摘要:

66 AESOHLIMANN LEES MCCLELAND AND NICKUN : X.-Organic Compounds of Arsenic. Part I I . Deriv-atives of the Arsenic Analogue of Carbaxole. By JOHN ALFRED AESCHLIMANN NORMAN DEIMPSTER LEES NIAL PATRICK MCCLELAND and GEORGE NORMAN NICKLIN. TURNER and BURY have shown (J. 1923 123 2489) that the closure of five-membered arsenic rings of the type As-methyl-dihydroarsindole can be accomplished without difficulty and two of us have found (J. 1924 125 2025) that the same applies to certain five-membered rings containing three atoms of carbon one atom of oxygen and one of arsenic ORGANIC COMPOUNDS OF ARSENIC. PART II. 67 It is now shown that the five-membered arsenic ring of analogues of carbazole can be closed with similar ease and it is hoped to give in a future communication an account of the formation of arsenic a,nalogues of indoxyl and related substances.o-Aminodiphenyl subjected to the Bart reaction yields diphenylyl-o-arsinic acid (I) and this is converted by warm concentrated sulphuric acid int'o 00'-diphenylyleneaminic acid (11). Similarly diphenylyl-o-arsenious chloride on distillation in a vacuum is converted into 00'-diphenylylenearsenious chloride. Various other derivatives of 00'-diphenylylenearsine have been prepared but the parent substance could not be isolated owing to the readiness with which it is oxidised in the air, The derivatives are all beautifully crystalline colourless with the exception of the iodide and non-fluorescent. The melting point is usually about 100"thigher than that of the corresponding diphenyl derivative.E S P E R I J I E X T A L . o-Amino~iiphe72yZ.-Hirsch's method for the preparation of this base (Ber. 1892 25 1973) was modified in that the diazoamino-benzene was prepared as a separate operation whereby the volume of solvent was much reduced and the tedious drying over potash obviated. Further since it was not necessary to isolate p-amino-diphenyl the separation of the required base from the other products of the reaction was considerably simplified. Diazoaminobenzene (150 g.) is covered with 400 g. of aniline (both thoroughly dry) in a large distilling flask and heated until (at about 150") a brisk evolut'ion of nitrogen begins; after which the reaction should proceed smoothly to completion the tem-perature slowly rising to 180".Care is necessary not to overheat the mixture as the reaction may then get out of control. After removal of the aniline the residue is distilled to about 250" (20 mm.) or until the distillate is very much coloured. The oily distillate is treated with warm dilute sulphuric acid (60 g. in 1 litre for 100 g. of the oil) the residue (diphenylamine and p-aniinodiphenyl sulphate) removed and the solution concentrated, alinost to dryness. The sulphate of o-aminodiphenyl crystallises, while most of the aminoazobcnzene sulphate remains in the mother-liquors. The base is obtained from the sulphate in the usual manner and distilled in a vacugm (yield about 25 g.). For further D 68 AESCHLIMANN LEES MCCLELAND AND NICKLIN : purification crystallisation of the hydrochloride from concentrated hydrochloric acid by cooling a saturated solution to - 10" is recommended.Diphenylyl-o-arsinic Acid (I).-Sodium arsenite is coupled with diazotised o-aminodiphenyl in alkaline solution a t 50-60" in pres-ence of a cupric salt. The acid crystallises from boiling water in bristle-like needles m. p. 205". Yield about 60% (Found C = 51.7 ; H = 4.1. C,,H,O,As requires C = 51.8 ; H = 4-00;;). Diphenylyl-o-arsenious chloride obtained by the reduction of the above dissolved in warm concentrated hydrochloric acid by sulphur dioxide in presence of an iodide is a heavy oil soluble in chloroform insoluble in water. On distillation in a vacuum it loses hydrogen chloride and yields 00'-diphenylylenearsenious chloride. DiphenyhyZ-o-arsenious oxide obtained by the action of alcoholic potash on the above is an amorphous substance with no definite melting point.00'- Diphenylylenearsinic Acid (II).-A solution of diphenylyl-o-arsinic acid in concentrated sulphuric acid is warmed on the water-bath for a few minutes and poured into water. 00'-Diphenylylenearsinic acid can be crystallised from very much boiling water m. p. 290" (Found C = 55.2; H = 3.5. C,,H,O,As requires C = 55.4; H = 3.5%). 00'-Diphenylylenearsenious Chloride.-Diphenylylenearsinic acid is suspended in concentrated hydrochloric acid an equal volume of chloroform added and sulphur dioxide and hydrogen chloride are passed in through a wide delivery tube opening under the surface of the chloroform. After some minutes a little potassium iodide is added and the reduction carried on under reflux on a water-bath when diphenylylenearsenious chloride passes into the chloroform layer.It is recrystallised from benzene. 00'-Diphenylylenearsenious chloride crystallises with remarkable readiness in colourless plates m. p. 161" b. p. about 230"/25 mm., readily soluble in chloroform or carbon tetrachloride less soluble in benzene or alcohol (Found C1 = 13.3. C,,H,CIAs requires C1 = 13.5%). Diphenylylenearsenious Iodide.-A suspension of diphenylylene-arsinic acid in 10% sulphuric acid is saturated with sulphur dioxide at 60° and a strong solution of potassium iodide added. After further reduction for an hour the solid is removed and taken up in benzene; the solution is dried filtered and evaporated to small bulk.It forms very beautiful golden plates m. p. 166" soluble in benzene or chloro-form practically insoluble in alcohol. The iodide is then precipitated with alcohol ORGANIC COMPOUNDS O F ARSENIC. PAET 11. 69 oo'-Di23heizySylenearse72ious oxide obtained by the action of warm alcoholic potash on the chloride or of concentrated aqueous am-monia on the iodide forms white crystals M. p. 178" readily soluble in organic solvents (Found C = 61-4 ; H = 3.4. C24H,cOAe2 requires C = 81.3; H = 3-47;). From alcohol it crystclllises in needles m. p. 117" containing alcohol of crystallisation. oo'-l)iphe72ylyleizca?;fenious Cya nide.-The oxide is dissolved in the least quantity of cold chloroform or of absolute alcohol and treated vith anhydrous hydrocyanic acid (4 vol.).The product is crystallised from warm absolute alcohol to which a little anhydrous hydrocyanic acid is added as the temperature falls. The cyanide forms long silky needles in. 13. 178" (like the oxide) soluble in the usual organic solvents (Found C = 61.5; H = 3.1 ; N = 5.5. C',,H,KAs requires C = 61.7 €1 = 3.2; K = 5.60,/,). d tt em pi c to Pre;iarc! oo '-Biphenyl y leizeu rsin e .-To diphenylylene-arsinic acid mixed with amalgamated zinc hydrochloric acid was added and the whole covered with a layer of ether the air in the flask being replaced by hydrogen. After some days the clear ethereal layer became cloudy after a short exposure to the air, indicating the presence of the arsine which could not however be isolated. The solution was colourlcss and non-fluorescent .Diphen ylylemrnet h ylarsine .-By the action of magnesium methyl iodide on diphenylylenearsenious iodide suspended in ether the yellow coiour of the latter was discharged. On working up the product in the usual way a substance was obtained which crystal-lived froin alcohol in large transparent prisms m. p. 46". It was probably the arsine required but analytical results were not very satisfactory even after several crystallisations (Found C = 65.0, 63-1 ; H = 4.4 4.4. C,,H,,As requires C = 64.5; H = 4-57;). The substance had a pleasant orange-like smell. nipF,eizylylenedimethyla1.3o?zi~m iodide obtained by heating the above with methyl iodide forms needles m. p. 190" soluble in alcohol insoluble in ether. The iodine is ionic and may be deter-mined by titration with silver nitrate (Found I = 33.3.C,,HI4IAs requires I = 33-1 "6). Methylcarbazole does not combine with methyl iodide. THE UNIVERSITY CHEMIC-AL LABOR \TORY, CAVBRIDGE. [Received October lGth 1924. 66 AESOHLIMANN LEES MCCLELAND AND NICKUN : X.-Organic Compounds of Arsenic. Part I I . Deriv-atives of the Arsenic Analogue of Carbaxole. By JOHN ALFRED AESCHLIMANN NORMAN DEIMPSTER LEES NIAL PATRICK MCCLELAND and GEORGE NORMAN NICKLIN. TURNER and BURY have shown (J. 1923 123 2489) that the closure of five-membered arsenic rings of the type As-methyl-dihydroarsindole can be accomplished without difficulty and two of us have found (J. 1924 125 2025) that the same applies to certain five-membered rings containing three atoms of carbon one atom of oxygen and one of arsenic ORGANIC COMPOUNDS OF ARSENIC.PART II. 67 It is now shown that the five-membered arsenic ring of analogues of carbazole can be closed with similar ease and it is hoped to give in a future communication an account of the formation of arsenic a,nalogues of indoxyl and related substances. o-Aminodiphenyl subjected to the Bart reaction yields diphenylyl-o-arsinic acid (I) and this is converted by warm concentrated sulphuric acid int'o 00'-diphenylyleneaminic acid (11). Similarly diphenylyl-o-arsenious chloride on distillation in a vacuum is converted into 00'-diphenylylenearsenious chloride. Various other derivatives of 00'-diphenylylenearsine have been prepared but the parent substance could not be isolated owing to the readiness with which it is oxidised in the air, The derivatives are all beautifully crystalline colourless with the exception of the iodide and non-fluorescent.The melting point is usually about 100"thigher than that of the corresponding diphenyl derivative. E S P E R I J I E X T A L . o-Amino~iiphe72yZ.-Hirsch's method for the preparation of this base (Ber. 1892 25 1973) was modified in that the diazoamino-benzene was prepared as a separate operation whereby the volume of solvent was much reduced and the tedious drying over potash obviated. Further since it was not necessary to isolate p-amino-diphenyl the separation of the required base from the other products of the reaction was considerably simplified. Diazoaminobenzene (150 g.) is covered with 400 g.of aniline (both thoroughly dry) in a large distilling flask and heated until (at about 150") a brisk evolut'ion of nitrogen begins; after which the reaction should proceed smoothly to completion the tem-perature slowly rising to 180". Care is necessary not to overheat the mixture as the reaction may then get out of control. After removal of the aniline the residue is distilled to about 250" (20 mm.) or until the distillate is very much coloured. The oily distillate is treated with warm dilute sulphuric acid (60 g. in 1 litre for 100 g. of the oil) the residue (diphenylamine and p-aniinodiphenyl sulphate) removed and the solution concentrated, alinost to dryness. The sulphate of o-aminodiphenyl crystallises, while most of the aminoazobcnzene sulphate remains in the mother-liquors.The base is obtained from the sulphate in the usual manner and distilled in a vacugm (yield about 25 g.). For further D 68 AESCHLIMANN LEES MCCLELAND AND NICKLIN : purification crystallisation of the hydrochloride from concentrated hydrochloric acid by cooling a saturated solution to - 10" is recommended. Diphenylyl-o-arsinic Acid (I).-Sodium arsenite is coupled with diazotised o-aminodiphenyl in alkaline solution a t 50-60" in pres-ence of a cupric salt. The acid crystallises from boiling water in bristle-like needles m. p. 205". Yield about 60% (Found C = 51.7 ; H = 4.1. C,,H,O,As requires C = 51.8 ; H = 4-00;;). Diphenylyl-o-arsenious chloride obtained by the reduction of the above dissolved in warm concentrated hydrochloric acid by sulphur dioxide in presence of an iodide is a heavy oil soluble in chloroform insoluble in water.On distillation in a vacuum it loses hydrogen chloride and yields 00'-diphenylylenearsenious chloride. DiphenyhyZ-o-arsenious oxide obtained by the action of alcoholic potash on the above is an amorphous substance with no definite melting point. 00'- Diphenylylenearsinic Acid (II).-A solution of diphenylyl-o-arsinic acid in concentrated sulphuric acid is warmed on the water-bath for a few minutes and poured into water. 00'-Diphenylylenearsinic acid can be crystallised from very much boiling water m. p. 290" (Found C = 55.2; H = 3.5. C,,H,O,As requires C = 55.4; H = 3.5%). 00'-Diphenylylenearsenious Chloride.-Diphenylylenearsinic acid is suspended in concentrated hydrochloric acid an equal volume of chloroform added and sulphur dioxide and hydrogen chloride are passed in through a wide delivery tube opening under the surface of the chloroform.After some minutes a little potassium iodide is added and the reduction carried on under reflux on a water-bath when diphenylylenearsenious chloride passes into the chloroform layer. It is recrystallised from benzene. 00'-Diphenylylenearsenious chloride crystallises with remarkable readiness in colourless plates m. p. 161" b. p. about 230"/25 mm., readily soluble in chloroform or carbon tetrachloride less soluble in benzene or alcohol (Found C1 = 13.3. C,,H,CIAs requires C1 = 13.5%). Diphenylylenearsenious Iodide.-A suspension of diphenylylene-arsinic acid in 10% sulphuric acid is saturated with sulphur dioxide at 60° and a strong solution of potassium iodide added.After further reduction for an hour the solid is removed and taken up in benzene; the solution is dried filtered and evaporated to small bulk. It forms very beautiful golden plates m. p. 166" soluble in benzene or chloro-form practically insoluble in alcohol. The iodide is then precipitated with alcohol ORGANIC COMPOUNDS O F ARSENIC. PAET 11. 69 oo'-Di23heizySylenearse72ious oxide obtained by the action of warm alcoholic potash on the chloride or of concentrated aqueous am-monia on the iodide forms white crystals M. p. 178" readily soluble in organic solvents (Found C = 61-4 ; H = 3.4. C24H,cOAe2 requires C = 81.3; H = 3-47;). From alcohol it crystclllises in needles m.p. 117" containing alcohol of crystallisation. oo'-l)iphe72ylyleizca?;fenious Cya nide.-The oxide is dissolved in the least quantity of cold chloroform or of absolute alcohol and treated vith anhydrous hydrocyanic acid (4 vol.). The product is crystallised from warm absolute alcohol to which a little anhydrous hydrocyanic acid is added as the temperature falls. The cyanide forms long silky needles in. 13. 178" (like the oxide) soluble in the usual organic solvents (Found C = 61.5; H = 3.1 ; N = 5.5. C',,H,KAs requires C = 61.7 €1 = 3.2; K = 5.60,/,). d tt em pi c to Pre;iarc! oo '-Biphenyl y leizeu rsin e .-To diphenylylene-arsinic acid mixed with amalgamated zinc hydrochloric acid was added and the whole covered with a layer of ether the air in the flask being replaced by hydrogen.After some days the clear ethereal layer became cloudy after a short exposure to the air, indicating the presence of the arsine which could not however be isolated. The solution was colourlcss and non-fluorescent . Diphen ylylemrnet h ylarsine .-By the action of magnesium methyl iodide on diphenylylenearsenious iodide suspended in ether the yellow coiour of the latter was discharged. On working up the product in the usual way a substance was obtained which crystal-lived froin alcohol in large transparent prisms m. p. 46". It was probably the arsine required but analytical results were not very satisfactory even after several crystallisations (Found C = 65.0, 63-1 ; H = 4.4 4.4. C,,H,,As requires C = 64.5; H = 4-57;). The substance had a pleasant orange-like smell. nipF,eizylylenedimethyla1.3o?zi~m iodide obtained by heating the above with methyl iodide forms needles m. p. 190" soluble in alcohol insoluble in ether. The iodine is ionic and may be deter-mined by titration with silver nitrate (Found I = 33.3. C,,HI4IAs requires I = 33-1 "6). Methylcarbazole does not combine with methyl iodide. THE UNIVERSITY CHEMIC-AL LABOR \TORY, CAVBRIDGE. [Received October lGth 1924.

ISSN:0368-1645    

DOI:10.1039/CT9252700066

出版商:RSC    

年代:1925

数据来源: RSC

摘要:

70 ADAM AND DYER SYNTBESIS OF XI.-Synthesis of Arachidic Acid and some Long-chain Compounds. By NEIL K. ADAM and JOSEPH W. W. DYER. THE melting points of methyl and ethyl arachidates and eicosyl alcohol recorded in the literature are several degrees higher than those proper to compounds of their length of chain in the respective series. The regular rise of melting point in the even series of long-chain compounds is more than a mere empirical relationship, since one of us showed (Proc. Roy. Xoc. 1922 [A] 101 528) that from this rise and other regularities a crystal structure could be predicted which has since been shown by X-ray methods to be correct (Muller and Shearer, J. 1923 123 2043 3152 3156). Having synthesised arachidic acid from stearic acid by means of malonic ester we find that the melting points of these derivatives are as follows.Ethyl arachidate 41.5" to 42.5" ; methyl arachidate, 46" to 47" ; eicosyl alcohol 65" to 65.5". Previously recorded values are; ethyl ester 49" (Schweizer Arch. Pharm. 1884 222 768), 50" (Gossmann Annalen 1854 89 10) ; methyl ester 54.5" (Haller, Compt. rend. 1907 144 598); 53" (Schweizer Zoc. cit.); alcohol, 71" (Haller Zoc. cit.). Our values are nearly the mean between the melting points of the compounds in the 18- and 22-carbon series; the older ones are in some cases higher than those in the 22-carbon series. The melting point of arachidic acid itself is 75" in agreement with previous results and with the position in the series. The synthesis from ethyl stearate gave a 41% overall yield of pure arachidic acid and appears to be much the easiest method of obtaining compounds of the Czo series pure.We record also a modification of the Bouveault and Blanc reduc-tion convenient for long-chain compounds ; and new preparations of eic 0s y 1 acetate eic 0s y lamin e hydrochloride eic 0s y Ic ar bamide , acetohexadecyl- and aceto-octadecyl-amides dioctadecylmalonic acid and dioctadecylacetic acid. E X P E R I M E N TAL. Reduction of Long-chain Esters with Sodium and Alcohol .-The higher ethyl esters are troublesome in the ordinary process owing to their small solubility in alcohol. Addition of a large bulk of light petroleum and substitution of wire or dust for the lumps of sodium give good yields of the alcohol. Octudecyl AZcohol.-Well-dried ethyl stearate (150 g.) dissolved in 1200 C.C.of light petroleum and 150 C.C. of absolute alcohol ARACHIDIC ACID AND SOME LONG-CHAM COMPOUNDS. 71 was added during $ hour to sodium wire (72 g.) covered with a little light petroleum to prevent oxidation at about 80"; heating was continued for 6 hours with occasional shaking. The solvents were distilled off the residual solid was treated with hot brine and after filtration the product was dried and extracted with ether. The ether was evaporated and the residue distilled a t 12 mm. pressure (yield 68.5%). For quantities less than 20 g. of ester the process was modified by using sodium pulverised under xylene and gave similar yields. Eicosyl alcohol from 4-82 g. of ethyl arachidate was obtained in 70% yield.It was not distilled but crystallised to constant m. p. (65-65.5') from 90% alcohol. Eicosyl acetate prepared by dissolving the alcohol in glacial acetic acid and passing hydrogen chloride was crystallised from aqueous acetone; m. p. 39*5-40.5" (Found C = 77.54; H = 13-04. Calc. C = 77-49; H = 13.0;jy0). Preparation of Iodides and of Derivatives of Jlnlonic Acid.-Passing hydrogen iodide into the molten alcohols (see Krafft Ber., 1886,19,2984) gave quantitative yields of the iodides the gas being practically completely absorbed until the reaction was complete. The iodide washed in ethereal solution was heated with the theoretical amount of sodium and ethyl malonate in absolute alcohol. The mixture became neutral and gave ethyl mono-octadecyl-malonate after 2 hours' boiling and standing over-night.Hydrolysis with strong aqueous potash was nearly instantaneous. The calcium salt was prepared and extracted with alcohol and ether and the malonic acid liberated in 700; yield (calculated on the iodide used) by rubbing the purified calcium salt with hydrochloric acid in pre-sence of a little ether which promotes wetting. Ethyl dioctadecylmalonate could not be prepared in one operation, but was obtained by heating for 6 hours 12.2 g. of the crude ruono-octadecylmalonic ester with 0-682 g. of sodium 11.5 g. of octadecyl iodide and 30 C.C. of absolute alcohol a little dry ether being added to obtain a homogeneous liquid. After 48 hours' standing the mixture was neutral. The ester was hydrolysed by heating on the water-bath with alcoholic potash for 10 hours ; the dioctadecyl-malonic acid was purified by means of the calcium salt as before, and recrystallisation from glacial acetic acid.M. p. 93-5-94' [Found C = 76.88; H ==12.33. (C,8H,,),C(C0,H) requires Dioctadecylacetic Acid.-Heating dioctadecylmalonic acid at 160" left a residue m. p. 80-42"; this was raised to 81-82" by crystallisation from acetic acid [Found C = 80.63; H = 13.39. (C,,H,,),CH*CO,H requires C = 80.76; H = 13.560/,]. C = 76.89 ; H = 12.57%] 72 ADAM AND DYER SYNTHESIS OF AR,ACHIDIC ACID ETC. Guthzeif (Annalen 1881 206 362) describes dicetylmalonic acid (m. p. 86-87') and dicetylacetic acid (m. p. 69-70"); his work has been criticised by Ihafft since the cetyl alcohol used was not pure. If the crystal structure of these compounds is generally the same as that of the simple fatty acids with the long chains packed side by side and the molecules arranged in pairs of layers, the polar groups of one layer of the pair being next to the polar groups of the other layer we should expect the difference of two carbon atoms to make a difference of about 3" in the m.p.'s of the dialkylmalonic acids and of about 6" in those of the dialkylacetic acids which would indicate for the pure dihexadecylmalonic acid m. p. about 91', and for dihexadecylacetic acid m. p. about 75". Arachidic Acid and its Esters.-The arachidic acid obtained by heating the monooctadecylmalonic acid distilled a t 203-205" (uncorr.)/l mm. and crystallised in leaflets from light petroleum ; m.p. 75-75-5". Titration in alcoholic solution with soda gave the molecular weight 313 (theory 312.3) (Found C = 76-73; H = 12.96. Calc. C = 76-85; H = 12.90y0). Methyl arachidate was prepared by passing hydrogen chloride into a solution of the acid in pure methyl alcohol and recrystallising from alcohol. M. p. unchanged on recrystallisation 46-47' (Found C = 76.96; H = 12.98. Calc. C = 76.85; H = 12.90y0). Ethyl arachidate prepared similarly and crystallised to constant melting point melted at 41.542-6". Preparation of Long-chain Arnicles.-Fileti and Ponzio's method of adding a solution of the acid chloride in ether to aqueous ammonia (Gaxxetta 1593 23 391) gives much better results than methods in which the ether is omitted. These frequently give a product with a melting point 10 degrees too low which probably consists largely of ammonium salt.Using ether as solvent for the chloride, large quantities of the amide may be prepared the chloride being added very rapidly and the product is practically pure without crystallisation. The ether is almost entirely driven off by the heat of reaction and appears to act as a very efficient cooling agent. The aqueous ammonia may be a t room temperature. Arachidamide m. p. log" and the nitrile m. p. 49.5" were pre-pared by the usual methods from the acid. Eicosylamine hydrochloride was prepared by a modification of Krafft's method (Ber. 1889 22 812) for hexadecylamine. The nitrile (9-7 g.) in 150 C.C. of absolute alcohol was boiled under reflux, 15 g. of sodium being added during 1 hour.The mixture was poured warm into dilute hydrochloric acid heated with 250 C.C. of absolute alcohol filtered from any inorganic chlorides diluted to about 85% alcohol and cooled. The solution deposited 8-5 g THE ADSORPTION OX CATALYTICALLY POISOXOUS JIETdLS KTC. of pure eicosylamine hydrochloride IL g. more being obtained 011 concentratling the mother-liquors. For analysis the chlorine was precipitated with alcoholic silver nitrate (Found Cl =T= 10-66. C,,H,,N,HCl requires C1 = 10.64y0). Eicosylcarbamide was easily prepared by evaporating the preceding compound to dryness n.ith excess of potassium cyariate and recrystal-k i n g from alcohol. M. p. 111.5" (corr.) (Pound C = 73.98; H = 13.13; C,oH,l*rU'M-C@-XK requires C =L 74.00; Moiiomolecular films of all thc compounds of the C, series were examined according to thc methods described in previous papers (Proc.Roy. Xoc. 1922 [ A ] 184 452 516) and were found t o have the properties expected for their i-especdive series and thi C, chiill, within experimental error ; a fact which confirms their identity. Aceto-octadecyZamicle.-Octadecylami:ie hydrochloride (1.4 g.), prepared in the same manner as eicosyIaniine hydrochloride i ~ a ~ distilled with quicklime the distillate warmcd with acetic mhyclride a few minutes and the product crystallised from acetic acid nit11 the aid of charcoal; m. p. unchanged by further crysdlisation, 79.5-80" (yield 66%). The action of acetyl chloride on the aririne gave a very poor yield of the desired substance (Found C = 77-23 ; $3 = 13.4 ; N = 4.73.Cl,H3i-NH*CO*CH requires &' == 75439 ; Acetohexadec$amicle was similarly prepared and crystallised from acetic acid and acetone to constant melting point (Found : C = 76.46; H = 13.35. C,,H,,-NH*CQ*CH requires C = 76-69; H = 13.22%). I n the monomolecular films the acetamides showed a characteristic behaviour described in another paper, which indicated that the c'ompunds were members of the same liomologous series and differed by two CM groups. N = S.25. H = 13.04; N = S*25",). H = 13.2; N = 4.50%). THE SORBY RESEARCH LABOR~~TORY, UNIVERSITY OF SHEWIELD. [Receiced June l l f h 1924. 70 ADAM AND DYER SYNTBESIS OF XI.-Synthesis of Arachidic Acid and some Long-chain Compounds. By NEIL K. ADAM and JOSEPH W. W. DYER.THE melting points of methyl and ethyl arachidates and eicosyl alcohol recorded in the literature are several degrees higher than those proper to compounds of their length of chain in the respective series. The regular rise of melting point in the even series of long-chain compounds is more than a mere empirical relationship, since one of us showed (Proc. Roy. Xoc. 1922 [A] 101 528) that from this rise and other regularities a crystal structure could be predicted which has since been shown by X-ray methods to be correct (Muller and Shearer, J. 1923 123 2043 3152 3156). Having synthesised arachidic acid from stearic acid by means of malonic ester we find that the melting points of these derivatives are as follows. Ethyl arachidate 41.5" to 42.5" ; methyl arachidate, 46" to 47" ; eicosyl alcohol 65" to 65.5".Previously recorded values are; ethyl ester 49" (Schweizer Arch. Pharm. 1884 222 768), 50" (Gossmann Annalen 1854 89 10) ; methyl ester 54.5" (Haller, Compt. rend. 1907 144 598); 53" (Schweizer Zoc. cit.); alcohol, 71" (Haller Zoc. cit.). Our values are nearly the mean between the melting points of the compounds in the 18- and 22-carbon series; the older ones are in some cases higher than those in the 22-carbon series. The melting point of arachidic acid itself is 75" in agreement with previous results and with the position in the series. The synthesis from ethyl stearate gave a 41% overall yield of pure arachidic acid and appears to be much the easiest method of obtaining compounds of the Czo series pure.We record also a modification of the Bouveault and Blanc reduc-tion convenient for long-chain compounds ; and new preparations of eic 0s y 1 acetate eic 0s y lamin e hydrochloride eic 0s y Ic ar bamide , acetohexadecyl- and aceto-octadecyl-amides dioctadecylmalonic acid and dioctadecylacetic acid. E X P E R I M E N TAL. Reduction of Long-chain Esters with Sodium and Alcohol .-The higher ethyl esters are troublesome in the ordinary process owing to their small solubility in alcohol. Addition of a large bulk of light petroleum and substitution of wire or dust for the lumps of sodium give good yields of the alcohol. Octudecyl AZcohol.-Well-dried ethyl stearate (150 g.) dissolved in 1200 C.C. of light petroleum and 150 C.C. of absolute alcohol ARACHIDIC ACID AND SOME LONG-CHAM COMPOUNDS.71 was added during $ hour to sodium wire (72 g.) covered with a little light petroleum to prevent oxidation at about 80"; heating was continued for 6 hours with occasional shaking. The solvents were distilled off the residual solid was treated with hot brine and after filtration the product was dried and extracted with ether. The ether was evaporated and the residue distilled a t 12 mm. pressure (yield 68.5%). For quantities less than 20 g. of ester the process was modified by using sodium pulverised under xylene and gave similar yields. Eicosyl alcohol from 4-82 g. of ethyl arachidate was obtained in 70% yield. It was not distilled but crystallised to constant m. p. (65-65.5') from 90% alcohol. Eicosyl acetate prepared by dissolving the alcohol in glacial acetic acid and passing hydrogen chloride was crystallised from aqueous acetone; m.p. 39*5-40.5" (Found C = 77.54; H = 13-04. Calc. C = 77-49; H = 13.0;jy0). Preparation of Iodides and of Derivatives of Jlnlonic Acid.-Passing hydrogen iodide into the molten alcohols (see Krafft Ber., 1886,19,2984) gave quantitative yields of the iodides the gas being practically completely absorbed until the reaction was complete. The iodide washed in ethereal solution was heated with the theoretical amount of sodium and ethyl malonate in absolute alcohol. The mixture became neutral and gave ethyl mono-octadecyl-malonate after 2 hours' boiling and standing over-night. Hydrolysis with strong aqueous potash was nearly instantaneous. The calcium salt was prepared and extracted with alcohol and ether and the malonic acid liberated in 700; yield (calculated on the iodide used) by rubbing the purified calcium salt with hydrochloric acid in pre-sence of a little ether which promotes wetting.Ethyl dioctadecylmalonate could not be prepared in one operation, but was obtained by heating for 6 hours 12.2 g. of the crude ruono-octadecylmalonic ester with 0-682 g. of sodium 11.5 g. of octadecyl iodide and 30 C.C. of absolute alcohol a little dry ether being added to obtain a homogeneous liquid. After 48 hours' standing the mixture was neutral. The ester was hydrolysed by heating on the water-bath with alcoholic potash for 10 hours ; the dioctadecyl-malonic acid was purified by means of the calcium salt as before, and recrystallisation from glacial acetic acid.M. p. 93-5-94' [Found C = 76.88; H ==12.33. (C,8H,,),C(C0,H) requires Dioctadecylacetic Acid.-Heating dioctadecylmalonic acid at 160" left a residue m. p. 80-42"; this was raised to 81-82" by crystallisation from acetic acid [Found C = 80.63; H = 13.39. (C,,H,,),CH*CO,H requires C = 80.76; H = 13.560/,]. C = 76.89 ; H = 12.57%] 72 ADAM AND DYER SYNTHESIS OF AR,ACHIDIC ACID ETC. Guthzeif (Annalen 1881 206 362) describes dicetylmalonic acid (m. p. 86-87') and dicetylacetic acid (m. p. 69-70"); his work has been criticised by Ihafft since the cetyl alcohol used was not pure. If the crystal structure of these compounds is generally the same as that of the simple fatty acids with the long chains packed side by side and the molecules arranged in pairs of layers, the polar groups of one layer of the pair being next to the polar groups of the other layer we should expect the difference of two carbon atoms to make a difference of about 3" in the m.p.'s of the dialkylmalonic acids and of about 6" in those of the dialkylacetic acids which would indicate for the pure dihexadecylmalonic acid m. p. about 91', and for dihexadecylacetic acid m. p. about 75". Arachidic Acid and its Esters.-The arachidic acid obtained by heating the monooctadecylmalonic acid distilled a t 203-205" (uncorr.)/l mm. and crystallised in leaflets from light petroleum ; m. p. 75-75-5". Titration in alcoholic solution with soda gave the molecular weight 313 (theory 312.3) (Found C = 76-73; H = 12.96.Calc. C = 76-85; H = 12.90y0). Methyl arachidate was prepared by passing hydrogen chloride into a solution of the acid in pure methyl alcohol and recrystallising from alcohol. M. p. unchanged on recrystallisation 46-47' (Found C = 76.96; H = 12.98. Calc. C = 76.85; H = 12.90y0). Ethyl arachidate prepared similarly and crystallised to constant melting point melted at 41.542-6". Preparation of Long-chain Arnicles.-Fileti and Ponzio's method of adding a solution of the acid chloride in ether to aqueous ammonia (Gaxxetta 1593 23 391) gives much better results than methods in which the ether is omitted. These frequently give a product with a melting point 10 degrees too low which probably consists largely of ammonium salt. Using ether as solvent for the chloride, large quantities of the amide may be prepared the chloride being added very rapidly and the product is practically pure without crystallisation.The ether is almost entirely driven off by the heat of reaction and appears to act as a very efficient cooling agent. The aqueous ammonia may be a t room temperature. Arachidamide m. p. log" and the nitrile m. p. 49.5" were pre-pared by the usual methods from the acid. Eicosylamine hydrochloride was prepared by a modification of Krafft's method (Ber. 1889 22 812) for hexadecylamine. The nitrile (9-7 g.) in 150 C.C. of absolute alcohol was boiled under reflux, 15 g. of sodium being added during 1 hour. The mixture was poured warm into dilute hydrochloric acid heated with 250 C.C. of absolute alcohol filtered from any inorganic chlorides diluted to about 85% alcohol and cooled.The solution deposited 8-5 g THE ADSORPTION OX CATALYTICALLY POISOXOUS JIETdLS KTC. of pure eicosylamine hydrochloride IL g. more being obtained 011 concentratling the mother-liquors. For analysis the chlorine was precipitated with alcoholic silver nitrate (Found Cl =T= 10-66. C,,H,,N,HCl requires C1 = 10.64y0). Eicosylcarbamide was easily prepared by evaporating the preceding compound to dryness n.ith excess of potassium cyariate and recrystal-k i n g from alcohol. M. p. 111.5" (corr.) (Pound C = 73.98; H = 13.13; C,oH,l*rU'M-C@-XK requires C =L 74.00; Moiiomolecular films of all thc compounds of the C, series were examined according to thc methods described in previous papers (Proc. Roy.Xoc. 1922 [ A ] 184 452 516) and were found t o have the properties expected for their i-especdive series and thi C, chiill, within experimental error ; a fact which confirms their identity. Aceto-octadecyZamicle.-Octadecylami:ie hydrochloride (1.4 g.), prepared in the same manner as eicosyIaniine hydrochloride i ~ a ~ distilled with quicklime the distillate warmcd with acetic mhyclride a few minutes and the product crystallised from acetic acid nit11 the aid of charcoal; m. p. unchanged by further crysdlisation, 79.5-80" (yield 66%). The action of acetyl chloride on the aririne gave a very poor yield of the desired substance (Found C = 77-23 ; $3 = 13.4 ; N = 4.73. Cl,H3i-NH*CO*CH requires &' == 75439 ; Acetohexadec$amicle was similarly prepared and crystallised from acetic acid and acetone to constant melting point (Found : C = 76.46; H = 13.35. C,,H,,-NH*CQ*CH requires C = 76-69; H = 13.22%). I n the monomolecular films the acetamides showed a characteristic behaviour described in another paper, which indicated that the c'ompunds were members of the same liomologous series and differed by two CM groups. N = S.25. H = 13.04; N = S*25",). H = 13.2; N = 4.50%). THE SORBY RESEARCH LABOR~~TORY, UNIVERSITY OF SHEWIELD. [Receiced June l l f h 1924.

ISSN:0368-1645    

DOI:10.1039/CT9252700070

出版商:RSC    

年代:1925

数据来源: RSC

摘要:

THE ADSORPTION OX CATALYTICALLY POISOXOUS JIETdLS KTC. S PI.-The Adsorptio7a of Catulyticully PO~SOPLOZ~.~ Netals by Platinum. Part I . The Adsorptiaq? of Lead and Mercuyy. By EDWARD BRADFORD MAXTED. I~~EASIJEEWEKTS have been described (J. 1921 119 225 ; 1922, 222 1760) relating to the inhibitive influence of salts of certain metals on the hydrogenation of unsaturated substances and on the dccoinposition of hydrogen peroxide. In each case it appeared D 74 MAXTED THE ADSORPTION OF probable on first principles that adsorption of the metallic salt, or rather of the catalytically poisonous ion by the catalyst took place; but since the degree of adsorption was unknown the inhibi-tive effect of the poison measured by the depression in the activity of the catalyst could only be plotted against the initial bulk con-centration of the inhibitant in the reacting system in place of-as would have been more logical-its actual concentration on the surface of the catalyst itself.Accordingly the present work was carried out with the object of obtaining data relative to the variation of this adsorbed concentration with the bulk concentration of the inhibitant. The present paper deals with the adsorption of lead and of mercury by finely divided platinum. E X P E R I M E N T A L . An aqueous suspension of platinic oxide was reduced with hydro-gen the precipitated metal washed several times with hot distilled water and ground thoroughly in an agate mortar in presence of a little water. This method of preparing the platinum was found preferable to the reduction of a platinum salt with formaldehyde or other reducing agent on account of the difficulty in such cases, of freeing the preparation from adsorbed impurities.In carrying out each adsorption experiment 1 C.C. of a stock suspension of platinum containing 4.48 mg. of platinum per c.c., was added to a system containing a known quantity of a lead or mercury salt dissolved in 9 C.C. of water the mixture was thoroughly agitated kept over-night a t 20° and an appropriate portion of the clear liquid taken for analysis. The concentration of lead or mercury salt remaining unadsorbed was determined by observing the toxic effect of a known fraction of the solution on the activity of a standard catalyst for the decom-position of hydrogen peroxide for which reaction the inhibitive effect of various known concentrations of the lead and mercury salts in question had previously been mapped for the catalysts employed.It was thus possible to estimate with considerable accuracy small fractions of a milligram of lead or of mercury. Adsorption of Lead.-An aqueous solution of lead acetate usually containing 0.1 mg. of lead per c.c. was employed; for certain experiments solutions of one-tenth and ten times this strength, respectively were used. Preliminary experiments with potassium acetate showed that the acetate ion is a t any rate in the concen-trations employed without appreciable toxic action on platinum for the decomposition of hydrogen peroxide. The result of a series of adsorption experiments in each case with 4.48 mg.of platinum is shown graphically in Fig. 1. It wil CATfiYTICALLY POISONOUS METALS BY PLATINUM. PART I. 75 be seen on plotting the weight of lead adsorbed against its initial concentration that a linear relationship exists between these two quantities up to a stage a t which the platinum surface apparently approaches saturation ; and further adsorption from this stage onwards takes place only to a slight degree on increasing the initial bulk concentration of the lead salt. The two graphs in the figure were obtained by plotting the weight of lead adsorbed per gram of platinum first against the initial bulk concentration and secondly, against the final bulk concentration of the unadsorbed lead in the system. This result is analogous t o those obtained by Euler and Hedelius (Arlziv Kern.1920 7 31) for the adsorption of a silver FIG. 1. Bulk concentration of lead. X g . in 10 C.C. salt by silver and gold for which also an initially linear adsorption graph was obtained. Adsorption of Mercury .-A dilute solution of mercuric chloride was employed the other conditions being similar to those adopted for lead. Fig. 2 gives the results of a series of adsorption experiments, carried out as before with 4-48 mg. of finely divided platinum. For initial concentrations of mercury below that corresponding with the saturation of the platinum the adsorption of mercury is practically complete ; and the very small concentration of mercury remaining after adsorption could be estimated with the required degree of accuracy only by virtue of t,he method of analysis employed (see above).D* 76 THE ADSORPTION OF CATALYTICALLY POISONOUS METALS ETC. The linear nature of the adsorption graph for mercury and the abrupt break in this graph immediately before the saturation point, are very striking. The form of the adsorption graph both for lead and for mercury, on platinum may be compared with that of the poisoning curve. It has previously been shown (Zoc. cit.) that the decrease in the activity of a platinum catalyst caused by a poison such as lead or mercury is for by far the greater portion of the poisoning curve, a linear function of the initial bulk concentration of the poison in the system. It has now been shown that the mass of such a poison, e.g. lead actually adsorbed by platinum-i.e.the concentration of the lead on the surface of the platinum-is also a linear function of this initial bulk concentration of the lead in the system. From FIG. 2. 10 4 PI 3 8 d 0 0.04 0.08 0.12 0.16 Bulk concentration of mercury. Mg. in 10 C.C. this it follows that the activity of the catalyst in the presence of such a poison is at any rate for this first stage a linear function of the actual concentration of the lead on the surface of the catalyst. This result was to be expected on theoretical grounds since the free valency forces on the surface lattice of the platinum will if they are saturated by a difficultly evaporable poison such as lead, no longer be free for the adsorption of or association with a poten-tially reactive system it being presumed that catalysis normally takes place by reason of such association.Therefore since each atom of lead thus obstructively adsorbed will cause a given number (one or more) of such valency bonds to become no longer active for normal catalysis the poisoning of this catalytic surface should be a linear function of the concentration of the poison on the surface, a result which has just been obtained experimentally. From Fig. 1 it is seen that the linear relationship between the concentration of the lead on the catalyst and its bulk concentratio THE ZXPLOSIOX OF ACETYLENE AND NITROGEN. PART IV. 77 in the solution ceases as is necessarily the case in the region border-ing on the saturation of the surface of the platinum by the lead, in which region the initially linear adsorption graph becomes more or less abruptly converted into a line parallel with the bulk coiiceii-tration axis and denoting saturation.I n the poisoning graphs previously obtained for such cases the initial linear portion-during which the activity of the catalyst is a linear function of the initial bulk concentration of the poison in the system-is also followed in a very similar way by a break, followed in turn by n far less steep portion which like the adsorption curve becomes approximatc~ly parallel with the bulk concentration axis. It appears of great interest to ascertain whether the break in the poisoning graph obtained by plotting activity against bulk concentration of the poison occurs a t the region of incipient satur-ation.If this is the case then the activity of the catalyst would seem to be linearly proportional to the actual concentration of poison on the surface of the catalyst not only during the major portion of the poisoning graph but also up to the complete extinction of catalytic activity. It is hoped to discuss this point more fully iil a later paper. ~IASOR ROAD, PENS WOLVERHANPTOS. [Received October 14th 1921. THE ADSORPTION OX CATALYTICALLY POISOXOUS JIETdLS KTC. S PI.-The Adsorptio7a of Catulyticully PO~SOPLOZ~.~ Netals by Platinum. Part I . The Adsorptiaq? of Lead and Mercuyy. By EDWARD BRADFORD MAXTED. I~~EASIJEEWEKTS have been described (J. 1921 119 225 ; 1922, 222 1760) relating to the inhibitive influence of salts of certain metals on the hydrogenation of unsaturated substances and on the dccoinposition of hydrogen peroxide.In each case it appeared D 74 MAXTED THE ADSORPTION OF probable on first principles that adsorption of the metallic salt, or rather of the catalytically poisonous ion by the catalyst took place; but since the degree of adsorption was unknown the inhibi-tive effect of the poison measured by the depression in the activity of the catalyst could only be plotted against the initial bulk con-centration of the inhibitant in the reacting system in place of-as would have been more logical-its actual concentration on the surface of the catalyst itself. Accordingly the present work was carried out with the object of obtaining data relative to the variation of this adsorbed concentration with the bulk concentration of the inhibitant.The present paper deals with the adsorption of lead and of mercury by finely divided platinum. E X P E R I M E N T A L . An aqueous suspension of platinic oxide was reduced with hydro-gen the precipitated metal washed several times with hot distilled water and ground thoroughly in an agate mortar in presence of a little water. This method of preparing the platinum was found preferable to the reduction of a platinum salt with formaldehyde or other reducing agent on account of the difficulty in such cases, of freeing the preparation from adsorbed impurities. In carrying out each adsorption experiment 1 C.C. of a stock suspension of platinum containing 4.48 mg. of platinum per c.c., was added to a system containing a known quantity of a lead or mercury salt dissolved in 9 C.C.of water the mixture was thoroughly agitated kept over-night a t 20° and an appropriate portion of the clear liquid taken for analysis. The concentration of lead or mercury salt remaining unadsorbed was determined by observing the toxic effect of a known fraction of the solution on the activity of a standard catalyst for the decom-position of hydrogen peroxide for which reaction the inhibitive effect of various known concentrations of the lead and mercury salts in question had previously been mapped for the catalysts employed. It was thus possible to estimate with considerable accuracy small fractions of a milligram of lead or of mercury. Adsorption of Lead.-An aqueous solution of lead acetate usually containing 0.1 mg.of lead per c.c. was employed; for certain experiments solutions of one-tenth and ten times this strength, respectively were used. Preliminary experiments with potassium acetate showed that the acetate ion is a t any rate in the concen-trations employed without appreciable toxic action on platinum for the decomposition of hydrogen peroxide. The result of a series of adsorption experiments in each case with 4.48 mg. of platinum is shown graphically in Fig. 1. It wil CATfiYTICALLY POISONOUS METALS BY PLATINUM. PART I. 75 be seen on plotting the weight of lead adsorbed against its initial concentration that a linear relationship exists between these two quantities up to a stage a t which the platinum surface apparently approaches saturation ; and further adsorption from this stage onwards takes place only to a slight degree on increasing the initial bulk concentration of the lead salt.The two graphs in the figure were obtained by plotting the weight of lead adsorbed per gram of platinum first against the initial bulk concentration and secondly, against the final bulk concentration of the unadsorbed lead in the system. This result is analogous t o those obtained by Euler and Hedelius (Arlziv Kern. 1920 7 31) for the adsorption of a silver FIG. 1. Bulk concentration of lead. X g . in 10 C.C. salt by silver and gold for which also an initially linear adsorption graph was obtained. Adsorption of Mercury .-A dilute solution of mercuric chloride was employed the other conditions being similar to those adopted for lead.Fig. 2 gives the results of a series of adsorption experiments, carried out as before with 4-48 mg. of finely divided platinum. For initial concentrations of mercury below that corresponding with the saturation of the platinum the adsorption of mercury is practically complete ; and the very small concentration of mercury remaining after adsorption could be estimated with the required degree of accuracy only by virtue of t,he method of analysis employed (see above). D* 76 THE ADSORPTION OF CATALYTICALLY POISONOUS METALS ETC. The linear nature of the adsorption graph for mercury and the abrupt break in this graph immediately before the saturation point, are very striking. The form of the adsorption graph both for lead and for mercury, on platinum may be compared with that of the poisoning curve.It has previously been shown (Zoc. cit.) that the decrease in the activity of a platinum catalyst caused by a poison such as lead or mercury is for by far the greater portion of the poisoning curve, a linear function of the initial bulk concentration of the poison in the system. It has now been shown that the mass of such a poison, e.g. lead actually adsorbed by platinum-i.e. the concentration of the lead on the surface of the platinum-is also a linear function of this initial bulk concentration of the lead in the system. From FIG. 2. 10 4 PI 3 8 d 0 0.04 0.08 0.12 0.16 Bulk concentration of mercury. Mg. in 10 C.C. this it follows that the activity of the catalyst in the presence of such a poison is at any rate for this first stage a linear function of the actual concentration of the lead on the surface of the catalyst.This result was to be expected on theoretical grounds since the free valency forces on the surface lattice of the platinum will if they are saturated by a difficultly evaporable poison such as lead, no longer be free for the adsorption of or association with a poten-tially reactive system it being presumed that catalysis normally takes place by reason of such association. Therefore since each atom of lead thus obstructively adsorbed will cause a given number (one or more) of such valency bonds to become no longer active for normal catalysis the poisoning of this catalytic surface should be a linear function of the concentration of the poison on the surface, a result which has just been obtained experimentally.From Fig. 1 it is seen that the linear relationship between the concentration of the lead on the catalyst and its bulk concentratio THE ZXPLOSIOX OF ACETYLENE AND NITROGEN. PART IV. 77 in the solution ceases as is necessarily the case in the region border-ing on the saturation of the surface of the platinum by the lead, in which region the initially linear adsorption graph becomes more or less abruptly converted into a line parallel with the bulk coiiceii-tration axis and denoting saturation. I n the poisoning graphs previously obtained for such cases the initial linear portion-during which the activity of the catalyst is a linear function of the initial bulk concentration of the poison in the system-is also followed in a very similar way by a break, followed in turn by n far less steep portion which like the adsorption curve becomes approximatc~ly parallel with the bulk concentration axis. It appears of great interest to ascertain whether the break in the poisoning graph obtained by plotting activity against bulk concentration of the poison occurs a t the region of incipient satur-ation. If this is the case then the activity of the catalyst would seem to be linearly proportional to the actual concentration of poison on the surface of the catalyst not only during the major portion of the poisoning graph but also up to the complete extinction of catalytic activity. It is hoped to discuss this point more fully iil a later paper. ~IASOR ROAD, PENS WOLVERHANPTOS. [Received October 14th 1921.

ISSN:0368-1645    

DOI:10.1039/CT9252700073

出版商:RSC    

年代:1925

数据来源: RSC

摘要:

