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Proceedings of the Chemical Society, Vol. 16, No. 227 |
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Proceedings of the Chemical Society, London,
Volume 16,
Issue 227,
1900,
Page 163-186
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摘要:
Issued 7 / 11/ 1 900 PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 16. No.227. July 5th. Extra Meeting. Professor TIIORPE,C.E., F.R.S., President, in the chair. Professor OTTO PETTEIWSON,of Stockholm, delivered the Nilson Memorial Lect lire. On the motion of Dr. AitwriioNc~,seconded by l’rofessor DEWBR,a vote of tlisnks was passed to Profcssor l’ettersson for hi,.; Lecture. The following are aljstrncts of tlie papers received during tlie vacation, and published in the Z’TCU~S~C~~O~LS;-Ill. I( Asymmetric optically active sulphur compounds ; chiethyl-ethylthetine platinichloride.” By W. J,Pope and S. J. Peachey. hltliough the earlier attempts of the authors to resolve methyletLy1- thetine into optically active components were unsuccessful, they hare :,iiice succeeded in preparing d-rnetl~ylctl~ylthctine platiiiicliloride. T\Iethylethylthetine bromide IV:W treated with silver cZ-c;iinphorsd-phonate. The residue, after ev‘ipomtion at n low tempi-atnre, was dissolved in absolute fclcoliol and precipitated by the addition of anhy-drous ether, and this treatment repeated about 40 times, when a spar-ingly soluble fraction was obtained, which seems to be cl-methylethyl-thetine d-camphorsulphonate. It melts at 118-1 20°, and gives [a],,= +lS*6Oand [MI,= +GS*Oo. The tl-broniocamphorsulphonntc was similarly preparetl.Wheil either of these salts is dissolved in absolute alcohol, a little strong hydrochloric acid and an :ilcoholic solution of platinic cllloricle 164 added, a yellow, crystalline platinichloride is deposited, having the constitution 2C2~>S<C''2'Co~H,PtU14, CH3 and giving [.ID = + 4 5" and [.ill],,=+30*5". 112.Sulvanite, a new mineral." By G.A. Goyder. This mineral was found in considerable quantity in some ore from a new mine near the Burra in South Australia. It appears to afford the first recorded instance of a sulphide mineral contain- ing vanadium as one of its principal constituents. The analyses given show that it, consists of cuprous sulphovana- date, 3clu,S,V2S,. Its hardness is 3.5, and its specific gravity 4.0. 113. (( Estimation of atmospheric carbon dioxide." By James Walker. A modification of Pettenkofer's bottle method is described which gives results accurate to 0.1 vol. carbon dioxide in 10,000 vols.air, when a bottle of 2.6 litres capacity (Winchester quart) is ern- ployed. The usual error due to absorption of carbon dioxide dur- ing titration is avoided by filtering the residual baryta solution into a known quantity of hydrochloric acid, and titrating back with standard baryta. The filtration takes place under diminished pressure through asbestos contained in a Soxlilot filter tube, atnio- spheric air being entirely excluded during the proc*oss of ljltering and washing. No special apparatus is employed, and an estimation occupies only half an hour. 114. '(On some periodides of substituted oxonium derivatives." ByJ,N.Collie, F.R,S., and B. D. Steele, B.Sc. During the investigation of the salts of tetrlzmethylpyrone, it was noticed that when the solution of the iodide was allowed to ovaporate in the air brownish crystals slowly separated, which were nesi-ly in-soluble in water.From their properties they scemcd to resemb!e the periodides of the pgridine bases. It was found that when free iocliiie in potassium iodide solution was added to a solution of the hydriodide of tetramethylpyrone or of dimethylpyrone, an immediate crystalline precipitate was produced. These periodides have the following constitution : from dirnethyl- pjrone, C7H,0213T,T, ; froin tctramcthylpyronc, C,H,20,TII,T,. They lose iodiue when heated, and are at once converted into di- and tetra-methylpyrone when treated with a solution of sod^. The action of iodine on the barium and sodium salts of dimethyl.165 pyrono proceeds in a quite different manner. The chief product is an oxidised iodinc compound, C7T1710,, which possesses rather remal*kable properties; it is not decomposed when warmed with solutions of soda or sodium ethylate, but gives free iodine at once when warmed with n, mincral acid. 115. Condensation of phenols with esters of the acetylene series. 11. Action of phenols on ethyl phenylpropiolate and ethyl acetylenedicarboxylate.” By Siegfried Ruhemann and Fred Beadow. The authors describe ethyl-P-m-cresoxycinnamate and the products of its transformation as well as the reaction between phenols and ethyl acetylenedicarboxylate. They find that in the latter case aryl ethers of ethyl hydroxyfumarate are formed, and not the ethers of ethyl hydroxymaleate, which were expected; this has been proved by a comparison of the products with the compounds obtained by tIhe action of the sodiophenolntes on ethyl chlorofumarate.The aryl ethers of ethyl hydroxyfumarate, on hydrolysis with alcoholic potash, give the correspondiug acids, which on heating are partially trnnsformcd into tho aryl ethers of hydroxymaleic acid ;these differ from their stereoisomerides in that lead acetate gives with their aqneous solutions precipitates of their lead salts, but not with the nryl ethcrs of hydroxyfumnric acid. 116. ‘‘ The vayour pressures, specific volumes, and critical con-stants of di-isopropyl and di-isobutgl. By Sydney Young, D,Sc., F.R.S., and Emily C.Fortey, B.Sc. The results here given, taken in conjunction with those of previous researches, show that an iso-or di-iso-paraffin bears very much the same relation to the isomeric normal paraffin as a lower does to a higher homologue. Thus the ratios of the absolute temperatures to the absolute critical temperatures, and of the volumes of saturated vapour to the critical volumes at corresponding pressures, as well as of the actual to the theoretical densities at the critical points, are higher for the normal parailins, whilst the ratios of the volumes of liquid to the critical volumes at corresponding pressures are lower.It was found that di-isopropyl shows marked peculiarities; it is exceptionally difficult to prepare by any method involving the com-bination of two (CH,),CH* groups; the specific gravity at0’and tho critical pressure are higher than those of normal hexane, whereas these constants in all other known cases are lower for the iso-and di-iso-paraffin than for the normal isomerides ;the critical density, the critical temperature, and the boiling point are also exceptionally high.117. iL The vapour pressures, specific volumes and critical constants of normal octane." By Sydney Young, D.Sc., F.R.S. The normal octane was obtained from Kahlbaum, and was easily purified by trcntinent with sulphuric and nitric acids and subsequent fractional distillation. A comparison of the data for normal pentnne, hexane, heptane and octane shows that the ratios of the absolute temperatures at any series of corresponding pressures to the absolute critical tempcrat ures, and also the ratios of the actual to the theorcticd clensities at the critical points, increase sliglitly with rise of moleculnr weight, whilst the ratios of tho volumes of liquid at corresponding pressures to the critical volumes diminish slightly.The ratios of the volumes of saturated vapour to the critical volume are, on the whole, very slightly lower thnn for normal Iicptane, but are liiglier than for licxane or pentane. 