Improvements in the Manufacture and Production of Colouring Matters.
Year: 1890

page_text: Date of Application, 27th May, 1890
Complete Specification Left, 9th Feb., 1891-Accepted, 14th Mar., 1891
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture and Production of Colouring
Matters.
I, JOHN HALL, of Clayton, near Manchester, in the County of Lancaster,
Chemist, do hereby declare the nature of this invention to be as follows:-
I have found that the diazo-compounds of dehydro-thio-para-toluidine and of its
sulphonic acid combine with
(a) The diamido-azo-compounds obtained by the action of diazo-benzole-chloride
or its sulphonic acid or the homologues of these bodies or of the diazo naphthalene
chlorides or sulphonic acids on meta-phenylene-diamine or meta-toluylene diamine.
(b) The dioxyazo compounds obtained by the action of the diazo derivatives.
mentioned under the foregoing clause (a) on resorcin and
(c) With triamido azo compounds such as the Bismark Browns yielding brown
combinations and also that very similar compounds can be obtained by combining
the diazo compounds of dehydro-thio-paratoluidene and of its sulphonic acid with
meta phenylene-diamine or meta toluylene-diamine and then adding to the product
of the diazo compounds referred to under the foregoing clause (a).
any
Most of the new combinations are soluble in alkaline water. The insoluble ones
are converted into sulphonic acids by treating with fuming sulphuric acid until the
product is soluble in alkaline water.
To illustrate my invention I give the following (the parts being by weight) but I
do not limit myself to the following precise details.
10 parts of crystallized naphthionate of sodium are dissolved in 200 parts of
water and 8 to 9. parts of hydrochloric acid are added and after stirring say for a
few minutes a solution of 44 parts of sodium nitrite in 15 parts of water is slowly
run in, stirring the whole time of mixing and for say about an hour after. Then
the whole is, run into a solution of 5-7 parts of meta phenylene diamine hydro-
chloride in 200 parts of water mixed with 12 parts of caustic soda solution of
75° Twaddle. After stirring for about 24 hours the diazo compound of dehydro-
thio-paratoluidine sulphonic acid suspended in water is added. It may be prepared
as follows:-11 parts of the sodium salt of dehydro-thio-para-toluidine sulphonic
acid and 25 parts of sodium nitrite are dissolved in 200 parts of water and run into
40 parts of water mixed with 9 parts of hydrochloric acid and stirred for say an
hour or thereabouts and then added to the previously obtained liquid as hereinbefore
mentioned. After about 24 hours the whole is warmed and on cooling the colouring
matter is salted out filtered pressed and dried.
The diazo compound of dehydro-thio-para-toluidine sulphonic acid may be run
into the alkaline meta phenylene diamine solution and after stirring for say 24 hours
the diazo compound of naphthionic acid is added, the whole stirred for some hours
and boiled and on cooling salted out filtered pressed and dried.
Deted this 27th day of Mov 1890
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.

page_text: COMPLETE SPECIFICATION.
Improvements in the Manufacture and Production of Colouring
Matters.
I, JOHN HALL, of Clayton, near Manchester, in the County of Lancaster,
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 :-
I have found that the diazo-compounds of dehydro-thio-para-toluidine and of its
sulphonic acid combine with :-(a) the diamido-azo compounds obtained by the
action of diazo-benzole-chloride or its sulphonic acid or the homologues of these
bodies or of the diazo-naphthalene chlorides or sulphonic acids thereof or diazo-azo-
benzol chloride or sulphonic acids thereof or the homologues of these bodies or
diazo-azo-naphthalene chlorides or sulphonic acids thereof on meta-phenylene-
diamine or meta toluylene-diamine-(b) the dioxyazo compounds obtained by the
action of the diazo derivatives mentioned under the foregoing clause a on resorcin
and (c) with triamido-azo compounds of the Bismark Brown series yielding brown
combinations and also (d) that very similar compounds can be obtained by com-
bining the diazo-compounds of dehydro-thio-para-toluidine and of its sulphonic
acid with meta-phenylene-diamine or meta toluylene-diamine and then adding to
the product either or any of the diazo compounds referred to under the foregoing
clause a.
Most of the new combinations are soluble in alkaline water. The insoluble
ones are converted into sulphonic acids by treating with fuming sulphuric acid until
the product is soluble in alkaline water.
To illustrate my invention I give the following examples (the parts being by
weight) but I do not limit myself to the following precise details.
1
(I) 10 parts of crystallized naphthionate of sodium are dissolved in 200 parts of
water and 8 to 9 parts of hydrochloric acid are added and after stirring say for a
few minutes a solution of 4.4 parts of sodium nitrite in 15 parts of water is slowly
run in, stirring the whole time of mixing, and say for about an hour after. Then the
whole is run into a solution of 5-7 parts of meta-phenylene-diamine hydro-chloride
in 200 parts of water mixed with 12 parts of caustic soda solution of 75° Twaddle.
After stirring for about 24 hours the diazo compound of dehydro thio-paratoluidinc
sulphonic acid suspended in water is added. It may be prepared as follows.
11 parts of the sodium salt of dehydro-thio-para-toluidine sulphonic acid and
2.5 parts of sodium nitrite are dissolved in 200 parts of water and run into 40 parts
of water mixed with 9 parts of hydrochloric acid and stirred for say an hour or
thereabouts and then added to the previously obtained liquid as hereinbefore
mentioned. After about 24 hours the whole is warmed and on cooling the colouring
matter is salted out, filtered, pressed and dried.
The colouring matter so obtained dyes unmordanted cotton a fine red shade of
brown.
II. Or the diazo compound of dehydro-thio-para-toluidine sulphonic acid may
be run into the alkaline meta-phenylene diamine solution and after stirring for say
24 hours the diazo compound of naphthionic acid is added, the whole stirred for
some hours and boiled and on cooling salted out, filtered, pressed, and dried.
If the diazonaphthalene sulphonic acid derived from the naphthionic acid of the
above examples be replaced by: an equivalent weight of any of the diazo compounds
mentioned under clause a other shades of brown are obtained. Thus by replacing
the 10 parts of naphthionate of sodium in Example I. by 3.1 parts of aniline and
proceeding otherwise as therein described a yellower shade of brown is obtained
whilst by using 155 parts of the amido-azo naphthalene disulphonic acid (derived
naphthionic acid) instead of the 10 parts of naphthionate of sodium a darker shade
of brown is produced. Further if the 5-7 parts of meta-phenylene-diamine-hydro-
chloride be replaced by 6.1 parts of meta toluylene-diamine-hydrochloride darker

page_text: shades are obtained. If 34 parts of resorcin be used instead of the phenylene diamine
hydro-chloride much yellower shades are obtained.
Having now particularly described and ascertained the nature of my said
invention, and in what manner the same is to be performed, I declare that what
I claim is :-
1. The manufacture of colouring matters by combining meta-phenylene-diamine
or meta-toluylene-diamine or resorcin with two diazo-compounds one of which is
derived from dehydro-thio-para-toluidine or its sulphonic acid and the other from
an aromatic amido compound or amido-azo compound or amido- or amido-azo
sulphonic acid.
2. The manufacture of colouring matters by combining diazo-compounds of
dehydro-thio-para-toluidine or its sulphonic acid with di-amido-azo compounds
obtained as described under clause a or with dioxy-azo-compounds obtained by the
action of the diazo derivatives named under clause a on resorcin or with triamido
azo compounds of the Bismark Brown series or with meta-phenylene diamine or
meta-toluylene-diamine and also with either or any of the diazo compounds referred
to under clause a.
3. The preparation of colouring matters as herein before described under the
Examples I. and II.
4. As new articles of manufacture the products obtained according to either of
the preceding claiming clauses.
1001
J. HALL.