VIII.—On the Action of Phosphide of Sodium on Haloid Ethers and on the Salts of Tetrabenzyl-Phosphonium

Letts; N. Collie

doi:10.1017/S0080456800029021

VIII.—On the Action of Phosphide of Sodium on Haloid Ethers and on the Salts of Tetrabenzyl-Phosphonium

Published online by Cambridge University Press: 06 July 2012

Letts and

N. Collie

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The phosphines, or substances derived from phosphuretted hydrogen by the partial or complete replacement of its hydrogen by hydrocarbon radicals, have formed the subject of many valuable researches; but although their discovery was anterior to that of the compound ammonias, their study has made comparatively little progress. This is no doubt mainly due to the difficulty attending their preparation, a fact which is immediately forced upon the notice of any one who wishes to investigate them.

Type: Research Article
Information: Earth and Environmental Science Transactions of The Royal Society of Edinburgh , Volume 30 , Issue 1 , 1881 , pp. 181 - 215

DOI: https://doi.org/10.1017/S0080456800029021 [Opens in a new window]
Copyright: Copyright © Royal Society of Edinburgh 1883

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^{page 182 note *} Comptes Rendus, vols. xxi. and xxv.

^{page 182 note †} Comptes Rendus, xli.

^{page 183 note *} Transactions Royal Society, London, vol. cl. p. 409.

^{page 183 note †} Journ. für prac. Chem., lxvi. p. 73.

^{page 183 note ‡} Comptes Rendus, xlix.

^{page 183 note §} Berichte der. deutsch. chem. Ges., iv. pp. 205, 372; v. p. 100.

^{page 184 note §} Liebig's Annalen, 181, p. 280.

^{page 186 note *} Hoffman, Ber. d. deutsch. chem. Ges., iv. p. 100.

^{page 191 note *} In 7 and subsequent experiments a quantity of the xylol was distilled off after the preparation of the phosphide of sodium, and before the chloride of benzyl was allowed to act on it. The numbers after the sign - show how much of the xylol was thus distilled off.

^{page 191 note †} The chloride was squeezed in a cloth filter until it was as dry as possible and then weighed.

^{page 192 note *} A higher temperature must be avoided, as we find that it materially diminishes the yield of phosphonium salt.

^{page 193 note *} The hydrogen in this experiment is too high and the carbon too low, probably because the salt had not been completely dried.

^{page 194 note *} In this experiment the salt was heated for a whole day, and probably some of it volatilised.

^{page 194 note †} Trans. Roy. Soc. Lond., vol. cxlvii. p. 575Google Scholar.

^{page 195 note *} In our notice of these experiments in the “Proceedings,” we stated that the action of sulphate of silver on the phosphonium chloride yields the acid sulphate, and not the normal sulphate of the phosphonium. There can be but little doubt that we did obtain and analyse the acid salt, but its formation was probably due to the fact that we acted on a boiling solution of the chloride with sulphate of silver, and the filtered solution therefore contained a considerable quantity of the latter salt which we decomposed by sulphuretted hydrogen, thus setting free sulphuric acid which combined with the normal sulphate; and as the acid sulphate thus formed is much less soluble than the normal sulphate, it is probable, as we analysed the first crop of crystals, that they consisted entirely of the acid sulphate. We have verified the correctness of this explanation by an experiment conducted in a similar manner.

^{page 204 note *} We have since proved that alkalies act very readily on chloride of tetrabenzyl-phosphoniuin. On boiling a solution of the chloride in alcohol with potash or soda for a few minutes, decomposition occurs, chloride of the alkaline metal is precipitated and the solution contains oxide of tribenzyl-phosphine, which is easily identified by its insolubility in water and other characteristic properties.

^{page 205 note *} Ber. d. deutsch. chem. Ges., xiii., 1665Google Scholar.

^{page 206 note *} One of Casella's.

^{page 206 note †} Volhardt's method.

^{page 206 note ‡} Hofmann's method.

^{page 206 note §} By precipitating the platinum with sulphuretted hydrogen and titrating the filtered solution.

^{page 207 note *} Trans. Roy. Soc. Lond., 1860, p. 418Google Scholar.

^{page 207 note †} The experiments of Crafts and Silva (loc. cit.) show that this replacement does not occur.

^{page 208 note *} By combustion with oxide of copper and chromate of lead.

^{page 208 note †} Fused in a silver dish with caustic potash and nitrate of potash, and subsequently titrated with uranium solution.

^{page 208 note ‡} Fused in a silver dish with caustic potash, and subsequently titrated by Volhardt's method.

^{page 213 note *} After fusion with, a mixture of nitrate of potash and caustic potash.

^{page 213 note †} Proceedings Roy. Soc, Edin.

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VIII.—On the Action of Phosphide of Sodium on Haloid Ethers and on the Salts of Tetrabenzyl-Phosphonium

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