Year: 1896

page_text: We, IVAN LEVINSTEIN and LEVINSTEIN LIMITED of Minshull Street,
Manchester in the County of Lancaster, Chemical Manufacturers, do hereby
declare the nature of this invention to be as follows:-
We have found that if the a, a, naphthylenediamine-ß-monosulpho acid produced
as set forth in the Specification left with our Application for Letters Patent No. 2946
dated 10th February A.D. 1896, is heated with an excess of glacial acetic acid
and dehydrating agents, preferably anhydrous sodium acetate, for some hours,
a monacetyl naphthylene-diamine-sulpho acid results which has probably the
following constitution
We, IVAN LEVINSTEIN and LEVINSTEIN LIMITED of Minshull Street,
Manchester in the County of Lancaster, Chemical Manufacturers, do hereby
declare the nature of this invention to be as follows:-
We have found that if the a, a, naphthylenediamine-ß-monosulpho acid produced
as set forth in the Specification left with our Application for Letters Patent No. 2946
dated 10th February A.D. 1896, is heated with an excess of glacial acetic acid
and dehydrating agents, preferably anhydrous sodium acetate, for some hours,
a monacetyl naphthylene-diamine-sulpho acid results which has probably the
following constitution
a1
.NH2
SO,H.
00°
NH.CO.CH,
According to our present invention, this new acid forms the basis for the
production of a series of new and very valuable colouring matters. The acetylation
of the a₁ a-naphthylenediamine sulpho-acid may be carried out as follows:-
One part of the dry naphthylenediamine sulpho-acid is heated with about three
parts of glacial acetic acid and one part of anhydrous sodium acetate, under a
reflux condenser for about 12 hours. The reaction is finished when a sample taken
from it is found to be completely soluble in water. When this stage is reached,
the excess of glacial acetic acid may be distilled off, and the new acetyl acid is
obtained in a form directly suitable for technical purposes. The new acetylated
acid may be purified by dissolving it in water and precipitating it from its solution
by an excess of cold hydrochloric acid. It is thus obtained in the form of silver-
white needles which are easily soluble in water and in alcohol. If treated with
nitrous acid, an acetamidodiazonaphthalene sulpho-acid results, which has a
canary-yellow colour and is very difficultly soluble in water. It re-acts very easily
with amines, phenols and the like, forming acetylamidoazo colours. Tetrazo dye-
stuffs may be produced from these by first saponifying them,-splitting off the
acetyl group-and then diazotising and combining a second time with colour
producing agents, for example, with amines diamines or phenols. Two series of
dye-stuffs may be thus obtained.
1. If in the first combination a pheuol was used, tetrazo colouring matters

page_text: C₁0H. - SO₂H.
- N N Ri.
-
in which R represents the rediazotisable middle component above referred to,
and Ri any well known colour producing component.
In order to produce the new colouring.matters we may proceed as follows:--
EXAMPLE I.
To produce a dye-stuff of the general formula :-
a1
- N N Ri.
=
-
C₁H SO.H.
-
- N N Rii.
= -
02
30-2 kilos. of a, az amidoacetnaphthalid-ẞ,-sulpho-acid are dissolved in
about 300 litres of water cooled with ice acidified with 24 kilos. of commercial
hydrochloric acid, and then diazotised in the well known manner with an aqueous
solution of 7-2 kilos. of sodium nitrite. The diazo compound separates out after
some time as a very difficultly soluble yellowish powder. If this is combined
with 35 kilos. of B-naphthol disulpho-acid R, in an alkaline solution, a deep red
colouring matter results which is precipitated in the usual manner with salt. The
separated dye-stuff is filtered off, and in order to saponify it, it is boiled
with 500 litres of 10 per cent., caustic soda until a sample mixed with acetic acid
shews a pure red violet colour. This colour however is not identical with the
amidoazo colour obtained by combining the diazo compound of the a, a, naph-
thylenediamine-B-sulpho acid with ẞ naphthol disulpho-acid R, as described in
the Example II set forth in the Specification left with our Application for
Letters Patent No. 2946 dated the 10th February A.D. 1896. To the colouring
matter obtained as above described there is added an excess of hydrochloric acid

page_text: or other suitable acid, and it is then diazotised by the addition of 7.2 kilos. of
sodium nitrite, care being taken to keep the temperature low. After a few hours
the original dye-stuff will be found to be completely transformed into the deep red
coloured diazo compound. If the latter is introduced into an alkaline solution
of 14.5 kilos. of ẞ naphthol, care being taken to avoid an excess of caustic alkali, a
dark blue dye-stuff is at once formed which is finished in the usual way. It dyes
wool, in an acid bath, a much greener and brighter blue colour than does the
isomeric colour described in the Example IV set forth in the Specification left
with our hereinbefore mentioned Application for Letters Patent No. 2946 of 1896
and it possesses also a much greater affinity for vegetable fibres.
Analogous dye-stuffs are obtained if, in the first combination, other components
such as phenols, naphthols, dioxynaphthalenes, tertiary amines, or their sulpho and
carboxylic acids and the like are used and in the second stage, any other well
known colour producing agent is substituted.
C10H5
-
- SO₂H.
- N N Ri.
d2
If, instead of the 35 kilos. of ẞ naphthol disulpho-acid R in the Example I,
24 kilos. of amidonaphthol sulpho-acid are used, and the obtained dye-stuff is
saponified and worked up as described in that example, the resulting colouring
matter contains two rediazotisable amido groups as will be obvious from its
formula:-
OH.
a1
-
( − N = N - CH
NH₂
C1, H.
-
SO, H
SO,Hy.
- NH₂
a2
It dyes wool, in an acid bath, a deep violet-black. In order to tetrazotise this
colour, it is dissolved in 10 parts of water, cooled with ice to a low temperature,
acidified with 70 kilos. of commercial hydrochloric acid, and, whilst stirring, an
aqueous solution of 14.4 kilos. of sodium nitrite is then allowed to run in. After
stirring for about 12 hours, the mixture is converted into the diazo compound, and
this is then run into an aqueous solution of 25 kilos. of metatoluylene diamine, the
excess of hydrochloric acid being neutralised with sodium acetate. The combination
is completed within a short time. The whole is then made alkaline, and the colouring
matter is salted out, filtered and pressed in the usual way. It dyes animal and
vegetable fibres a deep black.
If, instead of amidonaphthol sulpho-acid y-the equivalent amount of a naphthyl-
amine, or a naphthylamine-6-sulpho-acid, or a naphthylamine-ß,-sulpho-acid,
(Clève's acids) or amidonaphtholethers are used, and if instead of metatoluylene-
diamine, the equivalent amount of other suitable components as for example

page_text: naphthol sulpho-acids, amidonaphthol sulpho-acids, or dioxynaphthalene sulpho-
acids are used, dye-stuff's having analogous properties are obtained.
EXAMPLE III.
A further class of polyazo dye-stuffs is obtained if the diazo compound of the
a a, amidoacetnaphthalid sulpho-acid is combined with a diazotisable amine, then
Mazotised again, combined with an amine or phenol, and finally saponined. The
dye-stuffs obtained in this manner possess the general formula:-
Onenoi,
many saponined.
dye-stuffs obtained in this manner possess the general formula :-
=N=N=R-N-N-Ri.
C₁0H, SO₂H.
→
= NH,
in which R represents a rediazotisable middle component, and Ri., any well known
colour producing agent.
The diazo compound of 30-2 kilos. of a, a, amidoacetnaphthalid-ẞ-sulpho-acid,
obtained as set forth under Example 1, is poured into an aqueous solution of
18 kilos. of a naphthylamine hydrochloride, an excess of sodium acetate is added,
the whole is stirred, and after a few hours the combination is complete. The
precipitated dye-stuff is filtered and dissolved in about 500 litres of water containing
4 kilos. of caustic soda. To this solution there is then added an aqueous solution of
7-2 kilos. of sodium nitrite, and the whole is allowed to run, whilst stirring, into
36 kilos. of diluted commercial hydrochloric acid, the mixture being kept cold by
ice or otherwise. Stirring is continued for some hours and the diazo compound
thus formed separates out as a difficultly soluble brown powder. This diazo
compound is combined with 27 kilos. of amidonaphthol sulpho-acid y, in an alkaline
solution. The colouring matter thus obtained is filtered off and saponified by
boiling with 1000 litres of ten per cent. caustic soda, until the pure blue colour of a
diluted sample is not changed on the addition of acetic acid; it is then neutralised
with acid and the dye-stuff is salted out.
It dyes wool and cotton a deep black. Analogous dye-stuffs are obtained, if, in
this example, a naphthylamine is replaced by either a, B3 or a, ß, naphthylamine
sulpho-acid, or a, ß, amidonaphtholether. Instead of amidonaphthol sulpho-acid y,
any well known colour producing agent can be used in the last stage.
Dated this 29th day of July A.D. 1896.
W. E. HEYS & SON,
Agents for the Applicants.
We, IVAN LEVINSTEIN and LEVINSTEIN LIMITED, both of Minshull Street 3
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 :-
We have found that if the a, a, naphthylenediamine B1-monosulpho acid produced 4

page_text: as set forth in the Specification of Letters Patent granted to us No. 2946, dated
the 10th day of February A.D. 1896, is heated with an excess of glacial acetic
acid and dehydrating agents, preferably anhydrous sodium acetate, for some hours,
a monacetyl naphthylenediamine sulpho acid results which has probably the
following constitution:-
According to our present invention, this new acid forms the basis for the
production of a series of new and very valuable colouring matters.
The acetylation of the a, a, naphthylenediamine sulpho acid may be carried out
as follows:-
One part of the dry naphthylenediamine sulpho acid is heated with about three
parts of glacial acetic acid and one part of anhydrous sodium acetate, under a
reflux condenser, for about 12 hours. The reaction is finished when a sample taken
from it is found to be completely soluble in water. When this stage is reached, the
excess of glacial acetic acid may be distilled off, and the new acetyl acid is obtained
in a form directly suitable for technical purposes. The new acetylated acid may
be purified by dissolving it in water and precipitating it from its solution by an
excess of cold hydrochloric acid. It is thus obtained in the form of silver-white
needles which are easily soluble in water and in alcohol. If treated with nitrous
acid, an acetamidodiazonaphthalene sulpho acid results, which has a canary-yellow
colour and is very difficultly soluble in water. It reacts very easily with amines,
phenols and the like, forming acetylamidoazo colours. Tetrazo dye-stuffs may be
produced from these colours by first saponifying them, (splitting off the acetyl
group), and then diazotising and combining a second time with colour producing
agents, for example with amines, diamines, or phenols. Two series of dye-stuff's
may thus be obtained.
(1.) If, in the first combination, a phenol were used, tetrazo colouring matters
result by a diazotisation and combination, which have the following general
tution
in which Ri represents a phenol or a non-rediazotisable amnine, and Rii, any of the
well known colour producing agents.
(2.) If however, the acetylamidodiazonaphthalene sulpho acid is combined with
a diazotisable amine or amidophenol, with amidophenolether, or with their sulpho

page_text: in which R represents the rediazotisable middle component above referred to, and
Ri any well known colour producing component.
In order to produce the new colouring matters we may proceed as follows:-
EXAMPLE I.
To produce a dye-stuff having the general formula :-
a1
- N N Ri.
CH-SO,H.
- N N Rii.
a₂
30-2 kilos. of a a₂ amidoacetnaphthalid B, sulpho acid are dissolved in about
300 litres of water, cooled with ice, acidified with 24 kilos. of commercial hydro-
chloric acid, and then diazotised in the well known manner with an aqueous
solution of 7-2 kilos. of sodium nitrite. The diazo compound separates out after
some time as a very difficultly soluble yellowish powder. If this is combined with
35 kilos. of ẞ naphthol disulpho acid R in an alkaline solution, a deep red colouring
matter results which can be precipitated in the usual manner with common salt.
The separated dye-stuff is filtered off, and in order to saponify it, it is boiled with
500 litres of 10 per cent. caustic soda until a sample mixed with acetic acid shews a
pure red-violet colour. This colour is however not identical with the amidoazo
colour obtained by combining the diazo compound of the a, a,-naphthylenediamine
B sulpho acid with ẞ naphthol disulpho acid R, as described in the Specification
of the Letters Patent No. 2946 of 1896, hereinbefore referred to. To the colouring
matter obtained as above described, there is added an excess of hydrochloric or
other suitable acid, and it is then diazotised by the addition of 7.2 kilos. of sodium
nitrite, care being taken to keep the temperature low. After a few hours, the
original dye-stuff will be found to be completely transformed into the deep red
coloured diazo compound. If the latter is introduced into an alkaline solution of
14.5 kilos. of ẞ naphthol, care being taken to avoid an excess of caustic alkali, a
dark-blue dye-stuff is at once formed which is finished in the usual way. It dyes
wool, in an acid bath, a much greener and brighter blue colour than does the
isomeric colour described in the Example IV set forth in the Specification of the
Letters Patent No. 2946 of 1896 hereinbefore referred to and it possesses also a
greater affinity for vegetable fibres.
Analogous dye-stuffs are obtained if, in the first combination, other components
such as phenols, naphthols, dioxynaphthalenes, tertiary amines, or their sulpho and
carboxylic acids and the like are used; and, in the second stage, any other well
known colour producing agent is substituted.

