The Manufacture and Production of New Dyes relating to the Oxy-phenanthro-naphthazine Series and of New Intermediate Products.
Year: 1896

page_text: Date of Application, 18th July, 1896
Complete Specification Left, 20th Apr.. 1897-Accepted, 19th June, 1897
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Dyes relating to the
Oxy-phenanthro-naphthazine Series and of New Intermediate
Products.
J...
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 and Soda Fabrik of
Ludwigshafen-on-Rhine in the Empire of Germany) to be as follows:-
In the Specification of Letters Patent No. 18374 of 30th September 1893 the
manufacture and production of new basic dyes derived from phenanthrophenazine
is described. These dyes are: characterized by a nitrogen atom of the azine group
being combined with an alkyl rest and are capable of use for dyeing yellow shades
on cotton with the aid of a tannia mordant.
2.
My foreign correspondents have now discovered that dyes of this class derived
from phenanthronaphthazine and, having a hydroxylic group can be obtained and
these are especially suitable for dyeing very fast yellow shades on wool and silk.
These new dyestuffs are obtained by the treatment of phenanthrenequinones
a) with peri-hydroxy-diamido naphthalenes and subsequent treatment with
sulphuric acid;
1) with the sulpho acids of peri hydroxy diamido-naphthalenes;
c) with certain 1.2-diamido-naphthalene sulpho acids (the 1.2-diamido naphtha-
lene 4-mono sulpho acid and the 1.2-diamido-naphthalene-4'-mono sulpho acid are
not suitable). In this condensation new products are obtained in which subse-
quently a hydroxylic group OH is substituted for the sulpho group. This can be
effected by melting them with alkali. When the compounds finally resulting are
insoluble they can be converted into sulpho acids by sulphonating.
The following examples will serve to further illustrate the nature of the invention
but I do not limit myself to the details of these examples. The parts are by
weight.
THE MANUFACTURE OF A DYESTUFF BY CONDENSING PHENANTHRENE-
QUINONE WITH 1.2-DIAMIDO 11-NAPHTHOL AND SUBSEQUENTLY
SULPHONATING THE OBTAINED PRODUCT.
The 1.2-diamido-1'-naphthol which serves for the production of peri-oxy-
phenanthronaphthazine can be obtained by the reduction of sulphanilic acid azo
2-amido 1'-naphthol.
Take about thirty seven parts of the sodium salt of the said azo dyestuff and
reduce it with zinc dust, in the known way, in a neutral or weakly acetic acid
solution. The 1.2 diamido 1'-naphthol obtained being unstable is not separated.
Filter the solution from the zinc dust and add it in a weakly acetic acid condition
to a solution of 20 parts of phenanthrene quinone in one hundred parts of sodium
bisulphite 40° Bé, and one thousand parts of water and heat it at about ninety to
ninety five degrees Centigrade until no further separation of the product of
condensation takes place. To ascertain the end of the reaction filter a.test

page_text: PRODUCTION OF A DYESTUFF BY CONDENSING PHENANTHRENEQUINONE
WITH DIAMIDO-NAPHTHOL-SULPHO-ACIDS.
Suspend the azo dyestuff prepared in an acid solution of diazosulphanilic acid
and 2-amido-1'-naphthol-3-sulpho acid in about twenty times its weight of hot
water and add hydrochloric acid and stannous chloride until the liquid is
decolourized. After cooling, separate the crystals from the mother liquor, and
wash well with dilute hydrochloric acid. The 1.2-diamido-1'-naphthol-31-sulpho
acid so obtained is difficultly soluble in water. This acid as well as the herein-
after mentioned diamido-naphthol-sulpho acids are especially characterised by
their condensing with phenanthrenequinone to yield yellow dyestuffs which are
very fast against the action of alkali."
