Improvements in the Manufacture and Production of Disazo Colouring-matters.
Year: 1898

page_text: Date of Application, 12th Dec., 1898
Complete Specification Left, 12th Sept., 1899-Accepted, 14th Oct., 1899
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture and Production of Disazo
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 by The Badische Anilin & Soda Fabrik, of Ludwigshafen-on-Rhine,
in the German Empire,) to be as follows:-
My foreign correspondents have already invented the manufacture of a new series
of disazo colouring-matters obtained from nitro-amido-phenol-sulphoacids, a middle
component such as alpha-naphthylamine, and certain sulphoacids thereof, and an
end component.
The present invention relates to the production of analogous colouring-matters
from nitro-amido-phenols. As instances of the nitro-amido-phenols which can be
used in carrying this invention into effect I mention the ortho-amido-para-nitro-
phenol described by Stuckenberg (Annalen, vol. 205, page 72) and para-amido-ortho-
nitro-phenol described by Huebner (Annalen, vol. 210 page 381). Both these nitro-
amido-phenols can be readily diazotised by treatment with hydrochloric acid and nitrite
of soda. The diazo compounds obtained are with difficulty soluble and separate partly
from the solution.
As middle components in the manufacture of the new class of disazo dyes my
foreign correspondents use alpha-naphthylamine and the Cleve's sulphoacids of
alpha-naphthylamine, 1.6 or 1.7, or admixtures thereof, hereinafter termed Cleve's
acid, but other components, which, on combination with diazo compounds, yield an
amido-azo compound that can be readily diazotised, can also be used.
The intermediate products obtained with alpha-naphthylamine, or its sulphoacids
mentioned, separate from the combination liquid as but slightly soluble powders
having a green sheen. They are soluble in dilute caustic soda solution and also in
carbonate of soda solution, and can be readily diazotised further, and then be
combined with a further proportion of an end component to yield the secondary
disazo-dyes. As end components which are particularly adapted for use in this
invention, I mention the following, but the invention is not restricted to the use of
those mentioned:
-
2-naphthol-3.6-di-sulphoacid; 1 naphthol-4-sulphoacid; 1-naphthol-5-sulphoacid;
alpha-naphthylamine; 1.8-dioxy-naphthalene-4-sulphoacid, and the like.
The following examples further illustrate the nature of this invention which is not
confined to these examples. The parts are by weight.
EXAMPLE 1.
PRODUCTION OF A COLOURING-MATTER FROM ORTHO-AMIDO-PARA-NITRO-PHENOL AND
ALPHA-NAPHTHYLAMINE AND R-SALT.
Dissolve about one hundred and fifty-four parts of ortho-amido-para-nitro-phenol
in three hundred parts of hydrochloric acid, (containing about 30 per cent. real HCI),
diluted with five thousand parts of water, and diazotise by adding a concentrated
0 solution of sixy nine parts of sodium nitrite. The diazo compounds very soon

page_text: separate out in the form of yellow-brown crystals. Pour the whole into a solution of
about one hundred and fifty parts of alpha-naphthylamine in one hundred and fifty
parts of hydrochloric acid, (containing about 30 per cent. real HCI), and five thousand
parts of water. Stir the mixed solution whilst raising the temperature to fron 35
to 40 degrees Centigrade. Continue stirring at this temperature for about ten hours.
The intermediate product, which possesses a metallic lustre, separates out gradually
but completely. Filter and wash with water.
Next dissolve about three hundred and eight parts of the intermediate colouring-
matter, obtained as hereinbefore described, in about twenty-three thousand parts of
hot water, containing about one hundred and seventy parts of caustic soda lye
(containing 35 per cent. real NaOH).
Cool the solution, and add a concentrated solution of seventy five parts of sodium
nitrite, and pour this mixture into one thousand five hundred parts of water, acidified
with five hundred parts of hydrochloric acid, (containing about 30 per cent. real H.CI.).
When the diazotation is entirely completed, run the mixture into an alkaline solution
of about three hundred and fifty parts of R-salt, in alkaline solution. Precipitate the
colouring-matter by means of common salt and purify, if necessary, by re-dissolving
and re-precipitating.
In a similar way the new colouring-matters can be obtained from this nitro-ainido-
phenol with alpha-naphthylamine or Cleve's acids, and, for instance, alpha-naphthyl-
amine, or alpha-naphthol-alpha-sulphoacid as end components.
The following table gives a few instances of colouring matters obtained from ortho-
amido-para-nitro-phenol according to this invention :-

