Production of a New Sulpho-acid, and of Colours Derived therefrom.
Year: 1896

page_text: Date of Application, 10th Feb., 1896
Complete Specification Left, 27th Nov., 1896-Accepted, 2nd Jan., 1897
PROVISIONAL SPECIFICATION.
Production of a New Sulpho-acid, and of Colours Derived therefrom.
We, LEVINSTEIN LIMITED and IVAN LEVINSTEIN, both of Minshull Street
Manchester in the County of Lancaster, Chemical Manufacturers, do hereby
declare the nature of this invention to be as follows:-
The production of an a, a, naphthylene diamine sulpho-acid is described in the
Specification of Letters Patent No. 15444, dated the 14th day of August A.D. 1893.
This acid is obtained by nitration of the acetyl compound of a naphthylamine-ẞ
or B-sulpho-acid, and subsequent reduction and saponification. If treated with
nitrous acid it is decomposed and becomes incapable of reacting with amines or
phenols. We have however discovered a new a, a, naphthylenediamine sulpho-
acid which, when treated with nitrous acid produces an amide-diazonaphthalene
sulpho-acid, which readily reacts with amines, diamines, their alkylated and
phenylated compounds, with phenols, amidophenols, amidophenolethers, dioxy-
compounds both of the benzene and naphthalene series, as well as with their known
carboxyl- and sulpho-acids.
In these colouring matters thus formed, only one of the amido groups of the
naphthylene-diamine sulpho-acid enters. into reaction. The second amido group
remains free.
This second amido group may bo further diazotised, and thus diazo-azo-compounds
may be produced, which, combined with amines, diamines, their alkylated and
phenylated compounds, with phenols, amidophenols, amidophenol-ethers, dioxy-
compounds both of the benzene and naphthalene series as well as their known
carboxyl-.and sulpho-acids, produce tetrazo colours which dye shades from yellow
to deep black, and possess very valuable properties. These tetrazo colours may
be employed either for developing the colours on the fibre, or in the production of
colouring matters in substance.
The new a, a, naphthylene-diamine sulpho-acid may be used not only for the
production of azo and tetrazo colours but may also be employed, like all
paradiamines, in the manufacture of saffranines, indulines, and similar colours.
For the production of our new a, a, naphthylene-diamine B1-mono-sulpho-acid,
we may proceed, by way of example, as follows:-

page_text: SECOND STEP.-REDUCTION OF THE AZO COLOUR.
The pressed cake produced in the first step, is added to a boiling mixture of
36 kilos. of iron borings,
200 litres of water, and
.2 kilos. of ordinary commercial hydrochloric acid.
When the reduction is finished, the mass is made slightly alkaline with sodium
carbonate or other suitable alkali, and the free aniline is recovered by steam. The
remaining solution, which contains the sodium salt of the new naphthylene-
diamine-acid, is then separated from the iron by filtration or otherwise. The
filtrate is now acidified, when the new naphthylene-diamine sulpho-acid crystallises
out in fine needles having a slight red coloration.
This new acid is almost insoluble in cold water, more easily soluble in hot
water, and almost insoluble in alcohol. A very characteristic property of it is the
readiness with which it is oxidised in a neutral, or still more, in an alkaline solution,
even by the oxygen of the air. The product of oxidation is a yellow crystalline
substance, which, in an aqueous solution, shews a magnificent greenish-yellow
fluorescence resembling that of fluoresceine.
We do not confine ourselves to the above example, as, in the first step, that is
to say in the formation of the azo colour, we may use other suitable diazo bodies
in place of the diazobenzene, such for example as the diazo-compounds of toluidine,
xylidine, and a naphthylamine, or their sulpho-acids. We however give preference,
at present, to the use of aniline. In the second step also, we do not confine
ourselves to the specified method of reduction, as other well-known methods may
be employed. So far, we have found the method of reduction described, to be
economical and effective.
For the production of colouring matters by means of our new sulpho-acid, we
may for example, proceed as follows:-
α,
FIRST STEP.-CONVERSION OF THE a₁a, NAPHTHYLENE-DIAMINE SULPHO-
ACID INTO AN AMIDO-DIAZO-NAPHTHALENE SULPHO-ACID.
23.8 kilos. of the a₁ a, naphthylene-diamine sulpho-acid are dissolved in a solution
of about 5.3 kilos. of sodium carbonate in 200 litres of water, or other suitable
alkali in molecular proportion. Ice is added, and when the mixture is cool, the
naphthylene-diamine sulpho-acid is precipitated in a finely divided state by means
of 100 kilos. of dilute acetic acid containing 30 per cent. of acid. The mixture is
well stirred and diazotised with an aqueous solution containing 7.2 kilos. of
sodium nitrite.
The amido-diazo-naphthalene sulpho-acid separates after some time as a
difficultly soluble powder of a brownish-yellow colour. Instead of the acetic acid,
which at present we prefer to use, hydrochloric acid or other suitable acid or acids
may be employed.
SECOND STEP.-CONVERSION OF THE AMIDO-DIAZO-NAPHTHALENE SULPHO-
ACID INTO AN AMIDO-AZO COLOURING MATTER.
The amido-diazo-naphthalene sulpho-acid produced in the first step, and
obtained from 23-8 kilos. of a₁ a, naphthylene-diamine sulpho-acid, is added, at
ordinary temperature, whilst stirring, to an alkaline solution of 35 kilos. of
ẞnaphthol disulpho-acid R. The combination begins at once and is completed

