STUDIES IN THE CAMPHANE SERIES. PART XIII. 325 XXXVL-Studies in the Camphane Series. Part X I I I . Action of Niti*ogen Peroxide on 1 - Nitmcamphene By MARTIN ONSLOW FORSTER and FRANCES MARY GORE MICKLETHWAIT. IN connection with the study of isonitrosocamphor, it seemed probable t h a t a n examination of structural isomerides would furnish useful information, and we have therefore attempted to prepare a substance of this class from 1-nitrocamphene, the compound obtained by the action of silver nitrate on 1-bromo-1-nitrocamphane dissolved in alcohol (Forster, Trans., 1901, 79, 644). The behaviour of 1-hydroxycamphene toward:, bromine, which converts it into P-bromocamphor (Trans., 1902, 81, 264), renders it probable that the constitution of 1-nitrocamphene is expressed by the formula CH,.YH-CK, UH-C(CH,) C*NO, I ;PHJzl , I I and the fact that this compound readily yields additive derivatives with bromine, hydrogen bromide, and hydrogen iodide led us to hope that nitrogen peroxide would give rise t o tue nitrosate, from which on hydrolysis, followed by elimination of nitrous acid, an isonitrosocamphor having the constitution CH2*YH-CH2 1 yCHJ21 H ON : c' -C(C H 3) CO should be formed. On submitting 1 -nitrocamphene to the action of nitrogen peroxide, we obtained a compound having the composition C10H1506NS, and therefore containing the elements of N,O, in addition to thoEe of the original material. The substance, however, although empirically the nitrosate of 1-nitrocamphene, is not a genuine member of this class, because alcoholic ammonia and piperidine, instead of transforming it into a nitrolamine and a piperidide respectively, convert it into a substance, Cl0HI4O4N2, identical with the product arising from the limited action of alcoholic potash.Moreover, the high melting point VOL. LXXXV. Z326 PORSTER AND MICELETHWAIT : and sparing solubility of this nitrosate suggest a bimolecular character, but we have no evidence that it belongs to the class of dioxime peroxides. Furthermore, the treatment to which it has been subjected has failed to provide us with the structural isomeride of isonitrosocamphor . Circumst,ances having compelled us to interrupt the investigation, and costliness in time and material prezluding the likelihood of its being resumed, me confine ourselves to recording the changes which have been observed, without speculating on the constitution of the substances obtained.Action of Nitrogern Pwoxide on 1 -iVitvocarnphene. The nitrocamphene required for the investigation was prepared by the method alraady described (Trans., 1901,79,646), and on repeating this process 20 or 30 times it was found that when alcoholic silver nitrate acts on 1-bromo-1-nitrocamphane, a certain amount of the silver salt leaves the solution in combination with nitrocamphene. After evaporating off the grester portion of the alcoholic filtrate from the silver bromide, the liquid yielded colourless crystals when left for several hours, This product, when suspended i n boiling water, gave a solution of silver nitrate from which highly purified nitro- camphene was obtained by distillation in steam.The circumstances controlling the formation of the substance, however, could not be determined; it was isolated on several occasions, but in more frequent cases the crystalline deposit consisted of the compound of silver nitrate with silver bromide. The nitrogen peroxide mas prepared by heating dry lead nitrate, and was passed into solutions containing 10 grams of nitrocamphene in 60 C.C. of chloroform. The liquid gradually became pale brown, and a rise of temperature occurred ; when a considerable amount; of gaa had been absorbed, the colour became greenish-brown, and at 50° lustrous crystals appeared, and increased rapidly. The passage of the gas was then interrupted, and, after an interval of 12 hours, the intensely green, or bluish-green liquid was filtered.The conditions of this experiment have been considerably varied from time to time with the object of improving the yield, but although the operation has been repedted more than 50 times, we have not succeeded in obtaining the nitrosate in quantities exceeding 24 per cent. The crude substance is usually stained with blue, which is retained with some psrsistence. By recrystallisation from boiling alcohol, 100 C.C. of which are required by 1 gram, the substance is obtained in lustrous, snow-white, flattened needles which melt and completely decompose at 21'7''. The greatest difficulty has been experienced inSTUDIES IN THE CAMPHANE SERIES. PART XlII. 327 obtaining concordant results in the combustion of this compound, owing to the readiness with which nitrous gases are eliminated on heating ; whilst the determinations of nitrogen have served to distin- guish between the nitrosate and the nitrosite, we cannot claim t o have established conclusively the empirical formula CloHI,O,N, in preference to C*OH28O12~6.0.2262 gave 0.3670 CO, and 0.1222 H,O. 0.2043 N = 15-69. 0.1803 ,, 23.4 C.C. y y at 18' ,, 782 mm. N=15*58. C,,H,,O,N, requires C = 43.95 ; H = 5.50 ; N = 15.38 per cent. C,oH,,012N6 ,, C = 44.1 1 ; H = 5.01 ; N = 15.44 ,) CloH150,N, ,, C = 46.69 ; H = 5.84 ; N = 16.34 ,? C = 44.25 ; H = 6-05. 0.2003 ,, 0,3280 CO, ,, 0*1070 H,O. C=44*67; H=5*98. ,, 27.4 C.C. nitrogen at 1 7 O and 766 mm. One gram of the nitrosate requires nearly 600 C.C. of cold alcohol to dissolve it, and the compound is very sparingly soluble in all organic media; we have not been able, therefore, to determine its molecular weight, but this behaviour, and a comparison of the temperature at which i t decomposes with the melting points of the derivatives herein described, and of 1 -nitrocamphene ( 5 6 O ) , indicate the bimolecular ex- pression, C20H,o012N6.The substance is insoluble in boiling aqueous potassium hydroxide and in hot concentrated hydrochloric acid ; it dissolves in fused phenol, and develops an intense green coloration when the solution is warmed gently with concentrated sulphuric acid, but the colour disappears on dilution and is not regenerated by alkalis. In fuming nitric acid, it dissolves slowly, without rise of temperature, and is precipitated un- changed on dilution ; concentrated sulphuric acid dissolves it less readily, but on warming gently a clear, deep brown solution is formed, from which gas is slowly evolved.Action of Piperidine on the Nitrosate. Ten grams of the nitrosate were covered with 8 grams of piperidine, when the liquid became hot and the crystals dissolved. Having com- pleted the action by heating for a short time on the water-bath, the viscous product was poured into water, yielding a crystalline solid weighing G grams. On recrystallising the substance twice from hot absolute alcohol, it was obtained in transparent, flattened prisms melt- ing a t 123'. 0.1988 gave 0.385'7 CO, and 0,1136 H,O. 0.2470 C-52.90; H=6*39. 0.1875 ,, 0.3640 CO, ,, 0,1064 H,O. C==52*94 ; H= 6.35. ,, 26.8 C.C.nitrogen at 16" and 756 mm. N= 12-59. C,,Hl,O,N, requires C == 53.10 j H = 6.19 ; N 1= 12.39 per cent. z 2328 FORSTER AND MICKLETHWAIT : These results show that the product is not a piperidide, but is pro- duced by elimination of the elements of nitrous acid from the fore- going substance. It is insoluble in hot dilute sulphuric acid and in a 10 per cent. solution of potassium hydroxide ; it gives no coloration with ferric chloride, is indifferent towards fuming nitric acid, and does not give Liebermann's reaction. Phosphorus pentachloride has no action on it. Boiling petroleum dissolves i t very sparingly, and although only moderately soluble in cold alcohol, it dissolves readily in the heated liquid. A solution containing 0.5920 gram in 25 C.C.of chloroform at 21' gave aD - '7'32' in a 2-dcm. tube, whence [.ID - 159.0". The transformation of the nitrosate into th6 compound C,,H,,O,N, can be effected also by the action of alcoholic ammonia, and, under certain conditions, by alcoholic potash. When the former agent is employed, and heated with the nitrosate under a reflux apparatus, the crystals become completely dissolved in about 15 minutes, and the smell of ammonia is then scarcely perceptible ; on cooling the liquid, an oil separates and rapidly solidifies. If alcoholic potash is used, it is necessary t o limit the quantity of alkali, because the product undergoes further decomposition if an excess is employed. Ten grams of the nitrosate were suspended in 25 C.C. of hot absolute alcohol and treated with 5 grams of potassium hydroxide i n the minimum of water.After five minutes on the water-bath, a clear, yellow solution was produced, from which a crystalline precipi- tate separated on cooling. This was identical with the product obtained by the action of piperidine, and, on evaporating the alcohol from the filtrate, a residue was obtained which dissolved very readily in water; this solution set free iodine from potassium iodide, and yielded a dark green oil when acidified. Evidence of the elimination