77'i 



was also prepared synthetically from methyU'^'ocyaiiate and hydrazine: 

 NH,-NH, 4- 00 : N-CH3 = NH,-NH-CO-NH-CH,. 



The product m.p. 118° proved to be identical with the methyl- 

 semicarbazide obtained by reduction. The above-mentioned conden- 

 sation product with benzaldehyde (m.p. 166°) and the semicarbazones 

 formed with other aldehydes were also identical. 



b. D e c m p s i t i oji b y bases. The reaction with bases 

 affords a suitable means of deciding wiiether we are dealing with a 

 primary nitramine or with an alkylnilramide. A primary ipitramide 

 Ac-NH-NO.3 will, on hydrolysis, yield nitramide NH,N02, from which 

 is formed on subsequent decomposition nitrous oxide N^O, but an 

 alkylnitramide Ac-N(N02)R gives the monoalkylnitramine RNHNO,. 



Hence, the reaction of the a,a- and the (7,^;-metliylnitro-urea will 

 be expressed by the following equations : 



a,a — . CH3-N(N0,)-C0-NH, + 3K0H = 



= CH3-N-N0,K -f K,C03 + NH3 + H,0. ... (I) 

 a,b — . CH3-NH-C0-NHN0,-f 2 KOH = 



= CH3-NH,4-K,C03 + N,0 + H,0 (II) 



The methylnitro-urea m.p. 159'' on heating wi(h bases gives one 

 mol. of nitrous oxide; in addition methylamine is formed but no 

 melhylnitramine. These observations all agree with equation II, but 

 they all are opposed to equation I. 



The reaction of primary nitramides and alkylnitraraides with 

 ammonia differs somewhat from that with alkalis, but is still qnite 

 as nseful for distinguishing the two classes. The decomposition of 

 the two isomers by ammonia is represented by the following equations : 



a,a — . CH3-N(N0,)-C0-NH, + 2 NH3 = 



== CHg-N-NO.NH, -h NH,-CO-NH, . . (Ill) 



a,h — . CH3-NH-CO-NH-NO, + NH3 = 



= CH3-NH-CO-NH, + N,0 + H,0 . . (IV) 



The compound m.p. 159° gives on decomposition by ammonia 

 methylurea (identified in the form of its nitroso-derivative) and no 

 methylnitramine is formed. This tallies with equation IV", but not 

 with equation III. 



The reactions with alkalis and ammonia therefore prove that the 

 methylnitro-urea m.p. J 59° is, indeed, the ^/,(^?-compound. 



Further, 1 have investigated the crude nitration product before 

 it was treated with ammonia. 



This product which melts very unsharply (at about 90° — 100°) 