118. Separation of neobornylamine from bornylamine." By M. 0. Forster, and J. Hart-Smith, A.R.C.S. In the course of attempts to qppnrztc neohornylaminc from liornyl-amine, in addition to the Iytlyobyonzitle, hycl~iotlitle,nitmte, szclplmte, and benzoate of bornylnmine, the following substances havo been obtained.Canzp~oi~oxinzeaceticcccitl, C,,€II,,:NO*C'II,*CO,IT, which me1ts at 100-103", and gives [a],,= -5.9" ;the sodizinz and boi*nyltcnzinesalts are Tell defined. Bornyloxamide, CJ,,Hl7*NH*CO*CO*NH,, melting at 1G2", which gives [a],= -24.1'. l)ibornyloxaniide,C,,HI7*NH*CO*CO-NH CIOHII,which melts some-what indefinitely at 140°, and gives [all, = -39.6'. Purified neobornylarniiie melts at 1S4", and lins [a],,= -43.7' in absolute alcohol. The beizxplidene clorivative is an oil which boils at lS0' under 25 mm. pressure. 119. ''Aminoamidines of the naphthalene series.'' By Raphael Meldoln, F.R.S., and Lewis Eynon, A.I.C.Jt has been found by the authors that when dinitro-a-acetnaphthalido is reduced by iron and hydrochloric acid (Markfeldt, Be7*., 1898, 31, 1174), ihc etlienyl triaminonaphthalene produced is isomeric and not identical with that obtained when tin and hydrochloric acid are used (Meldola and Streatfeild, Tmns., lSS7, 51, 691). In this paper it is shown tlint the isoinerimi is entircly attrilmtnblo to tlic rccluciug 167 agent, since the same dinitro-a-acetnaphthalide has been used through- out. Descriptions and analyses are given of Markfeldt’s base and some of its salts, of the acetyl derivatives of both bases and their salts and of the isomeric phenylazo-derivatives. The pronounced difference in the properties of the latter compounds first indicated the isomerism of the respective anhydro-bases. It is suggested that the isomerism may be explained by the structural differences indicated by the formulae : ‘f )NH Experiments with the object of determining the constitution of the amino-amidines have been commenced, and the research will be extended in this direction.When the NH, group in Markfeldt’s base is replaced by hydrogen by the diazo-method an ethyldiamino naphthalene is obtained which is apparently identical with that Prager (Ber., 1885, 18,2161). 120. Note on the elimination of a nitro-group during diaiotisation.” By Raphael Meldola, F.R.S., and Elkan Wechsler. When acetorthoanisidide is nitrated with excess of fuming nitric acid in the cold in acetic acid solution, a dinitroacetanisidide is formed.This compound crystallises in light yellow needles melting at 162-1 63O, and on hydrolysis by alcoholic sodium hydroxide gives a dinitroanis-idine, crystallising in bright orange needles having a melting point of 186-1 88’. This dinitroanisidine, on treatment with sodium nitrite and an acid, forms a diazo-compound which crystallises in ochreous scales or yellow needles, having an exploding point of about 178’. The diazo-compound has the formula NO2*C,H3(0CH,) ON,*OH, so that one nitro-group is eliminated during the process of diazotisation. The corresponding iodonitromethylresorcinol crystallises in flat, yellow needles melting at 115-1 16’. The nitroazo-P-naphthol derivative, ob- tained by combining the diazo-compound with P-naphthol in alkaline solution, forms glittering, bronzy-green scales decomposing at about 250’.The constitution of the new dinitroanisidine is being investi- gated with the object of determining the particular configuration which is favourable to this easy displacement of a nitro-group. 168 121. "A contribution to the stereochemistry of sulphur ; an optiually active sulphine base." By S. Smiles, B.Sc. Methyl ethyl sulphide unites with o-bromacetophenone to form CH3>S<CH2C0Ph ; this,methyI-ethy2-pl~enacylszl.lpT~ine byomide, C2H5 Hr when treated in alcoholic solution with silver dextro-a-bromocamphor- sulphonate, gives rise to two salts, the molecular rotation of the less soluble of which is +250°, and of the more soluble +289O.This points to the fact that the basic methyl ethyl phenacyl radicle possesses a molecular rotation in aqueous solution of over 20". From the less soluble salt a laevorotatory sulphine picrate was ob-tained as yellow needles (m. p. 125') for which [ = -9.3" and [MID = -39.3'. The dextrorotatory picrate obtained from the more soluble salt, (yellow needles, m. p. 123-12d0) gave [a]. = +8.l0 and [MI = +34.2. It was not found possible, however, to separate two stereoisomers from methyl-ethyl-desyl-sulphine bromide, cH3>S<Br CHPh*COPh (32% which WRS obtained as a colourless mass of deliquescent needles. 122. Condensation of phenols with esters of the acetylene series. '4 Synthesis of benzo-y-pyrone." By S.Ruhemann and H. E. Stapleton. By the condensation of guaiacol and thiophenol with esters of the acetylene series the authors have obtained C,H5*C(OC,H;OCH3):CH* C0,Et and C,H,. C(SC,H,):CH* C0,Et; Ethyl B-o-methoxyphenoxycinnamate. Ethyl B-thiophenylcinnamate. these esters, on hydrolysis with alcoholic potash, give the corresponding acids which lose carbon dioxide and yield respectively C,H,* C(OC,H,OCH,) :CH, and C,H5*C(SC,H5):CH2. o-Methoxyphenoxystyrene. Thiophenylstyrene. Ethyl acetylenedicarboxylate condenses with thiophenol to ethyl thiophenylfumarate, which is decomposed by alcoholic potash, forming phenyl disulphide (C,H,S),. Along with the ethyl thiophenylfumarate, ethyl dithiophenylauccinate is also formed, having probably the formula CO,Et.C(SC,H,),* CH,* C0,Et.The analogous oxygen compound, along with ethyl P-phenoxyfumarate, is obtained by the action of phenol on ethyl ace tylenedicarboxylate. Ethyl P-phenoxycinnamate, by treatment with strong sulphuric acid, is not condensed into flavone, but decomposes into benzoylacetic acid 169 along with oxalic and acetic acids. Ethyl phenoxyfumarate, however, partially undergoes the desired change, forming benzo-y-pyronecarb- oxylic acid, which, on heating, loses carbon dioxide, giving benzo-Y-PJrone, C6H4<~-CH9 melting at 590."