IMPROVE- MENTS IN THE MANUFACTURE OF COLOURING MATTERS SUITABLE FOR DYEING " AND PRINTING
Year: 1882

page_text: LETTERS PATENT to John Erskine of 151 St Vincent Street. Glasgow. in the
county of Lanark, North Britain, Solicitor, for an invention of "IMPROVE-
MENTS IN THE MANUFACTURE OF COLOURING MATTERS SUITABLE FOR DYEING
"
AND PRINTING A communication from abroad by Carl Rumpff, of Aprath,
near Elberfeld, in the Empire of Germany, Chemical Manufacturer
county of Lanark, North Britain, Solicitor, for an invention of "IMPROVE-
MENTS IN THE MANUFACTURE OF COLOURING MATTERS SUITABLE FOR DYEING
"
AND PRINTING A communication from abroad by Carl Rumpff, of Aprath,
near Elberfeld, in the Empire of Germany, Chemical Manufacturer
PROVISIONAL SPECIFICATION left by the said John Erskine at the Office
of the Commissioners of Patents on the 12th May 1882.
و"
JOHN ERSKINE, of 151 St Vincent Street, Glasgow, in the County of Lanark,
North Britain, Solicitor, " IMPROVEMENTS IN THE MANUFACTURE OF COLOURING
MATTERS SUITABLE FOR DYEING AND PRINTING [A communication from abroad
by Carl Rumpff, of Aprath, near Elberfeld, in the Empire of Germany, Chemical
Manufacturer.]
The nature of this Invention consists in manufacturing colouring matters suitable
for dyeing and printing by the reaction of the Sulpho acids of Diazo and of Diazo-
Azo or Tetrazo derivatives of the aromatic hydro-carbons, preferably in the form
of the Sodium Salts or compounds of the said Sulpho acids on aqueous solutions
of the Napthylamines effected by means or with aid of acids as hereinafter
explained, or by the reaction of the non-sulphonated Diazo and Diazo-Azo
derivatives of the said aromatic hydrocarbons on such solutions of the Napthy-
lamines and by subsequent sulphonization of the product.
The Diazo bodies of the Benzole series, whether they be sulphonated or not, and
further the Diazo-azo bodies of the Benzole series, sulphonated or not, when brought
into contact with solutions of the Napthylamines (although not when brought into
contact with their Sulpho acids) yield brown dyestuffs which are soluble in spirit
or in water. In these reactions or processes it is important to have the Napthyl-
amines well dissolved, and, if watery solutions are employed, to add acid for the
purpose of effecting a thorough solution.-But beyond effecting the solution by
such addition of acid, the precise quantity or amount of Acid used, unless it go to

page_text: great excess, is not a point of very essential importance. If we wish to carry out
the reaction in watery solution, it is enough if there be just so much acid as is
necessary to convert the difficultly soluble Napthylamines into the more easily
soluble salts. A considerable excess of acid beyond what is barely necessary for
the constitution of the Napthylamine Salts does no harm. If the Napthylamines
were dissolved in Spirit there would be no need of any acid at all. In that case the
Diazo compound could be poured direct into the spirituous Napthylamine solution.
If we use aqueous solutions the Napthylamine must have at least so much acid
as to make it readily soluble, that is, so much acid as will convert it into its
corresponding salt. It does not matter much which acid we use to make the
soluble salt, or to effect the solution of the Napthylamine, but I prefer to use
a solution in water effected by the aid of Hydrochloric Acid, that is in effect to
use the Hydrochlorate of the Napthylamine. Nor unless there be a very great
excess of acid will it interfere with the reaction between the Diazo body, and the
Napthylamine that there is some and even a considerable amount of free acid
present. In any case of doubt on account of the excess of acid present, whether
the desired reaction will not be impeded or prevented thereby, an easy preliminary
experiment with small quantities will determine whether the Diazo body and the
Napthylamine solution will give the coloured Amido-Azo product. That is what
I mean by having the Napthylamines in acid solution-it is a watery solution of
their salts formed from acids, whether there be or be not free Acid besides. If
there is only so much Hydrochloric Acid used as will convert the quantity of
Napthylamine into the Hydrochlorate, the solution may in one sense be called
a neutral solution, but what I mean is that the Napthylamine is dissolved in
water by the aid of an acid, and that either just so much acid as to form the
corresponding Napthylamine Salt, or it may be something more. It is essential,
or at least of prime importance, in order to obtain the desired colouring matters
in an accurate and certain way, that the Diazotizing of the amido body, by which
the Dinzotised element of the combination is formed, should take place in a
different vessel from that in which the bringing together of the Diazo body and
the Napthylamine takes place. It is not absolutely impossible to get colouring
matters by making Nitrous acid act diazotisingly on a mixture, say for example
of Hydrochlorate of Naptbylamine with Amido Azo Binzol Sulpho Acid, but it is
a most inconvenient and irrational mode of procedure:
Instead of using the Sulpho Acids of the Diazo or Diazo-Azo body to react on
the Napthylamine dissolved in or by means of an acid as aforesaid, I may make
the non-sulphonated Diazo or Diazo-Azo body act on the Napthylamine and
Sulphonate in manner well known to Chemists for the sulphonating of organic
compounds the product of the reaction afterwards, and so obtain a dyestuff
practically the same as or similar to the dyestuff obtained by the reaction of
the sulphonated compound of the same Diazo or Diazo-Azo body on the same
Napthylamine.
By Diazo and Diazo-Azo or Tetrazo derivatives of the Aromatic Hydrocarbons,
mean the derivatives obtained by acting with Nitrous Acid (or a Nitrite and an
acid to liberate from the Nitrite its Nitrous acid) on the Amido and Amido Azo
bases corresponding to the Aromatic Hydrocarbons.
By the Aromatic Hydrocarbons I mean the Hydrocarbons of the series of the
Benzoles exclusive of Napthalene, and I include not only Toluol, and Xylol, and
what are called the homologues of Benzol, but such Hydrocarbons as Ethyl, Benzol,
Ethyl Methyl Benzol, and the like aromatic Hydrocarbons which are isomeric with
members of the homologous series. By the Napthylamines I mean Alpha and Beta
Napthylamine, and also the Alkylized compounds thereof, such as the Methyl, and
Phenyl Napthylamines.
As an example and illustration of the reactions in which my Invention consists
and of the process by which the same are effected, I give the following:-
I prepare a new brown dyestuff, or colouring matter, by causing Diazo Azo
Benzole Sulphonate of Soda to act on. Napthylamine Alpha or Beta in Acid

page_text: Solution, that is to say, dissolved by the aid of acid in water as before explained.
1 take 50 lbs. of Amido Azo Benzol Sulphonate of Soda dissolved in 500 lbs. of
water cooled down to 3° Centigrade. To this solution I add slowly 75 lbs. of
Muriatic Acid and thereafter 11 lbs. of sodium Nitrite dissolved in 40 lbs. of water.
After several hours rest the liquid is poured into a solution containing 25 lbs. of
Napthylamine, 50 lbs. of Muriatic Acid, and 500 lbs. of water. The new brown
dyestuff separates instantly as a voluminous precipitate which is filtered and dried.
The dyestuff when dried appears as a dark brown powder; it is soluble in hot
water and its aqueous solution takes a brown colour by the addition of alkalis.
Muriatic or Sulphuric Acid dyes the aqueous solution blueish red. It dyes wool
and silk of a dark reddish brown colour in an acidulated bath, and this colour is
fast against soap and light.
Other colouring matters may be got by substituting in the preceding process the
Sulpho Acids of the Diazo and the Diazo-Azo or Tetrazo derivatives of Toluol,
Xylol, Methyl Benzol, Ethyl Benzol, and of the other Aromatic Hydrocarbons (not
however including Napthalene) in the form preferably of the Sodium Salts of
Baid Sulpho Acids for the Diazo derivative of Amido Azo Benzol Sulphonate
of Soda.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said John Erskine in the Great Seal Patent Office on the 10th November
1882.
JOHN ERSKINE, of 151 St Vincent Street, Glasgow, in the County of Lanark,
North Britain, Solicitor "IMPROVEMENTS IN THE MANUFACTURE OF COLOURING
MATTERS SUITABLE FOR DYEING AND PRINTING," a communication from abroad
by Carl Rumpff, of Aprath, near Elberfeld in the Empire of Germany, Chemical
Manufacturer,
The nature of this Invention consists in manufacturing colouring matters
suitable for dyeing and printing by the reaction of the Sulpho Acids of Diazo and
of Diazo-Azo or Tetrazo derivatives of the aromatic hydro-carbons, preferably in
the form of the sodium salts or compounds of the said Sulpho Acids on aqueous
solutions of the Napthylamines effected by means or with aid of acids as herein-
after explained, or by the reaction of the non-sulphonated Diazo and Diazo-azo
derivatives of the said Aromatic Hydro-carbons on such solutions of the Napthyla-
mines and by subsequent sulphonization of the product.
The Diazo bodies of the Benzole series, whether they be sulphonated or not, and
further the Diazo-azo bodies of the Benzole series, sulphonated or not when
brought into contact with solutions of the Napthylamines (although not when
brought into contact with their Sulpho Acids) yield brown dyestuffs which are
soluble in spirit or in water. In these reactions or processes it is important to
have the Napthylamines well dissolved, and if watery solutions are employed, to
add Acid for the purpose of effecting a thorough solution. But beyond effecting
the solution by such addition of acid, the precise quantity or amount of Acid used,
unless it go to great excess, is not a point of very essential importance. If it be
wished to carry out the reaction in watery solution, it is enough if there be just so
much acid as is necessary to convert the difficultly soluble Napthylamines into the
more easily soluble salts. A considerable excess of acid, beyond what is barely
necessary for the constitution of the Napthylamine Salts, does no harm. If the
Napthylamines were dissolved in spirit there would be no need of any acid at all.
In that case the Diazo compound could be poured direct into the spirituous
Napthylamine solution. If aqueous solutions are used the Napthylamine must
have at least so much acid as to make it readily soluble, that is, so much acid as
will convert it into its corresponding salt. It does not matter much which Acid is
used to make the soluble salt or to effect the solution of the Napthylamine, but
it is preferred to use a solution in water effected by the aid of hydrochloric
Acid, that is in effect to use the Hydrochlorate of the Napthylamine. Now
unless there be a very great excess of Acid will it interfere with the reaction
between the Diazo body and the Napthylamine that there is some, and even
a considerable amount, of free acid present. In any case of doubt on account
of the excess of Acid present whether the desired reaction will not be impeded
or prevented thereby, an easy preliminary experiment with small quantities
will determine whether the Diazo body and the Napthylamine solution will
give the coloured Amido-azo product. That is what is meant by having the
Napthylamines in Acid solution-it is a watery solution of their salts formed from
Acids whether there be or be not free Acid besides. If there is only so much
Hydrochloric Acid used as will convert the quantity of napthylamine into the
Hydrochlorate, the solution may in one sense be called a neutral solution, but what
is meant is that the napthylamine is dissolved in water by the aid of an Acid and
that either just so much acid as to form the corresponding Napthylamine Salt or it
may be something more. It is essential or at least of prime importance in order to

page_text: obtain the desired colouring matters in an accurate and certain way, that the
Diazotizing of the Amido body by which the Diazotised element of the combination
is formed, should take place in a different vessel from that in which the bringing
together of the Diazo body and the Napthylamine takes place. It is not absolutely
impossible to get colouring matters by making Nitrous Acid act diazotizingly on
a mixture say for example of Hydrochlorate of Napthylamine with Amido Azo
Benzole Sulpho Acid, but it is a most inconvenient and irrational mode of
procedure.
