Improvements in the Manufacture of Basic Colouring Matter.
Year: 1889

page_text: Date of Application, 27th May, 1889
Complete Specification Left, 27th Mar., 1890-Accepted, 3rd May, 1890
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Basic Colouring Matter.
I, BENJAMIN WILLCOX, of 47 Lincoln's Inn Fields, in the County of Middlesex,
Patent Agent, do hereby declare the nature of this Invention, (which has been com-
municated to me from abroad by the Farbenfabriken vormals Friedrich Bayer & Co.,
of Elberfeld, in the Empire of Germany,) to be as follows:-
This Invention relating to the manufacture of basic colouring matter mainly consists
in melting together the materials hereinafter specified in the presence of dissolving or
diluting agents such as dimethyl aniline, alpha or beta naphthylamine, or glycerine at
a temperature of from about 150 to 180 degrees Centigrade as hereinafter described.
The materials referred to may be combined as follows.
1. The azo compounds (or the salts of the said compounds) obtained from diazo
benzene, ortho, meta or para diazo toluol, diazo xylol, alpha diazo naphthaline, beta
diazo naphthaline, tetrazo diphenyl tetrazo ditolyl, diazo benzene sulpho acid or alpha
diazo naphthaline sulpho acid and m oxy mono methyl aniline or m oxy mono ethyl
aniline melted with alpha naphthylamine, mono methyl alpha naphthylamine mono
ethyl alpha naphthylamine or di ethyl alpha naphthylamine or their salts.
2. The azo compounds or their salts obtained from the above mentioned diazo
compounds and m oxy dimethyl aniline or m oxy diethyl aniline melted with alpha
naphthylamine mono methyl, dimethyl, mono ethyl, diethyl alpha naphthylamine or
their salts.
3. The azo compounds or their salts formed from the above mentioned diazo
compounds and alpha naphthylamine or mono methyl mono ethyl or diethyl alpha
naphthylamine melted with m oxy mono methyl or m oxy mono ethyl aniline or their
salts.
4. The azo compounds or their salts formed from the above mentioned diazo
compounds and alpha naphthylamine or mono methyl, mono ethyl, dimethyl or diethyl
alpha naphthylamine melted with m oxy dimethyl or m oxy diethyl aniline or their
salts.
According to this invention blue colouring matters are obtained by the direct action
of the amido azo compounds or their salts upon the aromatic bases or their salts at the
aforesaid temperature of from about 150 to 180 degrees Centigrade.
It is preferable in order to obtain a better yield to employ the hydrochloric acid
salts of the components and a suitable diluting agent so as to enable the substances to
come in intimate contact and obtain a homogeneous melt.
+.
The azo compounds and aromatic amines specified in the following table are
especially well suited for the manufacture' of the new basic colouring matter according
to this invention.
TABLE]
[Azo compounds obtained from
diazo benzene om or p diazo-
toluol alpha or beta diazo
naphthaline, tetrazo diphenyl
tetrazo ditolyl and the like,

page_text: the above mentioned diazo or
tetrazo compounds
and
2 Alpha naphthylamine
Mono methyl alpha naphthylamine
Mono ethyl
"
"
Dimethyl
Diethyl
"
"
m oxy mono methyl aniline
+
""
"
"
"" "
"
ethyl
dimethyl
"
"
"
""
"i
ethyl
"
"
"
The combination of the azo compounds and amines in the second list produces the
same colouring matter as the condensation of those in the first list but in smaller
quantity. It is also to be observed that according to the first list in the combinations of
benzene-, toluol-, naphthaline,-alpha-naphthaline,-heta azo diphenylene, ditolylene
-disazo m oxy mono methyl or m oxy mono ethyl aniline in particular with dimethyl
alpha naphthylamine a very small yield of colouring matter with less pure shade is
.obtained.
By substituting phenyl alpha naphthylamine tolyl alpha naphthylamine or alpha
dinaphthylamine for the bases mentioned in the second column of the first division of
this table a small yield of blue colouring matter is obtained the salts of which are
spirit soluble but not water soluble.
On the other hand the hydrochloric acid and sulphuric acid salts of all the colouring
matters obtained according to Table I are more or less readily soluble in cold or hot
water.
