Improvements in the Manufacture and Production of Mordant Dyeing Colouring Matters.
Year: 1893

page_text: Date of Application, 23rd Oct., 1893
Complete Specification Left, 23rd July, 1894-Accepted, 25th Aug.,
1894
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture and Production of Mordant
Dyeing Colouring Matters.
I JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of
Middlesex Gentleman do hereby declare the nature of this invention (which has
been communicated to me from abroad by The Badische Anilin and Soda Fabrik of
Ludwigshafen-on-Rhine in the Empire of Germany) to be as follows :—
It is known that by suitably treating para-diamines containing a free amido
group (that is to say a non-substituted amido group) with a thiosulphate and an
oxidising agent, in the first instance para-diamine-thiosulphonic acids are obtained.
Also on suitably oxidising these thiosulphonic acids or the corresponding mercaptan
compounds or sulphides together with dimethyl-aniline or other primary, secondary
or tertiary amines, thionated indamines (that is indamines containing sulphur)
result such as indamine thio-sulphonates or sulphides for example. Further by
intra-molecular change and simultaneous oxidation of these thionated indamines,
dyes of the methylene-blue or thionine class are obtained.
Now my foreign correspondents have discovered that 1-2 dihydroxy-naphthalene,
1-2 amido-beta-naphthol sulpho acids and derivatives thereof, and analogous
compounds can be used in an analogous manner to the above mentioned amines in
the preparation of thionine dyes and the products so obtained possess the property
of fixing themselves on metallic mordants giving colour lakes of great fastness.
Thus for instance dihydroxy-naphthalene-sulpho acid (1·2·3¹) or the corresponding
amido-naphthol-sulpho acid (1·2·3) on oxidising with para-diamine thiosulphonic
acids (or the corresponding sulphides or mercaptan compounds) can be made to
yield dyes possessing the properties above described.
The manufacture of the desired mordant dyeing colouring matters takes place in
three steps or stages. 1st. A para-diamine-thiosulphonic acid, such as amido-
dimethyl-aniline-thiosulphonic acid or the corresponding mercaptan compound or
sulphide, the thiosulphonic acid of alkyl-benzyl-aniline-sulpho acid and the like, is
produced in any of the well-known ways. 2nd. A thionated indophenol or
indamine as the case may be is prepared by the oxidation of a mixture of
equi-molecular proportions of a para-diamine thiosulphonic acid (or analogous
body) with 1-2 dihydroxy-naphthalene, 1-2 amido-naphthol, or sulpho acids thereof
or the like. 3rd. The thionated indophenol or indainine obtained as the result of
the second step is converted into the thionine dye.
In the second stage of the process instead of preparing the thionated compounds
by oxidizing the aforesaid dihydroxy-naphthalene, amidonaphthol or derivatives
thereof as aforesaid and para-diamine-thiosulphonic acid or analogous compounds
by treatment with an oxidizing agent the requisite oxygen can be supplied in the
form of the nitroso-group. Thus for instance the nitroso-beta-naphthol-sulpho-
acid (1-2-31) on direct interaction with the aforesaid sulphur compounds of para-
diamines yields the thionated indamines without the intervention of an external
oxidizing agent.
In the third stage of the reaction, the conversion of the thionated indamines into
the desired dyes can be effected under similar circumstances or by the aid of such
condensing agents as in the case of the formation of methylene blue itself from
tetra-methyl-indamine-thiosulphonate.
My foreign correspondents have found that for instance chloride of zinc,
sulphuric acid, and copper sulphate can be used to effect the third stage but these
reagents are merely given as examples as many others can be used. For instance

