The Manufacture or Production of Direct-dyeing Colouring Matters.
Year: 1893

page_text: Date of Application, 4th Mar., 1893
Complete Specification Left, 1st Dec., 1893-Accepted, 6th Jan.,
1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of Direct-dyeing 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 described in the Specification of application for
Letters Patent No. 3495, dated 16th February 1893, the production of substantive
cotton dye stuffs, by combining mono alkylated a, a, dihydroxynaphthalene sulpho
acids with the diazo derivatives of the so-called thioamido compounds, viz. :
dehydrothio para toluidine, dehydrothiometaxylidine, dehydro-thio-pseudo cumidine,
primuline base or the sulpho acids thereof. These dye stuffs yield from red to
bluish-red shades, which are of great beauty, and possess great fastness against the
action of acids and alkalies.
Amongst these colouring matters, those which result from such sulpho acids of
the naphthalene series as contain one hydroxylic group and one sulpho group in
meta position, are of special value. It is noticeable, that the dye stuffs formed by
means of the last mentioned acids produce shades of a beautiful clear blue tinge,
and which also possess great fastness against the action of acids and alkalies. A
similar degree of fastness, as well as the meta position of the hydroxylic and sulpho
group, can be seen on observing the composition of the dye-stuff technically known
as "Erica," which is obtained from alpha-naphthol-epsilon-disulpho acid, and the
diazo compound of dehydro-thio-meta-xylidine.
In order to pursue further this interesting fact, my foreign correspondents have
allowed the different alpha-naphthol-mono sulpho acids to act on the diazo compounds
of dehydro-thio-para-toluidine, or the analogues thereof, or sulpho acids of such
thio-amido-products, and my foreign correspondents have found that in the employ-
ment of alpha-naphthol-mono-sulpho acid (OH: SO₂H = 1:3), dye stuffs result
which likewise yield deep blue shades of considerable fastness against the action of
acids and alkalies, whilst the colouring matters obtained by means of alpha-naphthol
mono sulpho acid 1:2, 1:6, or 1:7, produce only dull and technically valueless shades.
The dye stuffs resulting from alpha-naphthol-mono-sulpho-acid (1 : 3) also are
superior to the so-called "Erica," by their ability to strike with much greater ease
on the cotton fibre.
According to the last named results, my foreign correspondents believe that on the
one hand the fastness against the action of alkalies observed only in a few dye-stuffs
obtained from alpha naphthol-mono-, or alpha-naphthol disulpho acids, is caused by
the meta position between the hydroxylic and sulpho group, while on the other
hand the slight degree of fastness against alkalies of analogous azo colouring matters
obtained from such alpha-naphthol mono-, or alpha naphtholdisulpho acids as contain
a hydroxylic and sulpho group not in meta-position, is owing to the absence of such
meta-position. This influence appears, in an eminent degree, in the thio-azo dye
stuffs which are fast against the action of light, and result from naphthol-mono-, or
naphthol di sulpho acids (containing one hydroxylic group and one sulpho group in
meta-position), and the diazo derivatives of the aforesaid thio amido compounds, or
sulpho acids thereof. Hence it further follows, that only those amido naphthol-
mono, or amido naphthol disulpho acids, which likewise contain hydroxylic and

page_text: sulpho group in meta position, are adapted for the production of azo dye stuffs
suitable for dyeing cotton in alkaline baths.
By "analogues of dehydro-thio-para-toluidine," my foreign correspondents under-
stand those thio bases which contain one or several atoms of sulphur, and result on
heating para-toluidine, meta-xylidine, pseudo-cumine, with sulphur, that is to say,
the following compounds: dehydro-thio-para-toluidine, dehydro-thio-meta-xylidine,
dehydro-thio-pseudo-cumidine, primuline base, and the like, or the sulpho acids of
these and similar thio amido products.
The combination of the diazo compounds of the said thio-derivatives with alpha
naphthol mono sulpho acid (1 : 3), most practically is effected in alkaline solution,
as described in the following example, the parts being by weight.
COLOURING MATTER FROM DIAZOTISED
DEHYDRO-THIO-PARA-TOLUIDINE
SULPHO ACID, AND ALPHA NAPHTHOL MONO SULPHO ACID (1:3).
34.2 parts of the sodium salt of dehydro thio para toluidine sulphonate of sodium
are dissolved in 300 parts of water. After adding a concentrated solution, in water,
of 6-9 parts of sodium nitrite, hydrochloric acid is added (with continual stirring) to
the resulting liquid, until the latter assumes a strong acid reaction. After about
12 hours, the diazo compound formed is allowed to flow into a solution prepared by
dissolving 27 parts of the sodium salt of the alpha naphthol mono sulpho acid (1:3),
and rendered alkaline by means of sodium carbonate. The resulting mixture, after
twelve hours, is heated to 90 degrees centigrade, and when cool, common salt is
added, and the precipitated dye stuff is filtered off. It produces beautiful bluish-
red shades on unmordanted cotton.
The analogous dye stuffs result, if the dehydro-thio-para-toluidine sulpho acid
employed in the foregoing example, is replaced by the corresponding quantity of
another of the above mentioned thio amido compounds, or sulpho derivatives
thereof.
The colouring matters thus obtained, likewise yield deep blue shades possessing
great fastness against the action of acids and alkalies.
My foreign correspondents have described, in the above example, one method of
producing a colouring matter of the series defined, but they do not limit themselves
(in the production of this dye stuff and the analogues thereof) to the directions
given in the above example, as the method can be varied, and all those methods
can also be employed which are used for producing analogous or similar colouring
matters.
Dated this 4th day of March 1802
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Direct-dyeing 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 :-
In their Specification of application for Letters Patent No. 3495, dated
16 February 1893, my foreign correspondents have described the production of
substantive cotton dye-stuffs, by combining monalkylated alpha, alpha, dihydroxy-
naphthalene sulphonic acids with the diazo derivatives of the so-called thio-amido
compounds, such as dehydrothioparatoluidine, dehydrothiometaxylidine, dehydro-
thio pseudo cumidine, primulene base, or the sulphonic acids thereof. These

page_text: dye-stuffs in general yield bluish red shades, which are of a great beauty and
fastness.
My foreign correspondents have subjected other alpha naphthol monosulphonic
acids to the action of the diazo compounds of "dehydrothio paratoluidine, or the
analogues thereof," or sulphonic acids of such thio amido products, and have found
that, on using alpha, naphthol beta, monosulphonic acid (OH: SO₂H=1:3),
dye-stuffs are formed which also yield red shades, exhibiting a marked bluish hue,
and of considerable fastness in presence of acids and alkalies, whereas the coloring
matters obtained by means of 1:2, 1:6, or 1:7 alphanaphthalmono sulphonic
acids produce only dull and technically valueless shades. The dye stuffs formed
from alpha, naphthol beta, mono sulphonic acid (1:3) are also superior to the
dye-stuff technically known as "Erica," owing to the much greater readiness with
which they dye cotton fibres, yielding shades of a more bluish hue. My foreign
correspondents particularly point out that the last mentioned dye-stuff, "Erica,"
also contains a hydroxylic and sulphonic group relating in the meta position, as it
is formed by combining the diazo derivative of dehydro thio meta xylidine with
alpha naphthol epsilon disulphonic acid (OH: SO,H: SO,H=1:3:8).
From these results my foreign correspondents believe that, on the one hand, the
fastness in presence of alkalies observed only in the case of a few dye-stuffs froin
alpha naphtholmono or alpha naphtholdisulphonic acids, is caused by the meta
position of the hydroxylic, relatively to the sulphonic group, and that, on the other
hand, the slight degree of fastness in presence of alkalies, of analogous azo coloring
matters obtained from alpha naphtholmono or alphanaphtholdisulphonic acids
containing a hydroxylic and sulphonic otherwise than in meta positions, is owing to
the absence of such meta relationship.
By the expression "dehydrothio para toluidine or the analogues thereof" used
above, my foreign correspondents understand the thio bases containing one or
several atoms of sulphur, which are formed on heating paratoluidine, metaxylidine,
or pseudo cumidine, with sulphur, that is to say, the following compounds:
dehydrothioparatoluidine, dehydrothiometaxylidine, dehydrothiopseudo cumidine,
primuline base, and the like; the sulphonic acids of these and similar thio amido
compounds can also be used.
This invention, however, is not restricted to the use of the above named thio
amido compounds, as analogous products (such as the products known in commerce
as chromine, polychromine, thio chromogene, and the like) can also be used.
The combination of the diazo derivatives of the said thio amido compounds with
alpha, naphthol beta, monosulphonic acid (1:3) is best effected in alkaline solution,
as described in the following example, the parts being by weight.
SUL-
COLORING MATTER FROM DIAZOTISED DEHYDROTHIOPARATOLUIDINE
PHONIC ACID AND ALPHA NAPHTHOL BETA, MONO SULPHONIC ACID
(OH: SO,H 1:3).
=
34.2 parts of sodium dehydrothioparatoluidine sulphonate are dissolved in
300 parts of water, and mixed with a concentrated solution, in water, of 6.9 parts
of sodium nitrite; muriatic acid is then stirred into the liquid until the latter is
strongly acid. After about 12 hours, the diazo compound thus formed is allowed
to flow into a solution prepared by dissolving 24-6 parts of the sodium salt of alpha,
naphthol beta, mono sulphonic acid (OH: SO,H 1:3), rendered alkaline by
means of sodium carbonate. The resulting mixture is heated, after twelve hours,
to about 90 degrees centigrade, and the dye stuff is subsequently salted out and
filtered off. It produces beautiful bluish red shades on uumordanted cotton.
=
Analogous dye-stuffs are formed if, instead of the dehydrothioparatoluidine
sulphonic acid prescribed in the foregoing example, the corresponding quantity of
another of the above mentioned thio amido compounds, or sulphonic derivatives

page_text: thereof, be used.
The coloring matters thus obtained also yield red shades
exhibiting a marked bluish hue, and of great fastness in presence of acids and
alkalies.
In the above example, my foreign correspondents have described one method of
producing a coloring matter of the series defined, but in producing this dye-stuff
and the analogues thereof, they do not limit themselves to the directions given the
said example, as the method can be varied, and all the usual methods for producing
analogous or similar coloring matters can be used. The nature of this invention is
not altered by such variations or modifications, as it relates generally to the
production of azo dye-stuffs by combining one molecular proportion of the diazo
derivatives of dehydrothioparatoluidine, or analogues thereof, with one molecular
proportion of alpha, naphthol beta, monosulphonic acid, or salts thereof.
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 azo dye-stuffs by combining one molecular proportion
of alpha, naphthol beta, mono sulphonic acid (OH: SO₂H = 1:3), or an alkaline
salt thereof, with one molecular proportion of the diazo derivatives of dehydrothio-
paratoluidine, dehydrothiometaxylidine, dehydrothiopseudo cumidine, primuline
base, dehydrothioparatoluidine sulphonic acid, dehydrothiometaxylidine sulphonic
acid, dehydrothiopseudo-cumidine-sulphonic acid, primuline, or analogous thio-
amido compounds.
2. As new products of manufacture, the new coloring matters produced by the
process hereinbefore defined, or by any other process affording the same result.
Dated this 29th day of November 1893.
NEWTON & SON,
Agents for the Applicant.