The Manufacture and Production of Azo-colouring-matters and Materials for use therefor.
Year: 1898

page_text: Date of Application, 28th June, 1898
Complete Specification Left, 25th Mar., 1899-Accepted, 2nd June, 1899
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 and Soda Fabrik, of
Ludwigshafen on Rhine, in the Empire of Germany,) to be as follows:-
In the Specifications of prior applications for Letters Patent of even dute herewith
my foreign correspondents have described the manufacture and production of
secondary disazo-dyes from nitro-amido-phenol-sulpho-acids.
The present invention relates to the discovery that by nitrating the para-amido-
phenol-ortho-sulpho-acid a new nitro-amido-phenol-sulpho-acid can be obtained, to
which probably the following constitution must be attributed.
previ
This new sulpho-acid can be employed for the manufacture of new valuable
secondary black disazo-dyestuffs. These new dyestuffs possess great strength of
colouring power and an excellent fastness to light. They give, when treated with
chromates, shades very fast against washing and fulling. By this treatment in some
cases the shades are very decidedly changed towards green or deep-black and thus
effects are obtained which cannot readily be reached with colouring-matters obtained
from other nitro-amido-phenol-sulpho-acids.
In the manufacture of the new secondary disazo-colours the diazo-compound of the
new nitro-amido-phenol-sulpho-acid is combined with alpha-naphthylamine or
another amido-body known to be capable of use as a so-called middle component.
The ainido-az-body thus obtained is in turn diazotised and combined with 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.

page_text: As instances of the new colouring-matters, some of them are mentioned in the
following table giving their properties and shades.
Add about seven hundred and fifty six parts of para-amido-phenol-ortho-sulpho-
acid whilst stirring to about three thousand two hundred parts of concentrated
sulphuric acid containing about ninety-five per cent. real ₂SO, at the ordinary
temperature. When this
dissolved cool the mixture to a temperature of about
minus five degrees Centigrade. Then add slowly a cool mixture of about four hun-
dred parts of nitric acid (containing about sixty-two per cent. HNO3) and of about
four hundred paits of sulphuric acid mono-hydrate, taking care that the temperature

page_text: remains always below zero degrees Centigrade. When the mixing is effected pour the
nitration-mixture onto ice, wash the separated nitro-acid well with cold water, press
and dry.
The nitro-amido-sulpho-acid so obtained is nearly insoluble in alcohol and in cold
water; it dissolves a little more readily in boiling water giving a red-coloured solu-
tion and crystallises out from this in the form of brilliant, pale reddish-brown-
coloured needles. It yields a mono- and a di-sodium-salt; the first dissolves in water
with a reddish-yellow colour, the latter dissolves very readily in water giving a deep
red colour. From each solution after the addition of mineral acid, the free acid
gradually separates out again in the form of crystals.
COMBINATION OF THIS ACID WITH A MIXTURE OF 1-NAPIITHYLAMINE-31-AND-
21-SULPHO-ACID.
Dissolve about two hundred and thirty-four parts of nitro-para-ainido-phenol-ortho-
sulpho-acid whilst adding two hundred and thirty parts of caustic soda containing
about thirty-five per cent. real NaOH in about two thousand parts of water and add a
concentrated solution of about seventy parts of sodium nitrite. Add the mixture
whilst stirring to about four hundred and fifty parts of hydrochloric acid containing
about 30 per cent. HCl which previously has been diluted with about one thousand
parts of water. The diazotation is usually finished in a few minutes. Then pour the
clear brown-red solution of the diazo-compound into a solution of two hundred and
fifty parts of the mixture of the sodium-salts of the 1-naphthylamine-31-and-21-sulpho-
acid in ten times the quantity of water. Heat whilst stirring at a temperature of
about fifty degrees Centigrade. Cool after about ten hours, filter the dyestuff, pre-
cipitate, press and dry. The precipitate is usually in the form of bronze-lustre
crystals, which are difficultly soluble in water.
In a similar manner the combination with alpha-naphthylamine can be effected.
The colouring matter so obtained yields a green powder, which is insoluble in cold
water.
THE MANUFACTURE OF THE COLOURING-MATTER
NITRO-PARA-AMIDO-PHENOL-ORTHO-
SULPHO-ACID AND 1-NAPHTHYLAMINE-31-AND-21-SULPHO-ACID AND BETA-NAPIJTHOL-
DISULPHO-ACID R.
Dissolve about nine hundred and eighty parts of the intermediate product (obtained
in the manner herein before described in Example 2) in about thirty thousand parts
of boiling water, containing about four hundred and sixty parts of caustic soda lye
containing about thirty-five per cent. real NaOH. Cool very carefully down to about
zero degree Centigrade and add to the solution a concentrated solution of one hundred
and forty parts of sodium nitrite. Pour the mixture whilst stirring and continuing
to cool as described into one thousand parts of hydrochloric acid containing about
thirty per cent. HCI which has been diluted with about two thousand parts of
water.
A green solution is obtained which on the addition of much mineral acid becomes
yellowish brown; on strongly diluting with water or on the addition with sodium
acetate or soda it becomes deep bluish-violet.
Pour the diazo-compound
obtained into a concentrated soda-alkaline
solution of seven hundred parts of the sodium salt of beta-naphthol-disulpho acid
(R-salt).

