Improvements in the Manufacture of Coloring Matters suitable for Dyeing and Printing from Tetra-methyl-diamido Benzo-
Year: 1884

page_text: Improvements in the Manufacture of Coloring Matters suitable
for Dyeing and Printing from Tetra-methyl-diamido Benzo-
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 MANUFACTURE OF COLORING MATTERS SUITABLE FOR DYEING AND PRINTING FROM
TETRA-METHYL-DIAMIDO BENZO-PHENONE AND ANALOGOUS KETONE BASES" which
Invention has been communicated to me from abroad by Heinrich Caro, Chemist
to the Badische Aniline and Soda fabrik of Mannheim in the Empire of Germany
to be as follows :—
The manufacture of coloring matters from Tetra-methyl-diamidobenzophenone
and analogous ketone-bases has already been made by me the subject matter of a
series of applications for Letters Patent.
In the Specification of my application numbered No 4850 and dated the
18th of March of this year I have described the conversion of Tetra-methyl-diamido-
benzophenone and analogous ketone-bases into a new and remarkable class of
balogenderivatives endowed with extraordinary reacting power and thus capable of
acting as materials for or as intermediate products in the synthetical preparation
of a variety of coloring matters suitable for Printing and dyeing.
The preparation of purple, blue and green colouring matters resulting from the
action of the said halogen derivatives upon Dimethylaniline, Phenyl-Alphanaph-
thylamine, Chinoline and a great number of analogous aromatic bases is described
in the Specification of my application for Letters Patent numbered No 5038 and
dated the eighteenth of March of this year whilst the applications numbered and
dated respectively N° 5512 the twenty sixth of March and N° 5741 the thirty first
of March and of this year refer to the preparation of the so called "Auramines"
new class of yellow, orange and orange-brown coloring matters resulting from the
action of the said halogen derivatives upon ammonia, primary and secondary
amines.
a
In the before mentioned processes for producing coloring matters from Tetra-
methyldiamidobenzophenone and analogous ketone bases Oxychloride of Carbon

page_text: (Phosgene) is particularly recommended as an Agent capable of converting the said
ketone-bases into their corresponding halogenderivatives.
Now my foreign Correspondent has discovered that certain derivatives of
oxychloride of Carbon exert an action similar to that of Oxychloride of Carbon
itself and may on that account be conveniently employed in lieu of the said agent
in the processes described in the Specifications of my above recited applications
for Letters Patent.
The said derivatives of Oxychloride of Carbon are obtained by chlorinating the
Chlorocarbonic ethers in the manner hereafter described. The Chlorocarbonic
ethers are prepared according to a well known method by the action of the
corresponding alcohols upon Oxychloride of Carbon.
The most active reagent is produced from the Chlorocarbonate of Methyle whilst
the higher homologues are endowed with an energy decreasing in the ratio of
their increasing molecular weight.
In order to prepare the said derivatives and substitutes of Oxychloride of Carbon
a current of dry Chlorine-gas is passed through the Chorocarbonic ethers as long as
a vivid absorption of the gas accompanied by a considerable rise of temperature is
observed to take place. The reaction proceeds very quickly in direct sun-light and
at the commencement the developement of heat requires to be moderated by
external cooling. The progress of the action may be ascertained by withdrawing
a sample of the chlorinated product from time to time and testing its efficiency to
convert Tetramethyldiamidobenzophenone into its blue halogenized derivative fully
described in the Specifications of my herein before mentioned application for
Letters Patent numbered No 4850 and dated 13th March of this year.
Towards the end of the operation the absorption of chlorine requires to bo
assisted by the application of heat-The resulting product is then freed from the
excess of Chlorine which has remained unacted upon by passing a current of dry
air through it and it may then at once be employed or by preference be previously
submitted to a fractional distillation, in order to separate the most active portions
of the same.
In the manner before described Chlorocarbonate of Methyle yields a very
energetic fraction boiling between about one hundred and ten and one hundred and
twenty degrees centigrade.
From Chlorocarbonate of Ethyle a chlorinated product may be obtained, the
fractions of which boiling between about one hundred and twenty degrees and
about one hundred and sixty degrees Centigrade may be conveniently employed
Chlorocarbonate of Isobutyle yields a derivative boiling at about from two hundred
and ten to about two hundred and thirty degrees and the available portion of the
chlorinated compound prepared from Chlorocarbonate of Amyle boils at about from
two hundred and thirty to about two hundred and fifty degrees Centigrade.
I now proceed to describe the manner in which the above named derivatives of
Oxychloride of carbon may be employed in lieu of the said Agent in the manufacture
of colouring matters suitable for Dyeing and printing from Tetramethyldiamido-
benzophenone and analogous ketoue-bases.
As far as the preparation of the halogen-derivatives of the said ketone-bases by
means of the Chlorinated chlorocarbonic ethers is concerned I only need to refer to
the description of the preparation and characteristic properties of a chlorinated
derivative of Tetramethyldiamidobenzophenone contained in the Specification of
my before mentioned application for Letters Patent No 4850 and dated the 13th of
March of this year.
For instance about one part by weight of the ketone-base is to be intimately
mixed with about from one to two parts by weight of the chlorinated chloro
carbonic Ether by preference the Methyle or Ethyle-derivative-and the halo-
genizing action is allowed proceed at an ordinary or at a slightly elevated
temperature until a blue product possessing substantially the same or similar
properties as the halogen-derivative described in the Specification of my said
Application for Letters Patent, has been obtained as the final result of the

page_text: operation. The said blue product may then be further separated or purified by
the application of suitable solvents and precipitants or it may without any further
separation be at once added to or mixed with the compounds required for effecting
its transformation into colouring matters suitable for dyeing and printing.
"
For instance " Auramine may be produced by treating the blue product
resulting from the Action of the before described chlorinated Chlorocarbonate of
Ethyle upon Tetramethyldiamidobenzophenone with caustic ammonia in the
manner setforth in the Specification of my application for Letters Patent N° 5512
and dated the twenty sixth of March of this year-Or substituted "Auramines
may be produced according to the second method described in the Specification of
my application for Letters Patent N° 5741 and dated the thirty first of March
of this year, by allowing primary aromatic amines or their secondary alkylized
derivatives to react upon the halogenderivative of Tetramethyldiamidobenzophenone,
prepared as above described.
In order to employ the chlorinated Chlorocarbonic Ethers in the manufacture
of purple, blue and green colouring matters suitable for Dyeing and Printing
from Tetramethyldiamidobenzophenone and analogous Ketone-bases it is neither
necessary nor expedient (as I have stated in the Specification of my application
for Letters Patent numbered 5038 dated the eighteenth of March of this year) to
prepare beforehand the halogenderivatives in a separate and distinct process such
as above set forth, and then to effect their conversion into colouring matters by
a subsequent and distinct process. Such processes may be conveniently joined
together so as to form one single operation by preparing a mixture-no matter in
what successive order the ingredients are mixed-containing Tetramethyldiamido-
benzophenone (or analogous Ketone base) the chlorinated chlorocarbonic Ether, and
the aromatic base required for ultimately changing the halogen derivative, formed
at the commencement of the operation into the desired colouring matter.
The following is an example of the manner in which crystallized Methyl-Purple
may be produced from Tetramethyldiamidobenzophenone with the employment of
a chlorinated Chlorocarbonic Ether as halogenizing Agent.
About ten parts by weight of dry and finely powdered Tetramethyldiamido-
benzophenone are intimately mixed with or dissolved in about twenty parts by
weight of Dimethylaniline at a temperature of about 100 degrees centigrade.
The mixture or solution thus obtained is allowed to cool under constant stirring,
and then about twenty parts by weight of chlorinated Chlorocarbonate of Ethyle,
prepared as above described and boiling at about from 120 to about 160 degrees
Centigrade, are added.
The halogenizing action soon manifests itself by the mixture gradually assuming
an intense blue colour. The reaction is then allowed to proceed at a temperature
of about from forty to fifty degrees centigrade during the space of about 2 hours
and then the temperature of the mixture is maintained at about from seventy to
eighty degrees centigrade during the space of about from three to four hours, or
until the purple coloring matter thus produced no longer appears to increase
in intensity.
The result of the operation is a semi-solid crystalline mass of metallic-green or
bronze-like appearance. Its further treatment consists in dissolving the same in
hot water, adding caustic soda liquor in excess and distilling off the excess of
unused dimethylaniline, thus set free by a current of steam. The residual base
of the colouring matter is then separated from the alkaline liquor by filtration or
otherwise, washed with water and converted into its neutral hydrochlorate by
solution in the adequate amount of hot and diluted hydrochloric acid The purple
solution thus obtained is filtered-the unchanged Ketone base, if any, remaining
behind on the filter-and the filtered solution, whilst hot, is mixed with a small
quantity of salt water until a metallic-green film begins to form on the surface,
when upon cooling the Methyl purple, thus produced, will separate out in a well
crystallized condition.

page_text: In an analogous manner purple blue or green colouring matters suitable for
Dyeing and Printing (which according to their chemical constitution are members
of or closely allied to the Triphenylinethane series) may be obtained with the aid
of the above described chlorinated Chlorocarbonic ethers by their action upon
Tetramethyldiamidobenzophenone and analogous Ketone bases and by the con-
densation of the halogen derivatives thus produced with Diphenylamine, phenyl-
(tolyl- or xylyl-) alphanaphthylamine, dinaphthylamine and analogous secondary
aromatic amines, or with the tertiary alkylized substitution products of Aniline,
Orthotolindine Alpha Naphthylamine, Ortho anisidine, Metapheny-lenediamine,
Diphenylamine, Phenyl- (tolyl- or xylyl-) alphanaphthylamine alphadinaphthyla
mine and analogous tertiary aromatic amines or with chinoline substantially with
the results described in the Specification of my above referred to Application
for Letters Patent numbered 5038 and dated the eighteenth of March of this
year.
1

page_text: Improvements in the Manufacture of Colouring Matters suitable
for Dyeing and Printing from Tetramethyl-diamido Benzo-
"
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 MANUFACTURE OF COLOURING MATTERS SUITABLE FOR DYEING AND PRINTING
FROM TETRAMETHYL-DIAMIDO-BENZOPHENONE AND ANALOGOUS KETONE BASES
which invention has been communicated to me from abroad by Heinrich Caro,
Chemist to the Badische Aniline and Soda Fabrik Mannheim, Germany, and in
what manner the same is to be performed to be particularly described and
ascertained in and by the following statement:-
The manufacture of colouring matters from Tetramethyl diamido benzophenone
and analogous Ketone bases forms already the subject matter of a series of
Letters Patent granted to me as communications from my before named foreign
correspondent.
In the Specification of Letters Patent numbered No 4850 and dated the 13th day
of March A.D. 1884 I have described the conversion of Tetramethyl-diamido
benzophenone and analogous Ketone-bases into a new and remarkable class of
halogen derivatives, endowed with extraordinary reacting power and thus capable
of acting as materials for or as intermediate products in the synthetical preparation
of a variety of colouring matters suitable for Dyeing and printing.
The preparation of purple, blue and green colouring matters resulting from the
action of the said halogen-derivatives upon Dimethyl-aniline, Pheynl-Alpha-
napthylamine, Chinoline and a great number of analogous aromatic bases is
described in the specification of my Letters Patent numbered N° 5038 and dated
the eighteenth day of March A.D. 1884 whilst the Inventions described in the
Specifications of Letters Patent numbered and dated respectively No 5512 the
twenty sixth day of March, and No 5741 the thirty first day of March A D 1884
refer to the preparation of the so-called "Auramines a new class of yellow orange
and orange-brown colouring matters resulting from the action of the said halogen-
derivatives upon ammonia and upon primary and secondary amines.
"
In the before mentioned processes for producing colouring matters from Tetra-
methyldiamidobenzophenone and analogous Ketone bases Oxychloride of Carbon
(Phosgene) is particularly recommended as an agent capable of converting the said
Ketone-bases into their corresponding halogen derivatives.
Now my foreign correspondent has discovered that certain derivatives of
Oxychloride of Carbon exert an action similar to that of Oxychloride of Carbon
itself, and may on that account be conveniently employed in lieu of the said agent
in the processes described in my above recited Specifications of Letters Patent.
The said derivatives of Oxychloride of Carbon are obtained by chlorinating the
chlorocarbonic Ethers in the manner hereafter described. The chlorocarbonic.
Ethers are prepared according to a well known method by the action of the
corresponding alcohols upon Oxychloride of Carbon.

page_text: The most active reagent is the chlorinated chloro carbonic Ether produced from
the chlorocarbonate of Methyle, whilst the higher homologues of the said chlorinated
product, are endowed with an energy decreasing in the ratio of their increasing
molecular weight.
In order to prepare the said derivatives and substitutes of Oxychloride of Carbon
a current of dry chlorine gas is passed through the chloro-carbonic ethers as long
as a vivid absorption of the gas accompanied by a considerable rise of temperature
is observed to take place. The reaction proceeds very quietly in direct sun light,
and at the commencement of the operation the development of heat requires to be
moderated by external cooling. The progress of the action may be ascertained by
withdrawing a sample of the chlorinated product from time to time and testing its
efficiency to convert Tetramethyldiamidobenzophenone into its blue halogenized
derivative fully described in the Specification of my above recited Letters Patent,
numbered No 4850 and dated the 13th day of March A.D. 1884. Towards the end
of the operation the absorption of chlorine requires to be assisted by the application
of heat. The resulting product is then freed from the excess of Chlorine wbich
has remained unacted upon by passing a current of dry air through it, and it may
then at once be employed or by preference be previously submitted to a fractional
distillation, in order to separate the most active portions of the same.
In the manner before described chlorocarbonate of Methyl yields a very energetic
fraction boiling between about one hundred and one hundred and twenty degrees
centigrade.
From chlorocarbonate of Ethyle a chlorinated product may be obtained the
fractions of which, boiling between about one hundred and twenty degrees and
about one hundred and sixty degrees centigrade, may be conveniently employed
chlorocarbonate of Isobutyle yields a derivative boiling at about from two hundred
and ten to about two hundred and thirty degrees Centigrade and the available portion
of the chlorinated compound prepared from chloro-carbonate of Amyle boils at about
from two hundred and thirty to about two hundred and fifty degrees Centigrade.
I now proceed to describe the manner in which the above named derivatives of
Oxychloride of Carbon may be employed in lieu of the said agent in the manu-
facture of colouring matters suitable for Dyeing and Printing from Tetramethyl-
diamido benzophenone and analogous Ketone-bases.
As far as the preparation of the halogen-derivatives of the said Ketone-bases by
means of the chlorinated chloro-carbonic Ethers is concerned, I only need to refer to
the description of the preparation and characteristic properties of a chlorinated
derivative of Tetramethyl diamido benzophenone contained in my before mentioned
Specification of Letters Patent numbered N° 4850 and dated the thirteenth day of
March A.D. 1884. For instance about one part by weight of the above named
Ketone-base is to be intimately mixed with about from one to two parts by weight
of the chlorinated chlorocarbonic-Ether by preference with the before described
Methyle- or Ethyle-derivative-and the halogenizing action is allowed to proceed at
an ordinary or at a slightly elevated temperature until a blue product possessing
substantially the same or similar properties as the halogen-derivative described in
my above said specification of Letters Patent has been obtained as the final result
of the operation. The said blue product may then be further separated or purified
by the application of suitable indifferent solvents and precipitants in the manner
described in my above said specification or it may, without any further separation,
be at once added to or mixed with the compounds required for effecting its trans-
formation into colouring matters suitable for Dyeing and Printing. For instance,
"Auramine" may be produced by treating the blue product resulting from the
action of the before described chlorinated Chlorocarbonate of Ethyle upon Tetra-
methyl-diamido-benzophenone with caustic Ammonia in the manner set forth in
my specification of Letters Patent numbered N° 5512 and dated the 26th day of
March A.D. 1884.
Or substituted "Auramines" may be produced according to the second method
described in my specification of Letters Patent numbered Nº 5741 and dated

page_text: the 31st day of March A.D. 1884 by allowing primary aromatic armines or their
secondary alkylized derivatives to react upon the halogen-derivative' of Tetra-
methyldiamidobenzophenone prepared as above described.
In order to employ the chlorinated Chlorocarbon carbonic Ethers in the manu
facture of purple, blue and green colouring matters suitable for Dyeing and Printing
from Tetramethyldiamido-benzophenone and analogous Ketone bases it is neither
necessary nor expedient-(as I have stated in my specification of Letters Patent
numbered No 5038 and dated the 18th day of March A.D. 1884 to prepare before-
hand the halogen derivatives in a separate and distinct process such as above set
forth and then to effect their conversion into colouring matters by a subsequent
and distinct process. Such processes may be conveniently joined together so as to
form one single operation, by preparing a mixture no matter in what successivo
order the ingredients are mixed-containing Tetramethyldiamidobenzophenone (or
analogous Ketone base) the chlorinated Chlorocarbonic Ether and the aromatic
base required for ultimately changing the halogen-derivative formed at the
commencement of the operation, into the desired colouring matter.
The following is an example of the manner in which crystallized Methyl-Purple
inay be produced from Tetramethyldiamidobenzophenone with the employment of
a chlorinated Chlorocarbonic Ethel as halogenizing agent.
About ten parts by weight of dry and finely powdered Tetramethyldiamido-
benzophenone are intimately mixed with or dissolved in about twenty parts
by weight of Dimethylaniline at a temperature of about one hundred degrees
Centigrade. The mixture or solution thus obtained is allowed to cool under
constant stirring, and then about twenty parts by weight of chlorinated Chloro-
carbonate of Ethyle prepared as above described and boiling at about from 120 to
about 160 degrees Centigrade are added.
The halogenising action soon manifests itself by the mixture gradually assuming
an intense blue colour. The reaction is then allowed to proceed at a temperature
of from about forty to fifty degrees Centigrade during the space of about two
hours and then the temperature of the mixture is maintained at about from seventy
to eighty degrees Centigrade during the space of about from three to four hours
or until the purple colouring matter thus produced no longer appears to increase in
intensity.
The result of the operation is a semi-solid crystalline mass of metallic-green or
bronze-like apperance.
Its further treatment consists in dissolving the same in hot water, adding caustic
soda liquor in excess and distilling off the excess of unused dimethylaniline, thus
set free, by a current of steam.
The residual base of the colouring matter is then separated from the alkaline
liquor by filtration or otherwise, washed with water and converted into its neutral
hydrochlorate by solution in the adequate amount of hot and diluted hydrochloric
acid. The purple solution thus obtained is filtered-the unchanged Ketone-base, if
any, remaining behind on the filter-and the filtered solution, whilst hot is mixed
with a small quantity of salt-water until a metallic-green film begins to form on
the surface, when upon cooling the Methylpurple, thus produced, will separate out
in a well crystallized condition.
In an analogous manner purple, blue or green colouring matters suitable for
Dyeing and Printing (which according to their chemical constitution are to be
considered as members of or as closely allied to the Triphenylmethane-series) may
be obtained with the aid of the above described chlorinated Chlorocarbonicethers
by their action upon Tetramethyldiamidobenzophenone, Tetraethyldiamidobenzo-
phenone or Dimethyl-Diethyl-Diamidobenzophenone and by the condensation of
the halogen-derivatives thus produced with Phenyl-Tolyl- or Xylyl-Alphanaphthyl-
amine Alphadinaphthylamine, or with the tertiary alkylized substitution products
of Aniline, Alpha-Naphthylamine Orthoanisidine Metaphenylenediamine, Dipheny-
lamine Phenyl- (tolyl- or xylyl-) alphanaphthylamine Alphadinaphthylamine or
with Chinoline substantially with the results described in my abovo recited

page_text: specification of Letters Patent numbered N° 5038 and dated the 18th day of March
A.D. 1884
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
First The employment of the herein before described Chlorinated Chloro-
carbonates of Methyle, or Ethyle for converting Tetramethyldiamidobenzophenone
or Tetraethyldiamidobenzophenone or Dimethyl-Diethyl-diamido-benzo-phenone
into their corresponding halogen-derivatives, capable of being employed in the
manufacture of colouring matters, suitable for Dyeing and Printing substantially as
hereinbefore described.
Second-The hereinbefore described improved process for preparing purple,
Blue and Green colouring matters (suitable for Dyeing and Printing) by the action
of the above named chlorinated Chlorocarbonic Ethers upon mixtures of any of the
before named Ketone bases with any of the following aromatic bases videlicet.
I. Secondary amines: Phenyl-alphanaphthylamine Parotolyl-alphanaphthylamine
Orthotolyl-alpha-naphthylamine, Metaxylyl-alphanaphthylamine and Alphadi-
naphthylamine.
II. Tertiary amines: The tertiary Methyl Ethyl Isobutyl-Amyl or Benzyl-
substitution derivatives of Aniline or of Alpha Naphthylamine or of Ortho
anisidine or of Metaphenylene-diamine or of Diphenylamine or of any of the before
named Secondary amines.