Manufacture of New Colouring Matters from Benzidine Sulpho-acids.
Year: 1897

page_text: Date of Application, 15th Jan., 1897-Accepted, 27th Mar., 1897
COMPLETE SPECIFICATION.
Manufacture of New Colouring Matters from Benzidine
Sulpho-acids.
I, HAROLD IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in
the County of London, Chartered Patent Agent, do hereby declare the nature of
this invention (which has been communicated to me from abroad by the Firm of
Ferd. Petersen & Co., of Schweizerhalle, near Basle, Switzerland, Chemical
Manufacturers) and in what manner the same is to be performed to be particularly
described and ascertained in and by the following statement :-
For the production of polyazo colouring matters according to the Specification
to my Patent No. 13743/96 serve intermediate bodies of the composition :-
(In this constitution formula a sulpho-group has been bracketed because the
properties of the Griess' benzidine sulpho-acid which is easily soluble in hydro-
chloric acid, point to the assumption of a mono-sulpho acid.)
My correspondents have discovered that if in these intermediate bodies one or
both molecules of amidonaphtholsulpho acid y be replaced by one or by two molecules
5 amidonaphtholdisulpho acid H, that is to say, if intermediate products of the
composition :—

page_text: are formed, valuable polyazo colouring matters can also be obtained therefrom.
It has furthermore been found that intermediate bodies which are produced by
the combination of the Griess' benzidine-sulpho acids with one molecule of one of 5
the above mentioned amidonaphtholsulpho-acids and one molecule of an amine or
of a phenol, yield polyazo colouring matters which have very great affinity for
vegetable fibres.
The last named intermediate bodies have the composition :—
in which R₁ signifies an aromatic amine, or a phenol such as aniline, toluidine,
a- or 3-naphthylamine,_ metaphenylenediamine, metatoluylenediamine, ordinary
phenol, resorcine, a- or 3-naphthol.
By the reaction of the developing agent mentioned in the Specification to

page_text: Patent 13743/96 (aniline, o- or p-toluidine, metaphenylenediamine metatoluylene-
diamine, resorcine, phenol, a naphthylamine, ẞ naphthylamine, naphthionate,
a- or 3-naphthol, R salt & a-oxynaphthoic acid) upon the tetrazo derivatives of
the intermediate bodies represented by the formulæ I and II, there are obtained
polyazo colouring matters which are mainly suited for dyeing wool or halfwool
and similar fibres, giving tints which are distinguished by peculiar bluish hues.
These colouring matters are produced as black powders which are very readily
soluble in cold and hot water, and are slowly precipitated from their dilute solutions
by the addition of acids.
By means of the second above named intermediate bodies, namely those
represented by formulæ III and IV, there are obtained, by farther diazotising the
same, and combining the obtained tetrazo or diazo bodies with the above mentioned
developing agents, polyazo colouring matters that possess great affinity for vegetable
fibres and which produce on cotton blue-black to brown-black tints that are fast to
light and washing.
These colouring matters are formed as black powders which dissolve in concen-
trated sulphuric acid with a blue green to blue violet colour; on diluting their
solutions in sulphuric acid with water, brown precipitates are obtained. They
dissolve better in hot than in cold water, with a red-brown to red-violet colour.
In alcohol they are nearly insoluble. On the addition of hydrochloric acid to the
aqueous solution there are produced blue- to brown-black precipitates. If caustic
endo be added to the raueous solution he prominitates are obtained
.
EXAMPLE 111.
A quantity of Griess' benzidine-sulpho acid corresponding to a 10 kilo. nitrite is
diazotised, and the mass containing the tetrazo-derivative produced is rendered
alkaline and added to a solution of 17 kilo. y amidonaphthol-sulpho acid and 13 kilo.
calcined soda; immediately afterwards a solution of 22 kilo. a-naphthylamine in
44 kilo. hydrochloric acid of 19° Bé. and 1,100 litres water is added.
The combination takes place slowly.
After about 12 hours the liquid containing the intermediate product is rendered
alkaline, after which 10 kilo. nitrite are added to the obtained solution of the
intermediate product, and is well stirred up therewith, and lastly the mixture
obtained is poured into a solution of hydrochloric acid and ice.

page_text: After two hours there are added to the weakly acid solution 26 kilo. m-toluylene-
diamine, and it is then immediately rendered alkaline.
After standing for some time the colouring matter solution is boiled and the
colouring matter is separated in the usual manner. It constitutes a black powder,
dyes unmordanted cotton a deep black and is fast against light and washing.
It dissolves in hot water better than in cold, with a violet colour.
When hydrochloric acid is added, the aqueous solution of the colouring matter
gives a brown precipitate, and with caustic soda a dark red brown one.. In alcohol
the colouring matter is insoluble; in concentrated sulphuric acid it dissolves with a
blue colour, and it is precipitated from this solution with water as a brown-black
precipitate.
The intermediate products indicated by the formulæ I, II, III, and IV represent
tetrazo colouring matters which can be employed directly as such, that is to say,
without previous conversion into polyazo colouring matters. They dye unmordanted
cotton or wool from a red-brown or blue-brown to violet-black or black. These
tetrazo colouring matters can also be farther diazotised on the fibre and be combined
with developing agents.
.
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. Manufacture of new tetrazo colouring matters by the combination of one
-molecule of the tetrazo derivatives of the Griess' benzidine-sulpho acids with :
ay
2 molecules amidnaphtholdisulpho acid H or :
b, 1 molecule amidonaphtholdisulpho acid H and 1 molecule y-amidonaphthol-
sulpho acid, or :
c, 1 molecule amidonaphtholdisulpho acid H or y-amidonaphtholsulpho acid
and 1 molecule of an aromatic amine such as aniline, toluidine, a- or
B-naphthylamine, meta-phenylenediamine, or meta-toluylenediamine; or:
d, 1 molecule amidonaphtholdisulpho acid H, or y-amidonaphtholsulpho acid
and 1 molecule of a phenol such as resorcine, ordinary phenol, a or
ẞ naphthol.
2. Manufacture of new polyazo colouring matters by diazotising the tetrazo
colouring matters obtained according to (a), (b) or (c) of the first claim, and then
combining the thus formed tetrazo bodies, whether in solution or on the fibre, with
two of the same or different molecules of the following developers: aniline,
o or p-toluidine, metaphenylenediamine metatoluylenediamine, resorcine, phenol
a-naphthylamine, ẞ naphthylamine, naphthionate, a or ẞ naphthol, R salt and
a-oxynaphthoic acid.
3. Manufacture of new polyazo colouring matters by diazotising the tetrazo
colouring matters obtained according to (d) of the first claim and then combining
the diazobodies thus formed, whether in solution or on the fibre, with one molecule
of either of the following developers: aniline o- or p-toluidine, metaphenylene-
diamine metatoluylenediamine, resorcine phenol, a-naphthylamine, 3-naphthylamine,
naphthionate, a or ẞ naphthol R-salt and a oxynaphthoic acid.
4. As new industrial products, the colouring matters obtained according to the
1st 2nd and 3rd claims.
Dated this 15th day of January 1897
ABEL & IMRAY,
Agents for the Applicant.