ON THE TRANSFORMATION OF AROMATIC NITROAMINES. 101 
The Transformation of Aromutic Nitroamines and Allied Substances, 
and its Relation to Substitution in Benzene Derivatives.—Report of 
the Committee, consisting of Professor F. S. Kirpina (Chairman), 
Professor K. J. P. Orton (Secretary), Dr. S. RuneMaANN, Dr. A. 
LapwortH, and Dr. J. T. HEWITT. 
I. Nitroamines. (With W. W. Ruexp, B.Sc.) 
A pETAILED study of the conditions governing the transformation of 
2 : 4-dichloro-1-nitroaminobenzene (I.)! into the isomeric 2 : 4-dichloro- 
6-nitroaniline (IJ.) has been made : 
NH. NO, NH, 
a/~ cl “ No, 
| i | (11) 
NG eG 
Cl of 
This nitroamine was chosen for particular study in preference to 
others, having different positions vacant (ortho and para relative to the 
group, NH. NO,) into which the nitro-group may ‘wander,’ on account 
of the ease of its preparation,’ and the non-basic character of the nitro- 
aniline, of the above constitution, which is produced in the isomeric 
change. In testing the effect of minute quantities of acids as trans- 
forming agents, it is of great importance that the aniline should not be 
able to unite with the reagent, which would thus be withdrawn from the 
sphere of action. 
' A particular advantage which this transformation offers, in contrast 
to many others of a similar type, is due to the fact that the nitroamine is 
quite colourless, and forms colourless solutions, which may be preserved 
for long periods, whereas the nitroaniline crystallises in intensely yellow 
needles, and forms highly coloured solutions. Traces of the nitroaniline 
could thus be recognised, not only in solutions, but also in the crystals of 
the nitroamine. The conversion of the crystalline nitroamine into the 
nitroaniline is not merely indicated by a simple change of colour, but by 
the growth of yellow needles of the nitroaniline, apparently out of the 
colourless nitroamine—a process which can be readily followed photo- 
graphically. This phenomenon, which can be demonstrated with a single 
crystal of the nitroamine, has allowed of the testing of the effect of single 
(necessary gaseous) reagents as transforming agents in the absence of all 
solvent. 
The nitroamine was dried by sealing it up with phosphorus pent- 
oxide in glass tubes. When thus entirely freed from water the substance 
acquires greater stability, and loses a remarkable sensitiveness to light, 
which necessitates the use of a dark room when aqueous solutions are 
employed. 
After seven days’ drying in this manner the tubes were opened, the 
reagent introduced, and the tube resealed. The reagent, which was in 
most cases in aqueous solution (0°1-0:2 c.c.), was enclosed in a small 
tube, and was separated from the dried nitroamine by a column of 
phosphorus pentoxide, five to six inches in length. The water slowly 
evaporated, and was absorbed by the pentoxide, the gaseous reagent, now 
! Orton, Zrans. Chem. Soc., 1902, 81, 802. 
2 Orton, Berichte d. Chem. Gesell., 1907, 40, 370. 