page_text: The combination is quickly finished; the precipitated dyestuff is filtered and treated
in the culina
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
communicated to me from abroad by The Badische Aniline & 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 —
In the Specifications of Applications for Letters Patent of even date herewith
there are described the manufacture and production of secondary disazo-dyes from
nitro-amido-phenol-sulpho-acids.
The present invention relates to the discovery that by nitrating the para-amido-
phenol-ortho-sulpho-acid a new nitro-amido-phenol sulpho-acid can be obtained, to
which probably the following constitution must be attributed,
and which seems to be an ortho-sulpho-acid of the para-amido-ortho-nitro-phenol.
This new sulpho-acid can be employed for the manufacture of new valuable
secondary black disazo-dyestuffs. These new dyestuffs possess great strength of
colouring-power and an excellent fastness against the action of light. They give,
when treated with chromates, shades very fast against washing and fulling. By this
treatment, in some cases, the shades are very decidedly changed towards green, or
deep-black.
In the manufacture of the new secondary disazo-colouring matters the diazo-
compound of the new nitro-amido-phenol-sulpho-acid is combined with alpha-
naphthylamine, or the so-called Cleve's alpha-naphthylamine sulpho-acid, that is
1.21 and 1.31-sulpho-acid, either isolated or admixed with one another. The amido-azo
body thus obtained is again diazotised, and combined with a further component
hereinafter defined.

page_text: In addition to the end components mentioned in the above table the dyes can
also be prepared using their analogues including the naphthylamine, naphthol-
amido-naphthol and dioxy-naphthalene sulpho-acids in use as end components in the
manufacture of azo-dyes.
The following examples will serve to illustrate the nature of this invention, and
the manner in which it can be carried into practical effect, but it is not limited to
the precise details. The parts are by weight.
PRODUCTION OF THE NEW ORTHO-NITRO-PARA-AMIDO-PHENOL-ORTHO-SULPHO-ACID.
Add about seven hundred and fifty-six parts of para-amido-phenol-ortho-sulpho-
acid, (whilst stirring) to about three thousand two hundred parts of concentrated
sulphuric acid, containing about ninety-five per cent. real HSO;, at the ordinary

