Year: 1899

page_text: Date of Application, 23rd Nov., 1899
Complete Specification Left, 9th July., 1900-Accepted, 11th Aug., 1900
We, FRITZ ULLMANN and FRITZ KEHRMANN, both of the Ecole de Chemie,' Geneva,
Switzerland, Chemists, do hereby declare the nature of this invention to be as
follows:-
This invention relates to the production of azonium-compounds from azines and is
based on the observation that azines can easily be converted into such azonium-
compounds by dissolving them in an indifferent medium and treating the solution
obtained in open vessels with dimethyl sulphate.
This process may be applied to derivatives of the azine series--such as naphtho-
phenazine, dinaphthazine &c.—and likewise to derivatives of the eurhodine series-
such as neutral-red, amidonaphthophenazine &c. These parent materials are employed
in the form, either of the free bases, or of the corresponding acetyl-compounds. As
dissolving medium we may use benzene, nitrobenzene, chloroform, carbon tetra-
chloride and the like. The azonium-compounds resulting from the above mentioned
reaction are dye-stuffs which are soluble in water. Some of them have been found to
be identical with certain compounds of the azonium-series, which have already been
prepared and described.
"
Our new process for the production of azonium derivatives is much superior to the
method described in the German Patent No. 101,487 for the production of certain
azonium-compounds by the aid of alkyl halides, as will be proved by the following.
The use of dimethyl sulphate as a methylating agent is of great advantage because
by means of this agent the methylation can be performed in open vessels, whilst in
using methyl iodide or methyl chloride closed vessels and elevated pressure are
required. Moreover, the reaction with methyl sulphate can, be performed in open
vessels at elevated temperature, owing to the boiling point of this salt being as, high
as 188° C.; the reaction is therefore finished in considerably shorter time.
Dimethyl sulphate is much cheaper than methyl iodide; while being a liquid
it is preferable for technical purposes to the gaseous methyl chloride.
To further illustrate our new process we give the following directions
is dissolved in nitro benzene and to this solution, previously heated to about 150° C.,
kilo. of dimethyl sulphate, added quickly, while the liquid is well stirred., The
-mixture begins to boil and large quantities of crystals are immediately separated,
which, after refrigeration, are filtered, washed with ether, and dried. The dyestuff
5.thus produced forms yellow orange needles, easily soluble in alcohol and water; the
solutions obtained are of orange-yellow colour, and distinguished by a fine light green

page_text: fluorescence. The dyestuff dissolves in concentrated sulphuric acid, forming a
dichroic solution, which appears blue by reflected, and red by transmitted light.
The new colouring matter dyes silk and tannin-mordanted cotton, orange-yellow
tints. Its constitutional formula is :-
:-
In order to prepare the corresponding derivative from the so-called toluylene-red
we start from the acetyl-compound of this base which is produced by heating the
base with acetic anhydride, dissolving the crude precipitates in water and reprecipi-
tating the acetyl-compound by means of sodium carbonate.
1 kilo. of the product thus obtained is well dried and dissolved in hot nitrobenzene.
To the solution at about 100° C., 430 grammes of dimethyl sulphate are added while'
the liquid is well stirred. The dyestuff formed by this reaction can be isolated in
either of two ways.
Either it is precipitated, after refrigeration, by the addition of
ether, filtered, washed with ether and dried. Or after distilling off the nitrobenzene
with steam it is precipitated from the residual aqueous solution by means of common
salt, filtered, pressed and dried.
The dyestuff, in the form of its chloride, is represented by the formula.
It is moderately soluble in water yielding a black-violet solution. From this
solution, which is distinguished by its bitter taste, the dyestuff cannot be precipitated
by the addition of sodium carbonate. By concentrated sulphuric acid it is dissolved
yielding a green solution. It dyes silk and tannin-mordanted cotton dark Bordeaux-
red shades.
III. 1 kilo. of the acetyl-compound of amidonaphthophenazine (Berichte der
deutschen chemischen Gesellschaft XXVII, 3342) is dissolved in nitrobenzene at
about 150° C. and 440 grammes of dimethyl sulphate are added to the solution. The
dyestuff resulting from this reaction is then isolated in the manner described in
Example No. 1.
It is identical with the metho-sulphate of the acetyl-compound of methylrosin-
duline.
The dyestuff is easily soluble in water and alcohol, forming orange-yellow solutions,
which are distinguished by a bright yellow fluorescence. It dissolves in concentrated
sulphuric acid to a violet solution. When it is boiled with diluted acids, an acetyl-
group is readily eliminated methylrosinduline being formed; this latter product can
be precipitated from the solution in the form of the hydrochloride by means of common
salt. It dyes silk and tannin-mordanted cotton orange tints.

page_text: Instead of the acetyl-products the corresponding amido-bases can be introduced
into the reaction, as illustrated by the following examples:
IV. 1 kilo. of toluylene-red base is well dried and dissolved in nitrobenzene and
350 grammes of dimethyl sulphate are added at 150° C. to the solution.
The liquid
immediately turns magenta-red and part of the dyestuff separates on refrigeration.
After distilling off the nitrobenzene with steam and dissolving the residue in water
the dyestuff is precipitated from this solution by means of common salt, and zinc
chloride. It forms a dark red crystalline powder. The constitution of the compound
is represented by the formula:
r
The dyestuff is slightly soluble in cold water and alcohol, forming magenta-red">
solutions. It dissolves in concentrated sulphuric acid forming a green solution which
on addition of water turns, blue and finally red. From the aqueous solution the
dyestuff is not precipitated on addition of ammonia or alkali carbonate. It dyes silk
and tannin-mordanted cotton magenta-red. The tints are distinguished by a
considerable fastness to soap..
1
V1 kilo of amidonaubthophenazine (Berichte der deutschen chemischen
() is dissolved in hot nitrobenzene and 506 grammes of dimethyl sulphate are added at
about 150° C. The orange-yellow solution turns immediately blood-red and large.
...quantities of red crystals separate, which after refrigeration are filtered, washed with
benzene or ligroin; and dried.
As shewn by the following constitutional formula:
T
the compound is identical with the metho-sulphate of methyl-rosinduline.
It is easily soluble in water and alcohol, forming yellowish-red solutions which are
distinguished by a yellow fluorescence. It dissolves in concentrated sulphuric acid,
forming a green solution, which on dilution turns scarlet-red. It dyes silk and tannin-
30 mordanted cotton scarlet red tints; which are very fast to soap. i
!!

page_text: We, FRITZ ULLMANN and FRITZ KEHRMANN, both of the Ecole de Chemie, Geneva,
Switzerland, Chemists, do hereby declare the nature of this invention 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 the production of azonium-compounds from azines and is
based on the observation that azines can easily be converted into such azonium-
compounds. by dissolving them in an indifferent medium and treating the solution
obtained in open vessels with dimethyl sulphate.
This process may be applied to derivatives of the azine series such as naphthophen-
.azine, dinaphthazine, &c., and likewise to derivatives of the eurhodine series—such as
neutral-red, amidonaphthophenazine &c. These parent materials are employed in
the form either of the free bases, or of the corresponding acetyl-compounds.
As dissolving medium we may use benzene, nitrobenzene, chloroform, carbon
tetrachloride and the like.
The azonium-compounds resulting from the above mentioned reaction are dye-
stuffs which are soluble in water. Some of them have been found to be identical
with certain compounds of the azonium-series, which have already been prepared and
described.
Our new process for the production of azonium derivatives is much superior to the
method described in the German Patent No. 101487 for the production of certain
azonium-compounds by the aid of alkyl halides, as will be proved by the following.
The use of dimethyl sulphate as a methylating agent is of great advantage because
by means of this agent the methylation can be performed in open vessels, whilst in
using methyl iodide or methyl chloride closed vessels and elevated pressure are
required. Moreover, the reaction with methyl sulphate can be performed in open
vessels at elevated temperature, owing to the boiling point of this ethereal salt
being as high as 188° C.; the reaction is therefore finished in considerably shorter
time.
Dimethyl sulphate is much cheaper than methyl iodide; while being a liquid it
preferable for technical purposes to the gaseous methyl chloride.
To further illustrate our new process we give the following directions.
L. 1 kilo. of dinaphthazine
is dissolved in nitrobenzene and to this solution, previously heated to about 150°C., kilo
The mixture 3
of dimethyl sulphate is added quickly, while the liquid is well stirred.
begins to boil and large quantities of crystals are immediately separated, which, after
refrigeration, are filtered, washed with ether, and dried.
The dyestuff thus produced forms yellow orange needles, easily soluble in alcohol
and water; the solutions obtained are of orange yellow colour and distinguished by a
fine light green fluorescence. The dyestuff dissolves in concentrated sulphuric acid
forming a dichroic solution, which appears blue by reflected, and red by transmitted
light

page_text: The new
tints.
colouring matter dyes silk and tannin-mordanted cotton orange-yellow
Its constitutional formula is :
II. In order to prepare the corresponding derivative from the so-called. toluylene-
red we start from the acetyl-compound of this base which is produced by heating the
base with acetic anhydride, dissolving the crude precipitate in water and reprecipitating
the acetyl-compound by means of sodium carbonate.
1 kilo. of the product thus obtained is well dried and dissolved in hot nitro-benzene.
To the solution at about 100° C., 430 grammes of dimethyl sulphate are added while
the liquid is well stirred.
The dyestuff formed by this reaction can be isolated in either of two ways.
Either
it is precipitated after refrigeration by the addition of ether, filtered, washed with
ether and dried. Or after distilling off the nitro-benzene with steam it is precipitated
from the residual aqueous solution by means of common salt, filtered, pressed, and
dried.
The dyestuff, in the form of its chloride is represented by the formula.
From this
It is moderately soluble in water yielding a black-violet solution.
solution, which is distinguished by its bitter taste, the dyestuff cannot be precipitated
by the addition of sodium carbonate. By concentrated sulphuric acid it is dissolved
yielding a green solution. It dyes silk and tannin-mordanted cotton dark Bordeaux-
red shades.
III. 1 kilo. of the acetyl-compound of amidonaphthophenazine (Berichte der
deutschen chemischen Gesellschaft XXVII 3342) is dissolved in nitrobenzene at
about 150° C. and 440 grammes of dimethyl sulphate are added to the solution. The
dyestuff resulting from this reaction is then isolated in the manner described in
Example No. 1.
It is identical with the metho-sulphate of the acetyl compound of methylrosin-
duline.
J
The dyestuff is easily soluble in water and alcohol forming orange-yellow solutions,
which are distinguished by a bright yellow fluorescence. It dissolves in concentrated
sulphuric acid to a violet solution. When it is boiled with diluted acids, an acetyl-
group is readily eliminated, methylrosinduline being formed.
.
This hydrolysis is performed as follows:
1 kilo. of the methosulphate of acetylamido-naphtho-phenazonium is dissolved in
as little concentrated sulphuric acid as possible at about 40 to 50° C.; to this solu-

page_text: tion an equal volume of water is added while stirring well and taking care that 'the
temperature does not surpass 100° C. The liquid is kept at this temperature for 15.
minutes longer, and is then diluted with ten times its volume of water, and from the
solution thus obtained the product of the hydrolysis is precipitated by means of
common salt or zinc chloride; it is then filtered, pressed and dried. It dyes silk
and tannin mordanted cotton orange tints.
Instead of the acetyl-products the corresponding amido-bases can be introduced
into the reaction, as illustrated by the following examples.
IV. 1 kilo. of toluylene-red base is well dried and dissolved in nitrobenzene and 350
grammes of dimethyl sulphate are added at 150° C. to the solution. The liquid
immediately turns magenta-red and part of the dyestuff separates on refrigeration.
After distilling off the nitrobenzene with steam and dissolving the residue in water,
the dyestuff is precipitated from this solution by means of cominon salt and zinc)
chloride. It forms a dark red crystalline powder. The constitution of the compound
indh the faunilo
The dyestuff is slightly soluble in cold water and alcohol, forming magenta-red'
solutions. It dissolves in concentrated sulphuric acid forming a green solution which
on addition of water turns blue and finally red. From the aqueous solution the dye-
stuff is not precipitated on addition of ammonia or alkali carbonate. It dyes silk
and tannin mordanted cotton magenta-red. The tints are distinguished by a con-
siderable fastness to soap.
V. 1 kilo. of amidonaphthophenazine (Berichte der deutschen chemischen Gesells-
is dissolved in hot nitrobenzene and 506 grammes of dimethyl sulphate are added at
about 150° C. The orange-yellow solution turns immediately blood-red and large quan-
tities of red crystals separate, which after refrigeration are filtered, washed with benzene
or ligroin and dried.
Lallamine constitutional formule.
"
the compound is identical with the metho-sulphate of inethyl-rosinduline.
It is easily soluble in water and alcohol, forming yellowish-red solutions which are
distinguished by a yellow fluorescence. It dissolves in concentrated sulphuric acid
forming a green solution, which on dilution turns scarlet-red. It dyes silk and tannin
mordanted cotton scarlet red tints, which are very fast to soap.
1..
Having now particularly described and ascertained the nature of our said invention
and in what manner the same is to be performed, we declare that what we claim
...

page_text: 1. The berein described manufacture of azonium dyestuffs by acting with dimethyl
sulphate on azines or their amido-substituted or acetylamido-substituted derivatives.
2. The dyestuffs manufactured as above set forth.
3. The transformation of the acetyl-azonium-compounds obtained as described in
Claim 1 into the corresponding amidoazonium-compounds by hydrolysis.
4. The amidoazonium compounds manufactured as above set forth.
Dated this Oth day of Tule 1000
ABEL & IMRAY,
Agents for the Applicants.