Manufacture of Blue Colouring Matter.
Year: 1889

page_text: Date of Application, 25th July, 1889
Complete Specification Left, 22nd Mar., 1890-Accepted, 26th Apr., 1890
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE SOCIETY OF CHEMICAL INDUSTRY IN BASLE, of
Basle, Switzerland, Chemical Manufacturers.]
Manufacture of Blue Colouring Matter.
I, OLIVER IMRAY of No. 28 Southampton Buildings Chancery Lane in the County
of London, Fellow of the Institute of Patent Agents do hereby declare the nature
of this invention to be as follows:-
This invention relates to the production of a blue colouring matter from the hydro-
chloride of nitrosodimethylaniline and the crystallized condensation product obtained
from tannin with aniline.
Tannin heated for several hours with aniline produces (as described by H. Schiff,
Ber. d. deutsch. chem. Gesellsch. Bd. XV 7591) a substance which crystallizes easily.
Also the homologues: ortho- and para-toluidine and the technic xylidine, condensed
with tannin produce similar condensation products.
The constitution of these products is not yet ascertained, they seem to be anilid
combinations of the tannin.
If these condensation products, dissolved in boiling alcohol, are submitted to the
action of hydrochloride of nitrosodimethylaniline, blue colouring matters crystallize
out of the product of the reaction. These blue colouring matters (which are soluble
in alcohol) when heated with bisulphite of soda and alcohol, are transformed into
combinations which are soluble in water and crystallize in small light-green
needles.
These bisulphite combinations are nearly insoluble in cold water, but easily
soluble in warm water. With the aid of tannin, alum, or chrome-mordant they dye
cotton in shades from a brilliant blue to blue-violet. Used for printing on cotton
with alum- or chrome-mordant they produce blue shades.
EXAMPLE OF THE PROCESS.
1 Kilo. of the condensation product of tannin with aniline.
1. Kilo. of hydrochloride of nitrosodimethylaniline with 10 Kilos. of alcohol, or other
diluting agents (such as acetic acid, or water) are heated up to boiling until no intact
nitroso combination is left.
The brownish mass is filtered and washed with alcohol until the latter shows a pure
blue colour.
The colouring matter, a brilliant olive-green crystalline powder, remains in the
filter; it distinguishes itself from the products derived from gallic acid and nitroso
substances such as gallocyanine, prune &c., by its insolubility in water and alkalies.
Diluted acids dissolve it but little and produce a red colour.
In concentrated sulphuric acid it dissolves with a blue-violet shade. If this
solution is diluted with water the colouring matter precipitates in form of dark violet
flakes.
By recrystallization of the colouring matters from aniline a product of a copper-
coloured lustre is obtained; in concentrated sulphuric acid this product gives a
cherry-coloured solution, not a blue one.
By sulphurating the colouring matter at a low temperature with fuming sulphuric
acid of 24 per cent., a sulpho acid is obtained, the ammonia salt of which is soluble in
water and produces a pure blue shade.
Wool is dyed in an acidulated bath in shades similar to induline.

page_text: For rendering the colouring matter soluble in water the following method may be
adopted:
5 parts of colouring matter.
20
20
time.
در
"
99. "
alcohol.
a solution (40 per cent.) of bisulphite of soda are heated for some
The mass, at first of a dark colour, changes into a magma of light green
crystals. Diluted with water, filtered and pressed, it is ready for use in form of a
paste.
Combinations of like character are obtained if, instead of aniline, ortho- or para-
toluidine or xylidine are submitted to the action of tannin.
Also for the nitrosodimethylaniline can be substituted the uitroso-derivatives of
diethylaniline, of methylethylaniline or of chinondichloridümide.
But the products thus obtained do not present any advantages over the derivative
of nitrosodimethylaniline as described in the above example.
11
T
1000
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of Blue Colouring Matter.
I, OLIVER IMRAY of No. 28 Southampton Buildings, Chancery Lane in the County
of London, Fellow of the Institute of Patent Agents 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 relates to the production of a blue colouring matter from the hydro-
chlorate of nitrosodimethylaniline and the crystallized condensation product obtained
from tannin with aniline.
Tannin heated for several hours with aniline produces (as described by H. Schiff,
Ber. d. deutsch. chem. Gesellsch. Bd. XV 7591) a substance which crystallizes easily.
Also the homologues: ortho- and para-toluidine and the technic xylidine, condensed
with tannin produce similar condensation products.
The constitution of these products is not yet ascertained, they seem to be anilid
combinations of the tannin.
If these condensation products, dissolved in boiling alcohol, are submitted to the
action of hydrochlorate of nitrosodimethylaniline, blue colouring matters crystallize
out of the product of the reaction. These blue colouring matters (which are soluble
in alcohol) when heated with bisulphite of soda and alcohol, are transformed into
combinations which are soluble in water and crystallize in small light-green
needles.
These bisulphite combinations are nearly insoluble in cold water, but easily soluble
in warm water. With the aid of tannin, alum, or chrome mordant they dye cotton
is shades from a brilliant blue to blue-violet. Used for printing on cotton with alum-
or chrome-mordant they produce blue shades.
EXAMPLE OF THE PROCESS.
1 Kilo. of the condensation product of tannin with aniline.
1 Kilo. of the condensation product of tannin with aniline.
1 Kilo. of hydrochlorate of nitrosodimethylaniline with 10 Kilos of alcohol, or
other diluting agents (such as acetic acid, or water) are heated up to boiling until no
intact nitroso combination is left.
The brownish mass is filtered and washed with alcohol until the latter shews a pure
blue colour.
The colouring matter, a brilliant olive-green crystalline powder, remains in the
filter; it distinguishes itself from the products derived from gallic acid and nitroso

page_text: substances such as gallocyanine and prune &c., by its insolubility in water and
alkalies. Diluted acids dissolve it but little and produce a red colour.
In concentrated sulphuric acid it dissolves with a blue violet shade. If this
solution is diluted with water the colouring matter precipitates in form of dark violet
flakes.
By recrystallization of the colouring matters from aniline a product of a copper-
coloured lustre is obtained; in concentrated sulphuric acid this product gives a
cherry-coloured solution, not a blue one.
By sulphurating the colouring matter at a low temperature with fuming sulphuric
acid of 24 per cent.; a sulpho acid is obtained, the ammonia salt of which is soluble in
water and produces a pure blue shade.
Wool is dyed in an acidulated bath in shades similar to induline.
For rendering the colouring matter soluble in water the following method may be
adopted.
5 parts of colouring matter.
20
20
time.
>>
"
"
"
alcohol.
a solution (40 per cent.) of bisulphite of soda are heated for some
The mass, at first of a dark colour, changes into a magma of light green crystals.
Diluted with water filtered and pressed, it is ready for use in forin of a paste.
Combinations of like character are obtained if, instead of the aniline, ortho- or para-
toluidine or xylidine are submitted to the action of tannin. Also for the nitroso-
dimethylaniline can be substituted the nitroso-derivatives of diethylaniline, of
methylethylaniline or of chinondichloridümide. But the products thus obtained do
not present any advantages over the derivative of nitrosodimethylaniline as described
in the above example.
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 manufacture of blue colouring matter by treating anilid condensation
products of tannin with hydrochlorate of nitrosodimethylaniline or of its analogues,
substantially as described.
2. The colouring matters produced in the manner referred to in the preceding
claim.
.
1000