The Manufacture and Production of New Basic Colouring Matters.
Year: 1893

page_text: Date of Application, 19th July, 1893
Complete Specification Left, 16th Apr., 1894-Accepted, 19th May, 1894
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Basic Colouring Matters.
I, JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of
Middlesex Gentleman do hereby declare the nature of this invention which has
been communicated to me from abroad by The Badische Anilin and Soda Fabrik
of Ludwigshafen-on-Rhine in the Empire of Germany to be as follows:-
It is known that if fluorescein be suitably treated with ammonia a compound is
obtained containing amido-groups and an imido-group instead of the hydroxyl
groups and oxygen of the fluorescein. To this body the formula C2H₁, NO, and
the constitution represented by the formula.
20
has been attributed (see R. Meyer and Oppelt Berichte der deutschen chemischen
Gesellschaft 21, 3376). This body is hereinafter referred to as the "initial
material."
Up to the present invention it had not been usefully applied in any way. Now
my foreign correspondents have converted it into new yellow or orange dyes of
great beauty which constitute an important manufacture.
The said new dyes are obtained by submitting the initial material above defined
to esterifying processes that is to processes such as convert carboxylic acids into
their esters. Such esterifying processes are for instance :-
(1) Treating with an alcohol and hydrochloric or sulphuric acid and the like at
or about the temperature of the boiling water bath.
(2) Treating carefully with an alkylhalogen compound.
In these processes instead of the said initial material, analogues thereof may be
used such for instance as derivatives alkylated in one or both the amido groups.
One of these is described in the Specification of the German Patent No. 49850
(Friedländer Fortschritte der Theerfarben-fabrikation 2, 110); it is tetra-
alkylated and has received the name Flaveosine.
The new dyes appear as esters of the initial materials; they correspond to the
empiric formula C2H,R.NO, (Alk) and appear to have the constitution
represented by the formula:

page_text: has the composition C2, HN,O,(C₂H₂) and appears to be chemically diamido-
phenyl-acridin-carboxyethyl-ester.
The following description of a method of carrying out the invention will serve
as an example to further illustrate its nature without confining the invention to
this method.
Mix one part of the purified initial material C₂H₁NO₂ with ten times its weight
of ethyl-alcohol (containing about 96 per cent. C₂HÖH) heat the mixture on the
waterbath in a vessel fitted with a reflux condenser and pass in a stream of hydro-
chloric acid gas.
A solution of the hydrochlorate is soon obtained. Regulate the
heat so that the mixture boils slowly and pass hydrochloric acid gas in continuously
until no further production of the desired new dye takes place. This can be
ascertained by working up test portions of the mixture in the manner hereinafter
described for the whole product. Distil off the hydrochloric acid and alcohol on
the water bath and dissolve the residue in boiling water. Filter and precipitate
the dye with common salt. Collect and purify by redissolving in hot water and
filtering; then reprecipitate with common salt and collect on the filter. By
redissolving in hot water any initial material present becomes converted into the
base insoluble in water and is so eliminated. Repeat this purification if necessary.
Press and dry the purified dye.
In
The dye so obtained is an orange colored powder soluble in water and in alcohol
giving reddish yellow solutions possessing a strong yellow-green fluorescence.
its dyeing properties it resembles chrysaniline (phosphine) and can in many cases
be advantageously used instead of that dye.
Instead of using a vessel fitted with a reflux condenser in the production of the
new dye, as hereinbefore mentioned, closed vessels may be used and the esterifi-
cation be effected under pressure. Further the production of the new dye can be
effected by treatinent of the initial material in alcoholic solution with an alkyl
halogen compound. Again in the above example sulphuric acid and other mineral
acids acting similarly to hydrochloric acid can be used instead of that acid. Thus
for instance heat a mixture of one part (by weight) of the initial material, four
parts ethyl-alcohol and two parts of concentrated sulphuric acid for about eight to
twelve hours on the boiling water-bath in a vessel provided with an inverted
condenser. Work up the product in the way herein before described.
If the alkylating action be rendered more energetic, redder products are
obtained; this is especially the case when using alkyl-halogen compounds.
Instead of ethyl alcohol other alcohols such as methyl and amyl alcohol,
glycerine and the like can be used and the halogen alkyl compounds derived from
ethyl, methyl, ethylene, benzyl and the like can also be used.
Dated this 19th day of July 1893.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of New Basic Colouring Matters.
I, JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of
Middlesex Gentleman do hereby declare the nature of this invention (which has
been communicated to me from abroad by The Badische Anilin and Soda Fabrik
of Ludwigshafen on Rhine 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 :-
It is known that if fluoresceïn be suitably treated with ammonia a compound is
obtained containing amido groups and an imido group instead of the hydroxyl

page_text: 20
groups and oxygen of the fluorescein. To this body the formula C, H₁, N, O, and
the constitution represented by the formula.
has been attributed (see R. Meyer and Oppelt, Berichte der deutschen chemischen
Gesellschaft 21, 3376). This body is hereinafter referred to as the "initial
material."
Up to the present invention it had not been usefully applied in any way. My
foreign correspondents have converted it into new yellow, or orange, dyes of great
beauty which constitute an important manufacture.
The said new dyes are obtained by submitting the initial material above defined,
either in the crude form or after purification, to esterifying processes that is to
processes such as convert carboxylic acids into their esters.
Such esterifying processes are for instance :-(1.) Treating with an alcohol and
hydrochloric or sulphuric acid and the like at, or about, the temperature of the
boiling water bath; (2.) Treating carefully with an alkyl-halogen compound.
In these processes the initial material may be used in the crude form, as
obtained by treatment of fluorescein with ammonia, without any special purification,
or after purification with alcohol, or, if it be desired to obtain pure yellow shades
resembling auramine, it can be purified by conversion into its crystalline hydro-
chloric acid salt by treatment with alcoholic hydrochloric acid. Further, instead
of the said initial material, analogues thereof may be be used such, for instance, as
derivatives alkylated in one, or both, the amido-groups. One of these is described
in the German Patent No. 49850 (Friedländer, Fortschritte der Theerfarben-
fabrikation 2, 110); it is tetra-alkylated and has received the name "Flaveosine."
The new dyes appear to be esters of the initial materials; they correspond to
the empiric formula CH₁RN3O2 (Alk) and appear to have the constitution
represented by the formula:-
where R stands for either alkyl, or hydrogen, and Alk for alkyl. Thus the dye
obtained from the aforesaid initial material by esterification with ordinary alcohol
has the composition C₂HNO,(C,H,) and appears to be, chemically, diamido-
phenyl-acridin-carboxy-ethyl-ester.
20 14
The following examples will serve to illustrate the nature of the invention, and
means by which it can be carried into practical effect but the invention is not
confined to the particular methods described in these examples. The parts are by
weight.
20
2
Example 1. Mix one part of the crude, or purified initial material, C₂H1. N₂O
with ten times its weight of ethyl-alcohol (containing about ninety six per cent.
CH,OH); heat the mixture on the waterbath, in a vessel fitted with a reflux
condenser, and pass in a stream of hydrochloric acid gas. A solution of the
hydrochlorate is soon obtained. Regulate the heat so that the mixture boils
slowly and pass in continuously a slight stream of hydrochloric acid gas until no
further production of the desired new dye takes place. This can be ascertained

page_text: by working up test portions of the mixture in the manner hereinafter described
for the whole product. Distil off the hydrochloric acid and alcohol on the water-
bath and dissolve the residue in boiling water. Filter, and precipitate the dye
with common salt. Collect, and purify by redissolving in hot water and filtering;
then reprecipitate with common salt and collect on the filter. By redissolving in
hot water, any initial material present becomes converted into the base insoluble in
water and is so eliminated. Repeat this purification if necessary. Press and dry
the purified dye.
The dye so obtained is an orange-coloured powder soluble in water, and in
alcohol, giving reddish yellow solutions possessing a strong yellow-green fluoresence.
In its dyeing properties it resembles chrysaniline (phosphine) and can, in many
cases, be advantageously used instead of that dye.
Instead of using a vessel fitted with a reflux condenser, in the production of the
new dye, as herein before mentioned, closed vessels may be used and the esterification
may be effected under pressure. Further the production of the new dye can be
effected by treatment of the initial material in alcoholic solution with an alkyl
balogen compound. Again in the above example sulphuric acid and other mineral
acids acting similarily to hydrochloric acid can be used instead of that acid. Thus
for instance heat a mixture of one part initial material, four parts ethyl-alcohol and
two parts of concentrated sulphuric acid for about eight to twelve hours on the boiling
water-bath in a vessel provided with an inverted condenser. Work
up the product
in the way herein before described.
If the alkylating action be rendered more energetic, redder products are obtained;
this is especially the case when using alkyl-halogen compounds.
This is obviously due to an alkylation of the amido-groups taking place in
addition to the esterification of the carboxyl group and is illustrated in the following
example.
Example 2. Mix together about ten parts of the crystalline hydrochloric acid
salt of the initial material with about thirty parts of ethyl alcohol and about five
parts of ethyl chloride in an enamelled autoclave and heat the mixture under
pressure for about eight hours at a temperature of one hundred and fifty degrees
centigrade. Then heat the product of the reaction on the boiling water-bath and
so expel the volatile constituents. Dissolve the residue in hot water, filter hot and
precipitate the dye with common salt preferably after adding a little hydrochloric
acid.
The colouring matter so obtained dyes cotton mordanted with tannin giving
reddish-yellow shades. Dyes yielding different shades of yellow to orange result on
changing the duration of the reaction and temperature of treatment.
If desired the alkylating and esterifying processes which are accomplished in
one operation by working in the manner described in Example 2 can be effected
in two separate operations. Thus a product such as that obtained according to
Example 1 can be further treated with ethyl alcohol and an acid or with an
alkyl halogen compound, when it is converted into the more reddish-yellow colouring
matters.
In carrying out this invention instead of ethyl alcohol other alcohols such
as methyl and amyl alcohol, glycerine and the like can be used, and the halogen
alkyl compounds derived from ethyl, methyl, ethylene and the like can also be
applied.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed I declare that what I
claim is :-
1. The manufacture of new basic colouring matters by submitting the initial
material herein before defined or its analogues to an esterifying process.
2. The manufacture of new basic colouring matters by treating the initial material
hereinbefore defined or its analogues with an alcohol and acid substantially as
hereinbefore described.

page_text: 3. The manufacture of new basic colouring-matters by treating the initial material
hereinbefore defined or its analogues with an alkyl-halogen compound substantially
as hereinbefore described.
4. The manufacture of a new basic colouring-matter by treating the initial
material herein before defined with ethyl alcohol and hydrochloric or sulphuric acid
in the manner described in the foregoing Example 1.
5. The manufacture of a new basic colouring matter by treating the initial
material hereinbefore defined with ethyl-chloride in the manner described in the
foregoing Example 2.
6. As new articles of manufacture the new basic colouring-matters such as can be
obtained substantially as hereinbefore described.
Dated this 16th day of April 1894.
JOHNSONS & WILLCOX.