The Manufacture or Production of Colouring Matters, and a New Material therefor.
Year: 1894

page_text: Date of Application, 28th Dec., 1894
Complete Specification Left, 27th Sept., 1895-Accepted, 2nd Nov., 1895
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany.]
The Manufacture or Production of Colouring Matters, and a New
Material therefor.
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:-
-
It is known that motamidonaphtholsulphonic acids have not been used in practice
up to the present time, and it is also known that beta, amido a, naphthol, one of the
two theoretically possible metamidonaphthols; and beta, amido a, naphthol sulphonic
acids, have not yet been produced.
My foreign correspondents have now succeeded in preparing the first member of
beta, amido alpha, naphthol derivatives, uz, the beta, amido alpha, naphthol beta
sulphonic acid, by fusing with alkalies beta, naphthylamine alpha, beta, disulphonic
acid, or salts thereof
In order to illustrate some methods of preparing this new acid, the following two
examples are given. The parts are by weight
FIRST EXAMPLE
A mixture prepared from 1 part of beta, naphthylaminealpha, beta, disulphonate
of sodium or potassium, and 5 parts of potassa, is heated at 130 degrees Centigrade.
At this temperature, the reaction begins, and the color of the melting mass turns
from yellowish-red into dark brown, whilst the temperature rises to 185 degrees
Centigrade. The melting process is finished after a short time, and when cool, the
resulting mass 19 acidulated. The new amido naphtholmonosulpho acid thus
produced gradually separates in crusts from the acid solution.
SECOND EXAMPLE.
1 part of beta, naphthylamine alpha, beta, disulphonate of sodium or potassium
is mixed with 2 parts of potassa and 0-4 parts of water The resulting mixture is
heated in a closed vessel capable of withstanding pressure during about 8 hours, at
from 180 to 200 degrees Centigrade. The so-formed amidonaphtholsulphonic acid
is isolated in the manner described in the preceding first example.
The beta, amido alpba, naphthol beta, sulphonic acid, when separated, is but
slightly soluble in water. The watery solutions of its salts exhibit a weak green
fluorescence. It possesses the following formula

page_text: My foreign correspondents have further found, that the said beta, amido alpha,
naphthol beta, sulphonic acid 18 capable of combining with the tetrazo compounds
of paradiamines, to form so-called symmetrical and mixed disazo dye-stuffs. The
coloring matters obtainable from the said acid and the tetrazo compounds of
paradiamines, materially differ from the analogous coloring matteis derived from
other amido naphthol sulphonic acids, in that they do not produce blue, violet, or
dark shades, but that they yield chiefly magenta-red and reddish-violet shades,
which in general cannot be moduced by means of the aualogous dye-stuffs derived
from other amidonaphthol sulphonic acids. The new dye-stuffs are also distinguished
for the great clearness of their sbades My foreign correspondents believe that the
peculiar behaviour and the technical value of these coloring matters are caused by
the so-called meta position of the amido and hydroxylic group in the beta, amido
alpha, naphthol beta, sulphonic acid used for producing these dyes.
The following example is given, in order to illustrate the production of the
symmetrical dye-stuffs The parts are by weight
OF
COLORING MATTER OBTAINED FROM ONE MOLECULAR PROPORTION
TOLIDINE AND TWO MOLECULAR PROPORTIONS OF BETA, AMIDO ALPHA,
NAPHTHOL BETA, SULPHONIC ACID.
1
obot +
The tetraso solution prepared from 212 parts of tolidine, or the corresponding
quantity of a salt thereof, in muriatic solution, by means of 14 parts of sodium
nitrite, is, while cooling, allowed to flow into a solution obtained by dissolving
522 parts of the sodium salt of beta, amido alpha, naphthol beta, sulphonic acid,
and adding about 50 parts of sodium acetate, and a small quantity of acetic acid.
The formation of the dye, which begins immediately, is accelerated by repeatedly
stirring. After several hours, the mass is slowly heated to about 50 degrees
Centigrade, and the finished dye-stuff is subsequently isolated in the usual manner, viz.,
by filtering off, pressing, and drying
It produces, on unmordanted cotton, bluish magenta-red shades, distinguished
by reason of their fastness and cleaiuess Its composition is represented by
the formula
Other symmetrical dye-stuffs result, if other paradiamines are employed in place
of tolidine used in the preceding third example. The colong matters thus
obtainable produce, on unmordanted cotton, chiefly magenta red, reddish violet, and
violet shades, possessing great clearness. For instance, the dye produced from
benzidine yields bluish-ied shades, and the coloring matter obtained from dianisidine
produces violet shades.
The researches of my foreign correspondents have also shown that the said
beta, amido alpha, naphthol beta, sulphonic acid is capable of combining with an
I

