Manufacture of Naphthylendiamine-sulpho Acids.
Year: 1894

page_text: Date of Application, 6th July, 1894
Complete Specification Left, 16th Feb., 1895-Accepted, 16th Mar., 1895
[Communicated from abroad by ALFRED FISCHESSER & Co., of Lutterbach,
Alsace, Germany, Chemical Manufacturers.]
Manufacture of Naphthylendiamine-sulpho Acids.
I, CHARLES DENTON ABEL, of No. 28 Southampton Buildings, Chancery Lane,
in the County of London, Consulting Engineer and Chartered Patent Agent, do
hereby declare the nature of this invention to be as follows:-
-
For the manufacture of naphthylendiamine-sulpho acids the following processes
have heretofore been employed.
1. Sulphonation of naphthylendiamine.
2. Reduction of the corresponding azo compounds.
3. Reduction of the corresponding dinitro- and nitroamido naphthalinesulpho
acid.
4. Action of ammonia upon the corresponding dioxy- or amidooxynaphthalin-
sulpho acids.
My correspondents have discovered a new and generally applicable method
which consists in the reaction of sulphite solutions upon dinitronaphthalin.
A characteristic of this reaction is the entrance of sulpho groups into the
naphthaline nucleus simultaneously with the reduction of the nitro groups; the
number thereof varies with the description of the dinitronaphthalin employed and
the method of working adopted.
The following are examples of this method.
I. PRODUCTION OF 1.8 NAPHTHYLENDIAMINETRISULPHO ACID from
PERIDINITRONAPHTHALIN.
For the conversion of peridinitronaphthalin into 1.8 naphthylendiamine trisulpho
acid there is best used an aqueous solution of sulphites, as with this the reaction
proceeds most smoothly and without formation of by-products. The process is as
follows.
20 kilos. of finely ground peridinitronaphthalin are heated to boiling point in an
open or closed vessel together with 200 kil. of 40 p.c. sodium bisulphite solution
until the whole of the dinitronaphthalin is dissolved.
The deep yellow-coloured solution is concentrated to such an extent that on
cooling, the greater part of the formed sodium sulphate will crystallise out.
The solution is separated from the crystals and there is added an excess of
hydrochloric acid, as concentrated as possible, whereby the naphthylendiamine
trisulpho acid will separate as crystals in the form of the soda salt.
(NH)

page_text: diaminetrisulpho acid combines with 1 molecule of diazo-compounds to form azo
colouring matters; it is converted by nitrous acid into an azimido compound.
The acid barium salt which is less soluble than the soda salt crystallises from a
hot-aqueous solution with 3 molecules water of crystallization according to the
formula:
II. PRODUCTION OF A NEW 1.5 NAPHTHYLENDIAMINEDISULPHO ACID FROM
ANADINITRONAPHTHALIN.
For the conversion of anadinitronaphthalin into 1.5 naphthylendiaminedisulpho
acid there may be used with equal advantage acid and neutral sulphites.
In the first case the process may, for example, be carried out as follows.
20 kil. finely ground anadinitronaphthalin are boiled with reflux or in a
closed vessel together with 200 kil. 40 p.c. sodium bisulphite solution, until the
disappearance of the dinitronaphthalin.
The solution is then concentrated and allowed to cool in order that the Glauber
salts formed may mostly crystallise out, and to the lye separated mechanically from
the crystals is added an excess of concentrated hydrochloric acid.
The new
1.5 naphthylendiamine disulpho acid separates, is filtered off and can be purified
by recrystallization.
It is easily soluble in water, in particular in hot water, and is separated therefrom
by means of hydrochloric acid.
With diazo compounds the acid forms azo colouring matters, nitrous acid gives
a yellow moderately soluble tetrazo compound from which diazo colouring matters
can be obtained by means of amines and phenoles. The solutions of the very
soluble neutral alkali-salts have a bluish green fluorescence.
The acid alkali salts, which are obtained from the neutral salts by treatment with
acetic acid, are easily soluble in water, but soluble with difficulty in common salt
solution, their solutions are not fluorescent and are coloured reddish blue by means
of chloride of iron. The colour passes over into violet on standing for some time.
The acid barium salt is only moderately soluble in water and crystallises from it
with 5 molecules of water of crystallisation, corresponding to the formula:

page_text: The new acid is, according to its mode of formation, a derivative of 1.5
naphthylendiamine. Of 1.5 naphthylendiamine disulpho acids only one is known
up to the present time (German Patent 61174) which has the constitution :-
It is however different from the present 1.5 naphthylendiamindisulpho acid, as
according to the statement in the said Patent, it is also almost insoluble in hot water
and forms an insoluble tetrazo compound.
The new 1.5 naphthylendiamine disulpho acid is applicable for the manufacture
of colouring matters.
If it is desired to employ a neutral sulphite for the preparation of the
1.5 naphthylendiamine sulpho acid, the process must be about as follows:-
20 kil. anadinitronaphthalin are boiled with 200 kil. of a solution of neutral
ammonium sulphite of 23 Bé., until it is dissolved, which takes a shorter time
than when using sodium bisulphite. The solution is then concentrated and the
1.5 naphthylendiamine disulpho acid is precipitated by the addition of concentrated
bydrochloric acid.
Dad thin eh den of Tul- 1801
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of CRS
1, CHARLES DENTON ABEL, of No. 28 Southampton Buildings, Chancery
Lane, in the County of Loudon, Consulting Engineer and Chartered Patent Agent,
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 :-
For the manufacture of naphthylendiamine-sulpho acids the following processes
have heretofore been employed.
1. Sulphonation of naphthylendiamine.
2. Reduction of the corresponding azo compounds.
3. Reduction of the corresponding dinitro- and nitroamido naphthaline-sulpho
acid.
4. Action of ammonia upon the corresponding dioxy- or amido-oxynaphthalin-
sulpho acids.
My correspondents have discovered a new and generally applicable method
which consists in the reaction of sulphite solutions upon dinitronaphthalin.
A characteristic of this reaction is the entrance of sulpho groups into the
naphthaline nucleus simultaneously with the reduction of the nitro groups; the
number thereof varies with the description of the dinitronaphthalin employed and
the method of working adopted.

page_text: I. PRODUCTION OF 1.8 NAPHTHYLENDIAMINETRISULPHO ACID FROM
PERIDINITRONAPHTHALIN.
For the conversion of peridinitronaphthalin into 1.8 naphthylendiamine trisulpho
acid there is best used an aqueous solution of sulphites, as with this the reaction
proceeds most smoothly and without formation of by-products. The process is as
follows:
20 kilos. of finely ground peridinitro-naphthalin are heated to boiling point in an
open or closed vessel together with 200 kil. of 40 p.c. sodium bisulphite solution
until the whole of the dinitro-naphthalin is dissolved.
The
The deep yellow-coloured solution is concentrated to such an extent that on
cooling, the greater part of the formed sodium sulphate will crystallise out.
solution is separated from the crystals and there is added an excess of hydro-
chloric acid, as concentrated as possible, whereby the naphthylendiamine trisulpho
acid will separate as crystals in the form of the soda salt.
The acid soda salt of the new naphthylendiamine trisulpho acid is easily soluble
in cold water and very easily soluble in hot water.
The solution shews only very slight greenish fluorescence and, if not too dilute,
is precipitated by mineral acids common salt, and alcohol.
Chloride of iron colours the aqueous solution yellow brown. The naphthylendi-
amine trisulpho acid combines with 1 molecule of diazo compounds to form azo
colouring matters; it is converted by nitrous acid into an azimido compound,
The acid barium salt which is less soluble than the soda salt crystallises from a
hot aqueous solution with 3 molecules water of crystallisation according to the
formula:

page_text: II. PRODUCTION OF A NEW 1.5 NAPHTHYLENDIAMINEDISULPHO ACID FROM
ANADINITRONAPHTHALIN.
For the conversion of anadinitronaphthalin into 1.5 naphthylendiaminedisulpha
acid there may be used with equal advantage acid and neutral sulphites.
In the first case the process may, for example, be carried out as follows.
20 kil. finely ground anadinitronaphthalin are boiled with reflux or in a closed
vessel together with 200 kil. 40 p.c. sodium bisulphite solution, until the
lisappearance of the dinitronaphthalin.
The solution is then concentrated and allowed to cool in order that the Glauber
salts formed may mostly crystallise out, and to the lye separated mechanically from
the crystals is added an excess of concentrated hydrochloric acid. The new
1.5 naphthylendiamine disulpho acid separates, is filtered off and can be purified
by recrystallisation.
It is easily soluble in water, in particular in hot water, and is separated ther -
from by means of hydrochloric acid.
With diazo compounds the acid forms azo colouring matters, nitrous acid gives a
yellow moderately soluble tetrazo compound from which diazo colouring matters
can be obtained by means of amines and phenoles. The solutions of the very
soluble neutral alkali salts have a bluish green fluorescence.
The acid alkali salts, which are obtained from the neutral salts by treatment
with acetic acid, are easily soluble in water, but soluble with difficulty in commo
salt solution; their solutions are not fluorescent and are coloured reddish blue by
means of chloride of iron. The colour passes over into violet on standing for some
time.
The acid barium, salt is only moderately soluble in water and crystallises from
it with 5 molecules of water of crystallisation, corresponding to the formula:
5 It is however different from the present 1.5 naphthylendiamindisulpho acid, as
according to the statement in the said Patent, it is also almost insoluble in hot
water and forms an insoluble tetrazo compound.
The new 1.5 naphthylendiamine disulpho acid is applicable for the manufacture
of colouring matters.

page_text: If it is desired to employ a neutral sulphite for the preparation of the 1.5 naph
thylendiamine sulpho acid, the process must be about as follows:-
20 kilos. anadinitronaphthalin are boiled with 200 kilos. of a solution of neutral
ammonium sulphite of 23 Bé., until it is dissolved, which takes a shorter time
than when using sodium bisulphite. The solution is then concentrated and the
1.5 naphthylendiamine disulpho acid is precipitated by the addition of concentrated
hydrochloric acid.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
1. Manufacture of naphthylendiamine sulpho acids by the reduction of dinitro-
naphthalines by means of sulphites, substantially as described.
2. Manufacture of 1.8 naphthylendiamine trisulpho acid from peridinitro-
naphthalin, as herein described.
3. Manufacture of 1.5 naphthylendiamine disulpho acid from anadinitro-
naphthalin as herein described.
Dated this 16th day of February 1895.
ABEL & IMRAY,
Agents for the Applicant.