*GH 123. ''Contributions to the chemistry of hydrotetrazines and triazoles." By Oswald Silberrad, Ph.D. The action of hydrazine hydrate on diacetanilide gives dimethyldi- NH*Nhydrotetrazine, CH,CqX. NH>CCH3 ; its hydrochloride melts at 232'.Benzoyl chloride decomposes it with the formation of sym-dibenzoyl-hydrazine and acetic acid. Nitrous acid converts it into dimethyltriazole nitrate (m. p. 125'), from which the hydrochloride (m. p. 199') and the free base, CH,C<gH*N>CCH3 (m. p. 142O, b. p. 258' at 752 mm.), may be obtained. Its constitution is evident from its synthesis from acetarnide and acetylhydrazine, Diphenyldihydrotetrazine, C,H5C<g$z>CC,H,, may be ob-tained in almost theoretical quantity by heating benzoylhydrazine with hydrazine hydrate to 230'. It melts at 264'. Pinner gives 258' (Bey., 1894, 2'7,1006). Heated alone, benzoyl-hydrazine yields only traces of diphenyl-hydrotetrazine, the chief products being diphenyltriazole, C,H5U<NH>CN*N *C,H5,and diphenyl diazoxole, C,H,C<~~~>CC6H5. aa-Benzoylphenylhydrazine under similar treatment does not con- dense, but breaks down with production of benzophenone, benzoic acid and benzoylanilide.124, '' Isomeric dibenzylketone benzalanilines and deoxybenzoin- benzalanilines." By Francis E. Francis, Ph.D., B.Sc. Three isomeric addition products of the two ketones, dibenzyl ketone and deoxybenzoin, with benzalaniline are described. For the sake of convenience these are termed a-,p-, y-modifications. The a-is obtained from the pure ketone, the p-by the action of traces of piperidine on the a-or with greater difficulty on the y-, the y- by the action of traces 170 of sodium ethylate on either the Q-or p-.By the action of heat, the /3-and y-are transformed into the a-modification. The dibenzyl ketone benzalanilines are more basic than the deoxybenzoin benzal- anilines, the former yield normal, whilst the latter give basic hydro- chlorides. These salts are different in the case of a-and p-but identical in p-and y-. They are dissociated by water, giving the corresponding base, but with alcohol the a-hydrochloride appears to give a mixture of a-and y-base, whereas the p-or y-gives the a-modification nearly pure. 125. '(Condensation of methylic acetonedicarboxylate. Constitution of orcinoltricarboxylic eaters." By F. W. Dootson, M.A. It is shown that a moderate tenipernture is siifficient to condense methyl acetonedicarboxj late to trit~iethyl oi-cinol tricarboxylate, and that a good yield of the latter is obtained.The constitution assigned to ethyl orcinoltricarboxylate by Jerdan is confirmed, and the similarity of the methyl and ethyl esters is shown by nitration and subsequent reduction, when a lactam structure results in both cases, proving that in orcinoltricarboxylic esters the remaining hydrogen atom of the benzene nucleus is in the ortho-position to the side chain, thus : CH,CO,E t UH,CO,Et CH&O EtCO,/\ H -EtCO,/\NO, -EtCO,/) NH HOI'\//OH HO()OH HO!,, OH C0,Et @O,Et C0,Et 126. '(Contribution to the chemistry of the aromatic meta-diamines." By G. F. Morgan, D.Sc. In this paper the following compounds are described : l-bromo-2 : 4-phenylenediamine melting at 111-1 12"; its dibenzoyl and its diacetyl de-rivatives melting at 178.5"and 198"respectively ; dibenxoyl l-chloro-2 :4-phenylenediamine, m.p. 178", and chloi-ochrysoidine, PhN,C,H,Cl(NH,),, m. p. 149' ; m-~henylenecliacetyldicl~Zorc~~ine,Q,H,(NCl*Ac),, 1:'. p. 150-151O ; dicccetyl-1 : 5-tlichloro-2 : 4-~henyZenediamine,m. p. above 260°; 1: 5-dichloro-2 : 4-phenylenediamine melting at 136-137" and its dibenxoyl derivative at 187". Diacetyl-m-toluylenediamine, when chlorinated and then hydrolysed, gives 5-cldoro-2 : 4-toluZyZenediamine7 M. p. 120-121' ; its diacetyl derivative melts at 239-240". 127. 66 Action of aromatic aldehydes on derivatives of /3-naphthyl- amine." By Gilbert Thomas Morgan, D.Sc.The compound, C48H42N202,produced by the condensation of ethyl 6-naphthylamine (2 mols.) with benzaldehyde (3 mols.), crystallises in colourless leaflets and melts at 148'. Its constitution may be repre- sented by one of the following formulae : Ph.CH(NEt.CloH7),,2Ph*COH; C,,H7NEtCHPh*O*CHPh~NEt*CloH7,PliCOH; PhCH<O.CHPlr,NElt.cloH?. Its geceral behavioiir is in accordance O.CHPh*NEt.C,,H, with the third of these; but freezing point determinations seem to indicate that the substance, dissolved in banzene, corresponds with the second formula. The following anhydro-bases and their hydrocyanides, derived from 1-chloro-2-naphthylamineand its bromine analogue, are also described in the paper : benzylidene-l-broimo-2-naphthyZc~mine,rn. p.93-94', and its hydrocyanide, m. p. 92' ; the cuminylidene derivative and its hydro- cyanide, melting at 100-101' and 120' respectively ; the p-hydroxy- benxylidene and o-hydroxybenxylidene derivatives, melting respectively at 189-190' and 144', and the corresponding hydrocyanides at 144' and 152' ; p methoxyben~yZidene-1-bromo-2-napl~thyZarrzineand its hydrocyanide, melting at 107" and 140-143" ; cinnunayZidine-l-b?.omo-2-naphthyZccmine,rn. p. 126', and its hydrocyunide, m. p. 142-1 43'; benxylidene-l-chZoro-2-nuplzt~~yZamineand the corresponding cuminylidene derivative, melting respectively at 99' and 85', and their hydyocyunides at 77' and 117' ; cinnumyZidene-l-cl~lo?.o-~-)2a~~~LtT~?/Zc~mine,134O,m.p. and its hydrocyunide, m. p. 155-156' ; p-hydroxybenzylidene-1-chZoro-2-naphth$ccr~~ine and the corresponding ortho-isorneride, melting re- spectively at 191' and 153", and their hydrocyanides at 152' and 148O; p-methoxyEenxyZidene-1-chZoro-2-n~~~~~t~~yZanaine,m. p. 117", and its hydrocyanide, m. p. 132'. The following anhydro-bases do not combine with hydrogen cyanide : o-nitrobenxylidene-l-chloro-2-nc~phthyZctmine,rn. p. 142', and the corre-sponding bromo-compound, melting at 138' ; p-nitrobenxylidene- 1-cldoro- 2-naphthyZumine, m. p. 151', and its bromine analogue, melting at 154-155'. 128. Action of hydrogen peroxide on carbohydrates in the presence 6' of ferrous salts. 11." By R. S. Morrell, M.A.,Ph.D., and J, M. Crofts, M.A., B.Sc.Rhamnose when oxidised by hydrogen peroxide in the presence of ferrous sulphate yields an osazone which reacts with phenylhydrazine at the ordinary temperature to give rhamnosazone. 172 Similarly, cane sugar, when the hydrogen peroxide is neutral, is first ‘ inverted ’ and then oxidised, since on testing with phenyl-hydrazine, glucosazone is precipitated. The action of potassium persulphate on glucose in the presence of ferrous sulphate is slow at ordinary temperatures. On warming to 40’, oxidation proceeds more rapidly with formation of glucosone. The yield of the glucosone (measured by the weight of the glucosazone precipitate) is smaller than when hydrogen peroxide is employed as the oxidising agent. 120. ‘‘ The specific gravities of the halogens at their boiling points, and of oxygen and nitrogen.” By J.Drugman, Ph.D., and W. Ramsay, F,R.S. The determinations made by the authors of the specific gravities of the halogens at their respective boiling points under atmospheric pressure have given the following results : Iodine boiling at 184.5’ has the sp. gr. 3.706 Chlorine ,, -33.6’ ,, ,, 1,507 Fluorine ,, -187’ 7, 2, 1.108 The specific gravity of fluorine mas arrived at by using the data of Moissan and Dewar (PBoG.,1897, 13, 180) and calculating the specific gravity at its boiling point, corrections being made for the ex- pansion of the liquid fluorine and the change in the specific gravity of amber. Amber mas found to have the specific gravity 1.065 at 15’ and 1.10 at -187’.The specific gravities of oxygen and nitrogen were found to be 1,1315 and 0.7914 at their respective boiling points. 130. “ On hydroferrocyanic acid.” By K.C. Browning, B.A. The purification and some of the properties of hydroferrocyanic acid are described. This acid begins to evolve hydrocyanic acid at 120°, and its decomposition is complete at 300°, ferrous cyanide being left as a pale yellow powder. Ferrous cyanide decomposes above 430’ into iron, carbon and iron carbide. Reasons are given for con-sidering it to bz an isocyanide, but when strongly heated it seems to decompose partly as if it were a normal cyanide. From the decomposition of ethyl ferrocyanide it mould seem that a11 the cyanogen groups present have the isocyanide arrangement. 131.On the nature of metal-ammonia compounds in aqueous solu- (6 tion. Part I.” By H. M. Dawson and J. McCrae. The nature of various ammoniacal salt solutions has been studied by determining the aniount of ammonia extracted by shaking a known 1’73 volume of the aqueous solution with a known volume of chloroform. If pure aqueous ammonia be shaken with chloroform at a constant temperature till equilibrium is established, this condition is character- ised by the relationship CJC, =constant (26*3), where c1 = concentra-tion of ammonia in water and c2 that in chloroform. When this is done with ammoniacal solutions of cupric sulphate, cupric chloride, zinc sulphate, cadmium iodide, and nickel sulphate, the constant is found to give much higher values, and hence the amount in combination with the salt may readily be deduced.Ex-periments with calcium chloride solution also indicate the formation of a complex metal-ammonia compound, but the amount of ammonia combined per molecule of salt is very much smaller than in the case of the other salts investigated. Experiments were also made with ammoniacal copper oxide solution which indicate that the base Cu(NH,),(OH), is probably formed ; the copper sulphate compound has the formula Cu(NH,),SO,. November lst, 1900. Professor THORPE, C.B., F.R.S., President, in the Chair. Messrs. 5. S. Napper, G. E. Tomlins, 0. Silberrad, C. Watson, C. 1. F. Watts, and H. F. F. B. Fermor were formally admitted Fellows of the Society.The following certificates were read for the first time :-Messrs. George Lowe Bennett, 13 St. Doming0 Vale, Egerton, Liverpool ; Frederick Nisbet Binks, 2 Hollywell Terrace, Millbourne Avenue, Drumcondra, Dublin ; Herbert James Singleton Boyes, 9 Rua Episcopal, Szio Paulo, Brazil ; Theodore Ridley Burnett, 83 Coltart Road, Liverpool ; John Henry Cheesewright, 80 Sydney Road, Hornsey, N. ; Albert Walker Comber, Rio Marina, I. d’Klba, Italy ; Alexander Davidson, jun., 1Almond Bank Terrace, North Merchiston, Edinburgh ; Arthur Louis William Fechtner, 186 Spring bank, Hull ; Willie Ludford Freeman, 102 Marlboro’ Road, Oxford ; William Gasson, Kimberley, South Africa ; George William Gibbings, Standard Bank of South Africa, Ltd., Salisbury, Mashonaland ; John Gibson, Battle Hill, Hexham, Northumberland ; Walter Augustus Handcock, Southbank, 40 Avenue Road, Highgate, London ; William Arthur Hargreaves, Port Adelaide, South Australia ; George Harker, 35 Boulevarde, Petersham, Sydney, N.S.W. Frank C.R. Hemingmay, Albyns, Forest Road, Walthamstow ; John Brownlie Henderson, Brisbane, Queensland ; Samuel Hemitt, 3 Chester Street, Norwich ; William Henry Hewitt, 115 Fentiman Road, London, S.W. Adolf I74 Japp6, Broad Oak, Oak Avenue, Bradford; Humphrey Owen Jones, Clare College, Cambridge ; George Washington Kilner, 14 St. John’s Park, Upper Holloway, N.; Morris Charles Lamb, Herold’s Institute, Drummond Road, Bermondsey, London, S.E.;; George Druce Lander, 1 Balmoral Road, Nottingham ; William McCall, Rio Marina, Isola d’Elba, Italy ; Thomas Marginson Nightingale, 375 Bridgman Street, Bolton ; Alexander Pardy, Pietermaritzburg, Natal, S.Africa ; John Paul, Bacteriological Institute, Grahamstown, Cape Colony ; Ernest Vivian Pearce, The Beeches, Hayle, Uornwall; Henry !Ernest Stapleton, St. John’s College, Oxford ; Arthur Lambert Thornton, 2 Park Street Bolton ; Ferdinand Gerhard Wiechmann, 771 West End Avenue, New York’; George Sampson Valentine Wills, Southwood, Croham Road, South Croydon ; Walter Bourne Woodbridge, Grey Friars, Chichester ; Herbert Edwards Wright, 1 Brewers Street, St. Aldates’, Oxford. Of the following papers, those marked were read :-“132. (( Action of alkalis on nitro-compounds of the paraffin series.Part 11, The reactions and constitutions of methazonic acid and the formation of isoxazoles.” By Wyndham R. Dunstan, F.R.S., and Ernest Goulding, B.Sc. In a previous paper (Dunstan and Dymond, I’rans,, 1891, 59, 410) it was shown that trimethylisoxazole results from the action of alkalis on nitroethane, and triethylisoxazole from a similar action on nitro-propane. Nitromethane, however, furnished no isoxazole, neither did secondary nitropropane. Further investigation has shown that the action of alkalis, preferably ammonia, on nitromethane leads to the production of the substance briefly described by Lecco under the name of methazonic acid, C2H4N203,and regarded by him as an anhydride of nitromethane.The authors have obtained this substance in colourless crystalline plates melting between 60’ and 70°, and have prepared and described several of its salts. Both the acid and its salts, AgC2H3N,03, NH,C2H3N203,&c., are unstable, and are liable to explode when suddenly heated. When heated with acids or alkalis, methazonic acid breaks up into carbon dioxids, hydrogen cyanide, and hydroxylamine, according to the equation C,H,N,O, =CO, +NH,OH -tHCN. It is proved that one atom of nitrogen appears as hydrogen cyanide, and the other as hydroxylamine, whilst the carbon is equally divided between the car- bon dioxide and the hydrogen cyanide. On oxidation with permanganate, chromic acid, or hydrogen per- 175 oxide, methazonic acid furnishes carbon dioxide, hydrogen cgarde, and nitric acid.On reduction either in acid or alkaline solution with weak or strong reducing agents, the principal products are ammonia andfovrnic acid. No trace of ethylene-diamine or methylamine could be found. Alkyl derivatives of methazonic acid can be prepared, but they are highly unstable. The authors propose the formula H0R:C.O for methazonic acid 0 as satisfactorily accounting for its reactions. Adopting the view of Nef that the '' salts " of the nitroparaffins are to be regarded as derived from a tautomeride, and writing the formula -CH2:f10Naof sodium nitromethane as ,the authors show how meth- 0 azonic acid is formed by a process of intermolecular oxidation followed by condensation of the nitromethane residue with formaldoxime simul- taneously :produced, 2CH2:RoNa =NaC2H3N20,+NaOH.0 By a similar process of intermolecular oxidation, followed by con-densation with an oxime, it is shown how trimethylisoxazole, acetonitrile, and sodium nitrite are formed by the action of alkalis on nitroethane and how triethylisoxazole and similar products result from the action of alkalis on primary nitropropane ;also, how secondary nitropropane gives no isoxazole, but acetone, nitrite, and hydroxylamine.In this discussion it is assumed that nitro-compounds may be reduced to oximes (Dunstan and Dymond, Proc., 1894, 139), and grounds are now stated for concluding that whilst the nitroparaffins themselves may be reduced (in acid solution) to substituted hydroxylamines, their salts, when reduced (in alkaline solution), furnish oximes or their de- composition products.These facts afford further justification for the view that the (( salts " of the nitroparaffins are derivatives of a tauto-'N-OHmeride containing the group ' I I .0 "133. '' Hexachlorides of benzonitrile, benzamide and benzoic acid." By Francis Edward Matthews. Benzonitrile mixed with water is saturated with chlorine and ex-posed to light till the yellow colour of the chlorine disappears. This process is repeated four or five times. The mixture is then subjected to steam distillation till all the benzonitrile has passed over. A thick oil remains which, on purification by solution in, and subsequent 176 recrystallisation from, glacial acetic acid, gives colourless crystals of benzonitrile hexachloride, C,H,CI,* CN, melting at 157".The hexachloride is not easily hydrolysed, but heating with strong sulphuric acid at 170-180O converts it into the hexachloride of ben zamide. This, crystallised from acetic acid, melts at 187-188". On treating the hexachloride of benzamide with fuming nitric acid, the following change takes place : C,H5Cl,*CONH, +HNO, = C,H,C16*CO,H +N,O +H,O. The hexachloride of benzoic acid has been obtained pure and has been analysed. Its most striking property is the decomposition it undergoes on boiling with water, thus : CGH5C16*CO,H =C6H,Cl, + HCl + CO,. The benzoic acid hexachloride and the monochlorobenzenetetra-chloride are being further investigated.*134.('The influence of solvents on the rotation of optically active compounds. I." By T. 5. Patterson. Experiments to determine the influence of some solvents on the rotation of ethyl tartrate at various concentrations and temperatures were described. From the data obtained it is possible to deduce the rotation in each of the solvents dealt with, at any temperature within the limits of the experiments and at any concentration what- ever, with fair accuracy. The results obtained may be summarised thus : 1. Wates..-Ethyl tartrate in dilute aqueous solution has a much higher specific rotation than in the pure state. In solutions weaker than 55 per cent. the rotation diminishes with increase of temperature.2. Methyl Alcohol.-In dilute solution in methyl alcohol the specific rotation of ethyl tartrate is considerably higher than in the pure state. In all solutions the specific rotation increases with increase of temperature, and at much the same rate as that of the pure ester. 3. Ethyl AZcohoL-Dilute solutions of ethyl tartrate in ethyl alcohol have a specific rotation slightly higher than that of the pure ester. A maximum value of the specific rotation only seems to be reached at infinite dilution. Increase of temperature causes increase of rotation in all solutions, the rate of variation being much the same as in the pure ester. 4. Propyl AZcohoZ.-No mixture of ethyl tartrate and propyl alcohol seems to have a higher specific rotation than pure ethyl tartrate at temperatures below 30".At higher temperatures this is not the case. The specific rotation in all solutiona increases with increase of 177 temperature, the rate of increase being generally slightly great er than in the pure ester. 5. Glycerine.-Dilute solutions of ethyl tartrate in glycerine have a considerably higher specific rotation at low temperatures than the pure ester, but as in the case of ethyl alcohol, the maximum rotation appears to be reached only at infinite dilution. The influence of increase of temperature is in all cases to increase the rotation, the rate of increase being in dilute solutions less and in concentrated solutions greater than for the pure ester.The data obtained were then discussed in order to trace, if possible, t'he variation in rotation of the dissolved ethyl tartrate to some known property of the solvent, It was suggested that the property known as internal pressure possesses the necessary qualificat ions, and investigation seems to justify its choice. Since the data obtained render the calculation of molecular solution volume possible, this was first com-pared with the rotation, and it was shown that a regularity can be established, and that the variation of rotation with change of temperature may be explained by certain assumptions regarding the variation of the asymmetry of a molecule with the variation of its volume. These phenomena of rotation were then traced back a step further to internal presmre, or what is probably the same thing-heat of disgregation, when very similar regularities are observed, which seems to show that the original assumptions, regarding the dependence of solution volume on internal pressure and of rotation on both, are justified. "135."The action of heat on ethyl sulphuric acid." By William Ramsay and G. Rudorf. Ethyl hydrogen sulphate, when heated, yields as gaseous products of decomposition, sulphur dioxide, carbon dioxide and monoxide, and ethylene. The oxides of carbon,'after the reaction has fairly started, are present in approximately equivalent proportions ; this seems to point to the oxidation of the alcohol to oxalic acid, which is at once decom- posed by the sulphuric acid.But glycol, heated with sulphuric acid, yields no carbon monoxide, hence this explanation is of questionable validity. When ethylene is bubbled through hot sulphuric acid, the products are the same in kind, and approximately the same in relative amount, as when hydrogen ethyl sulphate is heated. It was proved, inconclusion, that even at 250° carbon monoxide does not deprive sulphuric acid of oxygen ;hence the formation of carbon dioxide in the preceding experiments cannot be attributed to the oxidation of carbon monoxide; it must have been a direct product of the reaction. “136. Contributions to the knowledge of fluorescent substances, I. The nitro-derivatives of fluorescein.” By J. T. Hewitt and B. W. Perkins. Attention has been called to the non-fluorescence of the alkaline salts of tetranitrofluorescein(R. Meyer, Zeit.phys.Chem., 1897, 24, 468; and Hewitt, Proc., 1900, 16,3; and Zeit.phys. Chem., 1900, 34, 1). This absence of fluorescence might possibly be explained by the existence of such tautomerism between the hydroxyl and nitro-groups as usually occurs with ortho- and para-nitrophenols, which would inhibit the double symmetrical tautomerism which, as one of the authors has previously pointed out, is so characteristic of many fluorescent substances. Under these circumstances it seemed very desirable to subject di- nitrofluorescein to a further study, since this substance has only been analysed as a hydrate, C,oH1,(N0,),06 (von Baeyer, Annalen, 1876, 183,32). In order to obtain the true anhydrous dinitrofluorescein, its diacetyl derivative, which may be prepared by the action of acetic anhydride on the hydrate, was hydrolysed with fairly concentrated sulphuric acid (80 per cent.). The :inhydrous compound thus obtained dissolves in cold dilute soda solution with an orange-brown colour and with no trace of fluorescence.On warming, the solution readily goes blue, a salt of the hydrate being produced. To determine the position of the nitro-groups in dinit)rofluorescein, potash fusion was re.;orted to, and a small quantity of a substance of m. p. 114’ (uncorr.) obtained. Nitroresorcinol (OH:OH: NO, = 1 :3 :4) melts at 115’. Tetranitrofluorescein has also been examined, but the authors have been unable to obtain von Baeyer’s numbers on analysis, the results al- ways pointing to the formula C,,H,,(NO,),O,.Hence arguments deduced from the non-fluorescence of alkaline salts of this compound have no bearing on the question as to whether a pyrone ring is a ‘‘ fluorophor ” as the pyrone ring does not exist in the compound. Hence the results obtained with regard to the non-fluorescence of the alkaline solutions of dinitrofluorescein are especially significant, since in this compound the pyrone ring may be preserved intact and the fluorescence inhibited by the nitro-groups alone. 137. Derivatives of ethyl a-me t hyl-/3- phenylc yanglutar a t e .” ByW. Carter and W. Trevor Lawrence. When ethyl cinnamate and ethyl sodiocyanacetate are allowed to interact in alcoholic solution, methyl iodide being subsequently added to the condensation prcduct, it is found that the neutral reaction 179 mixture consists almost entirely of equal quantities of the two stereoisomeric forms of ethyl a-methyl-P-phenyl-a-cyanglutarate, C(CO,Et)(CH,)( CN)*CH(C,H,) =CH,(C0,E t).The a-modification is a crystalline solid, crystallising from ligroin in prisms which melt at 89", the P-modification is a liquid boiling at 260' (100 mm.) ;both isomerides, on addition of alcoholic potash, are converted into microcrystalline potassium salts, which separate com- pletely from the mother liquor. From these potassium salts two distinct acids are obtained. The a-acid is fairly soluble in water, from which it separates slowly in prisms, melting with decomposition at 161'; the P-acid is much less soluble in water and melts at 194'.Both acids are converted by hydrochloric acid into methyl-phenyl- YO-NH-yoglutarimide, CH( CH,). CH(CtiH,)*CH,(prisms from water, m. p. 144O), and are completely hydrolysed by sulphuric acid with formation of methyl-phenyl-glutnric acid ; on prolonged boiling with aqueous potash, they are converted into a-methyl-P-phenyl-aa-y-propane-tricarboxylic acid, C(CO,H),(CH,)-CH(CGH,)*CH,(CO,*H), which crystallises from a mixture of chloroform and acetone, and melts, with decomposition, at 148". Acetyl chloride offers a means of differentiating between the two modifications, as it converts the a-acid into a substance melting at 1lo', which possesses acid properties, and is easily decomposed by water, whereas the P-acid forms a neutral substance melting at 146', which is fairly stable towards water.The following formulae have been assigned to the a-and @-esters, acids, and acetyl derivatives: a-. B-. CO,Ety(CH,)*CN CN*Y(CH,)CO,Et Esters H(C,H,) CH,*CO,Et yH(C,H,) CH,*CO,Et CO,H*Y(CH,)-YO CN*Y(CH,)CO,H Acids FHC,H, TH S]H(C,H,) CH,-CO CH,*CO,H Methylphenylglutsrimide-a-carboxylic acid. Methylphenyl-a-cyan-glutaric acid. Substances produced by action of acetyl chloride. Methylphenyl n-acetylglutar- Methylphenyl-a-cyan-imide-a-carboxylic acid. glutaric anhydride. CO,H*$!(CH,)-C;IO CN.C;I(CH,)--yO YHCGH, $.COCH, FHCGH5 ? CH,-CO CH,-CO 180 By this reaction methylphenylglutaric acid, previously obtained with great difficulty (Avery and Fossler, Am.Chem. J., 1899, 20, 516), may be easily prepared. a-Methyl-P-phenyIglutaricacid,CH(CH,)(CIO,H)*CH( C,13,)*CH2(C0,H) crystallises from water or ligroin in prisms (m. p. 125') ; theoretically, the acid should exist in two modifications, but up to the present time the authors have only isolated one form, which, from its easy conver- sion into the anhydride, is probably zhe &modification. Acetyl chloride converts theacidinto a doubleanhydride withaceticacid, which crystallises from benzene in asbestos-like masses, melting at 107'; its formula is [C(CO*O=COCH,)H(CH,)*CHC6H,*CH,~CO],0.Wben this is distilled, the true anhydride of methylphenylglutaric acid is obtained as a gum which slowly solidifies to a solid mass melt-ing at 74' ; the corresponding anilic acid is also a gum.Methylphenylglutaric acid is unacted upon by boiling perman-ganate solution; boiling with fuming nitric acid converts it into two nitro-derivatives, of which the less soluble melts at 208' and the moresoluble at 179'; both substances possess the formula C,,H1,0,*N02, and are probably 0-and p-nitrophenylmethylglutaric acid. 138. '( The nitration of acetamino-orthophenyl acetate (diacetylortho- aminophenol). A correction." By Raphael Heldola, F.R.S.,and Elkan Wechsler. The object of this note is to correct and extend the statement (Meldola, Woolcott, and Wray, Trans., 1896, 69, 1325) that the nitration of acetamino-orthophenol acetate under the conditions speci- fied gave a mononitro-derivative, which, on further nitration, gave a dinitro-derivative.A repetition of this work has led to the conclusion that a dinitro-derivative is produced under all conditions of nitration. The statement in the paper above referred to was based on an error of analysis. The dinitro-derivative crystallises from hot water in long, ochreous needles melting at 201°, and softening at a temperature some degrees lower. Two experiments gave N = 17-30 and 17.39 per cent. respectively. C,H,(NO,),*NHAc*OH requires N = 17.42 per cent. One acetyl group is split off during nitration. The dinitro-derivative is readily hydrolysed by boiling for a short time with sodium hydroxide solution, and the dinitro-aminophenol thus obtained proved to be picramic acid as shown by the melting point (167-16S0), by conversion, by the diazo-method, into 2-chloro-4 : 6-dinitrophenol of m.p. 110-1 1lo, and by a comparison of the properties of the diazoxide with the descrip- tion of this compound given by Griess (Annalen, 113,205). The nitration of diacetyl orthoaminophenol thus gives rise to the 181 direct forniation of 2-acetamino-4 :6-dinitrophenol, and the formulae given in that section of the previous paper must be revised accordingly. 