The Production of Sulphonated Thionines and Dyestuff's therefrom.
Year: 1890

page_text: Date of Application, 24th Nov., 1890
Complete Specification Left, 21st Aug., 1891—Accepted, 26th Sept., 1891 ·
PROVISIONAL SPECIFICATION.
The Production of Sulphonated Thionines and Dyestuff's therefrom.
1, SYDNEY PITT of Sutton in the County of Surrey, Gentleman, (a communi-
cation to me from abroad by Leopold Cassella & Co. of Frankfort-on-Main in
the Empire of Germany Chemists) do hereby declare the nature of this invention
to be as follows:-
This invention has for its object the production of sulphonated thionines and
dyestuff's therefrom.
i
My application dated March 4th 1890 No. 4596 describes the methyle- and
ethyle sulpho benzyle p. phenylene-diamine-thiosulphonic acids, the oxidation of
these acids in presence of basic bodies of the series of benzene and the transforma-
tion of the indamines thus formed into sulphonated thionines.
By condensation of these acids with certain products derived from napltalene a
series of new dyestuff's have now been obtained; in further explanation of which
invention I will describe examples as follows:
Example 1. A solution of 42 kilos sulphobenzyle-ethyle p., phenylenethio-
sulphonic acid is added to a solution of 18 kilos of a naphtylamine chlorhydrate. To
this a solution of 30 kilos bichromate of potash and 100 kilos of a concentrated
solution of chloride of zinc are added. Indamine of a dark green color separates.
By heating the solution for 1 hour at about 100° C. the corresponding thionine in
the shape of its insoluble chromic lake is obtained. The dyestuff is extracted
either by means of carbonate of soda or by acids. Difficultly soluble in water, it
yields by sulphuration dyestuffs which dye wool a deep blue.
The alkylated derivatives of a naphtylamine (methylenenaphtylamine and the
like) react in the same manner.
Example 2. Of the naphtylaminesulphonic acids the one described in the
German Patent application C3171 (called acid 1. 2.) in particular, yields a product
of remarkable intensity and fastness.
The aqueous solution containing 42 kilos of sulphobenzyle-ethyle p. phenylene-
diamine-thiosulphonic acid and 25.5 kilos of the sodium salt of a naphtylamine-
sulphonic acid 1. 2. is mixed with a solution of 30 kilos bichromate of potash.
After having added 100 kilos of a concentrated solution of chloride of zinc, heat to
the boil.
The dyestuff is easily soluble and dyes wool a very pure blue.
Example 3. The result of oxidation of sulphobenzyle-ethyle p. phenylene-.
diamine-sulphonic acid in presence of one molecule of a naphtol in a diluted solution
is a blue soluble indamine which, if heated to 100° C. is transformed into a dyestuff
difficultly soluble.
Example 4.
a
oxynaphtoëic acid combines in the same manner with sulpho-
benzyle-ethyle p. phenylene-diamine-thiosulphonic acid. The dyestuff is obtained
in the shape of a chromic lake.
Example 5. If instead of naphtol, a naphtol-sulphonic acid (1. 2.) is used, a
more soluble dyestuff is obtained, dyeing wool a reddish blue.
Dated this 24th day of November 1890.

page_text: COMPLETE SPECIFICATION..
The Production of Sulphonated Thionines and Dyestuffs therefrom.
I SYDNEY PITT of Sutton in the County of Surrey, Gentleman, (a communi-
cation to me from abroad by Leopold Cassella & Co. of Frankfort-on-Main
in the Empire of Germany Chemists) 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 has for its object the production of sulphonated thionines.
My application dated March 4th 1890, No. 4596, describes the .methyle- and
ethyle-sulphobenzyle p. phenylene-diamine-thiosulphonic acids, the oxydation of
these acids in presence of basic bodies of the series of benzene and the transforma-
tion of the indamines thus formed into sulphonated thionines.
By condensation of these acids with certain products derived from naphtalene, a
series of new dyestuffs has now been obtained, in further explanation of which
invention I shall describe examples as follows:-
Example 1. A solution of 42 kilos sulphobenzyle-ethyle p. phenylene-diamine-
thiosulphonic acid is added to a solution of 18 kilos of a naphtylamine chlorhydrate.
To this a solution of 30 kilos bichromate of potash and 100 kilos of a concentrated
solution of chloride of zinc are added. Indamine of a dark green color separates.
By heating the solution for one hour at about 100° C. the corresponding thionine in
the shape of its insoluble chromic lake is obtained. The dyestuff is extracted
either by means of carbonate of soda or by acids. Difficultly soluble in water, it
yields by sulphuration dyestuff's which dye wool a deep blue.
The alkylated derivatives of a naphtylamine (methylenaphtylamine and the like)
react in the same manner.
Example II. The 1. 2 naphtylaminesulphonic acid (which is obtained by heating
the salts of naphtionic acid) is the most important of the isomeric naphtylamine-
sulphonic acids for the purpose of our process.
The aqueous solution containing 42 kilos of sulphobenzyle-ethyle p-phenylene-
diaminethiosulphonic acid and 255 kilos of the sodium salt of a naphtylamine-
sulphonic acid 1. 2, is mixed with a solution of 30 kilos bichromate of potash. After
having added 100 kilos of a concentrated solution of chloride of zinc, heat to the boil.
The dyestuff is easily soluble and dyes wool a very pure blue.
Example 3. The result of oxydation of sulphobenzyle-ethyle p-phenylene-
diamine-thiosulphonic acid in presence of one molecule of a naphthol in a diluted
solution is a blue soluble indamine which, if heated to 100° C. is transformed into a
dyestuff difficultly soluble.
Example 4.-a oxynaphtoic acid combines in the same manner with sulpho
benzyle-ethyle p-phenylene-diamine-thiosulphonic acid. The dyestuff is obtained
in the shape of a chromic lake.
Example 5. If instead of naphthol a naphthol-sulphonic acid (1. 2) is used, a
more soluble dyestuff is obtained dyeing wool a reddish blue.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed, I declare that what I
claim is
a
1. The process of producing coloring matters by oxydizing ethyle- or methyle-
sulphobenzyle-p-phenylenediaminethiosulphonic acid together with one of the
following substances: a naphtylamine-methyle naphtylamine, naphtylamine-sul-
phonic acid 1. 2, a naphthol, a oxynaphtoic acid, a naphtholsulphonic acid 1. 2 and
transforming the products thus obtained into the corresponding thionines.
2. The new coloring matters produced as hereinbefore described.
CARPMAEL & Co.,
Agents for the Applicant.