The Manufacture of New Colouring Matters of the Safranine Series.
Year: 1897

page_text: PROVISIONAL SPECIFICATION.
The Manufacture of New Colouring Matters of the Safranine
Series.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Chancery Lane,
in the County of London, Consulting Engineer and Chartered Patent Agent, do
hereby declare the nature of this invention (which has been communicated to
me from abroad by The Actien-Gesellschaft für Anilin Fabrikation, of Berlin, in
the German Empire, Chemical Manufacturers), to be as follows: —
O. Fischer and E. Hepp (Ber. d. d. chem. Ges. 1896 p. 351 and p. 2752) have
discovered, that by heating aposafranine and isorosindulines with aniline in the
presence of hydrochloric acid and an anilido-radicle is introduced in ortho-position
to the imido-radicle. The reaction is represented by the following formulae :
By substituting, for isorosinduline, compounds derived from tertiary amines, as
for instance neutral blue, no reaction takes place. Neutral blue is not attacked
even by heating it with aniline and aniline hydrochloride.
Now my foreign correspondents have discovered, that a reaction takes place
between neutral blue or analogous compounds with ammonia and certain primary
amines. The products thus formed are not identical with the above mentioned
anilido-derivatives. The substitution takes place in the naphthalene nucleus,
symmetrical substitution products of safranines or isorosindulines being formed.
The reaction is represented by the following formula :—

page_text: R, R¹ and R2 representing aliphatic or aromatic radicles and X hydrogen or
one of the above mentioned radicles. The first condition for effecting the reaction
is the absence of mineral acids, as for instance hydrochloric acid; by mixing
with aniline etc. the free bases produced by addition of soda lye to the
hydrochlorides of the above mentioned compounds, the reaction takes place even
at ordinary temperature in the presence of atmospheric air. It is however
preferable to add an oxidizing agent, such as hydrogen peroxide, or to heat the
mixture.
If carbonates or acetates are substituted for the free amines, it is necessary
to heat the mixture up to a more elevated temperature for effecting the
reaction.
The colouring matters thus obtained may be sulphonated by means of the known
methods, if they are not soluble enough.
The shades produced by these new rosinduline derivatives are remarkable in
beauty and clearness, when compared with those of the original materials. They
vary from red to greenish blue.
The new colouring matters dissolve in concentrated sulphuric acid with the green
colour characteristic of rosindulines, while Fischer and Hepp's compounds show no
difference from the original dyestuffs.
For carrying out the new process the following materials are used.
I. Isorosindulines of the general formula
and their substitution products.
II. Ammonia, primary amines or diamines, their nitro,- oxy-, sulphonic or car-
boxylic derivatives, colouring matters containing free amido-groups, as for instance
amido-azo-dyestuffs, dyestuffs of the triphenylmethane, acridine or induline series, 2
etc.
20 parts of isorosinduline carbonate, prepared by means of nitrosodimethyl-
aniline and of ethyl-6-naphthylamine, are heated with 100 parts of alcohol and
50 parts of ammonia of 10% strength during 6 hours in a closed vessel up to 150°
to 160° C. A bluish red solution is formed from which the alcohol is distilled off
and the dyestuff isolated in the known manner in the form of its hydrochloride or
its zinc chloride double salt. It dyes tannin mordanted cotton clear bluish red
shades and is dissolved by concentrated sulphuric acid with bluish green colour.
A mixture of 1 part of isorosinduline carbonate, prepared by means of nitro-
sidiethylaniline and of phenyl-6-naphthylamine, with 3 parts of aniline is heated
up to 160° during 5 hours. The excess of aniline is removed by means of steam

