subsequent rectification over mercury and the iodide was then quite pure.The first 3of the distillate which pass over between l2OO and 146O C. also contaiiis much iodide of amyl and may be advantageously employed for the preparation of a further quantity by adding more iodine and phosphorus in the relative proportions -already given. Iodide of amyl is a colourless and transparent liquid refracting light strongly possessed of a weak ethereal odour and a sharp biting taste :it boils at 146O C. under a pressure of 175"" and not at l2Oo C. as stated by Cahours its specific gravity is 1.51113 at 11.5 C. Burnt with oxide of copper 0.3600grm. gave 0.4003 grm. carbonic acid and 0.1797 grm. water; numbers which give the following per centage composition Calculated. Found. C, ........30.36 30.32 H, ........ 5.55 5.55 I .........64.09 - 100~00 Some preliminary experiments shewed that iodide of arnyl is acted upon.by zinc with much more difficulty than the corresponding ethyl compound which seems to be principally owing to the very sparing solubility of iodide of zinc in the surrounding liquid and also to the comparatively low temperature at which iodide of amyl heated alone as well as with zinc is decomposed into free hydriodic acid and other gaseous products which I have not as yet more closely investigated. In consequence of these difficulties it requires a very nice management of the temperature to effect anything like a perfect *This fluid which is formed in large quantity and probably contains a compound of an acid of phosphorus with oxide of amyl merits closer investigation.DR. E. FRANKL4ND ON THE decomposition of the iodide by zinc alone. This led me to employ an anialgani of that metal which answered the purpose admirably; for on being subsequently heated with the liquid iodide the pasty metallic mass becomes perfectly fluid and owing to the agitation of the boiling liquid continually presents a fresh and bright surface. This amalgam acts considerably upon the iodide at the ordinary boiling-point of the latter but exposed to a temperature about loo C. higher in a sealed tube it undergoes decomposition with tolerable rapidity no gases are evolved but on distilling the resulting liquid the variation of the boiling-point from 30° C. to 160° C. shews the liquid to be a mixture of at least two bodies.For the purpose of submitting the iodide of amyl to the action of zinc-amalgam under pressure I employed strong glass tubes about 3 inch in diameter and 14inches long closed at one end and having the other drawn out to about Q inch in diameter and 3 inches long. Each of these tubes was filled to the height of 1.5 in. with zinc-amalgam of a pasty consistence above which was placed a layer of granulated zinc 2 inches deep which afterwards gradually dissolved in the mercury as the amalgam became diluted by the action of the liquid iodide. From 2 oz. to 1 oz. of the iodide of amyl being then introduced the open end oP the Lube was drawn out to a fine orifice which a€kr boiling the included Auid lor z1 moment to expel the air was hermetically sealed with 8 mouth-blowpipe.The tube was then immersed in an oil bath to ihe depih ol about 3 inches and main- tained at a temperature varying from 160° to 180° C. for several hours. Subsequently and after being allowed to cool so much of the drawn-out extremity was broken off as admitted of the intro- duction of from 1 to 2 grms. of potassium and the tube being again hermetically closed was subjected to the same temperature as before for about an hour. When perlectly cool the upper part was again cut off and a cork and bent tube adapted to the orifice. The bent tube led to a receiver which was kept cool by a freezing mixture of dilute sulphuric acid and snow; the decomposition tube was now immersed to nearly its whole length in a water-bath the temperature of which never exceeded 80" C.; about Q of the liquid contents of the tube distilled over J the receiver was then changed and the water-bath being removed the decomposition tube was carefully heated by means of a spirit-lamp until the remaining fluid had come over. As valyl according to Kolbe,* boils at 108O C. and the addition of the elements C H to the same volume of vapour must necessarily cause a considerable elevation of the boiling-point it appeared highly * Chem. SOC. Qu. J. 11 161. 0RGdN IC RA I)I CA LS. probable that the amyl if separated as such would be €oonud in the less volatile liquid which supposition was also strengthened by the analogous decomposition of iodide of ethyl ; I therefore first submitted the last-obtained product to investigation.This liquid which was colourless and possessed of a peculiar penetrating odour was not in the least acted upon by potassium even at its boiling point the fused metal remaining at the bottom of the fluid like a globule of mercury and presenting a surface of remarkable brilliancy. On being distilled its boiling point rapidly rose to 155O C. and remained nearly constant at this temperature uiitil the whole had passed over. The fluid which distilled at 155* C. was collected separately and submitted to analysis. I 0.1757 grm. burnt with oxide of copper”t’ gave 0.5426 grm. carbonic acid and 0.2433 grm. water. 11 0.2000 grm. gave 0.6207 grm. carbonic acid and 0.2732 grm. mater. 111. 0*1101grm. gave 0.1523 grm water.These numbers agree closely with those calculated from the formula of the hitherto unisolated radical amyl Cl %a* Calculated. Found. I-* .-> r-A-.-7 I. 11. 111. MEAN. C, . . . . . 60 84.5 84.2 84.6 84*4 H, . . . . 