The Manufacture or Production of Dye-stuffs by Means of Trihydroxynaphthalenemonosulpho Acid.
Year: 1894

page_text: Date of Application, 19th Jan., 1894
Complete Specification Left, 19th Oct., 1894-Accepted 24th Nov.,
1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of Dye-stuffs by Means of
Trihydroxynaphthalenemonosulpho Acid.
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 prepared some time ago a trihydroxynaphthalene-
monosulpho acid, by a process which consists in melting with alkalies, at
temperatures about 260 degrees Centigrade, either the naphthalenetetrasulpho acid
obtainable on sulphonating naphthalene B B disulpho acid, or the a-naphthol-
trisulpho acid, or the two isomeric dihydroxynaphthalenedisulpho acids which can
be prepared by melting with alkalies the said naphthalenetetrasulpho acid, at
temperatures under, respectively, 200 and 250 degrees Centigrade.
The researches of my foreign correspondents have now shewn, that the aforesaid
trihydroxynaphthalenemonosulpho acid possesses the property hitherto unknown
with respect to any hydroxynaphthalenesulpho acid, viz., capability of being coupled
with two molecules of a diazo compound in acidulated solutions, say, acetic acid
solutions, and my foreign correspondents have further found that in place of
coupling one molecular proportion of the above trihydroxynaphthalenemonosulpho
acid with two molecular proportions of a diazo product, one molecular proportion
of this trihydroxynaphthalene monosulpho acid can also be combined with two
molecular proportions of a diazo azo product, or with one molecular proportion of
the tetrazo derivatives of benzidine, or its analogues, or with two molecular
proportions of an "intermediate product" obtainable on coupling equal molecular
proportions of the tetrazo derivatives of benzidine, or its analogues, and an amine,
diamine, phenol, amidophenol, amidophenolether of the benzene or naphthalene
series, a sulpho or carboxylic acid thereof. In this manner, the so-called "simple
polyazo dyestuffs derived from trihydroxynaphthalenemonosulpho acid result.
According to the researches of my foreign correspondents, the combination of the
two molecules of diazo bodies with one molecule of the aforesaid trihydroxy-
naphthalenemonosulpho acid, does not take place at the same time, but the two
molecules are coupled the one after the other. My foreign correspondents, therefore,
have also succeeded in producing so-called "mixed" poly-azo dyestuffs derived
from the above trihydroxynaphthalenemonosulpho acid.
"
By the aforesaid expression "mixed poly azo dye stuffs," my foreign corre-
spondents particularly mean those which result from the combination of one
molecule of trihydroxynaphthalenemonosulpho acid, either with one molecule of a
diazo product, or diazo azo compound, and with one molecule of another diazo
product, or diazo azo compound, or with one molecule of one of the "intermediate
products" above defined, and with one molecule of another of these "intermediate
products," or with one molecule of a diazo compound, and with one molecule of a
diazo azo product; or with one molecule of a diazo compound and with one
molecule of an "intermediate product"; or with one molecule of a diazo azo
body, and with one molecule of a so-called "intermediate product." Of course,
my foreign correspondents mean "molecular proportions," when using the
expression "molecule"

page_text: My foreign correspondents mean by the above expression, benzidine or its
analogues, for instance, the following diamines, viz., Benzidine, orthotolidine,
diamidophenyltolyl, sulpho derivatives thereof, diamidomonoalkylhydroxydiphenyl,
diamidomonoalkylhydroxyphenyltolyl, diamidodiphenolether, benzidine sulphone,
tolidine sulphone, or sulpho acids derived therefrom, diamido diphenylene oxide,
diamidoditoluylene oxide, diamidocarbazol, paraphenylene diamine, paratoluylene
diamine, diamidostilbene, diamidostilbene disulpho acid, a, a, diamidonaphthalene,
a, a-diamidonaphthalene-ß, ẞ, disulpho acid. On producing the dye stuffs derived
from paraphenylene diamine, paratoluylene diamine, or the like, the corresponding
monoaceto compounds of the diamines, or the corresponding paranitroamines, are
profitably used as initial materials.
This invention, however, is not restricted to the use of the aforesaid diamines,
for other diamines, diamnidosulpho acids, or the like, which can be converted into
tetrazo derivatives, either directly, or with the aid of the corresponding monoaceto
compounds can likewise be used. Nitroamines, nitroamidosulpho acids, or the like,
can be used in place of the monoaceto diamines, monoacetodiamine sulpho acids, or
the like, in which case the nitro group of the resulting intermediate products, is to
be reduced at the appropriate time, whilst in case of employing monoaceto com-
pounds of diamines, or the like, the acetyl group is to be separated comparatively
at the same time.
My foreign correspondents describe, in the following examples, some methods of
producing several of the new dyestuffs above referred to. The parts are by
PRODUCTION OF A COLOURING-MATTER FROM EQUIMOLECULAR PROPORTIONS
OF DIAZOBENZENE, DIAZOBENZENE SULPHO ACID, AND TRIHYDROXY-
NAPHTHALENE MONOSULPHO ACID.
20 parts of aniline are diazotised in the well-known manuer by means of 15 parts
of sodium nitrite and 50 parts of muriatic acid. The resulting solution of diazo
benzene chloride is allowed to flow into a solution which is prepared by dissolving
30 parts of the acid potassium salt of trihydroxynaphthalenemonosulpho acid, and
20 parts of sodium acetate, and is kept acidulated by means of acetic acid. The
formation of the intermediate dye proceeds at once, and the latter either remains
dissolved, or is separated in the form of a reddish-yellow precipitate. After adding
39-5 parts of diazosulfanilic acid, the mixture is allowed to stand during about
12 hours. The complete dye-stuff, which is a dark brown precipitate, is filtered off,
pressed, and dried.
The "mixed" colouring matter thus obtainable, produces yellowish-brown shades
when it is dyed on wool in an acid bath. The shades withstand in a high degree
the action of light and washing. Its composition is represented by the
formule

page_text: The researches of my foreign correspondents have shown, that the same colouring
matter also results, if the trihydroxynaphthalenemonosulpho acid is, inversely,
coupled first with the diazo benzene sulpho acid, and subsequently with diazo-
benzene, equimolecular proportions of these agents being employed.
Colouring matters analogous to that obtainable as described in the above
Example A result, if the diazo products used therein are replaced by other
diazo derivatives derived from amines, amidophenols, amidophenolethers,
amidocarboxylic acids, or amidosulpho acids of the benzene or naphthalene series
(employing either the same or two different ones). The shades produced by means
of these dye-stuffs are likewise distinguished by their fastness to the action of
washing and light.
Other colouring matters are obtained if, in place of using diazo products, two
molecules of the same, or two different "intermediate products," or if two of the
aforesaid compounds containing diazo groups, are allowed to act on one molecule
of trihydroxynaphthalene monosulpho acid.
In case of the use of those diazo bodies which are derived from benzidine and its
analogues, dyestuffs are obtained which, in particular, are also adapted for dyeing
unmordanted cotton fibre, as they are possessed of a great affinity for the cotton
fibre.
Dye stuffs are obtained in every case which produce shades distinguished by
their fastness against washing and light.
The following example is given, in order to illustrate the production of one of
the aforesaid "mixed polyazo dyestuffs," the parts-being by weight :—.
COLOURING MATTER
OBTAINED FROM
TRIHYDROXYNAPHTHALENEMONO-
OF
SULPHO ACID DIAZOBENZENE, AND THE INTERMEDIATE PRODUCT
RESULTING BY COMBINING EQUAL MOLECULAR PROPORTIONS
TETRAZODIPHENYLCHLORIDE AND SALICYLIC ACID.
A solution of diazobenzene prepared in the usual manner from 20 parts of aniline,
is allowed to flow into a solution, acidulated by means of acetic acid, and containing
30 parts of the acid potassium salt of trihydroxynaphthalenemonosulpho acid and
20 parts of sodium acetate. The intermediate product which results from 39.4 parts
of benzidine and 30 parts of salicylic acid, is added, and the mixture is then
allowed to stand during 24 hours. The dyestuff so formed is filtered off and dried.
It dyes unmordanted cotton brown, and the shades will withstand the action of
light and washing. Its composition is represented by the following formula :-

page_text: EXAMPLE C.
The tetrazo compound obtained from 39-4 parts of benzidine is allowed to act on
the intermediate dyestuff resulting from the combination of 30 parts of the
trihydroxynaphthalenemonosulphonate of potassium with the diazo compound of
20 paits of aniline. When the formation of the intermediate product is complete,
it is introduced into a solution prepared by dissolving 30 parts of salicylic acid in
an excess of soda-lye. The production of the dye-stuff is finished within a short
time. The coloring matter so formed is precipitated by the addition of acetic acid,
and is subsequently filtered off, pressed, and dried.
In order to produce the above defined colouring matters derived from trihydroxy-
naphthalene sulpho acid, my foreign correspondents do not limit themselves to the
directions given in the foregoing examples, as the mode of working can be varied,
and the said dyestuffs can be produced by means of all methods known and in use
for the manufacture of analogous or similar colouring matters. Such modifications
do not alter the nature of this invention, which in general relates to the production
of dye stuffs based on the property of the above trihydroxynaphthalene monosulpho
acid, to combine in acid solution, especially in a solution rendered acid by means of
acetic acid, with two molecules of compounds containing an active diazo group,
the said property being discovered by my foreign correspondents, whilst an
analogous behaviour was not known up to the present time, of any other hydroxy-
naphthalene sulpho acid.
Dated this 19th dex of January 1891
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Dye-stuffs by Means of
Trihydroxynaphthalenemonosulpho Acid.
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 :-
My foreign correspondents some time ago prepared a trihydroxynaphthalene-
monosulphonic acid by the action of alkalies at temperatures above 240 degrees
Centigrade, on either the naphthalenetetrasulphonic acid obtainable on sulphonating
naphthalenebeta, beta, disulphonic acid, or those naphtholtrisulphonic acids, or
dihydroxynaphthalene disulphonic acids which can be prepared by the action of
alkalies on the said naphthalenetetrasulphonic acid, at temperatures lower than
200 and 250 degrees Centigrade respectively.
The researches of my foreign correspondents have now shown, that the aforesaid
trihydroxynaphthalenemonosulphonic acid may be coupled with two molecules of
diazo compound in acidulated solutions, say, acetic acid solutions, and my foreign
correspondents have further found, that instead of coupling a molecular proportion
of the above trihydroxynaphthalenemonosulphonic acid with two molecular pro-
portions of any diazo compound, a single molecular proportion of this acid can
be combined either with two molecular proportions of a diazo azo compound, or
with one molecular proportion of the tetrazo derivatives of "benzidine or its
analogues," or with two molecular proportions of an "intermediate product" obtain-
able by coupling molecular proportions of the tetrazo derivatives of "benzidine or
its analogues," and an amine, a diamine, a phenol, an amidophenol, amido
phenolether of the benzene or naphthalene series, a sulphonic or carboxylic acid
thereof. So-called "simple" poly-azo dye stuffs derived from trihydroxynaph-
thalenemonosulphonic acid are thus produced.

page_text: According to the researches of my foreign correspondents, the combination of the
two molecules of diazo compounds with the single molecule of the aforesaid
trihydroxynaphthalene monosulphonic acid, does not take place simultaneously,
but the two molecules enter into combination the one after the other. My foreign
correspondents have therefore also been able to produce so-called "mixed" polyazo
dye-stuffs derived from the above trihydroxynaphthalenemonosulphonic acid.
By the aforesaid expression "mixed polyazo dye-stuffs," my foreign corre-
spondents mean particularly those which are formed by the combination of a
molecule of trihydroxynaphthalene monosulphonic acid, either with a molecule of
some diazo compound or diazo azo compound, and with a molecule of another diazo
compound, or diazo azo compound; or with a molecule of one of the "intermediate
products" above defined, and with a molecule of another of these "intermediate
products"; or with a molecule of a diazo compound, and with a molecule of a
diazo azo compound; or with one molecule of a diazo compound and with
one molecule of an intermediate product; or with one molecule of a diazo azo
compound, and with one molecule of a so-called "intermediate product." Of course
my foreign correspondents mean molecular proportions when using the expression
"molecule."
The combination of the diazo compounds, diazo azo compounds, or intermediate
products herein before defined, with trihydroxynaphthalene monosulphonic acid, is
profitably effected in solutions acidulated by means of acetic acid, and in the
presence of sodium acetate.
My foreign correspondents mean by the above expression "benzidine or its
analogues," for instance, the following diamines, viz. Benzidine, orthotolidine,
diamidophenyltolyl, sulphonic derivatives thereof, diamidomonoalkylhydroxydi-
phenyl, diamidomonoalkylhydroxyphenyltolyl, diamidodiphenolether, benzidine
sulphone, tolidine sulphone, or sulphonic acids derived therefrom, diamido
diphenylene oxide, diamidoditoluylene oxide, diamido carbazol, paraphenylene
diamine, paratoluylene diamine, diamido stilbene, diamidostilbene disulphonic acid,
alpha, alpha, diamidonaphthalene, alpha, alpha, diamidonaphthalene beta, beta
disulphonic acid. In producing the dye-stuffs derived from paraphenylene
diamine, paratoluylenediamine, or the like, the corresponding monaceto compounds
of the diamines, or the corresponding paranitramines are profitably used as initial
materials.
This invention, however, is not restricted to the use of the aforesaid diamines, as
other diamines, diamidosulphonic acids, or the like, which can be converted into
tetrazo salts, either directly or by means of their monoacetyl derivatives, can also
be used. The corresponding nitroamines, nitroamidosulphonic acids, or the like,
can be used in place of the monacetylated diamines, monacetylated diamine-
sulphonic acids, or the like, in which case the nitro azo compounds which are first
formed, must be reduced, and the amido azo compounds again diazotised, while the
monacetylamido azo compounds which are formed on using monoacetylated diamines,
are treated in a suitable manner, in order to split off the acetyl group, and the
amido amido azo compounds so produced are again diazotised, and further combined
with dye-stuff components.
In the following examples, my foreign correspondents describe methods of
producing several of the new dye-stuffs above referred to. The parts are by
50 PRODUCTION OF A COLORING MATTER FROM MOLECULAR PROPORTIONS
OF DIAZO BENZENE CHLORIDE, DIAZOBENZENESULPHONIC ACID, AND
TRIHYDROXYNAPHTHALENEMONOSULPHONIC ACID.
9.3 parts of aniline are diazotised in the well-known manner by means of 7 parts
of sodium nitrite, and 25 parts of muriatic acid. The solution of diazo benzene

page_text: chloride is allowed to flow into a solution prepared by dissolving 29.4 parts of the
potassium salt the said trihydroxynaphthalenemono sulphonic acid, and 20 parts of
sodium acetate, acidulated with acetic acid. The formation of the intermediate
dye-stuff at once takes place, a portion remaining dissolved, the rest separating in
the form of a reddish-yellow precipitate. After adding the diazotised para-
sulphanilic acid prepared from 17-3 paits of para sulphanilic acid, the mixture is
allowed to stand during about 12 hours. The finished dye-stuff, which is a dark
brown precipitate, is filtered off, pressed, and dried.
The "mixed" coloring matter thus obtainable produces yellowish-brown shades,
when dyed on wool in an acidulated bath. The shades withstand the action of
light and washing in a bigh degree. It is represented by the formula :—
The researches of my foreign correspondents have shown, that this coloring
matter is also formed if the trihydroxynaphthalenemonosulphonic acid is, inversely,
coupled first with the diazo benzene sulphonic acid, and subsequently with diazo
benzene, molecular proportions of these agents being employed.
Other coloring matters are obtained in a manner analogous to that described in
the above first example, by using, in place of the diazo compounds above
mentioned, other diazo derivatives prepared from amines, amidophenols, amido-
phenolethers, amidocarboxylic acids, or amidosulphonic acids of the benzene_or
naphthalene series (using either but one or two different compounds). The shades
produced by means of these dye-stuffs are also distinguished by their fastness on
washing, and on exposure to light. The diazo derivatives of dehydrothiopara-
toluidine, dehydrothiometaxylidine, dehydrothiopseudo cumidine, primuline base,
dehydrothioparatoluidine sulphonic acid, dehydrothiometaxylidine sulphonic acid,
dehydrothiopseudocumidine sulphonic acid; primuline, or similar thioamido com-
pounds, or sulphonic acids thereof, can also be used. In this case, dye-stuffs are
formed which are also adapted for dyeing cotton materials. For instance, the
coloring matter from two molecular proportions of diazotised primuline, and one
molecular proportion of trihydroxynaphthalenemonosulphonic acid, produces
brown shades on cotton in neutral or alkaline baths, and similar shades on wool in
acidulated baths.
Other dye-stuffs can be produced, if, in place of diazo compounds, two molecules
of either a single or two different "intermediate products" are used, or if any two
of the aforesaid compounds containing diazo groups, are allowed to act on one
molecular proportion of trihydrozynaphthalenemonosulphonic acid.
On using diazo compounds derived from "benzidine and its analogues," dye-stuffs
are obtained which are also particularly adapted for dyeing unmordanted cotton, as
they possess a great affinity for cotton fibres.
In all cases, dye-stuffs are obtained producing shades which are distinguished by
their fastness on washing, and exposure to light.

page_text: The following example is given in order to illustrate the production of dye-
stuffs by means of so called "intermediate products," the parts being by weight.
COLORING MATTER OBTAINABLE FROM TRIHYDROXYNAPHTHALENEMONO-
SULPHONIC ACID, DIAZOBENZENECHLORIDE, AND THE INTERMEDIATE
PRODUCT FORMED BY COMBINING MOLECULAR PROPORTIONS Or
TETRAZO DIPHENYLCHLORIDE AND SALICYLIC ACID.
A solution of diazobenzenechloride prepared in the usual manner from 9-3 parts
of aniline, is allowed to flow into a solution containing 29.4 parts of the acid
potassium salt of tribydroxynaphthalenemonosulphonic acid, and 20 parts of sodium
acetate, and acidulated with acetic acid. The intermediate product prepared from
184 parts of benzidine and 13-8 parts of salicylic acid, is then added, and the
mixture is allowed to stand during 24 hours. The dye-stuff so formed is filtered off
and dried. It dyes unmordanted cotton, brown shades which withstand the
action of light and washing. Its composition is represented by the following
formula:-
The tetrazo compound obtained from 184 parts of benzidine is allowed to act on
the intermediate dye-stuff prepared by combining 294 parts of acid potassium
tribydroxynaphthalenemonosulphonate, with the diazo compound prepared from
59-3 parts of aniline. When the formation of the intermediate product is complete,
it is introduced into a solution of 13.8 parts of salicylic acid in an excess of soda
lye. The production of the dye-stuff is complete within a short time. The
coloring matter thus formed is precipitated by adding acetic acid,-and- is
subsequently filtered off, pressed, and dried.
The following table is given in order to show what a variety of coloring matters
are obtainable by means of the process herein before defined, and to indicate the
shades which these dye-stuffs produce. The different components of several

page_text: coloring matters of the new series are indicated in the first column of this table,
the shades which the dye-stuffs produce, some on wool, others on cotton, being
indicated in the second column.
·

page_text: One molecular proportion of diazotised
aniline, and one molecular proportion
of the intermediate product from
equimolecular proportions of tetrazo-
diphenylchloride, and alpha, alpha
amidonaphthol beta, beta, disulphonic
acid
One molecular proportion of diazotised
metanitraniline and one molecular
proportion of the intermediate product
from equimolecular proportions of
tetrazo diphenylchloride and salicylic
acid
In order to produce the above defined coloring matters derived from trihydroxy-
naphthalenemonosulphonic acid, my foreign correspondents do not limit themselves
to the directions given in the foregoing examples, as the mode of working can be
varied, and the said dye-stuffs can be produced by means of all methods known and
in use for the manufacture of analogous or similar coloring matters. Such
modifications do not alter the nature of this invention, which in general relates to
the production of dye-stuffs from the said trihydroxynaphthalenemonosulphonic
acid, and is based on the property which this acid exhibits, of combining, in acid
solution, especially a solution acidulated with acetic acid, with two molecules of
B

page_text: compounds containing an active diazo group, the said property being one discovered
by my foreign correspondents.
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 by
my foreign correspondents, I declare that what I claim is :-
1. The production of azo dye-stuffs from the trihydroxynaphthalenemonosulphonic
acid bereinbefore defined, which process consists in combining one molecular
proportion of trihydroxynaphthalenemonosulphonic acid, or an alkaline salt thereof,
with two molecular proportions of a "diazo" or "diazo azo" compound, or with
one molecular proportion of a tetrazo derivative of "benzidine or its analogues," or
with two molecular proportions of an "intermediate product" formed from
molecular proportions of tetrazo derivatives of "benzidine or its analogues,” and a
phenol, amine, amidophenol, amidophenolether, a diamine of the benzene or
naphthalene series, or a sulphonic or carboxylic derivative thereof, or with one
molecular proportion of a
"
diazo," or "diazo azo compound, or "intermediate
product," and one molecular proportion of another "diazo or "diazo azo
compound or "intermediate product."
66
"
"
2. The process for producing azo dye-stuffs by combining one molecular
proportion of the trihydroxynaphthalenemonosulphonic acid hereinbefore defined,
or an alkaline salt thereof, with :-
(a) Two molecular proportions of diazotised parasulphanilic acid, or alpha,
naphthylamine alpha, monosulphonic acid;
(b) One molecular proportion of diazotised aniline, and one molecular
proportion of diazotised parasulphanilic acid;
(c) One molecular proportion of diazotised aniline, and one molecular
proportion of diazotised alpha, naphthylamine alpha, monosulphonic acid;
(d) One molecular proportion of diazotised aniline, and one molecular
proportion of diazotised amido azo benzene sulphonic acid;
(e) One molecular proportion of diazotised meta nitraniline, and one molecular
proportion of diazotised parasulphanilic acid;
(f) Two molecular proportions of diazotised primuline ;
(g) Two molecular proportions of the intermediate product from molecular
proportions of tetrazo diphenylchloride, and alpha, alpha amidonaphthol
alpha, monosulphonic acid;
(h) Two molecular proportions of the intermediate product from molecular
proportions of tetrazodiphenylchloride and salicylic acid;
(i) One molecular proportion of diazotised aniline, and one molecular
proportion of the intermediate product from molecular proportions of tetrazo
diphenylchloride and salicylic acid;
(k) One molecular proportion of diazotised aniline, and one molecular
proportion of the intermediate product from molecular proportions of
tetrazodiphenylchloride and alpha, alpha, amidonaphthol alpha, mono-
sulphonic acid;
(1) One molecular proportion of diazotised aniline; and one molecular
proportion of the intermediate product from molecular proportions of tetrazo
diphenylchloride and alpha₁ alpha amidonaphthol beta, beta, disulphonic
acid;
(m) One molecular proportion of diazotised metanitraniline, and one molecular
proportion of the intermediate product from molecular proportions of tetrazo
diphenylchloride and salicylic acid; or
(n) One molecular proportion of diazotised amido azo benzene and one
molecular proportion of the intermediate product from molecular proportions
of tetrazo diphenylchloride and salicylic acid.

page_text: 3. As new products of manufacture, the new azo dye-stuffs produced by the
processes herein before defined, or by any other means producing the same result.
Dated this 15th day of October 1894.
NEWTON & SON,
Agents for the Applicant.