Chexical Society

View Article Online / Journal Homepage / Table of Contents for this issue Issued 10/2/1I OF THE CHEXICAL SOCIETY. Vol. 27. No. 381. Thursday, February Znd, 1911, at 8.30 p.m., Professor HAROLD B. DIXON,M.A., Ph.D., F.R.S., President, in the Chair. Certificates were read for the first time in favour of Messrs. : John Eric Collington, Claremont, Noel Road, Edgbaston. Clement Arthur Crook, 4, Dry Clough Lane, Halifax. William Henry Dickinson, Capt. (I.M.S.), M.B., Ch.B., Grant Medical College, Bombay. Ralph Roscoe Enfield, B.A., Toynbee Hall, Commercial Street, E. Oswald Mansell-illoullin, B.A., 69, Wimpole Street, W. Published on 01 January 1911. Downloaded by University of Prince Edward Island 30/10/2014 14:33:19. George Arncliff e Percival, 34, Cartwright Gardens, W.C. A41bert Cherbury David Rivett, B.A., B.Sc., Chemistry Dept., University, Melbourne. William Arthur Reginald Wilks, M.A., 50, Stowheath Lane, Priestfield, Wolverhampton. Of the following papers, those marked * were read: “26. ‘‘ The constancy of water of crystallisation in hydrated salts. Part I.” By Herbert Brereton Baker and George Henry Joseph Adlam. The authors have found that telluric acid always contains an excess of water over the calculated amount even when dried by phosphoric oxide for six months in a vacuum. This excess is due View Article Online 18 to water occluded in the crystals, and water vapour cannot pass through a thin crystal of this substance. Determinations of the ahrnic weight of tellurium have been made by estimating the weight of water given off in the decomposition of telluric acid, as well a$ the total loss of weight. The mean of four determinations of the ratio TeO,: 0 gave an atomic weight of 137.49. Experiments have. been made with other hydrated crystals to find if such substances can be obtained in such a state as to be available for atomic weight determinations. By keeping the salts in an atmosphere conbaining a quantity of the partly dehydrated salt, such salts can be completely freed from adherent moisture. One such experi- ment with crjstallised barium chloride (BaC12,2H,0) gave 14.772 per cent. of water instead of 14.747. The similar method used by Guye and Tsakalotos (-7. Chim. phys., 1909, 8. 3) gave with the same salt 14.6765 per cent. of water. It was shonn that if 8 salt be completely dehydrated and left in a moist atmosphere, it will take up almost exactly the amount of water which correspond4 with its water of crystallisation. For barium chloride the pel- centage was 14.750 instead of 14.747. Further, it has been shown that air will not pass through a crystal when the latter is used to close a vacuum tube. Water vapour will, however, pass through hydrated crystals from a nisiat atmosphere to a dehydrating agent, but a partial dehydration of the crystal on the side nearest to the dehydrating agent seems to be necessary. Water vaponr will not pass through anhydrous crystals: and therefore occluded water cannot be removed by placing in x desiccating atmosphere. D I s cu s s I ON. Published on 01 January 1911. Downloaded by University of Prince Edward Island 30/10/2014 14:33:19. The PRESIDENTasked whether it was possible to obtain anhydrous telluric acid, H,TeO,, and whether the ortho-acid, H,Te06, could be made by allowing the more or less anhydrous acid t'o take up moisture from an unsaturated atmosphere. Dr. SENTERsaid that if he understood the author rightly it was claimed that drying a salt hydrate over a mixture of the same hydrate and the anhydrous salt would remove all the moisture from the surface of the hydrate crystals. The method in question u~ould ensure against dehydration being carried too far, but it appeared open to doubt whether it could be relied on t\o effect the complete removal of adsorbed moisture in all cases when one remembered the remarkable tenacity with which such moisturc was sometimes held. The data given by the authors showed that the method was effective for barium chloride, but other salt hydrates in crystalline form might conceivably have much greater power of retaining adsorbed View Article Online 19 moisture. He wished to ask Dr. Baker if further data were available on this point. Dr. R. LESSINGasked if the size of crystals had any influence on the amount of (‘adherent ” or ‘‘ occluded ” water, and whether it was possibIe to facilitate the removal of this water by finely grinding the crystals. In reply to the President, Dr. BAKERsaid that anhydrous telluric acid took up water with extreme slowness. It was insoluble in water, and it did not become completely hydrated by remaining in water for three months. In answer to Dr. Senter, it was stated that the experiments now in progress would decide whether the method was a general one. *27. L‘ The triazo-group.” Part XVI. Interaction of nitrosates and sodium azide.” By Nartin Onslow Forster and Frederik Marinus van @elderen. The azoimide nucleus may be substituted for the nitroxyl group in nitrosates and ethereal nitrates. P-Triaao-P-rne t lz yl b tct an-y-oxime, N,*CM%*CMe:NOH, prepared from isoamylene nitrosate and sodium azide, melts at 34-35O; it is freely soluble in organic media, and is volatile in steam. El-Triaao- P-?nethyZbuta~-y-one,N,-CMe,*CO*CH3, produced on hydrolysing the oxime with dilute mineral acids, boils at 42O/14 mm., and has D 1.0057/ 18O. The semicarbazone, C,H,,ON,, and thiosemi- carbazone, C6H,$N6, melt at 127O and 106-107* respectively. The triazo-ketone leads to the amino-ketone on reduction, but this is stable only in the form of salts; alkalis convert these into hexamethyldihydropyrazine, which has been lately described by Published on 01 January 1911. Downloaded by University of Prince Edward Island 30/10/2014 14:33:19. Gabriel (Bcr., 1911. 44, 57). *28. “ The triazo-group. Part XVII. Nitroso-azides of phene and terpineol.” By Martin Onslow Forster and Sidney Herbert Newman. Nitroso-azides may be prepared by interaction of nitroso- chlorides and sodium azide. Pinene nitrosoazide, CloH,5(:NOH)*N3, crystallises in brilliant, transparent prisms, melting at 120O; it is unimolecular, and the acetyl derivative melts at 64O. Alcoholic piperidine or sodium ethoxide gives rise to nitrosopinene. An isomeride of pinene nitrosoazide arises when the original material is heated with water, and melts at 126O, the acetyl derivative melting at 71O; it also yields nitrosopinene with alcoholic sodium ethoxide, but the continued action of hot water leads to the oxime View Article Online 20 of hydroxydihydrocarvone, melting at 133’5O. The last-named substance is produced also by the action of alcoholic sodium ethoxide on terpheol nitrosoazide, OH=C,,H,,(:NOH)~N,,which is prepared from terpineol nitrosochloride and sodium azide, and melts at lllO. *29. b6 The synthesis of 3-/I-aminoethylindole.” By Arthur James Ewins. The condensation of y-aminobutyrylacetal and phenylhydrazine, by heating with zinc chloride to 1 SOo, yields S-~-aminoethyZindoZe (m. p. 146O), the amine derived from tryptophan by loss of carbon dioxide. Its most characteristic salt is the picrate, red needles, m. p. 242-243O. The hydrochloride, pkrolonate, and b enzoyl derivative were also described. The base is physiologically active. DIscu s SION. In reply to Dr. Pyman, Mr. EWINSstated that the yield of 3-P-aminoethylindole was from 40 to 50 per cent. of the theoretical. 30. The orientation of the nitro-group in nitromyristicinic acid.” By Arthur Henry Salway. In a previous investigation (Trans., 1909, 95, 1155) the author had occasion to prepare nitromyristicinic acid, the constitution of which could be represented by one of the two following formule : NO2 Published on 01 January 1911. Downloaded by University of Prince Edward Island 30/10/2014 14:33:19. CH,<OIO/\CO,H I CH2<$)C02H VNo2 \/ OMe OMe (1.1 (11.1 It has now been shown that this acid may be converted into cotarnic acid by the transformation of the nitro-group into a carboxylic group. The constitution of nitromyristicinic acid must therefore be represented by formula (I). 31 Lb The condensation of aromatic aldehydes with nitromethane.’ ’ By Frederic Ueorge Percy Remfry. The facility with which aromatic aldehydes condense with nitromethane in the presence of alcoholic potash is affected by the nature and position, with regard to the aldehyde radicle, of any View Article Online 21 substituting groups in the benzene ring. An attempt was made to ascertain the conditions which govern the condensation, and for this purpose a number of aldehydes, with different substituents variously placed in the ring, were condensed with nitromethane. The results obtained, however, did not permit of any generalisation being put forward, owing to the fact that anomalies were observed in some cases which at present have not been satisfactorily explained. The following compounds were described : w-N.;l.tro-o-,-m-, and -p-hydroxys t yrene, OH*C,H,*CHI CH-NO, (m. p. 133-1 34’, 132-133°, and 165O respectively) ; o-nitro-p-acetoxystyrene (m. p. 158-159) ; o-nitro-p-benzoyloxystyrene (m. p. 156O) ; ethyl o-nitro- styryl-p-oxyncetate, N0,*CH:CH°C6H,*O*CH,*C.02Et(m. p. 82’) ; ethyl o-nitrostyrgl-m-oxyacetate (m. p. 147-148’) ; p-chloro-o-nitro- styrene (m. p. 111-112°) ; o-3-dinitro-2-hydroxystyrene(m. p. 174-175’) ; o-3-dinitro-4-methoxystyrene (m. p. 165-166O) ; 8-3: 5-trinitro-4-met hoxy-a-phenyle thanol, O~~e=C,H,(NO,),*CH(OH)*CH,*NO,; P-nitro-2 : 5-di7~ydroxyphenylethamol(m.

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