CHEMISTRY — ACRDE. 



179 



tautomeric compounds, such as i-plienyl-4-methylurazole. The fact that 

 both the potassium salt and the silver salt of i-phenyl-4-methylurazole yield 

 a mixture of oxygen and nitrogen esters proves that Comstock's theory (I) 

 can not be used as a general hypothesis. 



Neither the oxygen derivative nor the nitrogen derivative rearranges into 

 the other, nor does the ratio of the two derivatives change w^ith change in 

 time or temperature during the reactions. These facts show that Wheeler's 

 theory (II) can not be used as a general explanation of such reactions. 



The experimental evidence leads to the conclusion that only the urazole 

 ions react with the alkyl halide, and that the reaction is one of the second 

 order. The theories of Nef and of Michael demand that in such cases all 

 salts should give the same ratio of oxygen and nitrogen esters. Since such 

 is not the case, the theories of Nef and of Michael are not adequate to 

 explain such reactions. 



All of the quantitative data at hand seem to show that the equilibrium 

 and reaction phenomena can be represented by the following scheme : The 

 molecular forms of the salts are in equilibrium. The alkyl halide reacts 

 only with the anions of the urazoles. The alkyl halide reacts as a molecule 

 and not (i) through primary dissociation into alkyl and halide ions (theory 

 of Bruyn and Steger) ; (2) through primary dissociation into a halogen 

 acid and an unsaturated olefine or alkylidene residue (theory of Nef) ; nor 



(3) through primar}' union with the cation and formation of a complex 



+ 

 cation, RI.M, which then reacts with the anion (theory of Euler). The 



evidence is in harmony with, but does not prove, the view that the alkyl 



halide unites with the anion and forms a complex unstable anion which 



decomposes at once into the ester and halide ions. 



0:C C:0 

 \ / 

 NCH, 



C«H,N-N 



^6"5 



I \ 



0:C C-.O^-Na+CgHsI 

 NCH3 



CeHsN-NCaHg 

 0:C C:0+-i^a + I 



\ / 

 NCH3 



CeHs.lf-N 

 0:C CONa 

 ■ NCHo 



C«H,N-N 



"6 "5 

 0:C, 



, CO+Na+CsHsl 

 NCHo 



C«H 



6.X5N-N 

 0:C^ COC2 

 NCH3 



H^ +Na-hI 