The colouring matter obtained from unsubstituted alpha naphthylamine form
sparingly soluble hydrochloric but readily soluble sulphuric acid salts; all the hydro-
chloric acid salts derived from alkylised alpha naphthylamine are readily soluble in
water.
The diazo compounds in the first column of Table I may be replaced by their
sulpho acids.

page_text: трия церкону
3) 1 molecule of
aipua vi
benzene p sulpho acid azo-
or naphthaline (alpha₁) m oxy mono methyl aniline
sulpho acid alpha₁₁ azo -
+1 molecule of mono ethyl alpha naphthylamine:
sulphanilic acid or
naphthionic acid}
=
+blue colouring matter.
4) One molecule of benzene azo m oxy dimethyl aniline + 1 molecule of p tolyl
alpha naphthylamine aniline+blue colouring matter (spirit soluble)..
5) One molecule of benzeneazodimethyl alpha naphthylamine + one molecule of
m oxy dimethyl aniline aniline blue colouring matter.
=
6) One molecule of the product of the coupling
of one molecule of tetrazo ditolyl)
with two molecules of m oxý mono + 2 molecules of mono methyl alpha
ethyl aniline.
naphthylamine.
tolidine + blue colouring matter.
According to the nature of the substances taking part in the reaction the following
may be employed as diluting agents namely: dimethylaniline, alpha or beta naphthyl-
amine, glycerine and the like.
The following is given as an example
About 12 parts by weight (12 kilos.) of benzene azo m oxydimethyl aniline with
about six parts by weight (6 kilos.) of hydrochloric acid (at 33 per cent.), about nine
and a half parts by weight (9.5 kilos.) of hydrochloric alpha naphthylamine and about
nine parts by weight (9 kilos.) of glycerine are stirred into a paste and gradually.
heated to from about 160 to 165 degrees Centigrade with stirring. When all the
water has been distilled out of the hydrochloric acid and glycerine the melt which at
first was thin and of a yellowish red colour becomes thicker or more tenacious and its
colour changes passing from brown to blackish green. It then becomes thin again
and finally turns blue with a short evolution of gas the new colouring matter
separating out in the form of lustrous green crystalline laminæ.
After a short time the reaction is completed. The melt being quickly stirred is
poured into about 150 parts (150 litres) of cold water and the separated colouring
matter after filtration is purified by a crystallising process with large quantities of hot
water. The hydro chlorate of the blue colouring matter sparingly soluble in cold
water crystallises out in the form of a bronze lustrous powder. It is rather easily
soluble in cold alcohol with a blue colour and deep dark red fluorescence and when
mixed with alkali produces a base which dissolves in alcohol and ether, with a red
colour and yellow brown fluorescence. By transformation into its sulphuric acid salt
the colouring matter is rendered readily soluble in hot water.
According to another example the following materials namely: about twelve parts
by weight (12 kilos.) of toluol azo m oxy monomethyl aniline about six parts by
weight (6 kilos.) of hydrochloric acid (at 33 per cent.), twelve parts by weight
(12 kilos.) of hydrochloric acid diethyl alpha naphthylamine and about the same
quantity of glycerine are treated as described in the preceding example.
After pouring into about 60 parts (60 litres) of hot water the product is mixed with
common salt; on cooling the hydrochloric acid salt of the new colouring matter first
separates in the form of resin which gradually solidifies. It can be easily purified by
repeatedly dissolving it in a small quantity of hot water traces of impurities remaining
undissolved filtering and salting out.
According to another example about 10-7 parts by weight (10.7 kilos.) of sulph-
anilic acid diazotised in the usual way with about 3.6 parts by weight (3-6 kilos.) of
sodium nitrite on the one hand and about 7 parts by weight (7 kilos.) of m oxy
dimethyl aniline on the other hand are dissolved in about six parts by weight of
hydrochloric acid (at 33 per cent.) and about 30 parts (30 litres) of water. These
materials being well stirred and cooled with ice acetate of soda is added in sufficient
quantity that on the addition of the solution of the diazo benzene sulpho acid all
.

page_text: hydrochloric acid is neutralised and the soda salt of the sulpho acid benzene azo
m oxy dimethyl aniline is formed. On salting out the orange yellow dye separates its
soda salt forming a soft mass on the sides of the vessel but after the removal of the
mother lye it gradually becomes firm.
After being dried in the air the substance thus obtained is heated to from about 160
to 165 degrees with about 9 parts by weight (9 kilos.) of dimethyl alpha naphthyl-
amine, about 15 parts by weight (15 kilos.) of glycerine and about 12 parts by
weight (12 kilos.) of hydrochloric acid (at 33 per cent.) until a sample of the
melt being mixed with hot water and a few drops of hydrochloric acid presents a
pure greenish blue colour. This appearance is suddenly assumed after 'from about
to 1 hours..
...
...
=
The melt is poured into about 100 parts (100 litres) of water, heated to from
about 50 to 60 degrees Centigrade mixed with about 3 parts by weight (3 kilos.) of
hydrochloric acid and afterwards with 'ammonia until precipitation is complete.
After filtration the base which is at first resinous and afterwards solid is dissolved
in about 15 litres of hot water and about 5.5 parts by weight (5.5 kilos.) of hydro-
chloric acid and filtered. The colouring matter is almost entirely precipitated from
the yet heated filtrate on the addition of about 5 parts by weight (5 kilos.) of common
salt being in the form of a dark tenacious resin which quickly sets and can be dried
at from about 30 to 40 degrees Centigrade. This product is readily soluble even in
cold water.
According to another example a solution of tetrazo ditolyl chloride corresponding
to about 10-6 parts by weight (10-6 kilos.) of tolidine base is added to a super
saturated solution mixed with acetate of soda of about 13-7 parts by weight (13.7 kilos.)
of m oxy mono ethyl aniline whereupon the new disazo compound separates as a free
base in the form of dark flakes.
i
After filtering, washing, pressing and drying this product at about 100 degrees
Centigrade the substance is heated to from about 160 to 165 degrees Centigrade with
about 26 parts by weight (26 kilos.) of hydro bromic acid mono ethyl alpha naphthyl-
amine twelve parts by weight (12 kilos.) of hydrochloric acid and about 40 parts by
weight (40 kilos.) of glycerine until the reaction described in the preceding example
takes place.
The colouring matter thus obtained being readily soluble in water is extracted from
its watery solution as described in the second example.
.
According to another example about fifteen parts by weight (15 kilos.) of naphtha-
line alpha azo alpha naphthylamine (alpha amido alpha azo naphthaline) are heated
to about 170 degrees Centigrade with about nine parts by weight (9 kilos.) of m oxy
diethyl aniline about seven parts (7 kilos.) of hydrochloric acid (at 33 per cent.) and
about 15 parts (15 kilos.) of glycerine with stirring in an oil bath until the final
reaction as herein before described takes place the operation being in other respects
conducted as in the first example.
According to another example a concentrated solution of diazotised naphthionic
acid corresponding to about 16 parts by weight (16 kilos.) of crystallised sodium
alpha naphthionate is allowed to flow into a solution (mixed, while cooled with ice,
with an excess of acetate of soda) of 8.5 parts by weight (8.5 kilos.) of m oxy diethyl
aniline in about six parts (6 kilos.) of hydrochloric acid and about 50 parts (50 litres)
of water: '
The soda salt of the resulting orange yellow colouring matter being completely
salted out with common salt is dissolved in about 40 parts (40 kilos.) of glycerine and
heated to from about 160 to 165 degrees Centigrade with about 9.5 parts (9.5 kilos.)
of hydrochloric alpha naphthylamine and about six parts (6 kilos:) of hydrochloric acid
until the melt assumes a blue colour."
tt.... IMY
1.
"After pouring into about 150 parts (150 litres.) of hot water the product is mixed
with ammonia and treated as described in the first and third example the hydrochlorate
of the resulting colouring matter being difficultly soluble in water.
According to another example about fourteen parts by weight (14 kilos.) of
benzidine sulphate are converted by the aid of about 7 parts (7 kilos.) of sodium,
AIL
**
+442 .b

page_text: nitrite into tetrazo diphenyl chloride in the known manner, and while being cooled
with ice and vigorously stirred are allowed to flow into a solution, mixed with an
excess of acetate of soda, of 16.5 parts (16.5 kilos.) of m oxy diethyl aniline in about
twelve parts (12 kilos.) of hydrochloric acid at 33 per cent.
After filtering, pressing and drying at about 100 degrees Centigrade the precipitate
in the form of a dark powder is mixed with about twenty four parts by weight
(24 kilos.) of hydrochloric acid diethyl alpha naphthylamine, about 12 parts (12 kilos.)
of hydrochloric acid and about forty parts (40 kilos.) of glycerine being heated in the
usual way to from about 160 to 165 degrees Centigrade.
The resulting melt is poured into about 80 parts (80 litres) of hot water mixed
with diluted sulphuric acid and filtered off from the separated benzidine sulphate.
The colour base is precipitated from the filtrate in the form of a resinous base on the
addition of an alkali and is dissolved and treated as hereinbefore explained in the
third example with about fifteen parts (15 litres) of water and about eleven parts
(11 kilos.) of hydrochloric acid (at 33 per cent.).
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Basic Colouring Matter.
I BENJAMIN WILLCOX, of 47 Lincoln's Inn Fields in the County of Middlesex,
Patent Agent do hereby declare the nature of this Invention which has been com-
municated to me from abroad by Farbenfabriken vormals Friedrich Bayer & Co.,
of Elberfeld in the Empire of Germany and in what manner the same is to be
performed to be particularly described and ascertained in" and by the following.
statement:-
This Invention relating to the manufacture of basic colouring matters consists in
melting together the materials hereinafter specified in the presence of dissolving
or diluting agents such as dimethyl aniline, alpha or beta naphthylamine, or glycerine
at a temperature of from about 150 to 20 degrees Centigrade as hereinafter described.
The materials referred to may be combined as follows:-
1. The azo compounds (or the salts of the said compounds) obtained from diazo-
benzene, ortho, meta- or para-diazo-toluene, diazo-xylene, alpha-diazo-naphthalene,
beta-diazonaphthalene, tetrazo-diphenyl-tetrazo-ditolyl-diazo-benzene-sulpho acid or
alpha-diazo-naphthalene-sulpho acid and inetahydroxy-mono-methyl-aniline or meta-
hydroxy-mono-ethyl-aniline are melted with alpha-naphthylamine, mono-methyl-
alpha-naphthylamine, mono-ethyl-alpha-naphthylamine or di-ethyl-alpha-naphthyl-
amine or their salts.
2. The azo-compounds or their salts obtained from the above mentioned diazo-
compounds and metahydroxy-dimethyl-aniline or metahydroxy-diethyl-aniline
are melted with alpha-naphthylamine, mono-methyl, dimethyl, mono ethyl-diethyl-
alpha-naphthylamine or their salts.
3. The azo-compounds or their salts formed from the above mentioned diazo-
compounds and alpha-naphthylamine or mono-methyl, mono-ethyl or diethyl-alpha-
naphthylamine are melted with metahydroxy mono-methyl-or meta-hydroxy-mono-
ethyl-aniline or their salts.
4. The azo-compounds or their salts formed from the above, mentioned diazo-
compounds and alpha-naphthylamine or mono-methyl, mono-ethyl, dimethyl or diethyl-
alpha-naphthylamine are melted with metahydroxy-dimethyl or metahydroxy-diethyl
aniline or their salts.
According to this Invention blue colouring matters are obtained by the direct
action of the amido-azo-compounds or their salts upon the aromatic bases. or their
salts at the aforesaid temperature of from about 150 to 200 degrees Centigrade.
It is preferable in order to obtain a better yield to employ the hydrochloric acid
salts of the components and a suitable diluting agent so as to enable the substances
to come into intimate contact and obtain a homogeneous melt.

page_text: The azo-compounds and aromatic amines specified in the following table are
especially well suited for the manufacture of the new basic colouring matters
according to this Invention.
TABLE 1.
On the one hand
Azo-compounds obtained from
diazo-
benzene, ortho, meta, or para-diazo-
toluene, alpha or beta-diazo-naph-
thalene, tetrazo-diphenyl, tetrazoditolyl
and the like and
metahydroxy-mono-methyl-aniline
metahydroxy-mono-ethyl-aniline
metahydroxy-dimethyl-aniline
On the other hand
Alpha-naphthylamine
Mono-methyl-alpha-naphthylamine
Mono-ethyl-alpha-naphthylamine
Dimethyl-alpha-naphthylamine
Diethyl-alpha-naphthylamine.
The azo compounds formed from the
above mentioned diazo- or tetrazo-com-
pounds and
Alpha-naphthylamine
Mono-methyl-alpha-naphthylamine
Mono-ethyl-alpha-naphthylamine
Dimethyl-alpha-naphthylamine
Diethyl-alpha-naphthylamine
On the other and
metahydroxy-mono-methyl-aniline
metahydroxy-mono-ethyl-aniline
metahydroxy-dimethyl-aniline
metahydroxy-diethyl-aniline.
By the combination of the azo-compounds and amines of the second Table the
same colouring matters are produced as those which result from the condensation of
the azo-compounds and amines of the first Table but in smaller quantity. It is also
to be observed, that according to the first list in the combinations of benzene-, toluene-,
naphthalene-alpha-, naphthalene-beta-azo-; diphenylene-ditolylene-disazo- meta-hy-
droxy-mono methyl or metahydroxy-mono-ethyl-aniline in particular with dimethyl-
alpha-naphthylamine a very small yield of colouring matter of a less pure shade is
obtained.
By substituting phenyl-alphanaphthyl-amine, tolyl-alpha-naphthylamine or alpha-
dinaphthylamine for the bases mentioned in the second column of the first division
of this Table, a small yield of blue colouring matter is obtained, the salts of which
are soluble in spirit but not in water.
. On the other hand the hydrochloric acid and sulphuric acid, salts of all the
colouring matters obtained according to Table I, are more or less readily soluble in
cold or hot water.
The colouring matters obtained from unsubstituted alpha-naphthylamine form
sparingly soluble hydrochlorides, but readily soluble sulphates; all the hydro-
chlorides derived from alkylised alpha-naphthylamine are readily soluble in water.
The diazo-compounds in the first column of Table I may be replaced by their
sulpho acids.
In all cases the process is so conducted that the azo-group of the azo-compound
causes the spliting off of 1. molecular proportion of the base or amido sulpho
acid.
For example
1. One molecular proportion of benzene-azo-metabydroxy-dimethyl-aniline plus one
molecular proportion of alpha-naphthylamine-gives aniline plus blue colouring
matter.
2. One molecular proportion of naphthalene-alpha (or beta)-azo metahydroxy-
diethyl-aniline plus one molecular proportion of alpha-naphthylamine-gives alpha
or beta-naphthylamine plus blue colouring matter.

page_text: 3. One molecular proportion of benzene-para-sulpho-acid-azo-meta-oxy-monomethyl
aniline or
alpha naphthalene sulpho-acid-azo-meta-hydroxy-mono-methyl aniline plus one
molecular proportion of mono-ethyl-alpha-naphthylamine-gives
sulphonilic acid ord
4. One molecular proportion of benzene-azo-metahydroxy-dimethyl-aniline plus one
molecular proportion of para-tolyl-alpha-naphthylamine-gives. aniline plus blue
colouring matter, soluble in spirit.
5. One molecular proportion of benzene-azodimethyl-alpha-naphthylamine plus one
molecular proportion of meta-hydroxy-dimethyl-aniline-gives aniline plus blue
colouring matter.
o. Une molecular proportion of the product of the coupling
of one molecular proportion
of letrazo-ditolyl with two (plus two molecular proportions
molecular proportions of meta of mono-methyl-apha
napthylamine.
gives tolidine plus blue colouring matter.
According to the nature of the substances taking part in the reaction the following
may be employed as diluting agents, namely, dimethylaniline alpha-for beta-naphthyl-
amine, glycerine and the like.
The following is given as an example :-
:-
J
About twelve parts by weight of benzene-azo-meta-hydroxy-dimethyl-aniline with
about six parts by weight of hydrochloric acid (33 per cent.) about nine and a half
parts by weight of hydrochloride of alpha-naphthylamine and about nine parts by weight
of glycerine are stirred into a paste and gradually heated (whilst being stirred). to
from about 160 to 165 degrees Centigrade. When all the water has been distilled
from the hydrochloric acid and glycerine, the melt which at first was thin and of a
yellowish red colour becomes thicker or more tenacious and its colour changes from
brown to blackish green. It then becomes thin again and finally turns blue, evolution
of gas taking place for a short time the new coloring matter separating out in the
form of lustrous green crystalline laminæ.
After a short time the reaction is completed. The melt, being quickly stirred, is
poured into about 150 parts by weight of cold water and the separated coloring
inatter after filtration is purified by a crystallising process with large quantities of hot
water. The hydro-chlorate of the blue colouring matter, sparingly soluble in cold
water, crystallises out in the form of a bronze lustrous powder. It is somewhat
readily soluble in cold alcohol, with a blue colour and deep dark red fluorescence
and when mixed with alkali, produces a base, which dissolves in alcohol and ether
with a red colour and yellow brown fluorescence. By transformation into its
sulphuric acid salt, the colouring matter is rendered readily soluble in hot
water.
According to another example, the following materials namely:-about twelve
parts by weight of toluene-azo-meta-hydroxy-monomethyl aniline, about six parts by
weight of hydrochloric acid (33 per cent.) twelve parts by weight of hydrochloride of
diethyl-alpha-naphthylamine and about the same quantity of glycerine are treated as
described in the preceding example.
After pouring into about 60 parts by weight of hot water the product is mixed with
common salt; on cooling the hydrochloric acid salt of the new colouring matter first
separates in the form of resin which gradually solidifies. It can be easily purified by
repeatedly dissolving it in a small quantity of hot water, traces of impurities remaining
undissolved, filtering and salting out.
According to another example about 10-7 parts by weight. of sulphanilic acid
diazotised in the usual way with about 3.6 par's by weight of sodium nitrite on the one
hand and about 7 parts by weight of metahydroxy-dimethylaniline on the other hand

page_text: 1
are dissolved in about six parts by weight of bydrochloric acid (33 per cent.) and about
30 parts by weight of water. These materials being well stirred and cooled with ice,
acetate of soda is added in such quantity that on the addition of the solution of the
diazo-benzene-sulpho-acid all hydrochloric acid is neutralised and the soda salt of the
sulpho-acid of benzene-azo-metahydroxy-dimethyl-aniline is formed. On salting out,
the orange-yellow dye separates, its soda salt forming a soft mass on the sides of the
vessel but after the removal of the mother liquor it gradually becomes hard.
After being dried in the air the substance thus obtained is heated to from about 160
to 165 degrees Centigrade with about 9 parts by weight of dimethyl-alpha-naphthyl-
amine, about 15 parts by weight of glycerine and about 12 parts by weight of
hydrochloric acid (33 per cent.) until a sample of the melt being mixed with hot water
with a few drops of hydrochloric acid therein presents a pure greenish blue colour.
This appearance is suddenly assumed after from about one to one and a half
hours.
The melt is poured into about 100 parts by weight of water, heated to from about 50
to 60 degrees Centigrade, mixed with about 3 parts by weight of hydrochloric acid
and afterwards with ammonia until precipitation is complete.
After filtration the base which is at first resinous and afterwards solid is dissolved
in about 15 parts by weight of hot water and about 5.5 parts by weight of hydrochloric
acid and filtered. The colouring matter is almost entirely precipitated from the hot
filtrate on the addition of about 5 parts by weight of common salt, being in the form
of a dark tenacious resin, which quickly sets and can be dried at from about 30
to 40 degrees Centigrade. This product is readily soluble even in cold water.
According to another example, a solution of tetrazo-ditolyl-chloride, corresponding
to about 10-6 parts by weight of tolidine base is added to a supersaturated solution,
mixed with acetate of soda, of about 13.7. parts by weight of meta-hydroxy-mono-
ethyl-aniline, whereupon the new diazo-compound separates as a free base in the form
of dark flakes.
After filtering washing, pressing and drying this product at about 100 degrees
Centigrade the substance is heated to from 160° to 165° Centigrade with about 26 parts
by weight of hydrobromic acid, mono-ethly-alpha-naphthylamine twelve parts by
weight of hydrochloric acid and about 40 parts by weight of glycerine until the
reaction' described in the preceding example takes place.
The colouring matter thus obtained being readily soluble in water is extracted from
its watery solution as described in the second example.
According to another example about fifteen parts by weight of naphthaline-alpha-
azo-alpha-naphthylamine (alpha-amido-azo-naphthaline) are heated (whilst stirring) in
an oil bath to about 170 degrees Centigrade with about nine parts by weight of meta-
hydroxydiethylaniline about seven parts by weight of hydrochloric acid (33 per cent.)
and about fifteen parts by weight of glycerine, until the final reaction as herein before
described takes place, the operation being in other respects conducted as in the first
example.
According to another example a concentrated solution of diazotised napthionic acid
corresponding to about 16 parts by weight of crystallised sodium-alpha-napthionate is
allowed to flow into a solution (mixed, while cooled with ice, with an excess of acetate
of soda) of 8.5 parts by weight of metahydroxy-diethyl-aniline in about six parts by
weight of hydrochloric acid and about 50 parts by weight of water.
The soda salt of the resulting orange-yellow colouring matter being completely
salted out with common salt, is dissolved in about 40 parts by weight of glycerine and
heated to from about 160 to 165 degrees Centigrade with about 9-5 parts by weight
of bydrochloride of alpha-naphthylamine and about six parts by weight of hydrochloric
acid until the melt assumes a blue colour.
After pouring into about 150 parts by weight of hot water the product is mixed with
ammonia and treated as described in the first and third examples the hydrochloride of
the resulting colouring matter being soluble in water with difficulty.
According to another example about 14 parts by weight of benzidine-sulphate are
converted by the aid of about 7 parts by weight of sodium nitrite into tetrazo-diphenyl-

page_text: chloride in the known manner and while being cooled with ice and vigorously stirred
are allowed to flow into a solution mixed with an excess of acetate of soda of 16.5 parts
by weight of meta-hydroxy-diethyl-aniline in about 12 parts by weight of hydrochloric
acid (33 per cent.).
After filtering pressing and drying at about 100 degrees Centigrade the precipitate.
which is in the form of a dark powder, is mixed with about twenty four parts by
weight of hydrochloride of diethyl-alpha-naphthylamine about twelve parts by weight
of hydrochloric acid and about forty parts by weight of glycerine and is heated in the
usual way to from about 160 to 165 degrees Centigrade.
The resulting melt is poured into about 80 parts by weight of hot water mixed with
diluted sulphuric acid and filtered off from the separated benzidine sulphate. The
colour base is precipitated from the filtrate in the form of a resinous base on the
addition of an alkali and is dissolved and treated as herein before explained in the third
example with about fifteen parts by weight of water and about eleven parts by weight
of hydrochloric acid (33 per cent.).
Having now particularly described and ascertained the nature of the said Inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The new process for the manufacture of blue basic colouring matters which
consists in melting together azo compounds resulting from the combination of either
diazobenzene, or diazotoluene, or diazoxylene, or diazo-naphthalene, or tetrazodiphenyl,
or tetrazoditolyl, or the sulpho-acids thereof and metahydroxy-mono-methyl- or ethyl-
aniline, metahydroxy-dimethyl or diethyl-aniline with alpha-naphthylamine, mono-
methyl, monoethyl- dimethyl- diethyl- alpha-naphthylamine in the presence of a solvent
agent at temperatures of about 150 to 200 degrees Centigrade.
2. The new process for the manufacture of blue basic colouring matters, which con-
sists in melting together azo compounds resulting from the combination of either
diazobenzene, or diazotoluene, or diazoxylene or diazonaphthalene, or tetrazodiphenyl
or tetrazoditolyl or the sulpho acids thereof and alpha naphthylamine, monomethyl-,
monoethyl-, dimethyl- diethyl- alpha-naphthylamine, with meta hydroxy monomethyl-
or ethylaniline, or meta hydroxydimethyl, or diethylaniline in the presence of solvents
at temperatures of about 150 to 200 degrees Centigrade.
Dated this 27th day of March 1890
J. H. JOHNSON & Co.,
Agents.