Improvements in the Manufacture of Blue Colouring Matters.
Year: 1890

page_text: Date of Application, 11th Jan., 1890
Complete Specification Left, 29th Oct., 1890-Accepted, 13th Dec., 1890
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Blue Colouring Matters.
We, ALFRED KERN and EDWARD SANDOZ, both of Basle, in the Republic of
Switzerland, Chemical Manufacturers do hereby declaro the nature of this invention
to be as follows:-
This invention relates to the manufacture of blue coloring matter.
In the proceedings of the German Chemical Society (Vol. XXI, page 1741)
R. Nietzki and Rich. Otto describe an aniline compound of gallocyanine which is
quite insoluble in water. We have found that this substance can be transformed by
ordinary sulphuric acid and by sulphuric acid containing anhydride into a sulpho-
acid which is soluble by itself in water, but whose salts are easily soluble, becoming of
a bluish violet color, and are in this form adapted for dyeing and printing. When
using the same bluish violet tints are obtained upon wool and silk in an acid bath,
these tints being much bluer than that of gallocyanine itself, which indeed presents
under these circumstances only a slight coloring power, whereas this power is very
great when the said sulpho-acid is employed. Upon wool or cotton mordanted by
means of chrome this sulpho-acid even produces greenish blue tints which are
remarkably fast.
We have moreover found that an aniline compound of gallocyanine is obtained by
heating the latter with an excess of aniline only at a temperature of 100 degrees
Centigrade. The gallocyanine is dissolved first, and after a short time the whole
congeals to a mass of crystals consisting of small green-shimmering lamina. This
analine compound yields, like Nietzki's under similar circumstances, a sulpho-acid
which is insoluble by itself in water, but whose salts dissolve easily and likewise
exhibit a great coloring power. The tints which are however obtained with this
sulpho-acid are considerably redder than those above-mentioned, yet they are very
different from those of gallocyanine. Accordingly we have to deal in this second case
with an aniline compound which differs from Nietzki's.
The following two examples have reference to one as well as to the other of the
said aniline compounds, which are both transformed into sulpho-acids under the
conditions stated.
Example 1.-1 kilogramme of aniline compound of gallocyanine and 4 kilogrammes
of ordinary sulphuric acid are heated, the temperature being kept for about two hours
at 100 degrees, and the molten mass is then poured into water. The sulpho-acid
separates, is washed out, dissolved with ammonia and evaporated.
Example 2.-1 kilogramme of aniline compound of gallocyanine is dissolved at the
ordinary temperature in 4 kilogrammes of sulphuric acid containing 20 per cent.
of anhydride. After the dissolution the mixture is poured upon ice, the
eliminated sulpho-acid is washed out and transformed into a salt, for example as
above stated.
For obtaining the same technical effect, that is to say producing coloring matter
which draws well, and dyes blue, in the case of unmordanted wool and silk and in the
case of wool and cotton mordanted by means of chrome use can also be made of
the homologues of aniline compounds of gallocyanine. Of these we may mention
more especially.
1. Paratoluiding compound of gallocvaning neadwood at 100°

page_text: For transforming these gallocyanine compounds into sulpho-acids and their salts we
heat, for example, 1 kilogramme of paratoluidine-compound of gallocyanine, or
1 kilogramme of orthotoluidine-compound of gallocyanine, or 1 kilogramme of
metaxylidine-compound of gallocyanine, together with 4 parts of sulphuric acid
of 66 degrees Baumé, keeping the same at a temperature of 100 degrees for about
two hours, then pour the molten mass into water, wash out the sulpho-acid which
separates in an insoluble state, and obtain the same as a salt by dissolution in an
alkali and evaporation.
In lieu of sulphuric acid of 66 degrees Baumé, use can be made of 4 parts of
sulphuric acid containing 25 per cent. of anhydride, the molten mass being left at the
ordinary temperature, and often stirred, until the gallocyanine compound has been
dissolved. It is afterwards poured upon ice, and the product is treated as above
stated.
We have also found that instead of gallocyanine, the allied coloring matters, the
so-called "prune," and the so-called "gallamine blue," can be employed, in the first
place, for the preparation of such aniline compounds, which then in the second place,
can likewise be transformed into sulpho-acids and their salts, the latter being also
blue-dyeing coloring matters of similar properties.
In the case of the aforesaid "prune we have also formed two aniline compounds,
one being produced at 100 degrees Centigrade, and another at upwards of 1:0 degrees,
whilst with "gallamine blue we have obtained an aniline compound only by causing
boiling aniline to act for a comparatively long time.
"
The transformation of these aniline compounds into sulpho-acids is effected with the
same quantitative proportions of concentrated sulphuric acid or sulphuric acid
containing 25 per cent. of anhydride at similar temperatures.
The sulpho-acids are applied in the same manner as described.
Dated thi th 1
1000
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, Agents for the Applicants.
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Blue Colouring Matters.
We, ALFRED KERN and EDWARD SANDOZ both of Basle, in the Republic of
Switzerland, Chemical Manufacturers, 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 blue coloring matters for use in dyeing
and printing.
In the publications (Berichte) of the German Chemical Society (Vol. XXI
page 1741) R. Nietzki and Rich. Otto give a specification of an aniline compound of
gallocyanine, which is entirely insoluble in water. It has been found, that this
substance can be transformed either by ordinary sulphuric acid or by sulphuric
acid containing anhydride into a sulfo-acid, which insoluble by itself in cold water,
but whose salts are easily soluble, producing a purple-blue colour suitable for dyeing
and printing.
On wool and silk blue-purplish shades or tints are obtained by dyeing in an acid
bath; these tints are considerably bluer than those obtained with gallocyanine, the
coloring power of gallocyanine by the same method of operating being considerably
inferior to that obtained when sulpho-acid as above described is employed.
By dyeing wool and cotton previously mordanted with chrome with this sulpho-acid,
greenish-blue shades of great fastness are produced.
In order to obtain the same technical result, namely the manufacture of colouring
matters suitable for producing by dyeing, blue shades as above mentioned on wool and
silk without mordant, and on wool and cotton mordanted with chrome, those products

page_text: Paratoluidine on gallocyanine.
Orthotoluidine
Metaxylidine
"
"
It has moreover been found, that by the reaction of aniline and its homologues on
the allied colouring matters of gallocyanine, which is produced by the reaction of
hydrochlorate of nitrosodimethylaniline on gallic acid commercially known under the
names of "prune," produced by the reaction of hydrochlorate of nitrosodimethylaniline
on methylic ether of gallic acid, and "gallamin blue" produced by the reaction of
hydrochlorate of nitrosodimethylaniline on gallamine-acid, compounds are obtained,
which can also be transformed into sulpho-acids and their salts; both sulpho-acids
and their salts thus obtained possess the properties of producing by dyeing in the
above mentioned manner, blue shades.
EXAMPLES.
1) One kilogramme of the compound obtained by the reaction of aniline on
gallocyanine and 4 kilogrammes of ordinary sulphuric acid (66 degrees Beaume)
are mixed and heated to a temperature of 70 to 100 degrees Centigrade as long as
necessary (about two hours) until the obtained product dissolves entirely in a cold
and diluted solution of ammonia. The whole sulphuric-acid solution of the colouring
matter is then poured into ten times its volume of cold water. The sulpho-acid
precipitates by itself and is filtered and washed out.
In order to obtain a soluble salt, the blue colouring matter is dissolved in ammonia
or in a soda-solution and then dried by evaporation.
2) One kilogramme of the compound obtained by the reaction of paratoluidine on
gallocyanine is dissolved at the ordinary temperature in 4 kilogrammes of sulphuric
acid containing 20 per cent. of anhydride sulphuric acid. The solution thus obtained
is poured upon ice, the precipitated sulpho-acid is filtered and washed out and trans-
formed into soluble salts as above mentioned.
The above examples have reference to the other compounds as stated above, as well
as to the ones obtained by the reaction of aniline and its homologues on gallocyanine
or on prune or gallamin blue.
Having now particularly described and ascertained the nature of our said inven-
tion, and in what manner the same is to be performed, we declare that what we
claim is :-
First. The preparation of blue colouring matters soluble in water suitable for dyeing
and printing by the transformation of the compounds obtained by the reaction of
aniline or its homologues on gallocyanine into sulpho-acids and their salts substantially
as hereinbefore described.
Second. The preparation of blue colouring matters soluble in water suitable for
dyeing and printing by the transformation of the compounds obtained by the
reaction of aniline or its homologues on "prune" into sulpho-acids and their salts,
substantially as hereinbefore described.
Third. The preparation of blue colouring matters soluble in water suitable for
dyeing and printing by the transformation of the compounds obtained by the reaction
of aniline or its homologues on "gallamine blue" into sulpho-acids and their salts,
substantially as hereinbefore described.
Dated this 29th day of October 1890
Dated this 29th
h day o
of October 1890
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, Agents for the Applicants.