Improvements in the Manufacture of Azo-colouring Matters.
Year: 1892

page_text: Date of Application, 4th Nov., 1892
Complete Specification Left, 4th Aug., 1893-Accepted, 16th Sept., 1893
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Azo-colouring Matters.
We, BROOKE, SIMPSON & SPILLER, LIMITED, of Atlas Works, Hackney
Wick, in the County of Middlesex, Aniline Dye Manufacturers, and ARTHUR
GEORGE GREEN, F.I.C., F.C.S., Chemist to the said Firm of Brooke, Simpson
and Spiller, Limited, of Atlas Works, Hackney Wick, aforesaid, do hereby declare
the nature of this invention to be as follows:-
This invention relates to the manufacture of colouring-matters, which dye wool
bright shades of scarlet from an acid bath, and are remarkable for their extreme
fastness to milling and scouring, which renders them available for various purposes
for which the azo-scarlets have up to the present been inapplicable.
We obtain these colours by combining the tetrazo compounds of azoxyaniline
(melting point 145° C.); azoxyorthotoluidine (melting point 168° C.); azoxyortho-
toluidine (melting point 148° C.); azoxyparatoluidine (melting point 148° C.);
azoxymetaxylidine (melting point 143° C.); azoaniline; azoorthotoluidine (melting
point 203° C.); azoorthotoluidine (melting point 175° C.); or azoparatoluidine
(melting point 159° C.); with 1 molecule of alpha-naphthol-para-sulphonic acid
(corresponding to Piria's naphthionic acid) and 1 molecule of beta naphthol. The
combination with the alpha-naphthol-para-sulphonic acid takes place in slightly
acid solution, an intermediate compound being formed which still contains a diazo
group; on adding an alkaline solution of beta-naplithol, further combination takes
place and the colour is produced. The colours being very sparingly soluble, separate
completely from the solution.
The following instance may be given as an example of the method of carrying
out our invention :-
A solution of 14 lbs. of sodium nitrite (96%) in 20 galls. of water, is added
gradually to an iced solution of 25 lbs. of azoxyorthotoluidine, of melting
point 168° C., dissolved in 100 gals. of water containing 4 gallons of hydrochloric
acid (31%). The solution of the tetrazo compound, thus obtained, is then added
to a solution of 25 lbs. of sodium alpha-naphthol-para-sulphonate and about 20 lbs.
of crystallised sodium acetate, in 100 gals. of water. A solution of 14 lbs. of betя-
naphthol, in 30 gals. of water, containing 10 lbs. of caustic soda, is then run in.
When the combination is complete, the colour is filtered off and dried, or is brought
into commerce in the form of paste. It dyes wool a brilliant scarlet, of about
RR shade,.from a boiling acid bath.
The process is substantially the same, if any other of the above mentioned azoxy-
and azo-bases is employed, the quantities used being in proportion to the molecular
weight. The shade of the colour obtained is about the same from the azoortho-
toluidine (melting point 203° C.), as from the azoxyorthotoluidine (melting
point 168 C.); whilst from the azoxyaniline, azoaniline, azoxyorthotoluidine
(melting point 148° C.), azoorthotoluidine (melting point 175° C.), azoxypara-
toluidine (melting point 148° C.), and azoparatoluidine (melting point 159° C.),
yellow shades of scarlet are obtained. On the other hand azoxymetaxylidine
(melting point 143º C.) gives a bluer scarlet.
Dated the 4th day of November 1892.
AMBROSE MYALL,
21, Cockspur Street, London, S.W., Agent for the Applicants.

page_text: COMPLETE SPECIFICATION.
Improvements in the Manufacture of Azo-colouring Matters.
We, BROOKE, SIMPSON AND SPILLER, LIMITED, of Atlas Works, Hackney
Wick, in the County of Middlesex, Aniline Dye Manufacturers, and ARTHUR
GEORGE GREEN, F.I.C., F.C.S., Chemist to the said Firm of Brooke, Simpson
and Spiller, Limited, of Atlas Works, Hackney Wick, aforesaid, 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 manufacture of colouring matters, which dye wool
bright shades of scarlet from an acid bath, and are remarkable for extreme fastness
to milling and scouring, which renders them available for various purposes for
which the azo-scarlets have up to the present been inapplicable.
We obtain these colours by combining the tetrazo compounds of, either azoxy-
aniline (melting point 145° C.); azoxyorthotoluidine (melting point 168° C.);
azoxyorthotoluidine (melting point 148° C.); azoxyparatoluidine (melting point
148° C.); azoxymetaxylidine (melting point 1430 C.); azoaniline; azoortho-
toluidine (melting point 203° C.); azoorthotoluidine (melting point 175° C.); or
azoparatoluidine (melting point 159°) with one molecule of alpha-naphthol-para-
sulphonic acid (corresponding to Piria's naphthionic acid) and one molecule of
beta-naphthol. The combination with the alpha-naphthol-para-sulphonic acid
takes place in slightly acid solution, an intermediate compound being formed, which
still contains a diazo group, on adding an alkaline solution of beta-naphthol, further
combination takes place and the colour is produced. The colours being very
sparingly soluble, separate completely from the solution.
The following instance may be given as an example of the method of carrying
out our invention.
A solution of 14 lbs. of sodium nitrite (96%) in 20 gals. of water, is added
gradually to an iced solution of 25 lbs. of azoxyorthotoluidine, of melting point
168° C., dissolved in 100 gals. of water containing 4 gals. of hydrochloric acid
(31%). The solution of the tetrazo compound, thus obtained, is then added to a
solution of 25 lbs. of sodium alpha-naphthol-para-sulphonate and about 20 lbs. of
crystallised sodium acetate in 100 gals. of water. A solution of 14 lbs. of beta-
naphthol in 30 gals. of water, containing 10 lbs. of caustic soda, is then run in.
When the combination is complete, the colour is filtered off and dried, or is brought
into commerce in the form of paste. It dyes wool a brilliant scarlet from a boiling
acid bath.
The process is substantially the same, if any other of the above mentioned azoxy
and azo bases is employed, the quantities used being in proportion to the respective
molecular weights. The shade of the colour obtained is about the same from the
azoorthotoluidine (melting point 203° C.) as from the azoxyorthotoluidine (melting
point 168° C.), whilst from the azoxyaniline, azoaniline, azoxyorthotoluidine
(melting point 148° C.), azoorthotoluidine (melting point 175° C.), azoxypara-
toluidine (melting point 148° C.) and azoparatoluidine (melting point 159° C.),
yellow shades of scarlet are obtained. On the other hand, azoxymetaxylidine
(melting point 143° C.), gives a bluer scarlet.
Having now particularly described and ascertained the nature of our said inven-
tion, and in what manner the same is to be performed, we declare that what we
claim, is:-
1. The herein described process for the preparation of a colouring matter, con-
sisting in the combination of the tetrazo compounds of, either azoxyaniline (melting
point 145° C.); azoxyorthotoluidine (melting point 168° C.); azoxyorthotoluidine

page_text: (melting point 148° C.); azoxyparatoluidine (melting point 148° C.); azoxymeta-
xylidine (melting point 143° C.); azoaniline; azoorthotoluidine (melting point
203° C.); azoorthotoluidine (melting point 175° C.); or azoparatoluidine (melting
point 159° C.); with one molecule of alpha-naphthol-para-sulphonic acid and one
molecule of beta-naphthol, and finally separating the colouring matter, substantially
as described.
2. As new articles of manufacture, colouring matters derived from, either azoxy-
auiline (melting point 145° C.); azoxyorthotoluidine (melting point 168° C.);
azoxyorthotoluidine (melting point 148° C.); azoxyparatoluidine (melting point
148° C.); azoxymetaxylidine (melting point 143° C.); azoaniline; azoortho-
toluidine (melting point 203° C.); azoorthotoluidine (melting point 175° C.); or
azoparatoluidine (melting point 159° C.); by conjoint combination with alpha-
naphthol-para-sulphonic acid and beta-naphthol, substantially as described.
Dated this 4th day of August 1893.
AMBROSE MYALL,
2, Lancaster Place, Strand, London, W.C., Agent for the Applicants.