Improvements in the Preparation of-Yellow, Orange, and Orange- brown. Coloring Matters, Suitable for Dyeing and Printing from Tetra-methyl-diamido-benzo-phenone and Analogous
Year: 1884

page_text: Improvements in the Preparation of-Yellow, Orange, and Orange-
brown. Coloring Matters, Suitable for Dyeing and Printing
from Tetra-methyl-diamido-benzo-phenone and Analogous
I JOHN HENRY JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of the said Invention for IMPROVEMENTS
IN THE PREPARATION OF YELLOW, ORANGE, AND ORANGE-BROWN COLORING
MATTERS SUITABLE FOR DYEING AND PRINTING FROM TETRA-METHYL-DIAMIDO-
BENZO-PHENONE AND ANALOGOUS KETONE BASES OR THEIR HALOGEN-DERIVATIVES
a communication to me from abroad by Heinrich Caro, Chemist to the Badische
Aniline and Soda Fabrik of Ludwigshafen on-the-Rhine in the Empire of
Germany to be as follows:-
This Invention relates to the preparation of yellow, orange, and orange-brown
coloring matters suitable for dyeing and printing According to their chemical
constitution the said coloring matters are substitution-derivatives of the yellow
coloring matters or "Auramines" the preparation of which has formed the subject
matter of a former application for Letters Patent by me dated the 26th day of
March 1884 and Numbered 5512.
In order to produce the said substitution-derivatives, various methods may be
employed.
.
According to one method Tetra-methyl-diamido-benzo-phenone and analogous
Ketone bases or their halogen-derivatives may be firstly submitted to the action of
ammonia substantially in the manner described in my before mentioned application
for Letters Patent. The yellow coloring matters or "Auramines" thus produced
may then be mixed with or dissolved in Aniline-Para- or Ortho Toluidine
Xylidine, Cumidine, Alpha or Beta Naphtylamine Meta or Para Phenylenediamine,
Chlor or Bromaniline, but likewise a great number of other primary aromatic
amines and their halogen-substitution-derivatives may be used for the same
purpose and the mixture or solution thus obtained is afterwards heated (according

page_text: to the known method of Phenylizing rosaniline) until the evolution of ammonia
has ceased or nearly so. The substitution derivatives of the Auramines thus
produced may then generally be separated from the excess of the Aromatic Amines
employed by exhausting the result of the operation with hot and slightly acidulated
water filtering and precipitating the solutions thus obtained with common salt,
chloride of zinc or other suitable precipitants, but other known methods of
separation may be used with due regard to the nature both of the aromatic amines
employed and of the coloring matters produced. Strong Acids and protracted
boiling with water ought to be avoided in the said separation of the coloring
matters for the reasons hereafter stated.
According to a second method the same or similar substitution derivatives of
Auramine may be obtained by allowing either the before mentioned primary
aromatic amines or their secondary Alkalized derivatives such for instance as
Monomethylaniline to react upon the Halogen-derivatives of Tetra methyl diamido
benzo phenone and analogous Ketone bases, the preparation of which derivatives
has formed the subject matter of a former application for Letters Patent by me
dated the thirteenth day of March 1884 and numbered 4850.
The said Halogen-derivatives may be used either in their Crude or in their
purified condition such as described in my before mentioned application for Letters
Patent (No 4850) and by preference in the state of their solutions in water alcohol
or other suitable solvents. Upon adding a sufficient excess of a primary aromatic
amine (such for instance as Aniline) or of a secondary alkalized aromatic amine
(such for instance as Monomethyl aniline) to the said halogen derivatives or their
solutions a quick change of their blue colour into an intense orange colour will be
observed to take place. The reaction proceeds at the ordinary temperature and
may be assisted by a gentle application of heat After several hours the coloring
matter thus produced may be separated in the before mentioned manner.
Neither the first nor the second of the before described methods for obtaining
the desired substitution derivatives of the Auramines are however sufficiently
direct and economical so as to contrast favorably with the direct third method
which I am about to describe and which mainly consists in the direct action of
the above named primary aromatic amines upon the Carbonyl-group of Tetra
methyl diamido benzo phenone and analogous Ketone bases The said primary
aromatic amines are to be employed in the state of their ealine compounds and
more particularly in the state of their hydro-chlorates. The reaction requires the
application of heat and proceeds with or without the presence of Chloride of zinc
or similar dehydrating agents. The following is an example of the manner in
which "Phenyl-Auramine' an orange coloring matter suitable for dyeing and
printing may be produced according to the said direct third method.
"
About ten parts by weight of dry and finely powdered Tetramethyl diamido
benzo Phenone are intimately mixed with about ten parts by weight of Chloride
of zinc and about eighteen parts by weight of Hydrochlorate of Aniline. The
mixture is then heated in an enamelled pan at a temperature of about one hundred
and eighty degrees Centigrade during the space of about one or two hours or until
a sample of the "melt" thus produced almost completely dissolves in hot water
with an intense orange yellow colour The result of the operation is then treated
with a small quantity of hot water in order to remove the excess of Chloride of
zinc and Hydrochlorate of aniline contained therein and the washed residue is
afterwards exhausted with a sufficient amount of hot water of about eighty
degrees Centigrade The Orange-yellow solutions thus obtained are filtered and
cooled as quickly as possible and then precipitated with common salt-The orange-
red precipitate may then be filtered pressed and dried at a temperature of about
forty degrees Centigrade-A similar result is obtained by heating the above named
mixture of Tetra methyl diamido benzo phenone and Hydro-chlorate of Aniline
without the presence of Chloride of Zinc or similar dehydrating Agents to a
temperature of about two hundred degrees Centigrade and separating the coloring
matter substantially in the manner before described.

page_text: The coloring matter or Phenyl Auramine" either resulting from the last
described direct action of Aniline upon the Carbonyle group of Tetra methyl
diamido benzo phenone or produced by the before named indirect methods of
Phenylizing Auramine or of causing Aniline to react upon the halogen-derivatives
of Tetra-methyl diamido benzo phenone, possesses the following characteristic
properties In the dry state and at the ordinary temperature it is a bright orange-
red powder which upon being heated conglomerates into an amorphous mass
possessing a green metallic lustre. It is soluble in water and more soluble in
Alcohol but insoluble in Benzole, Ligroine and Sulphuric ether. Strong Hydro-
chloric Acid when added in the cold state to a Phenylaurimine solution does not
at first effect any apparent change but when added at an elevated temperature the
orange yellow solution becomes gradually decolorized such change being caused by
the decomposition of the coloring matter into aniline and Tetra methyl diamido
benzo-phenone.
A similar decomposition takes place by the protracted boiling of neutral Phenyl-
auramine-solutions.
The coloring matter when treated in its alcoholic solution with sodium amalgam
becomes gradually changed into a colourless reduction-compound the Acetic solution
of which especially upon being heated quickly assumes an intense purplish-blue
colour owing to a decomposition thus taking place into Aniline and Tetra-methyl-
diamido-benzhydrol.
Phenyl-auramine can be employed for dyeing and Printing in a similar manner
as other known basic Aniline Colors-It dyes animal fibre without the aid of a
mordant and cotton with the aid of a suitable mordant, for instance Tannin or
Tannate of Antimony, thus producing bright orange yellow shades-The dyes
sufficiently resist the action of air and light but are destroyed from the reasons
before stated by strong boiling or steaming or by the action of Acids.
In an analogous manner colouring matters possessing the general character and
properties of the before described Phenyl-auramine may be produced by combining
Tetra-methyl diamido benzo phenone or analogous Alkalized derivatives of Para
diamido benzo phenone with a great number of other primary or secondary
Alkalized Aromatic amines as before said. For example "Metaxylyl Auramine" a
coloring matter suitable for dyeing and printing; bright golden yellow shades may
be produced by heating about ten parts by weight of Tetra-methyl-diamido-benzo
phenone with about twenty three parts by weight of Hydro-chlorate of Metaxylidine
during the space of about four hours at a temperature of about two hundred
degrees Centigrade and separating the coloring matter thus obtained in the before
described manner.
The employment of Para or Meta-phenylene diamine or of Alpha- and Beta
Naphtylamine in the before mentioned processes gives rise to the production of
correspondingly substituted Auramines dyeing various shades of orange-brown.
Para toluidine and Pseudo-Cumidine produce colouring matters similar in tint to
Metaxylyl-Auramine whilst "Ortho-Tolyl-Auramine" is an orange coloring matter
resembling the above described Phenylated derivative of Auramine.
Dated this 31st day of March 1884.
J. HENRY JOHNSON,
47, Lincoln's Inn Fields, London, W.C.

page_text: I JOHN HENRY JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of said Invention for "IMPROVEMENTS IN
THE PREPARATION OF YELLOW ORANGE AND ORANGE BROWN COLOURING MATTERS
SUITABLE FOR DYEING AND PRINTING FROM TETRAMETHYLDIAMIDOBENZOPHENONE
AND ANALOGOUS KETONE-BASES OR THEIR HALOGEN-DERIVATIVES," which Invention
has been communicated to me from abroad by Heinrich Caro Chemist to the
Badische Aniline and Soda Fabrik, of Ludwigshafen on the Rhine in the Empire of
Germany and in what manner the same to to be performed, to be particularly
described and ascertained in and by the following statement:-
This Invention relates to the preparation of yellow orange and orange-brown
colouring matters suitable for Dyeing and Printing. According to their chemical
constitution the said colouring matters are substitution-derivatives of the yellow
colouring matters or, "Auramines" the preparation of which has formed the
subject-matter of a former application for Letters Patent by me, dated the twenty
sixth day of March 1884 and numbered 5512.
In order to produce the said substitution derivatives three different methods may
be employed.
According to the first method Tetramethyldiamidobenzophenone, Tetraethyl-
diamidobenzophenone or Dimethyl-Diethyldiamidobenzophenone or the halogen-
derivatives of the said Ketone-bases, may be first submitted to the action of
ammonia substantially in the manner described in my before named application for
Letters Patent.
.
The yellow colouring matters or " Auramines" thus produced may then be treated
with any of the primary aromatic amines, which hereafter shall be defined; in a
manner analogous to the known method of phenylizing rosaniline. According to
the said method as is well understood, a phenyl-substitution is effected by heating
the said colouring matter with Aniline until the evolution of ammonia has ceased
or nearly so. Now in an analogous manner, Phenyl, Tolyl, Xylyl, Cumenyl or
Napthyl-substitution-derivatives of the Auramines may be obtained by mixing the
said colouring matters with, or by dissolving the same in Aniline or any of the
isomeric modifications of Toluidine, Xylidine, Cumidine or Naphtylamine and by
heating such mixtures or solutions afterwards to a temperature of about one
hundred and eighty degrees Centigrade until ammonia ceases to be freely evolved.
As an example of the manner in which a Phenyl-substitution-derivative of
auramine may be produced, about one part by weight of the hydrochlorate of
auramine (such as results from the treatment. of Tetramethyldiamidobenzophenone
with sal-ammoniac and dry chloride of zinc according to the manuer set forth in
the Specification of my above recited application for Letters Patent 5512 ] is
mixed with or dissolved in about three parts by weight of Aniline, and the mixture
or solution thus obtained is then gradually heated by means of an oil-bath, to a
temperature of about from one hundred and seventy to one hundred and eighty
degrees Centigrade, which temperature is to be maintained during about half an
hour or until the evolution of ammonia has ceased or nearly so. During the re-
action the mixture gradually assumes a dark orange-red colour. The result of the
operation is then allowed to cool, and, when cold the excess of free aniline is care-
fully neutralized with acetic acid or with dilute hydrochloric acid, -say with a
mixture of about three parts by weight of hydrochloric acid of about 1·18
specific gravity, with about six parts by weight of water. About fifty parts by
weight of a saturated sulution of common salt are then added, and in the event of

page_text: hydrochloric acid having been employed, sufficient acetate of soda to complete the
precipitation, and after several hours standing the colouring matter thus precipitated
is separated from the saline aniline solution by filtering, pressing and washing. It
may be further purified by solution in water slightly acidulated with acetic acid,
and previously heated to about eighty degrees Centigrade and the solution thus
obtained may be filtered and precipitated with common salt, chloride of zinc, nitrate
of soda or other soluble precipitants.
-
In a similar manner other substitution derivatives of auramines are produced by.
the employment of the different primary aromatic amines herein before named, and
other known methods of separation may be used with due regard to the nature
both of the aromatic amines employed and of the colouring matter produced.
Treatment with strong mineral acids and long continued boiling with water ought, :
in every instance to be avoided, for the reasons hereafter stated.
According to the second method the above named and analogous substitution-
derivatives of Auramine may be obtained by allowing either the before mentioned
primary amines or their secondary Methyl, Ethyl, Isobutyl Amyl, or Benzyl.:
derivatives [such for instance as Monomethylaniline] to react upon the halogen
derivatives of Tetramethyldiainidobenzophenone and analogous Ketone-bases the
preparation of which derivatives has formed the subject matter of a former.
application for Letters Patent by me, dated the thirteenth day of March 1884 and
numbered 4850.
"
The said halogen-derivatives may be used either in their "crude" or in their
purified" condition, such as described in my before mentioned application for.
Letters Patent (N° 4850 84) and by preference in the state of their solutions in
water, alcohol, chloroform nitrobenzole or other suitable solvents. Upon adding a
sufficient excess of any of the before named primary or secondary aromatic amines
to the said halogen-derivatives or their solutions a quick change of their blue colour
into an intense orange colour will be observed to take place.
The reaction proceeds at the ordinary temperature and may be assisted by a
gentle application of heat.
After several hours the colouring matter thus produced may be separated from
the excess of the aromatic amine employed substantially in the manner hereinbefore
described or by the application of any other known and convenient method.
As an example about twenty parts by weight of dry and finely powdered
Tetramethyldiamidobenzophenone are intimately mixed with or dissolved in about
fifteen parts by weight of nitrobenzole and then at the ordinary temperature about
ten parts by weight of oxychloride of phosphorus are added. The halogenizing
action is first allowed spontaneously to proceed and is afterwards completed by
heating the blue product thus obtained at a temperature of about seventy degrees.
Centigrade during the space of about fifteen minutes.
The result of the operation is then cooled down to the ordinary temperature and.
gradually mixed with about one hundred and twenty parts by weight of cold water
and about twenty parts by weight of aniline, due care being taken to moderate the
developement of heat caused by the reaction. The mixture thus obtained is then
strongly agitated during the space of about three hours and in order to remove the.
excess of aniline contained therein, the same is afterwards carefully neutralized with
acetic acid and then allowed to settle. The semi-fluid dark orange red deposit after
being separated from the supernatent aqueous solution is then freed from nitro- :
benzole by washing with a suitable solvent of the latter such as ligroine, and the
colouring matter thus obtained is further purified by solution in water of a tem-
perature of about eighty degrees Centigrade and slightly acidulated with acetic acid
and by precipitation from its filtered solution by means of common salt, nitrate of
soda or chloride of zinc.
Neither the first nor the second of the before described methods for obtaining
the desired substitution-derivatives of the Auramines are however sufficiently
direct and economical so as to be able to compete in practice with the direct third
method, which I now shall proceed to describe, and which substantially consists in

page_text: the direct action of the hereafter named primary aromatic amines upon the
carbonyle-group of Tetramethyldiamidobenzophenone, Tetraethyldiamidobenzo-
phenone and
'
Dimethyldiethyldiamidobenzophenone.
Although all primary aromatic amines hitherto tried have been found capable to
react in the before said direct manner, the present Invention however is confined
to the application of the following aromatic amines, Aniline and the isomeric
modifications of Toluidine Xylidine Cumidine, Naphthylamine and Chloraniline
Meta and Paraphenylendiamine and Metatoluylen diamine.
The said primary aromatic amines are to be employed in the state of their
hydrochlorates sulphates acetates, oxalates tartrates or benzoates but by preference
in the state of their hydrochlorates. The reaction requires the application of heat,
and proceeds without, but is considerably assisted by the cooperation of dry
chloride of zinc.
The following is an example of the manner in which the before mentioned
Phenyl-Auramine, an orange colouring matter suitable for Dyeing and Printing,
may be produced according to the said direct third method.
About ten parts by weight of dry and finely powdered Tetramethyldiamido-
benzophenone are intimately mixed with about ten parts by weight of dry Chloride
of Zinc and about eighteen parts by weight of hydrochlorate of aniline-The
mixture is then heated in an enamelled pan at a temperature of about one hundred
and eighty degrees Centigrade during the space of about one or two hours or until
a sample of the "
melt" thus produced almost completely dissolves in hot water
with an intense orange yellow colour.
The result of the operation is then treated with a small quantity of hot water in
order to remove the excess of chloride of zinc and hydrochlorate of aniline con-
tained therein and the washed residue is afterwards exhausted with a sufficient
amount of hot water of about eighty degrees Centigrade. The orange yellow
solutions thus obtained are filtered and cooled, as quickly as possible and then
precipitated with common salt. The orange red precipitate may then be filtered
pressed and dried at a temperate of about forty degrees Centigrade.
A similar result but an inferior yield of colouring matter is obtained by heating
the above named mixture of Tetramethyldia midobenzophenone and hydrochlorate
of Aniline without the presence of Chloride of Zinc to a temperature of about two
hundred degrees Centigrade, and separating the colouring matter, substantially in
the manner before described.
The colouring matter or "Phenyl-Auramine" either resulting from the last
described direct action of Aniline upon the Carbonyle group of Tetramethyldiamido-
benzophenone or produced by the before named first and second indirect methods
of phenylizing Auramine or of causing aniline to react upon the halogen derivatives
of Tetramethyldiamidobenzophenone, possesses the following characteristic proper-
ties In the dry state and at the ordinary temperature it is a bright orange red
powder, which upon being heated conglomerates into an amorphous mass possessing
a green metallic lustre-It is soluble in water and more so in diluted alcohol,
insoluble in benzole, ligroine and sulphuric ether; strong hydrochloric acid when
added in the cold to a phenylauramine solution does not at first effect any apparent
chemical change, but at an elevated temperature the orange yellow solution becomes
gradually decolorized, such change being caused by the decomposition of the
colouring matter with Aniline and Tetramethyldiamidobenzophenone.
A similar decomposition takes place by the long continued boiling of neutral
phenylauramine solutions-The colouring matter when treated in its alcoholic
solution with sodium-amalgum, becomes gradually changed into a colourless
reduction compound, the acetic solution of which, upon being heated, quickly
assumes an intense purplish-blue colour, owing to a decomposition thus taking
place into Aniline and Tetramethyldiamidobenzhydrol.
Phenylauramine can be employed for. Dyeing and Printing in a similar manner
as other known basic Aniline colours. It dyes animal fibre without the aid of a
mordant Upon cotton with the aid of a suitable mordant, for instance Tannin,

page_text: or Tannate of Antimony, it produces bright orange yellow shades. The dyes
sufficiently resist the action of air, and light, but are destroyed for the reasons
before stated, by strong boiling with water, or by steaming, or by the action of
acids.
In an analogous manner colouring matters, possessing the general character and
properties of the before described Phenyl-auramine, may be produced by com-
bining Tetramethyldiamidobenzophenone and the before named analogous alkylized
derivatives of Paradiumidobenzophenone with the primary aromatic amines herein-
before defined.
For example Metaxylyl Auramine a colouring matter suitable for dyeing and
Printing bright golden yellow shades may be produced by heating about ten parts
by weight of Tetramethyldiamidobenzophenone with about twenty three parts by
weight of Hydrochlorate of Meta xylidine during the space of about four hours at a
temperature of about two hundred degrees Centigrade and separating the colouring
matter thus obtained in the before described manner-The employment of Para or
Meta-phenylendiamine or of Metatoluylen-diamine or of Alpha and Beta-Napthyl-
amine in the before mentioned process gives rise to the production of correspondingly
substituted Auramines dyeing various shades of orange brown. Paratoluidine and
Pseudo-Cumidine produce colouring matters similar in tint to Metaxylyl Auramine
whilst "Ortho Tolyl Auramine " is an orange colouring matter resembling the
above described phenylated derivative of Auramine.
Having now particularly described and ascertained the nature of my said
Invention and in what manner the same is to be performed I declare that what
I claim is-
First Producing Phenyl Tolyl, Xylyl Cumenyl or Naphthyl substitution
derivatives of Auramines capable of being employed as yellow. orange or orange
brown colouring matters, suitable for dyeing and Printing by heating the auramines
produced from Tetramethyldianidobenzophenone Tetraethyldiamidobenzophenone
and Dimethyl-diethyldiamidobenzophenone (according to the manner setforth in
my herein before recited application for letters Patent dated the twenty sixth day
of March 1884 and Nod 5512) with Aniline or with the isomeric modifications of
Toluidine Hylidine Cumidine and Napthyl amine substantially as hereinbefore
described.
Second Producing the above named, and analogous substitution derivatives of
auramines by treating the halogen derivatives of the herein before named Ketone-
bases (the preparation of which halogen derivatives forms the subject matter of my
former application for Letters Patent dated the thirteenth day of March 1884 and
Numbered 4850) with the primary or secondary aromatic amines hereinbefore
defined in the description of my above said second method and employed in their
free or uncombined state substantially as herein before described.
Third Producing the above named and analogous substitution derivatives of
Auramines in a direct manner from the hereinbefore named Ketone bases by the
action of the primary aromatic amines (such as are defined in my above described
third method) upon the carbonyle group of the said Ketone-bases with or without
the cooperation of dry chloride of zinc and with the employment of the said
primary aromatic amines in the form of their above said saline compounds and
by preference in the state of their hydrochlorates substantially as hereinbefore
described.
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