The Manufacture or Production of New Disazo Colouring Matters.
Year: 1898

page_text: [Communicated from abroad by THE FARBENFABRIKEN VORMALS FRIEDRICH BAYER
& Co., of Elberfeld, Germany.]
The Manufacture or Production of New Disazo Colouring Matters.
I, HENRY EDWARD NEWTON, of the Office for Patents, 6, Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
In the French Patent No. 232,299 (dated August 12, 1893), colouring matters
were described as being obtained by first combining the diazo derivative of alpha,
alpha, acetnaphtylene diamine beta,- or beta sulphonic acid with a phenol; secondly,
splitting off the acetylic group; thirdly, diazotizing the amido-azo compound thus
obtained; and finally coupling the resulting diazo body with another dye-stuff
component.
By this process, a dye-stuff was obtainable having the following formula:—
Bearing in mind the hitherto accepted opinion about the nature and structural
composition of the azo dye-stuffs, it was reasonable to suppose that the same colour-
ing would result by first coupling a diazo derivative of mono-acidyle alpha, alpha,
naphtylenediamine with Clèves alpha naphtylamine betasulphonic acid (1.6 or 17);
secondly, diazotizing the so-produced amido-azo compound; thirdly, combining the
diazo-azo compound thus obtained with alpha, alpha, naphtolsulphonic acid; and
finally splitting off the acidyl group from the resulting disazo dye stuff.

page_text: My foreign correspondents have now made the surprising discovery that the
coloring matter obtained according to the last-mentioned method, which was unknown
up to the present time, is totally different from that obtained according to the
process described in the above cited French Patent.
The principal differences are the following:-
:―
The coloring matter obtained according to our new process, exhibits a greater
affinity for the vegetable fibre, and dyes unmordanted cotton brighter shades than
the known dye-stuff. The difference between the two coloring matters can be
observed still more distinctly, if the dye-stuffs are diazotized on the fibre. Whilst
the new dye-stuff is diazotized very easily, the diazo derivative of the known dye-
stuff is formed but slowly. The shades which the diazotized dye-stuffs exhibit on the
fibre are also different; that produced by means of the known dye-stuff is brown,
whilst that of the new coloring matter is violet. The differences are still greater, if
the two dye-stuffs, after being diazotized on the fibre, are developed "with the aid
of beta naphtol. Whilst the new coloring matter combines easily, at ordinary tem-
peratures, with the naphtol, yielding bright blue shades fast to washing, the dye-
stuff obtained according to the above mentioned French Patent combines but very
slowly with the naphtol, yielding dull blueish-gray shades.
Very similar differences are observed on comparing the results obtained from the
analogous dye-stuffs which contain other components instead of the alpha, alpha,
naphtolsulphonic acid.
It may be remarked that my foreign correspondents ascribe these striking
differences between the two series of dye-stuffs, to a different distribution of the
double ligatures in the dye-stuff molecule.
In order to illustrate the new process, the following example is given (the parts
heing by weight)
are diazotized in the usual manner, with the aid of 20 parts of muriatic acid
(containing 23 per cent. of HCI) and 7 parts of sodium nitrite. The resulting diazo
solution is stirred into a solution prepared from 27 parts of the sodium salt of Clève's
alphanaphtylamine beta sulphonic acid (1.6), 20 parts of crystallized sodium acetate,
and 500 parts of water, which solution has been cooled to 10 degrees Centigrade.
After stirring the reaction mixture for a short time, 30 parts of a 33 per cent.
soda-lye, and then 11 parts of sodium nitrite, are added. The resulting solution is
mixed with 110 parts of muriatic acid (containing 23 per cent. of HCl), and further
stirred for about 6 hours. Subsequently, the reaction mixture is filtered, and the
residue remaining on the fibre is mixed with 300 parts of water, and then poured
(with stirring) into an icy-cold solution of 25 parts of beta, beta, naphtolsulphonate

page_text: The
of sodium, and 35 parts of sodium carbonate (Na,CO) in 500 parts of water.
so-produced dye-stuff is completely salted out by means of common salt, filtered, and
pressed. The whole dye-stuff is then dissolved in 1000 parts of water, which solution
is mixed with 150 parts of a strong soda-lye (containing 33 per cent. of NaOH),
and boiled for a short time. Finally, 180 parts of common salt and 80 parts of a
23 per cent. hydrochloric acid are added. The resulting precipitate is filtered,
pressed, dried, and pulverized.
It is a black powder easily soluble in water with a blueish black colour, which
changes into pure blue on the addition of a strong soda-lye, or of acetic acid. It is
insoluble in concentrated hydrochloric acid, whilst it is dissolved by concentrated
sulphuric acid (66 degrees Baumé) with a pure blue color. From this solution, a
pure blue flaky precipitate is obtained, on the addition of a suitable quantity of ice.
The new coloring matter dyes unmordanted cotton greyish-blue shades. When
on fibre, the coloring-matter can be further diazotized and developed by means of
beta-naphtol, beautiful indigo blue shades being thus produced. These shades are
fast against acids, alkalies, washing, and the action of light.
The process proceeds in an analogous manner if, instead of the beta, beta, naphtol-
sulphonic acid, another of the known dye-stuff components, such as beta, beta, naphtol-
sulphonic acid, alpha, alpha, naphtolsulphonic acid, amidonaphtolsulphonic acid G,
or the like, is employed. On using, for instance, the last-named acid G, a coloring
matter is obtained that dyes unmordanted cotton dark-blue shades, which change
into a deep fast-black on diazotizing the dyestuff on the fibre, and "developing" it by
means of metaphenylenediamine.
My foreign correspondents do not intend to confine themselves to the particulars
given in the above Specification, as these can be varied within wide limits, without
altering the nature of the present invention, which in general relates to the production
of new disazo dyestuffs, by first coupling a diazo derivative of mono-acidylalpha,,
alpha, naphtylenediamine, with Clève's alphanaphtylamine betasulphonic acid
(16 or 17); secondly, diazotizing .the so-produced amidoazo compound; thirdly,
combining the diazo-azo compound thus obtained with the known dyestuff com-
ponents, such as amines, phenols, amido-phenols, diamines of the benzene or
naphthalene series, or the derivatives of the said compounds; and finally splitting off
the acidyle group.
Duted this 20th day of met 1000
GUMI LELE DI MUIFICATION.
The Manufacture or Production of New Disazo Colouring Matters.
I, HENRY EDWARD NEWTON, of the Office for Patents, 6, Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, do hereby declare the
nature of this invention and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement:-
In the French Patent No. 232299 (dated August 21st 1893), coloring matters
were described as being obtained by first combining the diazo derivative of alpha,
alpha, acetnaphtylene-diamine-beta,- or beta-sulphonic acid, with a phenol; secondly,
splitting off the acetylic group; thirdly, diazotizing the amido azo compound thus
obtained, and finally coupling the resulting diazo-azo body with another dye-stuff
component.

page_text: By this process, a dye-stuff was obtainable having the following formula:
Bearing in mind the hitherto accepted opinion about the nature and structural
composition of the azo dye-stuffs, it was reasonable to suppose that the same coloring
matter would result by first coupling a diazo-derivative of monoacidyl alpha, alpha-
naphtylenediamine with Clève's alpha-napthylaminebetasulphonic acid (1.6 or 1-7);
secondly diazotizing the so-produced amido azo compound; thirdly combining the
diazoazo compound thus obtained with alpha, alpha,-naphtholsulphonic acid and
finally splitting off the acidyl group from the resulting disazo dye-stuff.
My foreign correspondents have now made the surprising discovery that the
coloring matter obtained according to the last mentioned method is totally
different from that obtained according to the process described in the above cited
French Patent.
•
The principal differences are the following: The coloring matter obtained according
to our new process exhibits a greater affinity for the vegetable fibre, and dyes unmor-
danted cotton brighter shades than the known dye-stuff. The difference between
the two coloring matters can be observed still more distinctly, if the dye stuffs are
diazotized on the fibre. Whilst the new dye stuff is diazotized very easily, the
diazo derivative of the known dye-stuff is formed but slowly. The shades
which the diazotized dye-stuffs exhibit on the fibre are also different; that produced
by means of the known dye-stuffs is brown, whilst that of the new coloring matter is
violet. The differences are still greater if the two dye-stuffs, after being diazotized
on the fibre are "developed " with the aid of betanaphthol. Whilst the new
coloring matter combines easily, at ordinary temperatures, with the naphthol,
yielding bright blue shades, the dye-stuff obtained according to the above mentioned
French Patent combines but very slowly with the naphthol yielding dull blueish-gray
shades.
Very similar differences are observed, on comparing the results obtained from the
analogous dye-stuffs which contain other naphtholsulphonic acids, instead of the
alpha-alpha-naphtholsulphonic acid.
It may be remarked that my foreign correspondents ascribe these striking differences
between the two series of dye-stuffs to a different distribution of the double ligatures
in the dye-stuff molecule.
In order to illustrate the new process, the following example is given (the parts
being by weight).

page_text: are diazotized in the usual manner with the aid of 20 parts of muriatic acid
(containing 23 per cent. of HCI) and 7 parts of sodium nitrate. The resulting diazo
solution is stirred into a solution prepared from 27 parts of the sodium salt of Clève's
alphanaphthylamine-beta sulphonic acid (1.6), 20 parts of crystallized sodium acetate,
and 500 parts of water, which solution has been cooled to 10 degrees Centigrade.
After stirring the reaction mixture for a short time, 30 parts of a 33 per cent. soda lye,
and then 11 parts of sodium nitrate, are added. The resulting solution is mixed
with 110 parts of muriatic acid (containing 23 per cent. of HCI), and further stirred
for about 6 hours. Subsequently, the reaction mixture is filtered, and the residue
remaining on the filter is mixed with 300 parts of water, and then poured (with
stirring) into an icy-cold solution of 25 parts of beta, beta-naphthol-sulphonate of
sodium and 35 35 parts of sodium carbonate (Na2CO3), in 500 parts of water. The
so-produced dye-stuff is completely salted out by means of common salt, filtered,
and pressed. The whole dye-stuff is then dissolved in 1000 parts of water, which
solution is mixed with 150 parts of a strong soda lye (containing 33 per cent.
of NaOH), and boiled for a short time.-Finally, 180 parts of common salt and
80 parts of a 23 per cent. hydrochloric acid are added. The resulting precipitate is
filtered, pressed, dried, and pulverized.
It is a black powder, easily soluble in water with a bluish-black color, which
changes into pure blue on the addition of a strong soda lye, or of acetic acid.
It is insoluble in concentrated hydrochloric acid, whilst it is dissolved by concentrated
sulphonic acid (66 degrees Baumé) with a pure blue color. From this solution, a
pure blue flaky precipitate is obtained on the addition of a suitable quantity
of ice.
The new coloring matter dyes unmordanted cotton greyish-blue shades.
When on fibre, the coloring-matter can be further diazotized and developed by
means of betanaphthol, beautiful indigo-blue shades being thus produced. These
shades are fast against acids, alkalies, washing, and the action of light.
The process proceeds in an analogous manner, if, instead of the beta, beta,-naph-
tholsulphonic acid, another naphtholsulphonic acid, such as beta, beta-naphthol-
sulphonic acid, alpha, alpha-naphtholsulphonic acid, beta,-naphthol-beta-beta-
disulphonic acid, or the like, is employed.
My foreign correspondents do not intend to confine themselves to the particulars
given in the above Specification, as these can be varied within wide limits, without
altering the nature of the present invention, which, in general, relates to the pro-
duction of new disazo dye-stuffs, by first coupling a diazo derivative of monoacidyl-
alpha,-alpha, naphthylenediamine with Clève's alpha-naphthylamine beta sulphonic
acid (16 or 17); secondly, diazotizing the so-produced amidoazo compound;
thirdly, combining the diazoazo compound thus obtained with naphtholsulphonic
acids; and finally splitting off the acidyl group.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed (as communicated to me
from abroad), I declare that what I claim is
1. The process for producing new disazo coloring matters, which process consists
in first coupling a diazo-derivative of a monoacidyl-alpha,-alpha,-naphthylenediamine,

page_text: with Clève's alphanaphthylamine beta sulphonic acid (16 or 17); secondly, diazo-
tizing the so-produced amidoazo compounds; thirdly, combining the diazoazo com-
pounds thus obtained with naphtholsulphonic acids, and finally splitting off the acidyl
groups, substantially as herein before described.
2. As new articles of manufacture the new disazo coloring matters obtainable ac-
cording to the process hereinbefore described and claimed.
Dated 10th day of 1000
NEWTON & SON,
Agents for the Applicant.