IMPROVEMENTS IN THE PREPARATION OF COLOURING MATTERS SUITABLE FOR DYEING AND PRINTING
Year: 1883

page_text: LETTERS PATENT to Astley Paston Price of 47 Lincolns Inn Fields in the
County of Middlesex, Gentleman, for an Invention of "IMPROVEMENTS IN
THE PREPARATION OF COLOURING MATTERS SUITABLE FOR DYEING AND
PRINTING communicated to him from Heinrich Caro, Chemist to the
Badische Anilin and Soda Fabrik, at Mannheim, in the Empire of Germany.
"
PROVISIONAL SPECIFICATION left by the said Astley Paston Price at
the Office of the Commissioners of Patents on the 15th September 1883.
ASTLEY PASTON PRICE of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman "IMPROVEMENTS IN THE PREPARATION OF COLOURING MATTERS
SUITABLE FOR DYEING AND PRINTING" & communication to me from Heinrich
Caro Chemist to the Badische Anilin and Soda Fabrik at Mannheim in the
Empire of Germany
This Invention relates to the production of colouring matters suitable for
Dyeing and Printing by the joint action of Oxychloride of Carbon (Phosgene Co Cl 2)
and of anhydrous Chloride of Aluminium (or of similar condensing Agents (upon
Dimethylaniline Diethylaniline, Methylethylaniline or upon analogous tertiary
derivatives of aniline, in which the two hydrogen-atoms of its amido group are
substituted by alcohol-radicles. The action of Oxychloride of Carbon upon
Dimethylaniline and upon Diethyl-aniline has already been made the subject matter
of several known investigations (Proceedings of the German Chemical Society
A.D 1876) and amongst the bye-products, resulting from the said reaction, small
quantities of colouring matters have been noticed.
Now my foreign correspondent has discovered, that by calling in the aid of Chloride
of aluminium, the powerful condensing Agent introduced into Science by Friedel
and Crafts, the production of colouring matters may be made the principal result
of the Action of Oxychloride of Carbon not only upon Dimethylaniline and upon
Diethylaniline but likewise upon analogous tertiary derivatives of aniline, in which

page_text: the two hydro genatoms of its amido group are substituted by the same or by
dissimilar alcohol-radicles
The double chlorides of aluminium and sodium, or of aluminium and potassium
exert a condensing action similar to that of chloride of aluminium, whilst chlorido
of Zinc produces inferior results. The oxychloride of Carbon may be employed
either in its gaseous or in its liquified condition, or in a state of solution in
hydrocarbons, tetrachloride of carbon, chloroform, sulphide of carbon or other
suitable indifferent solvents.
The following is an example of the manner in which this Invention may be
applied to the preparation of a purple colouring matter from Dimethylaniline.
About twenty parts by weight of Dimethylaniline are intimately mixed with
about five parts by weight of anhydrous Chloride of aluminium and with due care
to prevent a considerable rise of temperature above about thirty degrees centigrade,
about three parts by weight of Oxychloride of Carbon are gradually added.
The reaction quickly sets in and manifests itself by the appearance of an intense
blue or purple colour. The mixture is then kept at a moderate temperature—say
at about from twenty to thirty degrees centigrade until the said blue or purple
color longer appears to increase in intensity.
In order to separate the colouring matter thus produced the ordinary methods
in use may be employed. For instance the result of the operation may be first
dissolved in water and submitted to a distillation with steam in order to distil off
the uncombined dimethylaniline or any other volatile products. The solution thus
obtained is then precipitated by the addition of common salt and allowed to cool.
The colouring matter separates out in a crystalline condition and may be
recrystallized from water or it may be converted into its crystallized sulphate or
oxalate in a manner well known to chemists.
The purple colouring matter thus produced differs considerably from the so
called Methyl-Purples or Violets, hitherto known in commerce under the appearance
of amorphous lumps or powder not only by its crystallised condition, but also by
the more blueish and brilliant shades which it is capable to produce in Dyeing and
Printing.
In an analogous manner colouring matters are produced by the joint action
of Oxychloride of Carbon and Chloride of Alluminium upon Diethylaniline
Methylethylaniline or upon the above said tertiary substitution-derivatives of
aniline

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed
by the said Astley Paston Price in the Patent Office on the 14th March
1884.
"
"
ASTLEY PASTON PRICE of 47 Lincoln's Inn Fields in the County of Middlesex
Gentleman "IMPROVEMENTS IN THE PREPARATION OF COLOURING MATTERS
SUITABLE FOR DYEING AND PRINTING a Communication to me from Heinrich
Caro, Chemist to the Badische Aniline and Soda Fabrik at Mannheim in the
Empire of Germany
This Invention relates to the production of colouring matters suitable for Dyeing
and Printing by the joint action of Oxychloride of Carbon (Phosgene Co Cl₁) and
of anhydrous chloride of Aluminium (or of similar condensing Agents) upon
Dimethylaniline, Diethylaniline, Methylethylaniline or upon certain analogous
tertiary derivatives of Aniline, in which the two hydrogen-atoms of its
amidogroup are substituted by Alcohol radicles. The The action of Oxychloride
of Carbon upon Dimethylaniline and upon Diethylaniline has already been mado
the subject matter of several known investigations. (Proceedings of the German
Chemical Society A.D. 1876) and amongst the bye-products, resulting from the
said reaction, small quantities of colouring matters have been noticed.
Now my Foreign correspondent has discovered that by calling in the aid of
anhydrous chloride of Aluminium the powerful condensing agent introduced into
Science by Friedel and Crafts, the production of colouring matters may be made
the principal result of the action of Oxychloride of Carbon not only upon
Dimethylaniline and upon Diethylaniline but likewise upon certain analogous
tertiary derivatives of aniline hereafter named in which the two hydrogenatams of
its amido group are substituted by the same or by dissimilar alcohol-radicles.
The double anhydrous chlorides of Aluminium and Sodium or of Aluminium
and Potassium exert a condensing action similar to but less energetic than that of
chloride of Aluminium whilst chloride of Zinc produces inferior results as far as
regards the yield of colouring matter. The Oxychloride of Carbon may be
employed either in its gaseous or in its liquified condition or in a state of solution
in hydrocarbons, tetrachloride of carbon, chloroform, sulphide of carbon or other
suitable indifferent solvents.
The following is an example of the manner in which this Invention may be
applied to the preparation of a purple colouring matter from Dimethyl-aniline.
About twenty parts by weight of Dimethylaniline are intimately mixed with
about five parts by weight of anhydrous Chloride of Aluminium and, with due care
to prevent a considerable rise of temperature above about thirty degrees Centigrade
about three parts by weight of Oxychloride of Carbon are gradually added.
The reaction quickly sets in and manifests itself by the appearance of an
intense blue or purple colour. The mixture is then kept at a moderate temperature
say at about from twenty to thirty degrees Centigrade during from five to six
hours or until the said blue or purple colour no longer appears to increase in
intensity.
In order to separate the Colouring matter thus produced the ordinary methods
in use may be employed. For instance the result of the operation may be first
dissolved in water and submitted to a distillation with steam in order to distil off
the uncombined dimethylaniline or any other volatile products. The solution thus
obtained is then precipitated by the addition of common salt and allowed to
cool. The colouring matter separates out in a crystalline condition and may be
recrystallized from water or it may be converted into its base or into its crystallized
sulphate or oxalate in a manner well known to Chemists. The purple colouring

page_text: matter thus produced differs considerably from the so-called Methysl-Purples or
Violets, hitherto known in commerce under the appearance of amorphous lumps or
powder, not only by its crystallized condition, but also by the more bluish and
brilliant shades which it is capable to produce in Dyeing and Printing.
In analogous manner purple colouring matters of a bluer shade are produced by
the joint action of Oxychloride of Carbon and chloride of Aluminium (or the
above named similar condensing Agents) upon Diethylaniline Methylethylaniline,
Di-isobutylaniline and Di-amylaniline.
Having now described and particularly ascertained the nature of the said
Invention and the manner in which the same is or may be used or carried into
effect I would observe in conclusion that what I consider to be novel and
original and therefore claim as the Invention secured to me by the hereinbefore
in part recited Letters Patent is :-
Producing purple colouring matters suitable for dyeing and printing by treating
Dimethylaniline, Diethylaniline Methylethylaniline, Di-isobutylaniline and Di-
amylaniline with Oxychloride of Carbon and anhydrous chloride of Aluminium or
similar condensing Agents as berein before defined and then effecting the separation
of colouring matter substantially as hereinbefore described.
In witness whereof I the said Astley Paston Price have to this my Specification
set my hand and seal this fourteenth day of March One thousand eight hundred
and eighty four.