Manufacture of New Bases and their Sulpho-acids.
Year: 1893

page_text: Date of Application, 4th Dec., 1893
Complete Specification Left, 27th Aug.. 1894-Accepted, 29th Sept., 1894
[Communicated from abroad by THE ACTIEN GESELLSCHAFT FÜR ANILIN
FABRIKATION, of Berlin, in the Empire of Germany, Chemical Manu-
facturers.]
Manufacture of New Bases and their Sulpho-acids.
I, CHARLES DENTON ABEL of No. 28 Southampton Buildings in the County
of London, Consulting Engineer and Chartered Patent Agent, do hereby declare
the nature of this invention to be as follows :-
M. Goldschmidt (D. Chem. Ges. XXIV pg. 1001) described a new class of
compounds, which are formed by the action of aldehydes on the ortho amido-azo
bodies. As contrasted with the products obtained by the reaction of aldehydes on
amido-bodies, the compounds above mentioned are very stable.
My foreign correspondents have discovered that a new series of substances may
be formed by reacting with aldehydes upon the diamido azo bodies, generally known
under the designation: chrysoidines; that is to say, the colouring-matters formed
by the action of diazotised amines, or their sulpho- or carbo-acids on the meta-
diamines. The said chrysoidines react very easily with aldehydes of the fat and
aromatic series. The bases thus obtained are very stable. They are not
decomposed even when heated under pression with mineral acids to 170°
or 180° C.
Owing to the presence of one amido-group, these products are strong bases.
They may be diazotised and combined with phenols, amines, the sulpho- and carbo-
acids of phenols and amines to form azo-colouring matters.
The constitution of these new bases is probably expressed by the following
H
The group R, signifying a radical of the benzene or naphthaline series.
By sulphonating these bases sulpho-acids are obtained which can equally be
employed with great advantage for the production of azo-dyes. Some of the
above mentioned sulpho-acids or their salts are moreover distinguished by their
very sweet taste.
The process may be carried out in the following manner.
25 kilos. chrysoidine (diamido azo-benzene chloride) and 11 kilos. benzaldehyde
are dissolved in 11 kilos. concentrated hydrochloric acid, and 50 kilos. common
acetic acid. The mixture is heated on the water-bath for about 6 hours until the
colouring-matter disappears. Then the solution is poured into 1000 litres of water,
filtered and the base is precipitated by addition of carbonate of soda.
For purifying the precipitate may be dissolved by boiling with dilute sulphuric

page_text: acid. The sulphate crystallizes from the cold solution in the form of white
needles. The base obtained from this sulphate is colourless, insoluble in water, but
easily soluble in hot alcohol and benzene.
According to the conditions, that is to say according to the quantity of the
fuming sulphuric acid and the temperature used, mono or disulpho-acids of the
above mentioned base may be prepared. In an analogous inanner may be
prepared the other members of the group of bodies, discovered by my foreign
correspondents.
Dated this 4th day of December 1893.
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of New Bases and their Sulpho-acids.
I, Charles DENTON ABEL of No. 28 Southampton Buildings, in the County
of London, Consulting Engineer and Chartered 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 :-
M. Goldschmidt (D. Chem. Ges. XXIV pg. 1001) described a new class of
compounds, which are formed by the action of aldehydes on the ortho amidoazo
bodies. As contrasted with the products obtained by the reaction of aldehydes on
amido bodies, the compounds above mentioned are very stable.
My foreign correspondents have discovered that a new series of substances which
shall be denominated "amidotriazines" may be formed by reacting with aldehydes
upon the diamido azo bodies, generally known under the designation chrysoidines;
that is to say, the colouring matters formed by the action of diazotised amines, or
their sulpho or carbo acids on the meta diamines. The said chrysoidines react
very easily with aldehydes of the fat and aromatic series. The products thus
obtained are very stable. They are not decomposed even when heated under
pressure with mineral acids to 170° or 180° C.
Owing to the presence of one amido group these products may be diazotised and
combined with phenols, amines, the sulpho and carbo acids of phenols and amines
to form azo colouring matters.
The substances which are prepared by means of chrysoidines containing no
sulpho or carboxyl group are strong bases. The constitution of the new products
may be most probably expressed by the following typical formula:
The group R₁ signifying a radical of the benzene or naphthaline series.
By the action of sulphonating agents the condensation products obtained from
aldehydes and chrysoidines may be sulphonated; according to the conditions, that
is to say according to the quantity of the fuming sulphuric acid and the temperature
used, mono or disulpho acids of the above mentioned base may be prepared.

page_text: These sulphonation products can equally be employed with great advantage for
the production of azo dyes. Some of the above mentioned sulpho acids or their
salts are moreover distinguished by their very sweet taste.
The following example may serve to illustrate in what manner the process may
be carried out.
1. 25 kilos. chrysoidine (diamido-azo-benzene-chloride) and 11 kilos. benzaldehyde
are dissolved in 11 kilos. concentrated hydrochloric acid and 50 kilos. common
acetic acid. The mixture is heated on the water bath for about 6 hours until the
colouring matter disappears. Then the solution is poured into 1000 litres of
water, filtered and the base is precipitated by addition of carbonate of soda.
For purifying, the precipitate may be dissolved by boiling with dilute sulphuric
acid.
The sulphate crystallizes from the cold solution in the form of white needles.
The base obtained from this sulphate is colourless, insoluble in water, but easily
soluble in hot alcohol and benzene. By the action of nitrite it yields a diazo
compound that is very stable and only sparingly soluble in water.
2. In order to transform the afore-described base into a monosulpho acid one
part of the same, or of a salt thereof, is dissolved in 3.6 parts of fuming sulphuric
acid (20 per cent. anhydride) and the mixture is gently heated for some time; the
reaction product is poured into cold water whereby the monosulpho acid formed
separates in the shape of crystalline white flakes. The monosulpho acid is
sparingly soluble in water, but its alkali salts are easily soluble. Treated with
nitrous acid the monosulpho acid yields a moderately soluble diazo compound.
3. By treating the amidotriazine described under 1. with fuming sulphuric acid
at higher temperature on the water bath for several hours, a disulpho acid is
formed, which is easily soluble in water and may be isolated in the well known
manner in the form of its lime or soda salt.
By starting, instead of from diamidoazo benzene, from other members of the
chrysoidine group, or by replacing the benzaldehyde by its substitution products
or other aldehyde of the aromatic or fat series, analogous amidotriazine derivatives
may be obtained.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
1. The herein described process for the production of new condensation products,
to be called amidotriazines, by the action of aldehydes of the aromatic or fat series
upon chrysoidines; chrysoidines being understood to designate the colouring
matters formed by the action of diazotised amines, or their sulpho or carbo acids
on the metà diamines.
2. The transformation of the products obtained according to the preceding claim
into new sulphonated derivatives by the action of sulphonating agents.
3. The products manufactured as set forth in Claims 1 and 2.
Dated this 27th day of Au 1001
ABEL & IMRAY,
Agents for the Applicant.