Production of Acridine Derivatives.
Year: 1899

page_text: Date of Application, 13th Mar., 1899
Complete Specification Left, 11th Dec., 1899-Accepted, 13th Jan., 1900
PROVISIONAL
SPECIFICATION.
Production of Acridine Derivatives.
1, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Buildings, 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
Actien Gesellschaft für Anilin-Fabrikation, of Berlin, in the Empire of Germany,
Chemical Manufacturers) to be as follows:
Compounds of the acridine series have been produced by allowing:
1.) B-naphthol to act on the condensation products from para-toluidine and
formaldehyde, or
2.) Para-toluidine to act on the condensation product from B-naphthol and
formaldehyde, or
3.) Formaldehyde, or its polymeric derivatives, to act on a mixture of para-toluidine
and B-naphthol, and oxidising the condensation products produced in any of these
ways.
In carrying these researches on this subject further, my foreign correspondents have
found that new acridine derivatives are obtained by substituting in the processes
above described for para-toluidine other primary aromatic amines such as aniline,
ortho-toluidine, meta-toluidine, acetyl-para-phenylenediamine &c. and either allowing
them to act directly on a mixture of B-naphthol and trioxymethylene or first
condensing them with formaldehyde and then acting with B-naphthol on the
anhydroformaldehyde dervatives forined.
By proceeding in the manner described there are for instance obtained from
B-naphtol aniline and trioxymethylene, naphthacridine, forming yellowish-crystals
melting at 1295° C.; from B-naphthol and anhydroformaldehyde-ortho-toluidine,
ortho-tolunaphthacridine melting at 143° C., from B-naphthol and anhydroformalde-
hyde-meta-xylidine, dimethylnaphthacridine, melting at. 152° C.; from B-naphthol
and anhydroformaldehyde-acetyl-para-phenylenediamine, acetyl-amidonaphthacridine,
formning yellowish crystals, melting at 255° C. and being easily transformed by
saponification into amidonaphthacridine, melting at 238° C.
1.1 do of Marah 1800
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE
SPECIFICATION.
Production of Acridine Derivatives.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Buildings,
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
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 he
particularly described and ascertained in and by the following statement:-
Compounds of the acridine series have been produced by allowing:
1.) B-naphthol to act on the condensation products of para-toluidine and
formaldehyde, or
2.) Para-toluidine to act on the condensation product of 8-naphthol and

page_text: 3.) Formaldehyde, or its polymeric derivatives, to act on a mixture of para-toluidine
and B-naphthol, and oxidising the condensation products produced in any of these
ways.
In carrying the researches on this subject further, my foreign correspondents have
found that new acridine derivatives are obtained by substituting in the processes
above described for para-toluidine other primary aromatic amines such as aniline,
ortho-toluidine, meta-xylidine, acetyl-para-phenylenediamine &c.
The following examples serve to illustrate this invention.
1. MANUFACTURE OF ACRIDINE DERIVATIVES BY THE ACTION OF B-NAPHTHOL ON
THE CONDENSATION PRODUCTS OF FORMALDEHYDE AND PRIMARY AROMATIC AMINES.
A. 6 kilos. of anhydroformaldehyde-ortho-toluidine are slowly added to 10 kilos.
of B-naphthol at a temperature of 150° C. The mass dissolves with a yellow colour
and the condensation is completed in a short time. The ortho-tolunaphthacridine
thus formed can be isolated by fractional distillation; it is rendered perfectly pure by
recrystallisation from a mixture of benzene and ligroin. It melts at 143° C.
B. When for anhydroformaldehyde-ortho-toluidine the homologous anhydro-
formaldehyde-meta-xylidine is substituted, the operations being otherwise executed
in exactly the same way as described in Example A, dimethylnaphthacridine is
obtained which is represented by the formula:
The compound is hardly soluble in hot alcohol. It may be purified by recrystallisa-
tion from benzene and melts at 152° C.
C. 5 kilos. anhydroformaldehyde-acetyl-para-phenylenediamine (produced by
dissolving acetyl-para-phenylenediamine in hot water, adding the theoretical quantity
of formaldehyde and after refrigeration filtering off the condensation product, which
forms white crystals melting at 195° to 200° C.) are melted with 12 kilos. of beta-
naphthol at 150° to 180° C. The product of the reaction is washed with diluted
caustic soda lye in order to remove an excess of ẞ-naphthol; the acetylamidonaphth-
acridine thus obtained is purified by recrystallisation from alcohol. It forms yellowish
needles, melting at 255° C.
From this product naphthoamidoacridine itself is obtained by saponification. It
crystallizes from alcohol in the shape of yellow needles, melting at 238° C.
Its constitutional formula is

page_text: 2. MANUFACTURE OF ACRIDINE DERIVATIVES BY THE ACTION OF PRIMARY AROMATIC
AMINES ON THE CONDENSATION PRODUCT OF FORMALDEHYDE AND BETA-NAPHTHOL
(B-B-DIOXYDINA PIITHYLMETHANE).
4 parts of aniline hydrochloride and 1 part of aniline are heated to 120º C.;
5 parts of B-ß-dioxydinaphthylmethane are slowly added to the mixture while the
temperature is elevated to 150° to 160° C.
Owing to the formation of the condensation product, the mass assumes a yellow
colour. In order to render the reaction complete the mass is finally heated to 200°
to 220° C. After refrigeration caustic soda lye is added and an excess of aniline is
removed by means of steam. The residue is extracted with diluted hydrochloric acid
and naphthacridine is precipitated from the acid solution obtained by caustic soda
lye. After purification by recrystallisation it melts at 130° C.
3. MANUFACTURE OF ACRIDINE DERIVATIVES BY THE ACTION OF TRIOXYMETHYLENE
ON A MIXTURE OF PRIMARY AROMATIC AMINES AND B-NAPHTHOL.
10 kilos. of B-naphthol and 8 kilos. of aniline is heated to 160° C. and 1 kilo. of
trioxymethylene is slowly added thereto. The mass assumes a yellowish-red
colour. After distilling off an excess of aniline and B-naphthol the mass is heated
up to the boiling point of naphthacridine, which thereupon distils over at about
430° C. In order to get the distillate free from B-naphthol it is washed with diluted
caustic soda lye and the residue is recrystallised from a mixture of benzene and
ligroin.
Naphthacridine thus produced forms yellowish crystals melting at 129.5° C.
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
1. The herein described manufacture of acridine derivatives by substituting in the
processes described in the Specification No. 16,475 of 1898 for para-toluidine other
primary aromatic amines, such as ortho-toluidine, meta-xylidine, acetyl-para-
phenylene-diamine etc.
2. The products manufactured as above set forth.
3. The herein described transformation of acetylamidonaphthacridines obtainable
as set forth in Claim 1 into amidonaphthacridines by saponification.
Dated this 11th day of December 1899.
ABEL & IMRAY,
Agents for the Applicant.