The Manufacture, and Production of New Azo-colouring Matters.
Year: 1894

page_text: Date of Application, 30th Apr., 1894
Complete Specification Left, 29th Dec., 1894-Accepted, 2nd Feb., 1895
PROVISIONAL SPECIFICATION.
The Manufacture, and Production of New Azo-colouring Matters.
I JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of
London Gentleman do hereby declare the nature of this invention (which has
been communicated to me from abroad by The Badische Anilin & Soda Fabrik of
Ludwigshafen-on-Rhine in the Empire of Germany) to be as follows:
This invention consists in the manufacture and production of a new series of
colouring matters which are mainly of a brilliant yellow, to orange, colour, and
which dye cotton without the aid of a mordant, giving shades which are characterized
by great fastness against the action of acids, washing and light. The said
colouring matters are the disazo dyes obtainable by the combination of the
tetrazo compounds of certain sulphonated diamido bodies or of primuline and the
like with nitro-meta-phenylene-diamine (see Berichte der Deutschen Chemischen
Gesellschaft 7, 1257).
The disazo compounds from benzidine and the like and meta-phenylene-diamine
are known but these are of no practical value as dyestuffs, on account of their
insolubility in water. Further the analogous compounds from benzidine-disulpho
acid and the like though soluble in water cannot resist the action of acid being
discoloured even by the carbonic acid of the air.
My foreign correspondents have discovered that nitro-meta-phenylene-diamine
possesses the property of combining with diazo- and tetrazo-compounds to yield
azo-dyes, differing in this respect from other nitro-amido- and nitro-phenolic bodies
such as nitro-salicylic acid, para-nitro-phenol, nitro aniline, nitro-dimethyl-aniline
and the like. They have further discovered that the azo-dyes obtained by the
combination of this component with benzidine disulpho acid and other sulphonated
diamido-bodies and with primuline and the like constitute valuable dyestuffs
possessing the properties herein before mentioned.
In the following example I describe the production of the colouring-matter
from benzidine-disulpho acid and nitro-meta-phenylene-diamine which is a
particularly valuable member of the class, but this is merely a typical example
which whilst further illustrating the nature of the invention is capable of variation
in many respects, in the various cases, without departure from the nature of this
invention. The parts are by weight.
EXAMPLE.
Dissolve about thirty four and a half parts of benzidine-disulpho acid in about
two hundred parts of water containing the requisite quantity of alkali, and add
when cold about fourteen parts of sodium nitrite dissolved in about two hundred
parts of water, next pour the mixture into about one hundred and sixty parts of
hydrochloric acid (containing about thirty per cent. real acid HCI) diluted with
about three times the quantity of water. Stir well whilst mixing and continuously
for say five hours and then add a solution containing about thirty two parts
nitro-meta-phenylene-diamine, fifty eight parts hydrochloric acid (thirty per
cent. HCI) and two hundred parts of water; this solution should be at a temperature
of about fifty to sixty degrees Centigrade. Next add about one hundred and
twelve parts of sodium acetate dissolved in about three hundred and thirty six

page_text: parts of water. Stir the mixture for say three hours longer and then add gradually
a solution of about one hundred and seventy parts calcined soda in about one
thousand parts water, then stir continuously for say twenty-four hours. Filter
press and dry.
The colouring matter so obtained-is a dark reddish-brown powder with a slight
greenish lustre readily soluble in water.
'As instances of the other amido-bodies which can similarly be used in the,
production of disazo-dyes from nitro-meta-phenylene diamine, I mention primuline
and the like, benzidine-sulphon-disiilpho acid, diamido-stilbene-disulpho-acid and
tolidine-disulpho acid, but I do not restrict myself to these.
Dated this 30th day of April 1894.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
The Manufacture and Production of New Azo-colouring Matters.
I JAMES YATE JOHNSON of 47 Lincoln's Inn Fields, in the County, of
London, 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) and in what manuer the
same is to be performed to be particularly described and ascertained in and by the
following statement :—
This invention consists in the manufacture and production of a new series of
colouring matters which are mainly of a brilliant yellow to orange colour and
which dye cotton without the aid of a mordant giving shades which are characterized
by great fastness against the action of acids, washing and light. The said
colouring matters are the azo-dyes obtainable by the combination of the tetrazo-
compounds of certain sulphonated diamido-bodies or the diazo compounds of
primuline and the like with nitro-meta-phenylene-diamine or the homologous and
equivalent body nitro-meta-toluylene-diamine (see Berichte der Deutschen
Chemischen Gesellschaft 7, 1257 and 3, 9).
The disazo compounds from benzidine and the like and meta-phenylene- and
toluylene-diamine are known but these are of no practical value as dye-stuffs on
account of their insolubility in water. Further the analogous compounds from
benzidine-disulpho acid and the like though soluble in water, do not resist the
action of acid being discoloured even by the carbonic acid of the air.
My foreign correspondents have discovered that nitro-meta-phenylene-diamine
and the equivalent derivative of toluylene-diamine possess the property of
combining with diazo- and tetrazo-compounds to yield azo dyes, differing in this
respect from other nitro-amido and nitro-phenolic bodies such as nitro-salicylic
acid, para-nitro-phenol, nitro-aniline, nitro-dimethyl-aniline and the like. They
have further discovered that the azo-dyes obtained by the combination of the
aforesaid nitro-diamines with benzidine-disulpho acid and other sulphonated
diamido-bodies and with primuline and the like constitute valuable dyestuff's
possessing the properties herein before mentioned.
In the following example I describe the production of colouring-matter from
benzidine-disulpho acid and nitro-meta-phenylene- or toluylene-diamine as
particularly valuable colouring matter is so obtained but this is merely a typical
example which whilst further illustrating the nature of the invention and the
manner in which it is carried into practical effect is capable of variation in many
respects in the various cases without departure from the nature of this invention.
The parts are by weight.

page_text: EXAMPLE.
Dissolve about thirty-four and a half parts of benzidine-disulpho acid in about
two hundred parts of water containing the requisite quantity of alkali and add
when cold about fourteen parts of sodium nitrite dissolved in about two hundred
parts of water, next pour the mixture into about one hundred and sixty parts of
hydrochloric acid (containing about thirty per cent. real acid HCl) diluted with
about three times the quantity of water. Stir well whilst mixing and continuously
for say five hours and then add a solution containing about thirty two parts
nitro-meta-phenylene-diamine (or the equivalent quantity of nitro-meta-toluylene
diamine) fifty eight parts hydrochloric acid (thirty per cent. HCl) and two hundred
parts of water; this solution should be at a temperature of about fifty to sixty
degrees Centigrade. Next add about one hundred and twelve parts of sodium
acetate dissolved in about three hundred and thirty six parts of water. Stir the
mixture for say three hours longer and then add gradually a solution of about one
hundred and seventy parts calcined soda in about one thousand parts water, then
stir continuously for say twenty four hours. Filter press and dry.
The colouring matter so obtained is a dark reddish-brown powder with a slight
greenish lustre readily soluble in water. The product obtained when using the
toluylene derivative yields more reddish shades on dyeing than does that from the
phenylene-compound but in other respects the products are practically identical.
As instances of the other amido-bodies which can similarly be used in the
production of azo dyes from nitro-meta-phenylene- or toluylene-diamine, I mention
primuline and dehydrothiotoluidine sulpho acid which yield golden-yellow dyes
and benzidine-sulphon-disulpho acid, diamido-stilbene-disulpho acid, toluidine-
disulpho acid and diamido-naphthalene-beta-disulpho acid which yield orange
colouring matters.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed I declare that what I
claim is
1. The manufacture of new azo-colouring matters by the combination of the
tetrazo- or diazo-compounds respectively derived from the sulphonated amido-
bodies hereinbefore set forth with nitro-meta-phenylene-diamine or nitro-meta-
toluylene-diamine.
2. The manufacture of new azo-colouring-matters in the manner described in the
foregoing example.
3. As new articles of manufacture the new azo-colouring-matters such as can be
obtained substantially as hereinbefore described and claimed.
Dated this 29th day of December 1894.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.