The Manufacture or Production of Colouring Matters.
Year: 1895

page_text: Date of Application, 20th Mar., 1895
Complete Specification Left, 19th Dec., 1895-Accepted, 29th Feb., 1896
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany.]
The Manufacture or Production of Colouring Matters.
I, HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
My foreign correspondents have found that valuable dyestuffs can be obtained
by subjecting to a joint oxidation monoalkylated orthodiamido compounds and
alphanaphthylamine, alphanaphthylamine sulphonic acids, or alkylated derivatives
of alphanaphthylamine or alphanaphthylamine-sulphonic acids, and subsequently
sulphonating the so-formed products, if desirable. The resulting dye-stuffs are
derived from eurhodines containing an alkyl group in combination with the one
nitrogen atom of the azine nucleus.
If, for instance, alphanaphthylamine or alkylalphanaphthylamine and non-
sulphonated monoalkylortho diamines. are oxidised together, the following equation
will illustrate the process :-
My foreign correspondents mean by the above used letters R and R', alkyl-
groups of the fatty or aromatic series (such as methyl, ethyl, benzyl, phenyl, tolyl,
or the like), and they also understand by the said letter R, hydrogen.
On adding sulphuric acid to the colouring matters hereinbefore defined, a reu
solution results, which is characteristic of such eurhodine dyes, & which is
changed first into green, then into red, by an addition of water. The colouring
matters obtainable as hereinbefore described distinctly differ by reason of this
property of their sulphuric acid solutions, from the so-called fluorindines, which are
also produced by oxidising monoalkylated ortho diamido compounds, as these
fluorindines dissolve in sulphuric acid, affording a blue coloured solution.
The process for producing the dye-stuffs herein before defined is illustrated by
following seamles
COLOURING-MATTER
OBTAINED FROM ALPHA-NAPHTHYLAMINE AND
ETHYL-ORTHO-TOLUYLENE-DIAMINE.
MONO-
A solution in water of 26-3 parts, by weight, of sodium dichromate is slowly added
to a solution prepared from 17.9 parts of alphanaphthylamine hydrochloride,
15 parts of monoethyl-ortho-toluylenediamine, 11 parts of muriatic acid, and the

page_text: necessary quantity of water. The liquid at once assumes an intense red color.
The dye-stuff thus formed being only partially separated, is completely separated
by salting out as usual. In order to purify the dyestuff, when filtered off, it is
redissolved and precipitated again. It produces yellowish-red shades on cotton
prepared with tannic acid or the like. This colouring matter chemically is the 5
hydrochloride of ethylhomoeurhodine, which possesses the following formula
-
Acid dye-stuffs result, if alphanaphthylaminesulphonic acids and monoalkylated
orthodiamine sulphonic acids are used in place of alphanaphthylamine and
monoethyl-ortho-toluylenediamine mentioned in the foregoing example, that is to 10
say, if the former sulphonic acids are subjected to a joint oxidation together with
monoalkylated ortho diamine sulphonic acids, as illustrated in the following
example:-
DYE STUFF PRODUCED FROM PARA-TOLYL-ALPHA₁ NAPHTHYLAMINE ALPHA
SULPHONIC ACID AND METHYL-ORTHO-PHENYLENE DIAMINE SULPHONIC
ACID.
A solution in water of 20-2 parts of methyl-ortho-phenylenediaminesulphonic
acid is added to a solution prepared by dissolving 31.3 parts of paratolyl-alpha-
naphthylamine-alpha, sulphonic acid, and the calculated quantity of sodium
carbonate, in the necessary quantity of water. The oxidation is effected by adding
to the mixture the calculated quantity of any oxidising agent (such as potassium
ferricyanide, potassium-permanganate, or the like) dissolved in water. The finished
dyestuff is salted out, filtered off, and purified by redissolving and precipitating
again. The formation of this dye stuff takes place according to the following
equation:-
Analogous dye stuffs are obtained, if, in the first example, alphanaphthylamine
is replaced by equivalent quantities of alkylalphanaphthylamine (such as methyl,-
ethyl,-benzyl,-phenyl,-tolylalpha-naphthylamine or the like), or if corresponding 3
quantities of other monoalkylated ortho diamido compounds are substituted for
monoethyl-ortho toluylene diamine used in the same example.
Acid dye-stuffs analogous to that obtained as described in the second example are
formed on using equivalent quantities of other alkylated alphanaphthylamine
sulphonic acids (such as methyl,-ethyl,-benzyl,-phenyl,-tolyl,-alphanaphthylamine 3
sulphonic acids or the like), or alphanaphthylamine sulphonic acids in place of

