Improvements in and relating to the Manufacture of Coloring Matters.
Year: 1896

page_text: Date of Application, 24th Sept., 1896
Complete Specification Left, 24th June, 1897-Accepted, 7th Aug., 1897
PROVISIONAL SPECIFICATION.
Improvements in and relating to the Manufacture of Coloring
Matters.
::
A communication from abroad by LA SOCIÉTÉ CHIMIQUE DES USINES DU RHÔNE,
anciennement, GILLIARD P. MONNET ET CARTIER, of Lyons, France, Manufacturers.
I, GEORGE BELOE ELLIS of the firm of J. C. Mewburn and Ellis of 55 and
56 Chancery Lane, in the County of London, Chartered Patent Agents do hereby
declare the nature of this invention to be as follows:-
This invention relates to a new and improved means of inanufacturing alkyl
derivatives of the class of dyestuffs known as "rhodamines," and to new compounds
produced by the same.
The discovery made by P. Monnet (Bulletin de la Société Chimique de Paris 1892,
page 253) of a new class of alkylated derivatives of the "rhodamines," which alkylated
rhodamines are known under the generic term of "anisolines," was not only of great
theoretical importance in largely modifying the ideas which obtained at the time as
to the constitution of the phtaleines generally, but also led up to an extensive series
of researches on these compounds.
Nevertheless, the chemical constitution of the "anisolines" is still an unsettled
question, and in the effort to throw fresh light upon this point my correspondents
have now discovered a novel method of introducing alkyl into rhodamines resulting in
the production of dyes of bluer shade. This method may be applied generally to all
rhodamines, whether di-alkylated or tetra-alkylated, derivates of phtalic, succinic, or
of other dibasic acids, etc., for the purpose of introducing alkyl. Some of the
products thus obtained appear to be identical with the anisolines.
It has been discovered that by the action of chlorides of phosphorus, a rhodamine
may be converted into an acid chloride. The latter hody, in accordance with the
general reaction expressed by the equation
R COCI ROH = HCl + R-COOR,
may react with alcohols, either monovalent or polyvalent resulting in the production
of the corresponding ether or ester.
In carrying out this invention the rhodamine salt or its base is preferably suspended
in oxychloride of phosphorus. One molecular equivalent of phosphorus pentachloride
may then be added, and the whole heated on a water bath. A lively reaction is
produced with disengagement of hydrochloric acid. When the energy of the reaction
has somewhat subsided the mass is boiled for some time under a reflux condenser,
and then the chlorides of phosphorus removed by distillation. A resinous mass with
brownish-red sheen remains, completely insoluble in water. This constitutes the
chloride of the rhodamine.
When cold, the resinous inass is powdered, suspended in absolute alcohol and boiled.
It is gradually dissolved with the formation of a coloring matter which possesses the
characteristics of an anisoline, On evaporation of the alcohol the product is left as a

page_text: crystalline mass which may be purified in the usual way by taking up in water,
addition of sufficient hydrochloric acid to form its salt, and precipitation with
salt.
Dated this 24th day of September 1896.
J. C. MEWBURN & ELLIS,
55 and 56 Chancery Lane, London, Chartered Patent Agents.
Improvements in and relating to the Manufacture of Coloring
Matters.
A communication from abroad by LA SOCIÉTÉ CHIMIQUE DES USINES DU RHÔNE,
anciennement GILLIARD, P. MONNET ET CARTIER, of Lyons, France, Manufacturers.
I, GEORGE BELOE ELLIS of the Firm of J. C. Mewburn and Ellis of 55 and 56
Chancery Lane in the County of London, Chartered Patent Agents, do hereby declare
the nature of this invention and in what manner the same is to be performed,
to be particularly described and ascertained in and by the following statement::
This invention relates to a new and improved means of manufacturing alkyl
derivatives of the class of dyestuffs known as "rhodamines," and to new compounds
produced. by the same.
The discovery made by P. Monnet (Bulletin de la Societe Chimique de Paris 1892;
page 253) of a new class of alkylated derivatives of the "rhodamines," which
alkylated rhodamines are known under the generic term of "anisolines," was not
only of great theoretical importance in largely modifying the ideas, which obtained at
the time as to the constitution of the phtaleines generally, but also led up to an
extensive series of researches on these compounds.
Nevertheless, the chemical constitution of the "anisolines" is still an unsettled
question, and in the effort to throw fresh light upon this point my correspondents
have now discovered a novel method of introducing alkyl into rhodamines resulting
in the production of dyes of bluer shade. This method may be applied generally to
all rhodamines, for example, di-alkylated or tetra-alkylated derivatives of phtalic,
succinic, or of other dibasic acids, etc., for the purpose of introducing alkyl.. Some
of the products thus obtained appear to be identical with the anisolines.
It has been discovered that by the action of chlorides of phosphorus, a rhodamine
may be converted into an acid chloride. The latter body, in accordance with the
general reaction expressed by the equation
R-COCI ROH = HCI + R-COOR
1
may react with alcohols, either monovalent or polyvalent resulting in the production
of the corresponding ether or ester.
In carrying out this invention the rhodamine salt or its base is preferably suspended
in. oxychloride of phosphorus, or it may be suspended or dissolved in chloroform,
bisulphide of carbon or in any other indifferent diluent or solvent. One molecular
equivalent of phosphorous pentachloride is then added, and the whole heated on; a
water bath. A lively reaction is produced with disengagement of hydrochloric acid.
When the energy of the reaction has somewhat subsided the mass is boiled for some
time under a reflux condenser, and then the chlorides of phosphorus removed by:
distillation. A resinous mass with brownish-red to greenish sheen remains,
completely insoluble in water. This constitutes the chloride of the rhodamine..
A purer product may be obtained if the operation is conducted in the cold with
constant stirring and the product precipitated by the addition of toluene.

page_text: When cold, the resinous mass is powdered, suspended in absolute alcohol, preferably
methyl or ethyl alcohol, and boiled. It is gradually dissolved with the formation of
a coloring matter which possesses the characteristics of an anisoline. On evaporation
of the alcohol the product is left as a crystalline mass which may he purified in the
usual way by taking up in water, addition of sufficient hydrochloric acid to form its
salt, and precipitation with salt.
Having now particularly described and ascertained the nature of the said
invention as communicated to me and in what manner the same is to be performed I
declare that what I claim is :-
1. The manufacture of coloring matters from the rhodamines whether alkylated or
not, of the phtalic or succinic or other dibasic series, by treatment in a state of
suspension or solution in indifferent diluents or solvents, such as phosphorus
oxychloride, chloroform or carbon bisulphide, with phosphorus pentachloride, and
boiling the separated product with alcohcl, preferably methyl or ethyl alcohol,
substantially as described.
2. As new products the chlorides of the rhodamines, substantially as described.
Dated this 24th day of June 1807
J. C. MEWBURN & ELLIS,
55 and 56 Chancery Lane, London, Chartered Patent Agents.