The Manufacture or Production of Dye-stuffs of the Acridine Series and of Intermediate Products for use therein.
Year: 1899

page_text: Date of Application, 17th Aug., 1899
Complete Specification Left, 10th May, 1900-Accepted, 30th June, 1900
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH BAYER
& Co., of Elberfeld, Germany.]
The Manufacture or Production of Dye-stuffs of the Acridine Series
and of Intermediate Products for use therein.
I, HENRY EDWARD NEWTON, of the Office for Patents, 6, Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, do hereby declare the nature
of this invention to be as follows:-
My foreign correspondents have found that very valuable dye-stuffs of the acridine
series, varying in shade from yellow to brown, can be obtained by means of the fol-
lowing process: The acidyl derivatives of metaamidoalkyldiamidobenzhydrols which
have been described by my foreign correspondents in the Specification of Letters
Patent No. 5711+, and which have the general formula
are condensed in the presence of acids with such amines or diamines of the benzene or
naphthalene series which, when condensed with alkylated diamidobenzhydrols, yield
condensation products containing the methane carbon in ortho position to a free
amido group. By heating the resulting condensation products with acids, valuable
acridine derivatives are obtained (ammonia being evolved), which, by the action of
oxydizing agents, such as the oxygen contained in the air, are transforined into the
finished dye-stuffs.
In order to illustrate this process, the following Examples A and B are given :-
EXAMPLE A.
To 32-7 kilos. of acetylamidotetramethyldiamidobenzhydrol, dissolved in 200 kilos.
of 10 per cent. acetic acid, 11 kilos. of paratoluidine are added. After the mixture
has been heated for a short time at about from 50° to 60° Centigrade, the whole
hydrol will have disappeared, the condensation being finished. Subsequently,
-100 kilos. of a 36 per cent. hydrochloric acid are mixed with the reaction mass, which
is then further heated in an enamelled autoclave for about 5 hours, at from
135° to 140° Centigrade. The dark yellow colored liquid thus produced contains
already the most part of the dye-stuff completely formed; therefore, an addition of an
[Price 8d1

page_text: oxidising agent (such as ferric chloride), in order to finish the reaction, is in most
cases unnecessary. The cooled solution is then partially neutralized by means of
sodium carbonate. Finally, the coloring matter is separated therefrom by the addition
of common salt and of zinc chloride, filtered off and dried.
The dye-stuff thus obtained represents a dark powder of a greenish-metallic lustre,
readily dissolving in cold water. It dies cotton, mordanted with tannin, and leather,
yellowish-brown shades.
.
EXAMPLE B.
32.7 kilos. of acetylmetaamidotetramethyldiamidobenzhydrol are dissolved in a
mixture prepared from 20 kilos. of a 36.5 per cent. hydrochloric acid, 300 kilos. of
water, and 25 kilos. of a 50 per cent. acetic acid. To the resulting solution, 12.2 kilos.
of metatoluylendiamine, carefully pulverized, are added. After allowing the mixture
to stand for a short time, the hydrol will have disappeared. By adding an excess of
caustic soda-lye, the new base thus produced is separated from the reaction mass in
the form of a slightly colored flaky precipitate. It is filtered off, and immediately dis-
solved in 300 kilos. of a 20 per cent. sulphuric acid. The solution thus obtained is then
heated in a closed vessel, lined with lead, for 6 hours, at about 130° Centigrade. The
acid liquid thus produced is partially neutralized by means of alkalies. Subsequently
the coloring inatter is separated therefrom by the addition of common salt, and of
zinc chloride. It is thus obtained in the shape of a brown resinous mass, which
becomes solid after a short time, and which can then be pulverized. The so obtained
brown powder dissolves readily in cold water with a yellow color, and dies cotton,
mordanted with tannin, and leather, very bright yellow shades.
The process proceeds in an analogous manner, if, instead of the amines used in the
foregoing examples, other of the above defined amido compounds such as para-
phenetidine, betanaphtylamine, metaphenylenediamine, metaamidodialkylaniline or
the like, are employed, or if other acedylated metaamidoalkyldiamidobenzhydrols are
employed.
In order to produce the herein before defined acridine dye-stuffs, it is not however
necessary to start from the acidylated amidoalkyldiamidobenzhydrols, but such bases
or starting materials may be employed as those amidoalkyldiamidodiphenyl methanes
from which (according to the process described in the above-mentioned Letters Patent)
the acidylated metaamidoalkyldiamidobenzhydrols are produced. Thus, for instance,
the dye-stuff described in the above Example B is easily obtained if, for instance,
amidotetramethyldiamidodiphenylmethane, of the formula:

page_text: In order to illustrate this method of proceeding the following Example C is
given:
EXAMPLE C.
27 kilos. of amidotetramethyldiainidodiphenylmethane are mixed with 20 kilos. of
metatoluylendiamine hydrochloride, and heated, in an enamelled vessel, at about 160º
Centigrade, while being continuously stirred. After a short time, the formation of
the yellow dye-stuff begins. After being heated for about 8 hours, or until the
quantity of the coloring matter no longer increases, the melt is dissolved in water,
slightly acidulated by means of hydrochloric acid. From the dark yellow-colored
solution thus obtained, the dye-stuff is precipitated by the addition of common
salt and of zinc chloride. The coloring matter thus separated exhibits the same
properties as the dye-stuff obtained according to the above Example B.
The process proceeds in an analogous manner, if the meta-amidotetramethyldiamido-
diphenyl methane is replaced by its analogues, or if, instead of metatoluylene-
diamine, other primary aromatic amines are employed, such as aniline, paratoluidine,
metaphenylenediamine, or the like.
My foreign correspondents do not intend to confine themselves to the particulars
given in the above examples, as these are merely typical, and can be varied within
wide limits.
T
1
VOALL LEIE
DIECIFICATION.
The Manufacture or Production of Dyestuffs of the Acridine Series,
and of Intermediate Products for use therein.
I, HENRY EDWARD NEWTON, of the Office for Patents, 6, Bream's Buildings,
Chancery Lane, in the County of London, 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 :-
My foreign correspondents have found that very valuable dyestuffs of the acridine
series, varying in shade from yellow to brown, can be obtained by means of the
following process. The acidyl derivatives of metaamidoalkyldiamidobenzhydrols,
which have been described by my foreign correspondents in the Specification of
Letters Patent 5711° and which have the general formula:

page_text: acids, with such amines or diamines of the benzene or naphthalene series as will,
when condensed with alkylated diamidobenzhydrols, yield condensation products
containing the methane carbon in ortho position to a free amido group. By heating
the resulting condensation-products with acids, valuable acridine derivatives are
obtained (ammonia being evolved), which, by the action of oxidizing agents, such as
the oxygen contained in the air, are transformed into the finished dye-stuffs.
In order to illustrate this process, the following Examples A and B are given, the
parts being by weight.

page_text: described in the above example B is easily obtained, if, for instance, amidotetra-
methyldiamido diphenylmethane, of the formula:
EXAMILL
27 kilos. of amidotetramethyldiamido diphenylmethane are mixed with 20 kilos. of
metatolnylenediamine hydrochloride, and heated in an enamelled vessel, at about
1600 Centigrade, while being continuously stirred. After a short time, the formation
of the yellow dyestuff begins. After being heated for about 8 hours, or until the
quantity of the coloring matter no longer increases, the melt is dissolved in water,
slightly acidulated with hydrochloric acid. From the dark yellow colored solution
thus obtained, the dyestuff is precipitated by the addition of common salt and of
zinc chloride. The coloring matter thus separated exhibits the same properties as
the dye-stuff obtained according to the above Example B.
The process proceeds in an analogous manner if the metaamidotetramethyldiamido-
diphenylmethane is replaced by its analogues, or if, instead of metatoluylenediamine,
other primary aromatic amines are employed, such as aniline, paratoluidine, meta-
phenylene diamine, or the like.
My foreign correspondents do not intend to confine themselves to the particulars
given in the above examples, as these are merely typical, and can be varied within
wide limits.
Having now particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be performed, as communicated to me
from abroad, I declare that what I claim is :-
1. The process for the production of new products of the triphenyl-, or of the
diphenylnaphthylmethane series, which process consists in condensing the acidyl
derivatives of metaamidoalkyldiamidobenzhydrols with such aromatic mono- or dia-
mines as furnish, with the said hydrols, condensation products containing the methane
carbon atom in ortho position with regard to a free amido group of the aromatic
mono- or diamine which was employed, substantially as herein before described.
2. The process for the production of from yellow to brown basic dye-stuffs of the
acridine series, which process consists in treating the products obtainable by the

page_text: process claimed under Claim 1, with acids or other agents which are capable of split-
ting off ammonia and oxydizing the leuco compounds thus obtained, substantially as
bereinbefore described.
3. The process for the production of from yellow to brown basic dye-stuffs, which
process consists in treating the metaamidoalkyldiamidodiphenylmethanes with salts of
primary aromatic mono- or diamines, substantially as hereinbefore described.
4. As new articles of manufacture, the new products obtainable by the processes
hereinbefore described and claimed.