Production of New Colouring Matters.
Year: 1888

page_text: Date of Application, 24th Sept., 1888
Complete Specification Left 24th June 1889 Accepted 27th July, 1889
PROVISIONAL SPECIFICATION.
Production of New Colouring Matters.
I, THOMAS RICHARD SHILLITO of 89 Chancery Lane, in the County of Middlesex,
Engineer, do hereby declare the nature of this invention, a communication to me from
abroad by John Rodolph Geigy of Basle Switzerland, Colour manufacturer, to be as
follows:-
This invention has reference to the production of several new colours and is based
upon the discovery that unsymetric substituted azoxy and azo-compounds may be
obtained by condensation of substituted aromatic amines with aromatic nitro-substances,
or by condensation of substituted aromatic nitro-substances with aromatic amines by
heating them with caustic alkalies.
The new base is like syrup, its nitrate and chloride readily crystallises and its
sulphate is scarcely soluble in water.
The product thus obtained is reduced, then treated with acid, to be diazotised and
combined with one or two of the following substances:
With a or ẞ naphtylamine,
With a or 3 naphtylamine sulpho-acids,
With a or
With a or
naphtol,
naphtol sulpho-acids,
With resorcine,
With phenol or
With their carbonic acids,
To carry out the invention I boil, say ;-
10 kilogrammes of orthotoluidine with
to obtain red.
to obtain blue violet.
to obtain yellow.
10 kilogrammes of caustic soda under gradual addition of
10 kilogrammes of nitro-benzine until the latter has completely disappeared.
The result is a red brown paste which is reduced with zinc powder after dilution
with water. It is then allowed to stand until cold, poured into concentrated muriatic
acid, boiled, diluted with water and filtered. Glauber's salt is then added to precipitate
the sulphate in the form of a paste, 100 kilogrammes of which containing 20 per cent.
of dry substance are mixed with 18 kilogrammes of muriatic acid, cooled and diazotised
by the addition of 9 kilogrammes of nitrite of sodium. The solution of the diazo-
compound is poured into a solution of 10 kilogrammes of soda and 45 kilogrammes of
naphtionate of sodium or the corresponding quantity of another of the aforesaid
substances.
Upon the formation of the colour I heat and precipitate with salt.
To produce colours of mixed composition the solution of the diazo-compound is
poured into a solution of 10 kilogrammes of soda with, say, 20 kilogrammes of
naphtionate. When the combination is finished I add 10 kilogrammes of naphtol and
4 kilogrammes of caustic soda, or the corresponding quantity of another of the
aforesaid substances.
These colours are adapted for dyeing textile fabrics without the use of mordants.
Dated this 24th day of September 1888.

page_text: COMPLETE SPECIFICATION.
Production of New Colouring-matters.
I, THOMAS RICHARD SHILLITO, of 89, Chancery Lane, in the county of Middlesex,
Engineer, do hereby declare the nature of this invention (a communication to me from
abroad by John Rodolph Geigy, of Switzerland, Colour-manufacturer,) 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 new colouring matters from unsym-
metrical substituted paradiamines for dyeing cotton without a mordant.
If aromatic substituted amines are heated with aromatic nitro-compounds or
substituted nitro-compounds with aromatic amines in presence of caustic alkalies, a
condensation takes place between the amines and nitro-compounds under formation of
so called azoxy and azo-compounds. These azoxy or azo-compounds are converted by
means of reduction into their corresponding hydrazocompounds which again are con-
verted into unknown paradiamines by treating the same with hydrochloric acid. If
for example, nitrobenzole acts on orthotoluidine in presence of caustic alkali, azoxy
and azophenyltolyle are formed, which after having been reduced and treated with
acids are converted into the new base diamidophenyletolyle.
In order to manufacture this product I proceed as follows:-
10 kilos of orthotoluidine are heated with 10 kilos of caustic alkali during the
gradual addition of 10 kilos of nitrobenzole.
A red brown paste results and the reaction is complete as soon as the odour of the
nitrobenzole has ceased which usually takes place within a few hours.
The red brown paste, representing a mixture of azoxy and azophenyletolyle is
diluted with water and boiled with zinc dust till the red brown solution is totally
discoloured.
After having been filtered the hydrazo-compound thus obtained is allowed to flow
into a solution of concentrated hydrochloric-acid. It is boiled and the formed diamido-
phenyletolyle isolated by adding glauber salts.
The new paradiamino closely resembles in its qualities benzidine and tolidine.
The diamidophenyletolyle represents the next higher homologue of benzidine,
(diamidodiphenyle) and the next lower homologous product preceding the tolidine,
(diamidoditolyle). Like the tolidine it forms a soluble hydrochloric acid salt and like
the benzidine a sulphate which is not easily soluble.
The tetrazo-compound of diamidophenyle-tolyle, which is easily soluble in water,
reacts with two molecules of an amine, phenole or their sulphonic or carbonic or
sulpho-carbonic acids producing direct dyeing colouring matters which, when derived
from amines, resemble in their shades the corresponding tolidine-dye stuff, and when
derived from phenols, the corresponding benzidine-dye stuffs.
By combining one molecule of the tetrazo compound of my new diamidophenyletolyle
with only one molecule of an amine, phenole or their sulphonic or carbonic acids, so
called intermediate products are formed which are not dye-stuffs themselves, but which
produce dye-stuffs when combined with another molecule of an amine; phenole or their
sulphonic or carbonic acids.
EXAMPLE I.
Diamidophenyletolyle + 2 mol Alpha-Naphthylamine.
In order to form this colouring matter a solution of tetrazophenyletolyle, which is
readily obtained by adding the required quantity of a solution of sodium nitrite to the
hydrochloric acid solution of 14 kilos of diamidophenyletolyle, is added to a hydro-
chloric acid solution of 25 kilos of Alphanaphthylamine. On the addition of acetate
of sodium the formation of the dye-stuff takes place. After standing for twelve hours
the temperature is raised to 80 degrees centigrade. The substance is then acidulated
and filtered off. The dye-stuff thus obtained dissolves in alcohol with a bluish red
colour.

page_text: In order to render this dye-stuff soluble in water 10 parts by weight of this product,
which is soluble in spirit, are introduced into 30 parts by weight of fuming sulphuric
acid, containing 20% of anhydride, at a temperature of about 15 to 30 degrees
centigrade; the melted product is allowed to stand till a sample dissolves readily in
alkaline water. Then it is poured onto ice, and the separated dye-stuff acid filtered off
and converted into the dye-stuff by dissolving in an alkali.
By means of common salt the dye-stuff is isolated; it will dye red shades in
cotton.
Diamidophenyletolyle + 2 mol alpha-naphylaminemono-sulphonic.acid.
A solution of the tetrazocompound of diamidophenyletolyle corresponding to
10 kilos of sodium nitrite is introduced into an acetic acid solution of 45 kilos of
lpha-naphthylamine-mono-sulphonic acid.
After standing for 24 hours the mixture is heated to 80 degrees centigrade and
made alkaline by the addition of caustic soda, it is then separated by means of common
alt filtered and dried. The colouring matter will dye cotton bluish red shades.

page_text: 2) The manufacture of direct dyeing colouring matters from diamidophenyletolyle
combining one molecule of the tetrazo compound of diamidophenyletolyle :-
a. With two molecules of an amine, phenole or their sulphonic or carbonic, or
sulpho-carbonic acids, substantially as described.
b. With one molecule of an amine, phenole or their sulphonic or carbonic or
sulpho-carbonic acids producing so called intermediate products which are
subsequently combined with another molecule of an amine, phenole or their
sulpho or carbonic or sulpho-carbonic acids, substantially as herein before
described.
3) The new colouring matters produced in the manner herein before described.
G. F. REDFERN & Co.,
4, South Street, Finsbury, London, Agents for the Applicant.