IMPROVEMENTS IN THE MANUFACTURE OF RED-COLOURING MATTER
Year: 1880

page_text: LETTERS PATENT to William Robert Lake, of the Firm of Haseltine, Lake,
& Co., Patent Agents, Southampton Buildings, London, for an Invention
of "IMPROVEMENTS IN THE MANUFACTURE OF RED-COLOURING MATTER." A
communication from abroad by Rudolph Krügener, of Elberfeld, in the
Empire of Germany.
PROVISIONAL SPECIFICATION left by the said William Robert Lake at the
Office of the Commissioners of Patents on the 6th February 1880.
WILLIAM ROBERT LAKE, of the Firm of Haseltine, Lake, & Co., Patent
Agents, Southampton Buildings, London. "IMPROVEMENTS IN THE MANUFACTURE
OF RED COLOURING MATTER." [A communication from abroad by Rudolph
Krügener, of Elberfeld, in the Empire of Germany.]
The colouring matters obtained by means of this Invention are suitable for
dyeing and printing, and are produced in the following manner, that is to say:-
Twenty (20) pounds of amidoazo-benzol are dissolved in from four hundred (400)
to six hundred (600) pounds of water, adding twenty five (25) pounds of muriatic-
acid of 30 per cent. strength. To the refrigerated mixture a solution of seven (7)
pounds of nitrite of soda in two or three parts of water is added by degrees, and
the mixture is kept standing and well refrigerated for half or three quarters of an
hour. Chloride of diazo-azo-benzol is now formed.
I also dissolve fourteen and a half (14) pounds of beta-naphtol with eight (8)
pounds of caustic soda (calculated on the base of 100 per cent. strength) in nearly
one hundred and fifty (150) pounds of water, and this mixture is also well
refrigerated.
The solution of the chloride of diazo-azo-benzol is slowly poured into the solution
of the beta-naphtol in caustic soda. The colouring matter thus formed is then
filtered and washed, and dried in a temperature of about from 60 to 70 degrees
Celsius. This dried colouring matter is insoluble in water. In order to make this
colouring matter soluble so as to be suitable for dyeing purposes, one part of the
same has to be dissolved in from two to five parts of Nordhausen sulphuric acid
(of nearly 20 per cent. of anhydride), the mixture being heated until a sample of
the same proves to be perfectly soluble in water. Then the sulpho-acids of the

page_text: colouring matter, heretofore insoluble, will have been formed. The superfluous
sulphuric-acid is neutralized by caustic soda, or milk of lime is added;
the gypsum
produced is then filtered and the lime salt transformed into soda-salt. Then the
colouring matter is precipitated by the addition of chloride of soda, or obtained in
a dry state by evaporation of the water.
A colouring matter similar in its shade to that above described can be obtained
by substituting for the amido-azo-benzol amido-azo-toluol, produced from ortho-
toluidine.
The operation for producing this colouring matter is the same as for that above
described, excepting that instead of twenty (20) pounds amido-azo-benzol I employ,
say, twenty two and a half (222) pounds of amido-azo-toluol, produced from
orthotoluidine.
A third colouring matter is obtained by using amido-azo-xylol from meta-
xylidine. The process is the same as the one first herein described, with the
exception that instead of twenty (20) pounds of amido-azo-benzol I use, say,
25.3 pounds of amido-azo-xylol.
The three colouring matters above described differ in their shade, and are pro-
duced by employing beta-naphtol.
I obtain three other colours which shew the same qualities as those just men-
tioned (but which are of a more yellow shade) by substituting in the three
processes above described phenole for the beta-naphtol. Instead, however, of using
fourteen and a half (141) pounds of beta-naphtol I use, say, nine and a half (91/2)
pounds of phenole.
Sixteen other colours can be obtained which are very similar in their shades to
those colours just mentioned, and which are produced by the same process from
mixed amido-azo combinations. The formulæ of these mixed amido-azo combina-
tions are as follows:-

page_text: (from meta-xylidine), I use one of the mixed amido-azo-combinations, the formulæ
of which are given above. In all these cases a different colour is obtained.
It remains to be observed that in the production of all the colouring matters
described in this Specification, the mixture, in which the colours become formed,
must remain in an alkaline state to the end of the reaction.
In order that the above description of this Invention may be more clearly
understood I will proceed to describe the production of one of the aforesaid mixed
amido-azo-combinations, according to the analogy of which all the others may be
obtained, but I desire it to be understood that the process hereinafter described for
producing these compounds forms no part of my Invention.
I transform one molecule of aniline by means of a quantity (precisely calculated)
of nitrite of soda and muriatic acid into diazo-benzol chloride, employing in this
operation about fifteen (15) parts of water, and refrigerating the mixture. After
half an hour's rest, and after the mixture has cooled down, it is poured by degrees
(whilst being well stirred) into the exactly calculated quantity of one molecule of
xylidine. In consequence of this the diazo-benzol-amido-xylol is produced, and this
will be now transformed into the isometric amido-azo-combination by the reaction
of the muriate of xylidine (C, H, NH, HCI) in excess. The xylidine employed
herein must be, however, meta-xylidino, as shown by the above formulæ.
The following are the formulæ of chemical combinations which appear in this
Specification, that is to say :-
Amido-azo-benzol
=
-
C, H, NN C, H. (NH)
Amida azo-tolual-CN - N
CHINAY

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed
by the said William Robert Lake in the Great Seal Patent Office on the 6th
August 1880.
WILLIAM ROBERT LAKE, of the Firm of Haseltine, Lake, & Co., Patent
Agents, Southampton Buildings, London. "IMPROVEMENTS IN THE MANUFACTURE
OF RED COLOURING MATTER." A communication from abroad by Rudolph
Krügener, of Elberfeld, in the Empire of Germany..
The colouring matters obtained by means of this Invention are suitable for
dyeing and printing, and are produced in the following manner, that is to say :-
Twenty (20) pounds of amido-azo-benzol are dissolved in from four hundred
(400) to six hundred (600) pounds of water, adding twenty five (25) pounds of
muriatic acid of commerce, that is to say, acid containing 30 per cent. of the true
acid.
To the refrigerated mixture a solution of seven (7) pounds of nitrite of soda
in two or three parts of water is added by degrees, and the mixture is kept standing
and well refrigerated for one half or three quarters of an hour; chloride of diazo-
azo-benzol is now formed.
I also dissolve fourteen and a half (142) pounds of beta-naphthol with eight (8)
pounds of caustic soda (containing 100 per cent. of Na O) in nearly one hundred
and fifty (150) pounds of water, and this mixture is also well refrigerated.
The solution of the chloride of diazo-azo-benzol is slowly poured into the solution
of the beta-naphthol in caustic soda. The colouring matter thus formed is then
filtered and washed and dried in a temperature of about from 60 to 70 degrees
Celsius. This dried colouring matter is insoluble in water. In order to make this
- colouring matter soluble so as to be suitable for dyeing purposes one part of the
same has to be dissolved in from two to five parts of Nordhausen sulphuric acid
(containing nearly 20 per cent. of anhydrous sulphuric acid), the mixture being
heated until a sample of the same proves to be perfectly soluble in water. Then
the sulpho-acids of the colouring matter, heretofore insoluble, will have been
formed. The superfluous sulphuric-acid is neutralized by caustic-soda, or milk of
lime is added;
the gypsum produced is then filtered, and the lime-salt transformed
into soda-salt. Then the colouring matter is precipitated by the addition of
chloride of soda, or obtained in a dry state by evaporation of the water.
A colouring matter similar in its shade to that above described can be obtained
by substituting for the amido-azo-benzol amido-azo-tolulol (produced from ortho-
toluidine).
The operation for producing this colouring matter is the same as for that above
described, excepting that instead of twenty (20) pounds amido-azo-benzol, I employ,
say, twenty two and a half (2212) pounds of amido-azo-toluol, produced from
orthotoluidine.
A third colouring matter is obtained by using amido-azo-xylol from meta-
xylidine. The process is the same as the one first berein described, with the
exception that instead of twenty (20) pounds of amido-azo-benzol I use, say, 25.3
pounds of amido-azo-xylol.
The three colouring matters above described differ in their shade, and are
produced by employing beta-naphthol.
I obtain three other colours or colouring matters which possess the same qualities
as those just mentioned (but which are of a more yellow shade) by substituting in
the three processes above described phenole for the beta-naphthol. Instead, however,
of using fourteen and a half (142) pounds of beta-naphthol, I use, say, nine and a
half (92) pounds of phenole.
Sixteen other colours or colouring matters can be obtained which are very
similar in their shades to those just mentioned, and which are produced by the same

page_text: process by employing the mixed amido-azo-combinations whose formulæ are as
follow:
:-
TT TT
The colours or colouring matters resulting from the said mixed amido-azo-com-
binations are produced according to the process mentioned in the first part of this
Specification, but instead of amido-azo-benzol, amido-azo-toluol (from orthotoluidine),
or amido-azo-xylol (from meta-xylidine), I use one of the said mixed amido-azo-
combinations. Therefore by combining the eight amido-azo-combinations above
named with beta-naphthol I obtain eight colouring matters, and by combining
them with phenole I obtain eight other colouring matters, that is to say, sixteen,
which differ from each other, but are somewhat similar in their shades to the first
named six colours or colouring matters.
It remains to be observed that in the production of all the colouring matters
described in this Specification the mixture in which the colours become formed
must remain in an alkaline state to the end of the reaction.
In order that the above description of this Invention may be more clearly under-
stood I will proceed to describe the production of one of the aforesaid mixed
amido-azo-combinations, according to the analogy of which all the others can be
obtained, but I desire it to be understood that the process hereinafter described
for producing these compounds forms no part of my Invention.
I transform one molecule of aniline by means of a quantity (precisely calculated)
of nitrite of soda and muriatic acid into diazo-benzol-chloride, employing in this
operation about fifteen (15) parts of water, and refrigerating the mixture. After
half an hour's rest, and after the mixture has cooled down, it is poured by degrees
(whilst being well stirred) into the exactly calculated quantity of one molecule of
xylidine. In consequence of this the diazo-benzol-amido-xylol is produced, and
this will be now transformed into the isometric amido-azo-combinations by the
reaction of the muriate of xylidine (C, H, NH, HCl) in excess.
The xylidine
employed herein must be, however, meta-xylidine, as shewn by the above
formulæ.

page_text: The following are the formulæ of chemical combinations which appear in this
Specification, that is to say:-