The Manufacture and Production of New Dyes of the Phenanthrene Series.
Year: 1893

page_text: Date of Application, 30th Sept., 1893
Complete Specification Left, 27th June, 1894-Accepted, 28th July, 1894
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Dyes of the Phenanthrene
Series.
I BENJAMIN WILLCOX of No. 47 Lincoln's Inn Fields in the County of
London, Patent Agent do hereby declare the nature of this invention (which
invention 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:-
This invention consists in the manufacture and production of a series of new and
useful dyes derived from phenanthrene. Colouring matters closely related to the
new dyes have already been obtained and described in literature but up to the date
of this present invention no dyes of commercial value have been obtained from the
said hydrocarbon and all efforts to find a useful technical application for
phenanthrene in the dyestuff industry have hitherto been unsuccessful.
The new dyes result from the interaction under suitable conditions of phenanthrene-
quinone and such amines of the benzene series as contain two amido groups in the
ortho-position one of which is mono-substituted. The said amines are therefore
bodies characterized by the possession of the atomic group.
In the above diagram R signifies an alkyl group such as methyl, ethyl and the
like or an aromatic residue such as phenyl tolyl and the like. Such aromatic
residues may themselves contain substituting groups such as amido groups and the
like. Further the benzene residue marked I in the above diagram may similarly
contain amido groups or substituted amido-groups.
By the use of the various components thus indicated a large number of dyes can
be obtained.
As aforesaid bodies closely related to the new dyes have been described in the
literature of chemical science, thus for instance Hinsberg has described certain
colourless bodies (phenanthrophenazine and phenanthrotoluazine) which are insoluble
in water and in dilute acids and which he obtained by the interaction of phenanthrene-
quinone with ortho phenylene-diamine and ortho toluylene-diamine respectively [see
Hinsberg, Berichte der Deutschen Chemischen Gesellschaft vol. 17, 323]. If instead
of these diamines their mono substituted derivatives be taken in accordance with the
present invention as above defined then yellow dyes are obtained which are soluble
in water and capable of use for dyeing cotton with the aid of a tannin mordant. As
instances of such mono substituted compounds I mention mono-methyl-ortho
toluylene-diamine and mono-tolyl-ortho toluylene-diamine but I do not confine
myself.to these instances.
Witt obtained an amido derivative of phenanthrophenazine by the interaction of
phenanthrene-quinone with 1. 2. 4 tri amido-benzene [ibid. vol. 19 page 445].
Notwithstanding the presence of the free amido-group, this body also possesses but
weak basic properties, thus its hydrochloric acid salt is but slightly soluble in water
1

page_text: and readily dissociates yielding the yellow base. If now in accordance with the
present invention mono-methyl-triamido-toluene
be condensed with phenanthrene-quinone a red dye is obtained which is readily
soluble in water and yields shades possessing great fastness against washing. The
salts of this dye yield the corresponding base when the red aqueous solution is
treated with a caustic alkali..
The dyes obtained from the bodies hereinbefore referred to containing an amido-
group (or substituted amido group) in the benzene residue at I of the diagram yield
red, brown or blue shades of colour and those which contain the said group in the
meta-position to the substituted nitrogen of the azine-group are as my foreign
correspondents have discovered of the greatest value. Those which contain the
group in other positions are as a rule less fast and the shades obtained with them
are not so bright or pure.
If in the condensation with phenanthrenequinone there be an aromatic residue
at R of the diagram the resulting dye is yellowish as above described and the
presence of an amido or substituted amido group in the said aromatic residue does
not essentially change this colour.
To further illustrate the nature of the invention I give the following directions
for the production of a few of the new dyes but the methods employed can be
considerably varied without departing from the nature of the invention.
WAARELE L
For the preparation of this dye it is not necessary to use mono-methyl-triamido-
toluene as such in the separated condition as my foreign correspondents have
discovered that the solution thereof obtained by suitably reducing the corresponding 3
azo-dye can be employed. For this purpose reduce the azo-dye from diazo-benzene
and mono-methyl-meta-toluylene-diamine
with zinc-dust in dilute acetic acid, conducting the operation in such a way that the
resulting solution is as saturated as possible. Pour this solution into a hot mixture 40
of phenanthrene-quinone and glacial acetic acid. The formation of the dye
commences at once and is soon complete. Work up as hereinbefore described.

page_text: 2
5
CH, NO, NHCH, CH,
with about ten times the weight of acetic acid (containing about 30 per cent. C₂H₂O₂)
and reduce with the requisite quantity of zinc dust. Mix the resulting liquid with
a hot glacial acetic acid solution containing about twenty parts of phenanthrene-
quinone. Add ten parts of hydrochloric acid (30 per cent. as above) and heat for
about fifteen minutes on the water bath and allow to cool. The dye usually begins
to separate out while the solution is still hot. When cold collect the dye and in
order to purify it dissolve in hot water, filter from impurities and precipitate with
hydrochloric acid. Collect and dry.
Instead of the nitro-compound used in the above example an azo derivative of
mono-methyl-para-toluidine can be taken or the separated mono-methyl-ortho-
toluylene-diamine itself may be used. In the latter case the base can be dissolved
in glacial acetic acid and phenanthrenequinone be added, the reaction will then, as
a rule, begin at ordinary temperatures but can be accelerated by heating.
EXAMPLE 4. PRODUCTION OF A BLUE DYE USING AMIDO DIPHENYL-
META-PHENYLENE-DIAMINE.
Dissolve about seven parts by weight of amido-diphenyl-meta-phenylene diamine
in about six times the quantity of glacial acetic acid at ordinary temperature add
about five parts phenanthrene-quinone to the solution and heat on the water-bath
whilst constantly stirring until the quinone is completely dissolved. During this
operation the melt assumes an intense and pure blue colour. Next pour the whole
into about twenty times the weight of water and precipitate the dye which for the
most part dissolves, by adding caustic soda till nearly neutral. The dye is thus
obtained it having a pitch-like consistency. Collect wash well with water till the
dye begins to dissolve more freely therein, then dry the residue at about seventy
degrees centigrade until a sample after cooling can be rubbed to powder.
The dye is readily soluble in alcohol and in acetine but is less soluble in water.
From the aqueous solution the hydrochlorate is precipitated on adding hydro-
chloric acid.
EXAMPLE 5. PREPARATION OF A YELLOW DYE USING ORTHO-AMIDO-
DIPHENYLAMINE.
Mix one part by weight of ortho-amido-diphenylamine and one part of
phenanthrene-quinone (or molecular proportions of these bodies) with about twenty
parts of glacial acetic acid and heat on the water bath. To ascertain the course of
the reaction take tests from time to time and boil with about twenty times the volume
of water acidified with hydrochloric acid. When successive tests shew no increase
in the intensity of colour the operation may be considered to be finished. Then
boil up the whole melt with twenty times its volume of water acidified with hydro-
chloric acid allow to cool and filter. Precipitate the dye from the filtrate with
chloride of zinc, collect, press, and dry.
The formation of the dye can also be effected at lower temperatures but more
slowly.
As in the previous examples so in this example also it is not necessary to use
separated ortho-amido-diphenylamine as the liquid resulting from the reduction of
.

page_text: the nitro compound with zinc dust in acetic acid solution can be used in a manner
similar to that hereinbefore described.
Dated this 30th day of September 1893.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of New Dyes of the Phenanthrene
Series.
I BENJAMIN WILLCOX of 47 Lincoln's Inn Fields in the County of London,
Patent Agent 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 :-
This invention consists in the manufacture and production of a series of new and
useful dyes derived from phenanthrene. Colouring matters closely related to the
new dyes have already been obtained and described in literature but up to the
date of this present invention no dyes of commercial value have been obtained
from the said hydrocarbon and all efforts to find a useful direct technical application
for phenanthrene in the dyestuff industry have hitherto been unsuccessful.
The new dyes result from the interaction under suitable conditions of
phenanthrenequinone and such amines of the benzene series as contain two amido
groups in the ortho-position one of which is mono-substituted. The said amines
are therefore bodies characterized by the possession of the atomic group

page_text: Notwithstanding the presence of the free amido-group this body also possesses
but weak basic properties, thus its hydrochloric acid salt is but slightly soluble in
water and readily dissociates yielding the yellow base. If in accordance with the
present invention, mono-methyl-tri-amido-toluene
EXAMPLE 2.
For the preparation of this dye it is not necessary to use mono-methyl-triamido-
toluene, as such in the separated condition, as my foreign correspondents have
discovered that the solution thereof obtained by suitably reducing the corresponding
10 azo dye can be employed. For this purpose, reduce the azo dye from diazo-
benzene and mono-methyl-meta-toluylene-diamine

page_text: with zinc-dust in dilute acetic acid, conducting the operation in such a way that the
resulting solution is as saturated as possible. Pour this solution into a hot mixture
of phenanthrenequinone and glacial acetic acid. The formation of the dye at
-once commences and is soon complete. Work up as hereinbefore described.
with about one hundred and seventy parts of acetic acid (containing about thirty
per cent. C,HO) and reduce with the requisite quantity of zinc dust. Mix the
resulting liquid with a hot glacial acetic acid solution containing about twenty
parts of phenanthrene-quinone. Add ten parts of hydrochloric acid (thirty per cent.
as above) and heat for about fifteen minutes on the water bath, and afterwards
allow to cool. The dye usually begins to separate out while the solution is still
hot. When cold collect the dye, and, in order to purify it, dissolve in hot water,
filter from impurities, and precipitate with hydrochloric acid. Collect and dry.
Instead of the nitro-compound used in the foregoing Example an azo derivative
of mono-methyl-para-toluidine can be used or the separated mono-methyl ortho-
toluylene-diamine itself may be used. In the latter case the base can be dissolved
in glacial acetic acid and phenanthrenequinone be added, the reaction will then,
as a rule, begin at ordinary temperatures but can be accelerated by heating.
EXAMPLE 4. PRODUCTION OF ▲ BLUE DYE USING AMIDO-DIPHENYL-META
PHENYLENE-DIAMINE.
-
in about six times the quantity of glacial acetic acid at ordinary temperature, add
about five parts phenanthrenequinone to the solution and heat on the water-bath,
whilst constantly stirring, until the quinone is completely dissolved. During this
-operation the melt assumes an intense and pure blue colour. Next pour the whole
into about twenty times the weight of water and precipitate the dye (which for the
most part dissolves) by adding caustic soda till nearly neutral. The dye thus
obtained has a pitch-like consistency. Collect, wash well with water, till the dye
begins to dissolve more freely therein, then dry the residue at about seventy degrees
centigrade until a sample, after cooling, can be rubbed to powder. The dye is
readily soluble in alcohol, and in acetine, but is less soluble in water. From the
aqueous solution the hydrochlorate is precipitated on adding hydrochloric acid.
EXAMPLE 5. PREPARATION OF A YELLOW DYE USING ORTHO-AMIDO-
DIPHENYLAMINE.
Mix one part of ortho-amido-diphenylamine and one part of phenanthrenequinone
(or molecular proportions of these bodies) with about twenty parts of glacial acetic
acid and heat on the water bath. To ascertain the course of the reaction take tests
from time to time and boil with about twenty times the weight of water acidified
with hydrochloric acid. When successive tests shew no increase in intensity of
colour, the operation may be considered to be finished. Then boil up the whole

page_text: melt with twenty times its weight of water acidified with hydrochloric acid, allow
to cool, and filter. Precipitate the dye from the filtrate with chloride of zinc,.
collect, press, and dry.
The formation of the dye can also be effected at lower temperatures but it then..
takes place more slowly.
As in the previous examples, so in this Example 5, also it is not necessary to use
separated ortho-amido-compound, as the liquid resulting from the reduction of the
corresponding nitro-amido-compound with zinc dust in acetic acid solution can be
used in a manner similar to that hereinbefore described. Further although the
use of glacial acetic acid as a diluent is described in the examples other diluents
can be employed therein such for instance as ordinary acetic acid, or dilute hydro-
chloric acid.
Having now particularly described and ascertained the nature of the 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 derived from phenanthrene by the interaction
of phenanthrenequinone with such amines of the benzene series as contain two
amido-groups in the ortho-position one of which is mono-substituted substantially
as hereinbefore explained.
2. The manufacture of new dyes in the several manners hereinbefore described.
under the several examples.
3. As new articles of manufacture new dyes of the phenanthrene series such as.
can be obtained substantially as hereinbefore described and claimed.
Dated this 27th day of June 1894.
JOHNSONS & WILLCOX,
Agents.