IMPROVEMENTS IN THE PREPARATION OF COLOURING MATTERS SUITABLE FOR DYEING AND PRINTING FROM HALOGEN-DERIVATIVES OF TETRAMETHYL-DIAMIDO BENZOPHENONE AND ANALOGOUS KETONE-BASES
Year: 1884

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 COLOURING MATTERS SUITABLE FOR DYEING AND PRINTING
FROM HALOGEN-DERIVATIVES OF TETRAMETHYL-DIAMIDO BENZOPHENONE AND
ANALOGOUS KETONE-BASES" which Invention has been communicated to me from
Abroad by Heinrich Caro, Chemist to the Badische Anilin & Soda Fabrik of
Ludwigshafen on the Rhine in the Empire of Germany to be as follows:-
This Invention relates to the synthetical preparation of purple blue and green
colouring matters suitable for dyeing and printing. According to their chemical
constitution the said colouring matters are members of the Triphenyl-methane
series or closely allied to the same. The process for their production chiefly
consists in the action of certain halogen derivatives of Tetramethyldiamido benzo-
phenone and analogous ketone bases the preparation of which forms the subject
matter of a former application for Letters Patent by me dated the 13th day of
March 1884 and Nod 4850 upon Dimethyl-aniline, Phenyl-Alphanaphtylamine
Chinoline and certain analogous aromatic bases (which hereafter will be defined)
with the cooperation of trichloride of phosphorous oxychloride of phosphorous oxy-
chloride of carbon or similar deoxydising and halogenizing agents named in my
before mentioned application for Letters Patent.
In order to practically carry out this Invention it is neither necessary nor
expedient to prepare beforehand the said halogen derivatives in a separate and
distinct process (such as set forth in the above said application) and then to effect
their conversion into coloring matters by a subsequent and distinct process: Such´

page_text: 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 an analogous ketone
base) the deoxydising and halogenizing agent the aromatic base required for the
synthesis of the Triphenyl-methane or allied molecule, and in some instances an
indifferent solvent or substance for the purpose of conveniently diluting the
mixture. Such mixture upon being kept for some time either at an ordinary or at
an elevated temperature, as the case may be will become gradually changed into
the desired colouring matter which may afterwards be separated by the application
of known methods.
The nature of this Invention will be fully illustrated by the following examples.
In order to produce alkylized derivatives of Pararosaniline and its homologues
the following methods may be employed.
First example. About ten parts by weight of dry and finely powdered Tetra-
methyl diamido 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 six parts by weight of Trichloride of phosphorous are
added. The Halogenizing action soon manifests itself by a spontaneous rise of
temperature and by the previously almost solid mixture gradually liquifying and
assuming an intense blue colour in consequence of the above mentioned halogen-
derivative being thus produced in the first stage of the operation-Soon afterwards
a crystallisation will be observed to set in accompanied by a strong developement
of heat which ought to be moderated by external cooling and which elevation of
temperature is caused by the subsequent condensation of the said halogen derivative
of Tetramethyl diamido benzophenone with Dimethylaniline-Gradually the re-
action subsides and the mixture begins to solidify owing to the crystallisation.of
methyl-Purple or methylated Pararosaniline thus produced After several hours
standing the result of the operation is dissolved in hot water, carefully neutralized
with a caustic or carbonated alkali and submitted to distillation with steam, in
order to volatilize and thus to recover the excess of uncombined dimethylaniline-
The residual solution is filtered the unchanged ketone-base, if any, remaining
behind on the filter-and the filtered solution is precipitated with common salt-
Upon cooling the purple colouring matter separates out in a crystallised condition,
and it may then be filtered and recrystallized from boiling water-The separation
of crystallized methyl-purple from the crude product of the above described
operation may likewise be effected by the application of any other known and
convenient method, as for instance by first treating such crude product with an
excess of caustic alkali and steam and then converting the base thus obtained into
its crystallized hydrochlorate sulphate or oxalate.
Second example. The same or a similar result may be obtained by the employ-
ment of oxychloride of phosphorous and by reversing the successive order of mixing
the ingredients in the following manner About twenty five parts by weight of
dimethylaniline are first mixed with about ten parts by weight of oxychloride of-
phosphorous and then about ten parts by weight of dry and finely powdered Tetra-
imethyldiamido benzophenone are gradually added. The same phenomena will be
observed as those described in the preceding example, the reaction of the oxy-
chloride of phosphorous however being less energetic than that of the trichloride,
the operation requires to be finished at the temperature of the waterbath.
In the case of oxychloride of carbon being employed as halogenizing agent it is
advisable to dilute the mixture with hydrocarbons or with nitro benzole or with
common salt or with similar indifferent solvents or substances in order to effect a
change as thorough as possible of the Ketone-base.
Analogous results are obtained with the other halogenizing agents named in
my above recited application for Letters Patent, but their employment is less
economical.

page_text: Purple colouring matters of a bluer shade, but not possessing any or the same
crystallising properties may be obtained by substituting Tetraethyldiamido-benzo-
phenone or analogous tetraalkylized derivatives of Paradiamido benzophenone for
the methylated ketone-base in the above described process, or by employing therein
methyl-ethylaniline Diethylaniline Diamylaniline or similar tertiary alkylized
derivatives of aniline or Ortho-Toluidine in the place of Dimethylaniline The
corresponding secondary alkylized derivatives such as for instance Monomethyl-
aniline are not suitable for the purpose of this Invention.
Third example. Benzylated Methyl purples of various shades of blueish purple
may be produced as follows.
About ten parts by weight of Tetramethyldiamido benzophenone are intimately
mixed with about ten parts by weight of Dibenzylaniline and then about nine parts
by weight of oxychloride of phosphorous are added-The reaction is first allowed
spontaneously to proceed until it subsides again and then the mixture is gradually
heated up to about one hundred and twenty degrees centigrade until a homogenous
bronze-coloured "melt" is obtained which solidifies upon couling-The result of the
operation is first washed with cold water and then dissolved in boiling water
slightly acidulated with hydrochloric acid. The solutions thus obtained are filtered
and precipitated with common salt. The precipitated Benzylviolet may then be
filtered and dried. It dyes a bright bluish-purple upon animal or vegetable fibre
less liable to be affected by acids than the shades produced by the ordinary
benzylated Methyl purples hitherto known in commerce.
Similar benzylated methyl-purples may be obtained by the corresponding action
of the halogen-derivatives of Tetra-ethyl-diamido-benzo-phenone and analogous
tetra-alkylized ketone-bases upon the Tertiary Methyl Ethyl Isobutyl, Amyl and
Benzyl substitution products of Benzyl-aniline or Benzyl-Orthotoluidine.
Fourth example. In order to produce a phenylated Methyl-Purple about two
parts by weight of Diphenylamine and about three parts by weight of Tetra-
methyl-diamido-benzo phenone are dissolved in about ten parts by weight of
Toluol and then about two parts by weight of Trichloride of Phosphorus are added.
The reaction requires to be finished by maintaining the temperature of the mixture
at about the boiling point of Toluol during about one hour. The said solvent is
then distilled off by steam and the residue after being well washed with water and
dried may then be freed from any unchanged Diphenylamine by treatment with
suitable solvents of the latter, for instance, Benzole or Petroleum spirit. A further
purification of the product thus obtained may afterwards be effected by dissolving
the same in hot and concentrated Hydrochloric Acid precipitating the filtered
solution by the addition of cold water and filtering washing and drying the
precipitated coloring matter. The phenylated Methyl-purple produced as above
described is a purplish blue dye-stuff soluble in boiling acidulated water and easily
soluble in Alcohol.
