Improvements in the Manufacture and Production of New Azo Dyes.
Year: 1893

page_text: Date of Application, 14th Nov., 1893
Complete Specification Left, 14th Aug., 1894-Accepted, 15th Sept., 1894
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture and Production of New Azo Dyes.
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:-
:-
In the Specification of the application for Patent No. 14678 of 1893 communi-
cated to me by my present foreign correspondents a new component and its use
in the manufacture of azo dyes is described. The said component is a new
disulpho acid of meta-phenylene-diamine and is obtained by treating this diamine
or salts thereof with fuming sulphuric acid, and sufficient acid being taken that at
least two molecular proportions of free or available sulphuric anhydride (SO,)
are present for one molecular proportion of meta-phenylene-diamine. Further in
the said Specification, instances are given of the production of azo dyes by the
combination of one molecular proportion of certain diazo compounds and one
molecular proportion of the new component. Now the present invention relates
to the manufacture of azo-dyes of a different type, from the said new component.
This type of dye is obtained by the combination under suitable conditions as
hereinafter set forth of two molecular proportions of diazo compound with one
molecular proportion of the aforesaid new component. Either two molecular
proportions of the same diazo-compound or one molecular proportion of one diazo
compound and one molecular proportion of a different one can be used.
In the production of the new azo-dyes according to the present invention, the
introduction of the first molecular proportion of a diazo compound can be effected
with comparative ease and either in alkaline, or in neutral, or in acetic acid
solution, but my foreign correspondents have discovered that the introduction of
the second molecular proportion of diazo-compound can only be effected with some
difficulty. The bodies must be allowed to interact for a more prolonged period
and in most cases the reaction is best effected in neutral or acetic acid solution.
As instances of combinations which constitute valuable products, I mention the
dyes obtainable by combining one molecular proportion of the new component on
the one hand with one molecular proportion of diazo-primuline and the like and on the
other hand with one molecular proportion of the diazo-compounds derived from
the following bodies :-Aniline, ortho-toluidine para-toluidine, meta-xylidine, alpha-
naphthylamine, beta-naphthylamine and the like, also sulphanilic acid, meta-
sulphanilic acid, naphthionic acid the beta-naphthylamine-sulpho acids (2.1', 2.31
and 2.4') and the like. (See Thorpe's Dictionary of Applied Chemistry. Article
Naphthalene.)
In preparing the dyes indicated in the foregoing paragraph, it is preferable,
when using the above named sulpho acids, to effect the combination with the
diazo-primuline first and subsequently with the diazo-compound of the sulpho
acid; but on the other hand when using a diazo-compound derived from one of the
unsulphonated amines above mentioned, it is preferable first to effect the
combination therewith and subsequently with the primuline diazo-body.
Although I have mentioned instances of the new dyes I do not confine myself
to those mentioned as the nature of the present invention consists in the com-
bination of two molecular proportions of any one diazo-compound or of any two

page_text: different diazo compounds generally, with one molecular proportion of the new
component.
Dated this 14th day of November 1893.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
Improvements in the Manufacture and Production of New Azo Dyes.
1 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 com-
municated to me from abroad by The Badische Anilin and Soda Fabrik of
Ludwigshafen-on-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 :-
In the Specification of the application for Letters Patent No. 14678 of 1893
communicated to me by my foreign correspondents a new component and its use in
the manufacture of azo-dyes is described. The said component is a new disulpho
acid of meta-phenylene-diamine and is obtained by treating this diamine or salts
thereof with fuming sulphuric acid and sufficient acid being taken that at least
two molecular proportions of free or available sulphuric anhydride (SO,) are
present for one molecular proportion of meta-phenylene-diamine. Further in the
said Specification instances are given of the production of azo-dyes by the com-
bination of one molecular proportion of certain diazo compounds and one
molecular proportion of the new component. Now the present invention relates to
the manufacture of azo-dyes of a different type from the said new component.
This type of dye is obtained by the combination under suitable conditions as
hereinafter set forth of two molecular proportions of diazo compound with one
molecular proportion of the aforesaid new component. Either two molecular
proportions of the same diazo-compound or one molecular proportion of one diazo-
compound and one molecular proportion of a different one can be used.
In the production of the new azo dyes according to the present invention, the
introduction of the first molecular proportion of a diazo-compound can be effected
with comparative ease and either in alkaline or in neutral or in acetic acid solution
but my foreign correspondents have discovered that the introduction of the second
molecular proportion of diazo-compound can in many cases only be effected with
some difficulty. The bodies must be allowed to interact for a more prolonged
period and in the most cases the reaction is best effected in neutral or acetic acid
solution.
As instances of the combinations which constitute valuable products I mention
the dyes obtainable by combining one molecular proportion of the new component
on the one hand with one molecular proportion of diazo-primuline and the like and
on the other hand with one molecular proportion of the diazo-compounds derived
from the following bodies:-Aniline, ortho-toluidine, para-toluidine, meta-xylidine,
alpha-naphthylamine, beta-naphthylamine and the like, also sulphanilic acid, meta-
sulphanilic acid, naphthionic acid, the beta-naphthylamine-sulpho acids (2.1, 2.31
and 2.4) and the like. (See Thorpe's Dictionary of Applied Chemistry. Article
Naphthalene.)
In preparing the dyes indicated in the foregoing paragraph it is preferable, when
using the above-named sulpho acids to effect the combination with the diazo-
rimuline first and subsequently with the diazo-compound of the sulpho acid; but
on the other hand when using a diazo-compound derived from one of the
unsulphonated amines above mentioned it is preferable first to effect the combina-
tion therewith and subsequently with the primuline diazo body.

page_text: EXAMPLE 1.
Convert about thirteen parts of aniline hydrochlorate in the usual way into
diazo-compound by treating with about seven parts of sodium nitrite and fifteen
parts of hydrochloric acid (containing about thirty per cent. real acid HCI).
Dilute the diazo solution to about five hundred parts and pour it into a solution of
about twenty-seven parts of meta-phenylene-diamine-disulpho acid and forty-five
parts of crystallized sodium acetate in about five-hundred parts of water. Stir
continuously for from five to eight days or thereabouts. Then add the solution of
diazotized primuline obtained from fifty-six parts of primuline or thereabouts:
(taking in any case the amount equivalent to seven parts of sodium nitrite) seven parts
sodium nitrite, five hundred parts water and forty-nine parts of hydrochloric acid
(containing about thirty per cent. real acid HCI). Stir again for a few days.
Finally precipitate the dye by the addition of hydrochloric acid, filter, mix the
dye with the quantity of soda necessary for the formation of the soluble sodium salt,
dry, and grind to powder.
The dye so obtained is a brown powder soluble in water giving an orange-brown
solution and it dyes unmordanted cotton giving reddish orange shades.
In the same way analogous products can be obtained by substituting for the
aniline in the above example the equivalent quantity of ortho-toluidine, para-
toluidine, meta-xylidine, alpha-naphthylamine or beta-naphthylamine or the like.
EXAMPLE 2.
Diazotize about fifty-six parts of primuline (or the quantity equivalent to seven
parts of sodium nitrite) in five hundred parts of water with seven parts of sodium
nitrite and forty-nine parts hydrochloric acid (containing about thirty per cent. real
acid HCI) and run the diazo compound into an ice-cold solution of about twenty-seven
parts of meta-phenylene-diamine-disulpho acid about twenty-eight parts of calcined
soda in about four hundred parts of water. Stir for about twenty-four hours then
add about thirty parts of crystallized sodium acetate and run in the diazo-compound
from about nineteen and a half parts of sodium sulphanilate, about seven parts of
sodium nitrite, about two hundred parts of water and about thirty-nine parts of
hydrochloric acid (containing about thirty per cent. real acid HCI). Stir for from
five to eight days or thereabouts heat the liquid, acidify with hydrochloric acid,
precipitate with common salt and work up in the way described in the foregoing
example.
A brown powder is obtained which dissolves in water giving an orange-red solution
and dyes unmordanted cotton a bright orange colour.
Analogous products can be obtained by substituting for the sulphanilic acid in
the above example the equivalent quantity of metanilic acid, naphthionic acid and
the other sulpho acids hereinbefore mentioned.
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-dyes by the combination of two molecular
proportions of diazo compound with one molecular proportion of meta-phenylene-
diamine-disulpho acid substantially as hereinbefore described.

page_text: 2. The manufacture of new azo dyes by the combination of meta-phenylene-
diamine disulpho acid first with the diazo compound derived from aniline or from
one of the other bases herein before mentioned and subsequently with diazo-primuline
substantially as herein before described.
3. The manufacture of new azo dyes by the combination of meta-phenylene-
diamine disulpho acid first with diazo-primuline and subsequently with the diazo-
compound derived from sulphanilic acid or one of the other sulphoacids hereinbefore
mentioned substantially as hereinbefore described.
4. The manufacture of azo-dyes in the manner set forth in the examples herein-
before described.
5. As new products the azo dyes such as can be obtained substantially as herein-
before described and claimed.
Dated this 14th day of August 1894.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents