Improvements in the Manufacture of Derivatives of the Naphthalene Series.
Year: 1897

page_text: Improvements in the Manufacture of Derivatives of the
Naphthalene Series.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Buildings,
Chancery Lane, in the County of London, Consulting Engineer and Chartered Patent
Agent, do hereby declare the nature of this invention (as communicated to me from
abroad by The Actien Gesellschaft für Anilin Fabrikation, of Berlin, in the Empire of
Germany, Chemical Manufacturers), to be as follows:-
A process for the transformation of 8-naphthoquinone derivatives into a-naphtho-
quinone derivatives has been described by Böniger (Ber. d.d. chem. Ges. xxvii.,
page 26). This transformation is effected by the action, upon s-naphthoquinone, of
primary amines or diamines or their sulphonic or carbonic acids and by decomposition
of the compounds of the anilidonaphthoquinone series thus formed into g-oxynaphtho-
In this
quinone derivatives and amines by boiling them with dilute mineral acids.
way Böniger has, for instance, produced B-oxy-a-naphthoquinone from 6-naphtho-
quinone-sulphonic acid. Evidently this process is very troublesome, the steps being
very numerous.
My foreign correspondents have now discovered a new process for the production of
a-naphthoquinone derivatives in a very simple way, which is a remarkable advance as
compared with the above named process.
This new process is based on the observation, that 8-naphthoquinone derivatives
are transformed into a-naphthoquinone derivatives by the action of concentrated
sulphuric acid. This process has the great advantage that it may be united with
other processes such as for instance sulphonation of, or introduction of a nitro group
into, the a-naphthoquinone derivatives.
By this new process for instance 8-oxy-a-naphthoquinone may be produced from
B-naphthoquinone-monosulphonic acid (1:2:4) by simple treatment with concentrated
sulphuric acid whereby at the same time the sulphonic group is split. off.
The new process may be carried out as follows: 28 kilos. of the sodium salt
8-naphthoquinone-monosulphonic acid are introduced at a temperature of from
50 to 10° C. into 120 kilos. of concentrated sulphuric acid of 66° Bé.
of
The temperature is then allowed to increase up to 25° C. and is kept at this point
It is then allowed to
during 8 to 10 hours, while the mixture is constantly stirred.
flow upon ice. B-oxy-a-naphthoquinone separates and is isolated by filtration, then
washed with water and dried. For completely purifying it, it is dissolved in soda lye
and precipitated by means of hydrochloric acid,

page_text: The transformation of this ẞ-oxy-a-naphthoquinone into a sulphonic acid having
probably the constitutional formula :-
Is еnected as follows:-
50 kilos. of ẞ-oxy-a-naphthoquinone are introduced at a temperature of from 1.5°
to 20° C. into 250 kilos. of fuming sulphuric acid of 25 per cent. anhydride and the
mixture kept at a temperature of 20° C. during 2 hours. The sulphonation is
complete if a sample is soluble in water. The mixture is then allowed to flow upon
ice and a concentrated solution of cominon salt is added. The sulphonic acid
separates in the form of its sodium salt, which after crystallisation from water forms
brilliant weakly yellowish coloured lamellae. It is easily soluble in boiling water, and
sparingly soluble in cold water. Soda lye being added to the cold aqueous solution,
yellow crystals of a di-sodium salt separate.
The quantity and the strength of the sulphuric acid naturally may be varied
within large limits, the temperature and the time being also suitably varied.
As already stated this sulphonation may be united into one process with the pro-
duction of B-oxy-a-naphthoquinone. It is therefore not necessary to isolate the
latter, and the sulphonation may be effected immediately after the above described
transformation.
In a similar way this transformation may be combined with the introduction of
a nitro group. For instance, nitro oxynaphthoquinone, which hitherto only has been
produced by a very troublesome process described by Diehl and Merz (Ber. d. d.
chem. Ges. xi. page 1370), may be produced in a very simple way by treating
B-naphthoquinone monosulphonic acid with a mixture of sulphuric and nitric acids.
t may, for instance, be prepared as follows:-
10 kilos. of potassium salt of B-naphthoquinone monosulphonic acid are dissolved
in concentrated sulphuric acid and a mixture of 30 kilos. of concentrated sulphuric
acid and of 10 kilos. of concentrated nitric acid is added.
The temperature increases spontaneously and must be kept below 50° C. by
cooling. The mixture is kept at this temperature during some hours and is then
allowed to flow upon ice. Nitro oxynaphtboquinone crystallises and is separated by
filtration.
It is not necessary to start with isolated ẞ-naphthoquinonemonosulphonic acid, but
its production from 1: 2: 4-amido-naphthol sulphonic acid may be combined with
the transformation into an a-naphthoquinone derivative and the introduction of the
nitro-group. It may be effected as follows:-
10 kilos. of 1: 2: 4-amidonaphtholsulphonic acid are introduced at a temperature
of from 15° to 20° C. into 80 kilos. of a mixture of equal volumes of concentrated
sulphuric and nitric acids. The temperature of the mixture is kept below 50° C. by
cooling, during 4 hours.
The nitro-oxy-a-naphthoquinone is separated in the manner above described.
Dated this 15th day of November 1907

page_text: CUMIEBIE FRUITUATION.
Improvements in the Manufacture of Derivatives of the
Naphthalene Series.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Buildings,
Chancery Lane, in the County of London, Consulting Engineer and Chartered Patent
Agent, do hereby declare the nature of this invention (as communicated to me from
abroad by The Actien Gesellschaft für Anilin Fabrikation, of Berlin, in the Empire
of Germany, Chemical Manufacturers), and in what manner the same is to be
performed, to be particularly described and ascertained in and by the following
statement:—
process for the transformation of ẞ-naphthoquinone derivatives into a-naphtho-
quinone derivatives has been described by Böniger (Ber. d. d. chem. Ges. xxvii.,
page 26). This transformation is effected by the action, upon ẞ-naphthoquinone,
of primary amines, or diamines, or their sulphonic or carboxylic acids and by
decomposition of the compounds of the anilidonaphthoquinone series thus formed
into B-oxynaphthoquinone derivatives and amines by boiling them with dilute
mineral acids. In this way Böniger has, for instance, produced ẞ-oxy-a-naphtho-
quinone from ẞ-naphthoquinone-sulphonic acid. Evidently this process is very
troublesome, the steps being very numerous.
My foreign correspondents have now discovered a new process for the production
of a-naphthoquinone derivatives in a very simple way, which is a remarkable advance
as compared with the above named process.
This new process is based on the observation that ẞ-naphthoquinone derivatives
are transformed into a-naphthoquinone derivatives by the action of concentrated
sulphuric acid. This process has the great advantage that it may be united with
other processes such as for instance, sulphonation of, or introduction of a nitro-group
into, the a-naphthoquinone derivatives.
By this new process for instance B-oxy-a-naphthoquinone may be produced from
B-naphthoquinone-monosulphonic acid (124) by simple treatment with concen-
trated sulphuric acid whereby at the same time the sulphonic group is split off.
The new process may be carried out as follows:-
28 kilos. of the sodium salt of ẞ-naphthoquinone monosulphonic acid are introduced
at a temperature of from 5° to 10° C. into 120 kilos. of concentrated sulphuric acid of
66° Bé.
The temperature is then allowed to increase up to 25° C. and is kept at this point
during 8 to 10 hours, while the mixture is constantly stirred.
It is then allowed to flow upon ice. B-oxy-a-naphthoquinone separates and is
isolated by filtration, then washed with water and dried. For completely purifying
it, it is dissolved in soda lye and precipitated by means of hydrochloric acid.
The transformation of this ẞ-oxy-a-naphthoquinone into a sulphonic acid having
probably the constitutional formula:-
:-

page_text: to 20° C. into 250 kilos. of fuming sulphuric acid of 25 per cent. anhydride and the
mixture kept at a temperature of 20° C. during 2 hours.
The sulphonation is complete if a sample is soluble in water. The mixture is then
allowed to flow upon ice and a concentrated solution of common salt is added.
The sulphonic acid separates in the form of its sodium salt, which after
crystallisation from water forms brilliant weakly yellowish coloured lamellae.
It is easily soluble in boiling water and sparingly soluble in cold water.
Soda lye being added to the cold aqueous solution, yellow crystals of a di-sodium
salt separate.
The quantity and the strength of the sulphuric acid naturally may be varied
within large limits, the temperature and the time being also suitably varied.
As already stated this sulphonation may be united into one process with the
production of 8-oxy-a-naphthoquinone.
It is therefore not necessary to isolate the latter, and the sulphonation may be
effected immediately after the above described transformation.
In a similar way this transformation may be combined with the introduction of a
nitro group.
For instance, nitro-oxynaphthoquinone, which hitherto has been
produced only by a very troublesome process described by Diehl and Merz
(Ber. d. d. chem. Ges. xi. page 1370), may be produced in a very simple way by
treating 8-naphthoquinone monosulphonic acid with a mixture of sulphuric and nitric
acids. It may, for instance, be prepared as follows:-
10 kilos. of potassium salt of 8-naphthoquinone monosulphonic acid are dissolved
in concentrated sulphuric acid and a mixture of 30 kilos. of concentrated sulphuric
acid and of 10 kilos. of concentrated nitric acid is added. The temperature increases
spontaneously and must be kept below 50° C. by cooling. The mixture is kept at this
temperature during some hours and is then allowed to flow upon ice. Nitro-
oxynaphthoquinone crystallises and is separated by filtration.
It is not necessary to start with isolated 8-naphthoquinone monosulphonic acid,
but its production from 1:2:4-amidonaphthol sulphonic acid may be combined with
the transformation into an a-naphthoquinone derivative and the introduction of the
nitro-group.
It may be effected as follows:-
10 kilos. of 1:2: 4-amidonaphtholsulphonic acid are introduced at a temperature
of from 15° to 20° C. into 80 kilos. of a mixture of equal volumes of concentrated
sulphuric and nitric acids. The temperature of the mixture is kept below 50° C. by
cooling, during 4 hours.
The nitro-oxy-a-naphthoquinone is separated in the manner above described.
Having now particularly described
and
ascertained the nature of this
invention and in what manner the same is to be performed, I declare that what I
claim is :-
1. The herein described manufacture of a-naphthoquinone derivatives by treating
B-naphthoquinone derivatives with concentrated sulphuric acid.
2. The herein described manufacture of sulphonated or nitrosubstituted derivatives
of a-naphthoquinone by effecting the transformation of the 8-naphthoquinone
derivatives as set forth in the preceding claim, in the presence of nitrating agents or
under such conditions that a sulphonation takes place.
3. The herein described manufacture of nitrosubstituted derivatives of
a-naphthoquinone by treating suitable amidonaphthol derivatives with a mixture of
sulphuric and nitric acids, thus intermediately transforming the amidonaphthol
derivatives into 8-naphthoquinone derivatives, which are then converted into
a-naphthoquinone derivatives as set forth in Claim 1.
Dated this 22nd day of July 1898.