The Manufacture or Production of Alpha, Beta,-dihydroxynaphtha- lene, a New Alpha, Beta2-dihydroxynaphthalenesulphonic Acid, and of Colouring-matters Derived from Alpha, Beta2-dihydroxy- naphthalene Sulphonic Acids.
Year: 1895

page_text: Date of Application, 8th Mar., 1895
Complete Specification Left, 9th Dec., 1895-Accepted, 11th Jan., 1896
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany.]
The Manufacture or Production of Alpha, Beta,-dihydroxynaphtha-
lene, a New Alpha, Beta2-dihydroxynaphthalenesulphonic Acid,
and of Colouring-matters Derived from Alpha, Beta2-dihydroxy-
naphthalene Sulphonic Acids.
1, 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 produced some time ago a new dihydroxynaphthalene
(alpha, beta-dihydroxynaphthalene, or naphtharesorcinol), and certain sulphonic
acids derived from this dihydroxynaphthalene.
My foreign correspondents have now succeeded in preparing the alpha, beta-
dihydroxynaphthalene in another way, and in obtaining a new alpha, beta,
dihydroxynaphthalenesulphonic acid (naphtharesorcinolsulphonic acid), and in
producing valuable cotton dye-stuffs by means of the naphtharesorcinolsulphonic
acids.
My foreign correspondents have found that the dihydroxynaphthalene disul-
phonic acid Y (described in the Specification of Letters Patent No. 25074), or
salts thereof, can be converted by heating with water or dilute mineral acids, at
elevated temperatures, into alpha, beta,-dihydroxynaphthalenemonosulphonic acid
(or naphtharesorcinolmonosulphonic acid), a sulphonic group being split off during
this operation. The resulting monosulphonic acid has been proved to be a
derivative of naphtharesorcinol, as it, when heated with water, or dilute mineral
acids, at still more elevated temperatures, is converted into alpha, beta,-dihydroxy-
naphthalene (naphtharesorcinol), melting at 124 degrees Centigrade. This fact
shews that the aforesaid dihydroxynaphthalenedisulphonic acid Y. is likewise a
derivative of naphtharesorcinol, which is further demonstrated by the property
possessed by the said disulphonic acid, of forming yellow monoazo dye stuffs, in
like manner as the monosulphonic acids of naphtharesorcinol produced by my
foreign correspondents, whereas the other dihydroxynaphthalene sulphonic acids
hitherto known do not exhibit this property.
One of the methods of producing the new naphtharesorcinolmonosulphonic acid
is illustrated by the following example. The parts are by weight.
FIRST EXAMPLE.
NAPHTHARESORCINOLSULPHONIC
ACID OBTAINED FROM
THALENE DISULPHONIC ACID Y.
DIHIDRAINAT
1 part of dihydroxynaphthalenedisulphonic acid Y, or an acid salt thereof, is
mixed with 5 parts of dilute sulphuric acid (containing 5 per cent. of pure sulphuric
acid). The resulting mixture is heated in a closed vessel capable of withstanding
pressure, and which is placed in an oil bath. The oil is brought to a temperature
of 210 degrees Centigrade, and the heating is continued during about four hours

page_text: at this temperature. The mixture is then quickly evaporated, and after some time
the mass becomes stiff, fine needles being separated. The crystalline mass is then
filtered off, pressed, and dried. An acid sodium salt of the new naphtharesorcinol-
monosulphonic acid is thus produced.
The same result is obtained, if other dilute mineral acids, or water alone, is used
in place of sulphuric acid used in the foregoing example.
The new acid and its salts dissolve with great ease in water, and solutions
in water of the neutral salts exhibit a yellow colour and an intense green
fluorescence.
A blackish-blue tint appears on adding ferric chloride to a solution in water of
the acid salts, but this colour soon becomes dull. An addition of chloride of lime
to watery solutions of the acid salts produces a slight brownish-yellow colour.
The new acid and salts thereof, when combined with diazobenzene chloride, yield a
yellow dyestuff.
Having in view the fact that the new naphtharesorcinolmonosulphonic acid
results from the dihydroxynaphthalenedisulphonic Y, which is obtained from
naphthalene-beta, beta,-disulphonic acid, and that the last sulphonic group can be
displaced only by heating at more elevated temperatures, my foreign correspondents
ascribe a beta position to this sulphonic group. The researches of my foreign
correspondents have further shewn, that this naphtharesorcinol monosulphonic acid
differs from the alpha,-beta,-dihydroxynaphthalene-beta-sulphonic acid, and there-
fore they assume that the new acid is alpha₁ beta,-dihydroxynaphthalene-beta-
sulphonic acid, having the formula :-
My foreign correspondents have further found, that the dihydroxynaphthalene-
disulphonic acid Y, and alpha, beta,-dihydroxynaphthalene-beta-sulphonic acid
herein before defined, or salts thereof, can, by heating with water or dilute mineral
acids, be converted into naphtharesorcinol (alpha, beta,-dihydroxynaphthalene).
In order to illustrate the production of naphtharesorcinol from dihydroxy-
naphthalenedisulphonic acid Y, the following example is given, the parts being by
weight.
SECOND EXAMPLE.
NAPHTHARESORCINOL FROM DIHYDROXYNAPHTHALENEDISULPHONIC ACID Y.
1 part of dihydroxynaphthalenedisulphonic acid Y. is mixed with 5 parts of
dilute sulphuric acid (containing 5 per cent. of pure sulphuric acid). The resulting
mixture is heated in a closed vessel, capable of withstanding pressure, placed in an
oil-bath. Heat is applied until the oil shews a temperature of 235 degrees Centi-
grade, and heating is continued at this temperature during 6 hours.
After cooling,
the mass consists of two layers, of which the upper is watery, whilst the lower is
oily. Hot water is then added until but a small quantity of a black resin remains
undissolved. The solution, when cold, is filtered, and the resulting filtrate is
extracted with ether. On distilling the ether liquid, an almost colourless oil
remains, which gradually becomes crystalline, the mass exhibiting the appearance
of rays, which mass is the naphtharesorcinol (alpha, beta,-dihydroxynaphthalene).
It is to be noted that when the dihydroxynaphthalene disulphonic acid Y, or
salts thereof, are heated at about 210 degrees with water or dilute mineral acids
during 4 hours, only one sulphonic group is split off, as described in the preceeding

page_text: first example, alpha, beta, dihydroxynaphthalene-beta sulphonic acid being thus
produced.
But when this dihydroxynaphthalenemnono sulphonic acid, or salts thereof, are
heated at more elevated temperatures than 210 degrees Centigrade, with water or
dilute acids, say, with dilute sulphuric acid (containing 5 per cent. of pure
sulphuric acid), they are converted into naphtharesorcinol, say, by the process last
described.
According to the researches of my foreign correspondents, the naphtha-resorcinol-
sulphonic acids, such as alpha, beta-dihydroxynaphthalene-alpha-monosulphonic
acid, alpha, beta, dihydroxynaphthalene-beta,-sulphonic acid, alpha, beta,-dihy-
droxynaphthalene-beta-monosulphonic acid, or the like, yield valuable azo dye-
stuffs, by coupling them, or salts thereof, with the tetrazo compounds of the known
paradiamines suitable for these purposes. The resulting dye-stuffs produce on
ordinary cotton very clear shades.
The process for producing these colouring matters, in general, consists in allowing
one molecular proportion of the said tetrazo compounds to act in solutions acidulated,
for instance, by means of acetic acid, or rendered alkaline by means of alkaline
carbonate or alkali lye, or two molecular proportions of the naphtharesorcinolmono
sulphonic acids, or salts thereof.
The following examples are given in order to illustrate some methods of
producing these azo dye-stuffs. The parts are by weight.
COLOURING-MATTER FROM BENZIDINE AND ALPHA BETA,-DIHYDROXYNAPH-
THALENE-BETA-MONOSULPHONIC ACID.
18.4 parts of benzidine are diazotised in the usual manner, and the resulting
tetrazo solution is allowed to flow into a watery solution of 48 parts of alpha, beta,
dihydroxynaphthalene-beta,-monosulphonic acid, mixed with an excess of soda lye.
The formation of the dye-stuff begins at once, and is complete after a short time.
The finished colouring matter is precipitated by adding acetic acid and common
salt. It is then filtered off, pressed, and dried. It dyes beautiful clear red shades
on unmordanted cotton, in an alkaline bath, containing, for instance, potassium.
carbonate. Its composition is represented by the formula
5 DYE-STUFF FROM DIANISIDINE AND ALPHA, BETA-DIHYDROXYNAPHTHALENE-
BETA-MONOSULPHONIC ACID.
The tetrazo solution obtained in the usual manner from 244 parts of dianisidine,
is allowed to flow into a solution prepared by dissolving, in water, 52-4 parts of the

page_text: acid sodium salt of alpha, beta-dihydroxynaphthalene beta, sulphonic acid, and
adding an excess of soda lye. The formation of the dye-stuff begins at once, and
is finished after about 24 hours. The finished dye-stuff is isolated by adding acetic
acid and common salt, filtering off the precipitate, pressing and drying the same.
It yields very clear reddish-violet shades fast against the action of light, when it
is dyed on cotton in a bath rendered alkaline, for instance, by means of potassium
carbonate. It possesses the following formula :-
Other colouring-matters are obtained in a manner analogous to that described in
the foregoing third and fourth examples, if, on the one hand, other paradiamines
suitable for such purposes are used in place of benzidine and dianisidine prescribed
in these examples, or if other naphtharesorcinolmonosulphonic acids are substituted
for. the alpha,-beta,-dihydroxynaphthalenemonosulphonic acids used in these
examples.
In the production of the dyestuffs hereinbefore defined, my foreign correspondents
do not limit themselves to the particulars given in the foregoing third and fourth
examples, as all methods known and in use for producing analogous dyestuffs can
be used. For instance, the combination of the naphtharesorcinolmonosulphonic
acids, or salts thereof, cau also be effected in solutions rendered alkaline by means
of sodium carbonate, or acidulated by means of acetic acid or the like.
According to the researches of my foreign correspondents, the naphtharesorcinol-
sulphonic acids, and salts thereof, possess the property of combining in equimolecular
proportions with the tetrazo compounds of paradiamines, intermediate products
being thus obtained, which contain a free diazo group, and can be further combined
with one molecular proportion of the known dyestuff components (amines, phenols,
amidophenols, amidophenolethers of the benzene or naphthalene series, sulphonic
or carboxylic acids thereof), to form so-called mixed disazo dye-stuffs.
Naturally the same mixed colouring matters can also be produced by first
coupling one molecular proportion of a tetrazo compound with one molecular
proportion of any dyestuff component, and subsequently combining the so-forined
intermediate products with one molecular proportion of a naphtharesorcinolmono
sulphonic acid, or a salt thereof.
The production of these mixed disazo dye-stuffs can be effected by the methods
known and in use for obtaining analogous or similar colouring matters. The
resulting dye-stuffs will yield a great variety of shades, depending on the different
components used.
Dated this 8th day of March 1895.
NEWTON & SON,
Agents for the Applicant.

page_text: The Manufacture or Production of Alpha, Beta,-dihydroxynaphtha-
lene, a New Alpha, Beta,-dihydroxynaphthalene Sulphonic Acid,
and of Colouring-matters Derived from Alpha, Beta,-dihydroxy-
naphthalene Sulphonic Acids.
1, 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 produced some time ago a new dihydroxynaphthalene
(alpha beta,-dihydroxynaphthalene or naphtharesorcinol), & certain sulphonic
acids derived from this dihydroxynaphthalene.
They have now succeeded in preparing the said alpha, beta,-dihydroxynaphtha-
lene in another way, and in obtaining a new alpha, beta,-dihydroxynaphthalene-
sulphonic acid (naphtharesorcinolsulphonic acid), and in producing valuble cotton
dyestuffs by means of the naphtharesorcinol sulphonic acids.
My foreign correspondents have found that the dihydroxynaphthalene disul
phonic acid Y (described in the Specification of Letters Patent No. 2507493), or
salts thereof, can be converted, by heating with diluted mineral acids, at elevated
temperatures, into alpha, beta, dihydroxynaphthalenemonosulphonic acid (or
naphtharesorcinolmonosulphonic acid), a sulphonic group being split off during
this operation. This monosulphonic acid has been proved to be a derivative of
naphtharesorcinol, as, when heated with diluted mineral acids, at still more
elevated temperatures, it is converted into alpha, beta,-dihydroxynaphthalene
(naphtharesorcinol), melting at 124 degrees Centigrade. This fact shows that
the aforesaid dihydroxynaphthalene disulphonic acid Y is also a derivative of
naphtharesorcinol, which is further demonstrated by the property possessed by the
said disulphonic acid, of forming yellow monazo dye-stuffs resembling those given
by the monosulphonic acids of naphtharesorcinol produced by my foreign
correspondents, whereas the other dihydroxynaphthalenesulphonic acids hitherto
known, do not exhibit this property.
One of the methods of producing the new naphtharesorcinolmonosulphonic acid
is illustrated by the following example. The parts are by weight.
NAPHTHARESORCINOLSULPHONIC ACID OBTAINED FROM DIHYDROXYNAPHTHA-
LENEDISULPHONIC ACID Y.
1 part of dihydroxynaphthalene disulphonic acid Y, or an acid salt thereof, is
mixed with 5 parts of diluted sulphuric acid (containing 5 per cent. of pure
sulphuric acid). The mixture is heated in an autoclave, in an oil bath, maintained
at 210 degrees Centigrade, and the heating is continued during about four hours.
When cool, the liquid is neutralised with slaked lime, and the calcium salt of the
naphtharesorcinolmonosulphonic acid is converted into the sodium salt, and the
solution of this salt, having been acidulated with muriatic acid, the liquid is
quickly evaporated. After some time, the mass becomes stiff, owing to the
separation of fine needles. The crystalline mass is filtered off, pressed, and
dried. An acid sodium salt of the new naphtharesorcinol monosulphonic acid is
thus produced.
The same result is obtained if other diluted mineral acids are used in place of
the sulphuric acid prescribed in the foregoing Example A.

page_text: The new acid and its salts dissolve with great ease in water, and solutions, in
water, of the neutral salts exhibit a yellow colour and an intense green
fluorescence.
A blackish-blue tint appears, on adding ferric chloride to a solution in water of
the acid salts, but this colour soon becomes dull. Chloride of lime produces a
slight brownish-yellow colour. The new acid, and salts thereof, yield a yellow
dyestuff, when combined with diazobenzenechloride.
Having in view the fact, that this new naphtharesorcinol monosulphonic acid is
derived from the dihydroxynaphthalene disulphonic acid Y, which is obtained
from naphthalene-beta, beta,-disulphonic acid, & that the second sulphonic group
can be displaced only by heating at elevated temperatures, my foreign
correspondents consider that this sulphonic group occupies the beta position.
Their researches have further shewn, that this naphtharesorcinolmonosulphonic
acid differs from the alpha₁ alpha, dihydroxynaphthalene beta,-sulphonic acid, &
therefore they assume that the new acid is the alpha, beta, dihydroxynaphthalene-
beta-sulphonic acid represented by the formula-
париспатенe), by neacing in wiin unu
mineral acius.
In order to illustrate the production of naphtharesorcinol from dihydroxy-
naphthalenedisulphonic acid Y, the following example B is given, the parts being
by weight.
EXAMPLE B.
NAPHTHARESORCINOL from DIHYDROXYNAPHTHALENEDISULPHONIC ACID Y.
1 part of dihydroxynaphthalenedisulphonic acid Y is mixed with 5 parts of
diluted sulphuric acid (containing 5 per cent. of pure sulphuric acid). The mixture
is heated to 235 degrees Centigrade, in an autoclave placed in an oil-bath, and
heating is continued at this temperature during 6 hours. When cool, the contents
of the digestor consist of two layers, of which the upper is watery, whilst the lower
is oily. A sufficient amount of hot water having been added, to dissolve all but a
small quantity of a black resin, the solution is cooled and filtered, and the filtrate
is extracted with ether. On distilling off the ether, an almost colourless oil
remains, which gradually becomes a radio-crystalline mass of naphtharesorcinol
(alpha-beta-dihydroxynaphthalene).
It is to be, noted that when dihydroxynaphthalenedisulphonic acid Y, or salts
thereof, are heated at about 210 degrees with water, or dilute mineral acids,
during 4 hours, only one sulphonic group is split off, as described in the preceding
example A, alpha₁-beta, dihydroxynaphthalene-beta sulphonic acid being thus
produced.
But when this dihydroxynaphthalenemonosulphonic acid, or salts thereof, are
heated at more elevated temperatures than 210 degrees Centigrade with diluted
acids, say, with dilute sulphuric acid (containing 5 per cent. of pure sulphuric acid),
they are converted into naphtharesorcinol, as by the process last described.

page_text: According to the researches of iny foreign correspondents, the naphtharesorcinol-
sulphonic acids, such as alpha, beta,-dihydroxynaphthalene-alpha, monosulphonic
acid, alpha, beta, dihydroxynaphthalene-beta-sulphonic acid, alpha, beta,-dihydroxy-
naphthalene-beta-monosulphonic acid, yield valuable azo dye-stuffs, on coupling
them, or salts thereof, with the tetrazo compounds of the known paradiamines
suitable for these purposes. The dyestuffs thus formed produce, on ordinary cotton,.
very clear shades, which withstand the action of light.
The process for producing these colouring matters, in general, consists in
allowing a molecular proportion of one of the said tetrazo compounds to act in
solutions rendered alkaline by means of an alkaline carbonate, or alkali-lye, on two
molecular proportions of the aforesaid naphtharesorcinolmonosulphonic acids, or
salts thereof.
The following examples are given, in order to illustrate some methods of
producing these azo dye-stuffs. The parts are by weight.
COLOURING MATTER FROM BENZIDINE AND ALPHA₁ BETA, DIHYDROXY-
NAPHTHALENE-BETA3-MONOSULPHONIC ACID.
18.4 parts of benzidine are diazotised in the usual manner, and the tetrazo-
solution is allowed to flow into a solution of 48 parts of alpha, beta,-dihydroxy-.
naphthalene-beta-monosulphonic acid, mixed with an excess of soda-lye. The
formation of the dyestuff begins at once, and is complete after a short time. The
finished colouring matter is precipitated by adding acetic acid and common salt..
It is then filtered off, pressed, and dried. It dyes beautiful clear red shades ou
unmordanted cotton in an alkaline bath containing, for instance, potassium
carbonate. Its composition is represented by the formula :—
DYESTUFF FROM DIANISIDINE AND ALPHA₁ BETA-DIHYDROXYNAPHTHALENE-
BETA MONOSULPHONIC ACID.
The tetrazosolution obtained in the usual manner from 24.1 parts of dianisidine
is allowed to flow into a solution prepared by dissolving in water 52-4 parts of the
acid sodium salt of alpha, beta, dihydroxynaphthalene-beta-sulphonic acid, and
adding an excess of soda-lye. The formation of the dye-stuff begins at once, and
is complete after about 24 hours. The finished dye-stuff is isolated by adding
acetic acid and common salt, filtering off the precipitate, pressing, and drying the
same. It yields very clear reddish-violet shades, which withstand the action of

page_text: light when it is dyed on cotton in a bath rendered alkaline, for instance, by means
of potassium carbonate.
It possesses the following formula :-
Other colouring matters are obtained in a manner analogous to that described in
the foregoing examples C and D, if, on the one hand, other paradiamines suitable
for such purposes are used in place of benzidine and dianisidine prescribed in thesc
examples, or if other naphtharesorcinol monosulphonic acids are substituted for
the alpha, beta,-dihydroxynaphthalenemonosulphonic acids used in these examples.
In the production of the dye-stuffs hereinbefore defined, my foreign correspondents
do not limit themselves to the particulars given in the foregoing examples C and D,
as all known methods in use for producing analogous dye-stuffs can be adopted.
For instance, the combination of the naphtharesorcinolmonosulphonic acids, or
salts thereof, can also be effected in solutions rendered alkaline by means of
sodium carbonate.
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 a new naphtharesorcinolmonosulphonic acid, which is
probably alpha beta2-dihydroxynaphthalene-beta-monosulphonic acid, from the
dihydroxynaphthalenedisulphonic acid Y described in the Specification of Letters
Patent No. 2507493.
2. The process for producing the said new naphtharesorcinolmonosulphonic acid,
or salts thereof, which process consists in heating, at elevated temperatures, the
aforementioned dihydroxynaphthalenedisulphonic acid Y, or salts thereof, with
diluted mineral acids.
3. The production of naphtharesorcinol (alpha beta,-dihydroxynaphthalene)
from the said dihydroxynaphthalenedisulphonic acid Y, or from the new naphtha-
resorcinolmonosulphonic acid defined in the foregoing claims one and two.
4. The process for producing naphtharesorcinol (alpha, beta, dihydroxy-
naphthalene), by heating with diluted mineral acids, at temperatures above
210 degrees Centigrade, the aforesaid dihydroxynaphthalenedisulphonic acid Y, or
the new naphtharesorcinolmonosulphonic acid defined in the preceding claims one
and two, or salts of either of these acids, and subsequently isolating the so-formed
naphtharesorcinol in a suitable manner.
5. The manufacture of symmetrical disazo dye-stuffs from alpha, beta, dihydroxy-
naphthalene-beta,-monosulphonic acid, or the hereinbefore defined new naphtha-
resorcinolmonosulphonic acid (which is probably alpha, beta, dihydroxynaphthalene
beta monosulphonic acid), or alkaline salts thereof, and the tetrazo derivatives of
the known paradiamido compounds.
6. The process for producing symmetrical disazo dyestuffs, by combining a
molecular proportion of the tetrazo derivative of a paradiamine or substituted

page_text: paradiamine, either with two molecular proportions of alpha₁ beta,-dihydroxy-
naphthalene-beta,-monosulphonic acid, or an alkaline salt thereof, or with two
molecular proportions of the new naphtharesorcinolmonosulphonic acid above.
referred to, or an alkaline salt thereof.
7. As new products of manufacture :-
hereinbefore defined, or in
a.) The new naphtharesorcinolmonosulphonic produced by the processes
acid, being probably alpha, beta2 dihydroxy-
naphthalene-beta-monosulphonic acid; and
b.) The new symmetrical disazo dyestuffs,
Dated this 7th day of December 1895.
any other manner afford-
ing the same results.
NEWTON & SON,
Agents for the Applicant.