Improvements in the Manufacture and Production of Disazo Colouring-matters and of Products for Use therein.
Year: 1898

page_text: Improvements in the Manufacture and Production of Disazo
Colouring-matters and of Products for Use therein.
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 relates to the manufacture of secondary disazo dyes from chlor-amido-
phenol sulpho acids, and from chlor-amido-phenols. The amido-phenol derivatives
are diazotised and used as the initial components. As intermediate components,
naphthylamine, or naphthylamine-sulpho acids, 1.6 or 1.7 or mixtures thereof (herein-
after referred to as Cleve's acids) or other amido compounds which on combination with
the diazo compounds, yield an amido-azo compound that can be readily diazotised and
combined with an ordinary final component are used. Naphthol sulpho acids and
other components (which may be such as are in ordinary use as final components) in
the manufacture of azo dyes, are employed as final components.
The chlor amido-phenol-sulpho acid which it is preferred to use can be derived from
nitro-amido-phenol-sulpho acid the said nitro acid being diazotised, and the diazo
compound treated according to Gattermann's process, with copper in a state of
exceedingly fine division in hydrochloric acid solution. A nitro-chlor-phenol-sulpho
acid is obtained and then reduced to the desired chlor-amido-phenol-sulpho acid.
The new acid is but slightly soluble in cold water, but is readily soluble in hot
water and crystallises from hot water in short thick crystals. On treatment with
hydrochloric acid and sodium nitrite a yellow diazo solution is obtained which shews
a green dichroism.
The following examples will serve to illustrate the nature of the invention, which
infined to thann neamule
Dissolve about two hundred and thirty four parts of the ortho nitro amido-phenol-
para-sulpho acid in one thousand parts of water, to which two hundred and thirty
parts of caustic soda lye (containing about 35 per cent. Na.O.H.) have been added.
To this solution add a concentrated aqueous solution of seventy parts of sodium
aitrite. Allow the whole mixture to run into a mixture of four hundred parts of
hydrochloric acid (containing about 30 per cent. real H.C!) diluted with five hundred
parts of water. Add to the diazo solution, thus obtained six hundred parts of
hydrochloric acid (containing about 30 per cent. real H.CI) and fifty parts of copper in
the finely divided state known as molecular copper. The copper is preferably added

page_text: in the form of a 50 per cent. paste and the mixture should be kept cool by means of
ice during this addition, so that the temperature at no time rises above 15 degrees
Centigrade. When no diazo compound is present in the solution filter and precipitate
the resulting chlor-nitro-phenol-sulpho acid by the addition of about four hundred
parts of potassium chloride. Reduce in any ordinary or suitable way, for instance by 5
means of iron filings and acetic acid. Render the product alkaline by means of
carbonate of soda, filter from the iron mud, concentrate the filtrate, if necessary, and
precipitate the chlor-amido-phenol-sulpho acid by means of hydrocloric acid. Purify,
if necessary, by redissolving and recrystallising.
THE PRODUCTION OF AN INTERMEDIATE COLOURING MATTER FROM ORTHO-CHLOR-ORTHO-
AMIDO-PHENOL-PARA SULPHOACID AND ALPHA-NAPHTHYLAMINE.
Stir to a paste one hundred and twelve parts of the chlor-amido-phenol-sulpho
acid and five hundred parts of water. Add about sixty parts of caustic soda lye
(containing about 35 per cent. Na.O.H.) so as to dissolve the acid. To the solution
add five hundred parts of water and one hundred and fifty parts of hydrochloric acid,
(containing about 30 per cent, real H.C) stir and add a concentrated solution of
thirty five parts of sodium nitrite in order to diazotise. Run the diazo solution into a
solution of about eighty parts of alpha-naphthylamine, in ninety-five parts of
hydrochloric acid (containing about 30 per cent. real H.Cl) diluted with two thousand
five hundred parts of water. Heat the mixture for about thirty six hours to a
temperature of from 60 to 70 degrees Centigrade. When on testing no further diazo
compound is found to be present in the liquid, allow the mixture to cool. Filter,
press, and dry or preferably preserve this intermediate colouring matter in the form
of paste for further use. The colouring matter so obtained is a dark green powder,
which is but slightly soluble in water but is soluble in alkalies forming a red solution.
In a similar manner intermediate colouring-inatter from Cleve's acid can be obtained.
This colouring matter is more soluble owing to the presence of an extra sulpho group,
but in other respects it closely resembles the intermediate colouring matter from
naphthylamine.
THE PRODUCTION OF AN INTERMEDIATE COLOURING MATTER FROM ORTHO-CHLOR-ORTHO-
AMIDO-PHENOL-PARA SULPHOACID AND ALPHA-NAPHTHYLAMINE.
Stir to a paste one hundred and twelve parts of the chlor-amido-phenol-sulpho
acid and five hundred parts of water. Add about sixty parts of caustic soda lye
(containing about 35 per cent. Na.O.H.) so as to dissolve the acid. To the solution
add five hundred parts of water and one hundred and fifty parts of hydrochloric acid,
(containing about 30 per cent. real H.C) stir and add a concentrated solution of
thirty five parts of sodium nitrite in order to diazotise. Kun the diazo solution into a
solution of about eighty parts of alpha-naphthylamine, in ninety-five parts of
hydrochloric acid (containing about 30 per cent. real H.Cl) diluted with two thousand
five hundred parts of water. Heat the mixture for about thirty six hours to a
temperature of from 60 to 70 degrees Centigrade. When on testing no further diazo
compound is found to be present in the liquid, allow the mixture to cool. Filter,
press, and dry or preferably preserve this intermediate colouring matter in the form
of paste for further use. The colouring matter so obtained is a dark green powder,
which is but slightly soluble in water but is soluble in alkalies forming a red solution.
In a similar manner intermediate colouring-inatter from Cleve's acid can be obtained.
This colouring matter is more soluble owing to the presence of an extra sulpho group,
but in other respects it closely resembles the intermediate colouring matter from
naphthylamine.
EXAMPLE 3.
THE COMBINATION OF THE NAPHTHYLAMINE INTERMEDIATE COLOURING-MATTER WITH
R-SALT.
Dissolve about thirty eight parts of the actual colouring-matter obtained according
to Example 2, preferably in the form of paste, undried, in one thousand parts of
water, to which twenty-five parts of caustic soda lye (containing about 35 per cent.
of Na.O.H) have been added. To the solution add seven parts of sodium nitrite in
aqueous solution, and then, whilst stirring, add about fifty-five parts of hydrochloric
acid (containing about 30 per cent. real H.CI) diluted with three hundred parts of
water. After stirring for about half-an-hour, the production of the diazo compound
is usually complete. It appears as a difficultly soluble brown-red mass, somewhat
soluble in alkalies, yielding a blue solution. Add the diazo compound to a soda
alkaline solution, of thirty-five parts of R-salt. The production of the new disazo
colouring-matter is complete in a short time. Precipitate with common salt, press
and dry.
The disazo colouring matters can be obtained in an analogous manner by using
other intermediate components and other final components. If a base such as alpha-
naphthylamine or ethyl-beta-naphthylamine be used as a final component it is
advisable to combine in weak acid solution, and to subsequently by treatment with
carbonate of soda, convert the colouring-inatter into its sodium salt.
THE COMBINATION OF THE NAPHTHYLAMINE INTERMEDIATE COLOURING-MATTER WITH
R-SALT.
Dissolve about thirty eight parts of the actual colouring-matter obtained according
to Example 2, preferably in the form of paste, undried, in one thousand parts of
water, to which twenty-five parts of caustic soda lye (containing about 35 per cent.
of Na.O.H) have been added. To the solution add seven parts of sodium nitrite in
aqueous solution, and then, whilst stirring, add about fifty-five parts of hydrochloric
acid (containing about 30 per cent. real H.CI) diluted with three hundred parts of
water. After stirring for about half-an-hour, the production of the diazo compound
is usually complete. It appears as a difficultly soluble brown-red mass, somewhat
soluble in alkalies, yielding a blue solution. Add the diazo compound to a soda
alkaline solution, of thirty-five parts of R-salt. The production of the new disazo
colouring-matter is complete in a short time. Precipitate with common salt, press
and dry.
The disazo colouring matters can be obtained in an analogous manner by using
other intermediate components and other final components. If a base such as alpha-
naphthylamine or ethyl-beta-naphthylamine be used as a final component it is
advisable to combine in weak acid solution, and to subsequently by treatment with
carbonate of soda, convert the colouring-inatter into its sodium salt.

page_text: The following table shews the properties of a few of the colouring-matters that can
be obtained from alpha-chlor-ortho-ainido-phenol-para-sulpho-acid, in accordance with
this invention.
Diazotise about one hundred and eighty parts of the hydrochloric acid salt of para-
chlor-ortho-amido-phenol with about seventy parts of sodium nitrite, and the
necessary quantity of hydrochloric acid. The diazo compound separates out in
part. It is of an orange colour. Run the diazo compound into an aqueous solution
of two hundred and forty-five parts of Cleve's acid, stir thoroughly, whilst
maintaining the temperature at about 45 to 55 degrees Centigrade, for about twelve
hours. When on testing no diazo compound can be found to be present allow the
mixture to cool, and filter off the intermediate colouring-matter obtained. This
appears as a dark violet powder with greenish reflex. Dissolve this intermediate
colouring-matter in dilute caustic soda lye. Add the requisite quantity of sodium
nitrite and run the mixture into dilute hydro-cbloric acid. The diazo compound is
brown and separates out to a great extent. When no further nitrous acid is
present in the liquid, add an aqueous solution of about eighteen parts of the
hydrochloric acid salt of naphthylamine. Stir, and, when the combination is
complete, make the solution alkaline by means of soda, boil and precipitate the
colouring matter from the boiling solution by means of common salt.
Similar colouring-matters can be obtained when using, for instance, di-chlor-ortho-
amido-phenol and when using other intermediate and final components. Of course,
when combining with acid components such as naphthol sulpho acids, the combination
is effected in alkaline solution.
The new disazo colouring-matters herein described dye wool deep-blue to violet-
black shades. They possess extraordinary dyeing capacity, and covering power;

page_text: and are further characterised by a high degree of fastness against the action o
light. On treating the dyed goods with chromates the shade changes slightly
towards green, or blue, and the degree of fastness of the resulting colour is greatly
increased.
Improvements in the Manufacture and Production of Disazo
Colouring-matters and of Products for Use therein.
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 Auilin & Soda Fabrik, of Ludwig-
shafen-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 relates to the manufacture of secondary disazo dyes from chlor-
amido-phenol sulphoacids, and from chlor-amido-phenols. The amido-phenol deriva-
tives are diazotised. and used as the first or initial components. As middle or
intermediate components, naphthylamine, or naphthylamine-sulphoacids, 1.6 or 17,
or mixtures thereof, (hereinafter referred to as Cleve's acids), or other amido com-
pounds which, on combination with the diazo compounds, yield an amido-azo-
compound which can be readily diazotised and combined with an ordinary end or
final component are used. Naphthol sulphoacids, and other components, which may
be such as are in ordinary use as end or final components) in the manufacture of azo
dyes, are employed as end or final components.
The chlor-amido-phenol-sulphoacid which it is preferred to use can be derived from
nitro-amido-phenol-sulphoacid, the said nitroacid being diazotised, and the diazo
compound treated according to Gatterinann's process, with molecular copper, that is,
copper in a state of exceedingly fine division, in hydrochloric acid solution. A nitro-
chlor-phenol-sulphoacid is obtained, and then reduced to the desired chlor-amido-
phenol-sulphoacid.