Instead of using the Sulpho Acids of the Diazo or Diazo-azo body to react on
the Napthylamine dissolved in or by means of an Acid as aforesaid, the non-
sulphonated Diazo or Diazo-Azo body may be made to act on the Napthylamine
and sulphonate in manner well known to Chemists for the sulphonating of organic
compounds the product of the reaction afterwards, and so obtain a dyestuff
practically the same as or similar to the dyestuff obtained by the reaction of the
sulphonated compound of the same Diazo or Diazo-azo body on the same
Napthylamine.
By Diazo and Diazo-ażo or Tetrazo derivatives of the Aromatic Hydrocarbons
is meant the derivatives obtained by acting with Nitrous Acid (or a Nitrite and
an acid to liberate from the Nitrite its Nitrous Acid) on the Amido and Amido
Azo bases corresponding to the Aromatic Hydro-carbons.
By the Aromatic Hydro-carbons is meant the Hydro-carbons of the series of the
Benzoles exclusive of Napthalene, and not only Toluol and Xylol, and what are
called the homologues of Benzols are included but such Hydro-carbons as Ethyl
Benzole, Ethyl Methyl Benzole, and the like Aromatic Hydro: carbons which are
isomeric with members of the homologues series. By the Napthylamines is meant
Alpha and Beta Napthylamine and also the Alkylised compounds thereof such as
the Methyl and Phenyl Napthylamines.
As an example and illustration of the reactions in which the Invention consists
and of the process by which the same are effected the following is given :-
A new brown dyestuff or colouring matter is prepared by causing Diazo Azo
Benzole Sulphonate of Soda to act on Napthylamine Alpha or Beta in acid
solution, that is to say, dissolved by the aid of acid in water as before explained.
Fifty lbs. of Amido Azo Benzole Sulphonate of Soda dissolved in 500 lbs. of water
cooled down to 3° Centigrade are taken. To this solution is added slowly 75 lbs.
of Muriatic Acid and thereafter 11 lbs of Sodium Nitrite dissolved in 40 lbs of
Wnter. After several hours rest the liquid is poured into a solution containing
25 lbs. of Napthylamine, 50 lbs. of Muriatic Acid, and 500 lbs. of water.
The new
brown dyestuff separates instantly as a voluminous precipitate which is filtered
and dried. The dyestuff when dried appears as a dark brown powder; it is soluble
in hot water and its aqueous solution takes a brown colour by the addition of
Alkalis. Muriatic or Sulphuric Acid dyes the aqueous solution, blueish red. It
dyes wool and silk of a dark reddish brown colour in an acidulated bath, and this
colour is fast against soap and light.
Other colouring matters may be got by substituting in the preceding process
the Sulpho Acids of the Diazo and the Diazo-Azo or Tetrazo derivatives of Toluyl,
Xylol, Methyl Benzole, Ethyl Benzole, and of the other aromatic hydrocarbons (not
however including Napthalene) in the form preferably of the Sodium Salts of
said Sulpho Acids for the diazo derivative of Amido Azo Benzole Sulphonate of
Soda.
Having now described and particularly ascertained the nature of the said
Invention, and the system, mode, or manner in or under which the same is or may
be used or practically carried into effect, it is to be observed in conclusion that
what is considered to be novel and original and therefore claimed as the Invention
secured to the Inventor by the hereinbefore in part recited Letters Patent is :-
The production of new colouring matters by the reaction of the Sulpho acids of
the Dinzo and Diazo-Azo derivatives of the Aromatic Hydrocarbons on aqueous
solutions of Napthylamine effected by means or with the aid of acids as herein before

page_text: described or by the reaction of the non-sulphonated Diazo and Diazo-Azo derivatives
of the said Aromatic Hydrocarbons on such solutions of the said Napthylamines
and by subsequent sulphonization of the product, all in manner hereinbefore
described.
In witness whereof I the said John Erskine have hereunto set my hand
and seal this Eighth day of November, in the year of Our Lord One
thousand eight hundred and eighty two.
SHATIT
JOHN
חחזוז: AA
ATTICATT
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