CHEMISTRY: STIEGLITZ AND COLLABORATORS 
205 
atom to go over into its stable negative form is not alone sufficient, as 
a rule, to cause the characteristic rearrangement of these compounds, 
but that the path to the formation of a univalent nitrogen derivative 
must usually, if not always, be open, this derivative being the substance 
that suffers the actual molecular rearrangement (see equation 3). This 
must signify that a positive halogen atom can secure two electrons from 
the nitrogen atom to which it is directly Hnked much more readily than 
from the carbon atom holding the nitrogen (see equation 3). Otherwise 
the rearrangement would proceed by a direct exchange of radicles fol- 
lowing a migration of the electrons from the carbon to the halogen atom. 
Furthermore, the characteristic contrast shown in the behavior of the 
rearranging compounds (R3C.NH(Hal+) — losing halogen acid — and 
R3C.NCl2'^ — losing chlorine—), on the one hand, and the non-rearrang- 
ing compounds (R3C.N(CH3) C1+ and R2C:NCl+),on the other hand, leads 
to the important conclusion that the electrons most easily captured 
from the nitrogen atom by the positive halogen atom are the two valence 
electrons beyond the normal electrons of the nitrogen atom rather than 
any of the electrons of the normal atom. Otherwise, again, we should 
have a rearrangement by a direct exchange of radicles following the 
exchanges of electrons. This conclusion is included in equation 3 of 
the preceding paper. 
The conclusions reached— (1) that a positive halogen atom can secure 
electrons more readily from the atom to which it is directly attached 
(nitrogen, in this case) than from one further removed from it, and (2) 
that the more readily available electrons are the two extra valence elec- 
trons of the nitrogen atom rather than its normal ones, seem not un- 
reasonable. The second conclusion is in agreement with the observa- 
tions of physical chemistry on the oxidation of negative ions Hke S=, 
I~, etc. This result seems to us the most important one established by 
the investigation, giving us a logical explanation, from the point of view 
of the electron theory of valence, of the real significance of the univalent 
nitrogen in the author's theory of the mechanism of this and similar 
rearrangements. 
THE MOLECULAR REARRANGEMENT OF jS-TRIPHENYLMETHYL 
/3-METHYL HYDROXYLAMINE 
WITH BERT ALLEN STAGNER 
While a great mass of evidence, gathered by the author as well as 
independent investigators,^ has shown that the molecular rearrange- 
ments of halogen amines, hydroxylamine derivatives and azides seem 
to proceed preferably by the path of an intermediate formation of uni- 
