The Manufacture of New Colouring-matters of the Naphthalene Series.
Year: 1898

page_text: Date of Application, 23rd Nov., 1898
Complete Specification Left, 10th Aug., 1899-Accepted, 16th Sept., 1899
PROVISIONAL SPECIFICATION.
The Manufacture 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
communicated to me from abroad by The Badische Anilin & Soda Fabrik, of
Ludwigshafen-on-Rhine, in the German Empire), to be as follows:
My foreign correspondents have already discovered and I have described in the
Application for Letters Patent No. 15708 of 1898, the production of a leuco
compound from the intermediate product of the naphthazarine melt and the
present invention relates to the conversion of such leuco compound into a series
of new colouring-matters.
My foreign correspondents have discovered that if the said leuco compound be
treated with fuming sulphuric acid, it is readily sulphonated and yields a most
beautiful new colouring-matter, which dyes mordanted, and also unmordanted,
wool very pure blue shades.
My foreign correspondents have further discovered that this new sulphoacid
is itself capable of conversion into a variety of colouring-matters; for example,
on treatment with mineral acids in aqueous solution, it is converted into a sulpho-
acid of naphthazarine.
Again, on treating this colouring-matter at a high temperature with aromatic
amines, either alone, or in admixture with their salts, a condensation takes
place which results in the formation of green colouring-matters which are
insoluble in water, but which, on sulphonation, yield valuable colouring-matters,
soluble in water.
Further, if the said colouring-matter be treated in boiling aqueous solution
with the salts of aromatic amines, blue colouring-matters are obtained which are
slightly soluble in water and are characterized by considerable fastness against
the action of light.
The following examples will serve to illustrate the nature of this invention,
but it is not restricted to these examples. The parts are by weight:-
EXAMPLE 1.
Mix together about ten parts of leuco compound obtained from the intermediate
product of the naphthazarine melt, and about one hundred parts of fuming
sulphuric acid (containing about 23 per cent. free S03). Heat the
mixture to a temperature of about 100 degrees Centigrade and maintain
it at this temperature for about two hours. Allow it to cool, and pour the melt
onto about two thousand parts of ice, and precipitate the colouring-matter from
the blue solution with common salt. The blue colouring-matter can thus be
obtained in the form of indigo-blue needle-like crystals. It yields a blue solution
in water, and a yellow solution in concentrated sulphuric acid; in caustic soda
lye the solution is blue, but the addition of an excess of caustic soda to the
aqueous solution precinitates the colouring-matter

page_text: On heating the colouring-matter with dilute sulphuric acid the colour of the
solution changes to a magenta-red.
The colouring-matter can be reduced by the aid of, for instance, tin salt
and hydrochloric acid, or sodium hydrosulphite, to a corresponding leuco com-
pound, and it can be used for dyeing either as such, or in the form of this leuco 5
compound, which yields the same shades on the fibre.
CONVERSION OF THE COLOURING-MATTER
OBTAINED ACCORDING TO EXAMPLE 1
INTO A SULPHO-ACID OF NAPHTHAZARINE.
Mix together about ten parts of the colouring-matter obtained according to
Example 1, about five hundred parts of water, and ten parts of hydrochloric acid
(containing about 32 per cent. real H.Cl). Boil this mixture for about half-an-
hour. The solution, which is at first blue, turns magenta red. Add chloride of
potassium to precipitate the naphthazarine sulphoacid formed. This can be
obtained in the crystalline form of small needles. Filter and dry.
The product
so obtained is a brownish-red powder, which yields a magenta-red solution in
water, a blue solution in the presence of caustic soda, and a violet-red solution
in concentrated sulphuric acid. This sulphoacid of naphthazarine dyes un-
mordanted wool from the acid bath, yielding brown-red shades, which are con-
verted into a deep black on chroming with sodium bichromate. The shades thus
obtained are characterised by a very high degree of fastness.
CONVERSION OF THE COLOURING-MATTER OF EXAMPLE 1 INTO A GREEN
COLOURING MATTER.
Mix together about ten parts of the colouring-matter of Example 1 with one
hundred parts of aniline, and forty parts of aniline hydrochlorate. Heat the
mixture till it boils, and maintain it at this temperature for about an hour.
The melt is, at first, of a beautiful blue colour, but afterwards turns green.
Pour the melt onto about two thousand parts of water, add about five hundred
parts of hydrochloric acid, and filter. The colouring-matter thus obtained can
be crystallised from glacial acetic acid, yielding beautiful needle-like crystals,
having a metallic lustre. Instead of aniline, other aromatic amines can be used.
The colouring-matter thus obtained is insoluble in water, but is soluble in
benzene, alcohol, and glacial acetic acid. Its solution in concentrated sulphuric
acid is at first of an olive colour, and then brown-red.
PRODUCTION OF THE SULPHO ACID OF THE GREEN COLOURING-MATTER OBTAINED
ACCORDING TO EXAMPLE 3.
Mix together about ten parts of the colouring-matter of Example 3, and two
hundred parts of concentrated sulphuric acid (containing about 95 per cent. H₂SO4)
for about twenty-four hours. Then pour the melt into about one thousand parts
of water, and precipitate with common salt.
The colouring matter has the appearance of a blackish powder, it yields a green
solution in water and in aqueous caustic soda, and a brown-red solution in
concentrated sulphuric acid.
The colouring matters obtained according to Example 3 can similarly be
sulphonated to yield similar colouring matters. These colouring matters dye
unmordanted wool from the acid baths yielding fast green shades.

page_text: CONVERSION OF THE COLOURING MATTER OF EXAMPLE 1 INTO A NEW BLUE
COLOURING MATTER:
Dissolve about ten parts of the colouring-matter of Example 1 in about
500 parts of boiling water, and add to the solution about twenty parts of aniline
hydrochlorate. Boil the solution thus obtained for about two hours. The
solution is, at first, blue but afterwards is converted into a violet-red. Allow it to
cool. The new colouring-matter crystallises out in needle-like crystals, possessing
a metallic lustre.
The colouring-matter is slightly soluble in cold water, and yields a pure blue
solution in hot water. The solution in concentrated sulphuric acid is violet,
and in aqueous caustic soda, blue. It dyes unmordanted wool from the acid bath,
yielding blue shades which are characterised by a considerable degree of fastness
against the action of light.
Instead of the aniline salt in the foregoing example, the hydrochloric acid
salts of ortho-toluidine, para-toluidine, and the like, can be employed and similar
products be obtained.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
The Manufacture 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
communicated to me from abroad by The Badische Anilin & Soda Fabrik, of
Ludwigshafen-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:-
-
My foreign correspondents have already discovered, and I have described in the
Application for Letters Patent No. 15708 of 1898, the production of a leuco
compound from the intermediate product of the naphthazarine melt, and the
present invention relates to the conversion of such leuco compound into a series
of new colouring-matters.
My foreign correspondents have discovered that if the said leuco compound be
treated with fuming sulphuric acid it is readily sulphonated, and yields a most
beautiful new colouring-matter which dyes mordanted, and also unmordanted,
wool very pure blue shades.
My foreign correspondents have further discovered that this new sulphoacid or
colouring matter is itself capable of conversion into a variety of colouring
matters; for example, on treatment with mineral acids, in aqueous solution, it
is converted into a sulphoacid of naphthazarine.
Again, on treating the said new sulpho-acid colouring-matter (obtained from
the said leuco compound as aforesaid) at a high temperature, with aromatic
amines, either alone, or in admixture with their salts, a condensation takes place
which results in the formation of green colouring-matters which are insoluble in
water, but which, on sulphonation, yield valuable colouring-matters, soluble in
water.
Further, if the said colouring matter (obtained from the said leuco compound
as aforesaid) be treated in a boiling solution of a salt of an aromatic amine, blue

page_text: colouring-matters are obtained which are slightly soluble in water and are
characterized by considerable fastness against the action of light.
The following examples will serve to illustrate the nature of this invention and
the manner in which it can be performed, but it is not restricted to these examples.
The parts are by weight.
EXAMPLE 1.
Mix together about ten parts of leuco compound obtained from the intermediate
product of the naphthazarine melt, and about one hundred parts of fuming
sulphuric acid (containing about 23 per cent. free S03). Heat the
mixture to a temperature of about 100 degrees Centigrade and maintain
it at this temperature for about two hours. Allow it to cool, and pour the melt
onto about two thousand parts of ice, and precipitate the colouring-matter from
the blue solution with common salt. The blue colouring-matter can thus be
obtained in the form of indigo-blue needle-like crystals. It yields a blue solution
in water, and a yellow solution in concentrated sulphuric acid. In caustic soda
lye the solution is blue, but the addition of an excess of caustic soda to the
aqueous solution precipitates the colouring-matter
On heating the colouring-matter with dilute sulphuric acid the colour of the
solution changes to a magenta-red.
The colouring-matter can be reduced, by the aid of, for instance, tin salt
and hydrochloric acid, or sodium hydrosulphite, to a corresponding leuco com-
pound, and it can be used for dyeing either as such, in the form of the colouring
matter itself, or in the form of this leuco compound, which yields the same shades
on the fibre.
EXAMPLE 2.
CONVERSION OF THE COLOURING-MATTER OBTAINED ACCORDING TO EXAMPLE 1
CONVERSION OF THE COLOURING-MATTER OBTAINED ACCORDING TO EXAMPLE 1
INTO A SULPHU-ACID UF NAPHTHAZARINE.
Mix together about ten parts of the colouring-matter obtained according to
Example 1, about five hundred parts of water, and ten parts of hydrochloric acid
(containing about 32 per cent. real H.Cl). Boil this mixture for about half-an-
hour. The solution, which is at first blue, turns magenta-red. Add chloride of
potassium to precipitate the naphthazarine sulphoacid formed. This can be
obtained in the crystalline form of small needles. Filter and dry. The product
so obtained is a brownish-red powder, which yields a magenta-red solution in
water, a blue solution in the presence of caustic soda, and a violet-red solution
in concentrated sulphuric acid. This sulphoacid of naphthazarine dyes un-
mordanted wool from the acid bath, yielding brown-red shades, which are con-
verted into a deep black on chroming with sodium bichromate. The shades thus
obtained are characterized by a very high degree of fastness.
CONVERSION OF THE COLOURING-MATTER OF EXAMPLE 1 INTO A GREEN
COLOURING-MATTER.
Mix together about ten parts of the colouring-matter of Example 1 with one
hundred parts of aniline, and forty parts of aniline hydrochlorate. Heat the
mixture till it boils, and keep it boiling for about an hour. The
melt is, at first of a beautiful blue colour, but afterwards turns green.
Pour the melt into about two thousand parts of water, add about five hundred
parts of hydrochloric acid, (containing about 32 per cent. real H.Cl) and filter.
The colouring-matter thus obtained can be crystallized from glacial acetic acid,
yielding beautiful needle-like crystals, having a metallic lustre. Instead of
aniline, other aromatic amines can be used. The colouring-matter thus obtained
is insoluble in water, but is soluble in benzene, alcohol and glacial acetic acid.

page_text: CONVERSION OF THE COLOURING-MATTER OF EXAMPLE 1 INTO A NEW BLUE
COLOURING-MATTER.
Dissolve about ten parts of the colouring-matter of Example 1 in about
500 parts of boiling water and add to the solution about twenty parts of aniline
hydrochlorate. Boil the solution thus obtained for about two hours. The
solution is, at first, blue, but afterwards becomes a violet-red. Allow it to cool.
The new colouring-matter crystallises out in needle-like crystals possessing a
metallic lustre.
The colouring matter is slightly soluble in cold water, and yields a pure blue
solution in hot water. The solution in concentrated sulphuric acid is violet,
and in aqueous caustic soda blue. It dyes unmordanted wool from the acid bath,
yielding blue shades which are characterised by a considerable degree of fastness
against the action of light.
Instead of the aniline salt in the foregoing example, the hydrochloric acid
salts of ortho-toluidine para-toluidine and the like can be employed and similar
products bo obtained.
Having now particularly described and ascertained the nature of this inven-
tion 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 leuco compound from the intermediate product of the naphthazarine
melt with fuming sulphuric acid substantially as herein before described.
2. The manufacture of sulphoacid of naphthazarine, by treating the colouring
matter obtained as hereinbefore described and claimed under the preceding
claiming clause, with a mineral acid, in aqueous solution substantially as
hereinbefore described.
3. The manufacture of green colouring-matters by treating the colouring matter
obtained as hereinbefore described and claimed in the first claiming clause with
an aromatic amine (either alone, or in admixture with a salt thereof) at a high
temperature substantially as hereinbefore described.
4. The manufacture of green colouring-matters soluble in water by sulphonat-
ing the colouring matters obtained as hereinbefore described and claimed in the
third claiming clause substantially as hereinbefore described.
5. The manufacture of blue colouring-matters by treating the colouring
matter obtained as hereinbefore described and claimed in the first claiming clause

page_text: with a solution of a salt of an aromatic amine substantially as hereinbefore
described.
6. The manufacture of colouring matters as hereinbefore described under the
examples.
7. As new articles of manufacture colouring-matters such as can be obtained 5
substantially as hereinbefore described and claimed.
Dated this 10th day of August 1899.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.