139. G6 Rhamnazin and rhamnetin.” By A. G). Perkin and J. R. Allison. In rhamnazin (quercetin dimethyl ether), the position of but one methoxyl group is known (Trans., 1897, g’71,SlS), whereas that in rhamnetin (quercetin monomethyl ether) (Herzig, Monatsh., 1888, 9, 548) has not been determined with certainty.On gentle decomposition, rhamnazin, rhamnetin and quercetin tetramethyl ether give the same phloroglucinol derivative, as in each case the latter reacts with diazobenzene to form a compound, occurring in orange-red needles, m. p. 251-252’. This is diaaobenxe?zephlorogl~c~nolrnmomethylether. (Found C = 65.17 ; H = 4.64 ; N = 15-57; CH, = 4.40 per cent.) ; consequently rhamnazin is methoxyrhamnetin, and both contain a methoxyl group in the (3) position. 0 OH OH CO Rhamnetin. 140. (‘Luteolin. 111.” By A. (3. Perkin and L. H. Horsfall. On methylation, luteolin (from weld) yields two ethers insoluble in alkali, (a), m.p. 191-192’ (Trans., 1896, 69, 206) and a more soluble compound (b), newly isolated, m. p. 161-163’. The latter, C,,H,O,(OCH,),, is the true luteolin trimethyl sthe?*, for on decom-position it forms vevatric ucid and phloroglucinol monomethyl ether (identified as its diazobenzene derivative, m. p. 251-252’). The ether (u), m. p. 191-192’, appears to be methylluteolin trimethyl ether, due to the existence of a methyl group entering the ring during methylation, or less probably to the presence of methyl-luteolin in weld. On gentle decomposition, verutric mid, and a crystalline phloroglucinol derivative result, the latter yield-ing, with diazobenzene, a derivative, in orange-coloured needles, m.p. 198--200’, C,H,07(C,H,N,),, apparently diaxobenxenemethyl phloroglucinok monometh yl ether. AcetyI rnethylluteolin, colour-less needles, melts when rapidly heated at 238-240’. Luteolin from the Genista tinctoria behaves similarly on methylation. The monopotassium and sodium salts of luteolin have now been crys-tallised, and have the respective compositions KC,,H,O, and NaC,,H,,O,,. Weld contains a trace of another colouring 182 matter, C,,H,,O,, which, on decomposition with alkali, yielded p-hydroxybenxoic acid, a trace of protocatechuic acid, phloroglucinol, and p-hydroxyacetophenone. By further reactions, it was identified as apigenin. By the gentle action of alkali, morin, a colouring matter of Morus tinctoria, yields, in addition to P-resorcylic acid and phloro- glucinol (Trans., 1896, 69,697), previously found, some quantity of P-resorcylic aldehyde.141. 66 Genistein. 11.'' By A. G. Perkin and L. R.Horsfall. Genistein dimethyl ether m.p. 137-139' (Trans., 1899, '75, 835) yields a monacetyl derivative m.p. 202-204', C14H702( OCH,),C,H,O, and on gentle decomposition gives p-methoxyphenylacetic acid and phloroglucinolmonomethyl ether, identified as its diazobenzene deriva- tive m.p. 251-252'. The second product of the methylation, m.p. 200-202' (previously given as 187-189'), appears to be a methyl-genistein dimethyl ether (compare luteolin). It forms a monacetyl derivative, C17H,,05*C,H30, m.p. 2 12-2 14O, and on decomposition gives methoxyphenylacetic acid and a phloroglucinol derivative whose diazobenzene compound (probably diaxobenxene methylphloroglucinoI- monomethyl ether), orange-coloured needles, melts at 198-200'. This is identical with that produced from methylluteolintrimethyl ether, Gsnistein diethyl ether, C,,H,O,(OEt),, colourless needles, m.p.132-134', and its monacetyl derivative, map. 16S-17Oo, have been obtained. On decomposition it gives p-ethoxyphenylacetic acid and a phloroglucinol compound. These results are in harmony with the constitution of a trihydroxyphen y lketocumaran previously suggested (loc. cit.} for genistein. Genistein from Genista tinctoria melts at 29 1-293'. 142. "The colouring matter of the flowers of Delphinium con-solida." By A. G. Perkin and E. J.Wilkinron. The presence of a yellow colouring matter in these flowers (in the form of glucoside) has been previously notified (Trans., 1898, 73, 275). This compound forms yellow needles, has the composition C,,H,,,O, (found C =62.85 ;H= 3.63 per cent.), and on fusion with alkali gives phloroglucinol andp-hydroxybenzoic acid (found C =60.71 ; H = 3.94). The tetracetyl compound, C,,H,OG(C,H30)4 (found C = 60.64; H=4.17), is peculiar, for when crystallised from alcohol it melts at about 114-1 16', resolidifies at a higher temperatnre, and again melts at 181-lS3'. This is not due to alcohol of crystallisation. The sulphate, C15H1006,H,S04, orange-red needles (found C =46.71 ; H = 3-39}, the hydriodide, C15Hlo06HI(found 183 C =44.25 ; I4 = 3*00), and the nzonopotnssi?in? saltl, CI5IT,0,;T< (found I< = 11*S5), have been obt;iinccl, biit nro less stable than is usually tlie case with such coinpound\. Tlic colonring matter has proper ties resembling those assignctl t,o knmpherol (Gordin, Diss.Esme, 1897), obtained by the deconiposition of its methyl ether, 1r,zmpherid, which exists in galangn root (11/pinia o~ci?2cc?~unz).Tho investigation will be continued with t!ie hop of ascertaining 1he identity ol this colouihg iiint tcr with cartninty. 143. (LNote on Gallinek’s amidomeehyln~phthiizlidazole.” By Raphael Neldola, F.R.S., and Frederick William Streatfeild. A paper by Gallinek has just been published (Be,.., 1900, 33, 2315) on n, sulphonic acid of the aiihydro-base obtained by reducing dinitro- a-ncetnaphthnlide.Gallinek assumes that the base lie has besn denling with is the same as that describod by the authors (Tmns., lSS7, 51, 691), and he considers that their failure to separ;Lte the bnsc in thc free state mas clue to their having had impure dinitro-a-acetIinp1ith:tl-itlc as their r;~wmaterial. The authors desire now to point out that Gdlinek is completely in error in his original assumption, and that the base described by him is isomeric, and not identical with that described by the authors in 18S7. Gdlinek does not state what reducing agent he employed, nor does he refer to the process pub- lished by Dlarkfeldt (Ber., 1898, 31, 1174), but his description of the base as being stable, solid and crystallisable from water renders it tolerably certain that he has been investigating Markfeldt’s base.Markfelclt also assumed that his base was identical with that describetl by the authors in 1887. The isomerism was recently made known and the properties of the base obtained by Markfeldt’s process some-what fully characterised (Meldola and Eynon, Trccm., 1900, 77, 1159). The authors think it necessary to indicate the trlie cause of the ap-pzrent discrepancy between the statements of the German investi- gators and themselves, because they are at prosent engaged in tho further investigption of the nature of the isomerism. 144. 