IMPROVEMENTS IN THE MANUFACTURE OF COLOURING MATTERS
Year: 1884

page_text: PROVISIONAL SPECIFICATION.
I GERARD WENZESLAUS VON NAWROCKI of 124 Leipzigerstrasse, Berlin in the
Kingdom of Prussia Germany do hereby declare the nature of said Invention
for "IMPROVEMENTS IN THE MANUFACTURE OF COLOURING MATTERS" (A communi-
cation to me from abroad by Paul Böttiger of the City of Lodz in the Empire of
Russia) to be as follows:-
This process consists in forming new colouring matters through combination of
Tetrazo-Diphenyl with Naphtyl-Amines and their sulpho-acids, and it is carried
out by bringing watery solutions of a or B salts of Naphtyl-Amines in contact with
watery solutions of a or B salts of Naphtyl-Amine sulpho-acids. Instead of watery
solutions of Naphtyl-Amine salts, alcoholic solutions of the two Naphtyl-Amines
may be used.
By combination of Tetrazo-Diphenyl with Naphtyl Amines, colouring substances
are obtained which are insoluble in water but soluble in alcohol, but they can
easily be transformed into their Mono- and Di-sulpho-acids by treatment with
sulphuric acid of 60° B, distilled or fuming sulphuric acid, Sulphuric-Anhydride or
with Sulphuric-Acid-Mono-chlorhydrine (S O¸ˆH Cl), and the sodic and ammoniacal
salts of these compounds form colouring matters of orange to red shades which are
soluble in water. By the combination of Tetrazo-diphenyl with the sulpho-acids
of the two Naphtyl-Amines, substances are obtained which are soluble in acid-free
waters, and whose alkaline salts form orange to red colouring matters. The
formation of the new substances is due to the combination of one molecule of
Tetrazo-diphenyl with two molecules of Naphtyl-Amine-Sulpho-acid.

page_text: The salts of the Tetrazo-diphenyls are as it is well known formed by the action
of nitrous acid on the salts of the Benzidines.
First Example: 28.2 kilogrammes sulphate of benzidine or an equivalent amount
of another benzidine salt are together with 30 kgr. hydrochloric acid of 20° B finely
divided up in 500 litres of water; an addition is then made of a solution of 13.8 kgr.
nitrite of soda in 150 litres of water under vigorous stirring and in small portions.
The sulphate of benzidine slowly dissolves and a solution of chloride of tetrazodiphenyl
is produced. This solution is then under vigorous stirring run into a solution of
36.5 kgr. hydrochlorate of naphtylamine (muriate of naphtylamine) in 2000 litres of
water. A sediment is at once formed, which after several hours rest is mechanically
separated from the lye, and washed and dried. This dry and fine powdered
sediment is then slowly and while cooling mixed in fuming sulphuric acid in the
proportion of 25 kgr of the sediment to 75 kgr of the acid. The mixture is then
Blowly heated until a sample of it dissolves clear and fully in ammoniacal water.
This point attained it is put in about 1000 litres of cold water whereby the sulpho
acid produced separates as a sediment, and when it has been mechanically separated
from the lye it is in the well known manner rendered into salt of soda or ammonia.
These latter salts produce fast red colours for wool and especially for cotton.
Second Example: 28.2 kgr sulphate of Benzidine are in the well known manner
as described in Example 1 transformed into Chloride of Tetrazo-diphenyl and the
solution of this latter is slowly and under constant stirring run into a solution of
55 kgr naphtionate of soda and 12 kgr acetate of soda in 1000 litres of water.
After having stood for about 12 hours, the pigment thus formed and deposited as
mud is separated from the lye by mechanical means and by the well known process
transformed into salts of soda or ammonia. The colouring substance thus obtained
will dye wool and cotton (this latter without the use of a mordant) a fast red, and
cotton dyed therewith will stand fulling.

page_text: I GERARD WENZESLAUS VON NAWROCKI of 124 Leipzigerstrasse Berlin in the
Kingdom of Prussia Germany do hereby declare the nature of said invention for
"IMPROVEMENTS IN THE MANUFACTURE OF COLOURING MATTERS" (a communi-
cation to me from abroad by Paul Bottiger of the City of Lodz in the Empire of
Russia) and in what manner the same is to be performed, to be particularly
described and ascertained in and by the following statement :-
This process consists in the production of new coloring matters by the com-
bination of salts of tetrazodiphenyl with napthylamines or their sulpho-acids.
It is carried out by bringing aqueous solutions of the salts of tetrazodiphenyl in
contact with aqueous solutions of the salts of a or ẞ napthylamine or of the salts
of or napthylamine sulpho acids.
Instead of aqueous solutions of the salts of the napthylamines the napthylamines
may be used in alcoholic solution or finely divided in water.
By combination of tetrazodiphenyl with the two napthylamines, coloring matters
are forined which are insoluble in water but soluble in alcohol, and which can
easily be transformed into their mono- and disulpho-acids by treating them
respectively with concentrated sulphuric acid, fuming sulphuric acid, sulphuric
anhydride, or sulphuric acid-monochlorhydrine, (SO, HCl). The alkaline salts of
the sulpho acids obtained by this process form coloring matters, of shades varying
from orange to red, which are soluble in water. The a napthylamine colors are of
a redder shade whilst the ẞ napthylamines yield the yellower shades. By the
combination of the salts of tetrazodiphenyl with the sulpho acids of the two
napthylamines, substances are obtained which are soluble in water, and whose
alkaline salts form likewise coloring matters of shades ranging from orange to red.
The substances can be produced: firstly, by introducing the aqueous solution of
a salt of tetrazodiphenyl into an aqueous solution of a salt of the a or ẞ napthyl-
amine sulpho-acids which is permanently kept alkaline, by which process alkalino
solutions of the new coloring matters are formed; or secondly, by adding the
aqueous solution of a salt of tetrazodiphenyl to a or ẞ napthylamine-sulpho acid
finely suspended in water or dissolved in alcohol.
The reaction, i.e. the formation of these new coloring matters is most readily
obtained by pouring the solution of a salt of tetrazodiphenyl into an aqueous
solution of a salt of one of the various sulpho acids of a or B napthylamine, to
which so much acetate of soda has been added that, after combination of the two
solutions, no mineral acid such as sulphuric or hydrochloric acid remains free, but
merely some acetic acid. Even then the formation of the coloring matters does
not take place instantaneously, but by degrees, requiring several hours for its
completion. The formation of the new colors is due to the combination of one
molecule of tetrazo-diphenyl with either two molecules of a or B napthylamine, or
with two molecules of a or ẞ napthylamine-sulpho-acid according to the following
equations:

page_text: =
10
N
+ 2 Na Cl.
CH, NNCH. NH. SO, HJ
The salts of tetrazo-diphenyl are, as is well known, formed by the action of
nitrous acid on the salts of benzidine.
First example:
25.7 kg of chloride of benzidine or 28.2 kg of sulphate of benzidine or an
equivalent quantity of another salt of benzidine are well mixed with 30 kg of
hydrochloric acid of 20° B and 500 litres of water; a solution of 13.8 kg of nitrite
of sodium of 100 % in 150 litres of water is then added gradually in sınall
portions, stirring well all the time.
°
It is suitable to use the salts of benzidine which are to be transformed into
chloride of tetrazodiphenyl not in their dry state but as a paste, because the dry
salts of benzidine are difficultly and slowly acted upon. The salt of benzidine
dissolves, and a solution of chloride of tetraz-diphenyl is produced. This solution
is then under vigorous stirring, run into a solution of 36.5 kg of hydrochlorate of
a napthylamine (muriate of napthylamine) in 2000 litres of water. A precipitate is
at once formed, which after several hours standing is separated mechanically from
the liquor, and washed and dried.
To convert the coloring matter thus obtained which is soluble in spirits-into
its monosulpho acid, 25 kg of the precipitate, well powdered and sifted, are slowly
added to 75 kg of fuming sulphuric acid (containing 20% of anhydride) which
must be kept cool meanwhile. The mixture is then slowly heated at 30° C until
a sample dissolves completely in ammoniacal water. This point attained, the mass
is poured out into about 1000 litres of cold water, thereby precipitating the sulpho-
acid produced, which is then separated mechanically from the liquor and converted
in the well known manner into the sodium-or ammonium-salt.
The substance obtained by the combination of tetrazo-diphenyl with a or B
napthylamine is converted into its disulpho-acid in the following manner. 25 kg of
the same e.g are added in the cold to 75 kg of fuming sulphuric acid containing
20% of anhydride; the same quantity of acid is then added again, and the
mixture heated at 50° 60° C. for about one hour. Then it is introduced into
about 30001 of water, heated up to boiling, saturated with milk of lime, filtered,
and the resulting solution of the calcium salt decomposed by carbonate of soda or
ammonia. Thus solutions of the soda or ammonia-salts of the disulpho-acid of
a amido-naphthaline tetrazodiphenyl are obtained which are either evaporated to
dryness after having been separated mechanically from the carbonate of calcium, or
the color contained therein is precipitated with common salt in the well known
manner. The new product dyes wool and especially cotton a fast red shade.
Second Example:-
25.7 Kg of chloride of benzidino or 28.2 Kg of sulphate of henzidine or an
equivalent quantity of another salt of benzidine are in the manner described in
example 1 transformed into chloride of tetrazodiphenyl, and the solution of this
latter is slowly and under constant stirring run into a solution of 55 kg napthionate
of soda and 12 Kg of acetate of soda in 1000 litres of water. After having stood
for about 12 hours the colouring matter thus formed and deposited as a precipitate
is separated from the liquor and by the well known process converted into the
sodium or ammonium-salt.
The colouring matter thus obtained will dye wool and cotton (the latter without
the use of a mordant) a fast red shade, which will stand fulling.

page_text: 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 as the invention communicated to me is:--
First: The production of colouring matters soluble in spirits by the combination
of salts of tetrazodiphenyl with a or B napthylamine or their salts.
Second: The transformation of the colouring matters as described in the previous
claim into their sulpho acids by the action of sulphuric acid, sulphuric anhydride
or sulphuric acid monochlorhydrine.
Third: The production of new colouring matters by the combination of the salts
of tetrazo-diphenyl, with mono- or disulpho-acids of a or ẞ napthylamine or their
salts.
BREWER & JENSEN,
Agents for the Applicant.