Year: 1898

page_text: Date of Application, 28th July, 1898
Complete Specification Left, 17th Apr., 1899-Accepted, 15th July, 1899
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Buildings,
Chancery Lane, in the County of London, Consulting Engineer and Chartered Patent
Agent, do hereby declare the nature of this invention (as communicated to me from
abroad by The Actien Gesellschaft für Anilin Fabrikation, of Berlin, in the Empire
of Germany, Chemical Manufacturers) to be as follows:-
This invention relates to the manufacture of new colouring matters which are
derivatives of naphthacridine:-
The formation of the naphthacridine nucleus from the raw materials used, may be
carried out in several ways, which are based on the same new principle. This is
shewn by the following explanation of the reaction illustrated by a typical example.
Amidotolunaphthacridine may be obtained by the action
1) Of ẞ-naphthol on the condensation products from m-toluylenediamine and
formaldehyde, or
2) Of m-toluylenediamine on the condensation product from 8-naphthol and formal-
dehyde, or
3) By reacting with formaldehyde, or with its polymeric derivatives on a mixture of
m-toluylenediamine and B-naphthol, and oxidizing the condensation products
produced in any one of these cases.
"
By proceeding in any one of these ways the products of the reaction are the same,
the leuco-derivative of amidotolunaphthacridine being formed in the first stage of
the reaction.
This leuco compound is however, during the condensation process partly oxidized
to the colouring matter, into which it is then completely converted by the action of
atinospheric air or another oxidizing agent.
The constitution of the new colouring matter obtained by this new process is
represented by the formula :-

page_text: In the typical case of its production from ẞ-naphthol and tetraamidoditolylmethane,
the reaction can be represented by the following equations:-
In the above example instead of tetraamidoditolylmethane, resulting from the re-
action of formaldehyde and m-toluylene-diamine in the presence of sulphuric acid,
the product obtained from these components in alkaline solution and representing
probably methylenedi-m-toluylenediamine or the product produced from the same raw
materials in a neutral solution and representing anhydroformaldehyde-m-toluylene-
diamine may be substituted with the same result.
If dioxydinaphthylmethane and m-tolulylenediamine be used as starting products
;the reaction proceeds according to the following equation:
It is easily understood from these typical equations how the reaction will proceed
in case of starting from a mixture of formaldehyde, ẞ naphthol and m-tolulvene-
diamine.
The production of the new colouring matter is best effected by melting together
molecular proportions of the ingredients above mentioned at temperatures from 150°
to 200° C.
The melt is then treated with dilute soda lye in order to remove an excess of
phenols, the residue is dissolved in diluted hydrochloric acid, the leuco derivative
formed is oxidized by means of air or another oxidizing agent; the solution obtained
is filtered off and the dyestuff salted out by means of common salt.
The new dyestuff dyes tannin-mordanted cotton very clear orange-yellow tints. By
substituting in the process above described formaldehyde or its condensation products
by other aldehydes or the condensation products thereof, colouring matters of similar

page_text: character are produced. If for instance benzaldehyde be used, phenylated amidotolu-
naphthacridine will be obtained which may be represented by the formula:-
Manufacture of New Colouring Matters of the Acridine Series.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Buildings,
Chancery Lane, in the County of London, Consulting Engineer and Chartered Patent
Agent, do hereby declare the nature of this invention (as communicated to me from
abroad by the Actien-Gesellschaft für Anilin Fabrikation, of Berlin, 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 state-
ment:
-
This invention relates to the manufacture of new colouring matters which are
derivatives of naphthacridine :—
The formation of the naphthacridine nucleus from the raw materials used, may be
carried out in several ways, which are based on the same new principle. This is
shewn by the following explanation of the reaction illustrated by a typical example.
Amidotolunaphthacridine may be obtained by the action,
1) Of 8-naphthol on the condensation products from m-toluylenediamine and formal-
dehyde, or
2) Of m-toluylenediamine on the condensation products from 8-naphthol and
formaldehyde, or
3) By reacting with formaldehyde, or with its polymeric derivatives in a mixture
of m-toluylenediamine and -naphthol, and oxidizing the condensation products
produced in any one of these cases.
.
By proceeding in any one of these ways the products of the reaction are the same,
the leuco-derivative of amidotolunaphthacridine being formed in the first stage of the
reaction.
This leuco compound is however, during the condensation process partly oxidized
to the colouring matter, into which it is then completely converted by the action of
atmospheric air or another oxidizing agent.

page_text: The constitution of the new colouring matter obtained by this new process is repre-
sented by the formula :-
In the above example instead of tetraamidoditolymethane, resulting from the
reaction of formaldehyde and m-toluylenediamine in the presence of sulphuric acid,
the product obtained from these components in alkaline solution and representing
probably methylene-di-m-toluylenediamine or the product produced from the same
raw materials in a neutral solution and representing anhydroformaldehyde-m-toluylene-
diamine may be substituted with the same result.
If dioxydinaphthylmethane and m-toluylenediamine be used as starting products
the reaction proceeds according to the following equation
:-
-
dioxydinaphthyl + m-toluylene leucoamido- + (-naphthol
methane
diamine
tolunaphth-
acridine
It is easily understood of these typical equations how the reaction will proceed in
case of starting from a mixture of formaldehyde, s-naphthol and m-toluylenediamine.
The production of the new colouring matter is best effected by melting together
molecular proportions of the ingredients above mentioned at temperatures from
150° to 200° C.
The melt is then heated with dilute soda lye in order to remove an excess of
phenols, the residue is dissolved in diluted hydrochloric acid, the leuco derivative
formed is oxidized by means of air or another oxyidizing agent; the solution obtained
is filtered off and the dyestuff salted out by means of common salt.
The new dyestuff dyes tannin mordanted cotton very clear orange-yellow tints. By
substituting in the process above described formaldehyde or its condensation products
by other aldehydes or the condensation products thereof, colouring matters of similar

page_text: character are produced. If for instance benzaldehyde be used, phenylated amidoto-
lunaphthacridine will be obtained which may be represented by the formula :-
The invention may be further illustrated by the following examples :-
1). 25 kilos. of tetraamidoditolylmethane are gradually added to 20 kilos. of 8-naph-
thol, heated to 150° C. The tetraamidoditolylmethane dissolves immediately, develop-
ing water vapors and forming a reddish-yellow melt. As soon as no more water-vapors
are given off, the melt is heated to 200° C., thereupon the melt is cooled and treated
with soda lye in order to remove the excess of naphthol or any other phenols formed.
The residue is dissolved in diluted hydrochloric acid heated, a current of air is passed
through the solution obtained, or another oxidizing agent is added thereto until a
dark colour is produced. By addition of common salt the dyestuff is then precipitated
in the form of its hydrochloride.
The constitution of the dyestuff thus obtained is represented by the formula :-
:-
The new colouring matter dyes tannin-mordanted cotton orange-yellow tints of
very clear shade. The free colour base, after recrystallisation by means of alcohol
forms lemon coloured crystals, melting at 240° C., nearly insoluble in water, little
soluble in ether, readily soluble in alcohol, acetic and diluted mineral acids. The
solutions in acids have orange-red colour and a strong yellowish-green fluorescence.
Acetic anhydride yields with the colour base an acetyl derivative of feebly yellowish
colour. Sulphuric acid dissolves the colour base producing orange-yellow colour and
strong green fluorescence. On diluting with water the orange yellow colour is not
changed.
2). The same colouring matter is obtained, if in the preceding example for the
tetraamidoditolylmethane is substituted the oily condensation product obtained from
25 kilos. m-toluylenediamine and 7.7 kilos. formaldehyde, dissolved in 5 litres of
alcohol with addition of 4-5 kilos. of sodium hydroxide.
3). By substituting for the tetraamidoditolylmethane in Example 1 14 kilos. of
anhydroformaldehyde-m-toluylenediamine, and otherwise proceeding in the manner
above described, the same dyestuff as in the preceding examples is obtained.
4). 30 kilos. of dioxydinaphthylmethane are heated to about 150-200° C., either
with 15 Kilos. of m-toluylene-diamine or with 10 kilos. of the saine and 10 kilos. of
its hydrochloride. The same colouring matter is formed as in the preceding examples
and it can be isolated from the melt in the manner above described.
5). The same dyestuff can also be obtained by adding i kilo. of trioxymethylene to
the mixture of 12 kilos. of m-toluylenediamine and 15 kilos. of 8-naphthol, heated
to about 150°. The colouring matter formed is isolated in the inanner above
described.
6). By substituting an equivalent quantity of benzaldehyde for the trioxymethylene,
otherwise proceeding in the manner described in the preceding example, a phenylated

page_text: derivative of amidotolunaphthacridine is obtained the constitution of which is
represented by the following formula :-
Having now particularly described the nature of this invention 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 acridine
series by allowing
(a) Aldehydes, such as formaldehyde or benzaldehyde, to act on. a mixture
of B-naphthol and of m-toluylenediamine, or
(b) B-naphthol to act on one of the condensation products obtained from m-toluy-
lenediamine and an aldehyde, such as formaldehyde, or benzaldehyde, or
(c) m-toluylenediamine to act on the condensation obtained from A-naphthol and
an aldehyde, such as formaldehyde or benzaldehyde.
2). The new colouring matters of the acridine series manufactured as herein
described.
ABEL & IMRAY,
Agents for the Applicant.