摘要:

1032 JAPP AND ME1,DRUM: INTERACTION OF CI.--Inte?*action of Pilena~ztki.apuilzone, Acetophenone, and Ammonia. By FRANCIS It. JAPP, F.R.S., and ANDREW N. MELDRUM, B.Sc. JAPP AND STREATFEILD showed (Trans., 1888,41,270) that phenanthra- quinone, acetone, and ammonia interact according t o the equation CI4H,O, + C,H,O + NH, = CI7H,,NO, + H,O, and to the compound thus formed the constitution ?6H40 (?(oH>.cH~o co*cH, was assigned by C,H,* CNH Japp and Miller (Trans., 1885, 4'7, 18). The results of the present investigation, however, lead us to ascribe to it rather the constitution gous to that of diacetonnmine, (CH,),C(NH,)*CH,* CO*CH,. Thus me find that phenanthraquinone, acetophenone, and alcoholic ammonia interact according to the equation yielding di~?~nac?lldin772ino~~~?lc~Top?~~ant?~rene. It is evident that a constitution analogous to that ascribed by Japp and Miller to the acetone-ammonia derivative is inadmissible in the case of this com- pound.The acetophenone-ammonia derivative is hydrolysed by aqueous oxalic acid according to the equation yielding p?~enc~cyl?~?ldroz~~~henu?~t~~~~one (acetol,?&snone~?~ena?~t?~?~~uinone) which melts at 125-130'. By the interaction of phenanthraquinone, acetophenone, and aqueou4PHENANTHRAQUINONE, ACETOPHENONE, AND AMMONIA. 1033 C,H,* 7(NH2)* CH,* CO*C6H, b6H,* CO 9 ammonia, phenacyZan~inop~cnnt?&rone, analogous to the acetone-ammonia derivative, was obtained. The same substance is formed by the action OF ammonia on phenacyl- hydroxyphenanthrone. The ease with which these compounds break up into their generating substances rendered a detailed study of their reactions impossible.Other ketones, such as methyl ethyl ketone and diethyl ketone, ap- peared to act in a similar manner with phenanthraquinone and ammonia; but it was found impossible to obtain the resulting com- pounds in a condition suitable for analysis. EXPERIMENTAL. Action of AZcoholic Ammonia o?b a Mixture of Phenanthraquinone and Acetop?~enone.-20 grams of phenanthraquinone, 28 grams of acetophenone, and a large excess of alcoholic ammonia were heated in an open flask on the water-bath. I n proportion as the ammonia was expelled and the boiling point of the mixture rose, the greater part of the phenanthraquinone passed into solution. The filtered liquid deposited, on cooling, yellow, lustrous needles, which, by their appear- ance and melting point ( 158-159O), were recognised as phenanthra- quinonimide.Later on, a colourless substance began to separate. 'l'he liquid was therefore again filtered, and, on standing overnight, deposited a large quantity of this second substance in tufts of colour- less, silky needles, which, when heated in a capillary tube, decomposed about 150°, without showing a definite melting point. I n some pre- parations of this substance, the portions first deposited showed a pinkish tinge; but, by filtering at this stage, the colourless substance was obtained from the filtrate. As we found it impossible to recrystal- lise this substance without decomposing it, it was merely washed with cold alcohol, and dried for analysis i n a vacuum desiccator.It was perfectly homogeneous in appearance. Analysis gave figures agreeing with the formula of aminodilqd~ophenanthrene, (JNH,)*CH,* CO*C,H,. C,H,* C(NH,)*CH,* CO*C,H, 0.15'70 gave 04657 CO, and 0,0794 H,O. C = 80.90 ; 0.1454 ,; 0.4317 CO, ,, 0.0738 H20. C=80*98 ; H = 5.62. H = 5.64, 0.3049 0.2928 ,, 155 ,, ,, 13' ,, 754 mm. N= 6.20. C,,H,,N,02 requires C = 80.72 ; H = 5.83 ; N = 6.28 per cent. Hydrolycris of Dip?~enacyZdiamino~iAy~~~op~~na~~t?~rene.--In this ex- periment, the method employed by Japp and Miller (Zoc, cit., p. 17) in ,, 16.2 C.C. moist nitrogen at 11' and 740 mm. N=6*17. VOL. LXXV,. 3 21034 INTERACTION OF PHENANTHRAQUINONE AND AMMONIA. the hydrolysis of acetonylaminophenanthrone t o acetonephenanthra- quinone, was followed.The diphenacyldiaminodihydrophenanthrene was first moistened with alcohol-since otherwise it is not readily wetted by water-ground with water to a thin cream, and then poured into a large excess of a cold concentrated aqueous solution of oxalic acid, stirring well. Almost everything dissolved. The solution was quickly filtered through a large folded filter-an operation which must be rapidly performed, a6 the separation of the new compound begins almost immediately-and the filtrate, which speedily became yellow and turbid and smelt strongly of acetophenone, was allowed to stand over night. There was a large deposit of a pale yellow substance ; this was filtered off, thoroughly washed with water, dried in a vacuum desiccator, and purified by recrystallisation, first from ether, allowing the solvent to evaporate spontaneously, and afterwards from ethylic acetate, the latter giving the better result.It was thus obtained in fairly large thick prisms or six-sided plates which had a scarcely per- ceptible yellowish tinge, and are doubtless colourless when pure. It melted between 125O and 130°, turning dark yellow. Boiling the sub- stance with solvents must be avoided, as this treatment decomposes it, Analysis gave figures agreeing with the formula of phenacylhydroxy- phenccia t hone ( ccce t ophenonephenant hraquinone), ($H4*F(OH)*CH,* CO*C,H,, C,H,*CC) 0.1716 gave 0,5053 CO, and 0.0791 H,O. C=80.31 ; H=5.12. 0.1568 ,, 0,4622 CO, ,, 0.0717 H,O. C = 80.39 ; H=5*08. C2,H1,0, requires C = 80.49 ; H = 4-85 per cent.As acetonephenanthraquinone, when boiled with fuming hydriodic acid, yields diphenylenemethylfurfuran (Trans., 1890, 57, 663), we subjected the foregoing compound to the same treatment, in the hope of obtaining a diphenylenephenylfurfuran, but found that it broke up, before reduction, into acetophenone and phenanthraquinone, the latter then yielding phenanthrone and tetraphenylenefurfuran. By passing gaseous ammonia into an ethereal solution of phen- acylhydroxyphenanthrone, we obtained ~~~encccykal?ainop?~enant~~rone, 7GH4* ?(NH2)*CH,* C0*CGH5. This compound is,however, more readily C,H,* CO prepared by the method described in the next paragraph. Action of Aqueous Am.nzonicc on a Mixture of Phenanthraquinolee and Acetophenone.-20 grams of phenanthraquinone, 14 grams of acetophenone, and an excess of the strongest aqueous ammonia were introduced into a strong flask; this was tightly corked, and the mix- ture shaken vigorously, at intervals, during several hours.The organic substance solidified in the form of yellowish granules, whilst thePURFURAN DERIVATIVES FROM BENZOIN AND PHENOLS. 1035 aqueous portion was red. The solid substance was separated, ground with water, thoroughly washed, and dried over sulphuric acid. It was then digested with a small quantity of chloroform in the cold, to re- move unaltered phenanthraquinone, after which the residue was treated with sufficient cold chloroform to dissolve nearly the whole. On adding light petroleum to the filtered chloroform solution, a bulky, white precipitate was obtained ; this was filtered off and dried at the ordinary temperature, The substance, which was yellowish after drying, was dissolved in cold ether which had been previously satu- rated with ammonia (in order to check the tendency of the substance to decomposition), and the solution was allowed t o evaporate sponta- neously, In this way, the compound was obtained in small, colourless, six-sided plates, which melted with decomposition about 1 60°, turning green and evolving gas. The loss in purification by the above method is very great. Heating with solvents decomposes the substance completely. Analysis gave figures pointing to the formula of a phenacykumino- pl~nunthrme, cult to burn, and the value for carbon was lorn. *C(NH2)*cH2*Co*c6H5a The substance was dig. &r:* 60 0.1 175 gave 0.3449 C'O, and 0.0570 H20. 0.3090 ,, 11.7 C.C. moist nitrogen at 18" ancl 754 mm. N=4*33. C = SO*OS ; H = 5-39, C,,H17N0, requires C = 80.73 ; H = 5.20 ; N = 4.28 per cent. CHEMICAL DEPARTMENT, UNIVEESITY OF ABERDEEN.

ISSN:0368-1645    

DOI:10.1039/CT8997501032

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

PURFURAN DERIVATIVES FROM BENZOIN AND PHENOLS. 1035 CII.-Fu?$wan Der.iz?atives jaom Bemoin and Pheizols. By FRANCIS R. JAPP, F.R.S., and ANDREW N, MELDRUN, B.Sc. BY the action of cold, concentrated sulphuric acid on a mixture of benzoin and phenol, Japp and Wadsmorth (Trans, 1890, 58, 965) ob- tained paradesylphenolsulphonic acid, from which, by hydrolysing it with strong hydrochloric acid at 1 50°, paradesylphenol, (1 :4), CoH5*QH*Co ' H *OH C6€15*C0 was prepared. We now find that by heating a mixture of benzoin and phenol with rsulphuric acid of 73 per cent. strength,* the foregoing condensation occurs mithont sulphonation of the resulting compound, and an * Corresponding with the hydrate H,SOJ,2H,0. A sulphuric acid of this strength was first used for coildensations by Bistrzycki n u 1 Oclilert (Be?.., 1894, 27, 2632). 3 2 21036 JAPP AND MELDRUM: FURFURAN excellent yield of paradesylphenol is obtained. The various condensa- tions about to be described were effected by means of sulphuric acid of this strength. If the desyl group were to take up the ortho-position towards the hydroxpl of the phenol, it is evident that, by a further elimination of water, a furfuran derivative might be formed : With phenol and benzoin, no such reaction occurs : the pam-com- pound alone is formed. With thymol and benzoin, however, a mixture of desylthymol and cymodiphenylfurfursn is obtained. I n the case of resorcinol and of quinol, either one or two diphenylfurfuran groups may be introduced. With phloroglucinol, only the compound contain- ing three such groups was obtained.Up to a certain point these reactions resemble those studied by Hantzsch and his pupils (Bey., 1SS6, 19, 1290, 2987, and 2934), in which furfuran derivatives were obtained by the action of ethylic a-chlorscetoacetate on the sodium compounds of phenols. Starting with phenol, a benzomonof urfuran derivative was thus prepared ; whilst from di- and tri-hydroxybenzeneP, compounds containing either one, or two, or three furfuran groups were obtained, just as in the reactions described in the present paper, But there is an important distinction t o be drawn between the mechanisms of the two sets of reactions. I n Hantzsch’s reactions, the first stage is the formation of an ether of the phenol in question-thus of ethylic a-phenoxyl- acetoacetate in the first of the syntheses referred to-and the linking of carbon to earbon is a subsequent process.I n the reactions here de- scribed, the first stage is tho linking of the desyl group to the nucleus of a phenol, whilst the closing of the furfuran ring by oxygen follows. Were this otherwise, phenol and benzoin mould yield only diphenyl- benzofurfuran, instead of, as actually happens, only parsdesylphenol. We may mention that the present research was completed last year, before the publication of Graebe’s investigation of benzoin yellow (Ber., 1898, 31, 2975), in which it is shown that, by the action of sulphuric acid on a mixture of benzoin and gallic acid, a compound containing a diphenylfurfuran group is formed.DERIVATIVES FROM BENZOIN AND PHENOLS.1037 EXPERIMENTAL. 1. Benzoin and Phenol. 20 grams of benzoin, 9 grams of phenol," and 80 grams of 73 per cent. sulphuric acid mefe heated by means of an oil-bath at 120-150° for 20 minutes, frequently shaking the flask. The product, which was dark-coloured, was allowed to cool, the aqueous portion was poured off, and the organic substance was boiled, first with water and then with a. solution of sodium carbonate, after which it was re- crystallised from a mixture of benzene and light petroleum. It melted constantly at 1333 and exhibited all the other properties of para- desjlphenol (Trans., 1890, 57, 966). The yield was good, and the method is a great improvement on that previously described (Zoc. cit.). Afterwards, when me had ascertained that various other phenols yielded furf a r b derivatives, a second preparation of the foregoing compound was made in order to ascertain whether any benzodiphenyl- furfuran mas formed at the same time.For this purpose, the operation was conducted as just described, except that the crude product, after extraction with sodium carbonate, was dissolved in ether, and the solution shaken with dilute caustic soda as long as the latter removed anything. Any benzodiphenylfurfuran would thus remain behind in the ether; but, on evaporating the ethereal liquid, only a small quantity of an uncrystallisable resin was obtained, closely resembling the product of the action of sulphuric acid on benzoin alone. 2. Benzoin and TILynaol. 20 grams of benzoin and 40 grams of thymol were melted to- gether, 80 grams of 73 per cent. sulphuric acid were added, and the mixture was heated, with shaking, for 20 minutes a t 150-170".The viscid product mas washed with water, and then steam-distilled as long as any thymol passed over. The dark-coloured solid which remained was dissolved in boiling alcohol. The filtered solution deposited, on cooling, ft resinous substance; the liquid, poured off from this, gave, on standing, cauliflower-like aggregates of crystals (A). The filtrate from these contained, along with much resin, 8 very soluble, crystalline substance : this was obtained, by crystallisation from a mixture of alcohol and light petrolcum, in colourless lamins melting at 126'. It is readily soluble in alcohol and benzene, sparingly soluble in light petroleum.Analysis gave figures agreeing with the C,H,* YH* C,H,(CH,)( C1,HII,)OH C,H,* CO formula of a desyZthpaol, * From our expericncc with other phenols, it is probable that the employmcnt ot an excess of phenol in this experiment would have given a still better result,1038 JAPP AND MELDRUM : FURFURAN 0.1591 gave 0.4882 (30, and 0.0999 H,O. C = 83.69 ; H = 6.98. 0.1778 ,, 0.5462 CO, ,, 0.1121 H20. C=83*78; H=7*01. C,,H,,O, requires C =: 83.72 ; H = 6.98 per cent. The position of the desyl group is uncertain, excopt that it is doubt- less not contiguous t o the hydroxyl, otherwise the compound would be uonverted, with elimination of water, into cymodiphenylfurfuran. Although desylthymol contains a phenolic hydroxyl group, it is almost insoluble in aqueous caustic alkali.A similar phenomenon has been observed in the case of Mazzara's benzylthymol and dibenzyl- thymol (Abstr., 1882, 42, 171), which are, however, quite insoluble in aqueous caustic alkali, although the benzyl groups replace hydrogen of the nucleus, I n the case of desylthymol, the addition of a very little alcohol to the aqueous caustic alkali causes the substance to dissolve -a property which might possibly be utilised in separating it from the cymodiphenylfurfuran (vide infra) formed along with it in the process of preparation. The presence of a hydroxyl group in desylthymol may be readily proved by boiling the compound with acetic anhydride, when it forms a monacetyl derivative which cry stallises from alcohol in colourless needles, melting at 110".On analysis, i t gave figures agreeing with H-c,H,(CH,)(C~H~)O.C,H,O the formula of cccetyZdes?/Zthy?)toZ, . 6 5 0.1503 gave 0.4431 CO, and 0.0918 H,O. C,,H,,O, requires C = 80.83 ; H = 6-74 per cent. The cauliflower-like aggregates of crystals (substance A, wide SU~TCG), obtained in the crystallisation of the crude product of the condensation, were washed with cold, and then recrystallised from hot, alcohol. As they were found to contain alcohol of crystallisntion, which was diffi- cult to expel completely, they were recrystallised from light petroleum. In this way, the substance was obtained in tufts of slender needles melting at 115-116". I t sublimes slowly when heated on the water- bath. It gave figures agreeing with the formula of a cymodiphnt&'h- CH, C=80*40; H=6*79.0.1895 gave 0.6109 CO, and 0.1171 H20. C = 87-95! ; H = 6.87. 0.1614 ,, 0*5308 00, ,, 0.1007 H,O. C =88.00 ; H = 6.93, C24'H,,0 requires C = 58.34 ; H = 6.74 per cent,DERIVATIVES FROM BENZOIN AND PHENOLS. 1039 3. Benzoin and Pyrocatechol. The dihydric phenols interact either with one 01' with two molecules of benzoin, yielding respectively mono- and di-furf uran derivatives. The former are soluble, the latter insoluble, in caustic alkalis. The result obtained with pyrocatechol was so unsatisfactory that me refrain from describing in detail the process employed. The greater part of the product dissolved in caustic soda, but the reprecipitated substance was so readily oxidisable that we were unable to purify it. A small portion, insoluble in caustic soda, was recrystallised from benzene, and was thus obtained in tufts of slender needles melting at 237O.The results of analysis left no doubt that it had the expected formula C34H2202, but the values for carbon were low, and the quantity of substance was insufficient for further purification. Found: C, 87.69, 87-53; H, 4.83, 4.80. Judging by the results obtained with the other dihydric phenols, the compound is o~t~obenxotetrc6p~en~~d~urfuri~n, Calculated : C, 88-31 ; H, 4-76 per cent. /--\ C,H,* C()--f>*C6H5. C,H,\C- 0 0 -C-C,H, 4. Benzoin and Eesorcinol. I n the reactions with the dihydric phenols, it was found advan- tageous to employ different proportions of the interacting substances according as the mono- or the di-furfuran derivative was required. In the former case, a large excess of the phenol-3 mols.of the latter to 1 of benzoin-was used ; in the latter, equimolecular proportions of the two substances-this being again an excess of the phenol, from the point of view of the desired reaction-gave the best result. 40 grams of benzoin and 62 grams of resorcinol were melted to- gether, 160 grams of 73 per cent. sulphuric acid were added, and the mixture was heated, with shaking, for 15 minutes at 120-130°. The dark coloured product, which solidified on cooling, was washed with water, and boiled with dilute caustic soda, in which it nearly all dis- solved. The filtered solution deposited R sodium salt in six-sided laminae with a satiny lustre ; these, when filtered off, cohered, forming a greasy mass. As the salt was pink coloured, it was recrystallised from boiling water, with the addition of a little caustic soda t o pre- vent the hydrolysis which otherwise occurs, until it was practically colourless.It gives a colourless, aqueous solution with a yellowish- green fluoresceuce, resembling that of uranium glass, It contains1040 JAPP ARD MELDRUM: FURFURAN water of crystallisation, which is entirely driven off at 110'. The anhydrous salt gave, on analysis : Na = 7.86, Required for C,,H,,O,Na : Na=7*47 per cent, The excess was doubtless due to the fact that the substance was deposited from a solution containing caustic soda. The substance could not be contaminated with the sodium compound of resorcinol, as that compound is very readily soluble in cold water, whereas the new sodium salt is only sparingly soluble.The potassium salt, on the contrary, is readily soluble. I n order to obtain the phenolic substance, the sodium salt was dis- solved in hot, dilute alcohol, and the boiling solution was acidified and poured into .excess of boiling water. The organic substance separated as a dark coloured, thick oil, which did not solidify on standing. I t s purification presented difficulties, owing to the tendency of the substance t o separate in an amorphous form from its solutions. It mas finally purified, although not without considerable loss, by dis- solving i t in chloroform and adding light petroleum gradually, so as to precipitate resinous impurities ; the colourless solution thus ob- tained yielded tufts of white needles with a satiny lustre, melting con- stantly at 117.5'.It is readily soluble in most orgmic solvents ; the alcoholic solution shows a violet fluorescence. Analysis gave figures agreeing with the formula of metahydroxybenaocliphenylfurfurnn, c,H,(oH)<~ C(C 0 H 5 )'C*C,H5. 0.2084 gave 0.6389 CO, and 0.0969 H,O. C = 83.61 ; H = 5-16. 0.1516 ,, 0.4655 CO, ,, 0.0687 H,O. C=83*74 ; H=5*03. C,,H,,O, requires C = 83-92 ; H = 4.89 per cent. OE the two possible isomeric hydroxybenzodiphenylfurfurans de- Judging rivable from resorcinol, only the !oregoing was observed. from analogy, its constitution is probably 0 Acetyt Derivative.-4 grams of the foregoing substance were boiled with 6 grams of acetic anhydride for 2 hours, and the resulting acetyl derivative was purified by recrystallisation, first from a mixture of benzene and light petroleum, then from alcohol, from which it was deposited in slender prisms melting at 117'.The practical coinci- dence of the melting point with that of the original compound is anomalous, inasmuch as acetyl derivatives in which acetyl replaces hydrogen of a hydroxyl group generally melt much lower than the hydrox y-coin pounds. Analysis of the substance, dried at loo', gave figures agreeing with the for mula of metacstox~beizzo~~p~~n y Zjhfuran,DERIVATIVES FROM BENZOIN AND PHENOLS, 1041 C,H,(OC,H,0)<C(C6H5~: 0- c! 'eH5. 0.2314 gave 0.6821 CO, and 0.1078 H,O. C = 80.39 ; H = 5.18. C,,HIGO, requires C = 80.49 ; H = 4.88 per cent. Metc~benxotets.a~,l~n~Zdiq~u~,c~n, C,H, grams of benzoin and 10 grams of resorcinol were melted together, 80 grams of 73 per cent.sulphuric acid were added, and the mixture was heated at 160' for 15 minutes, shaking it from time to time, and gradually adding a further 10 grams of benzoin. The melt, which became verytarry, was cooled, washed with water, and boiled with strong caustic soda; the mixture was then diluted with water,and filtered hot, so as to remove phenolic compounds. The insoluble residue was boiled up with a little alcohol, allowed to cool, and then filtered ; this removed a considerable amount of colouring matter. The substance was then crystallised several times from hot benzene, from which it was deposited in short, oblique prisms or plates, containing benzene of crystallisation, and finally from hot glacial acetic acid, from which i t separated in tufts of colourless, slender needles, melting at 217-219O.It is fairly soluble in hot benzene or glacial acetic acid, readily soluble in chloroform, only sparingly soluble in alcohol. All the solutions showed a violet fluorescence. Analysis gave figures agreeing with the formula of metabenzotetrc~~~en?/Zda~urful.an, 0.1380 gave 0.4462 CO, and 0.0610 H,O. C = 88.00 ; H = 4.91. 0.1443 ,, 0.4669 CO, ,, 0.0661 H,O. C=88.24; H=5*10. CY4H2302 requires C = 88.31 ; H = 4-76 per cent. 6 . Benzoin und Quinol. HOi\ C*C,H, 0 I J-8.C H .--20 \/\/ Paral~?/dro~ybencoc2;~~rien~lfu?~ur~n, grams of berizoin and 3 1 grams of quinol were melted together, SO grams of 73 per cent. sulphuric acid were added, and tho whole was heated, with shaking, a t 120-150° for about 20 minutes, gradually raising the temperature.The solid product was powdered and then thoroughly extracted with boiling water to remove quinol. It was then treated exactly like the corresponding resorcinol derivative, by dissolving it in caustic soda (when a considerable residue of parabenzotetraphenyl- difurf uran remained undissolved), purifying the sodium salt by recrys-1042 FURFURAN DERIVATIVES PROM BENZOIN AND PHENOLS. tallisation, liberating the phenolic compound, and pnrifying the latter by recrystallisation, first from a mixture of benzene and light petroleum, then from chloroform and light petroleum. It was thus obtained in rosettes of colourless, flat needles melting a t 158-160'. It crystal- lises much more readily than the meta-componnd.Analysis gave figures agreeing with the formula of l)C11.aji?JcEi.ox?lBenzod~~?~~~~- furfuvan, 0.1724 gave 0.5285 CO, and 0.0802 H,O. c! = 83.61 ; H = 5-17. 0.1505 ,? 0,4613 GO, ,, 0.0671 H,O. C=S3*59 ; H=4*95. C,oHI,O, requires C! = S3.92 ; 11 = 4.89 per cont. Jcetgl Derivative.-Half R gram of the foregoing compound was boiled with 2 grams of acetic anhydride for 3 hours, and the product recrystallised from alcohol. It formed laminx!, melting a t 137'. Analysis showed that i t was a monacetyl compound 0.1247 gave 0.3669 CO, and 0.0558 H,O. C = 80.24 ; H = 4.97. C,,H,,O, requires C = 80.49 ; H = 4.48 per cent. of benzoin and 10 grams of quinol were melted together, 80 grams of 73 per cent. sulphuric acid were added, and the mixture was heated at 150° for 15 minutes with frequent shaking.The resinous mass thus obtained was powdered and boiled with alcohol; this gave a deep blue solution, from which nothing definite was obtained, and a white residue. The latter was purified by recrystnllising it several times from benzene. It mas thus obtained in clusters of needles melting at 278'. The benzene solution was strongly fluorescent, the crystals slightly so. Analysis gave fignres agreeing with the formula of ~~c~r~ben~oteti~ccl,hen?/klifurficrcc?z. 0.1828 gave 05897 CO, and 0.0821 H,O. C = 87-98 ; H = 4-99. 0.1430 ,, 0.4619 CO, ,, 0.0623 H,O. C=8Se09; H=4*S4. C,,H,,O, requires C = SS.31 ; H = 4.76 per cent. Only the foregoing compound could be detected in the product of the reaction, although two isomerides are possible. 6. Benzoin mad PlJoroglzccinol. 50 grams of benzoin, 10 grams of phloroglucinol, and 80 grams of 73 per cent. sulphuricacid mere taken, and the process was coaciucted as in the previous experiments. The heating was continued for 15 minutes at 150'. It is best to add the whole of the sulphuric acid at once to the mslted mixture of benzoin and phloroglucinol ; in one experinlent in which only a, little was added at first, a vigorousINTERACTION OF BENZOIN WITE PHENY LENEDIAMINES. 1043 reaction took place, steam was given off, and the substance turned very dark. The dark brown product was boiled with water, with alcoholic sodium hydrate, again with water, then with alcohol alone, and finally with a small quantity of benzene, I n this may, an almost white residue was obtained, which mas recrystallised several times from solvent naphtha, and afterwards from benzene. It forms tufts of colourless, slender needles melting at 360'. Iluring the purification, fluorescent solutions were obtained ; but solutions of thc pure sub- stance are non-fluorescent. It is almost insoluble in alcohol, glacial acetic acid, and ethylic acetate ; but chloroform dissolves it readily. Analysis gave figures agreeing with the formula of bensohexnp?henyZ- 0.1747 gave 0.5642 CO, and 0.0751 H,O. C = 88.08 ; H = 4.75, 0.1488 ,, 0.4787 CO, ,, 0.0642 H,O. C=S7*74; 13=4.79, C,,H,,O, requires C = SS.07 ; H = 4-51) per cent. UNIVERSITY OF ABERDEEN. CHEMICAL DEPARTMEKT,

ISSN:0368-1645    

DOI:10.1039/CT8997501035

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

INTERACTION OF BENZOIN WITE PHENY LENEDIAMINES. 1043 CIII.-Intemction of Benzoin with Phenylenediamines. By FRANCIS R. JAPP, F.R.S., and ANDREW N. RIELD~ubi, B.Sc. BY heating benzoin with aniline and a little aniline hydrochloride, Ja,pp and Murray (Trans., 1894, 65, SSZ) obtained 3’ : S’-diphenyl- indole. The desylanilide, C,H,*CO*CH(NH* C6H,)*C!,H,, which is formed in the first instance, and which is the sole product if aniline alone is used, parts with water under the influence of the hydrochloric acid, yielding the indole. We have now studied this reaction with the phenylenediamines, in order, if possible, to obtain the corresponding benzodipyrrhole deri- vatives ; but only in the case of metaphenylenediamine did the reaction take place in the desired sense. 1 . Benzoin and Ort I ~ o ~ ~ ~ ~ e n ~ / l e p ~ e d .i t ~ ) ~ i ~ n e . By heating benzoin with orthophenylenedismine hydrochloride, phenylbenximidaxole hydrochloride, C,H,<?Z>C* C,H,, HCl, mas ob- tained, the benzoin molecule breaking up in the process. The free phenylbenzimidaxole melted at 285’ (instead of 29 lo).1044 JAPP AND MELDRUM: INTERACTION OF Benzoin and free orthophenylenediamine, on the other hand, yielded C H <Ni7:C6H5 diphenylquinoxdine, 6 N.C , oxidation taking place during 6 5 the process. The formation of the latter compound in this reaction had, as we afterwards found, been already observed by 0, Fischer (Ber., 1891, 24, 720). 2. Bennzoin and 2llet~~~~~iz?lle~zediarltine. Ten grams of metaphenylenediamine hydrochloride were dissolved in water, and the base was liberated by caustic soda and extracted with ether.The ethereal solution was dried with potassium carbonate and the ether distilled off. To the base thus obtained 23 grams of benzoin mere added, and the mixture was heated to 180". No reaction occurred ; but on adding a little metaphenylenediamine hydrochloride, there mas a vigorous effervescence ; water mas given off, and the mass solidified in spite of the high temperature. By extracting the melt with boiling alcohol and recrgstnllising the residue from solvent naphtha, the new compound was obtained in slender needles melting at 282". It is almost insoluble in alcohol and benzene, .soluble in chloroform. Dilute acids do not dissolve i t ; but it is soluble in con- centrated sulphuric acid, giving a faint red solution with a greenish fluorescence.Analysis gave figures agreeing with the formula of a nzetnbenzo- 0.1806 gave 0.5858 CO, and 0.0571 H,O. 0.2604 ,, 13.1 C.C. moist nitrogen at 14Oand 751 mm. N= 5*85, c'= 85.46 ; H = 5.36. C,,H24N, requires C = 88.70 ; H = 5-22 ; N = 6.09 per cent. Two constitutions are possible for this conipound, axid at present there is apparently no means of deciding between them. The same compound may be obtained by beating together benzoin and metaphenylenediamine hydrochloride, thus obviating the necessity of preparing the free base ; but the yield is bad, and the substance difficult to purify. 3. Benzoin mzcl Payapheng Zenedictntine. The only method that yielded a definite product was that described in the case of the meta-compound: namely, of heating together benzoin and the free base, and adding a little of the hydrochloride.Twelve grams of psraphenylenediamine hydrochloride were taken ; the base was liberated and extracted with ether, of which a largeBENZOIN WITH PHENYLENEDIAMINES. 1045 quantity was required on account OF the sparing solubility of the para-compound. The base which remained after distilling off the ether was heated along with 23 grams of benzoin until the whole melted. No action took place; but on gradually adding 3 grams of paraphenylene- diamine hydrochloride, the fused mass became pasty and ultimately solidified. The reaction was not so vigorous as in the case of the meta- compound, and less water was given off. The product was boiled with alcohol, and the undissolved portion, which was yellow, was washed with boiling water, dried, and recrystallised from benzene.It was obtained pure by a single crystallisation, and formed bright yellow, minute laminae which, when heated, showed signs of softening about 230°, and melted completely at 257". Analysis pointed to the formula C3,H,,N,0,. 0.1846 gave 0.5588 CO, and 0.0954 H,O. 0*2144 ,, 10.4 C.C. moist nitrogen at 13.5" and 743 mm. N = 5.62. C = 83.55 ; H = 5.74. C:,,H,sN,O, requires C = 83.36 ; H = 5-64 ; N = 5.64 per cent. The compound is formed according to the equation CH(OH)*C,IE, = c: b ,134[NH*yH*C,H,] C,H,(NH1), + 3 CO I C,H, CO. UGHc, ., + 2H,*, Paraplieiiyleiiediainiiie. and may receive the name clic2esyll,ccl.c~2~7~~~~~enecliaq~~i~~e. It corre- sponds with desylmilide (anilbenzoin) and the other compounds ob- tained by Voigt by heating benzoin with primary benzenoid amines (compare Trans., 1S94, 65, 890).DiacetpZ De.l.ivcctive. -Two grams of the foregoing compound were boiled with excess of acetic anhydride for 10 minutes. The solution, which was light red a t first and afterwards becamo darker, mas allowed to cool, and ether was added. A white, crystalline substance separated, which was recrystallised from czmylic alcohol, and was thus obtained in colourless, slender needles melting at 87 9". Analysis gave figures agreeing with those required for ditEesyZ~as.apheIzylene- 0.1217 gave 0.3507 CO, and 0,0616 H,O. 0,1166 C=7S.59 ; H=5*62. ,, 5.0 C.C. moist nitrogen at 14' and 768 mm. N=5*03. C,,H,,N,O, requires C = 78.68 ; H = 5.53 ; N = 4.S3 per cent. We tried to convert didesylparaphenylenediamine into the cor- responding benzodipyrrhole derivative by heating it with zinc chloride. It is possible that this transformation does take place, but the product was a mixture of two substances (needles melting at 318' and prisms melting at 335O-both yellow coloured) of almost1046 CHATTAWAY AND ORTON: A SERIES OF equal solubility ; so that, with the small quantity at our disposal, we were unable to separate them. The foregoing five papers form a continuation of a general in- vestigation of the reactions of ketonic compounds (compare Trans., 1897, 71, 123), and the expenses incidental to the work have for some years past been defrayed by various grants from the Government Grant Fund of the Royal Society. C!HEMIChL DEPARTMENT, UNIVEltSITY OF ABEILDEEN.

ISSN:0368-1645    

DOI:10.1039/CT8997501043

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

1046 CHATTAWAY AND ORTON: A SERIES OF CIV.-A Series of Substitzctecl Nitrogen Chlorides and tlzei?. Relation to the Substitu.tion of Halogeit in Anilides cantl Anilines, By F. D. CHATTAWAY and K. J. P. ORTON. COMPOUNDS in which a halogen is attached to nitrogen have been little studied, although a number of isolated examples are known. Among such may be mentioned nitrogen chloride, nitrogen iodide, the chlorine derivatives of tt few aliphatic amines (Tscherniak, Ber,, 1876, 9, 143; Norton and Tscherniak, Bull. Xoc. Chim., 1878, [ii], 30, 106), of acetanilide (Bender, Ber., 1886, 19, 2272), of benzamide (ibid.), of succinimide (ibid.), and of phenylnitramine (Bamberger, Ber., 1895, 27, 376), the bromine derivatives of the aliphatic amides (Hofmann, Ber., 1882, 15, 407 and 752), and of benzanilide (Line- barger, Aww.Chem. J., 1S94, 16, 218), the iodine derivatives of succin- imide (Bunge, Annalen Su&., 1870, 7, 119), of acetamide (Seliwanow, Ber., 1893,26, 985), and of forxuanilide (Comstock and Kleeberg, Amer. Chem. J., lS90, 12, 500), pzethylic and ethylic chlorimidocarbonates (Sandmeyer, Bey., 1886, 9, 862), and the chlorimide obtained from the oxime of benzophenone (Beckmann, Ber., 1886,19, '388). Some years ago, the attention of one of us was drawn to a substance obtained by Witt (Ber., 1875, 8, 1226) by the action of hypochlorous acid on acetanilide, and this was employed in a simple process for prepar- ing metadichlorobenzene in quantity (Chattaway and Evans, Trans., 1896, 69, 848). In continuation of our work upon nitrogen iodide, werecently took up the study of this compound, and have obtained a series of substituted nitrogen chlorides which undergo remarkable intramolecular transformations and are of extreme interest from their bearing on the theory of substitution.We find that, by the action of hypochlorous acid under carefullySUBSTITUTED NITROGEN CHLORIDES. 1047 regulated conditions, compounds of this nature can be obtained from most substances containing hydrogen attached to nitrogen. I n the present paper are considered the disubstitution products of nitrogen chloride containing formyl, acetyl, or benzoyl, together with a phenyl or chlorophenyl residue. These form a well-defined group of compounds, phenyl acetyl nitrogen chloride, discovered by Bender, being one of the simplest members.They are readily obtained from the corresponding formanilide, acetanilide, or benzanilide by inter- action with hypochlorous acid. R*CO*NR’H i- HOCl= R*CO*NR’Cl + H,O. They are all stable compounds of low melting point, crystallising well in large, colourless, transparent prisms or plates, and reacting very readily with alcohol, hydrochloric acid, hydrocyanic acid, potassium iodide, and alkaline hydrogen peroxide. ( a ) With alcohol, the anilide is reformed, and aldehyde, ethylic chloride, and other substances are liberated, ethylic hypochlorite, which breaks up into aldehyde and hydrochloric acid, being probably first produced. R*CO*NR’Cl + C,H,* OH = R*CO*NR’H + C,H,* OC1. CH,* CH,* OC1= HC1+ CH,*CHO. ( b ) With strong hydrochloric acid, chlorine is set free and the anilide regenerated.I n some cases, however, under the influence of the acid, a portion of the compound undergoes an intramolecular transformation similar to that which takes place when it is heated. (c) Withd hydrocyauic acid, the anilide and cynnogen chlorido are formed . R*CO*NR’Cl + HC1= R*CO*NR‘H + GI,. R*CO*NR’Cl + HCN = CNCl + R*CO*NR’H. ( d ) With an acid solution of potassium iodide, the anilide is repro- duced and iodine liberated. R*CO*NR’Cl+ 2HI = R*CO*NR’H + HC1+ I,. (e) With alkaline hydrogen peroxide, oxygen is liberated and the anilide reformed. R*CO*NR’Cl+ H,O, = R*CO*NR’H + HC1+ 0,. When warmed with various anilines, a vigorous reaction takes place, and the anilide is regenerated, whilst a chlorine substitution product of the aniline is formed, These compounds all undergo a remarkable isomeric change.When an unsubstituted phenyl residue is attached to the nitrogen, the1048 CHATTAWAY AND ORTON : A SERIES OF chlorine atom associated with the latter is transferred to the ring in the para-position relatively t o the substituted amido-group ; a change which was first observed by Bender in the case of phenyl acetyl nitrogen chloride. When the para-position is occupied, the chlorine is transferred to the ortho-position, and when both the para- and one ortho-position are occupied, to the remaining ortho-position. The behaviour of these substituted nitrogen chlorides resembles, i n this respect, that of the substituted nitramines and sulphamates (compare Bamberger, Ber., 1894, 27,359 ; 1895,28,399 ; 1897,30,1248,2247). In these transformations of the phenyl acyl nitrogen chlorides, how- ever, we have never, so far, observed t,he simultaneous formation of ortho- and para-compounds.The latter are formed when possible to the exclusion of the former. From the existence and behaviour of these compounds, it seems certain that, in the chlorination of nnilides or anilines, the halogen first replaces a hydrogen atom of the NH- or NH2-group, the nitrogen chloride thus formecl becoming subsequently transformed into an isomeric substituted anilide or aniline. The series of changes which takes place when an anilide is chlorinated may be illustrated by the following formuh, further chlorination proceeding on similar lines with the production, although less readily, of the 2 : 4 : 6-trichloro- anilide (p.1052). R*CO*NH R*CO*N*Cl R*CO*NH R*CO*N*CI R*CO*NH The study of these compounds affords, we believe, an explanation of many well-known facts. In the chlorination of anilides and anilinea, not only is the substitution unusually easy, but the entering halogen atom always takes up a position in the nucleus para- or ortho- relatively to the NH- or NH,-group, provided these positions are unoccupied, other substituting groups which may be present having apparently no directing influence. If, as me believe, the action of chlorine or a chlorinating agent on an anilide and probably on an aniline leads to tho production of a nitrogen chloride which then undergoes isomeric change, the position taken up by the halogen in the nucleus depends chiefly on the relation of the nitrogen atom to the carbon atoms of the riug, whilst other groups present have no oppor- tunity of exerting any specific orientating influence, It is possible that in every case an addition of hypochlorous acid to the amide precedes the formation of these nitrogen chlorides, and our work on nitrogen iodide, which proves that the latter is formed fromSUBEITITUTED NITROGEN CHLORIDES.1049 ammonium hypoiodite, supports this view. We have not, however, so far observed any indication of the existence of such compounds. We have prepared substituted nitrogen bromides which undergo exactly similar intramolecular transformations, and show that bromi- nation is effected in an exactly analogous manner. Phenyl Pormyl Nityoyen Chloyide, C,H,*NCl*CHO.This substance is best prepared by adding the calculated quantity of a solution of bleaching powder t o a saturated solution of formanilide containing an excess of potassium bicarbonate, or to formanilide suspended in a solution of the bicarbonate. It separates as an oil which slowly solidifies, and calcium carbonate is at the same time formed. The bleaching powder solution is run in very slowly, the mixture being vigorously stirred by the aid of a turbine; after the addition, stirring is continued for a n hour or so to ensure complete con- version of the anilide into the chloride. The solid is then filtered off, and the phenyl formyl nitrogen chloride extracted by chloroform, This solution must be rapidly evaporated by a blast of air, as the impure nitrogen chloride very quickly changes into parachloroformanilide if the solvent is distilled off or allowed to volatilise.The reddish- crystalline mass which separates from the chloroform is purified by recrystnllisation from a mixture of chloroform and light petroleuni. It is thus obtained in long, lustrous prisms terminated by pyramids. The melting point is 47'. 0,1934 gave 0.1790 AgC1. 01 = 22.89. C,H,NOCl requires C1= 32.83 per cent. It is very soluble in chloroform, carbon bisulphide, and benzene, but only sparingly so in light petroleum. It gives all the characteristic reactions of the nitrogen chlorides with hydrochloric acid, a solution of potassium iodide, and an alkaline solution of hydrogen peroxide, whilst with alcohol, formanilide is regenerated.On keeping for a few days, it shows signs of decomposition, developing n chlorous smell and becoming coloured. I n a short time, a considerable portion is found to have changed into parachloroformanilide. This change takes place very rapidly if the substance is warmed ; great heat is developed, and the action may become violent if more than cz small quantity is employed. This transformation takes place quietly when the chloride is warmed under water at about 50'; the transparent oil appears to boil, and considerable heat is developed. The darker oil which is formed solidifies, as the water cools, to a mass of cqstals of para- chloroformanilide (m. p. 102O), which is quite pure after crystallising once from water. The yield is quantitative. VOL.LXXV, 4 A1050 CHATTAWAY AND OBTON: A SERIES OF Parachlorophenyl Fovmyl Nitrogen Chloride, C6H4Cl *NCl*CHO. This chloride is prepared and purified in a manner exactly similar t o that used in the case of the preceding substance. It crystallises well i n long, colourless prisms terminated by pyramids, melts at 95-96', and has all the general characteristics of the group. On keeping, it soon becomes slightly pink, and slowly changes at the ordinary temperature into 2 : 4-dichloroformanilide. On heating at 200-210° for a few minutes, it is completely and quietly converted into the dichloroformanilide. 0.1954 gave 0.2950 AgC1. C1= 37.33. C7H,NOCI, requires C1= 37.37 per cent. 2 : 4-Dichlorophenyl Formy1 Nitrogen Cldoride, C,H,CI,*NCI*CHO. Formanilide can be directly converted into this compound by adding a solution in acetic acid to a large excess of a solution of bleaching powder and finally heating on the water-bath. The oil thus obtained is difficult to purify, as it generally contains a little unchanged para- chlorophenyl formyl nitrogen chloride.It is preferable therefore t o start with 2 : 4-dichloroformanilide. A solution of the latter in acetic acid is added t o an excess of a solution of bleaching powder, and the mixture heated and thoroughly shaken until the oil which separates becomes transparent. The chloride solidifies on cooling, and is re- crystallised from a mixture of chloroform and light petroleum. It forms thick, colourless, glistening plates melting at 44O. 0.2018 gave 0.3846 AgC11. C1= 47-12.C7H4NOCI, requires C1= 47.44 per cent. Although this chloride develops a marked chlorous smell on keeping, decomposition takes place only to a very small extent. On heating, no sudden change occurs, but at about 200' chlorine is evolved, and the residue consists chiefly of 2 : 4-dichloroformanilide. Phen y I A cet y I Nitrogen Ch lovide ( Acet oclJoranilide), C,H,*NCI* CO*CH,. This compound was first obtained by Bender (Zoc. cit.), who prepared it by adding bleaching powder to a saturated solution of acetanilide in water acidified with acetic acid. This method is unsatisfactory, as it is very difficult to obtain the nitrogen chloride in quantity," and as the slightest excess of acetic acid causes the complete conversion of * Castor0 (Gaxxetla, 1898, 28, ii, 312) recently failed to confirm Bender's observations.SUBSTITUTED NITROQEN CHLORIDES.1051 the substance into pmachloracetanilide. It is, however, very easily and rapidly prepared by the action of bleaching powder on acetanilide suspended in excess of a solution of potassium bicarbonate. The chloride is extracted with chloroform, and recryetallised from a mixture of chloroform and light petroleum. The yield amounts to 96 per cent. of the theoretical. It crystallises in large, transparent, apparently rectangular plates, not in needles as stated by Bender, and melts at 91'. It dissolves readily in dilute acetic acid, long needles of para- chloracetanilide separating as the liquid cools. This conversion also takes place slowly on keeping, being nearly complete in 2 or 3 weeks.On treatment with hydriodic acid, a reaction occurs analogous t c that which we have observed in the case of nitrogen iodide; one atom of halogen attached to nitrogen, in this case the whole of the halogen, liberates two atoms of iodine in accordance with the equation given on p. 1047. This reaction is characteristic of the nitrogen halogen link- ing. The determination of the iodine liberated is readily effected by dissolving the substance in chloroform, and shaking with a solution of potassium iodide acidified with acetic acid. 0.3952 liberated I = 46.02 C.C. N/10 iodine. C1, as :NC1, = 20.64. C6H,*NC1* CO*CH, requires C1, as :NU, = 20.9 per cent. Parachlorophenyl Acetyl Nitvogen Chloride, C,H,Cl*NCl* CO*CH,. This substance is prepared from parachloracetanilide in the manner described above.I n crystalline form, it resembles the phenyl acetyl nitrogen chloride very closely, and possesses all the general characters of the group, The melting point is 82'. C1= 34.61. C,H7NOCl, requires C1= 34.76 per cent. 0.1942 gave 0.2718 AgC1. The estimation of chlorine attached to nitrogen gave the following 0.4426 liberated I = 42.9 C.C. N/10 iodine. C6H,C1* NCl* CO*CQ, requires C1, as :NCl, = 17.38 per cent. A t 165O, transformation into 2 : 4-dichloracetanilide takes place almost explosively. This change occurs quietly and quantitatively when the substance is heated under water. It first melts, and, when the water begins to boil, becomes converted into its isomeride with considerable evolution of heat and apparent ebullition of the oil, which afterwards solidifies, results : C1, as :NCI, = 17.18.1052 CHATTAWBY AND ORTON: A SERIES OF 2 : 4-DiclJo~ophmyl AcetyZ Nitrogen, Chlwide, C6H,Cl,* NC1* CO*CH,. This substance can be prepared either directly from acetanilide, or, better, from 2 : 4-dichloracetanilide, The solution of acetanilide in acetic acid is poured into a large excess of a solution of bleaching powder ; the precipitated anilide gradually clots together as the action proceeds, and finally, when the mixture is warmed on the water-bath, forms a, clear, yellow oil which often solidifies on cooling t o a hard mass of the impure chloride.To remove 2 : 4-dichloracetanilide, and more especially parachlorophenyl acetyl nitrogen chloride, which are probably present as impurities, the product is redissolved in acetic acid and again poured into a solution of bleaching powder, the mixture being warmed; it is then recrystallised from a mixture of chloroform and light petroleum. It is simpler to pour a solution of the pure 2 : 4-dichloracetanilide in acetic acid into excess of bleaching powder and apply heat.The oil which separates is shaken with n warm acid solution of bleaching powder t o complete the conversion of the anilide ; it solidifies when cooled, and is finally purified by recrystal- lising from a mixture of chloroform and light petroleum, It melts at 7S0. The yield is quantitative. 2 : 4-Dichloropheayl acetyl nitrogen chloride resembles the two pre- ceding nitrogen chlorides very closely in appearance, properties, and behaviour towards reagents ; it is, however, more stable, and can be kept practically unchanged for months.It is decomposed, but very gradually, by heating under boiling water. Its solution in acetic acid evolves chlorine slowly when heated, but many hours boiling are required before it is completely converted into 2 : 4-dichloracetanilide. In a sealed tube, a nearly quantitative yield of 2 : 4 : 6-trichloracetanilide is obtained after 4 hours heating with acetic acid at 145O. Heated alone, it decomposes a t 200°, evolving chlorine and forming a dark, coloured mass, consisting largely of 2 : 4-dichloracetanilide. This compound has been carefully analysed and studied, as it appears to be the main constituent of a substance obtained by Witt (Ber., 1875, 8, 1226) by the action, at 80°, of excess of bleaching powder solution on a solution of ncetanilide in acetic acid.The oil thus formed could not be solidified, and was regarded as an additive product of hypochlorous acid and 2 : 4-dichloracetanilide, C,H,Cl,*NH* CO*CH, + H001. His analyses agree only approximately with this formula; for example, the carbon is 5 per cent. too high, and great difficulty was experienced in the combustion owing to a burst of chlorine which occurs when the substance is first heated, a peculiarity also observed by us in the case of the nitrogen chloride. We estimated the carbon and hydrogen qnite easily when the substanceSUBSTITUTED NITROUEN CHLORIDES. 1053 was mixed with a long layer of lead chromate, with the following results : 0.3194 gave 0.3238 CO, and 0.0515 H,O.0.3452 0516 liberated I = 43.7 C.C. N/10 iodine. C,H7NOCI, rcquires C = 40.26 ; H = 2.54 ; N = 5.88 ; C1= 44.65 ; C1, as :NCI, = 15.02 per cent. Two determinations of the molecular weight by Raoult's method were made, using 10 grams of benzene as solvent. 0.2010 lowered the freezing point 0.42". C=40*23 ; H=2*63. ,, 1'7.2 C.C. nitrogen at 13' and 756 inm. N=5.86. 0.1606 ,, 0.3906 AgC1. C1= 44-75. C1, as :NCl, = 14.88. 11. wt. = 234.5. 0.6442 ,, 9 , ,, 1.295'. M. wt. = 243.7. C,H,NOCl, requires a molecular weight of 238.45. The behaviour of Witts's oil is identical in every respect with that of our crystalline 3 : -l--dichlorophenyl ncetyl nitrogen chloride, When prepared by his method, it frequently solidifies with the greatest difficulty, owing to the presence of impurity, probably parachloro- phenyl acetyl nitrogeii chloride, which can only be removed by the treatment described above.Phenyl Benxoyl iVitroge?b Chloride, CGH,*NC1* CO* C,H,. This substance is prepared by the general method from benzanilide and bleaching powder in the presence of potassium bicarbonate, but the reaction takes place less readily than with the formyl and acetyl compounds. It crystallises in colourless plates from a mixture of chloroform and light petzoleum, and melts at 77". 0.2014 gave 0.1228 AgC1. On heating the melted chloride to 130-130°, benzoyl chloride is given off, whilst a portion is converted into parachlorobenzanilide, The latter change is brought about quantitatively if the nitrogen chloride is heated under water for some time, C1= 15-0s.C,,HI,NOC1 requires C1= 15.33 per cent. ParachlorophewJ Benxop l Xt/*oge?a Chloride, We have not succeeded in obtaining this substance pure, as para- chlorobenzanilide is not attacked at the ordinary temperature by hypoclilorous acid. A t 70-80°, either in the presence of potassium bicarbonate or acetic acid, a reaction takes place, but at this tempera- ture the chloride becomes partly converted into 2 : 4-dichlorobenz- anilide, which in turn forms, with the hypochlorous acid, 2 : Cdichloro- VOL, LXXV. 4 B1Og!i4 RYAN : SYNTHETICAL PREPARATION OF CILUCOSIDES. phenyl benzoyl nitrogen chloride. On extracting the product with chloroform, an oil is obtained which solidifies only with great difficulty. Analysis of the recrystallised product showed that it consisted of about 30 per cent. of parachlorophenyl benzoyl nitrogen chloride, together with 70 per cent. of 2 : 4-dichlorophenyl benzoyl nitrogen chloride. 2 : 4-Dic?~Zoro~,?~e~t~Z Bemoy Z Nityogen C?L l o d e , C,jH5CI,*NC1*CO*C,H5. This compound, like the corresponding formyl and acetyl derivatives, can either be obtained directly from benzanilide or from 2 : 4-dichloro- benzanilide, by the action of bleaching powder in the presence of acetic acid a t a temperature of from 80-90". It resembles other members of the group in appearance and properties, and melts at 86". On heating at 150--300°, benzoyl chloride is evolved and a tarry mass is left from which 2 : 4-dichlorobenzanilide can be isolated. 0.2096 gave 0.3993 AgCl. 01= 35.3. C1,H,NOCl, requires C1= 35.44 per cent, We have obtained similar compounds from ninny other su bstitutecl anilides, from secondary amines, and from other substances in which hydrogen is attached to nitrogen, and me desire to reserve the in- vestigation of these compounds. We have also obtained substituted nitrogen bromides resembling the nitrogen chlorides very closely in properties. CHEMICAL LABORATORY, ST. BARTNOLOMEW'S IIOSPITAL, E. C,

ISSN:0368-1645    

DOI:10.1039/CT8997501046

出版商:RSC    

年代:1899

数据来源: RSC

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10.54 RYAN : SYNTHETICAL PREPARATION OF CILUCOSIDES. CV.-SpthcticctI Prep rcctima of Glwosicles, By HUGH RYAN, M.A., 1851 Exhibition Scholar of the Queen’s College, Gal way. BY the action of alcohols and mercaptans on hexoses and pentoses in the presence of hydrochloric acid, Emil Fischer succeeded in preparing the glucosides of methy lie, ethylic, propylic, isopropylie, amylic, and benzylic alcohols, of ethyleneglycol, glycerol, and ethyl, amyl, and benzyl mercaptms (Bey., 1893, 26, 2400 ; 1894, 2’7, 674, 2453, 2985). Similarly, Emil Fischer and Jennings obtained amorphous condensa- tion products by the action of resorcinol, pyrogallol, and orcinol on different sugars. The method was found to be inaFplicable for the preparation of glucosides of the monohydric phenols (Ber., 1 S91, 27, 1358).RYAN : SYNTHETICAL PREPARATION OF GLUCOSIDES.1055 Phenol and its homologues can be converted into well crystallised glucosides by Michael’s method (Compt. rend., 1879, 89, 355) ; this, however, is troublesome, and as it gives poor results, its employment hitherto has been very limited, I sought to improve the process by employing inactive pentacetylglucose, which is more easily prepared than acetochloroglucose, but could not isolate any crystalline com- pound from the product of its reaction with potassium phenolate. The best results were attained by a slight modification of Michael’s method. The phenol (1 mol.) was dissolved in alcoholic potash (1 mol.) and t o the clear solution was added acetochloroglucose (1 mol.) dissolved in absolute alcohol.The acetochloroglucose required mas prepared by Colley’s method ( A s m Clkv2. Ph,y,s., 1870, [iv], 21, 363), with some slight alterations which render it more easily accessible. Pure, crystallised, anhydrous glucose (1s grams), after passage throngh n fine sieve, was mixed with acetyl chloride (39 grams) in n well-dried Volhard tube; this was sealed off at once and shaken during 34-30 hours at the ordinary temperature, The colourless solution was dissolved in chloroform, and shaken with ice cold sodium carbonate. The chloroform solution was filtered, dried with calcium chloride, and, after evaporation in a vacuum, gave a colourlesa, semi-solid mass of acetochloi*oglucosc. It may be nientioned that attempts to prepare acetochloroglucose in an open vessel protected from rttmospheric moisture by a calcium chloride tube were unsuccessful. When 30 mols.of acetyl chloride were employed with 1 mol. of glucose, the principal product was the dextrorotatory pentacetylglucose previously made by Erwig and Konigs by the action of acetic anhydride and zinc chloride on grape-sugar (Be?.., 1889, 22, 1464). The yield was satisfactory. It melted at l l O o , and on analysis gave the following result: 0.1389 gave 0.2490 CO, and 0,0717 H,O. C16H,,011 requires C = 49.3 ; I3 = 5.6 per cent. P-iccl)iLtl~?/ZgZucoside, C,Hl10,~O*Cl,H7.-A solution of wetochloro- glucose (70 grams) in absolute alcohol (150 c.c.) was added to P-naphthol (2s grams) and potassium hydroxide (1 1 grams) dissolved in rtbsolut e alcohol, the total volume of the well-cooled mixture being about 300 C.C.After a fern minutes, the solution became turbid, owing to the separation of potassium chloride. After remaining for three days a t the ordinary temperature, the yellowish-brown solution, which smelt strongly of ethylic acetate, was heated to boiling for 45 minutes under a reflux condenser, cooled, and filtered. After removal of the alcohol on the water-bath, a little water was added, and the solu- tion, on cooling, solidified. The poduct (46 grams), which con- tained some unchanged naphthol, was recrystallised from boiling water, and finally from absolute alcohol. It separated in groups of C = 48.9 ; H = 5.7. 4 ! E 21056 RYAN : SYNTHETICAL PHEPARATION OF GLUCOSIDES. long needles melting a t 184-186", and was dried at 105' before analysis. 0.1806 gave 0.415 CO, and O .O M 4 H,O. P-Naphthylglucoside is soluble in alcohol or hot water, sparingly so in acetone, and almost insoluble in benzene, light petroleum, cold water, or ether. It is readily hydrolysed by dilute acids or emulsin, reduces Fehling's solution only after hydrolysis, and is stable towards dilute alkali, in which it is scarcely soluble. The taste is disagreeable. A siinilar experiment with pnranitroyhenol did not lead t o the formation of a glucoside. I n orcler to find whether the failure of the reaction was due to the nature or position of the nitro-group, I examined the beliaviour of pnracresol towards scetochloroglucose, with results which show that the position of the radicle does not explain the failure in the case of nitrophenol. Puruc?*es2/~~12ccosicle, C,H,,O,* 0 C,H; CH,.-Acet och lorog Iucose (3 6 grams), dissolved in absolute alcohol. was added to a solution of paracresol (1 1 gr:~ms) and potassium hydroxide (6 grams) in alcohol. The mixture, which became yellow, was left for 14 hours in ice water, and then at tho ordinary temperature for a clay. The resulting crystal- line magma was diluted with absolute alcohol to 500 c.c., left for two d:iys, and thcn boiled gently €or l!j hours. Tho filtrate, when left in an evaporatiiig dish for a few days, p v e a separation of the glncoside in needles which were scarcely soluble in ether, benzene, light petroleum, or chloroform, sparingly so in acetone, and soluble in alcohol or water. It melted at 175-177", after drying at looo, and did not reduce Fehling's solution before, but readilyafter, hydrolysis, withemulsiii or dilute acids.The yield of pure product amounted t o 40 per cent. of the theoretical. C = 68.67 ; H = 5.81. C1,H1,06 requires C = 68.74 ; H = 5-88 per cent, 0.1737 gave 0.3652 CO, and 0.1015 H20. C: = 57.34 ; H = 6.74. C,,13,,0, requires C = 57.77 ; H = 6.66 per cent. 01.tl~ocs.es~ZgZucosicle, C,H,,O,* O*C6H,* CH,, mas prepared from orthocresol in a, similar manner. It crystallised from water in beautiful needles, melted a t 163-165", was scarcely soluble in ether but easily so in water or alcohol, and did not reduce Fehling's solution before, but readily after, hydrolysis by dilute acids or emulsin. It had a n intensely hitter taste. The yield was similar in amount to t h a t obtained from the para-clerivative. The crystals were dried a t 105-1103 before analysis.0.1406 gave 0.2966 CO, and O.OS01 H,O. C = 57.53 ; H = 7-06, CISHISOG reclnires C = 67.77 ; H = 6-66 per cent. Ca~ucccl.~lgZz~cosicle, C,II,,O,*O* C, H,(CI13) C,H, + $H,O, mas preparedRYAN : SYNTHETICAL PREPARATION OF CILUCOSIDES. 1067 from cnrvacrol in a similar manner. A yellowish, oily residue was obtained by the spontaneous evaporation of the filtrate from the potassium chlQride formed in the reaction ; this was evaporated with water several times on the water-bath until the odour of carvacrol disappeared, mid afterwards crystnllised from hot water. It separates in groups of beautiful needles, and when anhydrous softens at 118' and melts not quite sharply at 135".The glucoside, after drying over calcium chloride, but not in a vacuum, was analysed. 0.1806 gave 0.3964 CO, and 0.1279 H,O. 0.23S-i lost 0.0064 R,O a t 90" in a vacuum over phosphorus pent- C,,,H,,O, + iH,O requires C = 59.8 j H = 7.S ; H,O = 2.8 per cent. The anhydrous compound gave the follomiiig numbers : 0.1612 gave 0.3302 CO, and 0-1OSG H,O. C,6H,,0, requires C = 61.5 ; I1 = 7.7 per cent. Carvacrylglucoside is e a d y soluble in alcohol or acetone but less readily so in cold water or ether, and is almost insoluble in benzene, chloroform, or light petroleum. It does not reduce Fehling's solution before, but readily after, heating with euulsin or dilute mineral acids. The behaviour of carvacrylglucoside towards dilute aqueous alkali is characteristic.Just as if it retained an unchanged phenolic hydroxyl group, i t dissolves slowly, but completely, in dilute caustic soda. That its solubility is iiot due to decomposition of the glucoside into its components by tho action of the alkali is shown by the fact that it scarcely reduces Fehling's solution even after prolonged boiling. Similar properties seem to be possessed by a galixtoside obtained from P-naphthol and acetochlorogalactose, the latter substance having been prepared by the action of acetyl chloride on galactose. As glucosides of the type C,H,,O,*R*OH, to which carvacrylgluco- side and naphthylgnlactoside apparently belong, are unknown, the in- vestigation of these substances will be continued. Attempts to pre- pare glucovanillin and menthylglucoside have not been up to the present successful. Similar experiments will be made with anthranol and alizarin. It is noteworthy that all the glucosides hitherto prepared from acetochloroglizcose in alkaline solution are readily liydrolysed by emulsin, My best thanks are due to Professor E n d Fischor for his advice during the course of this investigation. C=Stf*S ; H=7*9. oxide. H,O = 2.7. C=61*2; H=7*9. FIMT CHEMICAL INSTI"JTE, BERLIN.

ISSN:0368-1645    

DOI:10.1039/CT8997501054

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

1058 MARSH: THE ACTION OF SULPHURIC ACID ON FENOHONE. CVI.-The Action of SLclpl~w'ic Acid 03% Ere~~,clio'~ze, By JAMES E. MARSH. IF fenchone is warmed with strong sulphuric acid, sulphur dioxide is given off and acetoxylene [Ale : Me : Ac = 1 : 2 : 41 is formed. This compound has been obtained synthetically by Claus by the action of acetyl chloride on ortliosylene in presence of aluminium chloride (J p. Chem., 1890, [ii], 41, 396). Armstrong and Kipping (Trans., 1893, 63, '75) obtained the same compound by the action of sulphuric acid on camphor ; they found that camphor is not readily acted on by sulphuric acid at a tempernture below looo, that, it was most ad- vantageous to heat, the mixture to lZO", that acetoxylene is not the only product of the reaction, and that it was not practicable to separate the compound in a pure state by fractional distillation; they effected its separation by preparing the crystalline phenylhydr- ttzone from it and decomposing this by hydrolysis.When .fenchone was warmed with five times its volume of strong sulphuric acid, the action began at a temperatnre below 50" with evolution of sulphur dioxide. The evolution of gas mas rapid at SO", and at 100' was complete in ft few minutes. I used 'small quantities of not more than 10 C.C. of fenchone in one operation. It appeared prefersble to keep the temperature at about SOo, and there was little or no charring. After cooling, the solution was poured into water and distilled in steam. The distillate mas shaken out with ether and the ethereal solution distilled under reduced pressure.After the ether and water had come off without condensing, the residue distilled almost entirely at 131" under 20 mm. pressure; it amounted t o about 70 per cent. of the fenchone taken. If me take into consideration the loss arising from the number of operations which the fenchone had undergone, and that only 10 grams were used, the yield of acetoxylene probably approximates to that required by theory. It was redistilled and the fraction boiling a t 131" under 20 mm. pressure was nnalysed. It gave C = 80.6 ; H = 8.3. The acetoxylene so obtained was a nearly colourless oil smelling somewhat of cinnamon. Its specific gravity mas Found to be 0.9968 at 2Ooj4". When treated with hydroxylamine hydrochloride and caustic potash in alcoholic solution, it gave a good yield of the oxime which crystallised from methylic alcohol, forming colourless crystals melting at 86-87'.Claus gives the melting point at 88-89", Armstrong and Ripping at 84.5-85.5O. To further establish its identity and constitution, cz small quantity CloH120 requires C = 81 '0 ; H = 8.1 per cent.MARSH: THE ACTION OF SULPHURIC ACID ON FENCHONE. 1059 was oxidised by warming gently with a slight excess of bromine dissolved in 4 per cent. caustic soda solution, until bromine was scarcely liberated by addition of acid. On filtering from the crystals of carbon tetrabromide, and on addition of dilute sulphuric acid, a thick precipitate m:is thrown down which, after crystallising from dilnte alcohol, melted at 163’. On analysis the product gave c1 = 71.6 ; H = 6.7.The silver salt was prepared and, on analysis, gave C,H,,O, requires C = $2.0 ; H = 6.6 per cent. Ag = 41 .S. C!,H,Me?* COOAg requires A g = 44 -0 per cent. The acid thus obtained by oxidation of acetoxylene is paraxylic acid [CH, : CII, : COOH = 1 : 2 : 41. It seeins reasonable to suppose that the almost quantitative con- version of fenchone into acetoxylene ought to have a n important bearing on the constitution of fenchone. I have attempted in a paper on “The Constitution of Camphor ” ( I m n s . Oqjbrd Ughiv. Jzm. Xci. Club N.S., 1898,110) to show how the formation of ncetoxylene from camphor, established by Armstrong and Kipping, niay be explained; I here only wish to point out that fenchone is probably still more nearly related in constitution t o acetoxyleiie than is camphor, judging from the ease with which this compound is obtained from fenchone com- pared with the dificulty of i t s production from camphor.The following formula for fenciioiie mas put forward last year by Wallach (Annnlen, lSDS, 300, 320) and by Gardner and Cockburn (Trans., 1898, 73, 70s) independently : CH,* F]H-CH*CH, UH,* CH-U0 I F(CH,), I The coincidence of two separate lines of re.;earch leading to the same conclusion might be regarded as affording a t least n presumption in favour of the formula. But the coincidence is less remarkable seeing that the formula is constructed on the model of Bredt’s camphor formula. Further, neither Wallach nor Gardner and Cockburn ex- press themselves as satisfied with the formula, and bring forward objections to i t which seem to me not less convincing than their argu- ments in its favour.To these objections I think ought to be added the formation from fenchone of ncetoxylene which i t seems impossible to reconcile with the formula proposed. I have from time to time ventured to criticise some of the formulze proposed for members of the terpene group, partly on the ground t h a t they do not account for the derivatives of benzene which are obtained from them by comparatively simple reactions. Nor does it seem to1060 HARCOURT : ON METHODS FOR ESTIMATING me obvious why it should be regarded a sounder principle to base the constitution of closed chain compounds, such as the terpenes, on the products obtained by breaking down their cyclic structure, than on those products in which a ring remains. At present there seems to be an inclination either to disregard the latter entirely, or in certain cases to make a selection of those benzene derivatives which may be accounted for, It is not unreasonable to require that any constitution assigned to a member of the terpene group must account for both the aromatic and the fatty derivatives obtained from it, I wish to thank Mr. Gardner and Mr. Cockburn for kindly giving me the samples of fenchone with wliich these experiments were made. UNIVERSITY hIusEm, OSPOKD.

ISSN:0368-1645    

DOI:10.1039/CT8997501058

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

1060 HARCOURT : ON METHODS FOR ESTIMATING CVIL-On a Jfetliocl for Proriditig c6 C.uwmt of Gaseous Chloiv f o m mixed with A ir i ) ~ cmy clcsirecl popo3"- tion, a t 7 cl O I L Mvtk ocls foi- Est i s w t iiig the c;'ccscoz6s Ck~lo ,*of o rm i ~ ? t Ji e Mixt u i m . By A. VERNON HARCOURT, MA., F.E.S., Lee's Reader in Chemistry at Christ Churah, Oxford. WHEN air is passed through a mixture of alcohol and chloroform, both liquids evaporate, and if the surface of contact of the air bubbles and the liquid is sufliciently extensive relatively to the total volume of air passed through, the m:~ximuiii tension is reached of each vapoiir a s given off from the actual mixture of the two a t tlie actual temperature. From the mixed gases, the vapour of alcohol may be withdrawn by passing them through sulphuric acid, the gases which go forward being a mixture of air and chloroform in proportions dependent upon the proportion of alcohol to chloroform in the mixed liquid and upon the temperature of the liquid, which must not exceed that of the air around.Since the density of alcohol is much less than that of chloroform, mixtures of the two liquids in diiferent proportions differ much in density, and the composition of a mixture can be adjusted and kept constant by bringing it to a known density by additions of either alcohol or chloroform. The method, resting upon these facts, which is here proposed con- sists in leading dry air through a bent tube to the bottom ofa Wolfe's bottle, which is half filled with glass balls and charged with a mixture of alcohol and chloroform, and thence through two washing vessels containing respectively sulphuric acid and water.The air issuing from a number of small holes made in the lower branch of theCHLOROFORM IN MIXTURES OF THE VAPOUR WITH AIR. 1061 tube passes up by many channels among the glass balls into the liquid above. With a bottle of about 1200 C.C. capacity, this contact is sufficient to saturate air passing a t the rate of at least 1 wbic foot per hour, as has been proved by analysing the gaseous mixture when produced at that rate, and with air passing at the rate of 4 cubic foot per hour, and finding that the composition was the same. The density of the liquid can be conveniently observed while the air is pnssing by means of two small bulbs, one of which floats and the other sinks when the liquid has the desired density.As the operation proceeds, the proportion of chloroform diminishes, and more is added until the lighter bulb again comes to the surface. I n order to ascertain what was the proportion of chloroform vapour mixed with air which had given satisfactory results as an anzesthetic, two methods were tried. I. The first method depends upon the action on chloroform of an alcoholic solution of caustic potash, which produces potassium formate and potassium chloride, CHCl, + 4ICIIO = 3ICC1+ H*COOIi + 2H,O. This reaction takes place slowly, and is, perhaps, accompanied t o a small extent by some other reaction, leaving other products. Even when an alcoholic solution of potash is heated with a small amount of chloroform to a temperature of 50-70" for some hours, the chloride formed does not correspond to the whole of the chloroform; and, con- sequently, quantitative estimations of chloroform depending upon this reaction yield results which are a few per cent.too low. Under con- stant conditions, however, the deficiency is nearly constant, and thus, by applying a correction, results are obtained which may be sufficiently accurate for the object in view. For bringing about the requisite contact between the alcoholic potash and the mixture of chloroform and air, either the mixed gases may be led slowly through the alcoholic solution, or they may be collected in a bottle or flask and there treated with the reagent. A short account may be given of the may in which each of these modes of testing was conducted.For the first, the air and chloroform were passed through a long and almost horizontal tube, the upper surface of which had been pressed in a t intervals of a few centimetres, so that while the solution with which it was charged moved about freely, the bubbles of gas were arrested at successive stages. A lamp placed beneath the tube, near its inlet, heated every portion of the liquid in turn to a temperature a t which the chloroform vapour which has been dissolved undergoes the above change, while the air about to escape at the opposite end gave up the last portions of chloroform to alcohol which had been freed from the chloroform already absorbed and mas1062 HARCOURT : ON METHODS FOR ESTIMATINd Relative Iiiasscs of chl6roform mil nlcol1ol.l’einpernturc. Chloroform. Alcohol. of a lower temperature. When the first part of the experiment was complete, the liquid WRS neutralised with dilute nitric acid, and in a portion of i t the mass of chlorine, and thus the mass of chloroform, tvns measnred by adding to it in a porcelain dish two drops of a sdution of potassium chroniate and a, standard solution of silver nitrate from a burette. In experiments made with a view to test the method, air was driven by a water-pump through ,z small meter, and thence through the vessel in which it was mixed, under the conditions to be tested, with the vapour from a known weight of chloroform, and thence through the washing-tube in which the chloroform tvas arrested and decomposed. Some of the results obtained by this method were as follows : Vol.of chloroform vnpour in 100 vols. of air and chloroform. Weight of Chlorofom. T&~II. Fon nd . Fonnd per ccnt. 0.236 0.219 03 0,226 0.212 94 0.312 0.197 93 0.225 0.2 18 97 9s 0.1”’ 0.1 79 13 0,140 0.1 35 96 I n the course of these successive experiments, as bhe results fell too low, various further precautions were taken, sach as nvoicling contact between chloroform vstpour and indin-rubber, which has an absorbent action. But the deficiency could oiily be reduced from 6 or 7 to 3 or 4 per cent. A plan, which led up to the method already described €or m a k i q a mixture of air with cliloroform suitable for anzesthetic purposes, was tested by this method. Mixtures of chloroform and alcohol mere brought into a tube similar to that which held the alcoholic potash, and the measured volume of air was passed through the two, bubble by bubble.I n the following t,able, the volume of chloroform vapour found has been increased by 4 per cent. :CHLOROFORM IN MIXTURES OF THE VAPOUR WITH AIR 1063 Since in the use of chloroform as an anssthetic air must be charged with the vapour at a far greater rate than that of the foregoing experi- ments, some bottles were filled with the mixture made in tlie manner described on p. 1060, and their contents mere displaced by water, and so gradually driven through the heated solution of potash in alcohol. But as in this method the chloroform vspour is exposed to the action of a large volume of water in which, even a t a lorn tension, it is t o some extent soluble, a i d the substitution of mercury on the same scale would be inconvenient, the second mode of testing was tried, that of bringing a measure of alcoholic potash into the bottle in which the chloroform and air had been collected, pressing and tying in the stopper of the bottle, and hesting the contents.Control experiments were first made, in which a weighed amount of chloroform was brought into the Bottlc in a bulb which was broken before the measure of alcoholic potash was iiitroduced. As tlie volume of gas within the bottle is increased by the amount of the chloroform vapour formed from the liquid, room was made for this amount by heating the bottle, whose sides were wet, before tlie stopper mas put in and the bulb broken. Thus, when the bottle which had cooled was opened to bring in the alcoholic potash, the iiiternul gaseous pressure was not in excess of the atinospliere pressure, and the only loss mas that, allowed for in the calculation, of a portion of the contained gases equal to that of the liciuid brought in.In some cases, the precaution mas taken of sealing up the alcoholic potash in a tube of thin glass, so that no contact should occur till the stopper had been securely fixed in the neck of the bottle. To charge the bottles, whose capacity had been measured, many times their volume of the mixture of chloroform and air to be antzlysed was passed through thein. I n order t o complete the reaction as far as possible, the bottles were immersed one-quarter in a water-bath, of which tlie temperature was gradually raised to about 60" and kept a t this point for several hours.The liquid contents were then poured and mashed out, and the amount of potassium chloride formed was determined with a standard solution of silver nitrate. The results thus obtained agree with those already given, as mill be seen from the following tnbles : IVeigRt qf CI~lovofoi*m. I alien. 0.032 0,031 97 0*016G 0.0 144 92 0.0378 0.0359 95 0.037 0.0344 83 0.056 0.054 96 0*0837 0.0801 96 ~ O l l l d . Found per cent. r 31064 HARCOURT : ON METHODS FOR ESTIMATINa The deficiency, in spite of all the precautions which repetitions of the experiment suggested, again amounts to 4 or 5 per cent. Accord- ingly, the percentage of chloroform in mixtures of air and chloroform, prepared by the method described on p.1060 and analysed by this method, have in the following table been increased by 4 per cent. : Relative masses of cliloroforin ant1 alcohol. Chloroform. Alcohol. To]. of chioroforin vaponr in 100 vols. of mised gases. 4 '45 4.37 4 *03 4.21 4 -28 The differences in the above results are mainly actual differences in the mixtures analysed. The probable error of the analysis does not exceed about 3 per cent., but this is rather large, and no method involving an empirical correction can be regarded as satisfactory. Consequently, a better method was sought for, and, after various experiments which need not be related, was found. 11. The second method depends upon the reaction between chloro- form vapour, air, and steam, in contact with a red-hot platinum wire.The final result of the reaction is expressed by the equation, 2CHC1, + 2H,O + 0, = 2U0, + 6HCI. The probable order of the reaction is that the chloroform molecules with air around them as they fly against the heated wire are burnt, like moths in a candle, and that the chlorine thus produced reacts similarly with the molecules of steam forming hydrogen chloride and oxygen. The reverse action of hydrogen chloride and oxygen one upon another also takes place, but to an extent which, if the requi- site, conditions are observed, is ultimately insignificant, in consequence of the alniost complete withdrawal of hydrogen chloride from the gaseous system by the water which is present. When the reaction is complete, the amount of hydrogen chloride which has been formed is determined.This may be done by means of a standard solution of silver nitrate, or equally well by means of a standard solution of ammonia. The conditions which must be observed in order that all the chlorine atoms in the niolecules of chloroform may pass into molecules of hydrogen chloride are as follows : (1.) The proportion of steam to oxygen must be sufficiently large.CHLOROFORM IN MIXTUHES OF THE VAPOUR WITH AIR. 1065 Experiments were made in which oxygen was used instead of air, and in which the water in the bottle mas not heated. In both cases, the gas within the bottle when it was opened smelt of chlorine, and the results were too low. (2.) The platinum wire must be heated to bright redness. I n experiments in which the wire was kept faintly red, the gas smelt of chlorine and the results mere many per cent.too low. (3.) The conditions of the change must be maintained for a suffi- cient time. If the wire is very bright, the change is complete in half a a hour, but it is better not to run any risk of fusing the platinum mire, and to allow one hour for the completion of the change. Pass the mixture of air and chloroform to be analysed into a round &-litre flask holding about 4 C.C. of water, so that the gas, delivered near the bottom, will escape near the top, and continue the passage of the gas till five or six times the volume which the flask contains has passed through it. Substitute for the cork and tubes used in charging tlie fliisk a cork with two tubes, into mliich stout platinum mires have been fused, which are joined by a loop of thin platinum wire.The tubes and stout wires are of such a length that the lowest part of the loop descends t o near the bottom of the flask. When the cork carrying these tubes has been pressed and tied into the neck of the flask, a little mercury is brought into each tube and copper wires are passed down the tubes; through these wires an electric current is passed sufficient t o heat the loop of platinum wire to bright rednees. The flask is supported in a shallow dish holding a little water, whose temperature is kept between 50’ and 60’. After remaining thus for an hour, the flask is allowed to cool, and more water is brought in little by little and shaken up with the contents. Finally, the amount; of dilute hydrogen chloride which has been formed is determined in the flask itself by means of a standard solution of ammonia. The results of the test experiments made with weighed quantities of chloroform are given in the following table : The method finally adopted is as follows. Veight of Cldoyofornz. Taken. Found. Found per cent. 0.0641 0.063s 99.4 0.0’726 0 * 0 7 3 5 101.3 O.OS82 O ~ O S ~ O 99.7 O.OS.15 0.083s 99.2 0.0803 o*osoo 99.6 This method has been applied in the an’elysis of mixtures of gaseous chloroform and air, prepared by the method described on p. 1060.1066 POPE AND PEACREY: The following is the composition of some of the mixtures of air and chloroform vapour thus produced from mixtures oE alcohol and chloroform in different proportions, and in one case at different tem- peratiires : Relative I ~ S S P S of c h l o ~ o f o r i ~ ~ and alcoliol. Chloroform. 20 a0 40 50 60 30 30 30 Blcohol. 80 iO 60 50 40 i0 70 i 0 Temperature. 15" 9 9 9 9 9 9 9 9 12 1-1 1s Vol. of chloroform vapour 111 100 volx. 2.34 4-23 5.16 7.17 9.85 4'06 4'1 0 4.65 The work here recorcled was d o i i ~ in the Laboratory of Christ Church, Oxford, with the assistance of Xr. G. W. F. Holroyd, to whose skill and perseverance the author is greatly indebted.

ISSN:0368-1645    

DOI:10.1039/CT8997501060

出版商:RSC    

年代:1899

数据来源: RSC

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1066 POPE AND PEACREY: By WILLIAM JACIiSON POPE and STAXLEY JOIIN PEACHEY. IN the present communication, we describe the separation of com- pensated tetrahydroquinaldine into its optically active components by means of Keychler's clestrocitlllphorsulphoaic acid ; we have previously discussed the reasons for using this acid in preference to tartaric acid (Trans., lS9S, 73, 893). The new method adopted, which is a generally applicable one, is based upon the following considerations. The solubilities of the salts (d13 tlA and ZB d A ) of a dextrorotntory acid ( d A ) with a dextro- and a lwo-base (tZR and ZB) mould hardly be expected to differ considerably, because the solubility is partly a func- tion of tho cheinicnl nature of the salts. If, however, the salt, ZB dA, is the less soluble ant1 only sufficient of the active acid, dA, necessary to the formation of this salt is added, the balance of acid required to dissolve the base befug made'up by adding the requisite amount of an optically inactive acid, such as hydrochloric acid, which forms corn-RESOLUTION OF TETRAHYDROQUINALDINE. 1067 paratively soluble salts with the base, it would be expected that on crystallisation the greater part of the lavo-base would separate as the sparingly soluble salt, ZB dA, whilst the mother liquors would retain the dextro-base of which the hydrochloride, dB HC1, is very soluble.The disadvantage of the ordinary method of separating externally compensated bases by cry stallisation with excess of tartaric acid lies very largely in the fact that the solubilities of the two salts, d B dd and ZBdA, are not suEciently different to permit of the pure salts being easily isolated by fractional crystallisation ; this is illustrated by Ladenburg’s observntion (Ber., 1894, 27, 77) that the crude dextro- tetrshydroqiiiiialdine dextrobitartrate obtained from the inactive base must be recrystsllised many times before it is obtained pure, By applying our method to this base (using one molecular proportion each of dextro-a-bromoctcmphorsulphonic acid and of hydrochloric acid for the dissolution of two molecular proportions of externally compensated base) and crystsllising the first separation twice from alcohol to remove mechanically retained impurities, a pure sample of Itwotetrahydro- quinaldine dextro-a-bromocamphorsulplionate is obtained.Although the sepczration mas best effectod in this WHY, instructive results were obtained by modifying the method of applying the principle above explained. Thus, hot aqueous solutions of one molecular proportion of ammon- ium dextro-a-bromocamphorsulphonste and of two inolecular proportions of racemic tetrahydroquinalcline hydrochloride were mixed and the liquid allowed to cool ; a large separation of lzevotetrahydroquinaldine dextro-~-bromocamphorsulpl~~nate was thus obtained in a practically pure condition, this being the least soluble salt whichcould be formed. A further great advantage of making use of the formation of a sparingly soluble salt of a strong acid in the resolution of externally compensated bases is found in the fact that such sparingly soluble salts are not decomposed by feeble acids.Thus, a fairly serviceable method of obtaining lavotetrahy droquinaldine dextro-a-bromocamphor- sulphonate consists in adding an aqueous solution of one molecular proportion of ammonium dextro-a-bromocamphorsulphonate to an acetic acid solution of two molecular proportions of the externally compensated base; the solution soon affords a copious deposit of crystalsof lsvotetrahydroquinaldinedextro-a-bi~o~oc~mphors~il~~~onate. I. LEVOTETRAHYDROQUINALDINE, L~votets.n~~ldPoz2Linalclilze DeztTo-a-bro~)1oca~~~p~~o~8su~~~~o~~(~CloH13N,Clo H,,BrO*SO,H. The most convenient method of preparing laevotetrahydroquinaldine dextro-a-bromocamphorsulphonate consists in mixing a hot con-1068 POPE AND PEACHEY: centrated solution of one molecular proportion of crude externally compensated tetrahydroyuinaldine hydrochloride with a hot concen- trated solution of one molecular proportion of the base in one mole- cular proportion of a concentrated dextro-a-bromocamphorsulphonic acid solution prepared as we have previously described (Trans,, 1898, '75, 895).By the time the solution has cooled to the ordinary tem- perature, the greater part of the salt of the laevo-base has crystallised ; the separation is filtered off, washed with dilute alcohol, and recrystal- lised from boiling absolute alcohol. After two recrystallisations, the substance is obtained as a mass of colourless needles melting at 323-225O. It is sparingly soluble in cold, and moderately so in hot alcohol or water; it is more soluble in glacial acetic acid, but nearly insoluble in acetone or ethylic acetate.The crystals deposited as the hot alcoholic solution cools are long, flattened needles with oblicluely placed end faces ; the extinction in the large flat face is straight with the sides, and through this face the bisectrix of a large optic axial angle emerges nearly normally. Tho double refraction is negative in sign and the optic axial dispersion is marked, the optic axial angle for red light being greater than that for blue ; the optic axial plane is parallel to the long edges of the crystals. No goniometrical measurements could be obtained. After melting the salt on a microscope slide under a cover slip and subsequently cooling quickly, it remains amorphous, and signs of crystallisation only appear a t the edges of the preparation after several days preserva- tion at the ordinary temperature.By alternately cooling and heating the liquid film several times, crystallisation may be started, and once started proceeds rapidly at temperatures not much below the melting point ; at tlie ordinary temperature, however, the crystallisstion proceeds with extreme slowness even after it has been started at a higher temperature. The crystalline film thus obtained consists of a radiate mass of long needles which crack across the direction of growth as cooling proceeds ; these needles are crystallographically identical with the crystals deposited from the alcoholic solution, and mostly show the optically negative bisectrix of a large optic axial angle emerging nearly normally to the plate.The following analytical results were obtained : 0.1969 gave 0.3793 CO, ancl 0.1104 H,O. 0.9654 ,, 25.9 C.C. of dry nitrogen at lGOand 749 mm. N=3*14. 0.6144 ,, 0.3534 AgBr and 0.3172 BaSO,. 5 r = 17.55 ; S = 7.09. C,oH2,0,NBrS requires C = 52.40 ; H = 6.11 ; N = 3.06 ; Br = 17.47 ; S = 6.99 per cent. The specific rotatory power of the salt was determined in absolute C = 52.54 ; H = 6.23. 0.1986 ,, 0.3843 CO, ,, 0,111 1 H,O. C = 52.77 ; H = 6-22.RESOT,UTION OF TETRAHYDROQUINAT.DIN E. 1069 alcohol and in glacial acetic acid solutions. A solution in glacial acetic acid of 0.5005 grain in 35.3 C.C. gave aU + 1-54' a t 31.3' in a 200 mm. tube, whence [a I,, + 38,s" a i d [Ill,, + 177.6". A solution i n absolute alcohol of 0.2005 grani in 25.2 C.C.gave a,+0*66° at 31' iii a 200 mm. tube, whence [ + 41.5" slid [ A1 J1, + 1W. Chef ully purified lrevotetr~tliydro~~iiinsldine dextro-a-brornocamplior- sulphonate is distilled in n current of steam with a slight excess of soda ; the base is obtained :is a colourless oil saspencled in the aqueous distillate and is extracted \I itli ether. The ethereal solution is dried with potash and the solvent distilled off; the residual pale yellow oil is then distilled uncle? reduced pressnrc. It passes over as a colourless oil boiling at 15s' under 59 inni. pressure, and is sparingly soluble in water, but miscible with the ordinary organic solvents ; it has a faint basic oclour and gridunlly beconies yellow on exposure to the air.The following nn:dgticul results were obtaiiied : 0.1Si6 gave 0.5593 CO, and 0.151 1 H20. 0.2977 ,, 34.6 C.C. of dry nitrogen a t 3loand 7GI mm. N=9.65. C = 81.31 ; I3 = 8.95. U,,H,,N requires C = 82-63 ; 13 = 8-84 ; N = 9.52 per cent, The base has a,-59*34' in n 100 r i m . tube a t 30'; whence [a],-5S.13° and [M]L,-S5*440 a t 20'. The relative density is 1.02365 at 14*5"/1". Further details as to the physical properties are given in a subsequent paper (this vol., p. 11 1 I), L c e t . o t e t , ~ * c c k ~ ( l ~ ~ o ~ u ~ ~ t ( ~ ~ ~ i ~ L e Hydvochloricle, C:,,,H,,N,IICl + H,O. A warm solution of piwe l ~ v o t e t ~ ~ l ~ y c l r o c ~ ~ u ~ i i ~ l ~ l i ~ ~ e in excess of concentrated hydrochloric acid yields on cooling a large separation of the hydrochloride as a white, crystalline pomdei- ; this is filtered on the pump? waslied with concentrated hydrochloric acid, in which the salt is moderately soluble, and recrystnllised from absolute alcohol.It melts a t 196*5--197*5'and is fairly soluble in water, less so in absolute alcohol, and sparingly soluble in acetone. The following analyses of the air-dried material show it to contain 1II,O which is lost a t 100" : Ob143S gave 0.1031 E20 and 0.3115 0,. 1,9828 lost 0.1765 H,O in 4 hours :xb 100'. C!,,H,,N,HC!l+ H,O requires C: = 59.5s ; H = 7.94 ; C1 r= 1'7.57 ; H,O = S.93 per cent. afterwards does not melt so sharply as before, C=59*55 ; €I= 7.94. 0.3162 ,) 03%S A.gUl. u1= 17.66. II,O=S*90. On prolonged heating at 1 OO', the material volatilises slowly, and VOL LXXV.4 c1070 POPE AND PEACHEY: The alcoholic solution, on spontaneous evaporation, deposits the hydrated salt. as large, transparent, lustrous tablets belonging to the orthorhombic system (Fig. 1). The form c{OOl) is dominant and gives very good results on measurement; the forms q{O11) and ~ { 1 0 1 ) are the next largest :tnd are well developed. The pyramid o(561) is always present and fairly large, but the dome d{501) is very rarely observed. There is a perfect cleavage parallel to ~ { l O l ) , and the optic axial iater- ference figure may be observed through a flake hacked parallel to b(010). The axis-b is the acute bisectrix, and the optic axial plane is af100) ; the optic axial angle is not large, and the double refraction is fairly strong and negative in sign.The optic axial dispersion is marked, the angle for red light being greater than that for blue. FIG. 1. FIG. 2, No evidence of the sphenoidal hernihedrisrn mas obtained. The form 0{561) is never completely developed, but usually only one half of its total number of faces is present; this, however, is apparently due to the crystal growing whilst resting upon the face c{OOT), which results in an imperfect development of those faces cutting tJhe negative end of the c-axis. Thus the crystals very usually present the appearance shown in Fig. 2, only the four faces (561), (561), (561), and (561) of the form o [56 1 being pisesent. We were unable to obtain any evidence of erantiomorphous hemihedrism by etching ; the action of water and alcohol upcn the faces of the pinacoid cjOOlf gives rise to etch- figures having the appearance shown in Figs.3 and 4 respectively, whilst upon a cleavage plate parallel to ~ ( 1 0 1 ) water produces etch- figures of the outline shown in Fig. 5. These figures appear t o be quite in accordance with holohedral symmetry. FIG. 3. tcM FIG, 4. up F I G . 5. Crystalline System.-Orthorhombic. a : b : c = 0 -8627 : 1 : 1 *4124. Forms observed.-c(OOl), p(O1 I}, r(101), ~'(501), and o(561).RESOLUTION OF TETRAHYDROQOINALDINE, The following angular measuremeiits were obtained : 1071 Anglc. cq =001 : 0 l i ‘14 = O l J : 011 c$J =001:011 cr = O O l : lo! 9’7’ = l O i : 101 C)’ =001: 101 C)” = 001 : 501 7.r’ = l 0 l : 501 w‘ = 101 : 501 ‘I/’ = 011 : 101 qo =011 :661 co =OOl: 661 co = O O l : 561 Number of observations. 37 14 12 41 16 24 70 11 14 6 18 15 7 Liini ts.54’19’- 55O11’ T O S - il 5 1.24 42 -12s 37 57 59-- 59 1 62 9 6:: 1s 121 4 ---l22 0 82 16 - 53 25 23 54 - 24 50 38 0 - 39 4 i d ii- 7’2 57 50 2 - 51 5 84 36 - 85 41 94 40 - 05 27 Mean observed. 5 i”42’ 70 40 165 15 5s 35 62 47 121 31 ti2 54 21 20 35 26 72 31 GO 35 85 4 94 59 Calculated. - iO”36, 126 18 6 2 50 121 25 83 2 24 27 35 23 i 2 28 50 40 85 9 94 51 - After cautionsly melting aiihydroiis I:-evotetrahydroqninaldine hydro- chloride under a cover slip 011 a microscope slide, it begins to crystallise quite readily a t about 60’, yielding a film which is macroscopically very transparent. As the temperature falls, however, the speed of growth decreases, and a t the ordinary temperature crystallisation proceeds so slowly that it cannot be followed microscopically, Further, the crystalline material obtained at temperatures not far removed from the melting point, consists of long needles or of large square plates showing straight extiiiction ; these are striated parallel to one side and the strice are the trace of the optic axial plane, n bisectrix of positive double refraction emerging normally to the large square face.The optic axes emerge outside the microscope field, and this material is of orthorhoinbic crystalline form. As the very transparent film cools, large patches of i t successively change with great rapidity, becoming very white and opaque; in a thick film, tho change is alinost explosive in character, sometimes even throwing the cover slip into the air.Notwithstanding this, it is very improbable that the change is due to polymorphism, as, although the material becomes so opaque, yet the optical properties can still be made out and are not appreciably altered; the rupture is apparently due to strain set up during cooling. At a little below the temperature at which the hydrochloride solidifies most readily, crystallisatioii still proceeds, although more slowly, the same modification being produced as at higher temperatures ; the crystallisation proceeds from ceutres just as before with production of radiate aggregates of long needles, showing well-defined extinction and optical properties. These aggre- gates, however, do not fly to pieces on cooling, but remain transparent, merely cracking across the longer dimensions of the needles. At the Q c 21072 POPE AND PEACHEY: In ailtieons solntion.ordinary temperature, the substance crystallises very sluggishly (about 1 mm. in 3 days), yielding a very opaque film showing aggregate polarisation ; this confused crystallisation is structurally identical with the broad needles produced so easily just below the melting point, because here and there in the mass transparent fragments may be observed having optical properties identical with those of the material produced a t the higher temperature, and also because no conversion of the one material into the other occurs on standing. Since crystallisa- tion only occurs readily at about GO', it is necessary, in order to obtain a crystalline film rapidly, to allow the hot molten film to cool until cryst.allieation starts from centres, and then to warm i t over the lamp until the whole has solidified.The rotatory power OF the hydrated salt, C!loI~$,IXCl + K,O, was determined in aqueous and absolute alcoholic solutions. 0,4932 gram, made up to 25.15 C.C. with water a t lS.9', gtve uD - 2.37' in a 200 mu. tube; 0.5451 gram, made ~p to 25.15 C.C. with absolute alcohol at 18*9', gave aD - 3.03' in a 200 mm. tube ; whence the following values : In alcoholic solution. C,,H,,N,HCl+ H,O ............... C,,H,,N,HCl ........................ C,,K,,N,HCI ........................ I I [a],, - 60.4" [ a ] , - 6 6 4 [MI, - 131.7 [a],) - 69'9" [a],, - 77.4 [MI,,- 140'8 Lcevotetral~~di.opui?zcclcliize Picrate, C,,T~,,N,C,H,(NO,),.OII. Laevotetrahydroquinaldine picrate is prepared by crystallising n mixture of the lxwo-base and picric acid in the requisite proportion from hot alcohol ; it forms dark yellow plates or needles melting at 148--150', but crystals suitable for goniometrical examination could not be obtained.It is sparingly soluble in water and moderately so in alcohol, acetone, benzene, or ethylic acetate. The following analytical results were obtained with material crystallised from absolute alcohol : 0-1693 gave 0.3145 CO, and 0.0670 H,O. C = 50.66 ; H = 4.39. 0,2146 ,, 0.4003 CO, ,, 0.0835 I€,O. C=50*S7; H=4*34. Cl,H,,07N, requires C! = 51.06 ; I€ = 4.26 per cent, A solution of 0.5014 gram, made with 25.3 C.C. of absolute alcohol at 20°, gave aD - 1.31' in a 200 mm. tube, wllence [.ID - 33.0' and [RI],, - 124'.Since the molecular rotatory power of hvotetrahydro. quinaldine in absolute alcohol is [bf]L, - 94*lo, it would appear that the picrate for the most part is not dissociated in alcoholic solution,RESOLUTION OF TETRAHYDROQUINALDINE. 1073 13enzoylZevotetrccl~ycEropzcinccltEine, C,,H,,N* COD C,H,. On suspending purified ltevotetrahydroquinnldine in warm caustic soda solution and running in rather more than the calculated quantity of benzoic chloride with continual agitation, an opaque, yellowish oil separates which rapidly solrclifies to LZ hard, crystalline mass ; this is ground in a mortar and filtered, being wall washed with water an3 dilute hydrochloric acid. The substance is best purified by crystsllisa- tion from acetone ; if, as sometimes happens, LZ green colouring matter is procluced, this is best destroyed by crystallisation from ethylic acetate.After ultimately crystnllising from absolute alcohol, the benzoyl derivative is obtained in colourless crystals melting at 11 7 - 5 4 1 So. It is very soluble in benzene and moderately soluble in cold alcohol, less so iu cold acetone or ethylic acetate ; it is nearly insoluble in light petroleum or boiling water. This substance is, as would be expected, appreciably more soluble than the corresponding racemic compound. The following resnlts were obtained on analysis : 0.1996 gave 0,5934 CO, and 0.1830 H,O. 0.6108 ,, 30.0 C.C. of clry nitrogen a t 21' and 7.55 mm. N = 5.69. C,,H,,OM requires C = 51.27 ; H = G.77 ; N = 5-58 per9 cent. I n order to obtain evidence as to the racemic nature of externally compensated benzoyltetrahydroqninaldine, it was necesswy to compare the densities and crystalline forms of the active and inactive sub- stances.The densities welie determined by Retgers' method (Zeit. ylqsill.cd. C'hem., 1889,3,497), using a solution of barium mercuric iodide diluted with water ; the results seem slightly more accurate than those obtained by Retgers with isomorphous mixtures, using organic liquids. The following results were obtained with crystals of benzoyllaevo- tetrahydroquinddine deposited from acetone or ethylia acetate solutions : C = 81.0s ; H = 6.84. 0.2066 ,, 0.6133 CO, ,, 0.12'76 H20. C=Sl.O-i; kI=G*86. c21~?'=1*2113 ; 1.2113 ; 1.2116 ; meau=1*3116 ; the molecular volume of the crystslline material is thus 207.1 6 at 14*5"/4".The crystallographic properties of the benzoyl derivatives of lavo- and dextro-tetrahgdroquinaldine were fully studied and compared ; the crystals of the two substances being enantiomorphously related, as was to be expected, the following crystallographic description includes both componnds. The opticrtlly active benzoyltetrahydro~uinaldi~ies are so soluble in benzene that good crystals could not be obtained from this solvent j1074 POPE AND PEACHEY: cold solutions in acetone or ethylic acetate, however, deposit on spon- taneous evaporation well-developed crystals suitable for goniometrical examination. The crystals are usually elongated in the direction of Pro. 7. the c-axis, and then a1-e generally developed o d y at one end; fre- quently, however, crystals o€ the typical habit shown in Pigs. 6 and '7 are obtained, and the examination of these crystals shows them to be FIG.8. FIG. 9. + 71" hemimorphic, the b-axis being polar. The pinacoids a(100) and b(010) are predominant, and generally of about the sitme facial development ; neither of these forms gives very good reflections. The form pw(il1) is usually fairly large, whilst the pyramid p o f l l l ) is quite small ;RESOLUTION OF TETRAHYDROQUINALDINE. 1075 crystals exhibiting the number of faces required in the holohedral di- vision of the monosymmetric system are often deposited from ethylic acetate solution, but the hemimorphism is generally betrayed by the unequal sizes of the faces, as in Figs. 8 and 9.There is a very perfect cleavage parallel t o cc[lOOj, and the acute bisectris emerges through a cleavage fragment a t the edge of the field ; observation of the estinctioii in b(010) shows that the acute bisectris lies in the plttiie of symuuuetry at 17.5” to the fnce-normal to ~~(100). Both optic axes are visible in convergent light uudor a l/l?lth inch oil immersion objective ; thc optic axial clispeilsion is marked, the optic asial angle for 13ed being greater thiill that for blue light. The double refraction is positive in sign, and the optic axial plane is perpendicular to the ylme of symnictry. Crystalline systcm.-~louohyiiillletric : Ileniimorpliic. CC: b : C = 1.0377 : 1 : 0.4361. p = 8S3 15’. Forms present on l ~ e n z o y l l ~ v o t e t r a l ~ y d r o ~ ~ ~ ~ i ~ i a l ~ ~ i n e (Figs.6 ixnd 8). -c(;lOO1, b;01O~,+pofllIf and +,u@i) ; sometimes also -pof11I) Pornrs present on beiizoyldeuti.otetrrLllyd~o~i~ii~:~ldii~e (Figs. 7 and 9).--~[100~, b10101, - - p o { l l l ; , -pzu[llli ; sometimes also + p o ( l l l ) -,,Lo;iii;. aacl + p‘”; 1 1 1 ;. The following angultir measurements were o1)tniiied : Azlgle. Calcnlat ctl . After melting the substnnce on a microscope slide un(ler n cover slip, tho liquid film can usually be cooled to the ordinary temperataro without any solidification occurring ; soinetiiiies, however, crystallisn- tion sets in whilst the film is very hot and then proceeds rapidly at the high temperature, but stops entirely when the slide cools. Tho crystallisation, having oiico st,arted, can be caused to proceed rapidly until complete by cautiously heating the film at ft temperature1076 POPE AND PEACHEY: below its melting point.The crystalline film consists of large, well- defined individual flakes; the larger faces of some of these are nearly perpendiculai- to the acute bisectrix of a fairly small optic axial anglo showing positive double ilefraction, but those of others are nearly perpendicular to tho obtuse bisectrix, in which the double refraction is apparently negative in sign. The optic axial dispersion is marked, the optic axial angle for red being greater than that for blue light. At the ordinary temperature, the liquid film solidifies very slowly indeed to a mass of interlaced needles showing aggregate polarisation ; some of these needles can be seen to lie perpendicularly to the optically negative bisectris of a large optic axial angle.Both the films obtained at high and low temperatures are probably structurally iden tics1 and also identical with the crystals deposited from solution. The rotation const:ints of benzoyllrc.votetrcihydroquindcline are of considerable interest, nticl show tlint the introduction of the acidic group has converted the 1,uro~otatory base into a highly dexti-o- rotatory compound. This is tlie more reinsrkn ble since the piperidine bases, dextro a-pipecoline, destroisopipecoline, coniine, and destroiso- coniine, have the specific rotatory powers [ + 369', + 33*29O, + 13*79", and + S.19" respectively, whilst their benzoyl clerivatives are also dextrorotatory and have tho values [.ID + 35.3?, + 33*35O, + 37*7", and + 29.1" respectively ; the introduction of the benzoyl group into the pipecolines scarcely nl tei-s the specific rotatory power (Ladenburg, Bey., 1893, 26, 854).A case somewhat similar to that of lxvo- tetrahydrocluinnldine and its benzoyl derivative has been iiivestigated by Forster (Trans., ISDS, 73, 386), who fiiuls that clextrobornylamine having [Ill,, + 69.6' yields a benzoyl derivative having the molecular rotatory power in alcoholic solution of [ill], - 56*0°, the molecular rotatory power thus changing by 126*63 ; in the case now recorded, a change of nearly 1000" in molecular rotatory power attends the conversion of the base into its benzoyl derivative. It is further of interest to note that, whilst the change of rotatory power occurs in the same mnke on passing from either bornylamine or neobornyl- amine to its hydrochloride and then to its benzoyl derivative, the direction of the cliange in rotntory power alters in the case of tetra- hydroquinaldine, as is shown in the following table : Rase ......................................Hydrocliloride in nlcohol.. .......... 9 , ,, water .............. Benzoyl derivative i n alcohol ...... I - 55'4" - 140's - 121.7 f 514 *7 Eoriivliuniiie, [MI,,. 4 69'6" $43'0 - 56 +O - Neobornyl- amine, [ h l ID. - 47'9O - 73.s - 114'8 -RESOLUTION OF TETRAHYDROQUINALDINE. 1077 The variation of the rotation constants of non-electrolytes with change of solvent has up to the present been but little stndied, its, with the exception of the work of Freundlor (dm.CJiim Z'Jqs., 1895, [ vii], 4, SSG), few results of theoretical importance have been derived from snch determinations. As, however, me sliow in a subsequent paper (this vol., p. 11 11) that vnlunble inforinntion concerning the strate of molecular aggregation of optically fictive substances is derivable from the variations in rotation constants referred to, a series of determinations of the specific rotatory powers of benzoyllzvotetrahydroqninsldine in vai*ious solvents hns been made. The results are stated in the following table, in which w denotes the weight of substance contained in v C.C. of solution a t teinpernture t, and c is the concentration i n grams per 100 C.C. of solution : Sol vent. lhnzcnc ............ ,, ............ ,, ............(!hl or0 f o m ......... A ce t one, .............. ICthyIic ncclate ... Acetic acid ........ Ethylic nlcoliol ... 11.. 0.2502 0 a . 5 0 0 7 1 .ooos 0.5010 0 . 4 99 3 0.5002 0 '5009 0'%000 2'. t. + 4.96' +9.9S + 19.93 4- 12.09 + 12.55 f 12'99 -?-1::.oo -t 14-41 [ J13 I,. + 623 '0" + 629.6 + 762.2 f 794'6 + 514.7 + 919.8 +911'1 + 630.8 IIydmlgsis qf 13eitxo!/llcevotP,i.l.rclr~cl~*oqzLii~~~~~l~~.--Siiice we proposed to prepare p r e clel;trotetraliydrocluin,zlcliiie by hydrolysing its benzoyl derivative, mid since nicemisation frequently accompanies chemical change, it mas desirable to ascertain whether benzoyl- hvotetrahydroquinaldine yields only the parent base on hydrolysis. The powdered benzoyl derivative WLS hydrolysecl by boiling for some days with concentrated Bydrocldoric acid ; after rendering alkaline with soda, and extracting with ether, the ethereal solution was washed with water m d evaporated to (zrynehs, hydrochloric acid being added towards the end.Tho crystidline hydrochloride was then ground up with acelone in an agate mortar, separated by filtration, and spread on a porous plate; it was colourless, and 0,5009 gram, dissolved in water and made np to 25.8 C.C. at 23*0", gave a,, - 3.63' in a SO0 mm. tube, whence [a], - 66.2'. This being the specific rotatory power of the Izevohydrochloride, i t is obvious that no rsceinisatioa attends the hydrolysis,1078 POPE AND PEACHEY: TI. EQUILIBRIA BETWEEN OPTICAL ISOMERIDES AND THEIR SOLUTIONS. EI?'CCCtZ.'O?LCd Crptcclliscition of C~zccle Dext~~otetrccl~yd~oquincckli~ze Dextrocnniplioi.su~~~onat z.Preliminary experiment,s showed that, on crystnllising externally compensated tet,rahydroquinaldiiie with destro-a-bromocamphor- sulphonic acid, the first separat,ion of 'crystals yielded a hvorotntory base on t,reatinent wit.11 alktdi ; similarly, it w:ts fonnd that, on c i y - tallising the iiiactive base with Reycliler's clext~rocam~~liorsiil~~ionic acid, tlie first separation of crystals gave a destrorotntory base when rendered alkaliue wit.11 socla and distilled in steam. We coiisequently expected that, after sepiw;zting the iiinjoi- 1)iLrt of tlic lzvo-isomeride as bromocnmpliorPulplion:tte, pire ~:lestroi;etri~liydr~~~~i~i~l~innldine woulcl be readily o1)t;tinnble from the mother liq~iors by isolating the base and converting it into dextroc~inpliorsulplio~~nte ; by recryst~dlising t.liis salt, we expected easily to obtain a pure salt of clestrot,et.ruliydro(~iiinxldine, and to dispense with the rather tedious process originally em- ployed by Laclenbuiig (fie?.., 1S94, 2'7, 77) f o r prepwing the destro- rotatory base. Singnlizrly eiioiigli, however, this plan was a failure, but the results obtained ;we of siiflicient interest to iiierit description.The crude destro-base was separated froiii tlie NO ther liquors and dissolvecl in a liot ethylic acetate solution of a molecular proportion of Reychler's dext roc.anipliorsul~~1ionic acid. On cooling, a copious separittion of t.he campliorsu1phona.t~ occurred, and this was re- peatedly crysttdlisecl from hot ethylic acetate, tlie s d t separating in colourless, aciculnr aggregates.The fresh crystals melt a t 65 -SOo, but after preliminary drying in a vacuum the iiielting point is 125-1 37" ; t.he lower inelting point is due ti.pp:irently to mechanically retaiiiecl solvent, because the crystals do not lose nplrecinbly in weighh at 100". The salt wts reci*ystnllisecl four t,irnes from ethylic acetate, the melting points, after hying, being (1) 1 2 1-1 3 3 O , (3) 125-1 2i0, (3) 135-13'io, and (4) l25-137", so t,li:Lt tlie material liad been recrystallised twice after att,aining the coustant melt,ing point 125-lSTo, and might rensonnbly be expected to be n pure salt. After treatment with soclii an51 distillation in steam, t,he base was obtained as a colourless oil boiling nt 156' under 54 nim.pressure. It gAre the rotatory power al,+ 39*4-i0 in a 100 niin. tnbe, and since the pure 1:evo-base gives aD - 59*3i0 in a 100 mu. tube, still contains about one-sixth of its weight of lt-cvo-base. The base ivas therefore again coiivei*ted into dest~oceii~pliorsulphon~ ate and crystdlised from boiling acetone ; the salt is very sparingly soluble in hot dry acetone, but dissolves readily if the solvent contains eeveral per cent. of water. The first separation melted at 125-12$",RESOLUTION OF TETRARYDROQUINACDINE. 1079 and after drying a t ZOO', a solution of 1 gram made up to 25 C.C. with water gave aD + 3.60' in a 200 mm. tube, whence [.ID + 45.0' ; the mother liquor gave a separation melting at 125-127', and after drying at 100° an aqueous solution of 0,4374 ,a~-nm of this, made up t o 25 C.C.with water, gave u,+1.53 in a 300 mm. tube, whence a,, + 44.3'. The main separation having [a],, + 45.0" was once more crystallised from acetone and again melted at 145---1373 ; an aqueous solution of 0,4374 gram of this in 35 C.C. gitve al, + 1.57' in a 200 mm. tnbe, whence [.ID + 44.9". These three fractions Iinving identical melt- ing points and practically the same specific rotatory power, the base wits again separated as before from the fritction having [air, + 44.9". After distillation under reduced pressure, the base had the rotatory power aD + 53.04" in a 100 mni. tube, a value considerably below that obt'ained for the pure Ix-vo-isomericle, namely, a, -- 59-24'. These results illustrate well the extreme difficulty which may be met with in isolating a pure salt of the type cZ13 clil, from a mixture of the types cZB clrf and Ill cld.Had we not possessed previous knowledge of the specific rotatory power of clestrotetrrtEiydroquinxIdine, we should, on the basis of the above results, have been justified in supposing the rotatory power of the destro-base to be uD + 53' in a 100 mm. tube. It is therefore necessary t o emphnsise the fact that in sepnrating a mixture of the type dB CEB, ZB tEA, no criterion of purity is necessarily afforded by the identity of melting point or rotatory power of several consecutive fri1ctions. Fructioncd C'rjystcdliscctioii of Crude I)extrotelrcc7c?lclropuisiccl~ille Hgdr och lwr it le . We have shown that l,.evotetrahyclroqiiinnldiiie hydrochloride has the coniposition C1,,H1,,N,HC1 + 8,0, whilst the mcemic isomeride is anhydrous ; it might therefore lie expected that by crystalliaing the hydrochloride of the destro-base containing a little of the lava-isomeride, dextrotetrahydroquinaldine hydi+ochloricle could easily be obtained in a pure state.Here ngsin we met with failure, and again the failure WAS more interesting than success would have been. A quantity of crude dextrotetrahydroquinaldine obtained in the manner described above from the inother liquors remaining after the preparation of l ~ v o t e t ~ n l i y d r o ~ ~ ~ i i i n l d i i i e destro-(z-bronrocaiiiphol.sul- phonate was converted in to hydrochloride, which wi~s then frnctionally crystallised from absolute alcoliol. The first fractions consisted almost entirely of the rnceiuic hydrochloride, which would be expected to be less soluble than its optically active com1ionent.s ; they had [ + 6' or + 7", and were only iuechanically contixminated with t'he dextro- hydrochloride by reason of adherent mother liquor.These fractions1080 POPE AND I'EACHEY: were recrystallised from absolute alcohol, and readily yielded pure racemic hydrochloride ; the mother liquors in which the dextro- hydrochloride had concentrated mere then added to the main mother liquor, and the fractionation continued. After a series of deposits had been obtained of this low rotatory power ( [ ~ ] , + 6 ~ to 7"), the specific rotatory power suddenly rose considerably ; thus a separation having [ .IL, + 6.28" was followed by one having [.ID + 41.90", and the succeeding fractions had specific rotatory powers varying from [aID + 55' t o + 58" in 2 per cent.aqueous solutions. Further, the repeated recrystallisation of these fractions failed on all occasions, with one exception, to yield a product having the specific rotatory power of dextrotetr~l~ydroquinaldine hydrochloride, namely, [a],, + 62.8' in aqueous solution, the specific rotatory power of the doposits varying from [u],+55" to +58". This behaviour showed that fractional crystallisation of a mixture of racemic and dextrorotatory tetral~ydroqnin~ldine hydrochlorides from alcohol could not be used as a practic:il method for obtaining the pure dextro-salt ; the racemic hydrochloride can be separated from the mixture until only a few per cent.of it remains with the deutro-salt, and further crystallisation fails to sensibly reduce this proportion. The explanation of this behaviour is to be found in Roozebooni's lucid discussion of the isothermnls for systems consisting of a solvent, a racemic compound and its optically active componeuts (Zeit. pkysiknl. Chem., 1899, 28, 494). In Fig. 10 the ordinates denote FIG. 10. the quantity of dextro-compound, and the absciss;le the quantity of Jsvo-compound in the saturated solution; the curve Zbcd is an iso- thermal representing the composition of saturated soltitions of the dextro- and lwo-compound and their mixtures at some particular temyerature. The branches Zb and dc of the curve represent solutiopsRESOLUTION OF TETRAHYDIiOQUINALDINE. 1081 in contact with levo- or dextro-material respectively, in contact, therefore, with one solid phase ; the branch bc represents solutions in equilibrium with the raceruic compound, again, therefore, with one solid phase.The points b and c, however, represent solutious which are in equilibrium with two solid phases, namely, the racemic and one optically active component. Suppose we start with a solution contain- ing both dextro- and lrevo-material in the proportion corresponding t o the point, Jl on tlie curve ; on crystallisation, the solution mill deposit raceniic compound, and the composition of the saturated mother liquor will change in the direction of the point c ; after the composition at c is reached, the subsequent fractions mill be of identical composition and specific rotation, b d h dextro- and raceiuic salt being deposited in a fixed proportion, and the solution retaining the composition at c until the whole of the solvent has evapor;tted.These considerations hold if the temperature of crystallisation remains constant, and in our attempts to isolate the dextro-salt from the mixture, crystallisation always oc- curred at the ordinixry temperature ; in spite of slight temperature fluctuations, me mere in general unable to change the composition of the mixture to any serviceable extent from that at the point c. This is ap- parently the first recorded instancein which equilibrium in contact withan optically active and racemic pliase at the point c has iiiterposed practical difficulty, and me hoped to overcome the difficulty by sowing dextro- hydrochloride into supersaturated solutions obtained by lowering the temperature or by cooling saturated solutions in contact with the dextro- salt so that the solution becomes a labile one of composition lying upon the branch ac.Only on one occasion, however, did we succeed in getting a separat ion of pure clextro te t rah y droquinaldine liy drochloride. This is somewhat noteworthy, because Bipping and Pope observed just the converse beliaviour with mixtures of potassium sodium dextro- and laevo-tartrates (Trans., 1899, 77, 45), and pointed out the ease with which ‘( a racemic compound might, under certain conditions, be resolved into its optically active components by simple crystallisation at tem- peratures at which the racemic compound is more stable than the mixture of the two optically active salts.” Attempts were made to change the composition of the solutions of the mixed hydrochlorides from that represented by the point c by alternate crystallisations from two solvents, on the supposition that the com- position a t this point mould differ for various solvents; our efforts in this direction were not successful, the only useful solvent besides alcohol being a mixture of alcollol and acetone.1082 POPE AND PEACHEY: Il'mctioiza Z CrystallisatioPz of Jiixtwes of Deetyo- and Bcicentic Benxoyt- t e t mlyd r o pzc i.r mldine.I n spite of our failure to isolate pure dextrotetrahydroquinsldine hydrochloride in quantity from its mixture with the racemic compound and the consequent expectation of a similar behaviour with the benzoyl derivatives, we mere able easily to obtain beiizoyldestrotetrsliydroquin- nldine in quantit8p by fractionally crybtallising a mixture of this sub- stance with its raccmic isorneride.Since we have previously shown that no raceinisation occurs on liyclrolysing bemoyllrevotetrahydroquin- aldine, we could readily obtain pure destrotetraliydroquinaldine in quantity from its beuzoyl derivative. The conversion of the mixture of clextro-base with a much smaller proportion of its hvo-isoruericle into benzoyl derivative is effected as previously described (p. 1073) ; the benzoyl derivative is then system- atically fractionated from its hot acetone solution by recrystallising the early separations, which consist largely of the raceinic compound, and adding the opticidly active mother liquors to the main solution. After the greater part of the raceniic material present has been eliminated, the subseqnent deposits consist of nearly pure benzoyldextrotetrahydro- quinaldine,mhilst occasionally a separution of low specific rotatory power occurs ; by continuing the fractionation and determining the specific rotatory power of each deposit, practically all of the original benzoyl derivative may be obtained in two lots, the one inactive, and the ocher baving [ u ] ~ - 2 .1 7 . 4 O in a 3 per cent. benzene solution a t 16'. Since our specimen of pure beuzoyl1~votetrahydroclrrin:Lldiiie had [ uID + 247.3' at 15" in benzene solution, the materid of [I air, - 247.4" is obviously a pure snbstiince.I n this case, therefore, the existence of the equilibrium point c (Fig. lo) causes no practical difficulty, owing, doubtless, to a greater facility of supersaturation. 111. DEXTROTETRAIIYD~~OQUINALDINE. Ir:en~o~~tlezt~otetrccl~~dl.oq'ZLiiZCilCZi.r2e. The general properties of benzoyldextrotetrahydroquinaldine need no separate description ; its crystalline form has already been discussed (p. 1074), and analyticd results proving its composition have been obtained. The deterniinatioiis of the density of beazoyldextrotetrshydroquin- aldme were niacle in the same way as were those of the antipodes and with the following results : ,,,14%. - - 1.2111 ; 1,2115 ; 1.2115. Alean= 1.2114, The iiiolecular volume at 15*6°/40 is thus 207.20 ; the mean density andRESOLUTION OF TETRAHYDROQUINALDINE. 1083 molecular volume differ by only 0.03 per cent, from the corresponding values obtained for benzoyllfevotetrahydi-oquinaldiiie.Benzoyldextrotetrahydroquinaldine is highly l,.evorotatory, and i t s rotation constants are given in the following table : Hoiixeiie ............... ,) ............... ) , ............... ) ) ............... C!llloroforlll.. .......... Bceto11u ............... E t.liylic acc- tate ...... Acetic acid ............ Etliylic a h a ( )I101 ...... w. - 1. 1 so 19 I 3 1 i I i 1 i I i l i I T 17 - a I,. A co1ilpikriso11 of these iiiimbers with those olhinecl with the antipodes shows tliat tlie two sets dif'fer nritmlmeticnlly but slightly, the difference being at8tributable to tlie different working temperature.In both cases, the solutioiis in glacial acetic acid Show far the highest rotation constiin t s. L)e;~~trotetrcch!/~~rozu~~~~~ Ztliiie. For the preparation of this base, finclr-powdered ~)enzoylclestrotetr~- hydrociuinaldiiie is heated in n yeilux al)pai-;ttus with excess of con- centrated hydrochloric acid ; after several ditys' heating, a copious separation of benzoic acid occurs 011 cooling, and ilie hydrolysis is complete. Slight excess of socln is :dcled and the product distilled in a current of steam ; the base is estr:icted with etlier niid purified RS before described ; the purity of the product \vils ascertained by it de- terminrttiou of its density and specific rotatory power. The density was found to be tl'.';: 1.01926, nud the rotatory power mas a,+5!3.2l0 in n 100 turn.tube at 20°, mlieuce [u],+58*01) at 20". Ladenburg gives the rotatory power, aI, + 6S.35" in a 100 im~. tnbe at IG", for this base, and calculates the specific rot;~tory power as [ a ID + 55*09O ; the density number, d';'' 1.043, which lie uses is somewhat too high (Ber., 1S91, 27, 76). I) ext yo t e t r*uliplclm pi n cc Z tliiz e II&o ck lor ide, C, 11 N, I4 C1+ 1% 0. The hydrochloride of dextrotetrr~liSdroquiiialdine was prepared i n the same may as t h a t of the lrevo-isoiiieride. It crystallises i n large, orthorhombic monohydrated tablets which melt at 196.6-197*5°, and are crystallographically indistinguishable from the crystals of the laevo-isomeride (Figs, 1 and 2, p. 1070).1054 POPE AND PEACHEY: The specific rotatory power of the salt dried a t 100' was determined in aqueous solution; 0.4806 gram of the anhydrous salt, made up to 25.3 C.C.with water a t 2 1 * 4 O , gave uD + 2'51' in a 300 mm. tuWe. The specific rotatory power is thus [ a ] [ , + 66*1', which compares perfectly well with the value [ alD - 66.4' obtained for laevotetrahydroquinaldine hydrochloride (p. 10.72). LV. ~IOLECULAR ROTATORY POWERS OF SALTS OP OPTICALLY ACTIVE BASES WITH OPTICALLY ACTIVE ACIDS. A simple law should connect the inolecular rotatory powers of optically active salts of the type d13 dA and 112 d A , in fairly dilute aqueous solutions, provided that the base aid acid, 1; and A , are so strong that the salts are pr:ictically wholly dissociated. The algebraic cliff erence between the molecular rotatory powers of the two salts should be equal to twice the molecular rotatory powers of the hydrochloride or similar salt of the active base, whilst the algebraic sum should be equal to twice the niolecular rotatory power of a metallic salt of the active acid.Since the truth of this consequence of the electrolytic dissociation hypothesis has previously only been tested by Walden upon Ealts of feeble bases, like morphine (Zeit. plqsSaZ. Cltem., 1894, 15, 206), it seemed desirable to prepnre salts of the strong bases, dextro- and Ievo-tetrahydroquinaldine, with a powerful optically active acid, when the principle enunciated above should be found to hold even more rigidly than in the case referred to. For this purpose, the salts of dextro- and Izevo-tetrahydroquinaldine with Reychler's destro- csmphorsulphonic acid mere prepared ; the former salt.wag also required in orcler to compare its properties with those of the impure compound obtained in the fractioaal crystnlliastion of the mixture. Dextrotetmh~lcl~oqu~~~c~Zi~~~~e L)extrocc~n~~~~o~s.zc~~l~onicte, Cl,~I~,,N,C,,H,,O~SO,H. Dextrotetrahydroquinaldine dextrocninphorsulphonate is obtained by crystallising a benzene solution of the component base and acid in long, colourless, flat prisms melting a t 128-129"; the prism zone is com- posed of six faces, whilst ruther obliquely placed end faces complete the crystal. An optic axis is observed to emerge through the large face, and the extinction in this face is practically parallel with the longer sides ; the crystals are very possibly anorthic, but good crystals could not be obtained for measurement.The salt is soluble in the ordinary organic solvents, including carbon bisulphide and ethylene dibromide, The following analytical results mere obtained with material dried a t 100' :ltESOLUTlON OF TETlihHYDROQUINAT~DINE. 1085 0.1246 gave 0.2887 CO, and 0.0879 H,O. 0.1317 ,, 0.3054 CO, ,, 0.0923 H,O. C = 63.24 ; H = 7.79. 0,4162 ,, 0.2699 B~xYO,. S=8*93. C = 63.18 ; H = 7.84. C,,H,,O,NS requires C = 63-32 ; H = 7.65 ; S = 8.64 per cent. The specific rotation was determined in aqueous solution : 0.507'7 grain, made up to 25 C.C. with water a t 19*1', gave a, + 1%5O in a 200-mm. tube ; whence [air, + 45.7" and [MI, + 173.3O. I n discussing the fractional crystallisation of a mixture of the dextro- caniphor~;ulphon,ztes of destro- and I~vo-tetr,zhydroquinaldine, it wts pointed out (p.1079) that we were unable to obtain tlie destrocainphor- sulphocate of a higher specific rotatory power than [ aID + 45.0' in aqueous solution, arid that this salt yielded a base having the rotatory power u~,+ 53' in place of + 59' ; since it is iiow shown that dextro- tetrit1iydroclnin:ldine clestrocani~ho~sulplioi~ate has [ u ID + 45*7', i t is evident that the inaterial previously obtained was, as we stated, still coiitnmiiiated with salt of the liero-base. Lcevo~etrccr7L2/~I~oqui,~a~cEis~e next,.ocnniiil~ol.szc~)?~o~ante, U , , , I r I , , N , C l o ~ ~ , , O . s ~ ~ ~ ~ . LE vot et rsh y clro~uinnldiiie d ex trocalllphorsulphon~ t e is prepmed by crystallisiug the requisite quantities of the biise and acid together from benzene solution ; it sepwates in colotirless, flattened needles melting a t 137-138".The needles are scluilre ended with truncated corners ; tlie extinction in the large face is sti*;light with the sides, aiid a, bisec trix emerges perpendicu1:wly through the face. The following analytical results mere obtained with material dried at 100" ; 0.2022 gzve 0.4680 CO, and 0.1416 H20. c! = 63.12 ; H = 7.78. 0.1209 ,, O.BS02 GO, ,, O.OS82 H,O. C = 63.21 ; 11 = 7.83. 0.4615 ,, 0.2S3S BdW,. 8=8*85. C,,H,,O,NS requires C = 63.33 ; I€ = 7.65 ; S = 8.64 per cent. 0.5073 gram, made up to 35 C.C. with mster at 19*1", gave aI, - 0.74" in a 200 mm. tube, whence [a]D - 18.3' and [ 1x3, - 69.5". Amntonium I)e~t,.ocai,LI~~oi.su~)~o~L(ite, C,,€I,,O*SO,NH,.The ammonium salt of des trocamphorsulphonic acid has been described by Reychler (Bull. Soc. C'him., 189S, [iii], 19, 120); we obtained it in long, colourless needles which, after drying at loo", gave analytical results agreeing with those required for the above formula. The following rotation determinations were made : 0.2503 gram, made up t o 25 C.C. with water a t 16", gave aD+0.i2* in a 200 mm. tube ; whence [ a ] , + 21*Oo. VOL. LXXV. 4 D1086 POPE AND PEACHEY: 0*5000 gram, made iip to 25 C.C. mith water at 18', gave uD+ 0.83' in a 200 mm. tube ; whence [.ID + 20.7". 1.0008 grams, made up to 25 C.C. with water at 18', gave aD+ 1.65' in n 200 mm. tube ; whence [.ID + 20.6'. Since we are dealing all through with solutions of about 3 per cent., me may take for compsrison with other salts the values [a I,, + 80 7' and [ 111: JD + 51.7'.The following table gives the specific and molecular rotatory powers of the various salts of dextrocamphorsulphonic acid with which me are concerned : d-C,,Hl SN, h C ' , ,,HI 5 0 *SO:3TI .................. Z-CIO H,:jN, d-("lo If l,O*SOylI ................. I-C,nI-TI ,N, HC1,. .................................. NH,, d-C?,oH,,O*SOsH ........................ $ 4 5 7 ' - 18.8 - 66 '.I + 2 O ' i -t 173.3" -I- 5 1 . i -69.5 7 1 - 121 *7 The algebraic cliff erence between the molecular rotatory powers of salts (1) and (2) is 343.8' and the half of this, namely, 121*4', should be equal to the molecular rotatory powers of active tetrahydroquin- aldine hydrochloride, namely, 12 1.7'.Further, the algebraic sum of moleculas rotatory powers (1) and (2) is 103.5, and the half of this, namely, 51*3', should be equal to the molecular rotatory power of ammonium dextrocamphorsulphonate, namely, 5 1 *7". The agreement even in these comparatively concentrated solutions is very close, V. EXTERNALLY COMPENSATED TETRAHYDROQUINALDINE. For the preparation of the tetrnhydroquinnldi~ie used in the present work, quinaldine was reduced with tin nud hydrochloric acid essen- tially as described by Walter (fie,.., 1S92, 25, 1261); when the reduction was complete, slight excess of soda mas added and the liquid subjected to prolonged clistillntiou in a current of steam. The tetrah ydroqninnldi ne was oxtr;tc t ed from the dis t illiit e with ether, the ethereal solution dried over potash and fractionally distilled ; the fraction boiling a t 240-250' wils taken as containing a11 the hydro- quinaldine and is sufficiently pure for immediate resolution into its optically active components as described above.Racemic Tet,.cc~~cll.oi.rLincclcl.iize IIyclrocl~loricEe, C1,,H,,N,HCl. A quanbity of the crude base boiling nt 240-250' was dissolved in large excess of hydrochloric acid aucl the solution allowed ta crystal-RESOLUTION OF TETRAHYDROQUINALDINE. 1087 lise ; the deposited hydrochloride was crystallised a number of times from absolute alcohol and then melted a t 196-197-5'. This salt was prepared by Fischer and Steche (Anncdeiz, 1887, 242, 358) and de- scribed as not very soluble in water, but easily soluble in alcohol ; it is, however, less soluble in alcohol than in water.Our analytical results show that the salt has the composition C,,H,,N,HCI, as deposited from aqueous or alcoholic solutions ; it is consequently a true racemic compound, because its optically active components under similar conditions ci-ystallise with water. I t separates on spontaneous evaporation of its pure aqueous 01' alcoholic solution either in small, colourless, transparent crystals of rhombohedra1 habit, or in lon& thin needles, both melting at 196-197*5°. These crystals are very poorly developed and the faces slicw considerable striation ; on microscopic examination, they are usually found t o be composite, a lnmellated twin structure somewhat resembling that characteristic of labradorite being observed. The goniometricnl examination of these crystals gave no result other than that the crystals are geometrically pseudorhom- bohedral in accordance with the lamellation detected microscopically.Large crystals better suited for measurement are obtained by spon- taneous evaporation of a solution of the salt in hydrochloric acid ; these consist of large, colourless, transparent tablets of Door facial development. The form c f 001) is domiii:mt Fro. 11. L (Fig. 11) and the prism p{ 110) is also well developed ; the pinacoicl CI [ 100) is usually smaller, and the faces of the dome r[lOll, are only observed as narrow replacements. There is nn extremely perfect cleavage parallel to c(OO1) and, when hacked in other directions, the cryst.& merely shear parallel to the cleavage. A bisectrix of positive double refraction emerges nearly normally to c(001), but the orientation or" the optic axial plane could not be ascertained.Crystalline system.-Monosymmetric, C.C b : ~ = 0 * 9 3 4 : 1 : 0.035. p= 71" 46'. Forms observed.-cc(100}, c(OOl}, p{110}, and ~ { l o l ) . 4 D 21088 POPE AND PEACHEY: The following angular measurements mere obtained : Angle. a11 = 100 : _I10 271, = 110 : lL0 pp =110 : 110 CM: = 1 0 0 : ~ 0 1 CT =001 : 101 fir =lo0 : 101 C]? =001 ' 110 C]? =ooi:rio p r =110 : 101 Number of observations. 31 18 15 42 31 3s 44 14 8 Limits. 40'48'- 42" 7' 96 4- 97 52 82 26- 84 1 70 4 i - 72 12 53 43- 55 26 53 6 - 55 13 75 19 - 77 14 102 54-101 7 63 0- 64 56 Mean. 41'35' 96 53 83 19 il 32 54 42 6 4 5 76 25 103 29 63 49 Cnlcnla tcd. - 96"50' 83 10 71 46 54 9 - - 103 32 63 55 After melting the racemic hydrochloride, it solidifies whilst hot less readily than the lavo-isomeride, but when cold solidifies with distinctly greater rapidity; it is quite easy to obtain a liquid film of the racemic substance at the ordinary temperature, but after 48 hours most of the liquid has crystnllised.On allowing the liquid film to cool considerably below the melting point and then again warnling, the whole may soon be made t o crystnllise ; crystallisation proceeds from centres and results in the production of broad, individual flakes, which are usually striated in n direction parallel to the extinction. The strk are parallel to the trace of the optic plane in the fragment, and a bisectrix emerges nearly norinally to the filce; the optic axial axes are outside the field, and the double refraction of the bisectris, probably the obtuse one, is of positive sign.As cooling proceeds, the plates crack considerably along lines perpendicular t o the direction of growth. Optically, this material is very similar to :'he orthorhombio plates of the hvo-hydrochloride, but morphologically it seems very different, the s p a r e plates never being observed ; the inactive material produced at the high temperature does not fall to pieces during cooling in the violent manner affected by the optically active substance. On rapidly cooling the molten film to the ordinary temperature, it remains liquid, but after a day or so a fringe of the modification described above, which polnrises brilliantly, forms round the edge of the preparation and subsequently a macroscopically opaque growth makes its appearance in the body of the film; this growth consists of minute, square-ended needles showing oblique estinction and, being of low double refraction, yolarises far less brillimtly than the first- described modification ; the needles exhibit an oblique optic axial emergence and are interlaced in a highly confused manner.After several days, this modification occupies nearly the whole of the film and encroaches upon the brilliantly polnrising fringe, the latterR ESO L U T I 0 N 0 1 T ETR AH Y D R 0 Q U I N A I, b I N E . 1089 Ftpparently becoming converted into the former. The externally compensated hydrochloride is therefore almost certainly dirnorphous.Race?& ~etr.al&ydl.oquinaZ~irre Picrute, C:,,H13N,C,H,(N0,),*OH, Racemic tetrahydroqninaldino picrate is obtained by crystallising the externally compensated base with the requisite quantity of picric acid from absolute alcohol ; it is more sparingly soluble in organic solvents and in water than the picrate of the hvo-base. The crystals deposited from the alcoholic solution melt a t 153-154’ and do not give good results on iiieasuremeiit ; they are apparently anorthic and consist of a predominant form n(100}, a smaller one, c[OOl}, and still smnller ones, p t l l 0 ; and p’(T10). The approximate angles are : QC = 100 : 001 = 74” 5.i‘ ((2) = 100 : 110 = 32’ 13’ cp = O O l : 110=8l 20 pp’= 110 :’110= 79 0 cp’ = 001 : 110 =; 7s 6 C$ =Too : i i o = 6s 47 There is a perfect cle2vage parallel to c(OO1) and the acute bisectrix emerges through ~ ( 0 0 1 ) ; the optic axial angle is large, the double refractim is negative in sign, and the optic axial dispersion is so marked that no defiuite extinction is observed for white light in c(OO1).The estinction in cc(100) is nearly straight with the edge ac, and the optic axial plane is nearly parallel to ~(100). The following analytical results were obtained with material crystallised from alcohol : 0.2055 gave 0.3523 CO, and 0.0829 H,O. C = 50.74 ; H = 4.48. 0.2107 ?, 0.3933 CO, ,, O*OSSS H,O. C=50*01 ; H=4*35. Cl,H,,07N, requires C: = 51.06 ; H =t 4-26 per cent. &xte~*nd~y Coqie?tsnted Tet,*nkyclror/u.i?anZdine, Cl,HI ,N. Carefully purified rscemic tetrahydroquinnldine hydrochloride is distilled in a current of steam with addition of a slight excess of soda ; the distillate is extracted with purified ether, the ethereal solution dried with potash, and the ether distilled off.The residual nearly colourless oil is then distilled under reduced pressure and practically all distils a t 196’ under 207.5 mm. pressure. The base has the same density as its Izvo-component, and its physical properties are dealt with fully in a subsequent paper, in which it is shown that this base is merely a mixture of the two optically active constituents, Rme?nic Beur;oy I tetycchyclroqu imcldine, Cl,Hl JY CO C, H,. This substance has been prepared from tetrahydroquinaldine by Walter (Bey., 1892, 26, 1 293), using the Schotten-Baumann reaction.It separates on spontaneous evaporation of its cold ethylic acetate1090 POPE AND PEACHEY: solutions in magnificent, lustrous, monosymmetric prisms (Fig. 12) melting a t 117-118°, and showing the form bf010) dominant ; the forms ~ ( 1 1 0 ) and q{Oll> are the next largest forms present, whilst the pinacoid a{ loo} is always small and frequently absent,. The pinacoid c(OO1) is well developed and gives good results on measurement ; the form ~(101) is generally well represented, whilst the form r’[lOl> is FIG. 12. FIG. 13. poorly developed and rarely observed. The crystals deposited from solutions in benzene (Fig. 13) differ greatly in habit from those obtained from ethylic acetate, and lend t homselves better t o crystallo- graphic measurement than do the latter ; they exhibit the form p[llO> predominant, and also shorn /(TO1 ] and o ( l l 1 ) well developed, whilst the pinacoids a[lOO) and b(010j itre comparatively small and frequently Frtr.14. absent, The facial development of the form ~ [ l O l ) is less than that of r ’ ( f O 1 t . Crystals are frequently deposited from benzene solution of the liemiliedrd habit depicted in Fig. 14 ; these consist of parts of the forms cfOOl), o(T11), and p [ l l O > . No indications of pyroelectrical properties could be obtained to show that this habit is due to hemi- hedrism, so that, it is probably due merely to abnormal conditions of growth.flESOLUT1ON OF TETRAHYDROQUINALDINE. 1091 Crystalline system .-Monosymmetric.CG : h : c = 0.6765 : 1 : 0.6675. /3 = S1° 4'. Forms observed.--(c~100~, b[010{, c[OOl), p [ l l O ! , q(Oll], ~ [ l O l ] , The following angular nieasnrements were obtained : + ( i o i ) nncl o p i i ; . Angle. up = l o o :110 ?y = 010 : l i 0 21p =I10 : 110 cq =001: 011 b y = 010 : 01-1 'I? =011:031 qr =011 : 101 pq =110 : 011 p,' =IlO: 101- pr'=llO : 101 pq =110 : y o qr'= 01 1 : 101 C/' = 001 : LO1 cr' =001 : 101 o / ~ ' = l O o : 101 or/ = l o o : 011 $7" =Oll : 111 ( I . ~ = l o o : 111 co =001 : 11 1 (31 =ill :Ti0 tp =go1 : 110 T'O =LO1 : 111 no =111:!11 (C/' = l(l0 : 101 bo =010 :111 ~11nll)cr of obserratioiis. I,il ni ts. 33'42' 50 17 67 29 3.3 24 5li 37 66 51 50 19 i 8 35 51 3 67 33 65 37 56 49 40 41 40 12 4s 56 49 57 s.:! :j t.; 48 '24 51 59 5-1 10 43 14 s2 33 27 14 5:: 5s 62 56 Chlculntcd.The extinctions in the faces b(010) and p(110) are practically straight with the side np. The obtuse bisectris emerges nearly normdly throngli cc{lOOj and the obtmse bisectris is chservecl through a section hacked nearly perpendicular to the zone [ O O l ] ; the optic axial angle is large and the double refraction is negative in sign. The optic axial dispersion is slight and tlie angle for blue light is greater than that for red ; tlie plane of symmetry is the optic mid plane. After melting, the substance solidifies fairly rendily a t high temper- atures, and the whole film niny be caused to crystallise by alternate heating and cooling; if, however, the film be rapidly cooled, it may be obtained at the ordinary temperature as n liquid film which crystallises extremely slnggishly.The crystalline film obtained at high temperatures is composed of long needles radiating from centres j1092 RESOLUTION OF TEI'RAHY DROQUI NA LDIN E. these extinguish nearly straight with the direction !of growth and, on cooling, crack extensively in different directions. Most of the crystalline individuals lie nearly perpendicular to the positive obtuse bisectrix of the optic axial angle and the optic axial plane is parallel t o the direction of growth. Sometimes the acute bisectrix emerges nearly normally to the surface of the crystal fragment; the optic axial angle is large and the optic axial dispersion slight. The double refraction is negative in sign. The optical properties of this modifica- tion agree closely with tliose of the crystals deposited from solution, and tlie two are structurally identical, so that externally compensated benzoyltetrahydroquinaldine melts and solidifies as a rncemic compound. The molten film nt ordinary temperatures crystallises very slowly, yielding a mass of needles which shows aggregate polarisation. The density of the crystals was determined as in the case of those of the optically active constituents with the following results : dli?= 1,3373 ; 1.2380 ; 1.33'73. iVIean- 1.3375. The moleculnr volume at 14.5"/'4" is thus 303.8. Since tlie optically active benzoylt~trnhydroqninal~lines have the molecular volume 20'7.2 a t tho same temperature in the crystalline state, it is obvious that the crystals of the racemic substance conform to Liebisch's rule (Ansmlen, 1895,286, 140), their density being greater than that of their optically active components. I n the formation of crystalline raceinic benzoyl- tetrahydroquinaldine from its crystalline optically activo components at 14*5O, a contraction of abont 2.124 per cent. in volume occurs. VI. IXELTISCI POINTS OF ~PTIC'hLTAS ACTIYE AND EXTERNALLY COMPENSATED ISOMERIDES. The great interest which has been imported into the pestion of the melting points of optically active and externally compensated isomer- ides by the recent work of Roozeboom (Zeit. p l q d n l . Chem., 1899, 28, 505) rendered desirable the investigation of tlie melting points of the hydrochlorides and benzoyl derivatives of the tetrahyboquinaldines. Careful determinations of the melting points of highly purified racemic and optically active tetrahydroquinaldine hydrochlorides gave the values 196--107*5° and 19695-1 97*5O respectively ;.the melting point of the racemic material is not quite so sharp as that of the dextro- or hvo-component. An intimate mixture of about equal weights of racemic and 1;levo-material melted at 180-1 84". Similarly, active benzoyltetrahydroquinaldine melted at 117.5-1 1 8 * 5 O and the racemic material at 117-llSo, the racemic again melting less sharply than the active isomerides. A mixture of about equal parts of each melted at 108-110".ItESO1,UTION OF TE’l’RAHYDROPARATO1,UQUrNALDINE. 1093 Although the active and iiinctive isomerides melt at practically the same temperature, the externally compensated substance melts a s a racemic compound, and the melting point curves for t h e mixtures mould seem t o belong to Roozeboom’s Type 2 ; attention does not seem t o have been drawn previously to examples of this type. Our thanks are due to the Research Fund Committee of the Chemical Society for grants enabling the purchase of inaterials used i n the foregoing work.

ISSN:0368-1645    

DOI:10.1039/CT8997501066

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

ItESO1,UTION OF TE'l'RAHYDROPARATOI~UQUrNALDINE. 1093 THE ease with which 1r.evotetrahyclroq~iinnlciine ctm be separated from the externally compensated base by the w e of dextro-a-bromo- camphorsuiphonic acid (Pope aiid Pcachey, this vol., 11. 1 O M ) , suggested that interesting results might be obtained by applying the same method to Doebner and von Miller's externally compensated tetrahydropara- toluquinaldine (Re,*., 1583, 16, 2564) ; this base, which is described as being an oil at oidinary temperLttures, we find to be crystalline and to melt at 31-32O. When tt half molecnlur proportion of :Lmmoniuin dextro-a bromocsinphorsulphonate is added to a solution of one molecular proportion of racemic tetrahycli~op~ratoluquinaldine hychochloride, the hvo-base separates as the broruocamphorsulphonate, just as in the case of tetr~liy~l.oqiiinalcliue, autl this 1;evo-base melts a t 52-43'.This method, which is new in principle, should prove of service in similar cases and has already been applied to the prepara- tion of dextrotetrahydro-P-naphthylnmine (Proc., 1899, 15, 170). The crude dextro-base remaining in the mother liquors can be sub- sequently isolated as hydrochloride, 2nd from this salt the dextro-base may be separated in the pure state.1094 POPE AND RICH: I. LBVOTETRAHYDROPARATOLUQUINALDINE. On adding an aqueous solution of one inolecalar proportion of ammonium dex tro-a- bromocampb orsulplionat e to a war In, aqueous solution of two molecular proportions of racemic tetrahydropara- toluquinaldine hgdrochloricle, an oil sepmntes which solidifies to a crystalline mass as the solution cools.This crude lrcvotetmhydro- paratoluquinaldine clextro-a-bromocampliorsulphonnte is obtained as a mass of colourless ueeclles af t.er sever:d recrystallisations from hot dilute alcohol, It melts a t 195--196O, is moderately soluble in water or alcohol, and when dry is sparingly solul>le in acetone or ethylic acetate ; if a little nioisture is present, however, the soln- bility increases very considerably. The following analytical results were obtained with the salt dried ;it 100' : 0.1623 gave 0.3163 GO, 2nd 0.0957 II,O. 0.3561 ,, 0.1553 Aglh ttiitl 0.1932 EaSO,. BIB= 17.11 ; 8=6.59. C21H,o0,NBrS requires C: = 53.39 ; H = 6-31 ; Er = 16.95 ; 8 = 6.78 (1 =i 5:3*16 ; 13= 6.55. 0.2014 ,, 0.3'339 CO, ,, 0.1164 H,O.C=53*2 ; ll=6.3'7. per cent. On allowing its cold solution in a mixture of ethylic acetate and alcohol t o evaporntespontaneously, the s:tlt separates in large, colourless, transparent prisms (Fig. 1) belonging to the monosymmetric system ; 'I" the form ni100) is predominant and the prism p{110), although small, is usually the nest largest form present. The pinncoid c{OOlj is well-developed, whilst the Forms s * ( l O l j and ~'(101) are present only as narrow replacements ; the faces of the crystals are always more or less conchoidal in character and give very poor results on measurement. There is a perfect cleavage parallel to c(OO1) and the faces of the form a(1001 are striated parallel to the trace of the cleavage plane.RESOLUTION OF TETRAHYDROPARATOLUQUINALDIKE. 1095 Crystalline system.-Monosymmetric.a : b : c = 2.1766 : 1 : 1.2556. p = 78" 58'. Forms observed.-u( loo;, c lo01 ), p ( 11 O ) , Y( 101 ;, and y'(T01). The following angular measurements were olst:Liaed : Aiigle. f(T =loo : 101 ('?' =CJo1 : lo? (w'= 100 : _lo1 CY' =001 : 101 up = l o o : I10 11)) =110 : 110 pr =110: 101 yc =I10 : 001 p r ' = i i o : i o i Numbcr of observ:itioiis. 36 38 19 14 42 20 9 15 11 Limits. Mean. 51"5f' 27 1 cia 34 32 23 64 55 50 i 74 55 S5 26 80 57 Calculsteil. - - 6S031' 39 28 50 10 74 51 55 21 81 5 - The optic axial plane is the plane of symmetry and one optic axis emerges nearly normally tlirough a cleavage plrLte parallel to c(OO1) ; the other optic axis is seen t o emerge through cc(lOO), but not perpendicularly t o the face.The optic axial dispersion is slight ; the bisectrix emerging through u ( l O O ) is of positive sign and since this is the obtuse bisectrix the double refraction is negative in sign. After melting the substnnce on a inicroscope slide under a cover slip, i t crystallises with great reluctnnce from the edge of the prepara- tion i n long, flat, striated needles ; crystallisation is hastened con- siderably by alternate heating mid cooling. The optic axial plane lies across the longer dimension of the needles and the acute bisectrix sometimes emerges nearly normally to the plate ; the double refraction is negntive in sign. Usunlly one optic axis only can be seen emerg- ing through the needle and then the obtuse bisectrix of positive double refraction emerges in the microscope field.The crystalline film is thus crystnllogrnphically identical with the material deposited from solution. Carefully purified l~votetrahyd~oparntol~iquiiial~line destro-a-bromo- camphorsulphonate is dissolved in warm wnter and a slight excess of soda added, when the base separates as a colourless oil which solidifies completely on cooling ; the white, crystalline mass is collected on the pump, repeatedly \vilshed with cold water, and dried in a vacuum desic-1096 POPE AND ItICH: cator. On dissolving i t in petroleum boiling at 35-40’, and allodng the solution to evaporate spontaneously iu the air, lt~votetrahydropara- toluquinuldine separates in magnificent, lustrous, monosymmetric prisms (Fig. 3) several centimetres in length; i t melts at 55-53O.PIG. 2. F I G . 3. The crystals are enantiomorphously related to those of dextrotetra- hydroparatoluqninaldine, described Inter, and represented in Fig. 3 ; the forms (c(lOO], r ( l O l j , aud r’IlOT} are doniinant, sometimes the one and sometiines the other being the larger. Usually, the crystals are only conipleted at the one end, that, namely, on which the form o - (1 11) is developed ; the other end is frequently ragged or obliterated by an hour-glass shaped structure which groms from it into the cryst~l. Sometimes, however, the form b + (010f is present. Although the substance volatilises fairly rapidly in the air, yet the fuces give fairly satisfactory goniometrical results. Crystalline system.-Nonosymmetric : Hemimorpllic.(6 : b : c = 3.27-12 : 1 : 1-4339. Forms observed on 1% vote t ixhyd ropnra t oluquinald i ne. -a 100 >, Fornis observed on dost ro tetra11 ydroparn to1 uqnina1dine.-a ZOO 1, The following angular measurements were made on crystals of both r f I O 1 } , Y’(~OT), b + [OIO), and 0’-(1111. +M;, l y o i t , b - (ole), and O + 1111;. the h v o - and dextro-isomerides : n 11 g 1 c . Calc11ln ted. n/’ = 100 : 101 (w’ L 100 : l o i 1’”’ =lo1 : 101 (1.U =I00 : 111 01’ =A01 :101 OY’ = A1 1 : 101 00 =111:111 b/* =010 : 101 tbb =130 : 010 37 2s 35 16 32 14 16 12 15 G2‘14’-63‘3S’ G O 31 --TO 2 46 49-4; 36 77 36 -78 4’5 65 36 -66 42 5‘5 5s -53 36 i 2 58 - i 3 49 89 45 -90 21 89 40 -90 17 63” 3‘ 69 43 47 14 i 8 9 66 cj 53 16 73 21 90 3 90 1 - 69”43‘ 78 4 53 22 73 16 90 0 90 0 - -1lESOLUTION OF TETKAH YDROPU ATOLUQUIN ALDIN E.1097 I3cmene ............ Acetone ............ Chlorofonn. ....... Etliylic alcohol. ... The optic axial plane is the plane of symmetry and one optic axis is seen emerging through the face a( 100) ; the optic axial angle is large, and the optic axial dispersion slight. The double refraction is negative in sign and fairly strong. After melting on a microscope slide under a cover slip, the base solidifies readily from centres in long. needles, which extinguish parallel to the direction of growth; the optic axial plane is perpendicular to the direction of growth, and the optically positive bisectrix of a large optic axial augle emerges in the field. These long needles alternate with material showing aggregate polari- sation.This crystalline modification is identical with that deposited from petroleum solution. The following analytical results were obtained : 0.1148 gave 0.3439 CO, and 0.0979 H,O. C=81*69; H=9*48. 0.1258 ,, 0.3774 CO, ,, 0.1082 H,O. C = 8l*S3 ; H = 9-56. C!,,HI,N requires C = S1*98 ; H = 9.32 per cent. The specific rotatory power was determined in various solvents, and the results are stated in the following table : 21" O*:iOO2 25-3 - 3.20" . SO.9" - 130.2" - 130.3" 1s 0.5517 26.8 - 2.52 - 59.1 -95.2 -93.1 18 0'5013 25.25 -3.13 -78.8 -126.9 -155.4 1s 0'5329 25'2 - 2-56 -67.6 -1OY.!l -94.1 I I I I I I I In the last column of the ta..ble are given the molecular rotatory powers obtained by Pope and Peachey (this vol:, p. 11 16) for Izevotetra- hydroquinaldine in the various solvents used ; it is a very suggestive fact that the molecular rotatory power of the two homologous bases in benzene, acetone, and chloroform solution respectively are almost identical.Lsevotetrahydropariitoluquinaldiue is nearly odourless, and does not become coloured on exposure to light ; it is extremely soluble in the ordinary organic solvents, and was only obtained in good crystals from its solution in light petroleum. L~voleti.c~~?ldo~~~rnto Zuquinnldine li?/cl~ocl~ ZowXe, C,,H,,N,HCl+ H,O. A solution of the base in excess of warm hydrochloric acid deposits, on cooling, Itevotetrshydroparatoluquinaldine hydrochloride in minute, colourless, monohydrated crystals which become an hydrous at 100" and melt at 194-196". The anhydrous salt gave the following analytical results :1098 POPE AND RICH: 0.1146 gave 0,2803 CO, and 0.0850 H,O.C = 66.71 ; 13 = 8.24. 0.1954 ,, 0.3062 UO2 ,, 0.0937 H20. C -- 66.59 ; H = 8.30. 0.2531 ,, 0.1844 AgCl. C1= 18.04. CllHISN,HC1 requires C = 66.53 ; H = S.10 ; C1= 17.92 per cent. 1.6421 air-dried salt lost 0.1339 at 100". C,,~L3,,S,€ICl+ H,O requires H20 = S.35 per cent. A cold solution of the salt in hydrochloric acid deposits on spon- taneous evaporation large, highly lustrous, transparent crystals (Fig. 4) beloaging to the orthorhombic system and showing sphenoidal hemihedrism. FIG. 4. I . The crystals are onaiitiomorphoiisly related to those of dextrotetra- hydroparatoluquiiialdine hydrocliloride (Fig. 5). The piiiscoid b f 0 1 O ] is usually dominant, and the prism p ( l l 0 ) is the next largest form present.The pinncoids ccf100) and ~ ( 0 0 1 ; anti the dome ~ ( 1 0 1 ) are always small but well-developed ; the hemipyrnmid o + [ 1 11 is large, whilst the faces of the complementary form, w - (111) are present as minute, triangular replacements. The form y ( 0 l l} is always repre- sented by large, lustrous faces ; the crystals give very good results on measurement. Crystalline system-Orthorhombic. Sphenoidal hemihedrism. a : b : c = 0.S165 : 1 : 0.5703. Forms observed on crystals of lzevotetrahydroparatoluquinaldine hydrochloride.-n(lOO), b(010], c{OOl), p { l l O i , yfOl t i , ~1101f, o + (lll), and w - (111). Forms observed on crystals of dextrotetrahydropnratoluquinaldine hydrochloride.--o(lOO}, b10103, c[OOl), p [ l l O ; ., q[Oll), r(101), o - (1111, and LO -I- {lll).RESOLUTION OF TETRAHYDROPARATOLUQUINALDINE. 1099 The following angular measurements were made on crystals of both the laevo- and the dextro-isomeride : Angle. ap =loo : 110 p p =110 : 110 h(1 =010 : 011 ' q = O O l : 0 l l pq =011 : 011 i l d =loo : 001 co =001:111 2'0 =110 : 111 $10 =110 : 111 00 =111: 111 a0 = l o o : 111 nq = 1 1 1 : ~ 1 1 O l f i =I11 : 111 hf) =010 : 111 OW = 111 : iii bw = 010 : iii 0)' =111 : 101 itr = 100 : 101 bp =O?O : 1 l O Number of observations. 26 45 20 39 15 32 1 3 27 18 10 39 36 34 14 48 35 18 21 32 Limits. 3S942'-- 39O.10' 50 17 - 61 14 i S 0 - i S 59 59 49 - 60 41 29 li- 30 6 5s 41 - 59 47 S9 4 i - 90 15 41 39- 42 30 47 25- 4 s 1'2 131 49 -132 16 s 3 42 - 81 29 55 27- 59 0 30 58 - 31 33 62 7 - G2 51 64 32 - 65 12 49 44-- 50 31 114 38 -116 39 24 40- 25 27 54 51 - 55 19 BIean.39"13' 50 46 7s 27 60 15 29 43 59 20 90 0 42 3 47 56 132 1 81 6 58 45 31 15 62 29 64 56 30" 50 6 115 4 25 4 55 6 Calculated. 39'14' it3 2s 60 18 39 12 59 23 90 0 42 2 47 5s 132 2 84 5 58 45 31 15 62 29 50 7 115 3 25 3 55 4 - - After melting on a microscope slide, the anhydrous salt crystal- lises readily from centres whilst still hot in long, individual flakes enclosing long, penr-shaped, vacuous holes ; the flakes extinguish parallel to their direction of growth and crack across considerably during cooling. The pieces usually lie perpendicularly to the bisectrix of a large optic axial angle of positive double refraction; the optic axes emerge outside the microscope field.At the ordinary temperature, the substance solidifies very slowly to a finely grained inass showing aggregate polarisation. The following determinations of the rotation constants mere made : 0.5583 gram of the air-driecl salt, having the composition C,,H,,N,HCl+H,O, made up to 25.3 C.C. with watei. at '19', gave the value a, - 2*S6' in a 300 inm. tube, whence [ a ] , -64.7' and [1\1],- 139.7'. 0,4803 gi*am.of salt dried a t loo', having the composi- tion C,,H,,N,HC!l, made up to 35.2 C.C. with ivatIer at 19', gave the value a, - 2.69' in c?, 200 mm. tube, whence [ a ] , - 70.6' and [MID - 139.4'. The molecular rotatory power of lzevotetrahydroparatolu- quinaldine hydrochloride, namely, [MI, - 139 *5O, is considerably greater than that of lsvotetrahydroquinnldille hydrochloride, namely, [MI, - I2l*'i0 (compare Pope and Peachey, this vol., p.1072).1100 POPE AND RICH: ~e)LTo~ZIct:vbtetrcch?/~rol,nratoZuquinacldine, C,,H,,N* CO*C6H,. Ikevotetrahydroparatoluquinaldine hydrochloride is converted into i t s benzoyl derivative by agitation with warm soda and benzoic chloride ; the oily product crystallises on standing, and is purified by repeated crystallisation from hot acetone. It crystsllises in long, colourless needles melting at 100-101', and is fairly soluble in hot alcohol, acetone, 01- ethylic acetate ; attempts t o obtain crystals suit- able for goniometricnl nieasiireiiient mere uusuccessful. The following analytical results were obtained : 0.1926 gave 0.5746 CO, and 0.1 268 H,O.C: = 81 *40 ; H = 7.32. 0.1664 ,, 0.4964 CO, ,, 0.1102 H.,O. C=81.36; H=7.36. C,,H,,ON requires C = 81.51 ; 13 = 7.17 per cent. I t s specific rotatory power mas det,erminecl in a benzene solution containing 0.5150 grain in 25.1 C.C. at 18'; the rotatory power was found t o be ~ , + 9 * 3 9 " iu a 300 mm. tube, whence [ ~ ~ ] , + 2 2 9 ~ and [ XID + 606". Although the molecular rotatory power of benzoyl- lrevotetr~liydrop~~.;ltolucyuinttlclie, [ M],) + 606", is rather less than t h a t of benzoyll~votetriL!iyCiL'ocl~iinnldine, namely, [ 311, + 630", yet both derivatives of the lrero~otatory bases w e highly destrorot.itory ; the following table gives the molecular rotatory powers- [ 11 1, of the two sets of couipouncls : &Base in benzene.. ....................Hydrodiloriilc of I-base.. ............. 13enzoyl derivative of 7-Lasc ......... - 130'3" - 121.7 + 630 - 130.2" - 139.5 -t 606 11. DESTROTETRAHYDI~OPARATOLUQUINALDINE. The liquors remaining after t h e deposition of ltevotetraliydropara- toluquinaldine dextrobromocamphorsulphonate yielded a separation of dextro-base containing some of i t s limo-isomeride when treated with soda ; the base, with the addition of a molecular proportion of dextro- cainphorsulphouic acid, was dissolved in hot ethylic acetate, and on cooling a copious crystalline separation occurred. After several recrystallisations from boiling acetone, this materisl-dextrotetmhydro- prc~tolupinaldine dexts*ocanzpltomdphonate --was obtilined in colourless needles melting at 194-196". The salt is sparingly soluble in ethylic acetate or acetone but very soluble in water ; on treating i t s aqueous solution with soda, a product melting a t 37-40' was obtained,RESOLUTION OF T~TRAHYDROPARATOLUQUINALDINE. 1101 so that evidently it did not consist wholly of the dextro-base (com- pare Pope and Peachey, this vol., p.1078). Dextrotetrcch?lclroparatolzcpu.ilzctld~ne If'drochloride, CllHl,N,HC1 + H,O. The whole of the impure dextro-base was converted into hydro- chloride and the salt repeatedly crystallised from boiling acetone con- taining a little water; the solution was allowed to become super- saturated to a considerable extent, and crystallisation induced by scratching in order, if possible, to avoid the diaculty met with in isolating dextrotetrahydroquinaldine hydrochloride (this vol., p.1079). As the result of a series of crystallisations, pure dextrotetrahydro- paratoluquinaldine hydrochloride was o btsined as a colourless, crystal- line powder melting a t 194-196'. On spontaneous evaporation of its hydrochloric acid solution, the salt was obtained in large, sybenoidally hemihedral orthorhombic crystals, of which measurements are given above (p. 1098). The following analytical results were obtained with the anhydrous salt : 0.1335 gave 0.3261 CO, and 0.0988 H,O. C = 66.62 ; H = 8.22. 0,1248 ,, 0,3054 (20, ,, 0.0931 H,O. C = 66.73 ; H=S*29. 0.2709 ,, 0,1982 AgC1. C1=18*11. CllHl,N,HCl requires C = 66.53 ; H = 8.10 ; C1= 17.92 per cent. 1.7730 air-dried salt lost 0.1500 H,O a t 100". C,,H,,N,HCl+ H,O requires H,O = 8.35 per cent.The value aD+2*86" was observed in a 200 mm. tube with an aqueous solution containing 0,5125 gram of the anhydrous salt in 25.2 C.C. at 18', whence [.ID +70*3' and [ h f ] D +138.9', numbers agreeing closely with those obtained for the optical antipodes. Dextrot e tmh ylthoprat o h i quina Zclhae, C, H,,N. On adding soda to an aqueous solution of the hydrochloride, the base separates as an oil which immediately solidifies to a white, crystal- line mass; when crystallised by the spontaneous evaporation of its solution in light petroleum boiling at 20-503, i t is obtained in hemimorphic, monosymmetric prisms melting at 52-53', of which goniometric measurements are given above (p. 1096). The following analytical results were obtained : 0.1168 gave 0.3503 CO, and 0*1030 H,O.C = 81.80 ; H= 9.70. 0.1236 ,, 0.3701 CO, ,, 0.1074 H,O. C= 81.66 ; H = 9.66. CllHl,N requires C! = Sl.98 ; H = 9.32 per cent. VOL. LXXV 4 E1102 POPE AND RlCB! A solution of 0.4924 gram, made up to 25*3 C.C. with bengene at 19', gave ~ , + 3 * 1 4 ' in a 200 mm. tube, whence [ ~ ] ~ + 8 0 * 7 ' and [ R.l 1, + 129.9' ; the corresponding nuubers obtained for the laaw- rotatory base were [a], - 80.9' and [ MI, - 130.2'. INACT~VE TETRAIIYDROPARATOLUQUINALDINE. Externally compensated tetrahydroparatoluquinaldine was described by Doebner and von JIiller (Uer., 1883, 16, 2464) as an almost colourless oil, but we found, on treating its hydrochloride with soda in aqueous solution, that it separates as a colourless oil which readily solidifies a t the ordinary temperature and is but slightly liable to superfusion; it would seem therefore that Doebner and von Miller never obtained the base in a pure state, After purification by crystallisation from light petroleum boiling at 25-30', the base is obtained as ft white, granular, crystalline mass, melting at 31-32', The following analytical results were obtained : 0.1203 gave 0.3602 CO, and 0.1042 H,O.C-S1.65; H=9*63. 0.1189 ,, 0.3563 CO, ,, 0.1024 II,O. C=81*72; H=9*57, CllHl,N requires C = 81.98 ; H = 9-32 per cent. The base could not be obtained in measurable crystals by crystallisa- tion from any of the ordinary organic solvents; it is distinctly more soluble in light petroleum than are its active components. After melting on 9 microscope slide, it solidifies readily in six-sided, mono- Rymmetric plates, the top face being n(100); the forms c{OOl) and 9{011) are also present.The plane angle 011 : 011 is about 112O, the optic axial plane is the plane of symmetry, and the positive bisectrix and one optic axis emerge through cc( 100). This similarity between the crystalline forms of the active and inactive bases, and the greater solubility of the latter in light petroleum, suggest that the externally compensated base is either pseudoracemic or a mere mixture of the two antipodes j this question will be subsequently investigated, Rcccemic Tetrcclk ydyopumto Zu qui22cilclbie IIgdroch lor ide, C,,H,,N, HC1. After reducing paratoluquinnldine by Doebner and von Miller's method, racemic tetrah yd~oparatoluqninnldine hydrochloride is obtained as a white, crystalline powder which, after crystallisation from alcohol, melts a t 180--1-S3', and unlike the optically active hydrochlorides is anhydrous.On analysis, the following results.were obtained : 0.1147 gave 0*280S CO, and 0'0863 H,O. C = 66T7; €€= 8.36, 0.1193 ,, 0.291'7 CO, ,, 0.0886 H,O. Ca66.68; H=8*26. 0'2613 ,, 0.1907 AgCI, C1= 18.07. C,,H,,N,HCL requires C = 66.83 j H = 8e10 j C1= 1792 per ceut,RESOLUTION OF TETRAHYDROPARAT0LUQU"ALDINE. 1103 It is very soluble in water, less so in alcohol, and only sparingly soluble in boiling acetone. On spontaneous evaporation of its solution in dilute hydrochloric acid, it separates in large, colourless, transparent, mono- symmetric prisms of calcite-like lustre (Fig. 6). The pyramid w(il1) is usually dominant, and the pinacoid c{OOl} is well developed ; the forms FIG.6. o { l l l f and p(810) are generally small, but their faces give good results on measurement. The extinction in w l r l l } makes about an angle of loo with the edge cw, and there is a perfect cleavage parallel to w{ll l } ; the bisectrix of negative double refraction and one optic axis are observed to emerge through a cleavage plate, so that the plane of symmetry is the optic axial plane. Crystalline system-llonosymnietric, a : b : c = 1.4140 : 1 : 1*0601, p= S1° 5'. Poi-mu observed.-c(001), p { 2 l O ) , o{lll}, wC111). The folloming angular measiirements were obtained : Angle. co =001: 111 010 =111 :I11 cw = 0 0 1 : 1 g pp =210:210 cp = 0 0 ~ : 2 1 0 cp =001:210 pzo =210 : 111 00 =111:111 w z ~ = i i 1 : ii1 'LL'w=111: 111 Number of 111 easareIllL!ll ts.26 29 48 38 44 36 8 16 19 14 Limits. 43"46'--60' 1' 74 57 -76 14 54 46-5G 0 69 27-70 13 82 16-83 27 96 45-98 5 44 56-45 59 75 38 -i7 42 33 45-85 17 94 37-96 1 hlean. 49'24' 75 48 55 26 69 52 82 42 97 29 45 33 76 31 s4 36 95 27 Calculated. 49"68' 75 36 - - - 97 18 45 44 76 2 84 30 95 30 After melting on a microscope slide, the raceuic hydrochloride solidifies more readily a t the ordinary temperature than its active com- ponents. It solidifies quite readily whilst hot from centres in long needles containing irregularly -shaped vacuous bubbles. Many of the 4 E 21104 RESOLUTION OF TETRAIlYDROPARATOLUQU~NALDIN~. fragments are of the same shape as cleavage flakes of the crystals deposited from solution, and exhibit identical optical properties ; it is therefore proved that the molten mass solidifies 8s a racemic compound.Racensic ~e?~xo?lltetrul~?l~ro~arcctoluquinucltline, C,,H,,N* COO C,H,. On treating the racemic hydrochloride with soda and benzoic chloride, the benzoyl derivative is obtained with ease, and after recrystallisntion from acetone forms long, colourless needles melting at 103-10d0 ; i t is sparingly soluble in cold alcohol, acetone, or ethylic acetate, but fairly readily soluble in the hot solvents. The following analytical results mere obtained : 0.1886 gave 0.3S48 CO, arid 0.0852 H,O. C = 51-47 ; 13 = 7.36. 0.1339 ,, 0.3994 CO, ,, 0.0877 H,O. C = 81.35 ; H= 7.25. C,,II,,ON requires C = Sl.51 ; XI= 7-17 per cent. On spontaneous evaporation of its solution in acetone, the benzoyl derivative is deposited in large, colourless, transparent, monosymmetric prisms (Fig. 7 ) ; the yinacoicl 6{010) is dominant, and the form Fro. 7. Since none but pinacoid forms were ] is the smallest present. observed, the axial r;itioa could not be determined ; all the faces are of conchoidal character, so that the measurements are not very good. Crystalline system.-Moiiosyrnmetric. a : b : c = l p = S4" 11'. Forms observed.-cc{lOO], b[O10), and cfOOl). The following angular measurements were obtained : Nuinber of Angle. ~ observations. ~ ae=100 : 001 crb=lOO : 010 Be = 010 : 001 2 4 18 21 82"1i'-86"20' SS 29-91 55 90"O' SS 40-91 16POPE : RESOLUTION OF RACEMIC CAMPHOROXIBlE. 1105 There is a perfect cleavage on cc{lOO) and the extinction in 6(010) makes about 1 5 O with the edge a b . The optic axial plano is per- pendicular to the plane of symmetry, and the acute optic axial bisectrix emerges through c{OOl) ; the optic axial angle is fairly large, and the angle for blue is greater than that for red light. Our thanks are due t o the Governnient Grant Fund Committee of the Royal Society and to the Research Fund Committee of the Chemical Society for grants enabling the purchase of apparatus and material used in this work. GOLDSMITHS' I,I'RTITUTE, NEW C11OSS, S.E.

ISSN:0368-1645    

DOI:10.1039/CT8997501093

出版商:RSC    

年代:1899

数据来源: RSC

摘要:

POPE : RESOLUTION OF RACEMIC CAMPHOROXIBIE. 1105 cx. -The Appl ica t bz. qf Po we 1fu7 Opticnlly Active Acids to tJie Resolzctioiz of ExternaIly Compensated Bccsk Sicbstajizccs. IZesoliitioir of Ruccnzic Cay~hor- OX2132t~, By 11’ ILLIAN JACKSOX POPE. ALTHOUGH tartaric acid may be used in separating the constituents of inactive mixtures of powerful optically active bases, being a weak acid it cannot be successfully used in conjunction with weak bases. I n the present communication, it is shown that the separation is readily effected, even in the case of so weak a base as cnmphoroxime, by means of the strong acid Reychler lias prepared by sulphonating camphor, This acid mas chosen instead of destro-a-bromocainphorsulphonic acid, because it is not so hygroscopic as the latter, and it is possible, there- fore, t o avoid access of water in working with it.Raceinic camphorosiine (60 grams) and carefully purified dextro- camphorsulphonic acid (90 grams) are dissolved in a small quantity of boiling acetone; as the liquid cools, a crystalline, but not homo- geneous, product separates, of which f iirther quantities may be obtained from the mother liquor. The whole of the crystalline material produced in the operation is then fractionally crystallised from boiling ether in a series of beakers, the mother liquors going in one direction through the series, and the crystalline deposits in the other. As the systematic fractionation proceeds, it is noticed that the deposits become more sparingly soluble in the ether, and ultimately two pure products are isolated ; the less soluble substance is dextroczmphoroxime* dextrocainphorsulphonate, and the more soluble is lsvocamphoroxime dextrocamphorsulphonate. * Thr: name dextrocainplioroxiiiic is retniucd for the hvorotatory oxiiue obtained from dex t rocamplior.1106 FOPE : RESOLUTION OF RACEMIC CAMPHOROXIME, Bextvocampho~oxime Bextrocam~horsuJphonate, ~,,~Hl,NoOH,C,oHI,O*SO,H + H,O, Dextrocamphoroxime dextrocamphorsulphonste separates in long, colourless, transparent needles from its ethereal solution ; it is very soluble in alcohol, benzene, acetic acid, chloroform, and most other organic solvents, and tho solutions on evaporation usually become syrupy, and crystallise with difficulty. It is very sparingly soluble i n ethylic acetate or ether and is precipitated as an indistinctly crys t a l h e mass on adding light petroleum to its solution in benzene.On spontaneous evaporation of its cold acetone solution, i t separates in magnificent, lustrous, transparent, orthorhomhic tablets, sometimes 30mm. in length (Fig. 1). The pinacoid 6(010’, is predominant, and the dome ~ ( 1 0 1 ) is the next best form represented ; the form p(110) is larger than p’!210], and both are larger than the pinacoid af100). All the forms observed give fairly good results on measurement. The crystals exhibit no external signs of hemiheclral structure, but there is a very perfect cleavage parallel to t(010), aid on etching cleavage surfaces. with benzene, etch-figures of the appearance represented in Fig. 2 are formed ; two of the bounding sides of these figares appear FIG.1. PIC. 3. a parallel to each other arid to the axis-c, but the other two sides seem t o be not parallel, and to make different angles with the axis-a. It is very difficult to be absolutely sure of t,his, but the etch-figures seem to indicate the sphenoidally hemihedral crystalline structure of the material. Crystalline system.-Orthorhoruhic : Sphenoidal hemihedrism. : 6 : c = 1*2024 : 1 : 0.8943. Forms observed.-a(100), b(010), p{llO), p’{210), ~ { l O l ] .POPE : RESOLUTION OF RACEMIC CAMPHOROXIYE. 1107 The following angular measurements were obbained : Angle. bp =010:110 3?p' =11o: 210 up' = l o o :210 p'p'= 210 : 2 i o 0,. =loo : 101 P,. = l o 1 : 101 pr =110:101 p't =210 : 101 Number of measurements. 42 17 19 14 23 39 12 5 Limits.39'1 6'-40'18' 18 51-10 34 30 45 -31 26 61 30 -62 28 5" 59-54 1 72 46 -73 35 67 1-68 9 53 47 -59 34 Mean. 39'4 5' 19 12 31 3 61 59 53 29 73 17 67 38 58 11 - Calculated, - 19'1 4' 31 1 62 2 53 21'5 67 34 5 9 14 - The acute bisectrix emerges perpendicularly through a cleavage plate ; the optic axial plane is a( 100) arid t.he axis-b is the acute bisectrix. The optic axial angle is large, and the double refraction positive in sign. After melting on n microscope slide and cooling, the material crystal- lises very slowly ; crystallisation may be started and caused to proceed fairly rapidly by cwtiously warming the preparation. The crystal- lisnt,ion is very confused, but consists mainly of long needles, many of which lie perpendicularly to the acute bisectrix of n large optic axial angle ; the double refmction is positive in sign, and this modification is crystallographically identical with tlie crystals deposited from the acetone solution. Deutrocamphoroxime dextrocmphorsulphonate has an odour of camphoroxime, and on exposure to air the percentage of sulphur grad- ually increases, owing to volatilisatiou of the osime.The carefully purified material crystallised from acetone, pomderotl, and dried for 8 short time in the air, melted at 91-93", and gave the following results on analysis : 0.1785 gave 0.37'78 CO, and 0.1341 H,O. 0.3528 ,, 0.2113 EaSO,. S = 5.29. 1.1331 required 27.1 C.C. X / l O NaHO for neutralisation. C,oH,O-SO,H C=57*72 ; H=8*34. 0.1964 ,, 0,4140 CG, ,, 0.1 494 H,O. C: = 57.49 ; IT = 8.46.= 55.49. C,oH,30,NS + H,O requires c1 = 5'7.55 ; H = 8.39 ; S = '7.67 ; C,,H1,O*SO,K = 55.63 per cent. The rotation constants of the salt were determined in absolute alcohol solution; 0.4377 gram, made up to 25 c.c., gave Q~ + 0.15' in a 200 mm. tube a t 21' ; whence [ + 4.3' and [&I JD + 1'7.9'.1108 POPE : RESOLUTION OF RACEMIC CAMPHOROXIME. L~voccc~n~~horoxinze Dextrocccmp~orszcZ~~onc~t~, ClOHl,N*OH,C,,H,,O*SO3H + H,O. Lzevocamphoroxime dextrocamphorsulphonate is even more soluble in the ordinary organic solvents than the salt of dextrocamphoroxime, and the solutions in alcohol, benzene, and acetic acid become syrupy on evaporation in the air. It crystallises on spontaneous evaporation of its solutions in ether, ethylic acetate, and acetone in tiny needles melt- ing a t 90-91', and attempts to obtain measurable crystals were unsuccessful.The small crystals are remarkably similar to those of dextrocamphoroxime dextrocamphorsulphonate in shape and crystallo- graphic properties ; they are flattened upon a six-sided face, b(010), and the acute bisectrix emerges nearly perpendicularly through this face. The double refraction is positive in sign, and the optic axial angle is large ; the plane angle between the two faces corresponding to (101) and (101) on the salt of dextrocamphoroxime was measured as 111-117°, as against 107' on the latter compound. After melting the substance on a microscope slide under a cover slip, it crystallises very slowly a t the ordinary temperature from centres in long, flattened needles j these are crystallographically identical with the crystals deposited from solution, and their formation is hastened by gently warming the plate.The following analytical results, obtained with material crystallised from acetone, powdered and dried in the air, shorn that the salt has the same composition as that from dextrocamphoroxime : 0.1865 gave 0.3937 CO, and 0.1407 H,O. C = 57.57 ; H = 8.38. 0.2197 ,, 0.463'7 CO, ,, 0.1663 H,O. C = 5'7.56 ; H= 8.41. 0.3804 ,, 0.2371 BaSO,. S= 8.64. 1-2285 required 29.4 C.C. A7/10 NnI-fOfor neutralisation. CloH,,0*S03H C,oH3,0,NS + H,O requires C = 57.55 ; H = 8.39 ; S = 7.67 ; CloHl,O*SO,H = 55.63 per cent. Although it seems to be proved by the analytical results given above that these two salts contaiu water of crystallisation, yet they are both decomposed on addition of water, with separation of the cor- responding camphoroxime.I n order to identify these, the salts were treated with water, when flocculent precipitates of the camphoroximes separated ; the solutions were just neutralised with ammonia and the precipitates filtered off, washed, dried, and crystallised from hot alcohol, 0.5765 gram of the oxime obtained from dextrocamphoroxime dextrocamphorsulphonate, made up to 35.2 C.C. with absolute alcohol at 21°, gave aD - 1.89' in a 200 mm. tube ; whence [.IZ, - 41.3", prov- ing the material to be dextrocamphoroxime, = 55.51.POPE : RESOLUTION OF ItACEMIC CAMPHOROXIME. 1109 0,5870 gram of the oxime prepared from laevocamphoroxime dextro- camphorsulphonate, made up to 25.1 C.C.with absolute alcohol at 22*5", gave + 1-95' in a 200 mm. tube ; whence [.ID + 41*7', proving the substance t o be laevocamphoroxime. A consideration of the molecular rotatory powers of dextro- and lsvo-carnphoroxime dextrocamphorsulphonate suggests very strongly t h a t these salts are wholly dissociated in alcoholic solution ; if such were the case, the difference between the molecular rotatory powers of the two compounds should be twice the molecular rotatory power of camphoroxime in alcoholic solution. I n fact, the numbers are 166.8 - 17.9 = 1489 = 2 x 74.4, whereas the molecular rotatory power of active camphoroxime in alcoliolic solution is 70" or 71"; the mole- cular rotatory powers, 70' and 74,' are equal within the rather wide limits of experimental error involved in dealing with these com- pounds.It might possibly bo expected t h a t other salts of tho camphoroximes should similarly dissociate in alcoholic solution ; Forster (Trans., 1897, 71, 1045') has given the specific rotatory power of dextrocamphoroxime hjdrobromide as [ alD - 35*S0, whence the molecular rotation may be calculated as - 88*'7', which, if the componnd dissociated in the alcoholic solution, should be equal t o the molecular rotatory power of dextrocamphoroxime, namely, [MI,, - 7 1 O . A consideration of the foregoing 1vor.k will make it obvious that we are for the first time in possession of a method for resolving ex- ternally compensated osimes into their optically active components, and that i t is therefore now possible, in many cases, to separate racemic ket.ones and aldehydes by purely chemical methods. Many im- portant applications of the new method are evident, such, for instance, as to the elucidation of the constitution of oximos. No chemical method affording direct evidence has yet been devised for judging between Ilnntzsch and Werner's and rival hypotheses as to the con- stitution of the oximes. According t o the one view, however, 0 N-phenylbenzsldoxime has the constitution CHPh<hph, and hence contains an asynimetric carbon atom, whilst, according t o other views, the constitution contains no asymmetric carbon atom, a distinction which may admit of recognition in this, or similar cases, by the use of a method like that now described. Experiments are in progress with this object in view. 1 % ~ hearty thanks are due to the Research Fund Committee of the Chemical Society for a grant defraying the cost of the materials used in this work. GOLDSMITIIS' IXSTITUTE, NEW Ceoss.

ISSN:0368-1645    

DOI:10.1039/CT8997501105

出版商:RSC    

年代:1899

数据来源: RSC