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



Sulphur acts on the primary bases. With the methyl and ethyl derivatives, com- 

 pounds have been obtained but not investigated.* With phenyl phosphine sulphur acts 

 slowly in the cold, rapidly at a high temperature.t Two substances are produced, one, 

 a thick liquid soluble in ether, having the composition (C 6 H 5 )PH 2 S, the other a crystalline 

 product to which Michaelis assigns the formula (C 6 H 5 P) 3 S. The first of these bodies 

 decomposes when heated in the following manner : — ■ 



2C C H 5 PH 2 S = C G H 5 PS + C 6 H 5 PH 2 + H 2 S . 



In view of the analogies existing between nitrogen and phosphorus, considerable 



interest is attached to the action of carbonyl chloride and bisulphide of carbon on the 



primary phosphines. Bisulphide of carbon acts upon both methyl and ethyl phosphine,| 



but the products have not been investigated. Michaelis and Dittler § have studied 



the action of both reagents on phenyl phosphine. When carbonyl chloride is 



passed slowly into that substance, an energetic reaction occurs in the following 



manner : — 



2CO Cl 2 + C e H 5 PH 2 = C e H 5 PCl 2 + 2CO + 2HC1 . 



Phenyl phosphine and bisulphide of carbon act upon each other when heated in a sealed 

 tube at 150°, and sulphuretted hydrogen is liberated. The product of the reaction is a 

 resinous body (C 6 H 5 PHCS) 2 S, and the reaction itself proceeds according to the equa- 

 tion, 



2C C H 5 PH 2 +2CS 2 = (C 6 H 5 PHCS) 2 S + H 2 S . 



Michaelis and Dittler were not successful in their attempts to prepare a phosphorised 

 mustard oil from this compound. 



They were equally unsuccessful in obtaining a phosphorised carbylamine by the 

 action of chloroform and caustic potash on phenyl phosphine. It is true that a reaction 

 occurs, but its course is completely different from that which takes place with an 

 amine, viz., 



C„H 5 PH 2 + 4KHO + CHCI3 = C c H 5 PHK0 2 + 3KC1 + CH 3 OH + H 2 . 



It thus appears that, in their behaviour with carbonyl chloride and a mixture of caustic 

 potash and chloroform, primary phosphines behave in an entirely different manner from 

 the corresponding amines, though there is a certain degree of analogy as regards the 

 action of both on bisulphide of carbon. This difference is no doubt due to the strong 

 affinity of phosphorus for electronegative elements, such as the halogens, oxygen, and 

 sulphur. 



Primary phosphines readily combine with alkyl iodides to give hydriodates of 

 secondary phosphines. 



♦Hofmann, Berichte, iv. (1871) pp. 433 and 610. + Michaelis, Berichte, x. (1877) p. 810. 



J Hofmaxx, Berichte, iv. (1871) pp. 433 and 610. § Michaelis and Dittler, Berichte, xii. (1879) p. 338. 



