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202

XXIII --Ox Aroma& Nidrosamifies.

O WITT,
B ~ O T TN. Ph.D.

IK 1864 G r i e s s published in the Philosophical Transactions his great

paper on the diazo-compounds, in which he so thoroughly described
the action of nitrous .acid on primary aromatic amines that subsequent
research has brough%to light no new facts of importance.
In 1874 I made a few experiments on the action of nitrous acid, and
especially its ethers, on secondmy and tertiary amines, and was aston-
ished to find that very beautiful substances were foimed in these
reactions. A few weeks after I had communicated my results to the
Chemical Society of Zurich, B a e y e r and C a r o published their paper
on nitrosodimethyianiline, the final product of the action of amylic
nitrite on dimethylaniline; I have therefore in my research con-
fined myself to the action of nitrous acid and its salts on secondary
%mines. The facts observed are shortly recorded in the Bem'ciite of
the Berlin Chemical Society ; and a detailed account of the formation
and properties of diphenylnitrosamine has been given in my inaugural
dissertation. Since the publication of the latter, in 187.5, I have
studied more carefully some complicated reactions of diphenylnitro-
samine, and the object of this paper is to bring before the Society a
description of the phenomena observed, of the new substances pre-
pared, and a short statement of my theoretical views on the subject.
Whenever a secondary amine is acted upon by nitrous acid, water
and a nitrosamine are formed. The term 4' nitrosamine " I apply to
any substituted ammonia which contains, instead of a t least one atom
of hydrogen, the univalent nitrosyl group, -NO, in immediate con-
nection with the ammoniacal nitrogen. Thus the action of nitrous
acid on diethylamine forms diethylnitrosamine-
C*& C2H5
I I
NH + NO.OH = HZ0 + N.NO;
I I
CZH5 c2H5

whilst diphenylnitrosamine is obtained by bringing diphenylamine

into contact with ethylic or amylic nitrite-
C6H5 C6H5
I I
NH + NO.OCzHs = N.NO + C2H,.OH,
I I
c ' a 5 ca5
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WITT ON AROMATIC NITROSAMINES. 203

or by the action of nitrous vapours on diphenylamine, or of metallic
nitrites on the hydrochloride of diphenylamine.
Diphenylnitrosamine is a substance remarkable for its great power
of crystallisation. It can be easily obtained in large honey-coloured
monoclinic crystals, melting a t 665", easily soluble in alcohol, ben-
zene, and similar solvents, and giving a striking reaction with concen-
trated snlphuric acid, in which it rapidly dissolves, imparting to it
a beautiful blue coloration, large quantities of pure nitric oxide gas
being given off. Powerful reducing agents cause the formation of
ammonia and reproduction of diphenylamine ; but by careful reduc-
tion it may be converted into diphenylhydrazine, one of a beautiful
series of new bases recently discovered by E m i l F i s c h e r . The
action of aniline, or any other primary monamine, on diphenylnitros-
amine iE1 violent; if carefully controlled, however, the result is simple
enough, being represented by the following equation :-
c6H5
I
ca5 CsH, N
I
N.NO
I
+ 2(NH,.CsHa) = NH + NII + HzO.
I I
c& I
NH
CSH,
I

A corresponding amount of diphenylamine is regenerated, whilst the

nitroso-group is employed in the formation of diazobenzene, which
immediately combines with another molecule of aniline, forming diazo-
amidobenzene. The latter then undergoes the usual ti-ansformation
into amidoazobenzene. Under certain circumstances a secondary re-
action takes place, giving rise to a beautiful substance of the formula
C,H& which is remarkable for a peculiar reaction. If heated with
concentrated sulphuric acid to the boiling point of the latter, a, fine blue
colonring-matter is obtained, possessing a beautiful crimson fluoremence
and a characteristic absorption spectrum with three dark bands.
If, instead of pure ethylic or amylic nitrite, the ordinary prodnct
obtained by leading nitrous vapours into ethylic alcohol be employed
in the preparation of diphenylnitrosamine, or if nitrous vapours be
introduced into a solution of diphenylamine, the products obtained
differ greatly from diphenylnitrosamine, and a few experiments suffice
t o prove that they are mixtures of different substances in varying
proportions. Their separation is, however, a matter of extreme diffi-
culty : for gradual decomposition sets in if repeated recrystallisation
is resorted to,and it was not until I found a means of preparing each
of the different substances, independently and separately, that I could
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204 WITT ON AROMATIC MTROSAMINES.

attempt a successful inquiry into their constitution. Here I encoun-
tered another serious difficulty : all these substances, when subjected
to organic analysis, suddenly give off large quantities of nitrous
vapours; and this takes place so ra;pidly that even the use of a
number of spirals of metallic copper does not always completely de-
compose the gas. On the other hand, the introduction of a large
amount of metallic copper is detrimental to the accumy of the
analysis, as recently pointed out by Lietzenmayer (Ber., xi, 306).
When the nitrous vapours are given off a, peculiar kind of very denRe
charcoal remains behind, the final combustion of which can be aceom-
plished only by the prolonged passage of oxygen through the tube.
Owing to all these difficulties my analytical data are marcely within
such close limits as I could have wished, although I have made quite
an unusual number of combustions with the greatest care and by
methods which, from long experience, I know to be perfectly tmst-
worthy. On the other hand, I have in almost all cases determined not
only carbon and hydrogen, but also nitrogen by the volumetric method.
It will be easily understood that analyses attended with such serious
difficulties could not suffice to clear up the nature of my new sub-
stances, and I therefore had recourse t o a closer study of their mode
of formation. I soon found that ordinary ethylic nitrite contains
invariably large quantities of nitric acid, the presence of which was
easily accounted for, when I convinced myself that none of the methods
employed for the production of what is commonly called nitrous
anhydride, N203, produce this compound; and that by far the hrger
portion of the product obtained by the action of nitric acid of different
strengths on either arsenious anhydride, or starch, or treacle, is nitric
tetroxide, N204, which may be regarded as a mixed anhydride of
nitric and nitrous acid. In contact with water or alcoliol it furnishes
both nitrite and nitrate, and this accounts for the invariable presence of
nitric acid in all nitrous ethers prepared by the introduction of nitrons
vaponrs into the corresponding alcohol. The nitric acid present proved
also to be the cause of the peculiar difference between the action of
pure and ordinary ethylic nitrite on diphenylamine.
This conclusion arrived at, I completely abandoned the use of ordi-
nary nitrite, and with the purpose of obtaining a thorough insight into
my experiments only employed mixtures of known quantities of pure
nmylic nitrite and nitric acid ; acting with this reagent upon weighed
quantities of diphenylamine and moderating or accelerating the reac-
tion by the use of various solvents.
I f 20 grams of finely powdered diphenylamine be placed in a dry
flask and a mixture of
15 C.C. of nitric acid, sp. gr. 1.424,
35 gmms of pure amylic nitrite,
100 C.C. of methylated alcohol,
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WITT ON AROMATIC NITROSAMINES. 205

be poured upon it, the diphenylamine dissolves instantaneously with
a dark coloration, and a rise of temperature is perceptible; the flask
is kept in constant motion, and the reaction, if necessary, accelerated
by gentle heating. Suddenly crystals begin to settle out ; and if the
flask be now placed in iced water, a beautifully crystalline deposit
i R obtained. When crystals cease to form, the precipitate is filtered
off and carefully washed with spirit, dried and recrystallised from
chloroform. It forms beautiful plates of light yellow colour fusible a t
133.5", easily soluble in chloroform, benzene, hot alcohol, and glacial
acetic acid.
The analytical data obtained with this substance are the follow-
ing :-
I. 11. 111. IV. V. VI. VII.
C... 39-90 59.70 59.84 60.03 59.60 - -
H .. 420 4.30 430 440 440 - -
N... - c - -
- 18.60 18.10

This substance may easily be recognised as a nitrosamine ; for it

imparts a fine violet coloration to pure concentrated sulphuric acid, at
the same time giving off nitric oxide gas. Now as the three available
ahmicities of the nitrogen in diphenylamine are thus proved to be
engaged in a manner identical with diphenylnitrosamine, the only
possible conclusion was,that some substitution had taken place in one
or both of the two phenyl groups of the diphenylnitrosamine, and that
the new substance was the nitrosamine of a substituted diphenyl-
amine. We possess, as I have shown before, a means of regenerating
the secondary amine from a nitrosamine by the action of aniline, which
was resorted to and proved to be effectual ; and equally good results
were obtained by splitting off the nitroso-group by means of alcoholic
potash. Whichever process was applied, it resulted in the formation
of a new substance crystallising from dilute alcohol in small glistening
scales of a pale yellow colour, melting at 132". This substance does
not colour sulphuric acid, but it dissolves with a fine red colour in
alcoholic potash ; subjected to organic analysis i t proved to be mono-
nitrodip henylamine :-
Theory for Experiment.
CSHpNH.CBEd.NOZ. I. 11.
C ........ 67.20 67.20 67.32
H ........ 4.66 5-06 5.35
N ........ 13.09 - -
0........ 14.95 - -
-
99.90
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206 WITT ON AROMATIC NITROSAMINES.

The product, from which this mononitrodiphenylamine wm ob-

tained, is therefore mononitrodiphenylnitrosamine; the following num-
bers-
C .................... 39-30
H .................... 3.70
N .................... 17.30
0 .................... 19.70
CsH5.N.NO.CsH4.N 0 2 = IOO*OO
indicated for this substance by theory agree as closely with the
results actually obtained rn can be expected under the dificulties
which the analysis of these substances offers.
Mononitrodiphenylnitrosaine, when dissolved in glacial acetic acid
and subjected to the action of bromine, yields a precipitate of a
canary-yellow colour, which is easily soluble in benzene and crystal-
lises from this solvent in long silky needles fusible at 208-5-209". If
this substance be again treated with bromine, and heated with it for some
time on the water-bath, another product is formed crystallising from
benzene, in which it is not so easily soluble as the first product, in
heavy, well-shaped small prisms, melting at 214-5-215".
Mononitrodiphenylamine is a colonring matter, though a very
weak one. Silk may be dyed yellow in its solution. The colonring
properties of this substance are due to the entrance of a nitro-group
into diphenylamine, which at the same time renders the imido-
hydrogen replaceable by metals-

Mononitrodiphenylamine. Potaeeium mononitro-

diphenylamine.

But as soon as the imido-hydrogen is replaced by the nitroso-group,

the colonring properties of the compound are destroyed, the influence
of the nitro-group being paralysed. This may be easily demonstrated by
introducing mononitrodiphenylnitrosamine into a very cold solution of
potash in alcohol. In the first instance no coloration is observed.
But on heating, or even on standing for a short time, a dark scarlet
coloration appears, due to the elimination of the nitroso-group and
the formation of mononitrodiphenylamine, which, as already observed,
is a colonring matter.
If the proportions of nitric acid and amylic nitrite be altered, and
the spirit be exchanged partly or entirely for another solvent, which
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WITT ON AROMATIC NITROSAMINES. 207

expedites the reaction, more nitro-groups may be introduced into the
molecule of diphenylnitrosamine. The following method has been
found to give satisfactory results.
17 grams of diphenylamine are introduced into a dry flask sur-
rounded by iced water. Then a mixture of-
50 C.C. of glacial acetic acid,
40 C.C. of nitric mid, 1.424,
50 C.C. methylated spirit,
48 grams nitrite of amyl,
is added all at once. The diphenylamine dissolves with a dark colour,
and very soon small granular crystalline aggregates begin to settle out.
When the precipitate no longer increases, it is filtered off on the filter-
pump, the mother-liquor is carefully removed, and the precipitate
washed with spirit and finally with ether. It is then dried at the
ordinary temperature, and appears, when dry, as a sandy powder of
light yellow colour. Recrystallisation may be effected from chloro-
form, in which the new compound is but sparingly soluble, but I have
not been able to detect, any difference in the analytical results ob-
tained with either the recrystallised or the crude product. Their
behaviour with reagents and their characteristic appearance are also
very much the same. The reaction of this body with sulphuric acid,
in which it dissolves with a dirty violet coloration, giving off nitric
oxide a t the same time, proves it to be a nitrosamine. The analytical
results, however, do not agree with any simple formula, but the num-
bers for at least the carbon and hydrogen are intermediate between
those required for di- and for tri-nitrodiphenylnitrosamine-
Theory for Experiment.
C12HSN405* CI,H;N,O,I. Crude. Recrystalbed.
I. 11. 111.
0...... 50-00 43.25 46.95 - 47.01
H...... 2.75 2.10 3.99 - 3.18
N...... 19.45 21.05 - 19-04 -
0...... 27.80 33.60 - - -
-
100*00 100*00
I therefore concluded that the new substance, although apparently
uniform and not separable by repeated recrystallisation, was contami-
nated with some impurity, and hoped to effect a more successful puri-
fication on removing the nitroso-group by means of alcoholic potash
or aniline.
For this purpose 20 grams of the product were placed in a flask,
together with 100 C.C. of spirit, and 50 C.C. of a 20 per cent. solution of
potassic hydrate in alcohol. On heating, a splendid purple coloration
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208 WITT ON AROMATIC NITROSAMINES.

appeared, which gradually increased in intensity until all was dis-

solved. Dilute hydrochloric acid was now added until the colour had
changed to a bright orange, and, finally, a large quantity of water was
introduced; the precipitate was collected on a calico filter, washed
carefully, pressed, and treated with about 400 C.C.of boiling methylic
alcohol. The solution was filtered from the part which remained undis-
solved (A), and on cooling deposited crystals of an obviously impure
product (B).
If aniline be employed for the removal of the nitroso-group, the
following method may be adopted :-

20 grams of the new product,

30 grams of pure hydrochloride of aniline,
25 grams of aniline,
50 C.C. of spirit,

are h a t e d for about half an hour on the water-bath. Plenty of dilute

hydrochloric mid is then added, and the precipitate boiled out three
successive times with extremely dilute nitric acid. All the amidoazo-
benzene is thm removed, and may be found in the extract. What
remains undissolved is treated with methylic alcohol as before, and
the part insoluble in the boiling alcohol (A) treated separately from
that which deposits on cooling (B).
The latter, B, is successively extracted with small quantities of
boiling methylated spirit and glacial acetic acid, and both solutions
removed by hot filtration. After this treatment the new substance
requires one crystallisation from ethylic, or, better, isobutylic alcohol
to be quite pure. It then forms long, thick, pointed needles of great
brilliancy and lustre, of a dark yellow colour, with a slight bluish
dichroism, fusible at 214". They dissolve in alcoholic potash with a
bright purple colour, which is destroyed by the addition of cold wafer,
but reappears on boiling. Analysis proved them to be dinitrodiphenyl-
amine :-
Theory Experiment.
For C12H9N304. I. 11. 111. IV.
C ........ 55-60 56.50 54.90 56.39 -
H ........ 3.50 4.80 409 4.07 -
N........ 16-20 - - - 16.M
0........ 24.70 - - - -

The substance A, insoluble in methylic aloohol, was boiled out two

or three times with this solvent, and then recryshllised from pure
sylene. From this hydrocarbon it is deposited elowly in small, indistinct
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WITT ON AROMATIC NITROSAMINES. 209

granular crystals of a vermillion colour, fusible a t 211.5'. It dissolves
in alcoholic potash with scarlet colour, and the solution behaves in a
similar manner to the purple solution of the body first described. On
analysing it I found that if was isomeric with the yellow substance,
and corresponds also to the formula of dinitrodiphenylamine :-
Theory Experiment.
For ClJ&,Na04. I. 11. In. IV.
C ........ 55-60 36.80 56-32 - -
H........ 3.50 4.25 4.17 - -
Nb........ 16.20 - - 9790 16.29
0......... 24.70 - - -
100~00
This fact ie by no means surprising. If we suppose that, in
the dinitrodiphenylamines obtainable by direct nitration, the two
nitro-groups enter two different phenyl-group, there are still three
dif€erent anbstanm likely to arise :-
NO*

0NH

Dipamnitro- Diortbnitro- Orthapmnitm-

diphenylamine. diphenylamine. diphenylamine.

The metaposition is out of the question, ~ E aJ nitro-group entering

into an a;l'omatic molecule never occupies a meta-position to a, basic
group already present. The two dinitrodiphenylamines here described
most likely correspond to the firat and third formulae, for they both
arise from further nitration of the same mononitrodiphenylamine,
which, in all probability contains its one nitro-group in the p m -
position.
All the substances hitherto described give, when treated with nitric
acid of the highest concentration, hexanitrodiphenylamine, a sub-
stance originally discovered by E. Kopp, more closely investigated by
Gnehm, and repeatedly introduced as an orange dye into commerce.
On careful nitration diphenylnitrosamine gives, as I observed some
time ago, and G n e h m recently published, tetranitrodiphenylamine.
Thus diphenylamine, through the agency of its nitrosamine, aliows of
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210 WITT ON AROMATIC NITROSAMINES.

the introduction of one nitro-group after the other up to six, with

exception of three and five, into its molecule, and we now know,
irrespectively of isomerides obtained with picric chloride and dinitro-
chlorobenzene by Clemm and P. T. Austen, the following nitro-
derivatives of diphenylamine :-
Mononitrodiphenylamine, C12H,,,N202.
Dinitrodiphenylamine, CI2H9N,Oa(two iaomers).
Tetranitrodiphenylamine, Cl2H7N5O8.
Hexanitrodiphenylamine, Cl2K5N7Ol2.
I do not doubt that my new method of nitrating substances in dilute
solutions with the aid of alkylic nitrites, will be found applicable in a,
great many cases, where nitration has hitherto offered unusual diffi-
culties. It would also appear that this method furnishes some sup+
port to the theory already advanced, that the formation of nitroso-
compounds always precedes the introduction of the nitro-group into
the molecule of aromatic substances.
Thus far I have described as much of my research on the action of
nitrous acid on secondary amines as has become fit for publication
since my last communication to the Berichte. I should have preferred
to wait until I could have given some account of the reduction-pro-
ducts of my new nitro-compounds, and investigated more closely their
brominated derivatives, had it not been for an incident which made it
desirable to publish without delay.
In February, Mr. Meldola communicated to the Chemical News a
note on “ A New Colouring-matter,” and, at the same time, was good
enough to send me two specimens of his preparations, one represent-
i n g the substance arising from the action of nitric tetroxide on
diphenylamine in an acetic acid solution, the other the product obtained
from the first by the action of aldoholic potash. On closely examin-
ing and comparing our specimens, we found the first product to repre-
sent a mixture of the nitrosamines described in this paper, whilst the
second was a mixture of the nitrated diphenylamines, which corre-
spond to the nitroso-compounds. On ascertaining that the subjects of
our investigations were identical, and that the action of nitrous acid
on diphenylamine and other secondary amines had occupied me for
several years, Mr. M e l d o l a was kind enough to relinquish his claim
to the continuation of this research, for which I have much pleasure
in thanking him : at the same time I wish to’point out that the prac-
tical application of mono- and di-nitrophenylamine as a dye-stuff, called
citronine, is solely and entirely due to Mr. Meldola. The shades
obtained on silk with citronine are truly magnificent, and no other
artificial colour can compete with it as regards this particular tint ;
unfortunately, owing to the inefficiencyof tho nitro-group as a chro-
mophor, and to the extreme weakness of the salt-forming groups in
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PERKIN ON SOME NEW DERIVATIVES, ETC. 211

citronine, it is not a strong colonring-matter, and this, combined with
its insolubility in water, renders it of less general applicability than it
otherwise deserves. Still, it is a very interesting fact, that in citro-
nine an artificial colonring-mtter has for the first time been found,
which, if it were not for the little difficulties just mentioned, might
with advantage replace turmeric and qnercitron.
I have the intention of bringing before the Society, in a second
paper, the results which 'I hope to obtain in the continuation of this
research.