Manufacture of New Trisazo Colouring Matters.
Year: 1895

page_text: Date of Application, 11th Nov., 1895
Complete Specification Left, 31st July, 1896-Accepted, 5th Sept., 1896
[Communicated from abroad by THE FARBWERKE, vormals MEISTER LUCIUS
AND BRUNING, of Hoechst a/Main, in the German Empire, Chemical
Manufacturers.]
Manufacture of New Trisazo Colouring Matters.
I, OLIVER IMRAY, of No. 28 Sonthampton Buildings, Chancery Lane, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention to be as follows:-
The dioxynaphthaline-mono-sulphonic acid S of the German Letters Patent
No. 67829 is capable of combining with 2 molecules of one and the same diazo
compound or with moleculo each of two different diazo.compounds.
When, in the coupling of this dioxynaphthaline monosulphonic acid S, a molecule
of a tetrazo compound is substituted for the second molecule of a dieze compound,
and the body thus obtained which is capable of being further coupled, is combined
with bases, phenols, naphthols, or their sulphonic or carbonic acids,. there are
obtained new trisazo colouring matters possessing very valuable qualities.
+
These colouring matters dye on wool and on cotton and excel the direct dyeing
cotton colouring matters at present available, in fastness to light and soap.
A
Those compounds that, in the capacity of second combination substance, have a
diazotisable amido group, on being further diazotised on the fibre with developers,.
such as phenol, a and Snaphthol, m-phenylendiamine, chrysoïdine, amido-
naphtholether, furnish tints ranging from violet to deep black of very remarkable
fastness to soap.
Example molecule of dioxynaphthaline-monosulphonate of sodium S and
about 3 molecules of sodium carbonate (caustic alkali, ammonia, &c.) are dissolved
in water forming a solution of from 10 to 15 per cent., then at a low temperature
one molecule of diazo-naphthionic acid is added and stirred for about 6 hours.
Afterwards about 4 molecules of sodium carbonate (caustic alkali, ammonia, &c.)
dissolved in a small quantity of water are added, and then at 0° C. 1 molecule of
the tetrazo compound of benzidine.
After standing for some time (from 1 to 2 hours) the intermediate product
being formed is poured while actively stirring into a solution of 1 molecule of
amidonaphtholdisulphonic acid H and from 2 to 3 molecules of sodium carbonate
(caustic alkali, ammonia, &c.) in a small quantity of water. 12 hours later the:
formation of colouring matter is complete; the colouring matter is separated and
purified in the usual manner.
The operation can also be performed in the following way, by producing first the
monoazo colouring matter and then combining 1 molecule of the tetrazo compound
from benzidine, with 1' molecule of amidonaphtholdisulphonic acid and causing:
this intermediate product to act upon the previously formed mono-azo-colouring!
matter.
The same colouring matters can also be obtained by successively combining in
alkaline solution the tetrazo compound from I molecule of benzidine with 1 molecule
of dioxynaphthaline monosulphonic acid S and 1 molecule of amidonaphthol
disulphonic acid' H and by treating an alkaline solution of the colouring matter.
when formed with 1 molecule of diazo-naphthionic acid.

page_text: For the benzidine, mentioned in the example, may obviously be substituted an
equivalent quantity of tolidine, dianisidine, diphenetidine &c., for the naphthionic
acid any other diazotisable substance capable of coupling, and for the amido-
naphtholdisulphonic acid H any other amido acid, amine, phenol, naphthol, their
sulphonic or carbonic acids &c.
Dated this 11th day of November 1895.
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of New Trisazo Colouring Matters.
I, OLIVER IMBAY, of No. 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 :-
The dioxy-naphthaline-mono-sulphonic acid S of the German Patent No. 67829
is capable of combining with 2 molecules of one and the same diazo-compound or
with 1 molecule each of two different diazo-compounds.
When in the coupling of this dioxy-naphthaline-nono sulphonio acid S a molecule
of a tetrazo-compound is substituted for the second molecule of a diazo-compound,
and the body thus obtained which is capable of being further coupled is combined
with bases, phenols, naphthols or their sulphonic or carbonic acids, there are
obtained new trisazo-colouring matters possessing very valuable qualities.
Those
These colouring matters dye on wool and on cotton and excel the direct dyeing.
cotton colouring matters at present available, in fastness to light and soap.
compounds that in the capacity of second combination substance have a diazotisable
amido-group, on being further diazotised on the fibre with developers, such as
phenol, a and ß-naphthol, m-phenylendiamine, chrysöidine, amido-naphthol-ether
furnish tints ranging from violet to deep black of very remarkable fastness
to soap.
:
Example 1 molecule of dioxy-naphthaline-monosulphonate of sodium S and
about 3 molecules of sodium carbonate (caustic alkali, ammonia etc. etc.) are
dissolved in water forming a solution of from 10 to 15 per cent., then at a low
temperature 1 molecule of diazo-naphthionic acid is added and stirred for about
6. houre. Afterwards about 4 molecules of sodium carbonate (caustic alkali,
ammonia etc.) dissolved in a small quantity of water are added and then at 0°C.
1 molecule of the tetrazo-compound of benzidine.
After standing for some time (from 1 to 2 hours) the intermediate product being
formed is poured while actively stirring into a solution of 1 molecule of amido-
Daphtholdisulphonic acid H and from 2 to 3 molecules of sodium carbonate (caustic,
alkali, ammonia etc.) in a small quantity of water. 12 hours later the formation of
colouring-matter is complete; the colouring matter is separated and purified in the
usual manner.
The operation can also be performed in the following way, by producing first the
monoazo-colouring matter and then combining 1 molecule of the tetrazo-compound
from benzidine with 1 molecule of amido-naphtholdisulphonic acid and causing
this intermediate product to act upon the previously formed mono-azo colouring
matter.
The same colouring matters can also be obtained by 'successively combining in
alkaline solution the tetrazo-compound from 1 molecule of benzidine with 1 molecule
of dioxy-naphthaline-monosulphonic acid S and I molecule of amido-naphthol-
disulphonic acid H and by treating an alkaline solution of the colouring matter
when formed with 1 molecule of diazo-naphthionic acid.
;

page_text: For the benzidine mentioned in. the example may obviously be substituted an
equivalent quantity of tolidine, dianisidine, diphenetidine, etc. for the naphthionic
acid any other diazotisable substance capable of coupling and for the amido-
naphtholdisulphoric acid H any other amido acid, amine, phenol, naphthol, their
sulphonic or carbonic acids etc.
The following compounds can for instance be obtained in the following,
manners:-
ine mentioned in. the example may obviously be substituted.
y of tolidine, dianisidine, diphenetidine, etc. for the naphthion
iazotisable substance capable of coupling and for the amid
ic acid H any other amido acid, amine, phenol, naphthol, the
nic acids etc.
compounds can for instance be obtained in the followi
Dioxynaphthalinemonosulphonic acid S.-
\a-naphthylamino (diaz.) amidonaphthol monosulphonic acid
Dioxynaphthaline monosulphonic acid-S.-
a-naphthylamine (diaz.) salicylic acid.
Dioxynaphthaline monosulphonic acid.
a-naphthylamine (diaz.) amidonaphtholmonosulphonic acid
Dioxynaphthalinomonosulphonic acid.S.
\a-naphthylamine (diaz.)-a-naphthylamine.
Dioxynaphthalinemonosulphonic acid S.-
Aniline (diaz.) amidonaphtholmonosulphonic acid G.
Dioxynaphthaliuemonosulphonic acid S.- :
Aniline (diaz.) Binaphtholmonosulphonic acid F. 2.7.
Dioxynaphthalinemonosulphonic acid S.-
o-toluidine (diaz.) amidonaphtholimonosulphonic acid G..
Dioxynaphthalinemonosulphonic acid S.-
o-toluidine (diaz.) a-naphtholmonosulphonic acid (Nev.
Winth.).
Dioxynaphthalinemonosulphonic acid S.-p-nitraniline (dia
Dioxynaphthaliṇemonosulphonic acid S.-p-nitraniline (dia
Dioxynaphthalinemonosulphonic acid S.
Naphthionic acid (diaz.). amidonaphtholdisulphonic aoid H
Dioxynaphthalinemonosulphonic acid S.-
Naphthionic acid (diaz.) amidonaphthol monosulphonic acid
Dioxynaphthalinemonosulphonic acid S.
Naphthionic acid (diaz.) naphthionic acid.

page_text: фикричито ноти ко
Naphthionic acid (diaz.) naphtholtrisulphonic acid, Germ. L.P
No. 56058.
Dioxynaphthalinemonosulphonic acid S.-
Naphthionic acid (diaz.) salicylic acid.
Dioxynaphthalinemonosulphonic neid S.-
Naphthionic acid (diaz.) a-naphtholmonosulphonic acid
(Nev. g. Winth.).
Dioxynaplithalinemonosulphonic acid S.-
Naphthionic acid (diaz.) amidonaphtholdisulphonic acid H.
Dioxynaphthalinemonosulphonic acid S.-
Naphthionic acid (diaz.) amidonaphtholdisulphonic acid H.
Dioxynaphthalinemonosulphonic acid S.-
Naphthionic acid (diaz.) amidonaphtholdisulphonic acid H.
'Dioxynaphthalinemonosulphonic acid S.—
Naphthionic acid (diaz.) naphtholtrisulphonic acid, Germ. L.P
No. 56058.
Dioxynaphthalinemonosulphonic acid.S.-
Naphthionic acid (diaz.) naphtholtrisulphonic acid, Germ. L.P
No. 56058.
Dioxyuaphthalinemonosulphonic acid 'S.-
Naphthionic acid (diaz.) naphtholtrisulphonic acid, Germ. L.P
No. 56058.
Dioxynaphtbalinemonosulphonic acid 'S.-
Naphthionic acid (diaz.) naphthionic acid.
Dioxynaphthalinemonosulphonic acid 'S.-
Naphthionic acid (diaz.) naphthionic acid.
Dioxynaphthalinemonosulphonic acid S.-
Naphthionic acid (diaz.) naphthionic acid.
Dioxynaphthalinemonosulphonic acid S.-
Naphthionic acid (diaz.) naphthionic acid.

page_text: Dioxynaphthalinemnonosulphonic acid S.-
Naphthionic acid (diaz.) amidonaphthol monosulphonic acid G.
Dioxynaphthalinemonosulphonic acid S.-
Naphthionic acid (diaz.) amidonaphthofmonosulphonic acid G.
Dioxyuaphthalinemunosulphonic acid S.-
Naphthionic acid (diaz.) amilonaphtholmonosulphonic.acid G.
Dioxynaphthalinemonosulphonic acid S.-
Naphthionic acid (diaz.) amidonaphthol monosulphonic acid G.
Dioxynaphthalinemonosulphonic acid S.—
Naphthionic acid (diaz.) amidonaphtholdisulphonic acid Ḥ.
Dioxynaphthalinemonosulphonic acid S.-
Naphthionic acid (diaz.) naphtholt risulphonic acid, Germ. L.P.
No. 56058.
Dioxynaphthalinemonosulphonic acid S.-
o-amidosalicylic acid (diaz.) a-naphtholmonosulphonic acid
(Nev. g. Winth.).
Dioxynaphthalinemonosulphonic acid S.-
p-amidosalicylic acid (diaz.) a-naphtholmonosulphonic acid'
(Nev. g. Winth.).
Dioxynaphthalinemonosulphonic acid S.-
Naphthionic acid (diaz.) amidonaphtholdisulphonic acid,
Gerin. L.P. No. 53023.
Dioxynaphthalinemonosulphonic acid S.-
Naphthionic acid (diaz.) salicylic acid.
Dioxynaphthaliuemonosulphonic acid S.-
Naphthionic acid (diaz.) amidonaphtholdisulphonic acid,
Germ. L.P. No. 53023.
Dioxynaphthalinemonosulphonic acid S-
Naphthionic acid (diaz.) salicylic acid.
Dioxynaphthalinemonosulphonic acid S.-
Naphthionic acid (diaz.) amidonaphtholdisulphonic acid,