Similar phenylated Purples of a more strongly marked basic character and
possessing a higher degree of solubility in water are produced in an analogous
manner by the employment of the tertiary alkylized derivatives of Diphenylamine
in the above process. For instance the bluish-purple coloring matter resulting
from the condensation of the halogen derivative with Methyl-diphenylamine forms
a Crystaline Oxalate readily soluble in hot water.
By the application of the same synthetical process to the tertiary alkalized
substitution-compounds of Ortho-anisidine and Metaphenylendiamine Alkylized.
oxy- and amido derivatives of the Methyl-purples are obtained.
Fifth example. About three parts by weight of Dimethylorthoanisidine about
two parts by weight of Tetra-methyl-diamido-benzo-phenone and about one and a
half parts by weight of Oxychloride of Phosphorus are mixed and treated in the
manner above described in the first and second before mentioned examples. The
coloring matter thus obtained is of a bright bluish purple exceedingly soluble
in water.

page_text: Tetramethyl-Metaphenylendiamine produces under the
blackish-purple readily soluble in water.
same
conditions a
Blue coloring matters allied to the Triphenylmethane series are obtained by the
employment of tertiary alkylized derivatives of Alpha-Naphthylamine. Certain
secondary derivatives of the same amine, produced by the substitution of phenyl,
Tolyl, Naphtyl or analogous aromatic Hydrocarbon radicles may likewise be used
for the purpose of this Invention. Secondary alkylized derivatives of Alpha-
Naphtylamine however are not capable of being employed in this process. The
following examples will serve to illustrate the preparation of the said blue
colouring matters.
Sixth example. About ten parts by weight of Tetramethyldiamido-benzophenone
are intimately mixed with about 25 parts by weight of Dimethyl-Alpha Naphtyl-
amine and about seven and a half parts by weight of Oxychloride of Phosphorous.
The reaction proceeds in the manner described in the first and second herein before
mentioned examples. At the close of the operation the mixture is heated by means
of a water bath until a semi-solid melt of bronze coloured appearance has been
obtained. The same may then be dissolved in water supersaturated with Caustic
Soda liquor in order to set free the organic bases contained therein and submitted
to a distillation with steam whereby the uncombined Dimethyl-Alpha Naphthyl-
amine may be recovered-The residual blue solution is afterwards filtered and
precipitated with common salt The coloring matter thus produced is easily
soluble in water and dyes purplish-blue shades.
Similar coloring matters ranging from purplish-blue to a pure or greenish blue
in proportion to the increasing atomic weight of the alcohol radicles contained
therein are obtained by the employment of the higher homologues of Tetramethyl-
diamido-benzophenone and of Dimethyl-Alpha Naphtylamine in the above described
process.
Seventh example.-About ten parts by weight of Tetramethyl-diamido-benzo-
phenone are intimately mixed with about nine parts by weight of Phenyl-Alpha
Naphtylamine and then about seven parts by weight of Oxychloride of Phosphorous
are added. After the elevation of temperature which has been spontaneously pro-
duced by the first reaction has subsided or nearly so, the mixture is gradually
heated up to a temperature of about one hundred and ten degrees Centigrade until
a bronze colored melt is obtained which solidifies upon cooling.
The result of the operation is then powdered washed at first with cold water and
afterwards dissolved in a large quantity of boiling water.
The solution thus
obtained is allowed to settle the clear liquor is drawn off filtered slightly acidulated
with Hydro-chloric acid and precipitated by common salt. The preciptated
coloring matter may then be redissolved in boiling water and in the same manner
reprecipitated from its filtered solution.
The dye-stuff obtained as before described dyes a very bright and pure blue.
By the same or similar process Alpha Dinaphtylamine produces a greenish-blue
coloring matter difficultly soluble in water but easily soluble in Alcohol.
Green coloring matters allied to the Triphenylmethane series are obtained by the
condensation of Chinoline with the halogen derivatives of Tetramethyldiamido
benzophenone and homologues Ketone bases-Their preparation may be illustrated
by the following example.
Eighth example. About 20 parts by weight of pure Chinoline are intimately
mixed with about 14 parts by weight of Tetramethyldiamido benzophenone and
about 9 parts of Trichloride of Phosphorous. The reaction which quickly sets in is
very energetic and requires to be moderated by external cooling. After a short
time a semifluid greenish-blue "melt" is obtained which is finally heated on the
water bath during about half an hour The result of the operation is then
dissolved in boiling water and the green solution thus obtained is treated with a
current of steam filtered and precipitated by the addition of common salt and
Chloride of zinc. The coloring matter thus precipitated is afterwards filtered

page_text: pressed and dried-The "Chinoline Green" obtained as before described is readily
soluble in water and dyes bluish-Green shades.
By the employment of Tetraethyl-diamido benzophenone or higher homologues
in the before described process green coloring matters of a purer or more yellowish
green tint are produced.
111
.
.
1004
J. HENRY JOHNSON,
47, Lincoln's Inn Fields, London, W.C.,
Agent for the said.
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 PURPLE BLUE AND GREEN COLOURING MATTERS SUITABLE FOR
DYEING AND PRINTING FROM HALOGEN-DERIVATIVES OF TETRA-METHYL-DIAMIDO-
BENZO-PHENONE AND ANALOGOUS KETONE-BASES," which Invention has been com-
municated 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 synthetical preparation of purple blue and green
coloring matters suitable for Dyeing and printing. According to their chemical
constitution the said colouring matters are members of the Triphenyl methane
series or closely allied to the same. The process for their production chiefly
consists in the action of certain halogenderivatives of Tetramethyl-diamido-benzo-
phenone Tetraethyldiamido benzophenone and Dimethyl-Diethylamido-benzo –
phenone, the preparation of which halogen-derivatives forms the subject matter of
a former application for Letters Patent by me dated the 13th day of March 1884
and Numbered No 4850, upon Dimethyl aniline Phenyl-Alphanaphthylamine,
Chinoline and certain analogous aromatic bases (which hereafter will be defined)
with the co-operation of trichloride of phosphorus, pentachloride of phosphorus,
oxy-chloride of phosphorus, oxy-chloride of carbon, or of the corresponding
bromine compounds of phosphorus nained in my before mentioned application for
Letters Patent.
In order to practically carry out this Invention it is neither necessary, nor
expedient to prepare before-hand the said halogenderivatives in a separate and
distinct process (such as setforth in the above said application) and then to effect
their conversion into coloring 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 any of the before named
ketone-bases), the deoxydising and halogenizing agent, the aromatic base required
for the Synthesis of the Triphenylmethane or allied molecule, and in some instances

page_text: an indifferent solvent or substance for the purpose of conveniently diluting the
mixture. Such mixture upon being digested for some time at a moderately
elevated temperature will become gradually changed into the desired colouring
matter which may afterwards be separated by the application of known methods.
The aromatic bases to which this present Invention applies are the following.
I. Secondary amines: Diphenylamine, phenyl-alpha-naphthylamine, Paratolyl
alpha-naphthylamine, Ortho-tolyl-alpha-naphthylamine Metaxylyl alpha-
naphthylamine Alpha-dinaphthylamine.
•
II. Tertiary amines: the Tertiary Alkylized derivatives of aniline, Alpha-
naphthylamine, Ortho-anisidine, meta-phenylen-diamine and of the before
named secondary amines, such as are produced by the substitution of
Methyl Ethyl Isobutyl Amyl or Benzyl for hydrogen in the amido group
of the said primary and secondary amines.
III. Chinoline: The nature of this Invention and the manner in which the same
is to be performed will be fully understood by the following examples.
L-PURPLE COLOURING MATTERS.
In order to produce alkylized derivatives of pararosaniline the following methods
may be employed.
First example.-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 six parts by weight of Trichloride of
Phosphorus are added. The halogenizing action soon manifests itself by a
spontaneous rise of temperature and by the previously almost solid mixture
gradually liquefying and assuming an intense blue colour, in consequence of the
above mentioned halogen-derivative being thus produced in the first stage of the
operation. Soon afterwards a crystallisation will be observed to set in accompanied
by a strong development of heat which ought to be moderated by external cooling
and which elevation of temperature is caused by the subsequent condensation of
the said halogen-derivative of Tetramethyldiamido benzophenone with Dimethyl-
aniline.
Gradually the reaction subsides and the mixture begins to solidify, owing to the
crystallisation of Methyl-Purple or methylated Pararosaniline thus produced After
several hours standing, the result of the operation is dissolved in hot water
carefully neutralised with a caustic or carbonated alkali and submitted to
distillation with steam, in order to volatilise and thus to recover the excess of
uncombined dimethylaniline-The residual solution is filtered, the unchanged
ketone base (if any) remaining behind on the filter and the filtered solution is
precipitated with common Salt Upon cooling, the purple colouring matter separates
out in a crystallised condition and it may then be filtered and recrystallised from
boiling water-The separation of crystallised Methyl-Purple from the crude product
of the above described operation may likewise be effected by the application of any
other known and convenient method, as for instance by first treating such crude
product with an excess of caustic soda liquor and steam and then converting the
base thus obtained into its crystallized hydrochlorate sulphate or oxalate.
Second example.-The same or a similar result may be obtained by the
employment of oxychloride of phosphorus and also by reversing the successive
order of mixing the ingredients, as will be shown by the following description-
About twenty five parts by weight of Dimethylaniline are first mixed with about
ten parts by weight of oxychloride of phosphorus and then about ten parts by
weight of dry and finely powdered Tetramethyldiamido-benzophenone are gradually
added-The same phenomena will be observed as those described in the preceding
example the reaction of the oxychloride of phosphorus however being less energetic

page_text: than that of the trichloride the operation requires to be finished at the temperature
of about from 90 to 100 degrees centigrade.
In the case of oxychloride of carbon being employed as halogenizing agent it is
advisable to dilute the mixture with benzole or toluol or with nitrobenzole, in
order to effect a change as thorough as possible of the Ketone base. For instance
about ten parts by weight of Tetramethyldiamido-benzophenone are mixed with
about twenty five parts by weight of dimethylaniline and then a solution of about
four parts by weight of Oxychloride of Carbon in about ten parts by weight of
toluol is gradually added. The reaction proceeds substantially in the manner
above described-At the end of the operation toluol is first recovered by distillation
with steam and afterwards the purple colouring matter is separated from the
excess of unaltered dimethylaniline by the addition of caustic soda liquor, and
renewed distillation with steam as above setforth in the first example.
It is obvious, that by the employment of oxychloride of carbon as an halogenizing
agent a complete synthesis of "Methyl-purples" or alkylized amido derivatives of
Triphenylcarbinol may be effected in a combined series of operations from tertiary
alkylized derivatives of aniline and from oxychloride of carbon only in as much
as the before named Ketone bases may be first produced by the action of
oxychloride of carbon upon dimethylaniline diethylaniline or methyl-ethylaniline
according to a well known method (Berichte of the German Chemical Society
Vol. IX page 716) and afterwards the result of the said action may be again
treated with oxychloride of carbon in the presence of the same or of a different
tertiary alkylized derivative of aniline substantially in the manner before
described. Analogous results are obtained with pentachloride of phosphorus or
with the bromine compounds of phosphorus named in my above recited application
for Letters Patent but their employment is less economical than that of the before
described halogenizing agents.
