Year: 1896

page_text: Date of Application (in United Kingdom), 13th June, 1896
Complete Specification Left, 4th Feb., 1897-Accepted, 13th July, 1897
I, HENRI RAYMOND VIDAL, of 95 Boulevard Beaumarchais, Paris, in the Republic
of France, Chemist, do hereby declare the nature of this invention to be as
follows:-
The action of sulphur upon paramidophenol produces a paradioxythiodiphenylamine,
studied by Bernsthsen under the name of thionol, which is vaguely referred to by
Villegerodth in a note appearing in the "Berichte." This substance, according to
the conditions of temperature realized in the experiment and according to the
proportions of the sulphur employed generates another compound, the existence of
which had not then been recognized. This compound is a colouring matter soluble
in sulphides and in alkaline sulphites and bisulphites, and in this state possesses the
characteristic property of dyeing all vegetable and animal fibres intensely black, the
colour offering a remarkable resistance to all agents and to the action of air and
light,
In the specification of my previous invention of which this forms an improvement
I have indicated the reaction of hydroquinone upon sulphur in the presence of
ammonia in view of producing precisely the same colouring matter soluble in
sulphides and in alkaline sulphites and bisulphites, hereinbefore referred to. This
colouring matter is only obtained in the reaction and under special conditions after
the production of paradioxythiodiphenylamine. It follows therefore that I can obtain
the same colouring matter by directly starting from paradioxythiodiphenylamine,
irrespective of what may have been the method of preparing this substance.
As a result of my experiments I have arrived at the conclusion which has enabled
me to attribute to my new colouring matter the following formula of constitution.

page_text: Owing to the action of sulphur upon paramidophenol, in the first place
paradioxythiazine is formed and one molecule of ammonia is set free.
In the reaction of ammonia and sulphur upon hydroquinone, described in the
specification above referred to paradioxythiazine is produced in the first place, and 1
paradioxytetraphenetrithiazine in the second place,
that is to say, the paradioxythiazine, of which two molecules in the presence of
sulphur and of ammonia unite together or are joined and thus form paradioxytetraph-
enetrithiazine, exactly as is the case in the action of sulphur upon paramidophenol.
1

page_text: Phospham P N H in the presence of a diphenol, has the characteristic quality of
restricting the action of this substance to one single function so as to bring about a
concentration of two molecules of diphenol by the substitution of one function (NH)
for two functions (O H) situated each in a different nucleus.
Example: paradiphenol or hydroquinone in the presence of phospham at an
appropriate temperature must produce: paradioxydiphenylamine.

page_text: This latter compound can be more economically obtained by causing sulphur and
alkaline sulphides to react upon paranitrooxyazobengol or upon the colouring matter
resulting from the combination of diazo of amidoazobenzol with one molecule
of phenol.
According to the statements which hereafter follow we have established the
existence of three new colouring matters which present different functions:

page_text: (1) Diphenolic; (2) Amineous and phenolic; (3) Diamineous.
These colouring matters derive their origin as hereinafter stated namely
the first:
(1) From the action of sulphur upon paraamidooxythiazine or any mixture capable
of generating the same;
(2) From the action of sulphur and ammonia or of phospham upon
paradioxythiazine or any mixture capable of generating the same; the second:
(1) From the action of sulphur upon one molecule of paraoxyamidothiazine and
one molecule of paradiamidothiazine or any mixture capable of generating
the same.
(2) From the action of sulphur and of ammonia or of phospham upon one molecule
of paradioxythiazine and one molecule of paraoxyamidothiazine; the third:
(1) From the action of sulphur upon two molecules of paradiamidothiazine.
(2) From the action of sulphur and of ammonia or of phospham upon two
molecules of paraoxyamidothiazine.
We may suppose a class of intermediate colouring matters between the thiazines
and the tetraphenetrithiazines and that is the class of triphenedithiazines.
I have realised the composition of these colouring matters.
(1) I have obtained paradioxytriphenedithiazine by heating; (1) One molecule of
paraamidooxythiazine and one molecule of amidophenol with sulphur; (2) One
molecule of paradioxythiazine and one molecule of hydroquinone with sulphur in the
presence of ammonia or phospham.
(2) I have obtained paraoxyamidotriphenedithiazine by heating; (1) One molecule
of paradiamidothiazine with one molecule of amidophenol in the presence of sulphur;
(2) One molecule of paradioxyamidothiazine with one molecule of amidophenol in the
presence of sulphur, ammonia and phospham; (3) One molecule of paradioxythiazine
and of paraamidophenol in the presence of sulphur, or of ammonia or of phospham;
(4) One molecule of paramidodioxythiazine and of hydroquinone in the presence of
sulphur and ammonia, or of phospham.
(3) I have obtained paradiamidotriphenedithiazine by heating; (1) One molecule
of paradiamidothiazine with one molecule of paraphenylenediamine in the presence or
sulphur; (2) One molecule of paraoxyamidothiazine with one molecule of
amidophenol in the presence of sulphur, ammonia or phospham.
These substances form black or blue colouring matters acting directly upon
vegetable or animal fibres in baths reduced either by sulphides or by alkaline
sulphites or bisulphites.
They may also be obtained; either by the action of sulphur upon
paradiamidodiphenylamine, paraoxyamidodiphenylamine, or by the action of sulphur,
ammonia or phospham upon paradioxydiphenylamine, upon paraoxyamidodipheny-
lamine.
If only phospham be caused to react upon two molecules of paradioxythiazine, a
union of joining of these two molecules is produced and a new colouring matter of
the following composition is obtained:

page_text: If paradioxythiazine is replaced by paraamidooxythiazine or one molecule of
paraamidooxythiazine and one molecule of paradioxythiazine, one obtains:
(1) The compound :
(1) Upon paradioxythiazine and hydroquinone.
(2) Upon paradioxythiazine and amidophenol.
(3) Upon paraamidooxythiazine and hydroquinone.
(4) Upon paraamidooxythiazine and amidophenol.

page_text: An Improved Manufacture of Dyes.
I, HENRI RAYMOND VIDAL, of 95 Boulevard Beaumarchais, Paris, in the Republic of
France, Chemist, 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:-
The action of sulphur upon paramidophenol produces a paradioxythiodiphenylamine,
examined and experimented upon by Bernsthsen under the name of thionol, which is
vaguely referred to by Villegerodth in a note appearing in the "Berichte." This
substance according to the conditions of temperature realized in the experiment and
according to the proportions of the sulphur employed generates another compound,
the existence of which had not then been recognized. This compound is a colouring
matter soluble in sulphides and in alkaline sulphites and bisulphites, and in this state
possesses the characteristic property of dyeing all vegetable and animal fibres intensely
black, the colour offering a remarkable resistance to all agents and to the action of air
and light.
In the specification of my previous invention of which this forms an improvement
I have indicated the reaction of hydroquinone upon sulphur in the presence of
ammonia in view of producing precisely the same colouring matter soluble in
sulphides and in alkaline sulphites and bisulphites hereinbefore referred to.. This
colouring matter, is only obtained in the reaction and under special conditions after
the production of paradioxythiodiphenylamine. It follows therefore that I can obtain
the same colouring matter by directly starting from paradioxythiodiphenylamine,
irrespective of what may be the method of preparing this substance.
As a result of my experiments I have arrived at the conclusion, which has enabled
me to attribute to my new colouring matter the following formula of constitution.

page_text: The disengaged molecule NH' reacts in the presence of sulphur upon two
oxydrites of two nuclei of paradioxythiazine and causes a union or joining of the
two nuclei with addition of sulphur so as to generate paradioxytetraphenetrithiazine.
In the reaction of ammonia and sulphur upon hydroquinone, described in the
specification above referred to, paradioxythiazine is produced in the first place, and
paradioxytetraphenetrithiazine in the second place.
that is to say, the paradioxythiazine, of which two molecules in the presence of 10
sulphur and of ammonia unite or are jointed and thus form paradioxytetraphene-
trithiazine, exactly as is the case in the action of sulphur upon paramidophenol.
Phospham PNH in the presence of a diphenol, has the characteristic quality of
restricting the action of this substance to one single function so as to bring about a
concentration of two molecules of diphenol by the substitution of one function (NH) 1
for two functions, (OH) situated each in a different nucleus.
Example: Paradiphenol or hydroquinone in the presence of phospham at an
appropriate temperature must produce: paradioxydiphenylamine.
CHOH

page_text: Consequently, if we cause phospham to react upon hydroquinone in the presence of
sulphur, we must likewise obtain, paradioxythiazine, as in the instances hereinbefore
referred to. This in fact is the case.
We therefore can say that paradioxytetraphenetrithiazine is produced by the action
of sulphur upon amidophenol owing to the action exerted by the ammonia in presence
of sulphur upon paradioxythiazine in the first place forined.
Example: We heat in an autoclave to a temperature of 210° to 240° C. for eight
house
5
If we replace paramidophenol by paraphenylenediamine and if we heat this latter
in the presence of sulphur up to from 150 to 180 degrees Centigrade, we obtain,
besides Lanth's violet or paradiamidothiazine, colouring matters the existence of
which has not heretofore been known.
These colouring matters have been produced by the concentration of two molecules
of paradiamidothiazine in the presence of sulphur, with elimination of one molecule
of ammonia. These colouring matters are formed by substances having diamido

page_text: This latter compound can be likewise obtained by the action of ammonia or of
phospham, in the presence of sulphur, upon paraoxyamidothiazine. It can likewise
be obtained by the action of sulphur upon paraamidophenol in the presence of
aminonia. The paramidophenol being either free or in the midst of alkaline
sulphides.
Example. We haat in an autoclave to a temperature of 2108 to 21001
If now, instead of employing two molecules of amidophenol or two molecules of
paraphenylenediamine, we cause one molecule of each of these substances to react
in the presence of sulphur, we obtain a series of different compounds.
Example: We heat to a temperature of 210° to 240° C in a cast iron pot placed
in an oil bath :
This latter compound can be more economically obtained by causing sulphur and
alkaline sulphides to react upon paranitrooxyazobenzol or upon the colouring matter 25
resulting from the combination of diazo of amidoazobenzol with one molecule of
phenol.
Example: We heat to a temperature of 210° to 240° C.

page_text: We have obtained paradiamidotriphenedithiazine by heating: (1) One molecule of
paradiamidothiazine with one molecule of paraphenylene diamine in the presence of
sulphur; (2) One molecule of paraamidophenol with one molecule of paraamidophenol
in the presence of sulphur, ammonia or phospham.
Example:
are heated for 8 hours at a temperature of 210° to 240° C.
These substances forın black or blue colouring matters acting directly upon
vegetable or animal fibres in baths reduced either by sulphides or by alkaline sulphites
or bisulphites.
They may also be obtained: either by the action of sulphur upon
paradiamidodiphenylamine, or paraoxyamidodiphenylamine, or by the action of
sulphur, ammonia or phospham upon paradioxydiphenylamine,
paraoxyamidodiphenylamine.
or upon
If only phospham be used to react upon two molecules of paradioxythiazine, a union
or joining of these two molecules is produced and a new colouring matter of the
following composition is obtained:

page_text: by the action of phospham.
(1) Upon paradioxythiazine and hydroquinone.
(2) Upon paradioxythiazine and amidophenol.
(3) Upon paraamidooxythiazine and hydroquinone.
(4) Upon paraamidooxythiazine and amidophenol.
Examples: I heat for 8 hours at a temperature of 210° to 240

