Manufacture of New Colouring Matters from Oxazines.
Year: 1898

page_text: Date of Application, 11th Mar., 1898-Accepted, 30th Apr., 1898 ed
Manufacture of New Colouring Matters from Oxazines.
I, JOHN IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, Chancery
Lane, in the County of London, Consulting Engineer and Chartered Patent Agent,
do, hereby declare the nature of this invention (which has been communicated to
me from abroad by La Société L. Durand, Huguenin et Cie., Manufacturers, St..
Fons, Rhône, France) and in what manner the same is to be performed to
be particularly described and ascertained in and by the following statement :-
"My foreign correspondents have discovered that new and valuable colouring:
matters can be obtained by treating oxazines with free or combined sulphurous
acid in a suitable medium.
«
"This fact is the more unexpected because two colouring matters are already known
in commerce which are obtained by the action of sodium bisulphite on gallo
cyanines, to wit the "violet solide B.S." of Messrs. L. Durand, Huguenin et Cie. and
gallamine blue" of Messrs. T. R. Geigy et Cie. The former of these colouring
matters is obtained from the ordinary gallocyanine resulting from the action of
nitroso-dimethyl-aniline hydrochloride on gallic acid, and the latter from the
gallamine blue resulting from the action of nitrosodimethylaniline hydrochloride-on
gallamic acid.
My foreign correspondents have obtained by their process new colouring matters
both from the ordinary gallocyanine and gallamine blue mentioned above and
from other oxazines and gallocyanines. Thus the violet solide B.S. or the
bisulphite compound of ordinary gallocyanine is a blue violet liquid giving a violet
shade when used for dyeing or printing, while the new product obtained from this
same gallocyanine is a paste which is but slightly coloured and gives a pure blue
shade when used for dyeing and printing. The gallamine blue bisulphite compound
is a grey paste giving a violet shade when used in dyeing and printing, while
the new product obtained from the same gallamine blue is a brownish paste yielding
a blue shade when used for dyeing and printing. These new blue colouring matters
are characterised not only by their distinct appearance and by the fact that they
yield bluer and purer shades than do the oxazines from which they are prepared,
but also by their greater dyeing power; they may be applied on metallic
mordants, particularly chrome mordants, both to cotton and wool for printing and
dyeing.
"All these colours are obtained as leuco-derivatives yielding in strong sulphuric
acid solutions which have comparatively little colour and are dichroic, changing
from yellowish green to wine red; oxidizing agents produce an intense blue
colour.
. I
.
These leuco-derivatives are easily oxidized by air; in the presence of alkalies the
oxidation is almost instantaneous. The oxidation products are different from : the
nement overines

page_text: The process for obtaining these new colouring matters consists in heating
the oxazines under pressure and with exclusion of air in a closed vessel, preferably
an enamelled or lead lined autoclave, with a solution of sulphurous acid or of an
acid or normal sulphite of an alkali, an alkaline earth or another metal. Obviously,
a solution of a sulphite or bisulphite acidified with an acid such as bydrochloric
acid or sulphuric acid may be substituted for a solution of sulphurous acid. So
also sulphuric or hydrochloric acid may be added after treatment with a bisulphite
or sulphite, in order to effect the reaction; a different result is obtained, however,
accordingly as the hydrochloric acid or sulphuric acid is added before or after the
treatment with the sulphite..
COLOURING MATTERS PREPARED FROM THE OXAZINE OBTAINED BY THE ACTION OF
NITROSODIMETHYLANILINE HYDROCHLORIDE ON GALLIC ACID (ORDINARY -GALLO-
CYANINE).
a) About 20 kilos. of ordinary gallocyanine, 100 kilos. of distilled water and
25 kilos. of normal sodium sulphite are heated together for some hours, 4 or 5 hours
for example, at a temperature of 100° C. under pressure in an autoclave, the
mixture being stirred during the process. The leuco-derivative obtained, when
used for dyeing and printing, yields on chrome mordanted wool shades which are
blucr and brighter, and on chrome mordanted cotton shades which are bluer, than
those yielded by the ordinary gallocyanine bisulphite compound (gallo-
cyanine B.S.).
b) About 20 kilos. of ordinary gallocyanine, 100 kilos. of distilled water, and
18 kilos. of sodium bisulphite solution (40° Baumé) are heated together. under the
conditions described above. The leuco-derivative obtained, when used for dyeing.
and printing, yields on chrome mordanted wool shades which are much bluer, and
on chrome mordanted cotton shades which are bluer, than those produced with the
ordinary gallocyanine bisulphite compound (gallocyanine B.S.). Thus, this new
leuco-derivative yields a blue shade on chrome mordants, while gallocyanine B.S.
yields a violet shade under the same conditions.
c) About 20 kilos. of ordinary gallocyanine 100 kilos. of distilled water, 18 kilos..
of sodium bisulphite solution (40° Baumé) and 7 kilos. of pure hydrochloric acid
(30 per cent. strength) are heated together under the conditions named above.
The leuco-derivative obtained, when used in dyeing or printing, yields on chrome
mordanted wool and cotton shades which are bluer and stronger than those obtained
with the ordinary gallocyanine bisulphite compound (gallocyanine B.S.).
$
COLOURING MATTERS PREPARED FROM GALLOCYANINE D.H. OBTAINED BY THE ACTION OF
AMMONIA ON THE OXAZINE RESULTING FROM THE ACTION OF NITROSODIMETHYL-
ANILINE HYDROCHLORIDE ON GALLIC ACID.
a) The procedure is as described in Example I a except that the water is omitted
and 200 kilos. of commercial gallocyanine D.H. (paste of 10 per cent. strength) are
substituted for the 20 kilos. of ordinary gallocyanine. The leuco-derivative
obtained, when used for dyeing and printing, yields on chrome mordanted wool
and cotton shades which are stronger and brighter than those yielded by
gallocyanine B.S. (ordinary gallocyanine bisulphite compound).
.
b) The process is as described in Example I b, except that the water is omitted
and 200 kilos. of commercial gallocyanine D.H. (paste of 10 per cent. strength) are
.substituted for the 20 kilos. of ordinary gallocyanine. The leuco-derivative obtained,

page_text: when used in printing or dyeing, yields on chrome mordanted wool and cotton
brighter and more intense shades than those yielded by gallocyanine B.. (com-
mercial ordinary gallocyanine bisulphite compound).
c) The process is as described in Example I.c except that the water is omitted and
200 kilos. of commercial gallocyanine D.H. (paste of 10 per cent. strength) are
substituted for the 20 kilos. of ordinary gallocyanine. The leuco-derivative
obtained, when used for dyeing and printing, yields on chrome mordanted wool and
cotton shades which are bluer and brighter than those yielded by gallocyanine B.S.
COLOURING MATTERS
PREPARED FROM THE OXAZINE OBTAINED BY THE ACTION OF
NITROSODIMETHYLANILINE HYDROCHLORIDE ON GALLAMIC ACID (GALLAMINE BLUE
NOT COMBINED WITH BISULPHITE).
The proportions and mode of operation are the same as those described in
Example I.
a) By proceeding as in "I a there is obtained a leuco-derivative which, when used
for dyeing and printing yields on chrome mordanted wool and cotton much bluer
and brighter shades than those yielded by the commercial gallamine blue bisulphite
compound.
3
:
b) By proceeding as in Iba leuco-derivative is obtained which, when used for
dyeing and printing, yields on chrome mordanted wool and cotton bluer shades than
those yielded by the commercial gallamine blue bisulphite compound; but the blue
is somewhat less pure than that yielded by the product mentioned in III a.
c) By proceeding as described in I c a leuco-derivative is obtained, which when
used for dyeing and printing, yields. the same shades as those mentioned in III b.)
With these three leuco-derivatives of gallamine blue, blue shades are obtained on
chrome mordants, while the commercial gallamine blue bisulphite compound gives
violet shades on the same mordants. Purified commercial gallamine blue bisulphite
compound is soluble in pure water and the solution is not precipitated by 'hydro-
chloric acid, while the aqueous solution of the aforesaid purified leuco-derivatives of
gallamine blue give a flocculent yellow precipitate of a greenish-brown substance
formed by the new colouring matter.
COLOURING MATTERS PREPARED FROM THE OXAZINE OBTAINED BY THE ACTION
: OF NITROSODIMETHYLANILINE HYDROCHLORIDE ON METHYL GALLATE ( PRUNE,
PURE").
The proportions and mode of operation are the same as those described' in
Example I.
a) By proceeding as described in I a a leuco-derivative is obtained which, when
used for printing and dyeing, yields on chrome mordanted, wool and cotton shades
which are more beautiful and more intense than those yielded by commercial prune;
pure.
t
b) By proceeding as described in Ib a leuco-derivative is obtained which, when
used for printing and dyeing, yields on chrome mordanted wool and cotton stronger
shades than those yielded by commercial prune, pure.
1
:
c) By proceeding as described in Ic a leuco-derivative is obtained which, when
used for dyeing and printing, yields on chrome mordanted wood much bluer shades
and on chrome mordanted cotton much bluer and more intense shades than those
yielded by commercial prune pure.
: ་ ར
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' 7

page_text: COLOURING MATTERS
PREPARED FROM THE OXAZINE OBTAINED BY THE ACTION OF
NITROSODIETHYLANILINE HYDROCHLORIDE, OR OF DIETHYLAMIDOA ZOBENZENE HYDRO-
CHLORIDE ON GALLAMIC ACID.
: .
The proportions and mode of operation are the same as those described in
Example I
:
a) By proceeding as in I a there is obtained a leuco-derivative which, when used
for dyeing and printing, yields on chrome mordanted wool and cotton shades which
are bluer, more beautiful and stronger than those yielded by the parent oxazine, that
is to say, the condensation product from nitrosodiethylaniline hydrochloride or
diethylamidoazobene hydrochloride with gallamic acid.
b) By proceeding as described in Ib a leuco-derivative is obtained which, when
used for dyeing and printing, yields on chrome mordanted cotton shades which are
bluer, more intense and more beautiful than those yielded by the parent oxazine,
and on chrome mordanted wool bluer shades than those yielded by the parent
oxazine, but less blue than those yielded by the, product mentioned in V a.
These three colouring matters have also the advantage over the parent
oxazine that they do not stain the whites when used for dyeing on chrome"
mordanted and discharged cotton. These three leuco-derivatives yield on chrome
mordants blue, shades which are more intense and brighter than the violet shades
obtained under the same conditions with the parent oxazine.
COLOURING.MATTERS PREPARED FROM THE OXAZINE OBTAINED BY THE ACTION. OF NITRO-
SODIMETHYLANILINE HYDROCHLORIDE ON 2: 7-DIOXYNAPHTHALENE (MUSCARINE).
..
:
✓ The proportions and mode of operation are the same as those described in
Example I.
When used for dyeing and printing, the three leuco-derivatives prepared in the
manner described in I a Ib and I c respectively yield on a tannin mordant bluish
black shades, while muscarine applied under the same conditions yields violet
blue shades.
COLOURING
MATTERS PREPARED FROM THE OXAZINE OBTAINED BY THE ACTION OF
.*NITROSODIMETHYLANILINE HYDROCHLORIDE ON B-NAPHTHOL-IN ALCOHOLIC SOLUTION
(MELDOLA'S BLue).
The proportions and the mode of operation are the same as those described in
Example I.
By proceeding in the manner described in I a Ib and I c respectively leuco-deriva-
tives are obtained which, when used in dyeing and printing, yield bluish grey
shades on a tannin mordant.
:
In the foregoing examples the proportions, temperature and duration of heating
may, obviously, be varied within certain limits.
... Instead of sodium sulphite or bisulphite, sulphites or bisulphites of the other
alkalies, the alkaline earths or other metals may be used, and the reaction may be
effected in another medium instead of water, such as alcohol, methyl alcohol,
glycerine; acetic acid and the like...
..
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

page_text: 1. A process for the manufacture of new leuco-derivatives of oxazines consisting
in heating the oxazines herein named with sulphurous acid or a sulphite or a
bisulphite under pressure in a closed vessel from which air is excluded, substantially
as described.
2. The leuco-derivatives of oxazines prepared by the process referred to
in Claim 1.