The Manufacture of New Dyestuffs Derived from Anthracene and Anthraquinone.
Year: 1891

page_text: Date of Application, 2nd Feb., 1891
Complete Specification Left, 10th Oct., 1891-Accepted, 14th Nov., 1891
PROVISIONAL SPECIFICATION.
The Manufacture of New Dyestuffs Derived from Anthracene and
Anthraquinone.
I, BENJAMIN WILLCOX of 47 Lincoln's Inn Fields in the County of Middlesex,
Patent Agent, do hereby declare the nature of this invention (which has been
communicated to me from abroad by Farbenfabriken vormals Friedrich Bayer
& Co. of Elberfeld in the Empire of Germany) to be as follows:-
:-
My foreign correspondents have now discovered that by employing dichloro or
dibromo anthracene in substitution for the anthraquinone employed in the process
described in the Provisional Specification accompanying my application for Letters
Patent dated 19th November 1890 No. 18729 new dyestuffs are produced of a
similar character to those obtained according to the said Specification. In this
new process it is likewise of importance to employ pure concentrated sulphuric
acid anhydride. When the anhydride is allowed to act at a moderate temperature
mordant dyeing neutral sulphuric acid ethers of colouring matters soluble with
difficulty in water are obtained which can be converted by the known process into
the colouring matter itself. At higher temperatures on the other hand there is
obtained water soluble sulphuric acid ether of sulpho acids of the dyestuff. By
splitting off the sulpho groups according to known methods the latter may be
converted into the unsulphurised colouring matter. The method of manufacturing
these substances is similar to that described in the aforesaid Provisional
Specification No. 18729*0.
In the Provisional Specification accompanying my application for Letters
Patent dated 4th November 1890 No. 17712 I have described certain new colouring
matters which result from the action of ammonia upon the intermediate product
formed in the process of oxidising alizarine-flavo purpurine and anthra purpurine
Bordeaux into the corresponding cyanines. By the action of sulphurising agents
such as sulphuric acid, fuming sulphuric acid sulphuric acid chlorhydrin and the
like these colouring matters can be smoothly converted into sulpho acids which as
well as the alizarine Bordeaux, and alizarine cyanine sulpho acids dye mordanted
wool with considerably brighter and clearer tones than do the unsulphurized
colouring matters the colours produced being also remarkably fast to fulling.
In manufacturing the sulpho acid of a colouring matter obtained according to
the said Provisional Specification No. 17712 and known by the name of "Alizarine
cyanine G the process is conducted as follows for example.
About 10 parts by weight of dry and ground "Alizarine cyanine G" and 10 parts
by weight of fuming sulphuric acid containing about 20 per cent. of anhydride are
heated to about 100 degrees Centigrade until a test portion taken from the mixture
dissolves in water so as to form a clear solution. The melt is then poured out into
600 parts of water and the dyestuff being separated in the form of an acid soda
salt by means of common salt is filtered pressed and dried.
The colouring matter or dyestuff thus obtained is in the condition of a violet
black powder which dissolves readily in water with a blue violet colour. By the
addition of a large quantity of concentrated hydrochloric acid the color is caused
to change to an onion red but reverts to violet when diluted with water. Ammonia
turns the solution blue and soda lye gives it a greenish blue color. In concentrated
sulphuric acid the solution is of a brown red color.
On wool mordanted with alumina the colouring matter produces pure blue shades
of great beauty presenting a greener tinge than those obtained with the unsul-
phurised dyes. With chromium mordants a beautiful green blue is obtained.
Similar colouring matters are obtained by sulphurising the produc's analogous to

page_text: the "Alizarine cyanine G" and obtained from flavo- and anthra-purpurine
Bordeaux.
Those colouring matters also which result from the action of ammonia upon
the sulphuric acid ether of alizarine Bordeaux and of its analogues and which I
have described in the Provisional Specification accompanying my application for
a Patent dated 13th August 1890 No. 12715 can be readily converted into sulpho
acids. The process is conducted in a similar manner to that herein before described.
The colouring matter in question is heated to 100 degrees Centigrade with three
times its weight of fuming sulphuric acid containing 20 per cent. of anhydride until
it becomes soluble in water. The melt is poured out into water and the resulting
sulpho acid salted out preferably with an alkaline chloride such as chloride of
potassium. The product thus obtained from the ammonia derivative of alizarine
Bordeaux sulphuric acid ether dissolves in water with a yellowish brown colour
and with a fuchsine red colour in concentrated sulphuric acid. The solutions in
alkali as well as the colours produced upon mordanted wool are bluer than those
obtained with alizarine Bordeaux sulpho acids.
The sulpho acids of the products obtained from the sulphuric acid ethers of
purpurine Bordeaux, flavo purpurine Bordeaux and anthra purpurine Bordeaux
by the action of ammonia possess similar properties to the alizarine derivatives
hereinbefore described.
Don of Wal 1901
COMPLETE SPECIFICATION.
The Manufacture of New Dyestuffs Derived from Anthracene and
Anthraquinone.
I BENJAMIN WILLCOX of 47 Lincoln's Inn Fields in the County of Middlesex,
Patent Agent, do hereby declare the nature of this invention which has been
communicated to me from abroad by the Farbenfabriken vormals Friedrich Bayer
& Co. of Elberfeld 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, by employing dichloro- or
dibromo-anthracene in place of the anthraquinone employed in the process described
in the Specification of my application for Letters Patent dated 19th November 1890
No. 18,729, new dyestuffs are produced of a similar character to those obtained on
operating according to the said Specification. In this new process as in that
described in the aforesaid Specification sulphuric anhydride should be employed
in as concentrated a form as possible and preferably in a pure state.
If the anhydride be allowed to act at a moderate temperature neutral sulphuric
ethers of colouring matters are obtained. These ethers are capable of dyeing with
the aid of mordants.and can be converted into colouring matters, which dissolve
with difficulty in water, by heating them with acids or by boiling their alkaline
solutions with acids. The method of manufacturing these substances is similar to
that described in the aforesaid Specification of the application for Patent No. 18,729
of 1890.
In the Specification of my application for Letters Patent dated 4th Novem-
ber 1890 No. 17,712 certain new colouring matters are described which result from
the action of ammonia on the intermediate product formed when alizariu-bordeaux,
flavopurpuriu-bordeaux, and anthra-purpurin-bordeaux are converted by oxidation
into the corresponding cyanines.
By the action of sulphonating agents such as sulphuric acid, fuming sulphuric
acid, sulphuric chlorhydrin, and the like, these colouring matters can easily be
converted into sulphc-acids which, like alizarin-bordeaux and alizarin-cyanine

page_text: sulpho-acids, produce, on mordanted wool, considerably brighter and clearer shades
than do the unsulphonated colouring matters, and the colours withstand fulling
remarkably well.
In manufacturing the sulpho-acid of a colouring matter obtained according to the
said Specification of the application for Patent No. 17,712 of 1890 and known by
the name of "Alizarin-cyanine G" the process is conducted as follows, for
example: The parts are by weight.
About 10 parts of dry and powdered "Alizarin-cyanine G" and 30 parts of
fuming sulphuric acid (containing about 20 per cent. of anhydride) are heated to
about 100 degrees Centigrade until a test portion of the mixture dissolves in water
forming a clear solution. The melt is then poured into 600 parts of water and the
separation of the dyestuff is effected by means of common salt in the form
of an acid sodium-salt. The dyestuff thus precipitated is filtered off, pressed,
and dried.
The colouring matter or dyestuff is thus obtained in the form of a violet-
black powder which readily dissolves in water with a blucish-violet colour; on
adding a large quantity of concentrated hydrochloric acid the colour of the liquid
is changed to an onion-red which again becomes violet when the solution is diluted
with water. Ammonia turns the solution blue and soda-lye gives it a greenish-
blue colour. The solution of the dyestuff in concentrated sulphuric acid is of a
brown-red colour.
On wool mordanted with alumina the colouring matter produces pure blue shades
of great beauty of a greener tinge than the shades produced by the unsulphonated
dyes. By the use of chromium mordants a beautiful green-blue is obtained.
Similar colouring matters result on sulphonating the products analogous to the
Alizarin-cyanine G" obtained from flavo-purpurin-bordeaux and anthra-purpurin-
bordeaux.
The colouring matters which are formed by the action of ammonia on the
sulphuric ethers of the Bordeauxs obtained from alizarin purpurin, flavo- and
anthra-purpurin, and which are described in the Specification of Letters Patent
No. 12715 dated 13th August 1890 can be readily converted into sulpho acids.
The process is conducted in a manner similar to that hereinbefore described. The
colouring matter is heated to 100 degrees Centigrade with three times its weight
of fuming sulphuric acid (containing 20 per cent. of anhydride) until it becomes
soluble in water. The melt is poured out into water and the resulting sulpho acid
is salted out preferably with an alkaline chloride such as chloride of potassium for
example. The product thus obtained from the ammonia derivative of alizarin
bordeaux sulphuric ether dissolves in water with a yellowish-brown colour and with
a magenta red colour in concentrated sulphuric acid. The solutions in alkali as
well as the colours produced upon mordanted wool are bluer than are those obtained
with alizarin bordeaux sulpho-acids.
The sulpho-acids of the products obtained from the sulphuric ethers of purpurin-
bordeaux, flavo-purpurin bordeaux, and anthra-purpurin bordeaux by the action
of ammonia possess properties similar to the alizarin derivatives hereinbefore
described.
Having now particularly described and ascertained the nature of the said inven-
tion and the manner in which the same is to be performed I declare that what I
claim is.-
1) The production of sulphuric ethers of new alizarin dye-stuffs by the action
of very concentrated sulphuric anhydride upon dichloro- and dibromo-anthracene.
2) The conversion of the sulphuric ethers, resulting from the action of sulphuric
anhydride on dichloro- and dibromo-anthracene, into the corresponding dyestuffs by
heating the said ethers with acids or by boiling the alkaline solutions of the ethers
with acids.
3) The conversion of the colouring matters obtained by the action of ammonia

page_text: on the intermediate products resulting when alizarin-bordeaux, anthra-purpurin-
bordeaux, or flavo-purpurin-bordeaux, are oxidised into their cyanines as described
in the Specification of the application for Letters Patent No. 17712 of 1890 into
sulpho acids by treating the said colouring matters with sulphonating agents at
moderately elevated temperatures.
4) The manufacture of sulpho acids from the colouring matters which are
obtained according to the Specification of Letters Patent No. 12715 of 1890 by
acting with ammonia on the sulphuric ethers of alizarin-bordeaux, purpurin-
bordeaux, flavo-purpurin-bordeaux, and anthra-purpurin-bordeaux by the treatment
of the said colouring matters with sulphonating agents preferably with fuming
sulphuric acid at moderately elevated temperatures.
Dated this 10th day of October 1891.
J. H. JOHNSON & Co.,
Agents for the Applicant.