Purple colouring matters of a bluer shade may be obtained by substituting
Tetraethyldiamido-benzophenone or dimethyl-diethyldiamidobenzophenone for the
tetramethylated Ketone-base in the above described process or by employing
therein Diethylaniline, Diisobutylaniline Diainylaniline Dibenzylaniline or other
tertiary alkylized derivatives of aniline containing two dissimilar alcohol radicals
such as methylethylaniline in the place of dimethylaniline (The corresponding
secondary alkylized derivatives of aniline such as for instance Monomethylaniline
are not suitable for the purpose of this Invention) Benzylated Methyl-Purples of
various shades of blueish purple may for instance be produced as follows—
Third example. About ten parts by weight of Tetramethyldiamido-benzo-
phenone are intimately mixed with about ten parts by weight of Dibenzylaniline
and then about nine parts by weight of oxychloride of phosphorus are added.
The reaction is first allowed to proceed without any external application of heat
until it subsides again and then the mixture is gradually heated up to about one
hundred and twenty degrees Centigrade until a hemogeneous bronze coloured
"melt" is obtained which solidifies upon cooling-The result of the operation is
first washed with cold water and then dissolved in boiling water slightly acidulated
with hydrochloric acid-The solutions thus obtained are filtered and precipitated
with common salt-The precipitated "benzylviolet" may then be filtered and
dried. It dyes a bright blueish purple upon animal or vegetable fibre less liable to
be affected by acids than the shades produced by the ordinary benzylated Methyl
purples hitherto known in commerce Similar benzylated Methyl purples of a still
bluer shade may be obtained by the corresponding action of the halogen derivatives
of Tetraethyldiamido-benzophenone and Dimethyl-diethyl-diamido-benzophenone
upon the tertiary Methyl, Ethyl, Isobutyl Amyl and Benzyl substitution products
of Benzyl Aniline.
Fourth example.-In order to produce a phenylated Methyl Purple about two
parts by weight of diphenylamine and about three parts by weight of Tetramethyl-
diamido-benzophenone are dissolved in about ten parts by weight of Toluol and

page_text: Blue coloring matters allied to the Triphenylmethane series are obtained by the
employment of the before defined tertiary derivatives of Alpha-Napthylamine,
certain secondary derivatives of the same amine, produced by the substitution of
Phenyl-Tolyl, Xylyl or Naphtyl as before defined, may likewise be used for the
purpose of this Invention [Secondary alkylized derivatives of Alpha-Naphtyl-
amine however are not capable of being employed in this process] The following
examples will serve to illustrate the preparation of the said blue colouring matters.
Sixth example. About ten parts by weight of Tetramethyl-diamido-benzophenone
are intimately mixed with about twenty five parts by weight of Dimethyl-Alpha-
Naphtylamine and about seven and a half parts by weight of Oxychloride of
Phosphorus. The reaction proceeds in the manner described in the first and
second hereinbefore mentioned examples. At the close of the operation the
mixture is heated by means of a water bath until a semi-solid "melt" of bronze-
colored appearance has been obtained. The same may then be dissolved in water
supersaturated with caustic soda liquor, in order to set free the organic bases
contained therein, and submitted to a distillation with steam whereby the
uncombined Dimethyl-Alpha-Naphthylamine may be recovered. The residual blue
solution is afterwards filtered and precipitated with common salt. The colouring
matter thus produced is easily soluble in water and dyes purplish-blue shades.
Similar colouring matters ranging from purplish-blue to a pure or greenish blue,
in proportion to the increasing atomic weight of the alcohol and hydrocarbon
radicles contained therein are obtained by the condensation of the halogen

page_text: derivatives of Tetramethyl diamido benzophenone (and its above named higher
homologues) with the higher homologues of Dimethyl-Alpha-Naphthylamine or
by their condensation with the secondary derivatives of Alpha-Naphthylamine and
the tertiary alkylized substitution products of the same such as are herein before
defined.
As an example I proceed to describe the preparation of a pure blue coloring
matter from Phenyl-Alpha-Naphthylamine.
