Manufacture of Basic Safranine Azodyestuffs Soluble in Water.
Year: 1898

page_text: Manufacture of Basic Safranine Azodyestuffs Soluble in Water.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, in the
County of London, Chartered Patent Agent, do hereby declare the nature of
this invention (as communicated to me from abroad by The Farbwerke vormals:
Meister Lucius and Brüning of Hoechst a/Main, in the Empire of Germany,
Chemical Manufacturers) to be as follows :―
By the action of diazotised safranines upon the molecular quantity of ẞ-naphthol
under appropriate conditions, blue basic dyestuffs soluble in water are obtained,
generally known as azodyestuffs.
They still maintain the first place in industry, notwithstanding that they are
deficient in fastness to alkalies.
:
My foreign correspondents have found that the diazo compounds of asymmetric
dialkylsafranines can act under certain conditions upon ẞ-naphthol in such a manner,
that 2 molecules of the diazocompound combine with 1 molecule of 8-naphthol. The
compounds thus obtained are blue basic dyestuffs, soluble in water, which greatly
surpass those mentioned (obtained by combination of 1 molecule of diazotised
safranine with one molecule of ẞ-naphthol) in fastness to washing and alkali.
Of asymmetric dialkylsafranines forming the primary material for the production
. the cllins have first to be nonsidered

page_text: hol. dimethyl-p-phenylenediamin + 2 mol.
anilin
anilin
diethyl-p-phenylenediamin + 2 mol.
dimethyl-p-phenylenediamin + 2 mol.
diethyl-p-phenylenediamin + 2 mol.
o-toluidin
o-toluidin
dimethyl-p-phenylenediamin + 1 mol.
anilin 1 mol. o-toluidin.
diethyl-p-phenylenediamin. + 1 mol.
anilin 1 mol. o-toluidin.
dimethyl-p-phenylenediamine + 1 mol.
anilin 1 mol. p-toluidin
diethyl-p-phenylenediamin + 1 mol.
anilin 1 mol. p-toluidin.
dimethyl-p-phenylenediamin + 1 mol.
o-toluidin +1 mol. p-toluidin.
diethyl-p-phenylenediamin + 1 mol.
o-toluidin +1 mol. p-toluidin.
The following example may illustrate the manufacture of the new dyestuffs.
16. kilos of diethylphenosafranine (2 mol.) are dissolved in 1700 litres of water; the
solution is cooled with ice and diazotised in the usual manner with 8.62 kilos of
hydrochloric acid (21° Bé) and 2.70 kilos of sodium nitrite. Into the resulting blue
diazo solution are slowly run, while well stirring, a solution of 3 kilos 8-naphthol
(1 mol.) in 3.8 kilos of caustic soda-lye (specific weight 1437) and 200 litres of water.
The formation of the dyestuff is complete after standing for several hours at
ordinary temperature; it is then heated to 60° or 70° C, the dyestuff is precipitated
with common salt and some chloride of zinc, filtered, pressed and dried.
In some cases it is preferable, but not necessary, to effect the forination of the dye-
stuff in presence of organic acids and in this case the process may, for instance, be as
follows:
6 kilos of as-dimethylphenosafranine, double salt of chloride of zinc (2 mol.)
containing water of crystallisation
are dissolved in 1,000 litres of water and diazotised with 8.62 kilos of hydrochloric
acid (21° Bé) and 2.76 kilos of sodium nitrite, as described in the foregoing example.
To the diazo solution thus obtained, are added 11 kilos of sodium acetate and a
solution of 3 kilos of B-naphthol (1 mol.) in 2 kilos of caustic soda-lye (specific
weight 1437) and 150 to 200 litres of water are run in it., The completion of the
dyestuff is effected exactly as in the previous example.
Instead of the naphthol sodium solution, ammoniacal B-naphthol solutions or
freshly precipitated, finely divided 8-naphthol may be employed; in the latter
case the diazo solution ought to contain correspondingly less of the free acid.
Instead of as-dimethyl or as-diethylphenosafranine, equivalent quantities of the
above mentioned homologous as-dialkylsafranine may be employed.
The dyestuffs thus obtained are easily soluble in water and dye vegetable fibre
unmordanted as well as mordanted with tannin tartar emetic a fast blue.

