The Manufacture and Production of New Black Colouring-matters derived from Naphthazarine.
Year: 1897

page_text: Date of Application, 16th Sept., 1897
Complete Specification Left, 26th May, 1898-Accepted, 9th July, 1898
The Manufacture and Production of New Black Colouring-matters
derived from Naphthazarine.
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 commu-
nicated to me from abroad by the Badische Anilin & Soda Fabrik, of Ludwigshafen-
on-Rhine, in the Empire of Germany,) to be as follows:-
My foreign correspondents have discovered that a new series of black colouring
matters can be produced by condensing naphthazarine with aromatic amines, with or
without, a condensing agent. The condensation products so obtained are black
colouring matters of great importance which yield, on the chrome mordanted animal
and vegetable fibre a lake which is much bluer than is that yielded by naphthazarine
itself. These condensation products are only slightly soluble in water but they can
be very easily converted into soluble compounds either by the aid of concentrated,
or fuming sulphuric acid, thus forming sulpho acids which are soluble in water and
dye chrome-mordanted wool a black shade, or by treatment with sulphites or
bisulphites of the alkalies. These water soluble coloring matters are of great.
importance, their chrome lakes being very fast.
The condensation can be effected in the presence of water, alcohol, glacial acetic
acid, or the like.
The presence of a condensing agent such as boracic acid, causes the reaction to
proceed with more rapidity. The products prepared in the presence of such a
condensing agent dissolve in caustic soda with a violet-blue color whilst the products
obtained without a condensing agent dissolve in alkali first with a greenish-blue
colour. Both compounds however on sulphonating yield sulpho-acids which cannot
be distinguished from one another.
The following examples will serve to further illustrate the nature of the invention
but the invention is not limited to the details as they can be varied. The parts are
by weight
Treat about one thousand parts of a twenty per cent. naphthazarine paste whilst
stirring, with a solution of about two hundred parts of aniline in about six hundred
parts of acetic acid. Add about two hundred parts of boracic acid to the mass and
keep the temperature at about forty degrees Centigrade for twelve hours. The reaction
is finished when no more naphthazarine remains which can be proved by dissolving a
test portion in caustic soda when (if no naphthazarine be present) it dissolves with a
reddish-violet colour instead of the cornflower-blue colour which is characteristic of
naphthazarine. Pour into water, filter and wash neutral. The new dyestuff can
directly be employed in the form of a paste- for dyeing and printing.

page_text: Heat about one hundred parts of the compound produced according to either
Example 1, or Example 2, on a water bath, with about five hundred parts of mono-
hydrate sulphuric acid (H₂SO₁) for about five hours whereby the greater part of the
'said compound is converted into a sulpho-acid easily soluble in water. Pour the
whole into about two thousand parts of water, boil, filter, salt the solution out with
common salt, filter, press, and dry. The colouring matter so obtained is a reddish
brown powder, which very easily dissolves in water with a red colour, and in caustic
soda with a violet-blue colour.
Instead of aniline other aromatic amines can be used with a similar result such are
for instance ortho-toluidine, para-toluidine, and alpha- and beta-napthylamine.
The condensation products of naphthazarine with the different aromatic amines
are very similar to one another in their reactions. In the following I give a table of
some reactions of the condensation products obtained according to Example 1.
Treat about eight hundred parts of the condensation product of naphthazarine and
aniline, in the form of a twenty per cent.- paste, with about two hundred parts of
sodium bisulphite (containing about forty per cent. of sodium bisulphite NaHSO),

page_text: and maintain it at a temperature of about ninety five degrees Centigrade for two
hours. The paste so obtained dissolves in water with a brown colour and can directly
be used for printing. The dry colouring-matter is a brown powder soluble in water.
The solution with caustic soda has a green colour, which is converted into blue on
exposure to the air or more rapidly when boiled. It dissolves in cold concentrated
sulphuric acid forming a solution of a dirty brown colour, which, on heating, becomes
beautiful violet.
The soluble bisulphite compounds of the condensation products of naphthazarine
with the other aromatic amines differ only slightly from one another.
Dated this 16th day of Santambon 1007
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
The Manufacture and Production of New Black Colouring-matters
derived from Naphthazarine.
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
communicated to me from abroad by the Badische Anilin & Soda Fabrik, of
Ludwigshafen-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
following statement :-
My foreign correspondents have discovered that a new series of black colouring-
matters can be produced by condensing naphthazarine with aromatic amines, with, or
without, a condensing agent. The condensation products so obtained are black
colouring-matters of great importance which yield, on chrome mordanted animal and
vegetable fibre, a lake which is much bluer than is that yielded by naphthazarine
itself. These condensation products are only slightly soluble in water but they can
be very easily converted into soluble compounds :-either by the aid of concentrated,
or fuming, sulphuric acid, (thus forming sulpho-acids which are soluble in water and
dye chrome-mordanted wool a black shade) or by treatment with sulphites or
bisulphites of the alkalies. These colouring matters soluble in water are of great
importance, their chrome-lakes being very permanent.
The condensation can be effected in the presence of water, alcohol, glacial acetic
acid, or the like.
The presence of a condensing agent, such as boracic acid, causes the reaction to
proceed with more rapidity. The products prepared in the presence of such a
condensing agent dissolve in caustic soda with a violet-blue colour, whilst the products
obtained without a condensing agent dissolve in alkali first with a greenish-blue colour.
Both compounds however on sulphonating, yield sulpho-acids which are either
actually identical, or so nearly resemble one another, that they have not at present
been distinguishable from one another.
The following examples will serve to further illustrate the nature of the invention
and the manner in which it can be carried into practical effect, but the invention is
not limited to the details as they can be varied. The parts are by weight.
EXAMPLE I.
Treat about one thousand parts of a twenty per cent. naphthazarine paste (whilst
stirring) with a solution of about two hundred parts of aniline in about six hundred
parts of acetic acid containing about 30 per cent. real acetic acid. Add about two
hundred parts of boracic acid to the mass, and keep the temperature at about forty

page_text: degrees Centigrade for twelve hours. The reaction is finished when practically no
more naphthazarine remains, which can be proved by dissolving a test portion in
caustic soda, when, if no naphthazarine be present, it dissolves forming a reddish-
violet solution, instead of the cornflower-blue solution which is characteristic of
naphthazarine. Pour into water, filter and wash neutral. The new dyestuff can
directly be employed in the form of a paste for dyeing and printing.
EXAMPLE 2.
Stir about one hundred parts of dry naphthazarine at the ordinary temperature
with about one hundred parts of aniline, and allow the mass to react for about
twenty four hours, then treat with about one hundred parts of hydrochloric acid and
about five hundred parts of water. Filter, and collect the residue, and wash and dry
it. The product so obtained is a black powder insoluble in water and having a
metallic lustre. In caustic soda it dissolves, the solution being greenish-blue,
which on exposure to the air gradually becomes pure blue. The dyestuff so obtained
can directly be used in the form of a paste, for dyeing and printing.
EXAMPLE 3.
Heat, on the water bath, about one hundred parts of the compound produced
according to either of the preceding Examples, with about five hundred parts of
monohydrate sulphuric acid (H, SO₁) for about five hours, whereby the greater part
of the said compound is converted into a sulpho-acid easily soluble in water. Pour
the whole into about two thousand parts of water, boil, filter from insoluble matter,
salt the solution out with common salt, filter, press and dry. The colouring-matter
so obtained is a reddish-brown powder, which very easily dissolves in water, forming
a red solution, and in caustic soda forming a violet-blue solution.
Instead of aniline other aromatic amines can be used with a similar result; such
other aromatic amines are, for instance, ortho-toluidine, para-toluidine, and alpha- and
beta-naphthylamine.
The condensation products of naphthazarine with the different aromatic amines, are
very similar to one another in their reactions. In the following I give a table of
some reactions of the condensation products obtained according to the preceding
Example 1.

page_text: Treat about eight hundred parts of the condensation product of naphthazarine and
aniline (in the form of a twenty per cent. paste) with about two hundred parts of
sodium bisulphite, (containing about forty per cent. of sodium bisulphite NaHSO,),
at a temperature maintained about ninety five degrees Centigrade for two hours.
The paste so obtained dissolves in water (the solution being brown) and can directly
be used for printing. The dry colouring-matter is a brown powder soluble in water.
The solution with caustic soda is green which becomes blue on exposure to the air,
or more rapidly when boiled. It dissolves in cold concentrated sulphuric acid,
forming a dirty brown solution which, on heating, becomes a beautiful violet.
The soluble bisulphite compounds of the condensation products of naphthazarine
with the other aromatic amines differ only slightly from one another.
Having now particularly described and ascertained the nature of this inven-
tion, and in what manner the same is to be performed, I declare that what I
claim is :-
1. The production of new black-colouring matters by condensing naphthazarine
with an aromatic amine (with, or without, the use of a diluent) substantially as
herein before described.
2. The production of new black-colouring matters by condensing naphthazarine
with an aromatic amine in the presence of a condensing agent (with or without the
use of a diluent) substantially as hereinbefore described.
3. The production of new black colouring matters soluble in water, by treating the
condensation products obtained according to the foregoing claiming clauses with
sulphuric acid substantially as herein before described.
4. The production of new black colouring matters soluble in water, by treating the
condensation products obtained according to the foregoing first and second claiming
clauses with sulphites, or bisulphites, of the alkalies, substantially as herein before
described.
5. The manufacture of the new black colouring matters in the manners set forth
in the several examples herein before given.
6. As new articles of manufacture the new black colouring-matters such as can be
obtained as herein before described and claimed.
Dated this 26th day of May 1898
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.