Seventh example.-About ten parts by weight of Tetramethyl-diamido-benzo-
phenone are intimately mixed with about nine parts by weight of Phenyl-Alpha-
Naphthylamine and then about seven parts by weight of oxychloride of phosphorus.
are added. After the elevation of temperature which has been spontaneously
produced by the first reaction, has subsided, or nearly so, the mixture is gradually
heated up to a temperature of about one hundred and ten degrees Centigrade,
until a bronze-coloured "melt" is obtained which solidifies upon cooling The
result of the operation is then powdered, washed at first, with cold water and
afterwards dissolved in a large quantity of boiling water. The solution thus
obtained is allowed to settle, the clear liquor is drawn off, filtered, slightly acidulated
with hydrochloric acid and precipitated with common salt. The precipitated
colouring matter may then be redissolved in boiling water and in the same manner
reprecipitated from its filtered solution.
The dyestuff obtained as before described, dyes a very bright and pure
blue. A still finer shade may be produced by the employment of Paratolyl-alpha-
naphthylamine.
By the same or similar process Alpha Dinanhthylamine produces a greenish blue
Green coloring matters allied to the Triphenyl methane series, are obtained by
the condensation of Chinoline with the halogen derivatives of Tetramethyl-
diamido-benzophenone and the before named homologous Ketone-bases.
Their preparation may be illustrated by the following example.
Eighth example.-About twenty parts by weight of pure Chinoline are intimately
mixed with about fourteen parts by weight of Tetramethyl-diamido-bonzophenone
and about nine parts of Trichloride of Phosphorus. The reaction, which quickly
sets in, is very energetic and requires to be moderated by external cooling. After
a short time a semi fluid greenish-blue "inclt" is obtained, which is finally heated
on the waterbath during about half an hour. The result of the operation is then
dissolved in boiling water and the green solution thus obtained is treated with a
current of steam, filtered and precipitated by the addition of common salt and
chloride of zinc. The colouring matter thus precipitated is afterwards filtered
pressed and dried. The "Chinoline green" obtained as before described is readily
soluble in water and dyes blueish-green shades.
By the employment of Tetraethyl-diamido-benzophenone or Dimethyl-Diethyl-
diamido-benzophenone in the before described process green coloring matters of a
purer or more yellowish-green tint are produced.
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, The preparation of purple colouring matters suitable for Dyeing and
Printing, by the action of halogen-derivatives of Tetramethyl-diamido-benzophenone,
or of Tetraethyl-diamido-benzophenone, or of Dimethyl-Diethyl-diamido-benzo-
phenone, the production of which halogen derivations forms the subject matter of
my application for Letters Patent dated the thirteenth day of March 1884 and

page_text: numbered No 4850,) upon Diphenylamine, or upon the tertiary Methyl,-Ethyl-,
Isobutyl, Amyl- or Benzyl-substitution-deratives of Aniline, Orthoanisidine, Meta-
phenylendiamine and Diphenylamine, with the co-operation of trichloride or of
pentachloride or of oxychloride of phosphorus, or of the corresponding bromine-
compounds of phosphorus, or of oxychloride of carbon, substantially as hereinbefore
described.
;
f
Second, The preparation of blue colouring matters suitable for dyeing and printing
by the action of the before named halogen derivatives upon Phenyl-alpha-naphty-
Jamine, Paratolyl-alpha-naphtylamine, Orthotolyl-alphanaphtylamine, Metaxylyl-
alpha-naphtylamine, Alpha-dinaphthylamine or upon the tertiary Methyl- Ethyl-,
Isobutyl-, Amyl-, or Benzyl-substitution derivatives of the said secondary amines
with the co-operation of the before named chlorine or bromine-compounds of
phosphorus or of oxychloride of carbon, substantially as hereinbefore described.
Third, The preparation of green coloring matters suitable for Dyeing and
Printing by the action of the before named halogen-derivatives upon Chinoline
with the co-operation of the before named phosphorus-compounds or of Oxy-chloride
of Carbon, substantially as herein before described.
1
1004