The new acid is but slightly soluble in cold water, but is readily soluble in hot
water, and crystallises, from hot water in short, thick crystals. On treatment with
hydrochloric acid and sodium nitrite a yellow solution is obtained, which shews a
green dichroisin.
The following examples will serve to illustrate the nature of the invention, and the
manner in which it can be carried out, but the invention is not confined to these
examples. The parts are by weight:
THE PRODUCTION OF ORTHO-CHLOR-ORTHO-AMIDO-PHENOL-PARA-SULPHO-ACID.
Dissolve about two hundred and thirty-four parts of the nitro-amido-phenol-para-
sulphoacid in one thousand parts of water, to which two hundred and thirty parts of
caustic soda lye (containing about 35 per cent. NaOH) have been added.
To this

page_text: solution add a concentrated aqueous solution of seventy parts of sodium nitrite.
Allow the whole inixture to run into a mixture of four hundred parts of hydrochloric
acid (containing about 30 per cent. real HCI), diluted with five hundred parts of
water. Add to the diazo solution, thus obtained, six hundred parts of hydrochloric
acid, (containing about 30 per cent. real HCI), and fifty parts of copper in the finely
divided state known as molecular copper. The copper is preferably added in the
form of a 50-per-eent. paste and the mixture should be kept cool by means of ice
during this addition so that the temperature at no time rises above 15 degrees
Centigrade. When no diazo compound is present in the solution, filter, and precipi-
tate the resulting chlor-nitro-phenol-sulpho-acid by the addition of about four
hundred parts of potassium chloride. Reduce in any ordinary, or suitable way; for
instance, by means of iron fillings and acetic acid. Render the product alkaline
by means of carbonate of soda, filter from the iron mud, concentrate the filtrate,
if necessary, and precipitate the chlor-amido-phenol-sulpho-acid by means of
hydrochloric acid. Purify, if necessary, by re-dissolving, and re-crystallising.
THE PRODUCTION OF AN INTERMEDIATE COLOURING-MATTER FROM ORTHO-CHLOR-
ORTHO-AMIDO-PHENOL-PARA-SULPHOACID AND ALPHA-NAPHTHYLAMINE.
Stir, to a paste, one hundred and twelve parts of the chlor-amido-phenol-sulpho-
acid and five hundred parts of water. Add about sixty parts of caustic soda-lye
(containing about 35 per cent. NaOH) so as to dissolve the acid. To the solution
add five hundred parts of ice and one hundred and fifty-five parts of hydrochloric
acid (containing about 30 per cent. real HCI). Stir and add a concentrated solution
of thirty-five parts of sodium nitrite in order to diazotise. Run the diazo solution
into a solution of about eighty parts of alpha-naphthylamine, in ninety-five parts of
hydrochloric acid (containing about 30 per cent. real HCI), diluted with two thousand
five hundred parts of water. Heat the mixture for about thirty-six hours to a tem-
perature of from 60 to 70 degrees Centigrade. When, on testing, no further diazo
compound is found to be present in the liquid, allow the mixture to cool. Filter,
press, and dry, or preferably keep this intermediate colouring-matter in the form of
paste for further use. The colouring-matter so obtained is a dark-green powder,
which is but slightly soluble in water, but is soluble in alkalies, forming a red
solution.
In a similar manner intermediate colouring-matter from Cleve's acid can be
obtained. This colouring-matter is more soluble, owing to the presence of an extra
sulpho group but in other respects it closely resembles the intermediate colouring-
matter from alpha-naphthylamine.
EXAMPLE 3.
THE COMBINATION OF THE NAPHTHYLAMINE INTERMEDIATE COLOURING-MATTER WITH
R-SALT.
Dissolve about thirty-eight parts (dry weight) of the colouring-matter obtained
according to Example 2, preferably in the form of paste, undried, in one thousand
parts of water, to which twenty-five parts of caustic soda lye (containing about 35 per
cent. of NaOH) have been added. To the solution add seven parts of sodium nitrite
in aqueous solution; and then, whilst stirring, add about fifty-five parts of hydro-
chloric acid, (containing about 30 per cent. real HCI), diluted with three hundred
parts of water.
After stirring, for about half-an-hour, the production of the diazo
compound is usually complete. It appears as a difficultly soluble brown-red mass,
somewhat soluble in alkalies, yielding a blue solution. Add the diazo compound to a
soda alkaline solution of thirty-five parts of R-salt. The production of the new disazo-
colouring-matter is complete in a short time. Precipitate with common salt, press
and dry.

page_text: The disazo colouring-matters can be obtained in an analogous manner by using other
middle components and other end components. If a base such as alpha-naphthylamine,
or ethyl-beta-naphthylamine, be used as the end component it is advisable to combine
in weak acid solution, and to subsequently, by treatment with carbonate of soda,
convert the colouring-matter into its sodium salt.
The following table shews the properties of a few of the colouring-matters that can
be obtained from chlor-ortho-amido-phenol-para-sulphoacid in accordance with this
invention.
are the chlorine derivatives of the ortho-amido-phenol (see Annalen, supplement,
volume 7, pages 189 and 193).
EXAMPLE 4.
Diazotise about one hundred and eighty parts of the hydrochloric acid salt of para-
chlor-ortho-amnido phenol with about seventy parts of sodium nitrite, and the necessary
quantity of hydrochloric acid. The diazo compound separates out in part. It is of
an orange colour.
Run the diazo compound into an aqueous solution of two hundred
and forty five parts of Cleve's acid, stir thoroughly whilst maintaining the tempera-
ture at about 45 to 55 degrees Centigrade for about twelve hours. When, on testing,
no diazo compound can be found to be present, allow the mixture to cool and filter
off the intermediate colouring matter obtained. This appears as a dark-violet powder
with greenish reflex. Dissolve this intermediate colouring matter in dilute caustic
soda lye. Add the requisite quantity of sodium nitrite and run the mixture into
dilute hydrochloric acid. The diazo compound is brown and separates out to a great
extent. When no further nitrous acid is present in the liquid, add an aqueous solu-
tion of about one hundred and eighty parts of the hydrochloric acid. salt of alpha-
naphthylamine. Stir, and when the combination is complete, make the solution
alkaline by means of soda, boil and precipitate the coloring matter from the boiling
solution by means of common salt.
Similar colouring matters can be obtained when using, for instance, di-cilor-ortho-
amido-phenol and when using other middle and end components. Of course, when
combining with acid components, such as naphthol sulphoacids, the combination is
effected in alkaline solution.
The new disazo colouring matters hereinbefore described, dye wool deep-blue to
violet-black shades. They possess extraordinary dyeing capacity, and covering

page_text: power, and are further characterised by a high degree of fastness against the action
of light. On treating the dyed goods with chromates the shade changes slightly
towards green, or blue, and the degree of fastness of the resulting colour is greatly
increased.
Having now particularly described and ascertained the nature of this 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 a chlor-amido-phenol-sulpho-
acid and a middle component and an end component both herein before defined.
(2) The manufacture of disazo colouring matters from a chlor-amido-phenol and a
middle component and an end component both herein before defined.
(3) The manufacture of ortho-chlor-ortho-amido phenol-para sulphoacid by con-
verting nitro-amido-phenol-para-sulphoacid into chlor-nitro-phenol-sulphoacid and
reducing this to the corresponding amido compound, all substantially as hereinbefore
described.
(4) The manufacture of disazo colouring matters of intermediate colouring matters,
and of chlor-amido-phenol-para-sulphoacid all substantially as herein before described
in the several examples.
(5) As new articles of manufacture and severally the new chlor-amido-phenol-
sulphoacid, the new intermediate colouring matters and the new disazo colouring
matters, such as can be obtained substantially as herein before described.
Dated this 15th day of Angust. 1899
August. 1899
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.