IMPROVEMENTS IN OBTAINING COLORING MATTERS SUITABLE FOR DYEING AND PRINTING
Year: 1878

page_text: LETTERS PATENT to John Peter Griess, of Burton on Trent, in the County
of Stafford, Chemist, for the Invention of "IMPROVEMENTS IN OBTAINING
COLORING MATTERS SUITABLE FOR DYEING AND PRINTING."
Sealed the 4th February 1879, and dated the 20th November 1878.
PROVISIONAL SPECIFICATION left by the said John Peter Griess at the
Office of the Commissioners of Patents on the 20th November 1878.
JOHN PETER GRIESS, of Burton on Trent, in the County of Stafford, Chemist.
"IMPROVEMENTS IN OBTAINING COLORING MATTERS SUITABLE FOR DYEING AND
PRINTING."
My Invention relates to an improved process for obtaining coloring matters
capable of replacing cochineal, lac dye, archil, or similar dyes in some of their
applications for dyeing and printing.
The said coloring matters belong to the class of the so called azo compounds, and
result from the action of phenols upon the diazo dompounds of phenolic ethers.
The said phenolic ethers are the methylic, ethylic, amylic, benzylic, or similar
ethers of the phenols and their homologues, and some of them are known to
chemists under special names, such as anisol or phenetol. The diazo compounds of
the phenolic ethers may be prepared from their amido compounds by the action of
nitrous acid in a manner now well understood by chemists, and coloring matters
may be obtained by allowing about equal molecules of the said diazo compounds
and of phenols to react upon one another, by preference, in alkaline solutions.
Instead of the phenols above mentioned, in some instances their sulpho acids may
be employed in an analogous manner, and instead of the phenolic ethers above
mentioned, their sulpho acids or their chlorine, bromine, iodine, hydroxyl, and nitro
substitution compounds may be used.
As an example of the manner in which my Invention may be carried into effect
and a red dye similar to cochineal may be obtained, I take any of the isomeric

page_text: modifications of the substance known to chemists as anisodine, that is to say, the
amido compound of anisol, and I obtain the hydrochlorate of diazo anisol by
treating an aqueous solution of hydrochlorate of anisodine with nitrous acid until
the latter ceases to be absorbed. I then mix the solution of, say, about one mole-
cule of the hydrochlorate of diazo anisol, thus obtained, with an alkaline solution of
about one molecule of the sulpho acid of beta napthol, and the dark red mixture
thus produced is afterwards precipitated by an acid or otherwise, and the coloring
matter may be further separated, purified, and obtained in a state suitable for
dyeing and printing by filtering, washing, drying, or by any other convenient
method.
In an analogous manner, purple dyes, similar to archil, may be obtained by
employing the methylic or other ethers of the napthols or their sulpho acids in the
above process, and by allowing the diazo compounds thereof to react upon the
isomeric napthols or their sulpho acids.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said John Peter Griess in the Great Seal Patent Office on the
20th May 1879.
JOHN PETER GRIESS, of Burton on Trent, in the County of Stafford, Chemist.
"IMPROVEMENTS IN OBTAINING COLORING MATTERS SUITABLE FOR DYEING AND
PRINTING."
My said Invention relates to an improved process of obtaining coloring matters
capable of replacing cochineal, lac dye, archil, or similar dyes in some of their
applications for dyeing and printing.
According to my said Invention I obtain coloring matters of the class of the so
called azo compounds by the action of phenols upon the diazo compounds of
phenolic ethers. The said phenolic ethers are the methylic, ethylic, amylic,
benzylic, or similar ethers of the phenols, and some of them are known to chemists
under special names, such as anisol or phenetol. The diazo compounds of the
phenolic ethers may be prepared from their amido compounds by the action of
nitrous acid in a manner now well understood by chemists, and coloring matters
may be obtained by allowing equal molecules of the said diazo compounds and of
phenols to react upon one another, by preference in an alkaline solution.
In lieu of the phenols above mentioned, their sulpho-acids may, in some cases, be
employed in an analogous manner, and in lieu of the phenolic ethers above men-
tioned, their sulpho acids or their chlorine, bromine, iodine, hydroxyl, and nitro
substitution compounds may be used.
As an example of the manner in which my said Invention inay be carried into
effect and a red dye similar to cochineal may be obtained, I take any of the isomeric
modifications of the substance known to chemists as anisodine, that is to say, the
amido compound of anisol, and I obtain the hydrochlorate of diazoanisol by treating
an aqueous solution of hydrochlorate of anisodine with nitrous acid until the latter
ceases to be absorbed. I then mix the solution of, say, about one molecule of the
hydrochlorate of diazoanisol thus obtained with an alkaline solution of one mole-
cule of the sulpho-acids of beta naphthol, and the dark red mixture thus produced
is afterwards precipitated by an acid or otherwise, and the coloring matter may be
further separated, purified, and obtained in a state suitable for dyeing and printing
by filtering, washing, drying, or by any other convenient method.
The following process has been found to give good results in practice :—
I take, say, about 10 lbs. of anisidine and mix the same with or dissolve the
same in about 30 lbs. of concentrated muriatic acid of a specific gravity of about
1-17, and about twenty gallons of cold water, and add thereto an aqueous solution
of nitrite of sodium containing, say, about 5 lbs. and 10 ounces of pure and dry
nitrite of sodium dissolved in about ten times its weight of cold water, or as much
as will be found necessary to convert the anisidine into its diazo-compound. In lieu
of using the pure nitrite of sodium as above named, its equivalent amount of com-
mercial nitrite of sodium or of any other nitrite may be employed, or nitrous acid
may be used in its gaseous condition and passed through the mixture until it ceases
to be absorbed.
The solution of the diazo-compound thus obtained is then gradually added to a
mixture of about 20 lbs. of the sodium salt of the betanaphthol monosulpho-acids,
with about four gallons of water, and care is taken to keep the mixture slightly
alkaline by adding thereto from time to time the necessary amount of an alkali or
an alkaline salt, by preference, of caustic soda or ammonia.
The operation may be considered at an end as soon as in a filtered portion of the
mixture no more coloring matter is produced either by the addition of the diazo-
compound or of the naphtholmono sulphate.
The result of this operation is a dark red precipitate and a solution from which
the coloring matter may be further precipitated by the addition of common salt,

page_text: and the precipitates thus produced are obtained in a solid state by filtering, pressing
and drying.
In lieu of the anisidine above named, its equivalent amounts of the homologous
amido compounds which are derived from the ethylic and amylic ethers of phenol
or cresol may be used in the same manner and with a similar result. The coloring
matters thus obtained are capable of replacing cochineal or lac dye for producing
scarlets or reds possessing a yellowish hue.
In order to produce red coloring matters of a bluer or more crimson shade, I
allow the above mentioned diazo compounds of anisidine and of its homologues to
react upon the betanaphthol disulpho-acids or upon mixtures of the betanaphthol
sulpho-acids, such, for example, as result from the treatinent of betanaphthol with
fuming sulphuric acid.
As an example of the mode of carrying out this operation I may proceed in the
following manner :-
I take, say, about 12 lbs. of betanaphthol and dissolve the same in and heat it with
about 24 lbs. of fuming sulphuric acid containing about eighty five per cent. of anhy-
drous sulphuric acid, and maintain the mixture at a temperature of, say, about
110° centigrade for about five hours. The further treatment consists in removing
the free sulphuric acid contained in the mixture by neutralization with caustic
lime, and the filtered solution is decomposed by carbonate of soda filtered and
evaporated to dryness, in order to obtain the sodium salts of the naphthol disulpho
acids in a manner well understood by chemists. I then prepare the coloring matter
by mixing the sodium salts of the naphtholdisulpho acids thus obtained with about
six gallons of cold water, and I gradually add to it, in the manner herein before
described, a solution of the diazo compound, such as results from the treatment of
10 lbs. of anisidine with nitrous acid, the mixture being maintained slightly
alkaline throughout this operation. At the close of the operation, the precipitation
of the coloring matter may be rendered more perfect by the addition of common
salt, and the precipitate resulting from the operation may be obtained in a solid
state by filtering, pressing, and drying.
As an example of the manner in which I obtain coloring matters by employing
the sulphoacids of the phenolic ethers I may proceed as follows:-
I first prepare the amido sulpho-acids of the phenolic ethers by either of the
following two processes.
First process. One part by weight of anisidine (or any of its homologues above
mentioned) is taken and mixed with about four parts by weight of concentrated or
rectified sulphuric acid of a specific gravity of about 184, and the mixture is
heated at a temperature of, say, about 100 degrees centigrade during from three to
four hours, or until a sample of the mixture produces a clear solution with water.
The further treatment consists in removing the excess of sulphuric acid contained
in the mixture by neutralization with caustic lime, and the filtered solution may
be decomposed with carbonate of soda filtered and evaporated to dryness in order
to obtain the sodium salts of the sulpho-acids of anisidine, and in a manner well
understood by chemists.
Second process. One part by weight of anisol (or of phenetol or of any of its
homologues above mentioned) is first converted into its corresponding sulpho-acids
in a manner well known to chemists, such as, for example, by dissolving it in about
two parts by weight of concentrated or rectified sulphuric acid of a specific gravity
of about 184, and by allowing the mixture to stand either at the ordinary temper-
ature or at an elevated temperature not exceeding about 100° centigrade and until
a sample of the mixture will be found to produce a clear solution with water or
nearly so. The results of this operation are then freed from the excess of sulphuric
acid and treated in the usual manner for obtaining the sulpho acids thus produced
in the state of their sodium or potassium salts.
The next step consists in preparing the corresponding nitro sulpho acids by
gradually mixing one part by weight of the sodium salt of the anisol sulpho acids
(or of their homologues as above mentioned) with about two parts by weight of

page_text: nitric acid of a specific gravity of about 1-48, care being taken to keep the mixture
well stirred and sufficiently cooled in order to prevent a rise of temperature exceed-
ing about 40° centigrade. The mixture gradually solidifies by the nitro sulpho
acids thus formed separating out in a crystalline condition. The further treatinent
consists in removing the excess of uncombined nitric acid by mechanical means,
such, for example, as by filtering and pressing, and the nitro-sulpho acids of anisol
(or of its homologues as above mentioned) may be further purified from water by
crystallization.
The next step is the transformation of the nitro-sulpho acids thus produced into
their corresponding amido compounds, and this result is obtained by employing the
usual reducing agents, such, for example, as tin and hydrochloric acid, as is well
understood by chemists. The reduction of the nitro sulpho compound being com-
plete, the new amido sulpho acids or the sulpho acids of anisidine (and of its homo-
logues as before mentioned) are obtained as a precipitate, and may be further
purified by redissolving them in an alkaline solution, such, for example, as a solution
of caustic soda, by filtering the solution thus obtained and adding thereto an excess
of hydrochloric acid in order to precipitate the amido sulpho acids, which precipitate
may again be filtered and recrystallised from water.
The next step is the conversion of the amido sulpho acids of the phenolic ethers
obtained by either of the two processes into their corresponding diazo-compounds.
As an example of the mode of conducting this operation, I inay proceed in the
following manner :—
I take, say, about 10 lbs. of the sulpho-acids of anisidine and mix the same with
about 15 lbs. of concentrated muriatic acid of a specific gravity of about 1.17 and
about fifteen gallons of cold water, and add thereto an aqueous solution of nitrite of
sodium containing about 3 lbs. and six ounces of pure and dry nitrite of sodium
dissolved in about ten times its weight of cold water, or as much as will be found
necessary to convert the amido sulpho acids into their diazo-compounds. In lieu of
using the pure nitrite of sodium as above named, its equivalent amount of commer-
cial nitrite of sodium or of any other nitrite may be employed, or nitrous acid may
be used in its gaseous condition and passed through the mixture until it ceases to
be absorbed.
I then proceed to prepare red coloring matters from the diazo-compounds thus
obtained by allowing them to react either upon betanaphthol, or upon the mono-
sulpho acids of betanaphthol, or upon the disulpho-acids of betanaphthol, or upon
mixtures of any sulpho-acids of betanaphthol, which may be prepared by the action
of sulphuric acid of any strength and concentration, whether fuming or not, upon
betanaphthol.
As an example of the mode of carrying out this process I may proceed in the
following manner :-
The solution of the diazo-compounds prepared as above described is gradually
added to an alkaline solution of betanaphthol, which is produced by mixing, say,
about 7 lbs. of betanaphthol with about seven gallons of water and about 14 lbs. of
a solution of caustic soda of a specific gravity of about 1.38, care being taken to
maintain the mixture slightly alkaline as before described. The result of this
process is a dark red precipitate which is subsequently filtered, pressed, and dried.
In an analogous manner I proceed, in order to prepare red coloring matters of a
more bluish or crimson shade, by allowing the diazo-compounds of the sulpho-acids
of the phenolic ethers to react upon the sulpho-acids of betanaphthol, and by
preference upon the disulpho-acids thereof, which I obtain by the action of fuming
sulphuric acid upon betanaphthol, substantially in the manner hereinbefore
described. For example, the diazo-compounds prepared from about 10 lbs. of the
sulpho-acids of anisidine (or the equivalent amount of their homologues) are made
to react upon the sodium salts of the sulpho acids of betanaphthol, such, for example,
as result from the treatment of about 7 lbs. of betanaphthol with about 14 lbs. of
fuming sulphuric acid, substantially in the manner hereinbefore described.
In an analogous manner purple dyes, similar to archil, may be obtained by

page_text: employing the methylic or other ethers of betanaphthol in lieu of the methylic or
other ethers of phenol and cresol in the above described process, and I wish it to be
understood that two processes above mentioned, for preparing the amido sulpho
.acids of anisol and its homologues, may be employed in a perfectly analogous
manner in order to prepare the corresponding naphthol compounds.
And although I have only mentioned betanaphthol in the above described process
on account of the superior results which I have obtained by its employment,-
I wish it to be also understood that I do not confine myself to its exclusive usc,
but that my process may likewise be applied to the production of red and purple
coloring matters from alpha naphthol, and from mixtures of the two isomeric
naphthols, all substantially in the manner herein before described.
Having now described and particularly ascertained the nature of my 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,―
Obtaining coloring matters suitable for dyeing and printing by the action of phenols
or their substitution compounds, as herein set forth, upon the diazo compounds of
phenolic ethers or their substitution products as herein set forth, all substantially as
hereinbefore described.
In witness whereof, I, the said John Peter Griess, have to this my Specifi-
cation set my hand and seal, this Fifteenth day of May, One thousand
eight hundred and seventy nine.
JOHN PETER GRIESS. (L.S.)