The Manufacture and Production of a New Naphthalene Derivative suitable for use in the Manufacture of Dyestuffs.
Year: 1890

page_text: Date of Application, 6th Oct., 1890
Complete Specification Left, 26th June, 1891-Accepted, 1st Aug., 1891
PROVISIONAL SPECIFICATION.
The Manufacture and Production of a New Naphthalene Derivative
suitable for use in the Manufacture of Dyestuffs.
I, JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of
Middlesex Gentleman do hereby declare the nature of this invention (which has
been communicated to me from abroad by Badische Anilin and Soda Fabrik of
Ludwigshafen on the Rhine in the Empire of Germany) to be as follows :—
If the sodium salt of beta-naphthol-di-sulpho-acid (commonly known as R-salt) be
melted with about twice its quantity of a caustic alkali at a temperature of about two
hundred and forty to two hundred and eighty degrees Centigrade, a di-hydroxy-
naphthalene-mono sulpho acid is obtained. The present invention is based upon the
discovery that this compound on further and more energetic treatment for instance with
larger quantities of caustic alkaline at higher temperatures, yields, not a tri-hydroxy-
naphthalene as might be expected, but a new di-hydroxy-naphthalene, which can
be used in the manufacture of dyestuffs. It is not necessary to start from isolated
and purified dihydroxy-naphthalene monosulpho-acid but, if desired, the new com-
pound can be obtained in one operation directly from the R-salt, by increasing the
action of the caustic alkali thereon (for instance, by taking more caustic alkali,
heating longer and to a higher temperature) beyond the degree required for the
production of the mono-sulpho-acid, so that the said mono-sulpho-acid produced as
an intermediate product is in the one operation further transformed into the afore-
said new di-hydroxy-naphthalene.
My foreign correspondents have also discovered that this same new di-bydroxy-
naphthalene can be obtained from the dihydroxynaphthalene-monosulpho-acid by
treating the latter with certain dilute mineral acids, and also by heating its sodium
salt alone as hereinafter described.
As a convenient means of illustrating the nature of the invention, I give the
following examples without binding myself to details.
EXAMPLE 1. PREPARATION OF THE NEW
DI-HYDROXY-NAPHTHALENE
MONO-SULPIIO-ACID
MELTING THE DIHYDROXY-NAPHTHALENE
CAUSTIC SODA.
BY
WITH
The di-hydroxy-naphthalene-mono-sulpho-acid can conveniently be prepared for
the purpose of this invention by melting together about sixty parts of caustic
soda and thirty parts of R-salt and mixing these ingredients with about eight parts
of water. The temperature of the melt is raised to about two hundred and forty
degrees Centigrade and maintained between this temperature and two hundred and
cighty degrees for about three hours or until the production of mono-sulpho-acid
has reached its maximum. This can be ascertained by withdrawing equal test
portions from the melt at intervals of say about ten minutes dissolving them in
sufficient hydrochloric acid containing about 10 per cent. of real hydrochloric
acid (HCI) to give an acid solution boiling and filtering and then precipitating
with common salt the dihydroxy-naphthalene-mono-sulpho acid formed.
As soon
as successive tests show no increase in the quantity formed, the operation is
interrupted. The whole melt is then dissolved and acidified with hydrochloric acid
(containing about ten per cent. of real hydrochloric acid. HCl), heated to boiling
filtered and the solution saturated with common salt. The sodium salt of the
desired sulpho-acid which separates out on cooling can be collected on the filter
pressed and dried.
It can be purified by dissolving again in hot water and
reprecipitating with sodium chloride.

page_text: To obtain the new di-hydroxy-naphthalene now take about twenty parts of
caustic soda and two and a half parts of water and heat the mixture to a temperature
of about two hundred and fifty degrees Centigrade, then add about ten parts of the
sodium salt of the mono sulpho acid obtained as herein before described. Raise
the temperature to from about three hundred to three hundred and twenty degrees
and maintain this temperature for about one hour or until no increase in the
quantity of product soluble in ether occurs in successive test portions after acidifi-
cation with hydrochloric acid.
This point being arrived at acidify the melt by mixing with about thirty parts of
ordinary concentrated sulphuric acid (containing about ninety six per cent. of real
sulphuric acid H, SO4) diluted with about two hundred parts of water.
Heat to
boiling point and filter hot. Allow the filtrate to cool and then extract either with
ether or with fusel oil. Distil off the solvent and extract the residual oil with
boiling water, filter hot, and allow the filtrate to cool, the di-hydroxy-naphthalene
separates out and is purified by repeated recrystallization from water. If the
temperature of the melt in the above and the following examples be maintained at
between two hundred and eighty and three hundred degrees Centigrade the
production of the di-hydroxy-naphthalene takes place more slowly, above three
hundred and thirty degrees decomposition takes place.
EXAMPLE 2. PRODUCTION OF THE DI-HYDROXY-NAPHTHALENE IN ONE
OPERATION FROM R-SALT.
Mix about forty parts of caustic soda with about five parts of water and heat the
mixture to a temperature of about two hundred degrees Centigrade, stir continuously
and add gradually at this temperature about ten parts of R-salt. After all the
R-salt has been added, raise the temperature to from about three hundred to three
hundred and twenty degrees Centigrade and maintain the melt at this temperature
until no further increase occurs in the quantity of product soluble in ether after
acidification. This usually takes from two to three hours. Next, dissolve and
acidify the melt with about one hundred and sixty parts of hydrochloric acid (con-
taining about twenty five per cent, real hydrochloric acid, H CH) diluted with about
an equal quantity of water. Boil until no more sulphurous acid gas is evolved and
extract after cooling, with ether or fusel oil and treat the solution thus obtained in
the manner hereinbefore described in the first example.
EXAMPLE 3. PREPARATION OF THE NEW DI-HYDROXY-NAPHTHALENE FROM
THE HEREINBEFORE MENTIONED
DI-HYDROXY-NAPHTHALENE-MONO-
SULPHO ACID BY TREATMENT WITH DILUTE MINERAL ACIDS.
Mix about ten parts of the sodium salt of the di-hydroxy-naphthalene-mono-
sulpho-acid obtained as hereinbefore described with about one hundred parts of
dilute sulphuric acid (containing about twenty five per cent. H. SO,) and heat the
mixture in a closed vessel, capable of withstanding pressure, to a temperature of
about two hundred degrees Centigrade for about twelve hours or until reaction
ceases which may be ascertained by the following test-take a sample of the
mixture and extract thoroughly with ether, add a slight excess of an alkali to the
aqueous solution and then, in the cold, a solution of di-azo-benzene chloride, if but
little azo-dyestuff of the dihydroxynaphthalene mono-sulpho acid be formed the
operation may be considered at an end. This point being arrived at, cool the
product and filter it and recrystallize from water the impure dihydroxy-naphthalene,
which remains on the filter.
If weaker acid be used than sulphuric acid containing 25 per cent. H, SO₁, the
operation takes longer and a higher temperature is necessary, and with stronger
acids it is possible to prepare the di-hydroxy-naphthalene at a lower temperature
and more quickly.

page_text: EXAMPLE 4. PREPARATION OF THE DIHYDROXY-NAPHTHALENE BY HEATING
THE SODIUM SALT OF THE MONO-SULPHO-ACID ALONE.
In a suitable vessel for subliming heat the sodium salt of the mono-sulpho-acid,
obtained as hereinbefore described, to a temperature above about two hundred and
thirty degrees Centigrade whereupon a crystalline sublimate of the di-hydroxy
naphthalene will begin to form. The temperature may be raised as far as three
hundred and forty degrees without causing the mono-sulpho-acid salt to char. It
is advantageous to drive off the dihydroxy-naphthalene as it forms, from the
subliming apparatus with super-heated steam subsequently collecting it in any
suitable way.
The di-hydroxy-naphthalene obtained by all the above processes crystallizes
readily from water and can consequently be easily purified, it melts when pure at a
temperature of about one hundred and sixty to one hundred and sixty one degrees
Centigrade. It combines with di-azo and tetrazo-compounds and gives to colouring
matters of which it forms a component, the valuable property of dyeing mordanted
fibre. On treatment of a cold aqueous solution with a little dilute ferric chloride
an intense blue colour is formed, which remains unchanged for hours.
Dated this 6th day of October 1890.
J. H. JOHNSON & Co.,
Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of a New Naphthalene Derivative
suitable for use in the Manufacture of Dyestuffs.
1 JAMES YATE Jouxson of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this invention which has been com-
municated to me from abroad by The Badische Anilin and Soda Fabrik of
Ludwigshafen on Rhine in the Empire of Germany and in what manner the same
is to be performed to be particularly described and ascertained in and by the
following statement :-
If the sodium salt of beta-naphthol-di-sulpho-acid (commonly known as R salt)
be melted with about twice its quantity of a caustic alkali at a temperature of about
two hundred and forty to two hundred and eighty degrees Centigrade, a di-hydroxy-
naphthalene-mono-sulpho-acid is obtained.
The present invention is based on the discovery that this compound on further
and more energetic treatment, for instance, with larger quantities of caustic
alkali at higher temperatures, yields, not a tri-hydroxy-naphthalene as might be
expected, but a new di-hydroxy-naphthalene which can be used in the manufacture
of dyestuff's.
It is not necessary to start from isolated and purified di-hydroxy-naphthalene-
mono-sulpho-acid, but if desired, the new compound can be obtained in one
operation directly from the R-salt, by increasing the action of the caustic alkali
thereon (for instance by taking more caustic alkali, heating longer and to a higher
temperature) beyond the degree required for the production of the mono-sulpho-
acid, so that the said mono-sulpho-acid produced as an intermediate product
is in the one operation further transformed into the aforesaid new di-hydroxy-
naphthalene.
My foreign correspondents have also discovered that this same new di-hydroxy-
naphthalene can be obtained from the di-hydroxy-naphthalene-mono-sulpho-acid by
treating the latter with certain dilute mineral acids, and also by heating its sodium
salt alone.
As a convenient means of illustrating the nature of this invention and the manner
in which it can be carried into practical effect I give the following examples, the
parts being by weight.

page_text: EXAMPLE 1.
MELTING
PREPARATION OF THE NEW
THE
CAUSTIC SODA.
The
DI-HYDROXY-NAPITHALENE BY
WITHI
DI-HYDROXY-NAPHTHALENE-MONO-SULPHO-ACID
di-hydroxy-naphthalene-mono-sulpho-acid can conveniently he prepared for
the purpose of this invention by melting together about sixty parts of caustic soda
and thirty parts of R-salt, and mixing these ingredients with about eight parts of
water. The temperature of the melt is raised to about two hundred and forty
degrees Centigrade and maintained between this temperature and two hundred and
eighty degrees Centigrade for about three hours or until the production of mono-
sulpho-acid has reached its maximum. This can be ascertained by withdrawing
equal test portions from the melt, at intervals of say about ten minutes and
dissolving them in sufficient hydrochloric acid containing about 10 per cent. of real
hydrochloric acid (H CI) to give an acid solution, boiling and filtering and then
precipitating with common salt the di-hydroxy-naphthalene-mono-sulpho-acid
formed. As soon as successive tests show no increase in the quantity formed, the
operation is interrupted. The whole melt is then dissolved in, and acidified with,
hydrochloric acid containing about ten per cent. of real hydrochloric acid, (H CI),
heated to boiling, filtered, and the solution saturated with common salt. The
sodium salt of the desired sulpho acid which separates out on cooling can be
collected on the filter, pressed and dried. It can be purified by dissolving again in
hot water and reprecipitating with sodium chloride.
To obtain the new di-hydroxy-naphthalene now take about twenty parts of
caustic soda and two and a half parts of water, and heat the mixture to a
temperature, of about two hundred and fifty degrees Centigrade; then add about
ten parts of the sodium salt of the mono-sulpho-acid, obtained as hereinbefore
described. Raise the temperature to from about three hundred to three hundred
and twenty degrees Centigrade and maintain this temperature for about one hour
or until no increase in the quantity of product soluble in ether occurs in successive
test portions after acidification with hydrochloric acid. This point being arrived
at, acidify the melt by mixing with about thirty parts of ordinary concentrated
sulphuric acid (containing about ninety six per cent, of real sulphuric acid H, SO,)
diluted with about two hundred parts of water. Heat to boiling and filter hot.
Allow the filtrate to cool and then extract either with ether or with fusel oil.
Distil off the solvent and extract the residual oil with boiling water, filter hot and
allow the filtrate to cool, when the di-hydroxy-naphthalene separates out and can
be purified by repeated recrystallization from water. If the temperature of the
melt in the above and following examples be maintained at between two hundred
and eighty and three hundred degrees Centigrade, the production of the di-hydroxy-
naphthalene takes place more slowly. Above three hundred and thirty degrees
decomposition takes place.
EXAMPLE 2. PRODUCTION OF THE DI-HYDROXY-NAPHTHALENE IN ONE
OPERATION FROM R-SALT.
Mix about forty parts of caustic soda with about five parts of water and heat the
mixture to a temperature of about two hundred degrees Centigrade, stir con-
tinuously and add gradually at this temperature about ten parts of R-salt. After
all the R-salt has been added, raise the temperature to from about three hundred
to three hundred and twenty degrees Centigrade and maintain the melt at this
temperature until no further increase occurs in the quantity of product soluble in
ether after acidification. This usually takes from two to three hours. Next
dissolve and acidify the melt with about one hundred and sixty parts of hydro-
chloric acid (containing about twenty five per cent. real hydrochloric acid; H CI)
diluted with about an equal quantity of water. Boil until no more sulphurous acid
gas is evolved and extract (after cooling) with ether or fusel oil and treat the

page_text: EXAMPLE 3. PREPARATION OF THE NEW DI-HYDROXY NAPHTHALENE FROM
THE HEREINBEFORE MENTIONED DI-HYDROXY NAPHTHALENE
SULPHO-ACID BY TREATMENT WITH DILUTE MINERAL ACIDS.
MONO-
Mix about ten parts of the sodium salt of the di-hydroxy-naphthalene-mono-
sulpho acid obtained as hereinbefore described with about one hundred parts of
dilute sulphuric acid (containing about 25 per cent. H, SO,) and heat the mixture
in a closed vessel capable of withstanding pressure to a temperature of about two
hundred degrees Centigrade for about twelve hours or until no dihydroxy-
naphthalene-mono-sulpho-acid remains unchanged which can be ascertained by the
following test. Take a sample of the mixture and extract thoroughly with ether,
add a slight excess of an alkali to the aqueous solution and then, in the cold, a
solution of diazo-benzene chloride and if but little azo-dyestuff of the di-hydroxy-
naphthalene-mono-sulpho-acid be formed the operation may be considered at an
end. This point being arrived at, cool the product and filter it, and recrystallize
from water the impure dihydroxy-naphthalene which remains on the filter.
If acid be used weaker than sulphuric acid containing 25 per cent. H, SO₁, the
operation takes longer and a higher temperature is necessary, and with stronger
acids it is possible to prepare the di-hydroxy naphthalene at a lower temperature
and more quickly.
As aforesaid the new dihydroxy-naphthalene can be obtained by heating the
sodium salt of the di-hydroxy-naphthalene-mono-sulpho-acid alone, but this does
not constitute an economical manufacturing process. When working on the manu-
facturing scale the best results are obtained by following the directions given in
Example 3.
The di-hydroxy-naphthalene obtained by all the above processes crystallizes
readily from water and can consequently be easily purified, it melts, when pure, at
a temperature of about one hundred and sixty to one hundred and sixty one
degrees Centigrade. It combines with diazo and tetrazo compounds and gives to
colouring matters, of which it forms a component, the valuable property of dyeing
mordanted fibre. On treatment of a cold dilute aqueous solution with a little dilute
ferric chloride an intense blue colour is formed which remains unchanged for
hours.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed I declare that what I
claim is.
First The manufacture of a new di-hydroxy naphthalene by first melting R-salt
with a caustic alkali to obtain a dihydroxy-naphthalene mono-sulpho-acid salt, then
melting this mono-sulpho-acid, or a salt thereof, with a caustic alkali to obtain the
new di-hydroxy-naphthalene, all substantially as herein before described.
Second The manufacture of a new dihydroxy naphthalene by the direct
action of a caustic alkaline melt on R salt in one operation substantially as
described.
Third-The manufacture of a new dihydroxy-naphthalene by the action of dilute
mineral acids on the herein before mentioned di-hydroxy-naphthalene-mono-sulpho-
acid or salts thereof substantially as hereinbefore described.
Fourth As a new article of manufacture the new di-hydroxy-naphthalene
melting at a temperature of about one hundred and sixty to one hundred and sixty
one degrees Centigrade such as can be obtained as hereinbefore described and
claimed.
1
.”
1001
J. H. JOHNSON & Co.,
Agents.