Manufacture of Acridinium Derivatives.
Year: 1899

page_text: PROVISIONAL SPECIFICATION.
Manufacture of Acridinium Derivatives.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Build-
ings, 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:-
Acridinium derivatives have hitherto been produced only by allowing alkyl
halides, such as methyl iodide and ethyl bromide or ethyl iodide to act on acri-
dine derivatives (compare Graebe and Caro, Liebig's Annalen 158 page 265;
Bernthsen, Liebig's Annalen 224, page 20). These reactions can be effected only
in closed vessels under pressure and at a high temperature. They give good
results and quantitative yields only when alkyl iodides are used.
My foreign correspondents have now found, that dimethyl sulphate is a most
suitable agent for converting acridine derivatives into the corresponding acri-
dinium compounds. To achieve this reaction the acridine derivative is dissolved
with aid of heat in an indifferent completely dry solvent, such as benzene, chloro-
form, nitrobenzene, and to the solution the calculated quantity of dimethyl sul-
phate is added. After a few moments the methosulphate of the methyl-acri-
dinium compound separates in crystalline form. The product thus obtained is
quite pure in the first instance and the yield in most cases is quantitative.
The use of dimethyl sulphate instead of the alkylising agents hitherto used for
the production of acridinium compounds is of great advantage, as the reaction
with dimethyl sulphate can be effected in open vessels and requires only a short
time for its completion giving a most satisfactory yield of the acridinium com-
pounds.
The methosulphates of the methyl-acridinium compounds produced. by the
above described reaction are crystalline substances most of which have a yellow
colour. They are easily soluble in water and have an intensely bitter taste.
Some of them are stronger, others weaker bases than ammonia. They produce
on cotton, and on tannin mordanted cotton yellow to orange-red tints.
The invention is illustrated by the following examples:"
EXAMPLE 1.
The naphthacridines described in Specification No. 16475 of 1898 and French
Specification No. 280,372 (brevet d'addition 14.3. 1899) can be easily and quan-
titatively converted into the corresponding acridinium compounds. If for in-
stance tolunaphth-acridine be used the reaction is effected in the following
manner:-
2 parts by weight of tolunaphthacridine are dissolved in 10 parts of benzene
and to the boiling solution is added 1 part of dimethyl sulphate. After heat-
ing for a short time, the mass solidifies to a thick yellow crystalline
paste, constituting the new acridinium base in pure form. The product is isolated

page_text: by diluting, after refrigeration, with some ether, benzene or ligroin, filtering
and drying.
The methosulphate of tolunaphtomethylacridinium thus obtained easily dis-
solves in water to a yellow coloured solution; this has a bitter taste and is
decolourised on addition of soda lye or ammonia, the free colourless acridinium
base being formed. Sodium carbonate or ammonium carbonate, however does not
decompose the salts of the colouring matter. The dyestuff dyes cotton yellow
tints.
A quite analogous dyestuff is produced by substituting for tolunaphthacridine
the dinaphthacridine which melts at 216° C.
EXAMPLE 2.
If the new reaction is applied to derivatives of phenylacridine nitrobenzene is
the best solvent and after the addition of the calculated quantity of dimethyl
sulphate the solution should be heated for 5 to 10 minutes at 180° C. Upon
refrigeration the acridinium compound thus formed separates rather slowly and
it is advantageous to precipitate it more completely by addition of ligroin.
The derivatives of phenylacridinium obtained in the manner described from
phenylacridine, phenyltolunaphthacridine and the like have weaker basic pro-
perties than have the derivatives described in Example 1); they are accordingly
precipitated not only by caustic alkali but also by carbonates.
EXAMPLE 3.
2 parts by weight of acetamidotolunaphthacridine (Specification 16474 of 1898)
are dissolved with aid of heat in 20 parts of nitrobenzene and to the boiling
solution 1 part of dimethyl sulphate is added. The new acridinium compound
separates immediately and quantitatively in pure form. The methosulphate of
acetamidotolunaphthomethylacridinium is very easily soluble in water with
yellow colour.
For acetamidotolunaphthacridine can be substituted in the preceding example
the acridine derivatives or their acetyl-products described in Specification
No. 16474 of 1898.
EXAMPLE 4.
The acetyl derivatives of diamido-acridines can likewise be easily converted
into the corresponding acridinium bases by means of dimethyl sulphate.
For instance 1 part of diacetyldiamidoditoluacridine (obtained by the action
of acetic anhydride and sodium acetate upon acridine yellow, Specification
No. 17971 of 1889) is dissolved with aid of heat in 20 parts of nitrobenzene and
to the solution is added 0'6 part of dimethylsulphate. The solution assumes a
brown colour and after a few moments solidifies to a thick yellow crystalline
paste. After refrigeration the mass is diluted with ligroin, filtered and dried.
Diacetyldiamidoditolumethylacridinium-methosulphate which is thus obtained
with quantitative yield, forms yellow-brown needles, dissolving easily in water
and less readily in alcohol to a yellow coloured solution. The aqueous solution
has an intensely bitter taste. It is not altered by addition of ammonia, turns
slightly darker on addition of sodium carbonate, while on addition of caustic
soda it becomes feebly red and after standing for some time, turbid. The dye-
stuff dyes tannin-mordanted cotton dull yellow tints.
If the diacetyl compound above described be saponified by means of dilute
hydrochloric acid the solution turns dark red and upon refrigeration solidifies
to a red crystalline paste consisting of the hydrochloride of diamidoditolylmethyl-
acridinium chloride. This product is very easily soluble in water to an orange
red coloured solution having a strong green fluorescence; the solution is not
altered by ammonia or sodium carbonate, by which reaction the new product is
at once distinguished from acridine yellow and phosphine. On addition of soda
lye it turns somewhat darker and after standing for some time becomes turbid

page_text: This dyestuff dyes tannin-mordanted cotton very clear yellow tints with orange
shade, while on unmordanted cotton yellow tints are produced.
EXAMPLE 5.
By substituting in the preceding example for acridine-yellow the benzoflavine
of Specification No. 9614 of 1888 there is obtained the methosulphate of diacetyl-
diamidodimethylphenylmethylacridinium in the form of a red oily precipitate.
In order to purify this, it is dissolved in water. By addition of some ammonia
traces of unalkylised substance are precipitated and these are separated by filtra-
tion. From the filtrate the new colouring matter is precipitated in the form of
the nitrate by addition of nitric acid and some nitre. The new dyestuff is easily
soluble in water to a yellow solution which is not altered by addition of alkalies.
The dyestuff produces on tannin-mordanted cotton dull orange yellow tints.
By saponifying the aforesaid diacetyl compound there is obtained the hydro-
chloride of diamidodimethylphenylmethylacridinium chloride, which separates
in the form of red crystals. This product is little soluble in cold water readily
soluble in warm water to a yellow solution having a green fluorescence. The
aqueous solution gelatinises ou cooling. The warm diluted aqueous solution is
not altered by addition of alkalies by which reaction the new dyestuff is dis-
tinguished from benzoflavine and phosphine. The dyestuff produces tints which
resemble those obtained with the product described in Example 4..
EXAMPLE 6.
Phosphine (chrysaniline) can also, after being previously transformed into the
acetyl-compound, be converted into an acridinium derivative by means of dime-
thyl sulphate. The diacetyl-compound thus obtained dyes tannin-mordanted
cotton dull orange-yellow tints. The aqueous solution of the dyestuff is not
altered on addition of alkalies. The free diamido-compound, obtained by saponi-
fication, produces on tannin-mordanted cotton flesh coloured red tints.
addition of concentrated soda lye the red acridinium base is precipitated.
By
Instead of starting from the acetyl-products of amido- or diamido-acridines,
as in the preceding examples the free amido- or diamido-acridines may be used
as parent material: for the dimethyl sulphate does not react, under the condi-
tions chosen, with the amido-groups. The reaction in this case is carried out in
exactly the same manner as described in the preceding examples.
Dated this 28th day of Angust 1899
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of Acridinium Derivatives.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Build-
ings, 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 statement:-
Acridinium derivatives have hitherto been produced only by acting with alkyl
halides, such as methyl iodide and ethyl bromide or ethyl iodide, on acri-
dine derivatives (compare Graebe and Caro, Liebig's Annalen 158 page 265;

page_text: are dissolved with aid of heat in 20 parts of nitrobenzene and to the boiling
solution 1 part of dimethyl sulphate is added. The new acridinium compound
separates immediately and quantitatively in pure form. The methosulphate of
acetamidotolunaphthomethylacridinium is very easily soluble in
water with
yellow colour.
For acetamidotolunaphthacridine can be substituted in the preceding example
the acridine derivatives or their acetyl-products described in Specification
No. 16474 of 1898.
EXAMPLE 4.
The acetyl derivatives of diamido-acridines can likewise be easily converted
into the corresponding acridinium bases by means of dimethyl sulphate.
For instance 1 part of diacetyldiamidoditoluacridine (obtained by the action
of acetic anhydride and sodium acetate on acridine yellow, (Specification
No. 17971 of 1889) is dissolved with aid of heat in 20 parts of nitrobenzene and
to the solution is added 0'6 part of dimethylsulphate. The solution assumes a
brown colour and after a few moments solidifies to a thick yellow crystalline
paste. After refrigeration the mass is diluted with ligroin, filtered and dried.
Diacetyldiamidoditolumethylacridinium-methosulphate which is thus obtained
with quantitative yield, forms yellow-brown needles, dissolving easily in water
and less rapidly in alcohol to a yellow coloured solution. The aqueous solution
has an intensely bitter taste. It is not altered by addition of ammonia, turns
slightly darker on addition of sodium carbonate, while on addition of caustic
soda it becomes feebly red and after standing for some time, turbid. The dye-
stuff dyes tannin-mordanted cotton dull yellow tints.
dis-
The hydrolysis of the diacetyl-compound may be performed as follows:
10 parts of diacetyldiamidoditolumethylacridinium-methosulphate are
solved in 100 parts of hot water; to the solution 20 parts of hydrochloric acid
(containing 40 per cent. of acid) are added and the mixture is boiled for some
time in a vessel connected with a reflux-condenser. On refrigeration the product
of the hydrolysis separates in the form of red crystals. It is very easily soluble
in water to an orange red coloured solution having a strong green fluorescence;
the solution is not altered by ammonia or sodium carbonate, by which reaction
the new product is at once distinguished from acridine yellow and phosphine.
On addition of soda lye it turns somewhat darker and after standing for some
time becomes turbid. This dyestuff dyes tannin-mordanted cotton very clear
yellow tints with orange shade, while on unmordanted cotton yellow tints are
produced.
EXAMPLE 5.
By substituting in the preceding example for acridine-yellow the benzoflavine
of Specification No. 9614 of 1888 there is obtained the methosulphate of diacetyl-
diamidodimethylphenylmethylacridinium in the form of a red oily precipitate.
In order to purify this it is dissolved in water. By addition of some ammonia
traces of unalkylised substance are precipitated and these are separated by filtra-
tion. From the filtrate the new colouring matter is precipitated in the form of
the nitrate by addition of nitric acid and some nitre. The new dyestuff is easily
soluble in water to a yellow solution which is not altered by addition of alkalies.
The dyestuff produces on tannin-mordanted cotton dull orange yellow tints.
By hydrolysing the aforesaid diacetyl compound there is obtained the hydro-
chloride of diamidodimethylphenylmethylacridinium chloride, which separates
in the form of red crystals. This product is little soluble in cold water readily
soluble in warm water to a yellow solution having a green fluorescence. The
aqueous solution gelatinises on cooling. The warm diluted aqueous solution is
not altered by addition of alkalies by which reaction the new dyestuff is dis-
tinguished from benzoflavine and phosphine. The dyestuff produces tints which
resemble those obtained with the product described in Example 4.

page_text: EXAMPLE U.
Phosphine (chrysaniline) can also, after being previously transformed into the
acetyl-compound, be converted into an acridinium derivative by means of dime-
thyl sulphate. The diacetyl-compound thus obtained dyes tannin-mordanted
cotton dull orange-yellow tints. The aqueous solution of the dyestuff is not
altered on addition of alkalies. The free diamido-compound, obtained by hydro-
lysis, produces on tannin-mordanted cotton flesh coloured red tints. By addition
of concentrated soda lye the red acridinium base is precipitated.
Instead of starting from the acetyl-products of amido- or diamido-acridines,
as in the preceding exampes the free amido- or diamido-acridines may be used
as parent material: for the dimethyl sulphate does not react, under the condi-
tions chosen, with the amido-groups. The reaction in this case is carried out in
exactly the same manner as described in the preceding examples.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed, I declare that what
I claim is:-
1. The herein described manufacture of acridinium-derivatives by acting with
dimethyl sulphate on acridines or amido-acridines or the acetyl-compounds of
the latter.
2. The acridinium-derivatives manufactured as above set forth.
3. The herein described process for converting the acetyl-amido-compounds
referred to in Claims 1 and 2 into the corresponding amido compounds by hydro-
lysis.
4. The amido-acridinium-derivatives manufactured as above set forth.