ii8 



NATURE 



[June 4* 1819] 



Chemical Society, May 7.— Dr. J. H. Gladstone, F.R.S., 

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

 read : — The action of alkalis on the nitro-compounds of the 

 paraffin series, by W. R. Dunstan and T. S. Dymond. The 

 paper contains the results of further investigation of the inter- 

 action of alkalis and nitroethane, of which a preliminary account 

 has already been given (Chem, Soc. Proc, 18S8, p. 117). 

 Nitroethane and alkali carbonates in the cold interact to yield 

 carbon dioxide, and the alkali derivative of nitroethane, which 

 is obtained when alkali hydroxide is employed. Ammonia com- 

 bines with nitroethane in the cold to form a crystalline compound, 

 analogous to the potassium and sodium derivatives. The action 

 of alkalis pro ceeds further on warming, and there are formed 

 alkali nitrite, acetonitrile, and a compound, boiling at 171°, and 

 solidifying to a crystalline mass when coiled to 3° '5. The 

 authors find that this compound is trimethylisoxazole 



CH3 . C-C.CHo 



I I 



CH3 , c o . 



\/ 



N 



It is very stable, and is almost unaflTected by heating in closed 

 tubes with strong acids and alkalis. Permanganate oxidizes 

 it to acetic acid, and nitric acid to acetic and oxalic acids. By 

 reducing-agents it is slowly decomposed with formation of am- 

 monia, acetic acid, and secondary butyl alcohol. By the action 

 of sodium on a well-cooled moist ethereal solution, a dihydride 

 CgHjiNO (m.p. 110°) is formed, which, when heated with water, 

 is decomposed into ammonium acetate and ethyl methyl ketone. 

 The mercuric Iiloride has the formula CfjHgNO, Hg.Clg, and the 

 aurichloride the formula CgHgNO, AuCig. Nitropropane, when 

 acted on by alkalis, yields triethylisoxazole, propionitrile, and 

 alkali nitrite, but the reaction occurs with greater difficulty than 

 in the case of nitroethane. Nitromethane is readily acted on 

 by alkalis, and hydrogen cyanide, alkali nitrite, and much resin 

 are formed. The parent isoxazole could not be isolated. Second- 

 ary nitropropane is attacked with difficulty by alkalis, and no 

 isoxazole is fjrmed. — Some new addition compounds of thio- 

 carbamide which affiard evidence of its constitution, by J. E. 

 Reynolds, F. R.S. Thiocarbamide combines with ammonium 

 bromide, iodide, and chloride at the temperature of boiling 

 alcohol, and forms compounds of the type (Il4N2CS)4H4NR^ 

 Under the conditions specified no compounds were obtained 

 containing less than four molecular proportions of the amide to 

 one of the ammonium haloid salt. Methyl-, ethyl-, allyl-, 

 phenyl-, diphenyl-, and acetylphenyl-thiocarbamides do not 

 yield compounds with ammonium bromide at the temperature of 

 boiling alcohol. Thiocarb amide and tetrethylammonium bromide 

 and iodide yield compounds of the type (H4N2CS)2Et4NR'. 

 Under the experimental conditions, no well-defined substance 

 was obtained containing more than two molecular proportions 

 of the amide to one of the tetrethylammonium salt. Thio- 

 carbamide and diethylammoniam bromide form the compound 

 (H4N.^CS)3Et2H2NBr. Thiocarbamide, when treated with 

 triethylammonium bromide yields a mixture of the two com- 

 pounds (H4N2CS)3Et3HNBr and (H4N2CS)2Et3HNBr. With 

 methylammonium bromide the amide forms the compound 

 (H4N2CS)4MeH3NBr. It does not, however, combine with 

 ethylammonium bromide, and when heated with the salt in 

 the molecular proportions 4 : i at 135° in a sealed tube, together 

 with alcohol, it yielded ethyl oxide and tetrathiocarbamidam- 

 monium bromide. The author points out that these facts 

 supply evidence against the symmetrical constitution of thio- 

 carbamide CS(NH2)2. and altogether in favour of the un- 

 svmmetrical constitution HN : C(SH)NH2.— The action of 

 acetic anhydride on substituted thiocarbamides ; and an im- 

 proved method for preparing aromatic mustard oils, by E. 

 A. Werner, Trinity College, Dublin. The action of acetic 

 anhydride on diphenyl-, ortho-, meta- and para-ditolyl-, 

 meta-dixylyl-, dibenzyl- and diethyl-thiocarbamides has been 

 studied. In the case of the aromatic derivatives, no acetylated 

 derivatives of the thiocarbamides were produced. The solution 

 of the thiocarbamide in acetic anhydride is accompanied by 

 simultaneous decomposition into " anilid " and mustard oil in 

 accordance with the equation CS{NHR), + (CH,CO),0 

 = CH3CONHR -f R.NCS -^ CH3COOH. When the 

 solution is heated for five minutes at the boiling-point of 

 acetic anhydride, an almost theoretical yield of mustard oil 

 is obtained. Prolonged heating produces a secondary re- 

 NO. II 2 7, VOL. 44] 



action expressed by the equation R . NCS -1- CH3COOH 

 = CH3CONHR + COS. In the case of fatty thiocarb- 

 amides a well-defined acetylated thiocarbamide is first produced, 

 and prolonged heating gives rise to the formation of mustard oil, 

 but the yield of the latter is never high, and as final product a 

 substituted amide is produced. — The decomposition of silver 

 chloride by light, by A. Richardson. When pure silver chloride 

 is exposed to light under water oxygen is evolved, part of which 

 is present as ozone ; when small quantities of water are present, 

 chlorine and hydrogen chloride are found in solution ; with large 

 quantities of water, hydrogen chloride, but no chlorine, is found. 

 The influence of hydrogen chloride in retarding the decomposi- 

 tion of silver chloride is considered, and is explained from ex- 

 perimental results given, which show that even minute quantities 

 of hydrogen chloride exercise a marked influence on the stability 

 of chlorine water when exposed to light, the rate of decomposi- 

 tion of the silver chloride being dependent on the readiness with 

 which the chlorine in solution and water interact to form hydro- 

 gen chloride. The author describes experiments which show 

 that the darkened product obtained by exposure of silver chloride 

 to light contains no oxygen, and he concludes that it is of the 

 nature of a sub-chloride rather than an oxychloride. — The addi- 

 tion of the elements of alcohol to the ethereal salts of unsaturated 

 acids, by T. Purdie and W. Marshall. The authors record the 

 results of experiments on the addition of the elements of alcohol 

 to ethereal salts of fumaric and maleic acids by the agency 

 of small quantities of sodium alkylate ; they also describe a 

 series of experiments with other ethereal salts, the object of 

 which was to ascertain if the ethereal salts of unsaturated acids in 

 general are capable of undergoing the same additive change. 

 By the action of a small quantity of .^odium methylate in the 

 cold, on a mixture of methylic alcohol and methylic fumarate, 

 an almost theoretical yield of methylic methoxysuccinate is ob- 

 tained. Methyl fumarate, on heating with alcoholic sodium 

 methylate, yielded a compound of the formula CuHigOy, 

 formed by the abstraction of 3 mols. of methyl alcohol from 2 

 mols. of methylic methoxysuccinate. Under similar conditions 

 methylic amylate gave methylic methylpropionate. Methylic 

 and ethylic crotonate gave methylic methoxybutyrate and ethylic 

 ethoxybutyrate. The authors think that the alkyloxy-group 

 attaches itself to the j3 -carbon atom. Ethylic methacrylate also 

 formed additive compound ; but pure products were not obtained 

 from the reaction. Ethylic angelate, ethylic allylacetate, 

 methylic and ethylic cinnamat e and ethylic o-{^) ethylcumarate 

 do not undergo additive change. — Notes on the azo-derivatives 

 of )3-naphthylamine, by R. Meldola, F.R.S., and F, Hughes. 

 The authors have completed the series of azo-derivatives ob- 

 tainable from the nitranilines and ;8 naphthylamine by pre- 

 paring orthonitrobenzene azo-)3-naphthylamine. The latter by 

 the action of nitrite in a warm acetic acid solution gives 

 orthonitrobenzeneazo-)3-naphthol. In cold acetic acid solution 

 the naphthyl acetate is formed. Acetyl derivatives of the 

 ortho-, meta-, and para-nitroazo-derivatives of jS-naphthylamine 

 have also been prepared. The pseudazimides from the 

 para- and metanitro-compounds have been prepared. These 



/N. 

 compounds have the formula CioHe^" j '>N . CgH^ . NO.^ 



(/ or m). The action of aldehydes on these .8-naphthyIamine 

 azo-derivatives gives rise to the formation of triazines, which 

 are being investigated. — A method for the estimation of nitrates, 

 by G. McGowan, Ph.D. This estimation is based on the 

 interaction HNO3 4- 3HCI = NOCl -f CI2 -f 2H2O. The 

 gaseous products are led into a solution of potassium iodide. 

 — New benzylic derivatives of thiocarbamide, by A. E, Dixon, 

 M.D. Are-examination of " monobenzyl-thiocarbamide" has 

 shown that the substance hitherto bearing this name is benzyl- 

 amine thiocyanate ; the latter can be converted into the isomeric 

 thiocarbamide by heating for a short time at l5o°-i6o^ The 

 author describes a great number of benzylic derivatives of 

 thiocarbamide. 



Linnean Society, May 24. — Anniversary Meeting. — Prof. 

 Stewart, President, in the chair. — The Treasurer presented his 

 Annual Report duly audited, and the Secretary having announced 

 the elections and deaths during the past twelve months, the usual 

 ballot took place for new members of Council, when the follow- 

 ing were elected: Messrs. C. B. Clarke, G. B. Howes, Arthur 

 Lister, St. G. Mivart, and F. W. Oliver. The President and 

 officers were re-elected. The usual formal business having been 

 transacted, the President proceeded to deliver his annual address, 



