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Proceedings of the Chemical Society, Vol. 6, No. 86 |
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Proceedings of the Chemical Society, London,
Volume 6,
Issue 86,
1890,
Page 107-138
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摘要:
Issued 14/8/1890. PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 86. Session 1890-91. June lYth, 1890. Dr. W. J. Russell, F.R.S., President, in the Chair. Certificates were read for the first time in favour of Messrs. J. Caird. 20, Springfield, Dundee ; D. G. Clark, 44, St. John’s Wood Park, N.W. ;Walter Henry Coleman, 42, Poynings Road, Junction Road, N. ; Thomas Rhymer Marshall, 4, East Castle Road, Edin- biirgh ; William Alexander McCubbin, Mi11 Bank House, West Derby, Liverpool ; William Stagg, 52, Seymour Road, Bristol. Of the following papers, those marked * were read :-X51. “Invertase : a contribution to the history of an enzyme or nnorganised ferment.” By C. O’Sullivan, F.R.S., and Fred. W. Tompson. The substance present in yeast, &c., known as invertase, which possesses the power, under suitable conditions, of inducing the hydrolysis of cane-sugar, has been studied by the authors with the object of determining the precise manner in which it acts and its constitution.The method adopted in determining the functions of invertase is essentially that developed by Vernon Harcourt in his paper “ On the observation of the course of chemical change.” Asolution of cane-sugar was mixed with a measured amount of invertase, and the action was allawed to take place at a known temperature during a definite time ; action was then stopped by the addition of alkali, and its extent determined. The authors arrive at the following conclusions :- 108 1. The rate of hydrolysis of cane-sugar by means of invertase may always be expressed by a definite time-curve ; this curve is practically that given by Karcourt as expressing a chemical change '' of which no condition varies excepting the diminution of the changing sub-stance." There are, however, some slight and apparently constant deviations from the ,theoretical curve, 2.Whatever the conditions may be under which hydrolysis is taking place, as long as these conditions remain unchanged, this curve is adhered to. 3. When the degree oE acidity is that most favourable for the action of invertase, the rapiaity of the action is in proportion to the amount of invertase present. 4. The most favourable concentration of the sugar solution at a temperature of 54" C.is about 20 per cent. Below that there is a ra,pid decline in the speed of hydrolysis. Greater concentrations are only slightly less favourable until about 40 grams per 100 C.C. is reached. In saturated solutions hydrolysis only proceeds with ex-treme slowness. 5. The speed of hydrolysis increases rapidly with the temperature until 55-60° C. is reached. At 65" C. the iinvertase is slowly destroyed, and at 75" C. it is immediately destroyed. At the lower temperatures the speed of the action increases with rise of tempera-ture in accordance with Harcourt's law : the rate being about doubled for 10" rise ; but above 30" C. the increase is not nearly so rapid. 6. Elevated temperatures have no permanent effect on the activity of the invertase so long as they are not sufficiently high to destroy it.7. The caustic alkalis, even in very srriall proportions, are instantly and irretrievably destructive of invertase. 8. Minute quantities of snlphuric acid are exceedingly f%vournble to the action, but a slight increase of acidity beyond the most favour- able point is very detrimental. The most favourable amount of acid increases to some extent with the proportion of invertase, and de- creases with rise of temperature, but the authors have not been able to discover on what it depends, 9. In studying the action of invertosc it is of the utmost im-portance that the most favourable amount. of acid should be employed ; otherwise correct results cannot be obtained. At a temperature of 60' C.the action is almost stopped unless exactly the right amount of acid is used, whilst if this factor is properly adjusted hydrolysis proceeds at (probably) the maximum speed. 10. The influence of alcohol varies in direct proportion with the amount present. 5 per cent. of alcohol decreases the speed of the action by about one-half. 109 11. The dextrose formed by the action of invertase is initially in the birotary state. 12. The optical activity of a solution undergoing hydrolysis is no guide to the amount of hydrolysis that has taken place. 13. If a caustic alkali be added to a solution undergoing hydrolysis, and the optical activity be allowed suEcient time to become constant, it is a true indicator of the amount of inversion that had taken place at the moment of adding the alkali.14. A sample of invertase which had induced hydrolysis of 100,000 times its own weight of cane-sugar was still active. 15. Invertase itself is not injured or destroyed during its action on cane-sugar. 16. There is no limit to the amount of sugar which can be hydro- lysed with the aid of invertase. 17. The hydrolysis of cane-sugar by means of invertase is a simple chemical change differing in no important way from those which inorganic substances undergo. 18. The products of hydrolysis have no influence on the rate of the action. 19. A solution of invertase will withstand a temperature 25' C. higher in the presence of cane-sugar than in its absence. 20. The authors ai-e of opinion that when invertase inverts cane- sugar combination takes place between the two substances, and thst the invertase remains in combination with the invert-sugar.This combination breaks up in the presence of molecules of cane-sugar. 21. A means of estimating the activity of a material containing invertase has been devised which consists in recording the result by means of the time factor k0 = x min. 111 this equation +O = a certain definite amount of work and x = the time necessary to per-form it. The expression means that the given inverting rnaterinl takes z minutes to invert a standard amount of cane-sugar under. standard conditions. The number x varies in inverse proportion to the actual amount of invertase contained in the material or materials under examination.22. If sound brewers' yeast be pressed and then kept at the ordi- nary temperature for a month or two, it does not undergo putrefac- tion, but changes into a heavy, yellow liquid ; the prcduct possesses no power of fermentation, but an apparent increase takes place in the invertive power. 23. From such liquefied yeast it is easy to filter off a bright solu-tion of high hydrolytic power. It is shown that all the invertase of the yeast is in this solution, which is termed yeast liquor. 24. Yeast liquor has a relative density of about 10@0. It will re- 110 main for a long time unaltered, excepting that the colour darkens. If exposed to the air it may slowly become covered with mould. 25. If spirit be added to yeast liquor until the mixture contains 47 per cent.of alcc~hol, the whole of the invertase separates with only a slight loss of power. This precipitated invertase may be washed with spirit of the same strength and then the residue either dehy- drated with strong alcohol and dried in ZIUCUO, or else it may be extracted by means of 10 to 20 per cent. aIcohol and then filtered. The filtrate contains the invertase. On one occasion the extent of the loss involved by this process was determined and it was found that all the invertase of the yeast liquor was present in the filtrate except 12.3 per cent. 26. The authors have not succeeded in further purifying invertase preparations carefully made in this manner. The slightestr attempt at purification destroys the invertase.27. They have prepared invertase almost free from ash. 28. The inverting power of pressed English yeast varies from 0 = 1000'' to +O = *3000", or about 8 of these amounts if cal-culated on tlie dry solid matter of the yeast. 29. The inverting power of the most active invertase preparation made was k0 = 25.1 on the dry solid matter. It is believed that pure invertase would approximately have +O = 22.5 min. 30. The dry solid matter of yeast contains from 2 to 6 per cent. of invertase. 5.8 per cent. of invertase was separated from one sample of yeast. 31. During the preparation of invertase from yeast liquor an albuminoid is obtained, which is not redissolved by water. This is termed yeast albuminoid.32. Invertase when it approaches apure state is a very unstable substance. The products of its decomposition have been carefnlly examined and are found to constitute a new series of substances be- longing to the invertan series. 33. The invertan series is a homologous series of substances which on analysis yield numbers which may be expressed in terms of an albuminoid and a carbohydrate. Seven members of the series are described. 34. The authors consider that invertase itself is a member of the invertan series, and call it /3-invertan. 35. If the products of the decomposition of p-invcrtan are examined, it is usually found that they consist of a-and F-invertan. The former contains more, and the latter less, nitrogen than invertase.36. a-Invertan is insoluble in water, and in all its other properties seems to resemble yeast albuminoid. It contains 8.35 per cent. N. It is a very stable substance. 111 37. /?