IMPROVEMENTS IN THE MANUFACTURE OF COLORING MATTERS OF THE ROSANILINE AND PARA ROSANILINE SERIES
Year: 1884

page_text: 'I FRANK WIRTH of the firm of Wirth and Company, Patent Solicitors, at
Frankfort on the Main in the Empire of Germany, do hereby declare the nature
of the said Invention for "IMPROVEMENTS IN THE MANUFACTURE OF COLORING
MATTERS OF THE ROSANILINE AND PARA ROSANILINE SERIES (A communication
to me from Emil Erlenmeyer, Doctor of Philosophy and Professor, a person
resident at Frankfort on the Main in the Empire of Germany to be as follows:-
This Invention relates to the manufacture of Pararosaniline and Rosaniline
coloring matters of the most various composition by means of Methylnitrogen
compounds together with oxidising agents.
Methyl combined with nitrogen exhibits a greater tendency to processes of
condensation under the influence of oxidising agents than does methyl combined
with carbon. Rosaniline coloring matters of the most various composition can
therefore be easier obtained by the action of methylnitrogen compounds (for.
instance, primary, secondary, tertiary, mono and Poly-methyl amines also
ammonium bases or their salts of the fatty and aromatic series, and their sub-
stitution products, coloring matters containing methylnitrogen and their Leuco
compounds, &c, &c) on aromatic primary, secondary and tertiary amines in the
presence of oxidising agents (for instance nitro-benzol and iron, arsenic acid,
chloride of copper, nitro-amines and chloride of zinc &c, &c) than by the action
of methyl-carbon compounds such as Toluidine, Xylidine, &c, in the presence of
oxidising agents or of carbon-oxygen compounds and carbon-halogen compounds
on the above mentioned amines.
So also Pararosaniline is easily formed on heating methyl substitution products
(or derivatives) of ammonium chloride with anilinliydrochlorate nitro-benzol and
iron, or with aniline and arsenic acid, &c to a temperature of from 160° to 180°.
Instead of only amines containing methyl others may be employed containing other
alkyls of the fatty and aromatic series. The following substances and proportions
have proved to be particularly adapted:
:-
180 Dimethylaniline, 390 Anilinbydrochlorate, 555 Nitrobenzol, and 15 Iron
filings; or
205 Methylviolet, 582 Anilinhydrochlorate, 555 Nitrobenzol, and 15 Iron
filings.
す

page_text: Mono and Di-methylated Pararosanilines can be obtained by. suitable augmenta-
tion of the methyl-nitrogen compound and corresponding diminution of the
· oxidising agent. To form common Rosaniline it is only necessary to partially
replace aniline by ortho-toluidine or nitro-benzol by ortho-nitro-toluol. The
corresponding, fusions are treated in the same manner as the ordinary fusehine
fusions. Pararosanilines can also be easily prepared having alkyls of the fatty and
aromatic series, or only of the latter in the place of amidhydrogen if methyl-
nitrogen compounds be allowed to act on aromatic secondary and tertiary amines
in the presence of oxidising agents. For instance 80 dimethylaniline, 170 Di-
phenylaminė, 50 Acetic acid of 50%, 100 sulphate of copper and 2500 common
salt are well mixed and subjected to a temperature of from 60° to 80° for 24 hours.
Thereupon Methyldiphenyl pararosaniline and Triphenylpararosaniline are produced
and may be separated from each other with facility by means of hydrochloric acid.
If only half as much dimethylaniline be employed almost only Triphenylpararos-
aniline is obtained.
170 Diphenylamine, 140 Methylphenylnitrosamine and 150 Chloride of zinc
heated for about 12 hours at 100° yield principally Triphenylpararosaniline, as do
also 200 Diphenylnitrosamine, 107 Monomethylaniline, and 150 Chloride of zinc.
As is evident, by suitably varying the substances and proportions, very many
alkyl substituted Pararosanilines and Rosanilines can be produced.

page_text: "
I FRANK WIRTH of the firm of Wirth and Company, Patent Solicitors, at
Frankfort on the Main in the Empire of Germany do hereby d-clare the nature
of the said Invention for "IMPROVEMENTS IN THE MANUFACTURE, OF COLORING
MATTERS OF THE ROSANILINE AND PARA ROSANILINE SERIES (A communication
to me from Emil Erlenmeyer, Doctor of Philosophy and Professor, a person
resident at Frankfort on the Main in the Empire of Germany and', in what
manner the same is to be performed, to be particularly described and ascertained
in and by the following statement:-
This invention relates to a process for the manufacture of red, violet and blue
colouring matters of the rosaniline series by oxydizing different combinations of
methylated amines with primary secondary and tertiary aromatic amines.
The known formation of methylviolet by means of heating dimethylaniline with
cupric chloride, as also the formation of violet by heating a mixture of mono-
methylaniline and dimethylaniline with cupric chloride, which take place so
remarkably easily, have led to the conjecture, that in general methyl combined
with nitrogen is particularly adapted for the carbon condensation and that it would
be possible to prepare para rosaniline and rosaniline as well as violet and blue
colouring matters of very different composition by the combination of mono- or
dimethylaniline with primary secondary and tertiary aromatic amines and the
simultaneous action of suitable oxydizing media.
Experiments have entirely confirmed this conje ture..
It must consequently also be possible to transform methylviolet into para.
rosaniline by combining it with auiline on the one hand and with diphenylamine
on the other hand under the influence of oxydizing media and in the latter case to
simultaneously produce diphenylamine blue. This expectation has also been
verified by experiment. The experiment has likewise shown that the hydroc-
chlorates of the methylamines can even be used as a means of condensation being
transformed into animonic chloride and that tetramethyldiamido-triphenylmethane
or carbinol may be employed in a similar manner.
.
I-Preparation of red coloring matters by the oxidation of combinations of
methylated amines with primary aromatic amines.
Either the arsenic acid or. the nitro-benzol process may be employed for the
p:eparation of these colouring matters. Dimethylaniline and methylviolet com-
bined with aniline or ortho-toluidine or with both the latter together are the most
suitable of the methylated amines.
Examples. For the preparation of pararosaniline or of other rosanilines I proceed
in the following manner.
(A). Arsenic acid process.
120 parts dimethylaniline 465 parts aniline, or 535 parts orthotoluidine, or
279 parts aniline and 214 parts orthotoluidine, and 920 parts arsenic acid at 75/0
or 123 parts methylviolet, 501 parts aniline. and 558 parts arsenic acid of 75% or
173 parts mineral green or 156 parts leuco-base, 558 parts aniline and 950 parts
arsenic acid at 75° are gradually raised while stirring to a temperature of 180° C
and constantly stirred and heated till a test portion after cooling becomes solid and
triturable. The melt is then treated in exactly the same way as the arsenic acid
fuchsine melt of the so called Rothöl.
,
This is boiled in water, until it no longer imparts much color to the water and
the filtered extracts are heated with as much common salt as the melt weighed (in

page_text: For the preparation of violet and blue coloring matters from dimethylaniline in
combination with diphenylamine. I proceed in the following manner:-80 parts
dimethylaniline, 170 parts diphenylamine 50 parts acetic acid (at 50°/。) 100 parts
blue vitriol and 2500 parts common salt are thoroughly mixed; the whole is spread
out on tins or heated for 24 hours at 60° to 80° C in a suitable mixer with access
of air. The formation of colour commences at the ordinary temperature a blue,
beautiful copper like lustrous mass is obtained from which the sodium salts are
next extracted with cold water. The dried residue is then treated with hydro-
chloric acid of 20° Beaumé until the liquid running off no longer gives a precipitate
on the addition of water (Extract A). The residue remaining after the hydro-
chloric acid treatment is now thoroughly washed with water dried and boiled with
alcohol. After having distilled off the alcohol the blue copper like lustrous residue
left behind is converted by known methods into the different sulpho acids, which
dye silk and wool a beautiful blue.
By the addition of water a blue violet copper like lustrous colouring, matter is
precipitated from the extract A soluble in slightly acidulated hot water forming a
blue liquid which dyes silk and wool similarly to violet 6 B.
By the gradual addition of soda to the filtrate of this copperlike lustrous blue
violet colouring matter, a lustrous bronze coloring matter soluble in water dyeing
silk and wool more of a red violet can be obtained.
If 80 parts dimethylaniline or 104 parts methylviolet with 680 parts diphenyl-
amine or 728 parts methyldiphenylamine or 788 parts ethyldiphenylamine or
1036 parts benzyldiphenylamine or 876 parts a phenylnaphthylamine or 1096 parts.
a dinaphthylamine and the aforementioned quantities of acetic acid, blue vitriol
and common salt be heated in the manner given, almost only blue colouring matters
are obtained.

page_text: 200 parts diphenylnitrosamine and 150 parts chloride of zinc are heated at 100° C
with frequent stirring for about 12 hours. The fusions thus obtained are treated
in a similar manner to those under II A. With the proportions given chiefly blue
and less violet colouring matter is obtained. Many different alkyl substituted
pararosaniline and rosaniline colouring matters can be obtained by suitably varying
the combinations of the substances and their proportions.
Besides the oxidizing media given which have hitherto proved to be the best,
others may be employed such as chloride of mercury, nitrate of mercury, chloride
of iron, other cupric compounds, the peroxides of manganese and lead, bromates,
chlorates and chromates &c.
Although the quantities by weight given in the specification have proved
practical, they may nevertheless be varied within certain limits and I do not
therefore confine myself to the exact amounts and proportions named..
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed I declare that what
I claim is :-
§ I. The herein described process for the preparation of red colouring matters by
the oxidation of combinations of methylanilines, or methylviolet, or malachite
green, or of the leuco-compounds of both the latter with aniline or with ortho-
toluidine or with both together, as described.
2. The herein described process for the preparation of violet and blue colouring
matters by the oxidation of combinations of the methylated amines mentioned
under §I with diphenylamine or a phenylnaphthylamine or a dinaphthylamine, or
methyldiphenylamine or ethyldiphenylamine or benzyldiphenylamine, also com-
binations of methylphenylnitrosamine with diphenylamine or of diphenylnitros-
amine with mono or dimethylaniline with the co-operation of chloride of zinc, as
described,