Manufacture of Acridine Derivatives.
Year: 1898

page_text: Date of Application, 28th July, 1898
17
2000
1000
Manufacture of Acridine Derivatives.
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
5 of Germany, Chemical Manufacturers) to be as follows:-
This invention relates to a new process for the manufacture of compounds of the
acridine series being derivatives of naphthacridine.
The formation of the naphthacridine series, may according to the investigations of
iny foreign corrrespondents be carried out in several ways which are based on the same
new principle. This will be shewn by the following explanation of the reaction illus-
trated by a typical example.
Tolunaphthacridine may be obtained by the action
1) Of B-naphthol on the condensation products from p-toluidine and formalde-
hyde, or
2) By the action of p-toluidine on the condensation product from ẞ-naphthol and
formaldehyde, or
3) By reacting with formaldehyde, or with its polymeric derivatives on a mixture
of p-toluidine and ẞ-naphthol
And oxidising 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 tolunaphthacridine being formed in the first stage of the re-
action. This leuco-compound is however during the condensation process partly
oxidized to the acridine derivative, into which it is then completely converted by the
action of atmospheric air or another oxidizing agent.
The constitution of the new acridine derivative obtained in the manner described,
is represented by the formula:

page_text: toluidine or methylene-diparatoluidine the reaction can be represented by the follow-
ing equations:
It is easily understood from these typical equations how the reaction will proceed 5
if one of the other methods above mentioned be used, starting for instance from a
mixture of 8-naphthol, p-toluidine and trioxymethylene, the polymeric form of other
suitable monamines.
If for instance in the example above given, benzaldehyde is used instead of form-
aldehyde, the phenyl-derivative of tolunaphthacridine is obtained according to the 1
equation.
Substitution products of these acridine derivatives may further be obtained by
introducing into the above reaction suitable substituted aldehydes or amido-products.
If for instance instead of benzylidene derivatives of p-toluidine the corresponding
p-nitrobenzylidene-derivative is brought to react with 8-naphthol, p-nitrophenyltolu-
naphthacridine is obtained.
Manufacture of Acridine Derivatives.
1, 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

page_text: of Germany; Chemical Manufacturers) and in what manner the same is to be per-
formed, to be particularly described and ascertained in and by the following state-
ment:-
This invention relates to a new process for the manufacture of compounds of the
acridine nucleus being derivatives of naphthacridine
The formation of the naphthacridine series, may according to the investigations of
my foreign correspondents be carried out in several ways which are based on the same
new principle. This will be shewn by the following explanation of the reaction illus-
trated by a typical example.
Tolunaphthacridine may be obtained by the action
1. Of 8-naphthol on the condensation products from p-toluidine and forma!-
dehyde, or
2. By the action of p-toluidine on the condensation product from 8-naphthol and.
formaldehyde, or
3. By reacting with formaldehyde, or with its polymeric derivatives on a mixture
of p-toluidine and 8-naphthol and oxidising 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 saine,
the leuco-derivative of tolunaphthacridine being formed in the first stage of the
reaction. This leuco-compound is however during the condensation process partly
oxidized to the acridine derivative, into which it is then completely converted by the
action of atmospheric air or another oxidizing agent.
The constitution of the new acridine derivative obtained in the manner described,
is represented by the formula:
methylened para-toluidine
B-naphthol
tolunaphthacridine
´p-toluidine
It is easily understood from these typical equations how the reaction will proceed
if one of the other methods above mentioned be used, starting for instance from a
mixture of ẞ-naphthol, p-toluidine and trioxymethylene, the polymeric form of
formaldehyde.

page_text: If, in the example above given, benzaldehyde is used instead of formaldehyde, the
phenyl-derivative of tolunaphthacridine is obtained according to the equation:
Substitution products of these acridine derivatives may further be obtained by
introducing into the above reaction suitable substituted aldehydes or amido-products.
If for instance instead of benzylidene derivatives of p-toludine the corresponding
p-nitrobenzylidene-derivative is brought to react with ß-naphthol, p-nitrophenyltolu-
naphthacridine is obtained.
The invention may be further illustrated by the following examples:
1. 3 kilos. of trioxymethylene are added to the melted mixture of 16 kilos. of
B-naphthol and 11 kilos. of p-toluidine at 150° C. The temperature is then raised
up to 200° C., the excess of toluidine, of B-naphthol and of formaldehyde is removed
by distillation at 300° C. The residue is then purified by dissolving it in nitric acid,
from which solution the nitrate of the tolunaphtacridine that is formed separates on
refrigeration. The free tolunaphtacridine melts at 158°.
2. The oily product resulting from the condensation of 20 kilos. of p-toluidine
and of 20 kilos. of benzaldehyde is introduced into the equal quantity of B-naphthol
at about 180° C. The temperature is raised up to 200° C. the melt is then cooled,
made alkaline and freed froin the volatile products by distillation by means of steam.
The residue is dissolved in diluted nitric acid from which solution, after cooling, the
nitrate of phenyltolunaphthacridine separates in the form of yellow crystals. By
treating this salt with soda lye the free base is obtained, which after recrystallisation
from diluted alcohol forms a crystalline powder of slight yellow colour, melting
at 213° C.
3. The product of the condensation of 76 kilos. of p-nitrobenzaldehyde and of
54 kilos. of p-toluidine is mixed with the same weight of ẞ-naphthol, and the mixture
is heated up to 190-195°. A violent reaction begins at once, the colour of the
melt becoming dark red. After refrigeration, the melt is extracted by means of
alcohol. The residue represents p-nitrophenylnaphthacridine, which constitutes a
yellowish-red powder, insoluble in most solvents.
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 acridine derivatives, by allowing aldehydes,
such as formaldehyde, or benzaldehyde to act on a mixture of B-naphthol and
p-toluidine, or
B-naphthol to act on one of the condensation products obtained from p-toluidine
and an aldehyde, such as formaldehyde, or benzaldehyde, or
p-toluidine to act on the condensation product obtained from B-naphthol and an
aldehyde, such as formaldehyde or benzaldehyde.
2. The new acridine derivatives manufactured as herein described.