page_text: the general formula
-N N-R-N-N- Ri.
CH, SO,H.
-
- N = N Ri.
az
-
If, instead of the 35 kilos. of ẞ naphthol disulpho acid R, in the Example I,
24 kilos. of amidonaphthol sulpho acid y are used, and the obtained dye-stuff is
saponified and worked up as described in that example, the resulting colouring
matter contains two rediazotisable amido groups as will be obvious from its
formula:-
α
.OH
- N = N – CH, NH,
= N - H.--
C10H
-
- SO,H
-
NH,
ag
SO,Hy.
It dyes wool, in an acid bath, a deep violet-black. In order to tetrazotise this
colour, it is dissolved in 10 litres of water, cooled with ice to a low temperature,
acidified with 70 kilos. of commercial hydrochloric acid, and, whilst stirring, an
aqueous solution of 14.4 kilos. of sodium nitrite is then allowed to run in. After
stirring for about 12 hours, the mixture is converted into the diazo compound and
this is then run into an aqueous solution of 25 kilos. of metatoluylene diamine, the..
excess of hydrochloric acid being neutralised with sodium acetate. The combination
is completed within a short time. The whole is then made alkaline and the
colouring matter is salted out, filtered and pressed in the usual way. It dyes
animal and vegetable fibres a deep black.
If, instead of amidonaphthol sulpho acid y, the equivalent amount of a naphthyl-
amine, or a naphthylamine ẞ, sulpho acid, or a naphthylamine ẞ, sulpho acid
(Cleve's acids), or amidonaphtholethers are used; and if, instead of metatoluylene-
diamine, the equivalent amount of other suitable components such for example as
naphthol sulpho acids, amidonaphthol sulpho acids or dioxynaphthalene sulpho
acids are used, dye-stuffs having analogous properties are obtained.

page_text: in which R represents a rediazotisable middle component, and Ri any well known
colour producing agent.
The diazo compound of 30-2 kilos. of a, a, amidoacetnaphthalid B, sulpho acid,
obtained as set forth under .Example I, is poured into an aqueous solution of
18.0 kilos. of a naphthylamine hydrochloride, an excess of sodium acetate is added;
the whole is stirred; and after a few hours, the combination is complete. The
precipitated dye-stuff is filtered and dissolved in about 500 litres of water
containing 4 kilos. of caustic soda. To this solution there is then added an aqueous
solution of 7-2 kilos. of sodium nitrite and the whole is allowed to run, whilst
stirring, into 36 kilos. of diluted commercial hydrochloric acid 18° Bé., the mixture
being kept cold by ice or otherwise. Stirring is continued for some hours and the
diazo compound thus formed separates out as a difficultly soluble brown powder.
The diazo compound is combined with 27 kilos. of amidonaphthol sulpho acid y, in
an alkaline solution. The colouring matter thus obtained is filtered off and
saponified by boiling it with 1000 litres of 10 per cent. caustic soda until the pure
blue colour of a diluted sample is not changed on the addition of acetic acid. It is
then neutralised with acid and the dye-stuff is salted out.
It dyes wool and cotton a deep black. Analogous dye-stuffs are obtained if, in
this example, a naphthylamine is replaced by either a ẞs, or a, ß, naphthylamine
sulpho acid or by a₁ B₁ amidonaphtholether. Instead of amidonaphthol sulpho
acid y, any well known colour producing agent can be used in the last stage.
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. The hereinbefore described method of or process for the production of amido-
acetnaphthalid sulphonic acid which consists in heating dry a, a, naphthylene-
diamine nonosulphonic acid with glacial acetic acid and a dehydrating agent or
agents, substantially as set forth.
2. The hereinbefore described method of or process for the production of
acetamidodiazonaphthalene sulphonic acid which consists in heating dry ai az naph-
thylenediamine B, monosulphonic acid with glacial acetic acid and a dehydrating
agent or agents and diazotising the intermediate product, substantially as set
forth.
3. The hereinbefore described method of or process for the production of diazo
colouring matters substantially as set forth under Example I.
4. The hereinbefore described process for or method of the production of tetrazo
colours substantially as set forth under Example II.
5. The hereinbefore described method of or process for the production of polyazo
colouring matters substantially as set forth under Example III.
6. As a new substance, the new amidoacetnaphthalid sulphonic acid hereinbefore
described.
7. As a new substance, the new acetamidodiazonaphthalene sulphonic acid
herein before described.
8. As new substances, the new acetylamidoazo colouring matters hereinbefore
described.
9. As new substances, the new tetrazo colouring matters herein before described.
10. As new substances, the new trisazo colouring matters hereinbefore described.
Dated this 28th day of April A.D. 1897.
W. E. HEYS & SON,
Agents for the Applicants.