PREPARING COLORING MATTERS SUITABLE FOR DYEING AND PRINTING, AND IN MATERIALS USED IN THE MANUFACTURE OF THE SAME.
Year: 1880

page_text: "
LETTERS PATENT to John Henry Johnson, of 47, Lincoln's Inn Fields, in the
IMPROVEMENTS IN
County of Middlesex, Gentleman, for an Invention of
PREPARING COLORING MATTERS SUITABLE FOR DYEING AND PRINTING, AND IN
MATERIALS USED IN THE MANUFACTURE OF THE SAME.' A communication from
abroad by Adolphus Baeyer, Doctor of Philosophy and Professor of Chemistry in
the University of Munich, in the Kingdom of Bavaria, Empire of Germany.
"
PROVISIONAL SPECIFICATION left by the said John Henry Johnson at the
Office of the Commissioners of Patents on the 15th December 1880.
JOHN HENRY JOHNSON, of 47, Lincoln's Inn Fields, in the County of Middlesex,
Gentleman. "IMPROVEMENTS IN PREPARING COLORING MATTERS SUITABLE FOR
DYEING AND PRINTING, AND IN MATERIALS USED IN THE MANUFACTURE OF THE
SAME." A communication from abroad by Adolphus Baeyer, Doctor of Philosophy
and Professor of Chemistry in the University of Munich, in the Kingdom of Bavaria,
Empire of Germany.
This Invention consists in the discovery that by the action of sulphuric acid
upon orthonitro-phenylpropiolic acid, a new product or material may be obtained
which, upon treatment with reducing or deoxydising agents, can be changed into
coloring matters of the indigo group and suitable for dyeing and printing.
In carrying out this Invention I first prepare a mixture of orthonitrophenyl-
propiolic acid with cold and strong sulphuric acid, and the said mixture, which
quickly assumes a bright orange colour, is allowed to stand in the cold or at an
ordinary temperature until it no longer contains any appreciable quantity of
unchanged orthonitrophenylpropiolic acid.
I then submit the new product or material thus produced to the action of suitable
reducing or deoxydising agents in order to effect its conversion into coloring
matters. In practice I have found a great number of metals, metallic oxides, and
salts to possess the required reducing or deoxydising properties, such, for instance,
as iron, zinc, tin, lead, copper, bismuth, nickel, or the lower oxides and protosalts
[Devine Ap

page_text: of iron, manganese, copper, tin, and others. But likewise sulphides, hyposulphites,
and sulphites, sulphocyanides, iodides, and bromides may be employed for the same
purpose. Any of the before mentioned substances upon being added in the cold to
the orange coloured mixture, resulting from the action of sulphuric acid upon
orthonitrophenylpropiolic acid, as above described, will be found gradually to
change the said orange colour into a deep blue. The said reaction is then allowed
to proceed at an ordinary temperature until the blue colour no longer increases in
intensity. The coloring matters thus produced may then be separated from the
acid mixture by diluting the same with water, and by filtering and washing the
precipitate thus obtained. A further separation may be effected by the application
of suitable solvents. For instance, an aqueous solution of sulphurous acid may be
employed in order to dissolve the coloring matters, and the solution thus obtained
may be filtered and reprecipitated by the addition of mineral acids, and by
preference under heat.
Analogous results are obtainable by employing homologues and halogen
substitution products of orthonitrophenylpropiolic acid in the above described
process.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed
by the said John Henry Johnson in the Great Seal Patent Office on the
15th June 1881.
JOHN HENRY JOHNSON, of 47, Lincoln's Inn Fields, in the County of Middlesex,
Gentleman. "IMPROVEMENTS IN PREPARING COLORING MATTERS SUITABLE FOR
DYEING AND PRINTING, AND IN MATERIALS USED IN THE MANUFACTURe of the
SAME." A communication from abroad by Adolphus Baeyer, Doctor of Philosophy
and Professor of Chemistry in the University of Munich, in the Kingdom of Bavaria,
Empire of Germany.
The said Invention consists in the discovery that by the action of sulphuric acid
upon orthonitro-phenyl-propiolic acid, a new product or material may be obtained
which, upon treatment with reducing or deoxydising agents, can be changed or
converted into coloring matters of the indigo-group and suitable for dyeing and
printing.
In carrying out the said Invention I first prepare a mixture of orthonitro-
phenylpropiolic acid with cold and strong sulphuric acid, and the said mixture,
which quickly assumes a bright orange colour, is allowed to stand in the cold or at
the ordinary temperature until it no longer contains any appreciable quantity of
unchanged orthonitro phenylpropiolic acid.
I then submit the new product or material thus produced to the action of
suitable reducing or deoxidizing agents, in order to effect its conversion into
coloring matters.
In practice it has been found that a great number of metals, metallic oxides and
salts possess the required reducing or deoxidizing properties, such for example as
iron, zinc, tin, lead, copper, bismuth, nickel, or the lower oxides, and proto-salts of
iron, manganese, copper, tin, and others, but sulphides, hyposulphites, sulphites,
sulphocyanides, iodides and bromides may likewise be employed for the same
purpose. Any of the before mentioned substances upon being added in the cold to
the orange-coloured mixture resulting from the action of sulphuric acid upon ortho-
nitrophenylpropiolic acid as above described will be found gradually to change
the said orange colour into a deep blue. The said reaction is then allowed to
proceed at the ordinary temperature until the blue colour no longer increases in
intensity. The coloring matters thus produced may then be separated from the
acid mixture by diluting the same with water, and by filtering and washing the
precipitate thus obtained. As an example of the manner in which this Invention
may be carried into effect, I proceed as follows:-About one part by weight of
orthonitrophenylpropiolic acid is mixed in the cold with, say, about from ten to
twenty parts by weight of sulphuric acid of, say, about 1.84 specific gravity, and
the temperature of the mixtures is not allowed to rise above, say, about 20° centi-
grade. As soon as a sample of the mixture, upon being tested for the presence of
orthonitrophenylpropiolic acid by means of glucose and alkalies, as is well under-
stood by chemists, no longer contains any appreciable quantity of the said acid. I
add about five parts by weight of ferrous sulphate, and I then allow the mixture to
stand at about the ordinary temperature for, say, about half an hour, or until the
blue color is fully developed. This point being arrived at the acid mixture is
thrown into a large quantity of cold water, whereby the coloring matters are
precipitated, and may afterwards be collected on a filter washed and dried.
A further separation and purification of the coloring matters thus obtained may
be effected by the application of suitable solvents, for example, sulphurous acid
either contained in an aqueous solution or otherwise may be employed in order to
produce a soluble compound, which by the action of mineral acids in conjunction

page_text: with the employment of heat is decomposed into sulphurous acid and into blue
coloring matters. In practice I proceed as follows:-The coloring matters obtained
as above described are exhausted by repeated treatment with a cold and aqueous
solution of sulphurous acid, or instead of uncombined sulphurous acid, I may also
employ an acid sulphite, such, for example, as an acid sulphite of soda or potash,
and the solution or extract thus obtained is filtered, and the clear solution is
precipitated either by the addition of chloride of sodium, whereby a blue precipitate
is produced, which after separation by filtration or otherwise, may be used for
dyeing and printing in a manner similar to that now adopted when extract of
indigo is employed, or the sulphurous acid compound produced as before mentioned,
and which is soluble in water, may be treated as follows:-The aqueous solution is
boiled with either dilute muriatic or sulphuric acid, and is thereby decomposed
under evolution of sulphurous acid, and with the simultaneous precipitation of an
insoluble blue coloring matter, which coloring matter after filtering, washing, and
drying, is suitable for dyeing and printing in a manner similar to that now adopted
when indigo blue is employed.
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 in conclusion that what I consider to be novel and original,
and therefore claim as the Invention secured to me by the hereinbefore in part
recited Letters Patent is, -
First. The preparation of coloring matters of the indigo-group and suitable for
dyeing and printing by the action of reducing or deoxydising agents upon the
orange-coloured compound or material resulting from the action of sulphuric acid
upon orthonitrophenylpropiolic acid, substantially as herein before described.
Second. The employment of sulphurous acid for the purpose of rendering the
blue coloring matters obtained under the first claiming clause soluble in water,
substantially as herein before described.
Third. The preparation of coloring matters insoluble in water by decomposing
by means of an acid or acids in the manner herein before referred to, the solution
obtained under the second claiming clause, substantially as herein before described.
In witness whereof, I, the said John Henry Johnson, have to this my
Specification set my hand and seal, the Fifteenth day of June, One
thousand eight hundred and eighty one.
J. HENRY JOHNSON. (L.S.)