The Production of Dinitrodibenzylbenzidine and Dinitrodibenzyl- tolidine and Transformation into Dia- andto respectively.
Year: 1889

page_text: -Date of Application, 1st Mar., 1889
Complete Specification Left. 8th May, 1889-Accepted, 6th July, 1889
PROVISIONAL SPECIFICATION.
[Communicated from abroad by Messrs. DAHL AND COMPANY, of Barmen, in the
Kingdom of Prussia, Manufacturing Chemists.]
The Production of Dinitrodibenzylbenzidine and Dinitrodibenzyl-
tolidine and Transformation of the same into Diamidodibenzyl-
benzidine and Diamidodibenziltolidine respectively.
I ADOLF BANG of Park Row Leeds in the County of York, Dye-Merchant do
hereby declare the nature of this invention to be as follows:-
This invention relates to new dye-stuffs, and, the modes or means for producing the
same.
The following new combinations or compounds are produced.
1°) By the action of 2 molecules of chloride of paranitrobenzyl on 1 molecule of
benzidin, a dinitro-dibenzylbenzidin is obtained which is transforined into a diamido-
dibenzylbenzidin by reduction. From this latter a tetrazo compound is obtained by
means of nitrous acid, which by combination with amines, phenols, naphthols and
sulpho acids of the same furnishes new substantive dye-stuffs.
Tolidin diamido-stilben and other diamines or their sulpho-acids may be employed
instead of benzidin.
Dated this 28th day of February 1889
J. CLARK JEFFERSON, A.R.S.M., Wh. Sc.,
2, East Parade, Leeds, Agent for Applicant.
COMPLETE SPECIFICATION.
The Production of Dinitrodibenzylbenzidine and Dinitrodibenzyl-
tolidine and Transformation of the same into Diamidodibenzyl-
benzidine and Diamidodibenziltolidine respectively.
I ADOLF BANG of Park Road Leeds in the County of York dye merchant 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:-
According to Strakosche (Berlin Ber 6 page 1056) the chloride of paranitrobenzyle
reacts readily with ammonia and substitutes of ammonia-for instance aniline-
forming nitrobenzyl derivatives of these substances. By reduction it is possible to
resolve the nitro group into the amido-group. This reduction does not however
always take place smoothly, as it sometimes happens that in the tertiary nitro-
benzylanine a split takes place, of such a nature that toluidine and secondary
amidobenzylamine are formed.
The reduction of nitrobenzylaniline is still more difficult, as the same will only yield
amidobenzylaniline under the observance of certain conditions.
My communicators have discovered, that a dinitrodibenzylbenzidine may be readily.
obtained through the influence of chloride of paranitrobenzyle on benzidine, and also that
it may be converted directly into diamidodibenzylbenzidine by reduction at a temperature
of from (90 to 100° C.) with tin and hydrochloric acid.
The dinitrodibenzylbenzidine forms a brown powder, which is insoluble in water,
alcohol, strong acetic acid or by any other dissolving means.
The diamidodibenzylbenzidine forms an amorphous powder, which up to the present
has not been crystallized. It is scarcely soluble in water, although not quite insoluble,
and can be pretty readily dissolved in alcohol.
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page_text: The chloride of the base is very easily soluble in water, neither sulphuric acid nor
a salt of sulphuric acid can produce a precipitate from its solution in water.
The diamidodibenzylbenzidine dissolves readily in dilute sulphuric acid, by which
means the same may be definitely distinguished from benzidine..
From the alcoholic solution of the base a sulphate may be easily precipitated by
dilute sulphuric acid, which sulphate in its moist condition is very soluble in water;
when however it has once become dry, it is difficult to dissolve it again, and even
with the addition of acids it is necessary to boil it for a considerable time in order to
effect its solution. The analysis of the sulphate precipitated from alcohol showed
12-5% sulphur whilst the supersalt
required 10.36 % sulphur.
The diamidodibenzylbenzidine as also the diamidodibenzyltolidine may be convered
into tetrazo combinations by means of nitrites, which (like benzidine) yield substances
for dyeing cotton goods direct, though the colours produced herefrom are yellower
than those of the corresponding benzidine or tolidine dyes.
The following example shews or illustrates how my Invention may be performed.
184 kilogrammes of benzidine and 34 kilogrammes of the chloride of paranitro-
benzyle are heated during three or four days at a temperature of 100° C in enamelled
boilers provided with circulating coolers and stirring apparatus.
The mass which at first is greasy forms itself in a few hours into lumps, which in a
few days resolve themselves into a fine powder of dinitrodibenzylbenzidine. As soon
as all the chloride of nitrobenzyle bas disappeared, the contents of the boiler are
poured on to a filter, the residue twice boiled out with dilute hydrochloric acid, and
then filtered in order to separate any benzidine which may have remained unchanged.
After the wash water has been thoroughly let off, the precipitate is scooped into an
enamelled boiler with stirring mechanism and there reduced with 35 kilogrammes of
tin and 15 kilogrammes of hydrochloric acid.
The product of the reduction is poured into water, the liquid then cleared of any
little impurities it may contain by filtration, and the tin is then eliminated from the
solution by means of zinc. The solution of diamidodibenzylbenzidine and chloride
of zinc ought not to precipitate a sulphuric benzidine by sulphuric acid, and it may
be used directly for the production of dyes.
Diamidodibenzyltolidine is produced in exactly the same manner.
Having now particularly described and ascertained the nature of my said Inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
The production of dinitrodibenzylbenzidine and dinitrodibenzyltolidine and the

page_text: resolving of the same into diamidodibenzylbenzidine and diamidodibenzyltolidine
respectively, by heating one molecule of benzidine, respectively tolidine, with 2
molecules of chloride of paranitrobenzyle to a temperature of 100° C in water
suspension and subjecting the nitro products so obtained to reduction.
D
3000
J. CLARK JEFFERSON, A.R.S.M., Wh. Sc.,
2, East Parade, Leeds, Agent for Applicant..