IMPROVEMENTS IN THE PREPARATION OF HALOGEN-DERIVATIVES METHYL-DIAMIDO-BENZO-PHENONE AND ANALOGOUS KETONE BASES 16 OF TETRA-
Year: 1884

page_text: [Communicated from abroad by Heinrich Caro, Chemist to the Budische Anilin
and Soda Fabrik, of Ludwigshafen on the Rhine, in the Empire of Germany.]
PROVISIONAL SPECIFICATION.
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 HALOGEN-DERIVATIVES
METHYL-DIAMIDO-BENZO-PHENONE AND ANALOGOUS KETONE BASES
16
OF TETRA-
" which Inven-
tion has been communicated to me from abroad by Heinrich Caro, Chemist to
the Badische Anilin and Soda Fabrik, of Ludwigshafen on the Rhine in the
Empire of Germany, to be as follows:-
:-
This Invention relates to the preparation of certain halogen-derivatives of Tetra-
methyl-diamido-benzo-phenone, Tetra-ethyl-diamido-benzo-phenone, and analogous
ketone bases by the action of deoxydizing and halogenizing agents such as the
chlorides, bromides, iodides of phosphorus, oxychloride of phosphorus, oxybromide
of phosphorus, sulphochloride of phosphorus, oxychloride of carbon or similar agents
upon the carbonyle-group of the said ketone bases.
The new halogen-derivatives thus produced aro remarkable on account of their
great instability and reacting power, owing to which properties they are capable
of acting as materials for or as intermediate products in the synthetical preparation
of a variety of chemical compounds.
Some of the products resulting from thoir reaction with ammonia, organic bases,
phenols and hydrocarbons are colouring matters suitable for dyeing and printing,
the preparation of which will be made by ine the subject-matter of separate
applications for Letters Patent.
The present Invention, as above stated, exclusively relates to the preparation of
the said halogen-derivatives, such derivatives being materials or intermediato.
products suitable for the production of colouring matters.
The nature of this Invention will be fully understood by the following description
of the preparation and characteristic properties of a chlorimated derivative of
Tetra-methyl-diamido-benzo-phenone.
In order to produce the said derivative, Tetra-methyldiamido-benzo-phenone, in a
erfectly dry and finely powdered condition, is intimately inixed with about one
alf of its own weight of trichloride of phosphorus at the ordinary temperature.
The halogenizing action soon manifests itself by a spontaneous rise of temperature

page_text: and by the mixture assuming a blue colour, which gradually increases in intensity.
In the event of larger quantities say several pounds by weight-being operated
upon it is advisable either to dilute the mixture with indifferent solvents or
substances (such as for instance :-hydrocarbons, tetrachloride of carbon, sulphide
of carbon, chloroform, nitrobenzole, dry sand, common salt) or to regulate the
reaction by external cooling, in order to avoid an excessive rise of temperature
which may result in the sudden destruction of the product thus formed.
The halogenizing action proceeds best at an ordinary or at a slightly elevated
temperature, say at about from forty to fifty degrees Centigrade, and is generally
accomplished in the space of several hours; it may however be accelerated by careful
application of heat by the employment of a water bath. The result of the operation
is an intensely blue product, containing as principal ingredient the new chlorinated
derivative of Tetra-methyl-diamido-benzo-phenone in admixture with phosphorus-
compounds and also with the above mentioned indifferent solvents and substances.
In most instances the product thus obtained nay without any further separation be
conveniently employed as a material suitable for the production of colouring matters,
inasmuch as it may at once be added to or mixed with the compounds required for
effecting its subsequent transformation. In several cases it may be convenient to
allow the halogenizing agent to react upon Tetra-methyl-diamido-benzo-phenone
mixed with or dissolved in the compounds capable of changing the product of such
reaction into colouring matter. In such processes the said halogen-derivative,
formed at the commencement of the operation, and changed during the progress
of the same, will act as an intermediate product.
If a separation of the halogen derivative be intended, the same may be effected
by the application of suitable solvents and precipitants. For instance the crude
product resulting from the action of Trichloride of phosphorus upon Tetra-methyl-
diainido-benzo-phenone, as above described, may be dissolved in Chloroform, and
the deep blue solution thus obtained may then be filtered and gradually poured
into a large bulk of perfectly dry Ligroine or petroleum-spirit under constant
agitation. The dark blue precipitate thus obtained exhibits the following
characteristic properties.
It cannot be dried without suffering partial decomposition, and is quickly
destroyed by the application of heat. Its solutions in water, alcohol, chloroform
and similar solvents are intensely blue and lose their colour slowly in the cold and
rapidly upon being heated. The aqueous solution thus decolorised deposits Tetra-
methyl-diamido-benzo-phenone and contains free hydrochloric acid. By the action
of ammonia, methylamine, aniline, and a large number of aromatic primary and
secondary amines the halogen derivate is quickly converted into yellow and orange
colouring matters (the preparation of which will form the subject matter of separate
application for Letters Patent). Mixed with or dissolved in Dimethylaniline or
certain analogous tertiary aromatic amines and with the co-operation of any of the
above named halogenizing agents it is changed, slowly in the cold and quickly
at an elevated temperature, into colouring matters belonging or allied to the
Triphenylinethane sories (the preparation of which colouring matters will likewise
form the subject matter of separate application for Letters Patent). In a simila
manner halogen derivatives possessing the same or similar characteristic properties
as before described, are obtained by the action of the above named deoxydizing
and halogenizing agents upon Tetra ethyldiamido benzo-phenone and analogou
ketone-bases.

page_text: I JOHN HENRY JOHNSON, of 47 Lincolns Inn Fields, in the County of Middlesex,
Gentleman, do hereby declare the nature of this Invention for "IMPROVEMENTS IN
THE PREPARATION OF HALOGEN-DERIVATIVES OF TETRA-METHYL-DIAMIDO-BENZO-
PHENONE AND ANALOGOUS KETONE BASES," which invention has been communi-
cated to me from abroad by Heinrich Caro, Chemist to the Badische Anilin and
Soda Fabrik, of Ludwigshafen-on-the-Rhine in the Empire of Germany, and in
what manner the same is to be performed, to be particularly described and
ascertained in and by the following statement :-
This Invention relates to the preparation of certain halogen derivatives of Tetra-
methyl-diamido-benzo-phenone and analogous ketone-bases, the representatives of
a new class of chemical agents which are remarbable on account of their great
instability and reacting power, owing to which properties they are capable of
acting as materials for or as intermediate products in the synthetical preparation
of a variety of chemical compounds.
Some of the products resulting from their reaction with ammonia, organic
bases phenols and hydrocarbons, are colouring matters suitable for Dyeing and
Printing.
The preparation of several of the said coloring matters has been made by me
the subject-matter of separate applications for Letters Patent which hereafter shall
be referred to.
The present Invention, as above stated, exclusively relates to the preparation of
the before mentioned halogen-derivatives and has moreover for its special object
the preparation of certain chlorinated or brominated derivatives, which hitherto
have yielded practical results as materials for or as intermediate products in the
synthetical production of the said coloring matters.
The said chlorinated or brominated derivatives are produced by the action of
trichloride pentachloride or oxychloride of phosphorous, or of oxychloride of carbon
or of the corresponding bromine-compounds of phosphorus upon the Carbonyle-
group of Tetramethyl-diamido-benzophenone, Tetraethyl-diamidobenzophenone of
Dimethyl-Diethyl-diamido benzophenone.
The desired change in the Carbonyle-group of the before named ketone-bases
takes place, whenever the same are treated with any of the before-named
deoxydising and halogenizing agents at the ordinary or at a gently elevated
temperature and it is therefore immaterial whether the said ketone-bases are
employed in their pure and isolated condition, or whether they are acted upon in
their crude state, in which for instance they are obtained by heating the chlorides
of dimethyl or of diethyl-para-amidobenzoic acid with about an equal molecule of
dimethyl- or of diethylaniline, as is well known from the investigations of Michler
(Berichte of the German Chemical Society 1876 p 710 and 1913).
The conversion of the said ketone-bases into their corresponding chlorinated or
brominated derivatives generally manifests itself by the appearance of an intense
blue colour and by other characteristic reactions of the product thus obtained,
which shall hereafter be fully described.
The nature of this Invention will be clearly understood by the following
description of the preparation and characteristic properties of a chlorinated
derivative of Tetramethyldiainido-benzophenone.
In order to produce the said derivative, Tetramethyl-diamidobenzophenone in a
perfectly dry and finely powdered condition, is intimately mixed with about one

page_text: half of its own weight of trichloride of phosphorus at the ordinary temperature.
The halogenizing action soon manifests itself by a spontaneous rise of temperature
and by the mixture assuming a blue colour, which gradually increases in intensity.
In the event of larger quantities say about two or more pounds by weight of the
ketone-base-being operated upon-the spontaneous rise of temperature, caused by
the reaction, ought to be kept down by external cooling, as otherwise it may
quickly exceed one hundred degrees Centigrade and finally result in the sudden
destruction of the product thus formed. In order to avoid an excessive rise of
temperature it is also advisable to dilute the mixture with indifferent solvents
(such as for instance Benzole, Toluol, Tetrachloride of Carbon, Sulphide of carbon,
Chloroform nitrobenzole) or with indifferent substances, (such as for instance dry
sand or common salt).
The halogenizing action proceeds best at a temperature of about from Forty to
fifty degrees Centigrade and is generally accomplished in the space of several
hours, it may however towards its end, be accelerated by careful application of
heat by the employment of a waterbath. The result of the operation is an intensely
blue, solid or semi-solid product, generally presenting a crystalline appearance and
a metallic-green or bronze-coloured lustre.
Its principal ingredient is the new chlorinated derivative of Tetramethyl-
diamidobenzophenone mixed with phosphorus-compounds [and also with the above
mentioned indifferent solvents or substances in case of their having been employed
for diluting the mixture, as before described].
In many instances the crude product thus obtained may without any further
separation be conveniently employed as a material suitable for the production of
coloring matters inasmuch as it may at once be added to or mixed with the
compounds required for effecting its subsequent transformation. In several cases
it may be convenient to allow the halogenizing agent to react upon the ketone-
base in admixture with or in presence of the compounds capable of changing
its halogen-derivative into coloring matter. For instance Tetramethyl-diamido-
benzophenone may be submitted to the action of Trichloride of phosphorus in the
presence of or in admixture with a tertiary aromatic amine capable of being
employed in the synthetical production of colouring matters belonging or allied to
the Triphenylmethane-series, as will hereafter be mentioned. In such cases the
halogen derivative, formed at the commencement of the operation, and changed
during the progress of the same, will act as an intermediate product in the
synthetical preparation of the said colouring mattors.
If a separation of the chlorinated derivative of Tetramethyl-diamido-benzo-
phenone be intended, the crude product resulting from the halogenizing action, as
before described, may be dissolved in a suitable indifferent solvent, such for
instance as chloroform, and the deep blue solution thus obtained may then be
filtered and gradually poured into a large bulk of perfectly dry ligroine or
petroleum-spirit under constant agitation. The dark blue precipitate then obtained
exhibits the following characteristic properties.
It cannot be dried without suffering partial decomposition, and is quickly
destroyed by the application of heat. Its solutions in water, alcohol, chloroform,
and similar solvents are intensely blue and loose their colour slowly in the cold
and rapidly upon being heated. The aqueous solution thus decolorised deposits
Tetramethyl-diamido-benzophenone and contains free hydrochloric acid.
By the action of ammonia, methylamine, aniline and a large number of aromatic
primary and secondary amines the halogen-derivative is quickly converted into a
new class of yellow and orange coloring matters (the preparation of which forms
the subject matter of my applications for Letters Patent numbered 5512 and
Number 5741, and dated respectively the Twenty sixth and Thirty first day of
March 1884).
Mixed with or dissolved in Dimethylaniline or certain analogous tertiary aromatic
amines and with the co-operation of any of the above named halogenizing agents,
the chlorinated derivative of Tatramathul diamidohenzonbanana in shealb

page_text: in the cold and quickly at an elevated temperature into colouring matters belonging
or allied to the Triphenylmethane series [the preparation of which coloring matters
forms the subject matter of my applications for Letters Patent numbered No 5038
and No 11159 and dated respectively the Eighteenth of March and the 11th day of
August 1884].
In a similar manner chlorinated derivatives possessing substantially the same or
similar characteristic properties as before described are obtained by the action of
Trichloride of phosphorus upon Tetraethyl-diamido-benzophenone and Dimethyl-
diamido-benzophenone, whilst in lieu of Trichloride of phosphorus equivalent
amounts of any of the before named chlorinating or brominating agents may be
employed in the above described process and thus the corresponding chlorinated or
broininated derivatives of the said ketone-bases may be produced in accordance
with the directions above set forth.
From the point of economy, preference is to be given to the employment of
Trichloride of phosphorus and to the oxychlorides of phosphorus or carbon. The
action of oxychloride of phosphorus is somewhat less energetic than that of the
trichloride and is on that account more easily managed. Oxychloride of carbon
may be employed in its gaseous condition but is more conveniently used in the state
of solution in benzole or toluol, especially in those cases in which the chlorinated
derivative resulting from its action upon the above named Ketone-bases is
intended to be used as an intermediate product, in the synthetical preparation of
colouring matters belonging or allied to the Triphenylmethan series as before
described.
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,
The preparation of chlorinated and brominated derivatives of Tetramethyl-
diamido-benzophenone, Tetraethyl-diamido-benzophenone and Dimethyl-Diethyl-
diamido-benzophenone capable of being employed as materials for or as intermediate
products in the synthetical preparation of coloring matters suitable for Dyeing and
printing and produced by the action of trichloride, pentachloride or oxychloride of
phosphorus, or of oxychloride of carbon or of the corresponding bromine-compounds
of phosphorus upon the Carbonyle-group of the herein before named keton-bases
substantially as hereinbefore described.
Dated the fifteenth day of December 1884.