The condensation is effected as follows:-
Mix about four hundred and two parts of a five per cent. paste of phenanthrene-
quinone with two hundred and sixty parts of a ten per cent. paste of 1.2-diamido-
1-naphthol-3-sulpho acid. Add about three hundred and fifty parts of water and
warm the mixture at a temperature of ninety to ninety five degrees Centigrade
until the phenanthrene quinone disappears and a test portion of the mixture is
soluble in hot water with a yellow colour. Then precipitate the condensed product
by means of common salt and filter. The yellow dyestuff so obtained is crystalline
and very difficultly soluble in water. It can be employed in the form of a paste.
The sodium salt is also only slightly soluble in water. In concentrated sulphuric
acid the dyestuff dissolves with a greenish-blue colour.
When either the 1.2-diamido-1-naphthol 4-monosulpho acid or the 1.2-diamido-
1-naphthol-4'-monosulpho acid is used instead of the 1.2 diamido 3' naphthol
sulpho acid of this example, dyes are obtained which are also difficultly soluble.in
cold water, but when the equivalent quantity of either 1.2-diamido 1'-naphthol
4'2' disulpho acid or 1.2-diamido 1' naphthol-3.31 disulpho acid is employed dyes
are obtained which are more readily soluble and have a purer yellow shade.
These diamido-naphthol-sulpho acids are best prepared by reducing the azo
dyestuffs of the corresponding amido naphthol sulpho acids. Thus the 1.2-diamido-
1-naphthol-4-monosulpho acid is prepared by reducing the azo dyestuffs which are
obtained by combining diazo-compounds with 1.1' amido-naphthol-4-mono-sulpho
acid in acid solution; the 1.2-diamido-1-naphthol-4'-monosulpho acid by reducing
an azo dyestuff prepared from 1.1' amidonaphthol-4'-monosulpbo acid in acid
:solution; the: 1.2-diamido 1'-naphthol-3.3' disulpho acid by reducing au.azo dye-
stuff prepared from 1.1 amido-naphthol-3.3 disulpho acid in acid solution and the
1.2-diamido-1-naphthol-4 2 disulpho acid by reducing an azo-dyestuff of the
1.1-amido-naphthol-4' 2'-disulpho acid. The said diamido-naphthol-sulpho acids
are obtained in a crystalline form by reduction with hydrochloric acid and stannous
chloride.

page_text: THE MANUFACTURE OF A DYESTUFF BY CONDENSING PHENANTHRENEQUINONE
1.2-DIAMIDO-NAPHTHALENE-DISULPHOACID AND MELTING THE
WITH
PRODUCT OF CONDENSATION WITH ALKALI.
As initial materials for the production of suitable diamido naphthalene-sulpho acids
the 1-naphthylamine-4.31-disulpho acid and the 1-naphthylamine 4.21-disulpho acid
are very appropriate,-they are combined in an acid solution with a diazo-compound
and the dyestuff so obtained is reduced in the manner hereinbefore described, but
allowing for the greater solubility of the resulting 1.2-diamido-naphthalene-disulpho
acids. The quantity of sodium salt of diamido-naphthalene-disulpho acid contained
in the solution obtained is determined by means of phenanthrene-quinone in a test
portion acidified by acetic acid.
Dissolve about thirty-six parts of the disodium salt of a mixture of 1.2-diamido-
naphthalene 4.31 and 4.21-disulphoacid in five hundred parts of water, acidify with
acetic acid and add this to a solution of twenty parts of phenanthrenequinone in
one hundred parts of a solution of sodium bisulphite of 40° Bé. and one thousand.
parts of water. Heat to 90 to 95 degrees Centigrade until no unchanged.
phenanthrene quinone separates out of the filtrate of a test portion diluted with.
water on acidifying with acid. Precipitate the product of condensation (the
phenanthrouaphthazine disulpho acid) by means of common salt, filter, press.
and dry.
Introduce forty parts of this disulphoacid at a temperature of two hundred!
degrees Centigrade into a melt of two hundred parts of caustic potash and twenty
parts of water, heat at a temperature of two hundred and fifty degrees Centigrade
until no further increase in the quantity of precipitate can he observed on adding
hydrochloric acid to solution of successive test portions of the melt. To isolate the
dyestuff obtained, dissolve the melt in water, precipitate the product with hydro-
chloric acid, filter, wash, and make it into a paste. The sulpho acid is difficultly
soluble both in cold and in hot water. Its sodium salt is readily soluble and it.
dyes wol a dull yellow colour in acid solution. The solution in concentrated
sulphuric acid is olive coloured.
THE MANUFACTURE OF A DYESTUFF BY CONDENSING PHENANTHRENE QUINONE
WITH 1.2 DIAMIDO NAPHTHALENE-DISULPHO ACID, MELTING THE
PRODUCT OF CONDENSATION WITH ALKALI AND THEN SULPHONATING.
When the phenanthronaphthazine sulpho-acids prepared from 1.2-diamido
naphthalene 4.31 (and 4.2) disulpho acids are melted' with alkali according to
Example III a hydroxylic group is substituted for one sulpho group and the
second sulpho group remains ur changed, but in other cases the second sulpho group
also is eliminated and a body (an oxyphenanthronaphthazine) is obtained free from
sulphur which body is insoluble both in water and in alkali. This body is, by
sulphonation, brought into a form suitable for dyeing wool. Au instance of the
above is furnished by the condensation of 1.2-diamidonaphthalene-4.1' disulpho
acid and phenanthrenequinone. The said diamido disulpho acid is obtained by
reducing an azo-dyestuff prepared from a diazo compound and the alpha naphthyl-
amine-3.1' disulpho acid, and the quantity of the diamido-naphthaline disulpho acid
in the solution obtained is determinated by phenanthrene quinone as described in
Example !II.
Dissolve thirty six parts of the disodium salt of the 1.2-diamido naphtha-
lene-3.1 disulpho acid in four hundred parts of water and condense with
phenanthrene quinone in the manner described in Example III.
Precipitate by means of common salt the phenanthro-naphthazine disulpho acid

page_text: obtained, filter, press and dry and melt with alkali as described in Example III
but continue heating until the quantity of the product insoluble in alkaline water
does not increase:: Stir the melt in water, filter the alkaline lye from the separated
product of the reaction and wash the latter with hot water. To purify the body
obtained boil it with about fifteen. parts of alcohol and then dry.
The product is very difficult!; soluble in the usual solvents, it contains. no
sulphur and does not melt at a temperature of two hundred degrees Centigrade.
In alcoholic sodium lye it dissolves with a brownish red colour. It dissolves in
concentrated sulphuric acid with a re:ldish blue colour. Probably it is an hydroxy
derivative of the phenanthro-naphthazine obtained by substituting OH for the
3-sulpho group and eliminating the 1' sulpho group.
To sulphonate it, heat it with five parts of sulphuric acid mono-hydrate on the
water bath until a test portion dissolves in hot alkaline water. Introduce the mass
into ice-water, separate the precipitated dyestuff from the sulphuric acid, dissolve
it in hot water, adding caustic soda and precipitate it from the solution by means
of common salt. The separated sodium salt is difficultly soluble in water, it
dissolves in concentrated sulphuric acid with a reddish blue colour and dyes wool
reddish yellow.
Dated this 18th day of July 1896.
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents.
The Manufacture and Production of New Dyes relating to the
Oxy-phenanthro-naphthazine Series and of New Intermediate
Products.
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 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:-
In the Specification of Letters Patent No. 18374 of 30th September 1893 the
manufacture and production of new basic dyes derived from phenanthro-phenazine
is described. These dyes are characterized by a nitrogen atom of the azine-group
being combined with an alkyl rest and are capable of use for dyeing yellow shades
on cotton with the aid of a tannin mordant.
My foreign correspondents have now discovered that dyes of this class derived
from phenanthro-naphthazine and having a hydroxylic group can be obtained and
these are especially suitable for dyeing very fast yellow shades on wool and silk.
