Manufacture of new Trisazo-colouring Matters capable of Dyeing Unmordanted Cotton and of Yielding Blue Shades by Develop- ment on the Fibre.
Year: 1898

page_text: Date of Application, 30th Mar., 1898-Accepted, 25th June, 1898
COMPLETE SPECIFICATION.
Manufacture of new Trisazo-colouring Matters capable of Dyeing
Unmordanted Cotton and of Yielding Blue Shades by Develop-
ment on the Fibre.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, Chancery
Lane, in the County of London, Chartered Patent Agent, do hereby declare the
nature of this invention (as communicated to me from abroad by the Society of
Chemical Industry in Basle, of Basle, Switzerland, Chemical Manufacturers,) and in
what manner the same is to be performed, to be particularly described and ascertained
in and by the following statement :-
In their Specification No. 4460 of 1894 my foreign correspondents have shewn that
the monazo-colouring matters derived from the diazonaphthol-sulphonic acids and
diamines and dioxy-derivatives of the aromatic series, may be used for the preparation
of black poly-azo-colouring matters by coupling, in alkaline solution, one molecular
proportion of one of the said monazo-colouring matters with one molecular propor-
tion of the tetrazo-derivative of a paradiamine and combining the intermediate
product thus obtained, which still contains a free diazo-group, with one molecular
proportion of nigrotic acid.
My correspondents have now found that the monazo-colouring matters derived
from diazonaphtholsulphonic acids and paracresidine, paraxylidine 1: 6-naphthy-
laminesulphonic acid of Cléve and 1: 2-naphthylaminesulphonic acid can be
analogously applied, and yield with tetrazo-compounds intermediary products which
give new trisazo-colouring matters with one molecular proportion of a naphthol
derivative; these colouring matters dye unmordanted cotton directly blackish violet,
grey and black shades, and possess by themselves no technical value. They are
bowever of technical importance in that when they are diazotised on the fibre in the
usual manner and developed by 8-naphthol, they yield violet and blue colours, under-
going a change of shade from black towards blue and at the same time increasing in
intensity and acquiring a greater degree of fastness to light and a very high degree
of fastness to washing.
To secure a pure blue shade when these new colouring matters are developed on
the fibre, it is necessary to use as the last component a naphthol or a sulphonated or
carboxylated naphthol and not amidonaphtholsulphonic acids which contain a
diazotisable amido-group and yield by development shades which are not pure blue
but tend towards black.
The new colouring matters which are the subject of this invention and can be
developed on the fibre, correspond with the following general formula :-
N P N N - naphthol or a naphthol derivative not containing a
-
diazotisable amido-group in which A stands for
the residue of 2:8:6-amidonaphtholsulphonic
acid or of 2:8:3: 6-amidonaphtholdisulphonic
acid and P for the residue of a paradiamine
such as

page_text: (a) benzidine, tolidine, ethoxybenzidine, a diamidodiphenol ether, diamido-diphenyl-
amine, and
(b) paramidoacetanilide, paramidoacettoluidide, paramidoacetcresidide, paramido-
acetnaphthalide and 1 : 4: 7- or 1: 4: 2-amidoacetnaphthalidesulphonic acid.
Under the heading "aromatic amine of the type of paracresidine" are included
primary aromatic monamines not substituted in the para-position, such as paracresi-
dine, paraxylidine, amidoparachlorotoluene, 1 : 2-a-naphthylaminesulphonic acid,
orthotoluidine, a-naphthylamine-6-sulphonic acid, and a 1 : 2-amidonaphthol
ether.
By a "naphthol or a naphthol derivative not containing a diazotisable amido-
group" are meant ẞ-naphthol, a-naphthol, 1: 4-naphtholsulphonic acid, 1 : 5-
naphtholsulphonic acid, 2: 6-naphtholsulphonic acid, 2: 7-naphtholsulphonic acid,
B-naphthol-disulphonic acid, 1 : 8-chloronaphthol-disulphonic acid, 18-alkyloxy-
naphthol-mono- or di-sulphonic acid, 1 : 8-dioxynaphthalenemono- or di-sulphonic
acid, alkylated amidonaphtholdisulphonic acid H, alkylated amidonaphtholsulphonic
acid y, B-oxynaphthoic acid, sulphonated a- and ẞ-dioxynaphthoic acids.
The colouring matters derived from the paradiamines named above under (a) can
be manufactured according to the Examples 1, 2, 3 and 10 described below, whilst
those derived from the paradiamines named under (b) can be made according to
Examples 4, 5, 6, 7, 8 and 9.
Colouring matter formed from one molecular proportion of the monazo-colouring
matter derived from 2: 8:3: 6-diazonaphtholdisulphonic acid and paracresidine,
one molecular proportion of tetrazodiphenyl and one molecular proportion of the
naphtholsulphonic acid of Neville and Winther.
34.1 kilos. of acid sodium 2: 8: 3: 6-amidonaphtholdisulphonate are diazotised by
6.9 kilos. of sodium nitrite. A cooled solution of 13.7 kilos. of paracresidine in 200
litres of water and 12 kilos. of hydrochloric acid (specific gravity 1-1) is then poured
into the diazotised solution and is followed by a solution of sodium acetate to substitute
acetic acid for the mineral acid. The whole is allowed to remain for 12 hours; the
colouring matter separates partially as a brown red precipitate and may be completely
precipitated by adding common salt, or the whole mixture may be employed for pre-
paring the trisazo-colouring matter.
A solution of 40 kilos. of sodium carbonate is now added to the mixture so as to
completely dissolve the colouring matter, a brownish yellow coloured solution being
obtained.
The solution is then well cooled and into it is poured a solution of the tetrazo-
derivative obtained from 18.4 kilos. of benzidine; the intermediate product is
immediately produced and separates as a black precipitate;
The reaction is soon over whereupon there is added a solution of 25 kilos. of the
sodium 14-naphtholsulphonate of Neville & Winther. After 12 hours the liquid is
raised to the boiling point and the colouring matter is precipitated by adding common
salt.
The colouring matter thus obtained is a black powder soluble in water giving a
violet red coloured solution. It dyes unmordanted cotton directly a blackish violet
red. When diazotised on the fibre and developed by ẞ-naphthol it yields a very full
reddish marine blue, the shade of which approaches that of azo-blue diamine 2 R.

page_text: molecular proportion of a tetrazodiphenol ether and one molecular proportion of
B-naphthol.
34.1 kilos. of 2:8:3:6 amidonaphtholdisulphonic acid (in the form of its acid
sodium salt) are diazotised and the diazo-compound is combined with 137 kilos. of
paracresidine. After 12 hours the monazo-colouring matter is dissolved by adding
40 kilos. of sodium carbonate and the tetrazo-derivative obtained from 24.4 kilos. of
dianisidine are poured into the solution. To the intermediate product which is
formed after a short time there is added a solution of 15 kilos. of B-naphthol in
150 litres of water and 14 kilos. of a soda lye of 30 per cent. strength; the whole is
allowed to remain for 12 hours, then raised to the boiling point and the colouring
matter precipitated by common salt in the usual way.
The trisazo-colouring matter thus obtained is a dark powder and dissolves in water
to a bluish black coloured solution; it dyes unmordanted cotton bluish-black shades
and when diazotised on the fibre and developed with ẞ-naphthol its shade changes to
a very beautiful marine blue.
Colouring matter formed from one molecular proportion of the monazo-colouring
matter derived from diazonaphtholsulphonic acid G and Clève's 1: 6-naphthylamine-
sulphonic acid, one molecular proportion of a tretrazodiphenol ether and one mole-
cular proportion of B-naphtholdisulphonic acid R.
24 kilos. of amidonaphtholsulphonic acid G are diazotised by 6.9 kilos. of sodium
nitrite and the necessary quantity of hydrochloric acid and while the solution is being
stirred there is poured into it a neutral solution of 22-3 kilos. of Clève's 1 : 6-
naphthylaminesulphonic acid; sufficient sodium acetate is then added to substitute
acetic acid for the mineral acid.
After the whole has been allowed to remain for 12 hours either the colouring
matter may be precipitated by adding common salt or the mixture may be directly
utilised for making the trisazo-colouring matter.
The partly precipitated colouring matter is dissolved to a red-brown coloured solu-
tion by adding 40 kilos. of sodium carbonate, and the tetrazo-derivative from 24.4
kilos. of dianisidine is poured into the well cooled solution, whereupon the inter-
mediate compound separates as a black precipitate; when the reaction is over the
final combination is effected by adding a solution of 35-5 kilos. of R salt.
The trisazo-colouring matter obtained is a black powder the solution of which in
water is of a greenish blue colour. It dyes unmordanted cotton bluish black. When
diazotised on the fibre and developed with 8-naphthol it yields a beautiful indigo
shade.
The subjoined table shews the shades yielded by the trisazo colouring matters
obtained according to the methods given in the three preceding examples.

page_text: If instead of paracresidine equivalent quantities of paraxylidine, amidoparachloro-
toluene or orthotoluidine are used, trisazo-colouring matters are obtained which yield
blue shades, tending rather to red, when developed on the fibre, while substitution of
an amidonaphthol either for paracresidine produces under the same conditions blue
shades which are rather greenish.
Those trisazo-colouring matters are particularly advantageous which contain
instead of the radical of benzidine of tolidine, of dianisidine or of diamidodiphenyl-
amine, the radical of paramidoacetcresidine, of paramidoacettoluidine, of paramido-
14: 2-amidoacet-
acetanilide, of 1: 4-amidoacetnaphtholide and of 14: 7- or
naphthalide sulphonic acid.
The preparation of these colouring matters is comprised in the following examples.
Colouring matter formed from one molecular proportion of the diazo-compound of
the saponified intermediate product derived from paramidoacetanilide and 1 : 4-
naphtholsulphonic acid, and one molecular proportion of the monazo-colouring matter
derived from diazo-naphtholsulphonic acid G and Clève's naphthylaminesulphonic
acid.
15 kilos. of paramidoacetanilide are diazotised with 6.9 kilos. of sodium nitrite and
the necessary quantity of hydrochloric acid and the solution is poured into an aqueous
solution of 24-5 kilos. of sodium 1 : 4-naphtholsulphonate and 20 kilos. of sodium
carbonate. After the whole has been allowed to remain for twelve hours sufficient
soda-lye is added to ensure that the mixture shall contain nearly 5 per cent. of
sodium hydroxide. The mixture is then boiled for from 2 to 3 hours, after
It is
which the saponified colouring matter is separated by adding common salt.
redissolved by boiling, and the necessary quantity of hydrochloric acid and 6.9 kilos.
of sodium nitrite are added to diazotise the colouring matter. The mixture having
been stirred for some hours, it is poured into an alkaline solution of the monazo-
colouring matter prepared, analogously to the manner described in Example 3, by
combining 24 kilos. of amidonaphtholsulphonic acid G with 22-3 kilos. of Clève's
16-naphthylaminesulphonic acid. After 12 hours, during which time the mixture
is frequently stirred, the whole is heated to the boiling point and the colouring
matter precipitated by adding common salt. This colouring matter dyes
unmordanted cotton bluish black and gives an indigo blue shade after diazotisation
on the fibre and development with naphthol.
a tetrazo-
An analogous colouring matter is obtained by saponifying the monazo-colouring
matter prepared from amidonaphtholsulphonic acid G and the diazo-derivative of
paramidoacetanilide, converting this monazo-colouring matter into
derivative and combining one molecular proportion of this, first with one molecular
proportion of Cleve's a-naphthylamine-6-sulphonic acid and then with one molecular
proportion of 1: 4-naphtholsulphonic acid; or by diazotising the saponified product
of the monazo-colouring matter derived from 1: 4-naphtholsulphonic acid and the
diazo-derivative of paramidoacetanilide, combining one molecular proportion of the
resulting diazo-derivative with one molecular proportion of 2:8: 6-ainidonaphthol-
sulphonic acid or 2: 8:3: 6-amidonaphtholdisulphonic acid, again diazotising the
mixed disazo-colouring matter thus obtained, according to the method which will be
indicated in Example 10, and combining one molecular proportion of this diazo-
compound with one molecular proportion of Clève's naphthylaminesulphonic acid.

page_text: paramidoacetanilide and amidonaphtholsulphonic acid G, one molecular proportion
of paracresidine and one molecular proportion of Neville & Winther's 1: 4-naphthol-
sulphonic acid.
15 kilos. of paramidoacetanilide are diazotised by 6.9 kilos. of sodium nitrite and
the necessary quantity of hydrochloric acid, and the diazo-derivative thus obtained is
united, in a solution rendered alkaline with sodium carbonate, with 24 kilos. of
amidonaphtholsulphonic acid G. After 12 hours the resulting monazo-colouring matter
is saponified by boiling it for from 2 to 3 hours with the quantity of soda lye necessary
to ensure that the solution shall contain about 5 per cent. of sodium hydroxide. The
product of the saponification is then separated by adding common salt, redissolved
and converted into a tetrazo-derivative by 13.8 kilos. of nitrite and the necessary
quantity of hydrochloric acid. Into this tetrazo-derivative, which should be at
a temperature of about 10° C. there is poured a solution of 13-7 kilos. of paracresidine
in 150 litres of water and 1-2 kilos. of hydrochloric acid (specific gravity 1.1) and
sufficient sodium acetate is added to substitute acetic acid for the mineral acid.
After stirring for from 2 to 3 hours the reaction is finished, whereupon the intermediate
product is poured into a solution of 25 kilos. of sodium 1: 4-naphtholsulphonate and
40 kilos. of sodium carbonate. After 12 hours the colouring matter is separated
in the usual manner.
The colouring matter obtained in this way dyes unmordanted cotton directly black;
when diazotised on the fibre and developed with 8-naphthol it yields a very full
indigo shade with a strong bronze lustre.
The paramidoacetanilide may be replaced by paramidoacet-a-naphthalide or
paramidoacetcresidide or paramidoacettoluidide; the 2: 8 6-amidonaphthol-
sulphonic acid by 283 6-amidonaphtholdisulphonic acid; the a-naphthyl-
anine-8-sulphonic acid by paracresidine, paraxylidine, a-naphthylamine, 1 : 2-a-
naphthylaminesulphonic acid, a sulphonic acid of 1: 2-amidonaphthol ; and the
14-naphtholsulphonic acid by naphthol, 8-naphtholsulphonic acid, 8-naphthol
disulphonic acid R, dioxynaphthalenesulphonic acids, monosulphonated a- and 8-
naphthoic acids, and the like.
The new trisazo-colouring matters capable of being developed on the fibre with
production of blue shades, which form the subject of this invention, can also be
prepared, instead of by the processes which have just been described, by the use of a
mixed disazo-colouring matter of the following composition:
This disazo-colouring matter may be again diazotised and combined with pa
cresidine, paraxylidine, amidoparachlorotoluene, Clève's naphthylaminesulpho
acid, a-naphthylamine, 1: 2-a-naphthylamine sulphonic acid, or an ether of 1:
amidonaphthol.
Furthermore, the tetrazo-derivatives quoted in Example 5, formed by t
diazotisation of the product of the saponification of the monazo-colouring matt
derived from one molecular proportion of paramidoacetanilide, paramidoacettoluidi
paramidoacetcresidide, 1 : 4-amidoacetnaphthalide, 1:4: 7- or 1: 4: 2-ami
acetnaphthalide-sulphonic acid and one molecular proportion of 2:8: 6-ami
naphtholsulphonic acid or 2:8: 3: 6-amidonaphthol disulphonic acid, instead

page_text: being coupled first with a primary monamido-compound of the type of paracresidine
and then with a naphthol compound not containing a diazotisable amido-group, may
be coupled first with a naphthol compound not containing a diazotisable amido-group
and only then with a primary monamido-compound of the type of par..cresidine;
or one molecular proportion of the tetrazo-derivative may be combined with two
molecular proportions of identical or different primary monamido-compounds of the
type of paracresidine, for one of which molecular proportions may be substituted,
if desired, one molecular proportion of amidonigrotic acid, amidonaphtholsulphonic
acid G or 1 : 4-naphtholsulphonic acid.
In all cases trisazo-colouring matters are obtained which dye unmordanted cotton
directly blackish shades and yield by diazotisation on the fibre very fast shades
varying from blue to blue-black and having a pronounced bronze lustre.
Colouring matter formed from one molecular proportion of the product of the
saponification of the monazo-colouring matter obtained from diazotised paramido-
acetanilide and amidonaphtholsulphonic acid y, one molecular proportion of
paracresidine and one molecular proportion of a-naphthylamine.