page_text: The new dyestuffs differ little in their properties one from another, but greatly
from those first mentioned obtained by combining 1 mol. of diazotised safranine
with 1 mol. of 8-naphthol.
The following table will shew this difference in one example.
Manufacture of Basic Safranine Azodyestuffs Soluble in Water.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention (as communicated to me from abroad by The Farbwerke vormals: Meister
Lucius and Brüning of Hoechst a/ Main, in the Empire of Germany, Chemical
Manufacturers) and in what manner the same is to be performed to be particularly
described and ascertained in and by the following statement:-
By the action of diazotised safranines upon the molecular quantity of B-naphthol
under appropriate conditions, blue basic dyestuffs soluble in water are obtained,
generally known as azodyestuffs.
They still maintain the first place in industry, notwithstanding that they are
dificient in fastness to alkalies.

page_text: My foreign correspondents have found that the diazo-compounds of asymmetric
dialkylsafranines can act under certain conditions upon ẞ-naphthol in such a manner,
that 2 molecules of the diazo-compound combine with 1 molecule of ẞ-naphthol. The
compounds thus obtained are blue basic dyestuffs, soluble in water, which greatly
surpass those mentioned (obtained by combination of 1 molecule of diazotised
safranine with one molecule of 8-naphthol) in fastness to washing and alkali.
Of asymmetric dialkylsafranines forming the primary material for the production
of these new dyestuffs, the following have first to be considered.
ol. dimethyl-p-phenylenediamine + 2 mol.
aniline
diethyl-p-phenylenediamine + 2 mol.
aniline
dimethyl-p-phenylenediamine + 2 mol.
o-toluidine
diethyl-p-phenylenediamine + 2 mol.
o-toluidine
dimethyl-p-phenylenediamine + 1 mol.
aniline +1 mol. o-toluidine
diethyl-p-phenylenediamine + 1 mol.
aniline 1 mol. o-toluidine
dimethyl-p-phenylenediamine + 1 mol.
aniline +1 mol. p-toluidine
diethyl-p-phenylenediamine + 1 mol.
aniline mol. p-toluidine
dimethyl-p-phenylenediamine + 1 mol.
o-toluidine + 1 mol. p-toluidine
diethyl-p-phenylenediamine + 1 mol.
o-toluidine +1 mol. p-toluidine.
The following example may illustrate the manufacture of the new dyestuffs.
16 kilos. of diethylphenosafranine (2 mol.) are dissolved in 1700 litres of water;
the solution is cooled with ice and diazotised in the usual manner with 8.62 kilos. of
hydrochloric acid (21° Bé.) and 2.76 kilos. of sodium nitrite. Into the resulting
blue diazo-solution are slowly run, while well stirring, a solution of 3 kilos. of
B-naphthol (1 mol.) in 3.8 kilos. of caustic soda-lye (specific gravity 1437) and
200 litres of water.
The formation of the dyestuff is complete after standing for several hours at
ordinary temperature; it is then heated to 60° or 70° C., the dyestuff is precipitated
with common salt and some chloride of zinc, filtered, pressed, and dried.
In some cases it is preferable, but not necessary, to effect the formation of the
dyestuff in presence of organic acids and in this case the process may, for instance,
be as follows:
16. kilos. of as-dimethylphenosafranine, double salt of chloride of zinc (2 mol.)
containing water of crystallisation
are dissolved in, 1,000 litres of water and diazotised with 8.62 kilos. of
hydrochloric acid (21° Bé.) and 2.76 kilos. of sodium nitrite, as described
in the foregoing example. To the diazo-solution thus obtained, are added

page_text: 11 kilos. of sodium acetate and a solution of 3 kilos. of ẞ-naphthol (1 mol.)
in 2 kilos. of caustic soda-lye (specific gravity 1437) and 150 to 200 litres
of water are run in. The completion of the dyestuff is effected exactly as in the
previous example.
Instead of the naphthol sodium solution, ammoniacal ẞ-naphthol solutions or
freshly precipitated, finely divided ẞ-naphthol may be employed; in the latter case
the diazo-solution ought to contain correspondingly less of the free acid.
Instead of as-dimethyl or as-diethyl-phenosafranine, equivalent quantities of the
above mentioned homologous as-dialkylsafranines may be employed.
The dyestuffs thus obtained are easily soluble in water and dye vegetable fibre
unmordanted as well as mordanted with tannin tartar emetic a fast blue.
The new dyestuffs differ little in, their properties one from another, but greatly
from those first mentioned obtained by combining 1 mol. of diazotised safranine
with 1 mol. of 8-naphthol.
The following table will shew this difference in one example:
Having now particularly described and ascertained the nature of this
invention and in what manner the same is to be performed, I declare that what I
claim is :-
The manufacture of blue, basic safranine azodyestuffs soluble in water, by allowing
one molecule of beta-naphthol to act upon two molecules of a diazotised as-dialkyl-
safranine, substantially as set forth.