The Manufacture or Production of Azo Dye-stuffs, and Materials therefor.
Year: 1894

page_text: Date of Application, 13th Mar., 1894
Complete Specification Left, 12th Dec., 1894-Accepted, 12th Jan., 185
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of Azo Dye-stuffs, and Materials
therefor.
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:-
"
My foreign correspondents have found that ẞ, amido a, naphthol can easily be
converted into B₁ amido a, naphtholmonosulphonic acids by a treatment with
sulphonating agents. According to the researches of my foreign correspondents,
two isomeric B₁ amido a, naphthol monosulphonic acids are thus produced, which
differ in their solubility, and the researches of my foreign correspondents have
shewn that the acid which is soluble with greater readiness, is produced in more
than double the quantity in which the less soluble acid is formed.
Ba-amidonaphthol (ẞ, amido a, naphthol) required for the said purpose, has been
prepared by my foreign correspondents by melting, with alkalies, the B₁ naphthyl-
amine a, monosulphonic acid at from 260 to 270 degrees Centigrade.
The
One method of converting B₁ amido a3 naphthol into the two isomeric ẞi-amido
a naphtholmonosulphonic acids, is illustrated by the following example. The
Darts are by weight.
PRODUCTION OF TWO ISOMERIC B₁ AMIDO α, NAPHTHOL-MONOSULPHONIC
ACIDS FROM ẞ₁ AMIDO
NAPHTHOL.
10 parts of ẞ, amido a naphthol are dissolved in 50 parts of concentrated
sulphuric acid (at 66 degrees Baumé), at from 20 to 30 degrees Centigrade. When
the amido naphthol has dissolved, the sulphonation is complete. The whole
mixture solidifies after some time, assuming a pap-like consistence. On pouring
the sulphonated mass into 200 parts of water, the two acids separate as a white
crystalline pap. The mixture of these two acids, when filtered from the sulphuric
liquid, is converted into the calcium salts, and the solution of the two calcium salts,
which is about 400 litres (in case the parts are kilos. by weight), is mixed with
muriatic acid in excess. One of the two B, amido as naphtholmonosulphonic acids,
viz., that which is soluble with relatively greater difficulty, separates in the form
of white flakes, which are filtered off, whilst the other isomeric acid is precipitated
by adding common salt to the resulting filtrate.
In order to produce the isomeric ẞ, amido a, naphthol monosulphonic acids from
ẞ, amido 03
naphthol, my foreign correspondents do not limit themselves to the
directions given in the above example, as these can be varied; for instance, a
stronger sulphuric acid, or even a weaker sulphuric acid (such as 60 degrees
Baume), can be used in place of the sulphuric acid at 66 degrees Beamé. When
using sulphuric acid (60 degrees Baumé), the mixture is to be heated at about
60 degrees Centigrade. The separation of the two isomeric -amido a naphthol-
monosulphonic acids can also be effected in a manner other than that described in

page_text: the above example, viz., by means of all methods which can be used in case two
substances are to be separated, the one of which dissolves with greater ease than
the other.
On following the directions given in the above example for sulphonating B₁-amido
as naphthol, about 3 parts of the less soluble ẞ-amido as naphtholmonosulphonic
acid and 7 parts of the readily soluble acid are relatively obtained.
The properties of these two acids, together with those possessed by the known
ẞ, amidou, naphthol-3,-monosulphonic acid, are hereinafter mentioned.
The less soluble B₁-amido as naphthol monosulpho acid forms a light yellow
diazo compound soluble with difficulty, which, in the presence of sodium carbonate,
is converted into a brown precipitate. Ferric chloride possesses, in watery
solutions of the said acid, a dull coloured precipitate, whilst an addition of chloride
of lime to the watery solutions, turns the colour into brown, and finally causes the
separation of a precipitate. When combined with tetrazodiphenyl salts, it yields a
tetrazo dyestuff, producing brownish violet shades, which, turn into blue when
treated with ammonia. The said tetrazo dye stuff, when fixed on the fibre, can be
diazotised and coupled with ẞ-naphthol, brown shades being thus produced.
The more soluble ẞ, amido-a3-naphtholmonosulphonic acid, yields a diazo
compound in the form of a yellow soluble precipitate. On adding the liazo com-
pound to a solution of sodium carbonate, a reddish-violet solution is first obtained,
a blue precipitate being finally separated. The solutions of the acid yield a bluish-
grey precipitate when ferric chloride is added, whilst an addition of chloride of
lime first turns the colour of the solution into brown, and subsequently causes a
precipitate. The dyestuff obtained from tetrazodiphenyl and the readily soluble
B-amido-a-naphtholmonosulphonic acid, dyes a reddish-violet, which turns into
red by a treatment with ammonia. Blue shades are obtained on diazotising the
last named dye stuff, when fixed on the fibre, and coupling with ẞ naphthol.
The B, amido a naphthol ẞ monosulphonic acid mentioned above, yields a diazo
compound in the form of soluble brown crystalline needles. On adding this diazo
compound to a solution of sodium carbonate, a reddish-violet solution first results,
a blue precipitate being subsequently separated. The watery solutions of the acid
assume a brownish-red or yellowish-brown color, when respectively ferric chloride
or chloride of lime are added thereto. The tetrazo dye stuff obtained from
benzidine and the said acid, produces on unmordanted cotton reddish-violet shades,
which are not altered by a treatment with ammonia. Bluish shades result on
diazotising the last-named dyestuff (when fixed on the fibre), and coupling with
beta naphthol.
My foreign correspondents briefly term the less soluble acid of the two ẞ, amido
as naphtholmonosulphonic acids, "ẞ, amido a naphtholmonosulphonic acid S.," and
the more readily soluble isomeric acid, B₁ amido as naphthol monosulphonic
acid L."
6
My foreign correspondents have shown that the B, amido a, naphtholmong-
sulphonic acid S., when combined with the tetrazo compounds of "benzidine, its
analogues or homologues," yields chiefly brownish-violet dye-stuffs which are of no
technical value, and yield valuable brown shades only when diazotised on the fibre
and coupled with suitable dyestuff components, whilst the isomeric ẞ₁ amido-
a-naphtholmonosulphonic acid L, when combined with the said tetrazo compounds,
yields dyestuffs which produce very clear and intense shades, varying from violet
to blue, and also possess the valuable property of being diazotisable when fixed on
the fibre, and also of combining with phenols, amines, diamines, amidophenols,
amidophenol ethers of the benzene or naphthalene series, sulphonic or carboxylic
derivatives thereof, shades from blue to bluish black, and distinguished for their
great intensity, being thus produced.
The process of producing the said dye-stuffs (so-called "symmetrical" and
"mixed" disazo dye stuffs) from the 3-amido-a, naphtholmonosulphonic acid L
berein before defined, in general consists, either in coupling two molecular
proportions of the said acid with one molecular proportion of the tetrazo compound
"..

page_text: of "benzidine, its analogues or homologues" (the so-called "symmetrical" disazo
dyestuffs being formed), or in coupling one molecular proportion of the said acid,
with one molecular proportion of the tetrazo compounds derived from "benzidine,
its analogues or homologues," and subsequently combining the intermediate
products so formed with one molecular proportion of another dye stuff component,
viz., amnine, diamine, phenol, amidophenol, amidophenolether of the benzene or
naphthalene series, a sulphonic or carboxylic derivative thereof, so-called "mixed "
disazo dye-stuffs being thus produced. The last named "mixed" disazo dyestuffs
can also be produced inversely, viz., by coupling one molecular proportion of a
tetrazo compound derived from "benzidine, its analogues or homologues," first with
one molecular proportion of one of the said dyestuff components, and subsequently
with one molecular proportion of B-amido-as-naphtholmonosulphonic acid L.
The combination of the last named ẞ-amido-a, naphthol monosulphonic acid L
with the aforesaid tetrazo compounds, or intermediate products, is most advan-
tageously effected in alkaline solutions."
In order to illustrate the production of the so-called "symmetrical" disazo dye-
stuffs from B, amido-as-naphtholmonosulphonic acid L, the following example is
given, the parts being by weight.
COLOURING MATTER OBTAINED FROM ONE MOLECULAR PROPORTION OF
DIANISIDINE, AND TWO MOLECULAR
ag NAPHTHOLMONOSULPHONIC ACID L.
PROPORTIONS OF ẞ, AMIDO
The solution of tetrazodiphenolether produced in the well-known manner from
244 parts of dianisidine, or the corresponding quantity of a salt thereof, is allowed
to run into an icy-cold solution prepared from 50 parts (two molecules) of the
sodium salt of ₁ amido as naphtbolmonosulphonic acid L, and rendered alkaline
by means of sodium carbonate. The formation of the "symmetrical dyestuff is
completed after a short time. It is isolated in the usual manner, viz., by salting
out, filtering off, pressing, and drying. The shades produced therewith, on
unmordanted cotton, are blue, and possess great clearness and intensity. It
possesses the following formula :-
Other symmetrical disazo dyestuffs are obtained in an analogons manner, if the
dianisidine used in the above second example is replaced by the equivalent quantity
5 of another of the diamines hereinbefore termed " benzidine, its analogues or
homologues." These colouring matters likewise yield on unmordanted cotton very
intense shades, varying from violet to blue, and possess in the same manner as the
colouring matter described in the above second example, the valuable property
of being further diazotisable when fixed on the fibre, and also of combining

page_text: with phenols, amines, diamines, amidophenols, amidophenolethers of the benzene
or naphthalene series, sulphonic or carboxylic derivatives thereof, shades
chiefly from blue to bluish-black and violet, and distinguished for their great
intensity and fastness against washing and fulling, being thus obtained. For
instance, the blue colouring matter obtainable as described in the above second
example, yields, when diazotised on the fibre, and coupled with ẞ naphthol, a blue
shade which is very intense, and withstands, to an extraordinary degree, the a action
of washing and fulling.
My foreign correspondents meau by the above expression "benzidine, its
analogues or homologues," for instance, the following diamido compounds, viz. :-
Benzidine, tolidine, diamidophenyltolyl, diamidodiphenolether, diamidoalkylhydroxy-
diphenyl, diamidoalkylhydroxyphenyltolyl, diamidoazobenzene, diamidoazotoluene,
diamidoazoxylene, diamidoazoxybenzene, diamidoazoxytoluene, diamidostilbene,
diamidofluorene, diamidonaphthalene, diamidocarbazol, diamidodiphenylene oxide,
diamidoditoluylene oxide, para phenylene diamine, paratoluylene diamine, benzidine
sulphone, tolidine sulphone, diamidophenyltolylsulphone, diamidodiphenoxyacetic
acid, diamidodiphenyleneketoxime, diamidodiphenylamine, diamidophenylbenzi-
midazol, amidobenzene-azo-a naphthylamine, amidotoluene-azo-a naphthylamine,
amidoxylene-azo-a-naphthylamine, amidobenzene azo-para-xylidine, amidotoluene-
azo-para-xylidine, amidoxylene-azo-para-xylidine, amido benzene azo-meta-amido-
para-cresolether, amidotoluene-azo-meta-amido-para cresol ether, amidoxylene
azo-meta amido-para cresolether, amidobenzene azo-ortho amido-para-cresolether,
amidotoluene azo-ortho-amido-para-cresolether, amidoxylene azo-ortho-amidopara
cresol ether, amidobenzene-azo-ẞ-ethoxy-a-naphthylamine, amidotoluene-azo-
B-ethoxy-a-naphthylamine, sulphonic derivatives, carboxylic derivatives, or sulpho-
carboxylic derivatives thereof.
My foreign correspondents, however, do not limit themselves to the employment
of the mentioned diamido compounds, as all diamines, sulphonic, carboxylic,
sulphocarboxylic, or other derivatives thereof, in general, may be used, which can
be converted into tetrazo compounds, either directly, or by means of the
corresponding monoacetodiamido compounds. In place of the monoaceto diamido
compounds, the corresponding mononitro amines, sulphonic or other derivatives
thereof, can be used; however, in the latter case, the first formed intermediate
nitro azo products are to be reduced at the appropriate time, effecting this reduction
at the same time when the acetyl group is displaced in the corresponding
intermediate monoaceto azo products resulting in case monoaceto diamines, or
substi-derivatives thereof, bo used.