of nitrous acid was obtained also in using piperidine. The filtrate from the solid substance precipitated by water was neutralised with dilute sulphuric acid, which precipitated a sticky, blue material ; on filtering the liquid, adding alkali, extracting with ether, and evaporating the solvent, an oil was obtained which gave Liebermann's reaction very intensely, and most probably con- sisted of nitrosopiperidine. Complete Hydrolysis of the Nitrosate.Although the compound C,,H,,O,N, is obtainable from the nitro- sate by the action alike of piperidine, alcoholic ammonia, and alcoholic potash, this fact is only true of the last named when the action is restricted, for if excess of the agent is employed the product is a,STUDIES IN THE CAMPHANE SERIES. PART xm. 329 potassium derivative which forms a dark brown solution in water and yields a green oil on acidification. This compound can be separated also as a by-product in the prepara- tion of the nitrosate, for if the chloroform filtrate from that substance is shaken with 10 per cent.potassium hydroxide, the latter becomes brown, and furnishes the green oil on treatment with acid. Owing to the unstable character of the liquid, we have not been able t o determine its composition, but crystalline derivatives have been obtained from it, and are described below. The ethereal solution, when dried with calcium chloride and evaporated, yields a bright green varnish, which turns brown spontaneously and evolves a gas without colour or odour; if a freshly prepared specimen is heated i n boiling water, it decomposes suddenly, emitting clouds of brown fumes with considerable violence, and becoming converted into a charred mass. I f a n attempt is made t o distil the green oil in steam the colour changes to brown, but nothing volatile is produced; the brown pro- duct, unlike the green substance from which it is obtained, is insoluble in sodium carbonate, but dissolves in caustic alkali.It has not been found possible t o obtain crystalline derivatives of the green oil by the action of phenyl isocyanate or of beuzoyl chloride. Concentrated hydrochloric acid does not eliminate hydroxglamine, atid reduction with sodium amalgam has failed to give a definite product ; oxidation with potassium permanganate takes place very readily in the alkaline solution, and appears to decompose the substance completely. Action of Potassiunt Perricyanide on the Green Oil. Twenty grams of the nitrosate were suspended in 150 C.C. of absolute alcohol and heated on the water-bath during two hours with 14 grams of caustic potash dissolved in the minimum quantity of water; the alcohol was then evaporated and the rssidue taken up with water, in which it dissolved cor~~pletely.To this liquid, which was pale brown, 500 C.C. of a 25 per cent. solution of potassium ferri- cyanide were added, when a dark brown colour was developed in the liquid, the temperature of which rose to about 40°, whilst slight effervescence occurred. After an interval of 12 hours, dilute sulphuric acid was added until a greenish-blue coloration was produced ; the viscous, brown oil which separated was removed and washed several times, when it became solid and was purified by reprecipitation from the solution in sodium carbonate, followed by crystallisation of the dried substance (about 14 grams) from light petroleum.The same substance has been obtained from nitrocamphene in the following manner. One hundred grams, after treatment with nitrogen330 FORSTER AND MICKLETHWAIT : peroxide in the manner described, having furnished 24.2 grams of the nitrosate, the chloroform filtrate was extracted with 300 C.C. of 30 per cent. potassium hydroxide solution, which became dark brown. This liquid was treated with 1200 C.C. of a 25 per cent. solution of potassium ferricyanide, and t.he mixture, which had evolved gas and risen in temperature, was acidified with dilute sulphuric acid after an interval of 3 hours; the brown oil quickly hardened and was redis- solved in sodium carbonate, filtered from little insoluble tarry matter, and reprecipitated. The pale brown solid obtained in this manner weighed 51.5 grams.As in the case of the nitrosate, we have encountered difficulties in analysing t h i s substance, which has, we believe, the empirical formula C10Hl405N2. 0.1786 gave 0.3275 CO, and 0.1067 H,O. 0.1954 ,, 19.8 C.C. nitrogen a t 20" and 763 mm. N = 11-63. C = 50.01 ; H = 6-64. C,oH,,05N, requires C = 49.59 ; H = 5-78 ; N = 11.57 per cent. It dissolves readily in organic media excepting light petroleum, 1000 C.C. of a boiling concentrated solution in the latter depositing 4.2 grams in the form of snow-white needles melting at 85-46". It dissolves readily in sodium carbonate forming a pale yellow liquid, and the solution in 2 per cent. sodium hydroxide yields an intense purple-blue precipitate with ferrous sulphate. The alcoholic solution develops with ethereal ferric chloride a red coloration which is not very intense, and on adding copper acetate dissolved in alcohol the deep bluish-green colour of the copper salt changes to grass-green, but no separation of crystals takes place.The compound does not decolorise bromine dissolved in chloroform, but hydrogen bromide is evolved on boiling the solution. The solution in phenol develops a green coloration when warmed with concentrnted sulphuric acid, chauging to a very deep bluish-green ; on dilution, the colour becomes pink and then changes to intense blue on adding alkali. Fuming nitric acid dissolves the substance without any rise of temperature taking place, and phosphorus pentachloride, nitrous acid, potassium permanganate, benzoyl chloride, alcoholic potasb, and boiling acetyl chloride are also without action.The substance is not affected by hot concentrated hydrochloric acid, and after heating it during 2 hours with alcohol and hydro- chloric acid in a sealed tube at looo, it crystallised from the liquid, and the filtrate did not reduce Fehling's solution even when boiled. Dry hydrogen chloride was passed into a solution of the ctimpound in methyl alcohol during 2 hours without producing a trace of a methyl derivative. By dissolving it in excess of standardised sodium hydroxide andSTUDIES IN THE CAMPHANE SERIES. PART XIII. 331 tit,rating with sulphuric acid in presence of phenolphthalein, con- cordant results have been obtained without difficulty. 0.0861 gram dissolved in 10 C.C. of sodium hydroxide solution (con- taining 3.926 grams per litre) required 5.7 C.C.of sulphuric acid (containing 4.92 grams per litre), whence 242 grams reqnire 46.0 grams NaOH. 0.1063 gram dissolved in 12 C.C. of sodium hydroxide solution required 6.7 C.C. of sulphuric acid, whence 342 grams require 46.0 grams NaOH. The ccmmonitim derivative separated when the substance was treated with concentrated ammonia, forming colourless needles which became yellow at about 115' and decompused violently a t 136O; after remaining during 2 days i n the desiccator, the substance did not change colour until heated a t about 140'; it decomposed a t 155'. N= 15.86. 0.2045 gave 27.8 C.C. nitrogen a t 18' and 767 mm. C,,H170,N, requires N = 16.21 per cent, The copFer derivative crystallised in blue needles on adding copper sulphate to the a,mmoniacal solution, becoming olive-green after 2 days in t h e desiccator.Cu = 7.72. (C,,H,,O,N,),Cu,C,,H,,O,N, requires Cu = S-0s per cent, 0 2152 gave 0.0208 CuO. The silver derivative formed a pale yellow, granular precipitate on adding silver nitrate (1 mol.) to a neutral solution of the ammonium derivative. 0.1326 gave 0-0404 Ag. Ag = 30.46. CloH1,0,N2Ag requires Ag = 30.96 per cent. It darkens rapidly on exposure to light, and dissolves in hot water. It will be recognised that the behaviour of the substance Cl,Hl,O,N, is remarkable, because, although its production by the action of potass- ium ferricyanide on an oximino-compound would suggest its classifica- tion as a secondary nitro-derivative, nevertheless, the acidity which characterises it is more pronounced than that of many carboxylic acids ; if i t belonged to t h e latter class, the indifference towards hydrogen chloride of a solution in methyl alcohol would be explained if the group were attached to tertiary carbon.The compound, however, although optically active t o a slight extent only, exhibits definite mutarotation, and we think that this fact, in conjunction with the experiments still t o be described, is evidence in support of the view that it is a secondary nitro-derivative. A solution containing 1,1925 grams in 25 C.C. of chloroform a t 200 was prepared in a darkened room, and transferred to the 2-dcm. tube332 FORSTER AND MICKLETHWAIT : without more than a minute's interval after dissolution ; the reading observed was 21', which fell to 10' while confirmatory observations were being made.In half a n hour, the solution gave aD -39', remaining constant at a, - l08', which was reached on the eleventh day. Thus, the initial and final specific rotatory powers are [a],, + 3.6' and [ - 11.9' respectively. Action of Yotccssiurn IZypobromite.--Ten grams were dissolved in aqueous potassium hydroxide and treated with potassium hypobromite prepared by adding 20 grams of bromine t o a n ice-cold, concentrated solution of caustic potash. A snow-white precipitate was foi.med immediately, and this was filtered, washed, and crystallised from hot alcohol, which deposited 13 grams ; on recrystallisation, i t was obtained in colourless needles melting at 157". 0.3314 gave 0,4543 CO, and 0.1106 H,O.0.2336 ,, 0,1367 AgBr. Br= 24.90. C,,H,,O,N,Br requires C = 37.38 ; H = 4.05 ; Br = 34.92 per cent. A solution containing 1.2415 grams in 25 C.C. of chloroform at 20" gave a, - 6'45' in a 2-dcm. tube, whence [a], - 68.0'. The substance dissolves sparingly in boiling light petroleum, from which it separates in minute needles, and is moderately soluble in benzene, alcohol, ethyl acetate, or glacial acetic acid, cryst,allising from the first named in well-formed, six-sided prisms ; acetone and chloroform dissolve i t freely. The Liobermann reaction is very intense in all its stages. When the bromo-derivative is heated with alcoholic potash, the compound C,,HI,O,N, is regenerated. Action of Hydroxylamine.-Ten grams of the substance were dis- solved in 250 c .~ . of abholute alcohol, and treated first with 20 grams of hydroxylamine hydrochloride aud then with 18.7 grams of potass- ium hydroxide, both dissolved in water; after 2 hours on the water- bath, the liquid was evaporated and filtered from the solid (1.2 grams) which separated on cooling. The filtrate was faintly alkaline and yielded a colourless precipitate (6.1 grams) on acidification. Both products were then crystallised from hot water, which deposited the former in lustrous, orange leaflets melting at 184". C = 37.39 ; H = 3.73. 0.1709 gave 19.4 C.C. nitrogen at 20" and 749 mm. N =I 12-80. C,,H,,O,N, requires N = 12-39 per cent. The substance is moderately soluble in alcohol, from which i t crys- tallises in thin, striated prisms.It dissolves in 2 per cent. sodium hydroxide, but gives no coloration with ferrous sulphate, and does not reduce Fehling's solution, although arnmoniacal silver nitrate is reduced immediately on boiling. The alcoholic solution develops a n intense purple coloration with ethereal ferric chloride, and, whenSTCDIES IN THE CAMPHANE SERIES. PART XIII. 333 treated with copper acetate in alcohol, destroys the colour of the first few drops and quickly yields a sage-green precipitate. It does not give Liebermann's reaction. The second product dissolves more readily in sodium carbonate than t h e foregoing substance, and crystsllises from boiling water in colour- less, transparent pyramids melting at 161°, the solution being acid to litmus. 0.3924 gave 26.4 C.C.nitrogen at 19" and 748 mm. N=7.61. CloHl,O,N requires K = 7.10 per cent. This compound gives no coloration with ethereal ferric chloride, and reduces ammoniacal silver nitrate very slightly on continued boiling. It does not, give Liebermann's reacbion, and gives no characteristic precipitate i n 2 per cent. sodium hydroxide with ferrous sulphate or with potsssium hypobromite. It is practically insoluble in light petroleum, dissolves very sparingly in chloroform and carbon bisulph- ide, and is only moderately soluble in hot alcohol or acetone. It neither decolorises dissolved bromine nor yields hydrogen bromide when warmed with the halogen, but the sodium carbonate solution reduces potassium permanganate freely. Beduction with AYodiunz Amalgam.--By this treatment, the com- pound C,,H1,0,N2 is converted into a deep red substance, and hydr- oxylamine is eliminated. Ten grams were dissolved in 50 C.C.of 10 per cent. sodium hydroxide and shaken with 360 grams of 2 per cent. sodium amalgam, which was added in quantities of 40 grams at intervals of half an hour, the liquid being kept cool and diluted occasionally with a few C.C. of water, With the first addition of amalgam, a turbidity appeared, followed by a pink coloration, which rapidly deepened to a n intense dark red .tint ; meanwhile, an ammoniacal odour became noticeable. When all the reducing agent had been used, a few C.C. of sodium carbonate were added, SO t h a t the product being soluble in both acids and alkalis, the next step, acidification, can be interrupted when effervescence begins.A vermilion preripitdte was thus obtained, and the filtrate reduced cold Fehling's solution immediately. The substance could not be recrystallised, but a specimen repre- cipitahed from a filtered solution in 10 per cent. potassium hydroxide was analysed. 0.1991 gave 15.2 C.C. nitrogen at 17" and 772 mm. N = 9-00, C,,H,,ON requires N = 8.48 per cent. C,,H3,0N, ,, N=S.92 ,, It is insoluble in light petroleum, but dissolves very freely in cold alcohol and in boiling water, forming red solutions which have no33% FORSTER AND MICKLETHWAIT : action on ammoniacal silver nitrate and Fehling's solution respectively. The solution in dilute sulphuric acid has the colour of potassium per- manganate, and the wine-red liquid produced by dissolving the sub- stance in 2 per cent.sodium hydroxide yields a dark brown precipitate with ferrous sulphate. An alcoholic solution gives no distinctive coloration with ethereal ferric chloride, but develops a magnificent purple with potassium hydroxide. Action of Potassium Hypobronzite 00% ihs Green Oil. Ten grams of the nitroeate were suspended in 75 C.C. of absolute alcohol and heated on the water-bath during 2 hours with 7 grams of caustic potash dissolved in the minimum quantity of water; tbe residue obtained on evaporation having been dissolved in ice-cold water, a freshly prepared solution of potassium hypobromite containing 30 grams of bromine was added. A heavy, yellow oil wasprecipitated, hardening immediateIy on treatment with cold water, and weighing 15 grams.This compound has been obtained also by treating with excess of potassium hypobromite the brown alkaline liquid formed on shaking wit,h aqueous potash the green chloroform filtrate from the nitrosate ; 16 grams were thus produced from 25 grams of nitrocamphene. The substance prepared by these methods dissolves in boiling light petroleum, and crystsllises in stellate aggregates of lustrouP, pale brown prisms melting a t 78'. 0.3201 gave 0.3040 CO, and 0.0885 H,O. C = 25.90 ; H = 3 09. 0.4382 ,, 22.6 C.C. nitrogen at 20" and 763 mm. N=5.93. 0.2542 ,, 0.2971 AgBr. Br=49*73. CloH,,O,N,Br, requires-c = 25.05 ; H = 2.30 ; N = 5.84 ; Br = 50.10 per cent. It is readily Foluble in ccld chloroform and ethyl acetate, and less freely in alcohol and acetic acid. A solution containing 1.2882 grams in 25 C.C.of chloroform a t 20' gives aD 26' in a 2-dcm. tube, whence [ + 4.2O. Although i t undergoes reduction in alcoholic solution with zinc dust, aluminium amalgam, and with potassium hydroxide, in no case has a crystalline product been obtained. The tribromo- derivative gives Liebermann's reaction with great intensity in all i t s stages. Met Ay Iccnainocnmpliene, C, oH,,*N H CH,. At one time it seemed possible that the object we had in view might be attained by the use of derivatives of aminocarnphene, and experiments were made with benzoylaminocamphene and methyl-STUDIES IN THE CAMPHANE SERIES. PART XIII. 335 aminocamphene, but without succesq. The latter substance was obtained by the process devised for the preparation of methylbornyl- amine (Trans., 1899, 75, 936) ; this consists in converting the benzyl- idene derivative of the primary base into the methiodide, and heating this with moist ethyl acetate, which hydrolyses it to benzaldehyde and the hydriodide of the methylated base. Six grams of benzylideneaminocamphene (Trans., 1901, 7Q, 650) were heated in a sealed tube with 22 grams of methyl iodide at 100' during 2 hourF, the product being treated with ether and filtered. The yellow crystals weighed 7 grams and had a faint odour of benz- aldehyde. 0.1309 gave 0.0828 AgT. I= 34.19. CloH1,*N:CH.C,H,,CH,I requires I = 33.34 per cent. 0.2188 ,, 0.1418 AgI. 1=34*21. Twenty-eight grams of this material were heated with 200 C.C. of undried ethyl acetate during 1 hour; 21 grams of methylaminocam- phene hydriodide were obtained and recrystallised from hot water. 0.2040 gave 0.1632 AgI. I = 43.23. C,,H,,NI requires I = 43.34 per cent. On decomposing the salt with caustic alkali, methglaminocamphene was obtained as a colourless oil which boils a t 202-203' under 756 mm. pressure, and has sp. gr. 0.91'71 at 22'. A solution contain- ing 0.5447 gram in 25 C.C. of absolute alcohol gave aD 1 O 1 7 ' in a 2-dcm. tube, whence [ aJD + 28.7'. The pkatinichloride melts and decomposes at 2 1 4 O . 0.1322 gave 0.0349 Pt. P t = 26.39. 09893 ,, 0.0763 Pt. Pt=26*37. (Cl,H,,N),,H2PtCI, requires Pt = 26.27 per cent, The salt dissolves readily in alcohol, from which it crysta!lises in minute needles. ROYAL COLLEGE OF SCIENCE, LONDON, SOUTH KENSIFGTOS, S. W.