Into the intermediate product, obtained according to Example 5 by coupling 13.7
kilos. of paracresidine with the tetrazo-derivative of the product of the saponification
of the monazo-colouring matter prepared by diazotising 15 kilos. of paramidoacetanilide
and 24 kilos. of amidonaphtholsulphonic acid G, is poured a solution of 14.3 kilos. of
a-naphthylamine in 250 litres of water and 12 kilos, of hydrochloric acid, and then
sufficient sodium acetate to substitute acetic acid for the mineral acid. After 12
hours, the liquid is heated to the boiling point and filtered; the colouring matter is
redissolved in a boiling aqueous solution of sodium carbonate and finally separated in
the usual manner.
It dyes unmordanted cotton directly black, the shade passing to indigo-blue by
diazotisation on the fibre and development with 8-naphthol.

page_text: the product of the saponification of the monazo-colouring matter obtained from
diazotised paramidoacetanilide and amidonaphtholsulphonic acid-y, one molecular
proportion of paracresidine and one molecular proportion of amidonaphtholsulphonic
acid-y.
13-7 kilos. of paracresidine are coupled in solution, in the manner described in
Example 5, with the tetrazo-derivative of the product of saponification of the
monazo-colouring matter from the diazo-derivative of 15 kilos. of paramidoacetanilide
and 24 kilos. of amidonaphtholsulphonic acid-y; the intermediate product thus
obtained is poured into a solution of 25 kilos. of amidonaphtholsulphonic acid-y and
40 kilos. of sodium carbonate. After 12 hours the liquid is heated to its boiling point
and the colouring matter is precipitated by adding common salt.
This colouring matter dyes unmordanted cotton directly blue black; when
diazotised on the fibre and developed with ẞ-naphthol it yields indigo blue shades
with a strong bronze lustre.
Colouring matter formed from one molecular proportion of the tetrazo- derivative of
the product of saponification of the monazo-colouring matter obtained from diazotised
paramidoacetanilide and 2:8: 6-amidonaphtholsulphonic acid, one molecular
proportion of 1:2-naphthylaminesulphonic acid, and one molecular proportion of the
1:4-naphtholsulphonic acid of Neville & Winther.
:
The diazo-derivative from 15 kilos. of paramidoacetanilide is combined with 24
kilos. of 28 6-amidonaphthol monosulphonic acid in solution rendered alkaline by
the addition of carbonate of soda, and the monazo-colouring matter thus obtained is
saponified by boiling for about 3 hours with the required quantity of soda lye.
After saponification there is added the necessary quantity of hydrochloric acid and
diazotisation is effected with 13.8 kilos. of sodium nitrite. Into the yellow-red solution
of the tetrazo-derivative thus obtained, there is poured while the solution is well
stirred a neutral solution of 22.3 kilos. of 1: 2-naphthylaminesulphonic acid, and acetic
acid is substituted for the mineral acid by adding sodium acetate. The intermediate
product which separates completely in the form of a dark precipitate is formed at the
end of a short time, after which it is poured into a solution of 25 kilos. of sodium 1:4-
naphthol monosulphonate and 40 kilos. of sodium carbonate. At the end of 12 hours
the colouring matter is isolated in the usual manner.
It dyes directly on unmordanted cotton grey black tints; when diazotised on the
fibre and developed with toluylenediamine or with ẞ-naphthol it gives blue black
tints. Still darker tints are obtained by replacing the naphtholsulphonic acid by a
naphthylamine or 2: 8: 6-amidonaphthol monosulphonic acid.
Trisazo-colouring matter obtained by diazotisation of the mixed disazo-colouring
matter derived from one molecular proportion of a tetrazodiphenol-ether, one mole-
cular proportion of 2: 8:3: 6-amidonaphtholdisulphonic acid, and one molecular
proportion of the 1: 4-naphtholsulphonic acid of Neville and Winther, and by com-
bination of one molecular proportion of the diazo-derivative of the said colouring
matter with one molecular proportion of paracresidine.
