DELL Manufacture of Coloring Matters, Dyeing Unmordanted Cotton, and their Salts and Sulpho Derivatives.
Year: 1894

page_text: Pat of Application, 30th Apr., 1894-Accepted, 2nd June, 1894
COME DELL
Manufacture of Coloring Matters, Dyeing Unmordanted Cotton, and
their Salts and Sulpho Derivatives.
I, FERDINAND PETERSEN-MÜLLER, of Bale, Switzerland, do hereby declare
he 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 a manufacture of coloring matters which dye unmordanted
cotton direct in violet to blue tints.
These coloring matters are produced if rosanilin is melted together with benzidine,
colidine, diamidophenyltolyl, diamidodiphenolalkylether, diamidooxydiphenylalkyl-
ether, or diamidostilben, in the presence of benzoic acid, acetic acid or other organic
acid, at temperatures from 130° to 185° C., the base of the coloring matter thus
obtained being then converted into a hydrochlorate salt.
The coloring matter bases prepared, for example, from rosanilin and benzidin
may contain the diphenyl rest of the benzidine once, twice or three times, according
to whether the melting is interrupted sooner or latter. In this it is not possible to
conduct the melting in such a way as to obtain in the same an absolutely pure
substitution product containing the diphenyl rest only once, twice or three times;
there is always contained in the melt together with the one product, also the others,
or at least one of the other products.
There will however be obtained a product as completely trisubstituted as possible,
that is, for example, when using benzidin, a product containing the diphenyl rest
three times, if :
1. If as much as possible diamido base (benzidin &c.) and as little as possible
rosanilin is taken ;
2. If the temperature is raised as high as possible;
3. If the melting is only interrupted when it is shewn that the tint no longer
increases in blueness and the colouring matter does not yet lose perceptibly in
strength.
A product mono substituted as much as possible that is, for example when using
benzidin, a product containing only once the diphenyl rest, is obtained if:
1. The smallest possible quantity of diamido base (benzidin &c.) and as much as
possible of rosanilin is taken.
2. The temperature is kept as low as possible.
3. The melting is interrupted before all the rosanilin has been substituted.
A product disubstituted as much as possible, that is, for example, when using
benzidin, a product containing the diphenyl rest twice, is obtained if the medium
between the quantities and conditions of temperature for obtaining the nono and
trisubstituted products are taken.
Example I. For producing a color base consisting mainly of the trisubstituted
product, that is, a product containing the diphenyl rest three times, 10 kilos. of
rosanilin are heated together with 2 kilos. benzoic acid and 100 kilos. benzidin to a
temperature of from 150° to 185° C. during about 2 hours. The melt which
contains the new color base is then boiled with water containing hydrochloric acid
when the benzidin and a great part of the new colour will dissolve. From the
hot solution the coloring matter is precipitated by means of common salt as a
hydrochlorate, and is then separated from the excess of benzidine by filtration.

page_text: The coloring matter thus obtained is in the form of a brown powder which dyes
uumordanted cotton blue in a slightly acid bath.
Example II. For producing a colour base consisting mainly of the mono
substituted product, that is, a product containing the diphenyl rest only once,
10 kilos. rosanilin are heated together with 0.5 kilos. benzoic acid and 15 kilos.
benzidin to from 130° to 145° C. during about 2 hours, and the melting is interrupted
before all the rosanilin has been converted.
The melt is treated as in Example I. The colouring matter obtained forms a
brown powder readily soluble in slightly acid boiling water, which dyes unmordanted
cotton a red-violet colour in a slightly acid bath.
Example III. For producing a colour base consisting mainly of the disubstituted
product, that is, containing the diphenyl rest twice, 10 kilos. rosanilin are heated
with 0.5 kilos. benzoic acid and 35 kilos. benzidin to from 140° to 160° C. during
2 hours.
The melt is treated as in Example I. The colouring matter obtained forms a
brown powder soluble in boiling acidulated water, which dyes unmordanted cotton
a blue-violet colour in a slightly acid bath.
Similar colouring matters are obtained if in the above examples the benzidin is
replaced by tolidin, diamido diphenolalkylether, diamidophenyltolyl, diamido-
oxydiphenylalkylether, diamido stilben, or a mixture of such diamido bases.
Also, the benzidin in the above examples can be replaced by a mixture of one
or more of the above diamido bases with one or more aromatic monamines, such as
anilin toluidin &c., or one or more of the diamines such as for example ortho-, meta-,
or para-phenylendiamin, a toluylendiamine &c., or a triamin such as triamido
benzol.
Obviously also, the operation can be divided, and the rosanilin be first substituted
with the one product and then with the other product.
In all cases it is observed that only after the diphenylrest of one of the above
named diamido bases has entered into the rosanilin, the colouring matter attains the
property of dyeing unmordanted cotton directly.
The colouring matters obtained are all more or less soluble in boiling acidulated
water, and they are precipitated from their concentrated solutions by means of
mineral acids; they also separate on the cooling of the solution.
Common salt precipitates them when dissolved in water in the same way as other
basic colouring matters.
In cold concentrated sulphuric acid the colouring matters dissolve with red-brown
colour and they are separated on diluting this solution with water.
In glacial acetic acid the colouring matters are only imperfectly soluble, in
alcohol they dissolve much easier, in particular when heated.
With sulphuric acid or other sulphonating medium the colouring matter bases can
be converted into mono, di, and trisulpho acid, in the same way as the known mono,
di and tri-phenylised rosanilines.
Having now particularly described and ascertained the nature of this inven
tion and in what manner the same is to be performed, I declare that what I
claim is-
1. Process for the manufacture of new colouring matters dyeing unmordanted
cotton tints varying from violet to blue, by heating rosanilin with benzidin, tolidin,
diamidophenyltolyl, diamidodiphenolalkylether, diamido stilben, diamidooxydi-
phenylalkylether, or a mixture of these, with one or more aromatic monamines
as for example anilin or toluidin, or one or more diamines as for example ortho-
meta- or paraphenylendiamin or a toluylendiamin or a triamin as for example
triamidobenzol, in the presence of benzoic acid, acetic acid, or another organic acid,
at from 130° to 185° C., and converting the colouring matter bases so obtained into
the hydrochlorate salt, or into mono- di or tri sulpho derivatives, substantially as
described.

page_text: 2. As new products, the colouring matters, their salts and sulpho derivatives,
obtained by the process referred to in the first claim substantially as described.
Dated this 30th day of April 1894.
ABEL & IMRAY,
Agents for the Applicant.