page_text: EXAMPLE 3.
A solution of 4 parts of neutral blue, of 1.5 parts of paramidosalicylic acid and
of 2 parts of potassium carbonate in 50 parts of alcohol is boiled, until a sample
dissolves in concentrated sulphuric acid with green colour. The colouring matter
sparingly soluble in water is precipitated. It dyes wool in an acidified bath a
reddish violet, and chrome mordanted wool a dark blue. By substituting, for
amidosalicylic acid, 2.5 parts of 1:4-naphthylenediamine-2-sulphonic acid, a
product insoluble in water is formed, which by sulphonating yields a colouring
matter dyeing reddish violet shades.
2 parts of neutral blue and 1.2 parts of amidoazobenzene hydrochloride are
dissolved in 30 parts of alcohol. A concentrated aqueous solution of 1 part of
potassium carbonate is added and the mixture boiled during 12 hours. The
colouring matter is nearly completely precipitated. It is insoluble in dilute mineral
acids and dissolves in concentrated sulphuric acid with a yellowish green colour.
Its solution in concentrated acetic acid or in alcohol shows a green colour.
4 parts of neutral blue and 3.5 parts of fuchsine are dissolved in 80 parts of
alcohol. 25 parts of soda lye are added and a current of air free from carbonic
acid is introduced, while the temperature is kept at from 25° to 300 and the mixture
well stirred. The colouring matter thus formed is dissolved in water, acidified by
means of hydochloric acid and is then precipitated by means of common salt. It
dyes tannin mordanted cotton a bluish violet.
By substituting phosphine for fuchsine a colouring matter soluble in water is
produced, which dves a gravish black
A solution of 4 parts of neutral blue, 5 parts of safranine, prepared as described
in Example 3, and 2 parts of potassium carbonate in 100 parts of alcohol is boiled.
The colour of the solution changes from reddish violet to bluish violet. The reaction
proceeds more quickly if 2 parts of copper oxide are added. The colouring matter
is extracted with dilute acids in order to remove any of the original material which
may remain unattacked. It dissolves in hot water with pure blue colour and dyes
tannin mordanted cotton blue shades.
4 parts of chlorisorosinduline, prepared by means of nitrosometachlordimethyl-
aniline and of phenyl-ẞ-naphthylamine, and 1 part of aniline are dissolved in 50
parts of alcohol. 1-5 parts of soda lye of 40° Bé. are added and a current of air
free from carbonic acid is introduced the temperature being kept at from
25° to 30° C. and the mixture well stirred.
The colouring matter is precipitated and the reaction is complete if a sample 4
dissolves in concentrated sulphuric acid with green colour. The safranine thus
formed is soluble in dilute acids and yields by sulphonation a colouring matter
dyeing wool a bluish violet. By substituting anilidoisorosinduline, prepared by

page_text: means of nitrosodimethylaniline and of 2: 7-diphenylnaphthylenediamine, for
chlorisorosinduline, a colouring matter insoluble in water is formed which, after
sulphonation, dyes wool blue shades.
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture of New Colouring Matters of the Safranine
Series.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Chancery. Lane, in the
County of London, Consulting Engineer and Chartered Patent Agent, do hereby
declare the nature of this invention (which has been communicated to me from
abroad by The Actien-Gesellschaft für Anilin. Fabrikation, of Berlin, in the German
Empire, Chemical Manufacturers), and in what manner the same is to be performed
to be particularly described and ascertained in and by the following statements:-
O. Fischer and E. Hepp (Ber. d. d. chen. Ges. 1896 p. 351 and p. 2752) have
discovered, that by heating aposafranine and isorosindulines with aniline in the
presence of hydrochloric acid an anilido-radicle is introduced in ortho-position to the
imido-radicle. The reaction is represented by the following formulae :

page_text: By substituting, for isorosinduline; compounds derived from tertiary amines, as for
instance neutral blue, no reaction takes place. Neutral blue is not attacked even by
heating it with aniline and aniline hydrochloride.
Now my foreign correspondents have discovered, that a reaction takes place between
neutral blue or analogous compounds with aminonia and certain priinary amines.
The products thus formed are not identical with the above mentioned anilido-
derivatives. The substitution takes place in the naphthalene nucleus, symmetrical
substitution products of safranines or isorosindulines being formed. The reaction is
represented by the following formula :—
R, R¹ and R2 representing aliphatic or aromatic radicles and X hydrogen or one of
the above mentioned radicles. The first condition for effecting the reaction is the
absence of mineral acids, as for instance hydrochloric acid; by mixing with aniline
etc. the free bases produced by addition of soda lye to the hydrochlorides of the
above mentioned compounds, the reaction takes place even at ordinary temperature in
the presence of atmospheric air. It is however preferable to add an oxidizing agent,
such as hydrogen peroxide, or to heat the mixture.
If carbonates or acetates are substituted for the free amines, it is necessary
to heat the mixture up to a more elevated temperature for effecting the reaction.
The colouring matters thus obtained may be sulphonated by means of the known
methods, if they are not soluble enough.
The shades produced by these new rosinduline derivatives are remarkable in beauty
and clearness, when compared with those of the original materials. They vary from
red to greenish blue,

page_text: The new colouring matters dissolve in concentrated sulphuric acid with the green
colour characteristic of rosindulines, while Fischer and Hepp's compounds show no.
difference from the original dyestuffs.
For carrying out the new process the following materials are used.
I. Isorosindulines of the general formula
and their substitution products.
II. Ammonia, primary amines or diamines, their nitro,-oxy-, sulphonic or carboxylic
derivatives, colouring matters containing free amido-groups, as for instance
amido-azo-dyestuffs, dyestuffs of the triphenylmethane, acridine or induline
series, etc.