page_text: within a short time. The colouring matter thus obtained is salted out, filtered,
pressed, and dried. It dyes wool, in an acid bath, a blue colour.
Other dye-stuffs may be obtained in an analogous manner if, in place of
ẞnaphthol disulpho-acid R, other compounds are used, such for example as amines,
diamines, their alkylated and phenylated compounds, or phenols, amidophenols,
amidophenol-ethers, dioxy-compounds both of the benzene and naphthalene series
as well as their known carboxyl- and sulpho-acids.
THIRD STEP.-CONVERSION OF AN AMIDO-AZO COLOURING MATTER INTO
A TETRAZO COLOURING MATTER.
62 kilos. of the azo dye-stuff prepared as above set forth and produced in the
second step of this example, are dissolved in about 300 litres of water acidulated
with 20 kilos of hydrochloric acid 20 Bè. To the diluted solution cooled with ice,
there is gradually added a solution containing 7.2 kilos. of sodium nitrite. The
whole mixture is well stirred and kept at a low temperature. The solution which
was originally violet-blue, changes to a deep red. After a few hours, the original
dye-stuff will be found to be completely transformed into the diazo-azo-compound
which may be either at once used for combination, or be precipitated by means of
common salt.
The diazo-azo compound, either in solution or in a precipitated form, is added,
whilst stirring, to an alkaline solution of 14.5 kilos. ẞ naphthol. An excess of
caustic alkali is to be avoided.
After the reaction is completed, the produced tetrazo colour is precipitated or
may be completely separated as a dark blue precipitate, by means of common
salt.
It dyes wool, in a neutral or acid bath, a deep blue to black.
Analogous dye-stuffs are produced if, in place of ẞ naphthol, other phenols or
amines, diamines or their alkylated or phenylated compounds, dioxy-compounds
both of the benzene and naphthalene series, as well as their known carboxyl- and
sulpho-acids are used.
Doted this 711 L
D 1000
W. E. HEYS & SON,
Agents for the Applicants.
Production of a New Sulpho-acid, and of Colours Derived therefrom.
We, LEVINSTEIN LIMITED, and IVAN LEVINSTEIN, both of Minshull Street,
Manchester in the County of Lancaster, Chemical Manufacturers, 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 :-
The production of an a₁ a, naphthylenediamine sulpho-acid is described in the
Specification of Letters Patent No. 15444 dated the 14th day of August A.D. 1893.
This acid is obtained by nitration of the acetyl compound of a, naphthylamine
B, or B, sulpho-acid and subsequent reduction and saponification. If treated with
nitrous acid it is decomposed and becomes incapable of reacting with amines or
phenols. We have however discovered a new a, a, naphthylenediamine sulpho-acid
which, when treated with nitrous acid, produces an amidodiazonaphthalene sulpho-
acid, which readily reacts with amines, diamines, their alkylated and phenylated

page_text: kulos. of iron borings,
200 litres of water, and
2 kilos. of ordinary commercial hydrochloric acid.
When the reduction is finished, the mass is made slightly alkaline, by means of
. Bodium carbonate or other suitable alkali, and the free aniline is recovered by
steam in the well understood manner. The remaining solution, which contains
. the sodium salt of the new naphthylenediamine sulpho-acid, is then separated
from the iron by filtration or otherwise. The filtrate is now acidified, when the
new. naphthylenediamine sulpho-acid crystallises out in fine needles having a slight
red coloration.
This new acid is almost insoluble in cold water, more easily soluble in hot water,
and almost insoluble in alcohol. A very characteristic property of it is the
readiness with which it is oxidised in a neutral, or still more, in an alkaline solution,
even by the oxygen of the air. The product of oxidation is a yellow crystalline
substance which, in an aqueous solution, shews a magnificent greenish-yellow
fluorescence resembling that of fluoresceine.
We do not confine ourselves to the above example, as, in the first step, that is
to say in the formation of the azo colour, we may use other suitable diazo bodies
in place of the diazobenzene, such for example as the diazo compounds of toluidine,

page_text: xylidine, and a naphthylamine or their sulpho-acids. We however usually give
preference to the use of aniline as described. In the second step also, we do not
confine ourselves to the specified method of reduction, as other well known means
may be employed; so far, we have found the described method of reduction to be
economical and effective.
For the production of colouring matters by means of our new sulpho-acid, we
FIRST STEP.-CONVERSION OF THE a₁ a, NAPHTHYLENEDIAMINE 3 SULPHO-
ACID INTO AN AMIDODIAZONAPHTHALENE SULPHO-ACID.
23.8 kilos. of the a, a, naphthylenediamine sulpho-acid are dissolved in a solution
of about 5-3 kilos. of sodium carbonate in 200 litres of water, or of other suitable
alkali in equivalent molecular proportion. Ice is added, and when the mixture
is cool, the naphthylenediamine sulpho-acid is precipitated in a finely divided
state by means of 100 kilos. of acetic acid containing 30 per cent. acid.
mixture is well stirred and diazotised by an aqueous solution of 7-2 kilos. of sodium
nitrite.
The
The amidodiazonaphthalene sulpho-acid separates after some time as a difficultly
soluble powder of a brownish-yellow colour. Instead of acetic acid, which we
prefer to use, other suitable acid or acids may be employed.
SECOND STEP.-CONVERSION OF THE AMIDODIAZONAPHTHALENE SULPHO-
ACID INTO AN AMIDO-AZO COLOURING MATTER.
The amidodiazonaphthalene sulpho-acid produced in the first step, and obtained
from 23.8 kilos. of a, a, naphthylenediamine sulpho-acid is added, at ordinary
temperature, and whilst stirring, to an alkaline solution of 35-0 kilos. of ẞ naphthol
disulpho-acid R. The combination begins at once and is completed within a short
time. The colouring matter thus obtained is salted out, filtered, pressed and
dried. It dyes wool, in an acid bath, a blue colour.
Other dye-stuffs may be obtained in an analogous manner, if, in place of
ẞnaphthol disulpho-acid R, other compounds are used, such for example as amines,
diamines, their alkylated and phenylated compounds, amidophenols, amidophenol-
ethers, dioxy compounds both of the benzene and naphthalene series, as well as
their known carboxyl- and sulpho-acids. In such cases it will be obvious to
chemists, that equivalent molecular proportions to those hereinbefore specified
should be employed.
THIRD STEP.-CONVERSION OF AN AMIDO-AZO COLOURING MATTER INTO A
TETRAZO COLOURING MATTER.
62-0 kilos. of the azo dye-stuff prepared as above set forth, and produced in the
second step
of this example, are dissolved in about 300 litres of water acidulated
with 70 kilos. of hydrochloric acid, 20° Bè. To the diluted solution, cooled with
ice, there is gradually added a solution containing 7.2 kilos. of sodium nitrite.
The whole mixture is well stirred and kept at a low temperature. The solution,
which was originally violet-blue, changes to a deep red. After a few hours, the
original dye stuff will be found to be completely transformed in the diazo-azo
5 compound which may either be at once used for combination, or be precipitated by
means of common salt.
The diazo-azo compound, either in solution or in a precipitated form, is added,
whilst stirring, to an alkaline solution of 14-5 kilos. of ẞ naphthol. An excess of
caustic alkali is to be avoided.

page_text: After the reaction is completed, the produced tetrazo colour is precipitated
or may be completely separated as a dark blue precipitate by means of
common salt.
It dyes wool, in a neutral or acid bath, a deep blue to black.
Analogous dye-stuffs are produced if, in place of ẞ naphthol, other phenols or
amines, diamines, or their alkylated or phenylated compounds, dioxy compounds
both of the benzene and naphthalene series, as well as their known carboxyl- and
sulpho-acids are used.
Having now particularly described and ascertained the nature of our said inven-
tion and in what manner the same is to be performed, we declare that what we
claim is :-
1. As a new substance, the new a, a, naphthylenediamine ẞ, sulpho-acid which is
produced by the process in that behalf hereinbefore described.
2. As a new substance, the new amidodiazonaphthalene sulpho-acid which is
produced by the process in that behalf herein before described.
3. As new substances, the new amidoazo colouring matters which are produced by
treating the a₁ a, naphthylenediamine B, sulpho-acid claimed in the first claim, with
nitrous acid so as to produce an amidodiazonaphthalene sulpho-acid, and causing
this acid to react with amines, diamines, their alkylated and phenylated compounds,
with phenols, amidophenols, amidophenol-ethers, dioxy compounds both of the
benzene and naphthalene series, as well as their known carboxyl- and sulpho-acids,
substantially as hereinbefore described.
4. As new substances, the tetrazo colouring matters which are produced by
diazotising the colouring matters claimed in the preceding claim and combining
them with amines, diamines, their alkylated and phenylated compounds, with
phenols, amidophenols, amidophenol-ethers, dioxy compounds both of the benzene
and naphthalene series, as well as their known carboxyl- and sulpho-acids, substan-
tially as herein before described.
5. The herein before described process for the manufacture or production of a
new a, a, naphthylenediamine ẞ, sulpho-acid substantially as set forth.
6. The hereinbefore described process for the manufacture or production of a
new amidodiazonaphthalene sulpho-acid, substantially as set forth.
7. The hereinbefore described process for the manufacture or production of
amido-azo colouring matters, substantially as set forth.
3
8. The herein before described process for the manufacture or production of
tetrazo colouring matters, substantially as set forth.
.. Dated this 25th day of November A.D. 1896.
"
W. E. HEYS & SON,
Agents for the Applicants.