24.4 kilos. of dianisidine are diazotised in the usual manner, and to the tetrazo-
derivative thus obtained, rendered alkaline by an addition of 40 kilos. of sodium
carbonate, is added a solution of 34.1 kilos. of 2: 8:3: 6-amidonaphtholdisulphonic
acid in the form of its sodium salt.
The formation of the intermediate product is completed at the end of a short
time, after which there is poured into the mixture a solution of 25 kilos. of sodium

page_text: 1: 4-naphtholsulphonate. After 12 hours the whole is heated, precipitated with
common salt, and filtered. The disazo-mixed colouring matter thus obtained is re-
dissolved, and its cooled solution is mixed with 6-9 kilos. of nitrite. This mixture is
then poured little by little, at a temperature of 10° C., and while actively stirring,
into a solution of 60 kilos. of hydrochloric acid of 1.1 specific gravity and 200 litres
water. After stirring for several hours and when the mixture no longer reacts upon
paper soaked in a mixture of starch and iodine, there is added a solution of 14 kilos.
of paracresidine in 200 litres of water and 12 kilos. of hydrochloric acid, after which
there is poured into the mixture a solution of sodium acetate in sufficient quantity to
substitute acetic acid for the mineral acid. After 12 hours the whole is boiled and
filtered, and the colouring matter is again dissolved by boiling with water containing
from 10 to 15 kilos. of sodium carbonate and it is then precipitated by means of
common salt, and separated from the liquor.
This colouring matter dyes unmordanted cotton a blue black, and gives a blue tint
by diazotising upon the fibre and subsequently developing with a-naphthol.
If for the paracresidine be substituted the equivalent quantity of an a-amido-8-
naphthol ether, there are obtained by development upon the fibre a more greenish,
but also a blacker blue.
The other colouring matters can be prepared in an analogous manner.
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. The herein described process for producing new trisazo-colouring matters dyeing
cotton without mordant and giving blue tints on development on the fibre, which pro-
cess consists in combining one inolecular proportion of the tetrazo-derivative of a para-
diamine such as benzidine, tolidine, diamidodiphenol ether, ethoxybenzidine and
diamidediphenylamine, with one molecular proportion of the monoazo-colouring
matter obtained from 2: 8: 6-diazonaphthol sulphonic acid or 2: 8:3: 6-diazo-
naphthol disulphonic acid and an aromatic primary monoainide compound of the type
of paracresidine such as paracresidine, paraxylidine, amidoparachlorotoluene, ortho-
tolaidine, a-naphthylamine-6-sulphonic acid of Clève, 1: 2-a-naphthylamine-sulphonic
acid or 1: 2-amido-naphthol ether, and with one molecular proportion of a naphthol
compound not containing a diazotisable amido-group, such as 8-naphthol, a-naphthol,
1 4-naphtholsulphonic acid 1: 5-naphtholsulphonic acid 2: 6-naphtholsulphonic
acid 2: 7-naphtholsulphonic acid 8-naphtholdisulphonic acid, 1: 8-chloronaphthol
disulphonic acid, 1:8 alkyloxynaphthol mono- or di-sulphonic acid, mono or disul-
phonic acid of 1: 8-dioxynaphthalene, alkylated amidonaphtholdisulphonic acid H,
alkylated amidonaphtholsulphonic acid y, 8-oxynaphthoic acid, and the monosulpho-
nated a and a dioxynaphthoic acids.
2. The herein described process for producing new trisazo-colouring matters,
consisting in preparing the mixed disazo-colouring matter resulting from the com-
bination of one molecular proportion of the tetrazo-derivative of a paradiamine such
as benzidine, tolidine, ethoxybenzidine, a diamidodiphenol ether and diamido
diphenylamine with one molecular proportion of 2:8: 6-amidonaphtholsulphonic
acid or of 2:8: 3: 6 amidonaphtholdisulphonic acid, and one molecular proportion
of a naphthol compound not containing a diazot isable amido-group, such as B-naphthol,
a-naphthol, 14-naphtholsulphonic acid, 1:5 naphtholsulphonic acid, 2: 6 naphthol-
sulphonic acid, 2: 7-naphthol-sulphonic acid, 8-naphthol disulphonic acid,
1:8-chloronaphthol disulphonic acid, 1: 8 alkyloxynaphthol mono- or disulphonic
acid, 18-dioxynaphthalene mono- or disulphonic acid, alkylated amidonaphthol-
disuiphonic acid H, alkylated amidonaphtholsulphonic acid-y, B-oxynaphthoic acid,
and the monosulphonated a- and ẞ-dioxynaphthoic acids, again diazotising the said
mixed disazo-colouring matter, and combining one molecular proportion of the
diazo-product thus obtained with one molecular proportion of paracresidine, of
paraxylidine, of amido parachlorotoluene, of orthotoluidine, of the a-naphthylamine-

page_text: B-sulphonic acid of Clève, of 1: 2-a-naphthylamine-sulphonic acid, or of 1 : 2-
amidonaphtholether.
3. The herein described process for producing new trisazo-colouring matters,
consisting in preparing the monazo-colouring matter resulting from the combination
of one molecular proportion of the diazo-derivative of paramidoacetanilide, of para-
midoacettoluidide, of paramidoacetcresidide, of 1:4-amidoacetnaphthalide, or of
1:4:7- or 1:4:2-amidoacetnaphthalide-sulphonic acid, with one molecular propor-
tion of a naphthol compound not containing a diazotisable amido-group, such
as 8-naphthol, a-naphthol, 1: 4-naphtholsulphonic acid, 1:5-naphtholsulphonic
acid, 2:6-naphtholsulphonic acid, 2: 7-naphtholsulphonic acid, 8-naphthol,
disulphonic acid, 1:8-chloronaphthol disulphonic acid, 1:8-alkyloxynaphthol-
mono- or disulphonic acid, 1: 8-dioxynaphthalene mono- or disulphonic acid,
alkylated amidonaphtholdisulphonic acid H, alkylated amidonaphtholsulphonic
acid, -oxynaphthoic acid, and monosulphonated a- and 8-dioxynaphthoic
acids, saponifying the monazo-colouring matter thus obtained, and again
diazotising the same for transforming it into a diazo derivative, and combining one
molecular proportion of this diazo-derivative with one molecular proportion of the
monoazo-colouring matter obtained from 2:8:6-diazonaphtholsulphonic acid, or
2:8:3:6-diazonaphtholdisulphonic acid and paracresidine, paraxylidine, amido-
parachlorotoluene, orthotoluidine, a-naphthylamine-8-sulphonic acid, Clève's
12-naphthylaminesulphonic acid, 1:2-amidonaphthol ether, a-naphthylamine or
a sulphonic acid of 1:2-amidonaphthol.
4. The herein described process for producing new trisazo-colouring matters, con-
sisting in preparing the monazo-colouring matter resulting from the combination of
one molecular proportion of a diazo-derivative of paramidoacetanilide, of paramido-
acettoluidide, of paramidoaceteresidide, of 1:4-amidoacetnaphthalide or of 1:4:7-
or 14 2-amidoacetnaphthalide-sulphonic acid, with one molecular proportion of
2:86-amidonaphtholimonosulphonic acid, or 2:8:3: 6-amidonaphthol-disulphonic
acid, in saponifying the monoazo-colouring matter thus obtained and in again
diazotising the saponified product to convert it into a tetrazo-derivative and in
combining one molecular proportion of the tetrazo-derivative thus obtained with the
following:
a) Firstly with one molecular proportion of paracresidine, of paraxylidine, of
amidoparachlorotoluene, of orthotoluidine, of a-naphthylamine, of the a-naphthy-
lamine-8-sulphonic acid of Cléve of 12 a-naphthylamine-sulphonic acid, of
1:2-amidonaphtholether, or of a sulphonic derivative of 1:2-amidonaphthol, and
then with one molecular proportion of a naphthol compound not containing a
diazotisable amido-group, such as 8-naphthol, a-naphthol, 1: 4-naphthol-
sulphonic acid, 1: 5-naphtholsulphonic acid, 26-naphtholsulphonic acid,
27-naphtholsulphonic acid, 8-naphthol-disulphonic acid, 1:8 chloronaphthol-
disulphonic acid, 18-alkyloxynaphthol mono- or disulphonic acid, 1:8-dioxy-
naphthalene mono- or disulphonic acid, alkylated amidonaphtholdisulphonic
acid H, alkylated amido-naphthol-sulphonic acid y, B-oxynaphthoic acid, and mono-
sulpho-u- and 6-dioxynaphthoic acids, or:
b) Firstly with one molecular proportion of a naphthol compound not containing
a diazotisable amido-group, such as 8-naphthol, 1 : 4-naphthol-sulphonic acid, 1:5-
naphtholsulphonic acid, 2: 6-naphthol-sulphonic acid, 2: 7-naphtholsulphonic acid,
8-naphthol-disulphonic acid, 1: 8-chloronaphthol-disulphonic acid, 18-alkyloxy-
naphthol mono- or disulphonic acid 1: 8-dioxynaphthalene mono or disulphonic acid,
alkylamidonaphtholdisulphonic acid H, alkylamidonaphthol-sulphonic acid Boxy-
naphthoic acid, and the monosulphonated. a- and 8-dioxynaphthoic acids, and then with
one molecular proportion of paracresidine, of paraxylidine, of amidoparachlorotoluene,
of orthotoluidine, of a-naphthylamine-8-sulphionic acid of Clève, of 1: 2-naphthylamine
sulphonic acid, of 1:2 amidonaphthol ether, of a-naphthylamine, or of a sulphonic
acid of 18 amidonaphthol; or
ولا
c) With two identical or different molecules of paracresidine, of paraxylidine, of
amidoparachlorotoluene, of orthotoluidine, of a-naphthylamine-6-sulphonic acid of

page_text: Clève, of 12-naphthylamine-sulphonic acid, of 1:2 amidonaphthol ether, of
a-naphthylamine, or of a sulphonic acid of 1:8-amidonaphthol, or:
d) First with one molecular proportion of paracresidine, of paraxylidine, of amido-
parachlorotoluene, of orthotoluidine, of a-naphthylamine-g-sulphonic acid of Clève, of
12-naphthylamine-sulphonic acid, of 12-amidonaphthol ether, of a-naphthy-
lamine, or of a sulphonic acid of 1: 8-amidonaphthol and then with one molecular
proportion of amidonaphthol-sulphonic acid G, of amidonigrotic acid,. or of 1:4-
naphthol-sulphonic acid.
5. The herein described process for producing new trisazo-colouring matters,
consisting in preparing the monazo-colouring matter resulting from the combination
of one molecular proportion of the diazo-derivative of paramidoacetanilide, paramido-
acettoluidide paramidoacetcresidide, 1 : 4-amidoacet naphthalide or 47- or
14: 2-amidoacet naphthalide-sulphonic acid, with one molecular proportion of a
naphthol compound not containing a diazotisable amido-group, such as B-naphthol,
a-naphthol, 14-naphtholsulphonic acid, 1 : 5-naphtholsulphonic acid, 2 : 6-
naphtholsulphonic acid, 2: 7-naphtholsulphonic acid, 1: 8-chloronaphtholdisulphonic
acid, 18-alkyl-oxy-naphthol mono- or di-sulphonic acid, 18-dioxynaphthalene
mono- or disulphonic acid, alkylated amidonaphthol disulphonic acid H, alkylated
amidonaphthol sulphonic acid-y, a-oxynaphthoic acid and mono-sulphonated
and 8-dioxynaphthoic acids, in saponifying the monazo-colouring matter thus
obtained, in again diazotising the saponified product to convert it into a diazo-
derivative, in combining one molecular proportion of this diazo-derivative with one
molecular proportion of 28: 6-amidonaphtholsulphonic acid or 2: 8:3 : 6-
amidonaphtholdisulphonic acid, in again diazotising the mixed disazo-colouring
matter thus obtained and in combining one inolecular proportion of the diazo-
derivative of the said mixed disazo-colouring matter with one molecular proportion
of paracresidine, paraxylidine, amidoparachlorotoluene, orthotoluidine, a-naphthyl-
amine, Cleve's a-naphthylamine-8-sulphonic acid, 1: 2-a-naphthylamine-sulphonie
acid, 1:2-amidonaphthol ether or a sulphonic acid of 1: 2-amidonaphthol.
a-
6. As new products the colouring matters obtained by the processes referred to in
the preceding claims.
Dated this 30th day of March 1808
ABEL & IMRAY,
Agents for the Applicant.