Year: 1887

page_text: Date of Application, 21st Mar., 1887
Complete Left, 21st Dec., 1887
Complete Accepted, 17th Feb:, 1888
I, Dr. WILHELM MAJERT of Berlin in the Empire of Germany do hereby declare
the nature of this invention to be as follows:-
This invention relates to the preparation of azo colouring matters.
According to the said invention
(1) 4 parts of a a naphthyldisulpho acid (obtained by the influence of 2 molecules
of chlorhydrin of sulphuric acid to 1 molecule of naphthaline) are melted with 3 to 4
parts of hydrate of soda or caustic potash until, on becoming liquid it developes
hydrogen. The molten mass is then dissolved in water when by means of an acid,
dioxynaphthaline is separated, which melts at 248-252° Celsius.
(2) This dioxynaphthaline forms with sulphuric acid mono- and bisulphuro acids as
follows:
(a) 10 kilograms of finely powdered dioxynaphthaline are mixed together with 20
kilograms of concentrated sulphuric acid and kept for about one hour at 60° Celsius.
The mass, when almost solid, is dissolved in water, the solution is then treated with
milk of lime until it reacts neutrally, and from the salt of lime the natronsalt, of the
dioxynaphthaline monosulpho acid is made in the known manner.
(b) 10 kilograms of dioxynaphthaline are heated to from 90 to 130° Celsius with
concentrated sulphuric acid. The bisulpho acids obtained are then reduced into
alkaline salts in the known manner.

page_text: (3) The dioxynaphthaline as well as its mono and bisulpho acids, form with tetrazo-
connection,
(a) The so called intermediate products form 1 molecule of the tetrazoconnection
and 1 molecule of dioxynaphthaline its mono- or bisulpho acids respectively.
H₁ OH
O Na
The intermediate connections arise if the combinations are effected in such a
manner that in the reaction a free acid is present or makes its appearance.
Example. 1 molecule of tretrazodiphenylchloride dissolved in water is added to a
solution of 1 molecule of dioxynaphthaline natrium (C
and 1 molecule
of acetic natrium. The intermediate connection separates in blue flakes. If dioxy-
naphthaline is replaced by the salts of monosulpho acids (C, H, OH
(a):
он
or the
(4) If the combination of 1 molecule of a tetrazoconnection and 1 molecule of the
dioxynaphthaline or its mono and its bisulpho-acids respectively in presence of carbonic
or caustic alkalis are taken then direct colouring matter is obtained.
Example a) I molecule of tetrazodilolylchloride dissolved in water is added to a
solution of 1 molecule dioxynaphthalinnatrium and 2 molecules of carbonic or caustic
natrium dissolved in water.
The colouring matter separates indissolubly and dyes non-macerated cotton violet.
Example ) The dioxynaphthaline of the above example is replaced by the neutral
O Na
natron salt of a dioxynaphthaline sulpho acid (C₁ H₂O H
S O₂ Na
The colouring
matter is very difficult to dissolve in water and dyes blue violet.
(5) 1 molecule of a tetrazoconnection and 2 molecules dioxynaphthaline or its mono-
or bisulpho acids form blue colouring matter.
Example a) 1 molecule of tetrazostilbenchloride, 2 molecules dioxynaphthaline and 3
molecules of carbonic natrium, all dissolved in water are mixed together. The
colouring matter is unsalted and dyes non macerated cotton blue.
Example 6) The watery solutions of 1 molecule of tetrazodiphenylebloride, 2
molecules of natronsalt of a dioxynaphthalinsulpho acid and three molecules of
carbonate of natrium are mixed together and a blue colouring matter arises.
Example c) If the dioxynaphthalinsulpho acid is replaced by a dioxynaphthalin-
disulpho acid a blue colouring matter is obtained.
a a
(6) The intermediate connections obtained in i may be combined with one molecule
of salycilic acid a or ẞ naphthol its mono or bisulpho acids respectively, dioxy-
naphthaline its mono or bisulpho acids respectively.
Example. The intermediate connection out of 1 molecule tetrazodiphenyl and 1
molecule of dioxynaphthalinsulpho acid suspended in water, is treated with a solution
of 1 molecule a naphtholsulpho acid natrium and then with 2 molecules of hydrate of
soda. Blue violet dying colour is formed at once.
(7) The same connections as preceding are obtained also if the intermediate
connections out of 1 molecule of tetrazoconnection and 1 molecule salycilic acid

page_text: a or naphthol, their mono or bisulpho acids respectively are compounded with 1
molecule dioxynaphthalin its mono- or bisulpho acids respectively.
Instead of sulphuric acid one can make use of fuming sulphuric acid or sulphuric
acid chlorhydrin for the reduction of the dioxynaphthalin into the sulpho or bišulpho
acids.
As tetrazo connection are here taken into consideration the tetrazoconnections
which form themselves out of nitrous acid from benzidin, tolidin, diamidostilben,
diamidonaphthylin, dianisidin, diamidodiphenetol, diamidobenzophenon as well as the
mono and bisulpho acids of these bodies.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London,
Agents for the Applicant.

page_text: WILHELM MAJERT, of Berlin, in the Empire of Germany, 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. :—
This invention relates to the preparation of azo colouring matters.
According to the said invention.
(1) 4 paris of a a naphthyldisulpho acid (obtained by the influence of 2 molecules
of chlorhydrin of sulphuric acid upon 1 molecule of naphthaline) are melted with
3 to 4 parts of hydrate of soda or caustic potash, until, on becoming liquid it developes
hydrogen. The molten mass is then dissolved in water when by means of acid the
new dioxynaphthaline is separated which melts at 248-252° Celsius.
(2) This dioxynaphthaline forms with sulphuric acid mono- and bisulpho-acids, as
follows:-
1
a) 10 kilograms of finely powdered dioxynaphthaline are mixed together with 20
kilograms of concentrated sulphuric acid and kept for about one hour at 60° Celsius.
The mass, when almost solid, is dissolved in water. the solution is then treated with
milk of lime until it reacts neutrally, and from the salt of lime the matron salt of the
dioxynaphthaline monosulpho acid is made in the known manner.
b) 10 kilograms of dioxynaphthaline are heated to from 90 to 130° Celsius with
concentrated sulphuric acid, The bisulpho-acids obtained are then reduced into
alkaline salts in the known manner.
(3) The dioxynaphthaline, as well as its mono and bisulpho acids, form with tetrazo-
connection
a) The so called intermediate products from 1 molecule of the tetrazoconnection
and 1 molecule of dioxynaphthaline its mono- or bisulphoacids respectively. The
intermediate connections arise if the combinations are effected in such a manner that
in the reaction a free acid is present or makes its appearance.
Example. molecule of tetrazodiphenylchloride dissolved in water
solution of 1. molecule of mono-sodium dioxynaph-haline (Co H. ON
Na
)
added to a
and 1 molecule
OH
of sodium acetate. The intermediate connection separates in blue flakes.
naphthaline is replaced by the salts of monosulpho acids (
10
If dioxy-
H, OH
or the

page_text: Sourum Sart Of 4 столу паризнание затро аст
SO, Na
The colouring
matter is very difficult to dissolve in water and dyes blue violet.
(5) 1 molecule of a tetrazoconnection and 2 molecules dioxynaphthaline or its mono-
or bisulpho-acids form blue colouring matter.
Example a) 1 molecule tetrazostilben-chloride, 2 molecules dioxynaphthaline and 3
molecules of sodium carbonate, all dissolved in water are mixed together. The
colouring matter is unsalted and dyes non-mordanted cotton blue.
Example ) The watery solutions of 1 molecule of tetrazodiphenyl chloride,
2 molecules of sodium salt of a dioxynaphthalinsulpho acid and 3 molecules of
carbonate of sodium are mixed together and a blue colouring matter arises.
Example c) If the dioxynaphthalinsulpho acid is replaced by a dioxynaphthalin
di-sulpho acid a blue colouring matter is obtained.
(6) The Intermediate connections obtained in 1, may be combined with one
molecule of salycilic acid a or ẞ naphthol its mono or bisulpho acids respectively,
a a dioxynaphthaline its mono or bisulpho-acids respectively.
Example: The intermediate connection out of 1 molecule tetrazodiphenyl and 1
molecule of dioxynaphthalin sulpho-acid suspended in water, is treated with a solution
of 1 molecule the sodium salt of a naphtholsulpho-acid and then with 2 molecules of
hydrate of soda blue violet dying colour is formed at once.
(7) The same connections as preceding are obtained also if the intermediate
connections out of 1 molecule of tetrazoconnection and 1 molecule salycilic acid,
a or B naphthol, their mono or bisulpho-acids respectively are compounded with
1 molecule of dioxynaphthalin its mono- or bisulpho acids respectively.
Instead of sulphuric acid one can make use of fuming sulphuric acid or sulphuric
acid chlorhydrin for the reduction of the dioxynaphthalin into the sulpho- or bisulpho-
acids.
As tetrazoconnection are here taken into consideration, the tetrazoconnections
which form themselves out of nitrous acid from benzidin, tolidin, diamidostilben,
diamidonaphthalen, dianisidin, diamidodiphenetol, diamidobenzophenon as well as the
mono and bisulphoacids of these bodies.
Having now particularly described and ascertained the nature of my said
invention, and in what manner the same is to be performed I declare that what
I claim is
First. The preparation,a a dioxynaphthaline melting at from 248 to 252 degrees, by
melting a a naphthalinedisulpho-acid or a-naphthaline a-sulpho acid with caustic soda

page_text: Second. The preparation of mono- or bisulphoacids of a a-dioxynaphthaline by the
action of concentrated sulphuric acid, fuming sulphuric acid or sulphuric hydro-
chlorine upon a a-dioxynaphthaline.
Third. The preparation of blue colouring matters by the action of tetrazodiphenyl,
tetrazoditoly, tetrazostilben, tetrazodianisol or tetrazodiphenetol upon a a-dioxy-
naphthaline or its mono- or bisulpho-acids.
Dated this 21st day of Dacomban 1987
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London,
Agents for the Applicant.