11 15.5 15.4 15.2 15.4 15.3 71 100.0 99-6 99.8 99.7 A determination of the specific gravity of its vapour yielded the following results confirmatory of the above formula Weight of liquid used . . *1670grm. Observed vol. of vapour . . 46.5 cbc. Temperature . . 19005~ C. Height of barometer . . . 738.1”“ , , inner column of mercury. 10*omm From which the specific gravity was calculated to be 48989. Amy1 is a colourless pellucid liquid possessing a slight ethereal dour and a burning taste ; exposed to a cold of‘ -30° C.it becomes * At the conclusion of each analysis a stream of oxygeii evolved from perchlorate of potash placed at the further e5d of the combustion tube was led over the reduced oxide of copper until the latter was completely reoxidized. The material used in analysis No. 11 was a separate preparation. VOL. IXI,-NO. IX. 1) DR. E. I~llANKLANI) ON THE thick and oily but does not solidify; its specitic gravity in the liquid form is 0.7704 at 1loC.,'that of its vapour 4,9062. According to the above determination of tlie specific gravity of its vapour this radical contains 5 vols. carbon vapour and 11 vols. hydrogen con- densed to 1vol. and is thus in this respect perfectly analogous to methyl ethyl and valyl. 5 vol.carbon vapour . . 4.1461 11vol. hydrogen . . 0.7601 -~ 1 vol aniyl vapour . * . 4.9062 Found by experiinent . . 4,8989 Amy1 boils at 155O C. at a pressure of 728n1lll; it does not ignite at ordinary temperatures ;but on being heated its vapour burns with a white smoky flame. It is insoluble in water but miscible in all proportions with alcohol and ether. It is not affected by fuming sulphuric acid aiid is but very 'slowly oxidized by boiling fuming nitric acid or by a niixture of nitric and sulphuric acids. During this oxidation the liquid acquires the odour of valerianic acid. The action of chlorine aiid bromine as well as of oxidizing agents upon aniyl aiid the two bodies noticed below will be described in a future conirnunication.It still remained to exaiuine the very volatile liquid which had distilled over €mm the decomposition tube at a tcrnperature not exceeding SOo C. This liquid possessed a very PO ~vcri'ui,penetrating and rather disagreeable odour much resembling that of the body C €I8 evolved during the electrolysis of valerianic acid and a taste at first rather sweet but aftei'mdrds iiameous and tar-like. It was so volatile that when the thin glass vessel containing it was held in the hand it imrnecliately entered into ebullition. To ascertain the relative quantities of carbon and hydrogen con-tained in this liquid and thus obtain some clue to its composition a portion of it was burnt with oxide of copper. 0.1577 grui. yielded 0.41870 grm. carbonic acid and 0.2260grm.water numbers which indicate the following per centage com-position Carbon . . 84.2 Hydrogen . . 15.9 lor~'l Since in tLe decomposition of iodide of ethyl by zinc a portion of the separated radical is transformed into equal volumes of C H and ORGAXIC RADICALS. C H3,* it was not improbable that a similar decomposition of aniyl had here taken place and that this volatile liquid contained the products which would in fact yield an analytical result similar to the one just given. To ascertain if this were the case I availed myself of the property which anhydrous sulphuric acid seems to possess of combining with carbo-hydrogens of the form C H, and leaving unacted upon those of the form C + H(n+v;and as the liquid was easily converted into a temporary gas I submitted it to the following experiment which at the same time gave the specific gravity of its vapour.A sinall and very thin glass bulb was filled as perfectly as possible with a weighed quantity of the fluid hermetically sealed and then introduced into a short eudiometer filled with quicksilver and inverted in an iron trough containing the same metal to which heat could be conveniently applied. A long glass Eylinder open at both ends was then lowered perpendicularly over the eudiometer and immersed to the depth of about 2 inches in the mercury; it was then filled to such a height with water that the enclosed eudiometer was conipletely beneath the surface. Heat being afterwards applied below the mercury trough the glass bulb in the eudiorneter soon burst and the enclosed Auid became converted into vapour.When the water in the glass cylinder had boiled for some time the volume of the vapour was accurately noted as well as the height of the barometer and the elevation of the column of mercury in the eudiorneter above that in the trough outside the glass cylinder. The water and cylinder were then removed and the whole apparatus allowed to cool until the vapour had again assumed the liquid form the temperature at which this took place was only a very few degrees above that of the surrounding atmosphere. A coak bullet saturated with a solution of anhydrous sulphuric acid in Nordhausen acid was then introduced on coming in contact with the carbo-hydrogen a quantity of vapour equal to about half the original volume was rapidly formed and maintained the gaseous condition at the temperature of the surrounding air although it was immediately condensed by cooling the tube a few degrees,--a proof that the body not absorbed by sulphuric acid has its boiling point near to but lower than that absorbed by the acid.Although the action of the sulphuric acid appeared to be nearly instantaneous yet in order to be sure that the absorption was quite complete the coak bullet was allowed to remain in the vapour for half-an-hour and the temperature of the mercury was raised loo or l2O C. before its withdrawal in order * Cliem. SOC. Qu. J. vol. 