The Manufacture and Production of Products suitable for use in the Preparation of Colouring Matters.
Year: 1899

page_text: Date of Application, 28th Oct., 1899
Complete Specification Left, 30th July, 1900-Accepted, 1st Sept., 1900
PROVISIONAL SPECIFICATION.
The Manufacture and Production of Products suitable for use in the
Preparation of 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 Ludwigshafen-
on-Rhine in the German Empire) to be as follows:-
This invention consists in the manufacture and production of halogen derivatives
of diamido-anthraquinone, and of the alphylated derivatives of diamido-anthraquinones
by treating their respective sulphoacids with either chlorine, or bromine. During
this treatment the sulpho groups are eliminated, and the halogen takes their place.
The treatment can be effected in aqueous solution, and an excess of halogen is usually
employed.
The following examples will serve to illustrate the nature of the invention, but the
invention is not confined to the examples. The parts are by weight :—
Dissolve about ten parts of 1-41-diamido-anthraquinone-disulphcacid in one hundred
parts of water, and treat the solution with about-thirty parts of bromine, at ordinary
temperature. Stir the mixture for about twenty-four hours. The bromine derivative
separates out as a red powder. Filter, wash and dry. The product so obtained appears
to be a mixture of various highly brominated diamido-anthraquinones, it is almost
completely soluble in boiling nitro-benzene and partly crystallises out on cooling,
yielding fine brown needles, which do not melt below 300° Centigiade. These are,
with difficulty, soluble in cold alcohol, glacial acetic acid, benzene, and nitro benzene,
but are more easily soluble on heating, especially in nitro-benzene.
In the above example the corresponding quantity of sulphoacids of isomeric diamido.
anthraquinones can be used; and, instead of bromine, chlorine can be employed. It
18 also unnecessary to isolate the sulphoacids before treating them with the halogens.
If desired the solution of the sulphonation melt in water can be employed directly.

page_text: the bromine derivative begins to separate out as a red precipitate. After about twelve
hours the separation is complete. Collect by filtering from the solution, which is
almost colourless, the brom- 1·41-di-anılıdo-anthraquinone obtained. Wash and dry.
The product, so obtained, 19 a red powder, which is, with diffioulty, soluble in cold
alcohol, more readily soluble in hot alcohol, and rather easily soluble in cold glacial
acetic acid; it readily dissolves in benzene, the solution being yellow-red, the solution
in concentrated sulphuric acid is a dirty violet. Instead of bromine other halogens
can be used, and the 14-di-anılıdo-anthraquinone-sulphoacid can be replaced by
sulphoacids of other di-alphylido-anthraquinones.
It is not necessary to isolate the sulphoacids as their solutions, obtained by pouring
the sulphonation melt, in which they are produced, upon ice, can be directly treated
with the halogen used. This method of production is illustrated in the following
example
=
Add about fifty parts of 1-4-di-anilido-anthraquinone to five hundred parts of I
fuming sulphuric acid (containing about 25 per cent. free anhydride) at ordinary
temperature. Then heat the mixture, for about ten hours, at a temperature of from
80° to 40° Centigrade. Allow the melt to cool, and pour it into two thousand
five hundred parts of wash-water. Then add, at ordinary temperature, whilst stirring
well, one hundred and fifty parts of bromine. After a short time the bromine 2
derivative begins to separate out as a brown precipitate. Filter, wash and dry. The
properties of the products so obtained are similar to those of the products obtained
in the foregoing Example 2. The dry powder is of a brown colour, slightly soluble
in cold alcohol and more readily soluble in hot alcohol. It is soluble in glacial acetic
acid and benzene the solutions being cherry red. The solution in concentrated 2
sulphuric acid 18 brown.
Dated this 28th day of October 1800.
The Manufacture and Production of Products suitable for use in the
Preparation of 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
communicated to me from abroad by the Badische Anilin & Soda Fabrik, of
Ludwigshafen-on-Rhine, in the German Empire) and in what manner the same is
to be performed to be particularly described and ascertained in and by the
following statement :-
This invention consists in the manufacture and production of halogen derivatives of
diamido-anthraquinones, and of halogen derivatives of dialphylido-anthraquinones, by
treating their respective sulphoacids with either chlorine or bromine. During the
treatment according to this invention, the sulpho groups are apparently eliminated, the
halogen probably taking their place, a body insoluble in water resulting. The treatment

page_text: can be effected in aqueous solution and an excess of halogen is usually employed, the
action of the halogen being allowed to continue until the sulphoacid is practically
entirely converted into an insoluble halogen compound.
The following examples will serve to illustrate the nature of this invention and
various inanners in which it may be carried into practical effect but the invention 18
not confined to the examples. The parts are by weight.
PRODUCTION OF BROM-1-4-DIAMIDO-ANTHRAQUINONE.
Dissolve about ten parts of 14'-diamido-anthraquinone-di-sulphoacid in one hundred
parts of water, and treat the solution with about thirty parts of bromine, at ordinary
temperature. Stir the mixture for about twenty four hours. The brotnine deriva-
tive separates out as a red powder. Filter, wash and dry. The product so obtained
appears to be a mixture of various highly brominated diamido-anthraquinones, it is
almost completely soluble in boiling nitro-benzene, and partly crystallises out on
cooling, yielding fine brown needles, which do not melt below three hundred degrees
Centigrade.
#
In the above example the corresponding quantity of sulphoacids of isomeric-
diamido-anthraquinones can be used, and, instead of biomine, chlorine can be em-
ployed It is also unnecessary to isolate the sulphoacids before treating them with
the halogens. If desired the solution of the sulphonation melt in water can be
emploved directly.
PRODUCTION OF BROWN DERIVATIVES OF 11 OR 1.3-DIAMIDO-ANTHRAQUI-
NONE.
Add a mixture of ten parts of 1-1-diamido-anthraquinone with ten parts of
anhydrous boracic acid to four hundred parts of fuming sulphuric acid (containing
20 per cent. free SO,). Heat the mixture at a temperature of one hundred and
fifteen degrees Centigrade until a test portion is practically completely soluble in
water. Cool the melt, pour it into ice water and add thirty parts of bromine whilst
constantly stirring. In twenty four hours the brom derivative will have separated
out. Collect, wash and dry. An analogous product is obtained when 1-3-diamido-
anthraquinone 18 employed in place of the 11-diamido-anthraquinone.
PRODUCTION OF A CHLOR DERIVATIVE OF 1-41-DIAMIDO-ANTHRAQUINONE.
Dissolve fifteen parts of 1.4-diamido-anthraquinone-di-sulpho-acid in two hundred
and fifty parts of concentrated hydrochloric acid (containing about 30 per cent H Cl),
and at ordinary temperature slowly add ten parts of potassium chlorate. When this
is finished stir well and gradually raise the temperature, finally heating for a long
time at the temperature of the boiling water bath or to boiling. The chlor derivative
which 18 formed separates out as a resu When cold, powder it, and wash with hot
water until the filtrate is colourless, or but slightly coloured. The residue is the raw
chlor-diamido-anthraquinone.
The following table indicates some of the properties of some of the bodies that
may be obtained in accordance with the foregoing Examples 1 to 3.

page_text: Appearance of
powder.
Solubility in
alcohol
and colour of
the solution.
Solubility in
glacial acetic
acid and
colour of the
solution.
Solubility in
benzene and
colour of the
solution.
Solubility in
nitro-benzene
and colour of
Colour of
solution in
concentrated
the solution. sulphuric acid.
On addition of
boracic acid
to the solution
in sulphuric
acid it
becomes

page_text: PRODUCTION OF HALOGEN
DERIVATIVES OF DI-ALPHYLIDO-ANTHRAQUINONES
DIALPHYLIDO-ANTHRAQUINONE SULPHOAOIDS AB INITIAL MATERIALS.
USING
Dissolve about fifty parts of 1-4-dianilido-anthraquinone sulpho-acid in fifteen
hundred parts of water at ordinary temperature. Stir well, and add one hundred and
fity parts of bromine. After a short time the clear red solution becomes turbid, and
the bromine derivative begins to separate out as a red precipitate. After about
twelve hours the separation is complete. Collect by filtering from the solution,
which is almost colourless, the brom-1-4'-dianilido-anthraquinone obtained. Wash
and dry.
It is not necessary to isolate the sulphoacids as their solutions, obtained by pouring
the sulphonation melt, in which they are produced, upon ice, can be directly treated
with the halogen used. This method of production is illustrated in the following
example.

page_text: Having now particularly described and ascertained the nature of this invention
and in what manner the same is to be performed, I declare that what I claim
18-
1. The manufacture of products suitable for use in the preparation of colouring
matters by treating diamido-anthraquinonesulphoacids or dialphylido-anthra-
quinone-sulpho-acids with chlorine or bromine, substantially as hereinbefore
described.
2. The manufacture of products suitable for use in the preparation of colouring
matters by treating diamido-anthraquinones or dialpbylido-anthraquinones with
fuming sulphuric acid and then with chlorine or bromine, substantially as herein-
before described.
3. The manufacture of products suitable for use in the preparation of colouring
matters, substantially as described in the several foregoing examples.
4. The products (suitable for use in the preparation of colouring matters) such as
can be obtained by treating diamido-anthraquinone-sulpho-acids or dialphylido-
anthraquinone-sulphoacids with chlorine, or bromine, substantially as hereinbefore
described.
5. The products (suitable for use in the preparation of colouring matters) such as
can be obtained by treating diamido-anthraquinones with fuming sulphuric acid
and then with chlorine, or bromine; substantially as hereinbefore described.
awu
LO SOLE
1000.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.