摘要:

1026 BRIGGS THE NATURE OF THE CXIV.-Yhe Nature of the ,%-Ferricyanides and the P-Fewocyanides. By SAMUEL HENRY CLIFFORD BRIGGS. IT was found by Belnnett (T. 1917 11 1 490) that the u- and tho 0-ferrocyanidw (Briggs T. 1911 99 1019) are! identical from a arystallographical point of view and it therefore appeareid prob-able that the P-ferrooyanides would prove t o be niixtures of the ordinary ferrocyanides with a very small amount of highly-coloured impurity. I n vielw of Bennett’s results it was decided t o makel a further investigation of the two ferrocyanidss and also of the a- and P-ferricyanides of Lock0 and Edwards (,ftmer. Chern. J . 1899, 21 193 413; selel also Bellucci and Sabatini A t t i R. Accad. Lincei, 1911 [v] 20 1; Piutti Ber. 1912 45 1830; Hauser and Bieealski, ibid.3516; Wells Amer. Chem. J. 1913 49 205). It is shown belolw that the P-ferricyanides are1 compounds of felrricyanide and aqu open t a cyan of elr r i at a wherelas the fi - f elrr oc y an id es ar el mixed crystals of ferrooyanidel and aquopentacyanolferroate the amount of the latter being far too small to be detecteld by any known methold of quantitative or qualitative analysis. The P-Ferm’cyunides. Locke and Edwards pointed to the formula 3K3Fe[ Fe ( CN ) o],K,[ Fe (CN ) 5H20] rather than t o Lmke and Edwards’ formula K,Fe(CN),,R,O but as it was scarcely possible to1 determine1 the exact formula of the double salt by analysis synthetical meaim were1 useid f o r this pur-pose. A simple1 method for the preparation of potassium aqnc-pentaoyanoferriate could not be devised howelver and recourse was therefore had to the sodium salt which oan readily be obtained by Hofmann’s method (Annulen 1900 312 1).It was found that a solution of this salt with three! and a-half molejcular equi-valents of sodium felrricyanide was precipitated a t onoe with bismut$h nitrate proving that free ferricyanidei was present whereas a solution containing two and a-half molecular equivalents of sodium ferricyanide did not give tt precipitate aftelr a week and consequently did not cont-ain free ferricyanide. The formula of sodium P-ferriuyanidet would therelf ore appear to1 be The analysis of the salt prepared according t o the direchiom of 3Na3[Fe(CN),],Na,[Fe(CN),H,0] @-FERRICYANIDES AND THE P-FERROCYANIDES. 1027 The ferricyanides in solution appear t o delmrnpose to some extent, as shown by t2he equation K3[Fe(CN)6] + H,O K,[Fe(CN),H,O] + KCN.The potassium cyanide produced givef; cyanide ions and these are relmoved on addition of acids owing to formation of the very slightly dissociated hydrogen cyanide. Acids theref ore inorease the velocity of the reaction towards the right. Alkalis and ammonia on the1 other hand decompose the aquopeintacyano-felrriate (comparel Hofmann Zoc. c i t . ) and cyanides convert the aquopentacyanofelrriate into ferricyanide thereiby increasing the, reaction towards the left. Thew transformations are1 shown by the colour changes developed in solutions of potassium ferricyanide when the abovementimed reagents are added acids causing an intlensification of colour owing to increase1 of aquopsntacyanof erriate whereas alkalis ammonia, and ciyanides diminish thel codour owing to removal of the1 intenselly coloured aquopentacyanoferriate.'CVhem pure brightl orangerred poltassium 'ferricyanide is recrystal-liseld from a solution containing 2 o r 3 per cent. of sodium aquo-pentacyanoferriate garnet-red crystals are1 obtained differing very much in habit from the orange-red crystials of the pure salt. These garnet-red crystals are analogous to potassium P-ferrocyanide as shown bellow. There is thus an explanation of the very deep colour olf many preparations of pot,assium ferricyanide madei by oxidising potassium ferrocyanide with chlorine for not only does the chlorine oxidise the ferrociyanidel but it also decomposes thei ferricyanide t o some extent according to the equation K,[Fe(CN),] + H,O + Cl,=KCl+ CNCl+ K2[Fe(CN),H20], as fousd by Cambi (Gazzetta 1911 41 i 157).The deeply coloured crystals are therefore mixed crystals of potassium ferri-cyanide and the double salt of ferricyanide and aquopentacyanoL ferriatel (P-ferricyanide). The A ction o f Bromine on Potassium Fervicynrtide. In view of the above-mentioneid obsmvatbons olf Cambi it appetared probable that the action of bromi'ne on potassium ferri-cyanide woald furnish a convenient method for the preparation of '' /I-ferricyanide," and this expectat<ion was realised further evidelnce thus being provided for the const-itution suggested above. Larger quantities of bromine gavel a brownish-black colloidal sub-stance of the formula IX or X whilst with excess of bromine 1028 BRIQQS THE NATURE OF THE greenish-black insoluble ferric cyanide was formed (compare Reynolds T.1888 53 769; Messner Zeitsch. anorg. Chem. 1895, 9 126). A sma,ll quantity of a white! solid sparingly solluble in holt watelr was produced tlogether with the ferria cyanidel. The analysis of this substance suggested ilr poilymeride of cyanic acid, but the amount was tola small for complette identification. The Actkm of Hydro1chJot-k Acid OIZ Potassium Fewkyalnide. The atchion of hydrochloric acid on potassium f efrricyanida (I) has been stxdied belyoad the st,age olf the folrmation of Locke and Edwards' P-ferricyanide (V) . Alt'hoagh the acid successively relmovels t'he three molecules of potassium cyanide with the final productiojn od ferrio cyanids (IV) it has not belen possib,le t o isola,te potassium aquo'pelntacyanafe:rria,t~ (11) or the hitherto unknolwn diaquot&aoyanolferriate (111).Noh only are the1 cojmpounds I1 and I11 extiremely soluble in wat'er and difficult t,o' iso1a;te in the crys6alline sta,te but the cornpounds I 11 111 aad IV have a pronounced t'endelncy to combine wit,h eauh other with or with-out elimina,t.ioln oif wa,ter molelcules to give the subst'ances V VI, VII a,nd X. K,IFe(CN).51 Kz[ (CN) H,O ] K [ Fe(CN)4 2H,O] (1.) ( 11.1 (111.) 3K[Fe( CN),] 2Fe( CN), 8H,O 3 K[ Fe( CN) J K,[ Fe( CN) H,0],H20 CN CN CN ... . . .FeCNFeCNFeCN.. . etc. 1 CN CN CN ... (VIII. ) (IX.) Fe(CN),,K[Fe(CN),],2K2[Fe(CN),H20] (X.) (XI.) Although the' formulae V-X are useful as showing the way in which the compounds are deriveld from potassium ferricyanide it is probable that these substlances a8re not simply double salts but rather salts of highly complex anioins containing several iron alt.oms and a correspondingly large number of clyanogeln groups.Evidence fo\r this viow is obtained from the distincrtlive precipitation reac-tions of Locke and Edwards' salt and also from tba propelrties o P-FERRICYANIDES AND THE ,~-FERROCYANIDES. 1029 ferrio cyanide which is a highly insoluble salt wit,h colloida.1 properties instead of a reladily soluble substance as would be expelcted from t'hel simplel formula IV. Ferric cya'nide would theref ore appe,ar to1 be1 highly polymeriseld possibly with each iroa amtom a t the cent$re of a' regular oct'aheldron a oyanojgen groap at eta.ch colrnetr and evetry cyanogea group unite'd to a t l w s t two iron atloms.The simplest st,ructure of t'his type is swn in the "chain " formula XI. The fl-Ferrocyaoz.icles. Pot'assium P-felrrocyanide crystdlisea on cooling from a warm, sa.t,uurateld sollution of t,he a-ferrolcyanide containing one pa,rt o'f sodium a,quopenta,cyanof erroate (compa,re Hojfmann Zoc. cit.) per hundred pa.rta of the ferrocyanide. The P-ferrocya.nides a.ro these fore mixed crysta.ls otf ferrocyanidel and aquopenta.cyanode,rroate,, the amount of the la,tter being far t,oo small to be detecteld by qua,lita.tive olr quantitative analysis. Since potassium P-ferrocyanide is f ormeld when the1 a-f erro-cyanide is repeatedly recryst'aJ1ised from water itl follows tha't t'he ferrooyanides in a,queous solut,ion a,re in a of equilibrium as sem from tlhe elquation The effelct of a.cids alkalis a.mmolnia, and ayanides on this equil-ibrium is ana810gous to that described above in the' case of the ferricyanides and need not bet rederred to in dotmail.It is sufficient to say thah a simple elxplaaatJoln is he'reby provided for t,hei va,ririo.us t(ransfolrma.t,ions mentiolneld in the fotrmelr pa.pelr (T. 1911 99, The pcrssib,ility t,ha<the P-ferrocyanides are a-f elrrocyanides coa-taining al tlra,w of a highly-coloared impurity was considered in tho fo,rmer paper but as tqwo I-menthylammonium ferrocyanidee were olbhined which diffemd considerab,ly in speicifia rot'ation i t was condudeld tha't the a- and P-ferrocya.nides were isomelric.The Z-menthylammonium a-f errocyaaide has [a]: - 42.4O aad the B-ferroloyanide [ag -28.5O- Further on adding a. trace of a,cid ta a solutiotn of the a-ferrocyanide in alcohol the1 spe'cific rotmation was &seirved to1 fall from -40'9O to -31.8O. The f mmer prepamration of l-menthhylammmium P-f errocyanide was no lolnger availablel bmut there can be no doubt from its propelr-ti@ a.s previously described thah it contrained aquopentaqanoc ferroiate as well as fsrrocya.nide. Whether its lolw roltlartolry power was due to some cha.nge of the nature of racemiSamtion in the 2-memthylammonium groups or t'ol t'he presence of solme impurity aannot now be decided and this point remains obscure.An ex-H,O + K,[Fe(CN),] K,[Fe(CN),H,O] + KCN. 1019) 1030 BRIGGS THE NATURE OF THE planation od the fall in rotation of the1 I-menthylammonium a-ferrocyanidel on the addition of acid has been furnished by a study of quininium primary ferrocyanide. When the quininium saltl was dissolved in alcohol or ac riel the specific robation was found to rise for somel days and then become constant the change being as much as 20° in some experiments. An examination of the product showed that ferricyanide was present the salt having undergone oxidation by atmospheric oxygen dissolved in the solu-tion. It was then observed that t7he preparation of Z-menthyl-ammonium ferrocyanide described in the former paper also under-went oxidation when its solution in aIcohoI was expoaeid t o the air for some time and fmm the residue pure Z-menthylammonium ferricyanide was isolated.This tendency of the1 f errmyanides of substituted ammonium bases to undergo oxidation by atmolspheric oxygen is probably the result of slight dissociation into base and acid for example, (C,oH,,-NH3),Fe(CN) 4C,,H,,*NH + H,Fe(CN),. The addition of acid will increase the! amount of t.he readily oxidisable hydrogeln f elrrocyanide and thereby accelerate the! change. This will accountl for the fall in rotatioln previolusly observed on the addition of acid to an alcoholic solution of I-menthylammonium a-ferrocyanide. The solution used was dilute, and the amount of oxygen required to oxidise all the1 ferrocyanide present was very mall and would easily be provided by air dissolved in the liquid.E x P E R I 11 E N T A L. Lo c Ic e and Edwards’ Pot asiurn p - F e w i c y anide . The salt preipared acaording to the1 directions otf Locke and Edwards (Zoc. cit.) was obtained as a yelllowish-green solid. I t s precipitation rebactions agreed exactly with the1 observations of Lo& and Edwards but the analysis was not in accordance with their formula K3Fe(CN),,H,0. They decomposed their salt with nitric acid and for this reason apparelntly thelir figures for the iron content were too low as it was found impolssible during the preselnt reisearch to obtain coimplete decomposition when using nitrio acid. On herating the1 salt with concentrated sulphuric acid, however the complex was entirely destqroyed.On diluting the product with a little water and ciarefully neutralising with ammonia the double salt of potassium and felrric sulphatee which is practiclally insoluble1 in the presence of aaid could be readily dissolved on warming and the analysis carried out in the usual manner P-FERRICYANIDES AND 'CHE P-FERROCYANIDES. 1031 K. Fe. N. H,Ot K,Fe(CN)@,H,O .................. requires 33-75 16.08 24.21 5-19 Found .......................................... 33.82 17-61 24.73 0.83 (at 160") 3K,Fe~CN),,K,[Fe(CN),,R,O] requires 33.87 17.59 25.37 1.42 4K,Fe(CN),,K,[Fe(CN),,H,O] , 34-23 17.46 25.41 1.1 3 BK,Fe(CN),,K,[Fe(CN),,&O] , 34.47 17.37 25.43 0.93 {::it. When heated to 210° the salt underwent furtheir decomposition, with loss of cyanogen. The analysis points to a compound of aquopent.aoyanoferriate aiid ferricyanide rather t'han to a salt of the formula K3Fe(CN),,H,0 but itl is scarcely possible~ to deter-mine the exact formula of the double salt by quantitative analysis alone.I n agreemelnt with the analytical data i t was found that the compound gave the characteristic reaction for iron pentacyano-derivatives described by Hofmann (Zoc. cit.) for when its solution was trelated with hydroxylamine hydrochloride1 rendered alkaline with sodium hydroxide and heateld itl beaame deep golden-yellow with mpious eff erveswnoe. An attempt was made to determine the constitution by titra-tion with potassium cyanide until the d o u r of quopentaoyano-ferriatel had disappeared but no1 delfiiiite end-point was obtlained, showing that potassium ferricyanide has a tlendency to decompose in solution according to the equation K,Fe(CN) + H,O K,[Fel(CN),E20] + KCN.During the titration of the 8-ferricyanide with potassium cyanide, i t was noted that the solution on keeping deposited a little Prussian-blue in agreelment with the obseavations of Hauser and Bimalski (Zoc. cit.). The Action of Bromine oot Poitmsium Ferm'cyanide. Preparation of Locke and Edwards' Salt .-Ten grams of potassium ferrioyanidel were dissolved in 50 o.c. of water and 1.4 grams of bromine were added to1 the cold solution. The mixture was kept in a stoppered bottle the bottle being occasionally shaken. After three days the solution no1 longer colntaineld free felrrioyanide, as shown by the1 absence of a precipitate with bismuth nitrate.On precipitating with 150 C.C. of alcohol (90 per cent.) the salt was obtained as a greenish-brown crystalline dihydrate (Loss over sulphuric acid in a vacuum=2*61. Calc. 2.75 per cent.). Analysis of the dehydrated salt gave K = 34.04 ; Fe = 17.64 ; N = 24.86. 3K3[Fe(CN),],K,[Fe(CN)5H20] requirels K = 33.87 ; Fel= 17.59 ; N = 25.37 per cent. When prefpared in this manner, the compound was free from Prussian-blue and therefore gave 1032 BRIOCIS THE NATURE OF "HE yellowish-whi tel precipitate with stannic chloride. gave Hofmann's reaction f o r iron pent'acyanol-compounds. The salt also The Brownish-black Colloid, Fe(CN),,K[Fe(CN),1,2K2[Fe(CN),H20]. -Eightl grams of brolmine were added to a solution of 12 grams olf potassium ferricyanide in 60 O.C.of cold water and the mixture was kept in a loosely stoppered bottle a t the summer tempera-ture (20-25O). Some gas was evolved and the solution after changing d o u r t o brolwn and then t*o violet delposited a blaak jelly. After ten days the mixture was poured into 200 C.O. of alcohol (90 per cent,.) and the1 black solid collected and dried in the air. It was then powdered and washed on a filter with cold water until free from soluble impurit<iels. The compound now increased greatly in volume owing to absoaption of water and the jelly-like mass whioh resulted was analysed after drying in a vacuum over sulphuric acid until its weight was constant (Found: K=21-60; Fe=24*OS; N=26*21. Calc. K=21*79; Fe=24*90; N=26-55 per cent.). The compound was soluble in hydrochloria acid with production of a characteristic greenish-blue oolour.It dissolved in warm water to a dark brown colloidal solution. The Acti0.n of Hydrochloric Acid on Potassium Ferricymide. The Rhis h-violet C m p m d , K,[Fe(CN),H20],K[Fe( CN),2H20]. -Ten grams of p&assium felrricyanide dissolved in 20 C.O. of water we're treated with 5 C.C. of hydrochloriD acid (D 1.15) in an open flask immersed in watelr a t 70-80° for forty minutw. The solution was allowed to remain overnight and filtered. The deep purple filtrate was then precipitated with two vollumesl of alcohol (90 per cent.). The semi-solid deposit was dissolved in a very small amount of water and precipitatled with two volumes of alcohol the process being repeated ten or twelve timw until the alcoholic layer had a bluish-violet colour without any red or yellow tinge.The product was now dissolved in the smallest possible quantity of watmr and a trace of Prussian-blue was removed by filtration. The filtrate was evaporated to dryness in a vaouum over sulphurio acid leaving an extremely soluble highly deliques-cent friable blaok solid. Three and a-half grams welre obtained from 35 grams of potassium ferrioyanide (Found K=23-70; Fe=21.69; N=24*00. Cala. K=22*69; Fe=21.59; N=24-38 per oent.). At 160° one molecule of water was evolved the loss in weight being 3-51 (Calc. 3.48' per cent'.). The Greenish-black C o r n p o d ~K[F~I(CN)~],F~(CN)~,H~O. /I-FERRICYANIDES AND THE /~-FERROCYANIDES. 1033 Twenty grams of potassium fesricyanide were dissolved in 40 C.C.of water and 16 C.C. of hydroohloric acid (D 1.15) added. The mixture1 was heated a t 55-60° the solution being filtered every teln hours to remove tahe precipitated ferric cyanide. After the fourth filtration only a small amount$ of ferric cyanide separated, and the acid reaction was very weak. The1 heating was continued a further twelve hours (fifty-two hours in all) and the cold solu-tion was then precipitated with two volumes of alcohol (85 per oent.). The black selmi-solid deposit was purified by repeated solution in water and precipitation with alcohol (85 per oent.) a t a room temperature of 20-25O the quantities used being 15 C.C. of water and 30 C.C. of alcohol once; 10 C.C. of water and 20 C.C. of alcohol twice; 5 C.C.of water and 10 C.C. of alcohol twioe; and 5 C.C. of water and 15 C.O. of alcohol three times. During the final &ages of purification the compound wits obtained in the solid state the yield of pure salt being half a gram. This was dissolved in a small quantity of water evaporakd to dryness over sulphuric mid and weighed f o r analysis. On exposurel for some weeks in a vacuum over sulphuric acid it slowly evolved a molecule of water (Found K=14.67; Fe=30.26; H,O=3*00. Calc. K=14.22; Fe= 30.47 ; H,O = 3.28 per cent.). The compound wm delliques-cent and vesy reladily soluble in water to a greenish-black solution. The Dark Blue Compound 31C[Fe(CN)4],2Fe(CN)2,8H20.-Forty grams of poltassium ferricyanide dissolved in 80 C.C. of water were heated a t 55-60° with 12 C.O.of hydrochloric acid (D 1.15). A furthelr 32 C.C. of hydrochloric acid were added in quantities of 8 C.C. a t intervals of tweflve hours the1 heating beling continued for twelve hours after the lastq portion of acid had been added or sixty hours in all. The filtrate from the dark green precipitate (,4) was greenish-blue1 (volume 100 c.o.). One hundred and fifty C.C. of alsohol (85 per cent.) were added and the viscid deposit was dissolved in 15 C.C. of water and filtered. The magnificent deep blue solution was precipitated with 45 C.O. of alcohol (85 per cent.) and the treatment repeated a few times 15 O.C. of water and 45 C.O. of alcohol being used on each occasion at a room temperature of 20-25'. The salt was finally obtained as a deep indigo-blue powder free from white crystals of potassium chloride.When exposed over sulphuric acid in a vacuum for three weeks it lost four moleculw of water and the weight themafter remained constant [Loss=7.73. Calc. 7.53 per cent. for a loss of 4H,O from 3K[Fe(CN)4],3Fe(CN)2,8H20. The residue then gave K - 13-19 ; Fe= 31.52 ; N = 25-96. 3K[Fe(CN),],2Fe(CN)2,4 11,O requires K = 13.26 ; Fe =- 31.55 ; N = 25.45 per cent.]. The green precipitate ( A ) after drying had the compositio 1034 BRIGGS THE NATURE O F THE @-FERRICYANIDZS ETC. Fe 2-78N 0*05K zH20. It therefore consisted of a slightly deloomposed ferric cyanide which salt was shown by Messnes (Zoc. cit.) to lose oyanogen with great easel. This decomposition explains the presence of ferrous iron in the deep blue compound.The compounds represented by the forinulze I1 t o X are all intensely coloured. Those compounds which had been subjecteld to prolonged treat-ment with alcohol1 in the course of purification gave an odour of isooyanidea when decomposeld with alkalis. This reaction may be due to the presence of a trace1 of the correaponding ethyl estelrs, and is significant in view of the results of Beillucci and Sabatini The conipounds VI VII VIII and X all give ferrocyanide as well as ferricyanide when decomposed by alkalis. It does not follow however that they all contain ferrous iron since Messner has shown (Zoc. cit.) that compounds like cuprio ferrioyanide, Cu,[Fe(CN),], bethave in the same way. (Zoc. cit.). Four grams of potassium ferrocyanide in 200 G.C.of water wetre added with stirring to1 a solution of 16 grams of quinine mono-hydrochloride in 400 C.C. olf water in the cold. After two days, the pure white icosahydrate was collleoted washed with water and dried in the air. On dehydration over sulphurio acid in a vacuum, it rapidly lost 17H20 and a further two molwules were evolveld more slolwly the weight becoming constant aftetr five weeks. The product was a hygrolsoopio yellow monohydrato. Analysis of the icosahydrate gave Fe= 3.08 ; H20 = 18.12 18.11. (C20H,0,N,),Fe(CN),,20H,0 requires Fe= 2-98 ; 19H,O = 18.27. The rnonohydratle gavel C = 67-22 67-46 ; H = 6.38 6.64 ; Fe= 3.69, 3-75. Calc. C=67.42; H=6.72; Fe=3.65 per cent. Quininium secondary ferrocyaiaide, (C,oH2G0,N,),Fe(CN),722H20Y separated as a black solid insoluble in all ordinary solvelnts from a solutioln of 5 grams 04 quinine bisulphate in 250 0.c. of water to whioh 2 grams of potassium ferrolcyaiiide in 10 G.C. of water had been addeld (Found Fei=4.42. Calc. Fe=4*43 per cent!.). On dehydration over sulphurio acid the hemihydrata was obtained (Loss = 31.16 ; 21$H,O requires 30.72 per centl.). Analysis of the hemihydrate gave C= 62.86 63-03 ; H = 5.83 6.20. Cala. : C=63*20; H=6*07 per cent. [Received May lath 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701026

