Year: 1899

page_text: I, FRIEDRICH KEHRMANN, Teacher of Chemistry, School of Chemistry, Geneva,
Switzerland; do hereby declare the nature of this invention to be as follows:-
It was first shown by Kehrmann and Messinger (Berichte der deutschen
Chemischen Gessellschaft XXIV, 584 and 2167) and later by Patent Specifications 'of
the Badische Anilin and Soda-Fabrik (compare German Patents 79564 and 79953) that
oxynaphthoquinoneimide and oxynaphthoquinoneanilide, which compounds would be.
more correctly named 4-amido-and 4-anilido-ß-naphthoquinone respectively, can be
condensed with ortho-diamines of the aromatic series which are mono-substituted in
one of the amido groups, and yield therewith colouring matters belonging to the class
of the rosindulines.
In carrying these researches further I have now found that chloro-derivatives of
alkyland aromatic ortho-diamines of the general formula :.
These new dyestuffs are distinguished from the heretofore known representatives
of this series by their considerably bluer shades and by their being easily converted.
into valuable colouring matters of the safranine series by treatment with amines.
The rosindulines known up to the present are not attacked by amines even at high.
temperature.
For the production of the new dyestuffs can be used the following derivatives of
B-naphthoquinone: 4-amido-ẞ-naphthoquinone, (formerly called oxynaphthoquinone-
imide), derivatives of this compound substituted in the amido-group, such as anilido-,
toluidido-, naphthylamido-B-naphthoquinone, the sulphonic acids of the latter
derivatives, such as for, instance the product of the reaction of sulphanilic acid on

page_text: B-naphthoquinone. Further may be used the products obtained by the action of
amines or their sulphonic acids on the 8-naphthoquinone-sulphonic acids, such as for
instance the compound..
.
B
The sodium salt of this product is easily obtained by mixing one molecular
proportion of 8-naphthoquinone-6-sulphonate of potassium, 1 molecular proportion of
the sodium salt of sulphanilic acid and 1 molecular proportion of sodium: acetate with
the necessary quantity of water to produce a thick uniform paste, separating the
chocolate coloured precipitate which is formed and washing it with a little ice-water.
The product thus obtained forms dark brown red needles, easily soluble in water with
blood red colour. On addition of sulphuric acid to the aqueous solution of the
compound no precipitate is produced, the free sulphonic acid being very easily
soluble in water.
The chloro-derivatives of mono- aromatic- or mono-alkyl-substituted ortho-
diamines suitable for my new process are, for instance, obtained by treating
Laubenheimer's dinitrochlorobenzene (NO NO, CI = 2: 4) with amido-
compounds, diamines or polyamines, and subsequent reduction of the reaction
products obtained. Such derivatives are for instance those represented by the
following formulie

page_text: chemischen Gesellschaft XXIII,3424): nitrochlorodiphenylamine,melting at 108.5°C.,
(produced by the action of aniline on Laubenheimer's dinitrochlorobenzene) and its
reduction product chlorophenyl-ortho-phenylenediamine, melting at 99° C. The
product obtained by the action of para-toluidine on Laubenheimer's dinitrochloro-
benzene forms prisms of orange-red colour, insoluble in water, more soluble in boiling..
alcohol. By heating it with tin, hydrochloric acid and some alcohol it is reduced to
the hydrochloride of chloro-para-tolyl-ortho-phenylenediamine, which forms.colourless
crystals. This compound is little soluble in acidified water, easily soluble in alcohol -
and begins to melt and to sublime at 100° C.
Another intermediate product suitable for my process is the chloro-ortho-nitro-
methylaniline obtained by the action of methylamine on dinitro-chlorobenzene.
This product forms orange yellow prisms melting at 105° C., little soluble in cold
water, fairly soluble in boiling water and dissolving easily in alcohol.
By reduction by means of stannous chloride and hydrochloric acid in aqueous
solution it yields the hydrochloride of methyl-chloro-ortho-phenylenediamine. This
compound forms colourless flat needles, easily soluble in water, less soluble in diluted
hydrochloric acid. The free base is liquid, easily soluble in water and quickly
oxidised by the air.
The invention is further illustrated by the following examples:
1.) Colouring matter from anilido-B-naphthoquinone and chlorophenyl-ortho-
phenylenediamine.
Molecular proportions of anilido-8-naphthoquinone and of the hydrochloride of
chlorophenyl-ortho-phenylenediamine are mixed with a sufficient quantity of alcohol.
to produce a thin paste which is then heated to gentle boiling until the ingredients
are completely dissolved to a imagenta-red coloured solution. A part of the alcohol
is then distilled off and, by addition of hydrochloric acid; the chloride of the dyestuff
is caused to crystallise in the shape of green needles with metallic lustre.
The dyestuff is filtered and dried. It is nearly insoluble in water, easily soluble
in alcohol and acetic acid to a violet coloured solution. Concentrated sulphuric acid
dissolves the dyestuff to a, green coloured solution without altering its composition
whereas fuming sulphuric acid produces a sulphonic acid, soluble in water, which
dyes wool violet-red tints.
2.) Colouring matter from 4-amido-3-naphthoquinone and methylchloro-ortho-
phenylenediamine.
T
LL

page_text: during the heating of the mixture, which shews a strong fluorescence, the chloride of
the colouring matter separates nearly completely in the shape of glittering particles
of gold lustre. Some hydrochloric acid is added and after allowing to stand for some
time the separated dyestuff is filtered off; washed with a little alcohol and dried. It.
dissolves in boiling water and alcohol to an eosine-red coloured. solution which has a
strong yellow-red fluorescence. The dyestuff produces on silk, wool and tannin-
mordanted cotton clear eosine-red to scarlet-red tints. Concentrated sulphuric acid
dissolves the dyestuff to a green coloured solution..
3.) Colouring matter from-sulphanilido-B-naphthoquinone and methylchloro-ortho
phenylenediamine.
is prepared by heating equimolecular proportions of the components in aqueous ·
solution for some time to boiling.
As soon. as the colour of the dark precipitate. which soon separates is no more 1
altered, the dyestuff is filtered extracted with boiling alcohol and dried: This
product is in the forin of a dark red crystalline powder of green metallic lustre. It
is nearly insoluble in water and alcobol, but dissolves easily in diluted alkali lyes to a
magenta-red coloured solution. Concentrated sulphuric acid transforms the dyestuff
into a crystalline sulphonic acid, easily soluble in water dyeing wool and silk clear 2
bordeaux-red tints..
4.) Colouring matter from; para-toluidido-8-naphthoquinone and para-tolylchloro-
ortho-phenylenediamine.
fish ranresented by the following formula :—
Its manufacturé is quite anologous to that of the dyestuff described in Example (1.)
The chloride of the dyestuff forms dark red needles which are nearly insoluble in
water, but easily soluble in alcohol and acetic acid, to a blueish-magenta-red coloured..

page_text: solution. Concentrated' sulphuric acid dissolves the product to a green coloured
solution while feebly fuming. sulphuric acid produces a sulphonic acid which is
soluble in water and dyes wool violet-red tints.
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of Chloro-substituted Rosindulines.
I, FRIEDRICH KEHRMANN, Teacher of Chemistry, School of Chemistry, Geneva,
Switzerland, 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 :-
It was first shewn by Kehrmann and Messinger (Berichte der deutschen Chemischen
Gesellschaft XXIV, 584 and 2167) and later by Patent Specifications of the Badische
Anilin and Soda-Fabrik (compare German Patents 79564 and. 79953) that
oxynaphthoquinoneimide and oxynaphthoquinoneanilide, which compounds would be
more.correctly named 4-amido-and 4-anilido-8-naphthoquinone respectively, can be
condensed with ortho-diamines of the aromatic series which are mono-substituted in
one of the amido groups, and yield therewith colouring matters belonging to the
class of the rosindulines.
In carrying these researches further I have now found that chloro-derivatives of
mono-alkyl-substituted and mono-aromatic-substituted ortho-diamines of the general
These new dyestuffs are distinguished from the heretofore known representatives
of this series by their considerably bluer shades and by their being easily converted
into valuable colouring matters of the safranine series by treatment with amines.
The rosindulines known up to the present are not attacked by amines even at high
temperature.
For the production of the new dyestuffs can be used the following derivatives. of
B-naphthoquinone: 4-amido-8-naphthoquinone, (formerly called oxynaphthoquinone-
imide), derivatives of this compound substituted in the amido-group, such as
anilido-, toluidido-, naphthylamido-8-naphthoquinone, the sulphonic acids of the latter

page_text: derivatives, such as for instance the product of the reaction of sulphanilic acid on
8-naphthoquinone. Further may be used the products obtained by the action of
amines or their sulphonic acids on the B-naphthoquinone-sulphonic acids, such as for
instance the compound:
The sodium salt of this product is easily obtained by mixing one molecular proportion
of potassium 8-naphtho-quinone-0-sulphonate, 1 molecular proportion of sodium
sulpbanilate and 1 molecular proportion of sodium acetate with the necessary quantity
of water to produce a thick homogeneous paste,, separating the chocolate coloured
precipitate which is formed and washing it with a little ice-water. The product
thus obtained forms dark brown red needles, easily soluble in water with blood red
colour. On addition of sulphuric acid to the aqueous solution of the compound no
precipitate is produced, the free sulphonic acid being very easily soluble in water.
The chloro-derivatives of mono-aromatic- or mono-alkyl-substituted ortho-diamines
suitable for my new process are for instance, obtained by treating Laubenheimer's
dinitrochlorobenzene (NO, NO, : Cl 1 2 4) with amido-compounds, diamines
or polyamines, and subsequent reduction of the reaction products obtained. Such
derivatives are for instance those represented by the following formulæ.
Of these products have already been described by Laubenheimer (Berichte der
deutschen chemischen Gesellschaft IX, 771) and by 0: Ernst, (Berichte der deutschen
chemischen Gesellschaft XXIII, 3424): nitrochlorodiphenylamine, melting at
108:5° C., (produced by the action of aniline on Laubenheimer's dinitrochlorobenzene)
and its reduction product chlorophenyl-ortho-phenylene-diamine, melting at 99° C. 2

page_text: The product obtained by the action of para-toluidine on Laubenheimer's dinitro-
chlorobenzene forms prisms of orange-red colour, insoluble in water, more soluble in
boiling alcohol: By heating it with tin, hydrochloric acid and some alcohol it is
reduced to the hydrochloride of chloro-para-tolyl-ortho-phenylenediamine, which
forms colourless crystals. This compound is little soluble in acidified water, easily
soluble in alcohol and begins to melt and to sublime at 100° C. Another inter-
mediate product suitable for my process is the chloro-ortho-nitromethylaniline
obtained by the action of methylamine on dinitrochlorobenzene. This product forms
orange yellow pristns melting at 105° C., little soluble in cold water, fairly soluble in
boiling water and dissolving easily in alcohol.
:
By reduction by means of stannous chloride and hydrochloric acid in aqueous solu-
tion it yields the hydrochloride of methyl-chloro-ortho-phenylenediamine. This
compound forms colourless flat needles, easily soluble in water, less soluble in diluted
hydrochloric acid. The free base is liquid, easily soluble in water, and quickly
oxidised by the air.
The invention is illustrated by the following examples :-
1.) Colouring matter from anilido-8-naphthoquinone and chlorophenyl-ortho-
phenylenediamine.
Molecular proportions of anilido-B-naphthoquinone and of the hydrochloride of
chlorophenyl-ortho-phenylenediamine are mixed with a sufficient quantity of alcohol
to produce a thin paste which is then heated to gentle boiling until the ingredients
are completely dissolved to a magenta-red coloured solution. A part of the alcohol is
then distilled off and, by addition of hydrochloric acid, the chloride of the dyestuff is
caused to crystallise in the form of green needles with metallic lustre.
The dyestuff is filtered and dried.
It is nearly insoluble in water, easily soluble in alcohol and acetic acid to a violet
coloured solution. Concentrated sulphuric acid dissolves the dyestuff to a green
coloured solution without altering its composition whereas fuming sulphuric acid
produces a sulphonic acid, soluble in water, which dyes wool violet-red tints.
2. Colouring matter from 4-amido-ß-naphthoquinone and methylchloro-ortho-
phenylenediamine.
The production of this dyestuff which is represented by the following formula;

page_text: particles of gold lustre. Some hydrochloric acid is added and after allowing to stand
for some time the separated dyestuff is filtered off, washed with a little alcohol and
dried. It dissolves in boiling water and alcohol to an eosine-red coloured solution
which has a strong yellow-red. fluorescence.
I
The dyestuff produces on silk, wool and tannin-mordanted cotton clear eosine-red
to scarlet-red tints.
7
Concentrated sulphuric acid dissolves the dyestuff to a green coloured solution.
3) Colouring matter from sulphanilido-6-naphthoquinone and methylchloro-ortho-
phenylenediamine.
This dyestuff which is represented by the following formula.
is prepared by heating equimolecular proportions of the components in aqueous
solution for some time to boiling.
When the colour of the dark precipitate which soon separates is no more altered,
the dyestuff is filtered extracted with boiling alcohol and dried. This product is in
the form of a dark red crystalline powder of green metallic lustre. It is nearly
insoluble in water and alcohol, but dissolves easily in diluted alkali lyes to a imagenta-
red coloured solution. Concentrated sulphuric acid transforms the dyestuff into a
crystalline sulphonic acid, easily soluble in water dyeing wool and silk clear bordeaux
red tints.
4. Colouring matter from para-toluidido-B-naphthoquinone and para-tolylchloro-
ortho-phenylenediamine.
This dyestuff is represented by the following formula —
2
Its manufacture is quite analagous to that of the dyestuff described in Example (1.) 2
The chloride of the dyestuff forms dark red needles which are nearly insoluble in
water, but easily soluble in alcohol and acetic acid to a blueish-magenta-red coloured -
solution. Concentrated sulphuric acid dissolves the product to a green coloured
solution while feebly fuming sulphuric acid produces a sulphonic acid which is
soluble in water and dies wool violet-red tints.

page_text: Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed, I declare that what
I claim is
1. The bereiu described manufacture of chloro-substituted rosindulines by
condensing alkyl- or alphyl-substituted derivatives of chloro-ortho-phenylene-diamine,
represented by the constitutional formula: