The Manufacture and Production of Asymmetric Diamidophenyl- acridines and their Alkyl Substitution Products.
Year: 1897

page_text: Date of Application, 19th June, 1897
Complete Specification Left, 7th Apr., 1898--Accepted, 7th May, 1898
PROVISIONAL SPECIFICATION:
The Manufacture and Production of Asymmetric Diamidophenyl-
acridines and their Alkyl Substitution Products.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Gentleman, do hereby declare the nature of this invention, (which has been com-
municated to me by The Badische Anilin & Soda Fabrik, of Ludwigshafen-on-
Rhine, in the Empire of Germany), to be as follows:-
This invention is based upon the discovery that the phosphines and their alkyl
substitution products, (substitution in the amido group), which latter have not been
previously known, can be obtained by condensing para-amido benzaldehyd, or its
substitution products, with the alphyl derivatives of the meta-toluylene-diamine.
In this process the colouring matters are directly obtained and contrary to expecta-
tion no leuco derivatives, which would have to be transformed into the colouring
matters by subsequent oxydation.
The following example will serve to further illustrate the nature of the invention.
In this example the application of the invention to a typical case is described but in
all cases the process can be varied in many respects. The parts are by weight.
of
Thoroughly mix three parts of dimethyl-para-amido benzaldehyd and five parts
phenyl-meta-toluylene-diamine-chlorhydrate in an enamelled vessel, stir and heat
at one hundred and forty, to one hundred and fifty, degrees Centigrade, until the
mass, which at the beginning is a thin liquid, has become tough and a test-portion
solidifies at once to a brittle mass.
Cool and break up the dark-brown melt, extract it with about two thousand parts
of hot water containing twenty-five parts of hydrochloric acid (of specific
weight 1.15) cool, filter off the solution and add a very little saltpetre to precipitate
resinous impurities. Filter off the solution from these impurities and then salt out
the colouring matter with saltpetre whilst cooling with ice. The new dyestuff so
obtained is a yellowish-red precipitate; filter, press and dry at a temperature
of thirty, to forty, degrees Centigrade. This dyestuff dissolves (difficultly in cold
water but easily in hot water) with a yellowish-red colour and separates from the
hot solution in long orange-coloured needles.
1007
The Manufacture and Production of Asymmetric Diamidophenyl-
acridines and their Alkyl Substitution Products.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Gentleman, do hereby declare the nature of this invention (which has been com-
Price 8d.

page_text: municated to me from abroad by The Badische Anilin & Soda Fabrik of Ludwig-
shafen-on-Rhein, in the Empire of Germany) and in what manner the same is to be
performed to be particularly described and: ascertained in and by the following
statement:
-
The colouring matter which has for many years been known in commerce as
phosphine is usually a mixture, it is regarded chemically as consisting mainly of
an asymmetric diamido phenyl-acridine, containing frequently admixed homologous
bodies. In its practical application it is specifically a leather dye; for over twenty-
five years it has been the most important yellow dye for leather.
The present invention relates to the manufacture of similar and analogous dyes
also suited for the same practical application being especially suited for dyeing
leather in various' shades of yellow. Some of these products are chemically
phosphines, which may be identical with some of the constituents of the original
phosphine obtained from fuchsine residues, others appear from their method of
formation and chemical behaviour to be new alkyl- substitution products thereof
(substituted in the amido-group): ""
יח
10
.
..:
***
The manufacture of these phosphine-like bodies is effected according to the
present invention by condensing para-amido-benzaldehyd or its substitution pro-
ducts (substituted in the amido-group) with the alphyl derivatives of meta-toluylene-
diamine.
The following examples will serve to illustrate the manner in which this invention
can best be carried into practical effect.
"
"
EXAMPLE 1.
Thoroughly mix three parts of dimethyl-para-amido-benzaldehyd and five parts
of phenyl-meta-toluylene-diamine-chlorhydrate in an enamelled vessel, stir and
heat at one hundred and forty to one hundred and fifty degrees Centigrade, until the
mass, which at the beginning is a thin liquid has become tough and a test portion
when cold solidifies at once to a brittle mass.i.
164
Cool and break up the dark-brown melt, extract it with about two thousand parts
of hot water containing twenty-five parts of hydrochloric acid (containing about
thirty per cent. H Cl) cool filter off the solution, and add a very little saltpetre.. A.
resinous precipitate of impurity or bye-product separates. Filter off the solution
from this precipitate and then salt, the colouring matter out with saltpetre whilst
further cooling: with ice. The new dyestuff so obtained is a yellowish-red precipi-
tate; filter, press and dry at a temperature of thirty to, forty degrees Centigrade.
This dyestuff dissolves difficultly in cold water but easily in hot water with a
yellowish-red colour and, when pure, separates from the hot solution in long
orange-coloured needles.
The new product so obtained contains as its principal ingredient a body which
may be regarded chemically as a dimethyl-substitution product of an asymmetric
diamido-methyl-phenyl-acridine. It is admirably suited for dyeing leather in
reddish-yellow shades in a manner similar to the phosphine hitherto in commerce.
EXAMPLE 2.
Mix, thoroughly three parts of dimethyl-para-amido-benzaldehyd and five parts
of phenyl-meta-toluylene-diamine-chlorhydrate. Heat in an enamelled vessel in
an oil-bath and maintain the temperature of the mass at about one hundred and
fifty degrees Centigrade for about half an hour. The melt becomes tough and after
cooling brittle as described in the foregoing example. Powder the melt and work
up by dissolving in ten parts of boiling alcohol, dilute the solution with about three
parts of water. Allow to stand in a cold place for about twenty four hours.
crystalline precipitate separates out. For further purification re-dissolve in water
filter and re-precipitate by salt or saltpetre. Filter press and dry.
A
The new product so obtained is regarded as a dimethyl-substitution product of
asymmetric diamido-methyl-phenyl-acridine in a fairly pure condition.

page_text: EXAMPLE 3.
Mix together about forty five parts of para-amido-benzaldehyd and ninety parts of
phenyl-meta-teluylene-diamine hydrochlorate, and heat the mixture with the aid of
an oil bath. Maintain the temperature of the melt whilst stirring for about one
hour at one hundred and sixty to one hundred and sixty five degrees Centigrade.
The melt finally becomes reddish-brown and tough. Allow to cool, powder the melt,
extract it by boiling for a short time with five hundred parts of alcohol and filter.
The residue can be further worked up into a better commercial form as follows:-
Dissolve it in about one thousand parts of boiling water containing about forty five
parts of hydrochloric acid-(containing about-thirty per cent.-real-H Cl) wash the
residue with about two hundred parts of water and to the united liquors add about
Cool the
two hundred parts of a cold saturated solution of sodium nitrate.
mixture in ice water and collect by filtration the colouring matter which separates
This product is the nitrate of a diamido-methyl-phenyl-acridine and is
probably identical or isomeric with one of the constituents of the phosphine of
commerce; it dyes leather very evenly and in very clear yellow shades.
out.
The same products as those obtained in the foregoing Example 3 result also if
the condensation be effected in the presence of alcohol as is illustrated in Example 4.
EXAMPLE 4.
Mix together about one hundred and twenty one parts of para-amido-benzaldehyd
and about two hundred and fifty parts of phenyl-meta-toluylene-diamine hydro-
chlorate with about seven hundred and fifty parts of alcohol; boil the mixture for
about four or five hours in a vessel furnished with an inverted condenser, distil off
about one third of the alcohol and allow the mixture then to stand for about two
days. A crystalline precipitate separates out and is filtered off.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed I declare that what I claim
is:-
1. The manufacture of colouring-matters by the condensation of para-amido-
benzaldehyd or its substitution products substituted in the amido-group with the
alphyl derivatives of meta-toluylene-diamine substantially as hereinbefore described.
2. The manufacture of colouring-matter from dimethyl-para-amido-benzaldehyd
and phenyl-meta-toluylene-diamine substantially as hereinbefore described in the
Examples 1 and 2.
3. The manufacture of colouring-matter from para-amido-benzaldehyd and
the manner described in
phenyl-meta-toluylene-diamine substantially in
Examples and 4.
4. As new articles of manufacture the colouring matters herein before defined as
new and such as can be obtained substantially as hereinbefore described.
Lay of Anil 1898
JOHNSONS & WILLCOX.
47, Lincoln's Inn Fields, London, W.C., Agents.
JOHNSONS & WILLCOX.
47, Lincoln's Inn Fields, London, W.C., Agents.