65
As above mentioned, the aforesaid ẞ,-amido-a-naphthol monosulphonic acid L.,
is also capable of combining with one molecular proportion of a tetrazo compound
derived from benzidine, its analogues or homologues" so-called intermediate
products being thus formed which contain a free diazo group, and therefore can be
coupled with one molecular proportion of another dyestuff component (such as
amine, diamine, phenol, amidophenol, amidophenolether of the benzene or
naphthalene series, a sulphonic or carboxylic derivative thereof).
66
The mixed disazo dyestuffs thus obtained can also be produced inversely, viz.,
by combining one molecular proportion of the tetrazo compounds derived from
benzidine, its analogues or homologues," first with one molecular proportion
of a dye-stuff component, and subsequently with one molecular proportion of
B, amido a, naphtholmonosulpho acid L. The mixed disazo dyestuffs obtained as
hereinbefore defined, produce, on unmordanted cotton, very deep red, violet, blue,
or bluish-black shades, and possess the valuable property of being further
diazotisable when fixed on the fibre and also of combining with the so-called
developers (amines, diamines, phenols, amidophenols, amidophenolethers of the
benzene or naphthalene series, sulphonic or carboxylic derivatives thereof) shades
being thus obtained which vary from violet-red violet, to blue and bluish-black,
and are distinguished for their extreme intensity and fastness against washing and
fulling.

page_text: One method of producing the mixed disazo dyestuffs hereinbefore defined, is
illustrated by the following example. The parts are by weight.
DYE-STUFF FROM EQUIMOLECULAR PROPORTIONS OF TOLIDINE, a₁ AMIDO
a NAPHTHOL-B, B3-DISULPHONIC ACID, AND AMIDO a₂-NAPHTHOL
MONO SULPHONIC ACID L.
21-2 parts of tolidine are converted, in the well known manner, into tetrazo
ditolylchloride, and the resulting tetrazo solution, whilst carefully cooling, is mixed
with a solution prepared by dissolving 36-3 parts of the neutral sodium salt of
amido a naphthol ẞ, B3 disulphonic acid, and an excess of sodium carbonate.
When the formation of the intermediate product is completed, a solution rendered
alkaline by means of sodium carbonate, and containing 25 parts of the sodium
salt of B, amido as naphthol mono sulphonic acid L., is added. The formation of
the mixed disazo dye stuff at once begins, and is finished by heating. The dye
stuff is isolated in the usual manner, viz., by salting out, filtering off, pressing, and
drying. It yields on unmordanted cotton a beautiful deep blue. Its composition
is represented by the following formula :—
A deep bluish-black shade results, if the colouring matter obtained as described
in the above second example is diazotised (when on the fibre) and combined,
likewise on the fibre, with ẞ naphthol.
απ
Other "mixed" disazo dye-stuffs result in an analogous manner, if either the the
amido
a naphthol ẞ, ẞ, disulpho acid used in the above third example, is replaced
by the corresponding quantity of another dye-stuff componeut (amine, diamine,
phenol, amidophenol, amidophenolether of the benzene or naphthalene series, a
Bulphonic or carboxylic derivative thereof), or if the tolidine is replaced by the
equivalent quantity of one of the other diamines hereinbefore termed "benzidine,
its analogues or homologues."
The "mixed" disazo dye-stuffs obtained as described in the foregoing third
example, can also be produced inversely, viz., by combining one molecular proportion
of a tetrazo compound, first with one molecular proportion of ẞ, amido a,-naphthol
monosulphonic acid L., or an alkaline salt thereof, and subsequently with one
molecular proportion of another dyestuff component.
"
According to the researches of my foreign correspondents, the "symmetrical
and "mixed" disazo dye-stuffs derived from B, amido a, naphthol monosulphonic
acid L., can, by a subsequent diazotisation, and combination with the known dye-
stuff components, be converted into new polyazo dye-stuffs, which yield extremely
intense shades varying from bluish-black to black. The production of these poly-
azo dye-stuff's is effected in the well known manner. As above mentioned the last

page_text: named process can also be carried out on the fibre, very intense and fast shades
being thus obtained.