6L The amount of chlorine in rain water collected at Cirencester.” By Edward Kinch. Tkc author has already published the resrilts (2’mns., lSS7, 51, 92) of the estimation of the chlorine in the water collected in a rain gauge at the Royal Agricultural College, 443 feet abovc sen level, and about 35 miles distant from the sea.The results of his determinations up to the present time are summariscd below. ’Hie rain wntcr for pcriods of six inonthq, iznnioly, sixrniiicr month~, April to Scl)Lrml)cr, :~n(lwint,cli* mniitlis, Oc.t801wrto March, iiiclnsivc, gave the following averagcs : I?qiiivnlent E:cliiivnlclrit to NaC‘l, to Itnitif,%ll Cliloriiic grams N:LCI, lbs. 1)~Pcrioils. in iiic~lic~s. tiiillion. ~wrgnllnii. 1)cr XXC. Mean of 14 winter pel-iocls to hlarch, 1900 .................. 12-2G 3.55 0.413 19.35 Mean of 14 summer periods to September, 1900 ............18.78 3-27 0 261 10.40 Average of 14 years to Sept- ember, 1900 .................. 37.01-3-91 0.337 29.75 Mean of 26 winter periods to I\larch, 1900 .................. 15.83 3.76 0.435 21-29 Mean of 26 summcr periods to September, 1900 ............ 14.78 3-58 0.302 14-81 Arcrage of 26 ycars to Scpt-civber 31ht, 1900 ............ 30.61 3-17 0.369 36-10 145. (‘Researches on the alkyl-substituted succinic acids. 111. Dis-sociation constants.” By W. A, Bone and c.H,G. Sprankling. l’he authors havc prcpnred, and determined tho dissociation con-stants of, n. number of ncw alkyl-sul,stitnted succinic wid..: as follows : hI. 1’. x. f f/ ,n/?S-195O 0.0225s?/7/z-Di-isobutylsucciiiic......................... \rl.s-...97-9s 0.056 tim/s-15S-lBO 0.0365nul-JIcth ylpropylsuccinic ......................... (cis-... 92-9:: 0.02il aal-Meth ylisobu tylsucciiiic ...................... /17l?lS-133 90 0.0427 ... 8%-0 -3236 act1-;\Ictliyl2‘~c:tinylsuccinic........................ / I/n/Lc-... 141-126 0‘0236 \cis-9:: 0 *oss5 aa-I)iiiietliyl-a,-etliylsucciiii~~............................... 139-1 10 0 0566 aa-I)im ethy1-a,-1”o pylsuCI: i11 ic. ............................ 1-15 0 .OGO aa-l>imcth~l-a,-~sopropyl~~ic~ir~ic........................ 141-142 O*OlBS aa-l~imetliyl-a,-irobutylsucciiiic........................... 143-1 4 1 0,0432 au-l)iiiiotliyl-a,-iso3mylst~cciiiic, ............................ 143-1411 O*OdlG They then discuss, in the light of the above aiitl pmyious rcsulbs, the effect of alkyl-substitution on the magnitude of the dissociation constant OF a succinic acid, and deduce the following conclusions.Ehcli alkyl group cxerts its own influcnce upon thc conbtmt de-pendent on its mass and structure. In tlic case of nowial radicles, where the influence of mass ’ only is to be traced, an increase in the imss of the alkyl is invnrinbly accompanied by n corresponding rise in the constant. In the case of ‘ is0 ’-rndicles, them is, however, a ‘structiirid’ effect opposed to tlint of imw:, exr.el)t in tho caie of tlw 185 cis-aal-substitutecl acids, which are separately discussed ;the magni- tude of this structural effect is always dependent on the proximity of the 'iso'-linkage to the c.mbon atom to which the carboxyl group is attached.146. ('The reaction between ethyl alcohol and hydrochloric acid." By T. Slater Price, D.Sc. The present investig,ition wits undertaken in order to measlire the velocity of reaction between Iiydrochloric acid and ethyl :~lcoliol. On re- determining the equilibrium constants it was found that they varied with the amount of acid used. (The constants (a) were calculated according to the equation a =(A -x)(B-x)/(C+ x)(B+x) where A, 13, C, and B are the concentrations of the alcohol, acid, water and ester respectively at the commencement OF the reaction, and x the amount of fresh ester formed when equilibrium is reached.) The results obtained agree with those of Zaitschek (Zeit.phys.Chern., 1897, 24, l),who investigated the action of sulphuric acid on alcohol. Determinations were made at 77", 99O and 129.5". The value of u decreases as the amount of acid increases ;this is well shown especially in the experiments at 77", as the lower the temperature the greater is the variation. The results obtained by the author arc fourid to agree very well with the equation dx/dO=k,(A -x)( I3 -x)~k,(C + x)(D+x)(U -x),-where k, and k, are the velocity co11stiints of the direct and reveise reactions, x is the amount of ester formed after the time 8, and A, B, C, and U liave the signification givou ahove. Tlie catalytic effect of the hydrogen ions is assumed to be proportional to the amount (B-x) of acid present, this holding good over a short interval of timc, and since both the direct and reverse reactions are affected thc factor (U -x) will be extra in each term of the velocity equation.The values of kl so obtained are cspocially good when no water is present to begin with, tli:it is, mhcn G= 0 (in no CA:O wiis ester present at thc Commencement of the reaction), hut ,wlicn the reaction mixture used contained water to start with, the values of k1 diminish as 8 in-creases. The vuluc of k, decreases as the concentration of the acid increases, and is also greatly diminished mlieii water is present. Tlie velocity of reaction incrcases very rapidly with the temperature, the increase beiug iiiuch greater than in the case of the action of organic acids on alcohol, ADDlTIONS TO THE LIBRAICY.I. Doructiorns. Bartley, D. C. Adulteration of Food. Statutes and cases dealing with coBee, tea, bread, seeds, food and drugs, margarine, fertilisers and feeding stuffs, &c., including the Food and Drugs Act, 1899. Second edition. London 1899. alowes, Frank, and Coleman, J. B. Quantitative chemical analysis. Fifth edition. London 1900. From the Authors. Duparc, L., Degrange, E., st Monnier, A. Trait6 de chimie aualytique qualitative suivi de Tables systbmatiques pour l'analyse min6rale. Genbve et Paris 1900. From Messrs. Sampson, Low and Co. Letts, E. A,, and Blake, It. F. The carbonic anhydride of the atmosphere. (Reprinted from tho Pvocesdi?$gs of the Royal Dublin Society). Dublin 1900.From the Authors. ~litchell,C. Ainswortli. Flesh foods, with methods for their chumical, microscopical, and bacteriological examination. London 1900. From the Author. ltoos, L. -Wine-m,zking in hot climates. Trnnslated by It.Dubois :md IV. P. Wilkiuson. Melbourne 1900. From the Translators. Sutton, Francis. A systematic handbook of volumetric analysis. Eighth edition. Loudon 1900. From tlie Author. Gerhardt, Charles, SA vie, son ceuvrc, sa correspondslice 1816-1856. Documeut d'histoirc tlc la chimie, par Edouard Grimsux et Charles Gerhardt. Paris 1900. From the Authors. Bedford, the Duke of, and Picliering, S. U. Second report on the morkiug and results of the Woburn Experimental Fruit Farm. London 1900. From the Authors. At the next iiieeting,.,011 'l'hursd;iy, NovcwLw 15111,tlie folluwifig pper will be cornmnuic:itcd. ('The bases contained in Scottish sliulc oil." J:y F. C. G:\rrott, lf.Sc., and J. A. Smytho, B.Sc., Y1i.D.
ISSN:0369-8718
DOI:10.1039/PL9001600163
出版商:RSC
年代:1900
数据来源: RSC
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