Improvements in the Manufacture and Production of Colouring. Matters of the Anthraquinone Series, and Intermediate Products relating thereto.
Year: 1899

page_text: Date of Application, 17th Apr., 1899
Complete Specification Left, 17th Jan., 1900-Accepted, 24th Feb., 1900
PROVISIONAL DIECITIGATION,
Improvements in the Manufacture and Production of Colouring.
Matters of the Anthraquinone Series, and Intermediate Products
relating thereto.
1, BENJAMIN WILLCOX, of 47, Lincoln's Inn Fields, in the County of London,
Patent Agent, 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,) to be as follows:-
If 1.4-diamido-anthraquinone be treated with bromine in the presence of glacial
acetic acid, or other suitable solvent, bromine derivatives thereof are obtained, and,
according to the energy with which the reaction be effected either di-, or tri-,
bromo derivatives result. These bromine derivatives constitute valuable initial
materials for the manufacture of colouring-matters. Thus, if the tri-bromo derivative
be treated with aromatic amines, colouring matters are obtained which, in the form
of their sulphoacids dye mordanted, and un-mordanted, animal fibre, giving bright
blue, to blue green, shades. The colourations thus obtained possess to a high degree
the properties of fastness against fulling and against the action of light. In the
production of these colouring matters the chlorine derivatives of diamido-anthra-
quinone which can be obtained by treating this body with an excess of chlorine in
the presence of a solvent can be employed.
The following examples will serve to further illustrate the nature of the invention,
but they are merely examples of the application of the invention to certain of the
materials to which it can be applied, and the invention is neither confined
to the use of these materials, nor to the conditions of working described in the

page_text: PRODUCTION OF COLOURING MATTER FROM TRI-BROM-DIAMIDO-
ANTHRAQUINONE AND ANILINE.
Mix together about ten parts of the tri-brom-derivative and about one hundred
parts of aniline. Heat the mixture slowly until it boils. The melt is at first red
but gradually and slowly changes to violet to violet blue and finally to a pure
blue. Continue heating until the colour of the melt remains unchanged. Allow the
nelt to cool down very slowly so that twenty four hours elapse before it reaches the
ordinary temperature and then let it stand a further twenty four hours. When
treated in this way the colouring matter separates out in steel blue crystals. Filter
wash with alcohol and dry.
PRODUCTION OF A COLOURING MATTER FROM TRI-BROM-DIAMIDO-ANTHRAQUINONE
AND PARA-TOLUIDINE.
Mix together about ten parts of the said tri-brom-derivative and one hundred parts
of para-toluidine. Melt the mixture and heat it until it boils. Similar changes of
colour are observed to those described in Example 1 and the further treatment is the
same but the working up of the cold melt has to be effected in a different way.
Powder the solidified melt roughly and boil it up with alcohol. The steel blue
crystals of the colouring matter remain undissolved and can be separated in this way
from para-toluidine.
PRODUCTION OF COLOURING MATTER FROM TRI-BROM-DIAMIDO ANTHRAQUINONE
AND PARA-PHENYLENE DIAMINE.
Mix together ten parts of the tri-brom derivative and one hundred parts of para-
phenylene-diamine and heat the mixture to a temperature of from 180-195°
Centigrade. Continue heating until a test portion of the melt dissolves in hot
alcohol giving a pure blue solution. When this point is reached run the melt into
one thousand litres of alcohol stirring well all the time. Boil the mixture and then
allow it to cool. The colouring-matter crystallises out and can be separated by
filtration from the alcoholic solution of para-phenylene-diamine. In the same way
colouring-matters can be obtained using other aromatic amines as instances of which
I mention ortho-toluidine benzidine alpha and beta-napthylamine.
In the above examples I have described the production of colouring matters from
the tri-brom-derivative but colouring matters can also be obtained from the di-brom-
derivative but ny foreign correspondents have discovered that this cannot be effected
by merely beating them with the aromatic amines in open vessels but in order to
obtain good results the reaction must be effected by heating under pressure.
The sulphonation of the colouring-matters can be effected by treating them with
the ordinary sulphonating agents such as concentrated sulphuric acid fuming
sulphuric acid chlor-hydrine-sulphuric acid mixtures of sulphuric acid with boracic
or meta-phosphoric acid with or without the addition of kieselguhr or the like. The
following examples will illustrate the sulphonation :-

page_text: toluidine, benzidine, aipua- and beta-napnenylamine,
EXAMPLE 8.
PRODUCTION OF COlouring matter FROM THE PRODUCT A of Example 3 AND
PARA-TOLUIDINE.
"Mix ten parts of Product A with one hundred parts of para-toluidine and heat the
mixture to the boiling point of the latter maintaining it at this temperature until the
melt, which is at. first red, and later blue-green, does not further change colour.
Allow the melt to cool and extract it by means of alcohol. The colouring-matter
remains behind in the form of indigo-like crystals which are with difficulty soluble.
in alcohol but are more easily soluble in benzene and aniline the solution being blue
and in nitro-benzene the solution being green-blue. Its solution in cold sulphuric
acid (containing about 96 per cent. H₂SO) is of an olive-green colour, which, on
warming to one hundred degrees Centigrade changes to violet, and on addition of
boracic acid, at this temperature, becomes green.
The conditions of working can of course be varied, for instance, by adding a
condensation agent such as para-toluidine hydrochloride to the melt, or by employing
a diluent such as naphthalene.
The corresponding chlorination product from raw diamido-anthraquinone (which
bas been obtained by reduction of the mixture of isomeric dinitro-anthraquinones,'
such as results when anthraquinone is directly nitrated) cannot be employed instead
of Product A, and other aromatic amines may be substituted for para-toluidine,
colouring matters of similar properties being formed.
The sulphonation of the colouring-matters can be effected by treating them with
the ordinary sulphonating agents, such as concentrated sulphuric acid, fuming
sulphuric acid, chlor-hydrine sulphuric acid or mixtures of sulphuric acid with boracic,
or meta-phosphoric, acid, with, or without, the addition of kieselguhr, or the
like.
Mix about ten parts of the said product with two hundred parts of concentrated
sulphuric acid, (containing about 96 per cent. H2SO4) at ordinary temperature, and
Then pour
stir the mixture, without heating, until a sample is soluble in hot water.
the melt into water. A sulphoacid, which is with difficulty soluble in cold dilute
acid, in large measure separates out. Add common salt, or chloride of potash, to
complete the precipitation. Filter and dry. In the same way sulphoacids can be