page_text: the desired conversion can readily be effected by treating the thionated indamines
with sodium thiosulphate in dilute acetic acid solution.
If desired the various steps of the reaction can be effected in one operation
without isolation of the intermediate products.
Dated this 23rd day of October 1893.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
Improvements in the Manufacture and Production of Mordant
Dyeing Colouring Matters.
I, JAMES YATE JOHNSON of 47 Lincoln's lun Fields in the County of
Middlesex Gentleman do hereby declare the nature of this invention (which
has been communicated to me from abroad by The Badische Arilin and Soda
Fabrik of Ludwigshafen of Rhine 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 :-
It is known that by suitably treating para-diamines containing a free amido
group (that is a non-substituted amido-group) with a thiosulphate and an oxidizing
agent, in the first instance para-diamine-thiosulphonic acids are obtained. Also
on suitably oxidizing thiosulphonic acids however obtained, or the corresponding
mercaptan compounds, or sulphides, together with dimethyl-aniline or other
primary, secondary, or tertiary, amines, thionated indamines (that is indamines
containing sulphur) result for example indamine thiosulphonates or sulphides.
Further, by intra-molecular change and simultaneous oxidation of these thionated
indamines; dyes of the methylene-blue, or thionine, class are obtained.
My foreign correspondents have discovered that certain sulpho acids of
1-2 dihydroxy-naphthalene and 1-2 amido-beta-naphthol can be used in an
analogous manner to the above mentioned amines in the preparation of thionine
dyes, and the products so obtained possess the property of fixing themselves on
metallic mordants giving colour lakes of great fastness. Thus the dihydroxy-
naphthalene-sulphoacids (1.2.3, 1.2.11 and 1-2-2¹), or the corresponding amido-
naphthol-sulpho-acids, on oxidizing with para-diamine thiosulphonic acids (or the
corresponding sulphides or mercaptan compounds) can be made finally to yield
dyes possessing the properties above described.
The manufacture of the desired mordant dyeing colouring-matters according to
this invention takes place in 3 steps or stages. Ist. A para-diamine-thiosulphonic
acid, such as amido-dimethyl-aniline-thiosulphonic acid or the corresponding
mercaptan compound or sulphide, the thiosulphonic acid of alkyl-benzyl-aniline
sulpho acid, or the like, is produced in any of the well-known ways. 2nd. A
thionated indophenol or indamine as the case may be is prepared by the oxidation
of a mixture of equi-molecular proportions of para-diamine thiosulphonic acid (or
analogous body) with the aforesaid sulphoacids of 1-2 dihydroxy-naphthalene and
1-2 amido-naphthol. 3rd. The thionated indophenol or indamine, the result of the
second step, is converted into the thionine dye.
In the second stage of the process instead of preparing the thionated compounds
by oxidizing the aforesaid sulphoacids of dihydroxy-naphthalene or amido-naphthol
and para-diamine thiosulphonic acid or analogous compounds by treatment with an
oxidizing agent as aforesaid the requisite oxygen can be supplied in the form of
the nitroso-group. Thus for instance the nitroso-beta-naphthol-sulpho acid (1·2·31)
on direct interaction with the aforesaid sulphur compounds of para-diamines yields
the thionated indamines without the intervention of an external oxidizing agent.
In the third stage of the reaction, the conversion of the thionated indamines into

page_text: the desired dyes can be effected under similar circumstances or by the aid of such
condensing agents as are employed in the case of the formation of methylene-
blue itself from tetra-methyl-indamine-thio sulphonate, but a more energetic
treatment is usually necessary in the present case.
My foreign correspondents have found that for instance chloride of zinc and
sulphuric acid can be used to effect the third stage and that the desired conversion
can most readily be effected by treating the thionated indamines with sodium
thiosulphate in dilute acetic acid solution.
If desired the various steps of the reaction can be effected in one continuous
operation that is without isolation of the intermediate products, but it is the
characteristic of the process according to this invention that each step is completed
before the next step is permitted to begin; for my foreign correspondents have
discovered that this is essential in order to obtain the best results with ease.
As aforesaid the first step in the new manufacture of mordant-dyeing colouring-
matters according to this invention consists in the production of amido-dialkyl-
aniline-thiosulphonic acid or the like in any of the known ways, I therefore do not
give any examples of methods of carrying out the first step, but the following
examples will serve to illustrate the manner in which the process can be carried on
through the remaining new phases and the invention put into practical effect.
The parts are by weight.
PRODUCTION OF AN INDOPHENOL THIO-SULPHONATE FROM 1.2.3¹ DIHYDROXY-
NAPHTHALENE-SULPHOACID.
Dissolve about twenty five parts of amido-dimethyl-aniline-thiosulphonic acid
in about six hundred parts of water, adding just sufficient dilute ammonia to
neutralize the acid. Dilute with about one thousand eight hundred parts of water
and acidify with about two hundred parts of acetic acid (containing about
thirty per cent. real acid C,H,O,). Then add a saturated solution of twenty four parts
of 12.31 dihydroxy naphthalene sulpho acid (or the corresponding quantity of a
salt thereof). Stir continuously and add about fifteen parts of potassium bichromate
in the form of a concentrated solution. The temperature of the mixture should
range between twelve and fifteen degrees centigrade or thereabouts. Allow the
mixture to stand for some time and precipitate the indophenol thiosulphonate
completely by the addition of common salt, with, or without, a little sodium
acetate.
In a similar manner a new indamine, or indophenol-thiosulphonate, can be
obtained from the 1-2 amido-naphthol 3¹ sulpho acid.
Instead of effecting the oxidation by means of a bichromate in acid solution, the
atmospheric oxygen may be used as the oxidizing agent in cold alkaline solution,
when the same new intermediate products are obtained. It is essential that the
mixture be not heated with alkali, as some of the intermediate product is then
destroyed.
PRODUCTION OF THE NEW INTERMEDIATE PRODUCT USING 12 NITROSO-
NAPHTHOL 31 SULPHO ACID.
Dissolve about twelve and a half parts of amido dimethyl-aniline-thiosulpho acid
and about fourteen parts of nitroso-naphthol-sulpho acid (Schaeffer's acid) in about
four hundred parts of water adding about nine parts of ammonium hydrate
(containing about twenty per cent. NH,). Acidify the solution with about eighty
parts of acetic acid (containing about thirty per cent. real acid C₂H,O,) and boil
the solution for about a quarter of an hour, or until the yellowish colour of the
solution has disappeared and the dirty violet colouration which ensues no longer

page_text: PRODUCTION OF THE NEW INTERMEDIATE PRODUCT USING AMIDO-DIMETHYL
ANILINE MERCAPTAN.
Dissolve ten parts or thereabouts of the zinc salt of the mercaptan mentioned, in
about four hundred parts of water containing about niue parts of hydrochloric
acid (containing about twenty eight per cent. real acid HCl) add sodium acetate
until the liquid begins to become cloudy, then add about two hundred parts of
acetic acid (containing about thirty per cent. real acid C,H,O,) and proceed
further as described in the foregoing Example 1.
CONVERSION OF THE NEW
INTERMEDIATE PRODUCTS INTO THE THIONINE
DYES BY MEANS OF CHLORIDE OF ZINC.
Mix about ten parts of the thiosulphonate (such as is obtained as described in
either of the foregoing examples) with about one hundred parts of a solution of
chloride of zinc (containing fifty per cent. ZnCl2). Heat to the boiling point and
concentrate the mixture gradually by evaporation until an intensely green
homogeneous mass is obtained. Pour this mass out into water.
The mordant
dyeing colouring-matter separates out in the form of a violet flocculent precipitate.
Collect by filtration.
CONVERSION OF THE NEW INTERMEDIATE PRODUCTS INTO THE THIONINE
DYES BY MEANS OF SODIUM THIOSULPHATE.
Take the acetic acid solution of the intermediate product obtained as described
in the foregoing Examples 2 and 3, or a corresponding solution prepared from the
isolated intermediate product and acetic acid, and heat it with a solution of.about
twenty five parts of sodium thiosulphate in sixty parts of water. After a few
minutes heating the mordant dyeing thionine colouring matter separates out in the
form of crystals possessing a brazen lustre. Filter and wash the product press and
dry or preserve as paste.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The manufacture of mordant dyeing colouring matters by first preparing
amido-dialkyl-aniline-thiosulphonic acid or equivalent body in any known or
suitable way, then oxidizing this in the presence of the 1-2 dihydroxy-naphthalene
or 12 amidonaphthol-sulpho acids hereinbefore referred to so as to obtain the new

page_text: intermediate products, indamine, or indophenol thiosulphonates, hereinbefore
described, and finally converting the said new intermediate products into mordant
dyeing thionine colouring matters, substantially as hereinbefore set forth.
2. The manufacture of mordant dyeing colouring matters by first preparing
amido-dialkyl-aniline-thiosulphonic acid or equivalent body in any suitable way,
then causing this to interact with 1-2 nitroso naphthol-3-sulpho acid so as to
obtain the new intermediate product hereinbefore described and finally converting
the said intermediate product into mordant dyeing thionine colouring-matters,
substantially as hereinbefore set forth.
3. The manufacture of indophenol thiosulphonates or indamine thiosulphonates
by oxidizing amido dialkyl-aniline-thiosulphonic acid or the like with the 1-2
dihydroxy-naphthylene and 1-2 amidonaphthol sulpho acids herein mentioned
substantially as hereinbefore described.
4. The manufacture of indamine thiosulphonates by the interaction of amido-
dialkyl aniline thiosulpho acid and 1-2 nitroso naphthol-3'-sulpho acid.
5. The manufacture of the new intermediate compounds and of the mordant
dyeing colouring matters in the manners set forth in the examples.
6. As new articles of manufacture the new intermediate products indamine- or
indophenol-thio-sulphonates such as can be obtained as hereinbefore described.
Dated the 23rd day of July 1894.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, W.C., Agents.