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Abstracts of the Proceedings of the Chemical Society, Vol. 3, No. 41 |
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Proceedings of the Chemical Society, London,
Volume 3,
Issue 41,
1887,
Page 89-103
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摘要:
ABSTRACTS OF THE PROCEEDINGS OF TEE CHEMICAL SOCIETY. No. 41. Session 1887-88. June 16th, 1887. Mr. William Crookes, B.R.S., President, in the Chair. Mr. William Henry Coates was formally admitted a Fellow of the Society. Certificates were read for the first time in favour of Messrs. George Carrington, B,A.,Missenden Abbey, Great Missenden, Bucks ; Yoshimosa Koga, Imperial Mint, Osaka, Japan ; William Henry Richardson, Dudley ; Arthur Walley Warrington, Dinglefield, Dingle Lane, Liverpool. The following were elected Fellows of the Society :-Messrs. Hugh Barclay, William Bott, L. C. Darmiell, Ernest Francis Ehrhardt, William Nathaniel Evans, Frederick William Freeman, Edward Day Gravill, Herbert James Gover, John Edward Green, Richard Nelson Jones, M.R.C.S., Khasberas B, Jodhara, J.&I.Kava-nagh, William Mar shall, Henyy Hewetson McMinnes, Fred. Lawrence Overend, B.A., J. Stanley Phillips, John T. Sheard, Walter Shelley Spencer, Charles Ernest Stedmsn, Henry Livingstone Snlman, Frank Traphagen, Ph.D., Frederick Percy Watson, and John William Young, B.A. The President announced that the following Address had been presented to Her Majesty :-TO THE QUEEN’S MOST EXCELLENT MAJESTY. MAYIT PLEASE YOURMAJESTY, On the happy completion of the fiftieth year of your Most Gracious Majesty’s reign we, the President, Council, and Fellows 90 of the Chemical Society, established in 1841 and incorporated under a Charter granted in the 12th year of your Majesty’s reign, desire to present to your Majesty our sincere congratulations and to express our loyal devotion to your August, Person and to your Throne.We humbly submit, amidst the general rejoicing, that we have special reason to rejoice in the growth of Science, and particularly of Chemical Science, which characterises your Majesty’s wise and beneficent reign. If it be borne in mind to what an extent the applications of Chemistry are now essential to the prosperity and the security of your Majesty’s Empire, this development assumes a truly national importance. Chemistry is of no nationality, yet the names of Black, Cavendish, Dalton, Davy, Paraday, and Graham fully testify to the vigour of its growth on British soil. From a variety of causes, however, its culti-vation in this counhry during the second quarter of the century seemed to be falling into neglect, and it is to His Royal Highness the late Prince Consort that the nation is very largely indebted for its revival.The turning point in the history of Cbemical Science in your Majesty’s Dominions was the foundation of the Royal College of Chemistry in the year 1845. To the success of this College the Prince Consort contributed, not merely by his personal munificence and by consenting to become its first President, but more particularly by using his influence to overcome the obstacles in the way of the appointmeiit of its first, Professor. The result cannot be exaggerated; indeed, a majority of British Chemists of the younger geueration are directly or indirectly the pupils of that College, while the discoveries in Chemical Science of its Students may well rank amongst the most brilliant achievements of your Majesty’s reign.If Chemical Science in this country is no longer ignored, but is recognised as essential to national prosperity, if Chemistry has won its rightful place in the curriculum of the higher education, and if laboratories properly organised for the conduct of this intellectual discipline are to be found in British Universities, Colleges, and Schools, these happy changes are mainly due to the exertions and influence of the late Prince Consort and to the impulse given by the Royal College of Chemistry in response to his encouragment. The Prince Consort’s enlightened zeal in the furtherance and development of Science in the country of his adoption is universally recognised, and we rejoice to find, thatl His Royal Highness the Prince of Wales treads in the footsteps of his illustrious Father.It is our most earnest prayer thaf your Most Gracious Majesty may long be spared to reign over a happy, loyal, prosperous, and united empire, and that your Majesty’s enlightened and beneficent example may steadily be followed and held in grateful remembrance. We remain, with profound respect, YOURMAJESTY’S SERVANTS.MOSTFAITHFUL The following Papers were read :-59. “A Study of the Thermal Properties of a Nixture of Ethyl Alcohol and Ethyl Oxide.” By William Ramsay, Ph.D., and Sydney Young, D.Xc.The authors have previousIy shown that for* both the gaseous and the liquid states, the relation of pressures to temperatures at constant volume may in thte case of methyl and ethyl alcohols, ethyl oxide and carbon dioxide, and presumably in the case of all stable liquids, be expressed by the formula p = bt -a; i.e., the isochoric lines, or lines of equal volume, for unit mass of the substance, are straight whcn mapped against pressures as ordinates and temperatures as abscisss. They also showed that in the case of the two dissociating substances, acetic acid and nitric peroxide, such isochoric lines are not straight, but are, at large volumes, tangential to the theoretical isochoric lines of minimum density at higher temperatures, and at lower tempera- tures probably tangential to the theoretical isochoric lines of maximum density.A comparison of the behaviour of such stable and dis- sociable substances has shown the effect of chemical union on the relations of pressure, temperature and volume. But the mixture of two liquids, such as alcohol and water, is known frequently to be accompanied by contraction and by evolution of heat. It therefore appeared of interest to thoroughly investigate the behaviour of such a mixture in order to throw light on the nature of this attraction. Experiments were therefore made with a view to dehermining the relations of volume, pressure and temperature between wide limits with a mixture of alcohol and ether, of which, individually, the constants have already been obtained.The most striking conclusions are (1)the dependence of pressure during condensation on volume, so that the vapour-pressures are represented not by a line but by A band ; (2) the curvature of the isochoric lines at temperatures and pressures near the condensing points of the mixture; (3) the great alteration of volume under certain conditions on mixing the two bodies, amounting, on the one hand, in some circumstances to a contraction of 4 per cent., and in others to an expansion of 115 per cent. DISCUSSION. Professor DEWARsaid that in dealing with the historical part of the subject the authors of the paper had in his opinion omitted to do full justice to the work o€ Amagst and other investigators.A short time ago, Messrs. Ramsay and Young had communicated a paper to the Royal Society, entitled "A Preliminary Kote on the Continuity of the Liquid and Gaseous States of Matter,'' which had been referred to that evening, purporting to contain a discovery which was nothing more than a simple elementary deduction from Van der Waals' formulz representing the continuity of the gaseous and liquid states of mafter. The Van der Waals formula had been improved upon by Clausius ; in its original form, however, it was still sufficient to account for Andrew's isothermal law and Amagat's law of the limiting volume of a gas under high pressure: two of the most important experimental deductions fiToru x vast number of observa-tions. Professor Amagat in continuing his work had discarded all antecedent theoretical views, and had confined his attention to the approximate laws he could deduce from the experimental facts.He had long ago given the equation that Messrs. Ramsay and Young evidently thought important enough to embody in the form of a paper. In dealing with this subject the mass of calculations made by the authors may satisfy some views, but real progress in this department of physico-chemical inquiry can only be made by reaching greater accuracy in the measurements ; always assuming that the substances examined are pure. Endless repetitions of details can only cumber the ground, not clear it. The experiments on the critical volume of PH4Cl,to which Dr. Young referred, were in reality made by a, pupil of the speaker (Mr.Skinner), and had already been publisf led. Dr. YOUNG,in reply, said that the work of Amagat and otters Wi1S referred to in the paper, but owing to the short time at his disposal he had been unable to do full justice to the histcry of the subject that evening. Although Van der W-aals' formula could be converted into theirs, the converse was not the case ; moreover, Van der Waals' formula did not represent the facts. 60. "Derivatives of Hydrindonnphthene and Tetrahydronaphtha- lene." By W. H. Perkin, Jun., Ph.D. The author describes experiments which have enabled him to prepare from orthoxylens derivatives of the closed chain hydro-carbons CaH*<g::>CHs and CG"*<cH,.cH,>CH2*CH2 Hydrindonaphthene.Tetraby dronaphthalene. 93 Hydrindonaphthenedicarboxylicacid was obtained from the ethylic salt forrned by the action of the dibromide, C6H4(CH2Br)2-prepared by heating orthoxylene with bromine at 125”-0n the disodium-derivative of ethylic malonate, CNa,(COOEt), ; when heated at 200”, this acid is resolved into carbon dioxide and hydrindonaphthene-carboxylic acid. Tetrahydronaphthalene-derivatives were obtained in two ways : 1. By the action of orthoxylylene dibromide on the disodium-deriva- tive of ethylic acetylenetetracai*hoxylate, qNa(COOEt), . CNa(COOEt),’ the end result of the following series of changes-ethylic sodio-monochloromalonate, CNaCl (COOEt),, having been submitted to the action of orthoxyly lene dibromide ; the resulting compound, C,H,[CH,-CCl(COOEt),],, was digested with zinc-dust and acetic acid, and the chlorine having been displaced by hydrogen, the product was CH,*CNa*(C0OEt)converted into the disodium-derivative, C6H, CH,*CNw(COOEt),’ which on treatment with iodine gave the theoretical amount of tetra-hgdranaphthalenetetracarboxylate.On heating the tetracarboxylic acid at 200”,it is resolved into CO,, water, and the anhydride of tetra-hydronaphthalenedicarboxylic acid ; on dry distillation of the silver salt of this latter acid, naphthalene is produced together with the anhydride of tetrahy dronaphthalenedicarboxylic acid, silver, CO?, and water. 61. “ The Synthetical Formation of Closed Carbon Chains in the Aromatic Series.” By F.S. Kipping, B.Sc., Ph.D. The author describes experiments which were instituted with the object of ascertaining whether it would be possible, by substituting meta- and para-xylene for ortho-sylene, to obtain isomeric tetrahydro- naphthalene-deri vatives OP the formulte- ~ CH2* CH*C00HA-cH,G H-coOH and 0 1 LCH,-CH-COOH The method of procedure was the same as that described in the pre- vious paper. Meta- and para-xylylene dibromides were each treated with ethylic sodiochloromalonate, the product was reduced with zinc- dust and acetic acid, and the reduction product was converted into the sodium-derivative, which was treated with bromine, The reaction appeared to take place with perfect regularity, sodium 94 bromide separating ; but on examination it was found that the greater part of the product consisted of the unchanged substaiice, and no new closed chain compound could be detected.It is difficult to understand what really takes place in tliese reactions, or what the precise action of the bmmine on the sodium compound is. DIscussmx Dr. MILLERthonght that since the authors had not yet proved even the possible existence of rings consisting of 7 and 8 carbon atoms, the experiments quoted by them could not be considered as proof that ring-formation from two side-chains attached to a benzene nucleus depends solely on position. The chain of 6 carbon atoms in the ortho- compound, CBHP<C~,.C~~(C~~E~),, CH2*CNa(COOEt)z might be expected to yield a ring composed of 6 carbon atoms, because such rings are not only possible but, possess very great stability.There is, however, nothing surprising in the fact that the chains .of 7 and 8 carbon atoms in the correspoiiding meta- and para-compounds do not yield corre-rpponding rings, .espscially when considered in conjunction with Dr. Perkin’s other unsuccessful attempt to produce a ring containiiig 3 atoms of carbon. The well-known property possessed by so many ortho-derivatives of readily yielding anhydro- and other ring-deriva- tives is without doubt a function of the 1: 2 position, but whether this is so in the case of the above-mentioned compound cannot be regarded as proved. Indeed it is conceivable that the length of the side-chains may be an important factor in determining the condensation.It would be interesting to asccrtain whether an ortho-derivative of similar con- stitution to the above, but containing an additional atom-of carbon in each side-chain, would also yield a ring-derivative ; if not, it would be an argument that ring formation depends on length of chain as well as position. Dr. KIPPINGsaid, in reply, that he had anticipated the objection raised to the theoretical conclusions he had deduced from his experi- ments. He had, therefore, tried a number of experiments on the action of metaxylylene bromide on the sodium-derivative of ethylic malonate. If a reaction analogous to that, which resulted in the forma- tion of hydrindonaphthene-derivatives from orthoxylylene bromide were to take place, a compound should have been formed containing a ring consisting of six carbon-atoms, in which, however, the junction was effected to carbon-atoms in the meta-position.In no case, how-ever, could such a substance be obtained. It, therefore, appeared to him that the main reason why ring formation did not take place when 95 meta- and para-derivatives of benzene were used, was that the side- chains were not in a suitable position. 62, '' The Product of the Action of Ethylene Bromide on' Ethylic Acetosodacetate." By P. C. Freer, Ph.D., and W. H. Perkin, Jun., Ph.D. The compound formerly described by W. H. Perkin, Jun., as ethylic acetyltetramethylenecarboxylatehaving been proved to con- tain a carbon-oxygen-ring, being an anhydride of a carboxylate of acetobutjlic alcohol, it was thought advisable to examine the product of the action of ethylene bromide on ethylic acetosodacetate, in order to finally settle the nature of the compound known as ethylic acetjl- trimethylene carboxylate.Ethylene bromide interacts with ethylic acetosodacetate, forming a compound, CBHI2O,,to which the following formulae are applicable :-That the first is inapplicable has been shown in a previous publica- tion ; further experiments show that the product is to be regarded as a,mixture of the compounds represented by the latter two formulae. That this is the case is proved by the decomposition of the acid obtained from the ethereal salt ; if this be distilled, GOz is given off, and an oil passes over, separable into two substances, one boiling at 112", which is insoluble in water, even after standing for weeks ; the other boiling 20" lower, which gradually dissolves in water, forming acetopropylic alcohol.It ia therefore safe to regard the ethereal salt CBHlz03as a mixture of ethylic acetyltrimethylenecarb- oxylate with a compound which it is proposed to call ethylic wethyl-deliy dropentonecarbo~cylate. The acids obtained on hydrolysing the ethereal salt just referred to are decomposed on boiling with water into Cc), and acetopropylic alcohol. This reaction is in entire accordance with the charact,er of the trimethg lene-ring, as shown in the change of trimethylenedicarb-oxylate into carbobutyrolactone.The ether CSHtI,,O3readily combines with hydrogen bromide, form-ing ethylic w-bromethylacetoacetate, a change which is likewise in accordance with the behaviour of the other trimethylene compounds. If this latter compound be boiled for some hours with dilute muri- atic acid, it is quantitatively converted into alcohol, CIO,, HBr, and acetopropylic alcohol. Ace topropylic alcohol is easily reduced by sodium amalgam, being converted into y-pentylenc glycol. 96 63. “ Derivatives of Pentainethylene.” By H. G. Colman, B.Sc., and W. H. Perkin, Jun., Ph.D. pi-Pentylene glycol, CH,-CH*( OH)*CH,*CH,~CH,(OH), is converted by the action of HBr into the corresponding y-pentylene dibromide, CH,,*CHBr.CH2*CH,*CH,Br. When this bromide is mixed with ethylic sodiomalonate in alcoholic solution the following reaction takes place :-CH,*CH*CH, CH,’ 1 + CH2<ggk + 2NaBr.‘CH,*C (C02Et), Ethylic methylpentamethylenedicarboxylateis a pleasant-smelling oil, b. p. 243-2.44”. The corresponding acid is crystalline, and melts at 173-175”, decomposing into CO, and methylpentamethylene-monocarboxylic acid. The latter is a coloui~less liquid which boils at 220”; it possesses a penetrating smell similar to tshat of butyric acid. 64. “ The Synthesis of Hexamethylene-derivatives.” By P. C. Freer, Ph.D., and W. H. Perkin, Jun., Ph.D. Hitherto all attempts to synthesiae hexamethylene-derivatives have been unsuccessful owing to the impossibility of obtaJning a penta-methylene dihromide of the formula CH,Br~CH,~CH,*CH,*CHBr, which could be submitted to the action of ethylic sodiomalonnte.The authors have, however, succeeded in preparing a homologue of the desired bromide from acetobutylic alcohol, Ac*CH,*CH,*CH,*CH,OH. This alcohol is readily reduced to 6-hexylene glycol by means of sodium amalgam, as Lipp has shown. This glycol is completely con- verted by treatment with hydrogen bromide into 3-hexylene dibromide, CH,*CHBr.CH,*CH2*CHz.CH,Br,which interacts with ethylic sodio- inalonate, forming ethylic methylhexamethylenedicarboxylate, CH,*CH.CH,*C H,*CH,* C Hz*C(C0 0 Et),. 65. “ An Attempt to Syn thesise Eeptamethylene-derivatives.” ByP. C. Freer, Ph.D., and W. €3. Perkin, Jun., Ph.D. If 8-hexylene dibromide, CH3*CHBr*(CHZ),*CH2Br, be treated with two molecular proportions of ethylic sodiomalonate, the tetracarbo- xylate, (COOEt),CH~CH(CH,)*(CH,),*CH(COOEt),,is produced.It appeared p robable that if the disodium-derivative of this compound were treated with bromine a closed &asin heptamethylene-derivative would result. This, however, was found not to be the case, the action taking place in some other manner not yet made out. DISCUSSION. Dr. ARMSTRONGsaid that the problem which Dr. Perkin and his associates were endeavouring to solve was one of great t,heoretical importance. In rcpresenting the compounds which had been described as derivatives of closed-chain hydrocarbons, they were undoubtedly formulating what would appear to be the simplest interpretation of the synthetical methods adopted ; but there was little independent conclusive evidence to support their view.In several respects the behaviour of the compounds was by no means that of closed-chain derivatives ;thns it was remarkable that the trimethylene-ring should be easily split by h-j-drogen bromide and by water, but not by bromine. If, however, a closed carbon chain could be split by such means, the conditions realised in the case of the trimethylene-compound described by Freer and Perkin were certainly those which would tend most to favour such a change. In illuatration of the difficulty of determining whether a compound was saturated, the speaker referred to xeronic acid, which Fiktig had represented as the derivative of a closed chain of 4 carbon-atoms, but which has recently been proved to be a diethylfnmaric acid.Assuming that the compounds described were closed-chain derivatives, the failure to obtain a heptamethylene-derivative gave weight to Dr. Miller's objection to Dr. Hipping's argu- ment, and justified the conclusion that the number of carbon-atoms as well as position had to be taken into account. Dr. JAEJPreferred to the hydrocarbon pyepared by Burton alnd himself from anhydracetonebenzil (Chern. SOC.Tmns., 1887,423) ; it is highly probable that this is a tetra-or pent'a-methylene-derivative, and it is noteworthy that it does not undergo any change if heated with iodhydric acid and phosphorus at 150".66. "The Composition of Shale-spirit." By A. I(.Miller, Ph.D., and T. Baker, B.Sc. The authors have sought to determine (a) whether shale-spirit contains any higher olefines than those found in the liquid mixture of hydrocarbons from oil-gas, and (b) the constitution of the olefines, Armstrong and Miller having. shown that heptylene was the bighest hydrocarbon of the C,H,, series present in oil-gas products, and that all the olefines from oil-gas