100 



distill which deposited in a crystalline loriii in the exit tuiie, wlien 

 tiie flask exploded with a loud report. 



In subsequent experiments the heating was therefore solely con- 

 ducted in vacuo at 100° in a waterhath and in this way I also 

 succeeded in obtaining small cpiantities of crystals, which after being 

 pressed between paper melted at 76° and gave no depression of the 

 melting point with «-wo-nitrosomethylethylketone. In addition there 

 distilled a little of a liquid acid, which, after neutralisation with sodiimi 

 carbonate solution gave with silver nitrate a white precipitate, which 

 on heating with water turned black. 



If the nitramine is heated with moist methyletliylketone a rather 

 violent action sets in, but otherwise the I'eaction proceeds as described 

 ai)Ove. If we take ketone that has been dried over calcium chloride 

 we also get a yellow, diacetyl containing distillate. 



If, however, we take nitramine that has been standing for some 

 days in a desiccator over sulphuric acid and ketone that has been 

 dried with phosphoric aidiydride, no reaction takes place at the 

 ordinary temperature even after two days. On heating in the 

 waterbatli the ketone passes over entirely colourless. If the distillation 

 is interrupted, the nitramine in the flask crystallizes unchanged. On 

 long continued heating in the waterbath the distillate first shows 

 traces of hydrogen cyanide and gnxdually also a faint yellow 

 coloration, which need cause no surprise because, on heating at 100°, 

 the nitramine itself yields traces of nitrous vapours. So much, 

 however, is pretty certain that in the experiment with moist ketone 

 the formation of the i'eaction products found will have to be attributed 

 largely to the action on the ketone of the nitrous acid generated by 

 the water, when the strongly acid phenol will also have exerted its 

 influence. 



The fact that the reaction takes place so rapidly in the ketone 

 solution even at the ordinary temperature may be caused by the 

 great concentration, but there also exists the possibility that the 

 presence of the acetone accelerat s the reaction. Expei'iments to make 

 sure about this and also to study the influence of the watei' on the 

 nitramine in other indifferent solvents are in progress. In water- 

 saturated ether a conversion of nitramine into phenol also takes 

 |)lacc fairly rapidly. 



Utrecht. (>iy. Cliem. Lah. lJ?i/rersili/. 



