May 21, 1891] 



NATURE 



71 



by directly interfering \yith the respiratory exchanges occurring 

 in the tissues. The objections to its use as an antipyretic are 

 that, owing to its poisonous properties, it is difficult to inject it 

 subcutaneously in sufficiently small doses, while it is not easy to 

 obtain a solution in any menstruum in which decomposition will 

 not take place. If a convenient method of dissolving it could 

 be devised, Ni(CO)4 might become a valuable antipyretic, the 

 modus operandi of which is intelligible.^ 



SOCIETIES AND ACADEMIES. 

 London. 

 Chemical Society, April 2.— Mr. W. Crookes, F.R.S., 

 Vice-President, in the chair. — The following papers were read : — 

 Citraconfluorescein, by J. T. Hewitt. Lunge and Burckhardt 

 have shown that maleic anhydride is capable of yielding a 

 fluorescein ; the author has obtained the corresponding fluo- 

 rescein from citraconic anhydride, by the action of resorcinol in 

 the presence of sulphuric acid. Citraconfluorescein is easily 

 soluble in alcohol and glacial acetic acid, fairly soluble in water ; 

 the aqueous solution is yellowish-brown and shows a green 

 fluorescence.— Ethylic thiacetacetate, by Dr. C. T. Sprague. 

 Hiibner obtained ethylic thiacetacetate by the action of sulphur 

 monochlonde, SoClj, on ethylic acetacetate. It has since been 

 obtained by Delisle by the action of sulphur dichloride, SClj, on 

 ethylic acetacetate ; by Schonbrodt by the action of sulphur on 

 the copper derivative of ethylic acetacetate; and by Michaelis 

 and Phillips from thionyl chloride and ethylic acetacetate. 

 Buchka proposed the formula S(CH.Ac.CO„Et)2, but an al- 

 ternative formula, S(O.C : CH.COsEtjj, was suggested by 

 Delisle. The author describes the preparation of the substance 

 and the products of its interaction with hydrazines ; and shows 

 that it behaves towards phenylhydrazine in the same manner as 

 ethylic acelacetate. The results are in accordance with the 

 formula proposed by Buchka.— The function of chlorine in acid 

 chlorides as exemplified by sulphuryl chloride, by H. E. Arm- 

 strong. A number of experiments carried out during recent 

 years in the author's laboratory show that sulphuryl chloride, 

 SOoClj, acts on benzenoid compounds simply as a chlorinating 

 agent. Sulphuryl chloride is easily formed by the direct union 

 of sulphur dioxide and chlorine in the presence of a catalyst, 

 such as camphor, charcoal, or acetic acid ; it is a highly mobile 

 liquid of low boiling-point, and is acted on with extreme slow- 

 ness by water and alkaline solutions. It is an inert substance 

 possessed of properties by no means such as are usually regarded 

 as characteristic of acid chlorides. The chlorine is apparently 

 but loosely held, and is easily withdrawn by a compound having 

 an affinity for chlorine, such as naphthalene. On warming a 

 mixture of this hydrocarbon and sulphuryl chloride, SO^ is 

 evolved and naphthalene tetrachloride is produced. The author 

 doubts whether the chlorine in aciJ chlorides is possessed of 

 special activity, and is inclined to the view that the activity of 

 acid chlorides is conditioned by the oxygen rather than the 

 chlorine ; this view being supported by the observations of 

 Wagner and SaytzefF, and the later ones of Pawlow {Annalen, 

 clxxxviii. 104). The author also discusses the action of SO3HCI, 

 and the analogous compound SO3. EtCl, and points out that pyro- 

 sulphuryl chloride, SgO.-.Clj. behaves much as if it consisted of 

 SO3 and SO2CI2. — The actipn of nitric acid on the ligno- 

 celluloses, by C. F. Cross and E. J. Bevan. Dilute nitric acid 

 attacks the ligno-celluloses when heated with them at 60°, with 

 the formation of a bright yellow derivative of lignone and nitrous 

 acid On further interaction, large quantities of nitrous oxide, 

 N„0, are evolved, together with carbonic anhydride and a small 

 proportion of nitric oxide. A sensible quantity of hydrogen 

 cyanide is also produced, the proportion being increased by 

 increase of temperature. The observations point to the entrance 

 of the NOH residue into the lignone molecule ; its interaction 

 with nitrous acid being finally the displacement of Hg by O. 

 The reaction is probably general for compounds containing-the 

 NOH residue, and the authors suggest that attention be paid to 

 the gaseous products of the interaction of nitric acid and carbon 

 compounds, as calculated to elucidate their mechanism. — The 

 Chairman, Mr. Crookes, gave a short verbal account of observa- 

 tions on the volatilization of metals in vacuo under the influence 

 of an electric discharge. 



' This investigation was carried on during last winter. It appears that M. 

 Hanriot made a communication of the subject to the Sjciete Chimigue on 

 February 27. He found the substance to bie more poisonous than CO, and 

 that the blood gave the spectrum of carbon-monoxide-hxinoglobin. 



