摘要:

472 ASTON A SIMPLE FORM OF APPARATUS FOR XXXVL-A Simple Form. of Apparatus foi- Xstimating the Oxugen Content of Air from the Uppe?. Atmosphere. By FRANCIS WILLIAM ASTON. FROM meteorological considerations it is probable that air in the stratosphere or isothermal layer is stagnant hence owing to their different densities the relative percentage of oxygen and nitrogen will not be identical with that in the troposphere where mixing is practically perfect. It is therefore af great importance that exact analyses should be made whenever possible of samples of air brought down from the great altitudes now available to aeroplanes in order to find out a t what height such gravitational separation becomes evident to chemical analysis. For this purpose it is enough t o determine the oxygen content of the sample after this has been dried and freed from carbon dioxide.A complete and exceedingly accurate method for determining the percentage of oxygen in air volumetrically has been described by Wi&son (T. 1911 99 1460). The apparatus which forms the subject of this paper is a modification of this in which by measur-ing the difference only in oxygen content between the sample and normal air very considerable simplifications may be made t h e pump and the cathetometer being rendered unnecessary. The samples are contained in test-tubes holding rather more than is required for an analysis (10 c.c.) in the tops of which have been fused a little potassium hydroxide. Here bhey remain over mercury for a t least two hours before analysis in order to remove carbon dioxide and water vapour.The measuring burette and barometer tube (see figure) are normally kept full of mercury with the stopcock A turned on t o avoid fracture by expansion. I n order to perform an analysis the capillary stopcock R is closed and the reservoir C lowered until t,he level of the mercury in the barometer tube is a little below it ESTIMATING THE OXYGEN CONTENT OF AIR ETC. 473 upper and broader part. The stopcock A is then closed and the sample tube held down over the inverted syphon tube in the mercury trough D. When the capillary stopcock R is now opened, the air flows into the upper part of the burette and the mercury rises again to the top of the barometer tube; in order to prevent this happening wit'h destructive violence the lower part of the barometer is made of capillary bore (less than 2 mm.).After waiting for a few moments for pressure and temperature to adjust G B themselves the sample tube is raised flooding the end of the inverted syphon with mercury the stopcock A is opened again, and by lowering the reservoir mercury is caused t o flow through the syphon and fill the capillary tube when B is turned off. It will be seen that the volume of air introduced in this way is constant being the volume of the upper part $of the barometer tube (in the actual apparatus a little less than 10 c.c.); the pressure being at4mospheric plus the small difference of level between th 474 ASTON A SIMPLT3 FORM OF APPARATUS FOR top of the syphon tube and the mercury in t3he trough the quantity will also be approximately constant.This quantity is now accx-rately measured by adjusting the mercury level in the burette exactly to t<he lower fixed reading point E,; this can be done with the greatest nicety by bringing the mercury nearly up to the mark by manipulation of the reservoir and stopcock and finally (with the latter closed) squeezing the short length of rubber pressure-tubing with the screw clip provided as indicated. The volumes of the burette and barometer are such that the surface of the mercury in tlhe latter will be somewhat as indicated in the diagram and the lower movable reading point F, may be exactly adjusted t o it by means of the micrometer screw G. The barometer and the parts of the burette where readings are taken are all made of the same piece of glass tube 0.9 cm.in internal diameter to eliminate meniscus error. The reading points are all sleeves od brass tube 1 cm. long fitting the glass tubes, clamped in the case of the fixed points sliding loosely in the case of the moving ones. ? The reading of the micrometer having been taken the air is now forced into the laboratory tube. This is a quartz test-tube holding rather more than 10 c.c. to the top of which (not quite in the centre) has been fused a pellet of phosphorus. These pellets may be easily made by allowing melted phosphorus to flow from a pipette with a narrow mouth into a tall cylinder of cold water. One spherule of about 2-3 mm. in diameter should be ample and this is introduced into the inverted quartz tube full oE mercury, shaken into position and fused into the side d h a touch from a Bunsen flame.When all the air has been tsansferred from the burette to the quartz tube the phospho'rus is inflamed and then heated to boiling point in order to ensure the complete removal of all oxygen. Some time is allowed f o r the phosphoric oxide to settle when the deoxidised air is drawn back into the burette. It was feared when the apparatus was designed that tot perform this operation satisiaetorily mightl be difficult or even impossible as m a l l bubbles of air were expected to remain behind on the walls of the quartz tube now of necessity contaminate'd with the pro-ducts of combustion. Such bubbles are formed but they can I;@ dislodged by touching with the syphon tube and then washed with a little mercury into the burette.I n Watson's apparatus the deoxidised residue was measured a t the same volume as the original air necessitating the determination of two widely different pressures. I n the present' one the residae is measured a t such a volume that if the air is normal the two pressures measured would be identical so that a very small differ ESTIMATING THE OXYGXN COhTTENT O F AIR BTC. 475 ence of pressure only need be determined. For this purpose the upper fixed reading point E2 is used this being set once for all during the construetion o$ the burette so that the upper part cf the burette holds exactly 79.0 per cent. of the whole. The upper movable reading point F, is also soldered to the sliding carrier a t exactly the same height above the lower one as that between the fixed points.Hence it will be seen a t once that for n o d a l air the mercury a t the measurement o€ the residue should stahd a t the upper movable reading point or if the dimensions of the apparatus are not quite correct a t a constant small distance aboke or below it a correction easily determined a t any time by an analysis of normal air. If on the other hand there is redaction in the percentage of oxygen present the mercury will stand a t a higher level the difference being measured on the micrometer. A decrease of oxygen from 21 per cent. to 20 per cent. corm sponds wi6h a change in height of mercury in the ratio of 79 t o 80; as the n m a l difference between the fixed and movable recd-ing points in the apparatus in use is 237 mm.this gives exactly 3 mm. per 1 per cent. change. The micrometer has a range of 10 mm. which is more than ample for the changes expected and analysis should be consistent to well within one-tenth per cent. on total air the head of the micrometer being divided in twentieths of a millhetre corresponding with one-sixtieth per cent. Temperature errors are minimised by the) immersion of the buretk and the most of the length of the barometer tube in a small water-jacket. As the time occupied in an analysis is only a few minutes they are not likely to be serious. The following readings of the micrometer in mm. obt'ained with the apparatus will serve as an example. The first set of three were obtained with pure air which is regarded as containing 21-00 per cent. oxygen the second with an artificial sample in which t.he oxygen content had been reduced by the addition of a known quantity of deoxygenated air t o 20.42 per cent.: Pure air. Sample. F ......... 3.65 3.38 4-83 4.52 6.55 5-40 F ......... 3-39 3-20 4-55 6.09 7.21 7-06 Diff. ...... 0.26 0.18 0.28 1-57 1.86 1.54 Mean diff. ...... 0'24 1.59 Decrease in percent age centage of oxygen in sample=20*39 in good agreement with the value expected. FARNBOROVQH. [Received B'ebruatuj 26th 1919.

ISSN:0368-1645    

DOI:10.1039/CT9191500472

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

476 KING THE RESOLUTION OF HYOSCINE AND ITS XXXVI1.-The Resolution of Hyoscine and its Com-ponents Tropic Acid and Oscine. By HAROLD KING. HYOSCINE or scopolamine the tropyl ester of oscine and one of the group of Solanaceuus alkaloids receives varied and extensive use in medicine and has on that account attracted the attention of many workers both from the chemical aspect and from the medicinal. During the last few years the subject has acquired an additional interest and importance as a result of the recognition that oscine (or scopoline) the basic hydrolytic product i s capable of resolu-tion into its constituents d- and I-oscine. This follows from the resolution of benzoyloscine by Tutin in 1910 (T. 97 1793) and from the partial elucidation of the structural formula of oscine by Schmidt and Hess and their co-workers whereby it seems certain that oscine unlike tropine is not internally compensated.Apart from these two separate results and in spite of the vast amount of work that has been carried out on oscine and hyoscine there was nothing known which definitely pointed to this conclusion. Since tropic acid is also capable of resolution and Gadamer (Arch. P h m . 1901 239 294) has shown that I-tropic acid may be obtained by hydrolysis of Z-hyoscine it follows that tropyloscine (hyoscine) might exist in ten or possibly eleven stereoisomeric form consisting of four optically active four partially racemic two fully racemic and one double racemic compound. The problem is in some ways analogous to that presented by the ten tetrahydro-quinaldinomethylenecamphors obtained by Pope and Read (T., 1913 103 1515) but with this difference that in the case of the hyoscines an approach is a t present (apart from the rarity of tthe materials) not possible from the synthetic side as hymcine has as yet not been obtained by the esterification of oscine by tropic acid.The elucidation of the chemistry of the isomeric hyoscines and the correct allocation of the medicinal properties t o be attributed to each is of considerable moment for both sciences. Our knowledge of the hyoscines as revealed by previous workers, so far as it appertains to the present subject may be very briefly summarised. Naturally occurring Zaevo-hyoscine has been obtained in a state of purity by several workers and in the form of its well-crystal-lised hydrobromide is a commercial product.In the plant it is apparently accompanied to some extent by 61-hposcine from whic COMPONENTS TROPIC ACID AND OSCINE. 477 it can be separated by fractional crystallisation of the hydro-bromides. Racmic hyoscine base which can also be obtained from I-hyoscine by the action of alkalis forms two hydrates one crystallising with two molecules of water and known a5 atroscine (Hesse) the other with one molecule of water. Two attempts to resolve racemic hyoscine are recorded the first by Schmidt (Arclt. Pharm. 1898 236 56) who found that the salt with thiocyanic acid did not separate into two mechanically separable crystalline enantiomorphs as was the case with racemic lupanine (Schmidt and Davis Arch.Pham. 1897 235 196) the second by Gadamer (Arch. Pharm. 1901 239 294)) who states that the quinic acid and d-mandelic acid salts of dl-hymcine are very readily soluble and possess little crystallising power and are therefore not suit-able for the resolution of hyoscine. The primary mode of attack adopted in the present investiga-tion is based on some unpublished preliminary experiments by Tutin who showed that I-hyoscine of commerce forms a soluble, deliquescent salt with d-bromwamphorsulphonic acid which can be recrystallised from dry ethyl acetate containing alcohol and also that when I-hyoscine is racemised by alkali the product as a salt with the same acid can likewise be recrystallised and the successive fractions of salt so obtained show a progressive variation in rotatory power.The author here gratefully acknowledges his indebtehess to Mr. Tutin for placing these results a t his disposal. A quantity of crystalline hydrobromides of feeble lzvorotatory power obtained as a by-product in the manufacture of the thera-peutically valuable I-hyoscine was fractionally crystallised as a salt with d-a-bromwr-camphorsulphonic acid when the first salt to be isolated was meteloidine bromocamphorsulphonate (m. p. 224-227O). This salt cryst'allises exceedingly well and contains i-meteloidine (compare Pyrnan and Reynolds T. 1908 93, 2077). On continuing the fractionation d-hyoscine bromo-camphorsulphonute was obtained in a state of purity. It melted a t 159-160° and crystallised in glistening acicular needles.d-Hyoscine -hydrobromide was prepared from it and found b crystallise with three molecules of water and t o possess a specific rotatory power [a], +23.l0 which corresponds with a value [a], + 3 3 ~ 4 ~ for the d-hyoscinium ion. For comparison some of the maximum values recorded by previous observers f o r the Iaeuo-salt are tabulated below I - H y oscinc Hydro 6 romide . [a] anhydrous salt. Schmidt' ..................... - 25.7" Hesse2 ........................... - 25.9 Thorns and Wentze13 ......... - 25.76 Carr and Reynolds4 ............ - 26.0 WillstBtter and Hug5 ......... - 26.0 King .............................. - 25.9 [aIU ionic value. - 32.5O - 32.7 - 32-5 - 32.8 - 32-8 - 32.7 d-Hyoscine Ilydrobromide. King7 ..............................-+ 26.3' + 33.2" 1 Arch. Pharm. 1892 230 207. 2 J . p. Chem. 1901 [ii] 64 353. Ber. 1901 34 1023. Zeitsch. physiol. Chem. 1912,79 146. P. 504. ' P. 503. 4 T. 1910,97 1330. These values show tlhat the purified Z-hyoscine hydrobrcumide of previous workers and the d-hyoscine hydrobromide now isolated for the first t'ime represent oae pair outl of the eleven possible stereoisomeric h.yolscines. On mixing equal weights of pure d- and Z-hyolscinei hydro-bromides and recrystallising the mixture from water dZ-hyoscine hydrobrolmide also crystallisiiig with three molecules od water and in a form indistinguishable from tlhe active components was obtained. It differs from the active components in that it very readily effloresces and in that the base obtained from it is crystal-line and contains two molecules of water.For the further charactell-isation of these three related coqpounds their auri-chlorides awdromides and picrates were prepafed. The results am shown in the following table: 1-Hyoscine. d-Hyoscine. dl-Hyoscine. RUW-Appearmce ...... 8;yrUp. syrup. Prisms. H,O ............... I - 2H,O M.p. ............... I - 38-400 Hydrobromide-Appearance ...... Large rhornbic Large rhornbic Large rhombic tablets. tablets. tablets. H,O ............... 3H ,O 3H,O 3H2O [aln (anhydrous) -25.9" -t- 26.3" - M. p. (anhydrous) 103-194 O 19 3- 194' 181-182" Picrate-Appearance . . . . Slender rntttted Slender matted Needles. needles. needles. 39. p. ............... 187-188O 187-1 88' 17306-1 74.5 COMPONENTS TROPIC ACID AND OSCINE.479 1-H.yosciiie. d-Hyoscine. dl -Hyoscine. Aurichlode-Appearance ...... Needles both Needles both Needles one edges serrated. edges serrated. edge serrated. M. p. ............... 204-205" 204-205' 2 1 4-2 1 5" Auribrornide-Appearance ...... Chocolate -red - Chocolate -red leaflets . leaflets. M. p. ............... 187-188" - 209-2 10" Some of these call f o r further remark in view of the results of previous observers. The racemic base crystallising with 2H20 is probably a purer form of Hesse's atroscine (Ber. 1896 29 1776), which melted a t 36-37O and was obtained by fractionally crystal-lising commercial samples of hyoscine hydrobromide. It was obtained on one other occasion by Gadamer (.A?&. Pharm. 1898, 236 382) who gives the melting point 37-38O.The dl-hyoscine hydrobromide agrees in its properties with those recorded by Hesse (A?L?talen 1899 309 75; J p r . Chem. 1901 [ii] 64 353). The picrates have been recommended for identifying the mydriatic alkaloids by Carr and Reynolds (T. 1912 101 949), who describe 7-hyosciiie ;tnd cll-hyoscine picrates as slender mattecl iieedles melting respectively a t 180-181° and 19P. Neither of these melting points is in agreement with the results here recorded, which however do find support in the only two other recorded iiielting points of the picrates Schmidt ( i l 7 - c I 1 . I'hm"?? . 1894 232, 409) describes Z-hyoscine picrate as melting a t 187-188° a i d Finiiemore and Braithwaite (Plzarnt. ,7. 1912 89 136) frmn 3x1 examination of commercial samples of hyoscine hydrobromide of varying rot'atory power give figures which show that I-hyoscine picrate melts a t 187-188O and clZ-liymcine picrzte a t 174-175O.The aurichlorides have been described by almost all previous workers on the hyoscines but there is complete disagreement between the recorded melting points. This is all the more sur-prising as several workers have had in hand pure Z-hyoscine hydro-bromide. To quote only two of these Schmidt (Arch. Pharm., 1910 248 641) states that Z-hymcine aurichloride of various origins has previously been shown to melt when quite pure a t 210-214° whereas Hesser (?7. p. Chcm. 1901 [ii] 64 274) states that after inany crystallisations he never found any salt to melt above 1 9 8 O . The melting points now recorded f o r the d- and Z-hyoscine aurichlorides are for salts prepared in two different ways and recrystallised to constant melting point.In substantial agree-ment with these values Thorns and Wentzel (Ber. 1901 34, 1023) give 2 0 4 O and Finnemore and Braithwaite (Zoc. cit.) recor 480 RING THE RESOLTTTION OF HYOSCINE AND ITS several almost pure commercial Z-hyoscine hydrobromides as furnish-ing aurichlorides melting a t 200-204°. Tropic Acid. The 4 cid Constituent of Hyolscinc. As has already been stated Gadanier showed that Lhyoscine on hydrolysis with the base tropine gave Z-t'ropic acid. This crude acid on purification by recrystallisation from water gave Z-tropic acid melting a t 125-126O and having a specific rotatory power in water [a] -7l.8*.Gadamer regarded this as optically pure, since Ladenburg and Rundt (Bey. 1859 22 2591) record the value [alD +71*4O for pure &tropic acid melting at 127-128'. Instead of employing a base for the hydrolysis Z-hyoscine has now been hydrolysed by boiling with dilute hydrochloric acid, when a crude Z-tropic acid (m. p. 125-127° [aID -70'5O) was obtained which on recrystallisation gave 7-tropic acid melting a t 127-12B0 and having [a] -76O in water. As this rotation was numerically considerably greater than the value recorded by the aforementioned workers it. was necessary to repeat the resolut?ion of tropic acid. A comparison of the results obtained with those of previous investigators is shown in the following table: Ladenburg and Hundt. Amenomiya.1 Quinine d-tropate-[aln 95 per cent.M. p. ............... 1SG-187' zF(o-looo dcohol ......... I -M. p. ............... 17s' 1 84- 1 S 5" Quinine 1-tropate-[aD 95 per cent. - alcohol ......... -d- Tropic acid-M. p. ............... 127-128' 126-127' [alD water ...... I -[alD alcohol ...... +71.4' +71-Y M. p. ............... 123' 126" [a]* water ......... - -72.7O [aIn alcohol ... - 65*1° 1 - T T O ~ ~ C acid--Arch. Pharm. 1902 24.0 501. King. 191*5-192.5" -114' 185-1 86" - 141' 128-129' + 81.6' + 7 1.8' 1 2 8- 129 O - 81.2O -It is a t once seen that Ladenburg and Hnndt's value [a] + 71.4" is the value in alcoholic solution Gadamer having regarded i t as t.he value in water as the aforementioned investigators were no COMPONENTS TROPIC ACID AND OSCINE.481 very explicit merely stating that t.he specific rotatory power was + 71'4O in solutions of various concentration. As previous workers appeared to have experienced some difficulty in obtaining pure quinine I-tropate from the mother liquors a variant was made by converting the recovered partly resolved I-tropic acid into the quinidine salt. Further by use of the two stereoisomeric alkaloids quinine and quinidine but cammencing the resolution with quinidine 55 per cent. of pure quinidine I-tropate was first isolated then an 80 per cent. yield of pure quinine d-tropate and simultaneously a 14 per cent. yield of pure quinine I-tropate. On reverting to quinidine a further 19 per cent. yield of quinidine I-tropate was obtained. I n this way, approximately 84 per cent.of the tropic acid was resolved into its constituents. It would however be probably an advantage other factors being equal to start the resolution with quinine and follow with quinidine since experiment showed that starting with quinine 66 per cent. of quinine d-tropate was obtained pure and, as stated above starting with quinidine only 55 per cent. of quinidine I-tropate could be separated. It is interesting to note that previous attempts to use quinine and quinidine for the resolution of externally compensated acids, in t.he above sense have not always been successful. Whereas Fischer Scheibler and Groh (Bw. 1910 43 3022) found that in the resolution of f ormyl-/3-alanine quinine separated the laevo-component and quinidine the dextro- Scheibler and Wheeler (Ber., 1911 44 2686) found that in the resolution of dl-leucine the same two alkaloids always gave the laevo-acid first.This was also the experience of McKenzie (T. 1899 75 969) in the resolution of mandelic acid. Oscine. The Basic Hydrolytic Product of Ryoscine. There are numerous instances recorded in the literature of the hydrolysis of I-hyoscine by alkalis but the basic hydrolytic pre duct oscine C8HI3O2N was invariably found to be devoid of optical activity even in the presence of borates or strong acids (Gadamer Arch,. Pharm. 1901 289 322). The only occasion on which I-hyoscine has been hydrolysed by acids is recorded by Hesse (Annulen 1892 271 loo) who carried out the hydrolysis with concentrated hydrochloric acid in a sealed tube a t 80-100°.This furnished the base oscine but there is no record of its polari-metric examination. To decide this matter pure I-hyoscine has now been hydrolysed by boiling with excess of 10 per cent.. hydrobromic acid the chang 482 RING THE RESOLUTION OF HYOSCINE AND ITS of rotation being followed pdarhetrically. When hydrolysis was complete %he Z-tropic acid was removed by extraction with ether and the residual solution of oscine hydrobromide was found to be devoid of optical activiky. As Tutin had shown thati benzoyld-oscine on hydrolysis with hydrochloric acid gave 6-oscine the hydrolysis of Z-hyoscine wae repeated using hydrochloric acid. Again the oscine hydrochloride solution was inactive. As it was conceivable that the benzoylation of mcine might have effected some fundamental change in the configuration of oscine whereby the benzoylated pro-duct became externally compensated and theref ore capable of resolution it was necessary to prove that oscine itself could be resolved into its conskituents d- and Z-oscine.Several salts of oscine with optically active acids were prepared and examined. The salt with Reychler's camphorsulphonic acid was not obtained crystalline but with d-a-bromo-a-camphor-sulphonic acid a markedly crystalline salt was obtained which melted a t 232-233O. This salt however pro'vved to be a partial racemate. With 6-a-bromo-P-caxnphorsulphonic acid a very readily soluble crystalline salt was isolated but beyond recording a single rotation it wag not followed further as &tartaric acid was found to be eininent'ly suitable for the resolution of oscine.The separation of 61-oscine into its two pnre cnantiomorphs can be effected by use of d-tartaric acid alone the acid salts being used for this purpose in aqueous solution. The more sparingly soluble salt which separated almost pure after two crystallisations, is 1-oscime d-hydroye?z tartrate rrionohydmte (m. p. 1 73-174', anhydrous) which crystallises magnificently in clear tablets 01' octahedra. Employing 14 grants oi oscine i n combination with IL like quaiitity o€ d-tartaric acid between 70 and 80 per cent. of this component was separated with no great difficulty. The d-oscine d-l;?/&ogen tartrate contained in the mother liquors can be obtained pure either by isolation as the nzonohyd~ate a very readily soluble metastable salt melting below looo or preferably, aa the stable anhydrous salt (m.p. 167-168O). The proportion of this salt obtained in a state ot purity is largely a function of time as il; crystallises very slowly butl unconimonly well in hexagonal-shaped tablets from the cold syrupy mother liquors. 1-OscZ'ue picrate hydrochloride and base were obtained without bringing into contact with alkali a t any stage but this was found afterwards to be an unnecessary precaution as Z-oscine is not racemisecl by boiling with 10 per cent. acid or alkali and only partly by satmated baryta a t 1 5 0 O . d-Oscine picrate hydrochloride and base were prepared in the usual manner by liberating the base from the hydrogen tartrat by a strong alkali.with the dl-oscine salte are shown in the following table: The properties of these salts as compared Base-Appearance ...... M.p. ............... [ a ] water ...... l'z'crate-Appcarttnce ...... M. p. ............... Appearance ...... HydrochZoride-121.p. ............... [ale in water of basic ion ...... d- %cine. Z- Oscine. Needles. Needles. 1O9-l1O0 109-110' -1- 54.8' - 52.4" Dimorphous Diinorphous rhombs and rhombs and needles. needles. 237-238' 237-238' Warts composed Warts composed of prisms. Very of prisms. Very deliquescent. deliquescent. 2 7 3-37 4' 273-274" +24*0' - 34.3' dl-Oscinc. Needles or tablets. 100-110" Ir'lattencd rhombs. 23 7-23 8 ' Warts composed of prisms (anhy-drous).Tablets (hydrated). 273--274" It is noteworthy that the active and dl-isomerides have the same melting points and mixtures of the active with the dl show no depressioii of the melting point. I n the case of the bases the meltiiig-point curve is thus of the sanie type as is found for the camp horoximes. By hydrolysis of benzoyl-d-oscine Tutin (Zoc. c i t . ) obtained a value for the d-oscinium ion of [ a ] +129*,* which he regarded as only approximate. As this was very different from the value recorded above it was necessary to repeat the reso'lution of benzoyl-oscine. Pure benzoyl-d-oscine hydrochloride was obtained having a value [a] + 1 3 * 4 O f o r the benzoyl-d-oscinium ion in agreement with the value + 1 2 * 9 O calculated from the rotation of the bromo-camphorsulphonate.This hydrochloride was submitted to hydro-lysis by acids and alkalis. I n both cases the result was the same, a solution being obtained which on removal of benzoic acid gave values [aID +26*Oo and [ a ] +25.8O by acid and alkali hydrolysis respectively for the d-oscinium ion. Moreover the hydrochloride and picrate were isolated from the product of acid hydrolysis and the properties were in agreement with the d-oscine salts obtained by the tartaric acid resolution of oscine. In t e rape t u t i o n of h? e s ul t s . The questio,n uow arises which of the eight possible optically active stereoisomeric hyoscines do1 d- and Z-hyoscine represent 5 * Tutin gives the value -k 77-7' having overlooked the loss of the benzoyl group 484 KING THE RESOLUTION OE" HYOSCINE AND ITS The various possibSties are shown in the following table the centre column representing optically pure forms which combined, as shown by the arrows yield partially racemic forms : Partid racemates.Optically pure forms. 1. I-tropyl-d-oscine 5 dl-tlopyl-d- / oscine , 2. I-tropyl-I-oscine \/' Partial racemetes. 3. d-tropyl-d-oscine -- J'\ 6. dl-tropyl-I-oscine -+ 8. d-tropyl-dl-osciric k\ 4. d- trop yl-l-osoine /* Of these 1 to 6 are a t once excluded since I-hyoscine on bydro-lysis with acid or alkali gives I-tropio acid and dlacine whereas benzoyl d-oscine under similar conditions yields optically pure d-oscine. On these grounds I- and d-hyoscine represented by 7 and 8 are therefore partially racemic esters I-hyoscine being a mole-cular combination of I-txopyl-d-oscine and I-tropyl-2-oscine whilst d-hyoscine is a similar combination of d-tropyl-d-oscine and d-tropyl-I-oscine.The known inactivation of I-hymcine by alkalis would on this basis simply consist in the change of configuration of the tropyl portion of the molecule probably through the intermediary of the CH,*OH CH,*OH CH,*OH I I OH iI CO,R enolic form and each constituent ester of the partial racernate should give rise to a new ester. In support of this some work which is reserved for future publication on the re-resolution of racemised d-hyoscine has resulted in the isolation of tlwo esters only d- and I-hyoscine which is not surprising as these being partial racemates would contain the four expected optically pure forms.As opposed to the partial racemic ester nature of d- and I-hyoscines may be cited the rarity of the occurrence of partial racemates in nature and the novel bebaviour of the hyoscines towards d-bromocamphorsulphonic acid which so far as d-hyoscine is concerned only resolves dl or weakly active hyoscine as far as the partially racemic ester stage. Although this behaviour is as far as it has been possible to ascertain unique it is only necessary to PhOC0,R =+ Ph*C:C<OR X Ph&H COMPONENTS TROPIC ACIb AND OSCINE 455 Double raceinate C. +‘ recall that in the early days of the application of Pasteur’s methods of resolution the formation of partially racemic salts was only rarely observed whereas a t the present time it’ is recognised as of very frequent occurrence.A t the present stage of the investigation there seem to be only two other possible alternatives both of which appear rather remote. In the first place d- and Z-hyoscines may be optically pure forms which owing to some specific effect of the tropyl group yield rZZ-mcine on hydrolysis or secondly oscine may possess a different configuration in the tropyl ester from that in the benzoyl ester and in the free state whereby the tropyl group is attached to an internally compensated $-oscine which on hydrolysis gives rise to a resolvable oscine. dZ-Hyoscine raises a further difficulty for there are three possible c!Z-hyoscines as is shown by the following arrangement : ‘Z- tropyl-Z-oscine ‘-+ d-tropyl-d-oscine /* ‘9-dl-tropyloscine ,4.dZ-tropyloscine B. l- t ropyl-d-oscine ,d-t ropyl- Z-oscine /-+ The optically pure forms may be combined in pairs as indicated, to form two different simple racemates,.A and B or all four forms may be combined to form a double racemate C. On the accepta-tion of the partial racemic ester nature of & and 2-hyoscines, dl-hyoscine hydrobromide crystallising with three molecules of water and obtained by crystallising together equal w e i g h of d-and Z-hyoscine hydrobromides constitutes a double racemic salt, the absence of any indication of the presence 0f another salt and the identical crystalline appearance of d- or Z-hyoscine hydre bromide and this salt supporting this view. Moreover the base crystallising with 2H20 is the base contained in this dJ-salt as both give the same picrate.As has already been indicated in the opening paragraph there is another hydrate of racemic hyoscine base containing 1H,O and meltling a t 56-57O. It was first obtained by Schmidt (Arch. Ph,arnz. 1894 232 409) was re-examined by Luboldt (ibid. 1898, 236 ll) and more fully investigated by Gadamer (ibid. 382). The last-named investigator showed that ths dihydrate can readil 486 KING THE RESOLUTION OF HYOSCINE AND ITS be converted ilito the monohydrate but the reverse change was only effected with difficulty. Both hydrates were afterwards described by Hesse ( J . pr. Gl~ent. 1901 [ii] 64 363) who could not substantiate Gadamer’s claims. In reply Knnz-Krause (ibicl., 1901 [ii] 64 569) examined Gadamer’s three-year-old specimens, and the dihydrate had in every case changed into the base (m.p. The author has not so far been successful in obtaining this monohydrate so is unable to state with certainty what is the rela-tion between these two racemic hydrates from the point of view of the partial racemic ester nature of d- and I-hyoscine. The bearing of these results on the structural formula of oscine deserves a passing notice. The most recent; and most complete formixla is that put forward by Hess (Bey. 1918 51 1007) who ascribes t o oscine the structure 51-550). where the linking u is regarded as being probably attached to one of the carbon atoms of the piperidine nucleus. The experiments on the stability of the active oscines towards racemising agents certainly support this linking.Pyman and Reynolds (T. 1908, 98 2077) have pointed out the close relationship which exists between tropine ornine and teloidine all of which contain eight carbon atoms and a hydroxyl group in the molecule. Moreover, t,heir acyl derivatives are found together in Datum meteloides. The author is tempted to make the suggestion that like tropine, the oxygen atom in question in oscine is attached to the y-position in the piperidine ring. Oscine would therefore be the internal anhydride of a trihydroxytropine and this trihydroxytropine may R l e Tropine. 318 d - or Z-Oscine COMPONENTS TROPIC ACID AND OSCINE. 487 H Me Teloidine ? 'Ieloidiue would thus be internally compensated and in support of this view may be cited the occurrence of meteloidine (tiglyl-teloidine) in nature devoid of optical activity and the non-resolu-tion of meteloidine by bromocamphorsulphonic acid.Further, Hess (loc. czt.) observed that dihydro-oscine which undoubtedly has the formula ,CH2-CN-CH*OH hMe I , \CH,-UH-CH*OH CH2< I readily produces a silver mirror wheh treated with ammoniacal silver nitrate solution. The author finds that teloidine and meteloidine unlike oscine also readily reproduce this characteristic of dihydro-oscine the reducing property being probably associated with the adjacent hydroxyl groups as is found in tartaric acid. E X P E R I M E NTAL. Resolutiom of Tropic Acid. IVith Q uin.ine.-Following the method described by Ladenburg and Hundt (Be?.. 1889 22 2591) tropio acid (25 grams) was neutralised to litmus with quinine base (48.8 grams anhydrous) in hot 50 per cent.alcohol. A 49 per cent. yield of a quinine tropate separated. It melted a t 176-179* and had [a] -126O in 95 per cent. alcohol ( c = l ) . For further purification it was recrystallised from 95 per cent. alcohol and after five crystallisa-tions 17 grams of quinine d-tropate were obtained pure. By working once more through the mother liquors a further 7.4 grams of pure salt were obtained without difficulty. These two separations combined represent 66 per cent. of the dexfrwomponent. Quinine d-tropate crystallises from 8 parts of boiling alcohol in VOL oxv. 488 KING THE RESOLUTION OH HYOSCINE -4ND ITS groups of radiating needles, It melts a t 191.5-192-5° (195.5-196.5O corr.) : In water it is very sparing soluble.0.1035 dried a t looo gave 0.2706 CO and 0.0633 H,O. C= 71.3 ; H = 6.8. C,oH,0,N,,C9H1003 requires C= 71.0 ; H = 7:O per cent. The specific rotation was determined in 95 per cent'. alcohol. c = 1.01 ; I = 2-dcm. ; aD - 2 O 1 8 1 ; [a] - 1 1 3 . 8 O . In absolute alcohol the rotation is smaller. C 1.013 j Z=2-dm. j aD - 2'6.4' ; Cali - 104.0'. c = 1.002 ; Z = 2-dcni. ; a - 2O5.4' ; [.ID - 104.3O. As previous observers appeared t o have experienced some diffi-culty in obtaining quinine I-tropate in a state of purity no attempt was made a t this stage to isolate this salt. The mother liquors were therefore combined and the t.ropic acid containing excess of the laevo-component was recovered. Small test samples were con-verted into the neutral salts with brucine cinchonine and quin-idine but although the two former gave cryst'alline salts the crystallising power of these was not so pronounced as the salt with quinidine.Accordingly 3.5 grams od this partly resolved tropic acid were crystallised as quinidine salt when 4.2 grams of quinidine I-tropate were obtained of constant specific rotatory power. Resolution with Quinidine and &uinine.-dl-Tropio acid (15 grams) was neutralised with quinidine dissolved in 50 C.C. of 95 per cent. alcohol. On keeping 22 grgms of crystalline material separated. It was obviously a mixture and had [a] +151° in 95 per cent. alcohol (c = 2). After four crystallisations the specific rotation was constant a t [a]= +145O and the collected quinidine I-tropate amounted to 5.5 grams.Quinidine 1-tropte crystallises from 95 per cent. alcohol in which it is soluble in its own weight atl 80° in clusters of well-formed stout transparent prisnis containing one molecule of water. These exhibit a pronounced heliotrope triboluminescence when powdered in the dark. The air-dried salt when heated in a capillary tube shrinks from about l l O o liquefies between 118O and 120° and effervesces a t 1 2 4 O . When however it' is exposed on a watch-glass to a temperature of 90° it melts completely and crystallises again on addition of alcohol : 0.2038 air-dried lost 0.0069 a t looo. 0.1029 , gave 0.2590 CO and 0.0672 HeO. C=6$7; H& =3-4. H = 7.3. C20H2402N,,C,H1003,HO0 requires H,O = 3.5 ; C= 68.5 ; H = 7.1 par cent COMPONEHTY 'I'ROPIC ACID AND OSUINa.4.89 I t s specific rotation was determined in 95 per cent. alcohol and is dependent on the concentration. c =0*979 ; E = 2-dm. ; a + 2O55.2' ; [a] 4- 149'1O. c = 1'995 ; Z=2-dcm. ; a + 5'46.5' ; [a] + 144.7'. The mother liquors were worked up further and gave an addi-tional 7.2 grams [aID + 146O. This is approximately a 55 per cent. yield of quinidine I-tropate. As the liquors now showed no tendency to crystallise a t all reladily they were combined and the tropic acid was recovered by use of ether and hydrochloric acid (10 per cent.). On now crystallising as the quinine salt after three crystalliuations 14.8 grams of quinine d-tropate were obtained pure [aID -114O ( c = l ) and a further 2.8 grams with [ a ] -115'.The first mother liquors on concentration deposited quinine I-lropate as a homogeneous crop (4.8 grams) of glistening tri-angular plates having [a] -139O and melting a t 184-185'. It was recrystallised twice froD 95 per cent. alcohol the specific rota-tion remaining constant a t [a], -140*7O and the melting point a t 185-186O but the form of the crystals changed t o needles very similar in appearance to1 quinine d-tropate. It is very much more readily soluble in hot alcohol than is quinine d-tropate. The diverse crystalline forms described above do not constitute a case of dimorphism but merely represent extreme crystalline forms. By suitably modifying the conditions of crystal-lisation a series of intermediate forms may be obtained consisting of more or less elongated trapezoidal plates.Unlike quinine dtropate this salt exhibits a very faint triboluminescence the intensity of which is 'not visibly affected by the form of the crystals : 0.1083 dried a t looo gave 0.2817 CO and 0.0668 H,O. Quinine I-tropate melts a t 185-186O (189-190° corr.). C=71*0; H=6*9. C20H,,0,N,,C9H,,03 requires C= 71.0 ; I€= 7.0 per cent. The tropic acid contained in the residual liquors was recon-verted into the quinidine salt when 4.3 grams of quinidine 2-tropate were obtained having [a] + 1 4 5 O . The residual solution was n o t further examined. By the use of the two bases quinidine and. quinine there were thua isolated in an approximate state of purity 88 per cent. of quinine and quinidine Z-tropates and 80 per cent.of qpinine d-tropatta. The proportion of tropic acid resolved is 84 per cent. Quinidine d-tropate was not isolated but on keeping in the ice chest a small crop of white woolly needles separated from the u 490 KmQ THE RESOLUTION 03' HYOSOTNE AND ITS mother liquors (together with quinidine Z-tropate) which was probably this salt in an impure condition. d-Trolpic Atid. Pure quinine d-tropate (16 grams) was acidified with 50 C.C. of 5 per cent. hydrochloric acid and completely extracted with purified ether. The crude acid so obtained (5.1 grams) melted a t 127-12S0 and had [a] +77.2O in water (c=l). On recrystal-lisation from water the melting point rose to 128-129O and the rotation t o [a]D +7g0. After two more crystallisations the melt-ing point remained unchanged but the rotation rose to [a] +81'6O.d-Tropic acid crystallises fram water in delicate lustrous scales, which become transformed on keeping in contact with the solution into elongated prisms of hexagonal cross-section. Both forms melt a t 128-129O (129-130° corr.) and are anhydrous: 0.2014 was equivalent to 11.9 C.C. N/l@baryta. M.W. = 169. The specific rotation was determined in alcohol and in water. In w a k : c= 1.027 ; I = 2-dm. ; a + 1O40.6'; [a] + 81.6'. In absolute alcohol: The yield was 3.1 grams. C,H,,O requires M.W. = 166. ~=0'997; Z=2-da.j a + 1°24*2/; [a] + 70.3'. c=2*472; Z=2-dcrn. ; QD + 3°33T; [a] +71-S0. The specific rotation of the ion was determined by dissolving 0.200 gram of &tropic acid and 0.0638 gram of anhydrous sodium carbonate in water and making up to 20 C.C.The dissolved carbon dioxide was not removed: Z=2-dcm.; a +l022*9/; [aID for ion+69*4O; [MID for ion+114*7O. Gadamer (Arch. Pharm. 1901 239 294) has previously noted a fall of rotation of I-tropic acid on converting into a salt but has not followed it quantitatively. l-Tropic Acid. l r r m Quini&ne 1-Tropat e.-Four grams of pure quinidine Ltropate on treatment with hydrochloric acid (10 per cent.) and extraction with ether gave 1.35 grams of I-tropic acid which, after three crystallisations from water gave 0.5 gram melting at 128-129O (129-130° corr.). The specific rotatory power was determined in water and was slightly lees than that of the purest &tropic acid : c = 0.995 ; I = 2-dcm.; a - 1'37'; [a,] - 81.2' COMPONENTS TROPIC ACID AND OSCINE. 491 From Quinine l-Tropate.-5*8 Grams of this salt gave 2.0 grams of Z-tropic acid which was recrystallised four times from water, giving 1.35 grams melting a t 128-129O and with a specific rota-tion -81.2O: c = 1.002 ; I = 2-dcm. ; a - 1O37.6' ; [a] - 81.2O. I-Tropic acid prepared in this way had the same general proper-It is very sparingly soluble in cold benzene, From ties as the dextro-acid. but freely so in cold methyl ethyl ketone or ethyl acetate. the latter solvent it crystallises exceedingly well in clear tablets : 0.1975 was equivalent t,o 11-72 C.C. N/lO-baryta. M.W. 168. C9H,,O3 requires M.W. = 166. The Resolution. of OsCinc. Partial Racemate with d-a-Bromn-.rr-cam~?i,orniilpholnic A c 2 .-Two and a-half grams of oscine were converted into this salt which was very conveniently recrystallised from absolute alcohol. The first crop of crystals weighed 4.9 grams melted a t 232O and gave [aID +58*8O in water (c=2). It was recrystallised twice more from absolute alcohol yielding finally 3.6 grams meltJng a t 232-233O. The specific rotation determined in water was prac-tically unchanged : c = 2.001 ; I = 2-dcm. ; a + 2O22.4' ; [a]= + 59.3O; [MI + 276.7O. The value for the molecular rotation 276.7O is in good agreement with the molecular ionic value 278.7 for bromocamphorsulphonic acid (Pope and Read T. 1910 97 2200). dl-Oscine d - a- b romo-?r -camphorsulp?& onat e crystallises exceed-ingly well from absolute alcohol in clear diamond-shaped plates.Ten parts by volume of boiling absolute alcohol are required to dissolve one part by weight of the salt. It melts a t 232-233O (237-238O corr.) : 0.0995 dried a t looo gave 0.1703 CO and 0.0526 H20. C,H,,O,N,C,,H,,O,BrS requires C= 46.34 ; H = 6.05 per cent. Re hauiozir with d-a-BromefLcamph orszrlphonic A cid.-Six and a-half grams of oscine were combined with an equivalent of d-a-bromo-&camphorsulphonic acid. The salt could not be obtained crystalline either from water or from a mixtlure of ethyl acetate and absolute alcohol. A very concentrated solution of the salt in absolute alcohol however crystallised as a cake of needles on keeping for a prolonged time in the icechest. It was too readily soluble for systematic fract-ionation from absolute alcohol and the addition of dry ethyl acetate unexpectedly prevented crystallisa-C= 46.69 ; H = 5-91 tion.and weighed 8 7 grams. ratation was determined in water: The first crop of cryshls from absolute alcohol was collected, It melted at l50-3Mo a d ib specific c = 2.00 ; I = 2-dcm. ; a + 2O27-4f ; [aJD + 61.4O ; [MI + 2 8 6 - P . This product was recryptallised f r o a absolute alcohol but in the meantime tartaric acid had effected the resolution of oscine quite simply so the investigation of the above salt was dis-continued. With Camphor-P-sulphonic A cid.-Attmpts to crystanise this salt were ineffective. Resolution b y d-Tartaric Aeid.-dZOsciae (13.9 grams) was oon-verted into its d-hydrogen tartrate by addition of 13.5 grams of d-tartaric acid in aqueous solution.The solution was concentrated to a low bulk and gave 13.8 grams of a salt crystallising in hexagonal plates and with a specific rotation [ujD +3*5O in water. After one more crystallisation it gave 14.2 grams a%d had [a] + Islo. This value was not appreciably altered by subquent repeaked crystallisation and represents the op&d constaQ6 of the salt I-oscine &hydrogen tartrate. 1-Oscine d-hydrogen tartrate crystallises with one molecule of water of crystallisation in large and cleap octahedra. Very often these have a flattened appearance and more rarely one-half the faces may be almost entirely suppressed with the formation of tetrahedra. Unbroken crystals melt at 1 3 4 O wit4 &ervemnce, but when powdered partly melt a t about 130° and gradually liquefy up to 160O.The anhydrous material meits ah 173-174O (176*5-177.5* corr.). It is readily soluble in cold water >bbut the crysbls can be washed with 50 per cent. alcohol with 3 W e loss. d?rom dilute alcohollio so1utiom this wit tends to saparah as an oil : 0.3126 dried at’ 1 0 5 O lost 0.0181. 0.1159 dried a t looo gave 0.1996 CO and 0.0690 H,O. H,O=5.8. C8HI3O2N,C4H6O6,H20 rbquirss H,O 5-6 pet cent. C=47.0; H=6*7. C,W,302N,C?4H,0 requires C = 47.2 H = 6.3 per cant. The specific rotation was determined in water : ~=2.007; 2=2-dcm. ; a + 2-56’; [a]D + 1-06’. The average value for nine different samples of the pure wlt of [ u ] ~ was -t 1 * 2 9 O the ext~en1e5 being +0*93’ and + 1.860. Taking fhh average value for [a]D the molecular rotatlion [MI ie ccll~u-lated as +4*18.O and employing Lrtnddt’s value (Ber.1873 6, 1075) for the molecular rotartion of ammoaium hydrogen Wtmfe +#2*W0 the value for the I-oscinium ion is [MJ -38*66O whence On continuing the fractionation of tihe mother liquors 71 per cent. of the E-mine &hydrogen tartrate present was isolated in a s t a h of purity. The separation was materially accelerated by inoculation of the less mobile solutions 'followed by addifioa of alcohol ih insufficient amount to precipitate an oil. The residual solutions BOW relatively rich in d-mcine d-hydrogen tartrate were concentrated to a syrup and on allo'wing t o remain in a deaiuchtor exposed to a dehydhting agent crystallised as a striated mass of cp'ystals.These were collected freed from the1 adhering syrupy mother liquor firs% by suction and then by very limited use of 50 per cent. alcohol as a 'washing agent. The salt was a &no-hydrate and gave [a]h +23.7O. It was recrystallised from water, and separated under similar conditions as a felted mass of needles. These now gave [aID + 2+7.3Q (anhydrous). d-Oadne d-h?ydrogen tartratu mmiohydkate melts from 55O t o G5O forming a meniscus a t the latter temperature. It readily effloresces when exposed t o the atmosphere and when dehydrated in a vacuum over sulphuric acid loses its water of crystallisation. The anhydrous material still melts atl 55-65O. This is probably the melting point of an amorphous form as on keeping it acquires the melting point of the crystalline anhydrous salt namely, 163-185" (see below).Three different samples of the salt were analysed for their water content. The first representing a freshly collected salt gave the following result : and a salt which showed some signs of e@oresc0nce gave the following : fafD -24*70. 0.4502 dried over H,SO, lost 0.0320. H,O =7.1; 0.2023 lost 0.0Ogl. On keeping for some time this salt had completely effloresced: 0.1180 dried a t looo lost nil. 0.1180 dried a t looo gave 0.2055 CO and 0.0649 H,O. H20 = 4.5. C8HI3O2N,C4H6Os,HzO requires H,O = 5.6 per cent. C=47.5 ; H= 6.15. C8H,,O2N,C4H6O6 requires C =47.2 ; Ef= 6.3 per cent. The specific rotation of the dehydrated salt was determined in water : ~~0.949; Z=2-dc~n.; (ED +31.1'; [a] +27.3O. When the hydrated salt is washed with.absolute alcohol it is transformed into a white crystalline powder which is th 494 RMQ THE RESOLUTION OF RYOSCINE AND ITS anhydrous salt and the stable form a t the ordinary temperature. When crystallised from water the anhydrous salt separates from a syrupy solution very slowly in large hexagonal-shaped tablets, which unlike the hydrated salt can be washed freely with 50 per cent. alcohol. If a syrupy solution is inoculated with a trace of both forms hydrated and anhydfous the hydrated form crystal-lises first filling the liquid space and on keeping disappears entirely being replaced by the stable anhydrous form. For the isolation of pure d-oscine d-hydrogen tartrate the latter form is the more convenient. The process is however very slow owing to the solubility of d-oscine d-hydrogen tartrate and the slow velocity of crystallisation from viscous solutions.d-Oscine d-hydrogen tmtrate melts a t 167-168O (170-171° curr.). The specific rotation was determined in water and for a salt which had been crystallised to constant rotation : 0=1*016; Z=2-dcm.; a +34'; [aID +27-87O; [MI +85*17O. This gives a value +42-3O for the molecular rot'ation of the d-oscinium ion and [a] +27-10°. This is somewhat greater numerically than the value [a] -24.7 obtained by a similar calcu-lation for the I-oscinium ion. As this is beyond t h s limits of experimental error it is probably another example of t.he pheno-menon first. drawn attention to by Pope and Read (T. 1912, 101 760) who show conclusively that the molecular rotatory power in aqueous solution of certain salts of the type I-base &acid is in agreement with the value calculated from the sepgrab ions, but that the combination d-base d-acid gives an abnormal value.1-Oscine Picrate .-Six grams of pure I-oscine d-hydrogen tartrate were added to a boiling saturated solution of 4-25 grams of picric acid in 80 C.C. of water. As the solution cooled the major portion of the salt crystallised in long needles but when only lukewarm a denser form appeared in the shape of small modified rhombs. The yield was 6-35 grams and the melting point 237O (decomp.). The combined product was recrystallised from 35 C.C. of hot water, and on removing the source of heat separated a t once in long, glistening needles.These were collected while the solution was still warm the filtrate continuing to deposit solely needles for some time and then rhombs. The filtrate was heated t'o dissolve all the crystals and when cold only deposited the rhomb-like f o m of crystal which closely resembles dl-uscine picrate. The yield of needles was 4-95 grams melting a t 237-238O (decomp.) (242.5-243-59 corr.) whilst the rhombs amounted to 0.95 gram, and also melted at 237-238O (decomp.). Both forms ar COMPONENTS 'IXtOPIU AOTD AND OSCINE. 49s anhydrous and either form when mixed with dLoscine picrate, which itself also melts a t 237-238O shows no depression of the melting point. At the ordinary temperature the needle form of picrate is certainly the unstable one as is readily shown by adding a drop of saturated picric acid solution-to a few small crystals of I-oscine d-hydrogen tartrate and rubbing with a glass rod.The crystals dissolve instantly and a homogeneous crop of needles first makes its appearance followed quickly by minute rhombs and in a short time the needles will have entirely disappeared their dis-integration and solution being readily followed. with the aid of a microscope. This behaviour is useful as a test as to whether one is dealing with active or dl-mine salts since dl-oscine picrate has always been observed to separate in small flattened rhombs. 1-Oscine Hyc2rochlom'de.-Four grams of E-oscine picrate (needle form) were decomposed by shaking witlh three molecular propor-tions of 5 per cent. hydrochloric acid and the piaric acid was removed by ether.The solution of the hscine hydrochloride was completely dehydrated by repeated evaporation to drynws with absolute alcohol leaving finally a white crystalline powder which waa dissolved in 10 C.C. of boilihg absolute alcohol. On keeping, I-oscine hydrochloride separated in aggregates of small prisms in the form of warts; a few isolated prisms wer0 also present. The product was collected and amounted to 1.4 grams. It melted and decomposed a t 273-274" (281-282O corr.). A mixture with dl-oscine hydrochloride (m. p. 273-274O) also melted a t the same temperature. Unlike dl-oscine hydrochloride the laevesalt is very highly deliquescent. A direct comparison of the two was made by exposing a few crystals of each on watch-glasses to the atmosphere.In a few minutes the Idem-salt had completely liquefied whilst the &salt was apparently unaffected. On keeping for an hour how-ever the latter showed signs of deliquescence and the deliquesced salt recrystallised in well-f ormed tablets melting partly a t about looo and probably representing the monohydrated dl-oscine hydro-chloride described by Luboldt (Arch. Pharm. 1898 236 18). The specific rotation of 2-oscine hydrochloride was determined in water employing a salt which had been dried a t looo: whence [a] for the I-oscinium ion is -24.2O whereas the value calculated from the molecular rotation of I-oscine &hydrogen tartrate was - 24'7O. l-oscine Hydrochloride from l-Oscine Picrate (Rhombs).-As has been indicated above dLoscine picrate and I-mcine picrate melt a t the same temperature and the stable modification of ~ = 0 * 9 9 7 ; I=2-dm.; a - 23.6'; {a]= - 19.71O; [MI -37.76'; u 4Q6 HINU THE BESOLUTION OF HYQSUIRE AND ITS Z-oscine picrate crystallises very similarly to dl-wcine picrate. It was therefore necessary to prove that this stable form of I-cmcine picrate did actually contain the active base. Accordingly 0.5 gram of E-oacine picrats (rhmbs) was converted as quantitatively aa pmsible by means of ether and t h r e molecular proportions of N / 10-hydrochloric acid into I-mcine hydrochloride. The solution was concentrated somewhat and made up to 20 C . C . I n a 2-dcm. tube the observed rotation was a -25*3' from which it is calcu-lated that the koscinium ion has [a] -2l0 a value in good agree-ment with that observed directly for I-oscinium hydrochloride.The solution was then dried and the hydrochloride recrystallised from alcohol. It gave 0.11 gram of highly deliquescent Z-oscine hydrochloride melting a t 271-272O' and when twted with satu-rated picric acid solution gave the unstable needle form of I-oscine picrate changing into rhombs. l-Oscime Base.-To avoid the action of alkalis which it was thought might cause partial racemisation l-oscine base was pre-pared as follows. I-Oscine picrate (4.75 grams) was treated with three equivalents of dilute sulphuric acid solution and the picric acid remaved by purified ether. After treating with charcoal t o remove the last traces of picric acid the solution was concentrated under diminished pressure to about 20 c.c.and excew of pure barium carbonate added. On allowing to remain overnight the solution was free from sulphanion and only contained I-oscine partly present as carbonate. The major portion of bhe I-oscine was readily removed by extraction with freshly purified chlorof o m the remainder being retained by the dissolved carbon dioxide. When the latlter solution was evaporated t o dryness in a vacuum over sulphuric acid and redissolved in a little water the rest of the oscine was readily extracted by chloroform. I n this way the I-oscine was recovered quantitatively as base. The first chloroform extract on complete removal of the solvent crystallised a t once. The product was white and amounted to 1.45 grams. It had a specifio rotatory power of [a], - 5 2 ~ 8 ~ in water.It melted a t 109-llOo the same as dl-oscine whilst a mixture of the two showed no depression of the melting point. When recrystallised from light petroleum it separated in long needles. The melting point was unchanged a t 109*5-110*5° (corr.). The specific rotatory power was determined in wat'er : c = 1.010; Z=2-dcm. ; a - 1O3.6'; [a]= - 52'4O. With Mayer's reagent (potassium mercuric iodide) Loscine base gives no precipitate but in the form of a salt it gives a crystal UOalZPOM.k!XTt” TROPIC ACID AND OSCINE. 497 line precipitate. The presence of a slightl excess of aci’d prevents the separation of crystals. dZ-Oscine behaves similarly. Action o j Acids and Alkalis 091. l-Oscine.-A solution of 0.2 gram of I-oscine in water having au observed rotation of a -lQ1.7/ in a 2-dcni.tube was treated with one drop (0.04 c.c.) of 60 per cent. potassium hydroxide solutioii. After nineteen hours the observed rotfation was unchanged a - 1*1*5/. The same solution was heated 011 tho boiiling-water bath f o r ail hour. A t the end of this period the rotation was stJ11 -l01.7/. Five C.C. of 50 per cent. potassium hydroxide were! now added and the solution was boiled for an hour. Making a correction for the change in volume the observed rotation was unchanged aD - 1O1.2’. This means that 0.2.gram of 1-ascine was not racemised by boiling for an hour with excess of 10 per cent. potassium hydroxide solution. There was however partial racemisation when 0.2 gram of Z-oscine was heated with 15 C.C.of saturated baryta solution for four hours at 150° the value of [uID having fallen to aboutl one-half its original value. The action of botling 10 per cent. hydrobromic acid also failed to racemise Z-oscine for 1 gram of I-oscine d-hydrogen tartrate in 30 C.C. of 10 per cent,. hydrobromic acid had an observed rotation, a, -21*lt in a 2-dm. tube and after three hours’ boiling the rotation was practically unaltered aD - 22’6’. d-Oscime Base.-One gram of pure d-oscine d-hydrogen tartrate was dissdved in 10 C.C. of 5 per cent. sodium hydroxide solution, and the base ext$racted with purified chloroform. The combined extracts were clarified by shaking with anhydrous potassium carbonate filtered and the solvent removed by distillation. The residual base crystallised instantaneously throughout on touching one spot with a glass rod.A similar very high velocity of crystal-lisation had previously been noticed with the chloroform-free Zaevo-oscine base. It was crystallised from light petroleum and separated in long radiating needles of ten forming f asciated growths. It melted a t 109-llOo (109.5-110.5° corr.) and a mixture with pure dZ-oscine also1 a t the same temperature. Its specific rotation was determined in water : c=1*029; I=Z-dcm.; a + l O ’ 7 . 6 ’ ; [a] +54*8O. d-Oscize Picm.te.-The solution of the base which had been ,used for determining the rotatory power was treated wit<h an equivalent of picric acid (0.3 gram) and rapidly concentrated to about 10 C.C. On allowing t o cool long radiating glistening needles of d-oscine u* 498 KING 'PEB RESOLUTION OF .HYOSCME AND ITS picrate (0.3 gram) separated.These melted a t 237-238' (242-5-243.5O corr.). The mother liquors were concent'rated, and when quite cold the stable dimorph separated in small, flatkened rhombs exactly as observed in the case of Z-oscine picrate. This form also melted a t 237-238O. A mixture with d-oscine picrate obtained by acid hydrolysis of benzoyl-d-oscine also melted a t the same temperature. d-Oscinc Hydrochlom'de .-To complete the analogy with the laeuo-series this salt was prepared and its specific rotatJon deter-mined. For this purpose 0.2078 gram of I-oscine base was neutralised with the calculated quantity. 13.4 c.c. of N/lO-hydro-chloric acid and the volume made up to 20 C.C.In a 2-dcm. tube was found a 30.11 whence [a] for the d-oscinium ion is +24*Oo, a value in agreement with [a] -24.2O observed for the l-osciniurn ion. The solution just employed was evaporated to dryness and the residue crystallised from absolute alcohol when d-oscine hydro-chloride separated in warts with a few isolated prisms. The melt-ing point was 273-274O and the salt was very deliquescent. Resolution of Bensoyloscine. This was effected substantially as described by Tutin (T. 1910, 97 1793). Five grams of dl-oscine hydrobromide were converted into the base which was heated t o 1600 with 10 C.C. of benzoyl chloride, when a brisk reaction ensued with simultaneous crystallisation of the benzoyloscine hydrochloride. The solid was collected washed with ether and dried at' looo.The crude product melted a t 240° and amounted to 5.45 grams that is an 83 per cent. yield. It was dissolved in water and the solution after decolorisation with a little charcoal was rendered alkaline with sodium hydrogen carbonate and completely extracted with chlorsf orm. The benzoyloscine left on removing the chloroform was neutralised to lit8mus with d-a-bromo-.rr-camphorsulphonic acid and the salt frac-tionated from absolute alcohol. The d-benzoyloscine bromo-camphorsulphonab was obtained pure after three crystallisations, and melted a t 247-248O (Tutin gives 346-246'5O). The specific rotation was determined in water : c=1.998; ll=2-dcm.; a,+ 2°11-3'; [uID +54*74O; [MI +312*3O. The calculated value of the inolecular rotatory power of the d-benzoyloscinium ion is therefore 312.3-278.7 = 33*6O whence [&ID for the d-benzoyloscinium ion is +12*9O COMPONENTS TROPIU ACID AND OSCME.499 Bemzo yl-d-oscirte Hydrochloride. Pure benzoyl-d-oscine bromocamphorsulphonate (2.8 grams) was triturated with 30 ‘c.c. of wahr and three molecular proportions of sodium hydrogen carbonate. Benzoyl-d-oscine base appeared to separate in needles which were immediately dissolved by chloro-form. The free base on removal of the solvent was exact’ly neutralised with N / 10-hydrochloric acid and after filtering from a little greasy matter was concentrated rapidly under diminishea pressure to a very small volume. On keeping for a short time the whole of the liquid became filled with perfectly formed rectangular leaflets which in a few hours were completely transformed into fine needles.These were collected and washed with absolute alcohol. They amounted to 1.1 grams and melted and decom-posed a t 280° (287O corr.) (Tutin gives 283-284O). The product was anhydrous. Its specific rotation was determined in dilute aqueous solution : c = 2.005 ; 1 = 2-dcm. ; a + 28.35‘ ; [a]= + 11’79O ; [MI + 34083~. From this is calculated [a] + 13’4O for tbe benzoyl-d-oscinium ion, a value which compares favourably with the value +12*90 calcu-lated above from the bromocamphorsulphonate. This value is somewhat higher than Tutin’s value [a] + 10*Oo which is obtained by calculation from the value [MI + 297.0° for benzoyl-d-oscine bromocamphorsulphonate. Hydrolysis uf BenzoyLd-oscine.With Hydrochloric A cid.-The solution just employed (20 c.c.), containing 0.4001 gram of benzoyl-d-oscine hydrochloride was treated with 9-7 C.C. of 31 per cent,. hydrochloric acid thus bring-ing the volume approximately to 30 C.C. and the strength of the acid to 10 per cent. The rotation was observed and the solution was then boiled gently to hydrolyse the benzoyl-d-oscine the rota-tion being observed a t intervals just as is described under the hydrolysis of 1-hyoscine (p. 507). Initial reading, After 1 hour’s boiling +20*5’. After 3 hours’ boiling +22.0’. + 20’; I = 2-dm. Hydrolysis was now complete as there was a copious separation of benzoic acid and the solution gave no turbidity with Mayer’s reagent. The observed rotation is therefore due to the d-oscinium ion and the final value +22’ corresponds with a specific rotation of the d-mcinium ion of +26O which i s of t,he same order m tha 500 KING THE RESOLUTION OF HYOSCINE AND ITS obtained by calculation from the rotation of d-oscine d-hydrogen tartratel namely [a]= 27*1° and that directly observed [a]= 24.0°, for d-oscinium hydrochloride prlepared from the tartrathe.The free benzoic acid was removed by extraction with purified ether and the aqueous liquor concentrated to a syrup under diminished pressure on the water-bath. On dehydration of the syrup by evaporation with absolute alcohol the residue crystal-lised. It was dissolved in a little hot absolute alcohol and on keeping 0.07 gram of crystals resembling ammonium chloride were collected. 'They melted and decomposed in the iieighbourhood of 243O (pure d-oscine hydrochloride melts a t 273O) and were highly deliquescent .Twenty milligrams of this salt wheln tseatad with an equal weight of picrk acid in hob aqueous solut.joln gave a picrate crystal-lising in long fine needles and later a few rhombs separated a behaviour which is exactly reproduced by the addition of picric acid solution to) the pure d- or I-oscine d-hydrogen tartrates (p. 495). This picrate when collected and dried melted ancl cieromposed a t 237--23%O. A mixture with d-mcine picrate melkd iji the same Lath a t 237--23S0. The alcoholic mother liquors of tjhe a l ~ ~ e 0.07 gram of d-oscine hydrochloride were combined with picric acid (both in aqueous solution). The addition of the picric acid first precipitated amorphous matter which was separated ancl later a well-crystallised picrate.This salt crystallimd in mall rhombs melted and delcomposed at 2 3 5 O and was in all probability the stable form of d-oscine picrate. Wit F A lka&.-P ur e b enzoyl-d-oscine hydrochloride (0 * 400 9 gram) was dissolved in water and 5 C.C. of 10 per cent. sodium hydroxide were added. The oily base) which separated rapidly, disappeared on boiling. After an hour t.he solution was uooled and neutralised to Congo paper with hydrochloric acid. The pre-cipitated benzoic acid was completely removed by &her extraction, and the extracted aqueous liquor was also free from non-hydrolysed benzoyloscine as was indicated by the absence of a turbidity on treatment with Mayer's reagent i n acid solution.In neutral or very faintly acid solution it gave the well-crystallised precipitate observed with oscine salts. The solution was rapidly conuentrated and made up t o 20 C.C. In a 2-dcm. tube it gave a, +32.8/, whence the d-oscinium ion has [alD +25*8O a value in good agree-ment with that obseirved by acid hydrolysis [ a ] +26*Oo and that observed for pure d-oscine hydrochloride [ u ] ~ + 24*0° COMPONEINTS TROPIC! AUID ABD OSCIME. MI1 The starting material f o r the isolation of d-hyoscine consihd of 75 grams of well-crystallised hydrobromides obtained a8 a by-product in the manufacture of I-hyoscine. It was slightly lavo-rotatory having [a] - 4*1° (a=2*3 ailhydrous) and contained 9 per cent,. of water of crystallisation which was lost over sulphufic acid.It was regenerated t.0 base using sodium hydrogen carbanate and chloroform for the purpose the weight of base being about 55 grams. This was converted into its rsalt with d-a-brompr-camphorsulphonic acid and crystallised from a mixture of dry ethyl acetate and absolute alcohol. In a few days there was a copious crystalline separation which was collected and amou'nhd la 38.5 grams. It was deliquescent and had [a]D +46*4O ( b = 2 ) , and on two more crystallisations gave 8.8 grams of pure meCel&line brornocarnphorsulphonate. M e t eloidine d-a-bromm-camphorndphonat e cryatallism exceed-ingly well from absolute alcohol in which it is soluble to the extent of about 1 part in 10 (boiling) or from a mixture with dry ethyl acetate in clustera of prisms.It also crystallises well from watxx. It melts a t 224-227O (228*5-231-5O corr.) and is anhydrous: C=49*3; H=6.4. 0.1410 gave 0.2547 CO and 0.0808 H,O. C13H2104N,C10H1504BrS requires C = 48.75 ; H = 6.4 per cent. Its specific rotlatory power was determined in water: ~ = 2 * 0 3 9 ; I = 2-dcm. ; UD + 1'56' ; [a] + 47.42' j [MID + 268.7'. This value for the molecular rotation is somewhat smaller than that given by Pope and Read for the bromocamphorsulphonic acid ion (T. 1910 97 2200). That the meteloidine was inactive was confirmed in two ways: (I) A small quantity of the above salt was converted into base, avoiding conditions which might favour racemisation by using sodium hydpogen carbonate and chlorof o m . The base crptallised readily and was identical in appearance and other properties with a sample of meteloidine kindly supplied by Dr.Pyman and which was known t a be inactive (Pyman and Reynolds T. 1908 93, 2077). (2) One-half a gram of i-meteloidine base was converted into its bromocamphorsulphonate and the solution evaporated to dry-ness with absolute alcohol. The crystalline residue was triturated with a little dry ethyl acetate in which the crystals are practically insoluble and collected. The rotatioii of this salt representin M)2 IUNQ THE RESOLUTION OF HYOSOINE AND ITS practically the whole of the meteloidine was found to be the same as the previously described salt: c=1*969; Z=2-dcrn.; a +l051'; [a] +47*0°; [MI +266*3O. It melted a t 224--225O and a mixture of the two salts showed no depression of the melting point.ZsoTcc tion of d -Nyosci,i G Bro mocnmpiLorsulpi~ona t e .-On continu-ing the fractionation the original mother liquors gave a second crop of crystals 24-5 grams [a], +44*5O which after ten re-crystallisations gave 11 *6 grams of pure d-hyoscine bromocamphor-sulphonate melting a t 159-160° and having [.ID +60.lo. This was twice more recrystallised and gave 8.3 grams with [a] +60*3O. d-Hyoscine d-a-bromo-r-camphorsuZpho~tate crystallises from a mixture of absolute alcohol and excess of dry ethyl acetate in clusters of glistening acicular needles. After being dried a t l l O o i t melts a t 158-160° (161.5-163*5° corr.). I t s specific rotation was determined in water at 1 6 O . c=2'005 ; I = 2-dcm. ; a + 2'25'; [a] + 60.3O; [MID + 3 7 0 ~ 5 ~ .From this it is calculated that. the molecular rotatory power of the d-hyoscinium ion is 91*8O and the specific rotatory power [a] is +30a20 (see d-hywine hydrobromide). The salt is not deli-quescent : 0.2730 lost 0.0022 a t looo. Loss=O-8. 0.1238 dried at looo gave 0.2394 CO and 0.0675 H20. C,,H,,04N,C,,H,,0,BrS requires C= 53.7 ; H = 5.9 per cent. The -fractionation of the various liquors was continued when further small quantities 4.5 grams in all of meteloidine brorno-camphorsulphonate and an additional 12.5 grams of pure d-hyoecine bromocamphorsulphonate [a], + 60-5O were obtained. The original mother liquors now gave 10 grams of a deliquescent salt [a], +30-f3° and 2.7 grams [aJn -t-27*3O both of which had the properties of a slightly impure I-hyoscine hromocamphor-sulphonate which requires a calculated value of [a] +29O.On recrystallisation these gave salts of higher specific rotation. It was not found possible to isolate pure I-hyoscine bromocamphor-sulphonate from the mother liquors. d-Hyoscine I/ydrobmmic?P .-Six Lgrams of pure d-hyoscine bromo-camphorsulphonate were converted into base using chloroform and sodium hydrogen carbonate for the regeneration. The base was neutralised with hydrobrmic acid and the solution concentrated under diminished pressure. d-Hyoscine hydrobromide separated on keeping in large tablets (2 x 1 cm.). C=52*8; H=6*1 COMPONENTS TROPIC ACID AND OSCME. 503 d-Hyoscifie hydro bromide crystallises exceedingly well from water in rectangular-shaped tablets with bevelled edges.It crystallises with three molecules of water the hydrate melting in a capillary tube a t 54.5-55O (54-5-55. corr.). It is rendered anhydrous by drying over sulphuric acid in a vacuum. The behaviour of the anhydrous salt on heating is very varied. It sometimes melts sharply at 168O resdidifies and melts a t 193-194O (197-198O corr.). Occasionally the intermediate melt+ ing point is not observed a t all or is only indicated by a slight shrinking. I f the anhydrous salt is dried for half an hour a t 120° only the higher melting point 193-194O is observed. The probable explanation is that the product which melts a t 168O is either an amorphous f o m or a metastable crystalline form of the anhydrous salt and the transformation of one form into the other is accelerated by rise of temperature.I-Hyoscine hydrobromide behaves similarly : 0.1842 dried over H,SO, lost 0.0228. 0.1813 dried at looo lost 0.0226. 0.1587 , looo gave 0.0778 AgBr. Br=20.85. C17H,,0,N,HBr,3H,0 requires H,O = 12.33 per cent,. C,,H,,04N,HBr requires Br = 20.80 per cent. H,O = 12.38. H,O=12*47. The specific rotatory power of the hydrated salt was determined in water : c = 2.842 ; I = 2-dcm. ; a + 1°18*t?1 ; [a] + 23.02O. c=2-525; I=2-dcm.; a +lolo’; [adD +23.10°. The mean of these values gives for the anhydrous salt, [a] +26*3O and for the d-hyoscinium ion [a]= +33*2O. The latter value is in approximate agreement with that calculated from the molecular rotsation of the bromocamphorsulphonate (p.502), namely + 30-2O. d-Eyoscine A rwichloride .-d-Hyoscine bromocamphorsulphonate (0.3 gram) was dissolved in 5 C.C. of warm water and 5 C.C. of 10 per cent. hydrochlolric acid were added followed by 7 C.C. of gold chloride solution (I in 30). The aurichloride separated, partly in isolated minute rectangular plates but for the most part in fern-like growths or spangles. It me’lted at 202-203O and weighed 0.32 gram. It was twice recrystallised from 2.5 per cent. hydrochloric acid the melting point each time remaining at. 204-205O (208-209O corr.) (decornp.). The recrystallised solid separated in long flattened orange-yellow needles with both edges serrated : 0.1266 air-dried gave 0.0387 Au. Au =30-6. C,~R2,O4N,AuCl3,HCI requires As ’;= 30.7 per cent 604 RING THE REEIOLUTION OF HYOSCINE AND ITS d-Hyoscine Picrate.-Prepared from d-hyoscine bromocamphor-sulphonate by dadble decomposition in aqueous solution this salt separated as a netted mass of needles melting and decompoeing a t 187-1 88" (see I-hyoscine picrate).1-HpCi71.c. 1-Hyomhe Hydrobronzide.-The properties of this salt are the same as those of d-hyoscine hydrobromide. The rotation of the purest hydrobromide crystallisd from water was a fraction leas than d-hyoscine hydrobromide. For various samples the follow-ing values were obtained : C= 2.454 ; I = 2-dcm. ; u = - 1°7' [aID - 2 2 ~ 7 5 ~ . c = 2.543 ; I = 2-dcm. ; a = - 1O9.3' ; [aID - 22-71? c=2*045; Z=2-dcm.; a = -55.431; [aID - 2 2 ~ 5 8 ~ . The mean of the first two values gives [u] -25.93O for the anhydrous salt and for the I-hyoscinium ion [@ID -32*73O whereas for the purest clrhyoscine hydrobromide the values were 26'3O and 33.go respectively. The use of I-a-bromo-7r-camphorsulphonic acid for purifying the I-hyoscine would no doubt lead to complete accord between the rotatory powers of the two enantimorphs. 1-Hy oscin e 4 urich lo ride .-1-H yosci 11 e h y dr obr omi de (0 * 2 gram) was converted into base using sodium hydrogen carbonate and chloroform. A solution of the hydrochloride was mixed with gold chloride solution and the I-hywcine aurichloride collected. It weighed 0.28 gram and melted and decomposed a t 204-205O. It was recrystallised from one hundred times itw weight of 2.5 per cent. hydrochloric acid and separated in complex needleshaped growths serrated on both edges exactly as observed for the destro-enantiomorph.The melting and decomposing point wa8 un-changed (208-209O c~rr.) : 0.1075 air-dried gave 0.0381 Au. C,7H,,0,N,huC13,HCl requires Au = 30.7 per cent. I-Hyoscine A ~ w i b romdde .-This was prepared by Jowett's method (T. 1897 71 680) by dissolving 0.2 gram of Z-hyoscine hydro-bromide in excess of hydrobromic acid and adding gold chloride solution. The yield was 0.4 gram (m. p. 187-188O). It was recrystallised from boiling 2.5 per cent. hydrobromic acid (40 c.c.), and gave 0.35 gram of long rectangular chocolate-red leaflets still melting and decomposing a t 187-1 88O (191-192O c m . ) : Au = 30.8. 0.1075 air-dried gave 0.0258 Au. 1-Byoscine Fz'crate.-0*20 Gram of I-hyoscine hydrobromide by AU =24*0.CI7H,,O4N,AuBr3,HBr requires Au = 24.0 per cent COMPONENTS TROPIC ACID AND OSCINE. 505 double decomposition with a hot saturated picric acid solution gave 0-25 gram of I-hyoscine picrate crystallising in slender primrose yellow needles (m. p. 187-18S0). It required a hundred times its weight of boiling water to dissolve it and then separated in flat irregular six-sided scales covered with striations. Occasion-ally these scales were united in the form of long flat' serrated needles. It now melted and decomposed a t 187-5-188.5° (191-192O corr.) and amounted to 0.2 gram. dl-Hyoscine. dl-Hyoscinle Hydro bromide.-Two and a-half grams each of the purest d-hyoscine and 1-hyoscine hydrobromides were combined and recrystallised from water.The product crystallised exceed-ingly well with three molecules of water of crystallisation and was iiidistinguishable from the active d- or I-hymcine hydrobromides. The crystals were collected and amounted to 3.3 grams. In a capillary tube the uncrushed crystals melted a t 55-58O but powdered crystals only partly melted up to 60° owing to rapid loss of water. The anhydrous salt melts a t 181-182O (185-186° corr.). The hydrated salt effloresces on expsiire to the air in this respect differing from the active components. A 2.5 per cent. solu-tion in water w a ~ optically inactive: H,0=12.36. 0.2217 uneffloresced salt lost 0.0274 in a vacuum. 0.1943 dried in a vacuum gave 0.0949 AgBr. Br=20*8. C17H,10,N,HBr,3H20 requires H,O = 12.33 per cent.C17H2,04N,HBr requires Br = 20-8 per cent. dl-Hyoscine Base .-One gram of 61-hyoscine hydrobromide was converted into base using chloroform and sodium hydrogen carbonate. The chlorof om-free base was moistened with water, and when kept for some hours in a freezing mixture crystallised in minute needles. The product was collected washed with water, and when dried in the air amounted to 0.55 gram. It melted a t 0.1034 in a vacuum over H2S04 lost 0.0104. C,7H,,04N,2H20 requires H,O = 10.6 per centt. It was recrystallised by dissolving in a little warm alcohol and adding water until a turbidity developed. On inoculation it crystallised slowly in well-formed transparent chisel-shaped prisms. The melting point was unchanged a t 38-40° (38-40O corr.). WheQ dried in a vacuum over sulphuric acid it lost two molecules of water : 38-40' : H20=10*1 506 K M B THE RESOLUTION OF HYOSCINE AND ITS 0°0770 lost 0.0082.H,O=10*6. C 1 7 ~ 0 N 2 H 0 requires H,O = 10- 6 per cent. The anhydrous material consisted of a clear varnish and had no definite melting point, The melting point of the dihydrate was unchanged after keep-ing in a Jena-glass tube for ten months. dl-Hyoscim Picrate.-This salt was prepared in aqueous solu-tion by adding a saturated solution of picric acid to a solution of dZ-hyoscine hydrobromide. An oil separated a t first but was dis-placed on warming by short needles which melted and decom-posed a t 173-174O. These were recrystallised from one hundred parts of boiling water and separated in rosettes of long needles, melting and decomposing at 173'5-174.5O (177-5-178*5° corr.).The same salt is obtained from the dZ-base. dl-Hymcine Aum'chloride .-This salt crystallises in long flat needles with one edge serrated on mixing aqueous solutions of the two componenh. It melted and decomposed a t 214-215O. On recrystallisation from 2.5 per cent. hydrochloric acid i t separated in stout boat-shaped crystals melting and decomposing a t 218-219O (COIT.) : 0.1175 gave 0.0358 Au. Au=30.5. C,7EI,0,N,AuC1,,HCl requires Au = 30.7 per cent. dl-Ryoscine A?rribromide.-On mixing dl-hyoscine hydrobromide dissolved in excess of hydrobromic acid with gold chloride solution, this salt crystalfises in chocolate-coloured leaflets of indefinite shape melting and decomposing a t 209-210°.On recrystallisation from 50 parts of dilute hydrobromic acid solution it separated in chocolatered leaflets very similar in appearance to the Zaeuo-salt. The melting and decomposing point was unchanged a t 213-214O (corr.) : 0.1123 gave Au = 0.0268. Au =23*9. C,,H,,O,N,AuBr,,HBr requires Au = 24.0 per cent. Jmett (Zoc. cit.) has described a hyoscine auribrmide melting a t 210° which probably indicates that his starting material, hyoscine hydrobromide was optically inactive or practically so. Hyd.rolysis of 1-Hyoscine. With Hydro bromie Aeid.-Pure hydrated I-hyoscine hydro-bromide (1.4447 grams) [a]b -22.7O (cf=2'5) was dissolved in 30 C.C. of 10 per cent. hydrobromic acid and the rotation deter-mined. The solution was then boiled gently under reflux th COMPONENTS TROPIC ACID AND OSCME.507 rotation being observed a t definite intervals by cooling the solu-tion and removiig the requisite volume for the observation. On completion of the latter the solutions were recombined and the boiling started afresh. The following data were obtained using a 2-dcm. tube: Initial reading ............ -141’ After 4 hours’ boiling ...... -159‘ ,) 2 hours’ , ... -153’ 9 9 9 99 ) ...... -157‘ After 1 hour’s boiling ... - 149‘ Y9 6 99 , ...... -161‘ The solution was now thoroughly extracted with purified ether to remove the I-tropic acid. The residual aqueous solution still showed a rotation of - 101 and contained non-hydrolysed hyoscine, as it gave a reaction with Mayer’s reagent (oscine gives no reaction in acid solution of this strength).The hydrolysis was continued for a further five hours when the rotation rose to -ll’ and the reaction for hyoscine was negative. On removal of the Z-tropic acid by ether the residual solution was inactive. The ethereal extracts gave 0.65 gram of crude I-tropic acid melt-ing a t 125-127O and having [a] -70-5O in water ( c = l ) . On recrystallisation from water it melted a t 127-128O and gave The dLoscine hydrobromide solution was concentrated rapidly under diminished pressure to a syrup when it acquired a purple colour which disappeared on dilution with water but in absolute alcohol became brown. The syrupy residue crystallised on inocu-lating with dLoscine hydrobromide. The crude product melted a t 270° and weighed 0.75 gram (theory 0.78).It was triturated with a little absolute alcohol and the crystals were collected. The product consisted of granular crystals with a violet colour (prob-ably containing traces of a perbromide (compare Schmidt Arch. Ph(zrrn. 1905 243 567) weighed 0.53 gram and melted a t 2 8 0 O . A mixture with pure dLoscine hydrobromide (m. p. 282O) also melted a t 280O. The filtrate was now evaporated to dryness under diminished pressure dissolved in 10 per cent. sodium hydroxide solution and completely extracted with chloroform. On removal of the chloroform 0.15 gram of base was obtained which only crystallised on ’ inoculation with the dZ-oscine base of commerce. It melted a t 98-looo and a mixture with pure oscine melted a t 103O. The products of the hydrolysis are therefore Z-tropic acid and With Hydrochloric Acid.-Pure I-hyoscine base prepared from 0.5014 gram of I-hyoscine hydrobromide [aID - 2 2 ~ 7 5 ~ (c =2*5), using sodium hydrogen carbonate and chlorof o m was dissolved in - 760 (c = 2). dZ-mCine SO8 KNOX AND RICHARDS THE BASIC PROPERTIXS OF 30 C.C. of 10 per cent. hydrochloric acid. as i n the case of the hydrobromide. The rotation was followed Iiiitial reading ................................. -Rftor 2 hours boiling ..................... - 55‘ ; 1 . 2 - d ~ ~ . - 56’ 3 7 4 9 3 9 ..................... I > 8 I ..................... -54.5’ 9 9 011 removal of the I-tropic acid (0.15 grain; m. p. 124-125”) by ether the acid aqueous solution was optically inactive and when evaporated to dryness with absolute alcohol gave 0.13 grani of dl-oscine hydrochloride crystallising in minute rectangular plates or associated together in fern-likel growths. It was coil-verted into the picrate which crystallised in small flattened rhombs or tablets melting and decomposing a t 2 3 1 O . A mixture with pure dl-osciiie picrate which crystallises similarly and melts and decomposes a t 237-238O melted intermediately a t 232O. I n conclusion the author desires to express his warmest thanks to Dr. Pyman for his advice and criticism throughout the course of the work. THE WELLCOME CHEMICAL RESEARCH LABORATORIES, LONDON E.C. [Received &lurch 26th, 1919.

ISSN:0368-1645    

DOI:10.1039/CT9191500476

出版商:RSC    

年代:1919

数据来源: RSC

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SO8 KNOX AND RICHARDS THE BASIC PROPERTIXS OF KXXVIII.-The Basic Properties of Oxygen in Organic Acids and Phenols; and the Quadrivalency of Oxygen. By JOSEPH KNOX and MARION BROCK RICHARDS. OKYGEN is usually regarded as a bivalent element in most com-pounds but its position in Group V I of t?he Periodic Table affords good ground for the assumption that it may in certain cases have a higher valency from analogy to sulphur selenium and tellurium, all of which may function not only as bivalent but also as quadri-valent and sexavalent elements. The quadrivalelicy of oxygen has been assumed from time t o time t o explain the constitution of certain compounds a summary of the earlier assumptions of this nature being given by Walden (Ber. 190-1 34 4185). The work of Collie and 'Tickle o OXYGEN IN OBGANIC ACIDS AND PHENOLS.509 dimethylpyrone (T. 1899 75 710) and of Baeyer aad Villiger (Ber. 1901 34 2679; 1902 35 lZOl) first drew general atten-tion to the subject. The former were of the opinion that only in specially favourable cases could additive compounds containing quadrivalent oxygen be formed but the latter showed that organic compounds of practically all classes containing oxygen such as ethers alcoholv aldehydes ketones etc. could combine with acids t o give crystalline salts. Since that time many similar asuump-Lions of the quadrivalency of oxygen have been made for example, by Bulow and Sicherer for salts of anhydrobeiizopyranols and benzopyranols (Ber. 1901 34 3916) by Kehrmann and Mattisson for salts of phenanthraquinone (Bey.1902 35 343) by Will-statter and Pummerer for compounds of pyrone with acids (Bet-., 1904 37 3740) by Farmer for acid salts of monobasic acids (T., 1903 83 1440) by Cohen and Gatecliff for compounds of ethers with nitric acid (P. 1904 20 194; but see also McIntosh J . Amer. Chem. Soc. 1905 87 1013) by Blaise for compounds of magnesium iodide and zinc iodide with ethers (Compt. rend. 1904, 139 1211; 1905 140 661) and by Meyer for salt-like compounds of quinones with acids (Ber. 1908 41 2568). Much work on this subject has been done by McIntosh aud his collaborators who have prepared additive compounds' of ethers, alcohols aldehydes ketones etc. with halogens and anhydrous halogen hydrides (T. 1904 85 919 1098; 1906 87 784; J . Amer. Chem. SOC.1905 27 26 1013; 1906 28 588; 1908 30 1097; 1910 32 542 1330; 1911 33 70; 1912 34 1273). Fewer instances have been recorded of t-he formation of additive compounds of organic acids aud phenols with other acids. Baeyer and Villiger obtained no crystalline compounds of acids with acids (Ber. 1901 34 2692). Hoogewerfl and van Dwp however pre-pared additive products of sulphuric acid with various organic acids and of phenols with phosphoric acid (Rec. truu. chim. 1899, 18 211; 1902 21 349). Maass and McIntosh obtained a com-pound of benzoic acid with hydrogen bromide and of resorcinol with hydrogen bromide and hydrogen chloride ( J . Amer. Chem. Soc. 1911 33 70). Pfeiffer also has prepared a number of qm-pounds of organic acids with acids (Ber., 1914 47 1593) and in a recent series of papers KendaH has described the isolation hy the frwzing-paint method of additive compounds of organic acids i n pairs of organic acids and phenols with sulphuric wid and of phenols with organic acids ( J .A?ner. Chem. SOC. 1914 36 1722, 2498; 1916 38 1309). It will be seen that the organic compounds which form t h a 616) KNOX AND RICHARDS THE BASIC PROPERTIES 02' additive products are of the most diverse types. In practically all the cases cited the organic compound is combined with an acid, forming an unstable additive compound so that! evidently the cam-pound formation is due to basic propelrties in oxygen of higher valency than two. These additive compounds are generally regarded as " oxonium " compounds containing quadrivalent oxygen derived from the hypothetical base H,O*OH analogous to the sulphonium compounds formed by the passage of sulphur from bivalency to quadrivalency.A typical example is Friedel's dimethyl ether hydrochloride (BUZZ. sbc. chim. 1875 [ii] 24, 160) (CH,),O+HCI = CHs>O<El the analogy of which to a CH, sulphonium compound is evident: The sulphonium salts are derivatives of the strongly basic sulphunium hydroxide R,S*OH so that in the salt-like character of the oxonium compounds and the basic properties of quadri-valent oxygen there is a parallel in the case of well-known sulphur compounds. To explain the formation of these additive compounds special kinds of valencies of oxygen have from time to time been assumed -crypto-valencies complex valencies residual affinities.In view of the fact however that oxygen may exhibit a higher valency than two in the ordinarily accepted sense there seems to be no reason to assign special kinds of valencies to oxygen any more than to sulphur or the other elements of the same group. The additive products of organic oxygen compounds with acids have mainly been isolated in the solid state and very little work has been done on the investigation of these compounds in solution. The compounds are all more or less unstable and for the most part are decomposed by water int'o their original constituents. Farmer, for instance could find no evidence for the existence of acid salts in solution (T. 1903 83 1440) but there is evidence to show that oxonium compounds do exist to a certain extent a t least in solu-tion.Thus Maass and McIntosh ( J . Amer. Chem. SOC. 1913 35, 535) by a study of the condudivit,y measurements of the two com-ponent systems-hydrochloric acid and ethyl ether hydrochloric acid and methyl ether hydrochloric acid and ethyl alcohol hydro-chloric acid and methyl alcohol-showed the probability of the existence of the compounds in solution. Rordam (J. Amer. Chem. Soc. 1915 37 557) by comparing the eonductivit,y of a solutio OXYGEN IN ORGANIC ACIDS AND PHENOLS. 511 of dimethylpyrone hydrochloride with that of a solution of hydro-chloric acid with the same concentration of chlorine ions electro-metrically measured proved that dimethylpyrone hydrochloride is a real salt showing electrolytic dissociation as well as hydrolytic dissociation into its components.Schuncke (Zeitsch. phygikal. Chem. 1894 14 331) found that the solubility of ether is greater in hydrochloric acid solutJons than in water and increases with the concentration of the hydrochloric acid and Jiittner (Zeitsch. physikal. Chem. 1901 38 56) gave as the reason the formation of ether hydrochloride in solution. Similarly Sackur (Ber. 1902, 35 1242) found that the solubility of cineole increases in hydro-chloric nitric and acetic acid solutions. It is possible therefore that the existence of other oxonium compounds in solution may be shown by solubility 'determinations, If additive compounds of organic acids with acids exist in solution, we should expect to find some influence of this salt-formation on the solubility of the organic acid in solutions of the other acids.I f no such dist'urbing influence comes into play the solubility of the organic acid should continuously diminish with increasing con-centsation of the solvent acid in accordance with the law that the solubility of an electrolyte is diminished by the addition of another electrolyte with a common ion. A few instances have actually been recorded where organic acids do not obey this law. Thus Herz (Zeitsclt. anorg. Chem. 1910, 66 93) found that for solutions of oxalic acid in boric acid the solubility increases continuously with the concentration of the boric acid. SGpanov (Amnden 1910 373 221) found that for picric acid in hydrochloric acid solutions the solubility diminishes to a certain point after which it begins to increase.Masson (T. 1912, 101 103) found a similar result for solutions of oxalic acid in hydrochloric and nitric acid solutions. It seems very probable that these cases may be instances of a general phenomenon and that the unexpected results obtained for the solubility curves are caused by the existence in solution of an oxonium compound formed by direct addition of the ions of the solvent acid to an oxygen atom of the organic acid according to the equation or for phenols, :>O+HX = R' H>O<E 512 KNOX AND RICHARDS THE BASE PROPEETIES OF This assumption would be sufficient to account for the observed results. At first with a strong solvent acid such as hydrochloric or nitric the effect of the common hydrogen ion prevails and the solubility diminishes.With increasing concentration of the solvent acid however the influence of the formation of the more readily soluble salt becomes stronger and tho solubility reaches a mini-mum and finally begins to increase. If the solvent acid is weak, for example boric acid the initial decrease may be too small to be measurable; hence the only perceptible effect would be the con-tinuous increase observed by Herz. I f the true explanation of the results observed by Herz, StBpanov and Masson is the formation of an oxonium compound in solution we should expect other organic acids to behave in a similar manner and the present investigation serves to prove that; this is actually t,he case. E Y P E R I M EN T A L . I. Acids. The solubilities of a number of organic acids of practically all classes have been determined in solutions of other acids.The number of organic acids which could be used was greatly limited by the lack of suitable methods of analysis. Many of the commonest acids could not be employed since no sufficienMy accurate method is known for their estimation or since even a t the ordinary temperature they volatilise from solution on evapor-ation. Much time was spent in testing various analytical methds given in the literature for a large number of acids and in deter-mining whether the acids volatilised from solution on evaporation. Amino-acids were avoided as the presence of tho basic amino-group might lead t o the formation of salts of the ammonium type. I n mas% cases the solvent acid is hydrochloric but experiments have also been performed in nitric sulphuric acetic formic and lactic acids.The following series have been investigated : Monobasic A cids .-Phenylacetic diphenylacetic benzilic o-nitro-benzoic mnitrobenzoic 3 5-dinitrobenzoic cinnamic diphenylene-glycollic trichlorolactic mandelic diphenic and salicylic acids in hydrochloric acid solutions ; trichlorolactic acid in sulphuric acid ; mandelic acid in sulphuric acetic and formic acids. Dibasic A cids.-Malonic acid in hydrochloric and sulphuric acids; oxalic acid in sulphuric acetic formic and lactic acids OXYGEN IN ORGANIC ACIDS AND PHENOLS. 51 3 phthalic acid in hydrochloric and nitric acids; suberic acid in hydrochloric nitric sulphuric and acetic acids ; succinic acid in hydrochloric nitric sulphuric acetic and formic acids ; and t'artaric acid i n hydrochloric sulphuric and acetic acids.Tribasdc A cid.-C'it,ric acid in hydrochloric and sulphurio acids. Method.-The solubilities were determined a t 25O excem of the solid being shaken for several days in a thermostat with solutions of the solvent acid of varying concentration. After saturation the clear solution was analysed both for dissolved and solvent acid by one of the following mathods : (1) Solvent acid determined gravimetrically ; dissolved acid by direct weighing after evaporation in a vacuum over soda-lime. This method was used for most of the sparingly solluble acids in hydrochloric acid solutions. (2) Total acidity determined by titration with standard sodium hydroxide; dissolved acid by weighing after evaporatioii either (a) in a vacuum or ( b ) on the steam-bath; solvent acid by cliff erence.This method was used for nitric acetic and formic and in a felw cases for hydrochloric acid solutions. (3) Total acidity by titration ; solvent acid gravimetrically ; dis-solved acid by difference. Sulphuric acid solutions were analysed by this method also cases of acids very readily soluble in hydroohlorio acid. (4) Permanganate methods for oxalic acid solutions total acidity by alkali ; oxalic acid by potassium permanganate either (a) directly in sulphuric acid solutions or ( b ) after precipitation as calcium oxalate in other cases ; solvent acid by difference. Where an evaporation method was used a preliminary test was made to ascertain whether the organio acid was left unchanged after evaporation from a solution in the solvent acid.The results of the various experiments are given in the follow-ing tables. The method of analysis is indicated in each case by a number corresponding with the above arrangement and refer-ence is made to the diagram in which the corresponding solubility curve is to be found. I n all cases the concentrations of the acids stre expressed in equivalent normalities (I) Yhenylacetic Acid in Hydrochlwic Acid. Method C,H,O ............... 0-1310 0.0984 0.0833 0.0763 0.0739 ..................... HC1 0 1.417 2.890 4-313 5.710 (2) Diphcnylacetic Acid in Hydrochloric Acid. HCl ..................... 0 1.620 2.913 4.512 5.973 C14H1202 ............ 0*00060 0.00047 0-00040 0.00036 0.00038 (3) Benzilic Acid in Hydrochloric Acid.MetJzod ..................... HCI 0 1.537 2.977 4.440 5.934 C14H120 ............ 0-00769 0.00332 0.00233 0.00182 0.00172 ( 4 ) o-Nitrobenzoic Acid in Hydrochloric Acid.* HCl ..................... 0 1.314 2-607 3.909 5.013 C,H,O,N ............ 0.0470 0.0280 0.0266 0.0239 0.0235 (5) m-Nitrobenzoic *4cid ia Hydrochloric Acid. ..................... HCI 0 1-416 3-310 4-308 5.953 C,H,O,N ............ 0.0214 0.0175 0.0178 0.9183 0.0205 * It may be mentioned that Kendall (Proc. Roy. Soc. 1911 [A] 85 200) gives results and salicylic acid in hydrochloric acid solutions ; but with the low concentrations of the decrease in solubilitv is observed HCI. ................. C,H,O,N ......... HCI. .................C,H,O ............ HCl. ................. C,,H,,O ......... HC1 ............... C,H,O,CI ...... H,SO ............ C,H,O,CI ......... HCI ............... C,H,O ......... (6) 3 5-Dinitrobenzoic Aeid in Hydrochloric Acid. 0 1.565 2.908 4.594 5.657 0.00635 0.00398 0.00470 0.00583 0.00690 (7) Cittnamic Acid in Hydrochloric Acid. 0 2.100 4.174 6.250 0.00385 0.00283 0.00272 0.003 18 (8) Dil3henyle7teglycollic Acid in Hydrochlom'c Acid. 0 1.952 3.907 0.01082 0.00492 0.00355 (9) Trichlorolactic Acid in Hydrochloric Acid. 0 1.234 2.837 4.388 5.982 7.675 4.024 2.545 1425 0,984 0.760 0.659 (10) Trichlotohctic Acid i m Sulphuric Acid. 0 2.525 6.166 9.588 12.75 4.024 1.896 0.67 1 0.353 0-26 (11) Salicylic Acid in Hydrochloric Acid.* 0 1-469 3.067 4.374 6.164 7,311 0.01613 0.00982 0.00822 0.00715 0.00654 0.00656 * See footnote on preceding page 516 KNOX ANI BIUHARDS THE BASIC PBOPHRTIES OP 00 Ot-mm rl ?t m m e ?c? so f- we4 mm c( t't? e m mm gg rl R * * .y o c o al 22 u -4 7-4 W n CQ F-l W r3 r3 a O r ; .. . . . . . . . . . . . . . . . . . . . . - 4 1 iq Xu" Fj a: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . g< w* uu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - . 6 6 x, wu . . . . . . . . . . . . . a 0 a x, w (18) Malonic Acid in Sulphuric Acid. Method H,SO ............... 0 2.727 7.050 11-76 c3H404 ............15-01 11.44 6.79 4-07 H,SO ............... 0 C2H204 ............... 2.409 C,H,O ............... 0 C2H204 ............... 2.409 CA202 ............... 0 C4H204 ............ 2.409 CZR4O2 ............ 0 C,H204 ............ 2.409 (19) Oxdic Acid in Sulphuric Acid. Jfethod 2.187 4.524 6.835 9.225 1.519 1.057 0.791 0.675 (20) Oxalic Acid in I;a.ctic Acid. Method 1.337 2.718 4.05 1 5.357 2-228 2.054 1.856 1.633 (21) Oxalic Acid in Formic Acid. Method 0.097 0.437 0-967 1.287 1-825 2.678 5.360 2.382 2.385 2.411 2.414 2.441 2.430 2.326 (22) OxaGc Acid in Acetic Acid. Method 0.135 0.321 0.923 1.361 1.844 8.583 5.721 2-366 2.361 2.395 2.402 2.401 2.351 2-168 (23) Phthalic Acid in Hydrochlm'c Acid. Ha.... ................. 0 1.729 3.113 4.693 6.100 C,H604 ...............0-0852 0.0422 0.0298 0.0216 0.017 HNO ............... C8H80 ............... Ecl. .................... C8Hl4O4 ............ HNO ............... C8Hl4OP ............ H2S04 ............... C8H1404 ............ CaH402 ............ C8H,,O ............ HCI .................. C,H,04 ............... (24) Phthctlic Acid in Nitric Acid. Method 0 2.077 4.077 6.718 9.027 0.0852 0.0582 0.0470 0-0375 0.0331 ( 2 5 ) Szcbem'c Acid in Hy&ochloric Acid. Method 0 1.423 2.858 4-281 8.691 0.0680 0.0498 0.0428 0-0412 0.0432 ( 2 6 ) Suberic Acid in Nit.& Acid. Method 0 0.307 0.555 0.906 1.543 2-021 4.035 0.0680 0.0594 0.0590 0.0634 0.0695 0.0839 0.0999 (27-j Suberic Acid in Sulphuric Acid. 0 1.858 5.233 7.524 0.068 0.039 0.037 0.042 ( 2 8 ) Suberic Acid in Acetic Acid.Method 0 0.435 0.887 2.112 0.0680 0.0776 0.0902 0.1340 (29) Succinic Acid in! Hydrochloric Acid. Method 0 2.751 6.964 7.335 8.950 1.352 0.681 0.402 0-353 0.33 (30) Succinic Acid in Nitric Acid. Method HNOs ......... 0 1-299 3.034 5.236 6.616 0 C4H4504,. * m . m m . 1.362 1.134 0.941 0.724 0.652 w c (31) Succi?zic Acid in Sulph~iric Acid. Method H,SOe7.. . . . . . . . 0 1.981 3-816 4.926 8-122 10.22 C,H,O,. . . . . . . . 1.352 0.908 0-683 0.563 0.388 0.34 (32) Succinic Acid in Acetic Acid. Nethod C,H,O . . . . . . 0 0.078 0.448 0.916 2.828 4.536 6.666 C,H,O,. . . . . . . . 1.352 1.384 1-415 1-452 1.592 1.643 1.639 (33) Stcccinic Acid in Formic Acid. &lethod CH,O . . . . I .. .. 0 0.090 0.446 0-930 3.730 5.547 7.500 11.29 C4H60 1.352 1.369 1.397 1.408 1.501 1.531 1.449 1.228 (34) Tartaric Acid in Hydrochloric Acid.Method HCA . . . . * . . . . 0 1.267 2.568 4.466 6.303 t- C,H,06 ...... 10.26 8.528 7.092 5.434 4-3 H,SO ............ C4H,06 .. ....... C,H,O, C4H606 . . .... . . . . . ... . . . HCl C6H,0 ......... . . ..... ... . . . H,SO ............ C 6H *O . . . . . . . . . HCl . . . . . . . . . . . . . . CBH,03N . . . . . . 0 10.26 0 10.26 0 12-54 0 12.54 (35) Turtaric Acid in SuJpl~& Acid. Method 1.798 4.043 6.807 9.895 12.54 8-51 6-64 4.73 3.18 2-43 (36) TuFta,ric Acid in Acetic Acid. Method 0.25 0-GO 1.23 2.63 4.24 10.09 9.875 9.515 8.717 7.718 (37) Citric Acid in Hydrochloric Acid. 0.949 2.189 3.795 5.718 11.03 9.30 7.36 5.38 (38) Citric Acid i ) ~ .Szrlphuric Acid. 1.689 4.206 7-145 10.83 11.46 10.57 7.97 5.61 3.28 3.07 (39) p-ilTitroplieitol in Hydrochloric Acid. illethod 0 1.850 3.277 4.993 0.1097 0.0962 0.09 13 0.093 (40) m-Xitrophenol in Hydrochloric Acid. Method HCl .................. 0 1-926 3.822 5.720 7.550 C6H603N ......... 0*0974* 0.0849 0.0834 0.0885 0.1009 (41) Pi& Acid .in Nitric Acid. HNO ............ 0 1.022 2.059 4.161 6.289 Method C&O,N ......... 0.0578 0.0108 0.0124 0.0237 0-0405 (42) #3-Na8phthol in Hydrochloric Acid. HCl .................. 0 1.466 2.952 4.343 5.786 C1,H,O ............ 0.00524 0.00410 0.00360 0.00333 0.00319 (43) Resorcirzol in Hydrochloric Acid. Method HC1 .................. 0 0.656 1.671 3.410 4.402 6.076 C8H802 ............6.515 5.705 4.570 3.020 2.307 1.616 * It may be remarked that the value found for the solubility of m-nitrophenol in 3G Vrtubel (J. p. Chem. 1895 [ii] 52 73) but as no definite particulars are given of t.he The compound used in the present case, k s recrystallised from water and melted at 96-97O. it cannot be regarded as very trustworthy ACI .................. C6H,0 ............ HCl .................. CGH6O3 ............ HC1 .................. C6H30 ,N ......... HXOs ............ CeRsOsN3 ......... HC1 .................. C6H603 ............ (44) Quinot in Hydrochloric Acid. Method 0 1.892 3.793 5.720 0.666 0.402 0.282 0*216 (45) Catechol* in Hydrochloric Acid. Method 0 1-68 3.5s 5.39 4.19 2.13 1.18 0.81 (46) Styphnic Acid im Hydrochloric Acid.0 1-410 2.814 4.221 6.634 0.02179 0.00062 0.00060 0.00072 0*00093 (47) Styphnic Acid in Nitric Acid. Method 0 1.785 4.171 6-234 8.368 0.02179 0.001403 0*002180 0.003274 0.005108 (48) Pyrogallol im Hydrochloric Acid. Method 0 1-53 3.18 5.12 6-4.02 2.81 1.86 1-26 1.01 * The preliminary test showed that catechol is very slightly volatile at the ordinary of the curve obtained seems to show that in spite of this the results are fairly accurate OXYGEN IN ORGANIC ACIDS AND PHENOLS. 623 11. Phenols. The solubility of a number of phenols has been determined in the same way the series investigated being: Mono hydm'c Phends .-PNitrophenol m-nitrophenol and 8-naphthol *in hydrochloric acid ; trinitrophenol (picric acid) in nitric acid.Bihydmc Phenio1s.-Resorcinol quinol catechol and trinitm resorcinol (styphnic acid) in hydrochloric acid ; trinitroresorcinol in nitric acid. Trihydric Phenol .-Pyrogallol in hydrochloric acid. Methods of A?zaZysis.-5. For all phenols in hydrochloric acid, the acid was determined gravimetrically and the phenol by weigh-ing after evaporation (a) in a vacuum or ( b ) 011 the steam-bath. 6. For picric acid and styphnic acid in nitric acid the concen-trat,ions of the nitric acid solutions were determined a t 2 5 O before adding the solid owing to the difficulty of titrating solutions con-taining these phenols. As the phenols are only sparingly soluble, however any change in volume that might occur when they dis-solve could have 110 appreciable effect on the results.The phenol was determined by weighing after evaporation (a) in a vacuum, or ( b ) on the steam-bath. Some of the phenols gave deeply coloured solutions but the residues obtained on evaporation were practically colourless and a preliminary experiment showed that they were leftl unchanged when evaporated Lo dryness with hydrochloric acid o r nitric acid. The results are given in tables 39 to 48 the solubilities of the phenols being given in gram-molecules per litre whilst the concentrat'ions of the solvent acid are expressed as before in eqiiivalen t norm a1 i ti es . Consideration of Results. A glance a t the solubility curves will suffice to show that the results observed by Herz StBpanov and Masson were no isolated phenomena but that as regards the solubility of organic acids and phenols in solutions of other acids deviation from Nernst's law is the rule and not the exception.It will be seen that the curves obtained are of two main types according as the solvent acid is a mineral or an organic acid but in each case the assumption of oxonium salt-formation is sufficient to account for the observed results. Owing to exigencies of space only a few typical solubility curves can be reproduced. The obher solubility curves which can b 524 KNOX AND RICHARDS THE BASIC PROPERTIES OF constriicted from the tables will be referred t o by the number of the table containing the necessary data. Thus (1) refers to the solubility of phenylacetic acid in hydrochloric acid and so on. The curves obtained for solutions in the mineral acids all resemble more or less those obtained by Stepanov and Masson that is the solubility diminishes rapidly a t first reaches a minimum, and afterwards increases steadily with increasing concentration of the solvent.acid. The results however vary somewhat' according FIG. 1. 0.15 0.13 f 0.11 3 2 5 0.09 3 3 2 u * * -E 0.07 0.05 0.03 I 2 4 6 8 10 12 Nortnnality of solvent acid. to the solubility of the organic acid or phenol and the concentra-tions attainable with the mineral acid. Thus with sparingly soluble acids and phenols such as phenylacetic (1 25 Fig. 1) and nitrobeiizoic acids (4 5) and the nitrophenols (39 40 Fig. 7), the curve in every case shows a distinct turning point. Other examples are 2 3 6 7 8 11 12 23 34 25 26 27 39 40 41, 42 46 47.With very readily soluble substances such as malonic, citric and tartaric acids quinol and cat.echo1 (17 Fig. 3) (34 OXYGEN IN ORGANIC ACIDS AKD PHENOLS. 525 Fig. 6) (37, acid reached of the curve, 43 44 45 48) the conceritratiori of hydrochloric is not' sufficient# t.0 show clearly the upward tendency although ths general shape makes it evident that the FIG 2. curve has reacheld its miiiimum a t the concent'ration attained and is just about to turn upwards-a conclusion which is furt.her justified by the fact that in sulphuric acid solutions where t-he concentrations athainable are considerably greater eveii the ver 626 RNOX AND RICHARDS THE BASIC PROPEBTTES OF readily soluble acids give a definite turning point (18 Fig.3), (36 Fig. 6) (38). When the solvent acid is organic modification of the shape of the curve results from two causes namely (a) the weakness of organic acids in general and ( b ) the wide difference between the FIG. 3. I I I 1 2 4 G 8 10 12 14 26 18 20 22 24 Normality of eolv~nt acid. solubilities of the dissolved acid in water and in the organic acid solvent. (u) When both solvent and dissolved acids are weak the effect of the common hydrogen ion is as a rule too small to be measured. Of the acids the solubilities of which were determined in an organic acid solution oxalic acid is the only one of sufficient acidic strengt OXYGEN .LN ORGANIC! ACIDS AND PHENOLS. 527 to show any perceptible initial decrease in solubility (21 22, Fig. 4). The others show increase in solubility from the beginning, except tartaric in acetic (36 Fig.6) -and oxalic in lactic acid (20 Fig. 4) where no evidence of salt-formation was obtained. ( b ) If the dissolved acid is more readily soluble in the solvent organic acid than in water the resulting curve shows a continuous increase-an increase which may be partly dus- tot salbfomation or entirely due to increasing solubility in the solvent acid so that FIG. 4. .-- - --2 4 6 8 10 12 14 16 18 20 Normality of solvent acid. 110 conclusion as to salt-formation can be drawn. An iiistaiice of this may bs seen in the curve for suberic acid in acetic acid (28). Other cases give clear evidence of salt-formation the curve show-ing an initial increase in solubility owing to the! formation of the more readily soluble salt with a subsequentl decrease caused by deereasing solubility in the! solvent acid.The curves which show this effect clearly are (1) succinic acid in acetic and formic acids (32 33 Pig. 5) (2) oxalic acid in acetic and formic acids (here the ionic effect is first perceptible before the increase due to salt-X 528 KNOX AND RICI~ARDS THE BASIC PROPNRTIES OP formation) (21 22 Fig. 4) and (3) mandelic acid in acetic and formic aoids (15 16 Fig. 2). (It will be observed that in three of these cases namely oxalic acid in acetic and formic acid solutions and mandelic acid in formic acid there is apparently a break in the curve. The cause of this has not been investigated but Masson who obtained a similar break for oxalic acid in nitsic acid attributed the result t o dehydration \of the oxalic acid,) FIG.5. 0.2 1 1 I 3 6 9 12 15 18 21 24 NormaEity of dissolved acid. From the curves it may be inferred that saltl-forrnation does not take place with equal readiness in all the mineral acids. Where curves have been determined for the same organic acid o r phenol both in hydrochloric and nitric acid solutions i t will be seen that in each case the nitric acid curve lies above that for hydrochloric acid evidently indicating that additive compounds are formed more readily with nitric acid; sm for example the curves for succiiiic (29 30 Fig. 5) pht*halic (23 24) suberic (25 26) an OXYGEN IN ORGANIC ACIDS AND PHENOIJS. 529 styplinic acids (46 47) in hydrochloric and nitric acid respect-ively.Again a comparison of the curves for tlhe same acid in hydro-chloric and sulphuric acid solutions shows uniformity of behaviour in all the cases investigated. There is at first a more rapid decrease in solubility in hydrochloric than in sulphuric acid (prob-ably due to the greater acidic strength of hydrochloric acid and the correspoiidingly greater ionic effect) butl the t,urning point' is more quickly reached and the hydrochloric acid curve sooii cuts the other from which we may infer that salt-formation takes place with greater ease in hydrochloric acid. A comparison of the curves f o r succiiiic (29 31 Fig. 5) citric (37 38) tartaric (34 35 Fig. 6). FIG. 6. 'A I 1 7 3 6 9 12 1s 18 21 24 Normality of solvent acid. lnalonic (17 18 Fig.3) mandelic (13 14 Fig. a) and trichloro-lactic acids (9 10) in hydrochloric and sulphuric acids respectively, will make this clear. (In the case) of suberic acid [25 271 the result appears t o be similar but owing to the small solubility of suberic acid and the necessity for estimating the suberic acid in sulphuric acid solutions by difference this curve is not sufficiently accurate to enable the distinction between the tlwo curves t o be clearly seen.) It would therefore appear that of the mineral acids sulphuric acid shows the least tendency t o salt-fo8riiiatioii, whilst nitric acid shows the greatest. No quantitative conliexion can be established between the turii-ing point of the curve and the strength of t'he orgaiiic acid in x* 530 THE BASIC PROPERTIES OE OXYGEN.question. Kendall found that in general for additive cor~ipounds, both of organic acids in pairs and of organic acids with sulphuric acid the tendency towards the formation of additivo compounds is dependent on the difference in acidic strengths. Very weak organic acids most readily form additive) compounds and an FIG. 7. I 0.080 I -2 4 6 8 10 12 Normulity o j solvent acid. increase in the acidic strength is accompanied by a dimiiiutioii or loss of this property. The rule is however merely qualitative. This result is in general aonfirmed by the present investigation, alt*hough t,he question is complicated by the fact that the turning point in the1 solubility curve depends largely on the solubility of the organic acid DEY AND GOSWAMI +-1 8-ISONAPHTHOXAZONES. 531 General S.ummary of Results. From determinations of tlhe solubility of organic acids and phenols in solutions of other acids i t has been shown that in such solutions compounds are formed between the organic acid or phenoll and the solvent acid. The most probable explanation is that the o'rrganic acids and phenols contain a basic oxygen atom, and that this forms salts of the oxonium type with the solvent acid the oixygen becoming quadrivalent. This view is strongly supported by the work of Kendall whose earlier papers were pub-lished during the prolgress of the present research. * Thanks are due to the Carnegie Trust for a Fellowship that has CHEMICAL DEPARTMENT, enabled one of the authors t o take part in this investigation. UNIVERSITY OF ABERDEEN. [Received Februarg 8th 19lg.

ISSN:0368-1645    

DOI:10.1039/CT9191500508

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

DEY AND GOSWAMI 9-1 8-ISONAPHTHOXAZONES. 531 XXXIX.-+l i 8-is0 Naphthoxazones. By BIMAN BIHARI DEY and MAHENDRA NATH GOSWAMI. BY the fusion of a pyridine with a benzene nucleus the condensed quinoline ring is formed and in a similar manner it is conceivable that the couniarin ring would give rise to a class of derivatives which might be represented as t)-P-naphthoxazones,+ their relation-* Kendall has since published other papers on the same subject reference t o which will be found in the concluding paper of the series ( J . Amer. Chem. SOC. 1917 39 2303) in which he sums up the results'of his investigations The above research was completed early in 1916 but for various reasons publicaation of the results has been delayed. -1 As the compounds described in this paper do not contain the true oxazine ring they are regarded as being derived from $-naphthoxazines thw : 0 co \/ 9-1 S-isuNaphthoxazone.+Benzo-l 8-isonaphthoxazone. Isomerides of 4-1 8-isonaphthoxaeone will thus receive the name 532 DEP AND GOSWAMI + - 1 Q-ISONAPHTWOXAZONES. ship to coumarins being analogous to that of quinoline t o benzene : 0 0 Subst'ances of the latter class so far as it? has been possible to ascertain are practically unknown only one instance being eiicountered in the literature where a coinyouiicl probably belong-ing to this category has been mentioned (Pechmann and Schwarz, Uer. 1899 32 3701). This subst'ance was obtained as a by-pro-duct in the cotidensation of m-aminophenol aiid ethyl acetoacetate. where' i l l addition to the expected 7-amiiio-4-methylcoumarin a small amount of a solid (in.p. 268O) was isolated which was regarded as a dihydrquinocoumarin and assigned the E o l l o ~ i ~ ~ g structure : 0 N The evidence adduced in favour of its constit'utiou is iiot complete, and no further work appears t o have been carried o u t on the subject. The reactions which are of general applicahility in the synthesis of quinoline and its allies namely the Skraup the Doebner-Miller, and the Knorr reactions are all based on the condensations of aniline or other primary aromatic amines; the same methods with slight modifications have now been applied t o the synthesis of the J/-naphthoxazones from the aniiiiocoumariiis and the amino-naphthacoumarins in which the amino-groups are attached to the benzene nucleus.These compounds have been shown by previous investigators to resemble the aromatic amines in their chemical behaviour and they may readily be' diazotised and reduced t o the corresponding coumarylhydrazines etc. (Morgan and Micklethwait, T. 1904 85 1233; Clayton P. 1911 27 246). These considerations led t o the present investigation a systematic study of this new class of substances being also con-sidered desirable in view of certain questions that arose with regard to the connexion between t.heir structure and physiological properties. The present communication deals with the application of the Slrraup synthesis t o the preparation of the J/-naphthoxazones th DEY AND GOSWAMI +-1 8-ISONAPHTHOXAZONES. 533 results obtained wit.h the other reactions being incomplete and reserved for a future communication.The Skraup reaction which depends on the condensation of aromatic aminm with glycerol and sulphuric acid in the presence of an oxidising agent, is apt t o be rather violent when applied to the aminocoumarins and it was found that the success of the operation depended t o a greatl ext'eiit on the careful regulation of the temperature at the commencement of the reaction. It was also observed that instead of using a mixture of nitro- and amino-coumarins as is generally done in these reactions the nitro-coumarins could be employed alone without diminishing the yield of the $-naphthoxazones to any appreciable extentn. This observation greatly simplified the process of this synthesis, as the aminocoumarins were sometimes rather difficult to prepare from the corresponding nitro-compounds.On treating 6-nit~ocoumarin with allyl alcohol it was reduced to the amino-compound (compare Brunner and Chuard Ber. 1885, 18 447) and it may therefore be legitimately assumed that allyl alcohol is formed in on0 of t'hs st'ages in the condensation and is then oxidised to the corresponding aldehyde by thel nitro-com-pound which is reduced in the process. The amino-compound now serves to combine with the acraldehyde after which the reaction takes the usual course: CH 0 0 0 In their chemical characteristics the $-naphthoxazones do not differ materially from the quiiiolines except in their behaviour towards h o t alkali hydroxides which dissolve these1 substances with a deep colour.This is evident;ly due to the hydrolysis of the pyrorie ring and the solution presumably contains an unstable acid; on carefully neutralising the alkaline solution in the cold, the original substance is slowly deposited in the crystalline stabe. The $-naphthoxazones as tertiary bases readily form salt's a large variety of the double salts having been prepared in the course of this investigation ; amongst these the dichromabs th 534 DEY AND GOSWAMT q-1 1 %T80NAPWTHOXAZONES. ferrocyanidee and the double potassium mercuri-iodides are very Characteristic and form cryst’als having a definite structure. They also give characteristic precipitates with the general alkaloidal reagents Wagner’s solution gives a deep orange-brown crystalline precipitate of the iodide Scheibler’s reagent gives a white crystal-line precipitate of the phosphotungstates and Sonnenschein’s reagent gives a curdy precipitate of the corresponding phospho-molybdate.Like the tertiary amines they also) unite with alkyl haloids in molecular proportions. A feature1 of solme interest which has arisen from a study of these N-alkyl iodides is the remarkable phenomenon of colour exhibited by members of the series in the solid state .and in solution. Although the +-naphthoxazones are generally colourless and form colourless solutions in dilute mineral acids their additive products wit,h the1 alkyl iodides possess a deep colour varying in shade from dark yellow to scarlet-red. The aqueous solutions of these iodides however which are strongly ionised are practically colourless .I n seelking an explanation f o r this behaviour the influence! of ionisation and also perhaps that of the alkyl group and the halogen has to be taken into account and it seelms feasible there-fore to suggestl that the ions basic and acidic are colourless, whilst the undissociated molecule of the T-alkyl iodide is intlensely coloured. If moreover this interpretation is correct it would be reason-able to expect that the solutions of these iodides in non-ionising media would be coloured. This has been observed t o be the case, for although the ordinary non-ionising- solvents like benzene, chloroform etc. were found to1 have little or no solvtmt action on these ioldides the latter dissolved in warm toluene or xylene the solutJons being generally purple1 witfh an intense pink fluorescence.I n the reduction of the +naphthoxazones the pyridine ring is first hydrogenised. The iJ7-tetrahydro-$-naphthoxazones crystal-lise in golden-yellow needles and their chemical behaviour coincides exactly with that of the fatty aromatic secondary amines; the presence of ths imino-gronp in their molecules is shown by the characteristic nitrosoi and acyl derivatives which they form with nitrous acid acetic anhydride etc. The problem of ascertaining the coinstitution of the $-naphth-oxazones has been greatly simplified by a consideration of the nature of the reactioas employed in their synthesis. The occur-rence of the pyridine ring in the molecule has been placed beyond doubt by t.he isolation of quinoline by the1 distillation of the un-substituted q-naphthoxazone with zinc dust.The next quest’io DEY AND GOSWAMI 9 - 1 $-TSONAPHTI~OXAZONES. 535 of importance that has to be settled in order to arrive at a definite structare for each individua! member of the series concerns the manner of attachment of the pyridine to the benzene nucleus. Thus the reaction by which $-1 8-naphthoxazone is synthesised from 6-aminocoumarin may follow two different courses according as the carbon atom adjacent to the amino-group taking part in the condensation occupies position 5 or 7 in t.he benzene ring. The coinpound in question may therefore be assigned either of the two following structures : 0 0 0 Although any direct evidence which might enable a decision to be made between these two possible constitutions is still lacking the formula I appears to be the more plausible and is also in harmony with certain general observations regarding the process of this condensation.Thus the substitution of a methyl group in posi-tion 7 does not hinder the progress of this reaction to the slightest extent and this behaviour would be difficult. to explain if i t were assumed that the pyridine ring attached itself in the first place t o the 7-carbon atom. The synthesis of alizarin-blue is another example of a similar nature where the condensation takes place smoothly with the peri-carbon atom corresponding with the ;?-position in the coumarin ring. The best solution of the problem appeared to lie in the synthesis of a $-naphthoxam~ne of structure I1 from 6-aniino-7-methyl-couniarin and glyoxal which in the presence of alkalis were ex-pected to condense in the following manner (compare Kulisch, Monnfsh.1895 15 277): Attempts in this direction however have hitherto been unfruitful, and further experiments are in progress. The determination of the structures of the $-benzoisonaphth-oxazones which have been obtained by analogous reactions from 6-nitre and 6-amino-1 2-a-naphthapyrones does not present much difficulty as in these cases only the carbon atam 5 is free t 536 DEY AND GOSWAMI +-1 8-TSONAPHTHOXAZONES. participate in the reaction. which can therefore proceed only in the following way : co co E X P E R I M E N T A L . 0 This substance was first prepared from 6-arninocoumarin by heating it with glycerol and sulphuric acid in the presence of G-nitrocoumariii as the oxidising agent according to the origin.il directions of Skrawp (Jfotiatdi.1880 1 316). The use of amiiio-coumarin was dispensed with later and the nit ro-cornpound employed alone the following conditions being found to give the most satisfactory results. 6-Nitrocoumarin (16 grams) and glycerol (19 c . c . ) were niixed together and concentrated sulphuric acid (1 7 grams) was gradu-ally added the mixture being cautiously heated in an oil-bath. A violent reaction set in a t 14t5-1500 and as soon as this occurreci the flask was removed from the bath and shaken vigorously. After the first reaction had subsided the contents which had now assumed a dark tarry appearance.were again gradually heated to 160-170° and maintained a t this temperature for five to six hours. After cooling the solid mass was broken up and repeatedly warmed with srriall amounts of water. and filtered until the filtrate ceased t o exhibit a blue fluorescence. The latter on keeping, deposited a small zttnount of crystals which were found to be unchanged nitrocoumarin. This was ~einoved and t h e acitl filtrate rendered alkaline with dilute sodium hydroxide care being taken to avoid an excess as the freshly precipitated $-1 8-isonaphth-oxazone dissolves to a considerable extent i n dilute alkali hydi*-oxide even in the cold. The voluminous pale yellow precipitate was colle:ted washed with cold water and crystallised twice from boiling dilute alcohol wihh the aid of animal charcoal DEY AND GOSWAMI +-1 8-ISONAPHTHOXAZONES.537 Thin silky needles were deposited having a faint yellow colour and melting a t 232O (uncorr.). The yield of the crystallised sub-stance amounted to a little more than 6 grams approximating to 40 per cent. of that required by theory : 0.0930 gave 0.2488 GO2 and 0.0326 H,O. 0.1333 , 8.3 C.C. N a t 30° and 745 mni. N=6*9. C,,H@,N requires C=73.1; H=3*5; N=7*1 per cent. The substance dissolves readily in alcohol &her chloroform etc., to form colourless solutions but its solutions in dilute sulphuric and hydrochloric acids exhibit a pale blue fluorescence which is bestl seen on dilution. The crystallised substance is insoluble in dilute sodium hydroxide solution in the cold but dissolves on boil-ing to give a deep yellow solution.The latter on cooling and carefully neutralising with dilute sulphuric acid slowly deposits the original material in a crystalline condition. The hydrochloride is precipitated on passing dry hydrogen chloride into a solution of the substance in 90 per cent. alcohol. It forms a whihe granular powder after being washed with absolute alcohol. The menurichloride crystallises from water in long colourless, so€ t needles. The potassifurn merciwi-iodide which is first obtained as a curdy, white precipitate on adding Meyer’s solution very quickly changes into lustrous leafy crystals. The picrate is precipitated on mixing the constituents in hot benzene solution. It forms a yellow crystalline powder melting a t 2 1 2 O .The pZati?zicido&h prepared by the usual method cryst.allises in yellowish-brown needles : 0.0757 gave 0-0177 Pt. P t = 2 3 . 4 . The azcrichloride forms a bright yellow crystalline precipitate, which rapidly turns brown in the air. The dichromate crystallises in orange-red priLms which are almost insoluble in water. The ferrocpmide forms a shining crystalline powder which has a very characteristic colour resembling that of catechu. It dis-solves in boiling water the solution having an intense blue iiuores-cence. The ferrocyanide appears to be partly deconlposed in the process of boiling its solution as on cooling the aqueous solution, the salt does not crystallise out4 but a deep blue powder is gradu-ally deposited along with clusters of small colourless needles which were identified as those of the original base.C=72.9; H=3.9. (C,,H70,N),,H,PtCl,,H,0 requires Pt = 23.6 per cent 538 DEY AND COSWAMI q-1 8-ISONAPHTHOXAZONRS. A series of ammonium iodides has been obtained from $-1 8-iso-naphthoxazonef by union with the alkyl iodides. These were pre-pared by the general method of heating the base with the alkyl iodide with the addition of a little absolute alcohol a t 140° in sealed tubes. They possess a dark yellow to red colour are fairly readily soluble in water and crystallise on concentrating their aqueous solutions. I)-1 8-isoTaphthomzm2e N-methiodide crystallises in thiu, scarlet-red plates melting a t 246O. The aqueous solution has a faint yellow colour : The following have been prepared : 0.1655 gave 0.1138 AgI.1737.15. C13Hlo02NI requires I = 3'7.46 per cent. It is practically insoluble in the ordinary organic solvents such as benzene ether chloroform etc. but readily dissolves in warm xylene to form a dark red solution with a fine violet fluorescence. The N-ethiodide C,,H,,O,NI forms orange-red crystals melting a t 206O. Its solution in xylene has a reddish-violet colour and exhibits an intense pink fluorescence. The N-n-bzct:yZ iodide C,,H,,O,NI forms a dark yellow powder melting and decomposing a t 209O. It agrees with the foregoing derivatives in its general behaviour. The N-amyr! iodide C,7€3,802WI melts and decomposes at 2 1 0 O . It closely resembles the butyl derivative in its physical properties. I n order to examine the effect of the displacement of the alkyl groups by other complex groups on the colour of these substances, the following compounds were prepared the first two of which were practically colourless whilst the last had a pale yellow Dint.The N-nlZyl bromide Cl,11,,02NBr forms small white needles melting and decomposing a t 320O. The N-ber2zyZ chloride @,9H,,0.,N@l crystallises from water in green needles melting a t 265O. The N-pJzewyZmcetyZ bromide C,,H,,O,NBr forms a pale yellow, crystalline powder melting and deconiposing at 350°. 5 6 7 8-Tetrahydio-t,b-l 8-isonaphthoxnzone. I)-1 8-isoNaphthoxazone (2 grams) was dissolved in concentrated hydrochloric acid (30 c.c.) granulated tin (5 grams) added and the mixture gently boiled on a sand-bath under reflux for seven to eight hours.Next ,day water was added and the tin was removed as sulphide. The filtrate was concentrabeld to about 100 c.c. and rendered alkaline with dilute ammonia; on cooling, t.he tetrahydro-derivative slowly separated in golden-yellow needles A single crystallisatian from hot water in which it was moderately soluble rendered it quite pure and the substance then melted sharply at 148O: 0.1624 gave 0.4257 CO and 0.0818 H,O. 0.1884 , 12.2 C.C. N a t 26c and 742 min. N=7-3. The N-nitroso-derivative prepared in the usual manner crystal-0.1448 gave 15.15 C.C. N2 a t 22O and 757 mm. The 7 emzoyl derivative C,,H,,O,N forms colourless plates , sparingly soluble in alcohol and melting a t 25.62O. g-Methyl-+-l 8-ison~p~~thoixaZo?ae was prepared from 6-nitro-7-methylcoumarin the same; precautions being taken as in the case of the preparation of the unsubstituted naphthoxazone.The pro-duct amounted to 3 grams from 8 grams of the nitro-derivative, the yield being approximately 35 per cent. of the theoretical. It crystallises in colourless needles melting a t ZOOo : 0.1040 gave 6.4 C.C. N a t 30' and 744 mm. C,,H,02N requires N = 6.63 per cent. The p'crate crystallises in prismatic needles melting a t 209O. The dichmmate crystallises from water in orange-yellow flat The fewocyanide forms a chocolate-red crystalline powder. The p7ati?iic?z,loride crystallises in deep yellow small needles. The auric?doiride forms an amorphous yellow precipitate. The nzerczwichloride crystallises in solft colourless woolly needles.The potmsiwn mere&-iodide forms clusters of pale yellow, prismatic needles. 5 6 7 8-Tetr~h?/dru-g-rnet~~yZ-~-~ ~ - i s o i i c c ~ l ~ t l ~ o ~ r ~ c i r o ~ i c prepared from the corresponcliug methylnapht~oxazoiie by reduction with tin and hydrochloric acid crystallises iii golden-yellow needles melting a t 180O: C=71*5; H-5.61. C12Rl,0,N requires C = 71-64 ; H = 5.47 ; hi =I. 7.00 per cent. lised from alcohol in almost colourless needles melting at 175': N=12-1. C,,H,,03N requires N - 12.17 per cent. N=6.8. prisms. 0.1650 gave 9.9 C.C. N a t 2 7 O and 751 mni. The nitrosoderivative C,,H,,O,N, forms a colourless crystal-line powder melting a t 155'. 4 9-Dimethyl-+-l 8-isotaaphthor.azone was obtained in a 30 per cent.yield by heating 6-nitro-4 7-dimethylcc1umarin (m. p. 3 5 0 O ) with glycerol and sulphuric acid under the1 usual conditions. It crystallises from warm alcohol in silky needles melting a t 238O : N=G*75. C,,HI,O,N requires N = 6.5 1 per cent 540 DEY AND QOSWAMI +-1 8-ISONAYHTHOXAZONES. 0.1249 gave 7 C.C. N a t 2 7 O and 748 mm. The picrate crystalliw in yellow needlecs melting a t 197O. 'fie &chromate forms a dark red crystalline powder. The ferrocyanide forms intense red small prisms decomposing above 300O. The methiodide C15H140&I cryst.allises from water in dark brown needles melting a t 195O. 5 6 7 8-Tetrahydro-4 9-dametiLyl-$-l 8-iso,iu~JLtJ~oxuz~ne crystdlises from alcohol in bright yellow needles melt.iiig a t 190°.It is practically insoluble in hot water : N=6.3. CI4Hl,O2N requires N = 6-20 per cent. 0.1438 gave 7.8 C.C. N a t 2 6 O and 748 nun. C,,H,,O,N requires N = 6.10 per cent. The nitroso-derivative Cl4HI4O3N2 prepared by adding a very dilute solution of sodium nitrite to a solutioii of the base in dilute hydrochloric acid at. Oo forms a mlourless powder melting a t 161O. N=6.15. co The starting point in the synthesis of this substance is 6-niti.o-1 2-a-17ai.'htha~~l.one C,,H70,N which does not appekr to have been described before. It was prepared by the ordinary process of nitrating 1 2-a-naphthapyrone dissolved in glacial acetic acid, adding concentrated sulphuric acid and warming the mixture on the water-bath. It separates from hot glacial acetic acid in pale yellow nodules melting a t 197O. The assumption that the nitro-group enters position 6 is based on the fact that t.he 6-nitro-derivative is formed first in the nitra-tion of 4-methyl-1 2-a-naphthapyrone (Dey T. 1915 107 1613). t,b-Benzo-1 8-iscmaphthoxazone crystallises in soft pale yellow needles melting a t 243O. The yield amounted to 30 per cent. of the weight of the nitro-compound employed : 0.1490 gave 7-8 C.C. N a t 2 4 . 5 O and 759 mm. C,H,O,N requires N = 5-65 per cent. 4-Methyl-$-7,enm-l 8-isonu~r71.tliornazo.1Le was prepared from 6-nitro-4-methyl-1 2-a-naphthapyrone and i t esllibited the same N=5*9 MERCURY MXRCAPTIDE N IT1lIT&3 ETC. PART. v. 54 1 characteristics as the foregoing compound. The yield in one instance amouiited to 50 per ceat. of t h e theoretical. it crystallises in pals yellow needles melting at' 234': 0.2291 gave 11.4 C.C. N atl 24O aiid 759 mm. N=5.6. C,7H,,0,N requires N = 5-36 per cent. ORGANIC CHEMICAL LABORATORY, PRESIDENCY COLLEGE, CALCUTTA. [Recciued March 16th 1010.

ISSN:0368-1645    

DOI:10.1039/CT9191500531

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

MERCURY MXRCAPTIDE N IT1lIT&3 ETC. PART. v. 54 1 X L.-Mercuiy Mercaptide Nitdes and t h e h lieact ~ O Y L with the Alkyl Iodides. Part V. Chain Com-pounds of SuZphur (continued). By SIR PRAFULLA CHANDRA RAY and PRAFULLA CHANDRA GUHA. THE present series of investigations has hitherto been confined to derivatives of monomercaptans; it has now been extended to those ob the dimercaptans of which 2 5-dithioll-1 3 4-thiodiazole may be taken as a typical representative. When this dimercaptan is treated with mercurlc nitrite a dimercaptide dinitsite, O,KHgS*C:N*N C- SHgNO, 1- s- I 9 is not obtained but the nitrous acid siinultaneou sly disengaged oxidises the hydrogen atoms of two three four and even six molecules of the dimercaptan and the sulphur atoms become linked togeither and give rise tol a n interesting series of closed chain com-pounds.The maximum number of sulphur atoms forming the connecting link between two adjacent nuclei in the condensed complex molecule tmhus formed has so far been found t o be twelve. Thus in the case of a trinuclear condensation we have * S*R”*S H 0 H S*R’’*s H 0 H s*R”oS I = ON OHg I tJg NO, hC.R”.M.S*R”.S.s.K”*S 1 t N,O + 3H,O. Hg I Hg--O-*C:N” C’ R’ denotes the bi\ alelit group I ” ’ 542 RAY AND GUHA MERCURY MERCAPTIDIJ NlTRXTES AN11 The heavy molecule of the dimercaptide dinitrite cannot retail) the load of two NO groups and hence rupture takes place as indicated by the dotted line and a closed chain sulphoxy-deriv-ative is finally formed with the liberation of nitrous fumes.The compounds thus generated are not as a rule nitrites. Some pre-parations however responded slightly to the nitrite tests but the percentage of nitrogen due to the presence of nitrite was very low proving that the proportion of the latter was insignificant. The occasional presence of some nitrite goes to establish the fact that the oxy-compound is in reality a decomposition product of the former. If instead of the dimercaptan itself its potassium salt is used, the tendency towards oxidation by nitrous acid is excluded and a mercaptide nitrite of the formula KS*C:N*N:C*SHgNO, I s - I is obtained. The sulphoxy-compounds may be represented by the general formula (C,N,S,),,Hg,O whelre x=2 3 4 or 6. A condensation product of five molecules has not yet been obtained.It is not easy to explain why in one operation the value of x should be two and in others it should rise to six; possibly the concentration of the parent substances is the main determining factor. It has .often been found that two preparations under similar conditions had identical compositions. I n the majority of cases the value of LL: was found to be three occasionally two and four and only rarely six. The preparatioiis could iiot have beeii admixtures because each of them strictly conformed to a definite formula. The most con-vincing proof of these compounds being of definite composit~oi~, holwever is afforded by their reaction with the alkyl iodides. These sulphoxy-compouiids behave exactly like mercaptide nitrites and yield as a rule hhe corresponding sulphonium derivatives and in a Sew cases those with a less number af nuclei.The reducing action of the alkyl iodide reinoves the oxygen atom of the sulphoxy-ring and the bonds being thus snapped an open-chain compound is formed thus: I I 1 I I I 0- -Hg I I 1 I ' I I -Erg-8. R". S 0s. It". s. 8. R" . S 12 i -+ IHgS It"* S S R" 8 H*R"*S HgI . The six sulphur atoms of the chain now become) quadrivalent by taking up the components of the alkyl iodide THEIR REACTION WITH THE AZKYL IQDIDES. PART V. 543 I n this manner a series of tetra- hexa- oct?a- and dodeca-sulphonium compounds have been prepared. Each 09 these with the exception of the propyl and butyl derivatives is characterised by its crystalline character and moreover its successive crops have the same melting point; the possibility of their being mixtures is thus precluded.Another interesting point is the shifting of the double bonds, thus : N-N N=N where R=meLhyl ethyl propyl or butyl. As a rule this is con-fined. only to one nucleus. There is here evidently an extleiision of Thiele’s theory to nitrogen compounds. I n one isolated instance and that in the case of the reaction with methyl iodide instead of there being a shifting of the double bonds both the pairs of nitrogem and carbon atorris throughout t,ho molecule were sai,iirated by talriiig 11 1) adtlit ional methyl groups, thus : N-N MeN-NMe s S EXPERIMENTAL. R t cl ph a x y - c ompo 1 I nds . Cene~u7 Method of I’reparation .-2 5-Dithiol-1 3 4-thiodiazole, prepared according to Busch’s method (Ber.1894 27 2518> in dilute alcoholic solution was added drop by drop with vigorous stirring to a solution of mercuric nitrite care being taken that the latter was always in excess. I n this manner a semi-gelatinous, pale yellow precipitate was obtained which was washed with water and dried in a vacuum desiccator. The powdered granular mms was then heated under reflux successively with alcohol1 and benzene to remove any adhering accidmtal orgaiiic iiiipurities namely the parent> dimercaptan or its oxidation procluct the disulphide. This precaution was however found to be unnecessary. The corn-poudds obtained in this way are always associated with some mole-cules of water 544 RAY AND GUHA MERCURY MERCAPTIDE NITRITES AND I’ottrssizrm Salt of 3 5-Dithiol-1 3 4-tlziodiasole a d Memmic Nitrite.With an aqueous solution of the potassium salt a compound of KS*C:N*N:C*XHgNO, the formula j -8 1 with 12H,O is obtained. Analysis of the substance gave: Found Hg=31.50; S=13*89; C-3.53; I1=5-34.* C,0,N3S,HgK,12H,0 requires Hg = 30.81 ; S = 14-79 ; C= 3.70 ; H = 3.70 per cent. S-C,N,S Y,*C,N,S*S,- C!,N,S* S Yri?) I I d e n t * S 1 I /id o I t ~ r o?n 1’ o I I rt d 1 I ’ I-Tg-- 0--Hg In this case each distinct preparation gave the compoiii~(1 C!on~pounGF with 8H,O. Found IIg=40.21; S=27-56; C=8*50; N=8.18. associated with 8 5 and i! iiiolecules of water respectively. C,jON,S,Hgl,8H,0 requires Hg = 39.85; S = 28.69 ; C = 7-17 ; N=8.37 per cent. Gomporriid with 5R,O.Found Hg = 42.07 ; S = 30.21 ; N = 9.36. C,0N,S,Hg2,513,0 requires Hg=42.11; S ~ 3 0 . 3 1 ; hT=8*84 per cent. Cornliound with 2H,O. Foulld Hg=45.33; S-31.40; N=9.52. C,0N,S,Hg2,2H20 requires Hg =44.65 ; S = 32.14 ; N = 9.38 per cent. On repeating the preparation the same trinuclear condensation * The percentage of hydrogen is often too high as traces of mercury vapour are apt t o be carried over t o the calcium chloritle tube; in many cases therefore the value of hydrogen has not been give THEIR REACTION WITH THE ALKYL IODIDES. PART V. 545 product was obtained although sometimes in an impure form, Thus in one preparation there was found Hg= 42.52 S = 34-54, and in another Hg=43-72 S=31.53. However on treating each of these with the alkyl iodides the same sulphonium compound was obtained (see p.546). Tetralvuclear Sulphoxy- corn pout1 GF (C,N,S,), Hg,O. Compozind with 3H,O. Pound €Ig = 37.94; S = 37.54 ; N = 11.48. C,0N,S,,Hg,,31-T20 requires €Ig=37.67; S=36*16; N=10*55 per cent. Compound with 5H,O. F O U ~ Hg = 37.21 ; S = 35.13 ; N = 9.55. C&ON8S,,Hg,,5H,0 requires IIg = 36-43 ; S = 34.97 ; N =- 10.2 per cent. Benetion m"h th c A lihyl 1odiAr.s. Cen~rtcl Method 01 Pt.epuiation,.- - The izhove sill pliosy-tleriv-atives were heated with the alkyl iodides on a water-bath under reflux for several hours the product being allowed t o remain over-night. Sometimes a crystalline mass and occasionally ;I heavy, dark brown oil settled a t the bottom; the excess of alkyl iodide was decanted or distilled off and the product dissolved in the minimum quantity of acetone and the solution filtered from t h e insoluble matter whenever necessary.On adding ether to the filtrate a pale yellow mealy crystalline precipitate was obtained, and this process was repeated in order further t o purify the substance. D i 1% zc c 1 e a r C n n d e n su t i o n . The Compownd C40N,S,Hg, and iWethyr! Iodide E'oi'mntion of the Compound, Me N-N Me Me N==K Me I I I l l I I The product melted a t 101-102° 54.6 RAY AND C-UHA MERCTJRY MERCAPTTDE NITRITES AND Found Hg = 25-94 ; I = 49.23 ; C = 7.75. C",,H1,N,S6Hg,16 requires Mg = 25.84 ; I'=49.33 ; C = 7.75 per cent. The corresponding compourwl with etlhyl iodide (11) was sparingly soluble in acetone and was therefore purified by crystallisation from the bodling solvent; it melted a t 107'.Found Hg=24.19 24-58; 1=43*20*; C = 11.25 11.42; N = 3.53. C16H30N,S6Hg,16 requires Hg=24*51 ; 1=46*69; c= 11.76; N=3'43 per cent.. The corresponding dinuclear t'etrasulphonium compounds with n-propyl and n-butyl iodides did not crystallise but consisted of dark brolwn pasty masses which were purifield by repeated p r e cipication with ether from acetone solution. Compound with n-propyl iodide (111). Found Hg = 23-89 ; I = 44.74 ; C = 14.05. Compound wi&h n-71 u f y l iodide (IV). C,',,H,4W,S,Hg,T reqiiircs Hg x= 23-22 ; T C,,H,,N,S6Hg,16 requires Hg = 23.31 ; I == 44.40 ; C = 15.38 per cent. Found Mg-21.77; 1-41-75; CT-17.66; N==3*11. 42.33 ; (1- 18-60 ; W L- 3.1 1 per cent.The product of the interaction was an oil. It was dissolved in hot acetone and the solution on coolling deposited a crystalline mass which when recrystallised from hot acet'one yielded needle-shaped crystals melting a t 101-102° identical with the compound, c 1 ~ ~ 1 ~ ~ & ~ ~ & 1 6 described above. The original mother liquor 0011 concentration gave two1 successive crops melting atl 85-86O. Found Hg=21.55; C=8-66. Cl4IL1N6SgHg2I requires Hg = 20.20 ; C = 8.48 per cent. '' As a large quantity of copper powder has to be used and the process is it tedious one the values for iodine and sulphur are sometimes too low (see T. 1916 109 611) TI-IEIR REAC'TION WITH THM RLKYL JOl>IDES. PART V. 547 The met8hold of preparatiofn and purification was the same as iii It is a white crystalline the case1 of the preceding compound.substance melting a t 9 4 O . Found Hg=18.24; S=11.36; c"=13*15; H=2.54. C,,H,,N,S,Hg,I requires Hg= 18.78; S= 13.52 ; (2- 13.52; H = 2.53 per cent. The formation of this type of compound has been observed only ill this one instance. Conzpoimd m~1ilh n-7'ropyZ 7odid'c (VII). This conforms t o the ordinary type. Found Hg=18-54; 1=44*61; (2-16.47. @3,€I,,jN,,S,Hg21s requires Hg= 18.14; 1=46*1; c"= 16-33 per cent. As will he noticed the trinuclear sulphoxy-compound gives with niethyl iodide compounds I and V the latter being the chief pro-duct. This tendency towards the formation of the dinuclear tetra-sulphonium compound from the higher nudear sulphoxy-compounds is particularly iioticeable in the case of the reaction with ethyl iodide when only the dinuclear sulphcnium compound (11) is obtained even from tri- and tetra-nuclear sulphoxy-derivatives.In all these cases of formation o f a lower member from the higher sulphoxy-corni)ounds a dark brown pasty sulstance with a penetrating odour and lachrymatory properties was always pro-duced which resisted all attempts a t purification. H e x a IL ZL c I c a t s C'o n rt e n s cc t i o n. the Compurzd, rEt N-N Et, ' l h i h melted a t 90-91* 548 RAY MERCURY MERCAYTIDE NITRITES AND THEIR Found I=50*03; N=3*90; C=13.14. C,,H70Nl,S,8Hg,Il requires I = 51.20 ; N = 4-54 ; C= 13-82 per ceiit. It will thus be seen that the type persists throughout in that the alteration in the position of the double bond is limited to olnly one nucleus of the chain. I n the previous communications the compounds there described were tentatively classed under tahe sulphonium group although no direct proof could be adduced in support of this view. One of the purest compounds of this series namely MeEtS,,HgI,,EtI (T., 1916 10.9 606) was selected for molecular weight determination i n acetone solution by the ebullioscopic method ; the value obtained was 712 that required by theory being 718. It is thus evident that the constitution is atomic (compare Hilditch and Smiles T., 1907 91 1396). A study of the physical properties of the interesting poly-sulphoiiiuui coiiipouiids treated of ill this paper is being under-taken which it is hoped will throw additional light on their constitution. CHEMICAL LABORATORY, UNIVERSITY OF (2ALCUTTA. [ftec.c.iwd Nouerr&r 30th 1918.

ISSN:0368-1645    

DOI:10.1039/CT9191500541

出版商:RSC    

年代:1919

数据来源: RSC

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548 RAY MERCURY MERCAYTIDE NITRITES AND THEIR X L L.-iVe~*ct~i*?j iWercaptide Nitrites a ~ i l tlLei?* R e -cxctioub with the Alkyl Iodides. Pcwt VI. (/IJLc~-CZ'II Compounds f Sulphur (continued). By SIR PRAFULLA CHANDRA RAY. THE present investigation deals with the chain compounds of sesa-valent sulphur. On treating the product of the interaction of thiocarbamide and mercuric nitrite namely the sulphoxynitrite, NN,*C(:NH)*S(BgNO,)<~~ (T. 1917 11 1 102) with ethyl iodide a yellow crystalline substance was obtained which was soluble in acetone and on purification by precipitation with ether, nielted a t 98-100*. Analysis proved it t o confolrm t o the formula Et,S,,EtI,2€Ig12; in other words it is a member of the disulphoniuni seried already described (T. 1916 109 134) with an additional molecule of mercuric iodide in combination t o which should be assigned the coiistitiitional formula I€Ig*SEt,I,*SEtI*HgI, REACTION WITH THE ALKYL IODIDES.PART VI. 549 one of the sulphur atoms in the chain becoming sexavalent. The formation of this compound suggested the possibility of the direct conversion of all the members of the series RR/S,,R’I,HgI into RR’S2,R’I,2HgI,. This anticipation has been realised with one notable exception. When the alkyl group happens to be methyl, combination with an extra molecule of mercuric iodide does not take place. The presence of the radicle ethyl on the other hand, favours the combination. Thus in the above series where R=Me and R’=Pra or butyl the extra valencies of the sulphur atom are not revive’d but if R’ happens to be ethyl this anomaly disappears.To what extent! the ethyl group favours the1 increase in valency will be evidentl from a typical case. When mercury ethyl-mercaptide nitrite EtS-HgNO, is treated with methyl iodide by an interchange of the radicle the Compound EtMeS,,€IgI,,MeI is obtained (T. 1916 109 603); but in this case although there are two methyl groups the presence of a single ethyl group is sufficient to counteract the prejudicial influence of the former and the com-pound EtMeS,,MeI,2Hg12 is readily formed. The marked genetic affinity of the radicle ethyl for sulphur and it’s influence on the increase in its valency is further ’evidenced by the factl that a compound of the empirical formula has also been obtained from ethyl sulphide by its reaction with ethyl iodide and mercuric iodide.On repeating Smiles’s experi-ment (T. 1900 77 161) under slightly altered conditions with a view to ascertain the maximum valsncy of sulphur it was noticed that whilst the main product was the compound Et,SI,HgI, as found by this author there was always a considerable amount of a shining crystalline substance practically insoluble in cold acetone. As it had a sharp melting point when crystallised from hot acetone it was analysed with the result that the formula given above was established. What evidently happens is that under the joint action of mercuric iodide and ethyl iodide or rather their ions the bivalent sulphur atoms of two adjacent mole-cules of ethyl sulphide become sexavalent with the formation of the compound SEt$,*SEt,I*HgI.It is remarkable that i f in the above reaction ethyl iodide is substitut<ed by methyl propyl or butyl iodide the product in each case is completely soluble in acetone and conforms to the general formula Et,RSI,HgI, but no product of bhe fusion of two ethyl sulphide molecules is formed. The different’ial property of ethyl as compared with other alkyl radicles is thus brought into relief. It was expected that the general method of the preparation of E t4S,,2 EtI,HgI 650 RAY MERCURY MERCAPTIDE KITRITXS AND THEIR the disulphonium compounds already described namely the treat-ment of ethyl mercurimercaptide nitrite EtS-HgNO, with ethyl iodide should also yield the chain compound containing both the sulphur atoms in the sexavalent state.This expectation has also been realised. The latter compound is produced in such small amount that on previous occasions its formation was overlooked. It has already been shown that ethyl disulphide ethyl iodide and mercuric iodide also combine directly to yield the disulphonium compound E~S,,HgI,,EtL (Zoc. czt.). Recently this preparation has been repeated and it has been found that the sexavalent disulphur compound is also formed in considerable quantity along with the former. It is thus evident that both the chain com-pounds containing quadri- and sexa-valent sulphur respectively, are formed simultaneously, It is of interest to note that Smiles and Hilditch who treated an acetone solution of molecular proportions of ethyl disulphide and mercuric iodide with ethyl iodide obtained diethylthioethyl-sulphonium dimercuric iodide (C,H,)3S21,2HgI (T.1907 911, 1396). It is evidently the same compound as has been described above. pr An explanation may be offered as t o why it is that in the first series of compounds only one of the two atoms of sulphur exists in the sexavalent condition ; here the quadrivalenb sulphur being already weighted with the heavy load of the ions HgI' and 1'; has lost the capacity of taking up an additional charge; in other words, of acquiring the maximum valency. In the solitary instance how-ever in which both the sulphur atoms happen t o be sexavalent it will be noticed that there is only one set of HgI' and I' ions; the sulphur atom combined with the latter has attached to it three additional comparatively light ethyl radicles whereas the other sulphur atom not having to bear the load of the heavy I-IgI-group, is in a position to take up three ethyl groups and two iodine atoms.Facts are already known which go to support the view that the maximum valency oE an element is often conditional on the load of the radicla. The author hopes in a succeeding communication to show that platinum when attached t o the radicle of 5-thiol-2-thio-3-phenyl-2 3-dihydro-1 3 4-thiodiazule is in the tervalent con-dition. It is none the less inexplicable why the light radicle methyl should stand in the way of one of the atoms of sulphur attaining its maximum valency. The anomalous behaviour of the first member of the alkyl series is however well known REACTION WITH THE ALKYL IODIDES.PART VI. 551 EXPERIMENTAL. The general method of preparation of the series R,S2,RI,2HgI, has already been incidentally described. These members are readily obtained by dissolving the corresponding disulphonium compound in acetone and adding mercuric iodide to the solution until no more is absorbed. The golden-yellow liquid is decanted from the undissolved iodide and on adding ether a copious deposit of yellow mealy crystals is obtained. Solution in acetone and pre-cipitation by ether is repeated until the product gives a fairly sharp melting point. It has been found that in some instances especi-ally in the case of the methylsulphonium compound, the acetone solution a t first takes up a considerable quantity of mercuric iodide but purification by the above process gradually removes all the mechanically held salt.C‘o mpo imd E kS,,E tI ,2 €€gIz.- ( a ) From the su lp hoxy nitrite derivative of thiocarbamide and ethyl iodide. The substance melted a t 9 8 O : 0.3656 gave 0.1250 Hg 0.3540 AgI and 0.1029 BaSO,. 0.2442 gave 0.0570 CO and 0.0356 H,O. ( b ) By the direct union of mercuric iodide with the compound 0.2118 gave 0,0711 Hg. €Ig=33.57. 0.2118 , 0.0532 CO and 0.0325 H,O. C=6*85; H=1-71. C,€€,,I,S2Hg requires IIlg = 33.73 ; I = 53-54 ; S = 5.4 ; C= 6.07 ; H=1.26 per cent. e S M eI ) H g I,, Hg= 34.19 ; I = 52.32 ; S = 3.87. C=6.37; H=1.62. Et@,,EtI,HgI,. The substance melted a t 100-lO1° : Compound MeEt&,EtI,2Hg12 (m. p. 38-40°) : 0.3840 gave 0.1236 Hg and 0.3768 AgI.0.2094 , 0.0452 CO and 0.0466 H,O. C=5*87; H=2*47. C,HI3I,S,Hg requires Hg=34*14; I=54*19; C=5*12; H=1*11 per cent.. Hg=32*19; 1=53*03. Compound MeEtS,,ll’leI,2Hg12 (in. p. 50-55O) : 0.2467 gave 0.2483 AgI and 0*0840 ITg. 0.1428 , 0.0286 CO and 0.0211 11,O. C=5-46; H=1.64. C4€I,,I,S,Hgr requires IIg= 34.55 ; I :- 54.84 ; C = 4.14 ; H = 0.95 per cent. Hg=34*05; I=54.39. Compound EtPraS2,PraI,2Hg12 -1- C3H,0 (m. p. 30-31O) .-This VOL. cxv. Y compound contains one molecular proportion of acetone 652 RAY AND SEN MERCURIC SULPHOXYCRLORIDE. 0.4410 gave 0-1400 Hg. Hg=31.75. 0.1629 , 0.0586 CO and 0-0352 H,O. C=9.81; H=2*40. C,H1915S2Hg2,C3H60 requires Hg= 31 *45 ; c = 10.38 ; H = 1.97 per cent. Compound Et(C,H,) S,,C,H,I,2Hg12 + 1*5C,H60 .-The substance had the consistency of treacle and contained 1.5 molecular pro-portions of acetone : 0.3879 gave 0.1153 Hg and 0.3272 AgI. Hg=29*72; I=45.58. 0.1340 , 0.0649 CO and 0.0363 H,O. C=13*21; H=3*01. C,,H2,1,S,Hg,,l.5~3H,0 requires Hg = 30.10 ; I = 47.79 ; C= 13.10 ; H=2.41 per cent. Compound containing two sexavalent sulphur atoms (m. p. It was very sparingly soluble in cold acetone but 0.2991 gave 0.063 Hg and 0.2916 AgI. Hg=21*06; 1=52*69. 0.4032 , 0.8400 Hg and 0.2042 BaSO,. Hg=20-86; S=6*96. 0.1930 , 0.1068 CO and 0.0538 H20. C=15-09; H=3.09. C,,H,I,S,Hg requires Hg = 21-14 ; I = 53.70 ; S = 6.77 ; C = 15.23 ; H=3-17 per cent. 146-147O). fairly readily so in the boiling solvent: CHEMICAL LABORATORY, COLLEUE OF ScImcE, UNIVERSITY OF CALCUTTA. [Received January 8th 1919.

ISSN:0368-1645    

DOI:10.1039/CT9191500548

出版商:RSC    

年代:1919

数据来源: RSC

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652 RAY AND SEN MERCURIC SULPHOXYCRLORIDE. XLlI .-Mercu& SuZphoxyohlwide, By SIR PRAFULLA CHANDRA R ~ Y and PRAFULLA K U M A ~ ~ SEN. THE close analogy between mercuric chloride and nitrite has been found to hold good throughout the investigations carried on from 1898 onwards. Thus whilst mercuric nitrate with sodium sulphate at once gives an abundant yellow precipitate of the oxysulphate, the chloride and the nitrite fail to give it (T. 1897 71 1103). The explanation lies in the fact that the latter salts are very feebly ionised in solution and thus have no tendency to yield basic cam-pounds. Ammonia amines and even a class of alkaloids have been found to behave towards mercuric nitrite in a manner similar to their act.ion on the chloride (T. 1913 103 3; 1917 11'1 507).The substituted thiocarbamides thiocarbimides thiobenzamide, etc. have been shown to give rise to a purely inorganic sulphoxy-nitrite of the empirical formula [S(SHgNO,),HgO], which is i RAY ,AND SEN MERCURIO SULPHOXYCHLORIDE. 563 reality a chain compound containing six atoms of sulphur linked together (T. 1917 111 104). An attempt has been made to isolate the radicle (SHgCl), which would be the analogue of mercuric iodosulphide (SHgI) (Zoc. cit., p. log) by treating mercuric chloride with some typical thio-compounds named above as also thioacetic acid and ammonium dithiocarbamate. It was expected that in each case the radicle, SHgCl would become detached from the parent substance and lead an independent existence. This expectation has been realised, but in a qualified sense.The radicle SHgC1 no sooner separates out than i t assumes the form [S(SHgCl),HgO], which is the exact analogue of the osynitrite. It has been shown already that the complex nitrite containing several nitro-groups by the elimination of nitrogen trioxide readily yields the oxynitrite. It is not easy a t first to understand how the chloride would also give rise to an oxy-salt. The explanation is obvious when i t is considered that water takes part in the reaction; the compound [ 3 (S HgC1) HgO Jr is formed thus : HgCl HgCl HgCl HgU1 I I I I I * I -1 I S*S*HgC! = --s--s --- ClHg*S*S I I HgCIHOHC1 U l H O H C I H g HgCl HgCl HgCl HgCl I I S*S*HgCl + 4HC1. I I I Hg- Hg ClHg.S.5--S--S--I n other words as soon as the radicle SHgC1 is formed three groups take up an additional molecule of mercuric chloride that is the radicles HgCl and Cl and a molecule of water simultaneously take part in the reaction four molecules of hydrogen chloride are generated and the oxygen atom forms the connecting link between the mercury atom the neighbouring sulphur atom and the two symmetrical complexes coalescing into a single molecule.It is necessary to point out that whilst the radicle SHgNO, has often a tendency to part company with the parent substance the radicle SHgC1 on the other hand often remains attached to it. Thus thiocarbamide when acted on by mercuric chloride yields the compound NH,*C:N€I*SHgCl,HCl which is actually a hydro-chloride as will be shown in a subsequent communication.If, however thiocarbamide is converted into its diacetyl derivative and then treated with mercuric chloride the molecule is ruptured, Y 554 RAY AND SEN MERCURIC SULPHOXYCHLORIDE. with t.he detachinelit of the radicle SHgCI and the forinatioii o f the oxychloride. s-Diplienylthiocar~)a~~iide also behaves similarly. Evidently the introduction of the negative radicles acetyl and phenyl neutralises the basic character of the compound due t o the presence of an amino- and imino-group and deprives it of the power of forming a hydrochloride in which character alone it is stable. It is a characteristic diagnostic property of mercaptans real and potential that with mercuric nitrite and chloride they yield the rnercaptide nitrite and chloro-mercaptide respectively.Thioacetic acid although an acid contains the group SH and behaves like a typical mercaptan thus : c'H,*CO*SB "a?$ CH,*CO*SHgCI. As soon as this compound is formed it acts on a molecule of water and the scission takes place as shown by the dotted line a C€J,*CO- -SHgCl H OH . CH,*CO-:-SHgCl molecule of acetaldehyde and acetic acid being formed. Ammonium dit.hiocarbamate assumes the tautomeric form, SH*C(:NH)*SNII, and both the radicles SH and SKH with mercuric chloride yield SHgC1 which separates out. Allylthiocarbimide C,H,*NCS combines with the elements of mercuric chloride and the compound C,H,-N:CSCl-HgCl is temporarily formed the sulphur atom becoming quadrivalent. As this configuration is unstable a rupture takes place along the line of least resistance the radicle :SCl*HgCl decomposes into the stable radicle SHgC1 and chlorine whilst the organic portion of the complex R*N:C with a molecnle of water yields a primary amine and carbon monoxide.E X P E H I M E N T A L . Method of Prepwution.-The thio-compound in aqueous or alcoholic solution as the case might be was added in a thin st'rearn by means of a pipette to an aqueous solution of mercuric chloride with vigorons stirring care being taken that the latter ingredient was always in large excess. A granular white precipitate was obtained which was washed first with water and then with alcohol and finally dried in a vacuum over sulphuric acid. A special precaution is necessary in the case of allylthiocarl~ir~iide. If an alcoholic solution of j L i RAY AND SEN MEROURIC SULPHOXYCHLORIDE.555 added to an aqueous solution of mercuric chloride the white pre-cipitate is obtained but a t the same time heavy oily globules begin to settle down a t the bottom and it is not always easy to separate them from the sulphoxychloride. It is best to add the dilute alcoholic solution of the allylthiocarbimide to an alcoholic solution of mercuric chloride. The mixture remains clear but on copious dilution with water and stirring the white precipitate begins to appear. The mixture is allowed to remain overnight and the product collected and treated as before. The interaction of each of the above-mentioned thio-compounds and mercuric chloride was repeated several times and the composi-tion throughout was found to be identical.It is therefore not necessary to give the analysis of each preparation; t,hat of one or t w o typical ones are given below. -4 c t io rL of d i e m uric Chloride on Dicc ce iylth iocarbamide . Diacetylthiocarbarnide (Rohmann .7. Amer. C'hem. Soc. 1915, 37 2130) was dissolved in water and added drop by drop to a solution of mercuric chloride from a pipette with constant stirring. A white amorphous precipitate was formed which on remaining for twenty-four hours became granular. It was collected washed with water and dried: 0.3276 gave 0.2591 Hg and 0.1354 AgCl. Hg=79*1; C1=10.2. 0.2419 , 0-1048 AgCl arid 0.1647 BaSO,. C1=10*7; S=9.4. [3(SHgCl),RgO] requires Hg = 78.7 ; C1= 10.5 ; S =9*4 per cent. The absence of carbon and hydrogen was confirmed by repeat.ed combustion.A ctiotz. of ~Vei~cicric CJLloride O I L s-I)ii.lhen~lthiocai.bamide. The hot. alcoholic solution of s-diphenylthiocarbamide was added to a solution of mercuric chloride and the mixture was heated on a boiling-water bath under reflux for several hours. The white precipitate was collected washed with hot alcohol and finally with water and dried: 0.2591 gave 0.1097 AgC1 and 0.1698 BaS04. Cl=10*47; S=9*0. 0.3684 , 0.9902 Hg. Hg-78.8. iIfercii.m'c Chloride attd Thiocicetic ricid. Result of analysis: 0.2587 gave 0.2370 HgS. Hg=79*0. 0.1465 , 0.0625 HgCl and 0*1070 BaSO,. Cl=10*55; s = 10.0 556 DENHAM THE PREPARATION OF UADMIW SUBOXIDE. Mercuric Chloride and Allylthiocarbimide. Result of analysis: 0.3402 gave 0.2631 Hg. Hg=77-34. 0.2795 , 0.1285 AgCl and 0.1818 BaSO,. C1=11.4; S=8.9. The absence of carbon was shown by combustion analysis. CHEMIOAL LABORATORY, COLLEGE OF SCIENCE, UNIVERSITY OF CALCUTTA. [Received October 1&h 1918.

ISSN:0368-1645    

DOI:10.1039/CT9191500552

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

556 DENHAM THE PREPARATION OF UADMIW SUBOXIDE. XlAI.-Th. Preparation of Cadmium Suboxide. By HENRY GEORGE DENHAM. VARIOUS suboxides of cadmium have long ago been described (Tanatar Zeitsch. anorg. Chem. 1901 27 433; Morse and Jones, A m e r . Chem. J . 1890 12 488 etc.) although other investigators have thrown doubt on the existence of these suboxides. The following experiments describe the efforts made to prepare a sub-oxide of cadmium in as pure a state as has been the case with lead suboxide. Decomposition of Cadmium O x d a t e . The first method attempted was that described by Tanatar ( l o c . cit.) namely the decomposition of the oxalate in a stream of carbon dioxide. A sample of cadmium oxalate (Cd=56*02 per cent.) was heated a t 300° in a rapid stream of carbon dioxide freed from traces of oxygen by passage through heated copper.A t the end of forty-eight hours the evolution of gas ceased and examina-tion revealed a small quantity of a green material unmistakably containing globules of cadmium whilst the leading tubes were lined with a deposit of the volatilised metal. This experiment, many times repeated always .gave the same result. Precisely similar results were obtained when the carbon dioxide was not employed the evolved gases being removed by means of a Sprengel pump. Even when the total pressure of these gases did not exceed 1 mm. the same green heterogeneous substance was produced. Analysis of this material always gave values closely approximating to Cd = 96.5 per cent. (Tanatar’s Cd,O contains Cd = 96.56 per cent.) DENHAM THE PREPARATION OF CADMIUM SUBOXIDE.567 Tanatar and Levin (Zoc. c i t . ) also describe how the oxide Cd,O, was obtained by the decomposition of a basic oxalate under similar conditions. A repetition. of their experiment always gave a heterogeneous grey mass containing free cadmium. An attempt was then made to remove by distillation the excess of metal present in the decomposition product. of the oxalate. The mixture was heated to 350° without undergoing any change in appearance. The pump was then put into requisition and in ten hours a large deposit of cadmium had volatilised out of the oven whilst the residue was a homogeneous green mass in which the microscope was no longer able to detect free metal. The following analytical results were obtained : Oxalate.Green substance. CdSO,. Cd. Grams. Gram. Gram. per cent. 2.0 0.0362 0.0628 93.5 2.6 0.0592 0.1025 93.4 2.0 0*0809 0.1401 93.4 Cd,O requires Cd--93*36 per cent. The method therefore appears to give a green oxide but owing to the strong reducing action of the evolved carbon monoxide and the difficulty of distilling out the free metal the method is not satisfactory . Reduction z1!/ Hydrogeti. An atteriipt was made to prepare t*he suboxide by reducing the brown oxide with hydrogen (see Glaser Zeitsch. anorg. Chem., 1903 36 1). A t 240° after twenty hours’ reduction the yellowish-green product appeared to be uniform but the micro-scope clearly revealed globules of free metal Reduction under varying conditions of temperature and pressure always led to this result.The excess of metal was afterwards removed by distills-tion and a uniform yellowish-green product obtained in which the microscope revealed no sign of free metal. Analysis how-ever showed that this substance was pure cadmium oxide (CdO), the colour change being either superficial or due to a different molecular aggregation. Reduction ziy C u ~ ~ b o n iMonorcide. It has been shown by Brislee (T. 1908 93 162) that the time-reduction curve of cadmium oxide a t 300° with carbon monoxide as the reducing agent shows a distinct break a t a point which corresponds with the compound Cd,O Although it appeare 558 DENHAM THE PREPARATION OF CADMIUM SUBOXIDE. difficult to stop the reduction a t the precise moment when the whole of the higher oxide had been reduced to the suboxide and none of the latter to the metal it seemed feasible to carry through the reduction in such a way that the higher oxide was reduced to a mixture of the suboxide and metal and this metal could then be removed by volatilisation.An analysis of Brislee’s time-reduction curve for 300° shows that the break occurs when the reduction has progressed for about twelve hours. An esperiment was therefore carried out in which carbon monoxide was circulated for fourteen hours a t 300° through two bulbs each containing about 0.6 gram of cadmium oxide. One bulb was then sealed off and the other heated in a vacuum for eighteen hours. The material in the first bulb was yellowish-green, containing visible globules of cadmium whilst the second bulb gave a perfectly uniform yellowish-green substance.Bulb I con-tained Cd=90*4 and bulb I1 Cd=87*5 whilst CdO requires Cd=87*57 per cent. This experiment was repeatedly carried out a t various temperatures between 300° and 310° and in all cases the bulb sealed off before exhaustion cont,ained a considerably higher percentage of cadmium than does CdO approximating often to that of Cd,O but a moderately good pocket lens was sufficient in every case to show that the reduction product was hetero-geneous and contained cadmium. Similarly the bulb from which the excess of cadmium had been volatilised a t the temperature of the experiment always gave a uniform yellowish-green product exactly similar to that obtained when hydrogen was the reducing agent.and the composition of this was undoubtedly that of CdO. As a means of preparation of cadmium suboxide this method therefore fails. Norse ctnd Jo?ies’s Method. Morse and Jones (loc. c i t . ) have described how anhydrous cadmium chloride when fused with cadmium gives a ‘ product having the composition Cd,Cl,. This they consider to be possibly a mixture of SCdCI,+CdCl. On treatment wit.h water the pro-duct gave cadmous hydroxide from which yellow cadmous oxide, Cd,O was readily obtained by dehydration. The author has repeated this work and succeeded in reproducing the results described by Morse and Jones but in spite of close attention to the details given in the original publication he has never succeeded in converting more than 5 per cent. of the original chloride into suboxide so that as a practical method of preparing the suboxide in quantity the method is not satisfactory FORMATION OF DLPHENYL BY AUTION OF CUPRIC SALTS ETC. 569 I n conclusion i t may be stated that the suboxide of cadmium may be obtained in small quantity by the method described by Morse and Jones as well as by the decomposition of cadmium oxalate. The latter method however is only of use when the excess of metal always formed during the decomposition is dis-tilled off in a vacuum but the aniount of residual cadmium sub-oxide is never more than 4 per cent. by weight of the original oxalate. The author desires to place 011 record his appreciation of the facilities placed a t his disposal by the Walter and Eliza Hall Trust for the prosecution of t,his research. TEE DEP~RTIKENT OF CHEMISTRY, UNIVERSITY OF QUEENSLAND, BRISBANE. [Received Noueiizber 7th 1018.

ISSN:0368-1645    

DOI:10.1039/CT9191500556

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

FORMATION OF DLPHENYL BY AUTION OF CUPRIC SALTS ETC. 569 XLIV.-Fownation of Diphenyl by the Action of Cupric Salts on Orgcmornetallic Compounds of Magnesium. By JACOB KRIZEWSKY and EC'STACE EBENEZER TURNER. A FEW years ago i t was shown (Bennett and Turner T. 1914, 105 1057) that chromic chloride react.4 quantitatively with magnesium phenyl bromide in the sense of the equation 2CrC1 + 2PhMgBr = 2Cfrc1 + 2ClMgBr + Ph*Ph, and the reaction was found to be a general one. It has now been found that anhydrous cupric chloride behaves similarly to chromic chloride. Thus when anhydrous cupric chloride is added to an ethereal solution of magnesium phenyl bromide the following reaction occurs : 2CuC1 + 2PhMgBr = Cu,Cl + 2ClMgBr + Ph*Ph, diphenyl being formed in almost the theoretical quantity.Furthermore the preparation may be simplified an equally good result being obtained by mixing a t the outset magnesium turn-ings ether bromobenzene and cupric chloride in the requisite proportions. The anhydrous cupric chloride used was either the commercial preparation or that obtained by dehydrating the hydrated salt a t looo 560 KRIZEWSKY AND TURNER FORMATION OF Anhydrous cupric sulphate reacts slowly with magnesium phen yl iodide cupric iodide apparently being formed as an intermediate compound. It is hoped that this will ultimately lead to the pre-paration of cupric iodide. The reactions summed up by the equation 2CuS0 + 2PhMgI = CU& + ZMgSO + PhOPh, however only proceed with difficulty partly owing no doubt t o the very sparing solubility of the anhydrous salt in ether.I n the presence of iodobenzeiie a st,eady reaction occur3 prob-ably according to the equations PhMgI + P h I + CUSO = MgSO + Cu12 + Ph*Ph, ZCuI + 2PhMgI = Cu,I + 2Mg1 + PhoPh. Thus when anhydrous cupric sulphate (1 mol.) is added to an ethereal solution of magnesium (2 atoms) and iodobenzene (3 mols.) a 65-70 per cent. yield of diphenyl is obtained. Comparative experiments showed that the diphenyl produced was due neither to initial interaction of the magnesium and iodo-benzene, 2PhI 1- Mg = MgI + Ph-l’h. nor to interaction between magiiesium phenyl iodide and iodo-benzene, PhMgI + P h I = Mg12 -+ PhOPh. The reactivity of cupric sulphate with magnesium phenyl iodide seems to depend on the instability of the cupric iodide formed.Magnesium phenyl bromide does not react with cupric sulphate under similar conditions. EXPERIMENTAL. ,4 ction of Anhydrous Cupric Chloride o n Magnesium Yhenyl Bromide. Magnesium turnings (4.9 grams) were covered with 150 C.C. of pure ether 28 grams of anhydrous cupric chloride and then 32 grams of bromobenzene were added and the mixture was well shaken. A vigorous reaction set in and was controlled when necessary by shaking and external cooling. When the initial reac-tion had subsided the misture was heated under reflux in warm water for two hours cooled decomposed with ice and water and treated with excess of concentrated hydrochloric acid in order to redissolve the precipitated cuprous chloride. The ethereal layer was separat,ed and the aqueous layer extracted repeatedly with ether.The unit.ed ethereal extracts were shaken with water t DIPHENYL BY THE ACTION OF CIUPRIC SALTS ETC. 561 precipitate the cuprous chloride remaining dissolved in the acidic ethereal solution dried and the solvent evaporated. Thirteen grams (that is about 85 per cent. of the theoretical) of pure diphenyl were obtained. Using 100 c.c. and 55 C.C. of ether instead of the 150 C.C. used above yields of 65 and 50 per cent. respectively were obtained. An increase in the volume of ether to 200 C.C. was not found to be advantageous. Interactiou of Iodobemerze and Jlagnesiziiit Yhenyl Iodide. Magnesium (4.9 grams) iodobenzene (41 grams) and ether (200 c.c.) were converted into the Grignard reagent which was treated with 41 grams of iodobenzene and the mixture heated under reflux for several hours.The product on decomposition, gave 2.5 grams of diphenyl half the iodobenzene used being recovered unchanged. Interccctl'on of A nhydrous Cupric Szdphate and Magnesium Phenyl Iodide. Anhydrous cupric sulyhate (32 grams) was added to the Grignard reagent prepared from 41 grams of iodobenzene 4.9 grams of magnesium and 200 C.C. of ether the mixture boiled for six hours under reflux and then left overnight. On working up the pro-duct 6 grams of diphenyl were obtained corresponding with a 39 per cent. yield on the iodobenzene used. Interaction o f Czipic Sitlphnte (1 mol.) Nagnesiztm (2 atoms), and Zdobenzene (3 niols.) in Ethereal Solution. Magnesium turnings (4.9 grams) were dissolved in 200 C.C. of pure ether in the presence of 62 grams of iodobenzene and to the clear solution 1 6 grams of anhydrous cupric sulphate were added. The mixture was then boiled for three hours under reflux cooled, decomposed with ice and the solution obtained after acidifying extracted with ether and so on. Sixteen grams of pure diphenyl were isolated corresponding with a 66 per cent. yield on the iodo-benzene used. THE UNIVERSITY CHEMIOAL LABORATORIES, CAMBRIDGE. [Received April 24th 1919.

ISSN:0368-1645    

DOI:10.1039/CT9191500559

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

562 OBITUARY NOTICE. OBITUARY NOTICE. EDWARD FRANK IIRRRZSOK. B O R N JULY 1869; DIED ~ O V E M l 3 E I 4TH 1317. EDWARD FRAXIC HAR~~ISON was educated a t the United IVest-minster Schools and in 1884 was apprenticed to a pharmaceutical chemist in North 1,ondon. I n 1890 he gained the Bell scholar-ship of the Pharmaceutical Society and proceeded to its school in Bloomsbury Square. There he was awarded medals and certifi-cates in chemistry botany and materia medica and after passing tho minor and major examinations he occupied several positions on the staff and carried out research on the alkaloids of aconite. While acting afterwards f o r five years with the fii-ni of Messrs. Brrtdy and Martin a t Newcastle he successfully used his leisure to prepare for the B.Sc.degree of London University. The next six years were spent as head of the analytical department of Messrs. Burroughs Wellcome and Co. I n 1905 he went into partnership in a school of pharmacy but finally took up the in-dependent practice of consulting and analytical chemistry. He was an eminent specialist in the analysis of drugs and medicinal substances and as analyst to the British Medical Association made nearly all the analyses of proprietary articles which were revealed in the two publications ”Secret Remedies” and “More Secret Remedies.” I n the Parliamentary inquiry which followed these disclosures, Harrison was a most important. witmess and made a deep impression on the Select Committee. The full value of this work to public hea1t.h and public economy has yet to be realised.Col. Harrison was a Fellow of the Institute of Chemistry and published a number of papers on his special province of tho science. His process for estimating the diastatic strength of malts is now in general use. He was active both as a student and a past student in the life of the Pharmaceutical Society’s School in which he was most highly regarded7 and to which as his a l m muter he was loyally devoted. He was a member of the board of esaminers, and in 1917 he delivered a thoughtful and valuable address a t the inauguration of the session. For three years he conducted the practical chemistry competitions maintained in the weekl OBITUARY NOTICE. 563 ~ ' i i 1 ~ 1 . r i z c c c e i i t i c n l Jo?irnnZ. His professional life was iiitfeed in l,he highest degree strenuous.As soon as the War broke out Harrison was impatient to join the forces. After being refused several times on the ground of age he became a special constable and a volunteer in the Inns of Court Reserve Corps. Later he succeeded in entering as a private in the Sportsmen's Battalion of the Royal Fusiliers. It was by an accident that he came under tlhe notice of the first helad of the anti-gas service at' home Col. Sir W. H. Horrocks, R.A.M.C. who with some difficulty succeeded in securing his services. H e was given the rank of lieutenant on the general list in July 1915 and from that time1 devoted himself to the anti-gas service. It was only in the last year that his duties extended over both branches of the gas service, He was promoted major in April 1916; 1ieut.-col.in January, 1917. H e was appointed Assistant Controller of Chemical War-fare in November 1917; shortly before his death his succession to Major-General Thuillier as Controller of Chemical Warfare had been settled and in a few days he would have attained the rank of brigadier-general. Harrison's work for the war may be considered as falling into two periods. I n the first period extending from the spring of 1915 until November of 1916 he was engaged in research work in the anti-gas laborat'ories a t the Royal Army Medical College, Millbank the chief subjects being the improvement of the anti-gas helmet the devising of first the large and then the small box respirator. I n the early part olf this period Harrison was constantly in the laboratory working late into the night.He realised from the first the critical importance of speed and the possession of the initiative and up to the last he never relaxed the pace. It is not easy to give an idea of the range of problems their variety and complexity that had t o be overcome in bringing to a st-ate of service efficiency such simple-looking appliances as the helmet and box respirator. The mechanical chemical physiological and, one may add even psychological questions raised were innumer-able. Many heads and hands contributed to achieve the success that ensued. The apportionment of credit does not arise here, but there can be little doubt that all concerned would agree in giving Harrison a f oremostl place. With his scientific knowledge were united a strong practical instinct and intuitive judgment, which enabled him to seize quickly the essence of a problem and the substance of a suggestion and to preserve a splendid sense of proportion.He improved i,he forrni-ila for the impregriatiig fl nic 564 OBITUARY NOTICE. of the helmet and worked out laboratory tests for controlling its component materials and for testing its efficiency. Hemade numerous experiments in which he fearlessly wore the helmet in gases for which suitable quantitative control tests had not then been devised. During the late summer and autumn of 1915 he was occupied chiefly in getting out the large box respirator. As is generally known this appliance was based on the admirable sug-gestion by Bertram Lambert of Oxford of a filter of perman-ganabsoda-lime granules.The realisation of this plan in the form of a box which in itself and its contents should be service-able under field conditions was a most difficult undertaking. By the end of the year i t was completed and an issue was made early in 1916. The production in large quantities a t a time when a high grade of protection was becoming indispensable for troops in special situations was a great achievement and the large box was in its chief essentials the prototype of the small box which not long after became and remained the standard protection for troops of all arms. For the design of the small box the members of the Gas Service in France were able to make valuable suggestions based on field experience wit,h the large box.Harrison also made many contributions based on his own practical trials. During the second period of his work Harrison was closely associated with Col. Sir W. H. Horrocks in the rapid organisation and development of factories for the manufacture of respirators. Though this withdrew him for the greater part of his time from the laboratory he remained in close touch with it and a t the weekly meeting of senior officers his genius for improvisation his sound chemical judgment and his foresight as to profitable lines of work were constantly evident. It was a t this period that the manufacture of a new type of granule and of absorptive charcoal was worked out in the laboratories and transferred under the direction of selected officers t o manufacturing establishments.I n the choice of officers Harrison’s judgment rarely led him astray, and his knack of getting the right. men into the right place con-tributed largely to the success of all his work. The great success of the small box respiratm and its remarkable freedom from faults were due in no small measure to the organisation of inspect-ing officers on which Harrison laid great stress. Harrison was held in high esteem by the officers of the Gas Services of our French Italian and American Allies. He was received with great cordiality a t their councils and his opinion was eagerly sought. It may be remarked as affording a tribute to the excellence of the British respirator that the Italians were supplied with several millions and that the Americans besides taking large numbers OBITUARY NOTICE.565 paid us the compliment of copying it as soon as the home manu-facture could be arranged. The French considered that the p r e tection it gave was even unnecessarily high. In the last year of his life Harrison was called on to participate in the offensive side of gas warfare and to exercise his great organising talent in what had become a very imposing and difficult undertaking. He had now reached the position to which his talents and labours so justly entitled him but before he could actually officiate as Director of Chemical Warfare the haunting fear of his friends was realised and he was prostrated by influenza. His bodily strength sapped by unceasing labour was unequal to the strain pneumonia supervened and he passed away as certainly as anyone on the battlefield a sacrifice of the war.His elder son had fallen in France in 1916. He was a man of the strongest character. The love of his country, its ideals of freedom its democratic institutions and his belief in the destiny of the British as leaders among free peoples were the inspiration of his life and work. He had no thought for himself when the lives of others were at stake. The inflexible sense of duty Mhich animated him communicated itself to those who worked with him and he gained in a remarkable degree their respect and affection. He faced all emergencies with imperturbability was never daunted or discouraged and preserved a clear head and a power of decision even when worn out with incessant labour. He was neither dogmatic nor impatient but always ready to improve on himself listening with patience and courtesy to all honest criticism or advice. He was a master organiser and the War brought him his opportunity. He died acknowledged and revered as a leader of men his great task accomplished. He was buried with full military honours mourned by a multitude of fellow-labourers who had learned something of his worth. Harrison died before he had received the public honours that would undoubtedly have been conferred on him. He had been made C.M.G. in 1917 and the French had shown their apprecia-tion of his services by making him Officer of the Legion of Honour. It is gratifying to know that a memorial to perpetuate his name is to be associated with the Chemical Society. What the nation owes him for the saving of life and the mitigation of suffering can scarcely be overestimated. It is not easy to do justice to Harrison’s personal qualities. A. S. H. S. R. VOL oxv. I

ISSN:0368-1645    

DOI:10.1039/CT9191500562

出版商:RSC    

年代:1919

数据来源: RSC