596 PROF. LETTS AND MR R. F. BLAKE ON 



A perusal of the preceding sketch of the different methods hitherto discovered for 

 the preparation of the phosphines will be sufficient to convince any one that to obtain 

 these bodies in quantity is no easy task, for in nearly every case operations are 

 involved which demand considerable expenditure of time and material, and frequently 

 the yield of product is small. 



One of us had for a long time sought for some easier and more direct method than 

 any of those mentioned, and had made many attempts with that object in view in 

 different directions, but without success. 



At last the idea presented itself that the germ of a new process for obtaining phosphines 

 ought to exist in the well-known and ordinary method for preparing phosphonium iodide. 



In this reaction, as every one knows, water is allowed to act upon a mixture of 

 phosphorus and its iodide, when iodide of phosphonium is obtained on the one hand, 

 while phosphoric and phosphorous acids are produced on the other. 



Now, it seemed not unreasonable to suppose that analogous reactions would occur, if 

 instead of water an alcohol were used, and if this were the case a new and simple process 

 for obtaining phosphines would be at hand. 



Our first experiments to test the truth of this surmise have been made with benzyl 

 alcohol, and the results have been unexpectedly gratifying, for not only does the reaction 

 occur with the greatest ease, but the number of phosphorised derivatives of benzyl 

 produced is remarkably large. Moreover, we have without the slightest difficulty obtained 

 most of them in considerable quantity, so that we have been able to make a fairly 

 exhaustive examination of their properties. 



In short, the method has placed at our disposal a number of highly interesting 

 substances, which could not have been obtained in sufficient quantity by any other means 

 as yet known, and we have thus been enabled to fill up many lacunae in the history of 

 the benzyl phosphines and their derivatives. We may, however, state at the outset that 

 the reaction which occurs between benzyl alcohol, iodide of phosphorus, and phosphorus, 

 does not take place in exactly the manner we anticipated. 



TJie Action of Benzyl Alcohol on a Mixture- of Phosphorus and its Iodide. 



We may remark at the outset that we employed in all our experiments the same 

 mixture of phosphorus and phosphorus iodide as is used for the preparation of phos- 

 phonium iodide. It was prepared as follows : — 40 parts by weight of vitreous phosphorus 

 (carefully dried) were dissolved in an equal weight of dry and freshly-redistilled 

 bisulphide of carbon, and to the solution 68 parts of iodine were gradually added. The 

 retort in which the mixture was made was then heated in a water-bath and a current 

 of dry carbonic anhydride passed through it until every trace of bisulphide had distilled 

 off. We shall call the product, for the sake of brevity, " the phosphorus mixture." 



We may also mention that in most of our experiments the quantity of benzyl alcohol 

 taken was about the equivalent of the quantity of water used in the preparation of 