Dated this 13th day of Merah 1901
NEWTON & SON,
Agents for the Applicant.

page_text: My foreign correspondents briefly term the less soluble acid "beta, amido alphas
naphtholmonosulphonic acid S," and the more readily soluble isomeric acid "beta
amido alpha, naphthol monosulphonic acid L."
The researches of my foreign correspondents have shown, that when combined
with the tetrazo compounds of "benzidine, its analogues or homologues," beta₁
amido alpha, naphthol monosulphonic acid S yields chiefly brownish-violet dye-stuffs,
which are of no technical value, and yield valuable brown shades only when
diazotised on the fibre and coupled with suitable dye-stuff components, whilst when
the isomeric beta, amido alpha, naphtholmonosulphonic acid L is combined with
the said tetrazo compounds, it yields dye-stuffs which produce very clear and intense
shades varying from violet or blue to red, and which also possess the valuable property
of being diazotisable when fixed on the fibre, and of then combining with phenols,
amines, diamines, dihydroxy compounds, amidophenols, amidophenolethers of the
benzene or naphthalene series, sulphonic or carboxylic derivatives thereof, yielding
shades of great intensity, which vary from blue to bluish-black.
The process of producing the said dye stuffs (so called "symmetrical" and
"mixed" disazo dye stuff's) from the beta, amido alpha, naphthol monosulphonic
acid L hereinbefore defined, in general consists either in coupling two molecular
proportions of the said acid with one molecular proportion of the tetrazo compounds
of "benzidine, its analogues or homologues" (so-called "symmetrical" disazo dye-
stuffs being formed), or in coupling one molecular proportion of the said acid with
one molecular proportion of the tetrazo compounds derived from "benzidine, its
analogues or homologues," and subsequently combining the intermediate products
so formed with one molecular proportion of another dye-stuff component, viz.:-an
anine, diamine, phenol, dihydroxy compound, amido phenol, amidophenolether of
the benzene or naphthalene series, a sulphonic or carboxylic derivative thereof,
so-called "mixed" disazo dye-stuffs being thus produced. The greater number of
the last named "mixed" disazo dye stuffs can also be produced inversely, viz., by
.coupling a molecular proportion of a tetrazo compound derived from "benzidine,
its analogues or homologues," first with a molecular proportion of one of the said
dye-stuff components, and subsequently with a molecular proportion of beta, amido
alpha naphtholmonosulphonic acid L.
The combination of the last named beta, amido alpha, naphtholmonosulphonic
acid L with the aforesaid tetrazo compounds, or intermediate products, can be
effected in alkaline solutions, and the researches of my foreign correspondents have
shown that dye-stuffs differing from those obtained in alkaline solution, are in
general obtained, if the combination of the beta, amido alpha, naphtholmono-
sulphonic acid L with the tetrazo derivatives of "benzidine, its analogues or
homologues," be effected in a solution slightly acidulated with muriatic or acetic
acid.
In order to illustrate the production of the so-called "symmetrical" disazo dye-
stuffs from beta, amido alpha, naphtholmonosulphonic acid L, the following example
is given. the parts being by weight.
COLORING MATTER OBTAINED FROM ONE MOLECULAR PROPORTION OF
DIANISIDINE AND TWO MOLECULAR PROPORTIONS OF BETA AMIDO
ALPHA, NAPHTHOLMONOSULPHONIC ACID L.
