The Manufacture and Production of New Basic Dyestuffs.
Year: 1892

page_text: Date of Application, 20th May, 1892
Complete Specification Left, 18th Feb., 1893-Accepted, 1st Apr., 1893
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Basic Dyestuffs.
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:-
My foreign correspondents have discovered that a new basic rhodamine dye can
be obtained by treating symmetrical di-ethyl-rhodamine, of the phthalic acid series,
in a manner such as to cause a further combination thereof with ethyl. This dye
can be used for dyeing silk and wool but appears to be best suited for dyeing
vegetable fibre when mordanted with tannin. To such material it imparts red
shades of colour, which cannot be equalled in beauty and fastness, by the use of
any known dye.
The invention can be applied to other di-alkyl-rhodamines which yield analogous
results and, in every case, instead of causing a further combination with ethyl,
any other alkyl group may be introduced whether mono- or poly-valent.
Having stated the nature of the invention I will further illustrate it by giving the
following examples but I premise that these can be varied considerably in their
details and that they are merely typical, illustrating the application of the invention
to particular cases. The parts are by weight.
EXAMPLE 1.
Dissolve about one part of symmetrical di-ethyl-rhodamine in about five parts of
ethyl- or methyl-alcohol and pass a current of dry hydrochloric acid gas through
the solution till it is saturated. The formation of the new dye will take place in
the cold but practically it is best to heat the mixture. For this purpose fit the
containing vessel with an inverted or reflux condenser and heat on the water-bath.
Continue to pass the hydrochloric acid gas slowly through the boiling solution.
Continue this treatment until no further conversion of the di-ethyl-rhodamine into
the new dye takes place. This usually is the case in about five hours.
To isolate the new dye distil off the alcohol and hydrochloric acid on the water
bath. Dissolve the residue in hot water and filter the hot solution if it be not clear.
On cooling the new dye separates out in the crystalline form. Its more complete
separation can be obtained by adding a little hydrochloric acid. Filter press, and
dry, at a low temperature.
EXAMPLE 2.

page_text: parts of ethyl- or methyl-alcohol in an autoclave for about ten hours at a temperature
of about one hundred and fifty degrees Centigrade. Work up as described in
Example 1.
EXAMPLE 3.
Heat about forty parts of diethylrhodamine base with about two hundred
parts of methyl or ethyl alcohol and about fifty parts of methyl or ethyl
autoclave which is heated
chloride. The operation is conducted in an
in a boiling saturated salt solution. Continue heating for about eight hours.
Distil with steam, filter the aqueous solution of the residue while hot, unchanged
di-ethyl-rhodamine base remains on the filter. On cooling the new dye separates
out in the crystalline form. A more complete separation can be obtained by adding
hydrochloric acid, and, if necessary common salt. Filter, press, and dry, at a low
temperature.
In all the above examples other dialkyl-rhodamines can be substituted for the
di-ethyl rhodamine; and instead of the ethyl and methol compounds mentioned
analogous compounds can be used. In the first example other acids can be used in
a manner analogous to the hydrochloric acid and in the second example other salts
In both cases other
than the hydrochlorate of diethyl-rhodamine can be used.
alcohols such as amyl-alcohol, or glycerol, can be employed instead of methyl and
ethyl alcohol. In the third example other halogen compounds of methyl and ethyl
can be used, and also analogous halogen compounds such as amyl benzyl-methylene
ethylene-chlorides and the like.
The compounds thus obtained resemble one another closely in properties. They
differ from the initial material in possessing increased colouring power and affinity
for fibre, and are also more soluble in water. On treating the new dyes with caustic
alkalies the dialkyl rhodamine appears to be regenerated.
Dated this 20th day of Day To
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
The Manufacture and Production of New Basic Dyestuffs. .
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:―
"
My foreign correspondents have discovered that a new basic rhodamine dye
can be obtained by treating symmetrical di-ethyl rhodamine of the phthalic acid
series in a manner such as to cause a further combination thereof with ethyl. This
dye (which may be called di-ethyl-rhodamine-ethyl-ester") can be used for
dyeing silk and wool but appears to be best suited for dyeing vegetable fibre when
mordanted with tannin. To such material it imparts red shades of colour which
cannot be equalled in beauty and fastness, by the use of any hitherto known
dye.
The invention can be applied to other di-alkyl-rhodamines of the phthalic and
succinic acid series which yield analogous results and in every case instead of
causing a further combination with ethyl, so as to obtain an ethyl ester, other

page_text: Heat about forty parts of di-ethyl-rhodamine base with about two hundred parts
of methyl- or ethyl-alcohol and about fifty parts of methyl- or ethyl-chloride. The
operation is conducted in an autoclave which is heated in a boiling saturated salt
solution. Continue heating for about eight hours. Distil with steam, filter the
aqueous solution of the residue while hot. Unchanged di-ethyl-rhodamine base
remains on the filter. On cooling the new dye separates out from the solution in
the crystalline form. A more complete separation can be obtained by adding
hydrochloric acid and if necessary common salt. Filter, press and dry at a low
temperature.
In both the above examples other di-alkyl-rhodamines can be substituted for
the di-ethyl rhodamine; and instead of the ethyl- and methyl compounds mentioned
analogous compounds can be used. In the first example other equivalent acids
such as sulphuric acid can be used in a manner analogous to the hydrochloric acid
and other alcohols such as amyl-alcohol or glycerol can be employed instead of
methyl- and ethylalcohol. In the second example other halogen compounds of
methyl- and ethyl can be used, and also anologous halogen compounds, such
as amyl-, benzyl-, methylene, and ethylene-chlorides iodides and the like.
The various compounds or esters thus obtained from any di-alkyl-rhodamine
resemble one another closely in properties. They differ from the initial material
in possessing increased colouring power and affinity for fibre, and are also more
soluble in water. On treating the new dyes with caustic alkalies the dialkyl-
rhodamine appears to be regenerated.
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 new basic dyestuffs by treating dialkyl rhodamines of the
phthalic or succinic acid series so as to cause a further combination with alkyl
substantially as hereinbefore described.
2. The manufacture of a new basic dyestuff by treating a dialkyl-rhodamine of
the phthalic acid series in an alcoholic solution with hydro-chloric acid gas
substantially as herein before described under Example 1.

page_text: 3. The manufacture of a new basic dyestuff by heating a dialkylrhodamine of
the phthalic acid series in the form of free base in alcoholic solution with
an alkyl-halogen compound substantially as hereinbefore described under
Example 2.
4. As a new product the new basic dyestuff hereinbefore described, being di-
ethyl-rhodamine-alkyl-esters such for example as can be obtained by treating
di-ethyl-rhodamine so as to cause a further combination with alkyl in particular
with ethyl or methyl.