THE EXPLOSIOX OF ACETYLENE AND NITROGEN. PART IV. 77 XIIL-The Explosion of Acetylene and 2l’itrogen. Part I V . Spectra of Explosions of Gases con-taining Hydrogen Carbon Nitrogen and Oxygen. B)7 WILLISM EDWARD GARXER alld SIDNEY FF7ALTER SAUNDERS. THE origin of the Swan and cyaiiogeii band spectra has frequently been discussed and although the former is usually ascribed to free carbon (Watts Phil. Mag. 1914 [vi] 28 117) and the latter to carbon and nitrogen opinion is not unanimous on these questions. Before 1914 i t was believed that the cyanogen bands were due to carhon niid nitrogen b u t Grotriaii and Runge (Yhysikal. Z. 1914, 15 545) reopened the discussion on the origin of this spectrum, and concluded as a result of their experiments with the electric arc that the so-called cyanogen spectrum was due to nitrogen alone.This view seems to have been widely accepted although neither Barratt (Proc. Roy. Soc. 1920 [A] 98 40) who experi-mented with flames nor Hernsalech (PhiZ. X a q . 1920 [vi] 39, 241) nor Kolst and Oosterhuis ( K . Acad. Amsterdam Proc. Sci., P!E1 23 1 727) who suppressed the cyanogen bands by immersin 78 GARNER AND SAUNDERS : their nitrogen and argon discharge tubes in liquid oxygen and so freezing out the cyanogen have confirmed it. The results obtained in this paper also indicate that the presence of both carbon aiid nitrogen is essential for the production of the " cyanogen '' spectrum .* It has been found that the nature of the spectrum emitted during explosions of acetylene in oxygen and nitrogen is very largely dependent on the ratio of gram-atoms of carbon to oxygen in the mixture.With low percentages of oxygen where large quantities of carbon are deposited during the explosion a continuous spectrum only is obtained. The carbon being an almost perfect black body acts as a screen cutting off the radiation emitted from the molecules activated during the explosion. As the ratio of oxygen to acetylene approaches unity the Swan CH and cyanogen bands, and metallic absorption and emission lines appear on the back-ground formed by the continuous spectrum which simultaneously diminishes in intensity. These band spectra persist into the region where oxygen)carbon but gradually fade away as the oxygen percentage is increased until finally with a still larger proportion of oxygen only the line emission and absorption spectrum of the metallic impurities are present.The Swan and cyanogen spectra appear and disappear together as the oxygen percentage increases. Their disappearance occurs approximately at the concentrations found previously (J. 1924, 125 1634) for the disappearance of free carbon and hydrocyanic acid from the h a 1 products of the explosion uiz. when the ratio of oxygen to carbon becomes unity. Thus the presence of free carbon in the products of the explosion is essential not only for the production of hydrocyanic acid but also for both the Swan and the cyanogen spectra. The Swan and cyanogen spectra persist into the region where oxygen is in excess (up to C 0 = 0.956 for mixtures of C2H2 and 0, and C 0 = 0.968 for mixtures of 0, N, and C,H,) but this does not invalidate the above conclusion for the spectrum of the explosion is a record of the radiation emitted throughout the whole of the explosive process and hence includes the radiation emitted before equilibrium is reached.On the molecular collision view of the propagation of the explosion wave undecomposed acetylene molecules immediately in front of the wave will be bombarded by swiftly moving molecules of carbon, hydrogen oxygen carbon monoxide etc. from the explosion wave itself. An oxygen molecule in collision with an acetylene mole-* Since this paper was written Freundlich and Hochheim (2. Physik 1924, 26 102) in furnace experiments have shown that elementary carbon is essential for the production of this spectrum THE EXPLOSION OF ACETYLENE AND SITROCEX.PART I V . 79 cule would be likely to give carbon monoxide but no free carf;on, C,H -j- 0 + 2CO + H, but any other molecule may bring about the change C,H + 2C + H,. Thus evenin the presence of' excess of oxygcn free carbon may be momentarily formed and it' the averags life of the carbon particles (C possibly) beiore rtxiioval as carbon nionoxide is long enough the Swan spectrum may be emitted. This would explain our results (Table I). The results of this investigation thus support the vie17 that carbon is necessary for the production of the cyanogen spcctrunl. That nitrogen also is necessary is evident from the abseiice of the cyanogen spcctrurn in the spectra of explosions of acetylene and oxygen alone.E X P E R I M E w T A L . examination has been made of the spectra from the follovVring series of explosive mixtures ( a ) pure acetylene ( b ) acct) Icnc~ md nitrogen (c) acetylene and oxygen (a?) acetylene o x ) - p i antl nitrogen ( e ) electrolytic gas (f) carbon monoxide and oxyge~i, (9) coal gas and oxygen. Appumtus.-A 2-litre phosphor-bronze bomb similnr to that described by Wheeler (J. 191 8,113 855) was fitted with a c.j~!indr.ic~al quartz window 6 mm. in diameter and 8 mm. thick placed oppo.-il e the collimator tube of a Hilger Constant Deviation Spectronictc.r.* Ignition of the gaseous mixture was usual1~- accomplishctl by fusion of a thin iron wire placed across the terminals in the ceritre of the bomb. In some experiments the position of firing of the mixture was changed and in others the iron wire was replaced by ~)latitiuin.Preparation of the Gases.-The acetxlene from a cylinder con taining the gas compressed in acetone was washed with water, dried over phosphorus pentoxide and stored over merciiry. It was completely soluble in a solution of animoniacal cuprous cliloritlc. Oxygen and nitrogen were prepared as described elsewhere (Loc. cit.). Carbon monoxide obtained by the &ion of sulphuric acid on sodium formate was washed with sodium hydroxide antl dried over phosphorus pentoxide. Electrolytic gas was prepared froin baryta. The gases were introduced into an encuated bomb, which had been previoiisly washed out six times with oxygen. This repeated washing was necessary in order to ensure the absence of nitrogen in the first series of experiments.The composition of the gaseous mixture was determined by pressure measureiuents. Xeasurement of Spectra.-Each photograph of the explosion spectrum was braclieted by photographs of a neon-helium lamp, the wave-lengths of the lines in this spectrum being knoxn an(l * A few measiirernents were made with a quartz spcctrometer SO GARNER AND SAUNDERS : the lines were measured by means of a travelling microscope. The extreme errors of measurement were & l k for the band spectra and 0.2 8. for the metallic lines. Results. (a) Acetylene and Oxygen.-With pure acetylene and also acetylene and oxygen mixtures up to 41% of oxygen a perfectly continuous spectrum was obtained (Table I). With I00 yo acetyl-ene the spectrum was rather more brilliant in the red than is the case with the mixture containing 41% of oxygen.The effect of the addition of oxygen on the position of maximum light intensity is to shift this maximum slightly towards the blue end of the spectrum, this being in agreement with Wien’s displacement law. TABLE I. Oxygen and Acetylene. P = 1 atm. % 0,. 76 C,H,. 76 C,H,/“/O 0,. Spectrum. - 100.0 * 35.22 64.78 41.10 58.90 Continuous with no line or 1.433 spectra. Swan and CH bands with metallic lines. 49-33 60.67 49.58 50.42 49.69 50.3 1 1.013 band faint 50.30 49.70 0-983 Swan and CH bands with metallic 51.12 48.88 0.956 } lines. 53.14 46-86 0-852 59.86 44.50 40.14 ::~:ftl afetallic lines only. 55.50 62-91 37.09 0-5SOtj * 3-2 atm.Platinum wire ignition. As the ratio (column 3) approaches unity the Swan ‘‘ the three,” and the CH bands appear on the continuous spectrum. The bands 61911,5635,5165,4737,4382,4371,4365 and 4314 A. were observed. These bands first appear when the value ~OC,H,/~OO, is between 1.433 and 1.035; the exact value was not found. It was anticipated that the Swan spectrum would disappear when ~0C,H2/~002<1 since a t the temperature of explosion, ca. 3000” the equilibrium constant for the reaction C + H20 5= CO + H is Kp = PmP,,/P, = 105 and hence practicaLy no free carbon can be present if the gaseous mixture attains equilibrium. Since the Swan spectrum is considered as being due to free carbon it was expected that this together with “the three ” and CH bands would disappear when the ratio 74,C,H2/~00 (1.It was found however that these bands persisted even when the acetylene-oxygen mixture had the ratio 70C2H,/7002 = 0.956, although they had all disappeared when the ratio became 0.882 THE EXPLOSION OF ACETYLENE AND KITROGEN. PART IV. 81 The cyanogen spectrum was not observed in this series of experi-ments. (b) Acetylene Xitrogen a.nd Oxyyen.-When nitrogen was added until the mixture had the composition 82% C,H, 187; N, and the niixture was fired under a pressure of about 3 atmospheres several units per cent. of hydrocyaiiic acid were ohtaineci and yet the spectrum was still continuous. Since the amount of free carbon could not be reduced sufficiently by the addition of nitrogen alone to enable emission and absorption lines to be obtained oxygen was added to the niixture until the ratio ~OC!,H,/~OO was between 1.1 and 1.This diminished the carbon sufficiently for the Swan, " the three," and the CH bands to be observed and in addition, the cyanogen bands 4216 A. and 3883 A. These all persisted when the ratio :bC',H,/Yb@ = 0.968 (Table 11). Further addition 0 ' 1 0 o-. -47.98 40.i2 48.G5 49.28 39-55 48.73 45.97 39.96 42.92 4l*T,!) 43.1 3 45.29 51.60 5ti-04 0; C,H,. s2.2 49.56 41-81 49.22 49.99 40.06 4G.14 45-25 39.1 1 41.49 40.28 39.45 37-3G 39.79 34.73 :b C21-I,/~~> 0,. Fpcctrum. Continuous spec t rii ni. -. Swan. CH cy-anogen bands and 1.033 faint metallic lines. 1.012 0.988 0.983 'I Swm CH cyanogen baiids and ~ ~ ~ ~ * j nietollic lines.0.968 0.915 Metallic lines only. 0.620 * S o band spectra. of oxygeii causes the disappearance of these spectra,. If Grotrian and Runge's contention be correct that nitrogen will give rise to the " cyanogen " spectrum if no appreciable amount of oxygen be present then the above-mentioned disappearance of this spectrum, when %C,K,/'300 = 0.915 is not easy to explain for in such a mixture at the temperature of the explosion there can be but little free oxygen." The disappearance of this spectrum is understand-able however if i t be due t o both carbon and nitrogen. The nature of the spectrum is the same whatever the position of the iron wire used for igniting the gases; placing the iron wire close to the side of the bomb or directly in front of the quartz n-indow made no difference.* Approsiinntely 0.001 yo of oxygen a t 3000" abs 82 MCPENZIE AND STRATHERN REACTIONS OF The only lines present in the spectra of the explosions of hydrogen and oxygen and carbon monoxide and oxygen were those due to the metallic impurities present e.g. sodium calcium iron etc. As would be expected on account of the lower temperature of these fiames the metallic lines were not so numerous as in the acetylene explosions. Summary. The spectra emitted during the explosion of mixtures of acetylene, The results indicate that nitrogen and oxygen have been studied. the cyanogen spectrum is due to both carbon and nitrogen. The authors wish to express their indebtedness to the Depart-ment of Scientific and Industrial Research for a maintenance grant to one of them (S.W. S.) and for an equipment grant towards the cost of apparatus. J THE SIR WILLIAM RAMSAY INORGANIC AND PHYSICAL CHEMICAL LABORATORIES, UNIVERSITY COLLEGE LONDON. [Received October Sbh 1924. THE EXPLOSIOX OF ACETYLENE AND NITROGEN. PART IV. 77 XIIL-The Explosion of Acetylene and 2l’itrogen. Part I V . Spectra of Explosions of Gases con-taining Hydrogen Carbon Nitrogen and Oxygen. B)7 WILLISM EDWARD GARXER alld SIDNEY FF7ALTER SAUNDERS. THE origin of the Swan and cyaiiogeii band spectra has frequently been discussed and although the former is usually ascribed to free carbon (Watts Phil. Mag. 1914 [vi] 28 117) and the latter to carbon and nitrogen opinion is not unanimous on these questions.Before 1914 i t was believed that the cyanogen bands were due to carhon niid nitrogen b u t Grotriaii and Runge (Yhysikal. Z. 1914, 15 545) reopened the discussion on the origin of this spectrum, and concluded as a result of their experiments with the electric arc that the so-called cyanogen spectrum was due to nitrogen alone. This view seems to have been widely accepted although neither Barratt (Proc. Roy. Soc. 1920 [A] 98 40) who experi-mented with flames nor Hernsalech (PhiZ. X a q . 1920 [vi] 39, 241) nor Kolst and Oosterhuis ( K . Acad. Amsterdam Proc. Sci., P!E1 23 1 727) who suppressed the cyanogen bands by immersin 78 GARNER AND SAUNDERS : their nitrogen and argon discharge tubes in liquid oxygen and so freezing out the cyanogen have confirmed it.The results obtained in this paper also indicate that the presence of both carbon aiid nitrogen is essential for the production of the " cyanogen '' spectrum .* It has been found that the nature of the spectrum emitted during explosions of acetylene in oxygen and nitrogen is very largely dependent on the ratio of gram-atoms of carbon to oxygen in the mixture. With low percentages of oxygen where large quantities of carbon are deposited during the explosion a continuous spectrum only is obtained. The carbon being an almost perfect black body acts as a screen cutting off the radiation emitted from the molecules activated during the explosion. As the ratio of oxygen to acetylene approaches unity the Swan CH and cyanogen bands, and metallic absorption and emission lines appear on the back-ground formed by the continuous spectrum which simultaneously diminishes in intensity.These band spectra persist into the region where oxygen)carbon but gradually fade away as the oxygen percentage is increased until finally with a still larger proportion of oxygen only the line emission and absorption spectrum of the metallic impurities are present. The Swan and cyanogen spectra appear and disappear together as the oxygen percentage increases. Their disappearance occurs approximately at the concentrations found previously (J. 1924, 125 1634) for the disappearance of free carbon and hydrocyanic acid from the h a 1 products of the explosion uiz. when the ratio of oxygen to carbon becomes unity.Thus the presence of free carbon in the products of the explosion is essential not only for the production of hydrocyanic acid but also for both the Swan and the cyanogen spectra. The Swan and cyanogen spectra persist into the region where oxygen is in excess (up to C 0 = 0.956 for mixtures of C2H2 and 0, and C 0 = 0.968 for mixtures of 0, N, and C,H,) but this does not invalidate the above conclusion for the spectrum of the explosion is a record of the radiation emitted throughout the whole of the explosive process and hence includes the radiation emitted before equilibrium is reached. On the molecular collision view of the propagation of the explosion wave undecomposed acetylene molecules immediately in front of the wave will be bombarded by swiftly moving molecules of carbon, hydrogen oxygen carbon monoxide etc.from the explosion wave itself. An oxygen molecule in collision with an acetylene mole-* Since this paper was written Freundlich and Hochheim (2. Physik 1924, 26 102) in furnace experiments have shown that elementary carbon is essential for the production of this spectrum THE EXPLOSION OF ACETYLENE AND SITROCEX. PART I V . 79 cule would be likely to give carbon monoxide but no free carf;on, C,H -j- 0 + 2CO + H, but any other molecule may bring about the change C,H + 2C + H,. Thus evenin the presence of' excess of oxygcn free carbon may be momentarily formed and it' the averags life of the carbon particles (C possibly) beiore rtxiioval as carbon nionoxide is long enough the Swan spectrum may be emitted.This would explain our results (Table I). The results of this investigation thus support the vie17 that carbon is necessary for the production of the cyanogen spcctrunl. That nitrogen also is necessary is evident from the abseiice of the cyanogen spcctrurn in the spectra of explosions of acetylene and oxygen alone. E X P E R I M E w T A L . examination has been made of the spectra from the follovVring series of explosive mixtures ( a ) pure acetylene ( b ) acct) Icnc~ md nitrogen (c) acetylene and oxygen (a?) acetylene o x ) - p i antl nitrogen ( e ) electrolytic gas (f) carbon monoxide and oxyge~i, (9) coal gas and oxygen. Appumtus.-A 2-litre phosphor-bronze bomb similnr to that described by Wheeler (J. 191 8,113 855) was fitted with a c.j~!indr.ic~al quartz window 6 mm.in diameter and 8 mm. thick placed oppo.-il e the collimator tube of a Hilger Constant Deviation Spectronictc.r.* Ignition of the gaseous mixture was usual1~- accomplishctl by fusion of a thin iron wire placed across the terminals in the ceritre of the bomb. In some experiments the position of firing of the mixture was changed and in others the iron wire was replaced by ~)latitiuin. Preparation of the Gases.-The acetxlene from a cylinder con taining the gas compressed in acetone was washed with water, dried over phosphorus pentoxide and stored over merciiry. It was completely soluble in a solution of animoniacal cuprous cliloritlc. Oxygen and nitrogen were prepared as described elsewhere (Loc. cit.). Carbon monoxide obtained by the &ion of sulphuric acid on sodium formate was washed with sodium hydroxide antl dried over phosphorus pentoxide.Electrolytic gas was prepared froin baryta. The gases were introduced into an encuated bomb, which had been previoiisly washed out six times with oxygen. This repeated washing was necessary in order to ensure the absence of nitrogen in the first series of experiments. The composition of the gaseous mixture was determined by pressure measureiuents. Xeasurement of Spectra.-Each photograph of the explosion spectrum was braclieted by photographs of a neon-helium lamp, the wave-lengths of the lines in this spectrum being knoxn an(l * A few measiirernents were made with a quartz spcctrometer SO GARNER AND SAUNDERS : the lines were measured by means of a travelling microscope.The extreme errors of measurement were & l k for the band spectra and 0.2 8. for the metallic lines. Results. (a) Acetylene and Oxygen.-With pure acetylene and also acetylene and oxygen mixtures up to 41% of oxygen a perfectly continuous spectrum was obtained (Table I). With I00 yo acetyl-ene the spectrum was rather more brilliant in the red than is the case with the mixture containing 41% of oxygen. The effect of the addition of oxygen on the position of maximum light intensity is to shift this maximum slightly towards the blue end of the spectrum, this being in agreement with Wien’s displacement law. TABLE I. Oxygen and Acetylene. P = 1 atm. % 0,. 76 C,H,. 76 C,H,/“/O 0,. Spectrum. - 100.0 * 35.22 64.78 41.10 58.90 Continuous with no line or 1.433 spectra.Swan and CH bands with metallic lines. 49-33 60.67 49.58 50.42 49.69 50.3 1 1.013 band faint 50.30 49.70 0-983 Swan and CH bands with metallic 51.12 48.88 0.956 } lines. 53.14 46-86 0-852 59.86 44.50 40.14 ::~:ftl afetallic lines only. 55.50 62-91 37.09 0-5SOtj * 3-2 atm. Platinum wire ignition. As the ratio (column 3) approaches unity the Swan ‘‘ the three,” and the CH bands appear on the continuous spectrum. The bands 61911,5635,5165,4737,4382,4371,4365 and 4314 A. were observed. These bands first appear when the value ~OC,H,/~OO, is between 1.433 and 1.035; the exact value was not found. It was anticipated that the Swan spectrum would disappear when ~0C,H2/~002<1 since a t the temperature of explosion, ca.3000” the equilibrium constant for the reaction C + H20 5= CO + H is Kp = PmP,,/P, = 105 and hence practicaLy no free carbon can be present if the gaseous mixture attains equilibrium. Since the Swan spectrum is considered as being due to free carbon it was expected that this together with “the three ” and CH bands would disappear when the ratio 74,C,H2/~00 (1. It was found however that these bands persisted even when the acetylene-oxygen mixture had the ratio 70C2H,/7002 = 0.956, although they had all disappeared when the ratio became 0.882 THE EXPLOSION OF ACETYLENE AND KITROGEN. PART IV. 81 The cyanogen spectrum was not observed in this series of experi-ments. (b) Acetylene Xitrogen a.nd Oxyyen.-When nitrogen was added until the mixture had the composition 82% C,H, 187; N, and the niixture was fired under a pressure of about 3 atmospheres several units per cent.of hydrocyaiiic acid were ohtaineci and yet the spectrum was still continuous. Since the amount of free carbon could not be reduced sufficiently by the addition of nitrogen alone to enable emission and absorption lines to be obtained oxygen was added to the niixture until the ratio ~OC!,H,/~OO was between 1.1 and 1. This diminished the carbon sufficiently for the Swan, " the three," and the CH bands to be observed and in addition, the cyanogen bands 4216 A. and 3883 A. These all persisted when the ratio :bC',H,/Yb@ = 0.968 (Table 11). Further addition 0 ' 1 0 o-. -47.98 40.i2 48.G5 49.28 39-55 48.73 45.97 39.96 42.92 4l*T,!) 43.1 3 45.29 51.60 5ti-04 0; C,H,.s2.2 49.56 41-81 49.22 49.99 40.06 4G.14 45-25 39.1 1 41.49 40.28 39.45 37-3G 39.79 34.73 :b C21-I,/~~> 0,. Fpcctrum. Continuous spec t rii ni. -. Swan. CH cy-anogen bands and 1.033 faint metallic lines. 1.012 0.988 0.983 'I Swm CH cyanogen baiids and ~ ~ ~ ~ * j nietollic lines. 0.968 0.915 Metallic lines only. 0.620 * S o band spectra. of oxygeii causes the disappearance of these spectra,. If Grotrian and Runge's contention be correct that nitrogen will give rise to the " cyanogen " spectrum if no appreciable amount of oxygen be present then the above-mentioned disappearance of this spectrum, when %C,K,/'300 = 0.915 is not easy to explain for in such a mixture at the temperature of the explosion there can be but little free oxygen." The disappearance of this spectrum is understand-able however if i t be due t o both carbon and nitrogen.The nature of the spectrum is the same whatever the position of the iron wire used for igniting the gases; placing the iron wire close to the side of the bomb or directly in front of the quartz n-indow made no difference. * Approsiinntely 0.001 yo of oxygen a t 3000" abs 82 MCPENZIE AND STRATHERN REACTIONS OF The only lines present in the spectra of the explosions of hydrogen and oxygen and carbon monoxide and oxygen were those due to the metallic impurities present e.g. sodium calcium iron etc. As would be expected on account of the lower temperature of these fiames the metallic lines were not so numerous as in the acetylene explosions. Summary. The spectra emitted during the explosion of mixtures of acetylene, The results indicate that nitrogen and oxygen have been studied. the cyanogen spectrum is due to both carbon and nitrogen. The authors wish to express their indebtedness to the Depart-ment of Scientific and Industrial Research for a maintenance grant to one of them (S. W. S.) and for an equipment grant towards the cost of apparatus. J THE SIR WILLIAM RAMSAY INORGANIC AND PHYSICAL CHEMICAL LABORATORIES, UNIVERSITY COLLEGE LONDON. [Received October Sbh 1924.

ISSN:0368-1645    

DOI:10.1039/CT9252700077

出版商:RSC    

年代:1925

数据来源: RSC

摘要:

82 MCPENZIE AND STRATHERN REACTIONS OF XIV.-Reactions of Displacement in the Tropic Acid Group. Part I. By ALEX. MCKENZIE and ROBERT CAMPBELL STRATHERN. THE proof of the constitution of a-aminohydratropic acid, NH,-CPhMe*CO,H was afforded by Tiemann and Kohler (Ber., 1881 14 1980) by the synthesis from acetophenonecyanohydrin and alcoholic ammonia. McKenzie and Clough (J. 1912 162, 390) in dealing with the Walden inversion described the resolution of the r-acid into its optically active components. The study of the isomeric p-acid NH,*CH,*CHPh*CO,H has not so far been advanced to the corresponding stage. For one reason this acid has no particular interest with relationship to the Walden inversion the amino-group not being directly attached to the asymmetric carbon atom.The identification of the acid has also been attended with some confusion. By the action of aqueous ammonia on p-bromohydratropic acid Merling (AnnaZen, 1881 209 11) obtained crystals m. p. 169-170" (compare also Fittig and Wurster ibid. 1879 195 158). Assuming that the reaction proceeded on the lines CH,Br*CHPh*CO,H + NIP,*CH,*CHPh*CO,H, Merling concluded that he had to deal with p-aminohydratropic acid and the analytical evidence supported this assumption DISPLACEMENT IN THE TROPIC ACID GROUP. PaRT I. 83 Posner however in continuation of his work on the action of hydroxylamine on unsaturated acids obtained from atropic acid an amino-acid which melted and decomposed a t 234" (Ber. 1903, 36 4315; Annulen 1912 389 109). All the evidence pointed to this substance being the true p-aminohydratropic acid.Since Posner (Ber. 1905 38 2316) had shown that the action of ammonia on p-bromo-p-phcnylpropionic acid leads to the formation not of p-amino- p-phenylpropionic acid but of p-hydroxy-p-phenylpro-pionamide he suggested that P-bromohydratropic acid might perhaps exhibit a similar behaviour and that Merling's product was not the amino-acid a t all but was the isomeric tropamide. The latter suggestion has been borne out. In the present paper it is show1 that r-p-chlorohydratropic acid is converted into r-tropamide (m. p. 170-171") by the action of aqueous ammonia. The amide was also prepared directly from ammonia and methyl dl-tropate; it has the same melting point and it possesses the same properties as the compound described by Merling.We have also examined the action of hydroxylamine on atropic acid and find that Posner's p-amino-acid is not the sole product, and that the oxime of phenylacetaldehyde is also formed. It is, however rather curious that the formation of tropic acid by the action of nitrous acid on the amino-acid proceeds in a somewhat irregular manner. The preparation of Z- p-chlorohydratropic acid is described the resolution of the r-acid being effected in methyl-alcoholic solution with morphine as the resolving alkaloid. When hydrolysed the Z-acid which has [.ID - 122.6" in benzene gave a lzvorotatory tropic acid with [ R I D - 58.1" (c = 2.4348) in ethyl-alcoholic solution whereas the value for the optically pure acid is [ R ] ~ - 72.5" (c = 2.578) in the same solvent (NcKenzie and Wood, J.1919 115 828). Although the chlorine is not directly attached to the asymmetric carbon atom some racemisation had apparently taken place during the substitution of the hydroxy-group for the chlorine. In the light of recent work in a different field (McKenzie and Roger J. 1924 125 214S) the action of ammonia on the E-chloro-acid was of some interest and we have therefore examined it for the purpose of finding if optical activity would persist in the trans-formation into the amide. Experiments showed that a levorotatory tropamide did actually result. Under the conditions employed, the rotation of the product was less than that of the amide obtained by the direct action of ammonia on ethyl I-tropate. This formation of an optically active tropamide has led us t 84 MCKENZIE AND STRATHERN REACTIONS OF conclude that a p-lactone is produced as an intermediate phase, thus : Th Ph Z-H-$-CH,Cl -+ Z-H-$+-CH,Cl + C0,H CO,*NH, Ph Fh Z-H-Y-CH2 -+ Z-H-Y-CH,*OH.cod CO*NH,. Although on those lines the actions do not occur by substitution of groups directly attached to the asymmetric carbon atom some racemisation accompanied the change. This was not altogether unexpected since in tropamide we have the phenyl hydrogen, and carbonyl groups all directly attached to the asymmetric carbon atom a system which a t any rate in the presence of alcoholic alkali is particularly prone to racemisation under certain conditions (McKenzie and Smith J. 1922 121 1348). In the field of optical activity it has been shown by Holmberg (ArEiv Kern.Min. CeoZ. 1917,6 No. 23 pp. 1-33 and earlier papers) that the formation of a p-lactone is a stage in the interconversion of d- and I-malic acids by the Walden inversion. Moreover Z-iodo-succinic acid when treated with ammoniacal silver nitrate gives a mixture of fumaric acid and d-p-malamic acid the latter being formed by the action of ammonia on the d-malo-lactone (compare Walden and Lutz Ber. 1897 30 2796; Lutz Ber. 1902 35, 2460 4369; 1908 41 841). Reference has already been made to the fact that Posner obtained r- p-hydroxy- p-phenylpropionamide by the action of ammonia on r- p-bromo- p-phenylpropionic acid. It seems reasonable to suppose that this action proceeds on similar lines to that of ammonia on P-chlorohydratropic acid : ph p Ph Vh H-TBr -+ H T - B r CH,*CO,H CH2*C0,*NH4 CH,*CO CH,*CO*NH,.It will be observed that the p-lactone which is suggested as an intermediate phase is isomeric with the one postulated in the scheme with p-chlorohydratropic acid. Arising from the results recorded in the present paper and more especially from former work by one of us it is desirable that Posner’s observation should be extended to the optically active p-bromo-p-phenylpropionic acids so as to enable the following scheme to be completed: -+ HT-? -+H-$+-O DISPLACEMENT m THE TROPIC ACID GROUP. PART I. 85 dext,ro- dextro-1 zvo - C,H5*CHBr*CH,*C0,H dextro - C GH ,*CH( OH) *CH,*CO*NH, (McKenzie and Humphries J. 1910 97 121; McKenzie and Martin J. 1913 103 112; McKenzie Martin and Rule J., 1014 105 1583; McKenzie and Smith J.1922 121 1348). Owing to the announcement in the current number of the Pro-ceedings (1924 p. 77) of a paper by Seiiter and Ward entitled " Studies on the Walden iiiversion. Part IX. The influence of the solvent on the sign of the product in the conversion of 3-bromo-p-phenylpropioiiic acids to 3- hydroxy- 9 -phenylpropionamides " TF'C are not meanwhile invcstigatiiig this matter further so far as the action of ammonia on the optically active $-bromo-F-phenyl-propionic acids is concerned. At present we are engaged on a further study of the action of nitrous acid on r-p-aminohydratropic acid and also propose to undertake the resolution of this acid with the object of examining the resulting optically active acids.E X P E R I Jr E 3 T A L. Action of Hydroxyhnine o n Atropic Acid.-Posner (Anncrieih, 1912 389 112) prepared r-$aminohydratropic acid by heating atropic acid with an alcoholic solution of hydroxylsmine for 1 hour. By analogy with his previous work (Ber. 190.5 38 2316; compare also McKenzie and Tuclhope J. 1924,125,928) i t might be expected that the formation of the amino-acid would be accompanied by that of phenylncetaldoxiin~.. Kydroxylamine hydrochloride (25 g.) in water (25 c.c.) was adclcd to a solution of sodium (8.5 g.) in ethyl alcohol (280 c.c.), and t hc precipitated sodium chloride removed. Atropic acid (2.3 g.) prepared by the dehydration of atrolactinic acid (McKenzie and Wood Zoc. cit.) was added and the solution boiled for 13 hours.Ammonium carbonate was deposited in the condenser tube. -4fter 3 clays in the ice-chest the amino-acid (8 g.) was collected; it was free from the hydroxylamiiio-acid sirice it did not reduce either Fehling's solution or ainrnoniacal silver nitrate ; i t melted and decomposed a t 222-224" (Posner gives 233"). An additional 0.5 g. was obtained by boiling the filtrate for 2& hours longer. After distillation of the bulk of the alcohol an exccss of water precipitated 8 g. of crude phenylaceta!dosime which crystallised from water several times gave the pure substance in lwtrous needles m. p. 103-104" (Found C = 70.9; H = 6.8. Calc., C = 71.1 ; H = 6.7%). Bouvcault and M7ahl (C'ompt. rend. 1002, 134 1147) gave m. p. 103". This osime was isolat cd as follows 86 MCKENZIE AND STRATHERN REACTIONS OF r- P-Aminohydratropic acid is sparingly soluble in water benzene, light petroleum acetone chloroform carbon disulphide and ether.Posner (Ber. 1903 36 4315) described this acid as a-amino-a-phenylpropionic acid (a-aminohydratropic acid) ; its solution in hydrochloric acid was acted on by nitrous acid to give an acid, m. p. 89-90" which was supposed to be atrolactinic acid. Posner was however working with small quantities of material and was misled by the erroneous data of other authors. In a subsequent paper (Annulen Zoc. cit.) the correct constitution of the amino-acid is given. The product which Posner obtained by the action of nitrous acid was apparently impure tropic acid. We have repeated this action several times and find that it proceeds by no means smoothly.The gradual addition of potassium nitrite to the solution of the amino-acid in dilute hydrochloric acid caused the deposition of an oil which was certainly not tropic acid nor did it appear to be a-isotropic acid since it showed no signs of solidifying when nucleated with the latter acid. The aqueous solution was separated from the oil and extracted with ether. By crystallising the resulting acid several times from benzene r-tropic acid was isolated in very small yield (0.1 g. of the pure acid m. p. 116-117" from 2 g. of p-aminohydratropic acid). Resolution of r- p-Chlorohydratropic Acid.-The solution obtained by boiling 49.5 g. of morphine (I mol.) in 820 C.C. of methyl alcohol was cooled to 42" and 30 g.of r-p-chlorohydratropic acid (1 mol.; prepared from atropic acid McKenzie and Wood Zoc. cit.) were added in one instalment with vigorous stirring. The acid dissolved quickly. When the temperature had fallen to 39' glassy prisms started to separate. After 18 hours in the ice-chest 56 g. of solid were deposited. After the evaporation of the methyl alcohol from the filtrate the acid obtained from the latter gave the following rotation in benzene I = 2 c = 3.924 a? + 3-71' [ c x ] ~ + 47.3", so that the resolution had proceeded markedly after one crystallis-ation. The further progress is indicated as follows 56 g. crystal-lised from 1350 C.C. of methyl alcohol + 35 g. 850 C.C. of alcohol + 19 g. 550 C.C. of alcohol + 13 g. 400 C.C. of alcohol + 9 g.360 C.C. of alcohol + 6 g. pure morphine I-salt. The solution of the crystals in methyl alcohol should be conducted as expeditiously as possible. The progress of the resolution was tested by the polarimetric examination of the acids obtained from the mother-liquors. The morphine salt which separates in rectangular prisms was decom-posed by dilute sulphuric acid the solution extracted with ether nine times and the ethereal extract dried with anhydrous sodium sulphate. The resulting acid (2.1 g.) after drying in a vacuum until constant in weight gave the following rotation in benzene DISPLACEMENT IN THE TROFIC ACID GROUP. PART I. 87 I = 2 c = 3.536 al,fi' - 8-66' [a]:' - 122.4". The acid was crystallised from light petroleum (b. p. 60-80") and gave a value for the rotatory power agreeing with the above within the limits of experimental error Z = 2 c = 3.536 a:" - 8-67' [a]:"' - 122.6." l-p-C~~Zorohydratropic acid m.p. 62-5-63.5" separates from light petroleum in rosettes of glassy plates. It is sparingly soluble in light petroleum and readily so in ether carbon disulphide, benzene and ethyl alcohol (Found C1 = 19.39. C,H,O,Cl requires C1 = 19-240/). I n acetone Z = 2 c = 3.2300 a:.'- - 7-46' [a]::'" - 115.5". Conversion of 1- p-Chlorohydratropic Acid into I-Tropic Acid.-A'-Sodium carbonate (11 c.c.) was gradually added (14 mins.) to a boiling solution of the 1-acid (1 g.) in 20 C.C. of water (reflux). The boiling was continued for 3 hours the cold solution extracted with ether to remove the styrene present' and the tropic acid obtained by acidification with dilute sulphuric acid and extraction with ether.Yield 0.7 g. I n ethyl alcohol Z = 2 c = 2.4348, A similar experiment was carried out with a lzevorotatory acid having [R]:" - 100.7" (1 = 2 c = 3.5504) in benzene. The resulting tropic acid (1.9 g.) gave the following value in ethyl alcohol I = 2 c = 2.716 a;;* - 2-68' [a]:' - 49.3". After one crystallisation of this product from benzene the value for the specific rotation was enhanced in ethyl alcohol 1 = 2 c = 2-548, Conversion of 1- p-Chlorohydratropic Acid into 1-Tropamide.-A solutioii of the I-chloro-acid (0-94 g.) in 60 C.C. of aqueous ammonia (saturated at 0") was kept for a week in a pressure flask at the ordinary temperature. When the solution was transferred to a crpstallising dish needles began to separate.Yield 0.3 g.; in. p. 195-199" (Found N = 8.7. Calc. N = 8.5%). In ethyl alcohol 1 = 2 c = 0.3472 E ~ T - 0.38". I n another experiment the resulting amide gave in ethyl alcohol : The concentrations employed were necessarily very small the aniide being sparingly soluble in water ethyl alcohol acetone, chloroform benzene and ethyl acetate. For the purpose of comparison the amide was prepared from I-tropic acid (obtained by resolution of the 1.-acid with morphine according to McICenzie and Wood) by acting on the ethyl ester with concentrated aqueous ammonia. After crystallisation from acetone the amide had m. p. 195-197.5"; in ethyl alcohol Z = 1, c = 0.377 cxI) - 0.24". Since the polarimetric determinations could be made with very dilute solutions only we have no proof 1 58.1".ai'i 5- - 2.830 1.1 50 -EliS 1 - 3-17" [a]\ - 62.2". I = 2 c = 0.3912 ",F" - 0.43" 88 TROTMAN PREPARATION OF QUATERNARY HYDROCARBONS. that we obtained the optically pure I-tropamide by this method, more especially since there was always the possibility of partial racemisation having taken place during the action of ammonia on the 2-ester. But we think it likely that we obtained the amide nearly pure if not quite so. I-Tropamide would be expected to undergo racemisation in the presence of a small amount of sodium ethoxide (McKenzie and Smith J. 1922 121 1348). When 0.5 C.C. of ethyl-alcoholic potash (0~6518N) was added to a solution giving aD - 0.24" ( I = l), the lzvorotation gradually dropped to zero after 30 hours and r-tropamide (m.p. 170-171") was isolated from the solution. Formation of r-Tropamide from r-Tropic Acid and r- p-Chloro-hydratropic Acid.-r-Tropic acid was converted into its methyl ester from which the amide was prepared by the action of aqueous ammonia. r-Tropamide m. p. 170-171" is sparingly soluble in cold water, ethyl alcohol acetone benzene carbon tetrachloride and light petroleum (b. p. 60-70"). It separates from water in needles (Found N = 8-4. C,H,,O,N requires N = 86%). A solution of r- p-chlorohydratropic acid (4 g.) in concentrated aqueous ammonia (65 c.c.) was kept for 18 days in a pressure flask. On pouring into a dish crystallisation started quickly. The crystals (1.5 g.) were collected and crystallised twice from water, when the pure r-tropamide (m.p. 170-171") was obtained (Found : C = 65.1 ; H = 6-8. The melting point was not depressed when this product was mixed with the r-tropamide obtained from methyl dl-tropate. Calc. C = 65.4; H = 6.7%). One of us (R. C. S.) wishes to thank the Carnegie Trust for the award of a Scholarship which enabled him to take part in. the above investigation. UNIVERSITY COLLEGE D UNDEE . UNIVERSITY OF ST. QNDREWS. [Received November 12th 1924. 82 MCPENZIE AND STRATHERN REACTIONS OF XIV.-Reactions of Displacement in the Tropic Acid Group. Part I. By ALEX. MCKENZIE and ROBERT CAMPBELL STRATHERN. THE proof of the constitution of a-aminohydratropic acid, NH,-CPhMe*CO,H was afforded by Tiemann and Kohler (Ber., 1881 14 1980) by the synthesis from acetophenonecyanohydrin and alcoholic ammonia.McKenzie and Clough (J. 1912 162, 390) in dealing with the Walden inversion described the resolution of the r-acid into its optically active components. The study of the isomeric p-acid NH,*CH,*CHPh*CO,H has not so far been advanced to the corresponding stage. For one reason this acid has no particular interest with relationship to the Walden inversion the amino-group not being directly attached to the asymmetric carbon atom. The identification of the acid has also been attended with some confusion. By the action of aqueous ammonia on p-bromohydratropic acid Merling (AnnaZen, 1881 209 11) obtained crystals m. p. 169-170" (compare also Fittig and Wurster ibid. 1879 195 158).Assuming that the reaction proceeded on the lines CH,Br*CHPh*CO,H + NIP,*CH,*CHPh*CO,H, Merling concluded that he had to deal with p-aminohydratropic acid and the analytical evidence supported this assumption DISPLACEMENT IN THE TROPIC ACID GROUP. PaRT I. 83 Posner however in continuation of his work on the action of hydroxylamine on unsaturated acids obtained from atropic acid an amino-acid which melted and decomposed a t 234" (Ber. 1903, 36 4315; Annulen 1912 389 109). All the evidence pointed to this substance being the true p-aminohydratropic acid. Since Posner (Ber. 1905 38 2316) had shown that the action of ammonia on p-bromo-p-phcnylpropionic acid leads to the formation not of p-amino- p-phenylpropionic acid but of p-hydroxy-p-phenylpro-pionamide he suggested that P-bromohydratropic acid might perhaps exhibit a similar behaviour and that Merling's product was not the amino-acid a t all but was the isomeric tropamide.The latter suggestion has been borne out. In the present paper it is show1 that r-p-chlorohydratropic acid is converted into r-tropamide (m. p. 170-171") by the action of aqueous ammonia. The amide was also prepared directly from ammonia and methyl dl-tropate; it has the same melting point and it possesses the same properties as the compound described by Merling. We have also examined the action of hydroxylamine on atropic acid and find that Posner's p-amino-acid is not the sole product, and that the oxime of phenylacetaldehyde is also formed. It is, however rather curious that the formation of tropic acid by the action of nitrous acid on the amino-acid proceeds in a somewhat irregular manner.The preparation of Z- p-chlorohydratropic acid is described the resolution of the r-acid being effected in methyl-alcoholic solution with morphine as the resolving alkaloid. When hydrolysed the Z-acid which has [.ID - 122.6" in benzene gave a lzvorotatory tropic acid with [ R I D - 58.1" (c = 2.4348) in ethyl-alcoholic solution whereas the value for the optically pure acid is [ R ] ~ - 72.5" (c = 2.578) in the same solvent (NcKenzie and Wood, J. 1919 115 828). Although the chlorine is not directly attached to the asymmetric carbon atom some racemisation had apparently taken place during the substitution of the hydroxy-group for the chlorine.In the light of recent work in a different field (McKenzie and Roger J. 1924 125 214S) the action of ammonia on the E-chloro-acid was of some interest and we have therefore examined it for the purpose of finding if optical activity would persist in the trans-formation into the amide. Experiments showed that a levorotatory tropamide did actually result. Under the conditions employed, the rotation of the product was less than that of the amide obtained by the direct action of ammonia on ethyl I-tropate. This formation of an optically active tropamide has led us t 84 MCKENZIE AND STRATHERN REACTIONS OF conclude that a p-lactone is produced as an intermediate phase, thus : Th Ph Z-H-$-CH,Cl -+ Z-H-$+-CH,Cl + C0,H CO,*NH, Ph Fh Z-H-Y-CH2 -+ Z-H-Y-CH,*OH.cod CO*NH,. Although on those lines the actions do not occur by substitution of groups directly attached to the asymmetric carbon atom some racemisation accompanied the change. This was not altogether unexpected since in tropamide we have the phenyl hydrogen, and carbonyl groups all directly attached to the asymmetric carbon atom a system which a t any rate in the presence of alcoholic alkali is particularly prone to racemisation under certain conditions (McKenzie and Smith J. 1922 121 1348). In the field of optical activity it has been shown by Holmberg (ArEiv Kern. Min. CeoZ. 1917,6 No. 23 pp. 1-33 and earlier papers) that the formation of a p-lactone is a stage in the interconversion of d- and I-malic acids by the Walden inversion. Moreover Z-iodo-succinic acid when treated with ammoniacal silver nitrate gives a mixture of fumaric acid and d-p-malamic acid the latter being formed by the action of ammonia on the d-malo-lactone (compare Walden and Lutz Ber.1897 30 2796; Lutz Ber. 1902 35, 2460 4369; 1908 41 841). Reference has already been made to the fact that Posner obtained r- p-hydroxy- p-phenylpropionamide by the action of ammonia on r- p-bromo- p-phenylpropionic acid. It seems reasonable to suppose that this action proceeds on similar lines to that of ammonia on P-chlorohydratropic acid : ph p Ph Vh H-TBr -+ H T - B r CH,*CO,H CH2*C0,*NH4 CH,*CO CH,*CO*NH,. It will be observed that the p-lactone which is suggested as an intermediate phase is isomeric with the one postulated in the scheme with p-chlorohydratropic acid.Arising from the results recorded in the present paper and more especially from former work by one of us it is desirable that Posner’s observation should be extended to the optically active p-bromo-p-phenylpropionic acids so as to enable the following scheme to be completed: -+ HT-? -+H-$+-O DISPLACEMENT m THE TROPIC ACID GROUP. PART I. 85 dext,ro- dextro-1 zvo - C,H5*CHBr*CH,*C0,H dextro - C GH ,*CH( OH) *CH,*CO*NH, (McKenzie and Humphries J. 1910 97 121; McKenzie and Martin J. 1913 103 112; McKenzie Martin and Rule J., 1014 105 1583; McKenzie and Smith J. 1922 121 1348). Owing to the announcement in the current number of the Pro-ceedings (1924 p. 77) of a paper by Seiiter and Ward entitled " Studies on the Walden iiiversion. Part IX.The influence of the solvent on the sign of the product in the conversion of 3-bromo-p-phenylpropioiiic acids to 3- hydroxy- 9 -phenylpropionamides " TF'C are not meanwhile invcstigatiiig this matter further so far as the action of ammonia on the optically active $-bromo-F-phenyl-propionic acids is concerned. At present we are engaged on a further study of the action of nitrous acid on r-p-aminohydratropic acid and also propose to undertake the resolution of this acid with the object of examining the resulting optically active acids. E X P E R I Jr E 3 T A L. Action of Hydroxyhnine o n Atropic Acid.-Posner (Anncrieih, 1912 389 112) prepared r-$aminohydratropic acid by heating atropic acid with an alcoholic solution of hydroxylsmine for 1 hour. By analogy with his previous work (Ber.190.5 38 2316; compare also McKenzie and Tuclhope J. 1924,125,928) i t might be expected that the formation of the amino-acid would be accompanied by that of phenylncetaldoxiin~.. Kydroxylamine hydrochloride (25 g.) in water (25 c.c.) was adclcd to a solution of sodium (8.5 g.) in ethyl alcohol (280 c.c.), and t hc precipitated sodium chloride removed. Atropic acid (2.3 g.) prepared by the dehydration of atrolactinic acid (McKenzie and Wood Zoc. cit.) was added and the solution boiled for 13 hours. Ammonium carbonate was deposited in the condenser tube. -4fter 3 clays in the ice-chest the amino-acid (8 g.) was collected; it was free from the hydroxylamiiio-acid sirice it did not reduce either Fehling's solution or ainrnoniacal silver nitrate ; i t melted and decomposed a t 222-224" (Posner gives 233").An additional 0.5 g. was obtained by boiling the filtrate for 2& hours longer. After distillation of the bulk of the alcohol an exccss of water precipitated 8 g. of crude phenylaceta!dosime which crystallised from water several times gave the pure substance in lwtrous needles m. p. 103-104" (Found C = 70.9; H = 6.8. Calc., C = 71.1 ; H = 6.7%). Bouvcault and M7ahl (C'ompt. rend. 1002, 134 1147) gave m. p. 103". This osime was isolat cd as follows 86 MCKENZIE AND STRATHERN REACTIONS OF r- P-Aminohydratropic acid is sparingly soluble in water benzene, light petroleum acetone chloroform carbon disulphide and ether. Posner (Ber. 1903 36 4315) described this acid as a-amino-a-phenylpropionic acid (a-aminohydratropic acid) ; its solution in hydrochloric acid was acted on by nitrous acid to give an acid, m.p. 89-90" which was supposed to be atrolactinic acid. Posner was however working with small quantities of material and was misled by the erroneous data of other authors. In a subsequent paper (Annulen Zoc. cit.) the correct constitution of the amino-acid is given. The product which Posner obtained by the action of nitrous acid was apparently impure tropic acid. We have repeated this action several times and find that it proceeds by no means smoothly. The gradual addition of potassium nitrite to the solution of the amino-acid in dilute hydrochloric acid caused the deposition of an oil which was certainly not tropic acid nor did it appear to be a-isotropic acid since it showed no signs of solidifying when nucleated with the latter acid.The aqueous solution was separated from the oil and extracted with ether. By crystallising the resulting acid several times from benzene r-tropic acid was isolated in very small yield (0.1 g. of the pure acid m. p. 116-117" from 2 g. of p-aminohydratropic acid). Resolution of r- p-Chlorohydratropic Acid.-The solution obtained by boiling 49.5 g. of morphine (I mol.) in 820 C.C. of methyl alcohol was cooled to 42" and 30 g. of r-p-chlorohydratropic acid (1 mol.; prepared from atropic acid McKenzie and Wood Zoc. cit.) were added in one instalment with vigorous stirring. The acid dissolved quickly. When the temperature had fallen to 39' glassy prisms started to separate.After 18 hours in the ice-chest 56 g. of solid were deposited. After the evaporation of the methyl alcohol from the filtrate the acid obtained from the latter gave the following rotation in benzene I = 2 c = 3.924 a? + 3-71' [ c x ] ~ + 47.3", so that the resolution had proceeded markedly after one crystallis-ation. The further progress is indicated as follows 56 g. crystal-lised from 1350 C.C. of methyl alcohol + 35 g. 850 C.C. of alcohol + 19 g. 550 C.C. of alcohol + 13 g. 400 C.C. of alcohol + 9 g. 360 C.C. of alcohol + 6 g. pure morphine I-salt. The solution of the crystals in methyl alcohol should be conducted as expeditiously as possible. The progress of the resolution was tested by the polarimetric examination of the acids obtained from the mother-liquors.The morphine salt which separates in rectangular prisms was decom-posed by dilute sulphuric acid the solution extracted with ether nine times and the ethereal extract dried with anhydrous sodium sulphate. The resulting acid (2.1 g.) after drying in a vacuum until constant in weight gave the following rotation in benzene DISPLACEMENT IN THE TROFIC ACID GROUP. PART I. 87 I = 2 c = 3.536 al,fi' - 8-66' [a]:' - 122.4". The acid was crystallised from light petroleum (b. p. 60-80") and gave a value for the rotatory power agreeing with the above within the limits of experimental error Z = 2 c = 3.536 a:" - 8-67' [a]:"' - 122.6." l-p-C~~Zorohydratropic acid m. p. 62-5-63.5" separates from light petroleum in rosettes of glassy plates. It is sparingly soluble in light petroleum and readily so in ether carbon disulphide, benzene and ethyl alcohol (Found C1 = 19.39.C,H,O,Cl requires C1 = 19-240/). I n acetone Z = 2 c = 3.2300 a:.'- - 7-46' [a]::'" - 115.5". Conversion of 1- p-Chlorohydratropic Acid into I-Tropic Acid.-A'-Sodium carbonate (11 c.c.) was gradually added (14 mins.) to a boiling solution of the 1-acid (1 g.) in 20 C.C. of water (reflux). The boiling was continued for 3 hours the cold solution extracted with ether to remove the styrene present' and the tropic acid obtained by acidification with dilute sulphuric acid and extraction with ether. Yield 0.7 g. I n ethyl alcohol Z = 2 c = 2.4348, A similar experiment was carried out with a lzevorotatory acid having [R]:" - 100.7" (1 = 2 c = 3.5504) in benzene.The resulting tropic acid (1.9 g.) gave the following value in ethyl alcohol I = 2 c = 2.716 a;;* - 2-68' [a]:' - 49.3". After one crystallisation of this product from benzene the value for the specific rotation was enhanced in ethyl alcohol 1 = 2 c = 2-548, Conversion of 1- p-Chlorohydratropic Acid into 1-Tropamide.-A solutioii of the I-chloro-acid (0-94 g.) in 60 C.C. of aqueous ammonia (saturated at 0") was kept for a week in a pressure flask at the ordinary temperature. When the solution was transferred to a crpstallising dish needles began to separate. Yield 0.3 g.; in. p. 195-199" (Found N = 8.7. Calc. N = 8.5%). In ethyl alcohol 1 = 2 c = 0.3472 E ~ T - 0.38". I n another experiment the resulting amide gave in ethyl alcohol : The concentrations employed were necessarily very small the aniide being sparingly soluble in water ethyl alcohol acetone, chloroform benzene and ethyl acetate.For the purpose of comparison the amide was prepared from I-tropic acid (obtained by resolution of the 1.-acid with morphine according to McICenzie and Wood) by acting on the ethyl ester with concentrated aqueous ammonia. After crystallisation from acetone the amide had m. p. 195-197.5"; in ethyl alcohol Z = 1, c = 0.377 cxI) - 0.24". Since the polarimetric determinations could be made with very dilute solutions only we have no proof 1 58.1". ai'i 5- - 2.830 1.1 50 -EliS 1 - 3-17" [a]\ - 62.2". I = 2 c = 0.3912 ",F" - 0.43" 88 TROTMAN PREPARATION OF QUATERNARY HYDROCARBONS. that we obtained the optically pure I-tropamide by this method, more especially since there was always the possibility of partial racemisation having taken place during the action of ammonia on the 2-ester.But we think it likely that we obtained the amide nearly pure if not quite so. I-Tropamide would be expected to undergo racemisation in the presence of a small amount of sodium ethoxide (McKenzie and Smith J. 1922 121 1348). When 0.5 C.C. of ethyl-alcoholic potash (0~6518N) was added to a solution giving aD - 0.24" ( I = l), the lzvorotation gradually dropped to zero after 30 hours and r-tropamide (m. p. 170-171") was isolated from the solution. Formation of r-Tropamide from r-Tropic Acid and r- p-Chloro-hydratropic Acid.-r-Tropic acid was converted into its methyl ester from which the amide was prepared by the action of aqueous ammonia. r-Tropamide m. p. 170-171" is sparingly soluble in cold water, ethyl alcohol acetone benzene carbon tetrachloride and light petroleum (b. p. 60-70"). It separates from water in needles (Found N = 8-4. C,H,,O,N requires N = 86%). A solution of r- p-chlorohydratropic acid (4 g.) in concentrated aqueous ammonia (65 c.c.) was kept for 18 days in a pressure flask. On pouring into a dish crystallisation started quickly. The crystals (1.5 g.) were collected and crystallised twice from water, when the pure r-tropamide (m. p. 170-171") was obtained (Found : C = 65.1 ; H = 6-8. The melting point was not depressed when this product was mixed with the r-tropamide obtained from methyl dl-tropate. Calc. C = 65.4; H = 6.7%). One of us (R. C. S.) wishes to thank the Carnegie Trust for the award of a Scholarship which enabled him to take part in. the above investigation. UNIVERSITY COLLEGE D UNDEE . UNIVERSITY OF ST. QNDREWS. [Received November 12th 1924.

ISSN:0368-1645    

DOI:10.1039/CT9252700082

出版商:RSC    

年代:1925

数据来源: RSC

摘要:

88 TROTMAN PREPARATION OF QUATERNARY HYDROCARBONS. XV.-Preparation of Quuternary Hydrocarbons. By EDWARD RUSSELL TROTMAN. IN the course of some investigations in progress in this laboratory, certain quaternary hydrocarbons of the type (C,M,*CH,),CR,R~, were required R and R being different alkyl radicals. No such compounds are known and indeed very few quaternary hydro-carbons of any kind have been described. The interaction of Grjgnard reagents and tertiary halogen derivatives which seeme TROTMAN PREPARATION OF QUATERNARY HYDROCARBONS. 89 to offer a suitable method €or their preparation has already been studied. Gomberg and Cone (Ber. 1906 39 1461 2975) succeeded in displacing the chlorii-ie atom of triphenylmethyl chloride by various aromatic and aliphatic hydrocarbon radicals in this way.On the other hand Davis arid Kipping (J. 1911 99 300) were unable to prepare yy-dibenzyl-n-hexane (C,H,*CH,),CEtPr by the action of magnesium propyl bromide on cr-bromo- rcc-dibenzyl-propane (C,K5*CH,),CBrEt ; in every case the product consisted mainly if not entirely of an unsaturated hydrocarbcn. Spiith (Monatsh. 1913 34 1963) who made an exhaustive study of the act ion of Grigiiard reagents on organic halogen derivatives found that although quaternary hydrocarbons were generally produced, tlie yield was always poor and a mixture of numerous products was obtained. It appeared therefore that the interaction of a Grigiiard reagent ancl a tertiary halide often takes quite an unexpected course and this conclusioii is confirmed by the results described below.A preliminary study of tlie proposed method was made with [$-byorno- x-pher,yl-P-meth?llbutane a compound readily prepred from imthy! ethyl ketone. This bromide reacted with magnesium ethyl bromide 153th evolution of ethane ancl ethylene but the product appeared to consist entirely of a mixturz of the olefine, C,H,*CH:CMeEt and the saturated conipound C,H5*CH,.CH3kEt , a i d the possible presence of a small proportion of the quaternary hydrocarbon could not bt proved. Attempts to preparc a quaternary hydrocarbon by first converting the bromide into a Grignard reagent and then treating the product with ethyl bromide were also unsuccessful ; although the bromide reacted with mag-iiesiuin in thc presence of dry ether magnesium bromide separated even at 0" and a mixture of the saturated hydrocarbon and the olcfine was formed.~-B~o~?~o-sr-p7~enyl-~-benx~lp~o~ane which was easily obtained in a pure crystalline form reacted with magnesium ethyl bromide with formation of a small proportion of ct6-diphen$l-[$y-dibeib~yl-~y-~~rneth?llbutcc?2e (compare Spiith loc. cit .) : 2CnleBr(CH,Ph),$-2~~gEtBr. = (CH,Ph),~le.C~le(CH,Ph) + C4H,0 4- MgBr,. The main product however as indicated by aiialysis and by the evolution of ethane and ethylene was a mixture of ay-dipkenyl-p-methylpropane (I) (Graebe Ber. 1874 7 1627) and an olefiiie, CIoH1, believed to be ccy-dipheiiyl-p-methyl-An-propene (11) : (I). CHRle(CH,Ph) + C,H4 + MgBr FFtBr CMeBr(CH,Pli),~ls"t"f The constitution of this olefine could not be established by C,H + MgBr + CHPh:CMeCH2Ph (11.90 TROTMAN PREPARATION OF QUATERNARY HYDROCARBONS. oxidising it to a mixture of benzoic acid or benzaldehyde and benzyl methyl ketone with potassium permanganate or ozonised oxygen since only benzoic acid was obtained; this result was doubtless due to the fact that benzyl methyl ketone is itself very readily oxidised. The structure assigned to the olefine is rendered very probable by the known behaviour of other bromides similar to p- bromo- cr -phenyl- p-benzylpropane (compare Orechov and Konovalov Ber. 1912 45 861; Orechov and Meerson ibid., p. 1926). p-Bromo-a-phenyl- p-benzylpropane reacted with magnesium benzyl chloride with the formation of a very small quantity of the quaternary hydrocarbon a-phenyl- p p-dibenzylpropane.The main product however was an olefine doubtless identical with I1 : CMeBr(CH,Ph) + CH,Ph*MgCl = (11.) + MgClBr + C,H5*CH3. Unlike p- bromo- a-phenyl- p-methylbutane p- bromo- a-phenyl-p-benzylpropane did not react with magnesium even when iodine was added so that the quaternary hydrocarbon could not be prepared by modifying the procedure. In boiling ethereal or benzene solution the bromide reacted with sodium but the above-described olefine was formed. Tribenzylmethyl bromide (Schmerda Monatsh. 1909 30 387), treated with magnesium ethyl bromide gave a small yield of hexabenzylethane (Schmerda Zoc. cit.) 2(CH,Ph),CBr + 2MgEtBr = (CH,Ph),C*C(CH,Ph) + C,H, + BMgBr, but the main product was ocy-diphenyl- p-benzyl-Aa-propene (111) (CH,Ph),CBr + MgEtBr = (111.) CHPh:C(CH,Ph)2 + C,H6 + MgBr,.This olefine, which has been described by Orechov and Grinberg ( J . Russ. Chern. Phys. Xoc. 1916 48 1713) as a viscous liquid was obtained in well-formed crystals m. p. 42-43" Tribenzylmethyl bromide was also treated with magnesium benzyl chloride; it gave a small amount of tetrabenxylmethune but the product consisted mainly of 111. The action of zinc ethyl on this bromide was also in-vestigated but the above olefine was the only product. As there seemed to be indications that the halogen atom of tertiary halides is more readily displaced by a benzyl than by an ethyl group the action was investigated of magnesium benzyl chloride on p-brm-a-phenyl-p-methyzpropane. A quaternary hydrocarbon of the desired type viz.a-phenyl-p-benzyl-p-methyl-propane wits in fact produced but about 50% of the product con-sisted of a-phenyl-p-methyl-Aa-propene (Klages Ber. 1904,37,1721). The results of these experiments show that in many cases the reaction between Grignard reagents and tertiary halogen deriv-atives does not follow the normal course. Spath (Zoc. cit.) expresse TROTMAN PREPARATION OF QUATERNARY HYDROCARBONS. 91 the view that during this reaction the organic halide and the Grignard reagent undergo dissociation so giving rise to free organic radicals : It's + RlMgX = R' + R + MgX,. The existence of these radicals however is only momentary ; those which are electropositive tend t o unite together but those which are more electronegative show a tendency to form olefines and paraffins containing the same number of carbon atoms as the radicals.The basis of Spiith's classification into positive and negative radicals is not very obvious and his views do not seem to afford a very satisfactory explanation of the results summarised above. ,4 few attempts mere made to obtain dilietones of the type C,H,*CO*CR(CH,*C,H,).CO.CH in the hope that subsequent reduction might yield a quaternary hydrocarbon. BenxylbenxoyZ-acetone was prepared but on treatment with sodium ethoxide and ethyl bromide it gave w-benzylacetophenone an acetyl group being eliminated. E x P E R I M E N T A L. p-Bronzo-x-phenyl-$-methylbulane C,H,*CH,*CMeEtBr a colour-less oil with a pleasant minty odour and an extremely irritating action on the eyes was obtained in almost theoretical quantity by saturating benzylmethylethylcarbinol (Konovalov J .Rziss. Chem. Phys. SOC. 1904 36 228) with hydrogen bromide a t the ordinary temperature. It decomposed when distilled even under 11 mm. and was therefore purified by washing it with dilute sodium carbonate solution and water (Pound Br = 34.0. CIoH,,Br requires Br = 35-27'0). Action of Grignayd Beagents on p-Bromo-cc-phenyl-p-?netfLylbutane. -When an excess of magnesium ethyl bromide was added to an ethereal solution of the bromide a vigorous reaction immediately occurred magnesium bromide mas formed and ethane and ethylene were evolved. The main product was an oil practically the whole of which distilled between 195" and 205". Its behaviour towards bromine and hydrogen bromide and analyses of the brorno-deriv-atives thus obtained indicated that it was a mixture of an olefine, believed to be cc-phenyl-p-methyl-Aa-butene and a saturated hydro-carbon probably a-phenyl- p-methylbutane b.p. 203-2004' (Tafel and Hahl Ber. 1907 40 3313). Since from its boiling point, it could hardly contain an appreciable quantity of the expected quaternary hydrocarbon and analysis showed the presence of a small proportion of benzylmethylethylcarbinol the oil was not further examined 92 TROTMAN PREPARATION OF QUATERKARY HYDROCARBONS. A solution of the bromide in dry ether had no action on mag-nesium until a trace of iodine had been added; a vigorous reaction then set in and magnesium bromide separated even a t 0". The product was a mixture b.p. 195-205" apparently identical with that described above. DibenxyZmethylcarbinol (C6H5*CH,),CMe*OH prepared from magnesium benzyl chloride and ethyl acetate is a colourless, viscous sweet-smelling liquid b. p. 195-200"/14 mm. (with slight decomp.) (Pound C = 85.5; H = 8.0. Cl6Hl8O requires C = p -Bromo- cr-phen yl- p - benxylpropane (C,H,*CH,),CMeBr obtained in good yield by saturating an ethereal solution of the unpurified carbinol with hydrogen bromide and recrystallising the product from light petroleum and from alcohol formed well-defined, prismatic crystals m. p. 78.5". It loses hydrogen bromide when heated and cannot be distilled even under 0-2 mm. It is readily soluble in ether alcohol or benzene and sparingly so in light petroleum (Found Br = 27.6.Action of Magnesium Ethyl Bromide on p-Bromo-a-phengl-p- benzyl-jwopane.-A solution of the bromide in ether (1 vol.) was added slowly to magnesium ethyl bromide (4 vols.) at the ordinary temperature. The gas which was soon evolved after being freed from ether with the aid of sulphuric acid contained about 42% of ethane and 58% of ethylene. After 8 hours the reaction mkture was boiled for 2 hours. The product isolated in the usual way, was a slightly yellow oil. Its solution in alcohol (8 vols.) deposited crystals of cr8 -diphen$ p y -dibenx yl- p y dimethylbutane , (C,H,*CH,),CMe*CMe( CHz*CsH5)z, which separated from much light petroleum in colourless plates, m. p. 171"; the yield was about 0.5 g. from 40 g. of the bromide (Found C = 92.0; H = 8.3; M cryoscopic in benzene = 389.C,2Ha requires C = 91.9; H = 8.1y0; M = 418). Separation of ay-Diphenyl-p-methylpropane (I) and ( ?) ay-Di-IphenyZ-p-methyl-Aa-propene (II).-The main product obtained as an oil when the above alcoholic mother-liquor was evaporated, distilled between 290" and 300". It combined with bromine in chloroform solution but the dibromide did not crystallise and very readily lost hydrogen bromide. Oxidation or treatment with sulphuric acid having failed to separate the olefine from the saturated hydrocarbon the oil was saturated with hydrogen bromide when about 50% of it was converted into crystalline p-bromo-a-phenyl-P-benzylpropane. The unchanged oil was separated from the bromide and treated with sodium amalgam and aqueous alcohol to reduce any remaining bromide.The final 85.0; H = 8.0y0). CIsH1,Br requires Br = 27.7y0) TROTMAN PREPARATlON OF QUATERNARY HYDROCARBONS. 93 product b. p. 290-294" was ay-diphenyl-p-methylpropane (Found : C = 91.2; H = S.4. Cl,H18 requires C = 91.4; H = 8.6%). Thus the quaternary hydrocarbon a-phenyl- p-benzyl- p-methyl-butane (calc. C = 9O.S; H = 9.2%) was not among the products of the reaction. The oleJine (11) a colourless oil b. p. 294-896" was obtained by boiling the bromide with an excess of pyridine for 8 hours. It combined with bromine in chloroform solution giving a di-bromide which could not be crystallised and readily lost hydrogen bromide when it was heated (Found C = 92.2; H = 7.6. C,,H1, requires C = 92-3 ; H = 7.7%). Action of Magnesium Benxyl Chloride on p-Bromo- a-phenyl-P-benxy1propane.-The Grignard reagent (4 mols.) did not react with the bromide in ether a t the ordinary temperature.The ether was evaporated and the residue heated a t 100" for 2 hours. Tlie product isolated in the usual way was an oil a solution of which in alcohol deposited crystals of a-plie?iyl-p~-clibenxylpro~une, (C,H5*CH,),CMe ; these separated from alcohol in needle-shaped prisms m. p. 113" which were sparingly soluble in alcohol or light petroleum but dissolved more readily in other organic solvents (yield about 5%) (Found C = 91.5; H = 7.9; Af cryoscopic in benzene = 294. C,,H, requires C = 92.4 ; H = 8-Oyo ; M = 300). The main product obtained as an oil when the alcoholic mother-liquor was evaporated contained the olefine (II) but the probable presence of ay-diphenyl-P-methylpropane (I) could not be proved owing to the impossibility of separating the dibenzyl which the oil contained.Action of Mugnes ium Ethyl Bromide on Tribenzylmethyl Bromide. -Tribenzylmethyl bromide (Schmerda loc. cit.) which is most conveniently prepared by saturating an ethereal solution of tri-benzylcarbinol with hydrogen bromide was treated in benzene solution with an excess of ethereal magnesium ethyl bromide ; magnesium bromide separated at once and a gas containing oiilp a vcry small proportion of olefine was evolved. After 2 hours, the reaction mixture was gently boiled for 1 hour. The product, isolated in the usual way was a very viscous oil ; froin its solution in alcohol colourless cubical crystals gradually separated.This compound after recrystallisation from alcohol melted a t 42-43" and was doubtless ay-diphenyl-$-benzyl-4a-propene (111) (coni-pare Orechov and Grinberg loc. cit.). Its identity was established by converting it into the crystalline dibromide m. p. 127-128", and also into tribenzylmethyl bromide with the aid of hydrogen bromide. When the alcoholic mot her-liquor from the crystalline olefine was evaporated there remained an oil from which hesa 94 TROTMAN PREPARATION OF QUATERNARY HYDROCBRBONS. benzylethane was isolated by converting the olefine into tribenzyl-methyl bromide (see above) and subsequently extracting the product with alcohol. From the alcoholic extract the hydrocarbon was deposited in crystals m. p.82-83". Schmerda (loc. cit.) gives the m. p. 81-82" (Found C = 92.4; H = 797. Calc. for C44H42, Tetrabenzylmethane C( CH,*C,H,),.-Tribenzylmethy~ bromide, dissolved in benzene was added to an ethereal solution of excess of magnesium benzyl chloride the solvents were then evaporated, and the residue was heated at 100" for 2 hours. The product, isolated in the usual way was an oil from which tetrabenxyl-methane (yield 5%) was precipitated on the addition of alcohol. It separates from ether in cubic crystals m. p. 164' which are very sparingly soluble in alcohol or light petroleum but dissolve more easily in other organic solvents (Found C = 92.7; H = 7.5. C,,HZ8 requires C = 92.5; H = 7.5%). The main product was ay-diphenyl-p-benzyl-Aa-propene (111). p-Bromo-a-phenyl- p -methylpropane C,H,*C~*cMe,Br obtained by saturating dimethylbenzylcarbinol (Grignard Compt.rend., 1900 130 1324) with hydrogen bromide and washing the product with sodium carbonate solution and water is a colourless pleasant-smelling liquid which loses hydrogen bromide very readily when it is warmed and does not distil unchanged under 11 mm. (Found : Br = 36.4. CIoH,,Br requires Br = 376%). a-Phenyl-p-benzyl- p-methylpropane (CH,Ph),CMe,.-Reaction set in a t once when the preceding bromide (1 mol.) dissolved in ether was added to magnesium benzyl chloride (2 mols.); after 4 hours the reaction mixture was boiled gently for 2 hours. The product isolated in the usual way consisted of an oil which was separated by distillation into a-phenyl- p-methyl-A,-propene, b.p. 181" and a fraction of higher boiling point; the latter solidified when cold and crystallised from alcohol in prismatic needles m. p. 68-69" (Found C = 90.95; H = 9.0. C,,H,, requires C = 91.1 ; H = 8.9%). ~-Phenyl-p-benzyl-p-methylpropane boils a t 293-294" is readily soluble in most organic solvents, and has a somewhat sweet odour. BenxyZbenzoy1acetone.-The sodium derivative of benzoylacetone, prepared from its constituents in ether was isolated and boiled for 1 hour with an excess of benzyl chloride the solution was filtered and the unchanged benzyl chloride removed by distillation under reduced pressure. From an alcoholic solution of the residual dark brown oil benxylbenxoylacetone was deposited in clusters of needle-shaped crystals m.p. 60-61" (yield 50%). The compound is insoluble in aqueous potassium hydroxide and gives no coloration C = 9246; H = 7.4%) ~ ~ 0 0 ~ AND LILLEY TRANSFORMATION OF 1 ~ ETC. 95 with ferric chloride (Found C = 80-6 ; H = 6.1. C1,Hl,O, requires C = 80.95; H = 6.35%). When an alcoholic solution of benzylbenzoylacetone containing sodium ethoxide and ethyl bromide is kept at the ordinary temperature for 24 hours sodium bromide separates but the product is mainly w-benzylacetophenone. The author desires t o express his thanks to Professor F. S. Kipping F.R.S. for suggesting this research and for his interest in its progress. UNIVERSITY COLLEGE NOTTIKCHAM. [Received August 29th 1924. 88 TROTMAN PREPARATION OF QUATERNARY HYDROCARBONS. XV.-Preparation of Quuternary Hydrocarbons.By EDWARD RUSSELL TROTMAN. IN the course of some investigations in progress in this laboratory, certain quaternary hydrocarbons of the type (C,M,*CH,),CR,R~, were required R and R being different alkyl radicals. No such compounds are known and indeed very few quaternary hydro-carbons of any kind have been described. The interaction of Grjgnard reagents and tertiary halogen derivatives which seeme TROTMAN PREPARATION OF QUATERNARY HYDROCARBONS. 89 to offer a suitable method €or their preparation has already been studied. Gomberg and Cone (Ber. 1906 39 1461 2975) succeeded in displacing the chlorii-ie atom of triphenylmethyl chloride by various aromatic and aliphatic hydrocarbon radicals in this way. On the other hand Davis arid Kipping (J.1911 99 300) were unable to prepare yy-dibenzyl-n-hexane (C,H,*CH,),CEtPr by the action of magnesium propyl bromide on cr-bromo- rcc-dibenzyl-propane (C,K5*CH,),CBrEt ; in every case the product consisted mainly if not entirely of an unsaturated hydrocarbcn. Spiith (Monatsh. 1913 34 1963) who made an exhaustive study of the act ion of Grigiiard reagents on organic halogen derivatives found that although quaternary hydrocarbons were generally produced, tlie yield was always poor and a mixture of numerous products was obtained. It appeared therefore that the interaction of a Grigiiard reagent ancl a tertiary halide often takes quite an unexpected course and this conclusioii is confirmed by the results described below. A preliminary study of tlie proposed method was made with [$-byorno- x-pher,yl-P-meth?llbutane a compound readily prepred from imthy! ethyl ketone.This bromide reacted with magnesium ethyl bromide 153th evolution of ethane ancl ethylene but the product appeared to consist entirely of a mixturz of the olefine, C,H,*CH:CMeEt and the saturated conipound C,H5*CH,.CH3kEt , a i d the possible presence of a small proportion of the quaternary hydrocarbon could not bt proved. Attempts to preparc a quaternary hydrocarbon by first converting the bromide into a Grignard reagent and then treating the product with ethyl bromide were also unsuccessful ; although the bromide reacted with mag-iiesiuin in thc presence of dry ether magnesium bromide separated even at 0" and a mixture of the saturated hydrocarbon and the olcfine was formed.~-B~o~?~o-sr-p7~enyl-~-benx~lp~o~ane which was easily obtained in a pure crystalline form reacted with magnesium ethyl bromide with formation of a small proportion of ct6-diphen$l-[$y-dibeib~yl-~y-~~rneth?llbutcc?2e (compare Spiith loc. cit .) : 2CnleBr(CH,Ph),$-2~~gEtBr. = (CH,Ph),~le.C~le(CH,Ph) + C4H,0 4- MgBr,. The main product however as indicated by aiialysis and by the evolution of ethane and ethylene was a mixture of ay-dipkenyl-p-methylpropane (I) (Graebe Ber. 1874 7 1627) and an olefiiie, CIoH1, believed to be ccy-dipheiiyl-p-methyl-An-propene (11) : (I). CHRle(CH,Ph) + C,H4 + MgBr FFtBr CMeBr(CH,Pli),~ls"t"f The constitution of this olefine could not be established by C,H + MgBr + CHPh:CMeCH2Ph (11. 90 TROTMAN PREPARATION OF QUATERNARY HYDROCARBONS.oxidising it to a mixture of benzoic acid or benzaldehyde and benzyl methyl ketone with potassium permanganate or ozonised oxygen since only benzoic acid was obtained; this result was doubtless due to the fact that benzyl methyl ketone is itself very readily oxidised. The structure assigned to the olefine is rendered very probable by the known behaviour of other bromides similar to p- bromo- cr -phenyl- p-benzylpropane (compare Orechov and Konovalov Ber. 1912 45 861; Orechov and Meerson ibid., p. 1926). p-Bromo-a-phenyl- p-benzylpropane reacted with magnesium benzyl chloride with the formation of a very small quantity of the quaternary hydrocarbon a-phenyl- p p-dibenzylpropane. The main product however was an olefine doubtless identical with I1 : CMeBr(CH,Ph) + CH,Ph*MgCl = (11.) + MgClBr + C,H5*CH3.Unlike p- bromo- a-phenyl- p-methylbutane p- bromo- a-phenyl-p-benzylpropane did not react with magnesium even when iodine was added so that the quaternary hydrocarbon could not be prepared by modifying the procedure. In boiling ethereal or benzene solution the bromide reacted with sodium but the above-described olefine was formed. Tribenzylmethyl bromide (Schmerda Monatsh. 1909 30 387), treated with magnesium ethyl bromide gave a small yield of hexabenzylethane (Schmerda Zoc. cit.) 2(CH,Ph),CBr + 2MgEtBr = (CH,Ph),C*C(CH,Ph) + C,H, + BMgBr, but the main product was ocy-diphenyl- p-benzyl-Aa-propene (111) (CH,Ph),CBr + MgEtBr = (111.) CHPh:C(CH,Ph)2 + C,H6 + MgBr,. This olefine, which has been described by Orechov and Grinberg ( J .Russ. Chern. Phys. Xoc. 1916 48 1713) as a viscous liquid was obtained in well-formed crystals m. p. 42-43" Tribenzylmethyl bromide was also treated with magnesium benzyl chloride; it gave a small amount of tetrabenxylmethune but the product consisted mainly of 111. The action of zinc ethyl on this bromide was also in-vestigated but the above olefine was the only product. As there seemed to be indications that the halogen atom of tertiary halides is more readily displaced by a benzyl than by an ethyl group the action was investigated of magnesium benzyl chloride on p-brm-a-phenyl-p-methyzpropane. A quaternary hydrocarbon of the desired type viz. a-phenyl-p-benzyl-p-methyl-propane wits in fact produced but about 50% of the product con-sisted of a-phenyl-p-methyl-Aa-propene (Klages Ber.1904,37,1721). The results of these experiments show that in many cases the reaction between Grignard reagents and tertiary halogen deriv-atives does not follow the normal course. Spath (Zoc. cit.) expresse TROTMAN PREPARATION OF QUATERNARY HYDROCARBONS. 91 the view that during this reaction the organic halide and the Grignard reagent undergo dissociation so giving rise to free organic radicals : It's + RlMgX = R' + R + MgX,. The existence of these radicals however is only momentary ; those which are electropositive tend t o unite together but those which are more electronegative show a tendency to form olefines and paraffins containing the same number of carbon atoms as the radicals.The basis of Spiith's classification into positive and negative radicals is not very obvious and his views do not seem to afford a very satisfactory explanation of the results summarised above. ,4 few attempts mere made to obtain dilietones of the type C,H,*CO*CR(CH,*C,H,).CO.CH in the hope that subsequent reduction might yield a quaternary hydrocarbon. BenxylbenxoyZ-acetone was prepared but on treatment with sodium ethoxide and ethyl bromide it gave w-benzylacetophenone an acetyl group being eliminated. E x P E R I M E N T A L. p-Bronzo-x-phenyl-$-methylbulane C,H,*CH,*CMeEtBr a colour-less oil with a pleasant minty odour and an extremely irritating action on the eyes was obtained in almost theoretical quantity by saturating benzylmethylethylcarbinol (Konovalov J .Rziss. Chem. Phys. SOC. 1904 36 228) with hydrogen bromide a t the ordinary temperature. It decomposed when distilled even under 11 mm. and was therefore purified by washing it with dilute sodium carbonate solution and water (Pound Br = 34.0. CIoH,,Br requires Br = 35-27'0). Action of Grignayd Beagents on p-Bromo-cc-phenyl-p-?netfLylbutane. -When an excess of magnesium ethyl bromide was added to an ethereal solution of the bromide a vigorous reaction immediately occurred magnesium bromide mas formed and ethane and ethylene were evolved. The main product was an oil practically the whole of which distilled between 195" and 205". Its behaviour towards bromine and hydrogen bromide and analyses of the brorno-deriv-atives thus obtained indicated that it was a mixture of an olefine, believed to be cc-phenyl-p-methyl-Aa-butene and a saturated hydro-carbon probably a-phenyl- p-methylbutane b.p. 203-2004' (Tafel and Hahl Ber. 1907 40 3313). Since from its boiling point, it could hardly contain an appreciable quantity of the expected quaternary hydrocarbon and analysis showed the presence of a small proportion of benzylmethylethylcarbinol the oil was not further examined 92 TROTMAN PREPARATION OF QUATERKARY HYDROCARBONS. A solution of the bromide in dry ether had no action on mag-nesium until a trace of iodine had been added; a vigorous reaction then set in and magnesium bromide separated even a t 0". The product was a mixture b. p. 195-205" apparently identical with that described above.DibenxyZmethylcarbinol (C6H5*CH,),CMe*OH prepared from magnesium benzyl chloride and ethyl acetate is a colourless, viscous sweet-smelling liquid b. p. 195-200"/14 mm. (with slight decomp.) (Pound C = 85.5; H = 8.0. Cl6Hl8O requires C = p -Bromo- cr-phen yl- p - benxylpropane (C,H,*CH,),CMeBr obtained in good yield by saturating an ethereal solution of the unpurified carbinol with hydrogen bromide and recrystallising the product from light petroleum and from alcohol formed well-defined, prismatic crystals m. p. 78.5". It loses hydrogen bromide when heated and cannot be distilled even under 0-2 mm. It is readily soluble in ether alcohol or benzene and sparingly so in light petroleum (Found Br = 27.6. Action of Magnesium Ethyl Bromide on p-Bromo-a-phengl-p- benzyl-jwopane.-A solution of the bromide in ether (1 vol.) was added slowly to magnesium ethyl bromide (4 vols.) at the ordinary temperature.The gas which was soon evolved after being freed from ether with the aid of sulphuric acid contained about 42% of ethane and 58% of ethylene. After 8 hours the reaction mkture was boiled for 2 hours. The product isolated in the usual way, was a slightly yellow oil. Its solution in alcohol (8 vols.) deposited crystals of cr8 -diphen$ p y -dibenx yl- p y dimethylbutane , (C,H,*CH,),CMe*CMe( CHz*CsH5)z, which separated from much light petroleum in colourless plates, m. p. 171"; the yield was about 0.5 g. from 40 g. of the bromide (Found C = 92.0; H = 8.3; M cryoscopic in benzene = 389. C,2Ha requires C = 91.9; H = 8.1y0; M = 418).Separation of ay-Diphenyl-p-methylpropane (I) and ( ?) ay-Di-IphenyZ-p-methyl-Aa-propene (II).-The main product obtained as an oil when the above alcoholic mother-liquor was evaporated, distilled between 290" and 300". It combined with bromine in chloroform solution but the dibromide did not crystallise and very readily lost hydrogen bromide. Oxidation or treatment with sulphuric acid having failed to separate the olefine from the saturated hydrocarbon the oil was saturated with hydrogen bromide when about 50% of it was converted into crystalline p-bromo-a-phenyl-P-benzylpropane. The unchanged oil was separated from the bromide and treated with sodium amalgam and aqueous alcohol to reduce any remaining bromide. The final 85.0; H = 8.0y0). CIsH1,Br requires Br = 27.7y0) TROTMAN PREPARATlON OF QUATERNARY HYDROCARBONS.93 product b. p. 290-294" was ay-diphenyl-p-methylpropane (Found : C = 91.2; H = S.4. Cl,H18 requires C = 91.4; H = 8.6%). Thus the quaternary hydrocarbon a-phenyl- p-benzyl- p-methyl-butane (calc. C = 9O.S; H = 9.2%) was not among the products of the reaction. The oleJine (11) a colourless oil b. p. 294-896" was obtained by boiling the bromide with an excess of pyridine for 8 hours. It combined with bromine in chloroform solution giving a di-bromide which could not be crystallised and readily lost hydrogen bromide when it was heated (Found C = 92.2; H = 7.6. C,,H1, requires C = 92-3 ; H = 7.7%). Action of Magnesium Benxyl Chloride on p-Bromo- a-phenyl-P-benxy1propane.-The Grignard reagent (4 mols.) did not react with the bromide in ether a t the ordinary temperature.The ether was evaporated and the residue heated a t 100" for 2 hours. Tlie product isolated in the usual way was an oil a solution of which in alcohol deposited crystals of a-plie?iyl-p~-clibenxylpro~une, (C,H5*CH,),CMe ; these separated from alcohol in needle-shaped prisms m. p. 113" which were sparingly soluble in alcohol or light petroleum but dissolved more readily in other organic solvents (yield about 5%) (Found C = 91.5; H = 7.9; Af cryoscopic in benzene = 294. C,,H, requires C = 92.4 ; H = 8-Oyo ; M = 300). The main product obtained as an oil when the alcoholic mother-liquor was evaporated contained the olefine (II) but the probable presence of ay-diphenyl-P-methylpropane (I) could not be proved owing to the impossibility of separating the dibenzyl which the oil contained.Action of Mugnes ium Ethyl Bromide on Tribenzylmethyl Bromide. -Tribenzylmethyl bromide (Schmerda loc. cit.) which is most conveniently prepared by saturating an ethereal solution of tri-benzylcarbinol with hydrogen bromide was treated in benzene solution with an excess of ethereal magnesium ethyl bromide ; magnesium bromide separated at once and a gas containing oiilp a vcry small proportion of olefine was evolved. After 2 hours, the reaction mixture was gently boiled for 1 hour. The product, isolated in the usual way was a very viscous oil ; froin its solution in alcohol colourless cubical crystals gradually separated. This compound after recrystallisation from alcohol melted a t 42-43" and was doubtless ay-diphenyl-$-benzyl-4a-propene (111) (coni-pare Orechov and Grinberg loc.cit.). Its identity was established by converting it into the crystalline dibromide m. p. 127-128", and also into tribenzylmethyl bromide with the aid of hydrogen bromide. When the alcoholic mot her-liquor from the crystalline olefine was evaporated there remained an oil from which hesa 94 TROTMAN PREPARATION OF QUATERNARY HYDROCBRBONS. benzylethane was isolated by converting the olefine into tribenzyl-methyl bromide (see above) and subsequently extracting the product with alcohol. From the alcoholic extract the hydrocarbon was deposited in crystals m. p. 82-83". Schmerda (loc. cit.) gives the m. p. 81-82" (Found C = 92.4; H = 797.Calc. for C44H42, Tetrabenzylmethane C( CH,*C,H,),.-Tribenzylmethy~ bromide, dissolved in benzene was added to an ethereal solution of excess of magnesium benzyl chloride the solvents were then evaporated, and the residue was heated at 100" for 2 hours. The product, isolated in the usual way was an oil from which tetrabenxyl-methane (yield 5%) was precipitated on the addition of alcohol. It separates from ether in cubic crystals m. p. 164' which are very sparingly soluble in alcohol or light petroleum but dissolve more easily in other organic solvents (Found C = 92.7; H = 7.5. C,,HZ8 requires C = 92.5; H = 7.5%). The main product was ay-diphenyl-p-benzyl-Aa-propene (111). p-Bromo-a-phenyl- p -methylpropane C,H,*C~*cMe,Br obtained by saturating dimethylbenzylcarbinol (Grignard Compt.rend., 1900 130 1324) with hydrogen bromide and washing the product with sodium carbonate solution and water is a colourless pleasant-smelling liquid which loses hydrogen bromide very readily when it is warmed and does not distil unchanged under 11 mm. (Found : Br = 36.4. CIoH,,Br requires Br = 376%). a-Phenyl-p-benzyl- p-methylpropane (CH,Ph),CMe,.-Reaction set in a t once when the preceding bromide (1 mol.) dissolved in ether was added to magnesium benzyl chloride (2 mols.); after 4 hours the reaction mixture was boiled gently for 2 hours. The product isolated in the usual way consisted of an oil which was separated by distillation into a-phenyl- p-methyl-A,-propene, b. p. 181" and a fraction of higher boiling point; the latter solidified when cold and crystallised from alcohol in prismatic needles m.p. 68-69" (Found C = 90.95; H = 9.0. C,,H,, requires C = 91.1 ; H = 8.9%). ~-Phenyl-p-benzyl-p-methylpropane boils a t 293-294" is readily soluble in most organic solvents, and has a somewhat sweet odour. BenxyZbenzoy1acetone.-The sodium derivative of benzoylacetone, prepared from its constituents in ether was isolated and boiled for 1 hour with an excess of benzyl chloride the solution was filtered and the unchanged benzyl chloride removed by distillation under reduced pressure. From an alcoholic solution of the residual dark brown oil benxylbenxoylacetone was deposited in clusters of needle-shaped crystals m. p. 60-61" (yield 50%). The compound is insoluble in aqueous potassium hydroxide and gives no coloration C = 9246; H = 7.4%) ~ ~ 0 0 ~ AND LILLEY TRANSFORMATION OF 1 ~ ETC. 95 with ferric chloride (Found C = 80-6 ; H = 6.1. C1,Hl,O, requires C = 80.95; H = 6.35%). When an alcoholic solution of benzylbenzoylacetone containing sodium ethoxide and ethyl bromide is kept at the ordinary temperature for 24 hours sodium bromide separates but the product is mainly w-benzylacetophenone. The author desires t o express his thanks to Professor F. S. Kipping F.R.S. for suggesting this research and for his interest in its progress. UNIVERSITY COLLEGE NOTTIKCHAM. [Received August 29th 1924.

ISSN:0368-1645    

DOI:10.1039/CT9252700088

出版商:RSC    

年代:1925

数据来源: RSC

摘要:

~ ~ 0 0 ~ AND LILLEY TRANSFORMATION OF 1 ~ ETC. 95 XVI.-Transformation of Mandelonitril e to M and el o -isonitrile. By CHARLES EDXUND WOOD and HAROLD SAMUEL LILLEY. MANDELONITRILE which has been. kept for some time becomes viscous and in some cases deposits a dark yellow solid owing to transformation of the normal nitrile to the iso-form; such material gives a poor yield (50%) of mandelic acid on hydrolysis. The rate of change of the nitrile to the iso-form is variable and depends on the purity of the potassium cyanide used in its prepar-ation. Crude commercial potassium cyanide gives products which remain clear for a long period (4-5 days) but 95yo potassium cyanide (Poulenc Freres) yields a nitrile in which the rate of change is much greater. The following results show the maximum observed rate of change with time in the nitrile and the corresponding reduc-tion in the yield of mandelic acid :-Time (days) ............0 0.25 0.5 0-75 1.0 2-0 3.0 4-0 yo Yield of acid ...... 94.6 91.0 86.5 82.0 78.1 65.0 56.4 50.3 The yields of acid obtained do not correspond with the corn-position of the mixture hydrolysed owing to a reversion of the is0 to the normal form under the conditions of hydrolysis. The results indicate that to give the best yield of acid the nitrile should be rapidly separated and hydrolysed (compare Pape Chem. Ztg. 1896, The change of the nitrile on standing is continuous no reaction product other than the yellow solid appears to be formed and a nearly theoretical yield of the isonitrile is ultimately obt~iiied.The reversibility of the reaction is indicated by the hydrolysis of the pure isonitrile which yields 38% of mandelic acid. A similar case is that of the cyclohexane analogue of mandelo-nitrile. The colourless oily hexahydrobenzaldehydecyanohydrin 20 90) 96 WOOD AND LILLEY TRANSFORMATION OF (Zelinsky and Gutt Ber. 1908 41 2677) becomes dark and viscous on standing and when hydrolysed gives as main product a dark brown tar and little hexahydromandelic acid. Investigation of the tar showed that the isonitrile was present in the product hydrolysed. E x P E R I M E N T A L . Fornzation of Mandeloisonitrile (a-liydroxy6enzylcarbylamine) from Mai2deZonitriZe.-Mandelonitrile on keeping deposits mandeloiso-nitrile as a yellow solid which after crystallisation from chloroform, melts a t 196" (corr.) (Found N = 10.7; 11.1 = 139 in chloroform, 136 in carbon tetrachloride 130 in camphor.Calc. N = 10.6y0; M = 133). The isonitrile is fairly soluble in alcohol ether or benzene more soluble in carbon tetrachloride and insoluble in water. It darkens on standing in air is not attacked by alkali, but is rapidly decomposed by dilute or concentrated mineral acids. With concentrated sulphuric acid it gives a bright green colour, whereas the normal nitrile gives a red one (Schiff Ber. 1899 32, 2701). The isonitrile structure was confirmed by reduction of the corn-pound to a secondary base oxidation to a carbimide and by examination of its hydrolytic products. This compound is distinct from the yellow solid m. p. 206", obtained by Minovici (Ber.1899,32,2206) by the action of hydrogen chloride on an ethereal solution of mandelonitrile for which the formula C,H,*CH(CN).C(oH)(CN).C,H was suggested. Even after repeated crystallisation our compound melted a t the temperature stated; moreover it differs from Minovici's compound in its solu-bility in alcohol and ether and in its inability to form a salt m. p. 222" with hydrochloric acid. Redaction.-The isonitrile (5 g.) was heated with a solution of 25 g. of " hydros " * in 100 C.C. of a mixture of equal parts of alcohol and water for 30 minutes on the water-bath the excess of hydros decomposed with warm hydrochloric acid and the liquid filtered into cone ent ra t ed aqueous ammonia when a- h y &ox y b e m y 1 -methylamine C,H5*CH(OH)*NH*CH, was precipitated.The crude product was purified by conversion to the ether-insoluble picrate decomposition of the salt with ammonia and crystallisation of the liberated base from petroleum (b. p. 60-80"). The low yield (50%) is probably due to sulphamation during reduc-tion. The base is a yellowish-grey solid m. p. 180" (decornp.), readily soluble in alcohol ether or mineral acids (Found N = 10.3. C,H,,ON requires N = 10-30/,). The nitrosoarnine prepared in the * Stannous chloride or ammonium eldoride and zinc dust may be employed MANDELONITRILE TO MANDELOZSONITRILE. 97 usual way is a yellow oil which solidifies on cooling. The picrate, prepared in ethereal solution is a dark yellow crystalline solid m. p. 238" (decomp.) (Found Picric acid = 62.1.C,H,,ON,C,H,O,N, requires 62.7%). Oxidation.-An ethereal or carbon tetrachloride solution of the isonitrile was heated with mercuric oxide (theor. quantity) on the water-bath for 1 hour. The dark red oil of disagreeable odour obtained on evaporating the filtered solution changed on standing, to a black amorphous mass probably a polymeride. The oily carbimide could not be purified for analysis but its structure was established by means of its reaction products. The oil was treated with gaseous ammonia in carbon tetrachloride solution n4en the red colour rapidly disappeared. The solution, on evaporation deposited almost colourless crystals of the carb-amide C,H,*CH(OH)*NH*CO*NH, m. p. 76" (Found N = 16.95. Theory requires N = 16.90/) readily soluble in water or alcohol, less soluble in benzene.The nitrate is fairly soluble in water but mercuric chloride precipitates from neutral aqueous solutions the slightly yellow almost insoluble mercurichloride, C,M,*CH (OH)*NH*CO*NH,,HgCl, (Found Eg = 45-58. The picrate prepared in ethereal solution was obtained as an orange crystalline solid easily soluble in ether or alcohol [Found : picric acid = 73.6. C6H,*C13( OH)*NH*CO*~\'H,,2C6H3O,N requires 7 3 *3 741. 1lydroZysis.-The isonitrile rapidly dissolved when treated on the water-bath with concentrated hydrochloric acid (5 parts). The small quantity of tarry matter produced was removed the filtrate distilled in steam and benzaldehyde extracted from the distillate, which then showed after neutralisation the characteristic reducing properties of formic acid.The benzaldehpde is produced by the decomposition of the primary base initially formed in the hydrolysis which may be represented as follows : OH*CHPh*NC + H*CO,H + OH-CHPh*P\rH + Ph*CHO+NH,. The amounts of formic acid and benzaldehyde found were not theoretical; in addition to the tarry matter deposited a certain amount of mandelic acid was extracted. By the hydrolysis of the pure isonitrile for 3 hours under the above conditions a 38% yield of mandelic acid was obtained. The mandelic acid was estimated by neutralisation of the filtered reaction product with ammonia followed by addition of zinc sulphate or cadmium chloride solution ; zinc or cadmium mandelate, Theory requires Hg = 45433%). VOL. CXXVII.98 SOPER THE HYDROLYSIS OF ACYLCHLOROAMINES IN WATER. precipitated on standing and shaking was filtered off dried and weighed. Small corrections (McKenzie J. 1899 75 969) were applied for the solubility of these salts. The use of the silver salt in the estimation is precluded owing to the presence of formic acid, and to a lesser extent benzoic acid. Hence the reaction normal nitrile -+ isonitrile is reversible proceeding under the conditions of hydrolysis from the is0 to the normal form (compare Guillemard, Compt. rend. 1907 144 141). Further when mixtures of the two forms are hydrolysed the yield of mandelic acid is greater than that corresponding with the initial composition of the mixture. Also on allowing the normal nitrile to stand the yield of acid on hydrolysis cannot fall below 38% although the change to the iso-form is complete.The observed tarry matter consists probably of compounds produced by the action of ammonia on the nitrile (SchifT Ber., 1899 32 2701). Hydrolysis of Hexahydromandeloisonitri1e.-The pure isonitrile has not been isolated but the normal form kept for 2 months and then hydrolysed gave large amounts of tarry matter and 20% of acid. The tarry product was polymerised hexahydrobenzaldehyde and its ammonia derivative for by treatment with dilute caustic soda solution followed by distillation in steam after acidification, the aldehyde was extracted from the distillate in quant'ity. Formic acid accompanied the viscous products. UNIVERSITY OF BIRMINGHAN, EDGBASTON. [Received October 2nd 1924.~ ~ 0 0 ~ AND LILLEY TRANSFORMATION OF 1 ~ ETC. 95 XVI.-Transformation of Mandelonitril e to M and el o -isonitrile. By CHARLES EDXUND WOOD and HAROLD SAMUEL LILLEY. MANDELONITRILE which has been. kept for some time becomes viscous and in some cases deposits a dark yellow solid owing to transformation of the normal nitrile to the iso-form; such material gives a poor yield (50%) of mandelic acid on hydrolysis. The rate of change of the nitrile to the iso-form is variable and depends on the purity of the potassium cyanide used in its prepar-ation. Crude commercial potassium cyanide gives products which remain clear for a long period (4-5 days) but 95yo potassium cyanide (Poulenc Freres) yields a nitrile in which the rate of change is much greater.The following results show the maximum observed rate of change with time in the nitrile and the corresponding reduc-tion in the yield of mandelic acid :-Time (days) ............ 0 0.25 0.5 0-75 1.0 2-0 3.0 4-0 yo Yield of acid ...... 94.6 91.0 86.5 82.0 78.1 65.0 56.4 50.3 The yields of acid obtained do not correspond with the corn-position of the mixture hydrolysed owing to a reversion of the is0 to the normal form under the conditions of hydrolysis. The results indicate that to give the best yield of acid the nitrile should be rapidly separated and hydrolysed (compare Pape Chem. Ztg. 1896, The change of the nitrile on standing is continuous no reaction product other than the yellow solid appears to be formed and a nearly theoretical yield of the isonitrile is ultimately obt~iiied.The reversibility of the reaction is indicated by the hydrolysis of the pure isonitrile which yields 38% of mandelic acid. A similar case is that of the cyclohexane analogue of mandelo-nitrile. The colourless oily hexahydrobenzaldehydecyanohydrin 20 90) 96 WOOD AND LILLEY TRANSFORMATION OF (Zelinsky and Gutt Ber. 1908 41 2677) becomes dark and viscous on standing and when hydrolysed gives as main product a dark brown tar and little hexahydromandelic acid. Investigation of the tar showed that the isonitrile was present in the product hydrolysed. E x P E R I M E N T A L . Fornzation of Mandeloisonitrile (a-liydroxy6enzylcarbylamine) from Mai2deZonitriZe.-Mandelonitrile on keeping deposits mandeloiso-nitrile as a yellow solid which after crystallisation from chloroform, melts a t 196" (corr.) (Found N = 10.7; 11.1 = 139 in chloroform, 136 in carbon tetrachloride 130 in camphor.Calc. N = 10.6y0; M = 133). The isonitrile is fairly soluble in alcohol ether or benzene more soluble in carbon tetrachloride and insoluble in water. It darkens on standing in air is not attacked by alkali, but is rapidly decomposed by dilute or concentrated mineral acids. With concentrated sulphuric acid it gives a bright green colour, whereas the normal nitrile gives a red one (Schiff Ber. 1899 32, 2701). The isonitrile structure was confirmed by reduction of the corn-pound to a secondary base oxidation to a carbimide and by examination of its hydrolytic products. This compound is distinct from the yellow solid m.p. 206", obtained by Minovici (Ber. 1899,32,2206) by the action of hydrogen chloride on an ethereal solution of mandelonitrile for which the formula C,H,*CH(CN).C(oH)(CN).C,H was suggested. Even after repeated crystallisation our compound melted a t the temperature stated; moreover it differs from Minovici's compound in its solu-bility in alcohol and ether and in its inability to form a salt m. p. 222" with hydrochloric acid. Redaction.-The isonitrile (5 g.) was heated with a solution of 25 g. of " hydros " * in 100 C.C. of a mixture of equal parts of alcohol and water for 30 minutes on the water-bath the excess of hydros decomposed with warm hydrochloric acid and the liquid filtered into cone ent ra t ed aqueous ammonia when a- h y &ox y b e m y 1 -methylamine C,H5*CH(OH)*NH*CH, was precipitated.The crude product was purified by conversion to the ether-insoluble picrate decomposition of the salt with ammonia and crystallisation of the liberated base from petroleum (b. p. 60-80"). The low yield (50%) is probably due to sulphamation during reduc-tion. The base is a yellowish-grey solid m. p. 180" (decornp.), readily soluble in alcohol ether or mineral acids (Found N = 10.3. C,H,,ON requires N = 10-30/,). The nitrosoarnine prepared in the * Stannous chloride or ammonium eldoride and zinc dust may be employed MANDELONITRILE TO MANDELOZSONITRILE. 97 usual way is a yellow oil which solidifies on cooling. The picrate, prepared in ethereal solution is a dark yellow crystalline solid m. p. 238" (decomp.) (Found Picric acid = 62.1.C,H,,ON,C,H,O,N, requires 62.7%). Oxidation.-An ethereal or carbon tetrachloride solution of the isonitrile was heated with mercuric oxide (theor. quantity) on the water-bath for 1 hour. The dark red oil of disagreeable odour obtained on evaporating the filtered solution changed on standing, to a black amorphous mass probably a polymeride. The oily carbimide could not be purified for analysis but its structure was established by means of its reaction products. The oil was treated with gaseous ammonia in carbon tetrachloride solution n4en the red colour rapidly disappeared. The solution, on evaporation deposited almost colourless crystals of the carb-amide C,H,*CH(OH)*NH*CO*NH, m. p. 76" (Found N = 16.95. Theory requires N = 16.90/) readily soluble in water or alcohol, less soluble in benzene.The nitrate is fairly soluble in water but mercuric chloride precipitates from neutral aqueous solutions the slightly yellow almost insoluble mercurichloride, C,M,*CH (OH)*NH*CO*NH,,HgCl, (Found Eg = 45-58. The picrate prepared in ethereal solution was obtained as an orange crystalline solid easily soluble in ether or alcohol [Found : picric acid = 73.6. C6H,*C13( OH)*NH*CO*~\'H,,2C6H3O,N requires 7 3 *3 741. 1lydroZysis.-The isonitrile rapidly dissolved when treated on the water-bath with concentrated hydrochloric acid (5 parts). The small quantity of tarry matter produced was removed the filtrate distilled in steam and benzaldehyde extracted from the distillate, which then showed after neutralisation the characteristic reducing properties of formic acid.The benzaldehpde is produced by the decomposition of the primary base initially formed in the hydrolysis which may be represented as follows : OH*CHPh*NC + H*CO,H + OH-CHPh*P\rH + Ph*CHO+NH,. The amounts of formic acid and benzaldehyde found were not theoretical; in addition to the tarry matter deposited a certain amount of mandelic acid was extracted. By the hydrolysis of the pure isonitrile for 3 hours under the above conditions a 38% yield of mandelic acid was obtained. The mandelic acid was estimated by neutralisation of the filtered reaction product with ammonia followed by addition of zinc sulphate or cadmium chloride solution ; zinc or cadmium mandelate, Theory requires Hg = 45433%).VOL. CXXVII. 98 SOPER THE HYDROLYSIS OF ACYLCHLOROAMINES IN WATER. precipitated on standing and shaking was filtered off dried and weighed. Small corrections (McKenzie J. 1899 75 969) were applied for the solubility of these salts. The use of the silver salt in the estimation is precluded owing to the presence of formic acid, and to a lesser extent benzoic acid. Hence the reaction normal nitrile -+ isonitrile is reversible proceeding under the conditions of hydrolysis from the is0 to the normal form (compare Guillemard, Compt. rend. 1907 144 141). Further when mixtures of the two forms are hydrolysed the yield of mandelic acid is greater than that corresponding with the initial composition of the mixture. Also on allowing the normal nitrile to stand the yield of acid on hydrolysis cannot fall below 38% although the change to the iso-form is complete. The observed tarry matter consists probably of compounds produced by the action of ammonia on the nitrile (SchifT Ber., 1899 32 2701). Hydrolysis of Hexahydromandeloisonitri1e.-The pure isonitrile has not been isolated but the normal form kept for 2 months and then hydrolysed gave large amounts of tarry matter and 20% of acid. The tarry product was polymerised hexahydrobenzaldehyde and its ammonia derivative for by treatment with dilute caustic soda solution followed by distillation in steam after acidification, the aldehyde was extracted from the distillate in quant'ity. Formic acid accompanied the viscous products. UNIVERSITY OF BIRMINGHAN, EDGBASTON. [Received October 2nd 1924.

ISSN:0368-1645    

DOI:10.1039/CT9252700095

出版商:RSC    

年代:1925

数据来源: RSC

摘要:

98 SOPER THE HYDROLYSIS OF ACYLCHLOROAMINES IN WATER. XVII.-The Hydrolysis of Acylchloroamines in Water. By FREDERICK GEORGE SOPER. THE slight extent of the reversible hydrolysis of chloroamines in water (Orton and Gray Brit. Assoc. Rep. 1913 135) :NCI + H,O + :NH + HCIO renders its quantitative study difficult, since it necessitates direct estimation of the concentrations of the hydrolysis products (as opposed to their estimation by difference), and further neither of the hydrolysis products is a sufficient'ly good electrolyte to allow of the application of sensitive electrical methods. Moreover the one partition method available that of estimation of the hypochlorous acid by distillation (Orton and Gray Zoc. cit.) is as will be shown later complicated by the fact that the chloroamine is itself volatile.I n order to increase the hydrolysis of a chloroamine and thu SOPER THE HYDROLYSIS OF ACYLCHLOROAMINES I N WATER. 99 allow of the general application of methods available for the examination of homogeneous equilibrium the concentration of one of the products of the hydrolysis may be still further reduced by its reversible combination with some other substance the conditions of equilibrium with which are known. Substances considered for this purpose were hydrochloric acid interacting with the hypo-chlorous acid to form chlorine or an alkali forming hypochlorite. Both these substances however may cause secondary reactions, the chlorine forming C-chlorinated products whilst the alkali may cause hydrolysis of and to a certain extent may form complexes with the acylamine present.The use of another amine which forms reversibly a chloroamine with the hypochlorous acid present, is free from the objections associated with the use of hydrochloric acid or an allrali but it demands a knowledge of the hydrolysis equilibrium of one chloroamine beforc calculation of other hydrolysis constants becomes possible. p-Toluenesulphondichloroamide was selected as this standard chloroamine for reasons that have already been given (J. 1924 125 1899). When the hydrolysis of the chloroamine under investigation has been displaced the method of examination employed is of a solu-bility type and depends on the following considerations. p-Toluene-sulphondichloroamide dissolves in solutions of anilides with the formation of the corresponding chloroamines : C ,H 7.S O,*NHCl C,H,*SO,*NCI + II@' BrAcKH 1 + HCIO -7 L4rllcKC1.1. C,H *S O,*NH, Hypochlorous acid is removed by combination with the added anilide and causes further solution and hydrolysis of the sulphondi-chloroamide. From the increase in the solubility of the sulphon-dichloroamide as measured by the thiosulphate titre of the saturated solution the concentrations of the chloroamines formed in solution can be calculated. This " solubility " of the sulphondichloroamide n a solution of an anilide is made up of the concentrations of the dichloroamide the monochloroamide the chloroamine formed from the anilide and the hypochlorous acid. If a is the equilibrium concentration of the dichloroamide in millimols.in solution T the t,hiosulphate titre expressed as milliequivalents per litre then [C,H,-SO,*NHCI] + [ArAcNCl] + [HCIO] = (T - 4a)/2, or neglecting the [HClO] for reasons discussed below and denoting the concentration of the chloroamine ArAcNCl formed from d millimols. of anilide by x and that of the sulphonmonochloroamide by b, ( 1 ) .c -/- I = ( T - 4CL)/2 - x . . . . E 100 SOPER THE HYDROLYSIS OB ACYLCHLOROAMINES M WATER. It is known that (J. 1924,125 1906) at 25", [C7H7*S02*NHCl][HC10] = 8.0 x 10-4 [C,H,*S02*NCl,] = 6-27 x 10-5 . . . . . (2) and [C7H7*S0,*NH2][HCIO] = 4-9 x 10-5 [C,H,-S02*NHCl] (3) while from the general conditions of equilibrium [C,H,*SO2*NH2] = x - 6 . . . . (4) Combining (3) and (4), eliminating HClO from (Z), and eliminating x from (l), [HClO](x - b)/b = 4.9 x 10-5; (X - b)/b2 = 0.781 ; 0*781b2+ 2b - S = O .. . . . (5) This equation allows of the calculation in millimols. of b of the concentration of hypochlorous acid from (2) and of that of the chloroamine formed from (1). The hydrolysis constant is given by the expression [HClO][anilide]/[chloroamine] = [HClO]x/(d - x). The omission of the hypochlorous acid concentration from equa-tion (1) is permissible because the progressive hydrolysis of the dichloroamide caused by combination between the anilide and hypochlorous acid results in an increase in the concentration of its hydrolysis product C,H,*SO,*NHCl and hence in a diminution of the concentration of the hypochlorous acid initially only 0.0079 millimols.since in presence of one solid phase wix. the sulphondi-chloroamide the expression [HC10][C,H,*S02*NHC1] is constant. It is this reduction in the concentration of the hypochlorous acid that makes the method of extensive use. For since the equilibrium concentration of the amine is measured by a difference d - x it is necessary that x(= [ArAcNCl]) should not approach d (the concentration of the anilide initially present) too closely in value, i.e. the hydrolysis of the chloroamine should always be extensive. This is effected by the automatic diminution of the concentration of the hypochlorous acid for the smaller the hydrolysis constant of the chloroamine (and therefore the greater the need for the dis-placement of its hydrolysis equilibrium) the smaller does the concentration of hypochlorous acid become due to the accumulation of the sulphonmonochloroamide in the system.The hydrolysis constants of the chloroamines of acetanilide, formanilide aceto-o- and -p-toluidides and 0- and p-chloroacet-anilides have been determined. The details of one determinat'ion and the mean values of Kh in the other cases are given in Table I SOPER THE IfYDROLYSIS O F ACYLCHLOROAMINES M WATER. 101 TABLE I. N-Chloroacetanilide. Conc. of Thio. titro anilide of sat. soh. b in ~t in HClO x 103. x lo?. M x 10-3. 171 x 10-3. x x 10-7. ILX 107. 0-511.1 O*ODGN 0.161 0.152 3.89 6.80 1.0 1.322 0.232 0.274 2.70 7-15 2.0 1.784 0.317 0.420 1.8s 7-44 5.0 2.734 0.506 0.706 1.24 7.53 &an 7.27 K ~ X 107. I < ~ x 107. N-Cliloroformanilide .........2.4 No-Dichloroacetanilide ...... 6.0 X-Chloroaceto-o-toluidide ... 3.3 ~p-Dichloroacetanilide ...... 150 AN-Chloroaceto-p-toluidido ... 22.0 I n Table 11 the hydrolysis constants of the chloroamines exatmined are compared with the ionisation constants of similarly substituted compounds and with the equilibrium constants of the hydrolysis of anilides into amine and acid (MacBain and Davies 2. p!~yskd. Cliem. 1911 78 369). TABLE IJ. 1 /IL. I</& (c:lloro- 1 (benzoic Group. aniinc). I< (anilide). h'b (amine). (phcnol). acid). €I ............ 0 . 7 3 ~ 4.1 4 4 x 10-10 7 . 3 x 105 113.7 x 103 o-CH ......... 0.33 1.7 3.3 - 8.3 p-CII ......... 2.8 6.4 20.0 - 19.4 c-C1 ............ 0.69 0.14 - 1.3 0.76 pC1 ............ 1.5 2-2 1-3 2.5 10.7 The relative effects of the o-methyl and the p-methyl goups 011 the hydrolysis of the chloroamines and the ionisation of the amines aro almost identical as are also the relative effects of the o-chlorine and the p-chlorine atoms on the chloroamines and the phenols.The iiifluciice of the chlorine atom compared with that of the hydrogen atQru on the hydrolysis of the chloroamines does not however, appear to be similar to its influence on the ionisation of other SlZl)EIcZi?CCS. Thc volatility cf the chloroamine when its aqueous solutions are subjected to distillation at 25" causes the estimate of the percentago of free hypochlorous acid in an aqueous solution of N-chloroacet -anilide (Orton and Gray loc. cit.) to be high. Thus on addition of successive quantities of acetanilide to the aqueous chloroamine solution the ratio of the thiosulphate titre of the distillate to that of the original solution decreases to a minimum value of 0.20, independent of the coiicentration of the chloroamine solution.This behaviour is unlike that observed in the distillation of soclium hypochlorite in presence of excess of sodium hydroxide the titre oi the distillate then falling to zero. The thiosulphate titre of the distillate obtained from a 0.1 yo solution of N-chloroacetanilidc was found (Orton and Gray Zoc. cit.) to be O-O0368N which afte 102 SOPER THE HYDROLYSIS OF ACYLCHLOROAMINES IN WATER. allowing for the volatility of the chloroamine corresponds to a concentration of 0-00016 mol. of hypochlorous acid in the distillate or 5.94 x 10-5 mol.of hypochlorous acid in the chloroamine solution. The calculated hydrolysis constant of N-chloroacetanilide is then 6.0 x 10-7 a satisfactory confirmation of the value obtained by the solubility method (7.3 x 10-7). The limited solubility of anilides in water has prevented extensive examination in this medium. The primary object has been the determination of a few hydrolysis constants as a basis for testing theories of the mechanism of the chloroamine-chloroanilide trans-formation. The effect of substituents on the hydrolysis is being examined in other media. E x P E R I M E N T A L. Betermination of the Solubility .-The determination of the solu-bility of p-toluenesulphondichloroamide in solutions of anilides was carried out in the same way as that in aqueous solutions of p-toluene-sulphonamide (Soper loc.cit.). The sohtion attained a practically constant titre after 3-6 hours. Since the chloroamines of anilides decompose slowly in water owing to hydrolysis of the anilides to anilines (Orton and Gray loc. cit.) one molecule of which removes a number of molecules of hypochlorous acid the concentration of hypochlorous acid falls and since the expression [HC10][C7H7*S0,*NHCI] is constant in presence of the solid dichloroamide the concentration of the monochloroamide increases. The net result is that the titre of the solution slowly increases on standing (i.e. after 24 hours). The following figures obtained during the solution of the dichloroamide in a solution'of acetanilide (2M x lO-3) are typical.Time ..................... 2 4 6 12 24 hours Titre of 20 C.C. in N/500-thio. ......... 13-71 17.80 17-86 17-92 18.05 C.C. D,istillat.ion of Aqueous Chloroamine Solutions.-The diagram of the apparatus used has been given elsewhere (Soper J. 1924,125,2230). The thiosulphate titre of the solutions was taken before and after the distillation. There was no appreciable change during this process. No further decrease in the ratio of the titre of the dis-tillate to that of the solution was obtained on increasing the acet-anilide concentration from 0*02M to 0.05M. I n conclusion I wish to express my thanks UNIVERSITY COLLEGE OF NORTH WALES, Orton F.R.S. for his interest in this work. BANGOR. [Received, to Professor K. J. P. September 27th 1924. 98 SOPER THE HYDROLYSIS OF ACYLCHLOROAMINES IN WATER.XVII.-The Hydrolysis of Acylchloroamines in Water. By FREDERICK GEORGE SOPER. THE slight extent of the reversible hydrolysis of chloroamines in water (Orton and Gray Brit. Assoc. Rep. 1913 135) :NCI + H,O + :NH + HCIO renders its quantitative study difficult, since it necessitates direct estimation of the concentrations of the hydrolysis products (as opposed to their estimation by difference), and further neither of the hydrolysis products is a sufficient'ly good electrolyte to allow of the application of sensitive electrical methods. Moreover the one partition method available that of estimation of the hypochlorous acid by distillation (Orton and Gray Zoc. cit.) is as will be shown later complicated by the fact that the chloroamine is itself volatile.I n order to increase the hydrolysis of a chloroamine and thu SOPER THE HYDROLYSIS OF ACYLCHLOROAMINES I N WATER. 99 allow of the general application of methods available for the examination of homogeneous equilibrium the concentration of one of the products of the hydrolysis may be still further reduced by its reversible combination with some other substance the conditions of equilibrium with which are known. Substances considered for this purpose were hydrochloric acid interacting with the hypo-chlorous acid to form chlorine or an alkali forming hypochlorite. Both these substances however may cause secondary reactions, the chlorine forming C-chlorinated products whilst the alkali may cause hydrolysis of and to a certain extent may form complexes with the acylamine present.The use of another amine which forms reversibly a chloroamine with the hypochlorous acid present, is free from the objections associated with the use of hydrochloric acid or an allrali but it demands a knowledge of the hydrolysis equilibrium of one chloroamine beforc calculation of other hydrolysis constants becomes possible. p-Toluenesulphondichloroamide was selected as this standard chloroamine for reasons that have already been given (J. 1924 125 1899). When the hydrolysis of the chloroamine under investigation has been displaced the method of examination employed is of a solu-bility type and depends on the following considerations. p-Toluene-sulphondichloroamide dissolves in solutions of anilides with the formation of the corresponding chloroamines : C ,H 7.S O,*NHCl C,H,*SO,*NCI + II@' BrAcKH 1 + HCIO -7 L4rllcKC1.1. C,H *S O,*NH, Hypochlorous acid is removed by combination with the added anilide and causes further solution and hydrolysis of the sulphondi-chloroamide. From the increase in the solubility of the sulphon-dichloroamide as measured by the thiosulphate titre of the saturated solution the concentrations of the chloroamines formed in solution can be calculated. This " solubility " of the sulphondichloroamide n a solution of an anilide is made up of the concentrations of the dichloroamide the monochloroamide the chloroamine formed from the anilide and the hypochlorous acid. If a is the equilibrium concentration of the dichloroamide in millimols.in solution T the t,hiosulphate titre expressed as milliequivalents per litre then [C,H,-SO,*NHCI] + [ArAcNCl] + [HCIO] = (T - 4a)/2, or neglecting the [HClO] for reasons discussed below and denoting the concentration of the chloroamine ArAcNCl formed from d millimols. of anilide by x and that of the sulphonmonochloroamide by b, ( 1 ) .c -/- I = ( T - 4CL)/2 - x . . . . E 100 SOPER THE HYDROLYSIS OB ACYLCHLOROAMINES M WATER. It is known that (J. 1924,125 1906) at 25", [C7H7*S02*NHCl][HC10] = 8.0 x 10-4 [C,H,*S02*NCl,] = 6-27 x 10-5 . . . . . (2) and [C7H7*S0,*NH2][HCIO] = 4-9 x 10-5 [C,H,-S02*NHCl] (3) while from the general conditions of equilibrium [C,H,*SO2*NH2] = x - 6 . . . . (4) Combining (3) and (4), eliminating HClO from (Z), and eliminating x from (l), [HClO](x - b)/b = 4.9 x 10-5; (X - b)/b2 = 0.781 ; 0*781b2+ 2b - S = O .. . . . (5) This equation allows of the calculation in millimols. of b of the concentration of hypochlorous acid from (2) and of that of the chloroamine formed from (1). The hydrolysis constant is given by the expression [HClO][anilide]/[chloroamine] = [HClO]x/(d - x). The omission of the hypochlorous acid concentration from equa-tion (1) is permissible because the progressive hydrolysis of the dichloroamide caused by combination between the anilide and hypochlorous acid results in an increase in the concentration of its hydrolysis product C,H,*SO,*NHCl and hence in a diminution of the concentration of the hypochlorous acid initially only 0.0079 millimols.since in presence of one solid phase wix. the sulphondi-chloroamide the expression [HC10][C,H,*S02*NHC1] is constant. It is this reduction in the concentration of the hypochlorous acid that makes the method of extensive use. For since the equilibrium concentration of the amine is measured by a difference d - x it is necessary that x(= [ArAcNCl]) should not approach d (the concentration of the anilide initially present) too closely in value, i.e. the hydrolysis of the chloroamine should always be extensive. This is effected by the automatic diminution of the concentration of the hypochlorous acid for the smaller the hydrolysis constant of the chloroamine (and therefore the greater the need for the dis-placement of its hydrolysis equilibrium) the smaller does the concentration of hypochlorous acid become due to the accumulation of the sulphonmonochloroamide in the system.The hydrolysis constants of the chloroamines of acetanilide, formanilide aceto-o- and -p-toluidides and 0- and p-chloroacet-anilides have been determined. The details of one determinat'ion and the mean values of Kh in the other cases are given in Table I SOPER THE IfYDROLYSIS O F ACYLCHLOROAMINES M WATER. 101 TABLE I. N-Chloroacetanilide. Conc. of Thio. titro anilide of sat. soh. b in ~t in HClO x 103. x lo?. M x 10-3. 171 x 10-3. x x 10-7. ILX 107. 0-511.1 O*ODGN 0.161 0.152 3.89 6.80 1.0 1.322 0.232 0.274 2.70 7-15 2.0 1.784 0.317 0.420 1.8s 7-44 5.0 2.734 0.506 0.706 1.24 7.53 &an 7.27 K ~ X 107. I < ~ x 107. N-Cliloroformanilide .........2.4 No-Dichloroacetanilide ...... 6.0 X-Chloroaceto-o-toluidide ... 3.3 ~p-Dichloroacetanilide ...... 150 AN-Chloroaceto-p-toluidido ... 22.0 I n Table 11 the hydrolysis constants of the chloroamines exatmined are compared with the ionisation constants of similarly substituted compounds and with the equilibrium constants of the hydrolysis of anilides into amine and acid (MacBain and Davies 2. p!~yskd. Cliem. 1911 78 369). TABLE IJ. 1 /IL. I</& (c:lloro- 1 (benzoic Group. aniinc). I< (anilide). h'b (amine). (phcnol). acid). €I ............ 0 . 7 3 ~ 4.1 4 4 x 10-10 7 . 3 x 105 113.7 x 103 o-CH ......... 0.33 1.7 3.3 - 8.3 p-CII ......... 2.8 6.4 20.0 - 19.4 c-C1 ............ 0.69 0.14 - 1.3 0.76 pC1 ............ 1.5 2-2 1-3 2.5 10.7 The relative effects of the o-methyl and the p-methyl goups 011 the hydrolysis of the chloroamines and the ionisation of the amines aro almost identical as are also the relative effects of the o-chlorine and the p-chlorine atoms on the chloroamines and the phenols.The iiifluciice of the chlorine atom compared with that of the hydrogen atQru on the hydrolysis of the chloroamines does not however, appear to be similar to its influence on the ionisation of other SlZl)EIcZi?CCS. Thc volatility cf the chloroamine when its aqueous solutions are subjected to distillation at 25" causes the estimate of the percentago of free hypochlorous acid in an aqueous solution of N-chloroacet -anilide (Orton and Gray loc. cit.) to be high. Thus on addition of successive quantities of acetanilide to the aqueous chloroamine solution the ratio of the thiosulphate titre of the distillate to that of the original solution decreases to a minimum value of 0.20, independent of the coiicentration of the chloroamine solution.This behaviour is unlike that observed in the distillation of soclium hypochlorite in presence of excess of sodium hydroxide the titre oi the distillate then falling to zero. The thiosulphate titre of the distillate obtained from a 0.1 yo solution of N-chloroacetanilidc was found (Orton and Gray Zoc. cit.) to be O-O0368N which afte 102 SOPER THE HYDROLYSIS OF ACYLCHLOROAMINES IN WATER. allowing for the volatility of the chloroamine corresponds to a concentration of 0-00016 mol. of hypochlorous acid in the distillate or 5.94 x 10-5 mol.of hypochlorous acid in the chloroamine solution. The calculated hydrolysis constant of N-chloroacetanilide is then 6.0 x 10-7 a satisfactory confirmation of the value obtained by the solubility method (7.3 x 10-7). The limited solubility of anilides in water has prevented extensive examination in this medium. The primary object has been the determination of a few hydrolysis constants as a basis for testing theories of the mechanism of the chloroamine-chloroanilide trans-formation. The effect of substituents on the hydrolysis is being examined in other media. E x P E R I M E N T A L. Betermination of the Solubility .-The determination of the solu-bility of p-toluenesulphondichloroamide in solutions of anilides was carried out in the same way as that in aqueous solutions of p-toluene-sulphonamide (Soper loc.cit.). The sohtion attained a practically constant titre after 3-6 hours. Since the chloroamines of anilides decompose slowly in water owing to hydrolysis of the anilides to anilines (Orton and Gray loc. cit.) one molecule of which removes a number of molecules of hypochlorous acid the concentration of hypochlorous acid falls and since the expression [HC10][C7H7*S0,*NHCI] is constant in presence of the solid dichloroamide the concentration of the monochloroamide increases. The net result is that the titre of the solution slowly increases on standing (i.e. after 24 hours). The following figures obtained during the solution of the dichloroamide in a solution'of acetanilide (2M x lO-3) are typical. Time ..................... 2 4 6 12 24 hours Titre of 20 C.C. in N/500-thio. ......... 13-71 17.80 17-86 17-92 18.05 C.C. D,istillat.ion of Aqueous Chloroamine Solutions.-The diagram of the apparatus used has been given elsewhere (Soper J. 1924,125,2230). The thiosulphate titre of the solutions was taken before and after the distillation. There was no appreciable change during this process. No further decrease in the ratio of the titre of the dis-tillate to that of the solution was obtained on increasing the acet-anilide concentration from 0*02M to 0.05M. I n conclusion I wish to express my thanks UNIVERSITY COLLEGE OF NORTH WALES, Orton F.R.S. for his interest in this work. BANGOR. [Received, to Professor K. J. P. September 27th 1924.

ISSN:0368-1645    

DOI:10.1039/CT9252700098

出版商:RSC    

年代:1925

数据来源: RSC

摘要:

THE ACTION O F AMINES ON SEMICARBAZONES. PART 11. 103 XVII1.-The Action of Amines on Semicarbaxones. Part I I . By FQRSYTH Jilni~s WrLsoN and ARCHIBALD BARCLAY CRAWFORD. Ie continuation of previous work (J. 1922 121 866) we have found that 1-menthylamine reacts normally with acetonesemicarbazone to give active acelor,e-6-)~e?zthylse~~car~a~o~2e CMe,:N*NH*CO*NH + C‘,,H,g*NIP2 = NH + C11,7e,:N*NH*C0.PU’H.C1,H1g from which 6-menthyZse?.iicurba,~ide7 N~2*NH*CO*NI-I*C,o~Ilg and its hydro-chloride have been obtained. These compounds including the beiizaldehyde derivative are laevorotatory in alcoholic solution. The action of esters of amino-acids on semicarbazones was next investigated. Ethyl m-aminobenzoate and acetonesemicarbazone re-acted normally on heating C~e,:PU’*NH*CO*nTH2+NH,=C6H,*CO,E t = CMe2:N*NH*C0.NH.CGH,.C0,Et + NH, giving acetone- 6- 3 - c a d -etho~~phenylsemicarbcczorze in good yield from which 6-3-carbethoxy-phe?zylsemicarbax ide NH,*KH*C O*NH*C 6H4*C O,Et and its hydro-chloride were obtained.Ethyl paminobenzoate also reacted normally with benzophenone- and acetone-semicarbazone (in the latter case with poor yield) giving the ketonic 6-4-carbetholry-phenylsemicarbaxones CR,:nT*NH*CO*NH*C6H4*Co,Et both of which underwent complete decomposition when hydrolysis was attempted. In view of what follows care was taken in all these cases to use dry materials and dry solvents so as to avoid any risk of hydrolysis. The ester, on heating with benzophenonesemicarbazone (molecular quantities), gave 3-diphe~aylnzethylelzeaminotetr~hydro~~~ina~oli~e-2 4-dioize (I), Methyl o-aminobenzoate reacted somewhat differently.this on hydroIysis with acid giving benzophenone and 3-amino -tetrahydroyuinazoline-2 4-dione (11) C6H4~c0-~.NH2 YH*CO de-scribed by Kunckell (Ber. 1910 43 1021). In addition methyl alcohol benzophenonecarbohydrazone (111) tetrahydroquinazoline-2 4-dione (IV) and small quantities of diphenyl ketazine and hydrazodicarbonamide were produced. Borsche and Merkwitz have shown (Ber. 1904 37 3177) that benzophenonesemicarbazone on heating gives (111) presumably by interaction with the hydrazone CPh,:N*NH*CO*NH +-NH,-N:CPh = NH + CO(NH*N:CPh,) (111) the hydrazone appar 104 WILSON AND CRAWFORD : ently resulting from the semicarbazone by loss of cyanic acid, CPh,:N*NH*CO*NH = CPh,*N*NH + HNCO.I n the present in-stance the formation of (111) and (IV) the latter investigated, among others by Griess (Ber. 1869 2 416) can be explained as resulting from the ester and the semicarbazone, which then gives (111) and (IV) the diphenyl ketazine and the hydrazodicarbonamide being produced by the decomposition of the semicarbazone as shown by Borsche and Merkwitz, gCPh,:N*NH*CO*NH = CPh,:N*N:CPh +NH,*CO*NH*NH*CO*NH2. The interaction of acetonesemicarbazone with methyl o-amino-benzoate proceeded quite abnormally as before molecular quan-tities were employed and care was taken t o use dry solvents. The acetone derivative (V) expected from the scheme CMe,:N-NH*CO*NH, was not produced; the products were ammonia methyl alcohol, 3-aminotetrahydroquinazoline-2 4-dione (11) (the chief solid pro-duct amounting to about half of the semicarbazone used) a con-siderable amount of dimethyl ketazine small quantities of tetra-hydroquinazoline-2 4-dione (IV) and of a substance m.p. 420", which could not be identified; it is noteworthy that no hydrazo-dicarbonamide was formed. It may be assumed that (V) 3-iso~o(pylideneam~~otetra~ydro~u~nazolin~e-2 4-dione (prepared by another method and described below) is fkst produced with formation of ammonia and methyl alcohol and that it may react further in one of two ways. It may decompose 2s A different explanation is necessary in this case. follows , A substance of the composition represented by (VI) was not obtained (the unidentified substance of m.p. 420" giving quite different analytical results) ; moreover it was found as mentioned later that (V) did not behave in this way on heating. The other possibility and the one which we regard as the probable explan-ation is that (V) reacts with acetonesemicarbazone to give dimethyl ketazine and the intermediate carbamino-derivative (VII) THE ACTION OF AMMES ON SEMICARBAZONES. PART 11. 105 C H <NHo?o + NH,*CO*NH*N:CMe = CiUe,:N*N:CMe + CQ -N*NH*CO*NH,, which then by loss of cyanic acid gives (11). Borsche and Merkwitz (Zoc. cit.) apparently assume loss of cyanic acid in a similar case. Auwers and others (Annden 1924 435, 277) have shown that tetrahydroindazole-2-carbonamide loses cyanic acid (identified as cyanuric acid) on heating a t 160°, CO-N*N:CMe, C6H4<NH'Y 0 (VSI.) C,H4<gH>NCO*NH -+ C6H,KN_>NH.A H Similarly Posner (Ber., RC :CH* R 1901,34,3976) found that compounds of the type m2,co.+ (R = akyl) obtained from semicarbazide and diketones give with silver nitrate the derivative R?:CH*!?R when R = Ph, A€"N the carbamino-compound is not formed on heating the reactants, the product being 3 5-diphenylpyrazole. The substance (IV) probably results together with (11) by interaction of (VII) with the ester : To test. these explanations (V) was prepared by boiling ordinary undried acetone with (11); curiously enough dried acetone did not react even on prolonged boiling 8 p-dichloropropane also proved unreactive. This substance (V) was easily hydrolysed into the parent compounds by water and by hot solvents containing water.It was scarcely affected by heating even at 220" for 2& hours it charred slightly and there was a slight odoixr of dimethyl ketazine, but most of the substance was recovered unchanged. Molecular quantities of (V) and acetonesemicarbazone on heating gave dimethyl ketazine and (11) this being in accordance with the explanation advanced by us. This work will be continued. E x F E R I 3lr E N T A L. 3-Bent7qlamine and Acetonesemicurbaxone.-The 1-menthylamine, prepased by the method of Beckmann (Annalen 1889 250 325) and of Wallach (ibid. 1893 276 327) wa8 distilled directly in a current of hydrogen into a polarimeter tube ; it gave [m] - 39-41' E 106 WILSON AND CRAWFORD : [Wallach records - 38.07"; Tutin and Kipping (J.1904 85 69) record - 39-92']. Equimolecular quantities previously heated to 165" were mixed and kept at this temperature for 15 minutes when solution with copious evolution of ammonia took place. The cooled melt dis-solved in a little alcohol was poured into dilute acetic acid the solid which separated dissolved completely in hot alcohol from which on cooling active acetone-8-menthylsemicarbazone was de-posited in clusters of small colourless needles m. p. 128" (Found : N = 16.62 16.73. C,,H2,0N requires N = 16.60 yo). 0.5024 Gram in 25 C.C. of absolute alcohol gave ar - 2.612" ( I = Z), whence [a]:" - 64.93". The substance was soluble in the usual organic solvents. Active 6-Menthylsemicarbaxide.-The semicarbazone was heated at 70" with Ilr-hydrochloric acid (5 parts) until completely dis-solved ; the residue obtained by evaporation under reduced pressure was recrystallised from alcohol which gave s-menthylsemicccrbazide hydrochloride as a gelatinous mass; after suction and washing with ether it assumed a fibrous apparently non-crystalline appearance and melted a t 203-204" (Found C1=14-02,14*22.C,,H,,ON,,HCl requires C1 = 14.22%). 0.5024 Gram in 25 C.C. of absolute alcohol gave a%' - 2.62" ( I = Z) whence [a]$" - 65-18". It was soluble in alcohol or hot water insoluble in ether or benzene and could not be obtained in a definitely crysta.lline form. 6-Menthylsemi-carbuzide obtained by dissolving the hydrochloride in hot dilute alcohol adding sodium hydroxide solution in slight excess and then immediately diluting and cooling in ice crystallised from light petroleum containing a little benzene in microscopic prisms, m.p. 138" (Found N = 19.89 19.83. CllH23ON3 requires N = 19.71%). 0-4994 Gram in 25 C.C. of absolute alcohol gave a$' -3.11" (1 = 2) whence [a]2Do' - 77.94". It was soluble in the usual organic solvents on heating solutions cannot be kept as they become green after one day. Addition of ethereal hydrogen chloride in slight excess to an absolute alcoholic solution precipitated the gelatinous hydrochloride. The benxylidene derivative obtained by shaking an alcoholic solution of the hydrochloride with a little benzaldehyde and then adding a little water solidified on standing and crystallised from alcohol in which it was very soluble in fine, rhombic prisms m.p. 111" (Found N = 13.96. C,,H,,0N3 requires N = 13.95%). 1.898 Grams in 100 C.C. of absolute alcohol gave ago - 1.79" (1 = 2) whence [a]?' - 47.18'. Solutions be-came green on standing. Ethyl m-Aminobenxmte and Acetonesemicarbaxone.-The two substances (1-6 mols. of the latter) were heated a t 165" until the Yield 65 yo THE ACTION OF AMINES ON SEiMICARBSZONES. PART 11. 107 evolution of ammonia began to slacken (20 minutes). The cooled melt was gently heated with a little alcohol which after filtration horn hydrazodicarbonamide deposited a solid on cooling ; this was mashed with a little alcohol and recrystallised from this solvent. A little more hydrazodicarbonamide was deposited followed by cal ourless plates of acetone- 6-3 -carbethosyphen ylserPzicarbazon e m.p. 146" (Found N = 1594 16.02. C13H1,03W3 requires N = 15.97y0). It was moderately soluble in alcohol very soluble in pyridine sparingly soluble or insoluble in other bolveiits. Yield S O X . Hydrolysis was effected by covering the substance with 3iN-hydrochloric acid and warming to 70"; the solid which scparated on cooling in ice gave after recrystallisation from alcohol, prisms of 6-3-carbetho~yphe3lylsemicnrbazicle hydrochloride m. p. 172" (Found C1 = 13.56 13-72. Cl0Hl3O3N3,HC1 requires C1 = 13-68:/,); it was readily soluble in hot (not very soluble in cold) water and hot alcohol and reduced Fehling's solution and am-nioniacal silver nitrate. 6- 3 - Carb et hoxyphenzylsemicarbaxide pre-pared in the usual manner from this salt with sodium hydroxide, separated from benzene in small prisms m.p. 119" ; it was Tery soluble in alcohol chloroform or hot benzene and sparingly soluble in water (Found N = 18-87 18-88. C,,-$,303N3 requires N = 15-83y0). The beizxylideize derivative prepared from a hot aqueous solution of the hydrochloride and benzaldehyde separated from alcohol in fine hair-like needles m. p. 144" very soluble in most solvents except water (Found N = 13-62 13-50. C1,H1,03N, requires N = 13.50:/0). Ethyl p-Arninobenzoate and BenxopheizonesernicarbaxolzP,.-The semicarbazone was added during 1 hour to the ester (2 mols.) heated at 230"; a gentle evolution of ammonia took place and the heat'ing was continued for 15 minutes after the last addition. The alcoholic extract of the cooled melt after filtering from hydrazo-dicarbonamide was poured into dilute acetic acid to remove excess of ester.The solid which separated on standing was extracted with cold toluene ; the insoluble portion on recrystallisation from benzene gave pearly plates of benxophenone-6-4-carbethoxyph.,nyl-semicarbazone m. p. 168" (Found N = 11.03 10.68. C,3H,10,Pa'3 requires N = 10.85%). The toluene extract contained diphenyl ketazine and benzophenonecarbohydrazone. The substance was soluble in most organic solvents but almost insoluble in cold benzene, toluene or light petroleum ; exposure to light converted it withoilt change of melting point into a lemon-yellow modification which gave colourless solutions. Ethyl p-Aminobenxoate and Acetonesemicarbazone.-The semi-carbazone was added during 20 minutes to the ester (1 mol.of Yield about 57%. E* 108 WILSON AND CRAWFORD: each) heated a t 190-200'. The alcoholic extract of the cooled melt atered from a small amount of hydrazodicarbonamide was evaporated and the residue recrystallised from alcohol. The crystals obtained were washed with cold acetone to dissolve a small quantity of a substance which was not identified (prisms from acetone m. p. 130" ; found N = 14.2%) ; several recrystallisations from alcohol gave hexagonal tablets of metone-6-4-carhethoxyphenyl-semicarbaxone m. p. 194'. There was some difficulty in separating it from a very small amount of a powdery substance m. p. 210°, which had almost the same solubility. The estimation of nitrogen in the semicarbazone offered considerable difficulty the results being high and not concordant due possibly to the production of methane (compare Haas J.1906 59 570; Dunstan and Carr, P. 1896 12 48) a 2-metre tube charged with lead chromate gave satisfactory results (Found N = 16.18 16.22. C,,H,,O,N, requires N = 15@7y0). The substance was soluble in alcohol or hot benzene slightly soluble in hot acetone insoluble in other solvents. Yield about 13%. Methyl o-Aminobenzmte and Benzophenonesemicarbazone.-Mole-cular quantities were heated a t 210" for 40 minutes; ammonia was evoked and methyl alcohol distilled over. The melt on extrac-tion with boiling benzene gave a residue which was shown by treatment with hot pyridine to consist of a little hydrazodicarbon-a'mide and tetrahydroquinazoline-2 3-dione.Concentration of the benzene extract gave a mixture from which 3-diphenylmethylene-aminotetrahydroquinazoline-2 4-dione was isolated by fractionally precipitating a chloroform solution with light petroleum. Con-centration of these mother-liquors gave benzophenonecarbohydr-azone. Further concentration of the benzene extract yielded a little diphenyl ketazine. 3-Diphe~ylmethyleneaminote~rahydroquina~oline-2 4-dione crystal-lised from alcohol in large prisms m. p. 240" and was moderately soluble in hot chloroform or hot pyridine insoluble in ether (Found : N = 12-32 12.54. C21H1502N3 requires N = 12-31y0). Boiling for & hour with 2&V-hydrochloric acid effected hydrolysis into benzophenone and 3-aminotetrahydroquinazoline-2 4-dione.Kunckell obtained the hydrochloride from the base and alcoholic hydrogen chloride ; evidently aqueous acid did not produce this salt. I f the reaction product is worked up in the usual way with acetic acid the 3-amino-compound is obtained and not the benzophenone derivative. Methyl o-Aminobenzoate and Acetonesemicarbaxone.-Equimole-cular quantities heated a t 195" for 3 0 4 0 minutes gave ammonia and a distillate containing methyl alcohol and dimethyl ketazine THE ACTION OF AMMES ON SEMICARBAZONES. PART 11. 109 water acetone or hydrazine was not present. A white sublimate, very small in amount and probably ammonium carbamate gradually formed and the melt ultimately solidified; it was then extracted with a little boiling benzene to remove resinous matter and un-changed ester.The residue was washed with light petroleum and fractionally recrystallised from pyridine which dissolved it com-pletely indicating absence of hydrazodicarbonamide. The f i s t crop of crystals coiisisted of 3-aminotetrahydroquiazoline-8 4-dione concentration yielded large regular efflorescent prisms, almost complete evaporation gave tetrathydroquinazoline-2 4-dione. The prisms after recrystallisation from pyridine charred at 390" on slow heating but melted at 420" in a previously heated bath (sodium-potassium nitrates). This substance which could not be identified contained about 38 % of pyridine of crystallisation which was expelled a t 105" ; analysis then gave C = 60.32 ; H = 4-00 ; N = 17-41; 0 (by diff.) = 18-27. The amount of this compound was relatively small; it was insoluble in the usual solvents includ-ing hydrochloric acid soluble in pyridine or sodium hydroxide.The solution in conccntrated sulphuric acid became pink on standing. obtained by boiling the 3-amino-compound with ordinary undried acetone until completely dissolved (5 hours) crystallised from dry acetone in prisms m. p. 212" (Found N = 19-55 19.58. C,,H1,0,N3 requires N = 19.35:/,). It was soluble in the usual organic solvents except ether and light petroleum; crystals from benzene were efnorescent containing apparently solvent of crystallisation. A mixture of this substaiice with acetonesemicarbazone on heating at 190" for 35 minutes melted at f i s t and then gradually solidified, ammonia was evolved and dimethyl ketazine distilled in quantity.The solid after removal of tarry matter by washing with ether and benzene was identified as 3-aminotetrahydroquinazoline-2 4-dione the evolution of ammonia was probably due to a decomposition of the semicarbazone which gives this gas on heating. The various substances mentioned were fully characterised as such by their properties and if necessary by analysis and pre-paration of derivatives. 3 -isoE'ropgl ideiz earninotetrahydroguiw azoline- 2 4-dio jie, In conclusion we wish to thank the Carnegie Trust for the Universities of Scotland for a grant which has partly defrayed the expenses of this work. THE ROSAL TECHNICAL COLLEGE, GLASGOW. [Eeceiced October 7th 1924. THE ACTION O F AMINES ON SEMICARBAZONES. PART 11.103 XVII1.-The Action of Amines on Semicarbaxones. Part I I . By FQRSYTH Jilni~s WrLsoN and ARCHIBALD BARCLAY CRAWFORD. Ie continuation of previous work (J. 1922 121 866) we have found that 1-menthylamine reacts normally with acetonesemicarbazone to give active acelor,e-6-)~e?zthylse~~car~a~o~2e CMe,:N*NH*CO*NH + C‘,,H,g*NIP2 = NH + C11,7e,:N*NH*C0.PU’H.C1,H1g from which 6-menthyZse?.iicurba,~ide7 N~2*NH*CO*NI-I*C,o~Ilg and its hydro-chloride have been obtained. These compounds including the beiizaldehyde derivative are laevorotatory in alcoholic solution. The action of esters of amino-acids on semicarbazones was next investigated. Ethyl m-aminobenzoate and acetonesemicarbazone re-acted normally on heating C~e,:PU’*NH*CO*nTH2+NH,=C6H,*CO,E t = CMe2:N*NH*C0.NH.CGH,.C0,Et + NH, giving acetone- 6- 3 - c a d -etho~~phenylsemicarbcczorze in good yield from which 6-3-carbethoxy-phe?zylsemicarbax ide NH,*KH*C O*NH*C 6H4*C O,Et and its hydro-chloride were obtained.Ethyl paminobenzoate also reacted normally with benzophenone- and acetone-semicarbazone (in the latter case with poor yield) giving the ketonic 6-4-carbetholry-phenylsemicarbaxones CR,:nT*NH*CO*NH*C6H4*Co,Et both of which underwent complete decomposition when hydrolysis was attempted. In view of what follows care was taken in all these cases to use dry materials and dry solvents so as to avoid any risk of hydrolysis. The ester, on heating with benzophenonesemicarbazone (molecular quantities), gave 3-diphe~aylnzethylelzeaminotetr~hydro~~~ina~oli~e-2 4-dioize (I), Methyl o-aminobenzoate reacted somewhat differently.this on hydroIysis with acid giving benzophenone and 3-amino -tetrahydroyuinazoline-2 4-dione (11) C6H4~c0-~.NH2 YH*CO de-scribed by Kunckell (Ber. 1910 43 1021). In addition methyl alcohol benzophenonecarbohydrazone (111) tetrahydroquinazoline-2 4-dione (IV) and small quantities of diphenyl ketazine and hydrazodicarbonamide were produced. Borsche and Merkwitz have shown (Ber. 1904 37 3177) that benzophenonesemicarbazone on heating gives (111) presumably by interaction with the hydrazone CPh,:N*NH*CO*NH +-NH,-N:CPh = NH + CO(NH*N:CPh,) (111) the hydrazone appar 104 WILSON AND CRAWFORD : ently resulting from the semicarbazone by loss of cyanic acid, CPh,:N*NH*CO*NH = CPh,*N*NH + HNCO. I n the present in-stance the formation of (111) and (IV) the latter investigated, among others by Griess (Ber.1869 2 416) can be explained as resulting from the ester and the semicarbazone, which then gives (111) and (IV) the diphenyl ketazine and the hydrazodicarbonamide being produced by the decomposition of the semicarbazone as shown by Borsche and Merkwitz, gCPh,:N*NH*CO*NH = CPh,:N*N:CPh +NH,*CO*NH*NH*CO*NH2. The interaction of acetonesemicarbazone with methyl o-amino-benzoate proceeded quite abnormally as before molecular quan-tities were employed and care was taken t o use dry solvents. The acetone derivative (V) expected from the scheme CMe,:N-NH*CO*NH, was not produced; the products were ammonia methyl alcohol, 3-aminotetrahydroquinazoline-2 4-dione (11) (the chief solid pro-duct amounting to about half of the semicarbazone used) a con-siderable amount of dimethyl ketazine small quantities of tetra-hydroquinazoline-2 4-dione (IV) and of a substance m.p. 420", which could not be identified; it is noteworthy that no hydrazo-dicarbonamide was formed. It may be assumed that (V) 3-iso~o(pylideneam~~otetra~ydro~u~nazolin~e-2 4-dione (prepared by another method and described below) is fkst produced with formation of ammonia and methyl alcohol and that it may react further in one of two ways. It may decompose 2s A different explanation is necessary in this case. follows , A substance of the composition represented by (VI) was not obtained (the unidentified substance of m. p. 420" giving quite different analytical results) ; moreover it was found as mentioned later that (V) did not behave in this way on heating.The other possibility and the one which we regard as the probable explan-ation is that (V) reacts with acetonesemicarbazone to give dimethyl ketazine and the intermediate carbamino-derivative (VII) THE ACTION OF AMMES ON SEMICARBAZONES. PART 11. 105 C H <NHo?o + NH,*CO*NH*N:CMe = CiUe,:N*N:CMe + CQ -N*NH*CO*NH,, which then by loss of cyanic acid gives (11). Borsche and Merkwitz (Zoc. cit.) apparently assume loss of cyanic acid in a similar case. Auwers and others (Annden 1924 435, 277) have shown that tetrahydroindazole-2-carbonamide loses cyanic acid (identified as cyanuric acid) on heating a t 160°, CO-N*N:CMe, C6H4<NH'Y 0 (VSI.) C,H4<gH>NCO*NH -+ C6H,KN_>NH.A H Similarly Posner (Ber., RC :CH* R 1901,34,3976) found that compounds of the type m2,co.+ (R = akyl) obtained from semicarbazide and diketones give with silver nitrate the derivative R?:CH*!?R when R = Ph, A€"N the carbamino-compound is not formed on heating the reactants, the product being 3 5-diphenylpyrazole. The substance (IV) probably results together with (11) by interaction of (VII) with the ester : To test. these explanations (V) was prepared by boiling ordinary undried acetone with (11); curiously enough dried acetone did not react even on prolonged boiling 8 p-dichloropropane also proved unreactive. This substance (V) was easily hydrolysed into the parent compounds by water and by hot solvents containing water.It was scarcely affected by heating even at 220" for 2& hours it charred slightly and there was a slight odoixr of dimethyl ketazine, but most of the substance was recovered unchanged. Molecular quantities of (V) and acetonesemicarbazone on heating gave dimethyl ketazine and (11) this being in accordance with the explanation advanced by us. This work will be continued. E x F E R I 3lr E N T A L. 3-Bent7qlamine and Acetonesemicurbaxone.-The 1-menthylamine, prepased by the method of Beckmann (Annalen 1889 250 325) and of Wallach (ibid. 1893 276 327) wa8 distilled directly in a current of hydrogen into a polarimeter tube ; it gave [m] - 39-41' E 106 WILSON AND CRAWFORD : [Wallach records - 38.07"; Tutin and Kipping (J. 1904 85 69) record - 39-92'].Equimolecular quantities previously heated to 165" were mixed and kept at this temperature for 15 minutes when solution with copious evolution of ammonia took place. The cooled melt dis-solved in a little alcohol was poured into dilute acetic acid the solid which separated dissolved completely in hot alcohol from which on cooling active acetone-8-menthylsemicarbazone was de-posited in clusters of small colourless needles m. p. 128" (Found : N = 16.62 16.73. C,,H2,0N requires N = 16.60 yo). 0.5024 Gram in 25 C.C. of absolute alcohol gave ar - 2.612" ( I = Z), whence [a]:" - 64.93". The substance was soluble in the usual organic solvents. Active 6-Menthylsemicarbaxide.-The semicarbazone was heated at 70" with Ilr-hydrochloric acid (5 parts) until completely dis-solved ; the residue obtained by evaporation under reduced pressure was recrystallised from alcohol which gave s-menthylsemicccrbazide hydrochloride as a gelatinous mass; after suction and washing with ether it assumed a fibrous apparently non-crystalline appearance and melted a t 203-204" (Found C1=14-02,14*22.C,,H,,ON,,HCl requires C1 = 14.22%). 0.5024 Gram in 25 C.C. of absolute alcohol gave a%' - 2.62" ( I = Z) whence [a]$" - 65-18". It was soluble in alcohol or hot water insoluble in ether or benzene and could not be obtained in a definitely crysta.lline form. 6-Menthylsemi-carbuzide obtained by dissolving the hydrochloride in hot dilute alcohol adding sodium hydroxide solution in slight excess and then immediately diluting and cooling in ice crystallised from light petroleum containing a little benzene in microscopic prisms, m.p. 138" (Found N = 19.89 19.83. CllH23ON3 requires N = 19.71%). 0-4994 Gram in 25 C.C. of absolute alcohol gave a$' -3.11" (1 = 2) whence [a]2Do' - 77.94". It was soluble in the usual organic solvents on heating solutions cannot be kept as they become green after one day. Addition of ethereal hydrogen chloride in slight excess to an absolute alcoholic solution precipitated the gelatinous hydrochloride. The benxylidene derivative obtained by shaking an alcoholic solution of the hydrochloride with a little benzaldehyde and then adding a little water solidified on standing and crystallised from alcohol in which it was very soluble in fine, rhombic prisms m. p. 111" (Found N = 13.96.C,,H,,0N3 requires N = 13.95%). 1.898 Grams in 100 C.C. of absolute alcohol gave ago - 1.79" (1 = 2) whence [a]?' - 47.18'. Solutions be-came green on standing. Ethyl m-Aminobenxmte and Acetonesemicarbaxone.-The two substances (1-6 mols. of the latter) were heated a t 165" until the Yield 65 yo THE ACTION OF AMINES ON SEiMICARBSZONES. PART 11. 107 evolution of ammonia began to slacken (20 minutes). The cooled melt was gently heated with a little alcohol which after filtration horn hydrazodicarbonamide deposited a solid on cooling ; this was mashed with a little alcohol and recrystallised from this solvent. A little more hydrazodicarbonamide was deposited followed by cal ourless plates of acetone- 6-3 -carbethosyphen ylserPzicarbazon e m. p. 146" (Found N = 1594 16.02.C13H1,03W3 requires N = 15.97y0). It was moderately soluble in alcohol very soluble in pyridine sparingly soluble or insoluble in other bolveiits. Yield S O X . Hydrolysis was effected by covering the substance with 3iN-hydrochloric acid and warming to 70"; the solid which scparated on cooling in ice gave after recrystallisation from alcohol, prisms of 6-3-carbetho~yphe3lylsemicnrbazicle hydrochloride m. p. 172" (Found C1 = 13.56 13-72. Cl0Hl3O3N3,HC1 requires C1 = 13-68:/,); it was readily soluble in hot (not very soluble in cold) water and hot alcohol and reduced Fehling's solution and am-nioniacal silver nitrate. 6- 3 - Carb et hoxyphenzylsemicarbaxide pre-pared in the usual manner from this salt with sodium hydroxide, separated from benzene in small prisms m.p. 119" ; it was Tery soluble in alcohol chloroform or hot benzene and sparingly soluble in water (Found N = 18-87 18-88. C,,-$,303N3 requires N = 15-83y0). The beizxylideize derivative prepared from a hot aqueous solution of the hydrochloride and benzaldehyde separated from alcohol in fine hair-like needles m. p. 144" very soluble in most solvents except water (Found N = 13-62 13-50. C1,H1,03N, requires N = 13.50:/0). Ethyl p-Arninobenzoate and BenxopheizonesernicarbaxolzP,.-The semicarbazone was added during 1 hour to the ester (2 mols.) heated at 230"; a gentle evolution of ammonia took place and the heat'ing was continued for 15 minutes after the last addition. The alcoholic extract of the cooled melt after filtering from hydrazo-dicarbonamide was poured into dilute acetic acid to remove excess of ester.The solid which separated on standing was extracted with cold toluene ; the insoluble portion on recrystallisation from benzene gave pearly plates of benxophenone-6-4-carbethoxyph.,nyl-semicarbazone m. p. 168" (Found N = 11.03 10.68. C,3H,10,Pa'3 requires N = 10.85%). The toluene extract contained diphenyl ketazine and benzophenonecarbohydrazone. The substance was soluble in most organic solvents but almost insoluble in cold benzene, toluene or light petroleum ; exposure to light converted it withoilt change of melting point into a lemon-yellow modification which gave colourless solutions. Ethyl p-Aminobenxoate and Acetonesemicarbazone.-The semi-carbazone was added during 20 minutes to the ester (1 mol.of Yield about 57%. E* 108 WILSON AND CRAWFORD: each) heated a t 190-200'. The alcoholic extract of the cooled melt atered from a small amount of hydrazodicarbonamide was evaporated and the residue recrystallised from alcohol. The crystals obtained were washed with cold acetone to dissolve a small quantity of a substance which was not identified (prisms from acetone m. p. 130" ; found N = 14.2%) ; several recrystallisations from alcohol gave hexagonal tablets of metone-6-4-carhethoxyphenyl-semicarbaxone m. p. 194'. There was some difficulty in separating it from a very small amount of a powdery substance m. p. 210°, which had almost the same solubility. The estimation of nitrogen in the semicarbazone offered considerable difficulty the results being high and not concordant due possibly to the production of methane (compare Haas J.1906 59 570; Dunstan and Carr, P. 1896 12 48) a 2-metre tube charged with lead chromate gave satisfactory results (Found N = 16.18 16.22. C,,H,,O,N, requires N = 15@7y0). The substance was soluble in alcohol or hot benzene slightly soluble in hot acetone insoluble in other solvents. Yield about 13%. Methyl o-Aminobenzmte and Benzophenonesemicarbazone.-Mole-cular quantities were heated a t 210" for 40 minutes; ammonia was evoked and methyl alcohol distilled over. The melt on extrac-tion with boiling benzene gave a residue which was shown by treatment with hot pyridine to consist of a little hydrazodicarbon-a'mide and tetrahydroquinazoline-2 3-dione.Concentration of the benzene extract gave a mixture from which 3-diphenylmethylene-aminotetrahydroquinazoline-2 4-dione was isolated by fractionally precipitating a chloroform solution with light petroleum. Con-centration of these mother-liquors gave benzophenonecarbohydr-azone. Further concentration of the benzene extract yielded a little diphenyl ketazine. 3-Diphe~ylmethyleneaminote~rahydroquina~oline-2 4-dione crystal-lised from alcohol in large prisms m. p. 240" and was moderately soluble in hot chloroform or hot pyridine insoluble in ether (Found : N = 12-32 12.54. C21H1502N3 requires N = 12-31y0). Boiling for & hour with 2&V-hydrochloric acid effected hydrolysis into benzophenone and 3-aminotetrahydroquinazoline-2 4-dione. Kunckell obtained the hydrochloride from the base and alcoholic hydrogen chloride ; evidently aqueous acid did not produce this salt.I f the reaction product is worked up in the usual way with acetic acid the 3-amino-compound is obtained and not the benzophenone derivative. Methyl o-Aminobenzoate and Acetonesemicarbaxone.-Equimole-cular quantities heated a t 195" for 3 0 4 0 minutes gave ammonia and a distillate containing methyl alcohol and dimethyl ketazine THE ACTION OF AMMES ON SEMICARBAZONES. PART 11. 109 water acetone or hydrazine was not present. A white sublimate, very small in amount and probably ammonium carbamate gradually formed and the melt ultimately solidified; it was then extracted with a little boiling benzene to remove resinous matter and un-changed ester.The residue was washed with light petroleum and fractionally recrystallised from pyridine which dissolved it com-pletely indicating absence of hydrazodicarbonamide. The f i s t crop of crystals coiisisted of 3-aminotetrahydroquiazoline-8 4-dione concentration yielded large regular efflorescent prisms, almost complete evaporation gave tetrathydroquinazoline-2 4-dione. The prisms after recrystallisation from pyridine charred at 390" on slow heating but melted at 420" in a previously heated bath (sodium-potassium nitrates). This substance which could not be identified contained about 38 % of pyridine of crystallisation which was expelled a t 105" ; analysis then gave C = 60.32 ; H = 4-00 ; N = 17-41; 0 (by diff.) = 18-27. The amount of this compound was relatively small; it was insoluble in the usual solvents includ-ing hydrochloric acid soluble in pyridine or sodium hydroxide.The solution in conccntrated sulphuric acid became pink on standing. obtained by boiling the 3-amino-compound with ordinary undried acetone until completely dissolved (5 hours) crystallised from dry acetone in prisms m. p. 212" (Found N = 19-55 19.58. C,,H1,0,N3 requires N = 19.35:/,). It was soluble in the usual organic solvents except ether and light petroleum; crystals from benzene were efnorescent containing apparently solvent of crystallisation. A mixture of this substaiice with acetonesemicarbazone on heating at 190" for 35 minutes melted at f i s t and then gradually solidified, ammonia was evolved and dimethyl ketazine distilled in quantity. The solid after removal of tarry matter by washing with ether and benzene was identified as 3-aminotetrahydroquinazoline-2 4-dione the evolution of ammonia was probably due to a decomposition of the semicarbazone which gives this gas on heating. The various substances mentioned were fully characterised as such by their properties and if necessary by analysis and pre-paration of derivatives. 3 -isoE'ropgl ideiz earninotetrahydroguiw azoline- 2 4-dio jie, In conclusion we wish to thank the Carnegie Trust for the Universities of Scotland for a grant which has partly defrayed the expenses of this work. THE ROSAL TECHNICAL COLLEGE, GLASGOW. [Eeceiced October 7th 1924.

ISSN:0368-1645    

DOI:10.1039/CT9252700103

出版商:RSC    

年代:1925

数据来源: RSC

摘要:

110 TIDESWELL AND WHEELER BANDED BITUMINOUS COAL. XIX-Banded Bituminous Coal. Studies in the Composition of Coal. By FREDERICK VINCENT TIDESWELL and RICHARD VERKON WHEELER. As the result of an investigation into the chemical nature of the ingredients of banded bituminous coal (J. 1919 115 619) it was found that the chief differences between them were expressed by a regular gradation in composition and in properties which could be accounted for by assuming the occurrence in each in different proportions of “ reactive ” and ‘‘ inert ” types of compounds. We are now able to offer as the result of later work more particularly that on dopplerite (J. 1922 121 2345) an explanation as to the character of these presumed “ reactive ” and “ inert ” constituents. The various plant entities and residues that have contributed to the formation of the organic substance of coal can conveniently be grouped according as they are : (1) Resistant to decay.Amongst the more important members of this group are ( a ) Spore-exines and cuticular tissues; and ( b ) resins. The members of this group are either : ( a ) Organised such as cellulosic and lignified tissues; or ( b ) amor-phous the contents of plant cells. (2) Xubject to decay. (3) The products of decay. An accumulation of plant remains immediately after de-position consists mainly of the first two groups but in an older deposit such as a peat bed certain changes have taken place. The members of group 1 are still present in an apparently unaltered form. The cellulose and lignin of group 2 however have suffered decay undergoing such minor alterations as dehydration produces, or becoming ulmified (probably in conjunction with certain of the cell-contents) or disappearing altogether.According to Fischer and Schrader (Brennstofl Chem. 1921 2 23) the lignin alone sur-vives in any form the cellulose of necessity vanishing (being con-verted into liquid and gaseous products through the agency of bacteria) but we cannot regard this view as either proved or prob-able and consider that ulmins can be produced from any plant material of carbohydrate type. Judging from the nature of peat, ulmification is the main chemical process during the decay of plants and it proceeds further the older the deposit thus whilst a young peat may yield only 10 or 20% of material soluble in alkalis from an older peat as much as 70 or 80% can be extracted.In a deposit of the age of coal it cannot be expect,ed that the The ulmins STUDIES IN THE COMPOSITION OF COA4L. 111 materials of any of the three groups will remain unaltered. Spore-exines and cuticular tissues may not be much changed nor need the resins but the cellulose that is not totally destroyed will in large part be converted together with the more resistant lignin and part of the cell-contents into the amorphous ulmins of group 3 (or products derived from them). There will also be material corre-sponding with group 2 (a) consisting of altered (but apparently not ulmified) woody tissues such as compose many lignites and are recognisable in many bituminous coals.We have a t present no knowledge as to what becomes of the non-ulmified portions of the cell-contents. As they finally appear in the coal cell-wall structures group 2 (a) may not differ much chemically from the amorphous ulmins but the materials of group 1 differ markedly. The more recent beds of plant remains the peats contain a large amount of alkali-soluble material the amount increasing with the age of the deposit but ‘( older ” fuels such as brown coals and lignites contain comparatively little whilst bituminous coals, unless they have been considerably weathered usually contain none. This diminishing content of alkali-soluble material after a certain stage has been passed would seem to be due to a change in the character of the ulmins through condensation dehydration and loss of carboxyl (with the formation of anhydrides and lactones) whereby their usual property of dissolving in alkalis t o form dark brown solutions is lost.The alkali-soluble ulmins that surround and permeate the plant structures in an old peat (see J. 1922 12l, 2345) may be presumed to have their counterpart in bituminous coal in the amorphous cementing material (insoluble in alkalis) in which the numerous plant structures are embedded. We have already (Eoc. cit. p. 2354) instituteda comparison and shown the similarity between dopplerite a typical peat ulmin which occurs segregated in bands in some peat bogs and vitrain, the brilliant structureless ingredient of banded bituminous coal. By analogy there should also be a close relationship between all the amorphous cementing material of bituminous coal whether segregated as in a vitrain or diffused as in a clarain and a durain, and the amorphous ulmins that form so large a part of the older peats and this relationship should extend to the amounts of amor-phous material normally contained in the two fuels.The correctness of this suggestion can be deduced from the data obtained during the study of the chemical nature of the ingredients of banded bituminous coal referred to a t the beginning of this paper. The (‘ reactivity ” of the vitrain clarain and durain of Hamstead coal as measured by their susceptibility to attack by solvent 112 FRANCIS AND WHEELER THE OXIDATION OF and reagents and by the amounts of liquid and gaseous products yielded on destructive distillation was found to diminish in the ratio 1.0 0.9 0.7 taking the ingredients in the order named, and it was concluded that the amounts of “reactive” material they contained diminished in the same proportion.Of the absolute amounts of “ reactive ” and “ inert ” materials present in any one of the ingredients no conclusion could be drawn at the time the experiments were made but with the recognition of vitrain as related to the nearly homogeneous ulmin dopplerite it follows that the bulk of vitrain should be regarded as “ reactive.” Whence since its composition had been found to be similar in all three ingredients it must be concluded that the reactive material of a clarain and a durain is essentially an insoluble derivative of the ulmins and that in the clarain and durain of Hamstead coal it is present to the extent of about 90 and 70% respectively.Actually the vitrain contained a certain amount of material other than insoluble ulmins (resins for example) so that these figures should be reduced somewhat. It is difficult to judge from an examination of transparent sections of coal as to the proportions of amorphous and organised material present but even if as appeared there is in the Hamstead durain, for example a greater proportion of plant tissues than the 30% indicated by calculation there are grounds for the belief that some plant remains in coal (woody tissues in particular) although they retain their organised structures have been partially ulmified and thus function as “ reactive ” material.Otherwise the plant entities (especially those of group 1) must constitute what we have termed the “ inert ” material of coal. DEPARTMENT OF FUEL TECHNOLOGY, SHEFFIELD UNIVERSITY. [Received October 17th 1924. 110 TIDESWELL AND WHEELER BANDED BITUMINOUS COAL. XIX-Banded Bituminous Coal. Studies in the Composition of Coal. By FREDERICK VINCENT TIDESWELL and RICHARD VERKON WHEELER. As the result of an investigation into the chemical nature of the ingredients of banded bituminous coal (J. 1919 115 619) it was found that the chief differences between them were expressed by a regular gradation in composition and in properties which could be accounted for by assuming the occurrence in each in different proportions of “ reactive ” and ‘‘ inert ” types of compounds.We are now able to offer as the result of later work more particularly that on dopplerite (J. 1922 121 2345) an explanation as to the character of these presumed “ reactive ” and “ inert ” constituents. The various plant entities and residues that have contributed to the formation of the organic substance of coal can conveniently be grouped according as they are : (1) Resistant to decay. Amongst the more important members of this group are ( a ) Spore-exines and cuticular tissues; and ( b ) resins. The members of this group are either : ( a ) Organised such as cellulosic and lignified tissues; or ( b ) amor-phous the contents of plant cells. (2) Xubject to decay. (3) The products of decay. An accumulation of plant remains immediately after de-position consists mainly of the first two groups but in an older deposit such as a peat bed certain changes have taken place.The members of group 1 are still present in an apparently unaltered form. The cellulose and lignin of group 2 however have suffered decay undergoing such minor alterations as dehydration produces, or becoming ulmified (probably in conjunction with certain of the cell-contents) or disappearing altogether. According to Fischer and Schrader (Brennstofl Chem. 1921 2 23) the lignin alone sur-vives in any form the cellulose of necessity vanishing (being con-verted into liquid and gaseous products through the agency of bacteria) but we cannot regard this view as either proved or prob-able and consider that ulmins can be produced from any plant material of carbohydrate type.Judging from the nature of peat, ulmification is the main chemical process during the decay of plants and it proceeds further the older the deposit thus whilst a young peat may yield only 10 or 20% of material soluble in alkalis from an older peat as much as 70 or 80% can be extracted. In a deposit of the age of coal it cannot be expect,ed that the The ulmins STUDIES IN THE COMPOSITION OF COA4L. 111 materials of any of the three groups will remain unaltered. Spore-exines and cuticular tissues may not be much changed nor need the resins but the cellulose that is not totally destroyed will in large part be converted together with the more resistant lignin and part of the cell-contents into the amorphous ulmins of group 3 (or products derived from them).There will also be material corre-sponding with group 2 (a) consisting of altered (but apparently not ulmified) woody tissues such as compose many lignites and are recognisable in many bituminous coals. We have a t present no knowledge as to what becomes of the non-ulmified portions of the cell-contents. As they finally appear in the coal cell-wall structures group 2 (a) may not differ much chemically from the amorphous ulmins but the materials of group 1 differ markedly. The more recent beds of plant remains the peats contain a large amount of alkali-soluble material the amount increasing with the age of the deposit but ‘( older ” fuels such as brown coals and lignites contain comparatively little whilst bituminous coals, unless they have been considerably weathered usually contain none.This diminishing content of alkali-soluble material after a certain stage has been passed would seem to be due to a change in the character of the ulmins through condensation dehydration and loss of carboxyl (with the formation of anhydrides and lactones) whereby their usual property of dissolving in alkalis t o form dark brown solutions is lost. The alkali-soluble ulmins that surround and permeate the plant structures in an old peat (see J. 1922 12l, 2345) may be presumed to have their counterpart in bituminous coal in the amorphous cementing material (insoluble in alkalis) in which the numerous plant structures are embedded. We have already (Eoc. cit. p. 2354) instituteda comparison and shown the similarity between dopplerite a typical peat ulmin which occurs segregated in bands in some peat bogs and vitrain, the brilliant structureless ingredient of banded bituminous coal.By analogy there should also be a close relationship between all the amorphous cementing material of bituminous coal whether segregated as in a vitrain or diffused as in a clarain and a durain, and the amorphous ulmins that form so large a part of the older peats and this relationship should extend to the amounts of amor-phous material normally contained in the two fuels. The correctness of this suggestion can be deduced from the data obtained during the study of the chemical nature of the ingredients of banded bituminous coal referred to a t the beginning of this paper.The (‘ reactivity ” of the vitrain clarain and durain of Hamstead coal as measured by their susceptibility to attack by solvent 112 FRANCIS AND WHEELER THE OXIDATION OF and reagents and by the amounts of liquid and gaseous products yielded on destructive distillation was found to diminish in the ratio 1.0 0.9 0.7 taking the ingredients in the order named, and it was concluded that the amounts of “reactive” material they contained diminished in the same proportion. Of the absolute amounts of “ reactive ” and “ inert ” materials present in any one of the ingredients no conclusion could be drawn at the time the experiments were made but with the recognition of vitrain as related to the nearly homogeneous ulmin dopplerite it follows that the bulk of vitrain should be regarded as “ reactive.” Whence since its composition had been found to be similar in all three ingredients it must be concluded that the reactive material of a clarain and a durain is essentially an insoluble derivative of the ulmins and that in the clarain and durain of Hamstead coal it is present to the extent of about 90 and 70% respectively.Actually the vitrain contained a certain amount of material other than insoluble ulmins (resins for example) so that these figures should be reduced somewhat. It is difficult to judge from an examination of transparent sections of coal as to the proportions of amorphous and organised material present but even if as appeared there is in the Hamstead durain, for example a greater proportion of plant tissues than the 30% indicated by calculation there are grounds for the belief that some plant remains in coal (woody tissues in particular) although they retain their organised structures have been partially ulmified and thus function as “ reactive ” material. Otherwise the plant entities (especially those of group 1) must constitute what we have termed the “ inert ” material of coal. DEPARTMENT OF FUEL TECHNOLOGY, SHEFFIELD UNIVERSITY. [Received October 17th 1924.

ISSN:0368-1645    

DOI:10.1039/CT9252700110

出版商:RSC    

年代:1925

数据来源: RSC