Production of Compounds of the Diphenylmethan Group and the Rosaniline Series.
Year: 1889

page_text: Date of Application, 23rd Dec., 1889
. Complete Specification Left, 18th Sept., 1890-Accepted, 18th Oct., 1890
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBWERKE VORMALS MIESTER, LUCIUS AND
BRUNING, of Hoechrst-am-Main, in the Empire of Germany, carrying on business
as Chemical Manufacturers.]
Production of Compounds of the Diphenylmethan Group and the
Rosaniline Series.
.I, OLIVER IMRAY of No. 28 Southampton Buildings, Chancery Lane in the County
of London, Fellow of the Institute of Patent Agents do hereby declare the nature
of this invention to be as follows:-
'
My foreign correspondents have discovered that by the action of formaldehyde
upon certain aromatic amines are obtained compounds of the diphenylmethan group,
for example:
:
PRODUCTION OF DIAMIDO DIPHENYLMETHAN. 1
By the action of formaldehyde upon aniline is produced in the first place anhydro-
formaldehyde aniline C,H,N = CĤ₂.
For the conversion of this compound into the diamido-diphenylmethan we proceed
as follows:
.
50 parts of anhydroformaldehyde aniline are heated on the water-bath and while
being kept agitated together with 70 parts of chlorhydrate of aniline and an excess of
aniline. The mass becomes by degrees semi-liquid. About 12 hours later it is
rendered alkaline and the excess of aniline expelled. The remaining oil solidifies in
the form of a crystalline mass of diamido diphenylmethan, which may be purified by
recrystallisation from benzol.
From benzol it separates in the form of compact crystals, from water in the form
of brilliant leaflets of a melting point of 87° C.
In the preparation of the diamido diphenylmethan, instead of first separating the
anhydroformaldehyde aniline and causing it to act subsequently upon aniline, the
two phases of the operation may be combined and the formaldehyde introduced directly
into the mixture of aniline and hydrochlorate of'aniline.
The homologues of diamido diphenylmethan are prepared in an analogous manner,
for example by the action of anhydroformaldehyde aniline upon hydrochlorate of
orthotoluidine and orthotoluidine,
Anhydroformaldehyde orthotoluidine upon hydrochlorate of aniline.and aniline,

page_text: orthotoluidine,
Anhydroformaldehyde orthotoluidine upon hydrochlorate- of orthotoluidine and
Anhydroformaldehyde aniline upon hydrochlorate of dimethylaniline and dimethyl-.
aniline,
Anhydroformaldehyde orthotoluidine upon hydrochlorate of dimethylaniline and.
dimethylaniline,
Anhydroformaldehyde aniline upon hydrochlorate of diethylaniline and diethyl-
aniline,
Anhydroformaldehyde orthotoluidine upon hydrochlorate of diethylaniline and
diethylaniline, etc.
II. PRODUCTION OF THE COLORING MATTERS OF THE SERIES OF THE ROSANILINES.
The production of these coloring matters is carried out in manner mentioned
above, by oxidation of the compounds of the diphenylmethan group, the preparation
of which is described above, together with an aromatic amine..
In this case also the production may be proceeded with by departing from the
anhydroformaldehyde amines Cx Hy N CH, and carrying out in one and the
=
same vessel the two phases of the operation:
1) The formation of the compound of the diphenylmethan group and
2) The oxidation
or by introducing the formaldehyde into the mass of the reaction, the operation
beginning by the formation of the anhydroformaldehyde amine.
The manner of proceeding is described in the following two examples:
.1) 100 parts by weight of anhydroformaldehyde aniline
:
50
hydrochlorate of orthotoluidine
COMPLETE SPECIFICATION.
Production of Compounds of the Diphenylmethan Group and the
Rosaniline Series.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the County
of London, Fellow of the Institute of Patent Agents 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:---
My foreign correspondents have discovered that by the action of formaldehydę

page_text: Diamido-diphenylmethan
Aniline
Pararosaniline
I. PRODUCTION OF COMPOUNDS OF THE DIPHENYLMETHAN GROUP.
PRODUCTION OF DIAMIDODIPHENYLMETHAN.
By the action of formaldehyde upon aniline there is produced in the first stage the
anhydroformaldehyde-aniline C,HN CH2. The conversion of this compound
into the diamidodiphenylmethan is proceeded with in the following way:
50 parts of anhydroformaldehyde aniline are heated on a water bath while being
kept agitated together with 70 parts of hydrochlorate of aniline and an excess of
aniline. The mass gradually becomes simi-liquid.
After about 12 hours it is rendered alkaline and the excess of aniline is driven off.
The oil remaining after this solidifies in the form of a crystalline mass of diamido-
diphenylmethan, which can be purified by recrystallisation from benzol, from which
it separates in the form of compact crystals; from water it separates in the form of
brilliant leaflets having a melting point of 87° C.
j
Instead of separating first the anhydroformaldehyde aniline and subsequently
causing it to act upon aniline, the production of the diamido-diphenylmethan may
be carried out by combining the two stages of the operation, introducing the formal-
dehyde directly into the mixture of aniline and hydrochlorate of aniline.
The homologues of the diamidodiphenylmethan are produced in an analogous way,
substituting for the anhydroformaldehyde the anhydro compounds of the toluidines
or xylidiues.
For example, anhydroformaldehyde-aniline is caused to act upon hydrochlorate
of ortho toluidine and ortho-toluidine.
ก
Anhydroformaldehyde-ortho-toluidine upon hydrochlorate of aniline and aniline,
Anhydroformaldehyde-ortho-toluidine upon hydrochlorate of ortho-toluidine and
ortho toluidine.
EXAMPLES.
a. PRODUCTION OF DIAMIDODITOLYLMETHAN.
100 parts by weight of anhydroformaldehyde aniline, 250 parts by weight of
hydrochlorate of ortho-toluidine, 500 parts by weight of ortho-toluidine are heated
to 100° C. in an enamelled vessel, while being kept agitated, until on boiling a sample
with dilute sulphuric acid; no formaldehyde can be distinguished. To the product of
the reaction are added 250 parts by weight of water and 230 parts by weight of soda
lye of 30 per cent.; the excess of ortho-toluidine and the regenerated aniline are
distilled off by a current of steam.
!:

page_text: The diamidoditolylmethan then remains in the form of a quickly solidifying oil
which is obtained by recrystallisation from water or alcohol in the form of brilliant
leaflets having a melting point of 149° C.
The hydrochlorate and the sulphate of this substance are very readily soluble in
water.
For the 100 parts by weight of anhydroformaldehyde-aniline may be substituted
an equal quantity of anhydroformaldehyde-ortho-toluidine or para-toluidine or
xylidine.
b. PRODUCTION OF DIAMIDOPHENYLTOLYLMETHAN.
100 parts by weight of anhydroformaldehyde ortho-toluidine, 250 parts by weight
of hydrochlorate of aniline, 500 parts by weight of aniline are heated to 100°. C. in
an enamelled vessel, while being kept agitated, until on boiling a sample with dilute
sulphuric acid, no formaldehyde can be distinguished.
To the reaction product are then added 250 parts by weight of water and 230 parts
by weight of soda lye of 30 per cent. anil the excess of aniline is distilled off by a
current of steam.
The diamidophenyltolylmethan remains in the form of a quickly solidifying oil,
which is obtained by recrystallisation from water or alcohol in the form of brilliant
leaflets having a melting point of 129° C.
The hydrochlorate and the sulphate of this substance are readily soluble in water.
In the same way as formaldehyde furnishes diphenylmethan derivatives with primary
aromatic amines in the presence of suitable condensation agents, compounds of the
diphenylmethan series are formed in the reaction of formaldehyde with secondary
aromatic bases.
Thus for example diphenylamine (2 molecules) in alcoholic solution and in presence
of hydrochloric acid condenses with formaldehyde (1 molecule) in violent reaction
forming a body which my foreign correspondents denominate "diphenyldiamido-
diphenylmethan."
The production of this body is carried out in the following way:
100 parts by weight of diphenylamine are dissolved hot in 200 parts by weight of
alcohol and then 22-2 parts by weight of formaldehyde of 40 per cent. are added to
the solution which is then heated to 60 C., 5 parts by weight of hydrochloric acid
of 20 per cent. being added.
There is violent reaction, the mixture becoming dark. When the reaction is finished
the diphenyldiamidodiphenylmethan is separated in the form of a solid crystalline
Left exposed to the air it assumes a yellow brown color.
mass.
The diphenyldiamido-diphenylmethan is of difficult solubility or almost insoluble
in all indifferent solvents. In aromatic bases alone it is somewhat easily soluble. In
diluted acids it is insoluble; but on being heated in concentrated sulphuric acid it
dissolves assuming a brown color.
In a like manner formaldehyde reacts with other secondary aromatic bases, such as
ortho- and para-tolylphenylamine, ortho-ditolylamine, alpha and beta-naphthyl-ortho-
tolylamine, alpha and beta-naphthyl-phenylamine and also with mixtures of these
secondary amines; thus for example there is formed from formaldehyde (1 molecule)
diphenylamine (1 molecule) and naphthylphenylamine (1 molecule) a condensation
product which is considered to be the naphthylphenyl-diamidodiphenylmethan.
All these products have qualities similar to those of the diphenyldiamido-
diphenylmethan above described.
The compounds of the diphenylmethan group produced in the manner described are
used for the production of coloring matters of the rosaniline series of great value, as
will be now set forth.
II. PRODUCTION OF COLORING MATTERS OF THE ROSANILINE SERIES.
As mentioned above, the production of these coloring matters is effected by
oxidising the compounds of the diphenylmethan group, the preparation of which is
above described, conjointly with an aromatic amine.

