The Manufacture and Production of Azo-Colouring Matters and Materials for Use therefor.
Year: 1898

page_text: PROVISIONAL SPECIFICATION.
The Manufacture and Production of Azo-Colouring Matters and
Materials for Use therefor.
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,) to be as follows:-
==
This invention consists in the manufacture and production of secondary disazo-
dyes from a certain nitro-amido-phenol-sulpho acid; a so-called middle component
(that is, an amido body capable of combining with the diazo-compound to yield an
intermediate product capable of renewed diazotising and combination with a further
component) with the addition of such a further component, which must be
one, known
to be capable of use in the ordinary way as an end-component in the manufacture of
azo-dyes.
The nitro-amido-phenol-sulpho acid which is used in this invention, has been
described in the Specification of the German Letters Patent No. 93443 and the following
constitution has been attributed to it :-
My foreign correspondents have now discovered a new process for the manufacture
of this nitro-amido-phenol-sulpho acid. This consists in first suitably treating phenol-
para-sulpho-acid with nitric acid whereby a dinitro-phenol-sulpho acid is obtained and
then partially reducing this sulpho acid by means of alkaline sulphides or other
alkaline or acid reducing agents.
Although the constitution of the nitro-amido-phenol-sulpho-acid has been cited,
this must not be understood to imply the impossibility of isomeric bodies being
present.
The monoazo dyes which have been prepared hitherto from this nitro-amido-phenol-
sulpho acid do not withstand the action of even dilute acids and are therefore of no
practical value.
If however the nitro-amido-phenol-sulpho acid be combined with alpha-
naphthylamine for example or an analogous middle component, and the intermediate
product so obtained be again diazotised and the diazo compound combined with suitable
further components, then the new disazo-colouring matters obtained are not merely
free from the aforesaid disadvantage but possess in addition further valuable properties
including great strength of colouring power and excellent fastness to light.

page_text: Another importaut quality found in most of the new colouring matters consists in
the fact discovered by my foreign correspondents, that if goods dyed with these new
colouring matters be treated with chromates a more greenish shade results and the
colour becomes extraordinarily fast to fulling.
As instances of the new colouring matters some of them are mentioned in the 5
following table giving also their properties and shades.

page_text: sulphonation mass to cool and pour it into one hundred parts of water; next add about
forty parts of nitric acid (containing about sixty two per cent. HNO,). Heat the
mixture to boiling and maintain it at this temperature until a test portion on cooling
begins to deposit crystals of dinitro phenol. Theu interrupt the operation and allow
the mixture to cool at once.
Filter from this dinitro-phenol, which separates out and treat the filtrate with about
ten parts of carbonate of potash. The potassium salt of the dinitro-phenol-sulpho-acid
separates out in yellow crystals.
For the partial reduction of this compound dissolve thirty parts thereof in about
three hundred parts of hot water and add about two hundred parts of ammonium
sulphide. The reduction proceeds accompanied by a slight spontaneous rise in
temperature and is usually complete after about two or three hours. The nitro-amido-
phenol sulpho acid formed can be precipitated as free acid by the addition of hydro-
chloric acid or by adding potassium chloride; after acidifying with acetic acid it can
be precipitated as potassium salt.
The potassium salt is but slightly soluble in cold water and more soluble in hot
water; the solution is brownish yellow in colour and on cooling the salt separates out
in the form of brown crystals. By the addition of mineral acids to the solution the
free acid can be precipitated in the form of crystals, which are usually of a pale grey-
brown colour.
The diazo compound is readily soluble in water; its aqueous solution possesses a
deep yellow colour.
EXAMPLE 2.
THE PRODUCTION OF THE INTERMEDIATE COMPOUND WITH ALPHA-NAPHTHYLAMINE.
Dissolve about twenty three and a half parts of nitro-amido-phenol-sulpho-acid in
about five hundred parts of water and diazotise by treatment with about fifteen parts
of hydrochloric acid (containing about thirty per cent. HCI) and about seven parts of
sodium nitrite at the ordinary temperature. Pour the diazo solution into a solution
of about fifty parts of alpha naphthylamine in six hundred parts of water and fifteen
parts of hydrochloric acid (containing about thirty per cent. HCl). Stir at a
temperature of about from thirty five to seventy five degrees Centigrade, till a test
portion on filter paper gives no reaction of diazo compound. This usually requires
from ten to twenty four hours, the time depending principally upon the temperature
maintained. Filter the intermediate colouring matter obtained and wash with cold
water.
PRODUCTION OF A NEW COLOURING MATTER WITH BETA NAPHTHOL-DISULPHO
ACID R AS END COMPONENT.
Dissolve the intermediate colouring matter obtained as described in the aforesaid
Example 2 in about two thousand five hundred parts of boiling water, to which about
seventeen parts of caustic soda lye (containing about thirty five per cent. NaOH) are
added. Allow the solution to cool, and add seven and a half parts of sodium nitrite
in the form of a concentrated solution. Pour this mixture into a dilute solution of
sulphuric acid containing about two hundred parts of ice, thirty parts sulphuric acid
(containing about ninety five per cent. H₂, SO) and ninety parts of water. Stir whilst
mixing and subsequently a precipitate separates out, which is at first dark in colour
and gradually becomes brown. Filter, stir with cold water and pour into a solution
of about thirty five parts beta-naphthol-sulpho acid R, which is rendered alkaline with
carbonate of soda. The formation of colouring matter is soon completed.
Add common salt to complete the precipitation of the colouring matter and filter
and press.
Purify if necessary, by redissolving and reprecipitating.
If desired the combination can be effected without first collecting the diazo
Couround by filtration

page_text: The production of colouring matters with other end-components is effected in a
similar manner; when alpha-naphthylamine is used as end-component, it is of course
desirable to effect the combination in weakly acid solution and the colouring matter
formed is subsequently converted into its sodium salt.
1000
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of Azo-Colouring Matters and
Materials for Use therefor.
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,) 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 secondary disazo dyes
from a certain nitro-amido-phenol-sulpho acid certain middle components (that is,
amido bodies capable of combining with the diazo compound to yield an intermediate
product capable of renewed diazotising and combination with a further component)
and certain further components, which must be such as are known to be capable of
use in the ordinary way as end components in the manufacture of azo-dyes.
The nitro-amido-phenol-sulpho-acid which is used in this invention has been
described in the Specification of the German Letters Patent No. 93443 and the
following constitution has been attributed to it :-
My foreign correspondents have now discovered a new process for the manufacture
of this ortho-nitro-ortho-amido-phenol-para-sulpho acid. This consists in first suitably
treating phenol para sulpho acid with nitric acid, whereby a dinitro-phenol-sulpho
acid is obtained, and then partially reducing this sulpho acid by means of alkaline
sulphides, or other alkaline, or acid, reducing agents."
Although the constitution of the nitro-amido-phenol-sulpho acid has been cited,
this must not be understood to imply the impossibility of isomeric bodies being
present.
The mono-azo dyes, which have been prepared hitherto from this ortho-nitro-ortho-
amido-phenol-para-sulpho-acid, do not withstand the action of even dilute acids and
are therefore of no practical value.
If however, the said nitro-amido-phenol-sulpho acid be combined with alpha-
naphthylamine, or the alpha-naphthylamine 2- or 3-sulpho acids whether pure or
mixed with one another, and the intermediate product, so obtained be again diazo-
tised, and the diazo compound combined with suitable further components, hereinafter
set forth, then the new disazo colouring-matters obtained are not merely free from
the aforesaid disadvantage, but possess, in addition further valuable properties
including great strength of colouring power and excellent fastness against the action
of light.

page_text: The said alpha-naphthylamine 21- and 3'-sulpho acids are known as Cleve's acid and
are so hereinafter referred to.
Auother important quality, found in most of the new colouring matters, consists in
the fact, discovered by my foreign correspondents, that if goods dyed with these new
colouring matters be treated with chromates a more greenish shade results and the
colour becomes extraordinarily fast to fulling.
As instances of the new colouring matters some of them are mentioned in the
following table giving also their properties and shades.

page_text: the parts are of eig
EXAMPLE 1.
PRODUCTION OF ORTHO-NITRO-ORTHO-AMIDO-PHENOL-PARA-SULPHO-ACID.
Convert about ten parts of phenol into phenol-para-sulpho-acid in the usual way
by warming with about thirteen parts of concentrated sulphuric acid. Allow the
sulphonation mass to cool and pour it into one hundred parts of water; next add
about forty parts of nitric acid (containing about sixty two per cent. HNO,). Heat
the mixture to boiling and maintain it at this temperature until a test portion on
cooling begins to deposit crystals of dinitrophenol. Then interrupt the operation
and at once allow the inixture to cool.
Filter from this dinitro-phenol, which separates out, and treat the filtrate with
about ten parts of carbonate of potash. The potassium salt of the dinitro-phenol-
sulpho-acid separates out in yellow crystals.
For the partial reduction of this compound dissolve thirty parts thereof in about
three hundred parts of hot water and, after cooling, add about two hundred parts of
ammonium sulphide. The reduction proceeds, accompanied by a slight spontaneous
rise in temperature and is usually complete in about two, or three, hours. The nitro-
amido-phenol-sulpho-acid formed can be precipitated as free acid by the addition of
hydrochloric acid, or by adding potassium chloride: after acidifying with acetic acid
it can be precipitated as potassium salt.
The potassium salt is but slightly soluble in cold water but is more soluble in hot
water the solution is brownish-yellow and, on cooling, the salt separates out in the
form of brown crystals. By the addition of mineral acids to the solution the free
acid can be precipitated in the form of crystals, which are usually of a pale grey-
brown.
The diazo compound is readily soluble in water, its aqueous solution is a deep
yellow.
EXAMPLE 2.
THE PRODUCTION OF THE INTERMEDIATE COMPOUND WITH ALPHA-NAPHTHYLAMINE.
Dissolve about twenty three and a half parts of the aforesaid nitro-amido-phenol-
sulpho-acid in about five hundred parts of water and diazotise by treatment with about
fifteen parts of hydrochloric acid (containing about thirty per cent. HCl) and about
seven parts of sodium nitrite at the ordinary temperature. Pour the diazo solution
into a solution of about fifteen parts of alpha-naphthylamine in six hundred parts of
water and fifteen parts of hydrochloric acid (containing about thirty per cent. HCI).
Stir at a temperature of about thirty five degrees Centigrade, till a test portion on
filter paper gives no reaction of diazo compound. This usually requires from ten to
twenty four hours, the time depending principally upon the temperature maintained.
Filter the intermediate colouring matter obtained and wash with cold water.
EXAMPLE 3.
PRODUCTION OF A NEW COLOURING-MATTER WITH BETA-NAPHTHOL-DISULPHO ACID RAS
END COMPONENT.
Dissolve the intermediate colouring-matter, obtained as described in the aforesaid
Example 2, in about two thousand five hundred parts of boiling water to which about
seventeen parts of caustic soda lye (containing about thirty-five per cent. NaOH) are
added. Allow the solution to cool, and add seven and a half parts of sodium nitrite

page_text: in the form of a concentrated solution. Pour this mixture into a dilute solution of
sulphuric acid containing about two hundred parts of ice, thirty parts sulphuric acid
(containing about ninety five per cent. H₂SO) and ninety parts of water. Stir whilst
mixing and subsequently a precipitate separates out, which is at first of a dark colour
and gradually becomes brown. Filter, stir with cold water, and pour into a solution
of about thirty-five parts of beta-naphthol-di-sulpho acid R, which is rendered alkaline
with carbonate of soda. The formation of colouring matter is soon completed. Add
common salt to complete the precipitation of the colouring-matter and filter and
press.
Purify, if necessary, by redissolving and reprecipitating.
If desired the combination can be effected without first collecting the diazo com-
pound by filtration.
The production of colouring-matters with the other end components is effected in
a similar manner. When alpha-naphthylamine or similar base is used as end com-
ponent, it is of course desirable to effect the combination in weakly acid solution and
the colouring matter formed is subsequently converted into its sodium salt.
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. Process for the production of ortho-nitro-ortho-amido-phenol-para-sulpho acid
which consists in nitrating phenol-para-sulpho acid so as to obtain dinitro-phenol-
para-sulpho acid, and partially reducing this body, all substantially as herein before
described.
2. The manufacture of disazo colouring matters from ortho-nitro-ortho-amido-
phenol-para-sulpho acid, and a middle and an end component herein before defined, all
substantially as herein before described.
3. The manufacture of ortho-nitro-ortho-amido-phenol-para-sulpho acid and of
disazo colouring matters therefrom substantially as herein before described in the
foregoing examples.
4. As new articles of manufacture the new disazo colouring matters such as can be
obtained, substantially as hereinbefore described.
Dated this 24th day of March 1899.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.