NO. II 25, VOL. 44] 



April 16.— Prof. A. Crura Brown, F.R.S., President, in the 

 chair.— The following papers were read :— Studies on the 

 formation of substitution derivatives, by H. Gordon. The 

 following experiments were undertaken with the object of 

 throwing further light on the laws which govern substitution in 

 the case of benzenoid compounds. The action of bromine on 

 diorlhonitrophenpl. -V^hen bromine is added to an acetic acid 

 solution of diorthonitrophenol at ordinary temperatures, the 

 normal product, namely parabromdiorthonitrophenol, is obtained. 

 However, if the mixture be heated at 100* for a short time, 

 a mixture is obtained consisting of parabromdiorthonitrophenol 

 and orthobromorthoparadinitrophenol. And if the heating be 

 prolonged, and small quantities of bromine added, the mixed 

 product is converted into orthobromorthoparadinitrophenol. 

 Parabromdiorthonitrophenol is therefore completely converted 

 by the action of heat, and bromine into the isomeric ortho- 

 bromorthoparadinitrophenol. The same isomeric change takes 

 place under the influence of nitric acid. An acetic acid solution 

 of parabromdiorthonitrophenol, when heated with a few drops of 

 nitric acid at 100°, is completely converted into the isomeric 

 orthobromorthoparadinitrophenol. Experiments were then under- 

 taken with the corresponding chloro-compounds. It was found 

 that chlorine had no action on diorthonitrophenol when dis- 

 solved in acetic acid at 100°, even in the presence of iodine. 

 Chlorination, however, takes place when chlorine is passed into 

 a solution of diorthonitrophenol in antimony pentachloride at 

 105°, and only the normal product parachlorodinitrophenol is 

 formed. Action of bromine on parachlordiorlhomtrophenol. -Ex- 

 periments to ascertain whether isomeric change could be effected 

 by the action of bromine on parachlordinitrophenol only gave 

 negative re>ults, the normal product, parachlororlhobromortho- 

 nitrophenol, being obtained in every case. The author considers 

 that in the case of the chlorine compound isomeric change does 

 not take place, because the chlorine is more firmly held than 

 bromine. Action of sulphuric acid on orthoparadichlorphcnol- 

 orthosulphonic atjV/.-The combined action of heat and sulphuric 

 acid on orthoparadichlorphenolsulphonic acid gave no indication 

 of any isomeric change taking place, although the reaction was 

 investigated under a great variety of conditions of temperature, 

 &c. The corresponding dibromphenol also gave negative results, 

 but as several secondary reactions set in, such as the formation 

 of tribromphenol, this reaction was not further investigated. 

 The chlorination and bromination of pheno/.-?henol when 

 chlorinated in the ordinary manner yields a mixture of para- and 

 ortho- chlorphenol. The author finds that a similar mixture is 

 obtained when SOjCl., is employed as the chlorinating agent. 

 He has also investigated the action of bromine on phenol under 

 the conditions described by Hiibner and Brenken {/Ur. vi. 170), 

 and finds that the product is practically pure parabromphenol. 

 7'he sulphonation of the «//w//i(?«(^/.y.-Orthonitrophenol and 

 paranitrophenol are, according to Armstrong, both readily 

 acted upon by SO3HCI ; the former yields the well-known 

 sulpho-acid ; the latter yields a product which is decomposed 

 by water, and was supposed by Armstrong to be the sulphate, 

 and this the author finds to be the case. The author considers 

 that the initial action in both cases is the same ; but that the 

 sulphate formed from orthonitrophenol at once undergoes 

 isomeric change, whereas the sulphate from paranitrophenol is 

 more stable. The author did not succeed in obtaining any 

 sulpho-acid by heating the sulphate from the paranitroi)henol 

 at 100°. But he obtained a fair yield of sulpho-acid by heating 

 the nitrophenol with two molecular proportions of SO3HCI at 

 100°. Hence, there is little doubt that the paranitrophenol- 

 sulphonic acid is formed by the sulphonation of the sulphate. 

 Metanitrophenol resembles the para- compound in being con- 

 verted into sulphate, but not into the sulpho-acid even by the action 

 of heat. — Compounds of dextrose with the oxides of nickel, 

 chromium, and iron, by A. C. Chapman. The nickel com- 

 pound is obtained by adding a solution of nickel hydrate in 

 ammonia to a solution of dextrose in 90 per cent, alcohol. It 

 is a green amorphous substance, insoluble in water and alcohol, 

 of the composition CgHijOg.aNiO -f- sHjO. The chromiunt* 

 compound, which appears to have the composition represented 

 by the formula CgHjjOg.CraOg -f 4HjO, is prepared by 

 dissolving an excess of dextrose in an aqueous solution of 

 chromic chloride, and pouring this solution into cold strong 

 ammonia. The precipitated hydrate partly dissolves on stand- 

 ing, and on pouring the purple solution so obtained into 90 per 

 cent, alcohol, the chromium dextrosate is obtained as a lilac- 

 coloured precipitate. The iron compound, iCeHjjOg.sFcjOj 



