The Manufacture and Production of New Mordant-dyeing Colouring-matters.
Year: 1898

page_text: The Manufacture and Production of New Mordant-dyeing
Colouring-matters.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Gentleman, do hereby declare the nature of this invention (which has been com-
municated to me from abroad by the Badische Anilin & Soda Fabrik, of Ludwig-
shafen-on-Rhine, in the Empire of Germany) to be as follows:-
It is known that naphthazarine can be prepared by the treatment of 15 dinitro-
naphthalene with concentrated, or fuming, sulphuric acid, with, or without, the
addition of reducing, or other, agents. In this manufacture an intermediate pro-
duct is formed which is contained in the sulphuric acid melt and which is
characterized by its property of dissolving in water giving a blue solution.
My foreign correspondents have now discovered that new mordant-dyeing
colouring-matters can be obtained by treating the said intermediate product with
phenolic bodies. The phenolic body is preferably added to the ordinary naphtha-
zarine melt containing the said intermediate product in sulphuric acid solution.
The phenolic bodies suitable for the purposes of this invention are phenol
itself, or its derivatives, such for instance as phenol carbonic acids, phenol-
sulpho-acids, nitro-phenols, halogen substituted phenols, alpha and beta naphthols
and the derivatives thereof such for instance as naphthol-sulpho acids, naphthol-
carbonic acids, dioxy-naphthalenes, nitro-naphthols, and the like.
The following examples of manners in which the invention can be carried into
practical effect will serve to further illustrate the nature of this invention
but I do not limit myself to these examples. The parts are by weight.
EXAMPLE 1.
Prepare a naphthazarine melt in the usual way that is by heating 15 dinitro-
naphthalene with concentrated, or fuming, sulphuric acid, with the addition of
a reducing agent. To about one thousand parts of this melt, obtained by the
use of about fifty parts of dinitro-naphthalene, add about fifty parts of phenol,
at the ordinary temperature. Stir the mixture thoroughly for about twenty-
four hours whilst raising the temperature to about fifty degrees Centigrade and
maintaining this temperature. By taking a test-portion of the melt from time
to time, and dissolving it in ice-water guidance as to the course of the reaction
can be obtained, as, when the reaction is complete, the test portion dissolves
in the ice-water forming a green solution. Pour the melt, thus obtained, onto
two thousand parts of ice. If it be desired to obtain the new colouring-matter
as pure as possible the solution is immediately filtered. The filtrate is allowed to
stand, when the new colouring-matter will separate in the form of a dark-coloured
crystalline powder which is collected, by filtering, washed and dried. If the
first filtration, after dissolving the melt, be omitted, the product obtained is less
pure but can be used for dyeing. The new dyestuff obtained is soluble in water,
yielding a violet-blue solution. Its solution in concentrated sulphuric acid is
violet and it yields a violet-blue solution in alcohol and a blue solution in aniline
It dyes chrome-mordanted wool greenish-black shades.

page_text: EXAMPLE 2.
To about one thousand parts of the naphthazarine melt obtained in the manner
described in the preceding example add about fifty parts of finely powdered picric
acid at the ordinary temperature.. Stir the mixture for about twenty-four hours
at a temperature of about thirty-five to forty degrees Centigrade. Pour the melt
into water and filter. Extract the residue with heated water in order to dissolve
any unaltered pieric acid, which may not have entered into the reaction. By
further extracting with hot water the formed dyestuff goes into solution and
separates from the filtrates in fine bronze-coloured crystals. The new dyestuff is
but slightly soluble in cold water. In hot water it dissolves with a violet colour.
Its solution in concentrated sulphuric acid is crimson-red. It yields a violet-
blue solution in alcohol and a blue solution in cold aniline. It dyes chrome-
mordanted wool bluish-black shades.
EXAMPLE 3.
