Year: 1891

page_text: Date of Application, 14th Apr., 1891
Complete Specification Left, 14th Jan., 1892-Accepted, 12th Mar., 1892
[1:2:6] C,H, (CH,) (NH,) N,OC,H,(NH,)(CH,)[6 :2:1],
mistance 10ay be given
61 parts of the consecutive nitro-ortho-toluidine (melting point 92° C.) are
suspended, and partially dissolved, in 2000 parts of boiling water, and to the boiling
solution is added a cold solution of sodium stannite, obtained from 150 parts of tin
crystals (stannous chloride) and 150 parts of caustic soda. The azoxy-ortho-
toluidine, which separates on cooling, is purified by dissolving it in hydrochloric
acid, filtering, and precipitating the hydrochloride, by the addition of an excess of
hydrochloric acid.
The conversion into colouring matters is performed according to the well-known
methods used in the preparation of the azo-colours. As an instance, we may
describe the preparation of a brilliant scarlet colouring-matter, which dyes cotton
without a mordant, and is unaffected by acids.
A solution of 14 parts of sodium nitrite (98%), in 100 parts of water, is added
to an iced solution of 25 parts of the new azoxy-ortho-toluidine, and 45 parts (by
volume) of hydro-chloric acid (30% HCl) in 1000 parts of water. The solution of
the tetrazo compound, thus obtained, is now run into a solution containing 50 parts
of sodium alpha-naphthol-para-sulphonate (corresponding to Piria's naphthionic
acid) and kept alkaline by the addition of sodium carbonate. The colouring matter
is precipitated by the addition of salt, filtered off, and dried. The properties of the
D

page_text: product are only slightly altered, if, in the above example, the 25 parts of azoxy-
ortho-toluidine are replaced by 24 parts of the new azo-ortho-toluidine.
Dated this 14th day of April 1891.
AMBROSE MYALL,
21, Cockspur Street, London, S. W., Agent for the Applicants.
COMPLETE SPECIFICATION.
The Production of New Bases and of Azo-colouring Matters
therefrom.
We, BROOKE SIMPSON AND SPILLER, LIMITED, of Hackney Wick, in the
County of Middlesex, Aniline Dye Manufacturers, and ARTHUR GEORGE
GREEN, F.C.S., F.I.C., of the same address, Chemist to the said Brooke Simpson
and Spiller, Limited, 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 :—
Our invention relates to the preparation of new bases, consisting of a new
azoxy-ortho-toluidine and a new azo-ortho-toluidine, and the manufacture of new
azo-colouring matters therefrom, by combining the diazo compounds of these
new bases with naphthol-sulphonic acids, or naphthylamines or their sulphonic
acids, or with phenols and amines generally, and their sulphonic acids.
These new bases are formed successively, by the alkaline reduction of the
consecutive nitro-ortho-toluidine,
C,H, (CH,) (NH,)(NO,)[1:2:61
which melts at 92° C., by means of zinc dust and caustic soda, sodium stannite, or
other suitable alkaline reducing agent.
The nitro-ortho-toluidine is obtained by reduction of fluid binitro-toluene
(Bernthsen, Ber. der Deut. Chem. Gesell. vol. 15, p. 3016), or as we have recently
found, together with the nitro-ortho-toluidine of melting point 107° C., by nitration
of ortho-toluidine at a low temperature, in presence of sulphuric acid.
In the latter case, the nitro-ortho-toluidine melting at 92° C., is precipitated
from the mother liquor from which that melting at 107° C. has separated, by
רי
..
[1:2:6]C,H, (CH,) (NH,) N,OC,11, (NH,) (CH,) [6 : 2 : 1],
[1: 2: 6] C,H,(CH,) (NH,) N,OC 11, (NH,) (CH,) [6 : 2 : 1],
molts at about [1097
The new azo-ortho-toluidine
[1 : 2 : 6] CgII, (CH,) (NH,) N,C,H, (NH,) (CHI,) [6: 2:1],
melts at about 175° C.
As an example of the method of preparation of these new bases, the following
instance may be given :—61 parts of the conscentive nitro-ortho-toluidine (melting
point 92° C) are suspended and partially dissolved in 2000 parts of boiling water,
and to the boiling solution is added a cold solution of sodium stannite, obtained
from 150 parts of tin crystals (stannons chloride) and 150 parts of caustic soda.
The azoxy-ortho-toluidine, which separates on cooling, is purified by dissolving it
in hydrochloric acid, filtering, and precipitating the hydrochloride by the addition
of an excess of hydrochloric acid."
To prepare azo-ortho-toluidine, the reduction of the nitro-ortho-toluidine is
simply pushed to its farthest point, or the azoxy-ortho-toluidine may be first
separated, as above described, and again treated until it is converted into azo-
ortho-toluidine.
The process for the preparation of these new bases is practically identical with

page_text: that described in the Specification of Green and Lawson, No. 14304 of 1889 for
the preparation of para-azoxy and para-azo-ortho-toluidine from para-nitro-ortho-
toluidine of melting point 107° C.; any reduction process applicable to nitro-ortho-
toluidine of that melting point, being ceteris paribus also applicable to that melting
at 92° C.
The conversion into colouring matters is performed according to the well known
methods used in the preparation of the azo-colours. As an instance, we may
describe the preparation of a brilliant scarlet colouring matter, which dyes cotton
without a mordant, and is unaffected by acids. A solution of 14 parts of sodium
nitrite (98°) in 100 parts of water, is added to an iced solution of 25 parts of
the new azoxy-ortho-toluidine and 45 parts (by volume) of hydrochloric acid,
(30% HCI) in 100 parts of water. The solution of the tetrazo compound, thus
obtained, is now run into a solution containing 50 parts of sodium alphia-naphthol-
para-sulphonate (corresponding to Piria's naphthionic acid) and kept alkaline by
the addition of sodium carbonate. The colouring matter is precipitated by the
addition of salt, filtered off and dried. The properties of the product are only
slightly altered, if, in the above example, the 25 parts of azoxy-ortho-toluidine,
are replaced by 24 parts of the new azo-ortho-toluidine, the shade of the colour
produced being somewhat bluer.
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 preparation of new bases, consisting of a new azoxy-ortho-toluidine
[1:2:6] C,H, (CH,) (NH,) N,OC,H, (NH,) (CH,) [6 :2:1]
melting at about 149° C., and a new azo-ortho-toluidine
[1:2:6] C,H, (CH,) (NH,) N,C,H, (NH,) (C11,) [6:2:1]
melting at about 175° C., produced successively by the alkaline reduction of the
consecutive nitro-ortho-toluidine
C.H. (CH) (NH.) (NO.) [1:2:6]
melting at about 149° C., and a new azo-ortho-tolumine
[1:2: 6] CH (CH,) (NH,) N,CH, (NH,)(C1,)[6 :2:1]
melting at about 175° C., produced successively by the alkaline reduction of the
consecutive nitro-ortho-toluidine
C.H. (CH.) (NH.) (NO.) [1:2:6]
by means of zinc dust and caustic soda, sodium stannite, or other suitable alkaline
reducing agent.
2. The preparation of nitro-ortho-toluidine, of melting point 92° C., by the
nitration of ortho-toluidine, at a low temperature in presence of sulphuric acid.
3. The preparation of colouring matters by conversion of the new bases, as set
forth in Claims 1 and 2, by combining the diazo compounds of the said bases with
naphthol sulphonic acids, or naphthylamines or their sulphonic acids, or with
phenols and amines generally, and their sulphonic acids, in accordance with the
methods used in the preparation of the azo-colours.
4. As new articles of manufacture, the colouring matters obtained as herein
set forth.
Dated this 11th day of January 1892
AMBROSE MYALL,
21, Cockspur Street, London, S.W., Agent for the Applicants.