The solution of tetrazo diphenolether produced in the well known manner from
24-4 parts of dianisidine (1 molecular proportion), or the corresponding quantity.of
a salt thereof, is allowed to run into an icy-cold solution prepared from 52.2 parts
(two molecular proportions) of the sodium salt of beta, amido alpha, naphtholmono-
sulphonic acid I, rendered alkaline by means of sodium carbonate. The formation
of the "symmetrical" disazo dye-stuff is completed after a short time. It is isolated

page_text: in the usual manner, viz. :-by salting out, filtering off, pressing, and drying. The
shades produced therewith on unmordanted cotton are blue, and of great clearness
and intensity. It is represented by the following formula :-
Other "symmetrical" disazo dye-stufts are obtained in an analogous manner, if,
instead of the dianisidine used in the above Example B, the equivalent quantity of
another of the diamines hereinbefore termed "benzidine, its analogues or
homologues," be used. These coloring matters also produce very intense shades
on unmordanted cotton, varying from violet to blue, and possessing, like coloring
matter described in the above Example B, the valuable property of being further
diazotisable when fixed on the fibre, and of then combining with phenols, amines,
diamines, dihydroxy compounds, amidophenols, anidophenolethers of the benzene
or naphthalene series, sulphonic or carboxylic derivatives thereof, shades varying
chiefly from blue to bluish black, and violet, and distinguished by their great
intensity and fastness on washing and fulling, being thus obtained. For instance,
when the blue coloring matter obtainable as described in the above Example B, is
diazotised on the fibre, and coupled with betanaphthol, it yields a blue shade which
is very intense, and withstands washing & fulling to an extraordinary degree.
As above mentioned, the combination of the beta, amido alpha, naphtholmono-
sulphonic acid with the tetrazo derivatives of "benzidine, its analogues or
homologues," can also be effected in solutions acidulated, for instance, by means of
hydrochloric or acetic acid, dye-stuffs being thus produced which in general differ
from the corresponding dye-stuffs obtained in alkaline solutions.
For instance, a symmetrical" red disazo dye stuff is obtained on allowing one
molecular proportion of tetrazodiphenylchloride to act on two molecular proportions
of beta, amido alpha, naphtholmonosulphonic acid L, in a solution acidulated with
hydrochloric acid, then heating after about 24 hours, rendering alkaline by means
of sodium carbonate, and subsequently isolating the dye-stuff by salting out and
filtration. The coloring, matter thus produced produces shades on unmordanted
cotton which are very fast on exposure to light.
My foreign correspondents mean by the above expression, "benzidine, its analogues
or homologues," for instance, the following diamido compounds, viz. :-Benzidine,
tolidine, diamidophenyltolyl, diamido diphenolether, diamidoalkylhydroxy-
diphenyl, diamidoalkylhydroxyphenyltolyl, diamido azo benzene, diamidoazotoluene,
diamido azoxylene, diamido azoxybenzene, diamido azoxytoluene, diamidostilbene,
diamidofluorene, diamidonaphthalene, diamidocarbazol, diamidodiphenylene oxide,
diamidodituluylene oxide, paraphenylene diamine, paratoluylene diamine, benzidine
sulphone, tolidine sulphone, diamido phenyltolylsulphone, diamidodiphenoxyacetic
acid, diamido diphenylene ketoxine, diamidodiphenylamine, diamidophenylbenz-
imidazol, amido benzene-azo-alpha-naphthylamine, amidotoluene-azo-alpha-naphthyl-
amine, amidoxylene-azo-alpha-naphthylamine, amidobenzene-azo-para-xylidine,
amidotoluene-azo-para-xylidine, amidoxylene-azo-para-xylidine, amidobenzene-azo-
B

page_text: meta-amido-para-cresolether, amidotoluene-azo-meta-amido-para-cresolether, amido-
xylene-azo-meta-amido-para-cresolether, amido-benzene-azo-ortho - amido - para-
cresolether, amidotoluene-azo-ortho-amido-para-cresolether, amidoxylene-azo-ortho-
amido-para-cresolether, amidobenzene-azo-beta-ethoxy-alpha-naphthylamine, amido-
azo-beta-ethoxy-alpha-naphthylamine, sulphonic derivatives, carboxylic
derivatives, or sulphocarboxylic derivatives thereof.
toluene
My foreign correspondents, however, do not limit themselves to the use of the
said diamido compounds, as in general all diamines, sulphonic-, carboxylic-, sulpho-
carboxylic, or other derivatives thereof, may be used, which can be converted into
tetrazo compounds, either directly, or by means of the corresponding monacetyl-
diamido compounds. In place of the monacetyldiamido compounds, the corresponding
mononitroamines, sulphonic or other derivatives thereof, can be used; but in the
latter case, the mononitroazo compounds which are first. formed, must be reduced,
then diazotised, and combined with dye-stuff components, whilst if monoacetylated
diamines are used, the monacetylamidoazo derivatives which are first produced,
must be first suitably treated in order to separate the acetyl group, then diazotised,
and combined with the dyestuff components..
As above mentioned, the aforesaid beta-amido-alpha,-naphthol mono-sulphonic
acid L is also capable of combining with one molecular proportion of a tetrazo
⚫compound derived from "benzidine, its analogues or homologues," so-called inter-
mediate products being thus formed which contain a free diazo group, and therefore
can be coupled with a molecular proportion of another dyestuff component (such as
an amine, diamine, phenol, dihydroxy compound, amidophenol, amido phenolether
of the benzene or naphthalene series, a sulphonic or carboxylic derivative thereof.
The greater part of the "mixed" disazo dyestuff's thus obtained can also be
produced inversely, viz., by combining a molecular proportion of the tetrazo
compounds derived from "benzidine, its analogues or homologues," first with one
molecular proportion of a dyestuff component, and subsequently with one molecular
proportion of beta-amido-alpha-naphtholmonosulphonic acid L. The "mixed
disazo dyestuffs obtained as herein before defined, produce on unmordanted cotton
very deep red, violet, blue, or bluish-black shades, and possess the valuable property
of being further diazotisable when fixed on the fibre, and of then combining with
the so-called. developers (amines, diamines, phenols, dihydroxy compounds, amido-
phenols, amidophenolethers of the benzene or naphthalene series, sulphonic or
carboxylic derivatives thereof), shades being thus obtained which vary from violet-
red, violet, to blue and bluish-black, and which are distinguished by their extreme
intensity and fastness on washing and fulling.
"
One method of producing the "mixed" disazo dyestuffs herein before defined, is
illustrated by the following example. The parts are by weight.
DYE-STUFF FROM EQUIMOLECULAR PROPORTIONS OF TOLIDINE, ALPHA-
AMIDO-ALPHA-NAPHTHOL-BETA, BETA:- DISULPHONIC ACID, AND BETAL
AMIDO-ALPHA-NAPHTHOL-MONOSULPHONIC ACID L.
When
21-2 parts of tolidine are converted, in the well known manner, into tetraz -
ditolylchloride, and the tetrazo-solution (carefully cooled) is mixed with a solution
prepared by dissolving 36.3 parts of the neutral sodium salt of alpha,-amido-alpha-
naphthol-beta, beta,-disulphonic acid, and an excess of sodium carbonate.
the formation of the intermediate product is completed, a solution rendered alkaline.
by means of sodium carbonate, and containing 26-1 parts of the sodium salt of beta,
amido-alphas-naphthol-monosulphonic acid ; is added. The formation of the
mixed disazo dyestuff at once begins, and is finished by heating. The dye-stuff is
isolated in the usual manner, viz., by salting out, filtering off, pressing, and drying.

page_text: A deep bluish-black shade is obtained if the colouring matter obtained as
described in the above Example C, is diazotised (when on the fibre), and then
combined, while on the fibre, with beta-naphthol.
Other mixed" disazo dye-stuffs are formed in an analogous manner, if, instead
of the alpha-amido-alpha-naphthol-beta, beta-disulphonic acid used in the above
Example C, the corresponding quantity of another dyestuff component (amine,
diamine, phenol, dihydroxy compound, amidophenol, amidophenolether of the
benzene or naphthalene series, a sulphonic or carboxylic derivative thereof) be used,
or if, instead of tolidine, the equivalent quantity of one of the other diamines
hereinbefore termed "benzidine, its analogues or homologues," be taken.
The "mixed" disazo dyestuffs obtained as described in the foregoing Example C,
can also be produced inversely, riz., by combining a molecular proportion of a
tetrazo compound first with a molecular proportion of beta,-amido-alpha-naphthol-
monosulphonic acid L, or an alkaline salt thereof, and subsequently with a
molecular proportion of another dyestuff component.
To obtain so-called mixed disazo dyestuffs, the beta-amido-alpha-naphthol
monosulphonic acid L can also be combined, in an acidulated solution (using hydro-
chloric or acetic acid), with the tetrazo derivatives of "benzidine, its analogues or
homologues," or with the intermediate products obtained by combining a molecular
proportion of the tetrazo derivatives with a molecular proportion of any other dye-
Etuff component, dyestuffs being thus formed which in general differ from the
corresponding colouring matters obtained by coupling the said beta, amido-alpha,-
naphthol-monosulphonic acid L in alkaline solutions.
•
A "mixed" red disazo dyestuff is, for instance, obtained by coupling a molecular
proportion of tetrazo diphenyl chloride with a molecular proportion of salicylic acid
(in a solution rendered alkaline by means of sodium carbonate), and then with one
molecular proportion of beta-amido-alpha,-naphtholmono-sulphonic acid L, in a
weak acetic acid solution, heating the liquid after about 24 hours, rendering
the mixture alkaline, and isolating the dyestuff thus formed by salting out and
filtering off.
Another "mixed" disazo dyestuff, producing shades which withstand the action
of light, is obtained on allowing a molecular proportion of beta-amido-alpha-
naphtholmonosulphonic acid L, to act, during about 36 hours, on a molecular
proportion of tetrazo-diphenyl chloride in a solution acidulated by means of hydro-
chloric acid, then adding sodium acetate, and a molecular proportion of amido-
naphtholmono sulphonic acid G, heating the liquid mixture at once to boiling,
rendering the mixture alkaline by means of sodium carbonate, and isolating the
finished dye stuff by salting out and filtering off.

page_text: According to the researches of my foreign correspondents, the "symmetrical" and
"mixed" disazo dye-stuffs derived from beta,-amido-alpha,-naphthol-monosulphonic
acid L, can be converted by a subsequent diazotisation and combination with the
known dye-stuff components, into new polyazo dye-stuffs, which yield very intense
shades, varying from bluish-black to black. The production of these polyazo-dye-
stuffs is effected in the well-known manner in common use for analogous purposes.
As above mentioned, the last named process, viz., diazotisation and combination, can
also be carried out on the fibre, very intense and fast shades being thus obtained,
the said diazotisation and combination being carried out in the well known
manner.
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 production of two new beta-amido-alpha, naphtholsulphonic acids, by
sulphonating beta-amido-alpha, naphthol.
2. The process for producing beta,-amido-alpha,-naphtholmonosulphonic S, and
beta-amido-alpha,-naphthol monosulphonic acid L, hereinbefore referred to, which
process consists in sulphonating beta, amido-alpha,-naphthol, or salts thereof, at low
temperatures, with concentrated or moderately fuming sulphuric acid, and subse-
quently separating, in a suitable manner, the less soluble S acid from the more
readily soluble L acid.
3. The production of "symmetrical" and "mixed" disazo dyestuffs from beta-
amido-alpha-naphthol-monosulphonic acid L, or salts thereof, and tetrazo com-
pounds of "benzidine," its analogues or homologues."
4. The process for producing "symmetrical" disazo dyestuffs, which process
-consists in combining a molecular proportion of the tetrazo derivatives of
"benzidine, its analogues or homologues," with two molecular proportions of beta-
amido-alpha-naphthol monosulphonic acid L, or an alkaline salt thereof.
5. The production of "mixed" disazo dyestuffs, by combining a molecular
proportion of "benzidine, its analogues or homologues" (in any order), with a
-molecular proportion of beta, amido-alpha-naphthol monosulphonic acid L, or an
alkaline salt thereof, and with a molecular proportion of an amine, a phenol, a
diamine, dihydroxy compound, an amidophenol, amidophenolether of the benzene or
naphthalene series, a sulphonic or carboxylic acid thereof.
6. The conversion of the "symmetrical" and "mixed" disazo dyestuffs herein-
before defined (as such, or when on the fibre), into polyazo dye-stuffs, by a further
diazotisation, and subsequent combination with suitable dye-stuff components.
7. As new products of manufacture :-
a. Beta,-amido-alpha,-naphtholmonosulphonic acid S.
b. Beta, amido-alpha,-naphtholmonosulphonic acid L.
c. The new colouring-matters derived from beta-amido-alpha, naphtholmono-
sulphonic acid L,
produced by the processes herein before defined, or by any other process yielding
the same result.
Dated this 10th day of December 190,1
NEWTON & SON,
Agents for the Applicant.