Improvements in the Manufacture of Colouring Matters.
Year: 1890

page_text: Date of Application, 18th Nov., 1890
Complete Specification Left, 18th Aug., 1891-Accepted. 26th Sept., 1891
PROVISIONAL SPECIFICATION.
[Communicated from abroad by Messrs. WIRTH & Co., of Frankfort-on-the-
Main, in the Empire of Germany, acting as Agents of A. Leonhardt & Co.,
of Mühlheim-on-the-Main, in the Empire of Germany.]
Improvements in the Manufacture of Colouring Matters.
I, HENRY HARRIS LAKE of the firm of Haseltine, Lake & Co., Patent
Agents, 45 Southampton Buildings, in the County of Middlesex, do hereby declare
the nature of this invention to be as follows:--
In the Provisional Specification accompanying the application for Letters Patent
dated August 28 1890 No. 13565 it has been shown that nitro-derivatives of
aromatic amines or chlorinides when brought into reaction with the higher
homologues of the metaamidophenols and especially with dimethyl-metaamidocresol,
yield new beautiful greenish blue dye-stuffs.
It has since been found that similar dye-stuffs can be obtained according to the
following methods riz. :-
1º. Instead of using the homolognes of dimethyl or diethyl-metaamidophenol
these substances themselves can be employed. In this case however for the most
part greyish blue dye-stuffs are obtained at first which in their totality appear of
little value, but it has been found that in these blue dye-stuff's there is contained a
pure blue colouring matter hidden at first by the other products of the reaction.
The avoidance as much as possible of these grey products depend upon the relative
quantity of cach component employed and it is further possible to separate the blue
from the grey products according to special methods, such as in systematical
dissolving and precipitating with chloride of zinc or common salt, or both of them
or by fractionally precipitating from the solution the grey products formed by
means of soda, acetate of sodium or the like, and separating the remaining blue
dye-stuff from the mother lye or in other suitable ways.
20. Instead of using nitroso-derivatives or chlorimides the corresponding amido-
derivatives (such as paraphenylene-diamine or paraamidodimethylaniline) can be
employed. In this case a mixture of the two components riz.:-on the one hand
the amido-derivatives and on the other hand the metaamidophenols or their
homologues, must be subjected to an oxidation in a suitable manner by the common
known agents. It can also be effected by means of amido-azo compounds; in this
case azo-dye-stuffs which by reduction yield paradiamines (such as amidoazobenzol,
benzol-azo-dimethylaniline etc.) are melted with the amidophenols preferably in
presence of a suitable diluting agent such as glycerine. It is probable that during
this reaction the azo-dye-stuffs are split and that the paradiamines thus formed are
condensed with the amidophenols yielding the blue dye-stuffs.
30. The nitroso-derivatives of dimethylmetaamidophenol or diethylmetaamido-
phenol are brought into reaction with aromatic metadiamines (such as meta-
toluylendiamine, metaamido-dimethylaniline or the like) preferably in presence of a
suitable dissolving or distributing agent for instance spirit or acetic acid.
The dye-stuffs thus obtained can also be purified if necessary as mentioned
under 10.
Dated this 18th day of November 1890.

page_text: COMPLETE SPECIFICATION.
Improvements in the Manufacture of Colouring Matters.
I, HENRY HARRIS LAKE of the firm of Haseltine, Lake & Co. Patent
Agents 45 Southampton Buildings in the County of Middlesex, 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 :-
In the final Specification 13565 I have shown that nitroso derivatives of
aromatic amines or chlorimides when brought into reaction with the higber
homologues of metaamidophenols and especially with dimethylmetaamidocresol
yield new beautiful greenish blue dyestuffs.
I have found since several methods according to which identical or similar dye-
stuffs can be obtained. These methods are the following:
FIRST METHOD.
Instead of using nitrosoderivatives or chlorimides, the corresponding amido-
derivatives (such as paraphenylenediamine or paraamidodimethylaniline) can be
employed. In this case, a mixture of the two components; viz.: on the one side
the amidoderivatives and on the other side the metaamidocresols must be subjected
to an oxydation in a suitable manner. As oxydizing agents, bichromates, or per-
oxyde of manganese together with accetic acid or sesquichloride of iron can be
employed; the latter giving the best results. The oxydation can also be effected
by means of amidoazocompounds; in this case azo-dyestuffs which by reduction
yield paradiamines (such as amidoazobenzol or benzol-azo-dimethylaniline) are
melted with the amidocresols preferably in presence of a suitable diluting agent,
such as glycerine or phenol. It is probable that during this reaction the azo-
dyestuffs are split and that the paradiamines thus formed are condensed with the
amidocresols yielding the blue dyestuffs.
As in these reactions, dimethylmetaamidocresol yields the greatest quantities of
blue coloring matter, this compound is especially mentioned in the following
examples.
Example 1st. 3 kilos. of dimethylmetaamidocresol, 26 kilos. of paraamido-
dimethylaniline (or a corresponding quantity of a salt of this base) and 10 kilos. of
acetate of sodium are dissolved in 150 litres of water and 30 litres of acetic acid
of 50%. To the boiling liquid are gradually added 70 litres of a solution of
sesquichloride of iron of 15% After boiling for some time the liquid is filtered
and cooled down, then filtered again and the coloring matter is precipitated from the
filtered liquid by means of common salt and chloride of zin. It can be purified
by dissolving and precipitating again.
Example 2nd. A mixture of 5 kilos. of benzol-azo-dimethylaniline, 4 kilos. of
dimethylmetaamidocresol, 4 litres of hydrochloric acid of 30% and 20 kilos. of
glycerine is gradually heated up to 140-160° C. At this temperature, the melt
gradually assumes an intensely blue tint. It is kept for, say, one hour at this
temperature and then extracted with about 500 litres of boiling water. T'o the
boiling solution are gradually added about 15 kilos. of acetate of sodium until the
solution shows a pure blue colour. It is then filtered and the coloring matter is
precipitated in the usual manner.
In a similar way I proceed when employing paraphenylenediamine instead of
paraamidodimethylaniline.

page_text: similar dyestuffs can be produced by employing, for instance nitrosodimethylaniline
and dimethylamidophenol or vice versa, dimethylaniline and nitrosodimethylmeta-
amidophenol, and I shall now proceed to show the results I have obtained in
each way.
First way. When dimethyl- or diethyl- metaamidophenol are brought into
reaction with nitrosoderivatives of aromatic amines or with chlorimides, for the
most part greyish blue dyestuffs are obtained which in their totality appear of but
little value. But I have found that in these greyish blue dyestuffs is contained a
pure blue coloring matter hidden by the other products of the reaction; and I
have succeeded in finding out methods by which the grey products are avoided as
much as possible, and by which the valuable blue dyestuffs can be separated from
the grey ones.
According to my experiments, the formation of the grey dyestuffs principally
depend on the relative quantities employed of each component. Thus, when equal
molecules of hydrochlorate of nitrosodimethylaniline and dimethylmetaamidophenol
are employed, a pretty pure blue dyestuff is directly obtained, while when I
increase the quantity of the nitrosoderivative up to say two or three molecules the
formation of the grey dyestuffs prevails to such an extent that the blue dyestuffs
sometimes are only to be found in small traces.
In order to separate the blue dye-stuffs from the grey ones, I repeatedly and
systematically dissolve the product of the reaction in water and precipitate it again
with common salt and chloride of zinc. At each such operation, the grey impurities
remain undissolved. Another method can be based on the fact that the two dye-
stuffs (the blue and the grey one) show a difference in their respective basic
properties. Thus, when I dissolve the product of the reaction in dilute acids and
then precipitate the solution fractionally by means of acetate of sodium or carbo-
nate of sodium or the like, I remove first the impurities, and finally there remains
a pure blue liquid in which only the blue dye-stuff is contained.
Second way--I have not succeeded in obtaining blue dye-stuffs from nitroso-
dialkylmetaamidophenol and dimethylaniline or aniline itself.
All the more I have been astonished to find that the metaamido-substituted
monamines are again capable of forming the blue dye-stuffs.
As metaamido-substituted nonamines, I have since tried metatolnylenediamine,
metaamidodiethylaniline,metaamidodiethylaniline,metaamidodiethylorthotoluidine;
as nitrosodialkylmetaamidophenols, nitrosodimethyl- and nitrosodiethyl-metaamido-
phenol.
I produce the coloring matters by heating the components (employing by
preference about equal molecules of each) in a suitable dissolving or distributing
agent, such as spirit or acetic acid, and I purify them in a similar way as indicated
above under "first way."
The following examples will show in which manner the second and third method
of producing blue coloring matters can be carried into practice.
Example 1st.-3.5 kilos. of quinone-dichlorimide are carefully heated with 4 kilos.
of diethylmetaamidophenol and 50 litres of spirit at the reflux cooler. The reaction
finished, the whole mass is diluted into about 300 litres of hot water, the spirit is
distilled over and, after cooling, the dye-stuff is precipitated with common salt and
chloride of zinc and is purified by a repeated dissolving and precipitating.
Example 2nd. A mixture of 6.5 kilos. of diethylmetaamidophenol, 7.5 kilos. of
hydrochlorate of nitrosodimethylaniline and 50 kilos. of glycerine is heated on the
water bath until the nitrosodimethylaniline has disappeared. The mass is then
extracted with about 700 litres of boiling water and the blue solution thus obtained
is cooled down and filtered and precipitated with common salt and chloride of zinc.
The coloring matter obtained is purified in the usual way.
Example 3rd.-5.5 kilos. of dimethylmetaamidophenol, 10 kilos. of chlorhydrate
of nitrosodimethylaniline and 30 litres of spirit are heated at the reflux cooler until
the nitrosodimethylaniline has disappeared. The grey colored produce of the

page_text: reaction is then dissolved in 500 litres of water acidulated with 10 litres of con-
centrated muriatic acid, and to the hot liquid a diluted solution of acetate of sodium
is gradually added, until a filtered sample shows a pure bluish color. Then the
whole is filtered and the coloring matter is precipitated from the filtered liquid and
further purified as indicated above.
By employing nitrosodiethylaniline instead of nitrosodimethylaniline the same
method of operating can be employed; however, the yield of blue coloring matter
is in this case less favorable.
Example 4th. 2 kilos. of chlorhydrate of nitrosodiethylmetaamidophenol are
heated with 11 kilos. of metatolnylenediamine and 10 litres of spirit until the
formation of coloring matter is finished. The mass is then extracted with boiling
water and filtered and the coloring matter is precipitated from the filtered liquid
with common salt and chloride of zinc and purified by a repeated dissolving and
precipitating.
5
Example 5th. 3 kilos. of chlorhydrate of nitrosodimethylmetaamidophenol are 1
heated with 2 kilos. of metaamidodimethylaniline and 20 litres of spirit until the
formation of coloring matter is finished. The mass is then extracted with boiling
water and the coloring matter is isolated and purified as indicated under 4th.
CLAIMS.
1º. The production of blue basic coloring matters by the hereinbefore described 2
process which consists in oxidizing together in a suitable way a mixture of
dimethyl-metaamidocresol and aromatic paradiamines, (paraphenylenediamine
and paraamidodimethylaniline being employed by preference), all substantially as
described under "first method of the present Specification.
"
2°. The blue basic coloring matters produced substantially as claimed under 1st. 2
3°. The production of blue basic dye-stuffs by the hereinbefore described process
which consists in heating preferably about equal molecules of a salt of nitroso-
dimethylaniline and nitrosodicthylaniline with dimethylmetaamidophenol or
diethylmetaamidophenol in a suitable dissolving or distributing agent and
purifying the obtained coloring matter, all substantially as hercin before described. 3
4°. The blue basic dye-stuffs produced substantially as claimed under 3°.
5°. The production of blue basic coloring matters by the herein before described
process which consists in heating preferably about equal molecules of a salt of
nitrosodimethylmetaamidophenol or nitrosodiethylmetaamidophenol with aromatic
metadiamines (metatoluylenediamine, metaamidodimethylaniline, metaamido- a
diethylaniline, metaamidodiethylorthotoluidine being employed by preference) in
a suitable dissolving or distributing agent and purifying the obtained coloring
matters, all substantially as herein before described.
6°. The blue basic dye-stuff's produced substantially as claimed under 5°.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, Agents for the Applicant.