page_text: 3 parts of isorosinduline, prepared by means of nitrosodimethylaniline and of
etliyl-ẞ-naphthylamine, and 1 part of ethylamine hydrochloride are dissolved in
30 parts of alcohol. 2 parts of soda lye are added, the temperature being kept low.
After some hours, standing in the presence of atmospheric air, the colouring matter is 5
separated in the form of brilliant lamellae, dyeing mordanted cotton red
shades.
2 parts of isorosinduline, prepared by means of nitrosomethyl diphenylamine and
of phenyl-ẞ-naphthylamine, and 1 part of metatoluylenediamine are dissolved in
20 parts of alcohol. 1 part of soda lye is added, the temperature being kept low and
an air current introduced into the solution. The reaction begins immediately and is
finished if a sample dissolves in concentrated sulphuric acid with green colour. The
dyestuff is sparingly soluble in mineral and dilute acids and dyes tannin mordanted
cotton blue shades.
4 parts of neutral blue and 1.5 parts of paranitraniline are dissolved in 80 parts
of alcohol. 1.5 parts of soda iye of 40° Bé. are slowly added, while a current of air 2
free from carbonic acid is introduced, the temperature being kept at from 25°
to 30° C. and the mixture well stirred.
The colouring matter is precipitated and the reaction is completed if the alcoholic
solution is but lightly coloured or if a sample dissolves in concentrated sulphuric
acid with yellowish green colour. It is insoluble in dilute acids and soluble in 3
alcohol. By sulphonating, a colouring matter is produced dyeing reddish violet
shades
4 parts of neutral blue and 2 parts of metanilate of soda are dissolved in 20 parts
of water and 40 parts of alcohol. The reaction is effected in the same way as in 3
Example 7. A safranine sulphonic acid insoluble in water is formed, which by
sulphonation yields a reddish dyestuff.
EXAMPLE 9.
A solution of 4 parts of neutral blue, of 1-5 parts of paramidosalicylic acid and
of 2 parts of potassium carbonate in 50 parts of alcohol is boiled, until a sample
dissolves in concentrated sulphuric acid with green colour. The colouring matter
sparingly soluble in water is precipitated. It dyes wool in an acidified bath a reddish
violet, and chrome mordanted wool a dark blue. By substituting, for amidosalicylic
acid, 25 parts of 1: 4-naphthylenediamine-2-sulphonic acid, a product insoluble in
water is formed, which by sulphonating yields a colouring matter dyeing reddish
violet shades.

page_text: EXAMPLE 10.
2 parts of neutral blue and 1-2 parts of amidoazobenzene hydrochloride are dissolved
in 30 parts of alcohol. A concentrated aqueous solution of 1 part of potassium
carbonate is added and the mixture boiled during 12 hours. The colouring matter
is nearly completely precipitated. It is insoluble in dilute mineral acids and dissolves
in concentrated sulphuric acid with a yellowish green colour. Its solution in
concentrated acetic acid or in alcohol shows a green colour.
4 parts of neutral blue and 3.5 parts of fuchsine are dissolved in 80 parts of alcohol.
2.5 parts of soda lye are added and a current of air free from carbonic acid is
introduced, while the temperature is kept at from 25° to 30° and the mixture well
stirred.
The colouring matter thus formed is dissolved in water, acidified by means of
hydrochloric acid and is then precipitated by means of common salt. It dyes tannin
mordanted cotton a bluish violet.
By substituting phosphine for fuchsine a colouring matter soluble in water is

page_text: are dissolved in JU
by adding 2 parts of soda lye. The colouring matter is nearly completely precipitated.
Its sodium salt is easily soluble in water. It is precipitated from the solution by an
excess of mineral acid in blue lamellae. It dyes wool in an acidified bath violet
shades and chrome mordanted wool blue shades.
EXAMPLE 16.
3 parts of isorosindulinesulphonic acid, prepared by means of benzeneazodimethyl-
anilinesulphonic acid and of phenyl-ẞ-naphthylamine, and 16 parts of amidoazo-
benzene hydrochloride are dissolved in 50 parts of alcohol. A concentrated aqueous
solution of 1.5 parts of potassium carbonate is added and the mixture boiled during
12 hours. The colouring matter separates as an insoluble precipitate, which is
purified by extraction with alcohol. After sulphonation it dyes wool green shades.
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. The herein described manufacture of new colouring matters of the safranine
series by treating, in the presence of oxygen or an oxidizing agent, isorosindulines or
their substitution products in the form of their free bases or of their carbonates
acetates or of her easily dissociated salts, with ammonia or primary amines or diamines
or with their substitution products such as nitro, hydroxyl, sulpho or carboxyl
derivatives, or with colouring matters containing free amido-groups and when the
products are insoluble in water, rendering them-soluble by sulphonation.
2. The colouring matters manufactured as set forth in the preceding claim.
301
CIL 1000