OP NITRITES TO HYDROXYAMINE. Ill 



As a means of the preparation of hydroxyamine, the action of 

 hydrogen sulphide upon a nitrite has no apparent value. The interest 

 of this reaction hes in the light it may help to cast upon the constitu- 

 tion of the oxygen compounds of nitrogen. Experiments made in our 

 laboratory, and already published in the Journal of tlie Chemical Society 

 of London^ serve to show that the metals of the zinc-tin class convert 

 nitric acid into ammonia^ and not hydroxyamine, when another acid is 

 absent; and into liydroxijamine, without ammonia, when acting in con- 

 junction with hydrochloric or sulphuric acid (J.C. S., 47, 615); and, fur- 

 ther, that in the conversion of nitric acid to hydroxyamine, no nitrous 

 acid, nitric peroxide, or iiitric oxide shows itself as an intermediate 

 product. It therefore, remained uncertain whether an (inorganic) 

 nitrite could be converted into hydroxyamine. By the reaction of 

 the nitrites of the silver class of metals with hydrogen sulphide this 

 uncertainty is now removed. 



In connection with the subject of this paper, the well-known 

 behaviour of the nitro-hydrocarbons is of interest to consider. The 

 application of reducing agents, if appropriate, converts them to amines, 

 but never to hydroxijamines. Yet the paraffin members of the series 

 yield simple or substituted hydroxyamines by certain treatment. 

 Plainly, it must be impossible by simple reduction to convert the nitro- 

 compound into the corresponding oxiinido- compound, because of the 

 difference in valency between the nitroxy- and oximido- radicals and 

 therefore the reaction proceeds probably as follows : — 

 Et N<iO., + 2H^EtN {OH), 

 and Et N {OH)., + 4H = Et NH, + 20H, 



But when, under special conditions, the hydrocarbon radical is made 

 to suffer change, it becomes possible to form an oximido compound 

 (Kissler), or, at least, hydroxyamine itself (V. Meyer). In these cases, 

 the hydrocarbon acts as the reducing agent upon the nitroxyl. Thus, 



