The Manufacture and Production of a New Amido Base, and of Colouring Matters therefrom.
Year: 1895

page_text: Date of Application, 1st Mar., 1895
Complete Specification Left, 26th Nov., 1895-Accepted, 28th Dec., 1895
PROVISIONAL SPECIFICATION.
The Manufacture and Production of a New Amido Base, and of
Colouring Matters therefrom.
We, ARTHUR GEORGE GREEN F.C.S. F.I.C. Consulting Chemist of 13 Kings
Drive, Heaton Moor, near Stockport, and ROBERT JANSEN, Ph.D. of 16 The
Grove, Victoria Park, Manchester both in the County of Lancaster Chemists to
The Clayton Aniline Company Limited of Clayton near Manchester aforesaid, do
hereby declare the nature of this invention to be as follows:-
By heating 2 molecules of paratoluidine or of metaxylidine with 4 atoms of
sulphur, thinamido bases are obtained which are known as dehydrothioparatoluidine
and dehydrothiometaxylidine, and are extensively employed for the production of
coloring-matters. In these reactions it is probable that the first stage of the
transformation' consists in the conversion of a methyl group (CH,) of one molecule
of paratoluidine or metaxylidine into the group C (SH), which then reacts with the
amido group (NH2) of another molecule of the amine, with the elimination of H₂S
aud formation of the thiazol grouping
N
(-s) -)
characteristic of these
bases. Acting upon this supposition we have endeavoured to prepare thioamido
bases derived from two dissimilar aminės, one of which should contain a reactable
methyl group and the other supply the nucleus to react with it.
Our present invention relates to the preparation and employment of a base
isomeric with dehydrothioparatoludine which base is obtained by the action of
sulphur (4 atoms) upon a mixture of metaxylidine (1 molecule) and aniline
(1 molecule). From its method of formation the new base should have a
constitution represented by one of the two following formulæ most probably
by 1 viz.
.
It may accordingly be named amidotoluenylamidothiophenol. The following
example may be given as illustrating" the general method of procedure for the
preparation of the new base, but we do not bind ourselves to the exact proportions
or details here given as these may be varied within certain limits:-
A mixture of 95 lbs. of aniline and 121 lbs. of metaxylidine is heated with
128 lbs. of sulphur for 10 or 12 hours until the evolution of hydric sulphide has
ceased and about 102 lbs. of the latter have been evolved. The temperature
slowly rises during the operation from 200° to 240° Centigrade. The melt on
cooling forms a dark reddish glassy mass which cau either be employed directly
for the preparation of colouring matters or may be purified by various means.

page_text: ԱՆ
sulphonic acids, diamines, salicylic acid, and the like. Amongst these the colours
which are obtained by combining these diazo compounds with certain derivatives
of naphthalene which contain a sulphonic group (HSO₂) in the meta (1 : 3) position
to an alpha hydroxy group (OH) are especially valuable. Such components are
'
10
10
a-naphthol-meta-sulphonic acid C₁H. (OH) (SO₂H) [1:3].
a-naphthol-s-disulphonic acid C₁, H, (OH) (SO,H)2 [1 : 3 : 8].
Alkyl-dioxy-naphthalene-sulphonic acids C₁,H, (OH) (OR) (SO₂H) [1:8:3].
Amido-naphthol-sulphonic acid C₁, H, (OH) (NH2) (SO,H) [1:8:3].
Amido-naphthol-sulphonic acid C₁H¸ (OH) (NH₂) (SO₂H) [1 : 6:3].
Amido-naphthol-disulphonic acid C₁H (OH) (NH2) (SO₂H), [1:6:3:5].
Amido-naphthol-disulphonic acid C₁H (OH) (NH₂) (SO,H), [1:8:3 : 6].
Chloro-naphthol-sulphonic acid C₁H, (OH) (CI) (SO₂H) [1 : 6 :
: 3].
Chloro-naphthol disulphonic acid C₁H. (OH) (CI) (SO,H), [1:6:3:5].
Chloro-naphthol-disulphonic acid C₁H (OH) (CI) (SO,H), [1:8:3:6].
10
The colouring matters thus obtained dye unmordanted cotton from an alkaline
bath and are distinguished by their brilliant blueish red shades and their resistance
to acids, alkalies and light. The colours derived from the (1:6:3) amidonaphthol
sulphonic acid and the (1:6:3:5) amidonaphthol-disulphonic acid contain a
diazotisable amido group and consequently possess the property (when fixed in the
fibre) of being further diazotisable and of then combining with phenols, amines
diamines, and the like to form new very fast shades
In addition to the series of azo colours above described colouring matters ca
also be obtained from the new base by alkylation according to the processes
described in the Specification of Letters Patent No. 6319 of 1888. Moreover
yellow colours of the diazoamido class can be obtained from the sulphonic acid by
combination with diazo compounds; for instance with para-nitro-diazo-benzen
chloride.
In order to further illustrate the general method of procedure for producing
colouring-matters according to this invention the following examples are given bu
we do not limit ourselves thereto.

page_text: 70° Centigrade and the dyestuff is salted out and dried. The colouring-matter
thus obtained is represented by the following formula :-
N
CH
C - CH (CH3) - N = N - C₁H, (OH) (SO₂Na)₂-
24 lbs. of the new base are diazotised as before and the diazo compound is
allowed to run into an alkaline solution of 25 lbs. of the meta sulphonic acid of
a-naphthol. The colour, which is at once formed, is separated by filtration and
dried. It dyes unmordanted cotton a bright bluish-red of bluer shade than the
corresponding colour from dehydrothioparatoluidine. Its constitution is represented
by the formula :—
CH,
-
C-CH, (CH) N = N - C₁H. (OH) (SO,Na).
Colouring Matters therefrom.
We, ARTHUR GEORGE GREEN, F.C.S. F.I.C. Consulting Chemist of 13 Kings
Drive Heaton Moor near Stockport and ROBERT JANSEN Ph.D. of 16 The Grove
Victoria Park, Manchester both in the County of Lancaster, Chemists to The
Clayton Aniline Company Limited of Clayton near Manchester aforesaid, 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:-
By heating 2 molecules of paratoluidine or of metaxylidine with 4 atoms of
sulphur thioamido bases are obtained which are known as dehydrothioparatoluidine
and dehydrothiometaxylidine respectively and are extensively employed for the
production of colouring matters. In these reactions it is probable that the first
stage of the transformation consists in the conversion of a methyl group (CH3) of one
molecule of paratoluidine or metaxylidine into the group C (SH), which then reacts
with the amido group (NH2) of another molecule of the amine, with the elimination
HS and formation of the thioazol grouping
N
C
characteristic of
these bases. Acting upon this supposition we have experimented with the view
of preparing thioamido bases derived from two dissimilar amines, one of which
shall contain a re-actable methyl group and the other of which shall supply the
nucleus to react with it.

page_text: The present invention relates to, the preparation and employment of a base
isomeric with dehydrothioparatoluidine, high base is obtained by the action of
sulphur (4 atoms) upon a mixture of metaxylidine (1 molecule) and aniline
(1 molecule). From its method of formation the new base should have a constitution
represented by one of the two following formulæ most probably by I viz. :
It may accordingly be named amidotoluenylamidothiophenol.
The following example may be given as illustrating the general method of
procedure which may be employed for the preparation of the aforesaid new base
but we do not limit ourselves to the precise proportions or details here given as
they may be varied within certain limits without departing from the nature of our
invention.
A mixture of 95 lbs. of aniline and 121 lbs. of metaxylidine is heated with
128 lbs. of sulphur for 10 or 12 hours until the evolution of hydric sulphide has
ceased and about 102 lbs. of the latter have been evolved. The temperature
slowly rises during the operation from 200° to 240° Centigrade. The melt on
cooling forms a dark reddish coloured and glassy mass which can be employed
either directly or after being purified for the preparation of colouring matters.
In order to obtain the new base in a state of purity the melt is distilled and the "
distillate crystallised from benzene and recrystallised from amyl alcohol. It then
forms small short prisms, which have a constant melting point of 196° Centigrade.
The difference of the new base from the isomeric dehydrothioparatoluidine is shewn
by its greater solubility in almost all solvents, its difference in crystalline
form, its higher melting point (5 degrees higher) and the difference_in
the shades of the colours derived from it compared with those of the corresponding
colours from dehydrothicparatoluidine. Moreover the acetyl derivative of the new
base melts at 210°-211° Centigrade whereas that of dehydrothioparatoluidine
melts at 225°-227° Centigrade. The said base is converted by fuming sulphuric
acid into a sulphonic acid the ammonium salt of which (in contradistinction to
that of dehydrothioparatoluidine sulphonic acid) is easily soluble in water. Its
dilute aqueous solution has a strong blue fluorescence. Both the base and its
sulphonic acid may be converted into colouring matters by combination of their
diazo compounds with the usual dyestuff components, such as phenols, amines,
diamines, amidophenols, oxycarboxylic acids, phenol sulphonic acids, and amido
phenol sulphonic acids. Amongst these the colours which are obtained by
combining these diazo compounds with certain derivatives of naphthalene which
contain a sulphonic group (HSO) in the meta (1.3) position to an alpha hydroxy
group (OH) are especially valuable. Of such components the following may be
especially mentioned :-

page_text: Chloro-naphthol-sulphonic acid C,H, (OH) (CI) (SO,H) [1:6:3].
Chloro-naphthol-disulphonic acid C₁H, (OH) (CI) (SO₂H), [1:6:3:5].
Chloro-naphthol-disulphonic acid C₁H, (OH) (CI) (SO,H), [1:8:3:6].
The colouring matters thus obtained dye unmordanted cotton from an alkaline.
bath and are distinguished by the brilliant bluish-red shades which they afford and
by their resistance to acids, alkalies and light. The colours derived from the
(1:6:3) amidonaphthol-sulphonic acid and the (1:6:3:5) amidonaphthol-.
disulphonic acid contain a diazotisable amido group and consequently possess the
property (when fixed in the fibre) of being further diazotisable and of then
combining with phenols, amines, diamines and the like to form new and very fast
shades.
In order to further illustrate the general method of procedure for producing
colouring matters according to this invention the following examples are given but
we do not limit ourselves to these examples.
EXAMPLE I.
CH
C - CH₂ (CH) - N = N C₁H₂ (OH) (SO₂Na),.
24 lbs. of the new base are diazotised in the usual manner and the diazo compound
is allowed to run into an alkaline solution of 25 lbs. of the meta sulphonic acid of
a-naphthol. The colour which is at once formed is separated by filtration and is
dried. It dyes unmordanted cotton a bright bluish red of bluer shade than the
colour obtained from dehydrothioparatoluidine. Its constitution is represented by
the formula :-
:-
Having now particularly described and ascertained the nature of our said
invention and in what manner the same is to be performed we declare that what
we claim is :-
1. The manufacture and production of a new thio base herein termed "amido-
toluenylamidothiophenol " by beating a mixture of metaxylidine and auiline with
sulphur.
2. The manufacture and production of the sulphonic acid of the said new thio
base by heating a mixture of metaxylidine and aniline with sulphur and treating
the product with fuming sulphuric acid.

page_text: 3. The manufacture of colouring matters by combining the diazo compound of
the above named new thio base or the diazo compound of its sulphonic acid with
such phenols, amines, diamines, amidophenols, oxycarboxylic acids, phenol
sulphonic acids and amido phenol sulphonic acids as are or may be employed as
components in the production of azo colouring matters.
4. The manufacture of red direct cotton colouring matters by combining the
diazo compound of the above named new thio base or the diazo compound
of its sulphonic acid with such derivatives of naphthalene as are hereinbefore
defined.
5. The manufacture of red direct cotton colouring matters according to the
examples hereinbefore given.
6. As new articles of manufacture the colouring matters produced by the process
herein before described or by any other process affording the same result.
Dated this 26th day of November 1895.
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents.