Improvements in the Manufacture of Colouring Matters.
Year: 1890

page_text: Date of Application, 26th Feb., 1890
Complete Specification Left, 24th Nov., 1890- Accepted, 27th Dec., 1890
PROVISIONAL SPECIFICATION.
Communicated from abroad by Messrs. WIRTH & Co., of Frankfort-on-the-Main,
acting as Agents of A. Leonhardt & Co., of Mulheim-on-the-Main, both in the
Empire of Germany, Manufacturers.]
Improvements in the Manufacture of Colouring Matters.
I, HENRY HARRIS LAKE, of the firm of Haseltine, Lake, & Co., Patent Agents,
Southampton Buildings, in the County of Middlesex, do hereby declare the nature of
this invention to be as follows:-
Dioxynaphtalene (melting point 216° C., obtained by melting B naphtalenedisulpho-
acid or Schäffer's B naphtalsulphoacid with alcalies) when heated with ammonia or
primary amines, especially in the presence of a salt of such, can be converted int
naphtylenediamine and its corresponding derivatives.
0
These derivatives when treated with salts of nitrosoderivatives of aromatic amines
(such as nitrosodimethylaniline or the like) yield green basic dyestuffs which are very
fast against light and soap.
The production of these colouring matters takes place in the usual way by heating
the two components in the presence of some dissolving or distributing agent, such as
spirit, acetic acid or the like.
Dated this Ofth day of Fahanan 1900
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, Agents for the Applicant
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Colouring Matters.
I, HENRY HARRIS LAKE, of the firm of Haseltine, Lake & Co., Patent Agents,
45, Southampton Buildings, in the County of Middlesex, 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 :-
Dioxynaphthalene of the melting point 216° (obtained by melting B naphthalene-
disulphoacid or Schäffer's B naphtholmonosulphoacid with alkalies) when heated
with primary aromatic amines in the presence of a suitable condensing agent is
converted into new substituted derivatives of the corresponding naphthylenediamine.
These new derivatives when heated with salts of paranitrosoderivatives of aromatic
amines such as nitrosodimethylaniline or nitrosodiethylaniline, yield new green basic
dye-stuffs, which are very fast against light and soap.
The process by which these green colouring matters are obtained is a new
application of a well known general method of producing basic colouring matters by
condensing nitrosoderivatives of aromatic amines with certain amines and phenols-
And as it is equally known to chemists that in this general method chinondi

page_text: substituted naphthylenediamines takes place by heating the former with primary
aromatic amines up to the boiling point of such amines, or near to it, and in the
presence of a suitable condensing agent.
As a condensing agent I employ by preference hydrochloric acid (or a corresponding
quantity of a chlorhydrate of the amine) but sulphuric acid or chloride of zinc would
also do.
Thus for instance by employing
Aniline
orthotoluidine
paratoluidine
I get
a new diphenylnaphthylenediamine,
a new orthoditolylnaphthylenediamine
a new paraditolylnaphthylenediamine.
As an example I give the following directions 30 kilos. of dioxynaphthalene (melting.
point 216° C.) together with 70 kilos. of aniline, and 25 kilos. of chlorhydrate of
aniline; are heated for several hours up to 170° C., until the whole dioxynaphthalene
has disappeared and no more water is distilling. The whole mass is then gradually
poured into cold water, kept slightly aciduous by means of hydrochloric acid in order
to dissolve the aniline remaining in excess. After agitating the mass for some time,
the diphenylnaphthylenediamine which has separated is filtered and dried. It is
insoluble in dilute acids or alkalies and can be purified by dissolving in boiling toluol,
filtering and leaving the solution to crystallize.
Second step. Production of the green colouring matters.
In order to produce the colouring matters I heat the substituted naphthylene-
diamines with a salt of the paranitrosoderivatives of aromatic amines or with chinondi-
chlorimide in presence of a suitable dissolving or distributing agent, such as methylic
alcohol, spirit, acetic acid or the like, until the reaction and the formation of colouring
finished
1st. 1 heat 10 kilos of diphenylnaphthylenediamine with 200 litres of spirit, up to,
say, 70° C., and gradually add about 10 kilos of chinondichlorimide, taking care that
the reaction does not become too violent by a too quick addition of the chlorimide. I
then keep the fluid boiling at the reflux cooler for some time, dilute it with hot water,
filter the liquid and after cooling down precipitate the dye-stuff out of the filtrate by
means of common salt.
2nd. 20 kilos. of orthoditolylnaphthalenediamine, about 30 kilos. of the chlorhydrate
of nitrosodimethylaniline, and 200 litres of methylic alcohol are heated at the reflux
cooler, until all nitrosodimethylaniline has disappeared. The whole mass is then
diluted with, say 800 litres of water and filtered and the colouring matter is precipitated
out of the filtrate by means of common salt.
By employing diphenylnaphthylenediamine instead of orthoditolylnaphthylene-
diamine, a part of the colouring matter crystallizes out of the alcoholic solution on
cooling and can be separated by filtering.
Instead of the chlorhydrate of nitrosodimethylaniline, other salts of this base, as for
instance the sulphate or nitrate, can be used. The nitrosodimethylaniline can further
be substituted by an equivalent quantity of nitrosodiethylaniline.
In the above directions I do not confine myself strictly to the proportions mentioned,
because they can be varied within certain limits without materially altering the result.
Thus for instance, when 20 kilos. of orthoditolylnaphthylenediamine are brought into
reaction with 25 or 35 kilos. of the hydrochlorate of nitrosodimethylaniline, the same
green colouring matter is obtained.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed as communicated to mė
by my foreign correspondent I declare that what I claim is:-
First. The production of substituted naphthylenediamines,such as diphenylnaphthy-
lenediamine orditolylnaphthylenediamine by the herein before described process which

page_text: consists in heating dioxynaphthalene of the melting point 216° C. with primary
aromatic amines, such as aniline or toluidine in presence of a suitable condensing
agent, substantially as set forth.
Second. The substituted naphthylenediamines produced,substantially as hereinbefore
described.
Third. The production of new basic green colouring matters by the hereinbefore
described process which consists in heating the substituted naphthylenediamines
mentioned in claim first and second with chinondichlorimide or with a salt of
paranitrosoderivatives of aromatic amines such as nitrosodimethylaniline or nitroso-
diethylaniline, in presence of a suitable dissolving or distributing agent, substantially
as set forth.
Fourth. The new basic green colouring matters produced, substantially as berein-
d this 24th day of November 1890.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, Agents for the Applicant.
D
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, Agents for the Applicant.