11 p. 281. D2 D11. E FRANKLAND ON THE to ensure the complete volatilization of the body left unabsorbed by the acid.On coming in contact with moist air the bullet still funied strongly which was a proof that the acid had been present in excess. A ball of hydrate of potash was now introduced and left in the vapour until every trace of sulphurous acid and vapours of sulphuric acid had been absorbed-in fact until the moment before the volume of the remaining vapour was read off which was effected along with the collateral observations after the glass cylinder and water had been replaced-and the whole heated to 42O C. R higher temperature was considered undesirable lest the elasticity of the vapour of the sulphuric acid compound traces of which still adhered to the sides of the eudiometer should introduce inaccuracy into the obsemation.The following results were obtained I. Cor. vol. at Diff. of mer-Barom. Oo C. and Ahstl. vol. Temp. C. cury Ievel 'i60mmpress. Vol. of vapour (dcy) 18.7 cbc. looo 109.2"" 756*Imfn11.65 Vol. after action of sulph. acid (dry) 8.9 , 42.09 142.2 , 752.2 , 6.20 11. Weight of liquid used . . 0.0356 grm. Observed vol. of vapour . . 18.7 cbc. Height of barometer . . . 760-3"" Difference of mercury level . . 109*2, Temperature * 1oooc. Specific gravity of vapour . . 2.4179 According to experiment No. I. it follows that 11-65 vols. of the vapour- contained 5.45 vol. absorbable by sulphuric acid and 6.20 vol. unabsorbable by that acid ; or 100 vols. consisted of Vapour absorbable by SO . . 46-78 Vapour unabsorbable by SO .. 53.22 100~00 These results are exactly analogous to those yielded by the gases produced by the transformation of ethyl into equal volumes of C €3 and C H3,* and indicate that a portion of the * Chem. SOC. Qu. J. 11 277. ORGANIC RADICALS. amyl has been similarly transformed into equal volumes of the hitherto unknown carbo-hydrogens having the empirical formuh and The specific gravity of the vapour of a mixture containing thcse two bodies in the proportions indicated by experiment No. I. would be 2.45533 as shewn by the following calculation 24~01s.carbonvapour=2.07305 CH{ 5 vols. hydrogen ==0*34550 Condensed to 1vol. == 2.41855 x 46.78 =113*140 24vols.carbonvapour =2*07305 6 cH{6 vols. hydrogen =0*41460 Condensed to 1vol.=2*48765 x 53*22=133.393 245.533 =2.45533 100 A number which closely corresponds with that found by direct experiment No. 11. (2.4179). It now only remained to separate one of these compounds in a state of perfect purity to prove the existence of both. To effect this the mixture of the two fluids was cooled to -looC. and mixed with an excess of a saturated solution of anhydrous sulphuric acid in Nordhausen acid. After standing for several hours and being repeatedly shaken no diminution in the volume of the ethereal fluid seemed to have taken place; but on distilling the mixture in a water-bath at a gentle heat about one half only of the clear colourless liquid floating upon the sulphuric acid distilled over ; the remaining portion which was volatile only at a very high temperature I have not further examined ; it consisted probably of the conjugate sulphuric acid homologous with that produced by the action of anhydrous sulphuric acid upon olefiant gas.The distillate was placed over pieces of caustic potash until every trace of sulphurous acid had been removed. It had now entirely lost the unpleasant smell which it possessed before treatment with sulphuric acid and emitted a very agreeable odour resembling chloroform. Burnt with oxide of copper 0.1237 grm. yielded 0,3779 grm. car- I>R. E. PltANICLiND ON THE bonic acid and 0.1856 grm. water nun1bers which exactly corn*- spond with the formula C H,. Calculated. Found. c5 ' r-7 . 30 83-33 83-32 H6 - .6 - 16.67 16.67 36 100~00 99.99 A determination of the specific gravity of its vapour gave thc following result Weight of liquid employed .. 0,0863 grm. Observed vol. of vapour . . 39.8 cub. c. Temperature . * 1000 c. Height of barometer . . 733.8"" Difference of mercury level . . 31.0"" Specific gravity of vapour . . 2*4657 This result shows that the body in question contains 2$ vols;. carbon vapour and 6 vols. hydrogen condensed to 1 vol.; for on this supposition the specific gravity ought to be 2.4876 a number which closely corresponds with that found. The composition of the body absorbed by sulphuric acid is also determined by the foregoing experiments which prove that it has a constitution homologous with olefiant gas but an atomic weight 2& times greater; for according to the vapour analysis 100 vols.consisted of Vapour absorbed by SO . . 46.78 Vapour not absorbed by SO . + 53.22 100*00 or by weight Vapour absorbable by SO . . 46.08 Vapour unabsorbable by SO . . 53.92 100*00 If then from the results of the combustion of the mixcd liquids by oxide of copper (page 34);the weight of carbon and hydrogen cor- responding to 53.92per cent of the body C H be deducted the remaining numbers give the proportion by volume C H =1 :2.10 which corresponds sufficiently near with the voluminal proportion C H = 1 2 when we consider how difficult it is to preserve the ORGANIC RADICALS. constant composition of a mixture of two such volatile fluids as those in question during a series of experiments in which the vessel con- taining them has frequently to be unstopped.With reference to the true constitution of the two bodies last described two views may be taken; for they may be regarded either as products of the splitting of 1eq. amyl into 1 eq. C5 H5 and 1 eq. c5 H,. or as resulting from the transformation of 2 eq. amyl into 1 eq. C, H, and 1 eq. C, H, Before giving preference to either of these views it appeared of importance first to ascertain whether iodide of amyl in presence of zinc and water undergoes a decomposition analogous to that of iodide of ethyl under similar circumstances and if so whether the resulting carbo-hydrogen is identical with the body C H or C, H, just described.I therefore submitted iodide of amyl mixed with rather more than an equal volume of water to the actioii of zinc in an apparatus similar to that already described. In this case the zinc was not previously amalgamated as it was fouiid that the unamalgamated metal effected the decomposition with great rapidity at a moderate temperature (about 140° C). As soon as the action appeared com- plete the tube was allowed to cool and after being cut off at the drawn-ocrt extremity was connected with a well-cooled receiver and then partially immersed in a water-bath heated to about 60 C. The colourless limpid ethereal fluid which rapidly distilled over in considerable quantity was placed over pieces of fused potash for twenty-four hours and then rectified in a water-bath at 35O C.The residue remaining in the decomposition tube consisted of oxy-iodide of zinc water and a trace of undecomposed iodide of amyl. Burnt with oxide of copper 0-1813grm. of the ethereal fluid gave 0.5540 grm. carbonic acid and 0.2702 grm. water corresponding to the following per centage composition and the empirical formula c H6. Calculated. Found. r--h---? c5 * .30 83.33 83.34 .6 16-67 16-56 H6 * -36 100.00 99.90 DR. E. FRANKLAND ON THE A determination of the specific gravity of its vapour gave the following numbers Weight of liquid employed . . 0.0965 grms. Observed vol. of vapour Temperature . . . . 44.3 cbc. loooc. Height of barometer . . 758.4'"" Difference of mercury level .. 62.0mm Specific gravity of vapour . . 2.4998 That this body is perfectly identical with that formed during the decomposition of iodide of amyl by zinc without the presence of water and to which we have assigned the empirical formula C5 H, the following comparison of their chemical and physical properties proves beyond all doubt. Body prodaced in the decom- Body produced in the decom- position of iodide of amyl by zinc position of iodide of arnyl by zinc without the presence of water. with the presence of water. Results of combustion with oxide of copper. Results of combustionwith oxide of copper. Carbon . . 83.32 Carbon . . . 83.34 Hydrogen . . 16.67 Hydrogen . . 16-56 -99.99 ~ 99.90 Specific gravity of liquid. Specific gravity of liquid.0.6385 at 14*2OC. 0.6413 at 11~2~ C. Specific gravity of vapour. Specific gravity of vapour. 2.4657 2.4998 Boiling point. Boiling point. 30° C. at 734"" pressure. 30° C. at 758"" presswe. 1 Further both bodies are equally unacted upori by fuming sulphuric acid and only with great difficulty by the most powerful oxidizing menstrua; they both possess the same odour and are perfectly similar in every respect. The decomposition of iodide of amyl by zinc in presence of water is perfectly analogous to that of iodide of ethyl under similar circum- stances and may be expressed by the following simple equation When TVC consider thc abovc facts in conncction with thc cxistcncc ORGANIC RADICALS. and products of decomposition of zinc-methyl and ziuc-ethyl in which the zinc is so evidently replaced by hydrogen and there can scarcely be a doubt that the rational constitution of thc body in question is Cl H,l and I therefore propose for it the name HYDRURET OF AMYL.Hydruret of amyl is a transparent colourless and exceedingly mobile fluid possessing an agreeable odour resembling chloroform. It is insoluble in water but soluble in alcohol and ether from the former of which it is again separated by the addition of water it is the lightest liquid known its specific gravity being only 0.6385at 149O C. Hydruret of amyl retains its fluidity at -24O C. ; it boils at 30° C. ; its vapour is easily inflammable and burns with a brilliant white flame; placed in a glass flask having its neck drawn out to a fine orifice and held in the hand a constant jet of gas issues which on being ignited gives a pure white light of surpassing brilliancy and devoid of smoke until the enclosed fluid is entirely evaporated.In accordance with two determinations of the specific gravity of its vapour it contains 1 vol. amyl vapour and 1vol. hydrogen united without condensation or 5 vols. carbon vapour and 12 vols. hydrogcn condeiised to 2 vols. 5 vols. Carbon vapour . . 4.1461 12 vols. Hydrogen . . 08292 2 vols. Hydruret of Amy1 . . 4.9753 49753 1 vol. of which therefore weighs -== 2.4876 2 Found by experiment 24657 24.998k* :: { Hydruret of amyl is not in thc least affected by prolouged contact with fuming sulphuric acid; it is a remarkably stable compound and IS only acted upoii with great difficulty by the most powerful re-agents.DR. E. FRANKLAND ON THE It can scarcely be doubted that this body was present in the liquid obtained by Reichenbach* in acting upon wood-tar with sulphuric acid and to which he gave the name Eupione as the boiling point of this liquid varied from about 47" C. to 260°C. it was evidently a mixture of several compounds. Reichenbach says that the niost volatile portion boiled at 47O C. or even lower; had a specific gravity 8.633;and formed a clear colourless and very mobile fluid of a some-what agreeable odour resembling narcissus flowers he states that the formula is either C 13 or some multiple of this or else one nearly approaching to such a multiple as C H,.It is highly probable