Manufacture of Basic Blue Dyestuffs.
Year: 1895

page_text: Date of Application, 12th Dec., 1895
Complete Specification Left, 12th Sept., 1896-Accepted, 17th Oct., 1896
[Communicated from abroad by THE FARBWERKE vormals MEISTER LUOIUS AND
BRUNING, of Hoechst a/Main, in the Empire of Germany, Chemical Manufacturers.]
Manufacture of Basic Blue Dyestuffs.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention to be as follows:-
In the lapsed German Patent No. 50467 was described the manufacture of dyestuffs
by melting pheno- and tolusafranines with p-phenylenediamine. It was found that
the products thus obtained had no technical value, owing to the high prices of the
components, pheno- and tolusafranines and para-phenylenediamine, and consequently
the patent was allowed to lapse.
It has also been found that the formation of these dyestuffs of an induline nature
takes place only on melting certain diamines with safranines, whilst certain other
diamines, such as the diamidodiphenylmethane bases, give no result according to this
method of operating.
My foreign correspondents have discovered a new method of manufacturing such
dyestuffs which, on the one hand, is applicable to all diamines, and, on the other
hand, employs raw materials so cheap that it can be carried out in practice with
advantage.
This method consists in heating safranines and diamines in indifferent solvents
under pressure, instead of melting them. Hitherto, the dyestuffs thus obtained from
safranines containing alkylated nitrogen, on the one hand, and diamido diphenyl
methane, diamidoditolylmethane, diamidodixylylmethane, p. and m. phenylenediamine,
on the other hand, have proved especially valuable.
EXAMPLES.
I. 50 kilos. dimethylsafranine (obtained from dimethyl-p-phenylenediamine and
aniline) 25 kilos. diamidodiphenylmethane and 250 litres of water are heated in a closed
vessel, provided with an agitator, for 4 to 6 hours at 180° C. until the reddish
violet safranine colour disappears. The product of the reaction is boiled with an
additional quantity of water and the necessary quantity of hydrochloric acid, by which
means complete solution without any residue takes place.
The
The dyestuff is precipitated by the addition of concentrated hydrochloric acid; the
precipitation may also be effected with common salt and chloride of zinc.
dyestuff is precipitated as a black sandy powder which, when dried, is very easily
soluble in water with a blue colour.
Acetate and carbonate of soda precipitate the violet red base. The dyestuff may
also be precipitated by addition of hydrochloric or sulphuric acid. It is soluble, but
with difficulty, in alcohol, giving a blue colour; it dissolves in sulphuric acid forming
a green solution which becomes blue on addition of water.
11. 50 kilos. dimethylsa franine, 25 kilos. diamidodiphenylmethane and 250 kilos.
alcohol treated as in Example I. give the dyestuff there described.
III. 50 kilos. of the safranine obtained from dimethyl-p-phenylenediamine and
xylidine, 25 kilos. diamidodiphenylmethane and 250 litres water, when treated as
[Price 8d.

page_text: above described produce a dyestuff which, except that it has a purer blue tint, has
properties similar to those of the dyestuff produced according to Example I.
IV. 50 kilos. of the safranine obtained from diethyl-p-phenylenediamine
and aniline,
25 kilos. diamidodiphenylmethane, 2:0 litres water produce a purer blue dyestuff with
properties like that of Example I.
V. 50 kilos. dimethylsafranine, 25 kilos. diamidodi-o-tolylmethane, 250 litres water
produce on treatment as in Example I. a dyestuff of similar tint with properties like
that of Example I.
VI. 50 kilos. dimethylsafranine, 25 kilos. diamido-di-p-xylylmethane, 250 litres
water produce on treatment as in Example I. a dyestuff of like properties.
VII. 50 kilos. dimethylsafranine (obtained from dimethylparaphenylene diamine
and aniline), and 300 litres of an aqueous solution containing 25 kilos. p-phenylene-
diamine are heated in a closed vessel with an agitator for 4 to 5 hours to 180° C.
until the red violet safranine colour disappears. The treatment of the product of the
reaction is as in Example I.
It is to be remarked that the base obtained by precipitating aqueous solutions of
the dyestuff with alkalies is pure blue and not reddish violet as in Example 1.
VIII. 50 kilos. safranine, obtained from dimethyl-p-phenylene diamine and xylidine,
and 300 litres of an aqueous solution containing 25 kilos. p-phenylenediamine are
treated as in Example VII. and give a somewhat purer blue dyestuff than that of
Example VII.
IX. 50 kilos. of the safranine obtained from diethyl-p-phenylenediamine and
aniline and 300 litres of an aqueous solution, containing 25 kilos. p-phenylenediamine,
produce on treatment as in Example VII. a dyestuff similar to that of Example VII.
X. 50 kilos..dimethylsafranine (obtained from dimethyl-p-phenylenediamine and
aniline) and 300 litres of an aqueous solution containing 25 kilos. m-phenylenediamine
are treated as in Example VII. and produce a dyestuff of a rather duller tint than
that of Example VII.
XI. 50 kilos. dimethylsafranice and 300 litres of an alcoholic solution containing
25 kilos. of p-phenylenediamine give on treatment as in Example VII. (after the
alcohol has been distilled off) the dyestuff described in that example.
Dated this 12th day of December 1895.
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of Basic Blue Dyestuffs.
I OLIVER IMRAY of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered Patent Agent, 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 :-
In the lapsed German Patent No. 50467 was described the manufacture of dyestuffs
by melting pheno- and tolusafranines with p-phenylenediamine. It was found that
the products thus obtained had no technical value, owing to the high prices of the
components, pheno and tolusafranines and para-phenylenediamine, and consequently
the patent was allowed to lapse.
It has also been found that the formation of these dyestuffs of an induline nature
takes place only on melting certain diamines with safranines, whilst certain other
diamines, such as the diamidodiphenylmethane bases, give no result according to this
method of operating.
My foreign correspondents have discovered a new method of manufacturing such
dyestuffs, which, on the one hand, is applicable to all diamines, and, on the other
hand employs raw materials so that it can be carried out in practice with advantage.

page_text: This method consists in heating safranines and diamines in indifferent solvents
under pressure, instead of melting them. Hitherto, the dyestuffs thus obtained
from safranines containing alkylated nitrogen, on the one hand, and diamido diphenyl-
methane, diamidoditolylmethane, diamidodixylylmethane, p. and m. phenylenediamine.
on the other hand, have proved especially valuable.
on the other hand, have proved especially valuable.
EXAMPLES.
I. 50 kilos. diamethylsafranine (obtained from dimethyl-p-phenylenediamine and
aniline) 25 kilos. diamido diphenylmethane and 250 litres of water are heated in a
closed vessel, provided with an agitator, for 4 to 6 hours at 180° C. until the reddish
violet safranine colour disappears. The product of the reaction is boiled with an
additional quantity of water and the necessary quantity of hydrochloric acid, by
which means complete solution without any residue takes place.
The dyestuff is precipitated by the addition of concentrated hydrochloric acid; the
precipitation may also be effected with common salt and chloride of zinc. The
dyestuff is precipitated as a black sandy powder which, when dried, is very easily
soluble in water with a blue colour.
Acetate and carbonate of soda precipitate the violet red base. The dyestuff may
also be precipitated by addition of hydrochloric on sulphuric acid. It is soluble, but
with difficulty, in alcohol giving a blue colour; it dissolves in sulphuric acid forming
a green solution which becomes blue on addition of water.
II. 50 kilos. dimethylsafranine, 25 kilos. diamidodiphenylmethane and 250 kilos.
alcohol treated as in Example I. give the dyestuff there described.
III. 50 kilos. of the safranine obtained from dimethyl-p-phenylenediamine and
xylidine, 25 kilos. diamidodiphenylmethane and 250 litres water, when treated as
above described produce a dyestuff which, except that it has a purer blue tint, has
properties similar to those of the dyestuff produced according to Example I.
IV. 50 kilos. of the safranine obtained from diethyl-p-phenylenediamine and aniline,
25 kilos. diamido diphenylmethane, 250 litres water produce a purer blue dyestuff
with properties like that of Example 1.
V. 50 kilos. dimethylsafranine, 25 kilos. diamidodi-o-tolylmethane, 250 litres water
produce on treatment as in Example 1. a dyestuff of similar tint with properties like
that of Example I.
VI. 50 kilos. dimethylsafranine, 25 kilos. diamido-di-p-xylylmethane, 250 litres
water produce on treatment as in Example I. a dyestuff of like properties.
VII. 50 kilos. dimethylsafranine (obtained from dimethylparaphenylene diamine
and aniline) and 300 litres of an aqueous solution containing 25 kilos. p-phenylene-
diamine are heated in a closed vessel with an agitator for 4 to 5 hours to 180° C.
until the red violet safranine colour disappears. The treatment of the product of the
reaction is as in Example I. It is to be remarked that the base obtained by
precipitating aqueous solutions of the dyestuff with alkalies is pure blue and not
reddish violet as in Example 1.
VIII. 50 kilos. safranine, obtained from dimethyl-p-phenylene diamine and xylidine,
and 300 litres of an aqueous solution containing 25 kilos. p-phenylenediamine are
treated as in Example VII. and give a somewhat purer blue dyestuff than that of
Example Vil.
IX. 50 kilos. of the safranine obtained from diethyl-p-phenylenediamine and
aniline and 300 litres of an aqueous solution containing 25 kilos. p-phenylene-
diamine, produce on treatment as in Example VII. a dyestuff similar to that of
Example VII.
X. 50 kilos. dimethylsafranine (obtained from dimethyl-p-phenylenediamine and
aniline) and 300 litres of an aqueous solution containing 25 kilos. m-phenylene-
diamine are treated as in Example VII. and produce a dyestuff of a rather duller tint
than that of Example VII.
XI. 50 kilos. dimethylsafranine and 30 litres of an alcoholic solution containing

page_text: .25 kilos. of p-phenylenediamine give on treatment as in Example VII. (after the alcohol
.has been distilled off) the dyestuff described in that example."
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The hereindescribed manufacture of blue basic colouring matters by heating
alkalised safranines with diamines of the aromatic series in indifferent solvents under
pressure.
Dated this 12th day of September 1896.
ABEL & IMRAY,
Agents for the Applicant
ABEL & IMRAY,
Agents for the Applicant