IMPROVEMENTS IN THE PRODUCTION OF COLOURING MATTERS SUITABLE FOR DYEING AND PRINTING
Year: 1879

page_text: LETTERS PATENT to Joseph Anthony Dixon, of 175, West George Street,
Glasgow, in the County of Lanark, North Britain, Solicitor, for the Invention
of "IMPROVEMENTS IN THE PRODUCTION OF COLOURING MATTERS SUITABLE FOR
DYEING AND PRINTING." A communication from abroad by Wilhelm Meister,
Eugen Lucius, and Adolphus Brüning, all of Hoechst-am-Main, in the Empire
of Germany, persons carrying on business as Chemical Manufacturers under
the Firm of Meister, Lucius, and Brüning.
PROVISIONAL SPECIFICATION left by the said Joseph Anthony Dixon at
the Office of the Commissioners of Patents on the 22nd November 1879.
JOSEPH ANTHONY DIXON, of 175, West George Street, Glasgow, in the County
of Lanark, North Britain, Solicitor. "IMPROVEMENTS IN THE PRODUCTION OF
COLOURING MATTERS SUITABLE FOR DYEING AND PRINTING." [A communication
from abroad by Wilhelm Meister, Eugen Lucius, and Adolphus Brüning, all of
Hoechst-am-Main, in the Empire of Germany, persons carrying on business as
Chemical Manufacturers under the Firm of Meister, Lucius, and Brüning.]
The Invention which I describe has for its object the production of new or
improved colouring matters by the oxidation by means of chlor-quinones or
chlorinated quinones (such as, for example, chloranil, otherwise called " tetrachlor-
chinon," CC O³) of,-—
First. The leucobases of the rosaniline series.
Second. The leucobases which originate from primary, secondary, or tertiary
monamines of the aromatic series through coupling with aldehydes or acid chlorides
(chlorides of acids).
Third. The sulpho acids of these leucobases.
Proceeding upon the fact discovered by Wilhelm Meister, Eugen Lucius, and
Adolphus Brüning, that chlorquinones are excellent oxidizing agents, they have
found further that the same are especially suited for the purpose of converting,
that is, of oxidizing the leucobases of the aromatic series, as well as the sulpho acids
of the same, into colouring matters.

page_text: By leucobases I understand not only the uncoloured and by two hydrogen
atoms richer bases of the rosaniline series, as, for instance,―
- H. NH
CH-C
Ủ H, NH.
C. H. NH, that is to say, diamido-triphenylmethan
H
was probably obtained first by Böttinger (Berliner Berichte, Vol. XII., p. 975)
from benzalchloride (C HCHC₁₁) and aniline. Some time later on O. Fischer
(Berliner Berichte, Vol. XII., p. 1693) produced it from benzoic, aldehyde, and
hydrochlorate of aniline in presence of zinc chloride, and he was the first who
discovered its constitution.
The diamido-triphenylmethan gives on oxidation with chlor-quinones (as, for
instance, with chloranil) a reddish blue colouring inatter of no especial brightness,
but on the other hand the methylized, ethylized, phenylized, and benzylized
derivatives of this base give very beautiful colouring matters in part directly
soluble in water. I produce these colouring matters in three different ways,―
a. By oxidation of the diamidotriphenylmethan and its homologues (as, for
instance, diamidoditolylphenylmethan or diamidotritolylmethan).
b. By oxidation of the bases which originate from the diamidotriphenylmethan
or its homologues by introducing methyl, ethyl, phenyl, or benzyl.
c. By oxidation of the methylized, ethylized, phenylized, or benzylized derivatives
of diamidotriphenylmethan or its homologues which are obtained direct from the
secondary and tertiary aromatic monamines by coupling with benzoic, aldehyde,
tolylaldehyde, salicylaldehyde, and the other analogous aldehydes.
As an example for the last method or process I describe the production of the
colouring matters from tetramethyldiamidotriphenylmethan.
I heat two parts of dimethylaniline, one part of benzoic aldehyde, and one part
of solid zinc-chloride, until the mixture has no longer the smell of benzoic aldehyde.
