The Manufacture of Polynitro Derivatives of Oxydialphylamines and of Colouring Matters therefrom.
Year: 1899

page_text: Date of Application, 5th July, 1899
Complete Specification Left, 4th Apr., 1900-Accepted, 5th May, 1900
IUNAL DIBUITIVATION.
The Manufacture of Polynitro Derivatives of Oxydialphylamines and
of Colouring Matters therefrom.
I, ROBERT BOLTON RANSFORD, of 41, Waldegrave Road, Upper Norwood, .in
the County of Surrey, Gentleman, do hereby declare the nature of this invention
(which has been communicated to me from abroad by Leopold Cassella and Co.,
of Frankfort-on-Main, in the Empire of Germany) to be as follows:-
In the Specification of the British Patent No. 25234" my foreign correspon-
dents have described the production of valuable black dyestuffs, which are
obtained by heating unsymmetrical dinitrooxydialphylamines with sulphur and.
sulphides. My foreign correspondents have now found that the sliade of the
resulting dyestuffs is considerably changed, if further nitro groups are intro-
duced into the nucleus containing the hydroxyl group: The resulting colouring
matters dye cotton dark brown to yellowish brown. Polynitro derivatives of the
oxydialphylamines of the said constitution may either be obtained by condensing
dinitrochlorbenzene with nitroamidophenols or by nitrating the products of con-
The
densation of dinitrochlorbenzene with amidonaphtols or their homologues.
transformation of these bodies into dyestuffs is carried out in the same manner
as described in the Specification No. 2523497.
The process is illustrated by the following examples:
Example 1: 10 kilos pieramic acid, 10 kilos dinitrochlorbenzene, 34 kilos ace-
tate of sodium, 30 litres alcohol of 50% are heated in a closed vessel for 3 to 4
hours to 120 to 130° C. The tetranitrooxydiphenylamine separates from the
cooled-solution in the shape of dark brown needles. By re-crystallisation from
glacial acetic acid, the substance may easily be obtained in a pure state; it
forms bright yellow crystals, melting at 203° C.
10 kilos tetranitrooxydiphenylamine are heated together with 60 kilos sul-
phide sodium and 4.5 kilos sulphur and some water, and the temperature is
gradually raised to about 140° C. The resulting blackish brown raw product can
be directly used for dyeing purposes. The dyestuff may be purified by precipi-
tating it with acids. It dyes coiton a yellowish brown in the presence of sul-
phide of sodium and common salt.
=
Example 2: The aqueous solution of 10 kilos p. amido. a. cresol (CH: OH :
NH
124) is boiled during several hours with 16.5 kilos dinitrochlor
benzene and 15 kilos acetate of sodium, 10 kilos of the dinitrophenyloxytolyl-
amine thus obtained are dissolved in 100 kilos sulphuric acid of 66° Bé. and at
a temperature of about 5° C. 10 kilos of a mixture of nitric and sulphuric acid,
containing 4.4 kilos HNO are slowly introduced. After all the mitric acid has
been added: the product of the nitration is kept standing for several hours and
then diluted with ice. Tetranitrooxyphenyltolylamine separates in the form of
an orange coloured precipitate, which is filtered off, washed and dried.
10 kilos of this tetranitrooxyphenyltolylamine are heated with 60 kilos sul-

page_text: phide of sodium and 15 kilos sulphur and some water up to about 120° C. The
colouring matter thus obtained dyes unmordanted cotton brown shades.
In an analogous manner the polynitro-derivatives of the dinitrooxydiphenyl-
amine, used in the Specification No. 252347 and its isomeres and homologues
are obtained. The dyestuffs obtained therefrom in an analogous manner all yield
dark brown to yellowish brown shades.
The Manufacture of Polynitro Derivatives of Oxydialphylamines and
of Colouring Matters therefrom.
1, ROBERT BOLTON RANSFORD; of 41, Waldegrave Road, Upper Norwood, in
the County of Surrey, Gentleman, do hereby declare the nature of this invention
(which has been communicated to me from abroad by Leopold Cassella and Co.,
of Frankfort-on-Main, 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 the British Patent No. 25234 my foreign correspon-
dents have described the production of valuable black dyestuffs, which aro
obtained by heating unsymmetrical dinitrooxydialphylamines with sulphur and
sulphides. My foreign correspondents have now found that the shade of the
resulting dyestuffs is considerably changed, if further nitro groups are intro-
duced into the nucleus containing the hydroxyl group. The resulting colouring
matters dye cotton dark brown to yellowish brown. Polynitro derivatives of the
oxydialphylamines of the said constitution may either be obtained by condensing
dinitrochlorbenzene with nitroamidophenols or by uitrating the products of con-
deusation of dinitrochlorbenzene with amidophenols or their homologues. The
⚫ transformation of these bodies into dyestuffs is carried out in the same manner
as described in the Specification No. 252347.
The process is illustrated by the following examples:-
Example 1-10 kilos picramic acid 10 kilos dinitrochlorbenzene, 14 kilos ace-
tate of sodium, 30 litres alcohol of 50% are heated in a closed. vessel for 3 to 4
hours to 120 to 130° C. The tetranitrooxydiphenylamine separates from the
cooled solution in the shape of dark brown needles. By recrystallisation from
glacial acetic acid, the substance may easily be obtained in a pure state; it
forms bright yellow crystals, melting at 2030 C.
10 kilos tetranitrooxydiphenylamine are heated together with 60 kilos sul-
phide of sodium and 4.5 kilos sulphur and some water, and the temperature is
gradually raised to about 140° C. The resulting blackish brown raw product can
be directly used for dyeing purposes. The dyestuff may be purified by precipi-
tating it with acids. It dyes cotton a yellowish brown in the presence of sul-
phide of sodium and common salt.
========
Example 2: The aqueous solution of 10 kilos p. amido. o: cresol (CH, : OH :
NH₂
124) is boiled during several hours with 16.5 kilos dinitrochlor-
benzene and 15 kilos acetate of sodium, 10 kilos of the dinitrophenyloxytolyl-
amine thus obtained are dissolved in 100 kilos sulphuric acid of 66°. Bé. and at
a temperature of about 5° C. 10 kilos of a mixture of nitric and sulphuric acid
containing 4.4 kilos HNO, are slowly introduced. After all the nitric acid has
been added the product of the nitration is kept standing for several hours and

page_text: then diluted with ice. Tetranitrooxyphenyltolylamine separates in the form of
an orange coloured precipitate which is filtered off, washed and dried,
10 kilos of this tetrauitrooxyphenyltolylamine are heated with 60 kilos sul-
phide of sodium and 15 kilos sulphur and some water up to about 120° C. The
colouring matter thus obtained dyes unmordanted cotton brown shades:
In an analogous manner the polynitro-derivatives of the dinitrooxydiphenyl-
amine, used in the Specification No. 25234 and its. isomeres and homologues
are obtained. The dyestuffs obtained therefrom in an analogous manner all yield
dark brown to yellowish brown shades.
- 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 hereinbefore described polynitro derivatives of the oxydialphylamines..
2. The production of dyestuff's by heating with sulphur and sulphides the pro-
ducts obtained by condensation of nitroamidophenols such as pieramic acid with
dinitrochlorbenzene or, the nitrated products obtained from the products of con-
densation of amidophenols or their homologues with dinitrochlorbenzene sub-
stantially as described.
3. The new colouring matters substantially as described.