These new dyestuffs are obtained by the treatment of phenanthrene-quinone:
(a) with peri-hydroxy-diamido-naphthalenes and subsequent treatment with
sulphuric acid ;-
(b) with the sulphoacids of peri-hydroxydiamido-naphthalenes;
(c) with certain 1.2-diamido-naphthalene-sulpho acids (the 1.2-diamido-naphtha-
lene-4 mono-sulphoacid and the 1.2-diamidonaphthalene-4-monosulphoacid are not
suitable). In this condensation new products are obtained in which subsequently
a hydroxylic group OH is substituted for the sulpho group. This can be effected
by melting them with alkali. When the compounds finally resulting are insoluble:
they can be converted into sulphoacids by sulphonating.

page_text: The following examples will serve to further illustrate the nature of the
invention, but I do not limit myself to the details of these examples. The parts
are by weight.
THE MANUFACTURE OF A DYESTUFF BY CONDENSING PHENANTHRENE-
QUINONE WITH 1.2. DIAMIDO-1-NAPHTHOL AND SUBSEQUENTLY
SULPHONATING THE OBTAINED PRODUCT.
The 1.2-diamido-1'-naphthol which serves for the production of peri-oxy-
phenanthro-naphthazine can be obtained by the reduction of sulphanilic acid-
azo-2-amido-1-naphthol such as results from combining diazo-sulphanilic acid.
with 2-amido-1-naphthol in an acid solution.
Take about thirty seven parts of the sodium salt of the said az-dyestuff and
reduce it by means of zipe dust in the known way in a neutral, or weakly acetic acidi
solution. The 1.2-diamido-1'-naphthol obtained being unstable is not separated.
Filter the solution from the zine dust and add it, iu a weakly acetic acid condition,
to a solution of twenty parts of phenanthrene-quinone in one hundred parts of
sodium bisulphite 40° Bé. and one thousand parts of water and heat it, at about
ninety to ninety five degrees Centigrade, until no further separation of the product.
of condensation takes place. To ascertain when the reaction is completed filter
a test portion and heat the filtrate. If no further separation takes place the
reaction is finished. Separate the peri-oxy-phenanthro-naphthazine so obtained.
from the mother-liquor by filtration, wash and dry and purify it by boiling with
alcohol.
It is nearly insoluble in the usual solvents. In concentrated sulphuric acid it
gives a greenish-blue solution.
Stir the dry oxy-phenanthro-naphthazine into five parts of cold fuming sulphuric
acid, containing twenty three per cent. free anhydride, until a test portion dissolves
in diluted soda-lye, and a sulphoacid will be obtained which is difficultly soluble,
even in hot water, and which dyes wool a rather dull yellow.
With five parts of fuming sulphuric acid containing twenty three per cent. free-
anhydride at a temperature of forty degrees Centigrade, a sulphoacid is obtained.
which is soluble in cold water. Its sodium salt is also very easily soluble and can
be precipitated from the solution by means of common salt. It also dyes wool a
dull vellow.
PRODUCTION OF A DYESTUFF BY CONDENSING PHENANTHRENE-QUINONE:
WITH DIAMIDO-NAPHTHOL-SULPHOACIDS.
Suspend the azo-dyestuff prepared in an acid solution of diazo-sulphanilic acid.
and 2-amido-1-naphthol-3-sulphoacid in about twenty times its weight of hot
water and add bydrochloric acid and stanuous chloride until the liquid is
decolourized. After cooling, separate the crystals from the mother liquor and wash
well with dilute hydrochloric acid. The 1.2-diamido-1'-naphthol-3'-sulphoacid so
obtained is difficultly soluble in water. This acid, and also the hereinafter
mentioned diamido-naphthol-sulphoacids, are especially characterised by their
condensing with phenanthrene-quinone to yield yellow dyestuffs which are very
fast against the action of alkali.
The condensation is effected as follows:-Mix about four hundred and two
parts of a five per cent. paste of phenanthrene-quinone with two hundred and sixty
parts of a ten per cent. paste of 1.2-diamido-1-naphthol-3-sulpho-acid. Add about
three hundred and fifty parts of water and warm the mixture at a temperature of
ninety to ninety-five degrees Centigrade until the phenanthrene-quinone disappears

page_text: It
and a test portion of the mixture is soluble in hot water, with a yellow colour.
