The Manufacture and Production of Azo-colouring Matters and Materials therefor.
Year: 1898

page_text: PROVISIONAL SPECIFICATION.
The Manufacture and Production of Azo-colouring Matters and
Materials 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) to be as follows:-
In the Specifications of former Letters Patent for Inventions communicated by mny
foreign correspondents there are described the manufacture and production of
secondary disazo dyes from nitro-amido-phenol-sulpho acids the special nitro-amido-
phenol-sulpho acids described being characterised by the ortho-position of the nitro-
group NO, to the hydroxyl-group OH.
The present invention relates to the application of a nitro-phenol-sulpho acid
which has the nitro-group in para-position to the hydroxyl group, for the production
of valuable secondary black disazo-dyes.
This new sulpho acid may be obtained by partially reducing the dinitro-phenol-
sulpho-acid, which is described by Post (Berichte der chemischen Gesellschaft, 7,
page 1323) for instance by treating the dipotassium-salt of this acid with alkali-
sulphides at not too high a temperature. The new acid crystallizes from the hot
aqueous solution in beautiful and nearly colourless, crystals which contain one mole-
cular proportion of water. It is decomposed on heating at a temperature of about
two hundred and eighty-five degrees Centigrade. The mono-potassium-salt easily
dissolves in hot water forming a reddish-yellow solution; on cooling it precipitates in
brilliant cinnabar-red needles. This new acid appears to be an amido-sulpho acid
|derived from para-nitro-phenol and probably has the constitution
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 other
amido-body capable of use as a so-called middle-component, such for instance as the
121 or 13 naphthylamine-sulpho acid or a mixture of these. The amido-azo-body
thus obtained is in turn diazotised and combined with a further component capable
of use in the ordinary way as a final-component in the manufacture of azo-

page_text: As instances of the new colouring-matters I mention some of them in the following
table giving their properties and shades.
The following examples will serve to illustrate the nature of this invention but I
do not limit myself to the details. The parts are by weight.

page_text: potassium-salt, a concentrated solution in water of one hundred and twelve parts
of potassium hydroxide. Dissolve, whilst stirring, and cooling, one thousand three
hundred and fifty parts crystalline sodium sulphide in the same quantity of water,
and add this solution in such a manner that the temperature does not rise above
twenty degrees Centigrade. The potassium-salt of the dinitro-acid is gradually dis-
solved and the potassium salt of the nitro-amido-phenol-sulpho acid precipitates in
reddish crystals. Filter and by means of mineral acid precipitate the free acid which
will in most cases be in the form of pale greyish-brown flakes.
EXAMPLE 2.
DIAZOTATION AND COMBINATION WITH ALPHA-NAPIITHYLAMINE.
Dissolve about two hundred and thirty four parts of nitro-amido-phenol-sulphoacid
in about six thousand parts of water, dissolve with it about one hundred and six parts
of calcined soda and precipitate it by about four hundred and twenty parts of
hydrochloric acid containing about thirty-two per cent. HCl, in very fine division.
Diazotise by the addition of a concentrated solution of sixty-nine parts of sodium
nitrite. The diazo-compound is very stable and dissolves easily in water forming a
greenish-yellow solution. Pour the diazo-solution so obtained into a solution of
about one hundred and sixty five parts of alpha-naphthylamine in one hundred and
fifty-four parts of hydrochlic acid containing thirty-two per cent. real HCI, and
twenty-thousand parts of water. First, and in the cold, a light-yellow crystal-pap
is at once precipitated, and this apparently is the naphthylamine-salt of the diazo-
sulpho acid. On heating at about seventy degrees Centigrade it disappears and
gradually in its place the violet coloured intermediate dyestuff is yielded. Stir for
about twenty-four hours at about seventy degrees Centigrade and the operation is
finished.
The colouring-matter obtained is completely precipitated in violet crystals; filter
when it is still hot and wash with hot water.
The
If 1-naphthylamine-21 and 3'-sulpho acids be employed, a salt of the diazo-
sulphoacid is not observed; but the reaction proceeds in the same manner.
intermediate product is precipitated, from a sufficiently concentrated solution, or
on adding potassium chloride to the more dilute solution, as a fine, dark-red
powder with greenish sheen in the dry condition and somewhat soluble in
water
DIAZOTATION OF THE INTERMEDIATE PRODUCT AND COMBINATION WITH 1.41 NAPHTHOL-
SULPHOACID.
Dissolve about three hundred and eighty-eight parts of the intermediate product
obtained in the manner described in Example 2 adding two hundred and twenty-nine
parts of caustic soda lye containing about thirty-five per cent. real Na OH, in about
twelve thousand to fifteen thousand parts of hot water, cool and add about four
thousand parts of ice and about sixty-nine parts of sodium nitrite. For diazotising
add about five hundred and seventy parts of hydrochloric acid containing about
thirty per cent. real H Cl. The diazo-compound separates out in the form of small,
granulous, brown crystals. Pour the mixture directly into a soda-alkaline solution
of two hundred and seventy-one parts of 1'4' naphthol-sulpho acid sodium.
The formation of the colouring matter is soon finished, by the addition of common
salt the partially effected precipitation of the colouring-matter is completed, filter,
and purify, if necessary, by redissolving.
In a similar manner the production of other dyestuffs with other dyestuff-com-
ponents is effected; thus for instance, when employing alpha-naphthylamine as final

page_text: component, the combination has to be effected in acid solution and the dyestuff so
obtained has to be subsequently converted into the sodium-salt.
Datad this 20th day of Inly 1808
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
The Manufacture and Production of Azo-colouring Matters and
Materials 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 Auilin & 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:—
In the Specifications of former Applications for Letters Patent Nos. 14252 and 14253
of 1898 for inventious communicated to me by my foreign correspondents there are
described the manufacture and production of secondary disazo dyes from nitro-amido-
phenol-sulphoacids, the special nitro-amido-phenol-sulpho-acids described being
characterised by the ortho-position of the nitro-group NO, to the hydroxyl
group OH.
The present invention relates to the application of a nitro-phenol-sulphoacid
which has the nitro-group in para-position to the hydroxyl-group, for the production
of valuable secondary black disazo-dyes.
one
This new sulpho-acid may be obtained by partially reducing the dinitro-phenol-
sulpho-acid, which is described by Post (Berichte der chemischen Gesellschaft, 7,
page 1323) for instance, by treating the di-potassium salt of this acid with alkali
sulphides at not too high a temperature. The new acid crystallizes from the hot,
aqueous solution, in beautiful, and nearly colourless, crystals which contain
molecular proportion of water. It is decomposed on heating at a temperature of
about two-hundred-and-eighty-five degrees Centigrade. The mono-potassium-salt
easily dissolves in hot water forming a reddish-yellow solution: on cooling it precipi-
tates in brilliant cinnabar-red needles. This new acid appears to be an amido-
sulpho-acid derived from para-nitro-phenol and probably has the constitution:
In the manufacture of the new secondary disazo colours the diazo compound of the
new nitro-amido-phenol-sulphoacid is combined with a so-called middle component,
namely, alpha-naphthylamine, or with the so-called Cleve's acid, that is, the 1.21- or
1.31-naphthylamine-sulphoacid, or a mixture of these. The amido-azo body, thus
obtained, is, in turn, diazotised and combined with a further component capable of
use in the ordinary way as a final-component in the manufacture of azo-dyes, and
hereinafter defined.

page_text: can be used, including all the sulphoacids of naphthol, naphthylamine, amido-
naphthol and dihydroxy-naphthalene in use as end components for 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 I do not limit myself
to the details. The parts are by weight:
Dissolve about two hundred and thirty-four parts of the aforesaid nitro-amido-
phenol-sulpho-acid in about six thousand parts of water, containing about one hundred
and six parts of calcined soda in solution and precipitate it by means of about four
hundred and twenty parts of hydrochloric acid containing about. thirty-two per cent.
H.Cl. in a state of very fine division. Diazotise by the addition of a concentrated
solution of sixty-nine parts of sodium nitrite. The diazo-compound is very stable and
dissolves readily in water forming a greenish-yellow solution. Pour the diazo-solution,
so obtained, into a solution of about one hundred and sixty-five parts of alpha-
naphthylamine in one hundred and fifty-four parts of hydrochloric acid containing
thirty-two per cent. real H.Cl, and twenty thousand parts of water. First, and in the
cold, a light yellow crystalline paste is at once precipitated, and this apparently is the
naphthylamine-salt of the diazo-sulphoacid. On heating, at about seventy degrees
Centigrade, it disappears and gradually, in its place, the violet-coloured intermediate
dyestuff is yielded. Stir for about twenty-four hours at about forty degrees Centigrade
and the operation is finished.
The colouring-matter obtained is completely precipitated in violet crystals, filter
whilst it is still hot and wash with hot water.
If 1-naphthylamine-21 and 31-sulpho acids he employed, a salt of the diazo-
sulphoacid is not observed, but the reaction proceeds in the same manner. The
intermediate product is precipitated, from a sufficiently concentrated solution, or on
adding potassium chloride to the more dilute solution, as a fine, dark-red powder with
greenish sheen in the dry condition, and somewhat soluble in water.
EXAMPLE 3.
DIAZOTATION OF THE INTERMEDIATE PRODUCT AND COMBINATION WITH 141 NAPHTHOL-
SULPHOACID.
Dissolve about three hundred and eighty-eight parts of the intermediate product
obtained in the manner described in Example 2 adding two hundred and twenty-nine
parts of caustic soda lye (containing about thirty-five per cent. real NaOH) in about
twelve thousand to fifteen thousand parts of hot water, cool and add about four

page_text: thousand parts of ice and about sixty-nine parts of sodium nitrite. For diazotising
add about five hundred and seventy parts of hydrochloric acid containing about thirty
per cent. real H Cl. The diazo-compound separates out in the form of small granular,
brown crystals. Pour the mixture directly into a soda-alkaline solution of two hundred
and seventy-one parts of 1-41-naphthol-sulpho-acid sodium.
The formation of the colouring-matter is soon finished, and, by the addition of
common salt, the partially effected precipitation of the colouring-matter is completed.
Filter and purify, if necessary, by re-dissolving.
.
In a similar manner the production of other dyestuffs with other dyestuff-com-
ponents is effected: thus, for instance, when employing alpha-naphthylamine as final
component the combination has to be effected in acid solution and the dyestuff so
obtained has to be subsequently converted into the sodium-salt.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the saine is to be performed, I declare that what I
claim is:
1. The manufacture of para-nitro-ortho-amido-phenol-ortho-sulphoacid by partially
reducing the ortho-para-dinitro-phenol-ortho-sulphoacid, substantially as hereinbefore
described.
2. The manufacture of disazo colouring-matters from para-nitro-ortho-amido-phenol-
ortho-sulphoacid and a middle and end component hereinbefore defined, all substan-
tially as hereinbefore described.
3. The manufacture of a para-nitro-ortho-amido-phenol-ortho-sulphoacid and of
disazo colouring-matters therefrom substantially as hereinbefore described in the fore-
going examples.
4. As new articles of manufacture the para-nitro-ortho-amido-phenol-ortho-sulpho-
acid and the disazo colouring-matters from it, such as can be obtained substantially
as hereinbefore described.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.