IMPROVEMENTS IN COLOURING MATTERS SUITABLE FOR DYEING AND PRINTING AND IN THE MANUFACTURE OF THE SAME
Year: 1880

page_text: LETTERS PATENT to Joseph Anthony Dixon, of 175, West George Street,
Glasgow, in the County of Lanark, North Britain, Solicitor, for an Invention
of "IMPROVEMENTS IN COLOURING MATTERS SUITABLE FOR DYEING AND
PRINTING AND IN THE MANUFACTURE OF THE SAME." A communication
from abroad by Doctor Carl Koenig, of Höchst-am-Main, in the Empire of
Germany, a Director of the Farbwerke vorm. Meister, Lucius, and Brüning,
a Company carrying on business there as Chemical Manufacturers.
PROVISIONAL SPECIFICATION left by the said Joseph Anthony Dixon at
"
the Office of the Commissioners of Patents on the 20th December 1880.
JOSEPH ANTHONY DIXON, of 175, West George Street, Glasgow, in the County
of Lanark, North Britain, Solicitor. "IMPROVEMENTS IN COLOURING MATTERS
SUITABLE FOR DYEING AND PRINTING, AND IN THE MANUFACTURE OF THE SAME.'
A communication from abroad by Doctor Carl Koenig, of Höchst-am-Main, in
the Empire of Germany, a Director of the Farbwerke vorm. Meister, Lucius, and
Brüning, a Company carrying on business there as Chemical Manufacturers.
This Invention has for its object the production of yellow colouring matters
distinguished by their brilliancy and fastness, also by their facility of application,
especially to silk and wool.
In the halogen derivatives of the aromatic hydrocarbons (including in that
expression those of napthalene), the halogen atoms are well known to be strongly
combined with the nucleus; they however become more moveable, or the force and
obstinacy of their combination appears to be loosened, by the introduction of nitro
groups. The process about to be described accordingly rests on the principle of
producing from mono-bromnaphtalene (or monochlornaph talene) by energetic
nitration (that is, treatment with nitric acid so as to produce the nitro substitution
compound or compounds), the tetra-nitro-compound, and then substituting the
now more easily replaceable halogen by other atoms, residues, or groups. In the
tetra-nitro-compound (the formula of which is C10 H³ (NO2)4 Br) the halogen atom
can be easily substituted or replaced by various molecular residues or rests (as the
hydroxyl, amido, phenyl-amido, and other like groups), and as the result of such

page_text: substitutions there originate derivatives that crystallize well and yield colouring
matters of greater or less value. Among these I signalize as of especial value for
the purposes of dyeing and printing the bodies that are obtained after the
following process, which I describe as an example of the detailed working out of
this Invention in a particular case. For example, I add carefully
parts of
monobromnaphtalene to 12 parts fuming nitric acid, and after the action has gone
on for some length of time I dilute the product of the reaction with much water,
and wash the nitro-products that have separated sufficiently with water. It is
advantageous to wash the so obtained bodies with ligroin, benzol, alcohol, or similar
liquids to remove any bye-products.
The thus obtained di-nitro-derivative of bromnaphtalene is added to the octuple
quantity of a mixture of equal parts of English sulphuric acid, and fuming nitric acid
and heated for some time. Then the whole is poured into water and the precipitate
is washed and freed from water as much as possible. In this way I obtain a
mixture of isomeric tetranitromonobromnaph talenes, among which the one suiting
my purpose is characterised by its greater solubility in various mediums, such as
glacial acetic acid (eisessig), benzole, acetic ethylether, acetone, or similar solvents,
and can be readily isolated.
The method of nitration hereinbefore described, as well as the mode of purifying
the obtained products, may be varied in different ways obvious to chemists.
"
The tetranitromonobrom-naphtalene so obtained is digested with a warm
solution of soda, whereby there is formed the soda salt of tetranitronaphtol, which
when purified by crystallization represents the colouring matter that I call
heliochrysin." For the last described reaction I give the following formula
or equation, namely:-C10 H³ (NO2)4 Br + Na³ CO³ = C¹º H³ (NO₂)4 ONa + Na Br
+CO. The solution of soda can be replaced by various agents well known to
chemists for such substitution processes, and the method can be varied
accordingly.
In the same manner other metallic salts of tetranitronaphtol can also be obtained
direct, and can be used as colouring matters, or they may be transformed into the
soda salts.
The substances that are formed from the described tetranitromonobromnaphtalene
by the action of ammonia, anilin, and other substituted ammonias, are more or less
easily decomposed on the analogy of the acid amides, and so give also tetranitro-
naphtol or its salts.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said Joseph Anthony Dixon in the Great Seal Patent Office on the
7th June 1881.
JOSEPH ANTHONY DIXON, of 175, West George Street, Glasgow, in the County
of Lanark, North Britain, Solicitor. "IMPROVEMENTS IN COLOURING MATTERS
SUITABLE FOR DYEING AND PRINTING, AND IN THE MANUFACTURE OF THE SAME."
A communication from abroad by Doctor Carl Koenig, of Höchst-am-Main, in
the Empire of Germany, a Director of the Farbwerke vorm. Meister, Lucius, and
Brüning, a Company carrying on business there as Chemical Manufacturers.
This Invention has for its nature and object the production, in manner
hereinafter described, of yellow colouring matters, distinguished by their
brilliancy and fastness, also by their facility of application, especially to silk
and wool.
In the halogen derivatives of the aromatic hydrocarbons (including in that
expression those of napthalene) the halogen atoms are well known to be strongly
combined with the nucleus; they, however, become more moveable, or the force
and obstinacy of their combination appears to be loosened, by the introduction of
nitro groups. The process about to be described accordingly rests on the principle
of producing from monobromnaphtalene (or monochlornaphtalene) by energetic
nitration (that is, treatment with nitric acid so as to produce the nitro substitution
compound or compounds) the tetra nitro compound, and their substituting the now
more easily replaceable halogen atom by other atoms, residues, or groups, so as
finally to obtain a compound in which the halogen is substituted by the hydroxyl
group (by which it will be understood that mean either OH or ONa, or other
analogous group, according to circumstances) and tetra nitro naphthol or its salts
is produced. In the tetranitro compounds, the typical formula of which is
Co HS (NO2)4 Br, the halogen atom can be easily substituted or replaced by various
molecular residues or rests (as by the hydroxyl group, or by the amido,
phenyl-amido, or other like group, which latter groups may again be replaced by
the hydroxyl), and as the result of such substitutions there originate derivatives
that crystallize well and yield colouring matters of greater or less value. Among
these I signalize as of especial value for the purposes of dyeing and printing the
bodies that are obtained after the following process, which I describe as an example
of the detailed working out of this Invention in a particular case, and as the
method and process by which I prefer to produce the said colouring matters, that
is to say, the tetra nitro napthol or its salts. For example, I add carefully 3 parts
of monobromnaphtalene to 12 parts of fuming nitric acid, and after the action has
gone on for some length of time I dilute the product of the reaction with much
water, and wash sufficiently with water the nitro products that have separated.
It is advantageous to wash the so obtained bodies with ligroin, benzol, alcohol, or
similar liquids to remove any bye products.
The thus obtained dinitroderivative of bromnaphtalene is added to the octuple
quantity of a mixture of equal parts of English sulphuric acid and fuming nitric
acid and heated for some time. Then the whole is poured into water and the
precipitate is washed and freed from water as much as possible. In this way I
obtain a mixture of isomeric tetranitromonobromnaphtalenes, among which the one
best suiting my purpose is characterised by its greater solubility in various
mediums, such as glacial acetic acid (eisessig), benzole, acetic ethylether, acetone,
or similar solvents, and can be readily isolated.
The method of nitration hereinbefore described, as well as the mode of
purifying the obtained products, may be varied in different ways obvious to
chemists.

page_text: The tetranitromonobrom-naphtalene so obtained is digested with a warm
solution of soda (or its carbonate or other suitable salt), whereby there is formed
the soda salt of tetranitronaphtol, which, when purified by.crystallization, represents
the colouring matter that I call "heliochrysin." "For the last described reaction I
give the following formula or equation, viz. :-
C10 H³ (NO)4 Br + Na³ CO³ = C10 H³ (NO₂) 4 ONa + Na Br + CO₂.
The solution of soda can be replaced by various agents well known to chemists
for such substitution processes, and the method can be varied accordingly.
In the same manner other metallic salts of tetranitronaphtol can also be obtained
direct, and can be used as colouring matters, or they may be transformed into the
soda salts:
The substances that are formed from the hereinbefore described tetranitro-
monobrom-naphtalene by the actions of ammonia, analin, and other substituted
ammonias, are more or less easily decomposed on the analogy of the well known
decompositions of the acid amides, whereby the hydroxyl group is made to replace
the NH or other corresponding ammonia group, and in this way, as will be obvious
to chemists, tetranitronaphtol or its salts may be obtained from the said substances
formed by the action of ammonia and substituted ammonias on tetranitro-
monobrom-napthalene, as well as by replacing the halogen atom of the last
mentioned body directly by bydroxyl, as in the process hereinbefore specially
explained or illustrated. But I do not recommend the use of these amids and
phenylamids as a source of tetranitro napthol, as these processes do not work well
in comparison with the direct process above described. I only mention the said
processes to prevent evasion by substituting the indirect for the direct mode of
replacing the halogen atom by hydroxyl in the tetranitromonobrom or other nitro
and halogen substituted compound of napthalene.
Having now described and particularly ascertained the nature of the said
Invention, and the manner in which the same is or may be used or carried into
effect, I would observe that what I claim as the Invention secured to me by the
hereinbefore in part recited Letters Patent is,―
The production of yellow colouring matters which consist of tetranitro-naphthol
or its salts, herein before described, in manner herein before described, that is to say,
by energetic nitration of a monohalogen compound of napthalene, so as to produce
the corresponding tetranitro halogen-substituted napthalene compound, and in
then directly or indirectly substituting in the latter hydroxyl for the halogen, in
manner before described, so as to produce the tetranitro napthol, or its sodium or
other salt before mentioned, or in any manner substantially the same.
In witness whereof, I, the said Joseph Anthony Dixon, have hereunto set my
hand and seal, this First day of June, in the year of our Lord One
thousand eight hundred and eighty one.
JOSEPH ANTHONY DIXON. (L.S.)