page_text: Dioxynaphthalinemonosulphonic acid S.—
Naphthionic acid (diaz.) salicylic acid.
/Dioxynaphthalinemonosulphonic acid S.-
Naphthionic acid (diaz.) amidonaphtholdi-sulphonio a
Germ. L.P. No. 53023.
Dioxynaphthalinemonosulphonic acid S.-
p-uitraniline (diaz.) red salicylic acid.
Dioxynaphthalinemonosulphonic acid S.-
p-nitraniline (diaz.) red naphthionic acid.
Dioxynaphthalinemonosulphonic acid S.—
p-nitraniline (diaz.) red amidonaphtholmonosulphonic acid
Dioxynaphthalinemonosulphonic acid S.-
:
p-nitraniline (diaz.) red amidonaphtholdisulphonic: a
Germ. L.P. No. 53023.
/Dioxynaphthalenemonosulphonic acid S.
p-nitraniline (diaz:) red amidonaphtholdisulphonic acid H
Dioxynaphthalinemonosulphonic acid S.
· p-nitraniline (diaz.) red salicylic acid.
Dioxynaphthalinemonosulphonic acid S.-
p-nitraniline (diaz.) red naphthionic acid.
Dioxynaphthalinemonosulphonic acid S.
p-nitraniline (diaz.) red amidonaphtholmonosulphonic acid
Dioxynaphthalinemonosulphonic acid S.-
p-nitraniline (diaz.) red amidonaphtholdisulphonic a
Germ. L.P. No. 53023.
Dioxynaphthalinemonosulphonic acid S.-
p-nitraniline (diaz.) red amidonaphtholdisulphonic acid H
Dioxynaphthalinemonosulphonic acid S.
p-nitraniline (diaz.) red salicylic acid.

page_text: Dioxynaphthalinemonosulphonic acid S.-
p-nitrauiline (dinz.) 'red naphthionic acid.
Dioxynaphthalenemonosulphonic acid S.--
p-nitraniline (diaz.) red amidonaphtholmmomsulphonic acid G.
Dioxynnphthalenemonosulphonic acid S.
p-nitraniline (dinz.) red amidonaphtholdisulphonic acid,
Germ. I.P. No. 53023.
Dioxynaphthalenemonosulphonic acid S.-
p-nitraniline (diaz.) red amidonaphtholdisulphonic acid H.
Dioxynaphthalenemonosulphonic acid S.-
p-nitraniline (diaz.) red salicylic acid.
Dioxynuplithalinemonosulphonic acid S.-
p-nitraniline (diaz.) red naphthionic acid.
Dioxynaphthalinemonosulphonic acid S.-
\p-nitraniline (diaz.) red amidonaphtholmonosulphonic acid G.
Dioxynaphthalenemonosulphonic acid S
p-nitraniline (diaz.) red amidonaphtholdisulphonic acid,
Germ. L.P. No. 53023.
Dioxynaplithalemonosulphonic acid S.-
p-nitraniline (diaz.) red amidonaphtholdisulphonic acid H.
Dioxynaphthalinemonosulphonic acid S.-
Sulphanilic acid (diaz.) salicylic acid,
Dioxynaphthalenemonosulphonic acid S.-
Sulphanilic acid (diaz.) naphthionic acid.
Dioxynaphthalenemonosulphonio acid S.
Sulphanilic acid (diaz.) amidonaphtholmonosulphonic acid G.
Dioxynaphthalenemonosulphonic acid S.
Sulphanilic acid (diaz.). amidonaphtholdisulphonic" acid,
Germ. L.P. No. 53023.

page_text: Dioxynaphthalenemonosulphonic acid S.-
Sulphanilic acid (diaz.) amidonaphtholdisulphonic acid H.
Dioxynaphthalenemonosulphonic acid S.-
Sulphanilic acid (diaz.) salicylic acid.
Dioxynaphthalenemanosulphonic acid S.-
Sulphanilic acid (diaz.) naphthionic acid.
Dioxynaphthalinemonosulphonic acid S.-
Sulphanilic acid (diaz.) amidonaphtholmonosulphonic acid G.
Dioxynaphthalenemonosulphonic acid S.—
Sulphanilic_acid (diaz.) amidonaphtholdisulphonic acid;
Germ. L.P. No. 53023.
Dioxynaphthalenemonosulphonic acid S.-
Sulphanilic acid (diaz.) amidonaphtholdisulphonic acid H.
Dioxynaphthalenemonosulphonic acid S.—
\Sulphanilic acid (diaz.) salicylic acid.
Dioxyuaphthalenemonosulphonic acid S.-
\Sulphianilic acid (diaz.) naphthionic acid.
Dioxynaphthalinemonosulphonic acid S.-
Sulphanilic acid (diaz.) amidonaphtholmonosulphonic acid G.
Dioxynaphthalenemonosulphonic acid.S.--
Sulphanilic acid (diaz.) amidonaphtholdisulphonic acid,
Germ. L.P. No. 63023.
Dioxynaphthalenemonosulphonic acid S.-
Sulphanilic acid (diaz.) amidonaphtholdisulphonic acid H.
Dioxynaphthalinemonosulphonic acid S.-
Sulphanilio acid (diaz.) salicylic acid..
Dioxynaphthalenemonosulphonic acid S.-
Sulphanilic acid (diaz.) naphthionic acid.

page_text: Dioxynaphthalenemonosulphonic acid S.-
Diphenetidine
Dioxynaphthalenemonosulphonic acid S.—
· Sulphanilic acid (diaz.) amidonaphtholmonosulphonic acid G.
Dioxynaphthalenemonosulphonic acid S.—
\Sulphanilic acid (diaz.) amidonaphtholmonosul
Dioxynaphthalenemonosulphonic acid S.-
Sulphauilic acid (diaz.) amidonaphtholdis
Germ. L.P. No. 53023.
Dioxynaphthaleuemonosulphonic acid S.-
Sulphanilic acid (diaz.) amidonaphtholdisulpho
Dioxynaphthalinemonosulphonic acid S.--
Sulphanilic acid (diaz.) m-phenylenediamine.
Dioxynaphthalinemonosulphonic acid S.-
Sulphanilic acid (diaz.) m-toluylenediamine.
Dioxynaphthalinemonosulphonic acid S.-
Naphthionic acid (diaz.) m-phenylenediamine.
/Dioxynaphthalinemonosulphonic acid S.-
Naphthionic acid (diaz.) m-toluylenediamine.
Dioxynaphthalinemouosulphonic acid S.-
Amidonaphtholsulphonic acid G (diaz.)
disulphonic acid H.
Dioxynaphthalinemonosulphonic acid S.-
Sulphanilic acid (diaz.).m-phenylenediamine.
Dioxynaphthalinemonosulphonic acid S.―
Sulphanilic acid (dinz.) m-toluylenediamine.
/Dioxynaphthalinemonosulphonic acid S.-
Naphthionic acid (diaz.) m-phenylenediamine.
Dioxynaphthalinemonosulphonic acid S.-
Naphthionic acid (diaz.) m-toluylenediamine.
articularly described and ascertained the nature of
at manner the same is to be performed, I deola
acture of mixed trisazo-colouring matters suitable
combining molecule of dioxyuaphthalinemonosu

page_text: with 1 molecule of a diazo-compound, coupling the monoazo-colouring matter thus
formed with 1 molecule of a tetrazo-compound and then coupling the intermediate
product thus formed with a further molecule of a phenol, naphthol, their carbonio
or sulphonic acids, an amido-sulphonio or carbonic acid.
2. The modified manufacture of the colouring matters by coupling 1 molecule of
the monoazo-colouring matter formed with one molecule of the intermediate product
obtained by combining 1 molecule of a tetrazo-compound with 1 molecule of a
phenol, naphthol, etc. etc., or further
3. The modified manufacture of the colouring matters by causing 1 molecule of
a diazo compound to act upon the tetrazo colouring matter obtained from
1 molecule of a tetrazo-compound and 1 molecule of dioxynaphthalinemono-
sulphonic acid S and molecule of a phenol, naphthol, or the like, substantially
.as described.
4. The colouring matters manufactured as set forth.
ABEL & IMRAY,
Agents for the Applicant.