page_text: The production may also be effected by starting with the anhydroformaldehyde-
amines Cx Hy. N=CH, themselves causing the two stages of the operation to go on
in the same vessel, that is to say :-
1. The formation of the compound of the diphenylmethan group.
2. The oxidation.
Also, the formaldehyde may be introduced into the reaction mass, so that the
operation may begin with the formation of the anhydroformaldelhyde-amine.
By joint oxidation of diamido-diphenylmethan, aniline and hydrochlorate of
aniline there is obtained para-magenta. The homologous magentas are obtained when
for the aniline are substituted its homologues.
If for the aniline is substituted dimethylaniline or phenylmethylaniline there are
obtained methylised and phenylised magentas.
Moreover, coloring matters of the rosaniline series are obtained when for the
diamidodiphenylmethan are substituted the above mentioned products of the reaction
between formaldehyde and secondary aromatic amines such as diphenylamine, and also
when this reaction mass is caused to act upon secondary aromatic amines, such as
diphenylamine and its hydrochlorate.
The process is more fully explained by the following examples :
50 parts of anhydroformaldehyde-aniline, an excess of aniline and hydrochlorate of
aniline, with addition of some ferrous chloride and about 100 parts of nitrobenzol are
kept at a temperature of about 170° C. until the melt assumes metallic lustre, the para-
magenta is obtained in the same way as in the preceding example.

page_text: As raw material for the production of this body is employed the product resulting
from the reaction between formaldehyde and diphenylamine in the presence of
hydrochloric acid. It is the product which has been herein before called "diphenyl-
diamido-diphenylmethan.”
10 parts by weight of diphenyldiamido-diphenylmethan
50
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hydrochlorate of ortho-toluidine
ortho-toluidine
ortho-nitrotoluol
ferrous chloride (iron filings)
are heated on an oilbath to 170° C. for 3 hours.
The hot mass of the reaction is poured into diluted hydrochloric acid, boiled and
filtered. The residue is hydrochlorate of diphenylrosaniline, which is easily soluble
in alcohol or aniline, and can be readily converted into sulphonic acids, available
commercially as coloring matters.
In the examples 5 and 6 may be substituted for the diphenyldiamido-diphenylmethan
any of the reaction products of formaldehyde with secondary aromatic bases that is to
say ortho- and para-tolylphenylamine, ortho-ditolylamine alpha and beta-naphthyl
phenylamine, alpha- and beta-naphthyl-ortho-tolylamine or mixtures of two of these
bases.
For the diphenylamine mentioned in example 5 may be substituted any of the
secondary bases enumerated above and for the ortho toluidine mentioned in example 6
may be substituted aniline or xylidine.
Also for the orthonitrotoluol of examples 5 and 6 may be substituted any of the
oxidising agents hereinbefore mentioned.
The compounds of the rosaniline series thus prepared are intended for use in dyeing
and printing.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, I declare that what I
claim is
1. The production of compounds of the diphenylmethan group by the action of the
anhydroformaldehyde produced from formaldehyde and aniline, orthotoluidine,
paratoluidine, or xylidine upon aniline or ortho-toluidine in presence of a condensing
.agent such as the hydrochlorate of an amine.
2. The production of compounds of the diphenylmethan group by the action of
formaldehyde upon alcoholic solutions of diphenylamine, ortho- and para-tolylphenyl-
amine, ortho-ditolylamine, alpha- and beta-naphthylphenylamine, alpha- and beta-

page_text: phthyl-ortho-tolylamine or the mixture of two of these secondary amines in the
sence of hydrochloric acid.
3. The production of coloring matters of the rosaniline series.
a. By treating the anhydroformaldehyde compounds of aniline, ortho-toluidine,
para-toluidine or xylidine in presence of aniline, ortho-toluidine or diphenyl-
amine and a hydrochlorate of the same with oxidising agents.
b. By treating diamidodiphenylmethan, diamidotolylphenylmethan, diamido-
ditolylmethan, diphenyldiamido-diphenylmethan or any other of the diphenyl-
methan derivatives produced according to claim 2 in presence of aniline,
orthotoluidine, diphenylamine, ortho and para-tolylphenylamine, ortho ditolyl-
amine, alpha-and beta-naphthylphenylamine or alpha-and beta-naphthyl-ortho-
tolylamine and a hydrochlorate of the same with oxidising agents.
4. The compounds of the diphenylmethan group and the coloring matters of the
saniline series produced as set forth in the first, second, and third claims.
ABEL & IMRAY,
Agents for the Applicant.
ABEL & IMRAY,
Agents for the Applicant. .