that the liquids described by Reichenbach under the name of eupione consisted of a whole series of bodies having the form C H (n+2) and differing from each other by C H, commencing with hydrnret of amyl and terminating with the hydrurets of the radicals of the wax- alcohols described by Brodie ;+ and as the gases evolved by the destructive distillation of wood and of coal are already known to contain hydruret of methyl (light carburetted hydrogen) there can be little doubt that the other members of the series intermediate between this last body and hydruret of amyl will also be found in them viz. Hydruret of ethyl . * c H, H , butyl * cfj H,> , valyl . C H, H 3 I Probably the illuminating power of coal gas depends to a great extent upon the presence of these bodies especially the hydrurets of butyl and valyl.That the methods hitherto employed in the analysis of coal- gas have not led to the discovery of these bodies will cease to create surprise when we consider that they are probably all unacted upon by fuming sulphuric acid and perchloride of antimony and that 1 vol. hydrogen with 1 vol. hydruret of ethyl 2 vols. hydrogen with 1 vol. hydruret of butyl and 3 vols. hydrogen with 1vol. hydruret of valyl give mixtures all of which have the same specific gravity as hydruret of methyl (light carburetted hydrogen) and further contain in the same volume the same relative and absolute quantities of carbon and hydrogen and would therefore yield on combustion with oxygen precisely the same eudiometrical results as hydruret of methyl.If however coal-gas after behg freed from the bodies of the form C H by being passed through fuming sulphuric acid or * Sehweigger Seidel's Journal LXVIII 117 atid hiin. Pharm. VIII 217. i-Ann. Ch. Pharni. 71. 14l. ORGAXIC RADIC.1LS. perchloride of antimony were allowed to stream through alcohol the compounds in question would no doubt be absorbed and could be afterwards separated in the gaseous form by the addition of water or by ebullition. The careful examination of wood and coal tars in connection with the gases evolved during their formation would certainly lead to highly interesting results as is indeed already rendered evident by Mansfield's late discovery of large quantities of hydruret of phenyl (benzole) in coal-tar naphtha.The great difficulty attending such investigations has hitherto consisted chiefly in the impossibility of separating the mixed hydrocarbons by fractional distillation. The cause of this difficulty and its remedy seem to be indicated by the foregoing experiments taken in connection with the boiling points of ethyl butyrene (c H,) and the amylene of Cahours; for taking the formulae expressing equal volumes of vapour we have the following series 'y-iF'$:)p:grl Boiling points. Differences Butyrene (C H,) . * c4 H4 -17*8O C*} 5.2n c. Ethyl . c4 H5 -23.0' , Valerene* (Clo HlO) C H 35:0° jf } 5.00 ,, Hydruret of amyl (CloH12) C H 30 Oo , Amylene (Go H20) ' ' Cl HI0 160:Oo 1 } 5.00 ,, Amy1 .ClO Hll 155 Oo , Thus it appears that a carbo-hydrogen having the formula C H, and its companion C H(n+lldiffer in their boiling points by only 5O C. or in other words the addition of 1 eq. hydrogen without increase in the volume of vapour depresses the boiling point 50 C. thus rendering the separation of two such bodies by distillation alone inipossible ; but by the employment of anhydrous sulphuric acid all the compouncis having the form C, H would in all probability be removed and as the bodies C Hcn+l)and C!n421H(,,+3),lying next to each other in the remaining series have boiling points differing so far as is yet known by at least 47O C. their separation by frac- tional distillation could be easily effected.Further it is not impossible that by regulating the temperature at which the destructive distillation of wood and coal is carried on considerable quantities of hydruret of amyl might be cheaply ob-tained which as illuminating material would surpass almost every other in convenience and brilliancy. * Thc body produced fioni amql simultaneously with liydruret of amyl. (See belotv.) DR. E. FRANKLAND ON THE VALERENE. The same reasons which led me to adopt the formula C, H, H for one of the products of the transformation of amyl point also to C, H, as the rational formula of the second; for if from 2 ey. amyl 1 eq. hydrurct of aniyl be deducted the elements C, H, remain and fill a vacant space in the olefiant gas series 2 eq.Amy1 . . . . - c20 H, 1eq. Rydruret of amyl = C, H,, -1 eq. Valerene . . = C, H, Our knowledge of the rational constitution of the whole series of bodies having the formula C H in which n is an even number is much too limited to allow of permanent names being given to any of them. I have named the body under consideration Valerene in accordance with the names given to the other known members of the same series; but without any reference whatever to its true constitution. Valerene is a colourless and transparent liquid possessed of a peculiar penetrating and hsagreeable odour much resembling butyrene (C H,) so far as these properties can be judged of from its mixture with hydruret of amyl. Its boiling point is about 35O C.It is rapidly and perfectly absorbed by anhydrous sulphuric acid and by perchloride of antimony with which last it no doubt forms the coni-pound analogous to the oil of olefiant gas Cl hl c12 On the supposition that it contains 5 vols. carbon vapour and 10 vols. hydrogen condensed to 2 vols. the specific gravity of its vapour would be 2.41855. 5 vols. Carbon vapour . . 4.1461 10 , Hydrogen . . 0.6910 2 , Valerene vapour . . 41.8371 48371 1 vol. of which therefore weighs -= 2.41855 2 The specific gravity as calculated from that of the mixture of valerene and hydruret of aniyl is 2.3863 which agrees sufficiently well with the theoretical number. I have not studied its properties further. In addition to tshc bodies above-dcseribed iodide of aniyl whcn ctccomposed by zinc yields zinc-arnyl a body h~in p propties quite 0RGANIC 11ADICALS .analogous to those of zinc-ethyl and zinc-methyl. The complete history of these compounds will be given in a future communication. The foregoing experiments show that the decomposition of iodide of amyl by zinc gives rise to four new bodies viz. Amy1 . . Cl HI Hpdruret of amyl . * CIO HI17 H Zinc-amyl . GI0 Hll Zn Valerene . * CIO HI0 Iodide of amyl is also decomposed by potassium with great rapidity when the fluid is heated to the fusing point of the metal; the results of the decomposition are precisely the same as those obtained by zinc except that no compound containing potassium analogous to zinc-amyl is formed.This process cannot however be conveniently employed for the preparation of amyl because the iodide of potassium assumes such a bulky form as to render necessary the distillation of the fluids from this salt at least five or six times before the decomposition can be completed which is attended with great loss. Perhaps no class of compounds within the whole range of chemistry has been so closely investigated and at the same time the subject of such difference of opinion as the bodies termed alcohols and their derivatives the ethers ; the well-marked properties and reactions of the whole series so far as its individiial members are known and the theoretical as well as practical interest connected with the subject make the development of the true constitution of these compounds one of the most important problems of chemical science.Gay-Lussac was the first to throw out a suggestion upon the possible rational composition of alcohol and ether which he hinted might be regarded as compounds of olefiant gas and water but still preferred to view them as ternary compounds of carbon hydrogen and oxygen. The former view was soon after taken up by Dumas and Bodlay,* and worked out into their well known theory in which they assume alcohol and ether to be hydrates of olefiant gas the oxalic acetic &c. ethers as compounds of the first hydrate of that body with the respective oxygen acids and the ethereal bodies formed by the hydrogen acids as compounds of these acids with olefiant gas.This hypothesis was principally borne out by the theta received views * ilnn. Chim. Phys. LXX 95. of the coiistitution of sulphovinic acid and oxande together with the belief then prevalent that sulphuric acid by the absorpiion of olefiant gas was converted into sulphovinic acid. D unias and Boullay regarded ether alcohol acetic and hydrochloric ethers as having the following rational constitution Ether . . C 13 + HO Alcohol . . C H + 2NO Acetic ether . * (C H + HO) + c H 0 Hydrochloric ether . . C H t H Cl. The subsequent development of the true constitution of oxamide and sulphovinic acid abstracting as they did the principal support of this theory led to the views of Kane Berzelius and Liebig being very generally adopted at least in England and Germany.Berzelius* proposed to regard ether as the oxide of a compound radical ethyl (C H5),tand alcohol as the oxide of the radical (C 14J; in this view so far as ether is concerned he was soon after supported by Liebig who however regarded alcohol as the hydrate of the oxide of ethyl; and these views he confirmed and illustrated by his beautiful researches on the constitution of the oxamidef procured by the action of ammonia on oxalic ether and on the process of etherification 11 which led hiin to the following conclusions :§ 1. “That the views of Dumas and Boullay on the constitution of ether according to which this body is the hydrate of olefiant gas are not supported by any single fact.” 2. “That the only consistent view which is contradicted by no fact but which on the contrary satisfactorily explains all phenomena connected with its compounds consists in regarding ether as the pro-toxide of a compound radical C H,.0.” The same chemist adds further ‘(1have no doubt that the radical of ether viz. the carbo-hydrogen C H,-will be obtained free from every other body.” The isolation of four of the compound radicals belonging to the alcohol series now excludes every doubt of their actual existence and fixrnishes a complete and satisfactory proof of the correctness of the * Pogg. Ann. XXVIII 626; and Annnal Report presented to the Acaderny of Sciences at Stockholm March 31st 1833. -f Kane was the first to regard ether as the protoxide of a cornpound radical C IS, which he named Ethereum (Diih.Jour. of Med. Science Jan. 1833). $ Ann. Chem. Pharm. IX 6 129. 11 Idem. KSX 129 j SXIII 12. 5 Idem. IX 15. ORGANIC RAD ICILS. 47 theory propounded by Kane Berzelins and Liebig fifteen years ago. The radicals already known in their free state-viz. methyl ethyl valyl and amyl-are suEcient to enable us to judge of the chemical relations of the whole series. As might have been predicted from their behaviour in combination they present in their free state the closest relations to hydrogen and the noble metals; like these elements they are when uncombined almost perfectly indifferent and withstand the niost powerful oxidizing influences whilst in statu” nascenti they readily pass from one state of combination to another and the con- stitution of the vapours of these compounds is always perfectly analogous to that of the corresponding.compounds of the simple radical hydrogen ; the following examples may suEce as illustrations 1 vol. hydrogen combines with Q vol. oxygen and forms 1 vol. watery vapour. I 1 , methyl ,) *7 a I? r ,) 1 , oxide of methyl. -1 1 , ethyl 1 , ether vapour. I? ,f 2 9 9) 17 1 1 , ainyl ?I 11 li 17 I? ?? 1 , oxide of amyl vapnur. 1 vol. H combines with I vol. C1 and forms 2 vols. I1 C1 7 I? 1 ? c H 9 1 77 c1 ,? 29 2 c H Cl 9 ,f 1 I c H , 1 1 c1 , , 2 c 11 c1 97 99 77 ?9 $9 1 c10 Hl 1 ? c1 2 ,I c,o H, c1 The conipounds of bromine iodine fluorine and cyanogen are also perfectly analogous to the above indeed so complete is the homology of the compound radicals methyl ethyl and amyl with hydrogen that even their haloid compounds present the closest relations to hydracids as is strikingly exemplified in the behaviour of their iodides for although these bodies do not possess the pro- perty of reddening litmus-paper yet this is probably owing to the insolubility of the colouring matter in these liquids; for even hydriodic acid gas itself when perfectly dry has not the slightest action upon dry litmus paper.It may be further objected that aqueous hydrochloric and hydriodic acids rapidly dissolve zinc at ordinary temperatures whilst the iodides of methyl ethyl &c. have no action upon that metal until aided by heat. To ascertain how far this objection is well-grounded I allowed dry hydrochloric acid gas to stream over commercial zinc freshly granulated ;not the slightest action took place the brilliant surface of the metal remained un- tarnished and the escaping gas was perfectly absorbed by water until the temperature of the zinc was raised to about looo C.; and even then the decomposition of the acid gas was only very partial and ceased almost entirely as soon as the surface of the zinc becanie covered with chloride although the temperature was raised until the metal fused into globules.This experiment proves that even hydi 3- DR. E. FHANKLSND ON THE chloric acid itself when free froin water is acted upon by zinc only when aided by heat and even then with difficulty. The facility with which the series of bodies beginning with hydriodic acid and termi-nating with iodide of amyl are decomposed by zinc appears to be inversely as the atomic weight of the electro-positive group,--or in other words the electro-negative character of the compound de- creases as the atomic weight increases; for hydriodic acid is decom- posed at loooC.iodide of methyl at 150° C. iodide of ethyl with more difficulty between 150° and 160° C. and iodide of amyl with very great difficulty at 190GC. The cause of this phenomenoii probably lies to some extent in the more difficult solubility of the iodide of zinc in the surrounding liquid as the latter approaches more nearly to the character of an oil. Further hydriodic acid is rapidly decomposed with separation of free iodine under the simultaneous influence of atmospheric air and faint diffused daylight ; iodide of methyl presents the same phenomenon but requires to be exposed to these influences for a much longer time; iodide of ethyl placed under similar circumstances side by side with the last did not exhibit a trace of colour at the end of four months but when exposed to stronger diffused light became brown from separation of free iodine in a few hours ;whilst iodide of amyl exposed to strong daylight for a much longer time did not exhibit any trace of colour and only does so according to Cahours when exposed to direct sunlight.The decomposition of these iodine compounds and of hydriodic acid by zinc gives perfectly analogous results as is seen from the following equatioiis H I + Zn = Zn I + H (C H,) I + Zn = Zn I i-(C H ) (C H ) I + Zn = Zn I + (C H ) (Cia Eli) 1 + Zn = Zn 1 + (Cia Hii)* Again the late beautiful researches of Hofmann on the Organic Bases,* appear to me to confirm the claims of the haloid compounds of these radicals to the character of hydracids in a most remarkable manner and at the same time verify the suggestion I threw out in a former memoir,? that these radicals would be found capable of replacing hydrogen in many of the combinations of that element; for Hofmann has shewn that these compounds combine with am- monia aniline &c.with an energy inferior only to that of the * Anii. Ch. Phwni. LXXIII 91. -f Chem. Soc Qn. J. IT 299. ORGANIC RADICALS.corresponding hydracids themselves. The most simple explanation of these reactions and one which at the same time satisfactorily explains every fact connected with them appears to me to consist in regarding the ethereal body as playing the part of a hydracid. Although the subsequent decomposition by potash of the salts thus formed seems at first sight to militate against this view yet I conceive a little closer attention to the nature of the compound formed and to the modus operandi of the alkali completely sets this difficulty aside; for if we grant the existence of ammonium we must also adrnit that when hydrochloric acid combines with ammoniacal gas the chlorine in the former remains no longer united with any single atom of hydrogen but on the contrary with the group (N H,) ; so also when ammo- niacal gas unites with bromide of methyl the bromine remains no longer in combination with the methyl but is united with the whole group-with ammonium in which 1 eq.of hydrogen has been replaced by methyl The action of potash upon such a compound could easily be pre- dicted; for as the bromine is not in combination with any particular atom of hydrogen or methyl and as the alkali has a much stronger affinity for hydrobromic acid than for the bromide of methyl the nature of the decomposition is thereby determined and the products are bromide of potassium water and the new base,-which last by being again treated with bromide of methyl has by a precisely similar process the remaining atoms of hydrogen replaced by methyl.The replacement of hydrogen by methyl is also strikingly exem- plified in Paul Th6nard’s* new bases containing phosphorus which although that chemist regards them as otherwise constituted are evidently nothing else but the three phosphuretted hydrogens in which the hydrogen has been replaced by methyl; for as phosphide of calcium in contact with hydrochloric acid gives rise to the three compounds of phosphorus and hydrogen P H, P H, and Pz H so by substituting chloride of methyl for the hydracid the cor-responding compounds of this radical are produced. According to this view the rational constitution of these compounds and their * Compt. Rend. XXV 892. VOL. 111-NO. IX. E SIR. E. PRANKL-4ND ON THE complete correspondence with the three phosphuretted hydrogens may be thus expressed Hydrogen compounds.Metliyl compounds. H c2 83 I3 and P C2 H3 (,,€I3 {C2H3 As P. Thenard mentions that he has also obtained a similar series containing ethyl there can be little doubt that another containing ainyl will also be formed. The remarkable relation of these bodies to animonia and to the bases of Hofmann and Wurtz cannot be overlooked. It would be interesting to ascertain whether or not the phosphuretted hydrogens themselves are possessed of basic qualities. Indeed Rose has already shown that one of them (I? H3)bears a close relation to amixonia and forms several salts isomorphous with those of that base. The remarkable property of conibining with hydrogen to form hydrurets which seems to be possessed by the radicals of the series to which methyl ethyl &c.belong and which appears to be par- ticipated in by the allied series beginning with phenyl leads to a very simple view of the constitution of a number of compounds whose rational formulz have hitherto been considered doubtful LiSht carburetted hydrogen . . . . C IT + €I =hydruret of methyl.* The gas formed by the action of water upon zinc- ethyl and by the transformation of ethyl into I C 115 + H= , , ethyl.? C H, and C H, H . . . . . Volatile liquid described above . . . . C, H, + H = , , amyl. Phenol (benzole) . . . . . . CI3H + I3 = , ,? phenyl. (I Toluol . . . . . . . C, €1 + H= , 1 toluyl. CumoI . . . . . -. C, H, + H = ,) , cumyl.Cymol . . . . . . . -C, H, + 11 = , , cymyl. The action of chlorine upon the so-called methyl from cyanide of ethyl increases still further the probability of this hypothesis whilst the formation of nitro-compounds of phenol toluol &c. (by the * Kolbe has already proposed this as the rational formula of light carburetted hydrogen. See u Ilandworterbuch der Chemie art. Grubengas.” ? It is highly probable that the so-called methyl gas generated by the decomposi- tion of cyanide of ethyl by potassium is also hydruret of ethyl and therefore only isomeric with the true raclieal methyl produced in the electrolysis of acetic acid and in the decompnsition of iodide of methyl by zinc. ORGANIC RADICALS. 51 replacement of 1 eq. of hydrogen by NO,) yielding on reduction with sulphuretted hydrogen the bases aniline toluidine &c.taken in connection with the true constitution of these bases recently so completely and satisfactorily demonstrated by Ho fmann gives additional weight to the evidence in favour of this view which also explains the production of light carburetted hydrogen and phenol by the dry distillation respectively of acetate and benzoate of potash with hydrate of baryta in the most simple and satisfactory manner Acetate of potash . Hydrate of baryta rc, H 3-Benzoate of potash (5,'03 1 I C,,Hg > = jKOCO2 Hydrate of baryta CRaO Co2 (F2 j I am at present engaged with some experiments to ascertain whether the dry distillation of the salts of metacetonic butyric and valerianic acids with hydrate of baryta will not yield in the same manner respectively the hydrurets of the radicals ethyl butyl and valyl; and.the results of these experiments I hope to lay before the Society at an early period. The conclusions to which the foregoing remarks lead may be briefly expressed as follows 1. That the radicals of the series to which methyl ethyl amyl &c. belong possess exactly the chemical relations and character of hydro- gen than which they are however less electro-positive. 2. That these radicals can replace hydrogen in every combination in which that element plays the part of a simple radical aud is not enclosed in a group acting the part of a compound radical. 3. That the haldid compounds of these bodies may be regarded as hydracids in which hydrogen is replaced by one of these radicals ; and the organic acids of the series (C HIn + 0, as formic acid in which the conjugate atom of hydrogen is replaced in the same manner.4. That the replacement of hydrogen in ammonia by these radicals as exemplified in the bases of I-Iofmann and Wurtz renders the assumption of the hypothetical radical amidogen superfluous. 5. That these radicals in addition to the propei.ty of combining E2 RELATIONS BETWEEN THE with the electro-negative elements possess also the faculty of uniting with hydrogen to form hydrurets. To Professor von Liebig in whose Laboratory the foregoing investigation was made I take this opportunity of returning my warmest thanks for his advice and extreme kindness in affording me every facility for the execution of the requisite experiments.