IMPROVEMENTS IN THE MANUFACTURE OF COLOURING MATTERS SUITABLE FOR DYEING AND PRINTING
Year: 1879

page_text: LETTERS PATENT to Joseph Anthony Dixon, of 175, West Goorge Street,
Glasgow, in the County of Lanark, North Britain, Solicitor, for the Invention
of "IMPROVEMENTS IN THE MANUFACTURE OF COLOURING MATTERS SUITABLE
FOR DYEING AND PRINTING." A communication from abroad by Carl Rumpff,
of Barmen, in the Kingdom of Prussin, Chemist, and Friedrich Graessler, of
Carmstadt. Chemist.
PROVISIONAL SPECIFICATION left by the said Joseph Anthony Dixon
at the Office of the Commissioners of Patents on the 6th December 1879.
JOSEPH ANTHONY DIXON, of 175, West George Street, Glasgow, in the County
of Lanark, North Britain, Solicitor. "IMPROVEMENTS IN THE MANUFACTURE OF
COLOURING MATTERS SUITABLE FOR DYEING AND PRINTING." [A communication
from abroad by Carl Rumpff, of Barmen, in the Kingdom of Prussia, Chemist, and
Friedrich Graessler, of Carinstadt, Chemist.]
This Invention has for its object the preparation of the colouring matters or
dyestuffs (chicfly yellows, reds, and reddish browns), which are formed when the
diazo compounds of azo-benzol, or of its homologues, or the chlorine, or other
substitution compounds or derivatives of such diazo compounds (as for example,
the hydrochloride of diazo-azo-benzol) are brought into reaction with the sulphonic
acids of phenoles or phenolic bodies (whether further substituted or not) such as
the sulpbo-acids of alpha and beta napthol, resorcin, orcin, dioxynapthalin, and the
like, or when the sulphonic acids of diazo-azo-benzol, or its homologues, or of the
further substitution compounds thereof are brought into reaction with phenoles or
phenolic bodies such as alpha and beta napthol and the other phenoles bereinbefore
mentioned, or the further substitution compounds thereof.
The process by which I prepare the said colouring matters by means of the
reactions herein before mentioned, I explain or illustrate by the following example:-
One molecule of the amido-azo-benzol-sulphonate of soda is dissolved in from forty
to fifty times its weight of water. The solution is mixed with two molecules of
bydrochloric acid and one molecule of nitrite of soda, whereby the amido is con:

page_text: verted into the diazo group, and the amido-azo-benzol-sulphonic acid into diazo-
azo-benzol-sulphonic acid according to the equation.
(Amido-azo-benzol sulphonic acid) (Nitrous acid.)
SO, CH, N = N-C₁₂H, NH + HNO
(Diazo-azo-benzol sulphonic acid.)
SO,, C, H.-N = N - C, H,
-
N
(Water.)
+ 2 H₂, O.
The liquor so prepared is allowed to run into an alkaline solution of one mole-
cule of beta naphthol or any other of the phenolic bodies hereinbefore mentioned,
with the precaution that a slight excess of alkali is constantly kept predominating.
The new body which is produced by the reaction between the diazo-azo body and
the phenolic body is precipitated by common salt, and is purified in the common
way by repeated solution and precipitation for use as a colouring matter or
dyestuff.
Instead of the phenoles or phenolic bodies themselves the sulphonic acids thereof
may also be used.
In the same way from the hydrochloride of amido-azo-benzol there may be
prepared the hydrochloride of diazo-azo-benzol, and from this diazo compound,
under the same conditions, there may be produced (first) by tho action of the
sulphonic acids of the said phenoles or phenolic bodies, a colouring matter soluble
in water, and (second) by the action of the phenoles or phenolic bodies themselves
(not sulphonated) a colouring matter insoluble in water, which last mentioned
colouring matter may be converted into the soluble sulphonic acid thereof by
treatment with four or five times its weight of fuming sulphuric acid, containing
from sixteen to twenty per cent. of sulphuric anhydride.