page_text: PRODUCTION OF DISAZO COLOURING-MATTER FROM PARA AMIDO-ORTHO-NITRO-PHENOL
AND CLEVE'S ACID AND ALPHA-NAPHTHYLAMINE.
Dissolve about one hundred and fifty-four parts of para-amido-ortho-nitro-phenol
in about four thousand five hundred parts of water, to which one hundred and twenty
parts of caustic soda lye (containing about 35 per cent. Na.O.H) have been added.
Treat this solution with about four hundred and fifty parts of concentrated hydro-
chloric acid, (containing about 30 per cent. real H.Cl) and then diazotise by the
addition of a concentrated solution of seventy parts of sodium nitrite.
The diazotising is completed after a short time, and a considerable portion of the
diazo compound separates out as yellow-brown crystalline powder.
Add the whole to a solution of about two hundred and fifty parts of the sodium salt
of Cleve's acid, and stir the mixture thus obtained for about ten hours, whilst main-
taining the temperature at from 30 to 45 degrees Centigrade. The colouring-matter
formed separates out as a black crystalline powder, having a greenish lustre. It is
practically insoluble in cold water.
Dissolve about three hundred and eighty-eight parts of this intermediate colouring-
matter in about twelve thousand parts of boiling water, to which fifty-three parts of
sodium carbonate have been added. Allow the solution to cool, and add about seventy-
five parts of sodium nitrite in the form of concentrated solution. Stir the mixture
and allow it to run, drop by drop, into five hundred parts of hydrochloric acid diluted
with about one thousand parts of water. Stir whilst mixing. Pour the diazo
compound so obtained, into a solution of about one hundred and fifty parts of alpha-
naphthylamine in about six thousand parts of water, to which one hundred and fifty
parts of hydrochloric acid, (containing about 30 per cent. HCl) have been added. Stir
for about six hours at the ordinary temperature, and then heat t a temperature of
about 30 degrees Centigrade till the reaction is completed. Allow the mass to cool,
collect the colouring-matter in the filter, press and dry.
Instead of alpha-naphthylamine as end-component, other end components can be
used, as herein before indicated, and the middle components also may be varied.
The following table indicates the properties of some of the colouring-matters that
can be obtained in accordance with this invention from para-amido-ortho-nitro-
phenol :―

page_text: Improvements in the Manufacture and Production of Disazo
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 :—
My foreign correspondents have already invented the manufacture of a new series
of disazo colouring matters obtained from nitro-amido-phenol sulphoacids, a middle
component such as alpha-naphthylamine, and certain sulphoacids thereof and an end
component.
The present invention relates to the production of analogous colouring matters from
nitro-ainido-phenols. The nitro-amido-phenols which can be used in carrying this
invention into effect are the ortho-amido-para-nitro-phenol described by Stuckenberg
(Annalen, vol. 205, page 75) and para-amido-ortho-nitro-phenol described by Huebner,
(Annalen, vol. 210, page 381). Both these nitro-amido-phenols can be readily
The diazo
diazotised by treatment with hydrochloric acid and nitrite of soda.
compounds obtained are soluble with difficulty and separate partly from the solution.
As middle components in the manufacture of the new class of disazo colouring matters
my foreign correspondents use alpha-naphthylamine and the Cleve's sulphoacids of alpha-
naphthylamine, 1.6 or 1.7, or admixtures thereof (hereinafter termed "Cleve's acid)
but such other components which, on combination with diazo compounds, yield an
amido-azo compound that can be readily diazotised, and are therefore usable in the
manufacture of disazo dyes, can also be employed.
The intermediate products obtained with alpha-naphthylamine, or its sulphoacids
mentioned, separate from the combination liquid as but slightly soluble powders
having a green sheen. They are soluble in dilute caustic soda solution and also in
carbonate of soda solution, and can be readily further diazotised and then be combined
with a further proportion of an end component to yield the secondary disazo dyes.
As end components which are particularly adapted for use in this invention I mention
the following: 2-naphthol-3.6-di-sulphoacid: 1-naphthol-4-sulphoacid: 1 naphthol-5-
sulphoacid alpha-naphthylamine: 1-8-dioxy-naphthalene-4-sulphoacid and the like,
but the invention is not restricted to the use of the end components mentioned, as
any end component usable in the manufacture of disazo-dyes can also be employed in
this invention.
The following examples further illustrate the nature of this invention and the
manner in which it can be performed but it is not limited to these examples. The
parts are by weight.
EXAMPLE I.
PRODUCTION OF A COLOURING MATTER FROM ORTHO-AMIDO-PARA-NITRO-PHENOL AND
ALPHA-NAPHTHYLAMINE AND R-SALT.
Dissolve about one hundred and fifty four parts of ortho-amido-para-nitro-phenol
in three hundred parts of hydrochloric acid (containing about 30 per cent. real HCI.)
diluted with five thousand parts of water, and diazotise by adding a concentrated
solution of sixty-nine parts of sodium nitrite. The diazo compounds very soon
separate out in the form of yellow brown crystals. Pour the whole into a solution of
about one hundred and fifty parts of alpha-naphthylamine in one hundred and fifty

page_text: parts of hydrochloric acid, (containing about 30 per cent. real HCl.), and five thousand
parts of water. Stir the mixed solution whilst raising the temperature to from 35 to
40 degrees Centigrade. Continue stirring at this temperature for about ten hours.
The intermediate product, which possesses a metallic lustre, separates out gradually
but completely. Filter and wash with water.
Next dissolve about three hundred and eight parts of the intermediate colouring
matter, obtained as hereinbefore described, in about twenty-three thousand parts of
hot water containing about one hundred and seventy parts of caustic soda lye (con-
taining 35 per cent. real NaOH).
Cool the solution, and add a concentrated solution of seventy-five parts of sodium
nitrite, and pour this mixture into one thousand five hundred parts of water, acidified
with five hundred parts of hydrochloric acid (containing about 30 per cent, real HCI.).
When the diazotation is entirely completed, run the mixture into an alkaline solution
of about three hundred and fifty parts of R-salt, in alkaline solution. Precipitate
the colouring matter by means of common salt, and purify, if necessary, by redissolv-
ing and re-precipitating.
In a similar way the new colouring matters can be obtained from this nitro-amido-
phenol with alpha-naphthylamine or Cleve's acids, and, for instance, alpha-naphthyl-
amine, or alpha-naphthol-alpha-sulphoacid as end components.
The following table gives a few instances of colouring matters obtained from ortho-
amido-para-nitro-phenol according to this invention

page_text: EXAMPLE 2.
PRODUCTION OF DISAZO COLOURING-MATTER FROM PARA AMIDO-ORTHO-NITRO-PHENOL
AND CLEVE'S ACID AND ALPHA NAPHTHYLAMINE.
Dissolve about one hundred and fifty four parts of para-amido-ortho-nitro-phenol
in about four thousand five hundred parts of water, to which one hundred and
twenty parts of caustic soda lye (containing about 35 per cent. NaOH) have been
added. Treat this solution with about four hundred and fifty parts of concentrated
hydrochloric acid (containing about 30 per cent, real HCl) and then diazotise by the
addition of a concentrated solution of seventy parts of sodium nitrite. The diazo-
tising is completed after a short time, and a considerable portion of the diazo
compound separates out as yellow brown crystalline powder.
Add the whole to a solution of about two hundred and fifty parts of the sodium
salt of Cleve's acid, and stir the mixture thus obtained for about ten hours whilst
maintaining the temperature at from 30 to 40 degrees Centigrade. The colouring
matter formed separates out as a black crystalline powder, having a greenish lustre.
It is practically insoluble in cold water.
Dissolve about three hundred and eighty eight parts of this intermediate colouring
matter in about twelve thousand parts of boiling water to which fifty three parts of
sodium carbonate have been added. Allow the solution to cool and add about
seventy five parts of sodium nitrite in the form of concentrated solution. Stir the
mixture and allow it to run, drop by drop, into five hundred parts of hydrochloric
acid diluted with about one thousand parts of water. Stir whilst inixing. Pour the
diazo compound, so obtained, into a solution of about one hundred and fifty parts of
alpha-naphthylamine in about six thousand parts of water to which one hundred and
fifty parts of hydrochloric acid (containing about 30 per cent. HCI) have been added.
Stir for about six hours at the ordinary temperature, and then heat to a temperature
of about 30 degrees Centigrade till the reaction is completed. Allow the mass to
cool, collect the colouring matter on the filter, press and dry.
Instead of alpha-naphthylamine as end component, other end components can be
used, as herein before indicated, and the middle components also may be varied.
The following table indicates the properties of some of the colouring matters that
can be obtained in accordance with this invention from para-amido-ortho-nitro-phenol.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed I declare that what
I claim is:
1. The manufacture of disazo colouring matters from the nitro-amido-phenols,
the middle components and end components hereinbefore defined,

page_text: 2. The manufacture of disazo colouring matters in the manners hereinbefore
described in the examples.
3. As new articles of manufacture the new disazo colouring matters such as can
be obtained substantially as herein before described.
Dated this 12th day of September 1899
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.