MECHANISM OF GUANIDINE NITRATION: II. TETRAETHYLNITROGUANIDINE
The preparation of sym-tetraethylnitroguanidine now shows that a ketimino group can be nitrated directly. The mode of nitration has been evaluated first by determination of the ionization of guanidine bisulphate (prepared anew) and tetraethylguanidine in nearly-anhydrous sulphuric acid by means of an improved cryoscope, and by comparison of these ionizations with those of substances the ionizing behavior of which may be reliably predicted. Subsequent studies show that the stronger base, sym-tetraethylguanidine, is nitrated more slowly than guanidine, both reactions being reversible. Detailed kinetic studies were not made because of the irreversible side-reaction yielding tetraethylurea. This irreversible reaction, which is suppressed by sodium bisulphate but not by nitric acid, is presumptive for the existence of an intermediate nitrotetraethylguanidinium salt out of which the tetraethylnitroguanidine or tetraethylurea may arise.