A Process for the Production of Para-rosanilin and its Homologues, as well as Mono, Di, Tri, Alkylized, Phenylized, or Naphthylized Derivatives thereof.
Year: 1886

page_text: Date of Application, 3rd May, 1886.
Complete Left, 2nd Feb., 1887.
Complete Accepted, 4th Mar., 1887
A Process for the Production of Para-rosanilin and its Homologues,
as well as Mono, Di, Tri, Alkylized, Phenylized, or Naphthylized
Derivatives thereof.
I, HEINRICH BAUM of Mannheim in the Empire of Germany Chemist do hereby
declare the nature of this invention to be as follows :-
The object of my Invention is the cheap and simple production of rosanilin
derivatives of definite constitution such as could not heretofore be obtained even by
the condensation process by means of para-nitro-benzaldehyd.
By this Invention it is as easy to obtain two leuco bases by employing two amines
as it is to obtain only one with two different phenyl residues. The action is easily
produced at a temperature of 130° to 140° C and the process proceeds with great
regularity.
As an example, I will describe the mode of producing para-fuchsin-To 129 kilo-
grammes of hydrochlorate of anilin I add 183 kilogrammes of para-nitro-benzyl-
anilin and twenty-five kilogrammes crystallized chloride of iron or a corresponding
amount of very concentrated solution. This mixture is heated for six hours to from
130° to 135° C and finally for a short time to 140° C. The mass first becomes bright
green, and later on gradually assumes a metallic lustre. The re-action is complete
when the mass has a green-gold shimmer and dissolves in spirits producing a pure
fuchsin red color generally in ten or twelve hours. The mass is now either boiled as
with the ordinary fuchsin compounds or by preference dissolved in ten times the
amount of water with one hundred kilogrammes of hydro-chloric acid this being
effected with hardly any residue. One hundred kilogrammes of common salt are
then added and the liquid is then left to cool. A small amount of bluish, dirty,
coloring matter will thereby be separated out which is to be filtered off. The filtrate
contains the para rosanilin in the form of chlor-hydrate. This is precipitated by
careful neutralization of the hydrochloric acid and recrystallized in the known way.
If, for the anilin salt 1 substitute hydro-chlorate of ortho-, meta-, or para-toluidin,
I obtain the corresponding homologous rosanilines so also with xylidin and with
naphthylamin I obtain the rosanilines containing naphthyl groups. The like object is
attained by substituting for the para-nitro-benzyl-anilin its higher homologues such as
para-nitro-benzyl-toluidin, xylidin, or naphthylamin.

page_text: If, in a similar manner for the hydro-chlorate of anilin I substitute halogen salts of
secondary aromatic amines such for instance as mono-methyl-anilin, diphenylamin,
alpha and beta-napthyl-phenylamin etc I obtain the mono-substituted rosanilines in
the form of violet-red to blue coloring matters. If I further substitute for the anilin
salt the halogen salts of tertiary aromatic amines I then obtain in the purest form one
class of di-substitued rosanilins.
If, for the para-nitro-benzyl-anilin I substitute tertiary para-nitro-benzylized
aromatic bases and at the same time for the anilin salt I substitute halogen salts
of secondary aromatic bases, then I obtain the symmetrical di-substituted rosanilins
of every desired composition in the form of violet to blue coloring matters.
If, lastly, for the para-nitro-benzyl-anilin I substitute para-nitro-benzylized tertiary
bases as for instance para-nitro-benzyl-ethyl-anilin etc, and at the same time for the
anilin salt I substitute halogen salts of tertiary aromatic bases for instance hydro-
chlorate of di-methyl-anilin then I obtain the tri-substituted rosanilins of unsym-
metrical nature in the form of violet to blue coloring matters.
According to this process then, it is possible to obtain coloring matters of definite
composition in a pure form which has heretofore not been possible by any other
process. The formation of the coloring matters takes place at 130° to 140° C as in
the case of para-rosanilin and the process may be accelerated by the addition of strong
lye of chloride of zine.
If it be desired to produce homogeneous rosanilin derivatives wherein only one base
is employed, then the mode of production may be in so far simplified that the mixture
of hydrochloric acid base and para-nitro-base may be produced directly by causing
one molecule of chloride of para-nitro-benzyl to re-act upon two molecules of the
base in the presence of water at eighty degrees to one hundred degrees C. during a
considerable time, and then after the chloride of nitro-benzyl has disappeared adding
chloride of iron or other metal and heating directly to from 130° to 140° C.
TT DATIM
H. BAUM
By A. M. & Wm. Clark,
53, Chancery Lane,
Patent Agents.

page_text: A Process for the Production of Para-rosanilin and its Homologues,
as well as Mono, Di, Tri, Alkylized, Phenylized, or Naphthylized
Derivatives thereof.
I, HEINRICH BAUM of Mannheim in the Empire of Germany Chemist 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:-
The object of my Invention is the cheap and simple production of rosanilin
derivatives of definite constitution such as could not heretofore be obtained even by
the condensation process by means of para-nitro-benzaldehyd.
By this Invention it is as easy to obtain two leuco bases by employing two amines
as it is to obtain only one with two different phenyl residues. The action is easily
produced at a temperature of 130° to 140° C and the process proceeds with great
regularity.
As an example, I will describe the mode of producing para-fuchsin ;-To 129 kilo-
grammes of hydrochlorate of anilin I add 183 kilogrammes of para-nitro-benzyl-
anilin and 25 kilogrammes crystallized chloride of iron or a corresponding amount
very concentrated solution. This mixture is heated for six hours to from 130°
135° C and finally for a short time to 140 C. The mass first becomes bright green
and later on gradually assumes a metallic lustre. The re-action is complete when
the mass has a green gold shimmer and dissolves in spirits, producing a pure
fuchsin red color generally in 10 or 12 hours. The mass is now either boiled, as with
the ordinary fuchsin compounds, or by preference dissolved in ten times the amount
of water with 100 kilogrammes of hydro-chloric acid, this being effected with hardly
any residue. 100 kilogrammes of common salt are then added and the liquid is then
left to cool. A small amount of bluish, dirty, coloring matter will thereby be
separated out which is to be filtered off. The filtrate contains the para-rosanilin in
the form of chlor-hydrate. This is precipitated by careful neutralization of the
hydrochloric acid and recrystallized in the known way.
If, for the anilin salt, I substitute hydro-chlorate of ortho- or meta-toluidine, I
obtain the corresponding homologous rosanilines; so also with xylidin, and with
naphthylamin I obtain the rosanilines containing naphthyl groups. The like object is
attained by substituting for the para-nitro-benzyl-anilin its higher homologues such as
para-nitro-benzyl-toluidin, xylidin, or naphthylamin.
If, in a similar manner, for the hydrochlorate of anilin, I substitute halogen salts of
secondary aromatic amines, such for instance as mono-methyl-anilin, diphenylamin,
alpha and beta-naphthyl-phenylamin etc, I obtain the mono-substituted rosanilines in
the form of violet red to blue coloring matters.
If, for the para-nitro-benzyl-anilin, 1 substitute tertiary para-nitro-benzylized
aromatic bases, for example the para-nitro-benzyl-methylanilin, and at the same time
for the anilin salt I substitute halogen salts of secondary aromatic bases, then I obtain

page_text: the symmetrical di-substituted rosanilins of every desired composition, in the form of
violet to blue coloring manners.
According to this process, then, it is possible to obtain coloring matters of definite
composition in a pure form which has heretofore not been possible by any other
process. The formation of the coloring matters takes place at 130° to 140° C. as in
the case of para-rosanilin, and the process may be accelerated by the addition of
strong lye of chloride of zinc.
If it be desired to produce homogeneous rosanilin derivatives wherein only one base
is employed, then the mode of production may be in so far simplified that the mixture
of hydrochloric acid base and para-nitro base may be produced directly by causing
one molecule of chloride of para-nitro-benzyl to react upon two molecules of the base
n the presence of water at 80° to 100° C. during a considerable time, and then, after
the chloride of nitro benzyl has disappeared, adding chloride of iron or other metal
and heating directly to from 130° to 140° C).
Having now particularly described and ascertained the nature of the said
Invention, and in what manner the same is to be performed, I declare that what
I claim is :-
The herein described process of manufacturing para rosanilin and its homologues,
and likewise mono, di, alkylized, phenylized, or naphthylized derivatives thereof by the
action of para-nitro-benzylized secondary and tertiary aromatic bases at a high
temperature on either the halogen salts of primary aromatic bases, or on the halogen
salts of secondary aromatic bases in the presence of certain metallic chlorides or the
corresponding bromides and iodides.
H. BAUM.
By A. M. & Wm. Clark,
53, Chancery Lane, London,
Patent Agents.