Manufacture of New Colouring Matters by the Action of Diazo Compounds on the Hydrazone Derivatives of Oxalyloacetic Ether.
Year: 1893

page_text: Date of Application, 16th Mar., 1893
Complete Specification Left, 16th Dec., 1893-Accepted, 17th Feb., 1894
PROVISIONAL SPECIFICATION.
Manufacture of New Colouring Matters by the Action of Diazo
Compounds on the Hydrazone Derivatives of Oxalyloacetic
Ether.
I, JOHANN HEINRICH ZIEGLER of Bâle, Switzerland, Chemist do hereby
declare the nature of this invention to be as follows:-
This invention is founded on the observation that diazo-compounds give a
reaction with the hydrazones of the general formula:
(where R and R, represent rests of hydrocarburets, X the rest of a hydrocarburet,
hydrogen, hydroxyle or ethoxyle) analogous to that observed and described by
Japp and Klingemann (Ann. Chem. Pharm. 247, 190). In both cases the hydrogen
of the methylencarbon is substituted by the group hydrazone; therefore it results
in the present case directly a representative of the class of osazones, so denominated
by its inventor E. Fischer.
EXAMPLE.
19 kilos. phenylhydrazine-sulphonic acid suspended in 100 litres of water
are mixed with 18.8 kilos. of oxalyloacetic ether and 15 kilos. crystallised
acetate of sodium. By agitating and heating to 50° C. the hydrazone compound
is produced. Then 5 kilos. carbonate of sodium are given in the liquor after
which the diazobenzolsulphonic precipitate prepared in the well known manner
from 22 kilos. sulphanilate of sodium. Immediately the liquor is coloured
intensely yellow by formation of the osazone compound of the ether of the
dioxytartaric acid. The dye stuff can be isolated by adding salt. By heating its
solution with the calculated quantity of hydrate of sodium the ether is trans-
formed into the same colour, which I have described in the American Patent
No. 324630 and The Badische Anilin and Sodafabrik in the English Patent
No. 9858 of 1885.
Instead of the hydrazone mentioned in the example above, there can be
employed those of phenylhydrazine, the tolyle-, xylyl- and naphthylhydrazines or
their sulphonic or carbonic acid-, their nitro-, hydroxy- and ethoxy derivatives.
Instead of the diazo-compound derived from the sulphanilic acid, there can be
employed those from aniline, the toluidines, xylidines, naphthylamines, benzidine,
tolidine and their sulphonic and carbonic acid derivatives, the nitro- and amido-
derivatives or the diazo-compounds from colouring matters like the amido-
azobenzene or other tetrazoic compounds.
Dated this 16th day of March 1893.
ABEL & IMRAY,
Agents for the Applicant.

page_text: COMPLETE SPECIFICATION.
Manufacture of New Colouring Matters by the Action of Diazo
Compounds on the Hydrazone Derivatives of Oxalyloacetic
Ether.
I, JOHANN HEINRICH ZIEGLER, of Bâle, Switzerland, Chemist, 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 :-
This invention is founded on the observation that diazo compounds give a
reaction with the hydrazones of the general formula :
(where R represents carbonethyl or a rest of a hydrocarburet R₁ represents a
rest of a hydrocarburet, and X the rest of a hydrocarburet, hydrogen, hydroxyle
or ethoxyle) analogous to that observed and described by Japp and Klingermann
(Ann. Chem. Pharm. 247, 190).
In both cases the hydrogen of the methylencarbon is substituted by the group
hydrazone; therefore there results in the present case directly a representative of
the class of osazones, so denominated by its inventor E. Fischer.
EXAMPLE.
19 kilos. phenylhydrazine sulphonic acid suspended in 100 litres of water are
mixed with 18.8 kilos. of oxalyloacetic ether and 15 kilos. crystallised acetate of
sodium. By agitating and heating to 50° C. the hydrazone compound is produced.
Then first 5 kilos. carbonate of sodium are given added at ordinary temperature
to the liquor after which is added the diazobenzolsulphonic precipitate prepared
by diazotising iceing in the well known manner 22 kilos. sulphanilate of sodium by
7 kilos. sodium nitrite & 22 litres hydrochloric acid at 33% in 100 litres water.
Immediately the liquor is coloured intensely yellow by formation of the osazono
compound of the ether of the dioxytartaric acid. The dye stuff can be isolated
by adding salt. By heating its solution with the calculated quantity of hydrate
of sodium the ether is transformed into the same colour which I have described in
the American Patent No. 324630, and The Badische Anilin and Sodafabrik in the
English Patent No. 9858 of 1885.
Instead of the hydrazone mentioned in the example above, there can be
employed those of phenylhydrazine, the tolyle-, xylyl- and naphthylhydrazines or
their sulphonic or carbonic acid, their nitro-, hydroxy-, and ethoxy derivatives.
Instead of the diazo compound derived from the sulphanilic acid, there can be
employed those from aniline, the toluidines, xylidines, naphthylamines, benzidine,
tolidine and their sulphonic and carbonic acid derivatives, the nitro and amido-
derivatives or the diazo compounds from colouring matters like the amido
azobenzene or other tetrazoic compounds.
Having now particularly described and ascertained the nature of this invention
and in what manner the same is to be performed, I declare that what I
claim is :-
1. The production of colouring matters by the action of the diazo compounds
of aromatic bases on the hydrazone derivatives of oxalylo acetic ether, substan
tially as described.
1

page_text: 2. The new colouring matters produced as set forth in the preceding claim.
3. Treating the colouring matters referred to in the preceding claims with
hydrate of sodium for the purpose herein set forth.
Dated this 16th day of December 1893.
ABEL & IMRAY,
Agents for the Applicant.