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Proceedings of the Chemical Society, Vol. 18, No. 258 |
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Proceedings of the Chemical Society, London,
Volume 18,
Issue 258,
1902,
Page 243-256
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摘要:
Zssued 211 103 PROCEEDINGS OF THE CHEMICAL SOCIETY. EDITED BY THE SECRETARIES. Vol. 18. No.258. Wednesday, December 17th, 1902. Professor J. EMERSON REYNOLDS,Sc.D., F.R.S., President, in the Chair. Certificates were read for the first time in favour of Messrs. : Edwin Bayles Atkinson, Scarthe House, Great Grimsby. William Bowen, Cleveden, Woodend Road, Erdington. R. C. Farmer, M.Sc., Ph.D., 154, Eglinton Road, Woolwich, S.E. Frederic Herbert Lees, 256, Park Road, Crouch End, N. A. H. Scholefield, B.A., B.Sc,, 4, Hartley Terrace, Wolverhampton. Charles Tilburn, 31,Hardy Street, South Yarra, Melbourne. Andrew Young, M.A., B.Sc., 1, Avenue Terrace, Cape Town. The following Certificates were authorised by the Council under Byelaw I. (3) : K.Bhaduri, M.A., Professor, Canning College, Lucknow. George Montague Prichard, Ramtek, Nagpur, C.P., India. Of the following papers, those marked * were read : “180.(‘A reagent for the identification of carbamide and of certain other nitrogen compounds.” By H. J. H. Fenton. In previous communications to the Society (Fenton and Gostling, Trans., 1899, 77, 423 ; 1901, 81, SOT), various derivatives of methyl- 244 furfural have been described which are obtained from ketohexoses, or substances which produce these on hydrolysis, and from cellulose. Amongst these derivatives, a crystalline condensation product mas mentioned having the formula C,,H,O,, the constitution of which is still under investigation ;the evidence obtained so far indicates that it is either met hyl-f uril,C,H,O CO-CO*C,H20CHQ,orthe ke tone-alde hyde, CHO*C4H2OmCO*C,H2O*CH3.The method of obtaining this substance has been considerably improved, so that it is now easyto prepare it in quantity.If a small quantity of this product be mixed with urea and t,he mixture treated with a trace of phosphorus oxychloride, acetyl chloride or dry hydrogen chloride-dissolved in any appropriate solvent-a very brilliant blue colour is obtained. The reaction is one of extreme delicacy, 0.1 milligram of urea giving a strongly marked colour, and with care it is quite easy to detect 0.01 milligram or less. This effect is due to a colourless base of which the salts have a blue colour. The intensity of the colour of these salts in aqueous solution varies markedly with the nature and concentration of the acid.The production of a blue colour in the manner here described is characteristic of carbamide and of mono-substituted carbamides, NH,*CO*NHR,in which the substituting radicle is an alkyl group or one of a similar character; acidyl substituted carbamides give no such reaction. Urethane gives a similar reaction, but the colour is red by transmitted light. This compound also reacts with primary amines in acetic acid solution to give very brilliant green compounds ;this change is produced at once on simply mixing the solutions without my condensing agent, and appears to be quite characteristic of primary amines. DISCUSSION. Mr. U. E. GROVESasked whether oxalic acid behaved like sulphuric and hydrochloric acids.Mr, FENTONreplied that the base gave a blue colour with oxalic acid also, the intensity of the colour being greater than that produced with acetic acid, but less than that with hydrochloric acid. *181. LL The rate of decomposition of diazo-compounds. Part 11. Diazo-compounds of the naphthalene series.” By J. C. Cain and F. Nicoll. The authors have extended their researches on the decomposition of diazo-salts (Twms., 1902, 81, 1412) to those of the naphthalene series, and find that the reaction is a unimolecular one in the case of the soluble diazo-salts prepared from the following amines : 245 1. a-Naphthylamine. 2. P-Naphthylamine. 3. Naphthylaminesulphonic acid, NH, : SO,H = 1 : 8.4. 9, =2: 6.79 19 5. =2: 7.Y7 Y, ,9 6. 9, disulphonic acid, NH, :SO,H :SO,H = 2 : 6 :8. YY 97. ¶I =2: 3: 6. 8. Amidonaphtholdisulphonic acid, NH, :OH :S0,H : SO,H = 1:8: 3 : 6. The unimolecular reaction, however, in the case of Nos. 1, 2, 4, 5, 7, 8, is hindered, after a considerable amount of decomposition has taken place, by the formation of azocolours, which is clearly shown by the rapid diminution of the values of C, calculated according to the 1Aequation ;logA= =C (a constant). The measurements were made at 60°, except in the case of No. 8, when the temperature was 80". The diazo-salts are thus very stable, In the case of the insoluble diazo-salts obtained from the following amines : 9.Naphthylaminesulphonic acid, NH2:SO,H = 1 :2. 10. YP 7, ,, = 1 : 4. 11. =I :5.99 Y9 Y, 12. AmidonaphtholsuIphonic acid, NH, ;OH :SO,H =2 : 8 :6. Xthe rate of decomposition is expressed by the equation -= K (a con-t stant), x being the observed volume of nitrogen evolved in the time t. In each case, an azo-colour is formed towards the end of the reac- tion, shown again by the rapid diminution of the values of K. These diazo-salts are very stable, the experiments being made at 70"or 80". In each case where an azo-colour is formed, the value of C or Ris constant for a considerable period, showing that, although both nayhtholsulphonic acid and diazo-salt are present, no combination takes place during this period.The authors suggest that this interesting fact may be explained by assuming that hydrolytic dissociation of the diazo-salt is necessary before combination takes place ; in the above experiments, the diazo- salt is not dissociated (especially in the presence of the free mineral acid, which has a retarding effect on the formation of an am-colour) until its concentration becomes considerably less. When this point is reached, the formation of an am-colour can proceed. 246 "182. State of carbon dioxide in aqueous solution." By J. Walker. The author gave a proof from the law of mass-action that carbonic acid (and similar substances) in aqueous solution must obey Ostwald's dilution law, independently of the proportions of the anhydrous and hydrated forms contained in the solution. The conclusion formerly drawn (Walker and Cormack, Tram., 1900, 77,8), that the carbon dioxide in solution is probably hydrated to the extent of 20 per cent., must therefore be rejected."183. Qualitative separation of araenic, antimony, and tin." By J. Walker. When a solution of the sodium thio-salts of arsenic, antimony, and tin is boiled with sodium peroxide, these salts are converted into sodium arsenate, antimonate, and stannate respectively. Any mercury which may have been dissolved from the copper group on warming with sodium hydroxide, is, by this treatment, reprecipitated as sulphide. The tin may be separated from the arsenic and antimony by boiling with excess of ammonium chloride, which precipitates stannic hydroxide, leaving the antimony and arsenic in solution.On addition of excess of acid, these may be separated by means of sulphuretted hydrogen in the cold, the antimony being at once precipitated as sulphide, whilst the arsenic remains dissolved. DISCUSNON. Dr. F. M. PERKINremarked that when stannous sulphide does not dissolve in caustic alkali, the addition of a little sodium or hydro-gen peroxide enables it to do so. The peroxide seems to exert very little, if any, oxidising action upon the sulphides of the copper group, hence there is no objection to warming the mixed sulphides of these two groups with caustic alkali and sodium peroxide and so obviating the use of ammonium sulphide. "184. "The hydrates and solubility of barium acetate." By J.Walker and W. A. Fyffe. The authors have been unable to confirm the observations of Krasnicki (Mornatshefie,1887, 8,Sol), who stated that the solubility of barium and 80' could be represented by a single curve concave to the temperature axis. On the contrary, they find that the solubility is expressed by three curves (for the trihydrate, mono-0' acetate between 247 hydrate, and anhydrous salt, respectively), which are all convex to the temperature axis. The curve for the monohydrate exhibits a minimum at 30°, and that for the anhydrous salt a minimum at 75'. The solubility and special dilatometric experiments showed the inversion temperature for Ba(C2H,0,),,3H,O Ba(C2H30,),,H,0 + 2H,O to be 24.7' ; that for Ba(C,H,O,),,H,O Ba(C,H,O,), + R,O being 41'.DISCUSSIO.N. Professor TILDENexpressed the belief that revision of many of the accepted data in regard to solubility was urgently required and hoped that Professor Walker would continue his work in this direction. Published estimations of solubility of many metallic salts at tempera- tures above the boiling point of water were absolutely valueless, inas- much as evident chemical change sets in and basic salts are visibly deposited. "185. (( cis-and trans-ap-Dimethylglutaricacid and the separation of the cis-and tmns-forms of substituted glntaric acids.'' By J. F. Thorpe and W.J. Young. The up-dimethylglutaric acids are best prepared by the condensation of ethyl P-methylacrylate with ethyl sodiocyanacetate and subsequent treatment of the sodium derivative formed with methyl iodide.Ethyl a-cyano-up-dimethy ZgEutavate, CO,Et*C(CN)(CH,)*CH(CH,)*CH,~CO,Et, is a colourless oil which boils at 185" (20 mm.), which, with cold methyl alcoholic potash, yields the potassium salt. a-cyano-a/?