To about one thousand parts of the naphthazarine melt,obtained in the manner
described in Example 1 add about seventy parts of alpha-naphthol at the
ordinary temperature. Stir the mixture for about twenty-four hours and pour
it into ice water. The dyestuff, which is rather difficultly soluble, separates
out in greyish-blue flocks. Collect by filtering, wash and dry. If the filtrate be
allowed to stand more dyestuff will separate out. The new dyestuff, when in
the form of a powder, has a grey appearance; it is easily soluble both in
hot and in cold water, yielding a greenish-blue solution. The solution in con-
centrated sulphuric acid is dirty reddish-brown. It is not readily soluble in
alcohol, and is but little soluble in cold aniline and yields, when heated therewith,
a bluish-green solution. When used as in dyeing with naphthazarine in the
boiling bath for say 2 hours and a half it dyes chrome-mordanted wool greyish-
blue shades. If dyed for about only one hour on the water bath the shades
obtained are of a much purer blue.
EXAMPLE 4.
To about one thousand parts of the naphthazarine melt obtained in the manner
described in Example 1 add about seventy parts of dry finely ground beta-
naphthol-sulpho acid Schäffer at the ordinary temperature: Stir the mixture for
about twenty-four hours with but slight heating and pour into water. The
dyestuff separates out in greenish-grey flocks, which are collected by filtering.
The new dyestuff, when in the form of a powder, has a black appearance. It
dissolves easily both in cold and in hot water the solution being dirty brown.
The solution in concentrated sulphuric acid is dirty blackish-brown. It is but
slightly soluble in alcohol and insoluble in cold aniline. It dyes chrome-mor-
danted wool greenish-black shades.
In the foregoing processes instead of the phenolic bodies named in the examples
other phenolic bodies as indicated before the examples can be used.
Dated this 9th day of May 1898.
The Manufacture and Production of New Mordant-dyeing
Colouring-matters.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Gentleman, do hereby declare the nature of this invention (which has been com-

page_text: municated to me from abroad by the Badische Anilin & Soda Fabrik, of Ludwig-
shafen-on-Rhine, 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 follow-
ing statement:-
It is known that naphthazarine can be prepared by the treatment of 15 dinitro-
naphthalene with concentrated, or fuming, sulphuric acid with, or without, the
addition of reducing, or other, agents. In this manufacture an intermediate pro-
duct is formed which is contained in the sulphuric acid melt and which is
characterised by its property of dissolving in water giving a blue solution.
My foreign correspondents have now discovered that new mordant dyeing
colouring-matters can be obtained by treating the said intermediate product with
phenolic bodies. The phenolic body is preferably added to the ordinary naphtha-
zarine melt containing the said intermediate product in sulphuric acid solution.
The phenolic bodies suitable for the purposes of this invention are phenol
itself, or its derivatives: such, for instance, as phenol-carboxylic acids, phenol-
sulphoacids, nitro-phenols, halogen-substituted phenols, di-alkyl-meta-amido-
phenol, resorcinal, pyrogallol, alpha- and beta-naphthols, and the derivatives
thereof, such for instance as naphthol-sulpho acids, naphthol-carboxylic acids,
dioxy-naphthalenes, nitro naphthols, and the like.
The following examples of manners in which the invention can be carried into.
practical effect will serve to further illustrate the nature of the invention
and the manner in which it can be performed, but I do not limit myself to
these examples. The parts are by weight:
EXAMPLE 1.
Prepare a naphthazarine melt in the usual way, that is, by heating 15 dinitro-
naphthalene with concentrated, or fuming, sulphuric acid, with the addition of
a suitable reducing agent. To about one thousand parts of this melt, obtained by
the use of about fifty parts of dinitro-naphthalene, add about fifty parts of phenol
at the ordinary temperature. Stir the mixture thoroughly for about twenty-
four hours, whilst raising the temperature to about fifty degrees Centigrade and
maintaining this temperature. By taking a test portion of the melt from time
to time, and dissolving it in ice-water, guidance as to the course of the reaction
can be obtained, as, when the reaction is complete, the test portion dissolves
in the ice-water forming a green solution. Pour the melt, thus obtained, onto
two thousand parts of ice. If it be desired to obtain the new colouring-matter
as pure as possible, the solution is immediately filtered. The filtrate is allowed to
stand, when the new colouring-matter will separate out in the form of a dark-col-
oured crystalline powder, which is collected by filtering, washed, and dried. If the
first filtration, after dissolving the melt, be omitted, the product obtained is less
pure but can be used for dyeing. The new dyestuff obtained is soluble in water,
yielding a violet-blue solution. Its solution in concentrated sulphuric acid is
violet and it yields a violet-blue solution in alcohol and a blue solution in aniline.
It dyes chrome-mordanted wool greenish-black shades.
EXAMPLE 2.
To about one thousand parts of the naphthazarine melt obtained in the manner
described in the preceding example add about fifty parts of finely powdered picric
acid at the ordinary temperature. Stir the mixture for about twenty-four hours
at a temperature of about thirty-five to forty degrees Centigrade. Pour the melt
into water and filter. Extract the residue repeatedly with a little warm water:
the first extractions dissolve any unaltered picric acid which may not have
entered into the reaction. From the later extracts, the formed dyestuff separates
in fine bronze-coloured crystals. The new dyestuff is but slightly soluble in cold
water. In hot water it dissolves with a violet colour. Its solution in concen-
trated sulphuric acid is crimson-red. It yields a violet-blue solution in alcohol,
and a blue solution in cold aniline, which appears red-violet in transmitted light.
It dyes chrome-mordanted wool, blueish-black shades.

page_text: EXAMPLE 3.
To about one thousand parts of the naphthazarine melt obtained in the manner
described in Example 1, add about seventy parts of alpha-naphthol at the
ordinary temperature. Stir the mixture for about twenty-four hours and pour
it into ice water. The dyestuff, which is rather difficultly soluble, separates
out in greyish-blue flocks. Collect by filtering, wash and dry. If the filtrate be
allowed to stand, more dye stuff will separate out. This colouring-matter can
be obtained in a state of greater purity by allowing the melt containing it
to stand for several days. The new dye then crystallizes out. Decant and wash,
by decantation, first with dilute sulphuric acid and then with water. The new dye-
stuff, when in the form of a powder, has a grey appearance, it is easily soluble both in
hot and in cold water, yielding a blue solution. The solution in con-
centrated sulphuric acid is dirty reddish-brown. It is not readily soluble in
alcohol, and is but little soluble in cold aniline, and yields, when heated therewith,
a bluish-green solution. When used, as in dyeing with naphthazarine, in the
boiling bath for say two hours and a half, it dyes chrome-mordanted wool, greyish-
blue shades. If dyed for about one hour only on the water-bath the shades
obtained are of a much purer blue.
EXAMPLE 4.
The
To about one thousand parts of the naphthazarine melt obtained in the manner
described in Example 1, add about seventy parts of dry finely ground beta-
naphthol-sulphoacid Schäffer, at the ordinary temperature." Stir the mixture for
about twenty-four hours, with but slight heating and pour into water.
dyestuff separates out in greenish-grey flocks, which are collected by filtering.
The new dyestuff, when in the form of a powder, has a black appearance. It
dissolves easily both in cold and in hot water, the solution being dirty-brown.
The solution in concentrated sulphuric acid is dirty blackish-brown. It is but
slightly soluble in alcohol and insoluble in cold aniline. It dyes chrome-mor-
danted wool greenish-black shades.
In the foregoing processes, instead of the phenolic bodies named in the examples,
other phenolic bodies, as indicated before the examples, can be used.
Having now particularly described and ascertained the nature of this in-
vention and in what manner the same is to be performed, I declare that what I
claim is:
1. The manufacture of mordant-dyeing colouring-matters by treating the
naphthazarine intermediate product herein before defined, with a phenolic body
hereinbefore defined; all substantially as described.
2. The manufacture of mordant-dyeing colouring-matters, substantially as here-
inbefore described under the several examples.
3. As new articles of manufacture the new mordant-dyeing colouring-matters, 4
such as can be obtained substantially as hereinbefore described.
Dated this 4th day of February 1899.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.