THE PRODUCTION OF NEW COLORING MATTERS BY THE REACTION OF THE DIAZOIC DERIVATIVES OF TOLUIDINES AND XYLIDINES UPON AMINES, AMIDES, AND PHENOLS
Year: 1878

page_text: LETTERS PATENT to John Clayton Mewburn, of 169, Flect Street, in the City
of London, Patent Agent and Consulting Engineer, for the Invention of "THE
PRODUCTION OF NEW COLORING MATTERS BY THE REACTION OF THE DIAZOIC
DERIVATIVES OF TOLUIDINES AND XYLIDINES UPON AMINES, AMIDES, AND
PHENOLS." A communication from abroad by Zacharie Roussin, Chemist, and
Alcide François Poirrier, Manufacturer, both of Paris, Franco.
:
'
PROVISIONAL SPECIFICATION left by the said John Clayton Mewburn at
the Office of the Commissioners of Patents on the 6th November 1878.
JOHN CLAYTON MEWBURN, of 169, Fleet Street, in the City of London, Patent,
Agent and Consulting Engineer. "THE PRODUCTION OF NEW COLORING MATTERS
BY THE REACTION OF THE DIAZOIC DERIVATIVES OF TOLUIDINES AND XYLIDINES
UPON AMINES, AMIDES, AND PHENOLS." [A communication from abroad by
Zacharie Roussin, Chemist, and Alcide François Poirrier, Manufacturer, both of
Paris, France.]
This Invention consists in producing new coloring matters by the reaction of the
diazoic derivatives of toluidines and xylidines upon amines, amides, and phenols.
The preparation of the diazoic derivatives is carried out in the following
manner :-
The toluidines (ortho or para) are all first transformed into sulpho-conjugated acid
at a temperature of about 356° Fahrenheit (180° Centigrade) by means of concen-
trated or fuming sulphuric acid. The reaction is finished when drops of the liquid.
poured into alkaline water do not cause a precipitate of toluidine. The sulpho-
conjugated acid thus obtained is precipitated by the addition of cold water, and the
crystalline mass after drying is transformed into sodic salt.
This sodic salt in aqueous solution is afterwards mixed with an aqueous solution
of nitrite of soda. These two salts are employed in equal equivalents. Into this
77

page_text: .
Preparation of the Coloring matters.
1st. Reaction of the above Diazoic Derivatives on Alpha Naphthol.-The two
matters are caused to react cold in a body of water, and vigorous agitation is kept
up for at least 24 hours. At the expiration of this time the coloring matter is pro-
duced. The pulpy mass is thrown on a cloth, drained, washed with cold water, and
compressed. The resulting compact mass is dried and reduced to powder. It can
also be transformed into a more soluble sodic combination. This matter will dye
wool and silk a poppy red.
2nd. Reaction of the Diazoic Derivative on Beta Naphthol.-The diazoic deriva-
tive and the beta naphthol are mixed in equal equivalents. The naphthol is
previously dissolved in the necessary proportion of alkaline water.
An orange
coloring matter is formed instantaneously, and can be purified by crystallization or
by precipitation with sea salt. The crystals are expressed and dried.
3rd. Reaction of the Diazoic Derivative on Diphenylamine. An equivalent of
diphenylamine very finely divided is agitated for from 24 to 48 hours with an
aqueous solution containing an equivalent of the diazoic derivative of the sulpho-
conjugated toluidine. The reaction is finished when a small portion of the mixture
dissolves entirely in ammoniacal water. The precipitate which is formed is col-
lected on a cloth, washed with cold water, and transformed into ammoniacal salt
or into sodic salt. This coloring matter will give shades of a fine bright yellow.
An analogous yellow compound is obtained under the same conditions by substi-
tuting for the diphenylamine either aniline, toluidines, or even xylidines.
By substituting phenic acid for the beta naphthol, and proceeding as described
under the second heading, a yellow coloring matter is obtained.
By substituting phenylene-diamine for the diphenylamine, and proceeding as
described under the third heading, a brownish yellow coloring matter is obtained.
Dinapthylamine and naphthylphenylamine substituted for the diphenylamine pro-
duce under the same conditions red coloring matters.
Lastly, an equivalent of sulphate of methylaniline reacting cold on a solution of
an equivalent of the diazoic derivative of the sulpho-conjugated toluidine produces
an orange red coloring matter which crystallizes readily as soon as the liquid pre-
viously heated to ebullition has cooled.
The diazoic derivatives of the sulpho-conjugated toluidines and xylidines produce
coloring matters which do not differ very sensibly in shades. The liquid alkaloids
produce compounds generally much more soluble.
In the foregoing combinations, which constitute as many coloring matters, the
sulphuric molecule is previously fixed on the alkaloids. This condition is not indis-
pensable, and it will be readily understood that the same products would be
obtained, first, by transferring the sulphuric group to the phenols, amines, and
amide bodies; secondly, by causing the diazoic derivatives of the toluidines or
xylidines to react on the phenols, amines, and amide bodies; and then, finally,
sulpho-conjugating the compounds thus produced.
In the production of the above coloring matters not only can the azoic derivatives
of the toluidines be employed, but also the same derivatives of the xylidiues,
their superior homologues, which produce compounds of analogous nature and
shade.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said John Clayton Mewburn in the Great Seal Patent Office on the 6th
May 1879.
JOHN CLAYTON MEWBURN, of 169, Fleet Street, in the City of London, Patent
Agent and Consulting Engineer. "THE PRODUCTION OF NEW COLORING MATTERS
BY THE REACTION OF THE DIAZOIC DERIVATIVES OF TOLUIDINES AND XYLIDINES
UPON AMINES, AMIDES, AND PHENOLS." (A communication from abroad by
Zacharie Roussin, Chemist, and Alcide François Poirrier, Manufacturer, both of
Paris, France.)
This Invention consists in producing new coloring matters by the reaction of the
diazoic derivatives of toluidines and xylidines upon amines, amides, and phenols.
The preparation of the diazoic derivatives is carried out in the following
nanner-
The toluidines (ortho or para) are all first transformed into sulpho-conjugated acid
at a temperature of about 356° Fahrenheit (180° Centigrade) by means of concen-
trated or fuming sulphuric acid. The reaction is finished when drops of the liquid
poured into alkaline water do not cause a precipitate of toluidine. The sulpho-
conjugated acid thus obtained is precipitated by the addition of cold water, and the
crystalline mass after drying is transformed into sodic salt.
This sodic salt in aqueous solution is afterwards mixed with an aqueous solution
of nitrite of soda. These two salts are employed in equal equivalents. Into this
mixture there is poured while agitating vigorously a solution containing one fifth
of concentrated sulphuric acid until the moment when all the soda of the two salts
is transformed into sodic sulphate. The diazoic derivative thus formed remains in
solution if the liquor is little concentrated; in the contrary case it is partially pre-
cipitated.
Preparation of the Coloring Matters-1st. Reaction of the above Diazoic
Derivatives on Alpha Naphthol.-The two matters are caused to react cold in a
body of water, and vigorous agitation is kept up for at least 24 hours. At the
expiration of this time the coloring matter is produced. The pulpy mass is
thrown on a cloth, drained, washed with cold water, and compressed. The resulting
compact mass is dried and reduced to powder. It can also be transformed into a
more soluble sodic combination. This matter will dye wool and silk a poppy red.
2nd. Reaction of the Diazoic Derivative on Beta Naphthol.-The diazoic derivative
and the beta naphthol are mixed in equal equivalents. The naphthol is previously
dissolved in the necessary proportion of alkaline water. An orange coloring matter
is formed instantaneously, and can be purified by crystallization or by precipitation
with sea salt. The crystals are expressed and dried.
3rd. Reaction of the Diazoic Derivative on Diphenylamine.-An equivalent of
diphenylamine very finely divided is agitated for from 24 to 48 hours with an
aqueous solution containing an equivalent of the diazoic derivative of the sulpho-
conjugated toluidine. The reaction is finished when a small portion of the mixture
dissolves entirely in ammoniacal water. The precipitate which is formed is collected
on a cloth, washed with cold water, and transformed into ammoniacal salt or into
sodic salt. This coloring matter will give shades of a fine bright yellow.
An analogous yellow compound is obtained under the same conditions by substi-
tuting for the diphenylamine either aniline, toluidines, or even xylidines.
By substituting phenic acid for the beta naphthol, and proceeding as described
under the second heading, a yellow coloring matter is obtained.
By substituting phenylene-diamine for the diphenylamine, and proceeding
as described under the third heading, a brownish coloring matter is obtained.
Dinapthylamine and napthylphenylamine substituted for the diphenylamine pro-
duce under the same conditions red coloring matters.

page_text: Lastly, an equivalent of sulphate of methylaniline reacting cold on a solution of
_ an equivalent of the diazoic derivative of the sulpho-conjugated toluidine produces
an orange red coloring matter which crystallizes readily as-soon-as-the--liquid-pre-
viously heated to ebullition has cooled.
The diazoic derivatives of the sulpho-conjugated toluidines and xylidines produce
coloring matters which-do_not_differ very sensibly in shades. The liquid alkaloids
produce compounds generally much more soluble.
In the foregoing combinations, which constitute as many coloring matters, the
sulphuric molecule is previously fixed on the alkaloids. This condition is not indis-
pensable, and it will be readily understood that the same products would be
obtained, first, by transferring the sulphuric group-to-the phenols, amines, and amide
bodies; secondly, by causing the diazoic derivatives of the toluidines or xylidines to
react on the phenols, amines, and amide bodies; and then, finally, sulpho-conjugating
the compounds thus produced.
In the production of the above coloring matters not only can the azoic deriva-
tives of the toluidines be employed, but also the same derivatives of the xylidines,
their superior homologues which give compounds of analogous nature and shade.
And having now described the nature of the said Invention and in what manner
the same is to be performed, I declare that I claim,-
The production of coloring matters by the reaction of the diazoic derivatives of
toluidines and xylidines upon amines, amides, and phenols, substantially as
herein before described.
In witness whereof, I, the said John Clayton Mewburn, have hereunto set my
hand and seal, this Sixth day of May, One thousand eight hundred and
seventy nine.
J. C. MEWBURN. (L.S.)