(Instead of benzoic aldehyde I can also use benzal-chloride or benzoyl-chloride).
The zinc-chloride is removed from the mixture by means of boiling water, and the
base thus obtained is in a proper way intimately mixed with from half to equal
weight of chloranil, and is kept heated to from 50° to 60° centigrade for some
length of time. The base, originally colourless, takes on a deep bronzelike
appearance, and when dissolved in spirit has now a bluish green shade. The
colouring matter is then made into a base with caustic soda lye, is dissolved in
diluted muriatic acid, purified with common salt and zinc-chloride, and is
precipitated ready for commercial purposes in the form of the zinc-chloride double
salt; dyed it gives exactly the same shade as malachite green, and is perfectly
identical with the same.

page_text: If I use in this method or process monomethylaniline instead of dimethylaniline
obtain a green considerably bluer. In a similar way I use diethylaniline,
imethyltoluidine, and higher homologues.
Further, by using toluylaldehyde or salicylaldhyde in manner described before
nstead of benzoic aldehyde I obtain a number of colouring matters considerably
ellower. The phenylized and benzylized derivatives of the diamidotriphenylmethan
ive only colouring matters soluble in spirit, but these can be converted into sulpho
cids soluble in water by means well known to chemists. I can however also first
onvert the leucobases into sulpho-acids, and then oxidize these with chloranil
the proner way
☐ obtain a green considerably bluer. In a similar way I use diethylaniline,
dimethyltoluidine, and higher homologues.
Further, by using toluylaldehyde or salicylaldhyde in manner described before
instead of benzoic aldehyde I obtain a number of colouring matters considerably
yel
ellower. The phenylized and benzylized derivatives of the diamidotriphenylmethan
give only colouring matters soluble in spirit, but these can be converted into sulpho
acids soluble in water by means well known to chemists. I can however also first
convert the leucobases into sulpho-acids, and then oxidize these with chloranil
in the proper way.
PRODUCTION OF RED COLOURING MATTERS.
In the same way as the leucobases of the triphenylmethan, all the leucobases
of rosaline (all the leucobases of crude rosaline or of "rosalineschmelze") can be.
converted into colouring matters by means of chloranil. Through this I have the
means in my hands of converting the leucanilines formed in no small quantity.in
the rosaniline process, into rosanilines or their sulpho acids.
The preparation of the colouring matters is explained in the following.
example:-
One part of leucaniline is intimately mixed in proper manner with from half
to equal weight of chloranil, and the mixture after slow and gentle heating is boiled
with caustic soda. The rosaniline base then obtained is dissolved in muriatic acid,
precipitated by common salt, crystallized, and brought into the market in form of
the well known crystals. In the same way as leucaniline is oxidized, but with
greater facility, the sulpho acids of leucaniline are oxidized to rosaline sulpho acids.
I am thus in a position to produce the sulpho acids of the colouring matters from
crude rosaniline (the "rosanilineschinelze ") in a new and very practical way by
converting the leucobodies which occur in crude majenta (the "fuchsinschmelze")
into sulpho acids, and then oxidizing these with chlor-quinones, as, for example,
with chloranil C° Cl* O*.
The described proportions and also the degrees of temperature may be varied
within certain limits which a practical chemist can easily determine for himself.
The described methods of purifying the colouring matters may also be modified
in convenient and suitable manners, which a practical chemist will determine for
himself.
PRODUCTION OF RED COLOURING MATTERS.
In the same way as the leucobases of the triphenylmethan, all the leucobases
of rosaline (all the leucobases of crude rosaline or of "rosalineschmelze") can be.
converted into colouring matters by means of chloranil. Through this I have the
means in my hands of converting the leucanilines formed in no small quantity. in
the rosaniline process, into rosanilines or their sulpho acids.
The preparation of the colouring matters is explained in the following.
example:-
One part of leucaniline is intimately mixed in proper manner with from half
to equal weight of chloranil, and the mixture after slow and gentle heating is boiled
with caustic soda. The rosaniline base then obtained is dissolved in muriatic acid,
precipitated by common salt, crystallized, and brought into the market in form of
the well known crystals. In the same way as leucaniline is oxidized, but with
greater facility, the sulpho acids of leucaniline are oxidized to rosaline sulpho acids.
I am thus in a position to produce the sulpho acids of the colouring matters from
crude rosaniline (the "rosanilineschinelze ") in a new and very practical way by
converting the leucobodies which occur in crude majenta (the "fuchsinschmelze ")
into sulpho acids, and then oxidizing these with chlor-quinones, as, for example,
with chloranil Cª Cl* 0°.
The described proportions and also the degrees of temperature may be varied
within certain limits which a practical chemist can easily determine for himself.
The described methods of purifying the colouring matters may also be modified
in convenient and suitable manners, which a practical chemist will determine for
himself.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said Joseph Anthony Dixon in the Great Seal Patent Office on the 20th
May 1880.
JOSEPH ANTHONY DIXON, of 175, West George Street, Glasgow, in the County.
of Lanark, North Britain, Solicitor. "IMPROVEMENTS IN THE PRODUCTION OF
COLOURING MATTERS SUITABLE FOR DYEING AND PRINTING." A communication
from abroad by Wilhelm Meister, Eugen Lucius, and Adolphus Brüning, all of
Hoechst-am-Main, in the Empire of Germany, persons carrying on business as
Chemical Manufacturers under the Firm of Meister, Lucius, and Brüning.
The said Invention has for its object the production of new or improved colouring
matters by the oxidation by means of chlorquinones or chlorinated quinones (such
as, for example, chloranil) of
1. The leucobases of the rosaniline series.
2. The leucobases which originate from primary, secondary, or tertiary monamines
of the aromatic series through coupling with aldehydes or acid chlorides (chlorides
of acids or acid radicles).
3. The sulpho acids of the said leucobases.
Proceeding upon the fact discovered by the said Wilbelm Meister, Eugen Lucius,
and Adolphus Brüning that chlorquinones are excellent oxidizing agents, they
have found farther that the same are especially suited for the purpose of converting,
i.e., of oxidizing, the leucobases of the aromatic series, as well as the sulpho acids of
the same, into colouring matters.
By leucobases I understand not only the uncoloured, and by two hydrogen
atoms richer bases of the rosanline series, as for instance,-
but also the bases which originate by coupling aldehydes or acid chlorides
(chlorides of acids or acid radicles) with primary, secondary, and tertiary aromatic
monamines.
The whole of the compounds which originate in this way can be converted
into colouring matters of more or less importance by the above named means of
oxidation.
The chlorquinones which I principally use are the tri and tetra chlorquinones,
or the crude chloranil as obtained according to the well known description of
Graebe (Annalender Chemie und Pharmacie, volume 146, page 1, et seq.) by the
action of hydrochloric acid and potassium chlorate on phenol.
As the number of the colouring matters obtained in the way mentioned is too
great for me to describe them all individually, I explain the methods or processes
of the Invention by some examples, as follows:—

page_text: benzalchloride (C, H, CH C₁₂) and aniline. Some time later on O. Fischer
(Berliner Berichte, vol XII., p. 1693) produced it from benzoic aldehyde and
hydrochlorate of aniline in presence of zinc chloride, and he was the first who
discovered its constitution.
The diamidotriphenylmethan gives an oxidation with chlorquinones (as, for
instance, with chloranil) a reddish blue colouring matter of no especial brightness.
But on the other hand, the methylized, ethylized, phenylized, and benzylized
derivatives of this base give very beautiful colouring matters, in part directly
soluble in water. I produce these colouring matters in three different ways.
(a). By oxidation of the diamidotriphenylmethan and its homologues (as, for
instance, diamidoditolylphenylmethan or diamido-tritolylmethan).
(b). By oxidation of the bases which originate from the diamidotriphenylmethan
or its homologues by introducing methyl, ethyl, phenyl, or benzyl.
(c). By oxidation of the methylized, ethylized, phenylized, or benzylized
derivatives of diamidotriphenylmethan or its homologues which are obtained direct
from the secondary and tertiary aromatic monamines by coupling with benzoic
aldehyde tolylaldehyde, salicylaldehyde, and the other analogous aldehydes.
As an example for the last method or process I describe the production of the
colouring matters from tetramethyldiamidotriphenylmethan.
I heat two parts of dimethylaniline, one part of benzoic aldehyde, and one part
of solid zinc chloride until the mixture has no longer the smell of benzoic aldehyde.
(Instead of benzoic aldehyde I can also use benzalchloride or benzoylchloride).
The zinc chloride is removed from the mixture by means of boiling water, and the
base thus obtained is in a proper way intimately mixed with from half to equal
weight of chloranil, and is kept heated to from 50° to 60° centigrade for some
length of time. The base, originally colourless, takes on a deep bronze-like appearance
and, when dissolved in spirit, has now a blueish green shade. The colouring
matter is then made into a base with caustic sodalye, is dissolved in diluted
muriatic acid, purified with common salt and zinc chloride, and is precipitated,
ready for commercial purposes, in the form of the zincchloride double salt. Dyed,
it gives exactly the same shade as malachite green, and is probably identical with
the same.
If I use in this method or process monomethylaniline instead of dimethylaniline,
I obtain a green considerably bluer. In a similar way I use diethylaniline,
dimetbyltoluidine, and higher homologues.
Further, by using toluylaldehyde or salicylaldehyde in manner described before,
instead of benzoic aldehyde, I obtain a number of colouring matters considerably
yellower. The phenylized and benzylized derivatives of the diamidotriphenyl-
methan give only colouring matters soluble in spirit, but these can be converted
into sulpho acids, soluble in water, by means well known to chemists.
I can,
however, also first convert the loucobases into sulpho acids and then oxidize these
with chloranil in the proper way, which is well known.
PRODUCTION OF RED COLOURING MATTERS.
:-
In the same way as the leucobases of the triphenylmethan, all the leucobases
of rosaniline (all the leucobases of crude rosaniline or of the " rosanilin-
schmelze") can be converted into colouring matters by means of chloranil. Through
this I have the means in my hands of converting the leucoanilines, formed in
no small quantity in the rosaniline process, into rosanilines or their sulpho acids.
The preparation of the colouring matters is explained in the following example :-
One part of leucaniline is intimately mixed in proper manner with from half
to equal weight of chloranil, and the mixture, after slow and gentle heating, is
boiled with caustic soda. The rosaniline base thus obtained is dissolved in muriatic
acid, precipitated by common salt, crystallized, and brought into the market in form
of the well known crystals. In the same way as leucaniline is oxidized, but with
greater facility, the sulpho acids of leucaniline are oxidized to rosaniline sulpho-

page_text: acids. I am thus in a position to produce the sulpho-acids of the colouring matters
from crude rosaniline (the "rosanilin schmelze ") in a new and very practical way
by converting the leucobodies which occur in crude magenta (the "fuchsin
schmelze ") into sulpho acids, and then oxidizing these with chlorquinones, as for
example, with chloranil.
The described proportions and also the degrees of temperature may be varied
within certain limits, which a practical chemist can easily determine for himself.
The described methods of purifying the colouring matters may also be modified
in convenient and suitable manners, which a practical chemist will determine for
himself.
Having now described the nature of the said Invention, and the manner in
which the same is to be performed, I claim as novel and as secured to me by the
herein before in part recited Letters Patent,-
The production of colouring matters suitable for dyeing and printing by oxidizing
by means of any of the chlorquinones, in manner hereinbefore described, the leuco
bases herein before specified or the sulpho acids thereof.
In witness whereof, I, the said Joseph Anthony Dixon, have hereunto set
my hand and seal, this Eighteenth day of May, in the year of our Lord
One thousand eight hundred and eighty.
JOSEPH ANTHONY DIXON. (LS.)