page_text: paratolyl alpha-naphthylamine-alpha, sulphonic acid, and subjecting these products
to a joint oxidation, together with methyl-ortho-phenylene diamine sulphonic acid,
or other monoalkylated orthodiamine sulphonic acids.
My foreign correspondents have also found, that alphanaphthylamine sulphonic
acids, or alkylated alpha-naphthylamine sulphonic acids (such as methyl,-ethyl,-
benzyl-phenyl,-tolyl-alphanaphthylamine sulphonic acids), can be subjected to
a joint oxidation together with non sulphonated alkylated ortho diamines, and
they have further prepared analogous dye-stuffs by oxidising together alpha-
naphthylamine or alkyl alphanaphthylamine (such as methyl,-ethyl,-benzyl,-
phenyl,-tolylalphanaphthylamine, or the like) and mono alkylated orthodiamine-
sulphonic acids. According to the researches of my foreign correspondents, those
of the resulting colouring-matters, which are insoluble, or soluble with difficulty,
are, by a suitable treatment with sulphonating agents, converted into dye-stuffs
which are soluble, or soluble with greater readiness.
The researches of my foreign correspondents have also shewn, that the dyestuffs
obtainable as described in the first example, from non-sulphonated components,
can be transformed into acid dye-stuffs by a subsequent treatment with sulphonating
agents.
The colouring matters berein before defined which contain no sulphonic groups,
are particularly suitable for dyeing cotton prepared with tannic acid or the like.
The acid dyestuffs obtainable as hereinafter defined are fit for dyeing wool and
silk, bright red shades being thus obtained, which are distinguished by reason
of their fastness against the action of alkalies and light, and for their evenness.
In the production of the dyestuffs herein before referred to, my foreign corre-
spondents do not limit themselves to the directions given in the foregoing two
examples, as ail methods known and in use for analogous purposes can be used.
Thus, for instance, the oxidation can be effected by means of other oxidising agents
(such as manganse dioxide, atmospheric oxygen, hypochlorites, or the like) in
place of sodium dichromate, potassium ferricyanide, or potassium permanganate
prescribed in the foregoing two examples. Such or similar modifications do not
alter the nature of this invention which in general relates to the production of dye-
stuffs by subjecting alphanaphthylamine, alkylalpha-naphthylamine, alphanaphthyl-
amine-sulphonic acids, or alkylated alpha-naphthylamine sulphonic acids, to a joint
oxidation, together with mono-alkylated orthodiamido compounds, or mono-
alkylated orthodiaminesulphonic acids, and subsequently sulphonating the so-formed
products, if desirable. Naturally, those naphthylamine sulphonic, and alkyl-
naphthylamine sulphonic acids, cannot be used in the processes hereinbefore
defined, which do not allow the formation of the azine nucleus.
Dated this 20th day of March 1895.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Colouring Matters.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, 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 :-
My foreign correspondents have found that valuable dye-stuffs can be obtained
by conjointly oxidising monalkylated ortho-diamido compounds, and alphanaphthyl-
amine, or alkylated derivatives of alphanaphthylamine, and, if desirable, sub-
sequently sulphonating the products. The dye stuffs thus formed are derived from
eurhodines containing an alkyl group in combination with one of the nitrogen

page_text: atoms of the azine nucleus, as will be seen on reference to the following general
equation representing the process :-
My foreign correspondents use the above letters R and R' as meaning alkyl
groups (such as methyl, ethyl, benzyl or the like), and the letter R also as
meaning hydrogen.
The dye-stuffs thus obtainable from monomethyl or monethylorthotoluylene
diamine are identical with those produced as described in the Specifications of the
German Patents No. 77226 and 78222, but the colouring matters obtainable, as
hereinafter mentioned, from monobenzyl orthotoluylene diamine, and alphanaphthyl-
amine or alkylated alphanaphthylamines, have not hitherto been produced.
On adding concentrated sulphuric acid to the coloring matters bereinbefore
defined, a red solution is obtained, which is characteristic of such eurhodine dyes;
this is changed first into green, then into red, on adding water. The coloring
matters obtainable as hereinbefore described are distinguished by this behaviour
towards sulphuric acid, from the so-called fluorindines, which are also produced
by oxidising monalkylated orthodiamido compounds, as, when these fluorindines
are dissolved in sulphuric acid, they afford a blue-colored solution.
The process for producing the dye-stuffs berein before defined is illustrated by
the following example. The parts are by weight.
COLORING MATTER OBTAINED FROM ALPHA NAPHTHYLAMINE
MONETHYLORTHO TOLUYLENE DIAMINE.
AND
A solution of 17.9 parts of alphanaphthylamine hydrochloride, 15 parts of mon-
ethyl ortho toluylene diamine, 50 parts of muriatic acid, and about 1500 parts of
water, is gradually stirred into a solution of 26.3 parts of sodium dichromate in
100 parts of water. The liquid at once assumes an intense red color, and the dye-
stuff partially separates. It is completely separated by salting out with zinc
chloride and cominon salt. In order to purify the dye-stuff, it is filtered off, and
repeatedly treated with boiling water. The red filtrates are rendered moderately
alkaline with ammonia, to precipitate a bye-product, which is filtered off, and the
alkaline solution is then acidulated with muriatic acid. On adding zinc chloride
and common salt to the acid liquid, the dye-stuff separates in a pure state. When
filtered off, pressed, and dried, it forms a brick-red colored powder. It produces
scarlet-red shades on cotton prepared with tannic acid or the like. The coloring
matter thus produced is the hydrochloride of ethylhomoeurhodine, represented by
the following formula :—
Analogous dye-stuffs are obtained by substituting, in the above example, for
alphanaphthylamine, equivalent quantities of alkylehenaphthylamines (such as 40
methyl, ethyl, benzyl alphanaphthylamine, or the like, or if corresponding quantities

page_text: of other monalkylated ortho diamido compounds are substituted for the monethyl-
orthotoluylene diamine used in the same example.
Thus, for instance, the analogous dye-stuff obtained from monethylorthotoluylene
diamine and ethyl alphanaphthylamine, yields similar shades, whilst that derived
from monethylorthotoluylene diamine and benzylalphanaphthylamine produces
slightly yellower shades. The corresponding dye-stuffs obtained from monomethyl-
orthotoluylene diamine and alphanaphthylamine, ethylalphanaphthylamine, or
benzylnaphthylamine, in chemical and dyeing properties, are similar to the coloring
matters derived from monethylorthotoluylene diamine.
Dye-stuffs which produce scarlet shades on cotton prepared with tannic acid, or
the like, are obtained on subjecting benzylorthotoluylene diamine to oxidation
conjointly with monethylalphanaphthylamine or alphanaphthylamine.
The said benzylorthotoluylene diamine can be prepared by benzylating nitro-
paratoluidine (CH, NO, NH, = 1:3:4), and subsequently reducing.
:
The coloring matters hereinbefore defined are particularly suitable for dyeing
cotton prepared with tannic acid or the like.
In producing the dye-stuffs hereinbefore referred to, my foreign correspondents
do not limit themselves to the directions given in the foregoing example, as all
known methods in use for analogous purposes can be adopted. Thus, for instance,
the oxidation can be effected by using other oxidising agents (such as manganese
dioxide, atmospheric oxygen, hypochlorites, potassium ferricyanide, potassium
permanganate, or the like), in place of the sodium dichromate prescribed in the
Baid example. Such or similar modifications do not alter the nature of this
invention, which, speaking generally, relates to the production of dye-stuffs by
subjecting alphanaphthylamine, or alkyl alphanaphthylamine, to oxidation conjointly
with monalkylated ortho diamido compounds.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed (as communicated to me
from abroad), I declare that what I claim is :-
1. The process for producing dye-stuffs belonging to the class of eurhodines
containing an alkylated azine nucleus, by subjecting monalkylated orthodiamido
compounds (such as monomethylorthotoluylene diamine, monethylorthotoluylene
diamine, monobenzylorthotoluylene diamine or the like) to oxidation conjointly
with alphanaphthylamine or alkylated alphanaphthylamine (such as methylalpha-
naphthylamine, ethylalphanaphthylamine, benzylalphanaphthylamine, or the like).
2. As new products of manufacture, the new dye-stuffs produced in the manner
hereinbefore defined, or in any other way affording the same result.
Dated this 16th day of December 1895.
NEWTON & SON,
Agents for the Applicant.