Instead of amido-azo-benzol the homologues thereof may be used in all the cases
heroin before mentioned.
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 5th
May 1880.
"
JOSEPHI ANTHONY DIXON, of 175, West George Street, Glasgow, in the County 3
of Lanark, North Britain, Solicitor. IMPROVEMENTS IN THE MANUFACTURE OF
COLOURING MATTERS SUITABLE FOR DYEING AND PRINTING." A communication
from abroad by Carl Rumpff, of Barmen, in the Kingdom of Prussia, Chemist, and
Friederich Graessler, of Carmstadt, Chemist.
This Invention has for its object the preparation of the colouring matters or 3
dyestuffs (chiefly yellows, reds, or reddish browns), which are formed when diazo-
azo-benzol, or any of its homologues, or a salt of such diazo-azo compound (as for
example, the hydrochlorate, sulphate, or nitrate of diazo-azo-benzol, or of diazo-
azo-toluol, and the like), is brought into reaction in manner hereinafter exemplified,

page_text: with a sulphonic acid of any of the phenoles or phenolic bodies (whether further
substituted or not), such as the sulpho acids of alpha and beta napthol, resorcin,
orcin, dioxynaphalin, and the like, or when any of the sulphonic acids of diazo-
azo-benzol or of its homologues is brought into reaction in manner after exemplified
with any of the phenoles or phenolic bodies themselves, such as alpha and beta
napthol and the other phenoles hereinbefore mentioned, or any of the sulphonic
acids thereof, or further substitution compounds of the said sulphonic acids. The
same series of colouring matters may be produced by a substantially equivalent
process, which however is not practically convenient, but might be used in order to
evade the rights under the before mentioned Patent, unless the same were herein
mentioned, and I therefore describe it here, but I do not recommend it, that is to
say, instead of using in the first instance as reagents on cach other a non
sulphonated diazo-azo body and a sulphonated phenolic body, or a sulphonated
diazo-azo body and a non sulphonated phenolic body, or a sulphonated diazo-azo
body and a sulphonated phenolic body, as hercin before described, by all of which.
reactions the said colouring matters are obtained soluble in water, it is possible to
use in the first instance as reagents on each other a diazo-azo body and a phenolic
body, such as are above described, but neither of them being sulphonated, and by
their reaction on each other to obtain as a first product a colouring matter which,
however, will not be soluble in water, and then to sulphonate this first product by
treatment with fuming sulphuric acid in manner hereinafter mentioned, whereby it
is rendered soluble in water. It is obvious that this last mentioned method is
equivalent to the others in so far that it is merely a transposition of the application
of the sulphuric acid from an earlier to a later stage of the operation. In the
methods first described the sulphuric acid is applied to the diazo-azo body or the
phenolic body, or both, before they are brought into reaction, while in the method
last described the diazo-azo and phenolic bodies are first brought into reaction and
then the sulphuric acid is applied, the final result in both cases being the same.
By the homologues of benzol I mean those hydrocarbons, the formulao of which
are expressed by substituting in the formula C, H, for one H or atom of hydrogen,
one group CH,, or for a multiple of H the like multiple of C H, and that whether
such hydrocarbons appear (like toluol and the xyloles) ready formed in or are
obtained from coal tar, or whether they are prepared by methylizing, ethylizing, or
otherwise alkylizing benzol, toluol, xylol, cumol, and the like hydrocarbons. And
by the diazo compounds of the homologues of azo-benzol I mean the diazo com-
pounds of azo-toluol, azo-xylol, and of the azo derivatives of the other homologues
of benzol above described. I do not mean to limit in any way the degree or extent
of the diazotising in the said diazo compounds of azo-benzol and its homologues.
The process by which the said colouring matters are prepared by means of the
reactions hereinbefore mentioned I explain or illustrate by the following example,
and I observe that the requisite modifications in the process according to circum-
stances will be obvious to chemists. One molecule of the amido-azo-benzol-sul-
phonate of soda is dissolved in from forty to fifty times its weight of water, the
solution is mixed with two molecules of hydrochloric acid and one molecule of
nitrite of soda, whereby the amido is converted into the diazo group, and the amido-
azo-benzol-sulphonic acid into diazo-azo-benzol-sulphonic acid according to the
equation.
(Amido-azo-benzol sulphonic acid.) (Nitrous acid.)

page_text: purified in the common way for use as a colouring matter or dyestuff by repeated
solution and precipitation.
Instead of the phenoles or phenolic bodies themselves the sulphonic acids thereof
may also be used whether the other reagent employed be the diazo-azo compound
itself or the sulphonic acid thereof, and the sulphonic acids of the diazo azo bodies
may be used to react on either the phenolic bodies themselves or the sulphonic
acids thereof. Both reagents, however, should not be non sulphonated, but one or
both ought preferably to be sulphonated, or at all events (as in the following
example of the action between the hydrochloride of diazo-azo benzol and a non-
sulphonated phenol), the colouring matter produced in the first instance must be
converted into the sulphonic acid compound thereof, in order to render it soluble
in water.
Thus from the hydrochloride of amido-azo-benzol there may be prepared the
bydrochloride of diazo-azo-benzol, and from this diazo compound there may be
produced (first) by the action of the sulphonic acids of the said phenoles.or
phenolic bodies, a colouring matter soluble in water, or (second) by the action of
the phenoles or phenolic bodies themselves (not sulphonated) a colouring matter
insoluble in water, which last mentioned colouring matter may be converted into
the water-soluble sulphonic acid thereof, by treatment with four or five times its
weight of fuming sulphuric acid containing from sixteen to twenty per cent. of
sulphuric anhydride.
Instead of amido-azo-benzol or the sulphonic acid thereof, or salt of such sul-
phonic acid, the homologues thereof, that is to say, the amido compounds of the
other azo hydrocarbons above defined, or the sulphonic acids or sulphonate salts
thereof, may be used in all cases as the source of the diazo-azo body which is to be
employed as hereinbefore directed.
A variety of colours or shades are obtained by varying the phenolic bodies acted
on by the diazo-azo-bodies. Thus by the action of diazo-azo-benzol and its
homologues, or the sulpho derivatives thereof, as the case may be, on phenol,
cresol, orcin, xylenol, resorcin, or their sulpho derivatives, as the case may be,
yellow colouring matters or dyestuffs are obtained by the action of the said diazo-
azo bodies, or their sulpho acids, on beta napthol or its sulpho derivatives, red
colouring matters or dyestuffs are obtained, and by the action of the said diazo-azo
bodies, or their sulpho acids, on alpha napthol or its sulpho derivatives, reddish
brown colouring matters or dyestuffs are obtained.
What I claim as novel and as the Invention secured to me by the said Letters
Patent is,―
•
The preparation of colouring matters suitable for dyeing and printing by
causing diazo-azo benzol, or any of its homologues, or a salt thereof, to react on or
be reacted on by the sulphonic acid or acids of any of the phenols or phenolic
bodies herein before described, or by causing the sulphonic acids of diazo azo benzol,
or of any of its homologues, to react on any of the phenols or phenolic bodies, or
the sulphonic acid or acids thereof hereinbefore described, or by bringing any of
the said diazo azo bodies and any of the phenolic bodies, hereinbefore described,
into reaction with each other in the first instance without either of them being
sulphonated and afterwards treating the product with sulphuric acid, all in the
manner or manners hereinbefore described or exemplified.
In witness whereof, I, the said Joseph Anthony Dixon, have hereunto set
my hand and seal, this Fourth day of May, in the year of our Lord One
thousand eight hundred and eighty.