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

MILLS AND EVANS THE CYANINE DYES. PART 11. 1035 CXV- The Cyanine Byes. Part II. The Synthesis of 0- A rninocinnarn ylideney uinaldine Methiodide. By WILLIAM HOBSON MILLS and PERCY EDWIN EVANS. IT has been generally recognised that in the formation of isooyanines by the action of alkalis on mixture6 of a quinoline with a quina,ldine alkyl iodidel a dominant part is playeld by the highly reiactive $-bases to which t*he action of alkalis on a quinoline alkyl iodide is known to give rise. Two vielws are1 held with respect t o the constitution of these +bases. I n addition to the cjrclia carbinol formula (I) suggested by Decker (Ber. 1892 25 3326) an open-chain alkylamine c!H (1.1 (11.) aldehyde formula (11) was proposed by Roser (Annalen 1892, 272 221; 1894 282 363) aad was supported with additional elxperimental evidence by Gadamer (Arch.Pharm. 1905 243, 12; 1908 246 89) and ICanfmann and Striibin (Ber. 1911 44, 680). It was pointed out by W. Konig ( J . p. Chem. 1912 [ii] 86, 166) that the polssibility that the quinolinium $-bases were to be reprelsented by the second of these formulz made it nemsary to take into1 accoantl a corresponding constitution for the isolcyanines. Accordingly in place olf the formula (111) which he had originally propoeeld ( J . p. Chem. 1906 [ii] 73 100) for t4his class of dyes, he now suggested the open-chain formula (IV) and gave reasons for preferring i t to the formulae which had previously been put forward . /\ R I (111.) /\ R I Witb a view to obta.in evidence which would bear o'n the 0011-stitut'ion of the isooya.nines we undertook the synthesis of a oom 1036 MILLS AND EVANS THE CYANINE DYES.PART II. poand of a type almolst identica.1 with tha,t relpresent,ed by formula IV. This substance was o-aminocin/namyZiideneq~~~riul~~~e m.eth-iodide (V) the stbruct8ural fo'rmule of which olnly diffeirs frolm Konig's but'adieae folrmula for dimeitlhylisoclyanine iodide1 in t,ha.t i t contains an amino)-groap in place olf a. methylamino-grolup a,ttlacheld to t.hel be,nze,ne nucleus in t'hel ort,hol-posit~ion with respect to the1 but,a.dieae chain. (V. 1 Meanwhile the facts desaribed in /\ Me I a preceding paper (Mills and Wishart this vol. 579) were discotvered. The& showed definitely that the isooyanines do not possess an opeln-ohain formula and the chief object of these experiments was tjhus attained in another way; we think however that the synthmis and properties of o-aminouinnamylidenelquinaldine melthiodide whioh in certain respects bears a distinct relatlionship t o the dyes of the cyanine class may still be of sufficient interest to be1 recolrdeld.o-Nitro-cinnamaldehyde was heated witlh quinaldine and zinc ohloride, wheln condensation took place with the1 folrmatioa of o-nitro-cinmumylide~equinul~ine NO,= C,H,-C€I CH *CH CH*C,TT,N. This was reduceld with iron and aceltio acid tot the correlsponding amino-coinpound which foms deep reddish-brown monocaclid salts and di-acid salts which are pale yellow and oharactlerised by their sparing solubility. To prepare the quaternary rnethiodidel of this base the1 amino-group was first protected by acylation.The acylamino-compound wm then converted into1 its methiodide by heating with methyl ioldide and finally the1 acyl group was eliminated. Various acyl derivatives having been examined the formyl compound was found tot give the1 belst resiults and its methiodide on hydrolysis with dilute hydrochlolric acid gavel o-aminocinnamylidenequinaldine methiodidel (V). It proved t o be a oompoand whioh forms delep relddish-brown solutions and crystalliseis in small obliqueended needles showing a dark olive-green metallic reflex; the crystals are strongly pleochroic but almost opaque. Its strongly coiloared aqueiousi solu-tions are at once turned pale yellow by the addition of mineral acids evidently on account olf the formation o€ di-acid salts.It The1 synthesis was effected in the following manner MILLS AND EVANS THE CYANTNE DYES. PART II. 1037 dye8s wool and especially silk a. be,aut,iful rich relddish-brown but the colour is surprisingly f ugit)ive in daylight. Its ab.sorption spe'ctrum in t'he visible region unlike1 t.he spelotra of the isocyanines, which are charactlerisetd by a dist'inctivel pa,ir of ba,nds shows olnly general absorptioa in the violelt and blue which in more concen-tmted solutiomns ext'eiids as far as the orange. It. has a,lsol no apprwiamblel selnsitising a,ction on a gela,tino-bromide phot'ographic plat'e. Apart t,helrefore from its instability t,olwa,rds light and it,s partial decolorisation by acids it shows litt,lel analogy in properties to t'hei isocya,nines.Atl the same timel the fact shoald notl be ovelr-looked tha8t on aacount o,f the1 presence olf the two ethylenia linkings in the batla.dien.e cha.in a colmpound od t.his struct'urel should be capable od elxist,encel in four geometlrically isomeiric f orms only olne if which is cloeely rehted in coafiguration to cyanine dyels namely, those of the1 a.t preselnt unknown a-a-class (VI) the proper6iea of which can howe'ver to solmel elxteint? be inferreid from those of the analogous conipoiunds of the benzothia,zole se'riea prepared by Hofma.nn (Ber. 1888 21 2262). /\ I R E x P E R I M E N T A L. o-NitrocinnanzaIdehyde.-We first prelpareld this substance by the method describeld by Diehl and Einhorn (Bev. 1885 18 2336), hut as the process proved troublesome to carry olut we1 sought for some1 method of nitrating cinnamaldehyde by which the1 o-nitro-derivative could be more easily obtained.Experiments on nitra-tion in the &sence of amtia anhydride1 showed that the process coluld be conducted so that o-nitrocinnamaldehyde was the sole crystalline produot. A solution of 25 grams of nitria acid (D 1-50) in 50 grams of glacial acetic acid was droppeld slowly with frequent shaking into an ioel-cold solution of 50 grams of cinnamaldehyde in 200 C.O. of acetic anhydride. The1 solution was allowed to remain for two days a t the ordinary temperature; dilute hydrochloric acid was tlhen added and the mixture well shaken. Coinsiderablei heat was develloped and on cooling o-nitrocinnamaldehyde crystallised in almost co~lourless needles.By recrystallising olnce from alcohol the compound was obtained pure in veiry pale yellow neeldles meltin 1038 MILLS AND EVANS THE CYANINE DYES. PART 11. a t 127O. This methold thus gives a very simple means of preparing o-nitroicinnamaldehyde and although the yielld is only 36 per wnt. of the weight of cinnamaldehyde taken it could probably be improved by further investigation of the process. &Nitro eirrrrcEmylic2ene~~~ina;ldine .-A mixture of o-nitrocinnm-aldehyde (10 grams) quinaldine (8.1 grams) and zinc chloride (2 grams) was belated on tlhe water-bath f o r five hours. The1 result-ing crystalline mass was dissolved in hot acetone and the solution, on oooling deposited the pure condensation product? in yelllow rhombs melting a t 149'.The1 compound dissolves readily in hot aceltone or chlolrrolform sparingly in alcohol benzene or ether (Found N = 9-28. p - NitrocinnumylidenepzLinaldine.-pNitrocinnamaldehyde (1.0 grams) and quinaldine (8.1 grams) were heated togetheir on the boliling-watfer bath f o r ten hours. The prolduct mas dissolved in alcohol t3he solution poured into water and the yelllow solid was co;llwted and crystalliseid from acetone. Pure p-nitrocimnamyZ-idenequinu.2dine was thus obtained in yellow neeidles melting at 185*5* (Found N=9*25. C,,H,,O,N requires N=9.27 per cent.). C19H140,N2 requires N = 9-27 per cent.). o- A r n i n ~ c i ~ a m y l i d e n e p u i n a z d i ~ ~ , NH,*C6H4*CH @IT* CH :CH* C,H,N. -An examination of the action of varioius relducing agents on o-nitrocinnmylidenequinaldinel showeld that the relduction could bet carried out most conveiniently by means of iron and awtio acid.The nitrecompound (10 grams) was dissolved in warm glacial acetic acid the solution diluteld with water and excess of iron added. The mixture whioh rapidly became a deep relddish-brown, was kept a t 60° for two hours and the excess of iron was then removed. On adding conmntrated hydrolchloric acid the sparingly soluble yellow dihydrochZoride of tThs new base was precipitated. It was colllected washed with concentrateld hydrochloric acid and decomposed with ammonia. On crystallising the1 batw thus formeld from aqueous alcohol it was obtained in yelllow needleg melting a t 135.5'. It is very reiadily soluble in alcohol o r chloroform, modelrately so in aceltone ethelr o r benzene and practically insoluble in water (Found C= 83-3 ; H = 5.9 ; N= 10.2.C,,H16N2 requirm C = 83.8 ; H = 5-9 ; N- 10.3 per cent.). o-Fovmylizmimocinnam ylidenequimldine, CHO*NH*C,H,*CH:CH*CH:CH*C~H,~. -0-Aminocinnamylidenequinaddine was heated with excess of 90 pelr cent. folrmic acid under relflux on the sand-bath folr three hours. After cooling the mixture was diluted with water rendered alkaline with ammonia and the1 precipitateld formyl derivative1 wa MTLLS AND EVANS THE CYANINE DYES. PARTII. 1039 colle.crted and crystallised from alcohol. It formed palei yellow needles meilting at 1 8 5 ~ 5 ~ . This compound is readily soluble in hot alcohol or chloroform fairly so.in acetone and sparingly SO in ether or betnzenel (Found N=9*4. C2JI160N2 requires N= 9.3 per cent.). Met hiodide .-Form yl-aminocinnamylidenequinaldine (2 grams) was helated with methyl iodide (6 grams) in a sealed tubel a t looo f o r three hours. The red mass obtained in this way crystalliseld from alcohol in dark red needlee which rneltetd at 218O. The substance! is soluble in hot water or alcohol sparingly so in acetone or chlolroform and insoluble in ether or benzene (Found I = 28.7. C2,H,,0N21 requires I= 28.7 per cent.). o - Formylanzinoczclznnnt ylideneptiinaZdine oiL4 c e t ylamin o cimarny lidene quinaldine, CM,-CO* NHoC,~H~* CH CH-CH CH-C,H,N. -The amino compound (10 grams) was helated f o r one hour on the watelr-bath with acetic anhydride (30 grams).The1 excem of acetic anhydride1 was then delcomposeld by heating with watelr and the acetyl deIrivative precipitated by tlhe addition of ammonia. It was collected and crystlallised from aquelolus alcohol from which it separates in pale yellow needles melting a t 179O. It is soluble in chloroform and dissolves vcry readily in aloohol. It is almost iiisoluble in etheir acetone water o r benzene (Found N = 9.1. C,,H,,ON requireis N = 8.9 per cent.). A ce t y Tam in o cinnant y liden e quinaldine Met /$iodide .-The acetyl delrivative (2 grams) was helated with methyl iodide (4 grams) in a sealed tube at looo for three1 hours. The bright red contents of the tubel were! crystallised from water and then recrystallised from alcohol. The1 methiod-ide obtained in this way consisted of bright red needles mellting a t 21G-217° (Found 1=27*75.C,,H,,ON,I relquires I = 27.85 per cent.). Itq is soluble in water alcohol or aceltonel sparingly so in chloro-form and insoluble1 in ether o r benzeael. Cwb oxyme t It ylaminocinnarn ylidenequinaldine, CH,*CO,*NH*C,H,*CH:CH*CH:CH*CSH,N. -A solution of o-aminocinnamylidenequinaldine (2.5 grams) in dry chloroform was heateld with methyl chloroformate (1 gram) under refflux f o r four holurs. Watelr was addetd and then ammonia until the red oolour of the hydrochloride disappearetd. The chlorodorm layer was separated the ohloroform evaporated and the residue crystalliseid from alcohol. The! compound formed lustrous yellow plates melting a t 1 7 5 ~ 5 ~ (Found N = 8.5.C21H1802N2 requires N=8.5 per cent.). This compound is readily soluble in hot alcohol or chloroform 1040 WENTWORTH AND BRADY: sparingly sol in acetone ether or benzene and practically insoluble in water. of-A m~~oc.irtnamy2ideneguinlxld~ne Methiodide (V) .-This sub-stanae was obtained by the hydrolysis of its acyl derivatives the reaction being most easily clarried out with the formyl compound. Fomylaminocinnamylidenequinaldine~ melthioidide is readily hydrol-lgseld by dissolving in hot water adding a little conaentratd hydrochloric acid and boiling for twenty minutes. To ensure geltking the iodide uncontaminated with chloride potassium iodide was aaddeld to the mixture( and the grelater part of thei acid was then neutraliseld with ammonia when a dark reddish-brown pre+ cipitate of the iodide was olbtained. This was recrystlallised from methyl alcohol to1 which a little1 aqueous potassium ioldide had been addeld. The salt forms neeldlea with a very dark olive(-green lustre melting a t 1 9 4 ~ 5 ~ . Iti is very rea,dily soluble1 in melthyl alcohol, less so in ethyl alcohol or water and sparingly so in acetone or chloroform. F o r analysis i t was drield in a vaciiiim at 70° (Found : C = 57.5 ; H = 4.6 ; N = 6.53 ; I = 30.4 30-8. C,,H,,N,I requires C=58*0; H=4*6; N=6*76; 1-30.7 per cent(.). UNTVERSTTP CHEMTUAL hBORATORY, CAMBRID GF . [Received Juh/ 27th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701035

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

1040 WENTWORTH AND BRADY: CXVI.-The Isonierism of the Qxinzes. Part I X . 2 4-Dinit?.obenzaldoxime and Bromo-substituted Hydrox y- and Meth oxy-benzaldoximes. By VERA WENTWORTH and OSCAR LISLE BRADY. ON the Hantzsch-Wernelr hypotheeis all substituteid benzaldoximes should elxist in two! stelreoisomeric forms. I n a number of cases, hotwerver all a,tt,empts to obtain the uiistamblel isomelrids have beleln unsucce'ssful (compare Brady and Dunn T. 1916 109 667) but from a study of thew cams there has emergeid no underlying principle1 detwmining the non-existence af the second form other tqhan the inhibiting effeld olf the hydroayl gro(up. A number of other subatJtutRid benzaldoximesl have now been investigated with a view to arrive a t somel generalisation. The nit.robeazaldoximes all exist in tlwo isomeric forms and although 2 4-dinit8robenzaldoxime has been prepared (Saohs and Kempf Ber.1902 35 1234)' its configuration has not beea detelrmined. It hw been found to1 possess the anti-configuration by the pi-eparation of its acetyl delrivative and hydrolysis of this compound to the original oxime according to1 Hantzsch's melthod THE ISOMERISM OF THE OXIMES. PART IX. 1041 It d m not however form a hydrochloride in the usud way acrid a.11 ah.t,empt's t o olbtain a second isomelride ha>ve been unsucoessf ul. In no oa.se has a sub,stituted be,nzaldo,xime coataining a hydroxyl group in the1 nucleus been cht-aine8d in tlwo forms a,lthough p-acet.oxybenza81doxi.me and a,nisa,ldoxime bBot,h give a syn-oom-pound. It was thought thafl subst,ituteld hydroxybenzaldoximeo, partJoularly tbow cont.aining a.hela.vy gro'up in tlhe ortho-posit,ion witch respect to tahe hydro'xyl groap might exist in t,wo forms a.s tshe ent,raace of &her groaps might- emrt a " storia hindranm " eff ect. 5-Bromovanillinoxime aad 5-iiitrovaiiillino~xime have already been investigateld witch negative results (Brady and D u n , T. 1915 107 lSSS) and 3 5-dibro~mo~-p-hydrsxybe~nzaldolxime and 3 5-dibromwo-hydroxybenzaldoxime have! nolw been studield . The fo'rmer yields a hydrochloride in the usual way but this regelnerahx the original oxime' on deoompositdon with sodium ca,rbo,nate solution ; thel 1att.e.r dotes not form a hydrochlolridel and cannot' thetrefore be convertled into an isome'ride. Alt'hough anisaldoximei rea'dily gives a syn-derivative( o-methoxy-beazaldoximel aad 3 4-dimethoxybe~nzaIdo~~ime~ (ve,ratraldoxime) e.xist8 only in the anti-form.The influence of the int4roduction of the1 bromine; atlom into1 these compounds has beeln inve,stigated a,nd, whilst it has been found t h t 5-b~rmno~o-me~thoxybsnza~ldo~xime camnot be c40nvertieid int.0 a syn-isomeride t,hro,ugh t,he hydrochloride, 5 -bromo1-3 4-dime8t.ho~xybenzaldoxime~ on the ot'her ha,nd yields a.n unusually stabmle sp-derivat'ive relmaskable in thatt its a.celtlyl delrivativel is not deco'mpsed to the1 nitrile by soldium carbonate solutioa but only by sodium hydroxide. so'lutbon. These relsultls have! not inadel lelss puzzling the fadlure to obtain syn-isomeridea from some' ,substituteld b,e8nzaldodmes.It is evident t.hat the inttroductlion od negative substituents is not a deltermining factor a.nd t,he inhibitive! elff elct of t'he hydrolxyl groap o a the folrmation of syn-isomelrides h'as beea further demo,n-st,ratleld. Two model benzaldoximes which do1 not. give hydro-chlolride\s wheln t8relatetd in dry elthemred so'lutio'n with dry hydrogsn ahloride have been atddetd t o tlhe previously unique case of' 6-nit.ropiperonaloxime~. E X P E R I M E N T A L . Attempted Coflversion of 2 4Dinitrobenzaldoxirne.-Ths oxime, pre,pared from the a,ldehyde hydroxylamine hydrochloride and sodium carbonate in alcohol was dissolveld in dry ethe'r and the solution saturated witah dry hydrogen chloride. No hydrochloride was precipitated and elvaporation of the elthsreal solution in a current of dry adr gavel the unchanged oxime.An att8ejmptl wa 1042 WENTWORTH AND BRADY made to1 bring about. the conversion by Dunstan and Thole's method (P. 1911 27 233) but without success. Ciamician and Silber (Ber. 1903 36 4268) found that the nitrobenzantialdoximes when exposed to sunlight in benzene1 solution in sealed tubes were con-verted into the1 nitrolbenzsynaldoximes. Similar eixperimelnts are being tried with 2 4-dinitrobenzaldoximel and other oximes; the rwults will be described in a subsequent communioaiion. A cetyl Dem'uative.-The configuration of the oxime was deter-mined by the preparation of its aceltyl derivative and the sub-sequent hydrolysis of this compoand to the oximei. The oxime was treated with about four times its weight of aoetliu anhydride and warmed t o 30°.The oxime dissolved and on decomposing the BXCW of acetia anhydride with sodium carbonate solution ths acetyl derivative separated ; from dilute aloolhol it forms yellow, miorwcopic crystals mellting a t 79O (Found Ao = 17-4. C,H,O,N, require8 Ao= 17.0 per cent.). On warming with 10 per cent. sodium hydroxide solution for some minutes the aaetyl compound dissollved and oln addition of dilute sulphuria acid the original oximel was precipitated. The Gnti-configuration of 2 4-dinitrobenzaldo~xime is thus established. 3 5-D.ibromol-p-hycEro~xybenzaldoxime.-Tol 28 grams of 3 5-di-bromo~-p~hydroxybenzalde~hyde prepared by Paal's melthod (Ber., 1895 28 2408) were added 100 C.C. of 10 per cent.sodium hydr-oxide solution; the aldehyde dissolved and the sodium salt crystal-lised out almost immediately. A furthelr 200 0.0. of water was added together with 8 grams of hydroxylamine hydrochloride in water and the mixture was left overnight. A t the end of that time the precipitated sodium salt of the aldehyde had completely disappeareid and on acidifying the solution with dilute sulphuric add the oxime was prelcipitated. It crystallises from alcohol in cololurless needles melting a t 199O (PaaJ and Kromschroder Ber., 1895 28 3236 give 194O) (Found Br=53.9. Calc. Br=54*2 per mnt.). The hyd;rochlo.ride prepared by saturating a solution of the olxime in dry ethelr with dry hydrogeln chloride was precipitlatad as it white crystalline powder melting and decomposing at1 190° (Found C1= 10.3.C,H,O2NBr2,HC1 requires C1= 10.7 per cent.). The hydrcmhlolrids was decomposed with sodium carbonate solution and the oxime precipitated with dilute sulphuric acid; this was found to be the unaltered anti-derivative. The Diacetyt Derivative.-The oxime is notl aceltylated w i t h the ease that is usually olbserved and one1 drop of concentrated sulphuric acid is needed as a catalyst. The oxime was covered witlh amtic anhydride and the sulphuric acid addeid; the1 compoun THB ISOMERISM OF THE OXIMES. PART IX. 1043 dissolved rapidly and the liquid became just appreciably warm. Excess of amtic anhydride was removed with sodium carbonate, and the awtyl derivative separated as a gum-like material. This subet,anm was difficult to1 crystallise but when dissolveid in the minimum mount of boiling absolute adcohol and the liquid cooled and ths walls of the vessel scratched f o r some minutes i L separated as a white crystlalline powder melting a t 1 2 2 O (Found Ac=22.8.Cl,H90,NEr requires Ac= 22.7 per cent.). When heated for fifteen minutes with 10 per cent. sodium hydrolxide the diacetyl oompound regenelrates the original oxime thus establishing the Q I ~ t i- coafiguration ot that subst anm. 3 5-Dibronzo-o-l~ydroxybenzaldoxime.-The prepara,tioa of 3 5-dibromobo-hydroxpbenzaldehyde has been described by Heerlelin (Uerz. Jehresb. 25 486) and Werner (Bull. Solc. chim. 1886 [ii], 46 277) but a more satisfactlory method consists in dissolving salicylaldehyde in glacial amtia acid and adding the calculated quantity of bromine in acetic acid the mixture being kept moll.Aft<er remaining f o r some time the addition of water precipitates the aldehyde which may be orystallised from alcohol. Ta a solu-tion of 16 grams of the aldehyde in alcohol 5 grams of hydroxyl-amine hydrochloride1 dissolved in a minimum quantity of watelr wetre added followed by 5 grams of sodium hydrolxide in concon-tratod aqueons so3utioa. The mixture wa5 allolweld tfo remain ovelr-night the oxime precipita-bed by the! addition of excess of dilute sulphuric acid and crystalliseld first from aloolhol and then from benzene. 3 5-Dibrorno-o-hydrolxybenxaldoxime separate8 from benzeae in coloarlas needles melting a t 204O (Found Br = 54.2. C7H,0,NBr2 requires Br = 54.2 per cent.).The diacetyl derivative prepared in the usual way crystallises from alcohol1 in colourlem neeldles melting at 1 1 1 . 5 O ' (Found : Ac = 22-4. Cl,H90,NBr refquires Ac= 22.7 per centl.). On hydro-lysis with 10 per cent. sodium hydroxide the diacetyl compound regenerated the original oxime which is accordingly the anti-isomelride. 5 - Bromo - o - nzet1~oxybenzctldoxirne.-5 - Bromo - o - methoxybenz-aldehyde was prepareld by Yeirkin (Anmdem 1868 145 304) by the bromination of o-methoxybenzaldehyde ; it may howelvelr be more economically prepared from 5 -bromosalioylaldehyde obtained by the bromination of snlicylaldehyde (Piria ,In?zuZen 1839 30, 171). Twenty grams of 5-brommalicylaldehyde~ were dissolved in a solution of 8 grams of sodium hydroxide in 200 C.C.of water and 24 grams of methyl sulphab added with consttaut shaking. The methyl ether separated as a solid and aftelr some time was collected and crystallised from alcolhol. Ten grams of the aldehyd 1044 WENTWORTH AND BRADY: were dissolved in 50 C.C. of alcolhol aad 4 grams of hydroxylamine hydrochloride! a,nd 4 grams of sodium hydroxide ea8ch dissolve,d in tihe minimum quantity of water wwe a,dderd. Aft,ec remaining overnight the oxime was predpit,ated by acidifying with dilute sulphurio acid a'nd crystlalliseld from met'hyl alcohol from which it selparateld in long colourless neletdles melting atl 1090 (Folund : Br = 34.5. CsH,O,NBr rquires Br = 34.8 per cent.). The acetyl deriva'tive crys.tlallises from akohol in cololoarlew prisms meltling ab 1 0 2 O (Found Ac = 15.3.CloH1,O3NBr requires Ac= 15.8 pelr cent.). Hydrolysis of this compoand to t'he 08rigina81 oxime wi t'h sodium hydroxide sollutioa elstlablished the anti-oonfigura,tion of the la,t,br. H y drochl oride of 5-Bromo~0~me t holx y b enzcaldoxirne .-The olxime wa,s dissohed in dry elther and the1 solution saturated witlh dry hydrogen chloride. The hydroichloride was precipita,ted as a ye8110w, cryst'alline powder mellting and dewmpoaing at 1 2 3 O (Found : C1= 13.1. C,H,O,NBr,HCl requires C1= 13.3 per ceab.). The hydrolchloride oln decomposition with sodium carbonate solution, p v e a crude oxime me'lt'ing at looo. Part was relcryst8alliseld from aoetlolnna and wa,ter when it gave a compolund which was prove'd to b,e the original oxime by the1 method of mixed melting p i n t s .The rest was treatled with acetJo a'nhydride and gave the1 a8mtyl delriva,tive whioh on hydrolysis gave the olrigina,l oximel. Acoo'rd-ingly no conversion to the syn-ismelride ha,d take'n plaw. 5-Bromo-3 4-dz'methoxybenzantiatdo~xime.-Eighte~e.n grams of 5 -bromolve~ra.traldehyde prepased from 5 -bro,movanillin by met'hyl-ation witih methyl sulphatel (Dakin Arner. Chem,. J. 1909 42, 494) weirel dissoflved in 50 C.C. of alc'ohol aad 6 grams olf hydroxyl-m i n e hydrochloride aad 3 g r m s of sadium hydrolxidel elach in the minimum amount' olf water were addeld. Aftelr remaining olver-night, the oxime warns preoipit'atetd by the addition of dilut,e sulphuric acid and relorysta,llised f rotm dilute alooihol when it seipa.rated in co810arless7 shining needlels melting a,t 83O (Found : Br = 30.4.C9H,,03NBr re,quires Br = 30.8 pelr cetnt.). The alcetyl deIrivatlive wa.s prepase.d in the1 usua,l way a'nd its hydrotlysis confirmeld the1 amti-configurafioln od the original o x h e . It arystallises with difficulty frojm dilute melthyl alcohol in micro-sc801pic q s t a l s melt8ing at 7 7 O (Found Ao= 14.3. C,,H,,O,NBr relquires Ac = 14.2 pelr cent.). Hydrochloride of 5-Bromo-3 4dinzethoxyb emaldoxime .-The anti-oxime x 2s dissolved in dry ether and the so1utio.n sa.tarated wit3h dry hydrogen chloride when the hydrochloride was preoipitated as a white crystalline powder melting and delcomposing at! 120-125° (Found C1= 11.8. C,H,,O,NBr,HCl requires C1= 12.0 per cent,.) THE ISOMERISM OF 'I'HE OXIMES.PART IX. 1045 5-Broms-3 4-a?im~ethoxybenzsynddolxinze.-Ths above hydroc chlolride was delco,mpwe,d with sodium carboiia8te solut'ioln and tlhe mudel oxime meltied at. 1 0 8 O . Cryetallisa,tioln from a.celt,onel and water gave t,he pure syn-oxim,e in small prisms melting a8t 1 1 6 O (Foand Br = 30.9. A cetyl Derivaiti've .-The( syn-oximel was treamtteld with aboutt folur times its weight of a,mtic anhydride the solut,ion warmed t o 30°, and the eixcess o€ a,cetitio a.nhydride decompolsed with soldium oarbosna.te ssluttion. Unlike1 t'hel acelt'yl de'rivatives of other syn-olximes that halve beeln stndield tha,t delriveld from 5-b$romo-3 4-dimeltholxybenzsynaJdolxime is noit decolmposed in t,hese circnni-stlances with the folrma,tioln of nitrilel and t,he s'olid which separat'eld proveld to be the1 aoeltyl de'rivative!.When cryst,allised f ro'm dilute alcokhol it tendeld to' sepamte as a,n oil which slowly solidified but a>fter t.wo reiorysttallisa.tio8ns it mellteld sharply a8t 73O (Foand : Ac = 13.9. C,,€I,,O,NBr relquires Ac = 14.2 per cent.). The acetyl deriva,tive was warmed wilh 10 per cent. sodium hydroxide wlut,ioii to 35O. After cooling and diluting t.he soilid was c,ryst3a611iseld froim alcoholl a-nd found to1 be 5-bromoveratt;ro+ nitrile (m. p. 117O) giving on bo,iling with sodium hydro'xide, ammoaia a.nd 5-brolmovelratrio acid. 5 -Brom ov e rat ?-on it rile. -For the1 purpose of ideInt.ifica ti on of the product olbtaineld by ttreat4ing the above acetyl compound with soldium hydroxide tlhel nitrile was prepared by boJling 5-brolmol-3 4-dimelthoxybenmntialdoxime wibh eixcress od a,mtic anhydride for threlei hours.The excess olf anhydride1 was deco'mposed witb sodium ca8rboaattle sollutloin and the1 solid was oryst8allisejd from alcoholl, when the nit7rile separated in mlo~urless microscojpio orysta.ls mellt-ing at! 117O (Foand Br = 32.8. C9HH,0,NBr mquires Br = 33.1 pelr cent . ) . The nitrile on boiling for thirty minutes with 10 pelr centl. soldium hydroxide solution is compleltely hydrolysed and oln acidifying t,he solutlion 5-broimovelratric acid (m. p. 189O) is pre-oipitatd. Zincks and Francke (AnmJen; 1896 293 183) who olbtained t.his acid from met'hyl 5-bromo~pro~to~cate~chua~te1 by methyl-at.ion and sub,sequentl hydrolysis give 191O as t,hel melting point, and Pscholrr (Annailen 1912 391 31) who obt,ained itn by t7he oixida,tion of 5-b~romovsrafsaldehyde~ gives 192-1 93O. C,H,,O,NBr requires Br = 30.8 pelr centl.). The authors desire t.01 elxprees thelir t,hanks t,ol tlhel Researoh Fund Committee of t,he Che~miaajl Solaieity for a grant which has in pa,rt, delf rayeld the elxpenses of this reaea,rch. ORGANIC CHEMICAL LABORATORIES, UNIVERSITY COLLEGE LONDON. [Receiued August 4th 1920.1 VOL. CXVlI. R

ISSN:0368-1645    

DOI:10.1039/CT9201701040

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

1046 WERNER THE dONS!I!ITUPION OF CARBAMIDES. PART XI. CXVlL-The Constitution of Carbarnides. Part X I . The Mechanism of the Synthesis of Urea ji*om Ammor~iurn Carbarnate. The Preparation of ce?*tccin Mixed Tri-substituted Carbamates and Dithiocccrbamates. By EMIL ALPHONSE WERNER. IN 1868 Basarov ( J . pr. Chern. [ii] 1 283; Journ. Chem. Soc., 21 194) obctaineld urea by the! action of he'at on ammolnium csasbamats under pressure. The change which is suppmed to1 be obviously explaineld by the simple1 equation = C O < i z + H,O, is always considered to representl the1 ootnversa of the ultimate hydrolysis of urea to ammoaium carbonatel and foil- this relason this synthesis is commonly cited as elvide~nce pur excellence in favour of the1 deiwlptivei " carbaniide " cclnfiguration.++ To satisfy this view it has been assumeld without any proolf, that water is elliminakld from the group *O*NH, the produotion of urea beling thus analogous to the formation od aaeltamide from ammonium acetate or of olxamidei from ammonium oxalab.As a mattsr of fact the mechanism of the formation of urea in this relaction is of quite a cliffelrant order since i t is nothing more than a moldifioation of Wohler's synthesis namely the production of urea from ammonia and cyanic acid (HNZCO) as the1 relsult of the fodlowing series od change6 : (HO*CN t HN:CO) + H20 ; (3) NH + HN:CO + HN:C<& YH* . So far as ammoaium oarbarnab is concerned the fact that urea and a,mmoaium uyanate were found in the p r d u d after vapor-ising the1 salt tlhrolugh a glass tnbe heiated t'o incipient reldness is not final proof tchat cyanio acid was produced as shown a<bove since Mixter (Amer.Chem. J. 1882 4 35) obtaineld urea from ca,rbon * It may be of interest to record that Kolbe in presenting Basarov's paper to the Society opens with the words " From the conviction that urea is not carbamide "-a remark which the author is equally convinced has been fully justified WERNER THE CONSTITUTION OF CARBAMIDES. PART XI. 1047 dioxide and ammonia at a red heat. cyanic acid was generated in this case thus, (see Expt. VI) as Mixter suggested. Convincing evidelnm however in support of the above series of changes has belen obtlaind from a study of the decmmposition of certain substituted ammonium carbamates and dithiocarbamates.Fichter and Beicker ( B e y . 1911 44 3473 3481) showed that methylammonium methylcarbaamate NHMe*CO-O*NH,Me and the elthylammoaium analogue gave the respective symmetrical disu bs t it u t ed carbami des whilst 1101 tetlrarsubs titu t eld carbamide could be oibtaineld from diethylammonium diethylcarbamate. Since direct dehydration of the carbama,tw was assumed to( repre-sent the mechanism of the change i t follolws that if the reaction There can be no doubt tha CO + NH3 * = IIN:CO + H,O was the resultl of the direct e(1imination of water from the group *O*NH,R there selemed no reason why the change should notl take place! with eveln grelater faoility tlhan in the1 case of reacttion (a). Since1 loss of watelr could take place in one way only and considering the stlability of teltra-substituted carbamides, these investigators were unable to elxplain the apparent a bn arm ali ty .Now according to the three-phase change or '' dissociation theolry " here put focward only carbamates which contain the system *CO*NHR capable of yiellding R*NCO can give rise to substituteld carbamides. Thus in the delcomposition of all such carbama,tes change ( a ) for example( is correctly represented by t,he f ollolwing general scheme : (Phase 111.) NH,R+ + +R*NCO + + \ (Phase I.) (Phase 11.) * This reaction may prove to be of considerable importance in the near future as a method for the fixation of nitrogen a s mea since it very probably only awaits the discovery of a suitable catalyst to realise the change on an economic scale.Of great interest in this connexion is the recent discovery by Mailhe (Ann. Chim. 1920 [ix] 13,226) that the change CO + NH,=HCN+ H,O is quantitative at 430-450" in the presence of thorium oxide. R R 1048 WERNER ’J!HE CONSTITUTION OF CARBAMIDES. PART XI. Whilst under normal prelssure carbamio acid and its mono+sub-stitatad homollogues are1 decomposed thus, CO<rER + CO,+NR,R, this change1 must be largely suppressed under high premure in favour of the! alternative1 one reprelsentneld by phase1 11. I n the case of a disubstitutetd carbamic acid the1 change1 alone prevails and hence a tetra-substituted carbamide is not f ormed . The soandnem od the present the,ory has been experimentally be&etd by pro’ving as predioted by the1 scheme’ tha8t oarbamatlea of type ( c ) CO yielded tri-substitmutad carbzmides as the result of phase! 111 RNCO + NHR,= CO<z:h) whilst those of ( NR I tiypef ( d ) co<o.rjB,R did not.Carbamafee of t’hei l a t h r typee, which have no tl beein -hither t’ol d elsor i bed w e’rel su mess f ull y prep a red by a methold baseid on the diffelreinces in the relative strengt-hs of the amines to1 which the author has recently dra.wn attleiition (T., 1918 113 899; 1919 115 1012). Beazylammonium beazylcarbamate in cold alcoholia solution was quantibativeily delcoimposeld by dimelthylaminei thus : Din~etkylammO~aiu/mm benzylcarbamate gave after folur hours a t 140-150° in a sealed tube! benzyld~nzeth?/1ca7.bamide7 N Me?* CQ NH CH,P h . DiethylanLmolniurn b enzylcnrbanzate gavel under like conditions, b e n,z y ldi e thy 1 car b amde, Hethylammolnium diethylcalrbnnznte NH,Me*O*CO*NEt (type d ) , was prepareid by the displaaement of dielthylamine from diethyl-ammonium diethyloarbamate by the stronger aminel methylamine.After four hours at 145-150° itl faileid t o yielld any methyldiethyl-aarbamide (Expt. V). It is 0;bvious that the theory of t h s direct dehydration of carbarnah which fails elntirelly tao explain the facts just recorded, must be abandonod in favour od the dissociation theory. As a logical sequelnm thereolf Basarov’s synthesis of urea can no longer be upheld as evidence1 of the ‘‘ carbamide ” structure WERNER - THE CONSTITUTION OF CARBAMIDES. PART xr. 1049 T h e D e com,pmi t ion o f D i t hi ocar b anza,t es .It is we,ll known that dithiocarbamates derived from the inter-acetion of carbon disulphide and primary amines namely, RHN.CS*S.NH,R (type e ) yie:ld symmet,rical disubstlituteld thiol-carba,mides whilst tlhose delrived from seoomnda8ry amines namely, R,N*CS*S*NH,R (type f) do1 not giedd t.e.tra,-subs~,it'uteld thiocarbamides. A study of the decompositioa of the following " mixed " dit,hio-carbama,tes of types whioh have not been hitherto prepared ha.s proweid t,hat the1 melchanism of t>he clhanges is similar to1 thah of catrbaxna8tes. Di.met hyla.mmonium bemykdithiocarba,ma t e , NH,M+* S C S NH*CH,P h, pre,pa.reld from benzylammonium benzyldithiocasb,amata by the dis-place8me8nt8 of lxmzylarnine by dimethylamine (Expt. 111) gave (7 e n,zyldi,nz e t h y l t h i,olcmr7,anaid e N Me,* C S N H CH,P h after a.n a.lcolho81ic so81ution was boilejd undelr reflux until hydrolgen sulphids celaseld t'o be elvolved.Dieth~ylnmam.oniZLnZ. b enqldit hiocwbamaat e, N€I,Et2*S*CS.NH*CH,Ph, simihrly gave benzyldzetl~?/lthLiocal.ba;mide (Expts. 111 and IV). whioh contain the system -S-NXI,R do n0.t jrield t8hioearbamidw thelre o m be nor doubt t,ha,t the a,bNolvvs regult-s wem the outcolme of a relaction between NHR and C,H,*CH,*NCS (pha.se HI) p r o d u d in accordance wit'h the gelneral scheme[. To prove tha,t thioca,rbamates of type ( g ) NH,R*S,*CS*NR, did not yield t'ri-subst\it.uted thiolcarb.amides methylamrncurLi,um climeth?yldit hio~casbanaate (m. p'. 90-91O) and metl~ylammo&um dieth~kditk~~ocairba;ma,te large hexa,golnal prisms (m.p. 1 0 3 O ) welre prepare'd. I n mch case methylamine and hydrogen sulphide were evolved whe'n adco,hoclio solut.ioas of the respective) salts welre heated t,o looo under resflux. Whilst no1 tri-substitutelcl thioca.rbamide could b,ei isolat,ed from tho produot, tlhel main c,ha,nge was a bimolecular decolmpositio,n osf the1 acid R,N*CS*SH produceld by dissocia.t,ion of t.he original salt a,s tlhe preliminary change. The theory t.ha,t t,hel f ormafion ol substituted thiocarbamides from dithioca,rba,mat8es is simply a direct eilimiiiation of hydrogec sulphide is thereif ore a fallacy. The well-kno'wn fact t,hat ammonium dithimasb,ama.t.e, H,N*CS*SNH, yiedds only ammo,nium thiocya,natel when decom-pomd by heah unde,r no,rmal prelssurel is duel t.o t.he change) ofccurring Since1 dithioc.arb,ajma4t'es of type ( f 1050 WERNER THE CONSTITUTION OF CARBAMIDES.PART XI. below the tempelrature at which an equilibrium HS*CN -L HN:CS, can obfain the form HN:CS beling essential ttol the production o t thiourea by its union with ammonia7 (T. 1912 101 2184; 1919, 115 1169). The Prepratiom of “ Mixed ’) Dithiocarhmates. Apart from their theoretical interest the1 preparation of dithio-oarbarnates of types CS<S.NH,R,” NHR’ an d CS<f.Eg,w is of some practioal importance since i t provides a simple means f o r obtain-ing various mixed di- and tri-subst.itatsd thiooarbamides by dis-pensing with the preparation of the otherwise nelwssary thio-carbimide R*NCS. The ‘ I displacement ” method is not recommended when there is only ai small diffesence beltween the relative stlrelngths o€ the aminea; tlhus in order t o realise the reaction, i t was necemary to1 use a considerable elxws of methylaminel (3-4 molecules) to complete tlhe change within a reasonable timel.On the otcher hand n-butylmine f o r elxample was readily displaced from n- bwtylammomhna n-but yldit hiocarbama t e C,H,N,S, by dimethylamine with the production of dimethylammonium n-butyl-dithiocarbamute C,H,,N,S (refractive hexagonal prisms M. p. With closely redated amines admirable results were obtaineld by dissolving the amine hydrochloride in either an aqueous or alcoholic solution of the sodium salt of the particular dithiocarbamic acid, prepared acoording t o the method described by Dellepine (Compt .rend. 1907 144 1126). Diethylammonizirn metltyl~~thioicarbamnte (prisms m. p. 89-goo) which could only be prepared according to the equation 93.50). C S < E g p + NHEt,,HCl = CS<NHMe S*NH,Et + NaCl, gave methyldie~thylthio~carbamidel in a yield equal to 72 per cent. of t’he theoret’ical. Dime th ylammoltvlim e t h yldit hiocarbamat e, NH,Me2-S*CS*NHEt, (m. p. lolo) from soldium elthyldithiwatrb~mab and dimethyl-ammoaium chloride gave a yield of dimethylet4hylthiocarbamide elqua1 to 67 pelr cent. olf the theoret.ica1 WERNER THE CONSTITUTION OF CARESMTDES. PART XI. 105 1 E X P E R I M E N T A L . Preparation of illired Benzylcarbarnntes and Benzyl Di t hiocar balrna t es . Expt . Z.-Thirteen grams of benzylammonium benzylcarb-amate (m.p. lolo) prepared by passing carbon diolxide through a solution od benzylamine in dry ether were placed in a stout tube of soift glass and 3.5 grams of dimethylaminel dissolved in 20 C.C. of alcohol were added. A clear solution was obtained after the mixture had remaineld atl the ordinary temperature f o r twenty-four hours when 40 C.C. of ether were addeld. The viscous dimethyl-ammonium benzylcmbmate was allowed to1 subside after which the mixture of ether and alcohol which contained free benzyl-amine was poured off. The product waa twice tmated with 15 a.0. of ether to remolve all free mines (Found by hydrolysis with ammoniacal calcium chloride and titrating the calcium carbonate with hydrochloric acid CO,= 21.73. Cl,H,,0,N2 retquires CO,=22.44 petr cent.).The tube was sealed and after heating a t 140° for four hours the semi-solid product was extlracted with wator. The1 insoluble hen,zyZdimethy2c~bnrmide (2.6 grams) crystallised from alcohol in colourlem glistening nwdles which melted atl 166O (Found N = 15-81. C,,HliON requires N= 15-73 per mnt.). The yield was equal to1 29.2 per cent. of the1 theoretical. A specimen preipared from benzyl cyanate and dimelthylamine had tho same1 melting point and a similar appearance. Expt. 11.-This was a repetition of I with dielthylamine in place olf the methyl compound. From diethylammoniuna bemzyl-carbarnate a viscous liquid 3.7 grams of b e n z ~ l ~ 2 i e t h y l c a r b a ~ ~ , slendelr glistening prisms melting a t 169-170° in a yield equal to 36 per cent.of the theotretical weire isolated (Found N=13.66. Cl2Hl8ON requires N = 13.59 per cent.). Expt. ZZ1.-Carbon disulphide (3.8 grams) was addeld t o benzyl-amino (10.7 grams) in 25 C.C. of aloohol. To the benzylammonium benzyldithiocarbamate formeld dimethylamine (4.7 grams) in 20 C.C. of alcohol was added. After twenty-four hours 9 grams of dimethylnnamonium h enzyldit hiocarbamate brilliant small, rhomboidal prisms welrel collleldeid (m. p. 116-117O) (Found : S = 28.19. Five grams of the salt, in 30 C.C. of alcohol were boiled under reflux until evolution of hydrogen sulphide had mased. On adding water b e T L z y l ~ i r n e t h y l t h i o c a r ~ u ~ n ~ ~ ~ was prelcipitateld in slender, rhombio prisms melting a t 95-96O. The yield (3‘2 grams) was equal t o 75.3 per cent.of thet theoretical (Found S=16-39; N =14.55. C,,H,,N,S requires S = 28.07 per cent,.). C,,IM,,N,S requires S = 16.49 ; N = 14-43 per cent.) 1052 WERNER THE CONSTITUTION OF CARBAMIDES. PART XI. Expt. ZV.-When dielthylaminel (5.4 grams) rep1a)md dimeithyl-amine in the previo'uus experinisntl 9.7 grams of diethyZammo.nium be?azyZdithioca~hamate stout helxagonal prisms melting a t 1 1l0, were obtained (Found S = 25.1 7. C,,H,,N,S requires S = 25.0 per celnt4.). Five grams ga,ve benzy7clietkyTtI~iolcarbarllzide (3.42 grams) silky nseldles melting at 67O in a yield equal to 79 per centl. od the t7heloiretical (Found S = 14.29. C,2H,8N2S resquires S = 14-41 per celntl.). Met hyhmmonium .Diet hylcnrba,m a.t e. Ex@. V .-Dielthylaxn.moniuxn diethylcmarbamatle (10 grams) prel-pared by t'hhe union of carbon dioxide and the vapour of pure die~thylamine as recommended by Fiohter and Becker (Zoc.tit.), was allolweld t.0 relmain foz twelnt.y-foar hours in cont*w,t with a solu-tion of me!thylamine (6 gra,ms) in a mixture! of ethelr and alcohol contlained in a q a s a t i n g funnell. The1 viscous liquid was subjectleld to a second t'rela,tme8nt wit-h met,hyla,mine (3 grams) a.fter which it, was well elxt,rac,ted wit,h pure elt3helr tot rernovei all free aminel. It' gave no1 prel&pit,atel with a. sdut*ion of calcium chloride in t,hel cold, but a coipious pre8cipita.tel of calcium carbona'te whea wa,rmeld [Folund CO (on hydrolysis) = 29.06. C,H,,O,N re'quirm CO = 29.72 per centl.].The1 o,riginal ethyl compound require8 CO,= 23.15 per cent. he'ncel the distpla,ueImen t- o'f t,hhe diethyhmmonium groap was pract,ically complelt.s. Five grams heated for four hours in a, s d e d tube at 140-150° ga,vve a pro,duct which. voslatilised com-pletedy ah looo. No melthyldiekhylm~rb~a;mide theref ore was f ormed. Formation of Urea and Ammovzizcm Cyanztzte from Ammomhm Car b amat e , Expt . VZ.-Ammo,nium ca,rbamah contakd in a. flask at,tached tloi a' tube oif hasd ghss (120 an. long and 1.5 m. bore) was vaporriseid in a current of dry a*mmonia while th,a tube was ma,in-tiaine'd a.t. a' low red heah o'velr a lelngth olf 80 cm. the forwa8rd portlion b,eling co,oled by a. circulating ourrent of watelr. The prelselnce of ammonium cyanab in the sub1imatt,e which wars collected was prove:d by tlhei formatdon of a prelcipitate of silvelr cyanatla in a solutJo,n of t,he product carefully neutralised by nitric aoid to which silve,r nitra't.0 had b'eeln prelvioasly a,dded to1 avoid loss of cynr~ic add by hydrolysis.Urela was detected by the sa.nth-hydro1l reactioln and by t,he- format,ion of its nitrate. Whilst. this esperime,nt may be consides4 a repetition o DIXAR A COMPARATIVE STUDY IN T ~ I E XANTHONE SERIES.. 1053 Mixter's (Zoc. c i t . ) the presence of ammonium cyanah which was not pointed out by this invefitigator is o'f much t,heo8relticad inte'rmt,, sinos in the author's opinion it is formed side by side1 with ure'a, and notl ne'cessarily from t,he laf'ter geneIrat,ed be.fo<rehand. Summary . (1) Tho formation of urea from ammonium carbamatei is no evidelnce olf the1 '( carbamide " structure since itq arisels from the int,eraotion of ammonia and cyanic acid (HN:CO) as in Wohlelr's synthelsis. (2) A scheme which eixplains the formation of substituted ureas and thioureas from substituted carbamates and thiooarbamates and is in agreement) with all the1 known facts has beelii expelrimentally proven. (3) Meltholds for the1 preparation of " mixed " dithiocarbamates are describeld from which corresponding di- and t'ri-substituteid thioureas may be conveiniently obtained. UNIVERSITY CHENICAL LABORATORY, TRINITY COLLEGE, DUBLIN. [Received July 27t12 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701046

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

DIXAR A COMPARATIVE STUDY IN T ~ I E XANTHONE SERIES.. 1053 CXVIII.-A Comparative Study in the Xait ihone By SURENDRA NATH DHAR. IN t3he selries of investigations of which this is Part I it is intended to compare1 xanthone with other compounds having simi-laritkiee in structure o r properties. In the fir& place such it comparison is attampteld with anthraquinone whioh has the greatelst similarit*y tot xnnthons. Not comparative study seems to have been made systematically by anyone1 except Helrtzig (NonatsA. 1891 12 161) who found that euxanthone is more stable than queroetin (a flavone) and Graelbe and Eiclhengrun (Bey. 1891 24 967) who1 compareid somet hydroxyxanthones with certain h y d roxy anthr aquin ones and h y d r ox y benzo p hen ones. 0 t her attempts at a comparison af xanthoinel with anthraquinone with resplsot to the colouring properties of their hydrmy-derivativee are etvidelncetd from a few isdatIed instances.Thus Graebe and Aders (AnmaLm 1901 318 365) shotwed the similarity of the hydroxyl group in poBition 1 in both the series. A. G. Perlrin and Everest Series. Part I. R R 1054 DHAR A COMPARATIVE STUDY have incidentally r a i s d the same quehon (“ The Natural Organic Colouring Matters,” pp. 126-127). They compare1 alizarin with 3 4-dihydrosyxanthone but rn a matter of fact 1 2-dihydroxy-xanthonel and not the) 3 4-derivative colrreaponds with alizarin. Attempt6 are being made tot synthesise 1 2-dihydroxyxanthone, and the reaults will be uommunicated in duel course. At the same time a systelmatia comparison is being attemptetd in the following directions (1) nitration ; (2) direct displacetment? of nitro-groups by halogens methaxy-group etc.and certain other important! relaotions with nitro-compounds such as Skraup’s synthesis, Doebnes and Miller’s and Knorr’s syntheses etc. ; (3) halogen-ation; (4) mobility of halogen atoms; (5) migration of diazo-groups. It is interestling to notel that xanthonel has been found to he much more reactive than antthraquinone~. Thus with nitric acid alone! xanthone giveis two dinitroxanthones (a and P) whereas anthraquinone gives a motnonitro-derivative only (Bey. 1883 16, 363). Again quite a number of tri- and tstra-nitroxanthones have very easily been prelpared whilst no such polynitro-deriv -ativea of anthraquinonel are known and further nitration of the dinitro-compounds has not yet been effecteld.Xanthone seems notl only t o be more reactivel but also more stable altjhough from the structure of theisel compounds such a fact is quite unelxpected. It is well known that wheln fuseid with potassium hydroxide xanthone decomposes into 1 1’-dihydroxy-b eln z op h e n o ne w h elreas an th r a qu i n on e is co m pl e t d y d egr ad ed to two molecules of benzoic acid. Similarly itl has beeln found that when furthelr nitration of 1 5- or 1 8-dinitroanthraquinone is attempted with mixtures of nitria and sulpliuric acids they decom-pose completely whilst both a- and P-dinit4rolxanthones are con-velrted into tekranitroxanthones a t an earlielr stage of such a treatr ment and the products are not decomposed on subsequent trelat-ment.It may also be nolted that tetrabromoxanthonel is nitrated and not decomposed by such a mixture (Dhar T. 1916 109, 740). So far as the behaviour of nitroxanthone has been studied it has bmn found thah the nitrot-groups in the xanthone series are much more reladily displaced by direct bromination than is the case in the anthraquinonei series (see this vol. p. 994). Skraup’s synthesis is effected much more readily in the xanthane ssries than in the anthraquinone selries and xanthone has also been found ta be muoh more reactive towards halogens than anthraquinone. Thus two hexabromo- and an ootabromo-xanthone have been prepared whereas no such correspondin IN THE XANTHONE SERIES. PART I. 1055 bronio-compounds a4re known in the anthraquinone wries.Wheln trefated wit.h bromine in s d e d tubes xanthone givee the 2 7-dibrmol-derivast~ive (Graebe Anwlen 1889 254 284) whilst antIhraquinom gives 1 2-dibromoanthraquinone. Theov-y of the Fwmation of Xamtholne. Staohbach has discussed in detail the va,rious theories put for-ward to elxplaJn the formaf,iotn of xa,nthone (Ber. 1901 34 4136). He attacked mainly the theories of Graebe a,nd Seifert and after proving them incapabllel of exphining all the1 experimental fa,& then known he t,ried to establish a new the,oy of his own tioget,her with a few empirical rules. One t,hing is however common to a.11 the t,heories and that is the supposition t<hat pheaol does not t8&e part in t'ha formatioln of xanthone or its derivatives.On the other hand if phenol is supposed to take part in the relackion, t,he formation of xantlhona bmmnes very simple and does not necessitate the suppmition of various int8ermediab products the existelnm od which is doubtdul or any tra.nsposit.ion of groups which Strohbach was compelleld to make. Thus in order to ascerhin whether phenol takes part or not experiments were ma,de on the prepa,ration of xanthone from salicylic acid using in ela.ch ca,se a.n equimo1ecula.r proportion of phenol. It is remark-a.ble t,hat the yie'ld of xanthone in each case was just doub,le whsn phenol was employed. That phenol a\otively takea pa,rt in the relarct,ion and ra,ises t!he yield in such a reimarkable a'nd systematio way is provd beyond doubt by t.he facts tha.t when nitrobenzene is used instead of phenol no increase in the yield of xanthone is etff eicted and whe'n oinitrophenol is used 4-nitroxant.hone is abstained.The formation of xant,hone may therefore be explained thus : C,Tf4(0H).C0,1L + C?,H,*OH = C,H4(O*C,H5)*C0,R + H2 0 Salicylic acid. Phenol. J. C,IT,<;~>C,Hg + H,O Xan t hone. Wheln only salicylic acid is used half is decomposed into phenol, and tra8ms of phenol oan act,ually be dehected in suclh experiments. The use of a dehydra,t.ing agent increasea t.he yield by removing the water formed in tha reaction. When acetic anhydride is weld the! first re.action is most probably the a.cetylat.ion of the phenolia group and this seems t,o be a.n import,ant facto'r in the yield.That is why +aceltoxybenzoic a.cid gives xa.nthone and t,he yielld is not a,ffecteld in the1 least whether ac&o anhydride is used or not. R R* 1056 DHAR A COMPARATIVE STUDY Now the folrmatkm of xanthone from phenyl salicylatle as well as all the other typical instances cited by Strohbach may be elxplaineld by t-his tlhelory and thel yield is necessarily poor wheln neither the phenolio groups are aceitylated nor any delhydrating agent is used. Thus the formation of xanthonel from phenyl salicylate promtds according to Graebei's first two1 equations (Zoc. &.) and the liberated salicylic acid and phenol are not wasted, as he has supposed but give xanthonel again although the yield in such a caw is quite inappreciable as will be sholwn in tkel experi-meatlal part (p.1061). The1 formation of 5-methyl- and 4 5 -dimelthyl-xanthone from phenyl homosalicylate supplies another instance in supportl of this theory. Thus: C,:R,Me(OH) *CO,*C,HI -+ C,H3Rle(O*C,H,)*C0,H + Pheiiyl homosalicylate. c,H,M~<$->c,H + H,O 5 -Meth ylxan thone. The watm formed here hydromlyses one mole,cule of the ester giving phenol1 a*nd homosalioylic atcid which masy give a furt,hec amount of the same metqhylxanthone but the main reactlion takes the following co'urse. One olf a pair oaf homojsalicylic a.cid moleoulee gives o1-crem1 just as salicylia acid gives phenol and t,he con-densatlion t.akee plaaa in the usua,l way giving 4 5-dimethyl-xanthonel. It is interesting t o note that according t'o Grmbe's theory only 5-rnelthylxantfholnei and according t'o Strohbach's the80ry only 4 5-dimethylxant.hoael is poasiblei and according to Seifeirt's t.he-ory none1 of these) is possible whelrea.s a,ocording to t,he preeelntl theory both prolducta can be forme'd.The other instanow cited in Stsohba.ch's pap& may bei exp1a.ine.d simihrly. After elucidafing t.he mechanism of the formation of xa.nt8hone, a few e,xperiments were ma.ds in order t o asoest'ain whether the cha,ngel takes pla.ce gra,dually or suddenly a,nd in t,hei case of a sudden change to find the temperatare a.t which it t,akes pla,ce. The tempe,ratare( of thet relaction mixture1 was t,he:refore recmded, particularly c,asefully when a single1 subst,ance wa,s used. The results show conclusively that the conversion take5 place gradu-ally as t'here was no sudden change1 in tahei tempelra.ture.Athmpts ha,vel also bete8n ma.del to syntlhesise xa,ntholne by various oither me't'hods and it has been found that the1 condeinsa,hion of 01-chloro-benzoia acid with pheno,l (Ullrna,nn's met'hod) gives most satis-f a,ct<ory reclult,s the1 yield of xanthone b'eing almostl t3helore~tica~l and the procms very simple. o.-Thiolbenzoic acid condeaseea with benzene1 a,nd ita simplei deriv IN THE XANTHONE SERJES. PART I. 1057 actives in the presence of sulphurio acid giving thiolxanthone and its derivative ( A m d e n 1896 149 250) but salioylio acid does nolt condense with benzene or its derivatives eithes under theee cmditions o r undelr the influence of phosphoryl chloride or with acetic anhydride in sealed tube.Fluorescence of Xanthomne and its Dei-ivatives. The fluorescelnw of the two nitroxanthones (2- and 3-) is rather unexpected as itl is generally found that the introduction of a nitro-group destroys the1 fluomscence (Ullmann A n w l e n 1907, 355 312). Still more striking is the fact that the d o u r of ths fluoreecenm is deeper in the case of the nitrscompounds. Thus xanthone shows only blue fluorescence( whelrelas 2- and 3-nitro-xanthone show greenish-blue and green fluorescence respectively. Very few di-derivatives o l a flnolrcacent substancel are found to1 be fluorescentl and of all the1 di-derivatives describeid in this paper, only dichloroxanthone is fluorescent. n’itroxan tholzea. Only four nitlra-derivatives of xanthone have been described.One (3-nitroxanthone) was prepared by Ullmann by condensing 2-c;hlorcr-4-.~itrobemoia acid with phenol (Anndert 1904 355, 341) and 2 4-dinitroxanthoine was prepared by Mayer (Ber., 1909 42 1132) by a similar method. The other tlwa (u- and P-dinitlrofxanthones) welre prepared by Perkin fT. 1883 43 1870) by the1 direct nitratioln of santhone with nitlrio and sulphuria adds. By a slighb modification of this methoid these compounds were obtained in a purer condition (T. 1916 109 746) but it4 has now been found that they can be preipareld from xanthone by tselating ib with nitric acid alone. As has been stateld xanthone diffelrs from anthraquinonel in its remarkable capacity for yielding nitIra-derivatives and the1 numbelr of these! has been increased from four to) fifteen and it is expected that many more can be prepareid without diffioulty.Two methods have mainly been employed, namely nitratioln and synt<hesis by Ullmann’s method (Zoc. cit .) . 3-Nitroxanthone which had prelviously been obtained only by synthesis has now been prepared by the careful nitratioln of xanthone. The othes three isomeric moiionitroaanthones have beein obtaineld by synthesis. 4-Nitroxamthovze is formeld whein salicylic acid and o-nitrophenol are heateid with acetio anhydride, but i t has not been possiblel to1 obtain tlhis compound by the con-densation of 0-chlorobenzoie acid with o-nitrophenol. The remark-able fact has beea observeld that nitroxanthones are! much mor 1058 DHAR A COMPARATIVE STUDY easily nitrated than xantqhone ikelf under t,he same conditions.Whereas xanthone give8 only dinitrolxanthonels 1 - and 4-nitlro-xan thone give tets anit'r oxantqhones and 2- and 3-ni t r oxant,hone give t8rinit,rolxanthones. As many as six te:t8ranitroxanthones have b,wn prepareid f r m lolwer nitroxa.nthones wit,h velry grelat ease. The orie8nta,t*ion of t,hesel telt'r a.nit8r occom p ou nds is still undelr invsstiga;tion but they have been distinguisheld from e a h othelr mainly by their bromination products. By t>his metho'd it has beeln found that thel al- and &teitranitrol-compounds are ident.ioa1, a8nd two of their nit,rol-groups a.re so stable tha.t t'hey are not removed by bromine even whea belated at 300° for twenty-six ho,urs (this vol. p. 995). Furt!helr nit'ratioln of some of them t&ranit;roIxa.nthones (ul- a2-? and P2-) has been a,t.te,mpted by boiling them with mixt8ums of sulphuric acid and fuming nitxio aoid in various proportioas but wi thou t8 su coess.A New Heterocyclic Type. Skraup's reactioa was utilisad by F. Mayelr (Ber. 1909 42, 3064) in order to fuse a pyridine ring on ta a thiolxanthone nucleus. He obtained thereby one thioxanthquinoline from 2-a;minot~hioxanthone but he neither studied this compound bhoroughly nor extended this relaction to any other melmber of the thioaanthona 'or xanthoae seriea. It was thered ore proposed to study this reaction particularly in the xanthone se~ies wihh the expsotation of obtaining a wries of tetracyclic compounds where1 one pyridine ring would bel uniteld with a pyroae ring together with tlwo belnzetne rings : co N co It will be see,n that the pyrone ring is protected on both side& by benzene rings whereas the pyridine ring is protected only on one side].Accordingly the respective1 stability of them pyrone and pyridine rings oan bei usefully studied IN THE It has beteln found, treateld with glyoelrol compound eixactly of ta8kee place witb such XANTHONE SERIES. PART I. 1059 as eispect8eld thatl an aminoaanthonel whe'n and sulphurio a,cid gives a heiterotoyclic thel type represented above. The reaction great readiness that i t is sufficient to use the nitroc instead of the amino-derivative. This naturally simplifies the1 syntheeis considerably and Dey and Goswavni (T., 1919 115 531) have noticed the1 same1 fact in similar syntheses in the coumarin selries.I n this way P-dinitlroxanthone gives nitrolltniiti~opzcinoliiz e. The utilisation of the othelr nitro+groap for fusing another pyridine ring to1 the already existing tetracyclio nucleus as well1 as the synthesis of this type1 of tetraclyclic com-pounds from othelr nitro-derivatives of xanthone are under investigation. d ciioii of Sodiunz Methox d e o n Sitroxnnthones. One1 remarkable relaction of the1 nit'roanthraquinoaes is the etase wit,h which a nitro group is displaceld by a methoxy-group. All the knowii dinitroanthraquinones have been converted into1 their correspondjng dimethoxy-compounds by boiling them with soldium methouide. Although xanthone bechaves like anthraquiiioneq in many important reactions i t differs entirely in this particular case.Nolnel of thel nitro-groups of a- o r @-dinitrosanthone is dis-placed by a methoxy-group when trelated with soldium metholxide, but the corresponding nitroxan thhydrols are produceld. Them substance8 dissolve in alkali hydroxide as well as in concentrated acids with distinctive colours. Colour in solutions of _- -_ - - -__L__ Substance. NaOH. H,SO,. HCI. HNO,. CH,'C02H. a-Dinitroxanthhydrol Yellow Deep yellow Yellow Pink Orange-red p-Dinitroxanthhydrol , Pale yellow - -Although xanthhytirol is quickly converteld into an ethelr these dinitroxanthhydrols dot not undergo this reaction perhaps because of the influeace of the1 nitro-groups. When boiled with mild oxidising agents they are convelrtsd into the1 origina,l nitro-xanth ones.Halogelintion. Three diffelrent methods have beeln employeld f o r the1 preparatioa of halogeln derivativm of xant'hone namely (1) direct halogen-at(ion ; (2) synthesis according t'o Ullmann's method (AnnaJen, 1907 355 359) and (3) direct displament of the! nitro-group by halogen 1060 DlIhR A COMPARATIVE STUDY Ch Zoroxanthon es. 2-Chlorolxanthoael was prelpareld by Ullmann (Zolc. ci,t. ; compare Ullma,nn and Wagnelr Annalen, 1910 371 388) while studying the condeasa,t,ioNn of 01-chlorobenzoic ac'id a.nd its delrivatives wit'h phenol 3-chloroxanthone~ was synthe'sised by Gombelrg and Cone (Anmailen 1909 370 142) by a. similar melthold and oct,a.chlo,ro-xanthone was prepa,re,d by Stediier (Monatsh. 1915 36 175) whilst stadying t'hel chlorinatio'n of cyclic kelt'oaes by means of antJmony pelnt,achlolride.It is proposed t'o study the1 chlorinat'ion of xa.nthoIne1 systema,t,ica.lly by ad1 the1 t8hre,el me8tlhods meat8io'ned abovel but a,t prelsent attention has mainly beea confined t o the second method by which all the1 poasiblel isomeric monochloroc xanthonea have! besen synt'hesiseld a ChlwinntioVn.-The direct' chlo,rinatdon of xant.hone has notl yet been casrield oiut syste,matically and the1 only melthold t.ha.t has been t'rield is by dissolving xamnt8holnei in a&io a,cid and passing chlolrine int.0 t,hel sodution using a trawl o f iodine1 as a ca,t,alyst. The produc.ts ase 3-0hlo~roxa.nthonel and a di,chZo.rolxarntholn.e ; the la,t'telr can easily be obtaine,d pure b,ut itl is very difficult' to remove t'he last tmces of it' from t.he formelr.UEZmtm's Synth.esi.s.-Of the four possible moao,chloro-x a,n t horn es 2 - and 3 -chl o'r o'xa n t<h one1 w elr e s y n th eeise'd b,y Ullni a nn and by Gomberg a.nd Conel respelctlvelly (Zoc. c d .) . The other two isolmerides havet now been prepareld. Bronmxan t hones. 5' r Omii~a~t,ioiz ,-JV hen x a.n thone in amtic acid solution is heateld with ojne molemlel of bromine and a' tmcel of ioldine S-bromo-xant,honei is obt,ained (Dhar T. 1916 109 745 ; compa,re A n n d e n , 1909 370 142) butl whe'ii conc,etnt8rateld sulphuric acid is used as a so$lveat4 instea,d of acet8ic acid thet prodmt is 2-bromolxantmhoael. Each of the,se brornohcompounds whe.n helat,e,d wit,h bromine1 passes elasily into the1 same1 dibromot-derivative and thelretolrel wheln a.slight e(xcelss oaf bro4minel is used in t'he preparation of a. molno-bromn-c,ompound dibromoxa,nthone is always formed. This is tlhe( maJn product of t'hel dire:& bromina,tioln otf xant,ho'ne when t,he opra.tJon is carried on under differentl. condit,ioNns and wit,h diffelrent oatdysts. One1 stxiking fact in connexian with tlhel direlott bromin-afio'n of xanthonet is that alt'hough xa,nt;honel is bmrominated in sulphurio acid solution by liquid b'rorninel it is nolt attacked by a mixtsre of potassium b,romide mid ptlassium b,romatel in sulphuric ac;id so1ut.io.n TN TI'EF XANTHONE SERIES. PART I. 1061 Synthesis.-2-Bromoxantlhonet has also been synthesised from oLchlolr otb elnzolic acid and p- bromo p helnol and 4 - br om ox an thone has been oibtained by a similar melthod.Direct Displacement of nTitro-grmp by Bromine.-By this method sevetral bromoxanthonels ha've beeln prepared. The met+hod serves as the only means of preparing certlain bromoc-derivativels, and there is a remarkable economy of bromine as the whole mount of bromine entws the nucleas. E X P E R I M E N T A L. Xanthone. One1 hundreid grams of salicylio acid whetn boileld with 100 grams of acetic anhydride and dist,illeld gave only 20 grams of xanthone (compa,re Graelbe Rn.nden 1889 254 280). The yielld wa,s not improved hy a.n increase in the amount' olf acetio anhydride1 or by extending the1 period of he,a,ting nor was' it. affect,eld a.pprecia.bly whea differmt samples od the1 ima,tesials we,ro used.It was how-ever raisetd to1 40 per ce'nt,. of t'hel sa,licylio a80id usetd by the1 addi-tioln of a molelcular proport,ion of phelnol t'o the mixturel. Thus a mixture of 50 gra;ms of sa*lioylic acid and 50 grams of phetnol, wheln b,oileld for six hours with 100 grams of amt'ic anhydride and distrilleld yielldeld 20 grams o t xanthoael. In a,ll t.helsel casm the yield is oxt-remely poior when no acetic aahydrida is employed and acet.ic a.cid has no ejffelct a't all. Whea o-acelto8xybenzoic a.cid is similarly boiled elit-her alone or wit.h acetic a,nhydridel it yiellds xanthonel elquiva'lent t'ol 20 per cent,. of its salicylic acid contentl. Mon omit r o xan t h ones . l-Nitro~xa.nthone.-m-Nit8rophe~no1 (1.6 grams) was dissolved in 20 C.C.of met'hyl alcohol1 contlaining 0.4 gram of soldium. 0-Chloro-benzoic a.cid (1.5 grams) was then a,dded to the1 solution and adso a tra.cet of copper powder. The! adcoho1 was emapora,td a,nd the dry brown substance began to soft'eln at ab,outl looo; the1 tempelra-t,uret o d the1 bat,h was raised tn l l O o wheln the1 cont,ents of the! vessed me(lted to a dark brown liquid which so~lidifield pa.r.tly at ab,out 140O. When cod the ccate,nts were powdereid and he,at-eld o(n a st8eta,m-ba,t.h fo,r ten miiiutels wit,h 15 c.c8. od concelnttra,t~eld sulphuric acid. Thei solution was cooleld poureld int'ot water and t.he precipita,tei co,ilect.e.d. The1 subst'ance orystdlised from a.lcoho,l in slendes bmwn needles mellting at 210° (Foand N=5*99. C,,H,O,N requires N = 5-80 pelr celnt.).It shows no fluolrescelnoe in coiicelnt,ra,teld sulphurio acid solut'ion, but givw a yellow d o u r o.nly 1062 DHAR A COMPARATIVE STUDY 2 -Nit rotxm tho n e .-p-Ni t r ophen 01 (4 * 2 grams) was dissolved in 20 C.O. of methyl alcolho3 and 0.7 gram of mehallio sodium was then a.dded to the solution. When i t waa clear 4.7 grams of 0-chlo'robenzoIc acid we're addeld and a trace o'f coppe,r powder was introduceld a's a' cat,alyst,. The alcohol1 wa,s e,vaporat8eld off slowly, aad then the telmpe,rature of the bath was raised very slowly tcr 14O0 when the orangebrolwn hard mass meIlt,ed to a viscid liquid olf the same1 colour. After some1 t,weat,y minut'es the colour began tto oha.nge1 and the liquid t'heln becamel convelrt'ed int,o a greyish-red jelly -1i kel substanc,eI.T he1 t,e'mper a tur e was very caatiousl y ra.iseld to 1 60° whe.n the1 dark-coloareld subst(a.nce1 solidified. The whole mass however bursts into flame1 a t about. this t,emperat,ure if more t.han one at'omic proportion of sodium is taken or i f the tempera'ture is raJssd sudde,nly. Tha substlance when cool was powdered and heat'ed on a ste'am-bakh with 50 C.C. of concentrated sulphuric acid for twenty-five minutes. The sotlution when cod, was poured int,o watec and t'he precipitate was collected (7 grams). The sub,stanm cryst.allised f ro'm alcohol in slender brown needles me31tling at 200° a,nd dissolving in sulphuric acid with a greenish-blue1 fluoreewnca (Found N = 5.56. C,,€I,O,N requires N = 5.SO per oe.nt.).3-iVitroxan,thone.-This was first prelpareld by Ullmann (koc. cit.) by the condelnsatkm of 2-chloro-4-nitmbenzoic acid with phelnol. It has however been possible' t o obtain this compound direlctly ,from xant'honel by nit,rat.ion in the folllowing way. Six g r a m o.f xant.ho,ne we're1 dissolved in 12 U.C. of conwntsateld sulphurio acid and 1.4 C . C . of nitric acid (D 1.500) a'ddd with shaking. Much heat was developd. The solution was kept over-night and then poureld into wat.er the1 precipitia8t,e (about 7 grams) being oollecteid and waaheld with water. Ab'out' 2 grams of the subst4anm which did not dissolve in alcohoil consisbid of P-dinitm-xan t,honei. From the1 alcohdi c s 01 u t,ion yelllow ish - whi te need l a were obtained which were found to conta.in tra,ces ot xa.nthone,.The nitro-compound was purified by furthelr crysta.llisat,ion from alcohol. Tra.ces of xa,nthone were found still to1 be assotdateld with it, and could b's relmoved only wit,h very gre8a,t difficulty because of the almo,st equal solubility of oach of these compoands in alcohol. On reduction tra,cm of xa.nt3hom welrel removed as this is in-soluble in dilutei hydrochloric ac.id whe,reias the1 amino#-compound was obtained as hydro:chlo.ride in tthel solutio'n. The1 frele amino-c.ompound isolatelcl by precipitation wit.h ammonia melts at' 232O (as given by Ullmann loc. cit.). 1Vhe.n 1 gram of 3-nit,rosaat.hoiie is dissolved in I0 C.C. o f con IN THE XANTHONE SERIES. PART T. 1063 centrated sulphuric acid and 5 C.C. of nit,ric a.cid (D 1.42) are added to the solution and the mixture kepb overnight a trinitro-xanthone is olb,t.ained.S-Nitr~~xant~hoInne dissolves in sulphuric acid wit,h it bluer fluorescence much st'ronger than that shown by xaathone itself. 4-Ni,trolxa3nn$hone.-A mixture of 50 grams of salicylio acid and 50 grams of o~-nitrophejiiol was boile'd with 100 grams of awtio anhydride for ten hours and t,hen dist,illed. Soma tarry matter pa'ssed over at a very high temperature. This was boiled with alcohol wit'h the additbon of anima,l chascoal a,nd from the filtra,te a.bout 2.5 grams of yellow needles were obt,a.ined melltJng atl 1 2 7 O (Found y= 5.71. C,,H,O,N requires N L= 5.80 per cent.). The mmpound disso1ve:s in sulphuric acid with a green colour and without fluorwcence.It is remarkable thah no xanthone c,ould be traced in the distilhte. At,tempts were1 ma,de to condense oLnitro-phenol witch o-chlorobenzoic a.cid by Ullma,nn's method but without' succe~s. Dz'nitrosan t h ones. This compound is deiscribed sub,setquelntly. a- and P-Dinit,roxanthoaes are ordinarily obtained by nitrating xanthone wit'h a mixture of nitric and sulphuric a,cids. They have also been prepared by nitrating xsnthonei wit.h fuming nitric acid alone. When 2 grams of xanthone are dissolved in 5 C.O. of nitric a,cid (D 1.500) and the solution is helatsd on a water-bath for ambout ten minuteea fine neeldlee oif P(or 2 7)-dinit.roxantmhone prec cipit,ahe and from the solution a-dinitroxanthone is obt,aine:d by precipit,ation with water a,nd purification with nit'ric acid.Similar r-ults are obtained with welaketr nitric a.oid (D 1*42) but t.he quant'ity of acid shofuld be proportionately grelater namely 10 c.c. for ea.ch gra,m of xanthone and the) mixture should be heated for about three hours. B(or 2 7)-Dinitrox~ntho.ne.-Onet gram of 2-nit,roxa8nthone was dissolved in a cold mixture of 25 C.O. of nitria acid (D 1.42) and 25 0.0. of conceatrat(ed sulphuric acid. The solut'ion was kelpt overnight and t,hen poureld into water. The yellow precipitate (1.5 grams) was collected and crystallised from nitrio a.cid when i t was obtained in whik needles melting at 254O. When mixed with 2 7-dinitroxanthone (m. p. 262*) i t mellted a t 254-260' (Found N = 9.79. Cab. N = 9-81 per .miit.). From the nitric acid filtmte a trinitroxanthonne was oIbt,aineld (see below).2 4-Dirfl.it~oxnnthome.-Thie componnd was prepared by Maym (Zoc. cit.) by the oondensation of sodium phsnoxide and 2-chloro~ 3 5-dinitrobenzoia acid. It ca,n also1 be1 prepared by condensing 2 4-dinitrophenol with 01-ohlorobenzoic acid in the following way 1064 DHAR A COMPARATIVE STUDY 2 4-Dinitrophe'nol (1.25 grams) and so,dium (0.17 gra,m) are dissollveid in met(hy1 alcohol (20 o.o.) a,nd to the olea,r solution o-chlocob,elnzolio acid (1.2 grams) and a t.race olf copper powder addeld. After eivaporamting the a81c.ohoNl t'he ye'llo'w residue mellts pa.rt!ly ah 160' and solidifies in a fe'w minutes. It is aolole:d, powdelred and helat,ed again to 160' wheln i t mellts and reaolidifiels as befo,re.This proloess is re,pelateld ab,outl ten t.imes when the condelnsatioa is compl.e8tel and t,he substance doss not mellt on heat ing t'ol 160O. If the temperature of the bahh is raiseld with the1 vietw of co~mpleIting the1 rea.ct.ioa in one1 olpelra'tion the whole mass suddenly inflamee. a,t a.bout. 200' without melting. Aft,er the mmpleItion of the condensathn the1 powdelred substanw is he.a,t'ed oin a st,elam-b,ath witch 20 C.C. olf concentrated sulphurio acid for fift,een minut,es. Whea co,ol the solution is poareld into1 wa,tes and t'hel pre8cipit,attel is collecteld . The substlance whe.n decoflorised witb animal charoolal in alcoholic solutlioa crystallism from t,his soJve.nt in yelllow nesdles melting atl 206" (Fomiznd N = 9.91. Calo. N = 9-81 per cant,.), l'ri?z:'t.ro xan t homes.2 3 7-T&nit?-oixan~t h0n.e .-When 2-nitroxantmhonel Wafs nit'rate,d (see &ow) 2 7-dinitmroxanthone was the first product and fromm the nitaria acid filt,rate a yellowish-whiter precipitla,te! was obtaineld by a,dding wa;t.elr. Aftlelr b'eling boiletd with alcohol1 to1 remove impuritJes it melteld a,t 205O (Found N = 12.74. C,3H,0,N, reiquirea N'= 12.63 per cent.). The same1 trinitroxa,nthone was obt,ained when 6 grams of 2 7-dinitroxmt~ho~ns were1 dissolved in 50 0.0. of c,oncelnt>ra,t.eld sulphuric a,cid 1.2 O.C. olf nitria a.cid (D 1.500) addeld aad the solut'ion was he1afe:d on a watsr-batlh fo,r twelnty-folur hoars. The unohangeid dinitrot-oompound was cryst'al-l i s d from nit,ric a,cid and collected and the filt,ra;tei on ooacentra-tion ga,vve yellow needlea melting a.t 205'.This cojmpound was a,lsoi obt,a.ineld by nitra,t'ing 3-nitlroxantlhoae8. Bimitromon oa.mirz oxan t hon e .-T hel trinihr 01-compound w a6 reduced wit'h a.lcolho3ic ammoaium sulphide a,nd the product separafed from alaohol as a dark brown po'wdeir mellt,ing and decomposing a8t 230' (Foand N = 14.55. D initrolzant h olnea'z 01-/3-n aph t h 01 .-T he1 dinit r oaminoxa.nt.hone1 was dia,zotised in the usuad way and coupled with P-naphtholl. Thel a.zo-compo1und separate6 from. aloohol as a dark red amorphous potwdelr meltling at' 370° (Found N = 12.25. C,3H,20,N requires N = 12.28 pelr cent.). C,,H70,N relquires N = 14.43 per uent.) IN THE XANTHONE SERIES. PART I. 1065 Trinitrolxarithone.-Twol grams of xanthoae were dissolved in 7 C.C.of conaelntrahd sulphurio acid wit,h the1 aid of heat and 2 C.C. of nitric acid (D 1.500) addeld to the cooled solutioin. The lattelr was the11 kelpt over the &earn-bath wheln a copious pre-cipitatel appelared in a few minutes oonsisting of yelloiw glisbning needlea which were filtered through asbestos and washed with dilute nitrio acid and finally with water. The1 substance dissolves freely in cold nitric acid (D 1.42). It melts a t 225O and is not i den tti ca 1 with the t r i n i t rot- c om p oun d p r eviolu sly m ein ti o iietd (Found : N = 12.72. Cl3H,O8N3 relquireis N = 12-63 per celnt.). Dinitrom uoz oiamino xanth o n e .-T his was ob t ainetd by reducing the trinitro-derivative with aloohollic ammonium sulphida in the usual way.It was obtained as a yelllow powder melting at 290° (Found: N = 14.47. C,,H,O,N requiree W = 14.43 peir cent.). T e tranityoxaot t hones. l-Tetmnitroimmthone.-This compoand was oIbt8aine,d by dis-so'lving 0.5 gram of l-nitlro~xa.nthons in 5 0.c. of concent,ra;te.d sulphuric a.cid and adding 2.5 C.O. of nit*ria acid (D 1.42). The solution oa keelping o~vvernight depo,sit'ed yellowish-whitsel nseidles me~lting af? 250O. It is elvideat~ly different from al- %- or &-tqetrajnit8roxanthones which do1 nost melltl a t 300° (Found : N = 14.64. C,,H,O,,N requires N = 14-89 per celnt,.). 4,-T e t ra,nilt rolxunt h one .-Half a gram omf 4-iiit.ro'xa.nt,h~llet was dissohwd in 5 C.C. of conoentlrat,eld sulphuric acid and 2.5 C.C. of nit'ric a,cid (D 1-42) were t3hsn added gra,dually with shaking.At t,hel firstl a,ddition olf nitlrio a,cid a. viojlentl re,act.ion ensueid a.nd the reaction veasel was cooled. After keeping the mixture for a fe'w days a reddish-yellow precipit4ate wa.s obtaineld which did not meilt at 300" (Foand N= 15.32. C,,H,O,,N require's N =14*89 per cent.). 4,-Te tranit ro,xan,t home .-When the1 fi1t.r a tie from the nitr 01-mm-pound dacribed aboIvve was a,ddeld t,ol watw the're was obt'a.ineld a brown polwder whioh c.ould not be1 cryst,allised from alcoho'l, benzene or nitrio acid. It melts and de1compose.s a t 200° (Found: N = 14.70. CI3H4Ol0N4 relquirems N = 14.89 per cent'.). a,- Te t r m i tmxan t hone .-Thir tsen grams of a-dinitr oxa#nthoae were a,dded t o a mixture1 of 150 C.C.of co~iment,rated sulphurio acid a.nd 150 U.C. off nitric acid (D 1.42). The mixtnre wag heat.ed on a stelam-ba,tqh when a deas solution was obt8aJned in a few minutes and shining yellowish-white c,ryst,als (10.7 grams) separated in about ~x hoars. Theeel did n o t melt a,t 300° (Found N'=14.79. C131~,01,N4 relquires M = 14-89 pe'r cent.). This substanw whe 1066 DHAR A COMYARATlVE STUDY helat,ed wit.h bromine1 and a t)race of iodine in a seialed tube gives dib~romo~dinitro~xa8nthone (m. p. 265') (see this vd. pp. 998-999). ~-Tetra,nitroea,n.tholrLe .-From the1 fi1t.ra.k frolm tho precelding compound cryst,als in the form olf broke'n plafes were obtained by adding watelr. They a.lso do nob medt a t 300° (Found: N = 14-69. C,,H,O,,N require6 N = 14-89 pelr oentl.).This subst,ance whelii treahd simihrly with b'rominel gives a tat8rab,romo~xanthme (m. p. 255'). P2-Tet;mstitroxa,ntho.ne .-Tea grams od 2 7-dinit~ro~xantho~e were a,dded t'o a& mixture of 150 C.C. olf c:oncelntrateld sulphuric a'oid a.nd 150 0.0. of nitric a,cid (D 1.42). The mixture was heiat8eld fo!r about six hours wheln bright yellowish-white crystals (9 grams) wetre precipit,a,t.e<d. The c.ompoaad was found to be identical with a1 - tletr a ni tar olxa 11 thonet as b o'th these1 substlaac:es g a8vel the same d ib r omoldi ni t r olx a n th o 110 when t mat ed simil a,rly with bromine. From the1 filtrate 3.5 grams of shining white b'rolken plabes were olbt.aineId which did n o t melt at 300" (Found N=14*69. C,,H,O,,N re,quires N = 14.89 per Gent.).When this substiamnce is heate,d with bromine exa&ly in t,ha same1 way as the1 other tet.ra.-nitro+compounds a helxabromoxanthone is obta.ineld which melts at 28'5'. Slz ra up's Sym t h esis w .i t h Din it r oxa1n t h owe . Three grams of 2 7-dinitIro.xa,nthonei were dissolveid in 5 C.O. of concent,rated sulphuriu acid and 12 C.C. of glycelro3 addeld. The additioln of the lat,ter precipita,ted the nit,rcE-compound. The mix-tlure was heatteld in a paraffin-bsath and act about 140' it began to froth whe,n the flask was shakea and tho tempelrature lowereld t o l l O o . Heating was continued folr four hours at about 120° and then for a further two hours at about 140° when a se:mi-sollid rna,ss resulteld. This was then hegateid f o r a further three hours untlil tbe bla,ok mixture became solid.The ma'ss was polwdelred and t'hhs crude product boileld wit+h water and filtered. The filtrate on being rendered alkaline gave a,n orange-red colloidal prelcipitate, which sehtled on keeping otvelrnight. a,nd was collected. The sub-stlance separa,teea f rom alco,holl as an ora.nge-red po,wde,r whioh sintms a t 200° and rnelte a,t 205-210' (Found N=9*75. C16B804N2 requirea N= 9.59 pelr mnt.). The substance dissolves re.adily in aloo,hol acids or exoefss of alkali hydroxidel Dl THE XANTHONE SERIaS. PART I. 1067 Santhhydrols. a-17)i~~itroaat~tl~~~y~~~~ol.-a-Dinitro~antho~ie (2.5 grams) was suspelnded in 100 C.C. olf methyl alcohol and 1 gram of sodium added in small pieces wit-h shaking. The colour of the mixture became first! orange and finally deep reld.It was boiled under relflux f o r half an hour when a char dark red solution was obtaimd; the boliling was continued f o r a further pelriokd of one and arhalf hours and the solution filtered hot. A yelllowish-brown precipitate was obtained on acidifying the solution with hydror chlolric acid and this crystallised from acetic acid in brown needles melting a t 185O (Foand N = 10.11. C,,M,O,N requires N=9*72 pelr cent.). The substance dissolveis in alcolhol and in cold dilute alkali hydrolxide in the latter solvent with a yeillow colour. Its solution in concentrated sulphuria or hydrochlorio acid is pale yelllow and in nitric acid it dissolves with a pink colloration. When helateld with glacial acedtic acid it dissolvea to an orange-red solution.@(or 2 7)-DinitrolxainthhydroZ.-This substance was obtained by trelating 2.5 grams of 2 7-dinitroxanthone with sodium and methyl alcohol as in the1 case of the1 a-dinitro-compound. It crystallised from alcohol in slelnder yeillowish-white needles melting and deem-posing at 196O (Found N = 9.65. C,,H,0,N2 requires N = 9-72 per cent.). The substance dissollves in colld aqueous alkali hydr-oxide as well as in concentrated sulphuric acid with a yellow coloration and in concentrated hydrochlolric acid to a pale yeillow solution. Each of thdse dinitroxanthhydrols when boiled with a mild oxidising agentr such as al dilute solution off hydrogea perolxide or potassium permanganate is converted into the corresponding di ni t r olxaii t hone.Chlwoxamt hones. 1-Chloroxantholne.-o-Chlorobenzoio acid (1.6 grams) m7chlore phenol (1.4 grams) and sodium (0.4 gram) were dissoflveid in methyl alcohol (10 c.c.) a trrace od cotpper powdelr beling added as a catalyst. The solutioln was heateld o n an oil-bath and the alcohol evapolrated when the1 substance medted a t about 200° and solidified a4t abolut 215O. It was cooleld powdered and belated on a steam-bsahh with 15 C.O. of coacentrated sulphuric acid f o r fiftelen minutee. Wheln cool the solution was poured into watelr and the pre-cipitate oolleoted. The substance crystalliseid from aqueous alcohol in whit0 neetdles melting a t looo. It dissolves in sulphuric acid with a green fluorescence. I n this synthesis elither 1-chloro 1068 DHAR A COMPARATIVE STUDY xanthone or 3-chloroxanthone or both may possibly be Polrind but only one produck was obtained.As it differed from 3-chloro-xanthone which melt a t 130° i t must be l-ckZolroxmthowe (Found C1= 15-46. l-A.n/iZ~~olccamth~ne.-One gram of the substance desuribed above was boiled with 3 C.C. of aniline and a trace of copper powder for six hours. A blue precipitate1 was obtained by poluring the solu-tion into water acidifisd with hydrwhloria acid. After being purified by extraction with alcohol it melted at 120-125° (Found : N,=4.86. C19H130,N requires N =4.87 per cent.). 1 -Ch 2orolt et ram i t r ox an t h o n e -H a1 f a gram of 1 -chlo r ox an thone was dissolved in 7 C.C. of concentrated sulphuria acid and 5 C.C. of nitria acid (D 1.42) were added to the solution with shaking.The solution wa5 kept overnight when white needles were obtained which melted at 195O (Found N = 13.70. Cl,H,O,N,C1 requirw N=13*69 per cent.). From the filtrate a white pre-cipitate was obtained which was to^ mall in amount for any detailed amination. Z - C ' ~ Z ~ ~ . ~ ~ ~ . n t ~ ~ ~ e . - ~ - C h l ~ r o F h e n o l (1 *4 grams) was dissolved in methyl aloohol (10 C.G.) and sodium (0-4 gram) and ol-chlorobenzoic acid (1.6 grams) and a trace of copper polwder were added to t$he solution. The alcohol was evaporated and the viscous semi-solid mass was heated to1 140° and kept at that temperature for half an hour when it darkened. It dried to a blaok solid mass a t 150O. The temperature was further raised to 200° and then the substa;lice was cmld powdered and heated on a water-bath with 15 C.U.of concentrated sulphuric acid for fifteen minutes. When cool the solution was poured into water; the precipitate was wlled,,ed crystallised from alcohol and obtained in white needles melting a t 165O (Ullmann Zolc. cit. givee 171O). It dissolves in sulphuric acid with a blue fluorescence (Found C1= 1 5 7 2 . Calc. : C1= 15.40 per cent.). 2-ChI~otetr~~trolxamth.one.-This compound was obtained by ni tlrati ng 2 -chloroa an thonel with concentrated sulphur ic and nitric acids. For each gram of substance 10 C.C. of sulphuric aoid and 7 C.C. of nitria auid were used. The substance was obtained in slender yellowish-white needl63 melting at 205O (Found N = 13.75.C,,H30,,N,C1 requires N = 13.69 per cent.). 4-Chtorolx~n.tho71e.-This substance was obtained by the con-densation of a-chloaolbenzoic aoid with o-chlorophenol in the manner dmcribed in the syntheses of l-chloroxanthone. It crystal-lised from alcohol in slender whib needlee mdting at 130O. It diwlves in concentrated sulphuric acid witqh a green fluoresmnce (Found C1= 15.36. 4 - C ~ Z ~ ~ t r i n c i t r ~ x a n t ~ ~ ~ n e .-This compound ww obtained by C,,H70,C1 requires C1= 15.40 per cent.). C13H,0,Cl requires C1= lii.40 per cent.) IN THE XANTIIONE SERIES. PART I. 1069 ni ttr a.tdng 4-ohlor oxanth one' w i t.h concedr ated sulphuric a.nd ni trio acids. Fo'r eNalch gram osf the! subst,anm 5 c o . o,f sulphurio acid and 4 0.0. od nitric acid weire used.IBrolwnish-ye8110w nwdles were obt'aineld on keeping t*hel relaction mixture overnightl. The sub-stlalncce melts a,t 235O (Fo'und N= 11.14. C13H403N3Cl requires N=ll.49 per cent.). 4-Chtwol&mits-oxanthone.-This substance was obtained from the filtrate of t'he tlriiiitmro-mmponnd as a' pale yellow powde,r melting and decomposing at 195-200° (Found N = 8.81. C,,H,O,N,Cl require8 N=8*73 per cent.). Dic htorolxm t home .-Xa,nt hom (7 * 5 grams) was dissolved in metic a8cid (50 o.c.) wit'h the aid of heat. A current of dry chlorine Wacs passed int'o tqhel sdutioln which was kept wa,rm by heafing t'hei relaction ve'ssetl ovetr a st,ea,m-b'ath until approximat,dy one molecular proportion of chlorine was absorbed. A trace oC iodine was use'd as a ca,talystl.The1 product (10 grams) crystallised fro'm a.lcoholl i n slelnde:r whit'el nesdles mellting a t 225O (Found : C1=26*86. C,,H,O,Cl requires C1= 26.8'0 per cent.). The sub-stance dissolves in conce.ntra.ted sulphuric acid witah a' strong green fluo,re,scenwl. From t'hel a.lcoholia filtra.tle from the dichloroxant8honel anothelr product mixed with it was obtained which a.ppa.re,d to be 3 -chloroixant8ho~ne f rorn it,s mellt,ing point and chlorine1 contelnt bcut it has not yet been polssiblel to1 purify itl c:o,mpletely. D.icl~toro~~~Lit~ollt.antjLone.-The dichlo~ro~conipound was nitrated in the cold with a mixture) of equal volumes o,f nitric (D 1-42) and coaceat,ra.teid sulphuric a,cids (180 0.c. foil- e.ach gram of t~hei sub-st4aiicel). On ke,eping thel solutiion o,ve:rnight, yellow iieeldles weire obt,ained which mellted at 240° (Found N = 8.10.C,,H,O,N,Cl, retquiree N = 7.88 per cent'.). Bronzozanthon es. 2 -Browzolxaaz t h0.n.e . -p-Bromopheno81 (2 * 5 grams) and sodi um (0.6 gram) we:re dissolve'd i n methyl alcohol (15 c.e.) and o~-chlcm-beinzcic acid (2.3 grams) a.nd a trace of copper polwdelr were added to1 the1 solution. It was helat.ed to1 160° when a hasd blaok mass was obtlaineld. The1 t,emperatturel was raise'cl to 220° but the1 sub-sta.nce did not4 fusei. It was cooled po,wdelreid and helated aver a steam-b,a,th with 25 C.C. of colnoentrated sulphuric acid f o r twenty-five minutee. Whea OO~O;~ the solution was8 poured into! wat.er a.nd the preicipit ate; colle.ctied. It cryatallised f rojm aqueous alcohol in brown needles melting a.t 150° and dissolveld in sulphuric aaid with a yelllow colour but.no fluoresoelnoel (Found Br = 29-00. C,,E,O,Br retquires Br = 29- 16 pelr aent,.). 2-Bromoxant,hone 'is also1 ob,tained when xantho,ne is b'rominated in concentra.h 1070 DHAR A COMPARATIVE STUDY IN THE XANTHONE SERIES. sulphuria acid so3ution with bromine! and a' trace olf ioldinel. It is vezy difficult, however Log isolatel the1 substance in at pure oondition, because the last. traaes of eithelr xanthone or dibrolmoxanthone, which a.re a,lwaysl assoc,iated with this compound cannotl easily be rmnoved . (0 - 7 gram) was dissolveld in c,oncelnt,ratad sulphuria acid (1 0 c. c .) and nitric acid (5 C.C. od D 1-42) then addeld gradually t'ot the! solutioa with shaking.No precipit'ats was formeld a,ft,er keleping it. for a few days. The solution wa's poured into1 watm and the1 pre,cipit,ate was boiled with alcohol in which it pastly dissolved. From the alcoholia solution the subst'ance was obtained in slender brown neodlee melting a.t' 210° (Found N = 12.02. C13H3010N,Br requires N= 12.31 pe'r mat.). 2-Bromo-~-tetra/nitro~xamtho~ne.-The residue of the nit,ro-com-pound describe.d abo'vve wa.s dissolved in benzene a,nd cryst?allised from this solution in brolwn needles melting at 270° (Found: N'= 12.21. C;,H3OloN,Rr requires N= 12.31 per cent-.). When 2-bmromoxa.ntthoner w8.s hela.te8d with bromine (1 or 2 molls.) in aceltic acid solut,ion and a tram off ioldinel oves a sa#nd-b,ath a dibromo-aompound was ota.ined which melt,ed atl 212O. This colmpound was identified as 2 7-dib,ronioxa,ntlhone by the1 mebhod of mixed mellt,-ing points. It is also olbt8a,ined by brominating xanthoine with bromine using iron filings as a catalyst,. 4-Brom.ox~;rt.tho~ze .-This compound was ob,t'ained by condenaing o-bromophelno'l wit'h o-chlo,robe,nzoio a,cid in t4hei usual way. It crystallised from alcohol in greyish-whits needles melting a t 140O. It shows no Auorescenm in sulphuric acid s,olution (Found: Br = 29.28. C,,H70,Br requires Br= 29.16 pe,r cent.). 4-Brom~in~itro~xa~thone.-4-Brorno~xant~honel was dissolved in the requisite amount off concentlramte:d sulphurio acid in t'he c,old, and nitric acid (D 1.42) was addod to the sodution (20 C.C. fo8r elach gram of the substance). On keeping the solution owrnight, yellowish-white ne'eldles were1 o,bt&ned which melted at 295O (Found N = 8.09. 2-Brom.ol- a-t e t mni trosant h on e . -2 -Br omo~xa~nt,ho~n.e C,,H,O,N,Br requires N = 7.67 per cent.). The author takea this olpportunity off elxpressing his thanks to Prolfessor J. F. Thorpe and Dr. M. A. Whitelely for their kind encouragement and to the Van't4 Hof? Memorial Fund Committee and to1 the Chemiclal Society for Reselasch Grants whicfh met4 part of the1 expensels. IMPERIAL COLLEGE OF SCIENCE AND TECHNOLOGY, LONDON. [ R t ~ ~ i w d ~ .J217?/ 12th 1920

ISSN:0368-1645    

DOI:10.1039/CT9201701053

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

PRICE AND DUFF COMPLEX METALLIC AMMINES. PART IV. 1071 CXTX. -Complex Metallic Amrnines. Part I V . cis-Sulphoacetato- cis- Methionato- and cis-Dimeth yl-rnalonato-diethylenediaminccobaltic Salts. By THOMASLATER PRICE and JAMES COOPER DUFF. WERNER (Annalen 1911 386 79) has shown that complex eobaltc ammines containing the malonato-radicle are easily prepareld but he was of the opinioa (ibid. pp. 26 81) that complexes contain-ing a higher numbelr of atoms to the ring than six could not be obtained. Price1 and Brazielr (T. 1915 107 1367) showed how-evelr that wheln a sulphur atom forms one of the components of the ring an eight-ring oan be obtained and were successful in preparing cis-sulphonyldiacetatodiethylenediaminecobaltic salts. The part played by the sulphur in enabling such compounds to be isollated is not clear.It may be that the presence1 of sulphur in the acid radicle elnableld ring-formation to1 take place] readily o r it may be that the compounds could be isolated because they were readily obtained in the crystalline form whemas the attempts by Werner t o obtain productqs containing the succinato- and other radicle3 only gave rise to uncrystallisablel syrups olr glasses. It was therefore] of interest to1 investigate1 the behaviour of other dibasic acids containing sulphur and the prelsent communication details the results obtained with sulphoacetic acid, SO,H*CH,* CO,H, and with methionic acid CH,(SO,H), both of which give rise to crystalline compounds. I n a previous paper (Prim and Brazier T. 1915 107 1713) it has bmn shown that malonic acid forms an additive compound with dichlorodiethylenediaminecobaltic hydrolgeln malonate namely, [Cl,Co en2]HA,H2A where H,A = CH,(CO,H), but that the1 sub-stituted malonic acids do1 noli give rise to suoh additive] compounds, and a tentatlive explanation of the results obtained was advanced.It was therefore of intelrest to ascertain whether ths substituteld malonic acid residue could be introlduced into the cobalt complex, giving compounds similar tol the malonato-compounds or whether some such steric hindrance1 as is postulated in the aforementioned paper prelvented their formation. The first elxperiments were made with dimathylmalonicl acid and we have been successful in prefparing dimethylmalonatodiethylenediaminecobaltic salts.The other suhtituted malonic acids have not yet been investigated but owing to the fact that one of us (T.S.P.) is taking up other duties, i t is considered advisable to publish the results hitherto obtained.* * These researches are being continued by Mr. Duff (T.S.P.) 1072 PRICE AND DUFF: The fa& t*ha\t! the! dime#hylmalonio a.cid residue oa,n be introduceld into the nucleus dwls not necasa.rily inva(1ida.t.e the eixplanatioln giveln previoiisly of tahe f oIrma,t,ion of a<dditJvel CompoIunds sinc.el as will be seetn in the1 experimeat,al part' a higher t,elmpeNraturel than the ordinasy was used wherelby the formation of a ring complex may be great.ly f acilitated. As will be seleln lactor sulpho8a,ce.t,io and methionio acids dot noit f om a,d di tive c olm p ounds with their dichlor o'dielt'h y 1 eln ediamine -cob'altiic acid salt's thus diffeiring marke,dly from t8he,ir analogue, malonic a,cid.No1 eixplanation od this is offelred a t present, since furt.her work is necessa,ry. E X P E R I M E N T A L . cis -S?i 1 ph oa c e t a t otdi e t h y ten ediamime c Obd tic Snl t s YX where To obtain the bromide YBr 5 grams 0.f carbo.na,todielthyle,ne. diaminelcob~altdo b,romidel were disso,lved in 80 C.G. 02 warm water, and a mlutdon of 2.19 grams of sulphoacetic acid in 20 C.C. of wa.telr was added. Eva,pocation o,f the mixeld slolut,ion on t h e wateIr-b,atlh tlol a small bulk only resultleld in a very poor yielld of crystals. It was foiund best to heat the1 solut'ion aft\er tahe evoilu-t6oln 0.f carbosn dioxide ha.d slackeaeld in a.cloaed bottk a t 1 0 5 O for four hours and t'hen evaporate to sma,ll bulk oln t,he wat.eir-ba,th. After remaining in t,hel ioe-chest ovelrnightl t'he anhydrous bromide separated in sma,ll carmine-red plates whioh were colllected and waahed with wa8tlelr and alcohol. The1 yielld was 2.4 grams but a furthelr sma,ll qua,ntity was obt,aineld by eva,posath of t,hel filtrato (Found Co = 14.87; Br = 20.08. C6Ml,0,N4BrSCo requires Col=14*85; Br=20.15 per cent..). The nitrate YNO, was obt,a.ine,d in brick-red elongated plates by preicipit,a,t.ing a solution of 2 grams of t,hel bromide in 50 C.C. otf water wit.11 tlhe elquiva,le.nt< quantity (0.86 gram) ocf silver nitgrate. A f h s shaking fomr olnel hour the silver bromide wa.s c,ollelcted aad the filtrate1 evapora,t,ed t o low bulk on thei wate,r-ba,th.The c,rystals of the n i t r a b separa,ted slolwly osn keeping in. the icechest. Yield, 0.8 gram (Folund Ca= 15.39 ; N = 18.24. C,H,,O,N,SCo~ relquires Ccr= 15.56 ; N = 18.47 per wlntj.). The thiocyanate YSCN was obtained by adding 1-5 grams of solid poitma.ssium thiocyma,ts t801 a satlurateid soilution oolntaining 3 gra,ms od the b,romidel. The pot<assium t'hiooyanate dissolved, and aft$e(r leiaviiig overnight in tihe1 ioe-clleisltl rnicrosaopic brick-red orysta,ls of hhe oomplex thiocyanato separated (Found Co= 15.62 COMPLEX METALLIC AMMINES. 1073 N = 18.91. C7H180,N,S,Co requires Cot = 15.73 ; N = 18.67 per cent.). The platinichloride Y2PtC1, was prepared by filtelring a satura'tted sollution containing 2 grams of the1 bromide1 into a 5 per cent.sollutioln of chloirolplatinic acid. Mioroscopie pale brolwn crystals slolwly sepa,rated ; these were collected after two1 hours and washed with alcohol and ethelr and dried in a vacuum desiccator [Found Co = 11.11 ; Ptl= 18.95. (C,H,,0,N,SCo~),PtC16 require6 Col=11*32; Pt=18.72 per cent.]. The hydrogem sulphoaceta*te YSO,*CII.I,*CO,H was obtlained by dissolving 6 grams of the carbona>to-bromide in 120 C.O. olf wahr and shaking t'hei cosoled solution with 4 grams of freehly prepared motkt silver oxide for half an hour. The product was then filtered into an aqueous sollutlion of 5.25 grams olf sulphQacetio acid the proportions being two1 molecules of the acid t o onel of t7hel carbolna8tol-base.The resulting sollutioln was evaporated to low bulk on the water-bath and after keleping ovelrnightl in the iceohest deposited microscopic pink crystals which dissollve readily in cold water. Yielld 2.8 grams (Found Co= 12-79; N = 12.33. C,H,,O,,N,S,Co requires Col= 12.93 ; N = 12.28 per cent.). &-He t hionat odi e t k y Jew ed iantin e colb aJ t i c SuJ t s Y X where The bromide YBr,2H20 was only obt.aineld after severad attempts had been made to prepare it from t'hhe aarbonatol-bromide according to the methold used by Price and Brazier in making sul p holn y 1 di acetat old iethy 1 enediaminecobalt ic cit . ) . It was found that on mixing solluticms od the aarbolnah-bromide and methionic acid in equivalent quantities and elvaporating on the watw-bath pink microscopic crystals sepa,rated in inareasing quantity as etvapolratdoln proceeded.These crystals howelver con-tained no brominel and were lafer identified as t'he methionab methionate (Found Ca= 13'20). On furtheir elvaporatlion the molther liquor gave no1 crystals of tlhs bromide a syrupy liquid resulting which contained some unused carbonatrocbromide. To avoid this forma,tiolii od the methimake it was fonnd best to1 dis-sollve 5 gra4ms of the1 carbonate-brodmide in 120 c . ~ . of watar and add a solut'ion of 2-73 grams of melthionic acid in 40 0.0. of water. The whole solution was then well boiled f o r twently minutes keep-ing the volume a t a b u t 150 C.C. by tlhe addition of boiling wa,ttelr.* After eva\poratling the resultling solution on the water-bath to low * This method of treatment hits already given successful results in the case of succinato-compounds which will be dealt with in a later paper by one of us.bromide ( Zolc 1074 PRICE AND DUFF: bulk and keeping for two days in the imchest t,he pure methiona,to-bromide seprated in purplish-red plateses which were collected and washed wit,h water and aleofhol. Yield 1.4 grams [Foand Col=12*50; Br= 17-02; S= 13.28; H,O (a.t looo) =7*74. C,Hl,06N4BrS,Co,2H,0 requires Col= 12.57; Br = 17.04; S= 13-64 ; H20 = 7.68' pe'r ce~~t'.]. The nitrate YN0,,21120 was obtla,ined by sha,king fo,r one hour a solution of 3 grams of t,he hydrated bromide in 60 c.c. of wa,t'elr with the equivalent qua.ntity (1.08 gra,ms) of silver nit,ra;tel. The silve'r bromide was thea collected and tbe filtrate evaporabd t,ol 10,w bulk on the wa,ter-bath.After keeping for sewral da,ys in the1 ice-chestl t'he nitrak separateid i n carmine-reld edongated plabs. Yield 0.5 gram [.FOUi1d Co=13*42; N=15*76; H,O (a.t l l O o ) = 7.94. C,Hl,0,N,S2Co,2H,0 requireis Coa = 13.08; N = 15.52; H,O = 7-98 per cleatl.]. The thiocyanate YSCN was prepared by adding 1.5 grams of solid pot,assium tbiolcyanate to1 a sa,turat,e.d solution od 3 grams of t,ha methionato-b,romidel. After keeping overnight t.he complex thiocyanah separa,ted in microscopio dark red crystads (Pound : Co= 14.68; N = 17.40. C,H,,O,N,S,Co requires Co = 14-35 ; N = 17.03 per cent.). The pZatinickZsridc Y,FtCl, was ob,t,ained by filtering a saturated solution of the methionat,ocbmromide into a 5 pelr cent.solution of chlotroplattinio aoid. Microscopic light brown cryst,ads rmdily separated which were washeld wit3h alcohol and ether and dried in a vacuum dwiccattlor [Fojund Col= 10.34 ; Pt = 17-83. (C,Hls06N4S,C'ol),PtC1 requires col= 10.58 ; Pt = 17.52 per centl.]. The hydrogen melt,hionate could notl be obtaineld although the same meithold was used t,ha.t has alwa,ys been successful in similar C,ILSW. Wheln two molelcular proport.ions of methionia acid in solu-tion were mixed wit.h one of t,he ca,rkronatol-baset the crystah which separated on evapolra,t.ion always proved to ba the normal methionah. When this was dissolved in a boiling solution of metthionia ac,id o'nly the1 unchangeid saltl separated on e,vaporation.The normal metkiomte CH,(SO,Y), was prepared by dissolving 7 grams (2 mols.) of tlhe casbolnatol-bromide in 120 O.C. o f warm water shaking for half an hour with 3.8' grams of freshly pre-pared silvelr o,xide a.nd filtering from t'he silver bromide into a solution mnt,aining 5.78 grams (3 mols.) of methionia acid. The mixed solution was t,hen evapora,M to lolw bulk on the water-bath. Complelh separation of tths normal me,thionate in pink, microlsoopia aryst.als only omrreld when a' little water was a,dded to the resulting syrup and the whole well stirred. The1 yield was 7.3 grams. The salt is almost insoluble in cold wat,er b,ut dis COMPLEX METALLIC AMMINES. 1075 solves readily in hot water (Found Cq=13*56; N=12*64; s = 21-37. C,lHB018N,S6Co requires c o = 13.41 ; N = 12.72 ; S=21*82 per cent.).The1 iiorinal methionat0 dissolves readily in cold dilute ammonia or sodium carbonate solution but is not1 repredpitated on acidify-ing. Barium hydroxide solution also dissolves it giving a Mod-red solution from which barium melthimate setparatea on keeping. Exmss of barium hydrolxide is required for solution so that the reaction cannot be used as at method f o r obtaining the methionatoc hydrolxide and hence ths chloride. When the nolrmal methionate is heated with a solution of barium chloride a blood-red solution results from which barium methionate separates on cooling. The filtrate from these crystals changes to a purple collour on evapor-atioa and small purple crystals of cis-dichlorodielthylenediamine colbaltic chloride! separate1 after a time (Found Col= 20.86.CaJa. : Go(= 20.67 per cent.). Concentrateld solutions of the methionabbromide~ do not give any precipitlate wheii mixed with a solution of mercurio bromide in potassium bromide solution. On boiling the resulting solution, however there is a t once formed the green double salt of mercuric bromide and the tra?w-dibromo-brolmide [Br2Col en,]Br,HgBr,, which separatm from thet hotl sollutioii in small flatbned needles (Found Co=7-47; Br =49*83. Calc. col=7.56; Br=51.28 per cent.). t r ans-D)ichlorrodie t h yl en edhm in e colb a1 t ic SaL ts . Since both sulpholacetic acid and methionia wid may be1 oon-sidered to be anaJolgues of malonic; aoid itl was expeoted thah they would give additive compounds with tlheiir acid salts of dichloro-diethylenediamineoobalt.This was found not to be tlhe case how-elver the substitution of *CO,H by *SO,€I thus playing a part which requires further investigation. Price and Brazier (Em. cit., p. 1737) found that sulphonyldiacletic acid which contains an SO2-groap in place of one of the CH,-groups of glutario acid did give rise to such additive compounds. t~rans-D~chlorodiethyZenedia~~iznecobalt~c hydrogen. sulplzmcetate, [Cl,Co ~I~,]SO,*CH,*CO,H separates immediately as merald-green, striated and elongated plates wheii 3 grams of the trans-dichloro-chloride are1 stirreld into1 a cold solution of 4.3 grams of sulpho-acetia acid in 15 C.C. of water. Yielld 3.1 grams (Found: Co=15*24; C1=18*37. C6H1,O,N4C1,SC~ requires C0l=15'16; C1= 18.23 per cent.).cis- Sulphoacekatodiethylenediminecobaltia chloride could not be obtaineld from the above hydrogen sulphoaoetate in the same way as o~xalatodiethylenediaminecobalt.ia chloride was obtained from th 1076 PRICE AND DUFl?: diclhlolro-hydrogen oxa,la.t,ei (Price a.nd Bra.zier Zoic. cit. p. 1726). When a sollution od the hydrogen sulphola.mtlate wa.s boileid the cotlour change'd t.o tlhs blood-red crodonr od a cis-salt butl oln ewapolr-atJoln to sma'll bulk oaly green crystals could be separa,t,eld. Repeatled boiling of thel solutlioln and. eivapomtion only resulted in t4he recovelry od the1 green crystals of the unchanged hydrogein sulphoace tattle:. trans-Dichlomdiet hyleltedialnz.ine cob altic met hiowzte; [ Cl2Co1 ea,],(S03)2CH2, separated in green e1onga;ted plates when 3 grams of the ti-ans-dichloirol-chloride wedel stirre!d int'ol a coild solutlion of 4.5 grams 0.f methiolnic aaid in 15 C.C.of water. The sepalratlion od mystlads was complete after t4wol hours in the ice+ohestl. Yielld 2.4 grams (Found Go!= 17.29 ; C1= 20.81 ; S=9.07. C,H,0,N,C14S,Co, require6 Co=17*50; C1=21*04; S=9*49 pelr celnt.). When this salt' was. dissollved in water togetqhes wit,h al molel-aula,r proporbion o,f melthionio acid and the solutioii boiled for fifteen minutles the mlour became deep red b,ut8 011-1 evaporadiing almost t.o dryness olnly grem crystals of the olriginal substanm sepasated. The a.cid salt could not be ob,tlained. Belfore clommencing the preparat'ion olf tohem salts t>he melthold dwcribed by Price and Brazier (Zoc.cit. p. 1373) for the1 pre-para t b n of cis-sulp ho n y ldia &atoldie8thylelnedi axnineico~b a1 t ic br omid u wals tested in the1 case of the malonato+bromide. This comisteld in the prepara;tion of the bromide direlotly by the intara,ction of one moleioular proportion of the carbolnato-bromide and onel molecular propostlion of malonio acid whereas Wernelr's method of prepar-ation olf such compounds is first txo pretpare the) carbonato+hydroxide and then add two moleleoular prolpolrtioins of malonic acid. The met.hod was found to1 be1 sataisfa&ory clis-mabonatodiethylene-dkmhecobdtic bromide [CH,(CO,),Co enz]Br,zH20 beling obtained in large rholmbia dark red platles which velry readily effloresced on elxposure to the air.A freshly prepareid specimeln which had slightdy elfnoresceld gave Co = 14.48 whereas C,H,,0,N4BrCo,zH20 requires Co1=14*21 for 3gi20 and Co1=14*86 f o r 2€1,0. The anhydrous substanw gave Co = 16.25 theory requiring Col= 16.34 pelr aontl. The) colrrespolnding thiocyanate C8H,B0,N,SCo was readily oEt<ained and possessed the properties describeld by Werner (ArtmZem 1911 386 8a) (Found Co= 17.19. Cah. Co= 17.39 per cent.) COMPLEX METALLIC AMMINES. 1077 To ob t ai 11 cis - dime t hylnta.lo+na,t odie thylen.ecliu8mitbe co b ultic bromide YBr,2H,O 5 grams of the1 carbona.t.o+bromidel weire dis-somlveid in 80 C.G. of warm wafer a,nd 2.07 grams (I moll. equiv.) of dimethylmalo~nic acid addeld. The resulting so,lutiojn was evaporated to low bulk on the waher-ba8t,h and after keeping in the i oe- chels t olvelrnigh t, crimson- red microor ys tallina pl af,es of t'he de'sired salt' sepasa,ted in small quantlty.Crystladlisaction olr it. may be t,he intmduction of the1 dimethylmalonatfo+residue8 int'ot t'he complex takes place velry slowly and it was necessary repela(te'd1y to collect8 the1 crystals wash with alcoholl and elvapo~ra.te the iiltlramtte a.nd wa.shings in olrdea to1 obtaJn any quantity of thel saltl. The solutioa cannot be1 boiled a,s was found tor be1 elffectivel in the case of the methionato-compound olwing tloN decoxnposit,ion of t,he dimethylma.lonic acid [Found Co= 13.82 ; H,O (at 130O) = 8.44. C9H,,O4N,BrCo,2H20 requires Cob= 13.87 ; H20 = 8.47 per celnt,. Found Br = 18.54. C,H,,O,N,BrCo~ relquires Br= 18.80 per cantl.].The nitrate YNO,,ZH,O was prelp/areld by the inttelra,otlioln in solutJon of equivalent quantities olf the! bromide (1.134 grams) and silvelr iiitrake (0.4532 gram). After shaking for osne hour the silver bromide' was collelct,e,d a,nd the1 filtlrafe evapolra4ted t,ol low bulk on the' water-ba,t~h. The sa,lt cryst.allise1d out4 velry slowly as a c.rimson micro8cryst.alline powder ofr in da'rk reld crust's omf indelfinitel sha.pe * [Found H,O (aftl 130') = 8.85. C,H,,O7N,Co 2 H20 reiquires H,O =8*85 per mint. Found Co= 15.58; N = 19.19. C9H2'207NfiC~ requires Co= 15.89 ; N = 18.87 pelr cent.]. The1 chlos-bde YC1,2H20 was obt(aSne1d by shaking a solution o'f the bromide! with an excess of frelshly precipit,a,ted silvelr chloride, md1ec:tdng the precipita,t,e and emapora,tlng the filtra.te to low bulk. It selpara t,eld in microc,ryst.allinel prisms which are1 velry so3uble in water [Foand H,O (at 1 3 0 O ) = 9.95.f- CgH220,N,ClCo,2H,0 relquires H,O = 9.47 pelr owit,. C,H,,O,N,CYCo rquires Co= 17.11 per cent.]. CHEMICAL DEPARTMENT, Foaad C o = 16.86. AfUSICIPAL TECHNICAL SCHOOL, BIRMINGHAM. [Received August 4th 1920.1 * Both in the case of the nitrate and the chloride which are very readily soluble in water it was difficult t o obtain a solution which was just of the right concentration for crystallisation ; ii too concentrated it formed a viscid mass. t. Only 0.2 gram of the salt was obtained so that the estimation of the water of crystallisation could not be repeated. The high value found was probably due to the salt not being quite air-dry owing t o the abnormally damp weather which prevailed at the time 3H,O requires H,O = 13.5G per cent. VOL. CXVTI. s

ISSN:0368-1645    

DOI:10.1039/CT9201701071

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

1078 WERNER THE CONSTITUTION OF CARBAMIDES. PART xn. CXX.-The Constitution of Carbamides. Part X I I . The Decomposition of Urea when Heated in Solution in the Presence of Acids. By EMIL ALPHONSE WERNER. IT was shown in Part1 V of the1 present series (T. 1918 113 84) that the1 deoomposition oC urela when heated in solution with hydra-chloria acid is primarily depelndentl on the dissociation of '' free" urea prewnt thus : Phase(1) HN:C<THs -+ (HNCO HOCN) + NH,. 0 The1 hydrollysis od cyanic a,cid which f ollolws immediatlely pro-ceeds a,t such a high ve4ocit.y t h t both pr0duct.s ojf dissociatioln amre remofved practieally 8,s fa,stl as t'hey are geineira,ted. Urea fixeld as a salt atl the outset' is thus rapidly (' freeld " to colntinuel the first phase of t,hel rea#otioln.Price (T. 1919 115 1354) strudield the1 decompolsition of ure'a in t,he presenm olf nitlria a.cid a,nd foand tlla,t the1 resotion vellocity a t looo was grelajt8elr than with hydrochloric acid as colmpaseld with the reaults obt'aineld by Fawsitt (Zeitsch. physikal. Chem. 1902, 41 601) with the1 lattler acid. Be,causel the a.dditioa of mmo~nium salts and oT wlrtamin salts containing an ioln commoln with tlhe ammonium satltl had a dist8inctl a.cc,ellelra8ting eff e.ctl o'n t,he demm-po"Sitdo8n of ure'a, Price iiifelrred that the a.uthor's ciissocia.t.ion thelory was appaselntlly nob applic,ablel to' the1 cha,ngel in t'hel presence1 oQ nit'ria a,cid. Nolw considelring tlhe straightforward cha,ractelr olf the1 coimplete d phase! of which is as follows: Phasel (2) (HNCO Z? HOCN) + I3,O + HX' =NH,X' + CO,, it is elvident tha,t the) nmchanism of the1 deaolmpositlon ojf urela must be similas with a,ll acids.The inferelnce drawn by Prim is the result of a misundelrstland-ing since sttriking prolo,f in support' o.f the1 dissociation theory has b,ele,n supplield by his elxpeIrimelnts showing t,he elffelctl of temperature on the1 velolcit,y 0.f t,he deicompolsitioln with nit'rio a'cid. Thus the va,lues at. looo 80° and a,t 70° were1 represeateid by the1 rsspeckive ra,t,ioe 102 9.3 alnd 2.4. Such a greia,t fa,ll in veilolcity compalreld with a re(lative1y m a l l fad1 in t,eimpera<ture is explaineld by the1 fact! t'hat the1 disso,cia.tion of urea o,nly st8arrte a t a fairly rapid rate ah abolutj 90°. A t GOo it is almost nil (wet remarks Pastl V Zoc.c i t . 1'. 94) WERNER THE CONSTITUTION OF CARBAMIDES. PART xn. 1079 Again as nitric acid is rather weaker than hydrochloric acid, the thelory predicts that the velocity of the1 relaction should be greater in the presence of the former acid since the concentration olf " frete" urea will be greater under similar conditions. Proof that the amountl of urea deleomposed is greater* the weaker the! acid is sholwn by a comparisoa of the follolwing results obtained in the presetnce of amtic nitric and hydrochlolria acids respectively. The1 ratio1 od urea tol acid was 1 2 mollelcular proportions. The cotnceatration a t the outset was urela = X / 2 acid = 171'. The1 elxperimelnte were1 performed a t looo and under reflux for reasoas which have been clearly pointeld out betfore (Part V).TABLE I. Acetic acid. Time. Per cent. 1 hour ......... 19-5 2 hours ......... 31.8 3 , ......... (a) 41.0 4 y ......... (b) 53.4 5 , ......... (c) 64.2 (Urea decomposed.) Nitric acid. Per cent. 15.7 25.8 35.0 46.4 57.0 (Urea decomposed.) Hydrochloric acid. Per cent. 13.3 23.2 32.2 40.8 48.4 (Urea decomposed). The above1 results welre calcuhted fro'm titaations of the1 reaidual acidity a t the end o'f e8a,clh eixpeirimentm with the elxceptio,n olf the va,luw ( b ) and ( c ) foir acetic acid which were obtained from dete'r-mina.t,ions of t$el residua,l uma the only trust'worthy melthold in these two) oases. As the1 concelnt,ration of ammoaium ace,ta,te pro-duced during the reactmion increawd there1 was 106s oQ ammonia b'y ih hydrollytlic diswciation whelre,by reaidua,l acidity gavel t,oa low a result.Whilst8 by the tit,ra,tion melthod ( b ) wa.s approlxim-a,teily 47 and ( c ) 51 thelrel was b,ut litltllel cliffelrelnciel in the ca'se of (a) when chelcked by the eetJmation of residual urea,. Whilst the ve'locit'y oS phaael (1) is direcltly proportional to the' omcentratlion of " free " urela the amount of the1 latter in so81utio,n a t any time1 is inverselly propostional to the st'reagth of the1 aoid prelmnt all olt.hetr colndit'ions being equal. He8nclel after a cert'ain time a shila,r csndit<io,n is ateained no ma.tt,er what a,cid may be * This is only demonstrable up to a certain point for an interesting reason.When the concentration of a very weak acid such as acetic falls considerably as the reaction proceeds i t is unable to fix ammonia to complete the change of phase (2) with the result that more or less urea is regenerated, thus 2HNCO +H,O=CON,H,+CO,. After potassium cyanate was added to an excess of a 2 per cent. solution of acetic acid urea was detected in the solution. s s 1080 WERNER THE CONSTITUTION OF CARBAMIDES. PART XII. premnt siiioel practioally all the reFjidua1 ureal will be1 '' fretel " when the mncentratioii of acid has falletn very lolw as a reault of its prolgressive nelutralisation. For this relason the1 decompositlion of all the urea is a very tedious process (compare Fawsitt Zoc. c i t . ) Now the decomposition of urea in the presielnoe of acids is not an ionio ohange."Free" urea is not ionised and hence the con-tention that the addition of an ammonium salt or of any salt, matlaining an ion co~mmon with the1 acid useid should retard the velocity of decomposition does not hold. The following results were obtained when ammonium nitrats ( N / 4 a t olutset) was added i n the presence1 of acetic acid and of nitric acid reapelotively and when ammonium chloride ( N / 4 ) was added in the1 preislencel of hydrolchloric acid. The) conceatrations of urela and olf aoid were as before. TABLE 11. Acetic acid+ Nitric acid+ NH,NO,. NEC,NO,. Time. Per cent. Per cent. 1 hour ......... 22.0 19.9 2 hours ......... 35-1 31.78 3 , ......... 45.4 37.40 (Urea (Urea decomposed.) decomposed.) Hydrochloric acid+ NH,CI.Per cent. 14-0 29.1 41.2 (Urea decomposed.) As the1 relact'iolii progressed the conce,ntra,tjoa 0.f ammonium sa1t.s iiwreased and in the oase olf the nit'ratel there was appreciable loss of a4mmolnia during t,hree hours' heahing and sinoel the1 reaults show sufficient,ly the1 gelnelral accedera.tioa wheln comparsd with t,he vadue's in t8ablel I elxperirnent,a we,re not catrried outt beyond this peiriod. The) amelelratio'n of thel decolmpositioln oif urela is hese due to the hydrollytia dissociation of the ammonium salts whelmby the1 vellocity of phase1 (1) is promoted. Whilst' the1 coastit'ut'ion of tlhe simple sadts of ainmoaia is still unsolveld thelir dissociat<ion * int'o aaid and ammonia is a welll-known fa,& their ionisaf'ion is a pheno-metnoin which has beean assumeld but nelve'r proveld and in thel antholr's opinio'n it plays no pa'rt in the1 rea'ctions under discussion. The dissocia.tion of "free" urea is much more selnsit.ivet to external conditions than might be1 suppweld ; thus va,riations in the lengtlh and diameter of the refflux tube aad in t.he shape1 and volume of the flask wetre sufficientl t o introduce distind dist'urbing effects. Hence two) flaalrs of simi1a.r form a,nd volume a.nd the1 one refflux tube] were' used in t'he experimelnts. * The presence of moisture being necessary is evidence of its hydrolytic character CHAUDHURI SYNTHESIS OF BORANILIDES. PART I. 1081 The mode of decoinposition of urea in the1 preseiicel of acids (and olf alkalis) is in itself sufficient t o throw discreldit on the " carbamide " formula. UNIVERSITY CHEMICAL LABORATORY, TRINITY COLLEGE, DUBLIN. [Received August 4th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701078

出版商:RSC    

年代:1920

数据来源: RSC

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CHAUDHURI SYNTHESIS OF BORANILIDES. PART I. 1081 CXX1.-Synthesis of Borclnilides. Part I. Bor-anilide and i t s Derivatives. BY TARINI CHARAN CHAUDHURI. THE chemical constitution and physiological action of anilides of organic acids have been studied in detail by Gibbs and Hare (Amer. Chem. J . 1890 11 435) and by Gibbs and Reichert (Zbid., 1891 13 289). It was hoped that if boric acid could be combined with aniline1 to form boranilide the latter would have important physiological propertiee and it was with this object in view that the study of the condelnsation of aniline with boric acid was undertaken. From the stable boranilide which was obtained a series of derivatives has been prepareld. Ditte (Compt. rend. 1887 105 813) prelpared aniline borate, NH,Ph,2B,03,4H,0 and Schiff (Annalea Suppl.1867 5 209) describes an “ anilide of boric acid,” prelpared from ethyl borate and aniline as being readily decomposed by water. It would appear that Schiff’s compound was idelntical with that prepared by Di tt el. I n the present work a mixture of mdelcular quantities of boric acid and aniline was heated at. 135-140° with the addition of a small quantity of zinc chlolride as condensing agent. Aniline does not howevelr condense with olrthobolrio acid olwing to the fact that at looo orthobrio aoid is convelrbd into1 metaborio acid with the elimination of one molecule1 of water; so that condensation a t the above temperature really takes place between aniline and meta-boric acid. As the oondeasation-produclts itre very stable it would appelar that the nitrogein atom is dirwtily linked with boron and noh with oxygen; in the latter evelnt the aompolunds would have beein more easily hydrolysed than was found t o be the case 1082 CHAUDHURI SYNTHESIS OF BORANILIDES.PART I. I n t,he compounds deecribe,d in this p a p r the presence oC the borio acid residue wa8s deitelcteld in mch case. The welll-known glyceao.1 me'thod f olr t,hel qua8ntitative est,ima,tion ot bolrio acid (prolduceld by decomposing the compounds witb sul-phuric acid wit,h or wit8houtl t'ha a,ddition of potassium dic;hroma,tlei) did nok give1 slat,isfa.dlolry results. The ejstimartion of carbon, a.lthough carelfully casried out, was vitiat'eld by t,hel absorption olf some volakilet borric acid in the pot'ash bulbs. The1 detelrminatbon of tihe mokcular weightl of bora,nilide by ana(1ysis oC the platinichloride as well as the1 estima8t,ioln of nitrogen by Dumas' mejt,ho,d conclusivelly sholw holwever tha,t t'hei condensastion t,askes place betlween molecula,r qua,ntities of bolricr alcid aad aniline( ats statled above.Boranilide sa8tlisfa.ct80rily respolnds tlo Ta.fel's colour re#a,ctioln for anilides (Ber. 1892 25 412). The constitution of boranilide C,H,-NH-BO is suppolrtejd by t'he fact t8hatl it yiellds nit,roNso- and othelr derivatives exa'dly as woald be elxpecct,e4d. It itppea'rs trhelrefom tlha8tl the anilide both in the frw sta,t,e and in a,cid solutio'n has t'he! abovel constitut,ioii whilst wheln dissoilved in alkali hydroxide solution itl has tho tmtomeric formula C,H,*N:BOH.E X P E R I M E N T A L . B ommiZide C,R,*N 13 B 0 . A mixture of 5 grams of borio acid and 7.5 grams of aniline was helateld tlo 135-140° when 1 gram of fused zinc chlolride was addeld and the1 mixture stirred. The1 pasty mass besame soilid on cooling and was sucomsively extracted with small pantitieis of wa,ter. . It was then washeld with very dilute hydrolchloric acid and repeateldly washed with warm water. The1 substlance crystallised from alcohol1 in whitel needles (6.5 grams) which did not melt at 2 1 2 O (Found N'=11.32; M.W. ( f r m platinichloride!) =119*7. C,H,ONB requires N= 11.76 per cent. The1 hydro-chto&de forms thin green plates decomposing a t 108-110° (Found c1= 22.40. C6E60NB,HCI relquirea c1= 22.82 per centl.). Thel pZatinichZoride forms small yelllow crystals which gradually become grelen (Found I%= 30.28.(C,H60NB),H,PtC1 requires Btl= 30.09 per cent.). BenzoyZb OmmiJide C6H,.NBz-B0. This was prepared by adding beinzoyl chlolride t o a solution of boranilide in glacial acetic acid o r by adding aqueolus pot-assium M.W. =119*0). Boranilidei dissolves in acids o r alkali hydroxides CHAUDHURI SYNTHESIS OF BORANILIDES. PART I. 1083 hydroxide to a solutioa of boranilide (6 grams) in benzoyl chloride (7 grams). The1 product is a whit0 polwder which mellts a t 166' (Found C = 69.59 ; H = 4.87. C,,H,,O,NB requires C = 69.95 ; H =4-48 pelr aent.). Thioboranilide C,H,*NH*BS. A mixture of boranilidel and excess of flowers of sulphur was heated until the sulphur melted when tlhei anilide dissolved in it.The heating was continued for ten minutes. I n another prepara-tion bsranilide was heateld with phosphorus pentasulphide. I n elach case1 a hard solid was produceid which was poiwdereid and repateidly washed with warm carboln disulphide. A yellowish-grey powder was obtained having a faint odour of mercaptan. It is insoluble in water alcohol or ether but soluble in acids and malts a t 109-110° (Found N=!3.91. C,H,NSB requires N = 10.37 per cent.). Nitrosoboran ilide C6H ,.N(NO)*BO. Bolranilide was dissolved in excess of hydrochloric acid and a solution of soldium nitrite addeld. A reddish-yellow oil was pro-duced which solidified after some time t o a brownish-pink solid. On adding alcohol to the oil it reladily solidifies in plates melting at 83'.The substanue dissolves in ether and the1 ethereal solution responds t o Lietbermann's reaction (Found N = 18.22. C,H,O,N,B requires N=18*91 per cent.). Bromo b orandides C,H,B r NH-BO. Of the three bromoboranilides which have been prepared t'hat having the highest melting point is assumeld t o bel t'hei parar that with the lowelst' the orthot- and the! remaining one the1 meta-isomeridel. p-Broniohora?a;lide. Brominel was addeld to an acetic acid solution of boranilide and the1 precipitate) was shaken with chloroform; a white powder remained which consisted of an acetatel soluble in water. On warm-ing the aqueous solution with potas5ium carbonate solutiocn the1 free compound melting a t 121-12207 was obtained (Foand Br = 39.86.C,H,ONBrB requires Ijr = 40.44 per cent.) 1084 CHAUDHUR~ SYNTHESIS OF BORANILIDES. PART I. o-Bromob oraiailide. On elvaporating the1 chloroform solution olbtained in the1 preced-ing elxperimelnt a pale pink powder was obtaiiield the aqueous solu-tion of which when warmed with potlassium carbonate gave a very pale yellow substance melting at 8 2 O (Found Br =40*14. C6H,0NBrB requires Br = 40.44 pelr celnt.). m-Bromo b oranilide. This was prelpareld by the1 action of a sulphuric acid solution of brolmine on a sollution olf boranilidei in sulphuria acid. Almost black minute crystals selparateld the aqueous solution of which, when boileld witlh potassium carbonate gave m-bronzobonzmiLk?e as a violet powder mellting at 96-97O (Found Br = 40.10. C,H,ONBrB require6 Br = 40.44 pelr cent.).Cmversioit of met'a- in t o ortho- a t d parrt-Iii.oniuboru,~iiZ~~Ze~. Without separating the almost black crystals from contact with sulphuric acid and on boiling this m-brorno- derivative1 for a short time with water a sudden change takes place and the black eub-stance is convelrted into1 a pale pink powder. This is gently warmed witlh chloroform when a white1 substtame remains whiah dissolves in watelr. Thel aqueous solution when boiled with po&assium car-banatel solution yiellds a compoand (m. p. 120-122O) which is eividelntly p-bromoiboranilide whilst the chloroform solution on elvaporatdon givels a substance! from whiah whein bodeid with pot,assium carbonate a pink powdeir (m. p. 83-84O) is produced, elviden tl y the o - b rom o -derivative .Ben z o y 1- p- b rolnao b ova n ilidc C,H,Br NB 2.33 0. Rciizoiyl chloride was gradually added to1 a solution of pbromo-boranilidel in glacial acetic acid when the sollution belcame turbid. On shaking gnd allobwing to remain miormcolpio whitel cubic crystals separat&d mellting at 128-130° (Found Br = 25.52. C,,H,O,NBrB requires Br = 26.51 per celnt.). Uo~yldzhzoanaino benzene C,H,*N:N-NPh*BO. Tot 5 grams of nitrosoboranilidel 3 grams of aniline1 were added, and then a mixturet of hydrochloric acid alcohol and ether. On boiling not act\ion apparently took placel but on adding water and boiling the solution became! red and a heavy oil separated which CIKAUDXIURI SYNTILESIS OF BORANILIDES. PART I. 1085 on cooling and shaking soon solidified to crystalline red pla,tes melting a t logo.Above 130° the aompound suddenly decompose5 with a feeble explosion. During combustion by Dumas' melthod t7he burners below the1 mixture 04 the1 substance1 and copper oxide as well as a little in front of and behind it were kelpt velry low. I n spite of this precaution a loqw result for nitrogen was obtained owing t o the rather sudden evolution and consequently incomplete1 reduction of the oxidw of nitrogen (Found h' = 18.13. Cl,Hl,0N3B relquires N=19*29 per mnt.). Bor y Zhy dra z oanzinab enz errt e CsHr *NH*NH*NPh*B 0. On adding stannous chloride ar,d hydrochloric acid or zinc and hydrochloric acid to the red alcoholic solution of horyldiazoamino-benzene the reld solutlion soon became1 colourlelss and the hydrazo-compound was isolated by relndering the1 solution alkaline and estraating with ether.It melts at 123-124O dissollves in hydro-chlolria acid and gives a yellow nitrosol-derivative which responds t o Liebermann's reaction. B o I o -a -1 h enJyl-j3 -arnk.aph e ti y lh y draz idc, NH,* C,H,*NH*NPh*BO. A solution olf 4 grams of the1 above hydrazol-compound was boiled with coaceatratod hydrolchloria acid and the hydrochloride basified with ammonia. The grelyish-yellow bas6 (3-4 grams) is soluhle in alcohol and melts a,t 163-166O (Found N = 17.97. C,,H,,ON,B requires N'= 18.66 per oeatj.). B oro-a- pk e n y 1 hydt ctzido b ewz en eaz opherrtoll, OH*C,H,*N:M*~~M,*NH*NPh.BO. Four grams of the above basei were dia,zcEtised and combined with 2 grams of phenol in alkaline solution. The broswn product (5-4 grams) is sparingly soluble in cold water more readily so in alcohol and dissolves reladily in acids or alkali hydroxides. It mellts a t 152-153' t o a delep violet liquid. The hydrochZoricje crystallises in dark brown needlm. The dibenzoy? derivative OBZ*C~H~*N:N.C,~H~*NRZ*NP~*BO, prelpared from 5 grams of the azol-compound by the Schotten-Bauma,nn reiaction (yield 8.2 grams) is a palei brawn subatance insoluble in water sparingly soluble1 in alcohol but readily so in elthelr from which it separates in needles melting at 113-115O' 1086 ARMSTRONG AND HILDITCH : The author desires to express his sincere thanks to t.he van’t Holff Committee oif Amsterdam for a,wwarding him a grant in aid od this work. RESEARCH LABORATORY, KRISHNATE COLLEGE, BERHAMPORE (BENGAL), INDIA. [Received Pebrvruayy 11th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701081

出版商:RSC    

年代:1920

数据来源: RSC

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1086 ARMSTRONG AND HILDITCH : CXXII. - The Ethylene - Ox id e St rue t ure of Sucrose and some Other Caybohydrcctes, By EDWARD FRANKLAND ARMSTRONG and THOMAS PERCY HILDI'I'CII. THE structural formula of suci*ose has long been a subject of research; the1 morel recent work of IIaworth and Law (T. 1916, 189 1314) has affolrded evidence that it is formed by the fusion of a molecule1 od a-glucose1 having the! butyleinel-olxide structure and of a- f ruot olsel having t hel e t h ylenet oxide st ructnre. W heln hydrolyseld in presence of acids these forms are1 the! first t o be produced but subsequently they undergot morel or less rapidly, isomeric changes f olrming first thel corresponding butylenel-oxide form of fructose1 and then the1 mixture of a- and P-modifications oif this in equilibrium and secondly the 8-butylemepoxide form of glucose as well as small quantities of the corresponding ethylene-olxide forms.The1 final mixture which has the1 well-known optical rotatory power and other physical charaoteristics of invert-sugar is thus a very colmplelx mixture of substances and there is little wonder that its crystallising power is low and that its nature is hard to1 establish. Haworth and Law's prolof of the preseince of the ethyleael-oxide1 form olf fructose in sucrosel is based on the complete methylation of the disaccharide and the identification of the methyl fructose formed after hydrolysis. I n a reoent communication (T. 1919 115 1410) we have adduced evidence of the elxistence in small proportions of an ethylene-oxide modification of glucose fructose etc.in presence of aoid and shown how the reduction of permanganate affords an indication of the amount of this form present. It appeared of interest therefore t o use this methold t o detect the initial liber-ation of the ethylelne oxide form of fructose from sucrose and so confirm the observations of Haworth and Law THE ETHYLENE-OXIDE STRUCTURE OF SUCROSE. 1087 The1 quickelstl and most dedica8tlel metlhold of hydrolysing sucrose is by rnela,ns of inverta.se1 and as thel adios is in nelutral solution, t'he subselqueat isomeric change,s a.re re;lative81y slolw . The figures quot'eld in t8ablel I sho'w a rapid increase1 in the reducing powelr t o pesmangana8te8 and indica,te oonclusive,ly the1 premnce olf wha.t we consider to be the ethylenemxide form oif fructose since ths b'utylene-olxide f orrn is relatiively stable t'ol pelrma,nga,natef.Wheln sucrosel is hydrollyseid in presetme of hydroohlmio acid, a40tlioin is slo'welr atlid isomeric clha'nge is promot,e,d by the a8cid. The figures in table I1 give1 velry little indication 04 the1 preseince of aay more! olf the1 eit$hylene8-olxide form than is nolrmadly produced by acid of this strelngth in at mixture! osf gluaosel a,nd fruct,ose and presumably t'he ethyleaet-o'xide f orin first produced had undergo'ne rapid rela~rra,ngementl int,ol t$ei butylelne-olxide form in premInce of t'he aloid. Anoma,lous results havel been obt,aineld however if t,he mixture of sugas and a#cid is nelut.radised beforel thel addition of perman-gana.tel.These solutions appeas ta be approlxima.te.ly twice as wnsitlva to pe,ma,ngana.te a.nd we am inc1ine.d to1 attribute1 this t o some as yet unexplained disturbing fa#ctor ot'helr tha'n the pelreist-eace ojf a n excess of the1 emt~hyleae-osic?et form. It may be1 recalleld that. we o,bserve8d that an a,cid sodutdon of glucose1 olr fruct,ose if neiut,ra,liseld simul t,a,ne ousl y wit,h t h el a d di t'io'n of perm ang ana't.el gave reduotion times a,lmost~ ident,ical with thoael of the acid solution, and we considereld t,ha,t this indicated t'hel persist,ence of t,he act'ive form of t.hei sugar aft'elr neutlralisatlion of tlhel acid ha'd taken pla,ce. I n o'ur prelvious communic;atioln we1 drelw att,e,ntion to t,hel relative, a,ct.ivitie,s of glucose mannolse and fruct.ose t'owa.rds peIrmanga.na,te, bo,th in a.cid a,nd in a3ka,linel soldion.We have1 nolw rnadei similar eixpelrimentls with galactose arabinolsei a'nd xylosei. The com-pa#rative times of relductIon of the; standa'rd quant'ity of perman-gana,tel by a,oid and alkaline1 solutio,ns of these1 sugars aad by the rels pelctiv e s o h ti oins when nen t 1- a41 i s ed simul t an elou sly with the addition oif pelrmanganate are : iV/lO-H c1. Age of Solution :- Fresh. Ti-\ Glucose 29.0 27 Mannose 13.0 12 Fructose 17.0 15 Galactose 8.0 12 Arabinose 2.5 11 Xylose 4.0 20 Acid. Neutd. Five hours. - Acid. Neutd. 20.0 28 12-0 12 16.0 18 5.5 21 2.5 11 6.0 18 NIls-NaO H. Fresh. - Alk. Neutd. 11 180 25 90 3 60 26 26 31 38 18 32 Five hours.Aik. Neu'td. 3.0 48 9.0 46 1-25 11 3.5 Indef. 1.5 75 1.5 7 1088 ARMSTRONG AND HIEDITCH : With the single etxception of mannose there is relatively little difference between the sugars in their behavioar in alkaline solu-tion and i t would appear that the configuration of the rest of the1 molelcule has but. little effect on the1 rmdiness to undelrgo enolisation. In acid solution the) differences are] more marked the pentoses being especially active as relducing agents there is no very apparent connelxion between activity and configuration. The1 proof of the existence of ethylene-oxide forms of the simple sugars has intlrolduaeld iti new colncejption into the struotural chemistry of the carbohydrates which may have far-reaching significancel.I n consequence until further elxperiinental evidence has been accumulated it is advisable to exercise caution in the interpretation of diff erelnce bettween the vsrious sugars such as we have just recorded. As it may bet some time lwfore we can return to this investigation we wish to place. the facts on record for the benefit of other wolrkers in this field. EXPERIMENTAL. Eydrolysis of Sucrose b y Invertme. A quantity of prelssed yeast was autolysed in the presencel of toluene for somel days and the aqueous filtrates were precipitated by exmas of alcohol; the invertase was collected redissolved in a little water and again precipitated by alcohol. The filtered pro-duct was dissolved in water and the solution divided into three equal portions two of these were employeld in the hydrolysis of 250 C.C.olf M/36- and 5M/3&solutions of sucrose (giving total hexwe concelntrations of M/18 and 521.1/18 as in our former work), whilst the third was made up to 250 0.0. with pure water. The! solutions were maintained a t 25O and 10 C.O. portions welre tested from time to1 time with 2 0.0. of N/IOO-permanganate; the coloar changes were not the1 same as with acid solutions but two fairly delfinitel tints were olbservablel namely al clear brolwn immedi-ately after the last tlrace of pink had faded and finally a very clear pak yellow. The solution of invertase in water alone was tested with the others and it was found that reduction of the pe'rmanganate was very slow the dear brown only being retached after seventy to ninetty minutee whilst the further change to pale yellow occupied many hours.An attempt was made to examine the effect of introducin THE ETHYLENE-OXIDE STRUCTURE OF SUCROSE. 1089 S/ 10-hydrochloric acid 011 the permanganak test but i t aypeareld that in presence osf acid the1 invortiasel alone acquired the power olf wry rapidly relducing permanganate. Tablet I illustrates thel results obkained with invertase in neutral solutions of M / 36- and 5iW/36-sucrose with the1 corresponding optical rotatory power of the solutiolns. Age of solution (hours). 0.0 0.5 1.0 1.5 2.5 3.0 3.5 4.5 5.5 10-3 24.0 M/36-Solution Permanganate test. - Brown. Yellow. (minutes.) 45 100 35 53 25 36 22 35 20 3 0 19 25 19 26 20 25 20 25 20 25 20 25 TABLE CUD3 * + 61.5' 41.7 28.3 20.0 --1.7 .- 10.0 18.3 20.0 21.5 I.5Af/3 6-Solution. I ~ Permanganate test. - Brown. Yellow. (minutes. ) j 30 100 28 22 18 19 16 1 7 14 9 9 9 1 :: I 1 8 I 7 11 Hyclrolysis of lCzwrvse b y N / 10-Hydroch Zoric A c i d . TABLE 11. M / 3 G -Soh tion. Permanganate test. Age of solution (hours). 0.0 1.0 3.0 6.0 23-7 30.0 72.3 Acid. Neutd. (minutes.) 230* 110* 155 40* 115 36* 100 35 31 17 Et - -* Indefinite end-point. Mean Comparative Figures [.Dl --t 63.3" 54-7 45.7 38.3 --12.3 2.7 - 6.0 18.0 21.0 5M/36-Solution. Permanganate test. Acid. Neutd. 142 67 + 62.8" 120 30 59.0 60 27 -49 23 49.0 19 17 32.3 16 10 24.0 18 10 4-0 t Precipitation set in. -A 7 (minutes.) [.Ill' for Fructose and Glucose. The following arel the1 mean times of relduction of pe'rmanganate, in the aoid and nentralised tlests found in the fo'rmer work folr solutions of fructose and glucose1 in nT/ 10-hydrochloric acid 1090 RAY TRIETHYLENE TRI- AND TETRA-SULPHIDES Calculated mean of M/36-Fructose + M / 18 -Fructose M / 18 -Glucose M / 1 8 -fructose M / 3 6 -Glucose (found) . (found). and 171/18-glucose. (found). Acid ......... 16-5 29.2 22.9 22.8 Neutralised 17-0 28.0 22-3 26.8 Calculated mean of 5M/18-Fructose 5M / 18- Glucose 5M/18-f ructose and (found) . (found). 5M/lS-glucoso. Acid ............ 7.7 19.4 13.6 Neutralised ... 7.8 19.0 13.4 [Received August 2nd 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701086

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年代:1920

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1090 RAY TRIETHYLENE TRI- AND TETRA-SULPHIDES CXXIII. - Triet h y Zene 2%- and Tetra-sulphid es. By Sir PRAFULLA CHANDRA RAY. IN the preparation of ethylene mercaptan by the interactioa of ethylene dibrolmide and alcohollic potassium hydrogen sulphide, after removal of aloohol and ethylene meroaptan by s k a m dis-tillation continued passage of s h a m furnishea a milky distillate solidifying to a crystalline mass which when relorystalliseid frolm hot alcohol melts a t 1 1 3 O and consists of triethylene trisulphide, (C2H4)3S3. The non-v~lat~ile oil remaining in the distilling flask a,lso solidified o1n cololing t o a crystalline mass consisting of a mixture of three polymeric ti-iethylene tetrasulphides. By extrac-tion with alcohol the a-modificatioa (m. p. 76O) was obtained; the remainder on extlraction with benzene gave the &modification (m.p. 102-104°) and thel insoiluble residue furnished t?he y-moldificatioln (m. p. 1 1 6 O ) . The alkaline liquid which remaineid behind in the flask yielded on acidificatioln an oil which has beein proved to be1 triethylene disulphide dimercaptam (C,R,),S,(SH),. On tzeiatment with mercuric chlolridel it gave the oorrelsponding chlo~om ercapt &Ye ( C2X14)3S2( S H g Cl) . This d imeir captan w heln treated in ethereal solution with an alcohollio solution of ioldine, gives the /3-tehrasulphide (m. p. 104O) and it8 methyl-alcoholic solution sloiwly olxidises in the air t o 8-tm'ethyleme tetrasulphide (m. p. 59-60O). The molecular weight olf this variety was fojund to be 816 which colrresponds with four times the formula, (C2HJ3S4.The P-modification is sparingly soluble in boiling benzene or chloroform and its molecular -welight could not b RAY TKCETHYLENE TRI- AND TETRA-SULPHIDES. 1091 delt.ermined witlh exaatness but' elvideince pointed to it's having a much highelr mo~le~cula,r weight, indicating t'hat in this case there was a aoa81esce8nce of more tha8n four simple moleculels. In boiiling chlolrofolrm the substanm undelrgoles partial s,lo,w spont,a.nelolus polymelrisa,tion 8,s Wafs prolveld by the f a.dl t$at successive1 clrops diffelreld in meilting point and welre o'nly sparingly soluble! in be'nzeine. The1 insolublel portion melted at about 1 1 4 O . It seems probable tha,t the y-moldifica,tion which is insolluble in ordimry s,olvelnts.has a much highe'r molletculas weight. The f ormat,ioln o'f t,he compo,unds may be expladned according t'o, the. following scheme'. The alcoholic sollution of poltassium hydr-oxidel on beling sa,turat,eld with hydrogeln sulphidel colntains potlassium sulphidel in a,dditioIn t,o pota.ssium hydrogen sulphide, a.nd this mixture acta OD ethylelne dibromide thus: 3C2H,Br + K2S + 2KSH -+ SH*C2H4*S*C,H,*S*C,H4*SH. Evident,ly t,hei tlelttrasulphides are the prolducts of spo,nt.a;nejows ae,rial olxidation of t'hel dimelraptan thus : S~C2H4*S~C,H4*S.C,H,*S Lpp--.--i Thel foirrna,t,ioa oC the trisulphidel may be! explaineld thus : s*c H 3C2H4Br i- 3K,S = C2H,<S.C2H4>S + 6KBr. 2 4 E x P E R I M E N T A L. The1 method of preparation (from 100 grams of elthylene dibroimidei) was eiIiactly as described by Fasbender (Be?.1857 28, 461). After removal of alcohol and ethyle\ne mercaptan by means o i steam there separated from the distillate a solid which was preisseld on porous plate (1.29 grams) and crystallised from alcohol, when it melted atl 113O and consisted of triethylene trisulphide (Found" C=37.84; R=6.80; S=53.06 53.54. C6H12S3 requires C=40-00; H=6-67; S-53.33 per cent.). The noln-volatile1 oil which soilidifield on cooling (6.5 grams) was * As these compounds are very rich in sulphur the length of the lead chromate in the combustion tube was much increased so as to preclude the possibility of sulphur dioxide escaping absorption. Moreover in some cases the alkali hydroxide in the potash bulb after analysis was oxidised with bromine wiwmed and acidified with hydrochloric acid and treated with barium chloride but no barium sulphate could be detected.In the estimation of sulphur Carius' method was adopted by which the compound was converted into the sulphonic acid. The acids were neutralised with sodium carbonate evaporated t o dryness and then fused with potassium nitrate so as t o transform the sulphonate into sulphate 1092 RAY TRIETHYLENE TRI- AND TETRA-SUI3HIDES. elxtracteld completely wit'h hot alcohol the solution furnishing crystals of a-triethylene tetrasdphide melting at 750 (Found : C = 33.88 ; H = 7.42. C,H,,S relquires C = 33.96 ; H = 5.66 per cent.). The relsiduei was then similarly trelate8d with boiling benzene!, which extracted P-trie thy1 ene t e trmulphide melting at 102-1 0 4 O (Found C = 33-92 ; H = 6-94.C,H,,S requires C = 33-96 ; H = 5.66 psr cent.). The final insoluble portion consisted of y-triethylene tetra-sulphade mellting at' 116O (Found C =34.30 33.59 ; H = 6.41 7.90 ; S = 59.07. C,H,,S requires C = 33.96 ; H = 5.66 ; S=60*38 per oent.). The alkaline liquid on acidification gave an oil which was extracteld with etThelr (8.5 grams) and c'onsiste'd of triethyzene d~suJphide dimercaptan boiliiig at 260-263O (Found S = 60.86. C,H,,S requires S = 59.80 per cent .). Its methyl-alcoholio solution on exposure to air gave 6-tri-ethylene tetrasulphide melting at. 59-60° (Found C = 33.05 ; H = 6.29 ; S = 60.55. M.W. by euullioscopic melthod in ohloro-form = 815.5 815.8. C24H48S16 require3 C = 33.96 ; H = 5.66 ; S= 60.38 per centl. On treafment with me'rcuric chloride it gave the dichloro-mercaptide (Found C=10*34; H = 2.22; C! = 9.40 10.81; S = 18.54; Hg = 58.44. C,,H12C1,S,Hg re,quiree C = 10.54; H=1*75; C1=10.40; S=18.74; Hg=58*57 per wlnt.). Various derivatives of the above polysulphides are in course o'f preparation. CHEMICAL LABORATORY, M.W. =848). COLLEGE OF SCLENUE, UNXVERSKTY OF CALCUTTA. [Received June 3rd 1930.

ISSN:0368-1645    

DOI:10.1039/CT9201701090

出版商:RSC    

年代:1920

数据来源: RSC