The Manufacture and Production of New Colouring-matters of the Naphthalene Series.
Year: 1899

page_text: Date of Application, 20th Oct., 1899
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Colouring-matters of the
Naphthalene Series.
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 from abroad by the Badische Anilin & Soda Fabrik of Ludwig-
shafen-on-Rhine, in the German Empire) to be as follows:-
In the Specification of Letters Patent 15708 of 1898, I have described the
manufacture of a new reduction product of the naphthazarine intermediate pro-
duct, and in the Specification of Letters Patent 15709 of 1898, I have described
the production of a colouring matter which is an oxidation product of the said
naphthazarine intermediate product. In the Specifications of German Patent
Applications B. 24633 and B. 24649 of the 24th and 26th April 1899 respectively
the reconversion of the said reduction and oxydation products into the naph-
thazarine intermediate product in a pure and crystalline condition is described.
The said reduction product is converted into the pure crystalline intermediate
product by oxydation with air in cold caustic soda solution and treatment of
the sodium salt so obtained with acetic acid. The said oxydation product can
be converted into the pure crystalline intermediate product by boiling it with
glacial acetic acid until the crystals which separate out, on cooling, dissolve in
concentrated sulphuric acid giving a brown solution.
The present invention relates to the manufacture of new green colouring-
matters from. the said intermediate product, preferably in this pure crystallised
form. The new green colouring-matters according to this invention are obtained
by treating the said intermediate product with an aromatic amine, with, or with-
out, the use of a condensing agent or solvent. The colouring-matters are first
obtained in the form insoluble in water, but can be readily sulphonated to soluble
sulphoacids. These sulphoacids dye unmordanted wool from the acid bath giving
beautiful green shades.
The following examples will serve to further illustrate the nature of the inven-
tion, but the invention is not confined to these examples:-
EXAMPLE 1.
Mix about ten parts of the naphthazarine intermediate product herein before
referred to with two hundred parts of glacial acetic acid and boil the mixture
until a complete solution is obtained. Then add slowly about twenty parts of
aniline, and heat the mixture at a temperature of 100° Centigrade, until
the solution which is at first blue-violet, turns to a beautiful blue-green.
Allow the melt to cool slowly, when the new colouring-matter usually separates
out in the form of long indigo-blue needles. Collect and dry. The colouring
matter so obtained is insoluble in water. To convert it into its sulphoacid mix
about ten parts of the dry colouring-matter thus obtained with about two hundred
parts of concentrated sulphuric acid (containing about 95 per cent. H₂SO). Heat
the mixture to a temperature of from 40°-50° Centigrade, and maintain it at

page_text: this temperature for about twelve hours. Then pour the reaction product into
water, and precipitate the sulpho acid formed by means of common salt and
collect. The product so obtained is a blue-black powder, readily soluble in water,
giving a brilliant blueish-green solution, in the presence of caustic soda and
sodium carbonate; the aqueous solution is green, and with concentrated sulphuric
acid the product dissolves forming a pure-blue solution.
EXAMPLE 2.
Mix together about ten parts of the naphthazarine intermediate product herein-
before referred to with about two hundred parts of glacial acetic acid and twenty
parts of paratoluidine. Boil the mixture until the solution (which is at first
blue-violet) becomes a beautiful blue-green colour. Allow the melt to cool slowly,
and collect the colouring-matter that separates out. The colouring matter, so
obtained, is insoluble in water; it can be readily sulphonated as follows:-
Add about ten parts of the product to about two hundred parts of fuming sul-
phuric acid (containing about 12 per cent. free SO). Keep the acid cold, that is,
below 5° Centigrade whilst adding the colouring matter. Allow the mixture
to stand for about an hour, and then pour the reaction mass into one thousand
parts of water, and precipitate the colouring matter by means of common salt.
The product thus obtained is a greenish powder, readily soluble in water the
colour being bright green.
EXAMPLE 3.
Dissolve about ten parts of the naphthazarine intermediate product herein-
before referred to in about one hundred parts of aniline and heat the mixture
to 100° Centigrade. Then add to the solution about forty parts of aniline
hydrochlorate. The solution which is at first blue-black turns green. In about
half an-hour the conversion is complete. Pour the reaction product into dilute
hydrochloric acid, filter and re-crystallise the precipitate from alcohol, or glacial
acetic acid. The colouring-matter so obtained has properties the same as those
of the insoluble product obtained according to Example 1.
In the foregoing examples the aniline, or para-toluidine, can be replaced by
other aromatic amines, such as for instance, ortho-toluidine para-phenylene-
diamine, benzidine, and the like, and similar products in each case be obtained.
Dated this 20th day of October 1899.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
The Manufacture and Production of New Colouring-matters of the
Naphthalene Series.
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 from abroad by the Badische Anilin & Soda Fabrik of Ludwig-
shafen on Rhine, in the German Empire) and in what manner the same is to be
performed, to be particularly described and ascertained in and by the following
statement:
In the Specification of Letters Patent 15708 of 1898, I have described the
manufacture of a new reduction product of the naphthazarine intermediate pro-
duct, and in the Specification of Letters Patent 15709 of 1898, I have described
the production of a colouring-matter which is an oxidation product of the said

page_text: naphthazarine intermediate product. In the Specifications of German Patents
108551 and 108552, of the 5th and 7th April, 1899, respectively, the conversion
of the said reduction and oxidation products into the naphthazarine intermediate
product in a pure and crystalline condition is described.
The said reduction product is converted into the pure crystalline intermediate
product by oxidation with air in cold caustic soda solution and treatment of
the sodium salt so obtained with acetic acid. The said oxidation product can
be converted into the pure crystalline intermediate product by boiling it with
glacial acetic acid until the crystals which separate out, on cooling, dissolve in
concentrated sulphuric acid giving a brown solution.
The present invention relates to the manufacture of new green colouring
matters from the said intermediate product, preferably in this pure crystallised
condition. The new green colouring matters according to this invention are
obtained by treating the said intermediate product with a primary aromatic
amine, or diamine, with, or without, the use of a condensing agent, or solvent.
The colouring matters are first obtained in the form insoluble in water, but can be
readily sulphonated to soluble sulphoacids. These sulphoacids dye unmordanted
wool, from the acid bath, beautiful green shades.
The following examples will serve to further illustrate the nature of the inven-
tion, and the manner in which it may be performed, but the invention is not con-
fined to these examples. The parts are by weight.
EXAMPLE 1.
Mix about ten parts of the naphthazarine intermediate product herein before
referred to with two hundred parts of glacial acetic acid and boil the mixture
until a complete solution is obtained. Then add slowly about twenty parts of
aniline, and heat the mixture at a temperature of one hundred degrees Centigrade.
until the solution, which is at first blue-violet, turns to a beautiful blue-green.
Allow the melt to cool slowly, when the new colouring matter usually separates
out in the form of long indigo-blue needles. Collect and dry. The colouring
matter so obtained is insoluble in water. To convert it into its sulphoacid mix
about ten parts of the dry colouring-matter thus obtained with about two hundred
parts of concentrated sulphuric acid (containing about 95 per cent. H₂SO). Heat
the mixture to a temperature of from forty to fifty degrees Centigrade, and
maintain it at this temperature for about twelve hours. Then pour the reaction
product into water, and precipitate by nieans of common salt the sulphoacid
formed and collect. The product so obtained is a blue-black powder, readily
soluble in water the solution being a brilliant blueish-green. In the presence of
caustic soda and sodium carbonate the aqueous solution is green, and with con-
centrated sulphuric acid the product dissolves the solution being a pure blue.
EXAMPLE 2.
Mix together about ten parts of the naphthazarine intermediate product herein-
before referred to, with about two hundred parts of glacial acetic acid and twenty
parts of paratoluidine. Boil the mixture until the solution (which is at first
blue-violet) becomes a beautiful blue-green colour. Allow the melt to cool slowly,
and collect the colouring matter that separates out. The colouring matter, so
obtained, is insoluble in water. It can be readily sulphonated as follows:-
Add about ten parts of the product to about two hundred parts of fuming sul-
phuric acid (containing about 12 per cent. free SO3). Keep the acid cold, that is,
below five degrees Centigrade whilst adding the colouring matter. Allow the mix-
ture to stand for about an hour, and then pour the reaction mass into one thousand
parts of water. and precipitate the colouring matter by means of common salt.
The product thus obtained is a greenish powder, readily soluble in water the
colour being bright green.
EXAMPLE 3.

page_text: before referred to, in about one hundred parts of aniline and heat the mixture
to one hundred degrees Centigrade. Then add, to the solution, about forty parts
of aniline hydrochlorate. The solution, which is at first blue-black, turns green.
In about half an hour the conversion is complete. Pour the reaction product
into dilute hydrochloric acid, filter and re-crystallise the precipitate from alcohol,
or glacial acetic acid, until sufficiently pure. The colouring matter so obtained
appears to have properties the same as those of the insoluble product obtained
according to the foregoing Example 1.
In the foregoing examples the aniline, or para-toluidine, can be replaced by
other primary aromatic amines and diamines. such as, for instance, ortho-tolui-
dine, para-phenylene-diamine, benzidine, and the like, and similar products
in each case be obtained,
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 colouring matters of the naphthalene series by
treating the aforesaid naphthazarine intermediate product with a primary
aromatic amine, or diamine, substantially as hereinbefore described.
2. The manufacture of new colouring matters of the naphthalene series by
treating the aforesaid naphthazarine intermediate product with a primary
aromatic amine, or diamine, in the presence of a condensing agent, or. solvent;
substantially as hereinbefore described.
3. The manufacture of new colouring matters of the naphthalene scries, by
sulphonating the colouring matters such as can be obtained in accordance with
the processes claimed in the preceding claiming clauses, substantially as herein-
before described.
4. The manufacture of new colouring matters of the naphthalene series, sub-
stantially as described in the foregoing examples.
can be
5. The new colouring matters of the naphthalene series such as
obtained by treating the napththazarine intermediate product, substantially as
herein before described and claimed by the foregoing first and second claiming
clauses.
can be
6. The new colouring matters of the naphthalene series such as
obtained by sulphonating the colouring matters claimed by the last preceding
claiming clause, substantially as hereinbefore described.
Dated this 17th day of July 1900.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.