possess a normal constitution. The shale-spirit was fractionally distilled, and the three fractions boiling respectively at 140-145", 120-125", and 75-85", were examined by the method described by Armstrong and Miller (Ohem. SOC.Trans., 1886, 74). Each fraction was found to consist of paraffin to the extent of about 50 per cent., the remainder being partly olefine and partly less unsaturated hydrocarbons of unknown con-stitution.The bromine addition-compounds of the latter are to a large extent decomposed by distillation in a current of steam, yielding tarry products, whilst the olefine bromides distil over unchanged. After distilling the bromides under reduced pressure, the olefines were recovered by the zinc-copper couple ; they were then fractioned ; and finally the fatty acids produced by their oxidation with potassium permanganate were examined. The results obtained show that not only the lower olefines, but also octylene and nonylene are present in shale-spirit. The nonyl- ene was readily obtained in a state of comparative purity, and its oxidation-products indicated it to be the pure normal olefine, heptyl- ethylene.The lower olefines were, however, more difficult to purify, and gave a more complex mixture of oxidalion-products. The octyl- em fraction (b. p. 120-122"), for instance, gave both heptylic and caproic acids (the latter in larger quantity), together with acetic and formic acids ; and in bhe same way the hexylene fraction (65-70") was found to yield more but,yric than valeric acid, these being also accompanied by formic and acetic acids. In the same way as the pro- duction of heptylic and formic acids indicates the presence of normal octylene, the formation of caproic and acetic acids might be regarded as evideuce that an isomeric octylene is also present ; but this is not necessarily the case, as acetic acid appears to be a constant product of the oxidation of normal olefines: so that no definite conclusion can be drawn from its presence, especially as it is produced to a relatively small extent; in fact, the authors consider that the caproic acid pro- bably owes its origin to the presence of heptylene in the octylene, the separation of the lower olefines by fractional distillation being accomplished with difficulty unless very large yuantitiev of material are dealt with.It is noteworthr that whereas in the manufacture of oil-gas the paraffins are all but destroyed and no olefine higher than heptylene is obtained, shale-spirit, which is produced by the decomposition of paraffins at a much lower temperature, is rich in paraffins and higher ole fines.67. "The Magnetic Rotatory Power of the Ethyl Salts of Maleic and Citraconic Acids and their Isomers." By W. H. Perkin, Ph.D., P.R.S. The result of the examination of the ethylic salts of maleic, citm- 99 conic and itaconic acids show that in the magnetic field they affect polarised light like most substances of the kind differing by 28 from normal saturated compounds. The author has already shown (Chew. Xoc. Trans., 1884, 561) that such nnsahxated compoiinds have a greater molecular rotatory power than saturated compouiids to the extent of a little more or less than 1.0; thus, the value for ally1 is about 0.914 higher than that of propyl, and the value for oleic compounds is about 1.112 higher than that for corresponding saturated compounds.In the case of the acids under consideration the increase is a little higher still, as the following comparisons show :-Ethylic rnaleate ..... 9.647 Ethylic itaconate .... 10.630 .. succinate. ... 8.380 1 ,, methylsucci-nate ...... 9.347 Difference ...... 1.267 --Difference ...... 1.283 Ethylic citraconate ............ 10.499 ,, methylsuccinate ...... 9.347 Difference .............. 1.1.52 The small difference between the molecular rotatory power of t)he itaconic and citmconic salts is undoubtedly due to the structure of the compounds beiiig somewhat dissimilar. The fumaric and mesaconic compounds afford very considerably higher values, thus :-Ethglic fumarate .. 10.119 Ethylic mesaconate . 11.269 ,, succinate .. 8.380 ,, methylsucci-nate .... 9.347 Difference ..... 1.739 --Difference .... 1.922 From these results, maleic, citraconic: and itaconic acids may be regarded as ordinary unsaturated compounds related to succinic and methyisuccinic in a similar way that a-crotonic and oleic acids are related to butyric and stearic acids. Fumaric and mesaconic acids belong to a different class of compounds. The interpretation to be given to the very high molecular rotatory powers of these compounds is not at present evident. The results of this iiivestigation do not appear, however, to be in favour of the foi*mul= lately suggested by Anschutz to explain the isomerism of maleic and fumaric acids.100 68, " The Temperatures at which various Sulphates undergo Decom- position." By G. H. Bailey, D.Sc., the Owens College. On account of the use which is frequently made of sulphates in atomic weight determiriat8ions7 it is important to ascertain to what temperature they can be heated without undergoing decomposition, as it is necessapy to apply heat in order to dehydrate and expel adherent acid. The author heats the sulphate containing excess of acid, in the apparatus which he has previously described, at a known temperature-say 360O-till of constant weigbt ; the temperature is then raised, and the heating continued, &c. For a considerable range of temperature the weight remains constant, but a point is ultimately reached at which further loss of weight occurs, indicating that the temperature has been reached at which the normal sulphate decom- poses. Zinc sulphate begins to decompose at 410",bismuth sulphate at, 405"; lead, magnesium and sodium sulphates are stable up to 500" at least.The behaviour of didymium sulphate is quite different from that of the other salts, and the limits of temperature within which it is stable are not sharply defined. 69. " The Reaction between Sulphites and Nitrites of Metals other than Potassium." By Edward Divers, M.D., P.R'S., aud Tamemasa Haga, F.C.S. Referring to a recent paper by Raschig (BeT,, 1887, 584), the authors state that. they have for a long time been awape that hydroxyl-ainine is producible from various nitrites by the action of sul-phurous acid and sulphites, and have only delayed making thia known that they might, at the same time communicate the results of their examination of the stages of the reaction when sodium salts are used.Fremy entirely failed to prepare sodium salts corresponding with the potassium compounds he bas described. The authors, however, have succeeded in preparing sodium salts which are unmistakably corn-pounqs of the simpler acids of which Fremy prepared potassium salts. On mixing solutions of sodium sulphite and nitrite slight heat is developed (when metasulphite is substituted the rise in temperature is more marked), and the mixture increases in alkalinity; when two formula weights of sulphite to one of nitrite are taken, all sulphite and nitrite, as nearly as possible, cease to exist as such, in about ten days' time.For some time after mixing sulphite can be precipitated as barium salt, nitrite being left in solution ; but when the interaction is complete, the barium precipitate is that of a hydroxylamine-sulphonate free from sulphite and sulpllste (tracea excepted), and the 101 mother-liquor contains a barium aminesulphonate and very little hydroxylaminesulphonate. On dissolving the barium precipitate in acid, no evidence of the presence of hydroxylamine is obtained until the liquid has been heated: a precipitate of barium sulphate is then produced, much hydroxylamine being then formed. The barium precipitate is probably the slightly soluble salt of hydroxylarnine-disulphonio acid, and the soluble barium salt, that of aminetri-snlphonic acid, which on heating becomes di-and mono-sulphonic acids, sulphuric acid separlating, By acidifying and heating a mixture of sodium sulphite and nitrite in suitable proportions, the authors have obtained almost all the nitrogen of the nitrite as hydroxylammonium sulphate. Metasulphite appears to be still better snited than the normal sulphite for the preparation of hydroxylamine.70, “ The Action of Acetyl Chloride on Acetoximes.” By Victor Meyer and A. IT.Warrington, B.Sc. The aukhors find that if the acetoxime obtained from isopropyl-ketone and hydroxylamine be treated with acetyl chloride at a low temperature, the corresponding aoetate is formed; but that if the temperature be allowed to rise the product is an isomer of the acetoxime.This isomer is a solid, and crystallises in colourless needles ; it melts at 102”, and boils at 210”. On hydrolysis it yields isobutyric acid and isopropylamine, and it may be pmpared firom isobutyric chloride and isopropylamine : an isomeric change therefore Oalces place, the nature of which may be seen on comparison of the formuh-CO* CH(CH,) a I (cH3)2cH} I(CH,) ?CH C N.OH NH*CH (C IT,) , Diisopropylacetoxime. Isopropylisobutyralnide. No such isomeric change occurs on similarly treating dipropylacet- oxime, the corresponding acetate being the only product. 71. “ Sulphinic Compounds of Carbamide and Thiocarbamide.” By George McGowan.The compounds described are- (CSN,H,),*( C1,C SO,), = dithiocarbamida ditrichloromethyl-sulphin ate. CSN,H,*C1,CSO2H = thiocarbamide trichIoromethylsulphin-ate. CON,H,~*Cl3CSO2H= carbamide trichloromethylsulphinate. CSN2H3-C13CS02(?)= trichloromethylsulphinylthiocarbamide. 102 The first of these is prepared from ammonium tricbloromethyl-sulphinate and dithiocarbamide dichloride ; the second by dissolving equimolecular proportions of thiocnrbamicle and ammonium trichloro- methylsulphinate in alcohol, and adding a slight excess of a con-centrated solution of hydrogen chloride ; the third is prepared in the same way as the second, avoiding water, which decomposes it, t8he fourth is obtained together with dithiwnrbamide dichloride by the action of trichloromethylsulphonic chloride on thiocarbamido.72. “Anacardic Acid.” By Dr. S. Ruhemann and S. Skinner, B.A. Anacardic acid was originally obtained by Staedler from the oil contained in the shell of the fi-uit of Anacardizem occidentale; he assigned to it the formula C,,H,,O, (C = 6). The authors find that it is an hydroxycarbolic acid of the formula C,,H,,O,. They describe several salts, and give the results of their analyses. ADDITIONS TO THE LIBRARY. I. Donatiom. Ausfuhrliches Lehrbuch der Chemie: Band IV, Th. 11: Or-ganische Chemie: von H. E. Roscoe and C. Schorlemmer : Braun-schweig, 1887 : from tthe Authors. The Norwegian North Atlantic Expedition, 1876-1878 : XVII. Alcyonida : by D.C. Danielssen : Christiania,, 1887 : from the Editorial Committee. Elements of Australian Agriculture : by A. Mankay : Sydney, 1885 : from the Aut>hor. A New Basis of Chemistry: by T. Sterry Hunt : Boston, 1887 : from the Publisher. Die Priifung Chemischer Arzneimittel : von A. Duflos : Breslan, 1866 : from Dr. Stevenson. Chemisches Apothekerbuch : von A. Duflos : Breslau, 1867 : from Dr. Stevenson. Die Chemie der Austrocknenden Oele : von G. J. Mulder : Berlin, 1867 : from Dr. Stevenson. Trait6 de Chimie Hydrologique : par J. Lefort : Paris, 1873: from Dr. Stevenson. Guide pour I’Analyse de 1’Eau : par E. Reichardt : Traduit par G. E. Strohl : Paris, 1876: from Dr. Stevenson. 103 California State Mining Bureau : 6th Annual Report of the State Mineralogist, Parts I and I1 for the Year ending June lst, 1886: Sacramento, 1886-1 887 : from the Bureau.4th Annual Report of the Bureau of Ethnology, 1882-1883 : by J. W. Powell : Washington, 1886 : from the Smithsonian Institution. The Chemistry of Tobacco : by J. Bell : London, 1887, two copies : from the Author. U.S. Geological Survey: Monographs X: Dinocerata: by 0. c. Marsh : Washington, 1886: from the Survey. A Questiio dos Vinhos (0s Vinhos Falsificados): pelo Campos da Paz: Rio de Janeiro, 1886: frdm the Author. 11. By Purchase. Anleitung zur Darstellung organischer Prgparate : von S. Levy : Stuttgart, 1887. Le Lait : Rtudes Chimiques et Microbiologiques : par E. Duclaux : Paris, 1887. Die kunstlichen organischen Farbstoffe : von P. Julius : Berlin, 1887. Kurzes Lehrbuch der organischen Chemie : von A. Bernthsen : Braunschweig, 1887. HARRISON AND SONS, PRINTERS IN ORDINARY TO EER MAJESTY, ST. MARTIN'S LANE.
ISSN:0369-8718
DOI:10.1039/PL8870300089
出版商:RSC
年代:1887
数据来源: RSC
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