-Invertan or invertase is soluble in water, and is the only member of the series which has the power of inverting cane-sugar. It contains about 3.69 per cent. N, and its optical activity is [a3 = + 80" (?I. 38. r-and &Invertan are the products of the simplification of invertase. One or other of these two substances seems invariably to be formed. They both contain less nitrogen than invertase, and are always accompanied by a-invertan. Both are readily soluble in water. They contain respectively 3.15 and 2.43 per cent. N, and their optical activity is [a]j= + 45"and + 54".39. +Invertan is formed from the slow breaking down of 8-invertan. At the same time an insoluble substance, resembling a-invertan, is formed. This probably consists of another member of the series coming between a-and @invertan. €-Invertan is soluble in water, and has [a]j= + 65". It contains 2.07 per cent. N. 40. <-Invertan results from the splifting up of e-invertan in the same way that the latter is formed from &invertan. Its optical activity is [z]j = + 75", and it yields 1.61 per cent. N. 41. v-Invertan is formed by the action of boiling sulphuric acid on y-invertan. It contains less nitrogen fhan the latter substance, but the substance has not yet been suf€iciently investigated to give reliable figures. 42.The further products of the action of sulphuric acid on c-in- vertan are two soluble substances, one containing a considerable amount of nitrogen, and the other with little or no nitrogen, a high cupric reducing power and a low (dextrorotatory) optical activity. 43. The properties of all the members of the series, except a-in- vertan, are very similar. They are all soluble in water, forming bright solutions, which do not cloud on boiling. They are all readily thrown out of solution by alcohol, provided a little acid is present ; the precipitates so formed are transparent colourless syrups, miscible with water in all proportions. The solutions are all dextrorotatory. 44.All the members of the invertan series, except q-invertan, yield a pink coloration on boiling with Millon's reagent.45. All the members of the invertan series, except a-invertan, when submitted to the action of an alkaline copper solution, readily yield a very characteristic copper compound, from which the invertan (except p-invertan) may be separated unaltered. Invertan can probably form several such copper compounds, all having a similar appearance, but affording different percentages of copper oxide. 46. In the presence of a very large excess of alkali, a copper com- pound is also formed from a-invertan, but on examination it is found that the a-invertan has been split up into an albuminoid and <-in- vertan, the copper compound being that of pinvertan. 112 47. It is believed that the members of the invertan series are com- binations of yeast albuminoid with 7-invertan, and that yeasr albu- minoid itself is probably a combination of yeast albuminoid with a carbohydrate.48. According to this theory the composition of the carbohydrate present in the invertan Peries, calculated from the average of all the analyses, would be C: =43-22 per cent. and H = 6.28 per cent. These numbers agree very closely with those required by a hypothetical carbobydrate coming midway between the in and the on groups. 49. It is thought that q-invertan contains 18 parts by weight of this carbohydrate to 1 of albuminoid, and that a-invertan contains 3 parts of the carbohydrate to 4 of albuminoid. 59. The other members of the series are formed by the union of these two substances according to the general formula 9 + an,where represents 7-invertan and a repi-esents a-invertan.In this way we look upon invertase (p-invertan) as 17z5. This splits up into a-and yinvertan according to the formula '7a5= 724 + a. rlx4 repyeseuts yinvertan, and this may be further transformed by elimination of a into 923,or &invertan. 60. The numbers calculated for the constitution of the above theoretical homologous series agree with considerable closeness with those obtained from the analysis of members of the invertan series. 61. The number obtained from a, single determination by Raoult's freezing process for the molecular weight of c-invertan is consider- ably less than the possible molecular weight of y-inv-ertan, according to the authors' theory of its constitution.*52. "The action of carbon monoxide on nickel." By Ludwig Mond, C. Langer, Ph.D., arid B. Quincke, Ph.D. When carbon monoxide is passed over finely-divided nickel, such as is obtained by reducing nickel oxide by hydrogen at about 400", at a temperature between 350" and 450",carbon dioxide is formed, and the nickel is gradually converted into a black, amorphous powder, consisting of carbon and nickel ; the composition of this deposit varies widely with temperature and time. A small quantity of nickel can thus change a very large amount of carbon monoxide, the action being complete and rapid at first, and continuing, although at a diminishing rate, for several weeks.A product containing as much as 85 parts carbon to 15 parts nickel has been obtained. Acids only partially remove the nickel ; the carbon is very readily acted on by steam, carbon dioxide and hydrogen without a, trace of carbon monoxide being formed at a temperature of 350". On allowing the substance to cool in a current of carbon monoxide, 113 it was noticed that the flame of a Bunsen burner into which the escaping gas was introduced became luminous, and when the tube through which the gas passed was heated, a deposit of nickel, mixed with a small quantity of carbon, was obtained. The authors were thus led to discover the existence of a volatile nickel compound. To prepare this compound, a combustion-tube is filled with nickel oxide and this is reduced by hydrogen at about 4OOp ; after cooling the nickel to abut loo", pure dry carbon monoxide is passed over it without further heating, and the issuing gas ii4 led through a tube placed in a freezing mixture : the major portion of the nickel com-pound condenses as a colourless liquid, but the gas retains about 5 per cent., and is therefore collected, dried and again passed over the metal.When no more liquid condenses, the nickel is again heated to about 400" in a slow current of pure carbon monoxide ; it is then cooled to about looo, and again submitted to the action of the gas. Nickel csrbonoxide thus prepared is a coloudess liquid, which boils at 43"under 751 mm. pressure ; its relative density at 17" is 1.3185.It solidifies at -25" to a mass of needle-shaped crystals. Its com- position is represented by the formula Ni(CO)+ It dissolves in alcohol, and more readily in benzene and chloroform ; dilute acids and alkalis have no action on it, but it is oxidised by coccentrated nitric acid. It reduces an ammoniacal solution of cupric chloride, and it also causes the separation of silver from an ammoniacal solu- tion of silver chloride. It interacts with chlorine, forming nickel chloride and carbon oxychloride. It is decomposed at 180" (in boil- ing aniline vapour) into nickel and carbon monoxide. The atomic weight of the deposited metal was found in three experiments to be 58-52-58.64, a result closely corresponding with Russell's value, 58.74. Numerous experiments to obtain similar compounds with other metals, notably with cobalt, iron, copper and platinum, led to negative results.On experimenting with specially purified cobalt, in the beginning a slight coloration of the Bunsen flame into which the gas was led was noticed, but after a time this was no longer observed. Commercial cobalt afforded a gas which deposited a mirror of pure nickel, it being possible, in fact, to purify cobalt from nickel by carbonic oxide. The nickel mirrors obtained by heating the carbonic oxide compound do not appear to contain any trace of cobalt. *53. "The interaction of iodine, water and potassium chlorate." By Henry Bassett. The author finds that the usual datement that the chlorine in potas- sium chlorate is directly displaced by iodine when subjected to treat- 114 ment in accordance with Millon’s directions is incorrect ; he considers that the evolution of chlorine observed by MiIIon is due to a secondary interaction, HIO, + 5HC1 = 3H20 + IC1 + 2C12,which takes place when the iodine is added all at once, and is due doubtless to the rapid formation of iodic acid and hydrogen chloride within the dense mass of iodine.His experiments show that the iodate is formed in accord- ance with the equation 61, + 10KC10, + 6H20 = 6KHI,0s + 4KCl +6HC1; and that on evaporating the solution to dryness on the water-bath, decomposition of a portion of the biniodate takes place : KHIZOE + 12HC1 = KC1 + 6HzO + IC1 + ICI.HC1 + 4C12. *54. “The milk of the Garnoose.’’ By A.Pappel and H. D. Rich-mond, Khedival Laboratory, Cairo. The milk of the Egyptian gamoose or buffalo (Bos BubaZus) is distinguished from that of the cow by its white colour and peculiar musk-like smell, The authors find the average composition to be as follows :-Water.. ............ 84.10 Pat ............... 5.56 Sugar .............. 3.41 Casein.. ............ 3.26 containing N 0.511 Albumin.. .......... 0.60 ,, 0.0947, 77Nitrogen bases ...... 0.09 ,, 0.035 Salts ............... 1.03 The fat was found to vary from 7.35 to 5.15 per cent., and the solids not fat from 10.67 to 10.07 per cent. The average relative density at 15’Fi” was 1.0354; the increase in eight hours after milking was 0*0006, and in 24 hours 0.0007.Gamoose milk, therefore, differs from that of the cow, both in the high percentage of fat and of solids not fat, the increase in the latter being largely due to the sugar. Comparing the fat with that of cows’ milk, the chief diBerences noted by the authors are, (1) the presence of small quantities of sulphur and phosphorus ; (2) the presence of fatty acids soluble in boiling water but not volatile in much larger amount than in cow8’ milk ; (3) the presence of fatty acids giving lead salts soluble in ether but not members of the oleic series; (4)the difference in the ratio between caproic and butyric acid-4 : 1 instead of 2 : 1. Other alcohols than glycerol do not appear to be present. The sugar appears not only to be different from milk sugar, but novel, its rotatory power being [a]= = 48.7, and its cupric-reducing power K = 73.7 ; it yields only dextrose on hydrolysis.It is proposed to name it tewJLikose. 115 The authors also state that the milk contains a small amount of citric acid. 55. "The action of heat on the chlorides and hydroxides of mixed quaternary ammonium compounds.'' By N. Collie, Ph.D., and S. B. Schryver, B.Sc. The object of the author's experiments has been to devise, if pos- sible, a general method for preparing mixed tertiary amines. One of them (Collie, Chem. Xoc. Trans., 1888, 718-726) has shown that mixed tertiary phosphines could be prepared by heating the quaternary phosphonium compounds, and the following results show distinctly a marked analogy between the compounds of nitrogen and those of phosphorus.Hofmann has already pointed out that when the hydroxides of mixed quaternary ammonium compounds containing ethyl are heated, one of the ethyl groups is invariably eliminated in the form of ethylene, e.g., (CzH5)3(C5H,,)N.0H =(CzH,),(CsH,,)N +CzHa+H,O; and Lossen has obtained similar results. But none of the mixed tertiary arnines were thus prepared in a state of purity ; both Hof-mann and Lossen were content to reconvert the products into quater- nary ammonium chlorides and analyse the platinum salts. The authors have used trirnethylamine and triethylamine, and from these tertiary amines have prepared the quaternary ammonium compounds by heating the alcoholic solution of the amine with the iodide or chloride of primary, secondary or tertiary hydrocarbon radicles of the C,H2, + series.The action of heat on the quatermry ammonium compounds containing the radicles allyl, benzyl and phenyl has also been studied. The mixed tertiary arnines which have thus been prepared for the first time in the pure condition are :-Dimethylethylamine, b. p.. ........ 45-46' C. Diethylm ethylamine ,, ......... 66-67' C. Dimethylamylamine ........... 113-114" C. Dimethylbenzylamine ,, ......... 178-179" C. 56. "Action of phosphoric anhydride on fatty acids." By F. Stanley Kipping, Ph.D., D.Sc. The investigation of the action of phosphoric anhydride on fatty acids has now been extended to palmitic acid and lauric acid, and some preliminary experiments have also been made with caproic acid.These compounds, like stearic acid and heptylic acid, are decomposed by phosphoric anhydride at a moderately high temperature in accord- aiice with the equation 2R-COOH = RICO + GOz + HzO. As the 116 ketone produced can easily be obtained in a pure condition and the yield is also good, this method may be conveniently employed for the preparation of the compounds in question. Palmitone, (CI5H,,),CO, can be prepared by heating palmitic acid at 200-210" and gradually adding a slight excess of the theoretical quantity of phosphoric anhydride. The dark-brown mass is allowed to cool, treated first with water and then with soda to free it from phosphoric acid, and the residue extracted several times with boiling alcohol ; on cooling, the ketone separates from the alcoholic extracts as a yellowish powder and can be obtained in a pure condition by recrystallising it from boiling alcohol.The yield of the pure pro- duct is more than 50 per cent. of the theoretical. It is a colour- less, crystalline powder melting at 82-83'. The hydroxime, (C15H3,),C:N*OH,forms peculiar fern-like crystals and melts at about 64-65". DipaZmityZcnrbinoZ, (C15H3r),CH*OH,is obtained by reducing palmitone with sodium in boiling alcoholic solution ; it crystallises from alcohcl in silky plates and melts at 84-85'. When boiled with acetic anhydride for several haurs, it is converted into a colourless, crystalline acetyl-derivative, (C15H31)2CH*OAc,melting at 49-50".Laurone, (C1,H,,),CO, can be easily prepared by heatiiig lauric acid at 220-230' with a slight excess of the theoretical quantity of phos-phoric anhydride; at R lower temperature the acid is not readily decomposed. The product is purified as described in the case of palmitone; the yield is about 40 per cent. of the theoretical. The hydroxime, (C,IH,,),C:N*OH, is foimed when the ketone is heated with hy droxylamine hydrochloride and excess of potash in dilute alcoholic solution ; it crystallises from alcohol in slender needles and melts at 39-40". DiZauryZcarbinoZ, (ClIH,,),CH*OH, is obtained when the ketone is reduced with sodium and water in ethereal solution ; it crystallises in colourless, waxy plates and melts at 75-76'.The acetyl-derivative, (C11H,,)2CH*OAc, is formed when the alcohol is boiled with acetic anhydride for some hours; it crystallises from methyl alcohol in colourless plates melting at 34-35". Caproic acid, at its boiling point, is decomposed by phosphoric anhydride, giving the ketone (C5Hll),CO; the product can be isolated by distillation with steam, The yield seems to be fairly good. 57. " aa'-Dimethyl-aa'-diacetylpentane." By F. Stanley Kipping, Ph.D., D.Sc., and J. E. Mackenzie, B.Sc. The conversion of aa'-diacetjlpentane into dimethyldiliydroxy-heptaruethylene on reduction (Kipping and Perkin, Proc., 1889, 145) 117 being an action to which much interest attaches, the authors have instituted experiments with a view to ascertain whether other diketones of analogous constitution can be converted into hepta- methylene-derivatives in a similar manner.The investigation is not yet completed, but ma'-dimethyl-a%'-diacetylpentaneand various other compounds have already been prepared. Ethylic aa'-dimet;hyl-aor'-diacety~imeZate,C,H,(CMeAc-CO,Et),, can be obtained by treating ethylic methylacetoacetate with trimethylene bromide and sodium ethoxide in absolute alcoholic solution ; a con- siderable quantity of compounds of lower boiling point is also formed, so that the yield of ethylic dimethyldiacetylpimelate is only 50-60 per cent. of the theoretical. It is a colourless oil boiling at about 250" under a pressure of 60 mm.On hydrolysis with alcoholic potash, the ethereal salt is decomposed into dimethyldiacetylpentane, dimethylacetylcaproic acid and dimethylpimelic acid, the relative quantity of each of these three compounds depending to a considerable extent on the concentration of the alcoholic potash and on the manner in which the hydrolysis is carried out. aa'-Dinzethy1-aar-diacety2yentane,CHMeAc*[CHZ],-CH3leAc, is a colourless oil boiling at 198-201" under a pressure of 112 mm.: it shows no signs of crptallising even when cooled to 0". The dihydroxime,OH*N:CMe*CHMe.[CH,],*CHM e.CMe:N*OH, crystallises from a mixture of benzene and light petroleum in colourless needles melting at 95-46". am'-DirnethypirneZic acid, COOH*CHMe*[CH2]3*CHMe*COOH,sepa-rates from light petroleum in compact, colourless crystals, and melts at 74-75' ; it is readily soluble in water and most organic solvents.The silver salt, C9H1404Agz,is a, colourless, seemingly amorphous compound, only sparingly soluble in boiling water. Etliylic dirnethylpimelnte, C9H1404Et2,is formed in large quantities when ethylic methylacetoacetate is treated with sodium ethoxide and trimethylene bromide in alcoholic solution in presence of a small quantity of water ; under these conditions the etliylic dimethyl- diacetylpimelate which is produced in the first case seems to be completely converted into the ethylic dimethyl pimelate. It is SL colour-less oil boiling at 190-191". On hydrolysis with alcoholic potash it is converted into dimethylpimelic acid.aw-Dimethyl-w-ncetylcaproicacid, CHMeAc*[CH,],*CRMe*COOH, is a thick, colourless oil boiling at about 2 18-220" under a pressure of 60 mm. ; it cannot easily be obtained in ft pure condition. 58. "Rerberine." Part 11. By W. H. Perkin, jun., Ph.D., F.R.S. In Part I of this research (cf. Chem. SOC.Trans., 1889, 63) the results of preliminary experiments on the oxidation of berberine with 118 mrying quantities of potassium permanganate were briefly described, and a short account of some new substances obtained during these experiments was appended. In the further prosecution of this research very large quantities of the alkaloid have been oxidised. The amounts used in the experiments varied considerably, but some of the best results were obtained where, in each operation, 7 grams of berberine, 9 grams of potassium permanganate and about 1gram of potassium carbonate were used. The product from a number of such operations was treated with sulphur dioxide until the whole of the manganese precipitate had beea brought into solution ; the result- ing yellow precipitate was then separated from the yellow solution (A) by filtration, washed with water, and warmed to 40" with a dilute sodium carbonate solution, by which means about one-half of the precipitate was dissolved (B).r11he insoluble residue contains, besides two substances-berberilic anhydride, C,,H,,NO, (m. p. 236-4237"), and berberal, CzoH1~N0~ (m. p. 150")-which have been already described, a new base, CzJLNO,, which is very sparingly soluble in water, and crjstallises in flat,yellow plates; and small quantities of two other substances.The alkaline solution (B) contains, as principal product, a-berberilic acid, CzoHI9NO9,which was described in the former paper. This acid, when heated to 180", is converted into berberilic anhydride ; in other respects it shows great similarity to /I-berberilic acid, which is described below. The solution (A) was evaporated in large flat basins to about half its bulk, filtered from the precipitate (C) which separates and then evaporated to s, small bulk (D). The precipitate (C) was warmed with dilute chlorhydric acid till free from inorganic matter, the residue washed with water, dried, and extracted with hot acetic acid, by which means a quantity of berberilic anhydride was removed.The insoluble residue was dried and dissolved in a small quantity of boll-ing aniline, from which solntion it was deposited, on cooling, in glittering, yellow plates, having the composition CzoHl,N06. This dubstance, which is formed in very small quantities, has only been superficially examined. It is characterised by its insolubility in the usual solvents, and by the fact that it yields a beautifully crystalline potassium salt when dissolved in alcoholic potash. The highly concentrated liquors (D) were extracted 30 times with ether, the ether evaporated and the semi-solid residue boiled with water until the greater part had dissolved (E). The residue dissolved almosh entirely in dilute sodium carbonate solution (P), leaving a dark brown pasty residue, from which, by treatment with glacial acetic acid, a substance crystallising in long, brown needles can be isolated.This substance melts at l67", has the formula CIuHIO~,and 119 dissolves in alkali with formation of an acid, which crystallises from water in long, glittering needles, m. p. 147". The alkaline solution (F), acidified with cblorhydric acid, deposits a brown, amorphous precipitate, which crystallises from glacial acetic acid in glittering, colourless plates which melt at 200" with decom- position and charring. This substance, which has the composition C20H1SN07,is a mono-basic acid, yielding highly characteristic salts, of which the siher salt, CZoH,,NO7Ag, was analysed.The calcium, lead and zinc salts are sparingly soluble, hut beautifully crystalline. The solution (F) was next examined. This was heated to boiling, rendered slightly alkaline with sodium carbonate and allowed to stand 24 hours. At the end of this time the liquid is found to be filled with a mass of glittering plates of a new base, CI0H9NO3,which will be deFcribed in detail later on. These are filtered off, the alkaline solution neutralised with chlorh ydric acid, and mixed with an excess of a st;rong solution of calcium chloride. No precipitate is produced in the cold, but on boiling, a crystalline calcium salt sepa- rates. This is collected, washed with a little water, dissolved in hot dilute hydrochloric acid, from which solution, on standing, a quantity of crystals separate.These crystals are a mixture of two acids, which both melt at 180°, and which can be separated b7 recrystallisa- tion from water. The more soluble acid is hemipinic acid. The second acid crysta,llises from water, without water of crystallisation, in colourless plates, which, on analysis, give numbers agreeing with the formula C&& The silver salt has the composition C,H406Ag,. This acid is most probably identical with hydrastic acid, which Freund and Lachmann (Berickte, 22,2324) obtained from hydrastinine, and which melts at 175". The following are the results of the examination of the principal products described above. 1. Berberilic anhydride (C20H,7N08,m.p. 236-237"), does not com- bine with phenylhydraziae. When boiled with acetic anhydride for some hours it is converted into an acetate, C20H16N07(C2H,@,), which crystallises from acetic anhydride in hard, light-yellow prisms melting at 140". Boiling dilute sulphuric acid decomposes this acetate quantita- tively into berberilic anhydride and acetic acid. Pentachloride of phosphorus converts berberilic anhydride into a' chloride, C20H,6NC107, which crystallises from benzene in hard, garne t-red prisms melting at 167". This substance is readily acted on by water and reconverted into berberilic anhydride. Berberilic anhydride dissolves readily in 120 warm dilute caustic soda solution, with formation of P-berberilic acid, which is precipitated on the addition of acids as a white, sticky mass, which becomes hard on standing.This new acid crystallises from dilute alcohol in warty masses, and melts at 180", being at this temperature reconverted into its anhydride. Its composition is CzoHlgN09,and it is isomcric with a-berberilic acid, which melts at about 140". A number oE salts were prepared by precipitating a neutral solu-tion of the ammonium salt with various agents. These salts, how- ever, are not derived from berberilic acid, C20H19N09,but all contain one molecule of water less, and are therefore derivatives of the anhy- dride C2,H,,NO8. The silver salt, Cz,H16AgN08,is a white, amorphous mass. The methylic salt, C',oH16(CH3)N08,prepared by the action of methyl iodide on the silver salt, crystallises from acetic acid in glit-tering plates which melt at 178-179".As it was thought possible that the methyl-group might be attached to nitrogen, the action of liydrogen iodide on this methyl salt was investigated, and it was found that thyee methoxy-groups were present, two belonging to the berberine molecule. The substance is therefore a true methylic salt. The most important reaction of f3-berberilic acid is the change which tlhis substance undergoes on hydrolysis. When boiled with dilute sulphuric acid (5 per cent.), it dissolves completely, being con- verted quantitatively into hemipinic acid and a new base : C2,Hl,NOg+ H,O = C10H1006+ C,,H,,NO,, small quantities of berberilic anhy- dride being always regenerated during the decomposition. After ext,racting the hemipinic acid by ether, the sulphuric acid liquors are evaporated to a small bulk, and tlien allowed to stand 48 hours, when the sulphate of the base separates in large, slightly brownish coloured tablets. These are collected, dissolved in water, treated by the calculated quantity of baryta-water, and the solution gently evaporated.The concentrated solution deposits the base in large, flat, monoclinic plates which melt at 180-182", and contain 1 mol. of water. The platinochloride, (Cl,H,lN0,HC1>zPtC14, crystal- lises from water in dark-yellow needles wiiich melt at about 620". Nitrous acid converts the base into a substance of the formula C10H804.which will be described later on.When heated to 180", or digested with strong potash solution, or even simply boiled with water for some time, the base loses the elements of a molecule of water, and is converted into another base, CioHgNO,. This important substance crjstallises from water in magnificent colourless, glittering plates which melt at 182". It is feebly basic, its salts being onlj stable in the presence of large quantities of acid. 121 It is a very stable substance, and when boiled with dilute nitric acid is principally converted into a nitro-derivative, C,oH~(NOz)NO,, which crystallises from water in yellow plates, m. p. 175-180'. If the base be dissolved in a large quantity of dilute chlorhydric acid (1HC1 to 2H,O), well cooled, and the calciilated quantity of sodium nitrite (1 mol.prop.) added, an immediate precipitate of a yellow nitroso-compound, C,oH,(NO)NOa, is produced. This crystallises from alcohol in glittering, yellow needles which melt at 195-196" with de- composition. When boiled with dilute caustic soda, this nitroso-com- pound rapidly dissolves with evolution of nitrogen, CloH8(NO)N0, + H20 = CloH,,05+ N,. The new substance melts at 146", and is readily soluble in hot water and most of the usual solvents. It is an acid, the salts of which are fairly characteristic. The silver salt, CIOHSAgOS, is crystal-line, aud soluble in hot water. When heated to 150", or boiled with water, this substance readily loses 1 mol. of water, and is converted into its anhydride, Cl0H8Oa.This substance crystnliises from water in large, flat plates which melt at 125;"and distils almost without decomposition. It is recon-verted by dissolution in alkalis into the acid CloH,o05. Nitric acid produces a light-yellow mononitro-compound, C,H7(N0,)04,which melts at 197". A number of experiments were tried with the object of oxidising the molecule to some well-known acid, but without success, the substance being either unncted on or else completely de- stroyed by the oxidising agents employed. Gently fused with potash, the substance yields a mixture of pyrocatechol and protocatechuic acid. When heated with hydriodic acid in Zeisel's apparatus, no trace of methyl iodide was evolved, a proof that the molecule contains no methoxyl-groups ; chlorhydric acid (1HC1to 4HzO) at 170-175" de-composes the substance, however, nzld apparently quantitatively, with deposition of carbon and formation of a new compound, C,H,O, = CjoHSO4 -C.This compound crystallises from water, in which it is very soluble, in warty masses which me15 at about 220-225". Its aqueous solu-tion shows with ferric chloride the most intense pyrocatechol reac-tion; it gives a white precipitate with acetate of lead, and reduces both Pehling's solution and ammoniacal nitrate of silver. The resiilt shows that all these derivatives contain the piperonyl- 0 group, CH,< 0>C6H4,the constitution and proposed nomenclature of these substances being apparent from the followiiig table :- w-Amidoethylpiper-onylcarboxylic acid.w-Amidoethylpiper-ony 1carboxy lic an-hy dride. w-Hydroxyethyl-piperony lcarboxylic acid. w-Hydroxyethyl -piperon ylcarboxylic anhydride. w-Hydroxyethpl-pyrocatec holcnrb- oxylic anhydride. Freund and Will (Berichte, 20, 2400), in their researches on hydrastine, describe a substance, oxyhydrastinine, obtained by the action of caustic potash on hydrastinine, which they subsequently 0 CO-NGH, prove to have the constitution CH2< 0>C,H,< ICH2--CH, If the formulae assigned to the compounds above be correct, this oxyhydrastinine must be a methyl-derivative of the compound CjoHgNO,, and in order to confirm these formulae every effort was made to convert the substance C,,H,NO, into osybydrastinine.The experiments first made in this direction are the following :-1. C,,H,NOs and C1,,H,,NO4 were treated with methyl iodide under various conditions, with and without the addition of alkali. 2. Cl0H,O, was heated with methylamine and with methylamine acetate in a fiealed tube. 3. CloHloO,was converted into the methylamine salt, and this was distilled. But, all these experiments failed to produce the chnuge desired. The transformation was, however, ultimately accomplished in the follow- ing way :-The compound CloH80,is conrerted by phosphorus penta- chloride into the chloride Cl,H,04Cl, which crystallises from chloro- form in glittering needles melting at 159". This substance is remarkable for the ease with which it loses hydrogen chloride, and is reconverted into CloH,04.This change takes place on heating to 150", or on heating with alkalis, or reducing with zinc-dust and acetic acid, and also on heating with methylamine in alcoholic solu- tion in a sealed tube. In order to prevent this, the cai%oxyl-group was protected by converting t'he chloride into its methylic salt. For this purpose, 123 C,,,H,O, was treated in chloroform solution with an excess of penta-chloride of phosphorous, the chloroform distilled off, and the residue poured into methyl alcohol. The methylic salt was thus obtained as a white powder, which crystallised from dilute methyl alcohol in beautiful woolly tufts of needles melting at 83". When this was heated with methylamine in alcoholic solution at 130" for six hours and the product was boiled with alcoholic potash, oxy-hydrastinine was almost quantitatively obtained, thus :-The substance obtained in this way melted at 98", and showed all the properties of oxyhydrastinine. m.2.Berbernl, C20H:17N07; p. 150".-When in a finely-divided state and very pure, berberal is moderately readily hydrolysed by boiling dilute sulphnric acid (containing 20 per cent. H,S04), a clear, slightly brownish-coloureci solution resulting. Ether extracts from this solution a colourless crystalline mass which, when treated with dilute sodium carbonaie, is separated into the base CI0H9NO3, described above, and a new acid. This latter substance crystallises from water in beautiful long, satiny needles which melt at 121", and on analysis give numbers agreeing with the formula CloHloO,. The analysis of the silver salt, CloH9A,aO5,showed the acid to he mono- basic.When treated with hydrogen iodide in Zeisel's apparatus, results were obtained which proved that the acid contained two methoxyl-groups. Fusion with potash converts the acid into proto- catechuic acid; but if caustic potash solution (sp. gr. 1.4) be em- ployed and the acid simply digested with this on a reflux apparatns, an almost quantitative yield of veratric acid, (cH30)zc6H3~ooH (m. p. 177-178"), is obtained. When subjected to the action of hydroxylamine in alkaline solu- tion at ordinary temperatures, a hydroxime, CIOH11N05, is produced.This crystallises in fine needles which, when heated, melt at 124", but. at once become solid again, and then do not again melt till the temperature is raised to 213". In order to investigate this decom- position, the pure hydroxime was heated to 180"for 15 minutes and the residue recrystallised from alcohol. Beautiful needles were thus obtained which melted at 224-226", and were readily identified ap h emi pini mide. The acid CloH,,05is readily reduced by sodium amalgam, beitrg converted into an acid which, when precipitated from its alkaline solution by the addition of an acid, at once loses water with formation of pseudomelconin, CH30H30>C6H2<gF>0. This substance cryst)allised from water in long needles melting at 122-123", and possessed all the properties ascribed to pseudome-konin by Solomon (Eer., 20, 884).These experimenh prove con-clusively that the acid CloH,oOshas the constitation represented by the formula CH30 CH,O/\COHI1 r,,COOE and it t,hns bears a very close relationship to opianic acid, CH,O CH~O(JCOOH which is brought out in a most interesting way by a parallel study of the reactions of the two substances ; thus, for instance, on reduc-tion both yield mekonins, and with hydroxylamino both yield hydroximes, which, when gently warmed, are converted into hemipin- imide. The acid Cl,H1oO, may therefore be called pseudopianic acid. These experiments throw considerable light on the constitution o berbeyaZ. This substance on hydrolysis yields pseudopianic acid and 0 CO -THthe base CH2<O>CJ12< CH2-CH2 ' its constitution is therefom probably represented by the formula Berberilic anhydride, C,H17NOe,yields on hydrolysis hemipinic acid and the base it has, therefore, possibly the following constitution :-These experiments also show :-1.The nature of all the oxygen-atoms in the molecule of berberine, C20H,,N04,tlbus precluding the hjpothesis that berberine owes its colour and titictorial power to the presence of a quinone-group. 125 2. That berberine is an isoquinoline-derivative. 3. That berberine is closely related to Eydrastine, narcotine and papaverine. Further experiments must decide the question of the exact con- stitution of berberine; but the author is of the opinion that the following formula explains well all the reactions of this alkaloid which have hitherto been investigated.The discussion of t,his formula will be attempted in the detailed paper. 59. “ Studies on the constitution of the tri-derivatives of naphtha-lene. No. 4. The constitution of a-naphthylaminedisulphonic acid Dahl No. 11. Naphthalene-1 : 2’-disulphonic acid.” By Henry E. Armstrong and W. P. Wynne. When naphthionic acid is sulphonated with 35 per cent. anhydro- sulphuric acid at a temperature not exceeding 30” according to Dahl and Co.’s German patent No. 41957, 1886, two disulphonic acids are produced, which are respectively known as a-naphthylaminedi -sulphonic acid No.I1 and No. 111, the latter constituting the chief product. The constitution of acid No. 111 has been given in a previoiis communication (these Proceedings, 1890, 16). With the object, of comparing the disulphonic acids obtained by the sulphonr-t- tion of a-naphthylaminc with those known to be produced by the sulphonation of a-naphthol, the autJiors have undertaken the investi- gation of acids Nos. I and I1 of Dahl and Co.’s patent, and are now in a position to communicate the results obtained by the examination of acid No. 11, for a liberal supply of which they are indebted to Messrs. Dahl and Co. The product received was in the form of potassium salt, and appeared to be uniform ; but on investigation it was found to contain a note- worthy quantity, perhaps 20 per cent., of an a-naphthylarninet~i-sulphonic acid, the formation of which, under the conditions above named, is specially interesting as throwing further light on the process involved in the production of isomeric disulphonic acids.When ~ediiced by the hydmzine method, this a-naphthglaminett.isu1- phonic acid yiclds a ?allyhthalenetrisulpho~ticacid characterised 11y forming a chloyide, C,,H,( SO,Cl),, which crystallises from a mix- ture of benzene and petroleum spirit in small prisms melting :tt about 191” ; whilst by the Sandmeyer method it is converted into a clr lorwaphthuleut trisulpho7iic acid characterised by forming a chloride, 126 C,,H,Cl( SO,Cl),, which crystallises from benzene in minute prismR from a mixture of benzene and petroleum spirit in small crystalline aggregates, and from acetic acid in small scales melting at 215".a-Naphthylaminedisulphonicacid No. 11,on conversion into naph- thalenedisulphonic acid by V. Baeyer's hydrnzine method, yields n liew acid, the salts of which will be described in a subsequent corn-munication. The chloride of this acid, CloH6(SO,Cl),, crystallises from benzene, in which it is readily soluble, in prismatic forms ; from a mixture of benzene and petroleum spirit in tufts of opaque irregular needles ; and from acetic acid in beautiful glistening plates ; it melts at 122.5", and on distillation with PCI, yields a dichloronaphthalene melting at 63-63*5", convertible by sulphonation, &c., into a sulpho-chloride, crystallising in needles, which become opaque and melt at 117".The acid is consequently the 1: 2'-disulphonic acid, and is the sixth known naphthalenedisulphonic acid. By the Sanduieyer method, acid No. I1 can be converted into a chlorodisulphonic acid the chZoride of which crystallises from a mixture of petroleum spirit and bmzene in minute needles, and from acetic acid in small prisms ; it melts at 126-127", and, on distillation with PCI,, yields 1:4 : 3'-tri-chloronaphthalene, characterised, among other properties, by melting both at 56" and 66" under the conditions already described (Zoc. cit.). Superposing these results, it follows t!hat 2-naphthylarninedisulphonic acid Dahl No. I1 is, as its mode of formation would seem to indicate, a sulphonated naphthionic acid, and that it has the constitution :-Dahl acid No.11.The authors reserve the investigation of the properties of the 1: 2'-naphthalenedisulphonicacid and its derivatives. 60. '' Studies on the constitution of the tri-derivatives of nnphtha-lene. No. 5. The constitution of the Schollkopf a-naphthylamine- disulphonic acid." By Henry E. Armstrong and W. P. Wjnne. The formation of the Schollkopf a-naphthylaminedisulphonicacid (German patent 40571) by the nitration and suhseqnent reduction of the authors' naphthalene-1 : 4'-disulphonic acid (Bernthsen, Bey., 1889 332'7) renders it evident that the generally accepted view of the constitution of this acid is a correct one. Having been favoured by the Actiengesellschaft fur Anilinfabrikntion with a supply of the material prepared by the method given in the Schollliopf patsent, the authors took occasion to submit this to examination.They find 127 that it is converted by the hydrazine method into naphthalene-1 : 4'-disulphonic acid, which was characterised by conversion into the chloride crystallising from benzene in prisms melting at 182", and into 1: 4-dichloronnphthalene melting at 107". On treatment by the Sandmeyer process it gave a chloradisulphonic acid, the chEoride of which crptallised from acetic acid in very small, prismatic needles which became opaque on drying, and from a mixture of petroleum spirit and benzene in sparingly soluble glistening flat plates ; it melted at 135O, and, on distillation with PCl,, was converted into 6-or 1: 4 : 1'-trichloronaphthalene melting at 131".These results place it beyond question that the constitution of the Schollkopf acid is expressed by the formula s NIEaa)s 61. " Studies on the constitution of the tri-derivatives of naphtha-lene. No. 6. The constitution of Cassella's /j-naph thylamine-6-di- snlphonic acid." By Henry E. Armstrong and W. P. Wynne. Messrs. Cassella and Co. having been good enough to furnish the authors with a supply of hheir p-naphthjlamine-6-disulphonicacid, prepared from the /%naphtholdisulphonic acid of their German patent No. 44079, it has been possible to determine its constitution by the hydrazine and Sandmeyer methods already described.On treatment by the hydrazine method, the amido-acid yields, in the first instance, a, peculiar ropy, gelatinous hydrazine, which can only be freed from tin salts with considerable difficulty. The disulphonic acid obtained from this hydrazine yields a chloride crystallising from benzene, in which it is sparingly soluble, in small, flat, spear-like needles; this chloride melts at 225", and on distillation with PCl, yields 2 : 3'-djchloronaphthalene melting at 135" : it is, therefore, naphtha- lene-2 : 3'-disulphonic acid-the P-disulphonic acid of Ebert and Merz, By the Sandmeyer method, the amido-acid is converted into a chlorodisulphonic acid, the chloride of which crystallises from beii-zene, in which it is very soluble, in small, characteristic radiate groups of very slender needles, and from a mixtare of petroleum spirit and benzene in small, opaque aggregates melting at 176" ; on distillation with PCI, it yields 2 : 3 : 2'-trichloronaphthalene melting at 90".Combining these results, it follows that Cassella's 6-naph- thylamine-6-disulphonic acid and the p-naphtholdisulphonic acid of the German patent No. 44097, from which it is derived, have the formula 128 and bhh are, therefore, tri-p-acids isomeric with the corresponding K-acids (these Proceedings, 1890, 12). 62. '' Studies on the constitution of the tri-derivatives of naphtha-lene. No. 7. The disulphonic acids obtained by sulphonating the isomeric heteronucleal P-naphthylaminesulphonic acids.'' (First notice.) By Henry E.Armstrong and W. P. Wynne, According to Gans and Co's German patent, No. 35019, 1884, /3-naphthylamine is converted into the amido-G-disulphonic acid by heating its sulphate with thrice its weight of 20-30 per cent. an- hydrosulphuric acid at 1l0-14Oo until soluble in water ; and the same product is said to result when "P-tiaphthylaminesulphonic acid " is similarly treated. But inasmuch as four monosulphonic acids are obtainable from p-naphthylamine, to determine the law of sulphom-tion, it was obviously necessary to examine the behaviour of each of these and to avoid tbP occurrence of secondary changes as far as possible ; experiments with this object in view were commenced several years ago: meanwhile an account of the behavionr of the Bronner acid under conditions similar to those specified by Gans and Co., have been published by Fording (Rerichte, 1688, 3496).(1.1 2 :l'-P-Naphthylamine-ac-sulphonicAcid (Badische acid) :-When the Badische acid is stirred into four times its weight of 20 per cent. anhydrosulphnric acid at n temperature not exceeding 20", and the mixture is allowed to stand, sulphonation proceeds slowly and is not entirely complete even at the end of three months, The product is found to consist almost entirely of an acid recognised as amido-G-disulphonic acid, inasmuch as it gave by the hydrazine and Sandmeyer methods all the products already described as charac- teristic of this acid (these Proc., 1890, 12). The naphthalenedisul- phochloride prepared from it melted at 137", and on distillation with PCl, gave 1: 3-dichloronaphthalene melting at 61.5" ; the chloro- naphthaleiiedisulphochloride from it melted at 169", and on distilla- tion with PC1, gave 1:3 :2'-trichloronaphthalene melting at 113".The subsidiary product formed on sulphonating the BadiscLe acid has not yet been prepared in sufficient quantity to admit of its examina- tion. (2.) 2 :4'-~-Naphthylamine-oc-sulphonicAcid (Dahl acid).-When stirred into four times its weight of 20 per cent. anhydrosulphuric acid at a temperature not exceeding 20", the Dahl acid gradually 129 uiidergoes further sulphonation, the process being usually com- pleted in from 116-120 hours. The product is found to coiisist of two isomeric acids, which are readily separated by crystallising out the minor product as normal potassium salt, and subsequently puri- fying the chief product by repeated crystallisation of its acid potas- sium salt.Chief Product.-The acid potassium salt of the ohief product crystallises in thistle-down like aggregates, and is very soluble in water; on reduction by the hydraaine method it gave naphthalene- 1:3-disulphonic acid which was characterised by means of the chloride melting at 137"; on distillation with PCI5, this gave 1:3-dichloronaphthalene melting at 61.5" (Zoc. cit.). On treatment by the Sandmeyer process, it was converted into a chlorodisulphonic acid, the chloride of which is very soluble in benzene, and crystallisd from a mixture of benzene and petroleum spirit in radiate groups of small prisms, from acetic acid in elongated prismatic needles show- ing good end-faces ; this chloride melted at l56",and on distillation with PC1, gave 2 : 2' : 4'-trichloronaphthalene crystallising in radiate groups of very slender, characteristic needles melting at SOo.It follows, therefore, that the chief product obtained by the further sul-phonation of the Dahl acid under the conditions named has the con- sti tut ion ,Hinor Product.-The normal potassium salt of this acid was ob-tained in well-formed rectangular tablets. The quantity prepared has not sufficed for its complete investigation by both methods, and it has therefore been examined by the Sandmeyer method alone.The corresponding chlorodisnlphonic acid yields a chloride which crystal- lises from benzene, in which it is sparingly soluble in the cold, either in prismatic needles or well-formed prisms, from a mixture of benzene and petroleum spirit in fiat needles and from acetic acid in long, prismatic, flat needles ; it meIts at 158", and on distillation with PCI, is converted into 1: 2 :4'-trichloronaphthalene, crystallising from alcohol in long, slender, flat needles melting at 78-78.5" (these Proc., 3Y89, 49). It follows, therefore, that this amido-acid has the con- stit ution S 130 (3.) 2 :3'-p-Naphthylam~ne-~-sul~r~~onicAcid (Briisaneracid).-When stirred into four times its weight of 20 per cent. anhydrosulphuric acid at a temperature not exceeding 20°, the Bronner acid is readily further sulphonated, the process being completed in from 16-20 hours.The product is found to consist of two isomeric acids ; the minor product, perhaps 20 per cent., has been identified as G-arnido- disulphonic acid by the hydrazine and Sand meyer methods (v.supra). Chief Product.-The acid potassium salt of this acid crystallises in opaque, white radiate aggregates of short needles, difficultly soluble in water ; but the crystalline form and solubility are much influenced by the presence of small quantities of amido-G-acid, and there is every reason to regard it as identical with the acid obtained by Forsling (Ber., 1888, 3496) by heating Bronner acid mith 3 to 4 parts of "fuming sulphuric acid '' (percentage of added SO, not stated) at 110" until the product was soluble in water.When reduced by the hydrazine process, the amido-acid constituting the chief product gave naphthalene-1 :3'-disulphonic acid, which was characterised by means of its sulphochloride melting at 12'7",and the derived 1:3'-dichloro-naphthalene melting at 48.5". On treatment by the Sandmeyer pro- cess, it was converted into a chlorodisulphonic acid, the chloride of which crystallised from benzene, in which it was readily soluble, in well. formed prisms, from a mixture of bcnzene and light petroleum in small prisms showing good faces, and from acetic acid in prismatic needles ; it melted at 124.5-L25", and on distillation with PCl, gave 1 :2 : 3'-trichloronaphthalene crystallising from alcohol in tufts of short, very slender needles meltling at 92" (these Proc., 1889, 52).Combining these results, the amido-acid constituting the chief pro- duct, and presumably Forsling's acid, has the constitution :-S By operating at higher temperatures the yield of this acid is di- minished, and that of the amido-G-acid increased. (4.) 2 :2'-~-Na~phthylamine-~-sul~~onicAcid (Bayer and nuisberg's delta-acid).-When stirred into four times its weight of 20 per cent. anhydrodpburic acid at a temperature not exceeding 25",delta-acid yields a complex product, which has not yet been satisfactorily separated into its constituents. Although the acid was very carefully purified and, it is believed, was freed from Brocner acid, one of the disulphonic acids obtained from it and forming a considerable pro- portion of the product, had the constitution and properties of the p-naphth ylamine-1 :3'-disulphonic acid prepared from pure Bronner 131 acid.Two other products were obtained and are at present under investigation ; one of these is converted by the Sandmeyer process into a chlorodisulphonic acid which seems to be identical with that derived from th'e sulphonated Dahl acid of the constitution The investigation of the changes which occur in the conversion of these various- acids into amido-R-acid on the one hand and the Cassella p-naph tfhylamine-6-disulphonic acid on the other are at present under investigation, and the authors hope to be in a position shortly to communicate in a final form results indicating the influence exercised by NHz, as compared with Cl and OH in a @-position on the formation of disulphonic acids.63. '' Studies on the const8itutfion of the tri-derivatives of naptha-leno. No. 8. p-Chloronaphthalenedisulphonic acids." (Firdt notice.) By Henry E. Armstrong and W. P. Wynne. As already indicated in a previous communication, the study of the disulphonic acids obtained by sulphonating chloronaphthalene- sulphonic acids of known coiistitution is being carried on pari puss?& with that of the acids derived from the various naptithylaminesul- phonic acids (these Proc., 1890, 18). A brief account of the results obtained with the four heteroriucleal ,%chloronaphthalenesulphonic acids under like conditions is now given, details with reference to the composition of the salts, &c., being reserved for a full communication.Sulphonation was effected by adding the theoretical quantit,y of sulphuric anhydride, employed in the form of 20 per cent. anhydro- sulphuric acid, to the dry potassium p-chloronaphthalenesulphonate and heating the warm mixture at 100" for an hour, the potassium sulphate iormed being removed by treatment with alcohol and the excess of sulphuric acid by means of barium carbonate. (1.) 2 : l'-P-Chloron~phthalene-a-s?~l~~lionicAcid.-This acid, under the conditions named , gives a uniform chl oronap ht 11alened isul phonic acid, the chloride, C,,H,CI( S0,Cl)2, of which crystallises from benzene, in which it is comparatively sparingly soluble, in beautiful radiate groups of long, slender, lustrous needles; it melts at 170", and on distillation with PCI, gives 1 : 3 : 2'-trichloronaphthalene melting at S /-iAc1 113".The constitution of the acid is therefore I 1 1 ,and cor- \A/ 132 responds with the G-amido-acid obtainable from the 2 : l'-p-naph-thylamine-a-sulphonic acid. (2.) 2 :4'-~-Chloronap7~thaler~e-~-s~l~~onicAcid.-This acid gives what seems to be a uniform product. The potassium salt of the chlorodisulphonic acid is particularly well characterised, since it crystallises in prismatic forms, whereas the corresponding salts of the isomeric acids crystallise in slender needles. The chloride, ClnH,C1( SO,Cl),, is apparently dimorphous and crystnllises from benzene for the most part in very lustrous scales, but occasionally in prismatic forms, both of which melt at 156-156.5", and on distilla- tion with PCI, give the same trichloronaphthalene melting at 79".This trichloronaphthalene has not yet been compared by sulphonation, &c., with the 1 :2 :4'-and the 1 :3 : 3'-trichloronaphthalenes, with one of which it must be identical, owing to the insufficient supply of material; most probably it has the consiitution 1 : 3 : 3'-and cor-responds with that derived from t'le arnido-acid constituting the chief product of the further sulphonation of the 2 : 4'-/3-naphthylamine-a-sulphonic acid. (3.) 2 : 3I-p-Chloronaphthalene-.&sulphonic acid.-Under the con-ditions named, this acid gives two chlorodisulphonic acids which are best separated by the fractional crystallisation of the potassium salts.The less soluhle potassium salt constituting the minor product yields a chloride CloH5C1(S0,Cl)2, which argstallises from benzene in aggre- gates of what at first sight seemed to be radiate prisms, but under a lens were found to be composed of bundles of very slender needles aggregated in prismatic forms, having a silky lustre ; it melts at 148", and on distillation with PCL, gives 1:3 : 2'-trichloronaphthalene, crystallising from alcohol in characteristic tufts of needles melting at 113". The more soluble potassium salt constituting the major prodact was found to give products identical with those obtained from the chlorodisulphonic acid derived from 2 :1'-p-chloronaphthalene-a-sulphonic acid (v.supru). The chloride crystaUises from benzene in radiate groups of needles melting at lti9", and on distillation with PCI, yields 1: 3 : 2'-trichloronaphthalene melting at 113". The constitution of the two acids is represented by the formulm- S Minor product. Major product. Cl(SO,Cl),, m. p. = 148'. Cl(SO,Cl),, m. p. = 169'. (4.)2 : 2l-13-Chloronaphthalene-P-sdphonic Acid.-This acid, under 133 the above conditions, yields a uniform chlorodisulphonic acid, the chloride of which, C,,H,C I (SO,Cl),, crystallises in beautiful radiate groups of flat, prismatic needles melting at 174". On distillation with PCl, the chloride is converted into 1 :3 :3'-trichloronaphthalene, crystallising from alcohol in radiate groups of long, slender needles melting at 80.5".The acid has, therefore, the constitution- 64. "The comparative influence exercised by the radicles C1, OH and NH, in naphthalene-derivatives on the formation of disulphonic acids.'' By Henry E. Armstrong and W. P. Wynne. The results obtained by the comparative study of the influence exercised by radicles such as C1, OH and NH, on the formation of diwlphonic acids, of which an account has been given in the fore- going notes and in previous communications by the authors, are such as to throw much light on the laws which govern substitution in the naphthalene series and are moreover highly suggestive.The results obtained in the case of the chloro- and smido-acids are collected in the following diagram. S S S S One fact to which attention may be directed, which appears to be most clearly established by the investigation of a very large number of disulphonic acids, is the "invincible objection " of two sulphonic radicles to remain in either contiguous or para-or peri-positlions. The expression " remain in " is used advisedly, as the authors believe that, inasmuch as action more often than not takes place in the first instance in accordance with the so-called a-law to which they have 134 repeatedly directed attention, such positions are sometimes initially assumed by two sulphonic groups. It is a question whether the final acquisition of other posifions than a-positions is a consequence of direct isomeric change, or of the formation of higher sulphonic acids and their subsequent partial hydrolysis. Different radicles undoubtedly exercise a very different and most important influence in determining such secondary changes.Thus /3-naphthol on treatment with sulphonating agents is converted into a sulphate which very readily undergoes isomeric change into the 2 : 3‘-sulphonic acid ; P-na,phthylamine sulphate undergoes a similar change, but much less readily, being converted into the 2 :3’-sulphonic acid only after long heating at a high temperature : in this latter case the formation of the sulphurnic acid probably precedes that of the sulphonic acid, and either the sulphamic acid is formed with difficulty from the sulphate, or, when formed, does not readily undergo isomeric change.a-Naphthylamine and a-naphthol differ in a similar manner. When excess of sulphuric acid is used, opportunity is given for sulphonat.ion to pursue a different course : the characteristic proper- ties of the phenol and amine are, in a sense, obliterated owing to tlie formation of sulphates, and these sulphates behave much as do corre- sponding derivatives containing a neutral radicle-chlorine, for example. Then, if /.3-naphthylic sulphate be sulphonated by S03HCl with-out application of heat, a disulphonic acid is at once obtained which, S there is reason to believe, has the constitution IA’‘ OH (ej.ll\A/Berichte, 1882, 204); the formation of this compound affords tthe most significarit indication of the course of change : evidently the homo-a-hydrogen atom contiguous to the O*S03H-group of tlie sulphate is first displaced ; the resulting sulpho-sulphate, how..ever, spontaneously undergoes isomeric change. /I-Naphthylamine sulphate, apparently, behaves somewhat differently, yielding the 2 : 1’-and 2 : 4’-monosulphonic acids : in this case the NH,.H,SO,-group may be supposed to remain unchanged; but it is not im-probable that the homo-+hydrogen atom contiguous to this group is primarily displaced by SO,H, which then passes spontaneously into the contiguous peri-a-position, giving rise to the ‘2 : 1’-acid : the formation from the 2 : 3’-and 2 : 4’-monosulphonic acids of disulph-onic acids containing the S03H-group in the homo-a-position con-tiguous to the NH, affords the strongest support to this view.The formation of the 2 : 4’-monosulphonic acid from i3-naphthylamine sulphate is perhaps the outcome of au independent action. 135 Tn the case of p-chloronaphthalene, it is conceivable that the 2 : 1-sulphonic acid is the immediate product, and that this spontaneously changes into the 2 : l’-acid which is actually obtained as chief pro-dnct ; the 2 : 3’-acid which is obtained as subsidiary product may be formed by spont,aneous isomeric chanqe from 2 : $’-acid initially produced on sulphonation rather than by the isomeric change of the 2 : 1’-acid at the moment of formation ; this view being supported hy the fact that p-iodona,phthalene affords a small proportion of 2 : 4’-acid (cf.these Proceedings, 1889, 120). In short, it is not impossible that the P-mono-derivatives all behave similarly on siilphonation, acting in a minor degree as naph-thalene itself would, but chiefly as mono-derivatives ; and that the differences in the structure of the ultimate products are due to the different manner in which secondary change takes place under the diverse influences of various P-radicles. The same argument would apply to 2-compounds. The peculiar differences manifest in the case of monosulpbonic compounds are also to be noted in the case of disulphonic (cf. diagram, p. 133)-the product of further sulphonation is, as a rule, simpler in the case of the chloro-acid than in the case of the amido-acid ; and chanye proceeds further in the case of the hydroxy- than in that of the NH,-compound, as is evidenced by the formation of R-to<gether with G-disulphohydroxy-acid under conditions which do not give rise to R-amidodisulpbonic acid.In the case of the 2 : 1‘-amidosulphonic acid, the homo-a-position contiguous to the NH, is, perhaps, screened from attack ; and either a 1: 4-disulpbonic acid is first formed, or, under the dehydrating influence of the sulphuric acid present in excess, a suZphhamic-suZphhonic acid is gradually produced, which then undergoes isomeric change : it appears not improbable, from the exceptionally slow manner in which sulphonation takes place, that the latter is the correct ex-planation. The remaining three isomeric p-amidomlphonic acids, in all pro-bability, are at an early stage-for it is possible that a sulphamic acid is the first product of sulphonation-if not initially converted into 2 : 1-homosulpho-derivatives; but it is a question whether these then undergo a simple isomeric change, or whether the final products are formed from them by their convereion into higher sulp’nonic acids which then suffer hydrolysis.The behaviour of 1 : 2-chloro-/3-naph-thylamine on sulphonntion (cf. these Proceedings, 1869,36,48) apptlars rather to support this latter view, as the passage of the sulpho-group through the positions 1 -2 -+ 3 takes place with a much greater facility than is usual in cases of non-spontaneous isorzieric change.It is true that the conditions under wliich snlphonation is effected are 136 such that no water is present; but, bearing in mind the tendency of H,SOI to combine with SO3, it is by no means improbable that H,SO, itself may effect the hydrolysis. Lastly, attention may be called to the occurrence of "homo-sulpho-nation " in the case of the two chloro-p-sulphonic acids ; the products in question are, perhaps, direct sulphonation-products, but it is also conceivable that the d : l-chloro-sulphonic acid is first formed, and that this undergoes isomeric change to the 2 : $-acid, in consequence of the guarding influence exercised by the hetero-IS-sulphonic radicle.The results obtained in the case of the Dahl No. I1 acid are of special interest, as one of the sulpho-groups is in the P-posit,ion alternative to that occupied in the acid which yields naphthol-yellow S ; it is, hence, possible that, in the first instance, naphthionic acid yields a peri-disulphonic acid, and not the Schollkopf acid. The solution of these various problems will necessitate much further study ; but obviously their settlement is of importance in relation to the theory of the formation of substitution-derivatives generally. 65. ''Note on the action of potash on naphthalene-1 : 3-disulphonic acid." By Henry E. Armstrong and W. P. Wynne. When the authors' naphthalenemetadisulphonic acid (these Proc., 1890, 13) is fused with 3-4 times its weight of caustic potash at 280-300" for several hours, it gives a product which consists chiefly of a trihydroxynaphthulene,C,,H,(OH), (C = 67.7 per cent., H = 4.6 per cent.).This crystallises from water in minut>e scales, from light petroleum (b. p. = 30")in small, white aggregates of no definite form, and melts at 120-121". It sublimes in lustrous, thin scales; is extremely soluble in ether, chloroform, carbon bisulphide, acetone and benzene ; and gives no characteris tic coloration with ferric chloride. The study of the action of potash on naphthalenemetadisulphoiiic acid is being continued. 66. "The acr,ion of zinc on dilute sulphuric acid." By F. Pullinger, B.A.,B.Sc., late Scholar of Corpus Christi College, Oxford.The author has carried out a series of experiments with zinc prepared by thrice distilling in vacuo zinc purchased as '' chemically pure," and has arrived at the following conclusions :-(i.) That zinc with a perfectly smooth surface is not acted on by dilute sulphuric acid which has been submitted to prolonged boiling. (ii.) That zinc with a rough surface is readily acted on by acids, but in a less degree by those which have been boiled than b17 those which have not. 137 (iii.) That oxidising agents, such as electrolysed sulphuric acid, hydrogen peroxide and nitric acid, increase the rate of dissolution. (iv.) That a reducing agent such as hydrogen iodide almost entirely prevents dissolution ; but that those containing sulphur, such as sulphur dioxide, are without effect.(v.) That in all probability persulphuric acid is the uwu causa of the dissolution of zinc in the so-called '' pure " sulphuric acid. (vi.) That pure dilute sulphuric acid would, at ordinary tempera- tures, be entirely without action on zinc, whether the surface of the latter were rough or smooth. 67. "Acetyltrimethylenecarboxylic acid." By T. Rhymer Marshall, D.Sc., and W. H. Perkin, jun., Ph.D., F.R.S. When ethylene bromide acts on ethylic sodacetoacetate, an oil, C8H1203,is formed which boils at 196" ; on hydrolysis this yields an oily acid, C,H,O,, to which the name Acetyltrimethylenecarboxylic CH,*C0.C. C00H acid a,nd the formula, /\ were assigned (Chem. SOC. CHZ-CH, Trans, 1885, 47, 834).In a research published a short time since, Lipp (Bey., 22, 1201) states, as the result of some experiments on acetopropyl alcohol, that this formula is incorrect, and must be CH,rC--C H*COOH replaced by O< I CH,*CHZ The authors have very carefully reinvestigated the subject with the following results :-Acetyltrimethylenecarboxylic acid and hydroxylamine readily interact forming a crystallin: hy droxime, CbK9NO3,which melts at 145". On reduction with sodium amalgam, the acid is converted into a-ethyl-/3-hydroxybutyricacid, CH,*CH(OH).CH(C,H,)COOH ; this forms a thick, colourless syrnp, yielding on distillation a-ethylcrotonic acid, CH,.CH:C (C2H5).COOH. A drop of a solution of pot<assiumpermanganate added to a. solution of acetyltrime thylenecar boxylic acid in a dilute solut'ion of sodium carbonate is not decolorised, even on long standing-a proof that the acid is a saturated compound, and cannot have the formula, ascribed to it by Lipp (compare Baeyer, Annulen, 245, 146).Acetyltrimethylenecarboxylicacid readily splits up on heating into CH2acetyltrimethylene, CH,.CO*CH< I ,and carbm dioxide. CH2 Acetyltrimethylene and hydroxylamine interact to form a hydr-cxime, C5HgN0,which crystallises from petroleum spirih in beautiful, glittering prisms. When reduccd by means of sodium (in moist 138 ethereal solution), acetyltrimethylene yields methylpropylcarbinol, CH,-CH(OH)*CH,*CH,*CH,,which boils at 119.5" (compare Saytzew, Wagner, Annalen, 179, 318).Methylpropylcarbonyl acetate, CH,*CH(C,H,O,).C,H,, obtained by boiling the alcohol with acetic anhydride, boiled constantly at 133.5.-CH,*S(OH)*C,H,Dimethy ldipropylglycob, CH,C(OH).C3H,' is produced, together with methylpropylcarbinol, by the. reduction of acetyltrimethylene. It is a thick oil which boils at 220-285" (Friedel, Jahwsb., 1869, 513). Fuming solution of hydrogen bromide converts acetyltrimethylene, at ordinary temperatures, quantitatively into acetopropyl bromide, CH3*C0.CH,.CH2*CHzBr(b. p. 120" at 75 mm.), a proof that CHz=C -CH, acetyltrimethylene cannot have the formula O< I . CH,.CH, CH,*Cz=C.C 0OH Methyldehydropentonecarboxylic acid, 0< I , is CH,-CH2 always formed in small quantities, together with acetyltrimethylene-carboxylic acid, by the action of ethylene bromide on ethyd sodaceto- acetate (Freer and Perkin, Chem.SOC.Trans., 1887, 51, 822). In one experiment, this acid was obtained in large quantities and free from acetyltrimethylenecarboxylic acid. It crystallises from benzene in large, apparently monoclinic prisms which melt at 150". It does not interact with hydroxylamine ;its alkaline solution decolorises perman- ganate instantly, in which respects it differs very markedly from acetyltrimet hylenecarboxy lic acid. When boiled with water, methyldehydropentonecarboxylic acid is ent'irely converted into acetopropyl alcohol, carbon dioxide being evolved. CH,.C=CH, ~ethyldehyd?.o~entone,O< I , is formed when the acid CHZ-CH, is distilled. It is a colourless, ethereal liquid ; b.p. 82", rel. den. at 15" = 0.9107, magnetic rdation 5.391. When shaken with water it rapidly dissolves, forming acetopropyl alcohol. A careful study of these results shows that acetyltrimethylene- carboxylic acid is a saturated ketonic acid, and that it cannot have the constitution proposed by Lipp. Lipp's formula represents an acid which may be identical with methyldehydropentonecarboxylic acid, but which in any case mnst possess properties closely allied to those observed in this acid, and which are entirely distiuct from the properties of acetyltrimethylenecarboxylicacid. HARBISON AND SONS, PRINTERS IN OBDlNABY TO Hblf MAJESTY, 6T. NARTIK'S LANK.
ISSN:0369-8718
DOI:10.1039/PL8900600107
出版商:RSC
年代:1890
数据来源: RSC
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