page_text: Inventi
claim is :-
wat mam
Che same 18 to be performed, I declare that what i
1. The colouring matters obtained by:
(a) The action of sulphur upon paradiamidothiazine or the mixtures capable of
generating the same, either alone or in the presence of amidophenol or of
paraphenylenediamine;
(b) The action of sulphur upon paraoxyamidothiazine, or the mixtures capable
of generating the same, either alone, or in the presence of amidophenol or of
paraphenlylenediamine.
(c) The action of sulphur and of ammonia or of phospham upon paradioxythiazine
or the mixtures capable of generating the same, either alone, or in the presence of
amidophenol or of hydroquinone.
(d) The action of sulphur alone or of sulphur in the presence of ammonia,
or of phospham upon: paradioxydiphenylamine, paraoxyamidodiphenylamine,
paradiamidodiphenylamine or the substances which can generate the same.
(e) The action of sulphur and of sulphuret of sodium upon paranitrooxyazobenzol
and upon the product resulting from the connection of the diazo compound of
amidoazobenzol with one molecule of phenol.
(f) The action of sulphur and of ammonia upon paramidophenol either in the
free state or in connection with alkaline sulphide.
2. The products resulting from the action of phospham;
(a) Upon paradioxythiazine and hydroquinone or paramidophenol;
(b) Upon paramidooxythiazine and hydroquinone or paramidophenol.
3. The production of all these colouring matters in the presence of alkaline
sulphides, by various compounds capable of generating amido and oxyamidothiazines
or dioxythiazines.
4. The use of these products for dyeing and printing purposes.
(a) In connection with alkaline sulphides for dyeing and printing on cotton and
other vegetable fibres:
(b) In connection with alkaline bisulphites for dyeing and printing on wool and
other animal fibres.
(c) In connection with neutral sulphites with an excess of alkali for printing on
vegetable fibres.
(d) In connection with alkaline sulphites and bisulphites for dyeing cotton and
other vegetable fibres.
Dated this 1th day of than 100
HASELTINE, LAKE & Co.,
45 Southampton Buildings, London, W.C., Agents for the Applicant.

page_text: Example: I heat to a temperature of 210° to 240° C
Paramidooxythiazine
Phospham
Example: I heat to a temperature of 210° to 240° C.
11
Paramidooxythiazine
Paradioxythiazine
Phospham -

page_text: nature
sand
invention and in what manner the same is to be performed, I declare that what I
claim is :-
1. The colouring matters obtained by:
(a) The action of sulphur upon paradiamidothiazine or the mixtures capable of
generating the same, either alone or in the presence of amidophenol or of
paraphenylenediamine;
(b) The action of sulphur upon paraoxyamidothiazine, or the mixtures capable
of generating the same, either alone, or in the presence of amidophenol or of
paraphenlylenediamine.
(c) The action of sulphur and of ammonia or of phospham upon paradioxythiazine
or the mixtures capable of generating the same, either alone, or in the presence of
amidophenol or of hydroquinone.
(d) The action of sulphur alone or of sulphur in the presence of ammonia,
or of phospham upon paradioxydiphenylamine, paraoxyamidodiphenylamine,
paradiamidodiphenylamine or the substances which can generate the same.
(e) The action of sulphur and of sulphuret of sodium upon paranitrooxyazobenzol
and upon the product resulting from the connection of the diazo compound of
amidoazobenzol with one molecule of phenol.
(f) The action of sulphur and of ammonia upon paramidophenol either in the
free state or in connection with alkaline sulphide.
2. The products resulting from the action of phospham;
(a) Upon paradioxythiazine and hydroquinone or paramidophenol;
(b) Upon paramidooxythiazine and hydroquinone or paramidophenol.
3. The production of all these colouring matters in the presence of alkaline
sulphides, by various compounds capable of generating amido and oxyamidothiazines
or dioxythiazines.
4. The use of these products for dyeing and printing purposes.
(a) In connection with alkaline sulphides for dyeing and printing on cotton and
other vegetable fibres :
(b) In connection with alkaline bisulphites for dyeing and printing on wool and
other animal fibres.
(c) In connection with neutral sulphites with an excess of alkali for printing on
vegetable fibres.
(d) In connection with alkaline sulphites and bisulphites for dyeing cotton and
other vegetable fibres.
HASELTINE, LAKE & Co.,
45 Southampton Buildings, London, W.C., Agents for the Applicant.