Manufacture of New Colouring Matters Varying from Blue-violet to Blue-green.
Year: 1894

page_text: Date claimed for Patent under Sect. 103 of Act,
.
being date of first Foreign Application (in '( 31st Oct., 1893
France),
Date of Application (in United Kingdom), 28th May, 1894
Complete Specification Left, 18th Feb., 1895-Accepted, 16th Mar., 1895
France),
Date of Application (in United Kingdom), 28th May, 1894
Complete Specification Left, 18th Feb., 1895-Accepted, 16th Mar., 1895
PROVISIONAL SPECIFICATION.
Manufacture of New Colouring Matters Varying from Blue-violet to
Blue-green.
"
We, JEAN CLAUDE LOUIS DURAND, DANIEL EDOUARD HUGUENIN and
ADOLPHE JEAN JAMES D'ANDIRAN, constituting the Firm of L. Durand
Huguenin & Co. Manufacturers, of St. Fons, (Rhone) France; do hereby.declare
the nature of this invention to be as follows:-
This invention relates to the manufacture of colouring matters varying from
blue-violet, to blue-green; by heating the mono-, di-; or poly-sulpho conjugated
dialkylamido-azo benzols, or their salts (salts of the sulpho conjugated derivatives)
with gallic acid, methylgallic or ethylgallic ether, gallamic acid, gallanilic acid, or
its higher homologues, or the gallo-naphthylamides, in the presence of suitable
solvents. There are thus obtained colouring matters some of which are directly
soluble in water while the others are soluble in alkaline water, which colouring
matters dye wool and silk directly (without mordant) in acid bath and present, on
the other hand, a great affinity for metallic mordants.
We will describe by way of example the preparation of two of these colouring
matters.
10 kilos, of gallic acid
17 of
100
15
"
'"
dimethylamidoazobenzolmonosulphonate of soda
of glacial acetic acid, and
of muriatic acid
are heated in an oil bath to about 120° C. until a sample taken from the mass no
longer shows the presence of free dimethylamidoazobenzolmonosulphonic acid.
On then pouring the product of the reaction directly into water, the colouring
matter is precipitated and can be separated by filtration and washed. This
colouring matter is then dissolved in alkaline water so as to transform it into an
alkaline salt which is recuperated by evaporation to dryness; or again, the free
colouring matter is precipitated from this alkaline solution by the addition of acid,
it is filtered, and there is thus obtained a carmine ready for use for dyeing.
In an acid bath this colouring matter dyes unmordanted wool, and silk a
violet-blue and chromed-wool a greener blue; in alkalies the colouring matter
dissolves, forming a solution having a violet colouration, which is converted into.
blue by an addition of acid, but which passes back into violet on adding an excess
of acid.

page_text: 10 kilos. of gallamic acid
dimethylamidoazobenzoldisulphonate of soda
of glacial acetic acid
22
"
of
100
"
"
of muriatic acid
are heated to 120° C. As soon as a sample taken from the mass shews no more
free dimethylamidoazobenzol disulphonic acid the product of the reaction is poured
into alcohol. The colouring matter, which is directly soluble in water, is pre-
cipitated in this alcoholic medium, and is separated by filtration, pressed and
washed, in the condition of an acid or of ammoniacal or other salt. This colouring
matter is directly soluble in water, and dyes unmordanted wool and silk in acid
bath a blue-green tint; on chromed wool, it gives greenish blue tints for medium
shades, and more reddish blues for deep shades. An excess of alkali or of acid
causes the solutions of the colouring matter to turn violet. This colouring matter
is soluble in saline water or in water to which chloride of zinc is added; the best
precipitant for it is alcohol.
Instead of employing for the preparation of these colouring matters the
dialkylamidobenzols in the form of sulphonates, they may of course also be used
in the form of free sulphonic acids, in which case the addition of hydrochloric
acid to the reagents can be dispensed with.
According to the dialkylamidoazobenzol, the sulphonic acids or the sulphonates
of which are employed, or according to the nature of the gallic derivative
employed, there will be obtained tints more or less green; as to the degree of
sulphonation of the dialkylamidoazobenzols, this only influences the degree of
solubility of the colouring matters obtained.
The solution used for producing the reaction can also be varied.
Dated this 28th dow of Mar 1801
ABEL & IMRAY,
Agents for the Applicants.
DI MUITIVATION.
Manufacture of New Colouring Matters Varying from Blue-violet to
Blue-green.
We, JEAN CLAUDE LOUIS DURAND, DANIEL EDOUARD HUGUENIN, and
ADOLPHE JEAN JAMES D'ANDIRAN, constituting the Firm of L. Durand
Huguenin & Co., Manufacturers, of St. Fons, (Rhone) France, do hereby declare
the nature of this invention and in what manner the same is to be performed to
be particularly described and ascertained in and by the following statement:-—
This invention relates to the manufacture of colouring matters varying from
blue-violet to blue-green, by heating the mono-, di-, or poly-sulpho conjugated
dialkyl-amido-azo benzols, or their salts (salts of the sulpho conjugated derivatives)
with gallic acid, methylgallic or ethylgallic ether, gallamic acid, gallanilic acid or
its higher homologues, or the gallo-naphthylamides, in the presence of suitable
solvents. There are thus obtained colouring matters some of which are directly
soluble in water while the others are soluble in alkaline water, which colouring
matters dye wool and silk directly (without mordant) in acid bath and present, on
the other hand, a great affinity for metallic mordants.
We will describe by way of example the preparation of two of these colouring
matters.

page_text: 10 kilos. of gallic acid
EXAMPLE I.
of dimethylamidoazobenzol monosulphonate of soda
of glacial acetic acid, and
17
33
100
25
5
of muriatic acid
""
are heated in an oil bath to about 120° C. until a sample taken from the mass no-
longer shews the presence of free dimethylamidoazobenzol monosulphonic acid.
On then pouring the product of the reaction directly into water, the colouring
matter is precipitated and can be separated by filtration and washed. Thi
colouring matter is then dissolved in alkaline water so as to transform it into an.
alkaline salt which is recuperated by evaporation to dryness; or again, the fre
colouring matter is precipitated from this alkaline solution by the addition of acid ;.
it is filtered, and there is thus obtained a carmine ready for use for dyeing.
In an acid bath this colouring matter dyes unmordanted wool and silk a
violet-blue and chromed wool a greener blue; in alkalies the colouring matter
dissolves, forming a solution having a violet colouration, which is converted into
blue by an addition of acid, but which passes back into violet on adding an excess.
of acid.
22
"
of dimethylamidoazobenzoldisulphonate of soda
of glacial acetic acid
100
5
وو
of muriatic acid
are heated to 120° C. As soon as a sample taken from the mass shews no more
free dimethylamidoazobenzol disulphonic acid the product of the reaction is poured
iuto alcohol.
The colouring matter, which is directly soluble in water, is precipitated in this.
alcoholic medium, and is separated by filtration, pressed and washed, in the
condition of an acid or of ammoniacal or other salt. This colouring matter is.
directly soluble in water, and dyes unmordanted wool and silk in acid bath a
blue-green-tint; on chromed wool it gives greenish blue tints for medium shades,.
and more reddish blues for deep shades. An excess of alkali or of acid causes.
the solutions of the colouring matter to turn violet. This colouring matter is.
soluble in saline water or in water to which chloride of zinc is added; the best
precipitant for it is alcohol.
Instead of employing for the preparation of these colouring matters the
dialkylamidoazobenzols in the form of sulphonates, they may of course also be
used in the form of free sulphonic acids, in which case the addition of hydrochloric
acid to the reagents can be dispensed with.
According to the dialkylamidoazobenzol, the sulphonic acids or the sulphonates
of which are employed, or according to the nature of the gallic derivative
employed, there will be obtained tiuts more or less green; as to the degree of
sulphonation of the dialkylamidoazo benzols, this only influences the degree of
solubility of the colouring matters obtained.
The solution used for producing the reaction can also be varied.
It is to be understood that the sulpho conjugated dialkylamidoazobenzols herein
referred to, must contain at least one sulpho group in the second benzene nucleus,.
which, on the splitting of the dialkylamidoazo compound, by its reduction causes
the formation of a diamido derivative; if the sulpho group is only contained
in the first benzene nucleus, the colouring matter herein described will not be
produced.

page_text: Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, we declare that what
we claim is :-
1. The process for the manufacture of new colouring matters varying from violet
blue to greenish blue by heating at suitable temperatures the mono sulpho disulpho
or polysulpho dialkylamido-azo benzols of the kind herein referred to, or the
mono-di- or poly-sulphonates of the said dialkylamido azo benzols with gallic acid
methylgallic or ethylgallic ether, gallamic acid, gallanilic acid or its higher
homologues, or the gallo-naphthylamides, in the presence of suitable solvents and,
if required, transforming the product of the reaction into a salt, substantially as
herein described.
2. As new products, the colouring matters obtained by the process referred to in
the preceding claim.
Dated this 18th day of February 1895.
ABEL & IMRAY,
Agents for the Applicants.