page_text: equ-molecular proportion of tetrazo derivatives of paradiamines, to form so-calle.l.
intermediate products, which contain a fice diazo group, and therefore can be
combined with another molecular proportion of a dye-stuff component, w., amine,
phenol, amidophenol, amidophenolether, diamine of the benzene or naphthalene series,
a sulphonic or carboxylic derivative thereof. So-called mixed disazo dye-stuffs
are thus obtained. The same coloung matters can also be obtained by combining
one molecular proportion of a tetrazo compound of a paradiamine, first with one
molecular proportion of any dye-stuff component (amine, phenol, amido phenol,
amidophenolether, diamine, sulphonic or carboxylic acid thereof), and subsequently
with one molecular proportion of the said beta, amido alpha, naphthol beta
sulphonic acid, or a salt thereof.
In order to illustrate the production of the mixed disazo dye-stuff's hereinbofore
defined, the following example is given, the parts being by weight .-
BENZI-
DYE-STUFF OBTAINED FROM EQUAL MOLECULAR PROPORTIONS OF
DINE, ALPHA NAPHTHOL ALPHA, SULPHONIC ACID, AND BETA, AMIDO
ALPHA NAPITOL BETA SULPHONIC ACID.
A solution of tetrazo diphenyl chloride, obtained in the well-known manner from
184 parts of benzidine, is allowed to flow into an ice-cold solution prepared
from 24-6 parts of the sodium salt of alpha, naphthol alpha, monosulphonic acid,
30 parts of sodium acetate, and a small quantity of acetic acid. When the
formation of the intermediate product is finished, a cooled solution in water
of 261 paits of the sodium salt of beta, amido alpha, naphthol beta, sulphonic
acid, is added, taking care that there shall be a weakly acetic acid tenction until
the combination is complete. After standing during several hous, the mixture is
heated for a short time at about 50 degrees Centigrade, and after cooling, the
finished dye-stuff is isolated by salting out, filtering off, pressing, and diying.
It produces reddish-violet shades on unmordanted cotton, and possesses the
following formula ..
if on the one
Other mixed disazo dye are obtained in an analogous manuer,
hand, the benzidine used in the preceding fourth example is replaced by the
corresponding quantity of another paradiamine, u if, on the other hand, another
dye-stuff component (amine, phenol, amidophenol, amidophenolether, diamine,
sulphonic or carboxylic acid thereof) is employed in place of alpha, naphthol
alpha, sulphonic acid used in this example.
As above mentioned, the last-defined mixed disazo dye-stuffs can also be
produced by combining the tetrazo derivative of a diamine, first with a molecular
proportion of beta, amido alpha, naphthol beta, sulphonic acid, or a salt thereof,
and subsequently with a moleculni proportion of another dye-stuff component

page_text: (amine, phenol, amidophenol, amidophenolether, diamine of the benzene or
naphthalene series, a sulphome or carboxylic acid thereof).
The mixed disazo dye-stuffs obtainable as leieinbefore defined, yield shades
varying according to the different components used, and these shades are likewise
distinguished for their clearness and fastness.
My foreign correspondents have described in the Examples One and Two some
methods of practically producing the beta, amido alpha, naphthol beta, sulphonic
acid, and they have illustrated the production of the symmetrical and mixed disazo
dye-stuff's derived from the said new acid by the foregoing Examples Three and
Four. As a matter of course, my foreign correspondents do not limit themselves to
the directions given in these examples, which are merely typical.
Dated this 28th day of December 1894
NEWTON & SUN,
Agents for the Applicant.
The Manufacture or Production of Colouring Matters, and a New
Material therefor.
I HENRY EDWARD NEWTON of 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:-
Beta, amido alpha, naphthol the one of the two theoretically possible met-
amidonaphthols and beta, amido alpha, naphtholsulphonic acids have not yet been
produced
My foreign correspondents have now succeeded in preparing a beta, amido
alpha, naphthol derivative uz. beta, amido alpha, naphthol beta, sulphonic acid
by fusing bela, naphthylamine alpha, beta, disulphonic acid or salts thereof with
alkalies.
The following two examples are given as illustrations of methods of preparing
this non acul
The nata are by weight.
PRODUCTION OF BETA1 AMIDO ALPHA, NAPHTHOL BETA, SULPHONIC ACID.
A mixture prepared from 1 part of beta, naphthylamine alpha, beta, disul-
phonate of sodium or potassium and 5 parts of potash is heated at 130 degrees
Centigrade. The action begins at this temperature, the color of the melting
mass turning from yellowish red to dark brown, whilet the temperature rises to
185 degrees Centigiade. The melting process is finished after a short time.
When cool the melt is acidulated in the usual manner The new amidonaphthol-
mousulphonic acid gradually separates in crusts from the acid solution.
1 part of beta, naphthylamine alpha, beta, disulphonate of sodium or potassium
is mixed with 2 parts of potash and 04 paits of water and the mixture is heated
Da closed vessel capable of withstanding pressure duing about 8 hours at
from 180 to 200 degrees Centigrade The so formed amidonaphtholsulphonic acid
1s isolated in the manner described in the preceding first example.
Beta, amido alpha, naphthol beta, sulphonic acid is but slightly soluble in water.

page_text: Solutions of its salts in water exhibit a weak green fluorescence. It is
by the following formula
represented
which follows from the fact that when the said amidonaphtholmonosulphonic acid
is heated with water under pressure at about 200 degrees Centigrade, it is
Converted into the dihydroxynaphthalenemouosulphonic acid which has been
obtained by heating the isomeric alpha, amido beta, naphthol beta, sulphonic
acid with 5 parts of a 5 per cent. solution of sulphuric acid at about 200 degrees
Centigrade.
The new beta, amido alpha, naphthol beta, sulphonic acid differs from the
sonicic amidonaphtholsulphonic acids in its properties and the azo dye stuffs
derived from this new amidonaphtholmonosulphonic acid aud tetrazo compounds,
exhibit dyemg properties other than those possessed by the corresponding azo
coloring matters derived from isomeric amidonaphtholsulphonic acid as hereinafter
described
The
My foreign correspondents have further found that the said beta, amido alpha,
naphthol beta, sulphonic acid is capable of combining with the tetrazo derivatives
of paradiamines to form so called symmetrical and mixed disazo dye stuff's
coloring matters obtainable from the said acid and the tetrazo derivatives of
para diamines, materially differ from the analogous coloring matters derived from
other amidonaphtholsulphonic acids, in that they do not produce blue violet or
dark shades but yield chiefly magenta red and reddish violet shades, which cannot
generally be produced by means of the analogous dye stuffs derived from other
amidonaphtholsulphonic acids. The new dye stuffs are also distinguished on
account of the great clearness of their shades. My foreign correspondents believe
that the peculiar behaviour and the technical value of these coloring matters are
due to the fact that the said beta, amido alpha, naphthol beta, sulphonic acid
contains the amilo group in the so called meta position relatively to the hydroxylic
group
The following example is given in order to illustrate the production of the
sy minetical dre stuffs. The parts are by weight.
COLORING MATTER OBTAINED FROM ONE MOLECULAR
PROPORTION OF
TOLIDINE AND TWO MOLECULAR PROPORTIONS OF BET AMIDO ALPIIA;
NAPHTHOL BETA, SULPHONIC ACID.
The cooled tetrazo solution prepared from 212 parts of tolidine or the
corresponding quantity of a salt thereof in muriatic solution by means of 14 parts
of sodium nitrite is allowed to flow slowly into a solution obtained by dissolving
52.2 parts of the sodium salt of beta, amido alpha, naphthol bota, sulphonic acid
and adding about 50 parts of sodium acetate and a small quantity of acetic acid.
The formation of the dye stuff which begins immediately is accelerated by
repeatedly stunting After several hours the mass 1 slowly heated to about
50 degrees Centigrade and the hmshed dye stuff is subsequently isolated in the
usual manner z by filtering off, pressing and drying.

page_text: If produces on unmordanted cotton bluish magenta red shades distinguished by
reason of their fastness and clearness Its composition is represented by the
formula
Other symmetrical dye stuffs me obtained, if corresponding quantities of other
paradiamines are used in place of toldme. The coloring matters thus obtainable
produce on unmordanted cotton, cluefly magenta red, reddish violet and violet
shades also of great cleainess. For instance the dye produced from benzidine
yields blush red shades and that obtained from dianisidue violet shades
The researches of my foreign correspondents have also shown that the said beta,
amido alpha, naphthol beta, sulphonic acid is capable of combining with a molecular
proportion of the tetrazo derivative of a paradiamine to form so called intermediate
products containing a free diazo group, which therefor can be combined with
another molecular proportion of a dye stuff component, uz an amine, diamine,
phenol, dihydroxy compound, amidophenol or amidophenolether of the benzene or
naphthalene series or a sulphonic oi carboxylic deivative thereof. So called
mixed disazo dye stuffs are thus obtained. The same colong matters can also
be obtained by inversely combining a molecular proportion of a tetrazo compound
of a para diamine first with a molecular proportion of any dye stuff component
(an amine diamine, phenol dihydroxy compound amidophenol oi amidophenolether
of the benzene or naphthalene series or a sulphonic or carboxylic acid thereof)
and subsequently with a molecular proportion of the said beta, amido alpha,
naphthol beta, sulphonic acid or a salt thereol.
In order to illustrate the manner of producing the mixed disazo dye stuffs
bereinbefore defined the following example is given the parts being by weight
DYE
STUFF OBTAINED FROM MOLECULAR PROPORTIONS OF BENZIDINE
ALPHA NAPHTHOL ALPHA, SULPHONIC ACID AND BETA, AMIDO ALPHAg
NAPHTHOL BETA SULPHONIC ACID.
A solution of tetrazo diphenylchloide obtained in the well known manner from
84 paits of benzidine is allowed to flow into an ice cold solution containing
24 6 parts of the sodium salt of alpha, naphthol alpha, monosulphonic acid 30 parts
of sodium acetate and a small quantity of acetic acid. When the formation of the
intermediate product is at an end, a cooled solution of 261 parts of the sodium
salt of beta, amido alpha, naphthol beta, sulphonic acid is added, care being taken
that the solution is maintained, weakly acid, by means of acetic acid until the
combination is complete. After standing several hours the mixture is heated
during a short time at about 50 degrees Centigrade and then after cooling it, the
finished dye stuff is 180lated by salting out filtering off pressing and drying. It

page_text: produces reddish violet shades on unmordanted cotton and is
following formula
represented by the
Other mixed disazo dye stuffs are obtained in an analogous manner on the one
hand by using instead of the benzidine of the preceding fourth example the
corresponding quantity of another paradiamine, or on the other hand, by using
another dye stuff component (an amine, diamine, phenol, dihydroxy compound,
amidophenol, amidophenolether of the benzene or naphthalene series a sulphonic or
carboxylic acid thereof) in place of alpha, naphthol alpha, sulphonic acid.
As above mentioned, the last defined mixed disazo dye stuff's can also be
produced by combining the tetrazo derivative of a diamine first with a molecular
proportion of beta, amido alpha, naphthol beta, sulphonic acid or a salt thereof
and subsequently with a molecular proportion of another dye stuff component
such as an amine diamine, phenol, dihydroxy compound amidophenol, amidophenol-
ether of the beuzene of naphthalene series a sulphome or carboxylic acid
thereof.
The mixed disazo dye stuffs obtainable as hereinbefore defined yield shades
varying according to the different components used and these shades are also
distinguished for their clearness and fastness.
In the first and second examples my foreign correspondents have descubed
methods of practically producing beta, amido alpha, naphthol beta, sulphonic acid
and they have illustrated the production of the symmetrical and mixed disazo dye
stuff derived from the said new acid by the foregoing thnd and fourth examples
but as a matter of course they do not limit themselves to the directions given in
these examples which are merely typical.
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 claun is.―
1. The production of beta, amido alpha, naphthol beta, sulphonic acid by
heating beta, naphthylamine alpha, beta, disulphonic acid or salts thereof with
caustic alkalies at elevated temperatures and subsequently isolating the amido
uaphtholmonosulphonic acid in a suitable manner.
2. The process for producing symmetrical disazo dye stuffs from beta, amido
alpha, naphthol beta, sulphonic acid which process consists in combining one
molecular proportion of the tetiazo derivative of a paradramine with two
molecular proportions of beta, amido alpha, naphthol beta, sulphonic acid or an
alkaline salt thereof.
3. The production of mixed disazo dyestuffs from beta, amido alpha, naphthol
beta, sulphonic acid which process consists in coupling one molecular proportion of
the tetrazo derivative of a paradiamine (in any order) with one molecular
proportion of beta, amido alpha, naphthol beta, sulphonic acid or an alkaline salt
thereof and also with one molecular proportion of the known dye stuff components

page_text: (such as amines, diamines phenols, dihydroxy compounds, amidophenols auido-
phenolethers of the benzene or uaphthalene series sulphonic or carboxylic acids
thereof.
4. As new products of manufacture
(a) The beta, amido alpha, naphthol beta,
sulphonic acid and
(b) The new symmetrical and mixed disazo
dye stuff's
Dated 1... 004 Jan
1005
Produced by the processes 5
here before defined or by
any other means affording the
same result.
NEWTON & SON,
[Agents for the Applicant.