Then precipitate the condensed product by means of common salt and filter. The
yellow dye-stuff so obtained is crystalline and very difficultly soluble in water.
can be employed in the form of a paste. The sodium salt is also only slightly
soluble in water. In concentrated sulphuric acid the dyestuff dissolves with a
greenish-blue colour.
When either the 1.2-diamido-1'-naphthol-4-monosulphoacid or the 1.2-diamido-
1-naphthol-4 monosulpho-acid is used instead of the 1.2-diamido-3-naphthol-
sulphoácid of this example dyes are obtained which are. also difficultly soluble in
cold water; but when the equivalent quantity of either 1.2-diamido-1'-naphthol-
42'-disulphoacid or 1.2-diamido-1'-naphthol-3.31-disulpho-acid is employed dyes
are obtained which are more readily soluble and have a purer yellow shade.
These diamido-naphthol-sulphoacids are best prepared by reducing the azo-
dyestuffs of the corresponding amido-naphthol-sulphoacids. Thus the 1.2-diamido-
1-naphthol-4 monosulphoacid is prepared by reducing the azo-dyestuffs which are
obtained by combining diazo-compounds with 1.1 amidonaphthol-4-monosulpho-
acid in acid solution; the 1.2-diamido-12-naphthol-4'-monosulpho acid is prepared
by reducing an azo dyestuff prepared from 1.1'-amido-naphthol-4'-mono-sulpho
acid in acid solution, the 1.2-diamido-1-naphthol-3.3'-disulpho-acid is prepared
by reducing an azo-dyestuff prepared from 1.1'-amido-naphthol-3.3 disulphoacid
in acid solution and the 1.2-diamido-1'-naphthol 4-2-disulpho acid is prepared by
reducing an azo-dyestuff of the 1.1' amido-naphthol-1.2'-disulphoacid. The
said diamide-naphthol-sulphoacids are obtained in a crystalline form by reduction
with hydrochloric acid and stannous-chloride..
THE MANUFACTURE OF A DYESTUFF
BY CONDENSING PHENANTHRENE-
QUINONE WITH 1.2-DIAMIDO-NAPHTHALENE-DISULPHOACID AND MELTING
THE PRODUCT OF CONDENSATION WITH ALKALI.
As initial materials for the production of suitable. diamido naphthalene-sulpho
acids the 1-naphthylamine 4.3' disulpho acid and the 1-naphthylamine 4.2' disulpho-
acid are very appropriate. They are combined in an acid solution with a diazo-
compound and the dye-stuff so obtained is reduced in the manner hereinbefore
described. The quantity of sodium salt of diamido-naphthalene-disulpho-acid
contained in the solution obtained is determined by means of phenanthrene quinone
in a test portion acidified by acetic acid.
Dissolve about thirty six parts of the di-sodium salt of a mixture of 1.2-diamido-
naphthalene 4.31 and 4.2' disulpho acid in five hundred parts of water, acidify with
acetic acid and add this to a solution of twenty parts of phenanthrene-quinone in
one hundred parts of a solution of sodium bisulphite of 40° Bé..and one thousand
-parts of water. Heat to 90 to 95 degrees Centigrade until no unchanged phen-
anthrenequinone separates out of the filtrate of a test portion diluted with water on
acidifying. Precipitate the product of condensation (the phenanthro-naphthazine-
disulphoacid) by means of common salt, filter, press and dry.
Introduce forty parts of this disulphoacid at a temperature of two hundred
degrees Centigrade into a melt of two hundred parts of caustic potash and twenty
parts of water, heat at a temperature of two hundred and fifty degrees Centigrade
until no further increase in the quantity of precipitate can be observed on adding
hydrochloric acid to solutions of successive test portions of the melt. To isolate
the dyestuff obtained dissolve the melt in water, precipitate the product with
hydrochloric-acid, filter, wash, and make it into a paste. The sulphoacid is
difficultly soluble both in cold and in hot water. Its sodium salt is readily soluble,
and it dyes wool a dull yellow colour in acid solution. The solution in
concentrated sulphuric acid is olive coloured.

page_text: EXAMPLE 4.
BY CONDENSING PHENANTHRENE-
QUINONE WITH 1.2 DIAMIDO-NAPHTHALENE DISULPHOACID, MELTING
THE PRODUCT OF CONDENSATION WITH ALKALI AND THEN SULPHO-
NATING.
THE MANUFACTURE OF A DYESTUFF
An
When the phenanthro-naphthazine sulpho-acids prepared from 1.2-diamido
naphthalene-4.3 (and 4.2') disulphoacids are melted with alkali according to the
foregoing Example 3 a hydroxylic group is substituted for one sulpho-group and
the second sulpho group remains unchanged, but in other cases the second sulpho-
group also is eliminated and a body (an oxyphenanthro-naphthazine) is obtained
free from sulphur, which body is insoluble, both. in water and in alkali. This
body is, by sulphonation, brought into a form suitable for dyeing wool.
instance of the above is furnished by the condensation of 1.2-diamido-naphthalene
4.1 disulphoacid and phenanthrene quinone. The said diamido disulphoacid is
obtained by reducing an azo dye-stuff' prepared from a diaz-compound and the
alpha-naphthylamine 3.1' disulphoacid and the quantity of the diami-lo-naph-
thalene-disulphoacid, in the solution obtained is determinated by phenanthrene-
quinone as described in the foregoing Example 3.-
Dissolve thirty six parts of the disodium salt of the 1.2-liamido-naphthalene
3.1'-disulphoacid in four hundred parts of water and condense with phenanthrene-
quinone in the manner described in the foregoing Example 3.
Precipitate, by means of common salt, the phenanthro-naphthazine-disulpho-
acid obtained, filter press and dry and melt with alkali as described in the fore-
going Example 3, but continue heating until the quantity of the product insoluble
in alkaline water does not increase. Stir the melt in water, filter the alkaline lye
from the separated product of the reaction, and wash the latter with hot water.
To purify the body obtained, boil it with about fifteen parts of alcohol and
then dry.
The product is very difficultly soluble in the usual solvents, it contains no sulphur
and does not melt at a temperature of two hundred degrees Centigrade. In
It dissolves in.
alcoholic sodium lye it dissolves with a brownish red colour.
concentrated sulphuric acid with a reddish-blue colour. Probably it is an hydroxy-
derivative of the phenanthro-naphthazine obtained by substituting OH for the
3 sulpho-group and eliminating the 1' sulpho-group.
To sulphonate it, heat it with five parts of sulphuric acid mono-hydrate, on the
Introduce the mass
water-bath, until a test portion dissolves in hot alkaline water.
into ice-water, separate the precipitated dyestuff from the sulphuric acid, dissolve
it in hot water, adding caustic soda, and precipitate it from the solution by means
of common salt. The separated sodium salt is difficultly soluble in water, it
dissolves in concentrated sulphuric acid with a reddish blue colour, and dyes wool
reddish yellow.
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 :
1. The manufacture of new dyes, relating to the oxy-phenanthro-naphthazine
series by the treatment of phenanthrene-quinone with perihydroxydiamido naph-
thalene and subsequently sulphonating the intermediate products obtained substan-
tially as hereinbefore described.
2. The manufacture of new dyes relating to the oxy-phenanthro-naphthazine
series by the treatment of phenanthrene-quinone with the peri-hydroxy diamido-
naphthalene sulpho-acids hereinbefore defined substantially as
described.
hereinbefore
3. The manufacture of new dyes relating to the oxyphenanthro-naphthazine

page_text: series by the treatment of phenanthrene-quinone with the diamido-naphthalene-
sulpho acids hereinbefore defined, then substituting a hydroxylic group for a
sulpho-group in the alkaline melt with, or without, the subsequent sulphonation of
the body so obtained, all substantially as herein before described.
4. The manufacture of new dyes in the several manners herein before described
"under the several examples.
5. As new articles of manufacture new dyes and intermediate products of the
oxy-phenanthro naphthazine series all such as can be obtained substantially as
hereinbefore described and claimed.
Dated this 20th day of Anil 1907
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents.