THE PRODUCTION OF NEW COLOURING MATTERS FROM THE SECONDARY AND TERTIARY MONAMINS OF THE AROMATIC COMPOUNDS BY THE ACTION OF CHLORQUINONES, SUCH AS TRI AND TETRA CHLORQUINONE, AND THEIR HOMOLOGUES UPON THE SAID MONAMINS
Year: 1879

page_text: LETTERS PATENT to Frank Wirth, of the Firm of Wirth and "Company">
Patent Solicitors, at Frankfort on the Main, in the Empire of Germany, for
the Invention of "THE PRODUCTION OF NEW COLOURING MATTERS FROM THE
SECONDARY AND TERTIARY MONAMINS OF THE AROMATIC COMPOUNDS BY THE
ACTION OF CHLORQUINONES, SUCH AS TRI AND TETRA CHLORQUINONE, AND
THEIR HOMOLOGUES UPON THE SAID MONAMINS." A communication from
Wilhelm Meister Eugene Lucius, Doctor of Philosophy, and Adolphus Brüning,
Doctor of Philosophy, trading under the Firm of Meister Lucius and Brüning,
of Höchst-on-the-Maine in the Empire of Germany
2
PROVISIONAL, SPECIFICATION left by the said Frank Wirth at the Office
of the Commissioners of Patents on the 23rd June 1879.
FRANK WIRTH, of the Firm of Wirth and Company, Patent Solicitors, at
Frankfort on the Main, in the Empire of Germany.. "THE PRODUCTION OF NEW
COLORING MATTERS FROM THE SECONDARY AND TERTIARY MONAMINS OF THE
AROMATIC COMPOUNDS BY THE ACTION OF CHLORQUINONES, SUCH AS TRI AND
TETRA CHLORQUINONE AND THEIR HOMOLOGUES UPON THE SAID MONAMINS."
[A communication from Wilhelm Meister Eugene Lucius, Doctor of Philosophy,
and Adolphus Brüning, Doctor of Philosophy, trading under the Firm of Meister
Lucius and Brüning, of Höchst-on-the-Maine, in the Empire of Germany.]
This Invention has for its object the production of new coloring matters from the
secondary and tertiary monamins of the aromatic compounds by the action of
chlorquinones, such as tri and tetra-chlorquinone and their homologues upon the
said monamins.
To obtain these coloring matters, I use principally the tri and tetra-chlorquinone,
or the crude chloranil as obtained according to the well known description of Graebe
(Annalen der Chemie and Pharmacie, volume 1 and 6, page 1), by the action of
hydrochloric acid and potassium chlorate on phenol.
The production of the coloring matters is effected as follows, that is to say :—
I. Violet coloring matters.
To obtain these violet coloring matters, I use chiefly, the mono and dimethylated
bases of the benzole series, as the following example shows:-
I stir
To two parts of dimethylaniline I add by degrees one part of chloranil;
this mixture and heat it during some time, to 60-70 degrees centigrade; thus I
obtain under development of bydrochloric acid, a copper looking matter, which,
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page_text: dissolved in spirit, gives a solution of splendid violet appearance. In order to
remove the dimethylaniline in excess, I boil this product of copper looking appear-
ance in water, afterwards I dissolve the remaining substance in three parts of spirit,
and precipitate with water; the precipitate thus obtained will be the pure coloring
matter. I dry and grind this matter, and obtain a metallic looking powder, which,
dissolved in spirit, gives on wool and silk brilliant violet shades. It can be made
soluble in water by treatment with concentrated sulphuric acid in such a manner as
to convert it into what is known to chemists as sulpho acids.
II. Blue coloring matters.
These blue coloring matters are obtained by the action of chloranil upon tertiary
bases of the methyldiphenylamin type, or of the aethyldiphenylamin type, and
their homologues.
To produce these blue coloring matters, I for instance heat, during some time, on
a water bath, two parts of methyldiphenylamin, and one part of chloranil, until the
matter becomes pasty; then I elevate the temperature to 120-130 degrees
centigrade, until a sample, after having got cold, can be powdered. The product
has a copper looking appearance, and contains a very pure blue, which I obtain in
a pure state, as follows, that is to say:-
3
I first wash the product several times with concentrated hydrochloric acid which
removes all the methyldiphenylamin in excess; afterwards I dissolve the remaining
substance in ten parts of spirit, filter and precipitate with ten parts of water. The
blue, which is insoluble in water, falls to the bottom of the vessel, is filtered, and
then dried. The product thus obtained is a powder of violet velvety appearance,
is soluble in spirit, and gives a solution of pure blue color, which used on silk
and wool, gives much purer blue shades than triphenylrosaniline.
I submit the herein before mentioned coloring matters to a treatment with con-
centrated sulphuric acid in such a manner as to convert them into what is known
to chemists as sulpho acids.
.
Similar blues are obtained from metbyldiphenylamine, and from their corre-
sponding ditolylamins and phenyltolylamins, and the like, and I can, by using the
various bases, produce a great number of new blue coloring matters, very valuable
for dyeing purposes.
III. Green coloring matters.
These green coloring matters are produced by the action of chloranil upon benzyl-
diphenlylamin and its homologues. For example, I heat on a waterbath three
parts of benzyl diphenylamin, to 60 degrees centigrade, and while stirring, add by
degrees one part of chloranil, and keep the temperature at from 60 to 80 degrees
centigrade, until a sample, after getting cold, can be broken. The product thus
obtained is of a violet black appearance, and dissolved in spirit, gives a yellow
greenish solution. To purify the coloring matter, the product is dissolved in fifty
parts of spirit, filtered, and then mixed with 2½ parts of water, and one part of
hydrochloric acid of 12 specific gravity. The coloring matter precipitates to the
bottom in a dark tarry cake, which dried and ground to powder of a dark greenish
appearance, gives, after having been dissolved in spirit, a dark green solution.
However, the coloring matter in this state, will give but very unsatisfactory results
in dyeing. But on the other hand, by treatinent with concentrated sulphuric
acid, it easily yields sulpho acids, which can be used in dyeing in the saine manner
as the soluble aniline blues, and which, like these, according to the more or less
active action of the sulphuric acid, can be obtained as alkaline green, or as soluble
green.
I do not confine myself to the exact proportions or materials herein before
described, the novelty of the said Invention consisting in the production of coloring
matters by the action of chlorquinones upon secondary and tertiary monamins of
the aromatic compounds, and the production of sulpho acids of these coloring
matters.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said Frank Wirth in the Great Seal Patent Office on the 16th December
1879.
FRANK WIRTH, of the Firm of Wirth and Company, Patent Solicitors, at
Frankfort-on-the-Main, in the Empire of Germany. "THE PRODUCTION OF NEW
COLORING MATTERS FROM THE SECONDARY AND TERTIARY MONAMINS OF THE
AROMATIC COMPOUNDS, BY THE ACTION OF CHLORQUINONES, SUCH AS TRI AND
TETRA CHLORQUINONE, AND THEIR HOMOLOGUES UPON THE SAID MONAMINS."
A communication from Wilhelm Meister Eugene Lucius, Doctor of Philosophy, and
Adolphus Brüning, Doctor of Philosophy, trading under the Firm of Meister Lucius
and Brüning, of Höchst-on-the-Maine, in the Empire of Germany.
This Invention has for its object the production of new colouring matters from
the secondary and tertiary monamins of the aromatic compounds by the action of
chlorquinones, such as tri-and tetra-chlorquinone and, their homologues upon the
said monamins.
To obtain these coloring matters I use principally the tri-and tetra-chlorquinone,
or the crude chloranil, as obtained according to the well known description of Graebe
in the Annalen der Chemi und Pharmacie, volume 146, page 1, by the action of
hydrochloric acid and potassium chlorate on phenol. I find that the said chlorqui-
nones and their homologues in their action on the said monamins play the part
merely of oxidants or oxidizing agents.
The secondary and tertiary aromatic monamins herein referred to are those which
may be considered as originating in the replacement of two or three of the typical
hydrogen atoms of a single molecule of ammonia by either one radicle of an aromatic
hydrocarbon (such as phenyl or tolyl), and one or two alkyl radicles (such two being
either the same or different), or by one alkyl radicle and one or two such aromatic
radicles (such two being either the same or different).
By the action of the chlorquinones upon the said secondary and tertiary monamins
of the aromatic compounds I obtain a great variety of different shades and colours,
and I will now proceed to explain how violet, blue, and green colours may be
obtained by means of the said reaction; as an illustration of the general method I
follow in operating with the chlorquinones on the said monamins.
The production of the coloring matters is effected as follows, that is to say :-
- I. VIOLET COLOURING MATTERS.
To obtain these violet coloring matters I use chiefly the mono and dimethylated
monamin bases of the benzole series, as the following example shews:-
I stir
To two parts of dimethylaniline I add by degrees one part of chloranil.
this mixture, and heat it during some time to 60-70 degrees centigrade; thus I
obtain under development of hydrochloric acid a copper looking matter, which
dissolved in spirit gives a solution of splendid violet appearance. In order to
remove the dimethylaniline in excess I boil this product of copper looking appear-
ance in water; afterwards I dissolve the remaining substance in three parts of
spirit, and precipitate with water. The precipitate thus obtained will be the pure
allin looking notedan

page_text: These green coloring matters are produced by the action of chloranil upon benzyl-
diphenylamin and its homologues. For example, I heat by a waterbath three parts
of benzyl-diphenylamin to 60 degrees centigrade, and while stirring add by degrees
one part of chloranil, and keep the temperature at from 60 to 80 degrees centigrade,
until a sample, after getting cold, can be broken. The product thus obtained is of
a violet black appearance, and dissolved in spirit gives a yellow greenish solution.
To purify the coloring matter the product is dissolved in 50 parts of spirit, filtered,
and then mixed with 2 parts of water and one part of hydrochloric acid.of 13
specific gravity. The coloring matter precipitates to the bottom in a dark tarry
cake, which, dried and ground to powder of a dark greenish appearance, gives after
having been dissolved in spirit a dark green solution. However the coloring matter
in this state will give but very unsatisfactory results in dyeing; but, on the other
hand, by treatment with concentrated sulphuric acid, it easily yields sulpho acids,
which can be used in dyeing in the same manner as the soluble aniline blues, and
which like these, according to the more or less active action of the sulphuric acid,
can be obtained as alkaline green or a soluble green.
-
Having thus fully described the said Invention, and the manner of performing
the same, I wish it understood that I do not confine myself to the exact propor-
tions or materials herein before described, but what I claim is,-
First. The production of coloring matters by the action of chlorquinones upon
secondary and tertiary monamins of the aromatic compounds, as above described.
Second. The production of sulpho acids of these coloring matters, as above set
forth.
.
In witness whereof, I, the said Frank Wirth, have hereunto set my hand and
seal, this Twelfth day of December, in the year of our Lord One thousand
eight hundred and seventy nine.
FRANK WIRTH. (L.S.)