Production of Azo Colouring Matters.
Year: 1892

page_text: Date of Application, 6th Aug., 1892
Complete Specification Left, 3rd May, 1893-Accepted, 2nd June, 1893
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE SOCIETY OF CHEMICAL INDUSTRY IN
BASLE, Basle, Switzerland.]
Production of Azo Colouring Matters.
I, OLIVER IMRAY, of 28 Southampton Buildings, Chancery Lane, in the County
of London, Chartered Patent Agent, do hereby declare the nature of this invention
to be as follows:-
As the starting point for the production of the new azo colouring matters which
form the subject of the present invention is taken dioxy-naphtoë-mono-sulpho-acid
of the following formula:
C10H
-OH
-OH
-
-
COOH
-SO₂H,
obtained by the action of caustic-alkalies on ẞ-oxy-naphtoë-di-sulpho-acid.
The colouring matters which are produced by the action of tetrazo-compounds
upon dioxy-naphtoë-mono-sulpho-acid have a remarkable affinity for unmordanted
Their tints range from red, violet to black.
cotton.
The dye-stuffs deriving from the secondary diazo compounds of a-naphthylamine
and dioxy-naphtoe-mono-sulpho-acid are specially suitable for dyeing black on wool
without a mordant or with a mordant of chromium salts.
The production of the said new azo colouring matters deriving from dioxy-
naphtoë-mono-sulpho-acid can be effected according to three different methods.
1. FIRST METHOD OF MANUFACTURE.
Colouring matters obtained by the action of one molecule of a tetrazo compound
upon two molecules of dioxy-naphtoe-mone-sulpho-acid or by combining the inter-
mediate product resulting from the reaction of one molecule of a tetrazo body and
one molecule of dioxy-naphtoë-mono-sulpho-acid with one molecule of any amine or
phenol or their sulpho- or carbon-acids.
EXAMPLE.
46 kilos. of benzidine are diazotised in the usual way with 3.5 kilos. of sodium
nitrite and 15 kilos. of muriatic acid; the tetrazo-compound thus produced is
poured into a cooled alkaline solution of 16.5 kilos. of dioxy-naphtoë-mono-
sulphonate of soda.
The black azo-dye is immediately formed.
After some hours repose the mixture is heated and the colouring matter is
precipitated by means of common salt; it is pressed and dried.
It dyes black on unmordanted cotton in a neutral or alkaline bath as well as on a
mordant of tannin and tartar emetic or pyrolignite of iron.

page_text: In treating the tints produced on unmordanted cotton with mordants such as
pyrolignite of iron or chromium salts, darker shades are obtained.
B. DIAMINES DERIVED FROM AZO-BODIES:
p-diamido-azo-benzene,
p-diamido-phenyl-azo-toluene,
p-diamido-azo-toluene,
p-amido-phenyl-azo-a-naphthylamine, p-amido-tolyl-azo-a naphthylamine, p-amido-
phenyl-azo-p-xylidine, p-amido-tolyl-azo-p-xylidine.
EXAMPLE.
6.5 kilos. of p-amido-phenyl-azo-a-naphthylamine are dissolved in
16 kilos. of muriatic acid and the necessary quantity of warm water.
The mixture is poured on to ice and
3.45 kilos. of sodium nitrite in a solution of 10 litres of water are slowly added.
The diazo solution is filtered, and introduced into a solution of:
165 kilos. of dioxy-naphtoë-mono-sulphonate of soda and 10 kilos. of soda and is
continuously stirred during 12 hours.
The colouring matter resulting from this process dyes unmordanted cotton from
grey to black according to the intensity of the tints.
C. The diamines mentioned in paragraph I (A and B) are diazotised and then
combined first only with one molecule of dioxy-naphtoë-mono-sulpho-acid.
The intermediate products thus obtained are allowed to react upon one molecule
of the following components:
Series
dioxy-naphtoë-mono-sulpho-acid.
(14) a-naphtol-mono-sulpho-acid of Nevile and Winther

page_text: 2.8
sodium nitrite.
"
"
By introducing this mixture into a solution of 6.5 kilos. of dioxy-naphtoë-mono-
sulphonate of soda rendered alkaline by addition of bicarbonate of soda, an inter-
mediate product is formed which can be combined further with any dye-stuff'
component of series 2 as enumerated above.
On allowing the aforesaid intermediate product to react upon a solution of
5-2 kilos. of 14 a-naphtol-sulpho-acid (Nevile and Winther) or 55 kilos. of
18 dioxy-naphthaline-mono-sulpho-acid S, new colouring matters are obtained
which dye from blue-black to blackish-blue the unprepared cotton, according to
the strength of the tints.
D. The process may be conducted inversely, that is to say, in preparing
intermediate products by means of one molecule of a tetrazo-compound and
one molecule of one of the phenols, amines, amido-phenols or of their sulpho- or
carbon-acids indicated in paragraph I letter C (series 1 and 2,) and in combining
them with the new dioxy-naphtoë-mono-sulpho-acid.

page_text: EXAMPLE 1.
3 kilos. of disulphonic acid of aniline (obtained by nitrification and reduction of
disulphonic acid of benzene) are diazotised with 0.7 kilos. of sodium nitrite and
3 kilos. of muriatic acid and combined with 1.78 kilos. of chlorhydrate of
a-naphtylamine.
The mixture is agitated during twelve hours and after adding another 3 kilos. of
nuriatic acid and 0.7 kilos. of sodium nitrite the azo-compound thus formed is
mixed with an alkaline solution of 33 kilos. dioxy-naphtoë-mono-sulpho-acid.
After some time the solution of the dye-stuff is heated and precipitated with
common salt.
The intermediate product obtained from diazotised naphtylamine-di-sulpho-acid
(German Patent No. +1957) and a naphtylamine is diazotised and combined with
dioxy-naphto-mono-sulpho acid.
The colouring matter produced by this process dyes also on wool intense blue-
black tints in an acid bath.
On chromed wool grey-black shades are obtained in a bath acidulated with
acetic acid.
Dated this 6th day of August 1892.
ABEL & IMRAY,
Agents for the Applicant.

page_text: COMPLETE SPECIFICATION.
Production of Azo Colouring Matters.
I, OLIVER IMRAY of 28 Southampton Buildings, Chancery Lane in the
County of London, 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 :-
As the starting point for the production of the new azo colouring matters which 5
form the subject of the present invention is taken dioxy-naphthoic-mono-sulpho

page_text: EXAMPLE.
13 kilos. of p-amidoacetanilid are diazotised with 30 kilos. of muriatic acid and
7 kilos. of sodium nitrite in a cooled solution which is added to 32 kilos. of dioxy-
naphthoic-mono-sulphonate of soda dissolved in alkali.
The intermediate compound is precipitated with common salt, filtered and saponified
in ebullition during some hours with caustic soda of about 4 p.c.
The cooled solution is mixed with the theoretical quantity of sodium nitrite and
acidulated.
After a short time the diazo compound is formed. It is filtered and introduced
into a hydrochloric solution of 14 kilos. of a-naphthylamine.
The necessary quantity of acetate of soda is added in order to neutralize the
muriatic acid and the mixture is allowed to stand for about 12 hours. It is then
heated and filtered; the separating colouring matter is washed with warm water,
re-dissolved in soda-solution and precipitated with common salt. It dyes a dark
black on unmordanted cotton and a blue black on wool prepared with chromium
salts.
B. Similar dye-stuffs may also be produced by substituting in the No. II method
of manufacture (letter A) for the first molecule of dioxy-naphthoic-mono-sulpho-
acid the naphthol-sulpho-acids mentioned in paragraph C (series 1) and by combining
the diazo derivatives of these intermediate products that are already known, with
one molecule of dioxy-naphthoic-mono-sulpho-acid.

page_text: EXAMPLE I:
3 kilos. of disulphonic acid of aniline (obtained by nitrification and reduction of
disulphonic acid of benzene) are diazotised with 0.7 kilos. of sodium nitrite
and 3 kilos. of muriatic acid and combined with 1.78 kilos. of chlorhydrate of
a-naphthylamine.
The mixture is agitated during 12 hours and after adding another 3 kilos. of
muriatic acid and 0.7 kilos. of sodium nitrite the azo-compound thus formed is
mixed with an alkaline solution of 3.3 kilos. dioxy-naphthoic-mono-sulpho-acid.
After some time the solution of the dye-stuff is heated and precipitated with
common salt.
The new colouring matter dras blue blook
11

page_text: naphthoic-mono-sulpho acid or by combining the intermediate product
resulting from the reaction of one molecule of a tetrazo body (paragraph I C)
and one molecule of dioxy-naphthoic-mono sulpho acid with one molecule of
any amine or phenol or their sulpho or carbon-acids;
b) By the combination of the well known intermediate products, resulting from
one molecule of a tetrazo-compound and one molecule of an amine, a phenol,
an amidophenol or a sulpho or carbon acid thereof (paragraph I D) with
the new dioxy-naphthoic mono-sulpho acid.
The process for producing new substantive tetrazo colouring matters
2) By first combining the diazo-derivatives from p-amido-acet-anilid,
p-amido-acet-toluid and p- (1-4) amidonaphthyl-oxaminic acid with dioxy-
naphthoic-mono-sulpho acid, saponification of the resulting azo-colouring
matters with acids or alkalies and combination of the intermediate products
thus obtained containing a diazotisable amido-group in the form of their
diazo derivatives, with a second molecule of dioxynaphthoic mono-sulpho
acid or with one of the components mentioned in paragraph I section C
(series 1 and 2)
3) By first combining the diazo derivatives from p-amido-acet-anilid, p-amido-
acet-toluid and p- (1.4) amido-naphthyl-oxaminic acid with one of the
naphthol sulpho acids mentioned in section C (series 1) and by combining
the well known diazo derivatives of these intermediate products after
saponification, with one molecule of dioxy-naphthoic-mono sulpho acid.
The process for producing new diazo colouring matters (capable of dyeing
in an acid bath) by combining the diazotised sulphonic derivatives of aniline,
and p-toluidine, xylidines, a- and B-naphthylamine with a-naphthylamine,
zotising the amido-azo compounds thus formed and coupling the diazo
cts with dioxynaphthoic mono sulpho acid.
As new articles of manufacture the colouring matters produced as set forth in
receding claims.
Dated this 3rd day of May 1802
ABEL & IMRAY,
Agents for the Applicant.