page_text: temperature. When this is dissolved cool the mixture to a temperature of about
minus five degrees Centigrade. Then add slowly a cool mixture of about four
hundred parts of nitric acid (containing about sixty-two per cent. HNO) and of
about four hundred parts of sulphuric acid monohydrate, taking care that the tempera-
ture remains always below zero degrees Centigrade. When the mixing is effected pour
the nitration mixture on to ice, wash the separated nitro-acid well with cold water,
press and dry.
The nitro-amido-sulpho-acid so obtained is nearly insoluble in alcohol and in cold
water, it dissolves a little more readily in boiling water, the solution being red and
it crystallises out from this in the form of brilliant, pale reddish-brown needles. It
yields a mono- and a di-sodium salt: The mono-sodiuin salt dissolves in water the
solution being a reddish-yellow, whilst the di-sodium salt dissolves very readily in
water, the solution being deep-red. From each solution, after the addition of
mineral acid, the free acid gradually separates out again in the form of crystals.
COMBINATION OF THIS ACID WITH
A MIXTURE OF 1-NAPHTHYLAMINE-31- AND
21-SULPHO-ACID.
Dissolve about two hundred and thirty-four parts of ortho-nitro-para-amido-phenol-
ortho-sulpho-acid (whilst adding two hundred and thirty parts of caustic soda, contain-
ing about thirty-five per cent. real NaOH) in about two thousand parts of water, and
add a concentrated solution of about seventy parts of sodium nitrite. Add the
mixture, whilst stirring, to about four hundred and fifty parts of hydrochloric acid,
containing about thirty per cent. HCl, which previously has been diluted with about
one thousand parts of water. The diazotation is usually finished in a few minutes.
Then pour the clear brown-red solution of the diazo-compound into a solution of two
hundred and fifty parts of the mixture of the sodium-salts of the 1-naphthylamine-31-
and 21-sulpho-acid in ten times the quantity of water. Heat, whilst stirring, at a
temperature of about forty degrees Centigrade. Cool after about ten hours, filter
the dyestuff, precipitate, press and dry. The precipitate is usually in the form of
bronze-lustre crystals, which are difficultly soluble in water.
In a similar manner the combination with alpha-naphthylamine can be effected.
The colouring-matter so obtained yields a green powder, which is insoluble in cold
water.
THE MANUFACTURE OF THE COLOURING-MATTER FROM ORTHO-NITRO-PARA-AMIDO-PHENOL-
ORTHO-SULPHO-ACID AND 1-NAPHTHYLAMINE-31-AND-21-SULPHO-ACID
NAPHTHOL-DISULPHO-ACID R.
AND BETA-
Dissolve about nine hundred and eighty parts of the intermediate product (obtained
in the manner herein before described in Example 2) in about thirty thousand parts
of boiling water, containing about four hundred and sixty parts of caustic soda lye,
containing about thirty-five per cent. real NaOH. Cool, very carefully, down to
about zero degrees Centigrade and add to the solution a concentrated solution of one
hundred and forty parts of sodium nitrite. Pour the mixture, whilst stirring and
continuing to cool as described, into one thousand parts of hydrochloric acid,
containing about thirty per cent. HCl, which has been diluted with about two
thousand parts of water.
A green solution is obtained, which, on the addition of much mineral acid, becomes
yellowish-brown. On strongly diluting it with water, or on the addition of sodium
acetate, or soda, it becomes deep blueish-violet.
Pour the diazo-compound so obtained into a concentrated soda-alkaline solution of
seven hundred parts of the sodium salt of beta-naphthol-disulpho-acid (R-salt.).

page_text: The combination is quickly finished. The precipitated dyestuff is filtered and
treated in the ordinary manner.
The production of other combinations is effected in a similar manner.
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 a new ortho-nitro-para-amido-phenol-ortho-sulpho-acid by
nitrating para-amido-phenol-ortho-sulpho-acid, substantially as herein before described.
2. The manufacture of disazo colouring-matters from ortho-nitro-para-amido-
phenol-ortho-sulpho-acid and a middle and end component hereinbefore defined, all
substantially as hereinbefore described.
3. The manufacture of ortho-nitro-para-amido-phenol-ortho-sulpho-acid, and of the
disazo colouring-matters therefrom, substantially as herein before described in the
foregoing Examples.
4. As new articles of manufacture the ortho-nitro-para-amido-phenol-ortho-sulpho-
acid and the disazo colouring-matters therefrom such as can be obtained, substantially
as herein before described.
Thatode dan of ALL 1900
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.