Manufacture of New Nitrated Oxazine Colouring Matters Dyeing with Mordants.
Year: 1895

page_text: Date of Application, 27th Dec., 1895--Accepted, 15th Feb., 1896
[Communicated from abroad by the Firm of L. DURAND HUGUENIN & Co.,
of Basle, Switzerland, Manufacturers.]
Manufacture of New Nitrated Oxazine Colouring Matters Dyeing
with Mordants.
1, CHARLES DENTON ABEL, of No. 28 Southampton Buildings, Chancery
Lane, 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:-
In the Specification to Patent No. 583 of 1891 (dated 13th June 1890 under
International Convention) a blue colouring matter is described which is obtained by
the action of anilin upon the condensation product of nitrosodimethylaniline-
hydrochlorate and tannin-anilide, and subsequent sulphonation.
It has been found by my correspondents that the said colouring matter can be
readily nitrated and that by the entrance of nitro groups the tint can be converted
into green. The mononitro derivative dyes chromed wool in bright green tints
which exceed the fast greens hitherto known in brightness of colour.
By the introduction of several nitro groups yellower tints but of less brightness
are obtained.
For the production of the mononitro derivatives the following method is
employed.
20 kilos. of anilidised condensation product of nitrosodimethylanilin hydrochlorate
with tannin anilide are introduced during from four to five hours into 100 kilos. of
a 92 p.c. sulphuric acid, under continual stirring.
The mixture is then gradually heated to from 80° to 85° C, and the sulphonating
mixture is maintained at this temperature until a sample dissolves in alkaline water,
which condition is arrived at in from 10 to 15 minutes.
The reaction product is cooled down to 0° C. and is gradually added to a
mixture of 24 kilos. of an 86.6 p.e. nitric acid and 6 kilos. of 96 p.c. sulphuric acid,
care being taken that the temperature does not rise above 10° C. during the
nitration. After standing from 10 to 12 hours at ordinary temperature, the
mass is poured into water, the nitro acid, which is insoluble in water, is filtered
off, washed and is converted into the ammonia-salt soluble in water.
The colouring matter dissolves in water with a blue-green colour; the solution
in concentrated sulphuric acid is of a crimson red. A similar colouring matter can
be obtained by nitrating the sulpho-acid of the anilidised condensation product of
nitrosodiethylanilin-hydrochlorate with tannin anilide.
In the above described body the nitro group is situated in the anilide-rest.
There may however be produced an isomeric binitroderivative, by reacting with
binitrobenzol-chloride (CH. Cl. NO. NO. 1. 2.4) upon the condensation product
of nitrosodialkylanilin-hydrochlorate, or dialkyl amidoazobenzol-hydrochlorate
with gallamic acid and subsequently analidising the nitrobody obtained. The nitro-
groups of the body thus obtained are clearly situated in the carboxylaniliderest.
ID

page_text: The reaction of the binitrobenzolchloride takes place according
formula:
to the following
OH
The new body forms a powder with bronze lustre, only slightly or hardly soluble
in hot water and alcohol as also in dilute acids and alkalies.
In concentrated sulphuric acid it dissolves with a violet colour; on adding water
there is first produced a crimson solution, and, after some time, a flocculent
precipitate.
The new binitroderivative cannot be sulphonated, in contradistinction to the
non-nitrated oxazine of Patent 11848 of 25th July 1889, the condensation product
from nitrosodialkylanilin and tanninanilide. On the other hand a bisulphite
compound soluble in water can be produced if 5 parts of the nitrooxazine derivative,
20 parts of alcohol, and 20 parts of a 40 p.c. bisulphite solution are heated for some
time on the water bath.
The bisulphite compound separates after a short time as a lustrous green
crystalline mass and dyes mordanted cotton in violet to blue tints.
Analogous to the oxazine of the English Patent 11848 of 1889, it is easy to
introduce a molecule of aniline into the nucleus of the new binitrobody, if it be
heated for some time on the water bath with an excess of aniline. The reaction
product forms a crystalline powder with bronze lustre that is slightly or hardly
soluble in hot water and alcohol; it is soluble in concentrated sulphuric acid with a
claret colour, which turns a red brown on the addition of water.
The anilidised body can be easily converted into a sulphoacid if it is heated for
some time on a water-bath with from 3 to 4 times its weight of a 95 p.c. sulphuric
acid.
On pouring into water, the new sulpho acid separates as a brown mass; it is
separated by filtration and converted into the ammonia or soda salt.
These salts dissolve readily in water with a blue-green colour and dye chromed
wool in bright green tiuts; the tint on unmordanted wool is greenish blue.
The constitution of this new colouring matter probably corresponds to the
following formula ;

page_text: For preparing this colouring matter the following method is employed:
21 parts of the hydrochlorate salt of the reaction product of nitrosodiethyl-
aniline hydrochlorate er diethylamido azobenzol-hydrochlorate on gallamic acid
are dissolved in about 1 litre of hot water; 2 litres of alcohol are added, after
which an aqueous solution of 5.3 parts of carbonate of soda and then the alcoholic
solution of 10 parts of binitro benzol chloride C,H,CINO,NO₂. 1. 2. 4. are added.
The mixture is heated on the waterbath for about three hours; after this time the
reaction will be completed in an approximately quantitative manner, and the new
body is separated as a crystalline mass of a cantharide green colour, it is filtered
pressed and dried.
10 parts of the binitrodody are stirred into 20 parts of anilin and the mixture is
then heated for about half an hour on the water bath. After cooling, the new
body separates as gold lustrous laminæ. It is filtered, washed with alcohol for
removing the anilin, and dried.
10 parts of the anilidised binitrobody are entered into 40 parts of a 95 p.c.
sulphuric acid and this is heated for a short time to about 90°, until a sample is
soluble in alkali. The mass is then poured into water, the sulphoacid is filtered off
and is converted into the ammonia or soda salt.
In the above example the binitrobenzol-chloride can be replaced by picryl-
chloride, whereby the trinitro derivative will be obtained.
The said reactions can also be carried out in the reversed order, that is, the
reaction product of nitroso dialkylanilin-hydrochlorate or dialkyl-amidoazo-benzol-
hydrochlorate on gallamic acid can be first auilidised, afterwards the anilide
compound can be condensed with binitro benzol chloride or picrylchloride, and the
reaction product thus produced be converted into sulpho acid.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, declare that what [
claim is :-
1. Manufacture of green oxazine colouring matters dyeing with mordant, by
nitrating the sulphoacid of the anilidised condensation product of nitroso dialkyl-
anilin-hydrochlorate with tannin auilide, substantially as described.
2. Manufacture of nitrated oxazine colouring matters by the reaction of binitro-
benzol chloride 4. 2. 1 or picryl-chloride, upon the condensation products of
gallamic acid with dialkylamidoazo-benzol hydrochlorate or nitroso dialkylauilin-
hydrochlorate substantially as described.
3. The conversion of the nitrobodies obtained as set forth in the second claim
into anilide compounds by heating them with anilin, substantially as described.
4. The conversion of the nitrobodies obtained as set forth in the second claim
into bisulphite compounds by heating them with a bisulphite solution substantially
as described.
5. The production of nitrated oxazine colouring matters by the reaction of
binitrobenzolchloride 4. 2. 1 or of picryl-chloride upon the abilidised condensation
product of gallamic acid with dialkylamidoazobenzol-hydrochlorate or nitroso-
dialkyl anilin hydrochlorate, substantially as described.
6. The conversion of the anilide compounds obtained as set forth in the third
and fifth claims, into sulpho acids by heating the same with sulphuric acid and
eventual conversion of the sulpho acids obtained into their ammonia or soda salts,
substantially as described.
7. As new commercial products, the colouring matters obtained as set forth in
the first, fourth, and sixth claims.
8. As new products applicable for the production of colouring matters, the bodies
obtained as set forth in the second, third, and fifth claims.
Dated this 27th day of December 1895
ABEL & IMRAY,
Agents for the Applicant.