摘要:

EFFECT OF D-LU A h l T I O N ON CORROSION Em. 2605 CCCLVIII.-L4n Investigation of the Efject of Digerential &ration on Corrosion by means of Electlrode Potential Neusurements. By A. L. MCAUUY and F. P. BOWDEN. h a recent paper (American Chemical Society Corrosion Sym-posium 1925; Id. Eng. Chem. 1925 17 363) Evans discnsses oxygen distribution as a factor in the corrosion of metals. The present investigation was undertaken with the object of measuring the potentials between solution and metal in the various zones recognised by Evam on a metal corroded by a partly azjrated solu-tion. The potential diilerences in merent zones were very clerrrly distinguished and on attempting to co-ordinate the results by measurements on standard surfaces it was found fhat the method provided a sensitive meam of detecting the commencement of corrosion and recognising the state of the surface.E x P E R I M E N T AL. In the first set of experiments the method of preparing the specimens described by Evans wm adopted. Sheets of zinc and iron were partly immersed in N/lO-sodium chloride and after 24 hours their d a m s were studied. Following Evans four distinct zone8 were recognised on the corroded epecimen (1) A zone unwetfed by the solution. (2) A zone over which the eolution hm crept necessarily well aerated. (3) A zone beneath but close to the surface of the solution also well aerated. (4) A zone of deficient ahtion at greater depths 2606 MCAUIAY AND BOWDEN AN INVESTIGATION OF THE EFFECT Zones 1,2 and 3 were bright and zone 4 waa more or less M y corroded.Measurements were made of the single electrode poten-tial between N/lO-sodium chloride and the various zones. In the second set of experiments the single electrode potentials between N/lO-sodium chloride and standard surfaces were meamred under mering conditions. These surfaces were extremely sensi-tive to exposure either to air or to electrolyte; e.g. to obtain the true potential of freshly deposited electrolytic zinc it was necessary carefully to plate the whole of the exposed surface wash with water, and measure the electrode potential before the zinc had completely dried. If the surface were allowed to become dry for more than a few minuw its electrical character changed completely. Broadly classxed all the surfaces were electrically in one of two standard conditions and the rapid changes were from one to the other of these standard conditions.Method of Neasurement and Appardt~.-Two distinct methods of mewurement were used. In the “ A ” method the specimen was dry and the single electrode potential was measured between the metal and a drop of N/lO-sdium chloride of about Q mm. diameter placed on the metal surface. It is necessary that the drop be very small as otherwise the effects of corrosion by the drop are marked owing to differential aeration. This type of measurement gives the true single electrode potential between solution and metal. In the ‘‘ B ” method of measurement the specimen or the region under investigation was flooded with sodium chloride solution or with water or occasionally was immersed to a depth of 0-5 cm.in the solution and the potential Merence between the electrolyte and the metal surface was measured at different places. This type of measurement gives the electrical conditions while corrosion is in progress. In the case of iron the specimens prepared by Evans’s method were not allowed to dry but were kept wet with water; this was necessary on account of the rapid decrease in the electrode potential of the corroded portion on exposure to air. The measurements were made against a normal calomel electrode, A (Fig. 1). This communicated with a tube By filled with N/10-sodium chloride the end of which was drawn out to a hollow tip with a diameter of about Q mm. This tip made contact with the solution above the metal plate C .The potential difference between the mercury of the calomel electrode and the metal plate was measured by a potentiometer. The apparatus was sensitive to a millivolt. Experirnents.-In the first series of experiments specimens of zinc and iron were corroded by partial immersion in XT,ilO-sodiu OF D- A&LATION ON CORROSION EN. 2m chloride for a period varying from 12 hours to 2 clap. The results of measnrements made on them by methods A and B are d d t with in the next section. In the second series of experiments measurements were made by method A on the following standard surface8 : Zinc freshly deposited electrolytically. Zinc freshly plished with sandpaper. Zinc exposed to a WeU-aGrated solution of NjlO-sodium chloride for 2 days.Zinc the surface of which had been exposed to air for a con-Zinc which had been heady oxidised by heating. Polished and oxidised iron surfaces were also examined. siderable time. As above mentioned all these surfaces fell into one of two broad classes one characteristic of freshly deposited metal which has never been exposed to air and the other characteristic of aiimted surfaces. Under the influence of air or differentially aerated electrolyte one surface would paas rapidly from one class to the other. In measuring the potential between standard surfaces and N/10-sodium chloride it was found that the potential Werence varied with the size of the drop. A small drop on a dry surface (with th 2608 MCAULBP AND BOWDEN AX INVESTIGATION OF TEE EFFECT exception of dried zone 4 on zinc) gave the potential associrtted with one class but if this drop were enlarged the potential immediately began to acquire the characteristic of that of the other class.This was found to be due to electrolytic action taking place between the well-aerated edge of the drop and its poorly aerated centre. The following measurements were made to confirm this result. A large drop from 1 to 2 cm. in diameter was placed on a zinc surface for about a minute and then blotted off and the potentials where the centre and the edge of the drop had rested were measured with a drop about Q mm. in diameter. The edge showed the potential characteristic of an aerated surface and the centre that characteristic of freshly deposited zinc. The latter very rapidly returned to its initial condition and when measured was usually between the two conditions and falling rapidly.To c o h further this result two zinc surfaces were prepared to simulate under very different experimental arrangements the conditions existing in large and small drops on the zinc surface. The specimen corresponding to a large drop was partly immersed in electrolyte and corroded under conditions of differential aeration. The potential of zone 4 was the same as the highest value obtained for the centre of the drop but the zone when visibly corroded did not return to the aerated state for several days. The potential of zone 3 was that of the outside of the drop. The specimen corre-sponding to a small drop was immersed in electrolyte which was well aerated throughout by bubbling air through it.It remained uncorroded and ita surface after treatment for more than 24 hours showed the potential characteristic of the small drop on a well-agrated surface. Discw&m of Results. In the corrosion of a metal immersed in an electrolyte the metal shows an equi-potential surface owing to the small currents flowing. There is however a fall of potential down the solution the positive regioas being situated where the metal is most negative to the solution. Such a region corresponds exactly to the negative plate of a simple primary cell and is called anodic. Figs. 2 and 3 summarise diagrammatically the general nature of the process that takes place. Chlorine ions move towards the anodic region under the influence of the electric field in the solution produced by the grater solution pressure in the corroded region.They there neutralise metallic ions lowering the potential difference between solution and metal and enabling more metallic ions to leave the metal. These ions on emerging restore the potential difference. Sodium ions migrate to the ennobled region and are neutralised by electrons drawn from the metal OF DIFFERENTIBL dRATION ON CORBOSION ETC. 2609 As a b d generahtion two types of d a c e may be recognised c l d e d by the potential between them and N/lO-sodium chloride. In the case of zinc the electrode potential of the first class against the normal calomel electrode is generally within 15 millivolts of -1.075 volts but may be more negative still where the corrosion is heavy.h h electrolytically deposited zinc and zone 4 of the corroded metal are in this class. They are the less noble regions on the corrosion specimens or the more anodic. The second class com-prises zones 1 2 and 3 on corroded specimens surfaces freshly polished with sandpaper specimens exposed to uniformly &mated electrolyte and all surfaces which have been exposed to air for more than a few minutes with the exception of zone 4 on corroded specimens which remains in the h t class even after prolonged FIG. 2. _- ++ 2c1A -2Na $ ++ ++ J-+ ++ ++ fi L+ Zn Zn Zn Zn Zn Zn Zn Oxidised surface. Corroded &ace. Potential diflerence -1.000 volt. Potential difference - 1.075 volt. FIG. 3. ++ ++-- -2Na ZnCG k ++ ++ ++ ++ -!+ ++ ++ Zn Zn Zn Zn Zn Zn Zn Oxidised d a c e .corroded surface. exposure to air. This second class of surface gives an electrode potential against the calomel electrode within about 15 millivolts of - 1.O00 volt. Values considerably less negative than this are obtained with specimens oxidised by heating in air. Surfaces in this second class are the more noble regions on the corroded specimens. In the case of iron few measurements against standard surfaces have been made. Measurements on corroded specimens and on polished specimens show the same general effects as with zinc the two classes of surface described above being recognised and occur-ring under similar conditions. The first class has a potential differ-ence against the calomel electrode of about - 0-540 volt the second class has a potential against the calomel electrode of - 0.340 volt.Iron surfaces of the h t class on exposure to air very rapidly chanse to the second class. This is true for zone 4 in iron which in zinc remains true t o type when exposed to air. VOL. CXXVII. 4 2610 EFFECT OF DIFFERENTLBL A.%RATION ON CORROSION ETC. Figs. 4 and 5 show diagrammatically corroded specimens of zinc and iron respectively. The potential differences as measured by method A against the calomel electrode are shown on the figures. All these potentials given against the calomel electrode include the contact E.M.F. due to the liquid junction N-KCl-N/lO-sodium chloride. No attempt wits made to standardise this contact and capillary tubes and plugs of filter-paper were in-cluded in the circuit.It is the relative rather than the absolute potentials of these zones which are of value. The principal results of the investigation may therefore be sum-marised as follows There are two normal states in which iron and zinc surfaces tend to exist one a more electro-negative state characteristic of pure metal and corroded regions the other a less electro-negative state characteristic of aerated regions. For zinc, the difference in single electrode potential between these states is about 75 millivolts; for iron it is about 200 millivolts. By drastic treatment (heavy corrosion in the first case heavy oxidation in the second) the potentials in these statestbecome more negative and more positive respectively. When drastically treated the surfaces are visibly heavily corroded and in the case of zinc do not rapidly change their condition without further drastic treatment. Experi-ments with drops have shown that surfaces having a clean bright appearance may be in either of the two s t a h and then very rapidly change from one state to the other with change of conditions. UNIVERSITY OF TASMANIA [Received August 7th 1925.1 HOBART

ISSN:0368-1645    

DOI:10.1039/CT9252702605

出版商:RSC    

年代:1925

数据来源: RSC

摘要:

PRODUCTION OF C~~TELLURIPENTAXEDIONE DICHLOBLDES. 2611 CCCLIX-Production of cycloTelluripentuned~m Dichlorides. By GILBERT T. MORGAN. [With FREDERICK JAMES CORBY OLIVER CECIL ELVINS EVELINE JONES RICHARD EATOUGH KELLETT and CYRIL JAMES ALLAN TAYLOR. ] THE search for co-ordination derivatives of tellurium and the P-diketones led to the discovery of two new groups of cyclic tellurium compounds in which the diketone concerned furnishes a bivalent chelate group. These cyclic substances are not the sole products of the condensation of tellurium tetrachloride with P-diketones and certain of the diketones examined have not given them but as the result of numerous experiments it now becomes possible to predict with a fair degree of certainty which p-diketones are likely to furnish the chelate groups required to implicate tellurium in the six-membered rings.Certain constitutioml features must be present in a p-diketone in order that it may function in the desired sense and within the limits imposed by these structural requirements the reaction is a general one. T e a 0 /\ \/ R-YH yH,R’’ R-YH VHR,” (I.) oc co -3 oc co C \/ C /\ R’ R’ /\ R’ R’ Formula I represents any P-diketone which would condense with tellurium tetrachloride to produce a cyclic telluridichloride (11) provided that the substituents R R’ and R” are of the appropriate chemical type. Acetylacetone the simplest case where R = R’ = R” = H, gives as the main product cyclotelluripentane-3 Ei-dione 1 l-di-chloride (formula II). It has however also yielded two other products both of which are non-cyclic; the h t of these is the tellwitrichloride CH,*C( OEf):CH-CO*CH,-TeCl, obtained by the intervention of ethyl alcohol present in ordinary chloroform the second is a telluridichloride which is still enolic, { CH,*C( 0H):CHCO CH,) 2TeCI,.These by-products arise evidently from interaction between tellur-ium tetrachloride and acetylacetone in its monoenolic form induced 4 s 2612 MORCAN : by migration of hydrogen from the median carbon atom. It is, however highly probable that the main cyclic product is due to con-densation with a dienolic modification m C ( OH)-CH,-C(OH):CH,, developed by twofold enolisation from the two terminal hydro-carbon radicals. The process probably takes place in two stages, the tellurium tetrachloride fht combining additively with the dienolic m&cation of the 8-diketone giving rise to the hypo-thetical addition product (IV) which by subsequent loss of two molecules of hydrogen chloride passes into the stable cyclotelluri-dichloride (11) .TeCI, It is of general interest in connexion with dynamic isomerism that in these condensations the tetrachlorides of selenium and tellurium behave dissimilarly and evoke a different response from the reacting tautomeric diketone. Selenium tetrachloride attacks the monoenolic isomeride produced by median enolisation or its analogously constituted copper derivative. Tellurium tetrachloride links up the unsaturated ends of a five-membered chain arising from twofold terminal enolisation.This explanation of the mechanism of the tellurium condensation is supported by the following experimental evidence. So long as 2R’ in the foregoing formule represent two hydrogen atoms there is considerable tendency for one of these to migrate to an adjacent oxygen atom thus giving rise to median enolisation. The result of this dynamic change in the cme of acetylacetone has already been mentioned; it leads fo two non-cyclic products. Similar non-cyclic products have been noticed with propionylacetone dipropionylmethane di-n-butyryl-methane and hexoylacetone. The last two diketones exhibit the interesting case of an enolic non-cyclic telluritrichloride, (C,H,*CH,-C( OH):CH*COCH(C,H,) 1 TeC1 and 1. Hedian enolisation. (C,H,,*CH,*C( OH):CH-CO*CH,)TeCl,.It is probable that the three types of non-cyclic tellurium com-pounds (O-ethyl-trichloride and enolic trichloride and dichloride) may be present in other condensations with non-3-alkylated p-di-ketones but that owing to instability and great solubility these products have not been isolated the experimental f i c u l t i e s becoming greater as the number of carbon atoms in the chain increases PRODUWON OF C@ITELLURIPENTAXEDIONE DICHLORXDES. 2613 2. Lengthening of the unbranched k i n . Providing that the tendency to terminal enolisation is not diminished by substitution of alkyl radicals for hydrogen in the reactive ferminal methylene groups R-WCO*C&-CO=mR' the lengthening of hydrogen chain R or R' does not prevent the formation of a cyelotelluri-pentanedione derivative and the general nature of the reaction has been demonstrated by condensing such higher ketones as n-octoyl-acetone n-nonoylacetone and n-duodecoylacetone (lauroylacetone) with tellurium tetrachloride.The last of these has yielded Z-n-hyZ-cycloteu.uripentune-3 5-dwne 1 l-didloride (VII) reducible to 2-n-decylcycloteUurope~m-3 5 - d i m (VIII). Sufficient examples have been selected to show that the pro-duction of cycZotelluripentanedione dichlorides and their reduction to cyclotelluropentane-3 5-diones are general reactions for all p-diketones having structural formula I when R and R" axe normal or unbranched hydrocarbon chains. 3. Alkylution of the median methylene group. When one B' is hydrogen and the other an alkyl group the tellurium condewation becomes simplified so that although many 3-alky1at.d fkliketones have been examined only one telluriferous product has been identified in each case.The 3-alkylacetylacetones react smoothly and give 4-alkylcyclotelluripentane-3 5-dione 1 1-dichlorides in good yield. The 3-lpropylprgmyi!acekmny~acetones (normal and iso) de-scribed below behave similarly and give rise to the two isomeric Z-~hy1-4-2wopyEcycloteuzcripentu~-~ & d i m 1 I-dichlorides (IT). 3-iso&tylacetylacetone also condenses smoothly with tellurium tetrachloride yielding only one product namely the cyclic telluri-dichloride (11). 4. Branched chzhs on the median carbon atom. 3-koBopyl-acetylac etone ( CH,) ,CH *CH (CO *CH,) and 3 - isopropylpropionyl-acetone (CH,),CHCHAc*CO*C,H, furnish interesting examples of the influence of chemical structure on median enolisation.They differ from their n-propyl isomerides in giving neither ferric nor cupric derivatives. 3-isoBut-ylacetylacetone, (CH,),CH*CH,*CH( CO-CH,),, in which a methylene group is interposed between the branched chain and the median carbon atom gives however both ferric and cupric derivatives just as readily as 3-n-butylacetyla~etone (J. 1924, 125 763). But although ordinary median enolisation is inhibited in the 3-isopropyl-P-diketones they react with tellurium tetra-chloride to give cyclic telluridichlorides. If enolisafion is an essential concomitant of the primary phase in this condensation, it is therefore more probably terminal than median. 5. 3 3-Didkyluted p - d i h e s .The fact that 3 3-dimethyl 2614 MOWAN : and 3 3-diethyl-acetylacetone both give cyclic telluridichlorides is conclusive evidence that any preliminary enolisation must be terminal since in these cases the possibility of median enohtion is absent (Morgan and Drew J. 1924,125 735 1601). In formula I the terminal chains are represented by the symbols R*CH,- and -CH2R” and it has been found that cyclic telluridichlorides are not produced unless both methylene groups ~ J X present. If cyclic condensation is prevented entirely by the conversion of one CH,R group into CHRR’ the p-diketones with one such branching chain give only non-cyclic telluritrichlorides and dichlorides. With two terminal branching chains as in diisobutyrylmethane, the formation of telluriferous products is reduced to a minimum, 90% of the tellurium is set free and the only telluriferous product is a non-cyclic telluritrichloride formed to a very slight extent (Morgan and Taylor this vol.p. 797). Benzoylacetone is incapable of twofold terminal enolisation and gives rise only to non-cyclic telluriferous compounds and for similar reitsons ill-defined products are obtainable from dibenzoylmethane. When present in the positions indicated by R R’ and R” phenyl radicals prevent completely the formation of cyclotelluridichlorides unless a methylene group is interposed. This intervention is effected at the median carbon atom by benzylating the sodium derivative of p-diketone as in 3-benzylprcvpionylacetone which condenses to form 4-benxyl-2-methylcyclotelluripentccne-3 5-dione 1 l-dichloride (VI).3-Benzyl- and 3 3-dibenzyl-acetylacetones have also been converted into cyclic telluridichlorides although condensation did not occur with 3 3-di-p-nitrobenzylacetylacetone (Morgan and Taylor la. cit.). A benzyl group waa introduced into terminal position R or R” (formula I) by operating with @-phenylpropionyZucetone which underwent condensation with tellurium tetrachloride in the normal way for although the cyclic telluridichloride was not isolated in a state of purity it was identified by conversion into its reduction product 2-benzyEcyclotellur~e~ne-3 5-dione (V). Te Te 6. Terminal branching c h i n s . 7. InJluence of aromatic groups. ,. \/ CHR R = n- or iso-C,H or CH2Ph PRODUC!L'ION OF CydQTELLlJRIPENTANEDIONE DICHLORIDES.2615 8. Reduction of cycloikUu~pentunedkme dkhhidtv to cyclo-teuuropentadiones. Apart from the chemical significance attach-ing to the new group of cyclic tellmidichlorides these derivatives are of interest from the point of view of chemical bacteriology, because each member of the group is readily reducible to a cyclo-telluropentanedione (V and VI) the reaction being a general one. Many of these cyclic telluro-derivatives are sufiiciently soluble in cold water to impart to the aqueous soluttions outstanding germicidal properties. The most powerful bacfericide of the series is 2 6-dimethylcycEotelluropntane-3 5-dione (from dipropionyl-methane) but as this derivative is difficult to produce in large amount the next most efficient members have been most exten-sively employed in bacteriological tests.These substances are 2-methylcyclotelluropentane-3 5-dione (from propionylacetone) and its 3-alkylated homologues. The methyl and ethyl derivatives have already been prepared whereas the n- and iso-propyl compounds and the benzyl derivatives all symbolised by the general formula VI, are described in the experimental part of this communication. The chemical con-stitution ascribed to cyclotelluropentane-3 5-diones (V and VI) as the result of the preceding experimental proofs is confirmed by the oximation of these substances. In general both monoximes and dioximes are obtainable, although it is evident that the progress of this reaction is affected by steric hindrance.2-Methylcyclotelluropentane-3 5-dione resembles syclotelluro-pentane-3 5-dione the simplest member of the series in yieldmg chiefly the dioxime whereas 2 -methyl- 4- e t hylc yclotellur opentane-3 5-dione yields both mono- and di-oximes and the monoxime is never entirely absent even when drastic oximation is employed. These examples and the earlier cases (Morgan and Drew Morgan and Taylor h. cit.) demonstrate the presence of two ketonic carbonyl groups in the cyclotelluropentane-3 5-diones. 9. Oximes of cyclotelluropentane-3 5-dimes. E x P E R I M E N T A L. [With FREDERICK JAMES CORBY.] 1. 2-Methyl-4-~~yEcycloteuur~entane-3 5-dione (VI). Sodium propionylacetone (23 g.) made from the diketone in dry ether wils heated for 8 hours with 80 g.of n-propyl iodide; reaction commenced a t 115" the temperature was maintained at 130" for 2 hours and finally raised to 150". The cooled mixture wm added to water the aqueous layer extracted with ether and the et,hereal extract added to the organic layer. The latter o 2616 MORGAN : fractionation furnished n-propglprophylacetone b. p. 210"/750 mm. with slight decomposition. This n-propyl diketone gave an intense bluish-purple coloration with ferric chloride quite distinct from the blood-red tints obtained with the non-3-alkylated diketones. The new diketone had a pleasant terpenoid odour and yielded with ammoniacal cupric acetate a greenish-grey voluminous precipitate of copper 3-n-propyZpropionylacetone readily soluble in acetone, methyl and ethyl alcohols and crystallising from benzene in greenish-grey silvery needles melting and decomposing a t 178" (Found Cu 16.8.2-Methyl-4-n-propylcyclotdluripentane-3 5-ddone 1 1 -Diclhloride, Cl,HMO,Cu requires Cu 17.0y0). COCH - CH,'[CH,120CH<C0.CH(CH3)>Tec1~. -After heating under reflux for 1* hours a mixture of 6 g. of 3-n-propylpropionylacetone 5-7 g. of tellurium tetrachloride and 50 C.C. of chloroform the orange filtrate from tellurium wm concentrated in a vacuum over calcium chloride until crystals of the telluri-dichIoride separated. The mother-liquor after extraction with light petroleum to remove unchanged diketone was again con-centrated and the process repeated so that three crops of crystals were obtained (yield 62%). Recrystallised from chloroform the dichloride separated in colourless prisms darkening a t 145" blacken-ing a t 150" (Found Cl 20.2; Te 35.9.CgHl,02C&Te requires C1 20.2; Te 36.15%). When suspended in ice-cold water and treated with potassium metabisulphite the dichloride was readily reduced to 2-methyl-4-n-propylc yclotelluropen tane-3 &dime (VI) with slight deposition of tellurium. The product was soluble in water but less soluble than its 3-methyl analogue ; it was recovered from aqueous solution by benzene. It was obtained from methyl alcohol in golden-yellow crystals m. p. 102" with slight decomposition (Found: C 38.3 ; H 5.1 ; Te 44.9. CgHl,O,Te requires C 38.4; H 5.0 ; Te 45*20/). 2. 2-iMethyZ-4-isopropylcyclotelluropentu,~ze-3 5-dime (VI). Sodium propionylacetone (23 g.) was heated with 120 g.of isopropyl iodide for 8 hours at 130". The cooled mixture was poured into water and the two layers were worked up as in t'he case of the n-propyl isomeride. 3-isoPrqyZpopionyZacelacetone CH3-CH,COCH(CHMe,)*CO*CH,, boiled at 195"/750 mm. with slight decomposition; it differed from 3-n-propylpropionylacetone in not developing any ferric coloration and in not giving a copper derivative with ammoniacal cupric acetate -Ten g. of the preceding diketone 9 g. of tellurium tetrachloride, and 80 C.C. of purified chloroform were heated under reflus for 2 hours and the orange filtrate waa concentrated to the cptallising point. The subsequent procedure was the =me as in the case of the n-propyl isomeride and the telluridichloride crysh- in colourless glistening prisms darkening at 168" and blackening at 173' (Found Cl 20.1; Te 35-8.C,H1,O,&Te requires C1, 20.2; Te 36.17%). Reduction in the normal way led with liberation of free tellurium, to 2-~~yZ-4-isopropylcycloteuur~ntu.~e-3 5-dione (VI) ; this pro-duct cqmtallised from methyl alcohol in light yellow needles, m. p. 127" ; it was much less soluble in water than the corresponding n-propyl compound (Found C 38.5; H 5.05; Te 44-85. C&€,,O,Te requires C 38.4; H 5.0; Te 45-10/,). An attempt was now made to prepre a third isomeride of the foregoing isomeric propyltelluro-derivatives. 3-Methylpropionyl-acetone prepared by the method formerly described (J. 1924, 125 7459 was dissolved in dry ether and converted info sodium salt.The latter was heated with 3 parts of ethyl iodide in an autoclave for 6 hours at 180" the pressure.being 10 atmospheres. The dialkylated diketone was extracted from the mixture by the procedure adopted for the two propylated diketones. On fraction-ation 3-methyl-3-ethyZprqpimylizcetone distilled at llSo/10 mm. (yield 25%). The diketone which had a fragrant odour gave neither coloration with ferric chloride nor precipitate with am-moniacd cupric acetate. In the condensation with tellurium tetrachloride and 3-methyl-3-ethylpropionylacetone tellurium was deposited and a consider-able amount of tar was produced; the telluridichloride was not isolated although it was probably present in the brown tarry chloroform solution since $his changed to bright yellow on treat-ment with aqueous metabisulphite.3. 4-BenzyZ-2-methylcyclotdluropentu.ne-3 5-dime (VI). 3-Benzylpropionylac~.-Sodium propionylacetone (34 g.) was heated under reflux with 13 g. of rectified benzyl chloride for 8 hours at 140" the product being worked up as in the caae of the propylated diketones. The benzylated diketone which dis-tilled at 185"/20 mm. waa a colourless liquid with fragrant odour; it developed an intense reddish-violet coloration with ferric chloride and with ammoniacal cupric acetate it yielded a wppm derivative 4 s 2618 MOMAN : readily soluble in alcohol acetnne or benzene to dark olive-green solutions. Copper 3- b e n z g l p ~ * m ~ ~ crystallised from these solvents in pale grey silvery needles m. p. 182" (Found Cu, 13.4. C,,H,O,Cu requires (31 1305%).4-Benzyl-2-mthyEcycloteUuripentane-3 5-dime 1 l-DkMoride, -The orange solution obtained by heating 8.5 g. of 3-benzyl-propionylacetone 5.8 g. of tellurium tetrachloride and 50 C.C. of dry chloroform for 2 hours was decanted from tellurium and con-centrated in a vacuum to the crystallising point. The mother-liquor was treated as in the caae of the propylated dichlorides and 5 g. of telluriferous product were obtained. Recrystallised from acetone the telluridichhide separated in colourless glistening prisms m. p. 168" (Found C1 17-7; Te 31.8. C,,H,,O,~Te requires Cl 17-75; Te 31.7%). Suspended in water and reduced with potassium metabisulphite, the dichloride yielded 4-benzyl-2-methylcyclotellur~entane-3 5-dione with very slight elimination of tellurium.This telluro-derivative crystallised from methyl alcohol in yellow needles m. p. 124" with decomposition. The crystals did not sublime in a vacuum and were only slightly soluble in water (Found C 47-5 ; H 4.4 ; ,Te, 38.4. CI3H,,O2Te requires C 47.3 ; H 4-3 ; Te 3843%). [With EVELINE JONES.] 1. 3-isoButylmetylacetone ( CH3),CH*CH2*CH(C0 *CH3)2. Rectified isobutyl iodide (b. p. 117-120") was obtained in 60% yield by Blaise's method (Bull. Soc. chim. 1911 9 1). A mixture of 161 g. of this iodide and 52 g. of sodium acetylacetone con-tained in a stoppered glass bottle was heated gradually in a rotating autoclave to 170" and was maintained at this temperature for an hour (pressure 150 lb. per sq. inch). The liquid contents of the bottle were drained from sodium iodide and unchanged sodium acetylacetone and the latter solids were extracted with ether.The oil and ethereal extracts were distilled together up to 124" to remove solvent and isobutyl iodide and the residue was fractionated under reduced pressure; the fraction distilling at 93-94"/10 mm. consisted of 3-isobutylacetylacetone which developed a bluish-purple coloration with ferric chloride and was purified by con-version .into its copper derivative by interaction with ammoniacal cupric acetate. Copper isobutyhtylacetone crystallised from petro-leum (b. p. 60-80") in well-defined steel-grey needles m. p. 158" (Found Cu 16-9. C,,HmO,Cu requires Cu 17-070) PRODUCTION OF C~C~!ELLURIPENTANEDIONE DICHLOIUDES. 2619 4-isoBzctylcycldeUur~~ne-3 ; 5 - d i m 1 I-&*-, -A mixture of 5.8 g.of isobutylacetylacehne and 5 g. of tellurium tetraddoride in 40 C.C. of purified dry chloroform was heated on the water-bath for 1-2 hours. The filtrate from a small deposit of tellurium ww concentrated at the ordinary temperature until acicdar crystals separated. R e c r y s t d . k d from acetone or chloro-form the dichibide separated in well-defined colourless need-, m. p. 142" (yield 2 g.) (Found Cl 20.3; Te 36-4. C&O,Te(& requires Cl 20-1; Te 36.2%). 4-isoButylcycloteUuropentane-3 Li-dione, -The foregoing dichloride when reduced with aqueous potassium metabisulphite yielded a yellow solid sparingly soluble in water. Recrystallised from benzene the tellnro-derivative separated in yellow leaflets m.p. 150" (Found C 38.4; H 5.0. C&Il4O2Te requires C 38.4 ; H 5.0%). 2. $- Phen ylpropion ylacetone C,H5*CH2*CH2CO*CH,-C0.CH,. Ethyl P-phenylpropionate prepared by boding 209 g. of P-phenyl-propionic acid for 2 hours with 900 C.C. of absolute alcohol con-taining 30 g. of hydrogen chloride was fractionated until boiling a t 244-245". The Claisen condensation was carried out with acetone and sodium in calculated quantities and ethyl p-phenyl-propionate (3 mols.) the acetone being diluted with six tima its volume of dry benzene. After 12 hours the mixture was heated on the water-bath cooled and poured on to ice the aqueous layer being treated successively with acetic acid and cupric acetate. The precipitate consisted of a mixture of copper a-phenylpropionate and copper P-phenylpropionylucetone which were separated by fractional crystallisation from benzene the latter compound being the more soluble.When purified it had a greyish-blue colour and melted a t 158" (Found Cu 14-4. C,,H,60,Cu requires Cu, 14.4%). 2-Benzylcyclotellurilientane-3 5 - d i m 1 l-Dic&&.-Hydrogen chloride was evolved with a slight deposition of tellurium when 5 g. of tellurium tetrachloride 5-3 g. of p-phenylpropionylacetone and 40 C.C. of purified chloroform were heated on the water-bath for 2 hours. The solution was concentrated in a vacuum desiccator to a dark brown jelly and stirred with light petroleum but the semi-solid maas showed no tendency to crystallise and accordingly it wm reduced with aqueous potassium metabbulphite when a 4 s* 2620 MORGAN : yellow solid sepamted mixed with tarry matter and tellurium.After extraction with hot alcohol the golden-yellow filtrate yielded 2-benzylcycloteUuropentane-3 5-dione (V) in small yellow crystals decomposing at 159" (Found C 46.8; H 3.9; Te 41.0. C1,Hl,O,Te requires C 46.6 ; H 3.8 ; Te 40.4%). [With CYRIL JAMES ALLAN TAYLOR.] 1. Copper duodecoylacetone prepared by the Claisen condens-ation from methyl undecyl ketone (Morgan and Holmea J . Xoc. Chem. Id. 1925 44 108~) was decomposed with sulphuric acid in presence of ether. The free P-diketone obtained from the ethereal layer melted at 31-32' and had the characteristic pro-perties of it8 series. 2-n-DecylcycloteUurientane-3 5-&one 1 I - D i c W (VII). (VII.) ~lo%*p*Te%*p2 C l P 2 1*(p-Te-p2 ( VI I I.) OC-CH,-CO OCLCH,-CO -Four g.of tellurium tetrachloride and 5 g. (1.6 mols.) of duo-decoylacetone were heated in chloroform solution for 3 hours. The dark brown oil obtained on evaporation was extracted repeatedly with petroleum (b. p. 40-60") to remove unchanged diketone and then left for 1 month in a vacuum desiccator. Crystallisation set in and the solid product was stirred successively with carbon tetrachloride and petroleum. The warm benzene extract of this producf was diluted with excess of petroleum when silvery-white flakes separated (yield 21%) (Found C1 16.4; Te 29.4. C,,H,,O,&Te requires C1 16.3; Te 29.2y0). 2-n-Decylcyclotelluripentane-3 5-dione 1 l-dichloride was readily soluble in cold benzene chloroform or acetone less soluble in carbon tetrachloride and dissolved only sparingly in petroleum; it melted a t 89'.2-n-D~~~ycloteUuropentane-3 5-dione (VIII) obtained by the reduction of the preceding substance with alkali bisulphite crystal-lised from aqueous alcohol in pale yellow woolly masses m. p. 98-99' (decomp.) (Found C 49.1 ; H 7.1. C,,H,,O,Te requires C 49.25; H 7.1%). This telluropentanedione derivative was readily soluble in cold benzene or alcohol insoluble in water but dissolved in dilute aqueous caustic soda especially on warming; on prolonged boiling, tellurium was deposited. 2. Tellurium Tetrachloride and 3-Phe.lzylpropionyt~n~. Four g . of tellurium tetrachloride were added to 6.0 g. (2 mols.) of 3-phenylpropionylaetone (Ber. 1925 58 340) in 25 C.C.of chloroform and the solution was boiled for 1-2 hours. Afte PRODUCTION OF CZJ~QTELLURTPENTANEDIONE DICHLORIDES. 2621 evaporating off the solvent the tarry residue waa extracted twice with light petroleum and digested with carbon tetrachloride and the solution in this solvent concentrated when crydalbation set in. The product which was much discoloured separated from carbon tetrachloride in colourless lamella! m. p. 64-68". It gave the enolic reaction with ferric chloride and was very sensitive to moisture; it did not evolve the earthy odour of an 0-ethyl P-diketone with cold alkali. The condensation was varied by changing the proportion of di-ketone but the products were similar and contained about 19-40/; of chlorine with C 27.1 ; H 2.6%.These numbers did not corre-spond with the values calculated for a cyclic dichloride X"TeC.&, or for di- and tri-chlorides of the type X'TeG and X'2TeC14. The reduction product with alkali bisulphite was unstable. It was therefore evident that the condensation of 3-phenylpropionyl-acetone with tellurium tetrachloride did not lead to a derivative of the cyclotelluripentanedione dichloride series. [With RICHARD EATOUGH KELLETT.] 1. 2-blethyEcyclote1lu~~opentane-3 5-dione Dioxhe, CH,.FH-Te-piH* NOH:C-CH, -Two g. of hydroxylamine sulphate in 30 C.C. of water were added to 0.7 g. of 2-methylcyclotelluropentane-3 5-dione (J. 1923 123, 450) in 50 C.C. of water ; the solution was neutralised with sodium hydroxide and warmed on the water-bath. The crude oxime separated on cooling in minute yellow crystals.Extraction of this precipitate with boiling benzene gave a small amount of soluble product probably monoxime blackening at 135-150". The residue dissolved in warm alcohol and separated in greykh-yellow crystals darkening at 153" and melting sharply at 161.5" (Found N 10-4; Te 47.0. C,H,,0~2Te requires N 10-4; Te, 47 -3 Yo). The dioxime was insoluble in hot water or benzene. 2. The O x i m of 2 - M e t h y l - 4 - e t ~ y ~ y c ~ o ~ ~ ~ ~ ~ - 3 5-dione. -Two g. of hydroxylamine sulphate in 50 C.C. of water were addd to 0.7 g. of 2-methyl-4-ethylcycluropentane-3 5-&one (J., 1924 125 758) in 50 C.C. of warm alcohol. Sodium acetate was added with sufficient water to bring the reagents into solution when heated on the water-bath.Some tellurium separated and after 10 minutes the cooled solution deposited a voluminous mass-of yellow crystals; the greater part of this dissolved readily in warm benzene but the nitrogen content of the crystalbed product waa 7-7 that is intermediate between 5-0 and 9-4 required fo 2622 MORGAN : the mono- and di-osimes respectively. The mixture ww extracted with either boiling water or a small amount of benzene. After repeated crystallisation the more soluble momxime was isolated in bright yellow crystah blackening at 135" and melting at 157" (Pound N 5.1 ; Te 45-1. C,H,,O;NTe requires N 5-0; Te, 45- 1 yo). 2 - ~ e t ~ y l - 4 - e t h y l c y c l o t e l l u r ~ e ~ ~ - ~ $dime wwrwxime (IX) was only sparingly soluble in hot water and decomposed slightly in aqueous solution.(IX.) 08-CHEt-C:NOH NOH%CHEzzOH (x') CH,. H-Te-YH CH,* H-T 2-~ethy~-4-ethyZcycloteZZu~opentane-3 5 - d i m Dioxime (X).-Oximation to the dioxime was never complete even on carrying out the condensation in solutions rendered alkaline with sodium hydroxide either by direct treatment of the diketone or by the further action of hydroxyla,mine on the monoxime. The mixed products from either of these operations were extracted with boiling benzene to remove monoxime and the residues crystallised from boiling alcohol in which they dissolved without decomposi-tion. The dioxime separated as a greyish-yellow cryst,alline powder blackening at 170" and decomposing at 182" (Found N 9-7 ; Te 42.7. The dioxime is practically insoluble in hot water or cold benzene, more soluble in the latter on boiling and dissolves with slight decomposition in warm acetylacetone.C,H,,O,N,Te requires N 9.4; Te 42.85%). [With OLIVER CECIL ELvrnTs.1 1. 4-sec.-Butylcyclotelluri(pentane-3 5-dione Bichloride. sa.-Butyl alcohol synthesised by Wood and Scarf's process ( J . Soc. Chem. Ind. 1923 42 1 3 ~ ) (74 g.) was converted into sec.-butyl iodide by treating with red phosphorus (20 g . ) and iodine (128 g.), the latter reagent being added in small quantities. After warming the mixture the iodide was distilled off washed with aqueous sodium carbonate dried and fractionated (b. p. 117-118"). 3 - sec .-But yZucet ylacetone (CH,-CO) ,CH- CH ( C2H 5 ) =CH was o b -tained by heating in a rotating autoclave at 14&160" for 2 hours (pressure 120 lb.per sq. inch) 35 g. of sodium acetylacetone and 10 g. of 8s.-butyl iodide. The resulting mixture was filtered the sodium iodide washed with ether and the combined filtrates were distilled first under the ordinary and then under reduced pressure. The fraction boiling at 110-113"/13 mm. was again rectified until it ceased to give the red coloration with ferric chloride. Th PEODUCIXON OF C ~ % T E . L L ~ E ~ A N E D I O N E DICHLOBXDIES. 2623 final product boiled at 109-111°/13 mm. but the yield was only 9% of theory. 3-sec.-Butylacetylacetone gave no copper derivative with am-moniacal copper acetate but underwent condensation with tellurium tetrachloride. A chloroform solution (30 c.c.) of the latter reagent (2-9 g.) and diketone (2-5 g.) evolved hydrogen chloride on boiling and 0-2 g.of tellurium was set free. The fltrate concentrated in a vacuum to a brown tar solidikd on treatment with light petroleum. The solid product c r y s m from benzene in lustrous, colourless prismatic peedles darkening at 162" and melting at 168-169" (yield 370/,) (Found Cl 20.0. C,H,,02C4Te requires 4-sec.-Butylcyclotripentane-3 5-dione 1 1-dichloride (XI) wa8 reduced with aqueous sodium bisulphite and the insoluble reduction product was extracted with benzene and c r y s m from alcohol. EEI,-Te%?H CH2-Te3H2 (XI.) 0-YH-CO b V H - C O (XTJ-1 CH3*CH*C2H5 CH3*CH-C2H c1 20.1y0). 4-sec.-ButyZcyclotelluropentane-3 5-dione (XI) was obtained in C 38.2; H 5.3. primrose-yellow needles m.p. 145" (Found : C,H,,O,Te requires C 38.45; H 540/b). 2. 4-sec.-dl-Amylcyclotelluripentune-3 5 - d i m 1 l-Dichloride. (m.1 CO- FH-60 CO-H-ZO (m-1 -An intimate mixture of 52 g. of dl-amyl iodide and 20 g of sodium acetylacetone was maintained at 130" for 2 hours in the rotating autoclave (100 lb. per sq. inch) and fhally at 160" for 30 minutes. The oily product and the sodium iodide were treated as in the preceding preparation (p. 2622). dl-sec.-Am?/lacetylacetone wit8 obtained as an oil b. p. 116"/15 mm. (yield 36%). In alcoholic solution this 3-alkylated diketone developed a purple coloration with ferric chloride the liquid becoming blue on addition of water. With ammoniacal cupric acetate the copper derivative was obtained ; it crystallised from methyl alcohol in greenish-grey needles m.p. 120" and was very soluble in chloroform benzene or petroleum (b. p. 80-100") but dissolved only slightly in light petroleum (b. p. 40-60") (Found Cu 16-2. C&€=04Cu requires Cu, 15.9y0). Condensation of the diketone and telIurium tetrachloride was effected in purified chloroform and the cyclic &chloride extracted aa in the preceding preparation (p. 2623) the yield being 35%. FQ-TeC&*H2 p2-Te- Hz CqCHMeEt CQCHMeE 2624 PRODUCTION OF CY~OTEUURIPENTANEDIONE DICHLOBIDES. 4-sec.-Amylcyclotelluri~en~~-3 5-dime dichbride (XIII) crys-tallised from benzene in colourless lustrous prismatic needles darkening at 136" and melting at 162" (Found CI 19.6; Te 34.5. Clo13,60,C&Te requires Cl 19.3 ; Te 34-8:4,).4-sec.-AmylcycloteUuro-pentane-3 5-dim (XIV) obtained from the preceding dichloride by reduction with bisulphite c r y a a from benzene or dilute alcohol in pale yellow leaflets dissolving sparingly in hot water and soluble in benzene but insoluble in petroleum (b. p.-40-60"); m. p. 138-139" (Found C 40.9; H 5.7. C,oH,,02Te requires C 40-6; H 5.45%). Although the two foregoing telluriferous compounds containing sec.-amyl groups were obtained as crystalline products the con-densation of tellurium tetrachloride with 3-sec.-amyZdipropionyl-methane resulted in oily products. This 3-akylated diketone was obtained without using the autoclave by heating under reflux 20 g. of sec.-amyl iodide and 5 g. of sodium dipropionylmethane for 1 hour at 140-145"; sodium iodide separated slowly and the oily product on distillation yielded 2.5 g.of the diketone b. p. 137"/15-17 mm. which developed a purple coloration with ferric chloride. Copper 3 -sec . -amyl&ipropion ylmethune was slowly formed on shaking the diketone with ammoniacal cupric acetate. Crystalljsed from petroleum b. p. 60-SO" it separated as a greenish-grey meal m. p. 105"; it was very soluble in benzene or chloroform (Found Cu 14-5. Addendum.-In addition to the copper derivatives obtained as above from the open-chain diketones the following metallic deriv-atives from the cyclic acetylmethylcyclohexanone (Leser Bull. Soc. chim. 1900,23 370; 1901,25 196) were examined. The diketone employed had D:T 1-024 and [a]& + 105.8". Its copper deriv-ative was examined for the presence of isomerides by fractional crysta,llisation from alcohol but no change in the melting point (186") was noticed.A benzene solution was too deeply coloured for determination of its rotation. Beryllium Acetylmethylcyclohmanone Be( C,Hl,02)2.-On shaking together a concentrated solution of beryllium acetate containing sodium acetate and 1.5 g. of acetylmethylcyclohexanone in 30 C.C. of alcohol a white precipitate of the beryllium derivative was obtained in quantitative yield. This producf was very soluble in benzene or chloroform; evaporation of the latter solution led to a glass which became crystalline on rubbing. Minute crystals obtained from petroleum (b. p. 80-100") melted at 159-160". Four crops of crystals obtained by fractionation from petroleum were examined at 17" in the polarimeter (0-5 g. in 10 C.C. of benzene ; 1 = 1). The rotations and melting points remained constant : C,H,,O,Cu requires Cu 13.9%) INTEB~CTIONS OF TELLURIUM TETB~CHM;BIDE ETC. 2625 a 2*66" 2-67" 2-66" 2-68' ; m. p. 160" 159-5" 160' 1596" ; whence [ a g + 106-4" or [MI + 335" (Found Be 2-95. C,,H&,Be requires Be 3.0%). The authors desire to express their thanks to the Advisory Council of the Department of Scientific and Industrial m h , to the Government Grant Committee of the Royal Society and fo the Research Committee of the University of Birmingham for grants which have helped to defray the expense of this investigation. UNIVEBSITY OF BIEWINGHAM, EDGBASTON. [Received October 2 4 1925.

ISSN:0368-1645    

DOI:10.1039/CT9252702611

出版商:RSC    

年代:1925

数据来源: RSC

摘要:

INTEB~CTIONS OF TELLURIUM TETB~CHM;BIDE ETC. 2625 CCCLX.-lnteractions of Tellurium Tetrachloride and 2MolnOketonM. By GILBERT T. MORGAN and OLNER CECIL ELVINS. A COMPREHENSIVE study of the interactions of tellurium tetra-chloride and p-diketones summarised in the preceding communi-cation furnishes considerable experimental evidence in support of the view that condensations leading to cyclotelluripentmedione dichlorides are due not to median enolisation of the p-diketones, but to a twofold terminal enolisation of these tautomeric substances. Tellurium tetrachloride combines additively with the two double linkings a ring structure is set up and then by loss of hydrogen chloride (2 mols.) the telluripentanedione ring is stabilised this condensation being characteristic of the majority of known (3-dikefones (see p.2612). If this explanation of the cyclotelluripenwedione condenst&ion is correct then it should be possible to bring about an interaction between tellurium tetrachloride ‘and a monoketone provided that the latter is capable of enolisation. The general chemistry of the monoketonm provides many examples of reactions explicable on the supposition that the immediately effective reagent is a dynamic isomeride produced by enolic change: RCOCH RC(OH):CEI& Our earlier knowledge of organic tellurium derivatives is derived largely from the researches carried out .by Michaelis and his pupils in the &stock laboratories. An investigation dealing inter dia with monoketones is due to Rust (Ber. 1897 30 2833) who described the reaction in anhydrous ether between tellurium tetra-chloride and acetophenone as leading to teUurium bbaeeto-phawm diclzhide (“ dichlorotelluroacetophenon ”) yellowish-white needles 2626 MOWAH AND ELVINS INTERACTIONS OF m.p. 186-187”. We have confirmed this observation except as regards the colour; we cannot substantiate the statement that “Mit gewohnlichen Aceton gelang es jedoch nicht ein solches Produkt zu erhalten.” Although the experimental difficulties are greater in the case of acetone than with some of its immediate homologues neverthe-leas interaction does occur with the formation of tellurium bisacetone dic?ihicZe (CH,*CO*CH,),TeC&. The yield is small-about 170//, of theory-due to the comparative instability of the purely aliphatic dichloride and also owing probably to the formation of an even more readily hydrolysable trichloride.The latter supposition is confirmed on passing to the next homologues of acetone methyl ethyl ketone and diethyl ketone which furnish respectively, in excellent yield tellurium methylethylketone trichlmide, CH3*CH,*CO*CH,*TeC13 and tellurium diethylketone trichloride, CH,-CH,*CO*CH(CH.,)*TeCl,. The lengthening of the normal chain in di-n-propyl ketone does not appreciably modify this tendency for in this case also the sole product is tellurium di-n-propylketone trichloride, CH3*[CH,],~CO*CH(C,H,)-TeC1,. On the other hand methyl n-propyl ketone methyl isopropyl ketone methyl n-butyl ketone and methyl isobutyl ketone resemble acetone itself in furnishing dichlorides (pp.2628-9). Accordingly the two modes of reaction may be generalised as follows : 1. RC(0H):CHR’ + Re?( OH)*yHR’ + R-CO-YHR‘ Cl-T&& Cl TeCl (1.1 TeCl, 2. R*C(OH):CHR’ R*CCl(OH)*yHR’ C & x e & + TeCl + (RCO*CHR‘),TeC4. The c a e of pinacolin or methyl tert.-butyl ketone is noteworthy, for in this instance both products were identified namely tdurium p i d i n trichloride (111) and tellurium bispinacolin dichbride (IV) . R*C( 0H):CHR’ R*CCl( OH)*CHR’ (11.) With pinacolin the enolisation can occur only in one way whereas in the other foregoing unsymmetrical ketones there are alternative possibilities of enolic change and these complications combined with the hydrolysable nature of the trichlorides have prevented the isolation of both telluriferous products.The respective solubilities of the di- and tri-chloro-derivatives vary irregularly with th TEIUJIUUM TETRACHLOBXDE AND MONO~ETONES. 2627 ascent of the homologous series so that except in the case of the pinacolin producfs only the less soluble compound is isolated. Moreover with the substitution of alkyl radicals for the hydrogen atoms of acetone there will be a diminished tendency for enolisation. With the p-diketones this substitution was found to be a deter-mining factor ; diisobutyrylmethane { (CH3)2CH*CO)2CH2 had lost the property of giving a cyclic tellurium derivative possessed by dibutyrylmethane (CH,CF&*C~CO),CH2. The effect of progressive alkylation of acetone has been tested. Methyl ethyl ketone diethyl ketone and methyl isopropyl ketone have given characteristic telluriferous derivatives.Two higher homologues ethyl isopropyl ketone and dikopropyl ketone also have been compared. The former undoubtedly reacts with tel-lurium tetrachloride for the inorganic reagent passes into solution and hydrogen chloride is evolved. The telluriferous product is, however oily and readily hydrolysable ; so that it was not isolated. Diisopropyl ketone behaves entirely Merently from all the other aliphatic ketones examined. Under the same experimental conditions the tellurium tetrachloride remains undissolved no hydrogen chloride is evolved and both reagents may be recovered quantitatively. Our observations were extended to mixed ketones containing aromatic radicals and the aliphatic homologues of acetophenone were shown to M e r from this substance in yielding tric-.An exceptionally stable t m ' c W e was also obtained from phenyl benzyl ketone. It is noteworthy that these arylated derivatives including tel-lurium bisacetophenone dichloride are colourless. The yellow tinge of the latter described by Rust may be due to a trace of the yellow etherate of tellurium tetrachloride due to the employment of dry ether as solvent (compare Rohrbaech Annalen 1901 315 9). E X P E R I M E N T A L . I. Alipilatic Ketones. Tellurium Bisacetone DicWde (CH3-CO*CH,),TeCI,.-Two g. of redistilled acetone (2 mols.) were heated under reflux with 4.7 g. of teIlurium tetrachloride (1 mol.) and 30 C.C. of dry chloroform. The turbid yellow solution rapidly evolved hydrogen chloride and after 40 minutes the filtrate from less than 0.1 g.of tellurium was concentrated to a brown syrup in a vacuum desiccator. A small portion was extracted with petroleum (b. p. 4-0-60") dissolved in carbon tetrachloride and the solution diluted with petroleum; crystals then separated which were used for seeding the remainder of the syrup. The resulting crop of colourless needles was draine 2628 MORGAH AND ELVINS INTERACTIONS OF on porous plates when 0.9 g. waa obtained being 16.7% of theory. Recrysfallised from carbon tetrachloride and chloroform in equal volumes the substance separated in colourless nacreous plates, m. p- 126-128" (Found C 22.8; H 3.35; Te 40-7 ; Cl 22-7. C,H,,O,~Te requires C 23.0; H 3-2; Te 40-8; Cl 22.7%). T'eUuriurn bbmetone die-e also separated from chloroform and light petroleum in colourless crystals a small amount of tel-lurium being eliminated.When reduced with aqueous bisulphite, the compound was decomposed with separation of tellurium. Tellurium Meth ykth yl ketone Trichbride C,H,*CO*C%TeCl .-The boiling turbid yellow solution of 4 g. of tellurium tetrachloride, 1.9 g. of methyl ethyl ketone and 28 C.C. of dry chloroform rapidly evolved hydrogen chloride and only a trace of tellurium separated. On concentration the brown syrup yielded 3.5 g. of trichlmide (75% of theory) which crystallised from carbon tetrachloride in small colourless prismatic needles m. p. 101-101-5" (Found: C1 34.7; Te 42-35. C4H70C&Te requires C1 34.9; Te 41.80/). The trichloride was readily soluble in chloroform; it decomposed slightly in b0iI.q solvents and blackened on keeping.TeUur i um Bismethpl -n-ywop yl ketone Dichlorid e, (C,H,*CO-CH,),TeCI,. -The yellow solution from 3 g. of methyl n-propyl ketone (b. p. 101~5-102") 4.1 g. of tellurium tetrachloride and 25 C.C. of chloro-form when decanted from tellurium (0-2 g . ) and concentrated to a syrup did not solidify until triturated with petroleum ; colourless needles then separated (0.8 g.). As this substance decomposed in contact with its mother-liquor it was rapidly dried on porous tile and recrystallised from carbon tetrachloride; m. p. 92-93" (Found Cl 19.5; Te 34.3. CloHl,O,C&Te requires Cl 19.3; Te 34.6%). Tellurium Bismet h ylisoluropy 1 ketone Dich bride, ((CH,),CH*CO*CH,)2TeC12.-Methyl isopropyl ketone (3 g.) 4-1 g. of tellurium tetrachloride, and 28 C.C. of chloroform rapidly evolved hydrogen chloride and the concentrated solution yielded 3-4 g. of crystalline product (52y0 of theory). The dichloride crystallised readily from carbon tetrachloride in colourless needles softening at 85" and melting at 90" (Found Cl 19.4; Te 34.3. C,,H,,O,Cl..Te requires CI = 19.3; Te = 34.6%). Tellurium Bismeth yl-n- but yl ketone Dichloride, ( C4€&*CO-CH,),TeC1,. -Methyl n-butyl ketone (3 g.) 2-7 g. of tellurium tetrachloride, and 20 C.C. of chloroform were treated as in the preceding preparation. The brown syrup yielded no solid product until extracted wit TELLURIUM TETFUCELOIUDE AED MONOKETOXES. 2629 petroleum to remove unchanged ketone.Thie extract yielded a small amount of solid and a further amount w a ~ obtained by extracting the residual oil with carbon tetrachloride (told yield 1.1 g.). After two crystallisations from this solvent nacreous, colourless plates were obtained m. p. 62" (Found Cl 17-8. C,,H&O,C&Te requires Cl 17.9%). TeUum'um B i s ? n e t h y l i a o h t y l ~ Dicklmi.de, { (CH,)2CH*~.CO=cH2),TecZ,. -The addition of 3.6 g. of tellurium tetrachloride to 3 g. of methyl isobutyl ketone in 20 C.C. of Chloroform resulted in a bulky yellow precipitate which decomposed rapidly on exposure to the atmo-sphere. On hating the mixture under reflux this precipitate dissolved with evolution of hydrogen chloride and the clear brown solution on concentration yielded 2-7 g.of colourless needles (45.5% of theory). Recryshllised from carbon tetrachloride the sub-stance separated in colourless plates m. p. 95"; the acicular form gave the same mixed melting point (Found Cl 17.8; Te 31-75. C,,&O,$Te requires Cl 17.9; Te 32.2%). TeUurium DietAylketone T r z k M CH,*C~CO~CH(CH,)-TeCl,. -Less than 0.1 5. of tellurium waa eliminated on boiling together 2 g. of diethyl ketone 3-1 g. of tellurium tetrachloride and 22 C.C. of dry chloroform; the filtrate on concentration yielded several crops of trichloride (3.1 g. or 84-6y0 of theory). R e c r y a m from carbon tetrachloride the t r i c M e separated in colourless plates m. p. 77-78' (Found Cl 33.4; Te 40-5. C,€€,OCl,Te requires c1 33.5 ; Te 40.0:/,). The trichloride decomposed shghkly in hot solvents.T eUurium Di -n-propgl ketone T richloride, CH3-CH,-CH2CO*CH( CH,*CH,)*TQ. -The concentrated solution from 3 g. of tellurium tetrachloride, 1.3 g. of butyrone and 20 C.C. of chloroform deposited mawes of greyish-brown silky needles (3 g. or 77% of theory). Recrystal-obbined in colourless needles m. p. 70" (Found Cl 30.7 ; Te, 37.1. C,H,,OCI,Te requirea Cl 30.7; Te 36.7%). This t'richloride waa somewhat unstable in hot acetone and underwent hydrolysis on exposure to moist air. Interactim of TeUurium T e t r a e m and Pidin.-The turbid yellow solution of 2.5 g. of pinacolin 3.4 g. of tellurium tetrachloride and 25 C.C. of chloroform evolved hydrogen chloride on boiling and after 40 minutes the brown liquid when treated with half its bulk of petroleum (b.p. M") yielded Wurium pinacolin t- . (formula 111) in colourl~ plates. When this waa recrys-tallised from carbon tetrachloride some elimination of fellurium lised from carbon tetrachloride and petroleum the triddmde W 2630 MORUAN AND ELVINS INTEEA~ONS OF occurred in the hot solvent; the filtrate deposited colourless, rhomboidal platelets softening a t 110" and melting at 114-115". The yield was 0.9 g. or 21% of theory (Found C1 32-0; Te 38-1. C,H,,ocI,Te requires Cl 32-0; Te 38.3%). The mother-liquor from the trichloride preparation furnished on concentration a crystalline residue which after two crystaktions from carbon tetrachloride separated in colourless needles m. p. 191-192"; yield 1.6 g. or 26% of theory (Found C 36.0; H, 5.7 ; Cl 18.25 ; Te 32.3.C,,GO,qTe requires C 36.3 ; H 5-55 ; a 17.9; Te 32.27'). Tellurium bbpinacolin dichlmide (formula IV) was much more permanent in air than the preceding trichloride but all attempfs at removing the chlorine were unsuccessful; the use of potassium metabisulphite or neutral sodium sulphite (Vernon J. 1920 117, 892) led to elimination of tellurium. Interaction of Tellurium TetrachEom'de and Ethyl isoPropyl Ketone. -Fifteen g. of diethyl ketone were alkylated with methyl iodide and caustic potash at 120-130" (Nef Annalen 1900 310 325). The product was fractionated and ethyl isopropyl ketone boiling at 114-116" was employed in the following condensations. Tel-lurium tetrachloride (2.7 g.) .was readily dissolved by boiling in 20 C.C.of dry chloroform containing from 1 to 2 g. of the ketone. Hydrogen chloride was evolved only a small amount of tellurium (0.1 g.) was eliminated and on concentration a brown syrup was obtained which did not however yield a crystalline product. Extraction with organic solvents' and the addition of hydrogen bromide or ferric chloride also failed to furnish solid derivatives. On exposure to air the oily syrup slowly evolved hydrogen chloride, and the final residue contained only inorganic compounds of tellurium. Tellurium Tetrachloride and Diisoprop yl Ketone.-Bisopropyl ketone b. p. 123-124" was prepared by Nef's method (loc. cit.) from ethyl isopropyl ketone and purified through its crystalline oxime (m. p. ZS") which was distilled under reduced pressure and hydrolysed with concentrated hydrochloric acid.Tellurium tetra-chloride ( 2 6 g.) was boiled for an hour with 2 g. of diisopropyl ketone and 20 C.C. of dry chloroform a process which in all the preceding experiments had led to condensation. In this case, however the tellurium tetrachloride remained insoluble and unchanged. 11. Mixed Retones containing Aromatic Radicab. Tellurium bisacetophenone dichloride prepared by Rust (h. cit.) by heating 2 mols. of acetophenone with 1 mol. of telluriu TELLURIUM TETRACHLORIDE AND MONOKETONES. 2631 tetrachloride in ether was then described a,s cryatallising in yellow needles m. p. 186-187". Three g. of acetophenone 3.5 g. of tellurium tetrachloride and 15 C.C. of chloroform were boiled under reflux and the dark brown solution was concentrated to a crystalline maw of dichloride.After two crystdbtions from chloroform tellurium bisaceto-phenone dichloride separated in colourless needles m. p. 18& 187" (Found (3 16.2. Calc. Cl 16.3%). Reduction of this dichloride with potassium metabisulphite led to the elimination of tellurium. Tellurium Phenylethylktone T & W , C ,H ,*CO-CH ( CH,) *TeCl . -After boiling for 45 minutes the solution of 3 g. of tellurium tetrachloride 3 g. of phenyl ethyl ketone and 25 C.C. of chloroform was concentrated to the crystallising point. The solid (2.5 g. or 61% of theory) was crystallised from carbon tetrachloride in a dry atmosphere to obviate hydrolytic decomposition by moisture when large colourless rhomboidal prisms separated m.p. 116115" (Found C 29.1 ; H 2-5 ; Cl 29.0 ; Te 35-0. C,H,OCI,Te requires C 29.4; H 2.45; (3 29.0; Te 34.7%). Tellurium Phen yl -n-prop ylketone Trichluride, C ,H 5*C 0 CH ( CH,*CH,)*TeC13. -The condensation of 2-8 g. of tellurium tetrachloride and 3 g. of phenyl n-propyl ketone in 20 C.C. of chloroform was carried out as in the preceding preparation. On concentration 2-8 g. of solid were obtained (71% of theory). Recrystallised from carbon tetra-chloride the product separated in colourless prisms blackening at 122" and melting at 128-129" (Found Cl 27.7; Te 33.1. C,,,Hl10C13Te requires Cl 27-95; Te 33.5%). Tellurium Phenylbenzylketone T r i c M c 6H5*CO*CH ( C6H 5)*TeC13. -Phenyl benzyl ketone was prepared by reduction of benzoin with zinc dust and glacial acetic acid (Sudborough J. 1897 71 219). Two g. were condensed with 2.7 g. of tellurium tetrachloride in 20 C.C. of chloroform. The concentrated solution furnished a greyish-green crystalline mass (2.6 g. or 60% of theory) which was recrystallised from carbon tetrachloride or from chloroform-petroleum when colourlw facetted prisms were obtained m. p. 142-143" (Found Cl 24.7 ; Te 30.1. CI4HllOCI3Te requires C1 24-8; Te 29.7%). This trichloride was readily reduced by aqueous potassium metabisulphite to a yellow solid which however waa very unstable and decomposed rapidly either on exposure or in chloroform solution 2632 EINU AND YURCH TRYPANOCIDAL ACTION The authors desire fo express their thanks to the Advisory Council of the Department of Scientific and Industrial Research and to the Government Grant Committee of the Royal Society for granb which have helped to defray the expense of this investigation. UNIVE~SITY OF BIILM~J~HAM, EDGBASTON. [Received Odober 2nd 1925.

ISSN:0368-1645    

DOI:10.1039/CT9252702625

出版商:RSC    

年代:1925

数据来源: RSC

摘要:

2632 EINU AND YURCH TRYPANOCIDAL ACTION CCCLX1.-Trypnocidal ,4ction and Chemical Con-stitution. Part 11. Srylamides of 4-Aminophenyl-arsinic Acid. By HAROLD KING and WILLIAM OWEN MURCH. IN Part I (J. 1924 125 2595) about 25 arylamides of 4-amino-phenylarsinic acid were described with their toxicities to mice and their curative action on experimental trypanosomiasis in mice. Of this series of substances the one clearly indicated for further development was 3’-aminobenzoyl-4-aminophenylarsinic acid (11; R = H) which had a toxicity of 0.6 and a temporary curative action in a dose of 0-18 milligram per gram of mouse. NO2 NH2 R/-\CO*NHr\As03H2 + R/-\CO-NH/-\ASO,H \-/ \-/ \-/ NO2 NH2 NH, \-/ \-/ \-/ (11.) \-/ NO2 \J (I.) -1 R /-\CO*NH/-\AsO,H + R r\CO*NHr\A~O,H, There were two obvious ways of modifying this structure with a view to following the change in its curative action.The one was to replace the m-aminobenzoyl group by other m-aminobenzoyl radicals substituted in the p-position. The parent p-substituted m-nitrobenzoic acids are readily accessible in quantity provided the p-substituent is op-directive by starting from the p-substi-tuted anilines which by the Sandmeyer reaction for the prepar-ation of nitdes saponification and nitration yield the required p-substituted m-nitrobenzoic acids. Anisic acid is however more readily accessible from anethole MeO*C6H1-CH:CHMe a process having been evolved whereby it may be obtained in large quantities in almost quantitative yield. The other way was to re-nitrate the mononitroarylamide {I) in the hope that the main product would be a dinitroarylamide of the type (111) which would give a series of interesting diamines (IV).P I . 1 (IV. AND CHEMICAL CONS!PITUTION. PABT II. 2633 This hw now been done a aeries of p-eubstitutd m-nitrobenzoic acids having been prepared in which R = Me OMe OEt O.CO&t, or Cl. These readily yield the corresponding acid chloridw which can be introduced into 4-aminophenylarsinic acid in ao--sOyo yield by suitable m&cations of the Schotten-Baumann method, e t h y l t + q l CW for instance being relatively sensitive to hydroxyl ions necessitating the use of sodium acetate as halogen acid fixative. The corresponding aminomink acids were obtained by reduction with ferrous chloride and alkali in 55-95 yo yield the et h yhrboncstonit robenzo y 1 -4-aminup7~n ylarsinic acid (U) being first converted into the hydroxynitro-acid (VI) by alkali.(v.1 EtO2C*Or~C0*NH<~AsO3H2 \-/ + NO2 NO2 HOC_>CO*NH<~>A.03H2 (VI.) The maximum dose tolerated by mice expressed in milligrams per gram of mouse of the six isomeric nitro-benzoylarsinic acids (I) with variation of the group R is shown below : R = .................. H. Me. OMe. OEt. OH. C1. Doeis toleruta ...... 0.6 0-2 0.2 0.2 0-8 0-2 whereas for the corresponding amino-acids (11) the maximum tolerated dose and the minimum curative dose on Trypamma equiperdum in mice are given, R = .................. H. Me. OMe. OEt. OH. C1. Doeis to2era.h ...... 0.6 0.3 0.7 0-6 0.5 0.1 D O S i 8 CU~&~VCZ ......0.18 0.15 0.4 0-6 0-2 0-075 ( T = 3) (T = 10) (T = 10) ( r = 7) r signifying the number of days during which the blood-stream remains free from trypanosomes. Of this group two members have effected permanent cures in mice and of these two the p-meth-osy-derivative was superior to the p-chloro-derivative. A m i n o h ~ d r o x ~ b e n z o y l - 4 - a ? n i ~ ~ n y ~ r s i n ~ acid the reduction product of (VI) was of special interest because it contained the o-aminophenol grouping of salvarsan (VII) and could therefore be reduced to an arseno-derivative (VIII) soluble in alkalis and suitable for experimental testing on trypanosomiasis. This -no-base was ten times as toxic (T = 0.05) as its parent amino-acid and on two-fifths of this dose (C = 0.02) a temporar 2634 KING AND MuacH TRYPANOCIDAL ACTION cure of mice was effected for 7 days.The therapeutic indices, CITY for the parent amino-acid and its arseno-derivative are thus identical. The acetylation of the amino-groups in substituted arsinic acids can readily be effected by dissolving in alkali and shaking with excess of acetic anhydride. When applied to the o-aminophenol grouping in 3'-amino-4'-hydroxybenzoyl-4-aminophenylarsinic acid, a practically quantitative yield waa obtained of the ON-diucetyl derivative which on standing in solution in A'-sodium hydroxide, gave the N-acetyl derivative. ON-Diacetylation under such con-ditions has apparently only once previously been observed by Raiford and Greider ( J . Amer. Chem. Soc. 1924 4.6 430) who obtained some diacetyl derivative on acetylation of o-aminophenol in sodium hydroxide solution it having been overlooked by Lumiere and Barbier (Bull.Soc. chim. 1905 33 783) who recommended aqueous acetylation. It seems however to be a general method for the preparation of ON-diacetyl derivatives provided the pro-duct when once it is formed is never subjected to high concen-trations of hydroxyl ions. Applied to o-aminophenol-p-arsinic acid it readily yields the ON-diacetyl derivative. 3'-Acetylamino-4'-acetoxybenzoyl-4-aminophenylarsinic acid proved to be devoid of trypanocidal action. The avenue opened by the curative action of aminoanisoylamino-phenyhrsinic acid was explored by the preparation of its N-acetyl and N-carbethoxy-derivatives of its formuldehydesulphoxylate and its carbamide.Of these four substances the former two were tested therapeutically but proved to be devoid of trypanocidal action. As this might be ascribed to loss of amphoteric character through acylation of the amino-group by non-basic radicals two, more complex tri-nuclear amides were prepared namely the 3"-a;minobenzoyZ-(R = H) and 3"-amin0-4"-anisOyl-(R = OMe) de-rivatives of 3'-amino-4'-anisoyl-4-aminophenylarsinic acid (IX) in which amphoteric character was preserved. These also were devoid of trypanocidal action. Both are f a r inferior to salvarsan. The nitration of a series of p-substituted benzoic acids in which the p-substituent is Me OMe OEt O*CO,Et or Cl has enabled us to effect both a comparison of the relative ease of nitration of these benzoic acids and the relative ease of replacement of the carbosyl group by the nitro-group during nitration.The firs AND CHEMICAL CONSTzTUTrON. PART II. 2635 three acids are readily nitrated on the water-bath by 70:$ nitric acid; the last two are unaffected by acid of this strengbh but are nitrated in 76 and 90% yield respectively by 94% nitric acid. If other comparable observations from the literature be included, the following series is obtained : HNO yo ......... 14-300,6. 70%. 92-940/,. R = ............... OH,1NMe22. Me,OMe,OEt. F,SBr,’CI,O.CO,Et. (l) Griess Ber. 1887,20,408. (2) Reverdin Ber. 1907,40,2442. (3) Rouche, (4) Hubner Philipp and Ohly Anden, 1867 la 248. This series is substantially the one to be expected from a con-sideration of the relative directive powers of a member of any one of these groups in competition with a member to the right of it, for nitric acid the two substituents being situated in the para.or ortho-positions with respesf to each other. Thus there is ample evidence in the literature that when either OH or NMe is set against Me OMe OEt F C1 Br in the para-position the NO, group enters mainly ortho to OH or NMe,; when the two groups are in the ortho-position to each other the evidence although not so complete supports the same conclusion. Again when Me0 or EtO is set against C1 or Br in the para- or ortho-position the NO,-group is preferentially directed ortho or para respectively to the Me0 or EtO group in both cases but in the relative directive powers of Me and halogens there is an element of doubt.* In 1912 Holleman and Wibaiit (Proc.K . A M . Wetensch. Amsterdam 15 594) from the nitration of o- m- and p-chlorotoluenes drew the conclusion that chlorine induces a velocity of substitution 1-5 times as great as that caused by the methyl radical. Later however Holleman (Re. trav. chirn. 1915 34 283) found that in the nitration of p-bromotoluene the methyl group had undoubtedly the superior orienting power. The latter result is more in accord with our own observations. We have been unable to find in the literature anything bearing on the relative orienting influence of the O=CO,Et group on an entering nitro-group. The relative directive powers for ortho-substitution of a nitro-group may therefore be written in the order OH,NMe > Me,OMe,OEt > F,Cl,Br,O=CO,Et.In every case during nitration partial replacement of the carb-oxyl group by the nitro-group takes place with formation of p-sub-stituted nitrobenzenes and is evidently a general phenomenon. This is contrary to the view of Rouche (Zoc. cit.) who claimed that there was no formation of chloro- or bromo-nitrobenzenes by nitration of the chloro- or bromo-benzoic acids. In addition, * This is confirmed by the recent work of Francis Hill and Johnston (J. Amw. Chem. Soc. 1925,47,2231). Bull. A d . roy. Be&. 1921 534 2636 gzNG AND MlJlWH TRYPBNOCIDAL AC!CION further nitration to 2 4-dinitro-derivatives takes place to some extent depending on the time of heating. The relative yields of non-acidic fractions obtained on pouring the nitration mixtures into water are shown below.R = ............ C1. Me. F.1 OMe. OEt. O-CO,Et Yield yo ............ 1.1 2 11 11.5 14 15-5 HNO yo ............ 94 70 92 70 70 94 Time of heating ... 10 30 120 30 10 10 mins. Rouche loc. cit. Owing to the variation in strength of nitric acid used and the time of heating the only deductions allowable are that 'O-substi-tuents and possibly fluorine greatly facilitate replacement of C0,H by NO, and that O*CO,Et has a different relative orienting power to para-substitution from that which it has to ortho-substitution. It would be of interest to know whether the accumulation of groups in 3 4 5-trimethyl- trichloro- or trifluoro-benzoic acids would enhance the ease of replacement of CO,H by NO just as accumd-ation of the Me0 results in increased displacement of the formyl (Salway J.1909,95,1155) or carboxyl (Harding J. 1911,99 1585) grouping. The sulpho-group also is replaced to the extent of 5'7; by the nitro-group during the nitration of p-toluenesulphonic acid, as wilI be shown in a future communication. For the saponification of p-toluonitrile Herb (,4nnalenY 1890, 258 10) recommended the use of 750/ sulphuric acid. When applied to p-ethoxybenzonitrile EtO*C,H,.CN this had an un-expected result p henol-p - sulp honic acid OH C 6H4*S 03H being formed in good yield and no trace of the required carboxylic acid. A weaker sulphuric acid (60%) however yielded the required acid and amide in satisfactory yield. The dinitration of this series of mononitroarylamides (I) proceeds smoothly but as might be anticipated only yields exclusively one product (111) when R is H Me or C1.When R is OMe or OEt, a mixture of two dinitro-acids is obtained which is from a practical point of view not separable into its components but the com-position of which can readily be determined by an examination of the products of hydrolysis. The isomeric dinitro-acid has the structure (X) and the two arsinic acids obtained on hydrolysis of this and its isomeride (111) are almost quantitatively separable by 0.5N-hydrochloric acid. By this mea.n, it has been shown that whereas in the cases where R = H Me or C1 the secon AND CHEMICAL CON-ON. PART II. 2637 NO,-group enters a Merent nucleus from the one in which the NO,-group is already present when R = OMe or OEt the NO,-group is distributed between the two nuclei in the ratios 3 7 and 3 5 respectively in favour of the nucleus without a NO,-group.The diQmines (IV) were obtained on reduction with ferrous chloride and alkali. The toxicities and curative action of the dinitro- and diamino-arsinic acids where determined are given below : R = ..................... H. Me. C1. H. Me. C1. Dosh tole& ......... 0.1 0-025 0.2 >3-5 1.0 1-25 D O S b ctlfYZ&tk% ......... 0.06 - - 2 0-75 0.5 Dinitro-wide. Diamino-acids. ( r = 2 ) ( r = 29) Comparison of this table with the previous one for the mono-amino-acids shows that the introduction of a second amino-group lowers the toxicity many-fold and at the same time the sub-stances acquire permanent curative properties.It is of interest that 3 3'-dinitrobenzoyl-4-aminophenylarsinic acid causes a tem-porary disappearance of trcvpanosomes from the blood-stream for 2 days. The isomeric 3' 5'-dinitrobenzoyl-4-aminophenyla~c acid was prepared but attempts to isolate the arsinic acid con-taming the m-phenylenediamine group from it by reduction were unsuccessful. We desire to acknowledge our indebtedness to Miss F. M. h h a m and Miss J. Marchal of this department for the painstaking care with which they have determined the toxicities and trypanocidal action of the compounds described in this paper. EXPERIMENTAL. 3 3'-DinitrobenzoyE-4-ami~p~ny~r~nic Acid (III ; R = €I).-Benzoyl-p-aminophenylarsinic acid (19.3 g.) dissolved in 45 C.C.of sulphuric acid was nitrated at 0" by addition of a mixture of 8-5 C.C. of nitric acid (d 1-4) and 11-4 C.C. of sulphuric acid. The crude product obtained by pouring on to ice was collected allowed to air-dry and digested on the water-bath with 100 C.C. of glacial acetic acid. The product was now crystalline and the filtrate could be used for subsequent batches. The yield was 9276 of the theor-etical. This acid crystallised from 170 parts of boiling glacial acetic acid in fine silky needles forming a monohydrate (Found : Loss at lOO" 5.1 5-0. 1H,O requires loss 4.2%. Found As, 18.1. C,,H,,O,N&s requires As 18.2%). With alkali (1 mol.), it forms sparingly soluble sodium and potassium salts. Hydrolysis of 3 3'-Dinitrobenwyl-4-amirwphenylarsinic Acid.-(a) With acid.When the dinitro-acid (8-2 g.) was boiled for 2 hour 2638 KING AND MDRCH !l'BYPANOCIDAL ACTION with 100 C.C. of 16% hydrochloric acid it was recovered mainly unchanged (6-4 g.). The other products isolated were a small quantity of o-nitroaniline m-nitrobenzoic acid and 3-nitro-4-amino-phenylarsinic acid. (b) With aZkaZi. The dinitro-acid (6.3 9.) was boiled for 2 hours with 100 C.C. of N-sodium hydroxide. Practically quantitative yields were obtained of m-nitrobenzoic acid and 3-nitro-4-amino-phenylarsinic acid. 3 3'-Diaminobenzoyl-4-aminophenylarsinic Acid (IV ; R = H).-The dinitro-acid (16.4 g.) was dissolved a t - 5" in 292 C.C. of 2N-sodium hydroxide and treated with 101 g. (10% excess) of ferrous chloride dissolved in 124 C.C. of water.To the mixture 292 C.C. of 2N-sodium hydroxide were added the temperature throughout being below 0" The ferric hydroxide was filtered off and extracted three times by thorough mixing with 600 C.C. of 0.2Ar-sodium hydroxide each time. The combined filtrates were made neutral to Congo-paper and after keeping for 24 hours a t 0" the separated diamino-acid was collected. The filtrate was made alkaline with concentrated ammonia treated with 50 C.C. of magnesium chloride solution (1 l) and heated for 30 minutes in the boiling-water bath. The precipitated magnesium salt was collected dissolved whilst still damp in N-hydrochloric acid and the acidity to Congo-paper removed by addition of saturated sodium acetate solution. The diarnino-acid crystallised readily (total yield was 7.8 g.or 56%). The diamino-acid so prepared crystallises in clusters of leaflets. It diazotises and couples with alkaline p-naphthol with production of a deep red colour (Found As 20.9. C,,H,,O,N,As requires As 21.3%). 3 5-Dinitrobenxoic AcZ-The following process is an improve-ment on that of Shukov (Ber. 1895 28 1800). Ten g. of fused benzoic acid were dissolved in 100 g. of sulphuric acid and treated with 18.2 C.C. of fuming nitric acid. The solution was heated on the water-bath for 10 hours and poured into a litre of ice and water. The product (10 g.) m. p. 202" was washed with a little hot water and reprecipitated from dilute ammonia. It then melted a t 203-204". 3' 5'-Dinitrobenzoyl-4-amin~frenylarsinic Acid (X ; R = H) .-Sodium p-aminophenj-larsinate pentahydrate (25-26 g .) dissolved in 320 C.C.of 5% sodium hydroxide and cooled to - 3" was treated with 40 g. (2 mols.) of 3 5-dinitrobenzoyl chloride dissolved in toluene. The mixture was stirred for 45 minutes after at1 the acid chloride had been added. After acidification the mixture of acids was collected dried and extracted with ether. The insoluble arsinic acid was reprecipitated from ammoniacal solution (yield There was no o-nitroaniline found AND CHEMICAL CONSTITUTION. PABT II. 2639 84%). This diaitro-minic mid c r y ~ t a b a from 80 part^ of b o a 90% formic acid in fine needles. In glctcirtl acetic acid it is much less soluble (Found As 18.3. C,H,,-,O~& requires AS 18.2%). The maximum tolerated dose for mice is 0-5 mg.per g. of mouse. Attempti3 fo obtain the diamino-minic acid by reduction in alkaline solution with ferrous chloride were unsuccessful. 2-Ndro-p-tohic Acid.-This acid wm prepared by the following process which is an improvement on that of Fittig and Ramsay (AnnuZen 1873 168 251). p-Toluic acid (20 g.) was suspended in 200 C.C. of nitric acid (d 1-4) and heated on the water-bath for 30 minutes. On pouring- into water the yield of nib-acid was 23.5 g. m. p. 186-187". By ether extraction of the acid in alkaline solution 0.4 g. and of its aqueous mother-liquor 0.6 g. of crude p-nitrotoluene were obtained m. p. 51". 2-Nitro-p-toluoyl chhride prepared by the action of phosphorus pentachloride boils at 167-168" (corr.)/l6 121111. and melts at 20-21" (corr.). This acid chloride has recently been described as an oil (Johnson and Soderman J .Anaer. Chern. Soc. 1925 47, 1392). 3'-Nitro-4'-toluqyl-4-aminopheny2arsinic Acid ( I ; R = Me).-This acid was prepared in the same way as p'-nitrobenzoyl-p-amino-phenylminic acid (J. 1924 125 2602). The acid chloride how-ever reacts so slowly that stirring has to be continued for 2 or 3 hours. The mixed acids obtained on acidification were dried and extracted with ether in a Soxhlet apparatus (yield 55%). This arsinic acid is sparingly soluble in boiling acetic or formic acid and crystallises in small needles (Found As 19.6. C&,O,N& requires AS 19.7%). 3'-Amino-4'-toEuoyl-4~m~~~~~~~n~ Acid (I1 ; R = Me).-3'-Nitrotoluoyl-4-aminophenylarsinic acid (1 1-4 g.) was dissolved in 110 C.C.of chilled 2N-sodium hydroxide and 40 g. of ferrous chloride (20% excess) in 50 C.C. of water were run in the tem-perature being maintained between 0" and - 5". Finally 130 C.C. of 2N-sodium hydroxide were added. The ferric hydroxide was filtered off and extracted with two successive portions each of 240 C.C. of 0-4N-sodium hydrozcide. The combined filtrates were neutralised to Congo-paper and the crude acids collected. These were warmed with mccessive portions of N-hydrochloric acid a t 50" until no diazotisable material waa left. On addition of satur-ated sodium acetate solution to the successive f?ltmt~~ the amino-arsinic acid w&8 precipitated in fan-shaped clusters of small white needles. A further small quantity can be isolated from the k t precipitation mother-liquors by addition of ammonia and magnesium chloride and heating the solution.The magnesium salt separate 2640 KING AND IKURCH TBYPANOCIDAL AC'MON readily is dissolved in excess of N-hydrochloric acid and the free acid precipitated by sodium acetate. The yield was 5-7 g. or 54% of the theoretical. This amino-arsinic acid is very sparingly soluble in cold 3N-mineral acids but dissolves readily on warming. The hydro-chloride crystallises in small needles the nitrate in minute needles, and the sulp7uzte in square plates. It diazotises and couples with alkaline p-naphthol with production of a blood-red colour (Found : As 21.2. C,,H,,O,N&s requires As 21.4%). 3 3'-Dinitro-4'-toluoyl-4-ami~~nylarsinic Acid (I11 ; R = Me). -The mononitro-acid (7-5 g.) dissolved in sulphuric acid (20 c.c.) was n i b t e d a t 0" with a mixture of 1.9 C.C.of sulphuric acid and 1-4 C.C. of nitric acid (d 1-4). The yellow solid obtained on pouring on to ice was collected and when digested on the water-bath with glacial acetic acid became crystalline (yield 8 g . ) . This dinitro-acid is sparingly soluble in boiling acetic or formic acid and crystallises in needles (Found As 17.7. C,,H,O,N,As requires As 17.6%). Hydrolysis of 3 3'-Dinitro-4'-toluoyl-4-aminopheny~~~in~c Acid. -Two g. of the acid were boiled for 2 hours with 30 C.C. of N-sodium hydroxide. The acids obtained (2.05 g.) on neutralisat.ion to Congo-paper were extracted in a Soxhlet apparatus with ether. The ether-soluble portion (0.8 g . ) consisted of pure 2-nitro-p-foluic acid and the ether-insoluble portion of 3-nitro-4-aminophenylarsinic acid (1.25 g.) the yields being practically quantitative.3 3'-Diamino-4'-toluoyl-4-am~~~nylarsinic Acid (IV ; R = Me).-The dinitro-acid (8.5 g.) was reduced in the way described for the acid without the methyl group (above) save that it was found advantageous to increase the excess of ferrous chloride used from 10% to 20% and with it the amount of alkali to secure faint alkalinity at the end of the reduction. The alkaline filtrates from the ferric hydroxide extraction on neutralisation to Congo-paper gave no precipitate of diamino-acid. The acid was however, precipitated as the magnesium salt in ammoniacal solution by heating on the water-bath. The magnesium salt was dissolved in 70 C.C.of N-hydrochloric acid and the diamino-acid liberated by addition of saturated sodium acetate solution (yield 4-2 g. or 57%). This diamino-arsinic acid separates when liberated as described above in sphmo-crystals (Found As 20.4. C,,H,,O,N,As requires As 20.5%). Diazotised with sodium nitrite in hydro-chloric acid solution it turns yellow and couples intensely with alkaline @-naphthol with production of a brownish-red colour. Preprution of Anisic Acid.-Pure crystalline anethole (11.1 g.) was stirred vigorously with 50 C.C. of water a t ruom temperature, and 34.4 g. of potassium pemanganate in 1076 C.C. of water wer AND CHEMICIIL COHSTlTUTION. PART II. 2641 added at a consta4t rate within 76 minutea. No attempt was made to regulate the temperature which at its xmximwn ~ & 8 below 35".The very slight excess of permaqanate was reduced by warming with alcohol. After ftlhtion and extmction of the manganese oxides with dilute alkali the combined filtrates gave, on acidification 9-0 g. of almost pure anisic mid. An aliquot portion of the filtrate extracted with ether indicated the presence of a further 1-5 g. of equally pure anigic acid. The total yield is about 92% of the theoretical. Oxidation at mom temperature with 32 g. of permanganate (4 atoms of oxygen) and with addition of 12 g. of potassium hydr-oxide gave 4-6 g. of aniaic mid and 2.3 g. of mkldehyde (semi-carbazone m. p. 216-217" con.; Walbaum J . pr. Ck. 1903, 68,235 gives m. p. 203-204"). Oxidation at 0" gave 6-6 g. of a mixture of anisic acid md d y l -ketocarboxylic acid and 0-85 g.of anisaldehyde. Oxidation of pure anethole by Ladenburg and Fib's method as applied to oil of anise using potas8ium &chromate and mlphuric acid gave a 47% yield of anisic acid. 3-Ndro-4-ani8oyl ChlOt.ide.4-Nitroanigic acid was prepared by Auwers's method (Ber. 1897 30 1477) by heating 20 g. of anisic acid with 200 C.C. of nitric acid (d 1.4) on the water-bad& for 30 minutes. From 75 g. of anisic acid there were obtained 3-7 g. of a non-acidic fraction which on distillation gave 2-65 g. m. p. M 5 " b. p. (external bath temperature) 170"/20 mm. These constants agree with those of 4-nitroanhole. The non-volatile reaidue (1.0 g.) on two crystaktions from alcohol gave 2 Pdi-nitroanisole (0.45 g.) m.p. 87". In another experimenf which was strictly comparable with the nitration of p-foluic acid there were isolated from the nitration of 20 g. of anieic acid 20.2 g. of nitmanhic acid m. p. 190"; by ether extraction of this nitro-acid in alkahe solution 2.3 g. of nitroanhles m. p- 84"; and by ether extraction of the original aqueous mother-liquor 1.45 g. of nitro-anisola m. p. 45". The nitroanisic acid was converted info 3-nit~o-4-ankyZ W i d e by phosphorus pentachloride. This boils a t 210"/15 mm. is sparingly soluble in low-boiling petroleum but readily soluble in warm ether from which it crystallises in broad needles m. p. 52.5-53.5" (corn.). 3 ' - N i t r o - 4 ' - a n i s o y l - 4 - a m ~ ~ ~ y ~ 7 ~ n ~ Acid (I ; R = OMe).-This nitro-acid w&8 prepared in the same way as the corresponding toluoyl derivative.The yield waa 48.37& It is soluble in boiling formic acid and c r y s t a h therefrom in needlea but is sparingly soluble in boiling acetic acid from which it separates in woolly needles (Found As 18.9. C,,H,O,N& requires As 1809%). VOL. CXXVTI. 4 2642 KING M D MURCE "BYPANOCIDAL ACTION 3 ' - A r n ~ n o - 4 ' - u n ~ ~ l ~ - a ~ ~ ~ ~ n y ~ ~ ~ n ~ acid (II ; R = OMe) waa p r e p d exactly as described for the corresponding toluoyl derivative. The yield waa 95%. When libemted from concen-trated solutions of its salts with acids by mans of saturated sodium acetate it separates in a gelatinous state but from dilute solutions in needles. The gelatinous form passes into the crystalline on contact with the needles.It is not soluble in acids weaker than 3N in the cold but dissolves readily on warming. The most characteristic salt is the hydrochlot.de which crystallises well in wedge-shaped plates. The 8uZphude separatea in sphaero-crysbls, the nitrate in microscopic woolly needles. It diazotises and couples with alkaline Ij-naphthol with production of a bright red colour (Found Bs 20-2. Cl,H1505N& requires As 20*5y0). 3 ' - A c e t y l a m i n o - 4 ' - a n ~ ~ ~ - 4 - a m ~ ~ ~ n y ~ r ~ n ~ c acid is most con-veniently prepared by shaking the amino-acid dissolved in N-sodium hydroxide (4 mols.) with excess of acetic anhydride. The yield is quntihtive (Found AB 18-8. C,,H,,O,N& requires As, 18-4Y0). This acid is almost insoluble in boihg acetic mid but extremely soluble in cold 90% formic acid.From more dilute formic acid it separates anisotropic in sphaero-crystals. The maximum dose tolemted by mice is 1.5 mg. per g. of mowe. Attempts to prepare the propionyl derivative by the same method were fruitless. anisoy14aminuphenylursinic Ac;&.-!l!he amino-acid (5.5 g.) wag dissolved in 15 C.C. of N-sodium hydroxide (1 mol.) and 2.4 g. of pure sodium formaldehydesulphoqlate were added. The solution WBS heated for 15 minutes in boiling water cooled and poured into a large volume of spirit. A gum separated which was obtained in a solid powdery condition by grinding under absolute alcohol (yield 2-6 g.) (Found Loss at 95" 0.5; As 15.8; S 7-0. C,,H,,O,N~AsNa requires As 15.4; S 6.6%).This sodium salt so prepared has no free amino-groups. It is however unstable towa;rds N-hydrochloric acid at 50" and evolves sulphur dioxide. 3'-Car~~ama'no-4'-anisoyl-4-ami~~ny~rorphenylarsinic acid was pre-pared by adding ethyl chloroformate (1.1 c.c.) in two portions to the amino-acid (3.7 g . ) dissolved in 15 C.C. of N-sodium hydroxide. The product was acidified and the precipitated solid extracted with N-hydrochloric acid at 50" to remove diazotisable material (yield 3.7 g . ) (Found As 17.5. C1,H1,O,N&s requires As 17.1%). The acid is practically insoluble in boiling acetic acid but readily so in boiling 90% formic acid and crystallises therefrom in micro-scopic leaflets. The maximum dose tolerated by mice is 0.75 mg. per g. of mouse. A d h of S d k m F~ldehy&esulphxi$i& ort ~'-ATw~o-~' AND m C A L CONSTITUTION.PART II. 2643 The s-Carbam& of 3 f - A m i n o d ' - c m n ~ ~ ~ m ~ ~ ~ y Acid.-The amino-acid (3.7 g.) dkolved in 100 C.C. of ha& saturated sodium wetate solution with the aid of 5 C.C. of BN-Sodinm hydroxide waa shaken with several molecules excess of carbony1 chloride in toluene (35 C.C. of 1205% solution). Tbe product obtained on acidification waa extracted with warm N-hydrochloric acid and precipitated finally from dilute ammonia by acid (yield 33%). This ciwbamide is precipifa;ted in the gelatin-ous state from its salts. It is insoluble in boiling glacial acetic acid but from boiling 90% formic acid in which it is very spar-ingly' soluble it crysta.llises in microscopic needles (Found As, 3" -Nitro-4" - a n ~ l - 3 ' - u m i n o - 4 ' - a n i s o y l - 4 - a m i ~ ~ n ~ ~ r a ~ ~ ~ Acid (corresponding with IX; R = OMe).-Aminoanisoylaminophenyl-arsinic acid (7-3 g.) dissolved in 50 C.C.of 10% sodium hydroxide at - 5" was treated with 8.3 g. of nitroanisoyl chloride in 15 C.C. of toluene and stirred vigorously for hours. Toluene WE)^ removed and the aqueous solution acidified. The precipitated solid was exfracted with N-hydrochloric acid to remove amino-arsinic acid. The dried solid was extracted with ether to remove nitroa,nisic acid and reprecipitated from dilute ammonia. This complex nitro-arsinic acid is precipitated as a voluminous gelatinous solid from solutions of its salts. It is very sparingly soluble in boiling glacial acetic acid but separates well in clusters of needles.It is somewhat more readily soluble in boiling 90% formic acid (Found As 13.6. C=%O&As requires Bs 1307%). !"he maximum dose tolerated by mice is 0-075 mg. per g. of mouse. 3"- Amino - 4"- anboyl-3'- amino-4'- aniaoyl - 4 - aminupknylur&nie Acid (IX; R = OMe).-The nitro-acid (5-2 g.) was reduced in the usual way with ferrous chloride and alkali. The combined alkaline extracts of the ferric hydroxide were made neutral to Congo-paper. The precipitated solid was collected and whilst s t i l l damp made into a thin cream with water and added to 2000 C.C. of N-nitaic acid (free from nitrous acid) at 50". The solution was rapidly filfered treated with charcoal and refiltered. On addition of saturated sodium acetate solution the hino-acid waa pre-cipitated in an amorphous condition in 75% yield.This acid is soluble in hot N-hydrochloric acid and deposits an indefinitely c m e but anisotropic solid. on cooling. It is almost insoluble in boiling N-sulphuric acid the gulphate crystallising in micro-scopic needles. In N-nitric acid it is soluble on heating and the nitrate crystallism in balls of needles (Found As 14-3. C,$O,N& requires As 14.6%). The maximum dose tolerated by mice is 0.02 mg. per g. of mouse. 19-6. C~80,1N,BS re~uirea As 194%). 4T 3 " - N i t r o b e n z o y E 3 ' - ~ ~ - 4 ' - a n ~ ~ ~ a m ~ ~ ~ n y ~ r ~ n ~ acid (corresponding with IX; R = H) was prepared in the same way as the corresponding 3"-nitroanisOyl compound (above).From 7.3 g. of 3'-amino-4'-anisoylaminophenylarsinic acid and 3-nitz-o-benzoyl chloride (2 mols.) there were obtained 5-8 g. of the required acid as a gelatinous precipitate. It is sparingly soluble in boiling acetic or 90% formic acid separating from the former in short, poinM needles and from the latter in squm tablets (Found: As 14-7. C,,H,,O,N& requires As 14.6%). The maximum dose tolerated by mice is 0-1 mg. per g. of mouse. 3"-Aminobenzoyl-3'-amino-4'-an~oyl-4-clminopinylur&nie acid (IX; R = H) was prepared in the same way as the corresponding 3"-aminoanisoylarsinic acid except that 1500 C.C. of N-nitric acid at 50" were su%cient to dissolve the amino-acid. The yield was 3-1 g. from 5.0 g. of nitro-acid. This complex amino-acid separates in needles when liberated from dilute acid solutions by addition of sodium acetate (Found As 15-4.C,,HM0,N3As requires As, 15.4%). With N-hydrochloric acid it forms a very sparingly soluble hydrodoride crystallising in microscopic rods. In 2N-sulphuric acid it is readily soluble the &ph& crystallking on keeping in h e woolly needles ; and in warm N-nitric acid it dissolves and gives an indefinitely crystalline but anisotropic nitrate on cooling. The maximum dose tolerated by mice is 1.0 mg. per g. of mouse. Nitration of 3'- Nitro 4'-anisoyl-4-amimphn ylursinic A~id.-Thi~ mononitro-arsinic acid was further mononitrated as described for the previous dinitro-arsinic acids. The product consisted of a mixture of 3' 5'-dini~o-4'-anisoyl4-aminophenylarsinic acid and 3 3'-dinitro-4'-anisoyl-4-aminophenylarsinic acid in the propor-tion of 3 7.These acids could not be separ-ated by fractional c-tion from 75% acetic acid nor by fractional crystallisation of the amhonium salb (Found As 17-0. C1,H,,0~& requires As 17.0%). The composition of the mixture waa r d y deter-mined by hydrolysis as follows. Three g. of the dinitro-acids were boiled for an hour with 45 0.0. of N-sodium hydroxide and then neutralised to Congo-paper. The mixture of ether-soluble arsenic-free acids was not examined in detail but 3 5-dinitro-4-hydroxybenzoic acid was identified. The ether-insoluble acids consisted of a mixture of a 4-aminophenylarsinic and 3-nifro-4-aminophenylarsjnic acid. These could be separated h o s t quantitatively by making use of the observation that 4-amh.10-phenylarsinic acid is readily soluble in 0-5N-hydrochlo1.i~ acid, whereas the nitro-acid is not appreciably soluble.From the h a 1 aqueous mother-liquors of the hydrolysis precipitation as mag-nesium salt in ammoniacal solution gave a further crop of 4-amino AND CHEMICdL WXSTITUaON. PABT II. 2645 phenylarsinic acid. In this way 1.25 g. of 3-nitro-4-aminophenyl-aminic and 0-4 g. of 4-aminophenylaminic were obtained or 96% of the theoretical yield. The reduction of the mixed dinitro-acids by ferrous chloride w88 Hydroly& of 4-Eth~xy&mitrile.-(a) By 75% sulphurk a d . Twelve g. of the nitrile were boiled for 1 hour with 72 g. of sulphuric acid and 24 g. of water. Ether extraction of the mixture diluted with water gave 0.36 g.of a phenolic fraction partly crystalline and giving a blue d o u r with ferric chloride in alcoholic solution and a violet colour in aqueous solution. The sulphuric acid liquom were worked up as barium d f s when after removal of barium sulphate a very soluble barium salt was isolated (yield 9 g.). On c r y m t i o n from water it separated in long glistening needles of barium phenol-4-sulphonate. It waa compared with a sample prepared bythe action of sulphuric acid on phenol (Found on air-dried salt loss at 95" 9.3; on salt dried at 95" Ba 27.8. Cl,HloO~Ba,3~0 requires loss of 2&40 804%. C&EC,,O&&l3a,~~O requires Ba, 27.9%). If the original solution be treated with ether inafead of water the free phenol-4-sulphonic acid crysfallises but is very hygroscopic (compare Ahin BUU.Soc. dim. 1887 47 879). Twelve g. of 4-ethoxybenzonitde were boiled for 30 minutes with 56-5 g. of sulphuric acid and 37-5 C.C. of water. The solid obtained on pouring into water waa separated by means of sodium carbonate solution into 3-1 g. of 4-ethoxyben.z-amide md 6-1 g. of 4-ethoxybenzoic acid. The amide was com-pletely hydrolysed to the acid by boiling with 60% sulphuric acid for 2 hours. 3-Nitro-4-ethozybenzoic Acid.4-Ethoxybenzoic acid (21 g.) was heated with 210 C.C. of nitric acid (d 1-42) on the mter-bath until solution had just been effected. The product waa poured into water the solid collected dissolved for the most part in ammonia, and ezctracted with ether which removed a low-melting crysfalline solid A weighing 3 g.The ammoniacal solution on acidification gave an 80% yield of 3-nitro4eth~xybenmic a&. This acid crystaUises well from spirit in recfangular plates or rods m. p. 2o0-201" (Found C 51-0; H 4.4. C,&O,N requires C 51.2; H 4.3%). The ether-soluble material A (4.5 g. from two batches) on fractional distillation under reduced pressure gave 1.6 g. m. p. 5s-5Qo b. p. 188" (external bath temperature)/22 mm. The residue 2-65 g. on recrystadisation from alcohol gave pure 2 4 dinitrophenefole m. p. 83" in excellent yield whilst the low-llnsatisf~tory. (b) By 60% sulphur& mid melting solid on c-htion from alcohol melted at 62" and proved to be 4-nitrophenetole. 3-Nitro-4-ethoxybenzql chloride is very sparingly soluble in boiling petrol but is more soluble in dry ether from which it crystallises in slender prisms m.p. 8 1 4 2 ' (con.). It boils at 215L216" (corr.)/20 111111. 3 ' - N i t r o 4 ' - ~ b e n z o y l - 4 - a m i ~ ~ n y ~ r ~ n ~ acid (I ; R = OEt) was prepared in the same way aa the corresponding 4'-ChlOrO-derivative using method 5. The yield was 49%. It is very spar-ingly soluble in boiling acetic acid and sparingly in 90% formic acid. It crystallises in fhe needles (Found As 18.5. C15H1507N&s requires As 18.3%). 3'-Amino-4'-et~~nzoyl-4-ami~~nylarsinic Acid (11 ; R = OEt).-The mononitro-acid (8-2 g.) was reduced as described for the corresponding 4'-toluoyl compound. On neutralisation of the alkaline extracts of the ferric hydroxide to Congo-paper the acid was precipitated in an amorphous condition.When dissolved in 200 C.C. of N-hydrochloric acid at 45" and precipitated by addition of saturated sodium acetate it separated crystalline (yield 5.8 g.). The originel mother-liquors gave a further crop of 0.7 g. of acid by precipitation as the magnesium salt from hot ammoniacal solution (total yield 86%). This amino-acid crystallises in micro-scopic woolly needles (Found As 19.3. C1,H,,O5N& requires Aa 19.7%). It is solublg in warm N-hydrochloric acid but very spazingly soluble in hot 3N-acid through formation of the hydro-c7bZur& which crystabes as a sandy powder composed of small tablets. It is soluble in 2N-sulphuric acid but rapidly crystallises as the sulpmate in small pointed prisms. In 3N-nitric acid it is readily soluble and the nitrate c r y s e e s from concentrated solu-tion in fine needles.The diazotised acid couples with alkaline /3-naphthol with production of a bright red colour. Nitration of 3'-Nitro-4'-~ybenzoyl-4-amino~~nylarsinic Acid. -Thi8 acid was re-nitrated as described for the corresponding 4'-anisoyla,rsi11ic acid. A mixture of 3 3'-dinitro-4'-ethoxybenzoyl-4-Rminophenylarsinic and 3' 5'-dinitro-4'-ethoxybenzoyl-4-amino-phenylmsinic acids in the ratio 5 3 was obtained as w&s proved by hydrolysis and quantitative separation of the arsinic acids as described for the anisoyl acids (Found As 16.5. C15Hl,0JST3As requires As 16-5y0). 4 ' - C r m o r o - 3 ' - n ~ r ~ n z o y l - 4 - a m ~ ~ ~ n y ~ r $ i n ~ Acid (I ; R = Cl) .A-Chloro-3-nitrobenzoic acid was prepared in 90% yield by heating 4-chlorobenzoic acid with nitric acid (d 1-5; 4 vols.) on the wafer-bath until solution was effected; 20 g. of chlorobenzoic acid gave 23.6 g. of chloronitrobenzoic acid m. p. 180" and as by-product 0.22 g. of p-chloronihbenzene m. p. 77" by extraction of the acid in dtrrrline solution and 0-5 g. of p-chloronitrobenzene, m. p. 82" by extraction of the original aqueous mother-liquors made alkaline. Boiling nitric acid (d 1-42) has no action on 4-chloro-benzoic acid. The acid cyoride waa prepared in the wual way, b. p. (external bath temperature) 180-19Oo/ZO-22 mm. It wm introduced with diiliculty into 4-am.jnophenylar~h.ic acid by the Schotten-Baumarm method using two mo1ecu.h proportions of acid chloride.No. Solvent. Temperature. Sodium Hydroxide. Yield yo. A vaxiety of conditions to improve the yield were tried. 32 ?? 18 1 Benzene 20-25' 10% 2 None 20-50 3 Benzene "10 40 5 Toluene -5-4 7 7 40 4 Benzene 20-30 & 22 Unchanged nitrochlorobenzoic acid wits readily recovered by ether extraction and unused 4-aminophenylarsinic acid by neutralising the aqueous mother-liquors to Congo-paper and evaporating until sodium chloride began to separate. 4 ' - C h l o r o - 3 ' - n ~ t r ~ ~ ~ - 4 - a ~ i ~ ~ n y ~ r ~ ~ ~ a d is very spar-ingly soluble in boiling acetic acid more readily in boiling 90% formic acid from which it crystatllises well in needles (Found: Cl 8-6. C,H,,O,N,ClAs requires Cl 843%). 4 ' - C ~ o - 3 ' - a m ~ ~ n z o y l - 4 - a ~ ~ ~ k n y l a r s 4 n i c Acid (II ; R = C1).-The nitro-acid (6.65 g.) was reduced with ferrous chloride (7 mob.) at - 5" as described for the toluoyl compound.The combined filtrates from the ferric hydroxide extractions on being made neutral to Congo-paper deposited the amino-acid in a crystalhe condition mixed with a small quantity of amorphous impurity. The amount contained in the mother-liquors and pre-cipitable as magnesium salt was negligible. The crude acid waa heated at 80" with 800 C.G. of 3N-hydrochloric acid; the amino-acid then dissolved. On addition of saturated sodium acetate to the rapidly filtered solution the amino-acid separated in leafleta (yield 80%) (Found Cl 9.4. C,,H,0,N2ClAs requires Cl 906%). It is very sparingly soluble in 3N-hydrochloric acid at 100" but from stronger acid the kydr&ide c m h in oval leaileta.In boding 2N-sulphuric acid it is insoluble but from a much stronger acid the sulphate crystallises in square tablets. It is soluble in hot 3N-nitric acid and this solvent freed from nitrous acid would probably be preferable to hydrochloric acid for its extraction in the above preparation. The diazotised acid couples with alkaline p-naphthol with production of a bright red colour. 4'-#lmo-3 3 ' - d i n i t r ~ e n z o y l - 4 - ~ y ~ r ~ n ~ A d (Iu ; R = a).-The mononitro-acid (8 g.) dissolved in 24 C.C. of sulphuri 2648 AND XUkCH TBYPAXOCIDAL ACXFION acid waa nitrated at - 5" with 2 g. of sulphuric acid and 2 g. of nitric acid (d 142); the mixture when at room temperature was poured on to ice.The product was collected dried and digested on the boiling-water bath with 40 C.C. of glacial acetic acid for 8 hour; it then became crystalline (yield 8.5 9.) (Found (3 8.1. c13~08N3c1As requires Cl 8.0%). The acid is very v g l y soluble in boilmg glacial acetic acid somewhat more soluble in boiling 90% formic acid from which it crystdises well in needles. Hydrolysis of 4'-chloro-3 3l-dinitrobenzoyl-4-arni~~nylarsinic Acid.-Two g. of the dinifro-acid were boiled for 30 minutes with 30 C.C. of N-sodium hydroxide. When cold the solution was neutrahed to Congo-paper and the precipitated acids were collected, dried and extracted with dry ether in a Soxhlet apparatus. The ether-soluble acid weighed 1.0 g. m. p. 175". A mixture of the substance with 4-chloro-3-nitrobenzoic acid which itself melted a t 182" melted at 177".The ether-insoluble material weighed 1-1 g. and was unchanged in weight after extraction with O-FiN-hydro-chloric acid to remove any possible 4-aminophenylarsinic acid. This proved to be 3-nitro-4-aminophenylarsinic acid. The original aqueous solution on ether extraction gave 0.05 g. of crystalline acid, m. p. 172". Mixed with chloronitrobenzoic acid this melted at 157" ; with 3-nitro-4-hydroxybenzoic acid m. p. 185" however, the melting point was raised to 175". 4'-chloro-3 3'-diaminobenzoyl-4-amino;plZenylarsinic Acid (IV ; R = Cl).-The dinitro-acid (6.5 g.) was reduced exactly as described for the corresponding dinitrotoluoylarsinic acid. The combined alkaline extracts of the ferric hydroxide when neutralised to Congo-paper gave an amorphous brown precipitate but on keeping a few hours the diamino-acid (3.0 g.) crystallised.The filtrate was made alkaline with ammonia and heated with magnesium chloride; a magnesium salt then separated which gave an additional 1-25 g. of acid. The combined crude acids were dissolved in 40 C.C. of N-hydrochloric acid with addition of 1 C.C. of concentrated acid and precipitated by addition of saturated sodium acetate until neutrality to Congo-paper was reached (yield 76%). The acid 80 prepared crystallises in rosettes of pointed plates (Found Cl 9.2. Cl,H,,0,N3ClAs requires C1 9.2 %). Preparation and Nitration of 4-Ethylcarbonatobenzoic Acid.-4-Hydroxybenzoic acid (34.5 g.) dissolved in 500 C.C.of N-sodium hydroxide (2 mols.) was shaken with 26.0 C.C. of ethyl chloroformate (1-1 mols.) added in four portions. Ether extraction removed a viscous pleasant-smelling oil (2.6 g . ) presumably (compare analogous case of salicylic acid D.R.-P. 117,267). Et0,C-O*C,H4=C0,C0,Et Th AND CHEMICAL CONSTITUTION. PABT II. 2649 aqueous SoIution on acidification gave 49.3 g. of 4ethyih*-benxoic acid (94% yield). This acid is best r e a p h b d * from 85 volumet3 of boiling water and separatea in long glistening needles, m. p. 154-156". It is very soluble in the usual organic solvents (Found C 57-0; H 4.9. CJIl0O5 requires C 5'7-1 ; H 4.8%). Ndrution. The acid (48.5 g.) was dissolved in 182 C.C. of fuming nitric acid (nitric acid d1-42 has no action) and hated for 10 minutes on the boiling-water bath.The product wm poured info water the solid collected dissolved in sodium bicarbonate solution, and extracted with ether which removed '7.5 g. of non-acidic d i d , A. The aqueous solution on acidification gave 44-6 g. '('76% yield) of 3 - n i t r o + t - e t h y h ~ n & d. This is best r-from 15 volumes of boiling benzene and separates in clear kr*-shaped plates m. p. 168-169" (Found C 47.3; H 3.7. C,&&+O,N requires C 47.1; H 3.6%). The non-acidic solid A was distilled in a vacuum when 6-35 g. passed over at 18 111111. and an external bath temperature of 192". This fraction on crystallisation from alcohol separated r d y in fine needlea m. p. 67-68O (corr.) in agreement with the propertie8 described by Ransom (Ber.1898 31 1064) for ethyl 4-nitrophenyl-cabonate. On hydrolysis with alcoholic soda it yielded 4-nitro-phenol. The non-volatile residue 1.6 g. was highly coloured and did not crystallise on keeping but was proved to be ethyl 2 4dinitro-phnykizrhnate by hydrolysis with alcoholic sodium hydroxide, which gave 2 4-dinitrophenol. 3 ' - N i t r o - 4 ' - ~ h y l c a r b o n a t o b e n z o y l - ~ - u ~ i ~ ~ n y l a r Acid (V). -The above-described 3-nitro-4-ethylcarbonatobenzoic acid (25.5 g.) wae shaken with 21.0 g. of phosphorus pentachloride until reaction took place. The phosphorus oxychloride was removed under reduced pressure by gentle warming. The residual syrupy nitro-e t h y h r W e n q 1 chloride which crystallisea readily in a freezing mixture and remains solid above room temperature after being evaporated to dryness once or twice with dry ether was added in three portions with vigorous shaking to 15.5 g.of sodium 4amho-phenylarsinate pentahydrate dissolved in 300 C.C. of half-saturated sodium acetate solution. The solid (34 g.) precipitated by making the solution definitely acid to Congo-paper waa divided by ether exfntction into 15.6 g. of unchanged nitro-acid and 18-1 g. (80% yield) of the required arsinic acid. !l!his acid is' soluble in boiling acetic wid more readily soluble h boiling 90% formic acid and crysttallises in needles (Found As 16.5. C,,H,,O~& requires As 1605%). 3 ' - N i t r o - 4 ' - A y d ~ ~ ~ n ~ ~ - 4 - u ~ i ~ k n y ~ r ~ n ~ Acid (VI) .-The crude acid (18-1 g.) as obtained above wa8 dissolved in 160 C.C.of 4 T 2650 T B Y P A X ~ A L ACTION AND CHEMICAL CONSTITUTION. PART n. N-sodium hydroxide and the solution just brought to its boiling point. Addition of acid to the cold dution precipitated a t an intermediate stage the s o d k n salt of the nitrohydroxy-acid in r e c w m plates but finally (acid to Congo-paper) the free acid a8 a primrose-yellow solid (yield 97%). This acid is sparingly soluble in boiling acetic acid crystaWg therefrom in minute clusters of needles but readily soluble in boiling 90% formic mid, from which it crysfallises in long silky needles (Found AS 19.4. Cl&Il,O,N& requires AS 1906%). Reduction of 3'-Nitro-4'-hydroxyben~l-4-ami~wph.t?ny~rsinic Acid. -(a) By hypomdphite.The nitro-acid (3.8 g.) in 25 C.C. of N-sodium hydroxide (2.5 mols.) waa treated with 6 g. of sodium h p u l p h i t e added in portions. The end-point waa determined by removing samplea and observing the absence of yellow colour on adding alkali. The separated solid consisting mainly of the odium salt of the required amino-acid was collected and dissolved in 240 C.C. of N-hydrochloric acid at 50". The iiltrate made neutral to Congo-paper by addition of saturated sodium acetate solution, deposited the pare amino-acid (2.1 g.) in small needles. This reagent used as frequently de-scribed in this paper reduced the nitro-acid very smoothly. The amino-acid was obtained quite pure in 936% yield by neutralisation of the al.kaJine filtrate from the ferric hydroxide.3'-Amino-4'-hydro~benzoyE-4-ami~wp~ny~~8~n~ acid iEi readily soluble in warm N-hydrochloric nitric or sulphuric acid the salfs of the former two crystallising in needles that of the latter being amorphous and gela,tinous. The acid diazotises with production of a pale yellow colour and even from very dilute solutions the diazo-oz&de separates in pale yellow needles. This couples with algaline p-naphthol with a cherry-red colour. The acid is soluble in satur-ated sodium hydrogen carbonate solution but the sodium salt ~oon separates in micro-crystals (Found As 21.5. C13H130,N&s requires As 2103%). 3'- Amino-4'- hydro~benzoyl-4-aminoarsenobenxene (VIII) .-Amino-hydroxybenzoylaminophenylars~c acid (3-3 g.) was suspended in 16-5 C.C. of hypophosphorous acid (d 1.137) with addition of 33 c.c of 50% acetic acid and a crystal of potassium iodide.The mixture was stirred at 50-55" for 1 hour; the whole of the originally crystalline suspenrjion had then become orange-yellow and amor-phous. The product wa8 centrifuged off washed several times with air-free water and treated with sodium hydrogen carbonate solution until permanently alkaline. The liberated base was re-centrifuged well washed and dried in a vacuum (yield 2-7 g.). This arseno-derivative is soluble instantly in sodium hydroxide, (b) By ferrowr chloride THE ACTION OF " I T S ACID UPON A'MTT)lW ETC. 2651 but not in sodium W ~ O M ~ . It is insoluble in hydrochloric acid of any strength but vanishes almost instanfly on addition of nitrite with intermediate development of a deep colour.It then couples with rtlkrrline @-naphthol (Found As 24.7 25-1. 3 ' - A c e t y l a m 6 7 a o - 4 ' ~ ~ A - . . n n ; ~ ~ ~ ~ ~ ~ n ~ Acd.-The aminohydroxy-acid (3-5 g.) waa dissolved in 40 C.C. of N-sodium hydroxide or sodium carbonate and 5 C.C. of acetic rmhydride were added in 1 C.C. portions with vigorous shaking. The solution waa acidified to Congo-paper and the precipitated solid well washed with water and dried (yield 3.8 g.). From weakly slkAline solution this acid is precipitated in fine needlea which are almost insoluble in boiling glacial acetic acid but extremely soluble in cold 90% formic acid. From more dilute formic acid it crysfallises well in fine, soft needles (Found As 16.9. C,,HI,O,N& requires As 17.2%). The maximum dose tolerated by mice is 1-75 mg. per g. of mouse. 3 ' - A ~ y l a m i n o - 4 ' - h ~ d r ~ ~ n ~ l - 4 a m 6 ~ ~ e n y k r r s ; n Acid.-When a solution of 1 g. of the preceding acid in 10 C.C. of N-sodium hydroxide (4 mols.) was kept for 20 hours at room temperature, then diluted and acidSed with 3N-hydrmhloric acid the N-dyZ acirl was obtained as a microc-e ahtropic powder (Found : As 192. CI5H,,O6N& requires As 19.0%). This acid is almost insoluble in boiling glacial acetic acid but very readily soluble in ~ a r m 9 0 ~ ~ formic acid from which it sepasates in microscopic needles. 3 - A ~ y ~ m i n o - 4 - a n ~ ~ ~ ~ n ~ Aeid.-3-Amino-4hydroxy-amink acid (2.33 g.; 0.01 mol.) wm dissolved in 25 C.C. of water with the aid of 3.5 g. (4 mols.) of sodium bicarbonate and a,cetylatd by addition in 1 C.C. portions of 5 cx. of acetic anhydride. When the solution was acidified with strong hydrochloric acid the &c acid separated in needles (yield 2-5 g.). It is soluble in boiling glacial acetic acid and readily soluble in cold 90% formic acid (Found As 23.7. C,~,,O,NAEI requires As 2306%). CZ6%04N4& r e q h 24.8%). THE NATIONAL INS- FOR MEDICAZ RESEABCH, 33.Am?SmA.D N.W.3. [Received Augwt 5th 1926.

ISSN:0368-1645    

DOI:10.1039/CT9252702632

出版商:RSC    

年代:1925

数据来源: RSC

摘要:

THE ACTION OF " I T S ACID UPON A'MTT)lW ETC. 2651 CCCLXI1.-The Action of Nitrous Acid u p Am& and Other G6 Amino "-mlXyund8. By ROBERT HENBY ADERS PLIMXEB. THE action of nitrous acid upon amino-compounds WM apparently k t used by Sachsse and Kormann (LmuZw. Vw&-Stat. 1874, 17 321) for the detection and estimation of these compounds in plant extnrots. H. T. Brown (Trans. Quinm Bes. Lab. 1903) 4 ~ * 2662 PLlMMER THE AmON OF NlTROUS ACID employed the reaction for studying the formation of amino-acids in the brewing process and improved the old type of appmtus. Not until Van Slyke ( J . BbZ. C h . 1911 9 185; 1912 12 275) devised a satisfactory apparatus for the estimation was the method extensively used and as is well known its chief use is for d i s h -guhhing the Merent forms of nitrogen contained in the amino-acids resulting from the hydrolysis of proteins.A special short analpis of proteins oan be made by the method of Van Slyke (J. Bid. Chem. 1911 10 15). The earlier workers tested only a few amino-acids; leucine and alanine gave off the whole of their nitrogen as nitrogen gas asparagine gaxe off only half of its nitrogen as gas. Van Slyke tested a con-siderable number of amino-compounds. All a-amino-acids reacted rapidly; presumably therefore the a-amino-group but not the amide group of asparagine reacted. The nitrogenous groups of guanidine and creatine did not react nor the guanidine group of arginine. The e-amino-group of lysine reacted slowly as also the amino-groups of certain purines. Dunn and Schmidt ( J .Biol. Chem., 1922 53 4-01) and Wright Wilson ( J . Biol. Chem. 1923 56 183) have further studied these slow reactions. Urea was found by Van Slyke to react slowly with sodium nitrite and acetic acid. Werner (J. 1917 111 863) working under different conditions, found no reaction in the presence of acetic acid but obtained an evolution of nitrogen in the presence of mineral acid. He found that the reaction was never complete and considered that the method was of no value for estimating urea. Krall (J. 1915 107 1396) observed an evolution of nitrogen from guanidine in the presence of mineral acid and Wright Wilson (bc. cit.) obtained nitrogen from creatinine using the Van Slyke apparatus. No other reference to the reaction of nitrous acid with " amino "-compound8 has been found on looking through the literature except the statement in the text-book of Organic Chemistry by Meyer and Jacobson (1907, I part 1) that amides give off nitrogen in the presence of strong sulphuric acid.These experiments were therefore undertaken t o find out the con-ditions under which amides guanidine and other amino-compounds react with nitrous acid and to reconcile the various discrepan-cies in the previous results. Some other amino-compounds besides the above-mentioned were also tested. EXPEBIMENTAL. The large form of apparatus described by Van Slyke was used in all the experiments. After the removal of air from the apparatus the acetic acid+mdium nitrite mixfure was always brought to th UPON AMJDES AND OTHEB "AMINO "-COMPOUNDS.2653 same level in the reaction chamber; its volume measured 12 C.C. Generally 5 c.c. sometimes 10 c.c. of the solution of the compound under investigation were delivered from a pipette into the burette of the apparatus and run into the reaction chamber; the burette was then washed twice with 1 C.C. of water and the washings were run into the apparatus. Reaction was dowed to proceed for p e r i d varying from 1 to 24 hours; during the short periods the appamtns was continuously shaken during the long periods it ww &&en for the last half-hour. If the volume of gas evolved tended to fdl the gas burette the gas was passed into the permanganate vessel for absorption of nitric oxide and not returned to the burette until the reaction time was completed.In the experiments with mineral acid concentrated hydrochloric acid was added 1 C.C. at a time in the same way aa the water used in washing the burette and in its stead. After the addition of 3 C.C. of hydrochloric acid gas evolution was very rapid still more rapid after 4 C.C. In these cases the evolved gas was quickly passed into the permangamte vessel and further quantities were added only when the rate of gas evolution diminished. The rapid gas evolution usually ceased after 5 to 10 minutes and became slow after 1 to 2 hours so that the apparatus could be safely left for the long reaction periods amounting to 24 hours. The evolved nitrogen gas was hally measured and by the use of Van Slyke's table its amount was con-verted into mg. ofmitrogen. Usually 1% solutions of the compound under examination were used.The total amount of nitrogen in these solutions was determined by a Kjeldahl estimation in another aliquot portion. All the figures of the estimations were calculated to g. of nitrogen per 100 C.C. of solution. The results of the experi-ments are in the following tables. D~cussion of R d . Amidm.-The experiments with the above amides show clearly that these do not give off an appreciable quantity of nitrogen with nitrous acid in the presence of acetic acid in 24 hours and are thus sharply distinguished from the simple amino-acids which were shown by Van Slyke to react rapidly and completely in from 5 to 30 minuW. The diITerence in behaviour is clearly shown with asparaghe; only one amino-group reacts in a period of 23 horn under these conditions.On introducing hydrochloric acid to the reaction mixture com-plete reaction of the amide group did not occur until 5 C.C. of con-centrated acid had been added. This amount of acid gave a con-centration of approximately 2N-HC1. In the caae of asparaghe, the whole of its nitrogen was then evolved as gas 2654 PIXMMEB THE AOTION OF NITaOlJS ACID Fomumide. Ezpt. 1. Tdal N per 100 C.C. = 0.2884 9. A m i h . Acetumide. EX@. 1. TOW N per 100 C.C. = 0.1512 9. Nepo*ped %Z N evohed Time @per % o f Time @. Per With (hours). Temp. 1OOkc.). htal N. With @cars). Temp. 1OO.c.c.). N. 2 C.C. H,O 1-5 15' 0.0088 3-1 ,) , 2.5 16 0.0080 2.8 , , 24.5 16 0.0092 3.2 Expt. 2. 2 C.C. IfCl 19 11 0.0191 10.6 4 , , 24 16 0-0923 51.1 6 , , 6 18 0.1609 89.1 6 , ,) 19 14 0.1427 79.0 6 , ,) 22 15 0-1805 100.0 Total N per 100 C.C.= 0.1806 9. Expl. 3. Total N per 100 C.C. = 2 C.C. K&O 26 17 0.0162 2 , HC1 24 16 0.0234 3 , , 24-5 16 0-0228 3 ,) , 24 15 0.0344 4 , ,) 22 14 0.0604 5 , , 22 13 0.1415 6 , , 23 13 0-1732 7 , , 26 12 0-1882 7 , , 24 13 0.2139 0.2240 g. 7.2 10.3 10.2 15-4 27.0 63.2 77.3 84.0 95.5 Propknamide. TO^ N p 50 C.C. = Ezpt. 1 . 2 C.C. H,O 0.5 13 0-0006 0.5 2 , ) 2 14 0.0017 1.5 2 , , 17.5 14 0.0039 3.4 2 ,) y y 46.5 13 0-0037 3.2 Ex@. 2. 2 C.C. H,O 23 11 0-0014 0.7 2 , HCI 25 11 0.0156 8-0 3 , , 23 11 0.0154 8-0 4 , , 23 12 0.1491 76.6 5 , , 22 12 0.1967 101.0 0.1155 9. Total N per 100 C.C. = 0.1946 g.2c.c. H,O 1 12" 0-0011 0.7 2 , , 4.5 13 0*0011 0.7 2 , ,) 17.5 11 0.0011 0.7 Expt. 2. Total N per 100 C.C. = 2c.c.H,0 23 17 0.0032 2 , HCI 24 17 0-0082 3 ,) , 24 17 0.0360 4 ) , 5 17 0.0644 4 , , 8 16 0.0696 4 , , 12 17 0.0882 4 ,) , 25 17 0-1042 5 , , 6 17 0.0964 5 , ) 17 17 0.1112 5 , , 24 18 0.1185 0.1148 9. 2-8 7.1 31-3 56.1 60.6 76-8 90-1 83-9 96.9 103.2 Aapuragine. Expt. 1. 2 C.C. H,O 0-25 17 0.1039 49.5 2 ,) , 0-5 15 0.1043 49-7 2 , , 1-0 15 0.1060 50.6 2 , , 3-5 16 0.1093 53.0 2 ) , 17-5 13 0.1112 53.0 Expt. 2. 1 C.C. HCl 1 18 0.1061 60.5 2 , , 2.0 18 0.1079 57.4 3 , , 18-0 15 0.1135 54-0 5 , , 7-0 14 0.1615 76.9 7 , , 23-0 16 0.2209 105.2 8 , ) 23 15 0.2142 102.0 Expt. 3. 2 C.C. H,O 23-5 13 0.1699 54.5 2 , HCl 23 13 0.1842 59.1 3 ., , 23 13 0.1917 61.5 4 , , 23 12 0.1881 59.7 5 , , 23-5 13 0.3014 96.7 6 ) , 23.6 15 03264 104.4 TOW N per 100 C.C.= 0.2100 g. Total N per 100 C.C. = 0.2100 g. Total N per 100 C.C. = 0.3115 9 UPOH AMIDES AND OTHER " AMINO "-COMPOUNDS. 2655 EX@. 1. Total N (pet 100 C.C. = 0.2866 9. N evolved Time @.per %of 2c.c.H20 0-5 11" 0.0164 5.7 2 , y 1.0 11 0.0329 11.5 2 ,) ,y 2.5 12 0.0958 33-5 2 , ,y 3.5 12 0.1652 54.3 2 ) , 6.5 12 0.2198 77.0 2 , ,) 8-5 11 0.2315 81.1 2 , , 15.0 11 0.2657 93.0 2 , , 24.5 10 02767 96.9 With (hours.) Temp. 100 c.c.). totel N. Ezpt. 2. 2 C.C. HzO 8-5 20 0.2512 103.7 2 , , 23.0 18 0.2495 103.0 2 , , 47.0 19 0.2456 101.4 Total N v 100 C.C. = 0.2422 9. Expt.1. TOW N p 100 C.C. = Time @Per tdJbl With (hours). Temp. 100c.o.). N. 2 C.C. H,O 1 16O 0-0023 1-3 2 , , 3-5 16 0.0061 3.5 2 y y ) 23-5 8 0.0165 9.4 0-1764 9. N evolved yo of Expt. 2. 2c.c. H,O 23 15 0.0568 30.5 Total N per 100 C.C. = 0.1862 g. 14 0.0929 49.9 1 y HCl 2 , HCI 24 12 0.1137 61.1 3 y ) 23.5 14 0.1309 70-2 4 , , 23 14 0.2143 116.1 Expi. 1. 2 C.O. H,O 0.5 14 04081 12.3 EX@. 1. TOM N 100 C.C. = 2 ,y , 1.5 15 0-0080 12-2 2c.c. H,O 1.0 11 0.0117 4.1 2 ) ,) 17-5 14 0-0132 20.1 2 , , 5.5 11 0-0326 11.3 T ~ k d N v 100 C.C. = 0-0658 9. Biuret. 0.2884 9. 9' '3 16.5 1' 8E :::! E q t . 2. Total N per 100 C.C. = 2 Y 9 40 0.1904 g. EX@. 2. 2 c.c.H,O 6 21 0.0566 2 , ) 17 19 0-0708 2 Y 23 22 0.0763 2 , HE1 24.5 21 0.1035 3 y ,y 23 22 0.1116 4 , yy 24 20 0.1439 5 , , 23 19 0-1411 6 .,) 24 17 0.1448 Total N pt?? 100 C.C. = 0.1551 g. 2 C.C. H,O 0.5 14 0.0161 8.4 2 ) ) 2-6 15 04304 16.0 2 , , 4-5 15 0-0320 16.8 36.4 2 ,) ,) 16.5 14 0.0515 27.0 49-3 2 ,y ) 4-5 15 0.0714 37.5 45.6 ;;:; Ex@. 3. Tdal N p 100 C.C. = 0-1218 9. 92-6 90.8 2 C.C. Hpo 25 16 0.0689 58.6 93.3 2 , HCl 23 22 0.0764 62.7 2 ) , 23.5 17 0.0613 60.3 3 , y 24 18 0.0595 48.8 3 , , 23 19 0.0463 37.2 4 ) , 24 17 0-2037 167-2 5 , , 24 18 0-2817 231.3 6 , , 23 20 0.2859 234. 2666 PIJMMER !FHE AC!CION OF NITaouS ACID Guanidine and Derimfiues. Expt. 1. TofalNper100c.c. = 0.1316g. Expt.l. TotalNperlOOc.c.=0*2590g. N evolved N evolved % of Time Time @.per total 2 C.C. H,O 1.0 15" 0.0029 2-2 2 C.C.H,O 0-5 12" 0.0177 6.8 2 , ,) 3.5 15 0-0016 1.2 2 , ,) 1.5 11 04465 17.9 2 , , 5.5 15 0.0029 2-2 2 , y y 2.5 14 0.0510 19.7 2 , ) 15-5 11 0-0060 4.6 2 ,) , 17.5 11 0.0608 23.5 2 ,) yy 40.5 14 0.0104 7.9 2 , )) 24-5 15 0-0617 23.8 E:E:E:E:E:E:E:E:E:E:E:~,~. TotulNper lOOc.c.=O-3185 g. 9' " 2575 l6 0.0659 25*4 2 )) , 48-5 11 0-0709 27.4 2 C.C. H,O 25 13 0.0319 10.0 2 ,) ) 50 15 0.0777 30.0 2 , HCI 24 11 0.0639 20-1 Guanidine Carbonate. Aminogwznidinc Acetde. With (hours). Temp. 106 ' per c.c.). t~&lN. ' Of with @oars). Temp. 100c.c.). N. ; : i ii t:ig; ;;: Expt. 2. Total N per 100 C.C. = 0.3402 9. 6 , , 24 10 0-2553 80.1 7 ,) , 24 13 0.2784 87.4 2c.c. H,O 24 13 0.0731 21.5 2 HC1 24 13 0.1052 30.9 Ezpt.3. TotalNper 1OOc.c. = 0.2968g. 3 : ) 24 12 0.1067 31.4 2 C.C.HzO 24 10 0.0104 3-5 4 , , 24 12 0-1855 54.5 2 , HCI 23.5 9 0.0368 12.4 5 , , 24 12 0.2750 80.8 3 , y9 23.5 10 04437 14.7 6 ,) , 25 14 0.3112 91.5 4 1 23.5 11 0.0826 27.8 7 , , 24 16 0.3168 93.3 5 19 9) 25 11 0.2132 71.8 8 , 24 16 0.3154 92.7 6 , ) 24 12 0.2420 81.5 7 y y , 23.6 14 0-2622 88.4 8 ,) ) 23 14 0.2688 90-5 Arginine Carbonate. Expt. 1. Total N per 100 C.C. = 0.1078 g. 2 C.C. H,O 0.5 16 0-0267 24.8 2 )) ) 1 16 0-0294 27.3 2 ., , 1 15 0-0280 26.0 2 )) , 1 16 0.0267 24-8 2 , ,) 2 14 0-0280 26.0 2 ) , 4 14 0.0304 28-2 2 Y 21-5 17 0.0504 46.7 2 , HG 4 19 0.0402 37-3 2 )) ) 26 16 0.0698 6 4 7 2 , , 30 16 0.0680 63-1 Expt. 1. Totul N per 100 C.C. = 0.07 g. ~ c . c . H,O 1 15 0.0018 2.6 2 ,) , 3.5 15 0-0011 1.6 2 , , 4.0 15 0-0023 3-3 2 , , 18-5 15 0.0045 6-4 Creatinc.,2. Totd N per 100 C.C. = 0-1456 g. H,O 23.5 14 0.0231 15.9 HCI 25 14 0-0394 27.0 ,) 24 14 0-0494 33.9 , 24 16 0.0483 33.2 , 24 13 0.0574 39.4 ) 24 14 0.0967 66-4 , 24 15 0.1081 74-2 , 24 14 0.1008 69.2 Arginine carbonate. Total AT per 100 C.C. = Expt. 2. 2 C.C. H,O 0.5 20 0-0212 17.5 2 , ,) 1.0 19 0.0266 22-0 2 9 Y 24 13 0-0566 46-7 2 ,) He1 24 14 0.1044 86-2 3 ) 24-5 13 0.1006 83.1 4 ) ) 24.5 14 0.1118 92.3 6 ) , 24 15 0.1173 96.9 7 ) , 25 19 0.1167 964 8 , , 24 17 0.1237 102-1 0.1211 9. Creatinine. Expt. 1. Total N per 1OOc.c. =0*2898 g. 2 C.C. H,O 1 15 0%766 22.9 2 , ) 4 17 0.1027 35-4 2 , , 15.5 15 0.1075 37-1 2 .. .. 23 17 0.1164 40.1 19 17 13 14 16 14 17 15 14 0.1211 0.1208 0.1221 0.0886 0.0540 0-0646 0.0478 0-0506 0-0455 41.8 41.7 42-1 -30.6 18-6 22.3 16.5 17.5 15.7 Amnumiurn acetate.Hydrazine mdphtc. T0ta2 N per 100 C.C. = 0-3304 9. 2 C.C. H,O 0.5 13 0.1061 32.1 2 C.C. H,O 0.5 13 0.0641 111.7 2 , , 2-5 16 0.3385 102.4 2 , , 4.5 13 0.1424 258.5 2 , ) 18.5 14 0.3408 103.1 2 ) ) 17.5 14 0.1573 274-0 Total N per 100 C.C. = 0.0574 9 UPON ABIDES AND OTHES " AMINO "-COMFOUNDS. 2667 The formation of nitrogen in the presence of hydrochloric acid is not due to hydrolysis of the amide. Experiments were made fo fest this possibility by alloffing 20 C.C. of the amide solution to stand for 24 hours with 6 C.C. of concentrated hydrochloric acid. The solution was then rendered alkaline with sodium carbonate and any ammonia produced estimated by the eration method of Polin.Acetamide gave 26.2 propionamide 26-3 aspamgine 4.9%. Formamide was apprently completely hydrolysed with the forma-ation of 96.2% of ammonia. If the reaction of amino-acids with nitrous acid ih acetic acid solution is taken as an indication of the presence of a primary amino-group the difference in the behaviour of amides should be represented by giving amidea the alternative formula R*C(OH):N€€ which may be regarded as being converted in the presence of mineral acid into the more usual formula R*CO*m which shows the presence of an -NK2 group. This alternative formula is supported by the form-ation of unstable salts of amides which are decomposed by water. Urea and Derimtives.-Van Slyke has stated that urea reacted slowly with nitrous acid in the presence of acetic acid.These results show that at low temperatures (from 10" to 12") the reaction is not complete but that complete decomposition occurs at 18" In 20". Werner under different experimental conditions did not obseme complete reaction and attributed the incompleteness to the formation of ammonium salts. As seen from the experiment with ammonium acetate it is completely decomposed in 24 hours. The difference in the results seems to be due to the length of time of the reaction. As urea was decomposed in the presence of acetic acid no experiments were made in the presence of hydrochloric acid. On comparing the results with those of amides it appears that urea possesses the alternative formula HN=C<? which changes mzl in presence of acids to HN=CLNH, /OH aa proposed by Werner.The substance with the latter form& showing an -NH p u p would be attacked by nitrous acid; imyanic acid which is eady hydrolysed to ammonium carbonate would also yield nitrogen. This alternative formula for urea is supported by the behaviour of semicarbazide and urethane. One-third of the nitrogen of semi-carbazide was obtained as gas in the presence of acetic acid rather more in the presence of 2 or 3 C.C. of hydrochloric acid. One of the three nitrogen atoms would thus be present as an - group. In presence of more hydrochloric acid large volumes of gas were evolved suggesting that hydrazine was formed by decomposition. Hydrazine in another experiment was observed to produce larg 2658 PLTMMEB TEE A W O N OF NITROUS ACID volumes of gas probably resulting from reduction of nitrous acid by hydrazine.Urethane behaved like the simple amides no evolution of nitrogen in presence of acetic acid but complete reaction in presence of hydrochloric acid. It would thus appear to have the alternative formula OEt.C(OH):NH which changa into OEtCO-NH in presence of mineral acid. The behaviour of biuret with nitrous mid is most easily explained by Werner's formula NH:C(OH)*NH*C(OH):NH. In presence of acetic acid this would change to NH:C(OH)mNEl-CO*NH with liberation of one-third of its nitrogen as gas as found by experi-ment ; in the presence of 2 to 3 C.C. of hydrochloric acid the formula would become N€&-CO-NH*CO*NH ; two-thirds of the nitrogen was given off.In presence of 4 to 6 C.C. of hydrochloric acid the whole of the nitrogen was evolved indicating that the molecule was completely broken down. Ghunidine and Derivatives.-Guanidine reacted only slightly in presence of acetic acid two-thirds of its nitrogen was given off in presence of 5 C.C. of hydrochloric acid and the reaction was nearly complete in presence of 8 C.C. of hydrochloric acid in 23 hours. The alternative formula HN=C<yG proposed by Gall is indicated for guanidine. This changes to the usually adopted formula NH:C(NH,), in presence of mineral acid which explains the liberation of two-thirds of its nitrogen in presence of hydro-chloric acid. Arginine behaved in a similar way to guanidine.Only the a-amino-group reacts with nitrous acid in presence of acetic acid. This reaction is used in its analysis. An excew of nitrogen over one-third was found by Plimmer (Bimhem. J. 1924 18 105) if the reaction were prolonged. The whole of its nitrogen is given off as gas in the presence of hydrochloric acid. Aminoguanidine gave off one-quarter of its nitrogen &s gas in presence of acetic acid but larger quantities in presence of hydro-chloric acid. Corresponding with guanidine the whole of the nitrogen was not evolved as gas. Creatine reacted in a similar way to guanidine and appeam to have an alternative formula such as C02H*C€&*NMe*C<xH3, which changes to the usual formula CO,H~CH,=NMe*C(:NEl)*~, in presence of hydrochloric acid. A volume of nitrogen was evolved corresponding to two nitrogen atoms.The third nitrogen atom to which the methyl group is attached would not be expected to yield nitrogen. Creatinine which was also found by Wright Wilson to N UPON ~ E S AND cmnm “ ~ O ” - C O M P O U N D S . 2659 react with nitrous acid in presence of acetic acid showed an un-expected behaviour indicating the presence of an amino-group. It would thus appear to have an alternative formula such as (I) insw of (II). N NH /\ m:(( yo (11.1 A-(1.) Nlq ((0 M e L q Me3T-W The effect of mineral acid in diminishing the volume of nitrogen evolved may be due to a change of the new alternative formula to the commonly adopted one. The formation of the smaller amounts of nitrogen in the experiments may be due to the method of adding the hydrochloric acid I C.C.at a time; a certain volume would be liberated before the whole of the 6 or 8 C.C. could be introduced. Summary. 1. Amides and urethane do not react with nitrous acid in presence of acetic acid. 2. Both react quantitatively in presence of approximately 2N-hydrochloric acid. 3. Urea reacts quantitatively with nitrous acid in presence of acetic acid. 4. Biuret reacts with one nitrogen atom in presence of acetic acid, with two nihgen atoms in presence of small amounts of hydrochloric acid with three nitrogen atoms in presence of 2N-hydrochloric acid. 5. Guanidine and creatine do not react with nitrow acid in presence of acetic acid but give off nitrogen in presence of hydro-chloric acid. Arginine excepting its primary a-amino-group behaves in a similar way. 6. Creatinine gives off nitrogen corresponding to one nitrogen atom with nitrous acid in presence of metic acid; the volume of nitrogen evolved is dimirriclhed in presence of hydrochloric acid. 7. If nitrous acid in presence of acetic acid is a reagent for the presence of an -NH group amides and the other compounds investigated wiU possess alternative formulae which in presence of hydrochloric acid change to the usually accepted formulae for these compounds. The author d e s h to express his thanks to the Government Grant Committee of the Royal Society for a grant out of which the expenses of this remarch have been defrayed. ST. THOU’S HOSPITAL MEDICAL SCHOOL, LONDON. [Rmeiued Aecgzcat 5& 1925.

ISSN:0368-1645    

DOI:10.1039/CT9252702651

出版商:RSC    

年代:1925

数据来源: RSC

摘要:

2660 OILUSTONE mm POUND SOLUBILITY INFLUENCES. CCCLXIII.-Solubility Influences. Part I . The EiJect of Some xalts Sugars and Temperature on the Solubility of Ethyl Acetate in Water. By S m GLASSTONE and ALBERT POUND. ALTHOUGH much work has been done on the influence of salts on the solubility in water of various non-electrolytes (for chief refer-ences see Eyre Brit. Assoc. Rep. 1910 447 ; 1912 820; Rivett and Rosenblum Trans. Faraday Soc. 1914 9 297; Linderstrom-Lang Conapt. Rend. Trav. Lab. Curbberg 1924 15 No. 4) there seems to have been very little attempt made a t a systematic investigation. Very little work too has been done on the influ-ence of non-electrolytes such as sugars on the solubility of other non-electrolytes such as ethyl acetate ether and aniline and as far as the present author is aware there has been no systematic investigation of the effect of a mixture of substances either elec-tzolytes or non-electrolytes on the solubility of a sparingly soluble, neutxal substance.It seemed very probable that a complete examination of the so-called " salting out " effect would throw mme light on the larger problem of solution and the work described below was intended to be a contribution towards a more systematic survey of the problem than has yet been made. In the present work the solubility of ethyl acetate has been determined at 25" and a t 50" in pure water and in the presence of various sugars and of the chlorides bromides and iodides of the alkali metals and of ammonium. Some rough measurements have also been made of the solubility of various salts in ethyl acetate saturated with water (about 3%) and an interesting qualitative connexion between these values and those of the solubility of ethyl acetate in salt solutions has been established.The solubility of ethyl acetate in water has also been determined a t 0" lo" and 37". Philip (J. 1907 91 711) has shown the advantage of expressing solubility results of this kind in terms of grams or gram-moles per lo00 grams of solvent rather than per litre of solution. A further change is now made the results being expressed in terms of the number of gram-mols. of water required to dissolve one gram-mol. of ethyl acetate in the presence of various molecular quantities of added sugar or salt; in this form the results are useful for various calculations and for comparison with one another.EXPERIMENTAL. Ethyl acetate made by Roberts's method ( J . Soc. Chem. Id., 1924 43 295~) was purified from alcohol by distillation over calcium chloride and then by several fractionations over phos PART I. THE EFFECT OF WISE SALTS suams ETC. 2661 phorua pentoxide; only the final constant-boiling fraction was used in this work. The salts and sugars were the pnrest com-mercial specimens mainly supplied by the British Drng HOW, LM. and no attempt w a made to purify them; slight impurith had very little effect on the solubility of ethyl acetate and this was probably less than the experimental error. The variom solutions were made up by careful weighing of the substance and the water and were saturated with ethyl acetate a follows Since the solubility of ethyl acetate in water and in aqueous solntions decreases with rise of temperature (see below) the solution was shaken with a sllght excess of the ester at a temperature below 25" or 50" and placed in a thermostat at 25" or 50"; the e x w of ethyl acetate then separating caused the liquid to become cloudy.In the course of an hour or two the aqueous liquid waa clear again, and was a saturated solution of the ester at the temperature of the thermostat. Care was always taken that the excess of ethyl acetate present was not so lmge that the amount of water or salt dissolved by it could not be neglected. For analysis a quantity of the saturated solution (3 to 8 g., depending on the ester concentration) was traderred rapidly in a warmed pipette to a stoppered bottle and weighed; care was taken that none of the acetate layer was drawn into the pipette.In the cases of the various salts which it was desired to recover, and of the sugars the weighed solution was diluted with water, washed into a distilling flask and the ethyl acetate and some water distilled over and collected in water in such a way as to avoid loss of ester. The residue in the flask wa8 always tested to make sure that no acetic acid which might have resulted from the hydrolysis of the ester by boiling water remained behind. The ester wa8 then hydrolysed with standard sodium hydroxide and estimated in the usual way. When the original solution contained an ammonium salt distillation wa8 always n-, and in case the salt had become hydrolysed during this process and ammonia distilled over the solution after alkali hydrolysis, was boiled for a few minutes without the reflux condenser in order to expel ammonia.If distillation wtw unnecessary the weighed sohtion was diluted and hydrolysed directly. Resulk-The columns headed m and w give the number of g.-mols. of added substances and of water respectively required to make a solution which will be saturated with 1 g.-mol. of ethyl acetate at the temperature stated. The significance of the figures in the column headed R is explained onp. 2664. In the absence of any added substance the value of w (wo) is 66.15 at 25" and 80.98 at 50" 2662 QLdssTONE AXD POUND SOLWIIZl!Y z " C E S . Lithium chloride.712. to. n. 0.667 76-67 15-7 2.27 98.92 14-5 6.28 133.7 10.7 24-85 231-5 6.7 134.5 476.2 3-3 0.858 98.65 20-6 2.905 125.9 15.0 8.08 171.8 11.2 31.55 294.1 6.7 181.2 641-0 3.1 Sodium chloride. 0.219 70.68 20.7 0.477 76.65 22.0 1.540 94.34 18-3 4-86 142.0 15.6 12.03 218.8 12-7 27-10 352.1 10.6 59.30 581.4 8.7 0.273 88-12 26-1 0.589 94.80 23.4 2-02 123.5 21-0 6-43 188.0 16.6 14.40 261.8 12.6 33.42 434-8 10-6 85-00 833-3 8.9 Potassium chloride. 0-168 69.15 17-8 0.369 74-75 23.3 1.093 86.21 18-3 3-06 112.9 15-2 6.96 155-0 12.7 12-19 203.7 11.3 22.90 284.9 9.5 0.213 87.67 -0.458 92.73 25.5 1.438 113.3 22.4 4.09 162.7 17.6 8.87 197.6 13.1 14-70 245.7 11-2 31.07 386.1 9.8 Rubidium chloride. 0-578 77-52 19-7 1.454 93.10 18-5 5.22 135-9 13-3 14.20 224.7 12-5 67-8 546-4 7.1 Lithium bromide.m. w. n. 25". 0.287 68-16 7.0 0.777 71-19 6 4 1.824 77.14 6.0 4.85 91.19 5.2 13-26 96-27 2.3 15.66 40.65 -50". 0.354 84.03 8.6 0.936 85-47 4.8 2-325 98-46 7.5 6.12 115.2 5.6 18.40 133-3 2-9 19.58 83.5 -Sodium bromide. 25". 0.229 71-10 -0-630 76.76 16.8 1.560 87.72 13.9 4.91 121.2 11.2 12-10 173.3 8.8 47-40 367-6 6.4 50". 0.294 91.66 -0.794 96-64 19-6 2-69 116.3 13.1 6.43 158-7 12.1 15-48 221.7 9.1 52.60 408.2 6-2 Potassium bromide. 25'. 0-249 69.20 12.3 0.610 76.70 17.3 1.39 84-03 12.8 4-29 114.9 11.3 9-44 148.6 8.7 21-90 220.8 7.0 50". 0-370 85-09 11.0 0-737 92.59 15.7 1.774 107-1 14.7 5.46 146.0 11.9 12-65 199.2 9.3 30.68 308.6 7.4 Rubidium bromide.25". 0.421 73.53 17.5 0-993 80-65 14.5 2-65 94-69 11.2 7-66 132.5 8-6 24-00 222-7 6.5 Lithium iodide. m. w. n. 0.476 65.90 -0.906 62.60 -1.967 58.40 -3.44 38.5 -0.566 78.5 -1.112 76.9 -2.36 70.5 -5.02 56.0 -0.912 4-56' -Sodium iodide. 0.163 67.14 6.7 0-432 68-25 4.8 0-774 68-78 3-5 2.165 73.37 3.3 6-46 82.58 2.5 21.32 109-4 2.0 0-243 84.37 13.6 0.535 84-75 7.0 0.978 86.58 5.6 2-81 95.24 5.0 8-44 107.8 3.2 27-76 142.5 2.2 Pota,ssium iodide. 0.150 68.03 12.6 0.395 69-69 9.0 0-860 71.43 6-1 2.02 75.19 4.5 6-45 87.72 3.3 20-19 125-0 2-9 0.181 82-26 7.0 0.473 83-33 4.9 1.045 86.81 5.5 2-44 90.91 4-1 7.71 106.7 3.3 24-22 149.9 2.8 Rubidium iodide. 0.298 66-82 2.2 0.635 68.78 4.1 1475 69-69 2.4 2.66 73.42 2.7 5-69 82-58 2.9 12.53 107-0 3.PABT I. !PEE EFBECI! OF SOME SAL!l!S SUGAES ETO. 2663 Rubidium chloride. m. W. n. 0.742 94.5 18.2 6-62 172-4 13.8 84.4 680.3 7.1 c8?sium chloride. 0.427 74.52 19.6 1-004 86-21 20.0 3-065 113.6 15-5 7.04 163.1 12.4 26-70 294-1 8.5 132.5 671-1 4.6 0.530 92-59 21.9 3-802 141.0 16-7 29.95 330.0 8.3 197.8 1ooO-0 4-6 Ammonium chloride. 0.525 76-54 1-568 89.14 4-28 112.4 8.41 139.7 14.95 174-5 0.632 92.14 1.973 112-2 5-66 148.4 11-42 189.8 18.61 216.9 Dextrose. 0.0692 68.6 0-1423 69.3 0-392 73.6 0.871 78-6 1.486 84.1 2-262 90-6 3-315 98-5 0.0826 81.8 0*1708 83-1 0.462 86.6 1.016 91.5 1-705 96.6 2.593 103-6 3.722 110-7 194 14-7 10.8 8.7 7-2 17.6 15.8 11.9 9.4 7.8 25.4 22-0 19.0 14.3 12-1 10-8 9.7 9.7 12.3 12-1 10.3 9.1 8.7 8.0 Rubidium bromide.m. 10. n. 60'. O-SO2 87-64 13.2 3-23 119-8 12-0 40.5 375.9 7.2 Caesium bromide. 25". 0.321 70.68 14-1 0-693 74.52 12-1 1-835 86.81 11.2 3.47 97.96 9-1 8-80 135.0 7.8 50". 0.400 88.12 17.8 2-236 105.8 11.1 11.92 179.9 8-3 35-10 275.5 5.5 Ammonium bromide. 25". 0.273 70-0 0.725 74-4 1.680 81-9 4.33 94-0 8-55 109.5 16.38 122.7 50'. 0.338 86.5 0.839 90-8 2.107 102.5 5.55 120.6 11-77 160.8 21.78 177-0 L~VUloSe. 0.394 73.8 0.867 78-3 1.445 81-9 2.178 87-0 4.270 99-8 8965 131-0 25'. 50'. 0-475 89.0 1-045 94-3 1-720 97-4 2.620 101.0 4-76 111-2 8.89 134.6 13.6 11.4 9.4 6.4 5-1 3-5 16-2 11-7 10-2 7.1 5-9 4.4 19-4 14.0 10.9 9-6 7-9 7.5 16.6 12.7 9.5 7-9 6-3 6.1 Rubidium iodide.m. w. n. 0.358 80.33 -1.788 84.37 1.9 7-26 106.3 3.3 C h u m iodide. 0.237 67-79 6.9 0.638 68.87 6.1 1-241 70.78 3.7 2-70 72.30 2-3 0.290 82.88 6.5 1487 84-79 2.6 3-44 93-01 3.5 Ammonium iodide. 0.422 64.4 -0.866 63.2 -1.87 60.8 -4-74 57.4 -12.42 62-1 -0.613 80.4 -1.094 79.6 -2.418 78.7 -6.28 76.2 -16-32 88.8 0-5 sucn>ee. 0-0734 0.190 0-406 0.696 1.010 1-936 3-57 6.10 0.091 0.233 0.508 0.833 1.206 2.36 4.18 6-81 66.4 68.5 12.9 69.6 8.5 75-0 12.7 77-6 11.3 86.7 10.6 101.5 9.9 115.9 8.1 82.1 83-9 87.0 89.6 92.9 106.4 119.0 €29.2 12-1 12.4 11.8 10.3 9.9 10.4 9.1 7-Lactose.25". 50". m. W. 0-0706 69-4 0.190 72.5 0-423 77-4 0.739 83.0 1 -094 55.7 1-575 94.7 I 7 n. m. 46-0 0.0545 33-4 0,222 26-6 0-487 21-4 0-854 20-6 1.234 18-1 1.762 W . 83.3 84.7 89-0 1oc)-o 105-9 94.8 7 n. 27.1 16-7 16.4 16.2 15-6 14.1 DiscusSion. In general the effect of one substance in reducing the solubility of another has been explained along two merent lines. Euler (Z. phySiW. Chem. 1899 31 360) suggested that the addition of a mlt to water increases the internal pressure md this results in a decreztsed solvent power for a neutral solute; this theory was supported by Geffcken (ibid.1904 49 257) but watj adversely criticised by Levin (ibid. 1906 55 503). On the other hand, Rothmund (ibid. 1900 33 401) suggested that the reduction in solubility is due to the added salt becoming hydrated in solution, so that the molecules of water involved in the hydration are no longer available for the dissolution of another substance. Although Rothmund later criticised this point of view (ibid. 1909 69 523), it received support from Baur (Ahren's Samdung 1903 8 466), Lowry (Trans. Fura~?uy Soc. 1905 1 197) and Philip (J. 1907, 91 711). The last author was the fist to make use of solubility determinations in salt solutions in order to calculate the hydration values of various salts ; by assuming that the reduction in solubility of the neutral substance is entirely due to the water molecules removed in the salt-hydrate average values for the number of molecules of hydrate water per molecule of salt can be obtained.Philip's method of calculating hydration values has been applied to the results obtained in the present work and the average degree of hydration of the salts etc. at various concentrations which is equal to (w - w,,)/m is given in the column headed n. Since there is some doubt it5 to the condition of molecules and ions in concentrated solutions the hydration values for different salts are beat compared at infinite diIution; consequently all the hydration numbers obtained above have been extrapolated roughly to zero concentration. The results are given below ; as the values do not vary appreciably between 25" and 50° average results are recorded.Hydration of Salts at InJinite Dilution. LiCl ... 27 XaPl ... 24 KCI ... 22 hiH,C1 ... 21 RbCl ... 20 CsCl ... 20 LiBr ... 9 ? XaBr... 19 KBr. .. 17 NH,Br ... 16 RbBr ... 16 CsBr ... 15 LiI ... ? NaI ... 14T KI ... 129 NHJ ... ? RbI ... 5 ? CsI ... 8 ' PLBT I. THE EmEm or SOME SALTS m u m. 2665 The multa for the lithium rralte and almost all the iodides are uncertain; the solubility Sgnres in i@cs (pp. 2662-3) show that lithium bromide at the high& concentrations and lithium and ammonium iodides at almost d concentrations increase the solubility of ethyl acetate in water. The increase is probsbly connected with the formation of a compound between the salt and the ester; concenfrated solutions of iodides containing ethyl acetate have a distinct yellow colour which is not due to the presence of free iodine and can be attributed only to the presence of some complex aubgtance in solution.There was no evidence of a meta-thetical reaction between the salt and the eerfer. The remarkable fact that at 25" ethyl acetate and a 60% solution of lithium iodide in water are miscible in all proportions merib further investigation. Some experiments have been made on the solubility of the various salts in ethyl acetate saturated with water; lithium chloride, d u m potassium ammonium rubidium and durn iodides are slightly soluble whilst lithium bromide and iodide are comider-ably soluble (roughly 30% and Myo respectively at 25"). It is with the salts which are soluble in ethyl acetate therefore that anomalous results have been obtained; it follows then that whenever the added salt either combines with or is soluble in the neutral solute the hydration values calculated by the method described above are useless.Although the hydration values given above a,re in good agree-ment with those calculated by other authom from a variety of solubility measurements (Philip loc. cit.; Philip and Bramley, J. 1915 107 377; McArthur J . Physical Cbm. 1916 20 496; Thorne J. 1921 119 262; Manchot Jahrstorfer and Zepter, 2. umrg. Ch. 1924 141 G) it d m not follow thaf hydration is the main or even the subsidiary cause of salting-out. This effect may be due to some other fundamental property of each ion or molecule which is independent of the nature of the mb-etance being salted-out provided no compound formation o(x1111& In the case of the mgm some of the hydration vdues calc~&td by the method described above appear to be incredibly large and to vary considerably with temperature and so it is probable a t other factors are operative.It is seen also that molecules of a non-electrolyte have the power of reducing very considerably the solubility of ethyl metab in water. Euler and his co-workers (2. lYW-. 1917 23 192; 2. plrysid. Ch. 1924 140 113) appeatr to have tacitly assumed that only ions are responsible for salting-out but it is clear that this assumption is not justifiable. McKeown also ( J . Amer. Ciaem. SOL 1922 44 1203) in attempting to aswas the salting-out power 2666 GIJBSL'ONE AND POUND SOLUBILlTY INFLUENCES.PART I. of sodium- and chlorine-ions amume~ that the dting-out effect of undksociated molecules is very small; he finds that when ether is salted out with sodium chloride the effect is entirely due to the chlorine ions. It should be pointed out however that since the equations from which this result is obtained me admittedly approximate the conclusion is of little value; h o s t equally good agreement with most of the equations may be obtained by rising entirely Werent values from those of McKeown. In the case of ethyl acetate it is clear that both anions and Bations have definite salting-out power; the kations would be placed in the order Li>Na>K>NH,>Rb>Cs and the anions in the order c1> Br > I. Various authors have attempted to obtain equations which connect the solubility of a neutral substance in a salt or other, solution with the concentration of added salt; in general an equation of the type log 8 = a - kc has been found to be most satisfactory where 8 is the solubility of the neutral substance, c the concentration of salt and a and k are constants (for references, see Thorne h.cit. and Linderstrom-Lang loc. cit.). In the present work it has not been possible to find any one equation which will fit all the results up to the highest concentrations of added salt ; in general the logarithmic equation was found to hold good in the form log w = h / w + a where a and k are con-stants for a given salt and w and rn have the same meaning as before up to concentrations of 2-3N.For some salts-Bodium, potassium and rubidium chloridethe agreement waa very good almost up to the srtturation point. In those cases in which the d t was soluble in ethyl acetate the logarithmic equation waa not obeyed at all. In the presence of lithium chloride the solubility of ethyl acetate may be expressed by the straight-line equation w = lcma + a and a similar equation holds good for the more concentrated sugar solutions. The fact that the results will not all conform to one simple equation suggesh that the salting-out effect is due to several difEerent factors on which it is hoped, further investigations will throw light. 8olubility of Ethyl Acetate in Water. As the literature is very deficient in measurements of the solu-bility of ethyl acetate in water at different temperatures a number of determinations have been made by the method described above for salt solutions with the following results :-Grams of Ethyl Acetate dissolved by 100 gram~ of Water.10.40 at 0"; 8.96 at 10"; 7-39 at 25"; 6-65 at 37"; 6-04 at 50' The following @ma have been obtained by interpolation from a graph :-7.85 86 20" ; )I.W 8f 30" ; 6.50 8t 40". The solubility thus decreases steadily aa the temperature is raised from 0" to 50". stbmmw. (1) The solubility of ethyl acetate has been determined at 25" and 50" in solutions of the chloride bromide and iodide of the alkali metals and of ammonium and in solutions of dextrose, laevulose sucrose and lactose. (2) It is shown that hydration of the salt may be one of the factors responsible for the salting-out effect; this effect may, however be due to some other fundamental property of salt ions or molecules. Molecules aa well as ions probably have considerable salting-out power. (3) The solubility of ethyl acetate in salt solutions is best e x p d by a logarithmic equation e.g. log w = kmlw + a; the application of this equation however is limited to the more dilute salt golutions. (4) The solubility of ethyl acetate in water has been determined at 0" lo" 25" 37" and 50" ; the solubility decreases with increasing temperature. The authors are indebted to the Chemical Society for a grant from its Research Fund which defrayed part of the expense of this work. Their t h a h are also due to Mr. A. L. Stephens B.Sc., and Mr. W. R. P. Hodgson B.Sc. for valuable d t a n c e . UN'IVEaSrrP COLLEGE b T E B . [Received Aolguet 11M 1925.

ISSN:0368-1645    

DOI:10.1039/CT9252702660

出版商:RSC    

年代:1925

数据来源: RSC

摘要:

CCCLXIV.--The Preparation of Tertiary Arsines by the Friedel-Craf ts Beaction. By B~THOR FBEDEI~ICK HUNT and EUSTACE EBENEZEB TUB;Nm. M first succeBBful application of the F’riedel-craffs reaction to the preparation of tertiary amines wm the conversion of phenylmethyl-chloroarsine into diphenylmethylarsine (Burrows and h e r J., 1921 119 426). If the reaction were generally applicable to the preparation of tertiary arsines cases would arise where it would be preferable to syntheses involving the me of the Grignard reagent. A few examples have been studied and it has been found that p h e n y l m e t h y l c h e (chosen because of its ready scceslsibility) condenses with mesitylene to give phyZmaityZdgbrt?im and with toluene and bromobenzene to give mainly the para-compounds ~ k y Z - p - t ~ Z y Z n d i y l a ~ ~ i ~ ~ a d p - b ~ d i p h y Z d y h ~ ~ ~ mt-ively.Proof of the constitution of the ?wo laat-named compounds has been obtained by independent syntheses using the usual methods. In other Friedel-Crafts reactions bromobenzene gives mainly para-compounds (Dilthey J . pr. Chem. 1925 109 273). It appears to be advisable in the case of Friedel-Crafts reactions with arsenic compounds to use an excess of the non-arsenical com-ponent and to remove the hydrogen chloride as fast as it is formed by keeping the reaction mixture gently boiling under diminished pressure. In the reaction with bromobenzene a little of the latter is converted into 4-bromodiphenyl. E s P E R I M E N T A L. Prepra-tion of Pheny1methylchloroarsine.-The substitution of methyl chloride and sulphate for methyl iodide in the methylation of phenylarsenious oxide (Burrows and Turner loc.cit.) gave unsatisfactory results (yields of phenylmethylchloroarsine 56% and 55% respectively). Preparation of PhenyZ-p-toly1methylQrsine.-( a) From phenyl-methylchloroarse'ne and toluene. To a mixture of 15 g. of phenyl-methylchloroarsine and 60 g. of toluene were added 15 g. of powdered anhydrous aluminium chloride and the resulting red solution was heated under reflux for 2-5 hours ; evolution of hydrogen chloride had then almost ceased. The dark-coloured product was poured on to a mixture of ice and hydrochloric acid when a brownish-red precipitate and a green fluorescent oil separated. The oil was removed and filtered washed with sodium hydroxide to remove unchanged chloroarsine dried over anhydrous sodium sulphate and freed from toluene by distillation.The residue when distilled under diminished pressure gave 8 g. of phenyl-p-tolylmethylarsine (aee below) an almost colourless liquid b. p. 164-165"/12 mm. (Found As 29.1. C,H,,As requires As 29.1%). The arsine has an unpleasant Sshy odour and slowly oxidises on keeping with gradual separation of colourless crystals. It combines with methyl iodide slowly a t the ordinary temperature (2 to 3 weeks) and rapidly at lOO" with production of phen yl-p-tolyldimethylarsonium iodide colourless prisms m. p. 93" (Found I 31.7. C,,H,,IAs requires I 31.8%). Phenyl-p-tolylmethylarsine combines readily with ethyl iodide at 1W" to give the phenyl-~-~ly~ethylethylilrsonium iodide obtained by Michaelis (Annalen 1902 321 160) from phenyl-p-tolyIethylarsine and methyl iodide.The iodide W&B described by Michaelis as melting a t 145" or at 150-151" when crystallised from alcohol or from water respectively. The compound has no been found to melt at 150" when crystallised from alcohol and at 158" when c w from water. Once it had been q a t a b e d from water recryddiaation from either solvent did not affect the m. p. (158") (Found I 30.6. Calc. I 30*7%). Phenyl-p-tolyhethylarsine forma with mercnric chloride a white, crptdline additive componnd which may be c r p t a h d ' from glacial acetic acid. (b) From m~gneSium p-toZyZ iodide and phenylmethykhlmoarshe. A Grignard reagent made from 24 g.of p-iodotoluene 2.6 g. of mag-nesium and 100 C.C. of ether waa slowly treated with 20-4 g. of phenylmethylchloroarsine dissolved in 20 C.C. of ether. When the initial reaction was over the whole waa heated under reflux for 2 horn and worked up in the d manner. In this way 18 g. (76% yield) of phenyl-p-tolylmethy~~ine were obtained b. p. 167"/14 mm. The odour of thie sample waa less pronounced than that of the sample from (a) but both substances otherwise poesessed similar pmpertiea. The arsine from (b) gave the aame methiodide (m. p. 92") aa that from (a) a miXtnre of the two methiodides melting at 92". P*paratim of Phenylmaitylmetlryllrrsine.-A mixtnre of 15 g. of phenylmethylchloromine and 35 g. of mesifylene treated with 15 g. of a1uminim.u chloride became alightly warm and tumed red.It waa boiled gently under reflux at 75-80"/45 mm. for some horn ; when the evolution of hydrogen chloride slackened the product waa poured on to a mixture of ice and hydrochloric acid. The d t i n g oil waa extracted with benzene the extract fdkred from a reddhh-brown precipitate shaken with alkali and worked up in the normal manner; 15 g. of mesitylene and 7 g. of phyZ&tylMhylargm (yield 30%) were obtained. The latter is a colourless mobile liquid having a faint fhhy odour oxidises slowly in the air to give a white, crystalline solid and boils at 164'117 mm. (Found Be 26.6. C16H19 Be requires As 2602%). The mine combines readily with methyl iodide at 100" to give phenyZm&tyZdimethyZur~mhn iodide which is moderately soluble in alcohol and separates from that solvent in colourleas prigms, m.p. 187" (Found I 29.6. C 1 ~ I A s requires As 29.7%). The arsine combines with benzyl bromide slowly at the ordinmy temperature and rapidly at 100" to give phenylwmitylbenzylmethyl-armium bromide which crystallises from alcohol or better from water in colourless p h s m. p. 179-180" (Found Br 17.7. CS€&J3rAs requires Br 17.5%). Prepratkm of p - B r ~ i p ~ n ~ l ~ y ~ r ~ ~ . - ( a ) From pknyf-methykhoargrae and hmwberazene. A mixture of 20 g. of the chloroamine 60 g. of bromobenzene and 20 g. of aluminium chlorid 2670 !l!EE PBEPABA!CION OF TlEaTIdsp ARSINES ETC. waa kept briskly b o i i under diminished pmsure (bath at about 35"). after an hour when the evolution of hydrogen chloride had almost ceased the cooled product was poured on to ice and hydro-chloric acid and wm worked up in the usual manner.On distii-lation 35 g. of bromobenzene were recovered. At 14-0-160°/15 mm., 2 g. of 4-bromodiphenyl distilled (white plates m. p. 81". Found : Br 33-9. At 170-200"/15 mm. 5 g. of p-bromodiphm&aethylarsine (see below) distilled aa a colourless liquid (Found As 23.6. The h e combined readily with methyl iodide in a closed tube at 100" to give a crystalline product which could not be recrystallised from the usual solvents. The combination of the arsine with methyl iodide in the cold (2 to 3 weeks) however gave p-bromodiphenyl-dinwthyhrsonium iodid,e. This waa precipitated by absolute ether from ite solution in absolute alcohol and formed very pale yellow prisms m.p. 87' (Found I 27.0. C,,H,,BrIAs requires I 27.3%). The benzobromide of p-bromodiphenylmethylarsine was obtained as a colourless viscid mass which could not be crystallised. (b) From p-br~hnylmethyliodoczrsine. p-Bromophenylarsinic acid was propared from p-bromoadine in the usual manner; and reduced with hydrochloric-hydriodic~ulphurous acid when p-brumophenyldiine was obtained. The crude red dichloro-arsine when treated with sodium carbonate in presence of warm wafer gave p-brmphenylursenious oxide as a sticky yellow solid. It waa p d e d by dissolving in alcohol and precipitating with water, and then formed white prisms m. p. 259-261" (Found AE 30-7. C,H,OBrAs requires As 30.4%). The oxide may be methylated direct but tia some pure dichloroarsine was required for another purpose the oxide was converted into the latter in the usual manner.p-Bromophenyldichlorowaine was thus obtained as a heavy orange-coloured liquid boiling at 164"/18 mm. and having physiological properties similar to those of phenyldichloroarsine (Found C1,236 C,H,qBrAs requires CI 234%). The dichloroarsine (30.2 g.) and 16 g. of sodium hydroxide were dissolved in a mixture of 200 C.C. of water and 200 C.C. of alcohol, 16 g. of methyl iodide were added and the mixture was left for 12 hours. Concentrated hydrochloric acid (500 c.c.) and a little potas-sium iodide were added and the solution waa saturated with sulphur dioxide. The dark-coloured oil which separated was dried over sodium sulphate and distilled under diminished pressure when 25 g.(70% yield) of p-bromophenylmethyliodoarsine were obtained b. p. 178-180"/23 mm. The iodoamine became solid on cooling and formed pale yellow needles m. p. 36.5" (Found I 34.1. C7H7BrIAs requires I 3400%). Calc. Br 34.3%). CI3H1$rAE requires As 23.2%) BENNETT AND HOCK ~'-DIHLOBODIPBOPYL SULPEIDE 2671 A Grignard reagent was prepared from 12 g. of bromobenzene, 24 g. of magneaium and 250 C.C. of ether and a solution of 24 g. of the iodoaraine was slowly added a vigorow reaction occurring. The mixture WM heated under reflux for 0-5 hour and decomposed in the usual manner. The ethereal extract waa shaken with alkali before being dried over d m sulphate. p-Bromodiphenylmethyl-arsine (12 g. 60% yield) was finFluv obtained having properties similar to those of the product of the Friedel-crafts reaction. Identity of the two products wa8 established through the methiodides which did not depress each other's m.p. During the c o r n of this work the following compounds were prepared incidentally : p-ChbrophenyldiWmrsine a colourless highly refractive liquid, b. p. 277" or at 160'123 mm. [Found Cl (attached to arsenic), 27.5. C,H,C]BS requires Cl 27.6%]. p-Chophenybramk oxide, which crysfallisea from benzene in white needles m. p. 198" (Found : chlorour&ne a pale yellow solid m. p. 51" (Found Cl 31.8. C&,C$Bs quires Cl 3200%). h 36.4. C~H~OCIAs quires Bs 3700%). D i - p - ~ h h ~ h y l -Part of the expense of this investigaton was met by a grant from the Chemicd Society Research Fund for which the authors express their thanks. EAST LONDON COLLEGE, UNIVERSITY OF LONDON. [Rece;ved Septmlbe~ 1 3 h 1925.

ISSN:0368-1645    

DOI:10.1039/CT9252702667

出版商:RSC    

年代:1925

数据来源: RSC

摘要:

BENNETT m HOCK ~‘-DIHLOBODIPBOPYL SULPEIDE 2671 CCCLXV .-+- Dichloro&iprop yl Sdphide. By GEORGE MACDONALD B~nnmrr and BLF~ED Loms HOCK. THE remarkable chemical reactivity of @@‘-dichlorodiethyl sulphide muat be attributed to the influenceof the sulphur atom upon the two chlorine atoms. A high degree of reactivity is in fact generally shown by the chlorine atom in compounds of the general fornula R-S*C€&CK&l and there is a correspondingly high reactivity in the hydroxyl group of the pazent compound R*S*W-CX&-OH (compare Bennett J. 1922,121,2140). The isomeric aa’-dichlom-diethyl sulphide (Bales and Nickelson J. 1922 121 2137; Mann and Pope J. 1923 123 1172) readily yields its chlorine when boiled in solution with alcoholic sodium hydroxide; the chlorine is therefore in a reactive condition.No data however are avail-able for a quantitative compazison of the propertiea of chlorine atoms sitmted in the a- and @-positions. ~ ‘ - W h o d i p r o p y Z dphide the first simple chlorosulphid 2672 BEKNETT AND ~ o o g ~ ' - D I ~ O B O D I P B O P Y L SULPIDE. having the chlorine a4nm.h the y-@tion has now been preprtred. It is decidedly less reactive than @p'-dichlorodiethyl sulphide and fip'-dichlorodipropyl sulphide (Coffey J. 1921 119 94; Pope and Smith M. 396). It waa prepared from ~'-d&ydroxydipopyi &phi& obtained by the acfion of sodium sulphide on +doropropyl alcohol but the replacement of the hydroxyl groups in the dihydroxy-sulphide by chlorine was as exceptionally difEcult as the analogous reaction is surprisingly easy with 9-hydroxy-sulphides.Whereas the latter operation is complefed in a few minutes by boiling con-centrated hydrochloric acid (Clarke J. 1912 101 1583; Coffey, loe. cit.) replacement of the hydroxyl groups of w'-dihydroxy-dipropyl sulphide did not occur when any of the usual reagente such as hydrochloric acid phosphorus tri- or penta-chloride or phosphorus tri-iodide were employed and hydrogen chloride at 150" reacted only slowly to give a poor yield of chloro-compound. The hydroxyl groups in this sulphide are therefore less reactive than is usual in a primq alcohol. The use of thionyl chloride alone gave no better result but the dichlorodipropyl sulphide waa obtained wily in good yield when this reagent waa used in presence of dimethyladine (Damens Compt.rend. 1911 152 1314). The ditlerence in charmter of the p- and the y-chlorine atoms ia well shown by the action of potassium cyanide in alcoholic solu-tion upon pp'-dichlorodiethyl and yy'-dichlorodipropyl sulphidea . Whereas Davies has shown that the former is converted into an unexpected substance of the formula C6H1,S,(CN) (J. 1920 117, 298) we find that the latter is smoothly converted into the dinitrile of thiodibutyric acid (Gabriel Ber. 1890 23 2493). A study of the oxidation of yy'-dichlorodipropyl dphide showed that the sulphur atom in the molecule hrts unusual properties. Although the action of sodium hypobromite nitric acid or hydrogen peroxide upon the sulphide at laboratory temperature might be expected to furnish a sulphoxide these reagents produced the same compound which resulted from oxidation with chromic anhydride in boiling glacial acetic acid namely the mJ$one, of m.p. 66". It thus appears to be a property of the sulphide to take up two atoms of oxygen per molecule instead of one. More-over neither a sulphilimine nor a mercurichloride could be obtained from it and ite dibromide which can be prepared only in the presence of a very large excess of bromine is even more unstable than the dibromide of pp'-dichlorodiethyl sulphide so that there seems to be a general reluctance to form derivatives involving quadri-valency of the sulphur atom. A comparison o€ the rates of reaction of pp'-dichlorodiethyl and SO2(CH2-CH,CH2C1), BENXEFC AND HOCK ~Y'-DI~ORODIFBOPYL SULFHIDE.2673 yy'-dichlorodipmpyl adphinee with sodium hydroxide in ethyl alcohol ahowed that the course of the two reactions being assumed fo be s.im.&w the former r w t a sixty the8 &8 fa& as the latter. We hope fo make a sysfematic comparison of these and other chloro-sulphidea when a synthesis of a 8-cblom-mlphide has been com-pleted. E X P E R I Y E N TAL. Adion of So&iu7n Sdphiri&e 012 y-Chhmpqy1 AhM.-A solution of sodium sdphide (95 g. Na$,SI&O) in an equal weight of w a k waa added cautiously in three portions to y-chloropropyl alcohol (60 g.) the mixture heafed under reflux for 3 hours and then dis-tilled with steam until the distillate no longer gave a whih precipi-tate with mercuric chloride. The distillate was boiled with an excea of yellow mercuric oxide filtered concentrated and cooled; B small quantity of the mercupt& of y-hydmxypopyl mermptan, Hg(S°C3H6*OH), then separated out.It crystabed from wbutyl alcohol in silvery plates m. p. 132-134" (Found Hg 52.9. CBE,,0,SJ3g requires Hg 52.5 %). The solution remaining in the distillation fiask was made acid with hydrochloric acid and concentrated on the steam-bath. The bulk of the sodium chloride wa8 removed by filtration after dilution with acetone the solution dried and the acetone evaporated. The residual viscous oil was heated in a current of dry air at 100" under diminished pressure and finally poured off from a little sodium chloride which it deposited from solution. w a Viscous oil which could not be distilled or induced to crystallise, and wa8 not analysed.With phenylwbimide it reacted at once to give the bisphenylurethune S(C,H,*O*CO*NHPh), colourlem needles from benzene m. p. 146-148" (Found C 62-1 ; H 6.5. C&04NS requires C 6143 ; H 6.2%). Action of Thionyl Chloride P h m p h Halida and Hydrogen Cliloride upon yy'-Dihydroxydiprol>yl Sdph&.-The dihydroxy-sdphide waa not appreciably affected by heating for 2 hours with boiling concentrated hydrochloric acid. The action of thionyl chloride phosphorus tri- or penta-chloride or phosphorus tri-iodide led to the production of non-volatile substances which were pre-sumably esters of the correspon- hydroxy-acids. For example, after the dihydroxy-compound had reacted in presence of dry benzene with phosphorus tri-iodide (213 mol.) the material recovered aad when kept in a desiccator it slowly hardened to a resinous ma88 without crystallising an odour of mustard being simulfaneously developed.~ ' - D i h y d r o x y d i p r ~ y l dphide S(C,H,*OH), ww thus obtained from the solution could not be distilIed under dimirriRh ed P=-, VOL. CXXVII. 4 2674 BENNETT AHD HOCK yy'-DIOHLOEODIPROPYL SUISHIDE. The replacement of the hydroxyl group was h t achieved as follows the dihydroxypropyl sulphide wm heated a t 150-160" while a stream of dry hydrogen chloride was p d inb it for 2-6 hours. The product was distilled; a small quantity of an oil, b. p. 135-150"/25 mm. waa obtained which consisted of prsctically pure dichlorodipropyl sulphide (yield 17 yo). yy'-DiehZorodipropyZ SzclpiCide.-Thionyl chloride (80 g .) was added drop by drop to a well-cooled mixture of y~'-dihydroxy-dipropyl sulphide (45 g.) and dimethylaniline (80 g.) kept below 60".The mixture was then heated a t 100" for + hour poured into an excess of dilute hydrochloric acid the oil extracted with chloro-form and the extract washed with water dried and distilled. yy'-Dkhlurodipropyl sulphide S(C,H,Cl), was thus obtained as a faintly yellow oil of pronounced dour b. p. 162"/43 mm. (yield 83%) (Found C 38.9; H 6-5; C1 38.2; S 16.7. C,H1,C@ requires C 38.5; H 6.3; C1 37-9; S 17.15%). The following constanfs were determined OF (vac.) = 1.175 n i = 1.5075, whence mL] = 47.42 (calc. 47-25). The liquid did not crystal-lise when cooled to the temperature of liquid air and allowed to revert slowly to normal temperature.Compound with Platinic Chloride.-Thia was obtained in greenish-yellow plates m. p. 83-5-85" by adding platinic chloride (0.86 g.) in acetone to the chloro-sulphide (0.46 g.) also dissolved in acetone (5 c.c.) the product crystallking in the course of a few hours. It had the composition 2S(C,H6C1),,PtC1 (Found : Pt 27-7. An unstable dibromkk s(C3H6c1),Br2 was obtained from the chloro-sulphide (0.94 g.) with bromine (4 g.) in carbon tetrachloride (5 c.c.). The crystals were quickly filtered off washed with a little of the pure solvent dried on porous tile and analysed at once since the substance decomposed completely when kept over-night (Found : Br 57.7. C,Hl,Cl,Br2S requires Br 5943%). Repeated attempts to prepare a sulphilimine led only to the isolation of toluene-p-sulphonamide m.p. 137" (Found C 48.8; H 5.3. Calc. C 49-1; H 5.3%). Action of Methyl lodide.-When the chloro-sulphide was mixed with methyl iodide (5 mols.) crystals appeared in the liquid within hour of m. p. 179-181" but a sufEcient quantity for analysis could not be collected. I f left in the liquid the crystals soon redissolved and a viscous oil separated. This oil was almost entirely aoluble in water but the solution deposited an oil again on evapor-ation m d hociation of the sulphonium compound evidently took place with liberation of the original sulphide. The residue obtained by evaporating the excess of methyl iodide from the original mixture C1,H,Cl,SPt requires Pt 27.4%) BEKN-S~T ~ K D HOCK ~~'-DICHLOBODYPBOPYL SUISHIDE.2675 could not be induced to mlidify but it readily combined with mercuric iodide to produce a mlid which c e from acetone chloroform in yellow needlea (the chlom-sulphide ifself is quite indif€erent to mercuric iodide). After three recrgsfallisations the substance had m. p. 84-88' and analysis showed it to be di-c ~ o d i ' p ~ Z m e t l b y ~ h o n ~ ~ m mermri-iodide (C,H,Cl)@MeI,HgI, (Pound Hg 27-1 ; C,H15C&SHg qnireS Hg 25.65; AgCl + AgI 126.5%). This compound was evidently not quite pure but further purification was not possible since &-sociation of the substance occurred in solution an odour of the original chloro-sulphide being always developed during recrystsl-hation. Addon of Ozidbing Agenta.-The chloro-sulphide wm shaken with an ice-cold solution of sodium hypobromife (1.8 mols.) the mixture heated at 50" for 5 minutes and hally cooled in ice ; the oil obtained solidified fo a mass of crystals which were recryatallised from benzenelight petroleum.This substance was yy'-die7ilmdipmZ-d p h (C&H,Cl),SO, m. p. 65-66" (Found C 32-7; H 5-6; Cl 32.4. C,H,,O,CL# requires C 32.9; H 5.5; C1 3204%). It is appreciably soluble in water and readily soluble in most organic solvents with the exception of light petroleum. In view of the unexpected nature of this product the analyses were repeated-with similar results. The substance was also produced when the chlom-sulphide was (i) dropped into a mixture of fuming (2 vols.) and con-centrated (1 vol.) nitric acid cooled in a freezing mixture; (ii) dissolved (0-94 g.) in glacial acetic acid (2 c.c.) mixed with hydrogen peroxide (0.7 g.in 2 C.C. of 60% acetic acid) slowly with cooling and kept at laboratory temperature for 48 hours; and (iii) heated for 2 hours in boiling glacial acetic acid with chromic anhydride (twice the calculated amount to produce a sulphone). yy'-DiphmwxydipropyZ Sdphid-e (PhO*GH,),S.-The chloro-sulphide (1.2 g.) was heated at 180" for 2 hours with phenol (6 g.) and sodium ethoxide (from 0-3 g. of sodium). The mixture was m d e acid and distilled with s h m . The residual oil solidified when washed with a little aqueous alkali and was then recrysta,llised from methyl alcohol; m. p. 45" (Found C 71-35; H 7-4. Cl,E,0&3 reqnires C 71-35; H 7.3%).yy'-Di-p-tolybxydiprqyl sulphide prepared in a similar way from jp-craol had m. p. 5(&52" (Found C 72-9; H 7.9. C A 6 0 # requires C 72.7 ; H 799%). Action of Piperidine on the Chloro-sulphide.-When a midm of the chloro-sulphide with piperidine (8 mols.) was kept for 24 hours, cryatah of piperidhe hydrochloride separated out. The mixture waa made alkaline and distilled with &am. The residual oil 4u2 AgCl + AgI 123.7 2676 BENKETC AND HOOK ~~'-DICXELORODIPZ~OPYL SULPE~E. waa removed in ether the extract dried and evaporated when yy'd@p&didiprqqZ mdph& (C6H1,,N-CsIj[6)&3 waa left as an oil which did not crystalhe. It readily yielded a picrate which crystabed from methyl alcohol in yellow needles m. p- 199-200' (Found C 45-3 ; H 5-8.c28~8014N8s requires c 45.3 ; H 5.2%). Action of Potassium Cyankde.-The chloro-sulphide (1.87 g.) ww heated in boiling ethyl alcohol for 9 hours with potasaium cyanide (2 g. = 3 mols.). The alcohol was evaporabd water added the precipitated oil removed in ether and the ether evaporated. The crude dinitrile thus obtained wa,s at once hydrolysed by boiling with concentrated hydrochloric acid (15 c.c.) for 2 hours. The cold diluted solution was extracted several times with ether and the extract on evaporation left a solid (0.8 g.) which waa crystabed once from a little water and once from benzene-light petroleum. Thirr substance was thiodibutyric acid of m. p. 99-101" (Gabriel, loc. cit. and Davies J. 1920,117,297) (Found by titration equiv., Adion of Potiz.!?aium SuZphide.-The chloro-sulphide (4.0 g.) was heated for 3 hours with a boiling ethyl-alcoholic solution of freshly prepaxed pobsium sulphide (from 4.8 g.of potassium hydroxide); the mixture was then distilled with steam. The residual oil which solidified on cooling crystallised from carbon disulphiddight petroleum as a white powder melting indefinitely between 50" and 70". Repeated crystallisation failed to separate any substance of sharp melting point. This material although evidently not a pure chemical individual had approximately the composition of a polymeride of IkxumdhyZene disulphide (Found: C 48-0; H 8.4; M cryoscopic in camphor 1400 1740. C,H,,S, requires C 48-65 ; H 8-1 % ; M 148). It closely resembles the " polymeric " diethylene disulphide which reaults from the action of alkali sulphides upon ethylene dibromide or dichlorodiethyl sulphide and both axe probably mixtures of substances having a long open-chain structure (compare Bennett and Whincop J., 1921 119 1861; Staudinger Hdu.Chim. Acta 1925 8 67). C m p a ~ m with pp'-Dichlorodiethyl Sulphide with rmpect to Speed of Reaction with Ahholic Sodium Hydroxide.-A solution of dichloro-diethyl sulphide in ethyl alcohol (10 C.C. ; 0-23 mol. per litre) was added to boiling alcoholic sodium hydroxide (25 C.C. ; 06115N) and the mixture boiled under reflux. It was found by titration that after 5 minutes the reaction had completed itself to the extent of 71.5%. An approximately equivalent solution of yy'-dichloro-dipropy1 sulphide (10 C.C. ; 0.25 mol. per litre) ww mixed with the m e volume of the same solution and boiled for 5 hours ; the reaction had then completed itself fo the extent of 71.7%. 105. WC. 103.1) We wish to express our thanks to the West Riding County Council for a echolamhip which has enabled one of us (A. L. H.) to take part in this inveatigation and to the Chemical Society for a grant which has defrayed much of the expense involved. T€i3Z UNIVERSITY SEKEFFIELD. [Received September lst 1925.

ISSN:0368-1645    

DOI:10.1039/CT9252702671

出版商:RSC    

年代:1925

数据来源: RSC

摘要:

CCCLXVI.-Reseurches on Sulphuryl Chloride. Part I K Further Studies on a New Chlorinating Agent. Preparation of Polychkwo-derivatives of Toluene. By Oswm SILBXRRAD. h previous communications (J. 1921 119 2029; 1922 121, 1015) it was shown that anhydrous aluminium chloride and sulphuryl chloride interact to form aluminium chlorosulphoxide AlCl&SO,; and that in the presence of sulphur duminium sulphur chloride, AlClJ3Cl*SaAlc1, is produced further that tow& sulphuryl chloride both these compounds act as potent catalysts the latter being quite the most convenient chlorinating agent at our disposal, and also one of the most powerful. It is with the object of extending our knowledge of this reagent hitherto restricted to its action on benzene (Zoc. cit.), that the present research on the chlorination of toluene waa underhiken.The only earlier work that has any bearing on this mbject is that of Witte (Phrrn. Rec. New York Dec. 16 1889) Tohl and Eberhard (Ber. 1893 26 2943) and -ken (Rec. tmo. dim., 1911 30 381). These experimenters all investigated the action of sulphuryl chloride on toluene in the presence of aluminium chloride under conditions conducive to the Friedel-Crafts reaction and obtained mixtures composed of o- and p-toluendphonyl chlorides aa the chief ingredients together with lesser amounh of o- and p-chlorotoluenes ditolylsulphone (T. & E.) and o- and p-folnens-sulphonic acids (B.). If however sulphuryl chloride containing about 1% of sulphur chloride be run into a mixture of toluene and anhydrous aluminium chloride previously heated at about 7Q0 aluminium sulphur chloride b instantamously formed and chlorination takes place aa rapidly a,s the mixture is added an h o s t theoretical yield of mono- di-, tri- or penta-chlorotoluene being produced with equal eatm and rapidity by simply adjusting the relative proportiom of hydro-carbon and reagent.progressive chlorination proceeds in accord 2678 SILBEBRAD RESEARCHES ON SULPHURYL CHLOBLDE. PBBT rv. ance with the following scheme indeed the isomeridea therein depicted a m produced almost to the exclusion of aU others : Me Me Me Me f Me f /\ / '4 f / Me The nature and proportions of the various isomerides produced M e r sufEciently from those hitherto obtained by direct chlorination to render it necessary to refer briefly to each stage of the chlorination.Mom&motoZuenes.-The ratio of the para-compound to the ortho in the product is slightly higher than that in the case of chlorination in presence of an aluminium-mercury couple (Cohen and Dakin J. 1891 79 1119) but lower than that obtained by the electrolysis of a mixture of toluene and hydrochloric acid (Cohen, Dawson and Crossland J. 1905 87 1035). DiclrlototoZuene.-Here the 2 4-isomeride is produced almost in a state of chemical purity. This is surprising for the only chloro-toluene higher than the mono-derivative hitherto produced by the action of sulphuryl chloride on toluene is the 3 4-isomeride which Tohl and Eberhardt obtained in small quantity by heating a mixture of theae substances in a sealed tube at 160" (Ber.1893 26 2942). All other meam of preparing dichlorotoluene by direct chlorination of the hydrocarbon give rise to complex mixtures of the following isomerides-3 4- (Beilstein and Kuhlberg AnnuZen 1868 146, 319) 2 6- (Aronheh and Dietrich Ber. 1875 8 1402) 2 4- and 2 3 - (Seelig AnnuZen 1887 237 157) 2:5- (Wynne P. 1901, 17 116); compare also &hen and Dakin (J. 1901,?9,1119) who, by working with 0- and p-chlorotoluene separately showed that the product obtained by chlorinating toluene in the presence of an aluminium-mercury couple contained all these isomerides with the possible exception of 2 5-dichlorotoluene. TricialorotoZuenes.-AA waa to be expected from the nature of the &chlorination product the addition of the required quantity of the new reagent to toluene leads to the formation of practicaIly nothing but the 2 4 5- and 2 3 4-trichloro-derivatives indeed they are so free from other isomerides that these two compounds can be easily separated and in this respect the product compares very favourably with that obtained by any of the known processe FURTHER STITDIES ON A NEW CHLOWATING AGENT ETG.2679 of chlorinating toluene which lead to mixtures of 2 3 4- 2 4 6-, 2 3 6- and 2 4 5-trichlorotoluenes (Iimpricht Annden 1866, 139,303; Beihtein and Kuhlberg Aronheirn and Dietrich Seelig, loc. dt. &hen and Dakin J. 1902 81 1324). Tetra;c7alorotoluenes.-In this instance some doubt appears to exist as to precisely what isomeridea are formed by direct chlorination.Limpricht (h. cit. p. 327) obtained a tetrachlorotoluene melting at 96" (the 2 3 4 5-isomeride melh at 98.1"). On the other hand working with antimony pentachloride Beilstein and Kuhlberg (AnnuZen 1869,150 287) isolated a compound the m. p. of which (91-92") agreed more closely with that of the 2 3 4 6-isomeride (91.5-92"). Again &hen and DIlkin (J. 1904 85 1283) who subsequently investigated this subject by further chlorinating the trichloro-compounds in presence of an aluminium-mercury couple, obtained from the 2 3 4-isomeride a product melting at 89-91" and giving a nitro-derivative m. p. 149" which they concluded to be 2 3 4 6-tetra,chlorotoluene (m. p. 91*5-92"; nitro-derivative, m. p. 153"); and from 2 4 5-trichlorotoluene a product melting at 86-88" which they took fo be the 2 3 4 5-derivative.The same experimenters however subsequently showed that this particulax isomeride melts at 97-98" (J. 1906 89 1453) so there still remains some doubt as to its formation. The resdts obtained with the new chlorinating agent appeaz to c o b this and Lim-pricht's observation that the isomeride (the 2 3 4 5-) ia the principal one obtained by introducing four chlorine atoms info toluene. The method cannot however be recommended for the preparcation of any of the tetrachlorotoluenea for not only are the isomerides formed in such proportions that there is considerable difficulty in separating them but also the trichlorotoluenes ahow a great tendency to pass directly fo the pentachloro-derivative under the influence of the reagent behaving in this respect in a manner analogous to that observed in the preparation of penh-chlorobenzene (Silberrad J.1922 121 1020). In this connexion it is to be observed that both these compounds are penta-subetituted derivatives of benzene. PeniWdorotoZuen.-Unl.jke other powerful chlorinating agenb, which lead to products contaminated with hexachlombenzene (Beilstein and Kuhlberg An& 1869 150 898; Fichter and Glantzstein Ber. 1916 49 2473) the new reagent does not attack the side chain at all ; this is neither substituted nor split off. Penta-chlomtoluene which is formed with the utmost ease is the end-product of the reaction; the yield is nearly theoretical and the product practicdy pure 2680 SILBEBXAD RESEARCHES OK s m m n CEILORXDE.PBT rv. E X P E B I M E N T A L. The preparation of the reagent and the general procedure adopted were similar to those previously described (J. 1922 121 1018). The apparatus consisted of a suitable-sized flask fitted with and ground to a 6-bulb reflux condenser,* the upper portion of which waa connected through a trap to a flask containing 10 litres of water to absorb the sulphur dioxide and hydrogen chloride which are copiously evolved during the reaction. The required quantity of the reagent (Le. sulphuryl chloride containing 1% of sulphur chloride) was run into toluene mixed with anhydrous aluminium chloride the apparatus being immersed in a water-bath previously heated to about 70". Chlorination took place at the rate at which the reagent was run in.The actual time occupied waa approxim-ately 9 hour per chlorine atom introduced; thus trichlorotoluene waa obtained after 14 hours and the pentachloro-derivative after 24 hours. This period may be much shortened if desired. 2 and 4-chloroto~uenes.-~ adding the chlorinating agent (280 g. = 23% excess) to a mixture of toluene (184 g.) and anhydrous aluminium chloride (10 g.) under the conditions described above a vigorous reaction took place at once; the product waa at &t brilliant purple but rapidly became ruddy-brown. After washing with hot water 247 g. of an oil were obtained which distilled almosf wholly between 153-165"/758 mm. yielding 222 g. in one instance and 227 g. in another (88% of the theoretical). The nature and proportions of the isomerides present were determined by oxidiaing 50 g.of the product with permanganate; 21 g. of p- (m. p. 236") and 16 g. of o-chlorobenzoic acid (m. p. 137") were obtained; no meta-acid could be defected. 2 4-DichZorotoZuene.-The chlorinating agent (560 g.) wa8 run into a mixture of toluene (184 g.) and anhydrous aluminium chloride (10 g.) as above described and the reaction completed by heating at 100" for a few minutes the total time occupied being 1 hour. The deep brown reaction product yielded 240 g. of a heavy oil when boiled with water and 220 g. of almost puie 2 4-diChlOrO-toluene on subsequent fractionation. Preparation of 2 4-dkhloro-3 5-dinitrotohene. In order to identify it the above oil (100 9.) waa run into a mixture of nitric acid (200 C.C.; d 1-48) and sulphuric acid (400 C.C. ; d 1-84) at 60" ; the reaction mixture waa then heated at 105" for 4 hour. On pouring the product into'water an oil separated which on cooling, set to a paIe yellow crystalline mass this filtered off from the * A very convenient form of apparatus for the purpose is obtainable from Xessrs. Townson and Mercer Ltd. 34 Camomile St. E.C FURTHER STUDIES ON A NEW CHLOILINATINQ AGENT ETC. 2681 adherent oil washed with cold alcohol and r e c r y A W from the same solvent yielded 94 g. of pure 2 PdiChlOrO-3 5-dinitrotolnene, m. p. 104.3" (con.) (Cohen and Dakin give 104" and See@ 103") (Pound Cl 28.3%). The oily residue from which the above product had separated waa boiled (20 g.) with nitric acid (200 c.c.; d 142) and mercuric nitrate (2 9.) for 120 hours.On coolmg 11 g. of 2 4-dichloro-3 5-dinitrobenzoic acid (m. p. 210-211". Found C1 25.22%) crystcLuised; no other isomeride could be detected. It must therefore be concluded that on chlorinating toluene it8 above described the product consists of almost pure 2 4-diChlOrO-toluene. 2 4 5- and 2 3 4-Tr&chlorotoluenes.-Into a mixture of toluene (184 g.) and anhydrous aluminium chloride (10 g.) at TO" the chlorinating agent (840 g.) was run during 14 hours. On boiling the dark vandyke-brown reaction mass with water and fraction-ating the oily product (324 g.) passed over between 215" and 245" ; this slowly set to a crystalline mass consisting of almost equal parta of 2 4 5- and 2 3 4-trichlorotoluenes (yield 83%).I s o & h and denti+i;tion of 2 4 5-trichlorotoluene. The crystal-line maas waa freed from oil washed with cold alcohol and recrystal-lised from the same solvent whereby 151 g. of pure 2 4 5-frichloro-toluene separated as glistening needles or leaflets m. p. 82-4" (corr.) (Found Cl 54.3%). From this 2 4 5-trichloro-3 6-dinitrotoluene m. p. 227" was- prepared. The residual oil and mother-liquors from which the 2 4 5-isomeride had been sepassted yielded on fractionation 158 g. of an oil b. p. 225-239", together with 17 g. of a lower fraction which consisted chiefly of dichlorotoluene. On standing the main fraction set to a wax-like mass; this was macerated with 300 C.C. of cold alcohol. The residue 7-2 g. consisted chiefly of the 2 4 5-isomeride and melfed after several recrystallisations at 81-82".Water was added to the alcoholic extract until a permanent opalescence appeared just sdicient alcohol added to redissolve this at 20" and the solution kept at 0" for several days ; the wax-like crystalline solid which waa obtained (74 g.) on recrystallisation from alcohol melted at 41" and proved to be 2 3 4-trichlorotoluene (Found Cl 54.4%). The yield of the pure substance was 56 g. Preprattion of 2 3 4-trichloro-5 6-dinitrotoZuene. On adding water to the mother-liquors from which 2 3 4-trichlorotoluene had crystallised an oil (70 g.) was precipitated which on nitration as described in the preparation of 2 4-dichloro-3 5-dinitrotolueneY Preprdion of 2 4-dkhbro-3 5-dinitrobenzoic acid.Isdation and identiwwn of 2 3 4-trichlorotoluene. 4 0 2682 SILBERL4D RESEARCHES OX SULPHURYL CHLORIDE. PART IV. yielded 64 g. of 2 3 4-trichloro-5 6-dinitrotoluene m. p. 141" (Found C1 44.2%). No derivatives of other isomerides could be isolated. The above results therefore correspond to a yield of 400/6 of 2 4 5-trichlorotoluene and 34% of the 2 3 4-isomeride. 2 3 4 5-Tetrachlorofduene.-The direct preparation of this compound from toluene is not to be recommended because on freating toluene (184 g.) with sufficient of the chlorinating agent (1120 g.) to produce the tetrachloro-derivative as above described, besides trichlorotoluene (104 g.) and pentachlorotoluene (130 g.), a mixture of isomeric tetrachlorotoluenes (87 g.) is obtained the separation of which presents the greatest difliculty.The trichloro-toluene so produced consists chiefly of the 2 3 4-isomerideY from which it would appear that when a mixture of 2 3:4- and 2 4 5-trichTorotoluenes is subjected to the action of the new chlorinating agent the 2 4 5-isomeride is converfed into the pentachloro-derivative before the 2 3 4-compound is attacked fo any appreciable extent. An experiment with a mixture of these isomerides conlinned this conjecture whilst a further experiment with pure 2 3 4-trichlorotoluene led to a result similar to that above described where toluene was the initial material. Pure 2 4 5-trichlorotoluene was therefore used for the preparation of the tetrachloro-derivative to this end this compound (98 g.) was mixed with anhydrous aluminium chloride (5 g.) the swrounding water-bath raised to incipient ebullition until the trichloro-compound had completely melted and the chlorinating agent (70 g.) was then run in.On cooling the product set to a dark brown scaly mass. This was boiled with 100 C.C. of toluene and 50 C.C. of water the toluene solution separated and mixed with an equal volume of alcohol; the bulk of the pentachlorotoluene present (12 g.) slowly crystallised in long glistening needles. The mother-liquor which contained the whole of the tetrachloro-toluene was freed from solvent and fractionally distilled. The first fraction b. p. 230" &- 15" (11 g.) consisted chiefly of unaltered 2 4 5-trichlorotoluene. The second fraction b.p. 273" & 15" (49 g.) was again treated as above described for the removal of pentachlorotoluene and a further 2 g. were thus removed; the mixed solvent was then distilled off and the residue ground up with 25 C.C. of cold absolute alcohol; this treatment repeated twice the alcoholic extract being filtered off each time yielded 4 g . of 2 4 5-trichlorotoluene. The solid residue (40 g.) consist'ed chiefly of 2 3 4 5-tetrachloro-toluene and after eleven recrystallisations from a series of solvents (light petroleum-benzene ; alcohol ; and dilute alcohol) was obtained in long flexible silky needles closely resembling asbesto FURTHER STUDIES ON A NEW ~ H L O ~ A T I N G AGENT E"C. 2683 in appearance melting a t 98.1" (corr.) and giving 2 3 4 5-tetra-chloro-6-nitrotoluene m.p. 159.6" (corr,) on n i b t i o n under con-ditions War to those described above in the prepamtion of 2 bdichloro-3 5-dinihtohene. ICientiJication of 2 3 4 6-tetraChlorotuluene and prepration of 2 3 4 6-tetPachloro-5-nitrM. "he compounds present in the mother-liquors from which the 2 3 4 5-isomeride had separated were bulked freed from solvent redissolved in alcohol and roughly separated into three fractions by precipitation. Each fraction was nitrated as described above and the nitro-products were fractionally cryefallised from alcohol of va,rying degrees of dilution. Worked up in this manner the &st and second fractions only yielded product8 having constant melting points; that from the former melted at 159" and was evidently 2 3 4 5-tetrachloro-6-nitro-toluene and that from the latter melted at 154" and a p p e d to be 2 4 5 6-tetrachloro-3-nitrotoluene (Found Cl 51-1.C,H,O$CI requires Cl 51.6%). It s e e m probable therefore, that the compound m. p. 153" obtained by &hen and Dakin as the final product of nitrating 2 3 4 6-tetrachlorotoluene (J., 1904,85,1231) was the true nitro-derivative and that the substance melting at 131-134" which they took to be 2 3 4 5-tetrachloro-3-nitrotoluene owed its low melting point to the pmnce of the unnitrated compound; indeed as these investigators point out, their analysis shows the presence of a considerable quantity (about 10%) of this impurity. The true melting point of 2 4 5 6-tetra-chloro-3-nitrotoluene therefore appears to be 154".Unfortunately, the quantity obtained by this most tedious process was too small to admit of a more complete identification. PentachZorotoZuene.-T~luene (184 g.) mixed with aluminium chloride (10 g.) was treated with the chlorinating agent (1632 g. = 20% excess) as above described the reaction being completed by heating in the boiling water-bath for Q hour. During the chlorination the reacting mixture became successively a brilliant purple liquid, a red-brown liquid a dark brown scaly mms an almost white, crystalline lump. On boiling the product with 3 litres of benzene and 100 C.C. of water separating the benzene solution and allowing it to cool the pentachloro-compound (380 9.) crystallised in almost colourless needles which on recrystallisation melted at 217.5" (uncorr.) (Found Cl 67.1%).Pentachlorotoluene is soluble in 3.4 vols. of toluene a t 87" and in 22 vols. a t 17". Action of the Chlom'nuting Agent on Pentachlorotoluene.-A mixture of pentachlorotoluene (100 g.) anhydrous aluminium chloride (10 g.) and the chlorinating agent (200 g.) WM heated on the water-bath for 8 hours. On recrystallking the product from benzene, 4 0 * 2684 ~ ~ I C B AND P~CRKIN REDUCTION PRODUCTS OF 88 g. of pentachlorotoluene m. p. 217" were recovered wWt the residue which wm almost insoluble in benzene after recrystallis-ation from chlorobenzene melted at 272-274' and appeared to be a condensation product possibly nonochlor ophenyltolylme thane , C,Cl,*C€&-C,C14-CH, produced by the condensation of penta-chlorotoluene (2 mols.) under the influence of anhydrous aluminium chloride (Found c1 64-4.C,,H,CI requires Cl 65.0%). Pentachlorobenzoic a;cid.-Owing to the great similarity existing between hexachlorobenzene and penhchlorotoluene and the very slight influence the addition of the former has on the melting point of the latter the purity of the pentachlorotoluene recovered as above described was further established by oxidising 20 g. with nitric acid (200 c.c.; d 142) and mercury (2 g.) by boiling the mixture until solution was complete (150 hours). On pouring the acid liquor into water a white crystalline precipitate separated; this redissolved completely in ammonia and proved to be practically pure pentachlorobenzoic acid m. p. 199.5" (Found C1 59.6. Calc. Cl 60.2%). The acid is very soluble in toluene or alcohol. It ha8 the extraordinary property of separating from the latter solution a8 an oil on dilution in spite of its high melting point. It is best crystallised from toluene-light petroleum from which it separates in large truncated prisms. My thatnlrs me due to Messrs. A. Boake Roberts and Co. Ltd., of Stmtford for supplying the aulphuryl chloride required for this investigation. ! k E SILSEBRAD &SEARCH LABORATOIWLES, BUCKWILST HILL ESSEX. [Received September lltA 1925.

ISSN:0368-1645    

DOI:10.1039/CT9252702677

出版商:RSC    

年代:1925

数据来源: RSC

摘要:

2684 - AND P~CRKIN REDUCTION PRODUCTS OF CCCLXVII.-Beduction Products of the Hydroxyunthru-quinones. Part VII. By W m BERTRAM MILLER and A R T H ~ ~ GEORGE PERKIN. A COBWAXISON of the formula of the hydroxyanthrones obtained during the reduction of 1-hydroxyanthraquinone and of 1 2-dihydroxganthraquinone (alizarin) is of interest because whereas the former (I) contains the hydroxyl adjacent to the carbonyl group, in the latter (11) the hydroxyls are in the 3 4-positions thereto TEE EYDBOXYAXl!ERAQUINONES. PART VII. 2685 As is well known the hydroyxl group adjacent to the carbonyl group in hydroxy-ketones difEers in properties from those present in other positions and to explain this it is assumed to be involved with the carbony1 to form an ortho-quinonoid or a six-membered, chelate grouping (Sidgwick and Callow J.1924,125 627) or that in any case some form of attraction exists between the two. If the reduction of the hydroxyanthraquinones follows the scheme applicable to anthraquinone ifself, it is reasonable to assume that owing to the attraction of the a-hydroxyl for carbonyl in the change from b to c these will take up adjacent positions as indeed occurs with the 1-bydrownthrone (I) derived from 1-hydroxyanthraquinone. For a similaz reason, it is to be expected that zw the a-hydroxyl is present in alizarrin a h , this on reduction will yield the 1 2-dihydroxyanthrone whereas as a matter of fact the 3 4dihydroxy-compound is produced @I). To account for this it seems likely that in this caae the attraction of the a-hydroxyl for the carbonyl is either non-existent or is auppmmed by the greater atfraction of the p-hydroxyl for the para-position thereto and thus in the change from (b) to (E) the 3 4-dihydroxy-compound mults.In mpprt of thie is the fact that 2-hydroxyanthraquinone when reduced givw 3-hydroxyanthrone (V) and therefore there is reason to presume that in these cases the p-hydroxyl is the determining factor or that in other &ds a para-quinonoid structure is preferred even when a- and @-hydroxyh are gimnlfaneously present. It waa inte&ing therefore to study the behaviour of alizarin 2-methyl ether * in these c k d n c e s , for owing to the etherification of the 2-hydroxyl group this compound more closely resembles in general propertiea 1-hydroqmnthquinone than alizarin itself and it was to be anticipated that I-hydroq-2-methoxyanthrone (IV) would result.With stannous chloride and hydrochloric acid as reducing agent this is the case although in According to Graebe and Th& (An& 1906 349 207) alizarin h - 1 ether d u d With dnat and giVea 3 I - d h & h O q -anthrone together with 8 second compound probably 1 2-dimsthoxy-8 n t b 2686 XILLER AND PERXIJY REDUCTION PRODUCTS OF addition to this compound which is the main product a small amount of 4-hydroxy-3-methoxyanthrone (deoxyalizarin mono-methyl ether ; III) is produced accompanied by much viscid matter. In order to determine the constitution of these compounds recourse was had to the bemanthrone reaction followed by a study of the behaviour of each product when methylated by means of methyl iodide and alkali.From the pale yellow anthrone (III) in this manner benzalizarin methyl ether (VI) was obtained and in proof of this an identical compound was prepared from benzalizarin itself (J. 1920 117 702). On the other hand the orabge-coloured anthrone (IV) gave, although in small amount a compound to which formula (VII) has been assigned demethylation having occurred during the reaction; it has not been ascertained however whether the hydroxyls occupy the 3 :4- or 5 6-positions. Whereas it waa previously shown (h. cit.) that both hydroxyls of benzalizarin are readily methylated with methyl iodide and alkali with the compound (VII) for which the name isobenzalizarin is suggested this is not the case as under drastic tratment with these reagents only a monomethyl ether is produced.Evidently therefore a hydroxyl is here present adjacent to the cwbonyl group and this view is supported by the fact that, whereas numoacetylisobendizurin is readily obtained the diacetyl compound can be prepared therefrom only by prolonged digestion with boiling acetic anhydride and pyridine. Be '. and isobenzalizarin differ widely in their dyeing properties with mordants for whereas the former gives shades analogous to those of alizarin itself (loc. cit.) the latter dyes yellow and is scarcely a strong colouring matter. This is of intemt, because it is generally assumed that the tinctorial properties of the hydroxyanthmquinone dyestuffs as e.g. alizarin are due at least in part to an ortho-quinonoid or some similar arrangement in which the l-hydroxy- and the adjacent carbonyl group are involved.In such a sense however benzalizarin must be regarded as a para-quinonoid and isobenzalizarin as an ortho-quinonoid dyestuff and this suggests that the dyeing properties of alizarin,* which resemble those of benzaliza;rin but differ markedly from those of isobenzalizarin , * -4 para-quinonoid structure was suggested by one of us for the mono-alkali salta of the hydroxyanthraquinones (J. 1899 75 433) THE HYDBOXYANTHRAQUIXONES. PART YII. 2687 may be due to the presence of a para-quinonoid rather than to an ortho-quinonoid grouping. If a survey be made of the phenolic mordant dyestuffi and more especially of those in which adjacent hydroxyl groups are present, it wiIl be observed that for most of them a para-quinonoid arrange-ment only is possible; of the very numerous instances which can be given hetin (VIII) and the dihydroxybenzylideneoumaranone (IX; Fridiinder and Rudt Ber.1896 29 878) both powerfnl dyestuffs may be cited. 0 OH 0 (VIII.) co (IX4 On the other hand whereas other colouring adjective class as for instance gallacetophenone (X) and the hydroxyanthraquinones may be considered to dye by virtne of either an ortho- or para-quinonoid grouping there is with the exception of such feeble dyes as euxanthone which do not contain adjaeent hydroxyls an almost complete lack of colouring matters to which an ortho-quinonoid grouping only can be applied. Experiments are in progress with t6e hope of obtaining in addition to isobendizarin dyes which come under the latter category.A preliminaq study of the behaviour of anthrapurpurin 2 7-di-methyl ether on reduction has at present resulted in the isolation in small yield of but one anthrone which is probably the 4-hydroxy-3 6-dimethoxy-compound. Much viscid matter is simultaneously produced. E x P E R I M E N T A L. Alizurk 2-Met4yZ Ether.-To a boiling solution of commercial alizarin paste (150 g.) in 10% sodium hydroxide solution (525 c.c.), methyl sulphate (110 c.c.) was gradually added and the mixture was repeatedly treated with sodium hydroxide solution (50 c.c.) and the equivalent quantity of methyl sulphate.* The product was collected stirred with sodium carbonate solution to remove alizarin the crude methyl ether (30 g.) dissolved in benzene and precipitated therefrom as potassium salt by alcoholic potassium hydroxide ; some alizarin dimethyl ether remained in solution.The potassium salt was decomposed with acid and the alizarin 2-methyl ether thus obtained was recrystallised from benzene until the melting point 229-230" was constant (Found C 70.8; H 4.05%). In addition to the alizarin dimethyl ether m. p. 214-215" a second In all, 875 C.C. of caustic sods solution and 195 C.C. of methyl dphate were employed. A modilkation of the method of Gmbe and mode (h. cif.) 2688 MILLER AND PERKIN REDUCTION PRODUCTS OF dimethyl ether of identical appearance but melting at 169-171" could be isolated from the final mother-liquor if the crude alizarin 2-methyl ether was crystalli~ed from benzene.Thig w&s evidently a methylalizarin dimethyl ether derived from 2-methylalizarin present in the dyestuff employed in that it could not be produced by the further methylation either of alizarin 2-methyl ether or of alizarin dimethyl ether with methyl sulphate and alkali. Reduction. A mixture of alizarin 2-methyl ether (10 g.) stannous chloride (100 g.) and 33% hydrochloric acid (500 c.c.) wa8 boiled for l$ hours. The crystah without apparent solution were con-verted into a brown tar which on cooling solidified to a hard, brittle mass some yellow crystals simultaneously separating from the acid liquid. The ground product was dissolved in about 100 C.C. of alcohol and the crystals which separated on cooling were collected (yield 6 g.).The dark-coloured mother-liquor on evaporation yielded an orange-brown resin from which nothing defbite could be isolated. The crystals when extracted with a little boiling benzene gave a pale yellow residue (A) in small amount whereas from the extract orange-red needles (B) separated on cooling. (A) crystallised from much benzene with the aid of animal charcoal gave pale yellow needles which were recrystallised from alcohol (Found C 75.1; H 5.1; CH, 6-1. Cl,H1,O requires C 75.0 ; H 5.0 ; CH, 6.25%). 4-Hydmxy-3-~h~xyanthrm, m. p. 202" yields an acetyl compound which crystallises in lemon-yellow needles m. p. 185-186" and is oxidised by chromic acid in acetic acid solution to acetylalizarin 2-methyl ether. (B) crystallised from alcohol in which it w a ~ less soluble than A, in orange-red needles m.p. 135-137" (Found C 74-9; H 5.0; CH, 6-2. c1&&03 requires C 75.0; H 5.0; CH, 6.25%). l-Hydr~~-2-methnthrmte is thus obtained in much larger amount than its isomeride. Like this on oxidation it yields alizarin 2-methyl ether. The diacetyE derivative crystallises from alcohol-acetic acid in yellow plates m. p. 202" (Found C 70.3; H 4-9; C2H402 36.7. C,,Hl,O5 requires C 70-4 ; H 4-9 ; C,H,02 37.0%). Benzalizarin Monomethyl Ether.-A mixture of 4-hydroxy-3-methoxyanthrone (4 g.) sdphuric acid (47 c.c.) water (23 c.c.), and glycerol (8 g.) was gradually heated a t 125-130" being well stirred and kept for 1 hour. The solution when cold was poured into water the green precipitate collected washed dried, and in the ground condition repeatedly treated with boiling alcohol.The extra,ct was concenfrated poured into much ether the solution filtered washed with water evaporated to dryness and the pale brown friable residue (1-4 g.) titurated with ether to remove resinous matter. By acet'ylation crystals were obtained which after re THP H Y D B O X Y A N ~ Q ~ O N ~ . PART VII. 2689 CFygtalliSation from alcohol-acetic acid gave 0.4 g. of pale yellow needles m. p. 205-207" (Found C 75-3; H 4-15; CH, 4.85. C&EZI4O4 requires C 75-4 ; H 4-4 ; CH& 4.7 yo). This compound which is uc&yZbt?nzuZizarin met789 ether when hydmlysed with hydrochloric acid in presence of acetic acid gave 86-13y0 of bendizamn lnonometiryl ether whereas theory requires 86.8%.The latter is thus obtained as long orange needles m. p. 247-249" sparingly soluble in caustic soda solution and in alcohol, soluble in sulphuric acid with a violet-red coloration (Found: C 78-0 ; H 4.55. Sulphuric acid in presence of acetic acid gives the oxonium sulphate as long hair-like maroon-coloured needles. The product from the Zeisel determination of the acetyl compound was poured into bisulphite solution. The crystals produced had all the properties of benzalizarin and yielded an acetyl compound, the melting point of which 202-204" was slightly bigher than that previously given (h. cit.). Benzalizarin monomethyl ether waa also obtained by the -1 methylation of benzalizrtrin itself. Acetylbemalizasin (0-95 g.) in boiling methyl alcohol (20 c.c.) and methyl iodide (8 c.c.) was gmduaIly treated with caustic potash (0.35 g.) in methyl alcohol.The crystalline substance produced (0.64 g.) m. p. 247-249O after recrystallisation wit8 identical with the benzalizarin methyl ether described above. A small amount of benzaljzarin dimethyl ether wm present in the original mother-liquor. isoBenzaEizarin.-A mixture of l-hydroxy-2-methoxyanfhrone (substance B) (4 g.) sulphuric acid (47 c.c.) water (2-5 c.c.) and gIycerol wm heated at 12O-130" for 1 hour. The solution was poured into water the precipitate collected dried and the colouring matter present isolated by means of the alcohol and ether treatment described under benzalizarin methyl ether. The orange-red powder thus obtained (1.4 g.) was washed with acetone to remove resin, and after recrystallisation from the same solvent gave 0.6 g.of orange-yellow needles. These by treatment with boiling acetic anhydride and pyridine for a few seconds gave a crystalline deposit of the acetyl compound which crystallised from much acetone in bright orange-yellow flat needles (0.3 g.) ; * m. p. 243-246" (Found : C 74.85; H 4.35. CI9Hl2O4 requires C 75.0; H 309%). This compound nwnamtylisobend izarin is very sparingly soluble in acetone or alcohol. It contains no methoxy-group and C,,H,O requires C 78-3 ; H 4.3%). Thie mudl yield of kobenzalizarin was evidently due to the I-hydroxy-8-methoxyanthne d e r i n g alteration on heating with dphuric acid. An amorphous product waa thus produced which was soluble in caustic soda with a reddish-brown tint and in cold acetone with a red colour 2690 REDUGTIOX PRODUCTS OF THE HYDROXYANTHBAQUINONES.when hydrolysed givea 86.6% of isobenzalizarin theory requiring 8602%. This crystallised from nitrobenzene in orange needles, m. p. 260-262" (Found C 77.8; H 3.9. Cl,Hlo03 requires C 77.9; H 308%). iSoBenzalizarin givea with sulphuric acid a green fluorescent, orange-red liquid and with boiling dilute alkalis orange-yellow solutions with which baqta water yields orange-red precipitates. By dige-sting the monoacetyl derivative with boiling alcoholic potassium acetate orange needles of a potassium salt are deposited. It is undtered by long boiling with hydriodic acid. isoBenzalizarin is somewhat resistant to fbll acetylation but by a long digestion with acetic anhydride and pyridine a diacetyl derivative is obtained which crystallises from acetic anhydride in yellow needles m.p. 214" (Found C 73.3 ; R 4.0. C21H1405 requires C 72-8 ; H 4.0%). isoBenzalizarin Monomethyl Ether.-A mixture of isobenzalizarin (0-3 g.) methyl alcohol (20 e.c.) and methyl iodide (8 c.c.) was boiled during 8 hours caustic potash (0.2 g.) * in methyl alcohol being gradually added. The crystals produced were washed with hot dilute hydrochloric acid to decompose a potassium salt present and crystallised from much alcohol giving deep yellow needles (0.186 g.), m. p. 196-198" (Found C 78.2 ; H 4-15 ; CH, 5.17. C1,Hl,O, Tbe mother-liquor contained a small amount of the same com-pound but the presence of a more highly methylated product could not be detected.By prolonged digestion with acetic anhydride and pyridine the trace of isobenzalizarin methyl ether available gave an acetyl compound which crystallised in yellow needles m. p. about 178-180". isoBenzalizarin dyes mordanted woollen cloth shades which are very distinct from those given by benzalizarin. boBe '* * . Brownish- Greenish- Pale Brown. Be- . Bmwnish- Dullreddish- Bright Brownish-reqnire~ C 78.3; H 4.3; CH, 5.4%). chromium. A l u m i n i n . Tin. Iron. yellow. yellow. yellow. m o o n . orange. orange. black. Anthraprpurin Dimethyl Ether.-Triacetylanthrapurpurin (5 g. ) was methylated as in the preparation of alizarin 2-methyl ether (wide mpa) 37 C.C. of methyl sulphate and 185 C.C. of caustic soda solution being used in all.After removal of the anthrapurpurin trimethyl ether present and crystallisation from benzene the dimethgl ether wat3 obtained in orange-red needles m. p. 234-235" * Approximately 2f timea the quantity required for the production of a dimethyl ether KARTUNG STUDIIS WITH THE MICBOBAL4XCE. PART II. 2691 (Found C 67.9 ; 33 4.2 ; CH, 10.4. H 4.2 ; CH 10.6%). C,,H,,O requires C 67.6 ; The &yZ compound forms yellow needles m. p. 2-205". A&hrvprimnthranul DiMhyl Ethr.-A miXtnre of a n t b -purpurin dimethyl ether (5 g.) sfannous chloride (50 g.) and 30% hydrochloric acid (250 c.c.) boiled for 14 hours yielded a black, granular mass which was collected washed with dilute hydrochloric acid and dried. The product dissolved in alcohol was poured into ether the precipitated amorphous impurity removed the cleas liquid evaporated and the sandy residue washed with acetone until colonrless. This on digestion with acetic anhydride and pyridine yielded diacetyhndhraprprinunthrad dimethyl ether which c v - from alcohol-acetic acid in colourlem needles m. p. 178' (Found C 69.6; H 5.0. C&E€lsOs requires C 67-8; H, 5-1 %). The authors are much indebted to the British AGzarine Go. Ltd. TEE UNIVXBSITP LEEDS. for the alizarin and anthrapurpurin u d in this investigation. [Receiue& Augclet 16th 1925.

ISSN:0368-1645    

DOI:10.1039/CT9252702684

出版商:RSC    

年代:1925

数据来源: RSC