-% rnethylglutavic acid is a white solid which separates from ether and light petroleum in microscopic needles melting at 132-133". When this substance is heated with concentrated hydrochloric acid, it is in part converted into ap-diinethylglutarimide, CHI*CH<CH(CH3)'co>NH, which crystallises from water in longCH,-CO needles melting at 113') and in part into trans-ap-dimethylgtutaric acid, which appears to be a liquid at the ordinary temperature.The imide, on hydrolysis with sulphuric acid, +yields cis-a/?-dimethyl- ylutaric acid, which crystallises from concentrated hydrochloric acid in needles melting at 87". The tranns-acid is unacted upon byacetyl chloride, but when boiled with acetic anhydride or when slowly distilled under atmospheric pressure it is converted into the unhydride of the cis-acid, which may also be prepared by the action of acatyl chloride on the cis-acid. It is a liquid boiling at 255' (765 mm.). The annilic acid separates from dilute 248 a coho1 in lustrous plates melting at 149'. The cis-acid, on heating in a sealed tube with concentrated hydrochloric acid, is converted into a mixture of the cis-and trans-acids. The authors described the preparation of up-dimethylpropanetri-caTboxylic acid, (C02H),:C(CH,) -CH(CH,)*CH,*CO,H, which crystal-lises from dilute hydrochloric acid in white needles melting with evolution of carbon dioxide at 165".When heated to 200°, this acid is converted into a mixture of cis-and trans-ap-dimethylglutaric acids. The cis-and trans-forms of substituted glntaric acids may be separated by converting the mixed acids into their ammonium salts and heating them in a sealed tube at 160" for 4 hours. In this way, the ammonium salt of the cis-acid is converted into the imide, which, on hydrolysis with sulphuric acid, yields the cis-acid, whilst the trans-ammonium salt remains unchanged. The imide and ammonium salt are separated by means of ether.The separation of cis-and trans-ua'-dimethylglutaric acids, of cis-and trans-a-methyl-/?-isopropylglutaricacid, and of cis- and tmns-aa'PP-tetramethylglutaric acids have been thus effected. "186. Constitution of metallic cyanides." By J. E. Marsh. Volhard (Annalen,1890,259,378) has shown that potassium cyanide is oxidised by potassium permanganate to potassium cynnate. Other cyanides are similarly oxidised. Ammonium cyanide is thus con-verted directly into urea. There are two exceptions among metallic cyanides ; silver and mercury cyanides are not oxidised by potassium permanganate. This reaction brings the cyanides of silver and mer-cury into relationship with the nitriles, which are also unatkacked. On the other hand, the other cyanides are brought into association with the readily oxidisa ble carbarnines.The author thinks that silver cyanide should be represented as Ag*CiN,and potassium cyanide as K*N:C. DISCUSSION. Dr. WADEsaid he thought it was unsafe to infer a difference in the constitution of potassium and silver cyanides from the difference in behaviour of these salts towards oxidising agents. The potassium salt is freely ionised in aqueous solution, whilst the silver salt is insoluble and not appreciably ionisable ; the stability of the latter towards oxidising agents is thus explained without having recourse to the hypothesis of a nitrilk constitution. Potassium cyanide resembles the alkyl isocyanides in readily undergoing oxidation, as in most other respects (Trccns., 1902, 81, 1606), but its ready ionisability in this 249 case destroys the parallel ; the products of the oxidation of the undis- sociated alkyl iso-cyanides are complex and not comparable with the alkali cyanates, which are formed by the oxidation of iso-cyanogen ions."187. "Auto-reduction of mercury and silver cyanides." By J. E. Marsh and R.de J. F. Struthers. On the hypothesis that silver and mercury cyanides have the nitrile constitution, attempts have been made 60 bring about the hydrolysis of the (CN) group, if possible without breaking off the metal. In all the reactions tried in which the (CN) group is hydrolysed, it is broken off from the metal. When mercuric cyanide is heated with a strong solution of potassium hydroxide, the salt is reduced to metallic mercury.The same re-duction is brought about by boiling the salt with a solution of sodium or potassium hydroxide or ethylate in excess of alcohol. Cyanide and cyanate of the alkali are formed. The alkali cyanide formed protects the mercury salt from reduction, so that only half of the mercury is reduced. If potassium cyanide be previously mixed with the mercury silt, no reduction occurs. An intermediate product is being further in- vestigated. Silver cyanide is also reduced in the same way. When mercury cyanide is heated with from sixty to eighty tirues its weight of a mixture of equal volumes of sulphuric acid and water, hydrogen cyanide and carbon dioxide are evolved at about 130" and the whole mass sets to a jelly, from which mercurous sulphate is ob- tained on filtration ; ammonium sulphate is also formed.The decom- position of the cyanide may be represented thus : 2HgC2N2+ 2H20+ H,SO, =Hg,SO, + 3HCN + CO, +NH,. The decomposition of the cyanide is, however, not complete, and if the temperature is allowed to rise above 140", whether the precipitate is previously removed or not, a further reduction takes place, with separation of metallic mercury. If mercury cyanide is heated with water in a sealed tube, the salt is completely decomposed, giving mercury, carbon monoxide, and ammonium carbonate. The reaction begins below 230" and may be thus expressed HgC2N,+ 4H20=Hg + CO + (NH,),C03. No oxalic acid was obtained, but it was found that ammonium oxalate, under the same conditions, breaks up into carbon monoxide and ammonium carbonate.Silver cyanide is also reduced to metallic silver when heated with water. 250 188. ‘(Note on the action of acids on cellulose.” By Miss lK, Gostling, B.Sc. In previous communications it has been shown that all forms of cellulose, when heated to about 80’ with a saturated solution of hydro- chloric or hydrobromic acid in chloroform or carbon tetrachloride, yield w-chlorobromomethylfurfural, and that dextrose (which could be extracted with water after separation of the methyl furfural derivative) was formed at the same time. Hence the presence of a ketose as well as an aldose nucleus in cellulose was conclusively proved.In every case, about 40 per cent. of a black residue which re-tained the fibrous structure of the original celIulose was left after the action of the acids. In the hope of throwing Further light on the constitution of cellu-lose, the nature of this residue was investigated, and it was pre- pared free from any of the original cellulose by repeated treatment with hydrochloric acid until no more of the furfural derivative was formed, Chlorine acted very slowly on this black residue, giving yellow derivatives containing from 25-7 to 34.35 per cent. of chlorine. The action of bromine was similar. Nitric acid (sp. gr. 1.2) and alkaline permanganate oxidise it to oxalic acid. The original black residue is quite insoluble in alkalis, water, alcohol, ether, and other organic solvents.The composition and general character of this residue is therefore closely allied to the substances known as artificial humus, obtained by Conrad and Guthzeit and by Sestini by the action of dilute acids on sugars. It corresponds most nearly with sacculmin (prepared by Sestini by boiling cane sugar with dilute sulphuric acid), which was a black, amorphous mass, insoluble in potash solution, giving, with chlorine, yellow chlorine compounds. Sestini gives to sacculmin the formula C44H38015(C =65.5 ; H =4.8 per cent.), a slightly higher percentage of carbon and hydrogen than that in the black residue from cellulose (found C =62.31 to 62.70 ;H =3.64 to 4.29). 189. I‘ Nitrotartaric acid and some of its ethereal salts.” By P.I?. Frankland, IF. I,,Heathcote, B.Sc., and Mias H.Rartle, B.Sc. The announcement in the current number (Dec. 6th) of the Berichte that a paper is to be communicated to the Berlin Society on Dec. 8th by Professor P. Walden on the nitromalic and nitrotartaric esters, 251 compels the authors to publish without delay the results of work on which they have been engaged during the past four years. Their investigation has included the preparation and characterisation of the following compounds : dinitrotartaric acid, dimethyl dinitro- tartrate, diethyl dinitrotartrate, dimethyl mononitrotartrate, and diethyl mononitrotartrate. Of these, dinitrotartaric acid was first obtained by Reinsch (Jahrb.,1849, 329) and Dessaignes (Jahd., 1852, 475) whilst Henry (Bey., 1870, 3,530) professes to have pre- pared diethyl dinitrotartrate ;the other compounds are, as far as the authors are aware, described for the first time.The only reference to the optical properties which they have been able to discover in chemical literature is the statement by Dessaignes that Chautard had found dinitrotartaric acid to be optically active and dinitroracemic acid inactive. With regard to diethyl dinitrotartrate, the authors are of opinion that Henry must have been dealing with the mononitro- tartrate, inasmuch as he gives no analysis, and the melting point 45-46’, which he records is very different from that which the authors have found, 27’, for the dinitro-, but very similar to that, 47*, which they have found for the mononitro-compound.The authors have determined the optical activity of all these com- pounds dissolved in methyl and in ethyl alcohol, and, except in the case of dinitrotartaric acid, in benzene also. The influence on the optical activity of the introduction of the nitro-group into the moIecules concerned was also discussed. 190. The nitration of diethyl monobenzoyl- and mono-ptoluyl- tartrates.” By P. F. Frankland, H. L. Heathcote, B.Sc., and C. J. Green, M.Sc. For the reasons given in the preceding abstract, the authors wish to communicate the results which they have obtained in this investigation, which was also commenced four years ago. Diethyl mono-benzoyltartrate and mono-p-toluyltartrate were nitrated in the cold in the hope of obtaining their mono-nitrates.In both cases, however, only compounds io which the nitro-group had entered the benzene ring were obtained. By hydrolysis it was shown that the m-nitrobenzoyl group was present in the one case, and the nitro-p-toluyl group (OH, :NO, :CO = 1:2 :4) in the other. The rotation of these compounds wits determined in solution in ethyl alcohol, ethyl acetate, benzene, pyridine, and chloroform. Their optical activity was enormously influenced by the solvent, thus the mono-m-ni trobenzopl compound was inactive in benzene, although it exhibited considerable activity in the other solvents employed. 252 191. Interchange of halogen for hydroxgl in chloro- and bromo-naphthalenediazonium hydroxides.Preliminary notice." By K. J. P. Orton. It has recently been shown by the author that s-trichloro- and a-tribromo-benzenediazonium compounds undergo a remarkable iso-meric change under certain conditions. If aqueous solutions of such salts as the diazonium nitrate or hydrogen sulphato are kept for a short time, the presence of chloride may soon be recognised by means of silver nitrate; at the same time, the solution becomes yellow, owing to the formation of the o-diazophenol (0-diazoqninone) The salts of a weak acid, such as the acetate, undergo the same change far more rapidly. These facts lead to the conclusion that this change is a transforma-tion of the diazonium hydroxide, C6H2X,*N(OH)iN, formed by hydro- lytic dissociation ; the weaker the acid, the larger mould be the pro-portion of the diazonium hydroxide present at any one time, and con- sequently the more rapid the change.Moreover, the presence of a sufficient excess of acid stops the change. Treatment with excess of alkali (hydroxide or carbonate), on the other hand, does not effect the elimination of halogen, but merely converts the diazonium compound, C6H,X,*N(A)iN, into the diazotate (iso-or cc.nti-diazotate), C,H,X,-N:N.OM'. If dilute acid is cautiously added to a solution of the diazotate, halogen is also eliiriinated. On treatment with acid, the alkali diazotate should first of all yield the corresponding acid, the diazohydrato, C6H,X,*N:N*OH, but, as is well known, these acids appear to change immediately into neutral substances, probably primary nitrosoamines.In the reaction here described, it mould seem that the diazo-hydrate (I)is either transformed into the diazonium hydroxide (11) (or its ions), and then into a complex (111) of the quinone type, or else directly into this complex; from this quinonoid compound, hydrogen chloride (or bromide) is eliminated, and a diazo-quinone produced, or the halogen wanders to the nitrogen, a phenol diazonium salt being formed. As the tendency to pass into the quinone type seems to be greater in the naphthalene series than in the benzene series, it would be ex-pected that this transformation would take place with greater readiness 253 in the case of naphthalenediazonium compounds.Meldola and Streat- feild (Trans.,1895,67,908), who first observed this type of replacement of bromine by hydroxyl, have obtained 4-bromo-2-diazo-1-naphtholby treatment of 1: 4-dibromo-2-naphthylamine, dissolved in acetic acid, with sodium nitrite, and subsequent boiling of the mixture with water. The author has studied the transformation of chloro- and bromo-naph thalenediazonium hydroxides, the solid salts of which have not hitherto been prepared. 1-Chloro-2-naphthalenediazoniumhydrogen sulphate,C,,,H,Cl-N (S0,H)i N, prepared from 1-chloro-2-naphthylamine, can be obtained (but with considerable difficulty) in the form of colourless needles, very soluble in water and acetic acid and moderately so in methyl alcohol.Exposed to the air, the crystals become yellow in a few minutes. The aqueous solution of the hydrogen sulphate, which is of course strongly acid, very rapidly becomes yellow and turbid. In the presence of sodium acetate, the change was complete in a few hours, and 2-diazo- 1-naphthol (2-diazo-l-naphthoquinone),O:C,,H,:N,, had separated in long, slender, golden-ye!low needles (m. p. 76-77') ;at the same time, a small quantity of an amorphous, yellow solid containing chlorine was formed ; it is probably an azo-condensation product. The chloride formed in the solution fell but little short of that contained in the diazonium salt. On passing dry hydrogen chloride into an ethereal solution of the diazonaphthol, a nearly colourless, crystalline hydro-chZomXe is obtained.2 :4-Dibronao-l-na~~hthcZened~a~o~~u~hydrogen sulphute, 0,,H5Br,*N(S0,H)iN, crystallises in colourless needles which are considerably more stable than the /3-naphthalene derivative just described (compare Knoeven- agel, Ber., 1895, 28, 2052). The aqueous solution of this salt rapidly becomes yellow, and after a short time begins to deposit the diazo- naphthol in small rosettes of needles. In the presence of sodium acetate, the diazonium salt is completely decomposed in 24 hours, one atomic proportion of bromine being found in the solution. 4-Bromo-l-diccxo-2-nctixhthol (4-6ronro-l-diaxo-2-naphthoquinone),O:C1,H,Br:N,, crystallisex from dilute alcohol in rosettes of bright yellow needles, which melt and decompose with evolution of gas at 132-133'; it yields a nearly colourless hydrochbovide.192. Purpurogallin." By A,G.Perkin and A.B.Steven. The discovery of Niet,zki and Steinmann (Ber., 1887,20, 1277) that purpurogallin, on distillation with zinc dust, yields naphthalene has been confirmed. On methylation, purpurogallin gives a tyimethyk ether, 254 C,,H,O,(OCH,),, orange-yellow needles, m. p. 174-1 77O, which forms a monoacetyl derivative, C,, H,O,( OCI13),*C2H,0, needles, m. p. 140-143', and by the action of alcoholic potash at 170Oyields a crystalline acid, m. p. 197-199". The latter, on distillation, is converted into an anhydride, m. p. 164-166". By digestion with 50 per cent. potassium hydroxide solution, purpurogallin is converted into two isomeric compounds possessing almost identical reactions, to which the names puurpurogallone and isopurpurogallone have been given.The former, minute yellow needles, m. p. 260-262", has probably the formula C,,H,O,, and gives the anhydroacetyl compound C11H204(C2H30)29colourless, prismatic needles, m. p. 174-1 76", whereas the latter, Cl,H,O,, yellow needles me1 ting above 300", gives, with acetic anhydride, the compound Cl,H,04(C2H,0)2, colourless, prismatic needles, m. p. 280-282". It is probable that both compounds contain a carboxyl group. 193. 6L Note on the destructive distillation of ethyl gallate." ByA. G. Perkin. According to Schiff (Annalen, 1872, 163,217), on distillation, ethyl gallate givospyrogalloland ethyl alcohol.This isso, butat the same time, towards the end of the operation, a considerable quantity of a red colour- ing mattor sublimes, which has been identified as rujgallic acid (hexa- hydroxyanthraquinone) (found, C =55-14; H =2*63), by its acetyl derivative, C,,H,04(C,H,0), (found, C =55-78, H =3.85 ;C1,H,04= 55-09), m. p. 282--283' (not previously given), and by its dyeing properties. The yield was approximately 7 per cent., but considerable carbonisation occurs when this colouring matter is distilled. The re- action may be expressed as 2C6H,(OH),*C0,Et =C,,H,O, +2EtOH. Gallic acid itself, on distillation, yields a small quantity of the same substance (acetyl compound, C =56.17 ;H =3*77), whilst protocatechuic acid and its ethyl salt give a trace of a colouring matter resembling rufiopin./3-Resorcylic acid does not give rise iu this way to any anthraquinone derivative. 194 ('A series of double chromates." By S. H. C. Briggs. The author has found that freshly precipitated copper hydroxide or carbonate dissolves in one equivalent of chromic acid to give a clear solution in the presence of tlventy or thirty equivalents of copper sulphate, or ten to fifteen equivalents of copper silicofluoride, although in the absence of these salts the dichromate and a precipitate of basic salt are produced. 255 A double salt, (NH,),Ni(CrO4),,6H,O, was obtained by adding ammonium chromate to a solution of a nickel salt. This could be re- orystallised from water below 40°, although nickel chromate has never been obtained from aqueoiis solution, and ammonium chromate can only be recrystallised from solutions contaiping ammonia. Attempts to prepare the potassium nickel chromate and dauble chromates of ammonium and copper, zinc, cadmium, and manganese were un-successful.By the action of ammonia on the mother liquors from the prepara- tion of (NH4)2Ni(Cr04)2,6H20 from the chloride, a double salt, (NH,)2Ni(Cr0,)2,2NH,, was obtained, and corresponding copper, zinc, and cadmium compounds were formed by the action of ammonia on the dichromates. These double salts, on heating, lose water and ammonia, and undergo sudden decomposition between 200° and 300°, leaving a mixture of oxides. ADDITIONS TO THE LIBRARY.I. Donations. Naylor, William. TraderJwaste :its treatment and utilisation with special reference to the prevention of rivers pollution. A hand-book for borough engineers, surveyors, architects, and analysts. Pp. xvi, 267, ill. London 1902. From the Author. Blochmann, Reinhart. Guide to preparation work in inorganic chemistry for students of chemistry and pharmacy. Authorised translation by James Lewis Howe. Pp. viii, 74, ill. Lexington, Va. 1902. From the Translator. Moureu, Ch. Notions fondamentales de chimie organique. Pp. 292. Paris 1902. From the Author. Ronna, A. Rothamsted : un demi-sibcle d’exphriences agronomiques de MM. Lawes et Gilbert. Pp. vi, 607. Paris 1900. From the Lawes Trust Krauch, C. The testing of chemical reagents for purity, Authorised translation of the third edition by J.A. Williamson and L. W. Dupre. With additions and emendations by the author, Pp. 350. London [1902]. From the Publishers. Warington, Robert. The chemistry of the farm. Fifteenth edition (fourth revision). London 1902. From the Author. 256 London County Council. Bacterial treatment of crude sewage. Fourth report by Dr. Clowes. London i902. From Dr. Clowes. New South Wales, Technological Museum. A research on the Eucalypts, especially in regczrd to their essential oils. By Richard T. Baker and Henry G. Smith. (Being No. 13 Technical Education Sevies). Sydney 1902. From the Authors. 111. Pamphlets. Meyerhoff er, Wilhelm. Die chemisch-physikalische Beschaff enhei t der Heilquellen.Pp. 32. Hamburg 1902. Hantzsch, Arthur Rudolf. Die Diazoverbindungen. Stuttgart 1902. (Sammlung. Vol. viii.) Hollandsche Maatechappij der Wetenschappen. Herdenking van het hondervijftigjarig bestaan op 7 Juni, 1902. ’s Gravenhage 1902. Hall, A. D., and F. J. Plymen. S.E. Agricultural College, Wye. First Report to the Technical Education Committeesof Kent and Surrey on a chemical and physical study of the soils of Kent and Surrey. Ashford 1902. At the next ordinary meeting on Wednesday, January 21st, 1903, at. 5.30 p.m., the following papers will be communicated : By F. S. Kipping and A. E. Hunter.‘‘ *‘The absorption spectra Phenocycloheptene.” of laudanine and laudanosine in relation to their chemical constitution.” By J. J. Dobbie and A. Lauder. ‘‘ The relation between the absorption spectra and the chemical structure of corydaline, berberine, and other alkaloids.” By J. J. Dobbie and A. Lauder. RIUHARlJ CLAY AND SONS: LIMITF,D, LONUON AND RUIVU\Y.
ISSN:0369-8718
DOI:10.1039/PL9021800243
出版商:RSC
年代:1902
数据来源: RSC
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