diamines of Stilbene and Fluorene.
Year: 1886

page_text: Date of Application, 31st May, 1886.
Complete Left, 17th Feb., 1887.
Complete Accepted, 18th Mar., 1887..
diamines of Stilbene and Fluorene.
I, CARL ALEXANDER MARTIUS of Berlin in the Kingdom of Prussia, Empire of
Germany, Direktor of the Actiengesellschaft für Anilinfabrikation do hereby declare
the nature of this invention to be as follows:
-
It is a well known fact that the azo-colours which are produced by the combination
of para-tetrazo-compounds with naphthylamine-sulpho-acids, naphthole-sulpho-acids,
or phenole-carbo-acids, possess the property of dyeing the vegetable fibre without the
use of a mordant.
Hitherto, the para-diamines of diphenyle, ditolyle, or dixylyle, and a number of
derivatives of these bases have been used for the production of such azo-colours.
I have found that diamido-fluorene and diamido-stilbene are also well adapted for
the above purpose. The formation of the colour takes place in a manner similar to that
of the above cited diamido-compounds, viz: by first converting the base into its
tetrazo-compound by means of nitrous acid, and by combining afterwards the tetrazo-
compound with an amine, a phenole, or one of their sulpho-or carbo-acids.
The reaction takes place here also in the same way viz: the tetrazo compound com-
bines first with one molecule of the amine or phenole to an intermediate product which
acts afterwards upon a second molecule. If different molecules of an amine or a
phenole with one molecule of the tetrazo compound, are combined, the so called
mixed azo-colours are formed.

page_text: ABEL & IMRAY,
28, Southampton Buildings, London, W.C.,
Agents for the Applicant.

page_text: A FTOCESS TO FroducOS OF
diamines of Stilbene and Fluorene.
I, CARL ALEXANDER MARTIUS of Berlin, in the Kingdom of Prussia, Empire of
Germany, Direcktor of the Actiengesellschaft für Anilin fabrikation 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 is a well known fact that the azo-colours which are produced by the combina-
tion of para-tetrazo coumpounds with naphtylamine-sulpho-acids, naphtole-sulpho-
acids, or phenole-carbo-acids, possess the property of dyeing vegetable fibre without
the use of a mordant.
Hitherto, the para-diamines of diphenyle, ditolyle, or dixylyle, and a number of
derivatives of these bases, have been used for the production of such azo-colours.
I have found that diamido-fluorene and diamido-stilbene are also well adapted for
the above purpose.
I will in the first instance describe the mode of producing diamido-fluorene and
diamido-stilbene but it is to be understood that the production of these substances
does not form part of my present invention.
f. DIAMIDO-STILBENE.
The principal material for the production of diamido-stilbene is p-nitro-benzyle-
chloride.
According to the observation of Strakosch (Ber. vi, 328) two molecules of p-nitro-
benzyle-chloride combine to p-dinitro-stilbene when caustic potash is entered into an
alcoholic solution of p-nitro-benzyle-chloride, whereby chlorate of potassium separates
at the same time. By the reduction of this nitro-compound, for instance by means of
tin and hydrochloric acid, the diamido-stilbene is formed which crystallizes in needles
or small leaves melting at a temperature of 226-227° C. The hydrochlorate and the
sulphate of the base are not readily soluble in water.
The same base is also obtained by reducing with tin and hydrochloric acid the
amorphous red compound which is produced by heating p-nitro-toluole with alcohol and
caustic soda. It is, therefore, identical with that compound which Klinger (Records of the
Deutsche Chemische Gesellschaft, 1883, 945) describes under the name of diamido-
phenyle-tolyle-methan. It can, further, be obtained by treating the p-nitro-benzylene-
bromide in an analogous manner as the p-nitro-benzyle-chloride with caustic soda,
and by reducing the nitro compound thus obtained by means of tin and hydrochloric
acid.

page_text: fractionated distillation and crystallisation of those parts of the coal tar which boil at
a temperature of about 290-330° C. By acting upon it with concentrated nitrous
acid it is converted into dinitro-fluorene which by reduction yields the diamido-
fluorene melting at a temperature of 157° C.
Production of colours from diamido-stilbene and diamido-fluorene.
The production of azo-colours from the two diamido-compounds of stilbene and
fluorene takes place by first converting one of these bases into its tetrazo-compound
by means of nitrous acid and by combining afterwards the tetrazo-compound with an
amine, a phenole, or one of their sulphonic or carbonic acids.
The reaction always takes place in such manner that the tetrazo-compound com-
bines first with one molecule of the amine or the phenole to an intermediate product
which acts afterwards upon a second molecule. This property can, therefore, be taken
advantage of for the production of the so called mixed azo-colours by combining
two different molecules of an amine or a phenole with one molecule of the tetrazo-
compound.
The following combination of the tetrazo-compounds of stilbene and fluorene with
amines and phenoles may serve as examples for the process described above.
Colour from diamido-stilbene and a-naphtole-mono-sulpho-acid. 28.3 Kg. of
hydrochlorate of diamido-stilbene are dissolved in 5000 liters of water, mixed with
24 Kg. of hydrochloric acid of 20° Bé, and converted into its tetrazo-compound by
pouring into the above mixture 138 Kg. of nitrate of sodium dissolved in 200 liters
of water. The tetrazo-compound is, then, entered under vigorous stirring into an
alkaline solution of 49,2 Kg. of a-naphtole-mono-sulphonate of soda in 5000 liters of
water. After one day's standing the mixture is heated up to boiling, and the colour
precipitated by salt, pressed and dried. It dyes cotton direct from a soap bath a bluish
violet shade.
2. Colour from diamido-stilbene and ß-naphtole-disulpho-acid R.
If instead of the quantity of a-naphtole-mono-sulphonate of soda stated in
example I 69.6 Kg. of BB-naphtole-disulphonate of soda (R salt) are used, a colour is
obtained which dyes cotton from an alkaline soap bath a greenish blue shade.
3. Colour from one molecule of diamido-stilbene, one molecule of B-naphtole-
disulpho-acid R, and one molecule of naphtole-mono-sulpho-acid.
If the above mentioned tetrazo-compound (one molecule) from. 28.3 Kg. of
hydrochlorate of diamido-stilbene acts first upon a solution of 34.8 Kg. of B-naph-
tole-disulphonate of sodium, a red precipitate separates which is formed by the
combination of equal molecules of tetrazo-stilbene and B-naphtole-disulpho-acid.
This compound contains a free diazo-group which enables it to act upon a second
molecule of a phenole or an amine. By entering the compound into an alkaline
solution of 24.6 Kg. of a-naphtole-mono-sulphonate of soda a colour is obtained
which dies cotton from a boiling soap-bath a bluish violet shade and which stands with
regard to shade and solubility between the colours described in Examples 1 and 2.
The colour forms slowly by leaving the mixture standing, quicker by stirring it, and
at once by heating it.
4. Colour from one molecule of diamido-stilbene, one molecule of. B-naphtole-
disulpho-acid, one molecule of a-naphtole B-naphtole, or B-naphtole-mono-sulpho-
acid.
If the quantity of a-naphtole-mono-sulphonate of soda stated in Example 3 is
replaced by 14.3 Kg. of a-naphtole or by 14.3 Kg. of B-naphtole or by 24.6 Kg.
of naphtole-mono sulphonate of soda (salt of Schaeffer's acid), colours are obtained
which dye cotton from an alkaline bath in shades from blue to blueish violet.
5. Colour from diamido-stilbene and salicylic acid.
A yellow colour is obtained by combining the tetrazo-stilbene (from 28.3 Kg. of
hydrochlorate) with an alkaline solution of 27.6 Kg. of salicylic acid.

page_text: 6. Colour from diamido-fluorene and a-naphtylamine-sulpho-acid.
19.6 Kg. of diamido-fluorene are dissolved in 2000 liters of water and 50 Kg. of
hydrochloric acid of 20° Bé, and converted into its tetrazo-compound by entering
into the solution 13.8 Kg. of nitrite of sodium dissolved in 200 liters of water. This
tetrazo-compound is slowly entered into an alkaline solution of 63.4 Kg. of crystallised
a-naphtylamine-sulphonate of soda in 1000 liters of water. After about 12 hours
standing 2000 liters of water are added, the mixture heated up to boiling, and the
colour precipitated by salt, filtered and dried. The colour dyes cotton direct from a
boiling soap bath a red shade.
7. Colour from diamido fluorene and B-naphtole-disulpho-acid R.
A blue azo-colour is obtained by converting (in the manner described above)
19.6 Kg. of diamido-fluorene into its tetrazo compound and by acting with it upon an
alkaline solution of 69.6 Kg. of ẞ-naphtole-disulphonate of soda (R-salt). The colour
dyes cotton direct from an alkaline soap-bath.
Having now particularly described and ascertained the nature of this invention and
in what manner the same is to be performed I declare that what I claim is :-
:-
The production of azo-colours which dye cotton direct from a soap bath, by
combining one molecule of the tetrazo-compounds of stilbene or fluorene such as are
herein described with two similar or different molecules of an amine such as Aniline,
Toluidine, Xylidine, Benzidine, Tolidine, a-naphtylamine, ẞ-naphtylamine, dimethyle
aniline, diethyle aniline, diphenyl-amine, phenyle-naphty lamine, tolyle-naphty lamine
or a phenole such as carbolic acid, cresote, resorcine a-naphtole, and ẞ-naphtole or of
a sulphonic or carbonic or sulpho-carbonic-acid of an amine or a phenole.
ABEL & IMRAY,
Agents for the Applicant.