IMPROVEMENTS IN OBTAINING COLORING MATTERS SUITABLE FOR DYEING AND PRINTING
Year: 1877

page_text: LETTERS PATENT to John Peter Griess, of Burton-on-Trent, Chemist, for
the Invention of "IMPROVEMENTS IN OBTAINING COLORING MATTERS SUITABLE
FOR DYEING AND PRINTING."
Sealed the 30th November 1877, and dated the 4th October 1877.
PROVISIONAL SPECIFICATION left by the said John Peter Griess at the
Office of the Commissioners of Patents on the 4th October 1877.
JOHN PETER GRIESS, of Burton-on-Trent, Chemist. "IMPROVEMENTS IN
OBTAINING COLORING MATTERS SUITABLE FOR DYEING AND PRINTING."
'
My Invention relates to an improved process for obtaining coloring matters suit-
able for dyeing and printing, and possessing yellow, red, brown, purple, or other
hue.
In carrying out my Invention I take the substances known to chemists as nitro-
phenols, or I take the substitution compounds of the said nitro-phenols in which
one or more atoms of hydrogen are replaced or substituted by chlorine, bromine,
iodine, by the nitro group, sulfo group, or carboxyle group, and I submit these com-
pounds to the reducing action of substances capable of converting or reducing their
nitro groups, partly or wholly, into amido groups, as is well understood by chemists,
I then act upon the amido-plienols or their substitution compounds thus obtained
with nitrous acid or its salts in such a manner as to convert these amido compounds
into their corresponding diazo compounds, as is well understood by chemists.
Now according to my Invention I convert these substances into coloring matters
by combining them with substances belonging to the phenolic series; this combina-,
tion I generally prefer to carry out by mixing the said diazo compounds with an
alkaline solution of the substances belonging to the phenolic series as long as combi-
nation is observed to take place; I then separate the coloring matter by means of
an acid, or otherwise, and if necessary submit the product thus obtained to a process
of filtering, washing, pressing, and drying, or otherwise treat it in order to render
the coloring matter suitable for dyeing and printing.
The substances mentioned above as belonging to the phenolic series may be

page_text: phenols, properly so called, or the hydroxyle compounds of aromatic hydrocarbons
such as phenylic, cresylic, and naphthylic alcohols, resorcin, orcin, or other similar
substances, or they may be the substitution products thereof in which one or more
atoms of hydrogen are replaced or substituted by chlorine, bromine, iodine, by the
nitro group, sulfo group, or carboxyle group.
As an example of the application of my Invention I produce a brown coloring
matter by taking picric acid, converting the same into picramic acid, and combining
the diazo compound thereof with orcin. In order to effect this combination I add
the acid solution of the diazo compound to a strongly alkaline solution of orcin until
a sample of the mixture, after being precipitated by means of a mineral acid, filtered
and again rendered alkaline, no longer produces any brown coloration by the
addition of the diazo compound. I then precipitate the whole mixture by means of
an acid, filter, wash, press, and dry the product thus precipitated, which in this state
will be a coloring matter suitable for dyeing and printing.
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 3rd
April 1878.
"IMPROVEMENTS
JOHN PETER GRIESS, of Burton-on-Trent, Chemist.
OBTAINING COLORING MATTERS SUITABLE FOR DYEING AND PRINTING."
IN
My Invention relates to an improved process for obtaining coloring matters suit-
able for dyeing and printing.
In carrying out my Invention I take the substances known to chemists as nitro-
phenols, or I take the substitution compounds of the nitro-phenols in which one or
more atoms of hydrogen are replaced or substituted by chlorine, bromine, or iodine,
or by the nitro group, or by the sulpho group, or by the carboxyl group, and I
submit these compounds to the reducing action of substances capable of converting
or reducing their nitro groups, partly or wholly, into amido groups, as is well under-
stood by chemists; then act upon the amido-phenols or their substitution compounds
thus obtained, with nitrous acid or with nitrates, in such a manner as to convert
these amido compounds into their corresponding diazo compounds, as is well under-
stood by chemists.
Now according to my Invention I convert the substances before referred to into
coloring matters by combining them with substances belonging to the phenolic
series. This combination I prefer to effect by mixing the said diazo compounds with
an alkaline solution of the substances belonging to the phenolic series until about
one corresponding equivalent has been employed; I then effect the separation of the
coloring matters by means of an acid or otherwise, and if necessary I submit the
product thus obtained to a process of filtering, washing, preserving, and drying, or
it may be otherwise treated in order to render the coloring matters suitable for the
purposes of dyeing and printing.
The substances before mentioned belonging to the phenolic series may be phenols
properly so called, that is to say, either the hydroxyle compounds of the aromatic

page_text: bydrocarbons, such as phenylic, cresylic, and naphtylic alcohols, resorcine, orcine, and
other substances, or they may be the substitution products thereof, in which one or
more atoms of hydrogen are replaced or substituted by chlorine, bromine, iodine, or
by the nitro group, or by the sulpho group, or by the carboxyl group.
In carrying out my Invention I have found the following nitro-phenols to give
good results, videlicet:-Trinitro-phenol or picric acid, dinitro-cresol, dinitro-phenol
or its mono-chlorinated substitution compounds, or the sulpho acids of the mono-nitro-
phenols, or of the chlorine, bromine, and iodine substitution compounds thereof, or
of nitro-salicylic acid or nitro-sulphosalicylic.
Nitro-phenols or mixtures of the same may be converted into their diazo com-
pounds, as is well understood, and by acting with the same upon any of the following
compounds, or substances, or mixtures of the same, which chemists understand as
belonging to the group known as phenols, videlicet, for example, phenol or carbolic
acid, cresol, resorcine, orcine, alpha and beta, napthol dioxy-naphtaline; and upon
the mono-sulpho acids or bisulpho acids of the before-mentioned phenols the desired
coloring matters are produced.
In carrying out this part of my Invention I prefer to employ about equal equiva-
lents of the diazo compound or compounds derived from the above-mentioned nitro-
phenols and of the before-mentioned compounds, products; or substances belonging
to the phenolic series, and I prefer that the action and re-action ensuing should be
effected at or about the ordinary temperature, and that the solution should be
maintained in an alkaline condition.
As an example of the manner in which my Invention may be carried into effect
in order to produce yellow or brown coloring matter from trintro-phenol or picric
acid I proceed as follows:-Picric acid is first converted into picramic acid or into
amido dinitro-phenol by the reducing action of sulphide of ammonia, or by any other
method, as is well understood by chemists. Picric acid thus converted into picramic
acid may be employed in about the following proportions, videlicet.The piéramic
acid, in about the proportion of twenty pounds, is added to about ten gallons of water,
to which is subsequently added about eleven pounds of hydrochloric acid of about.
the specific gravity of 118. To this mixture is then added a solution of nitrite of
soda containing about seven pounds of the same, dissolved in about ten gallons of
water, which is by preference to be added gradually, and the mixture be main-
tained in a state of agitation. The mixture thus made is allowed to remain until
the desired re-action has taken place in order that the diazo compound may be,
obtained.
Having thus obtained the diazo compound before mentioned, it is brought into.
contact with a solution consisting of about 9.5 lbs. of carbolic acid dissolved in about
20 gallons of a solution of caustic soda, containing about five pounds of caustic soda,
to the twenty gallons employed.
The mixture thus resulting is allowed to remain until the desired re-action has
been completed, which may be ascertained either by the entire, or almost the entire,
solution of the before-mentioned diazo compound and the nonformation of any further
dyes or coloring matters.
The coloring matter or matters thus resulting may be separated and obtained in
an available form by the addition of an acid, such, for example, as hydrochloric
acid.
The coloring matter or matters thus obtained may be separated by means of
filtration, and freed from any other soluble impurities, and may thus be combined
with an alkaline base so as to render them soluble, and to be capable of being
employed as useful products in the arts.
A similar result may be obtained by employing about an equivalent proportion of
cresol or cresylic-alcohol in place of the carbolic acid before mentioned.
In accordance with my Invention maroon and chocolate colored dyes may be
prepared from picric acid by substituting for the carbolic acid, as described in the
above-mentioned process, about their equivalent weights of the diatomic phenols,
such, for example, as resorcine or orcine. I have found that when the before-

page_text: mentioned substances are employed in about the proportions of 11 lbs. of resorcine,
or about 12.4 lbs. of orcine as substitutes for the 9-5 lbs. of carbolic acid mentioned
in the process before described satisfactory results may be obtained.
In order to produce purple coloring matters from picric acid:-The resulting diazo
compounds prepared, for example, from about 20 lbs. of picramic acid, as above
described, are added to a solution and by preference rendered and maintained
alkaline, consisting of about 145 lbs. of beta-naphthol. The precipitate thus obtained
may then be separated by subsidence or by filtration, and a solution of the same may
be employed for the purpose of dyeing and printing.
A similar result may be obtained, and coloring inatters more soluble in water
than the foregoing compound may be produced, by acting with the diazo compounds
prepared from about twenty pounds of picramic acid, as before described, upon the
sulpho acids of beta-naphthol, such, for example, as result from the treatment of
about 145 lbs. of beta-naphthol with about their equal weight of concentrated
sulphuric acid at a temperature of about 100° centigrade, and in a manner well
understood by chemists; after the addition of the diazo compounds I prefer to effect
the precipitation of the coloring matter or matters by the addition of common salt,
and to wash and dry the precipitate thus obtained.
In the two last-named processes alpha-naphthol and the sulpho-acids thereof may
be substituted for their isomeric modifications mentioned above, in order that
coloring matters may be obtained therefrom.
It will of course be understood by chemists that instead of employing picric acid
the dinitro compounds of carbolic acid or cresol may be substituted and converted
into their corresponding amido nitro-phenols and into the diazo compounds thereof,
and by the action of the diazo compounds thus obtained, upon the substances before
mentioned as belonging to the phenolic series, coloring matters may be obtained
similar to the coloring matters produced from picric acid, as before described.
As another example of the manner in which this Invention may be made
applicable for the production of coloring matters from the sulpho acids of the mono-
nitro-phenols, I take, for example, a salt of the nitro-phenol sulphuric acids, such,
for example, as the potassium salt of the nitro-phenol sulphuric acid, as described
by Kolbe and Gaupe, and which may be prepared by the action of nitric acid upon
paraphenol sulphuric acid.
In order to obtain the desired coloring matters I take about 20 lbs., for example,
of the potassium salt of nitro-phenol sulphuric acid which I convert in a manner
well understood by chemists into the amido sulpho-phenol compound. For this
purpose I prefer to employ tin and hydrochloric acid. The solution of amido sulpho-
phenol thus obtained is then freed from any tin which may be contained therein by
any of the well-known methods, such, for example, as by the employment of
sulphuretted hydrogen, or of zinc. To this solution thus treated a solution in water
of nitrate of soda is added in slight excess or until the evolution of free nitrous acid
occurs, indicating that the amido compound is converted into the corresponding
diazo compound. The solution of the before-mentioned diazo compound is then
gradually added to a solution consisting of about 11.2 lbs., of beta-naphthol dissolved
in about 10 gallons of a solution of caustic soda containing about 4 lbs. of caustic
soda, care being taken to maintain the solution alkaline.
From the solution, which will be found to be of a deep crimson-red tint, the
coloring matters may be precipitated by means of an acid, such, for example, as
hydrochloric acid, and the coloring matters thus separated after washing may be
converted into a sodium or aluminum salt. The coloring matters thus obtained
will be found to produce when employed in conjunction with alumina or with tin
mordants scarlet and pink colors.
I have found that a series of coloring matters may be obtained by the combina-
tion of the above-mentioned nitro-phenols after having been converted into their
corresponding diazo compounds with the before-mentioned substances belonging to
the phenolic series.
Having now described and particularly ascertained the nature of my said

page_text: 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 herein-before in part
recited Letters Patent is, the production of coloring matters suitable for dyeing and
printing by converting nitro-phenols or the substitution compounds thereof into
their corresponding diazo compounds, and acting with the said diazo compounds
upon substances or upon derivatives belonging to the phenolic series, substantially
in the manner as herein described.
In witness whereof, I, the said John Peter Griess, have to this my Specifica-
tion set my hand and seal, the First day of April, One thousand eight
hundred and seventy-eight.
JOHN PETER GRIESS. (L.S.)