matters and Intermediate Products of the Anthracene Series.
Year: 1899

page_text: matters and Intermediate Products of the Anthracene Series.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Gentleman, do hereby declare the nature of this invention (which has been communi-
cated to me from abroad by The Badische Anilin & Soda Fabrik, of Ludwig-
shafen-on-Rhine, in the German Empire,) to be as follows:-
5 It is known that if 1.4-di-ortho-nitro-anthraquinone be boiled with aniline, a
product is obtained which crystallises in deep-red needles and dissolves in hot
alcohol, the solution being purple (see Römer, Berichte of the German Chemical
Society, Volume 16, page 363).
If, on the one hand, other primary aromatic amines be used instead of aniline, or,
on the other hand, isomeric dinitro-anthraquinones be employed analogous com-
pounds are obtained, and these appear to be chemically alphylated amido-
anthraquinones.
My foreign correspondents have discovered that the said alphylated di-amido-.
anthraquinones can be converted into colouring matters in several ways. If they be
5 suitably treated with bromine, or chlorine, halogen derivatives are obtained, and these,
on condensation with primary aromatic amines, yield green colouring matters, which
after sulphonation, are soluble in water, and dye unmordanted wool, or wool that has
been mordanted with chrome, giving valuable fast green shades.
Another way in which the said alphylated amido-anthraquinones can be converted
O into useful colouring matters consists in treating them with sulphonating agents,
whereby they are converted into colouring matters which fix themselves on animal
fibre, giving brilliant shades varying from bordeaux and red-violet to yellow-red.
In the following Examples I describe the manner in which the alphylated amido-
anthraquinones can be obtained and converted into the useful colouring inatters.
These will serve to further illustrate the nature of the invention, but the invention
is not confined to the examples. The parts are by weight.
EXAMPLE 1.
PRODUCTION OF AN ALPHYLATED AMIDO-ANTHRAQUINONE FROM 1.41-DINITRO-ANTHRA-
QUINONE AND ANILINE.
Mix together about ten parts of 1.4¹ dinitro-anthraquinone and one hundred parts
of aniline. Heat the mixture for from three to four hours, so that it boils. A
vigorous reaction takes place at first, but the heating is continued until this ceases.

page_text: Allow the mixture to cool. The alpbylated amido-anthraquinone crystallises out.
Work up in any suitable way.
Instead of using the pure 1.4-dinitro-anthraquinone in the above example, crude
dinitro-anthraquinone, obtained by nitrating anthraquinone, can be employed, and,
in an analogous manner, the isolated isomeric dinitro-anthraquinones can be used, the
corresponding alphylated amido-anthraquinones being obtained.
Instead of aniline, in the foregoing example, other primary aromatic amines can
be used, the corresponding alphylated amido-anthraquinones being obtained.
In the next Examples I illustrate the production of the halogen derivatives of the
alphylated amido-anthraquinones. The general process by which they are obtained
may be described as consisting in treating alphylated amido-anthraquinones in a
suitable solvent with an excess of bromine, or of chlorine.
PRODUCTION OF A NEW BROMINE DERIVATIVE FROM THE ALPHYLATED AMIDO-ANTHRA-
QUINONE OBTAINED FROM 1.41-DINITRO-ANTHRAQUINONE AND ANILINE.
Dissolve about ten parts of the alphylated amido-anthraquinone obtained according
to Example 1 in about six hundred parts of carbon bisulphide. Heat the mixture to
facilitate solution. Then add about thirty parts of bromine, and boil the mixture
till no further evolution of hydro-bromic acid is observable. Distil off the carbon
bisulphide until only about one hundred and fifty parts remain, and dilute the residue
with about five hundred parts of alcohol. The new bromine derivative separates out
as a crystalline precipitate. Filter and dry.
PRODUCTION OF A NEW BROMINE DERIVATIVE FROM THE ALPHYLATED AMIDO-ANTHRA-
QUINONE OBTAINED FROM 1.41 DINITRO ANTHRAQUINONE AND PARA-TOLUIDINE.
Suspend about ten parts of the aforesaid alphylated amido-anthraquinone in about
one hundred parts of glacial acetic acid, and add at the ordinary temperature twenty
parts of bromine. Stir the mixture thoroughly and warm gently for some time.
Allow to cool. The bromine derivative separates out. Collect by filtering.
PRODUCTION OF NEW CHLORINE DERIVATIVES OF THE ALPHYLATED AMIDO-ANTHRAQUINONE
FROM 1.4 DINITRO-ANTHRAQUINONE AND ANILINE.
Make a suspension of about ten parts of the aforesaid alphylated amido-anthra-
quinone, in about one hundred parts of glacial acetic acid, and treat the mixture at
the ordinary temperature with gaseous chlorine until the evolution of hydrochloric
acid ceases.
Allow the mixture to stand for about twelve hours. A portion of the
product of reaction (which I term Product A) separates out; this generally contains
some unchanged alphylated product. The solution that remains contains higher
chlorinated derivatives of the alphylated product, (which term Product B). Collect
the separated chlorinated product by filtering and to the filtrate add water to pre-
cipitate the higher chlorinated product. Collect this in the usual way.
In the following table I state the properties of various halogen derivatives obtained
by treating the various alphylated amido-anthraquinones herein indicated in the
manner described in the foregoing examples. These are all mixtures of various
highly substituted halogen derivatives. They all possess the characteristic property
that on treatment with aromatic amines they are converted into valuable colouring-
matters, which, in the form of their sulpho acids, dye unmordanted, or chrome-
mordanted, wool, valuable green shades.

page_text: Bromine derivative from conden-
sation product of 1.1' dinitro
anthraquinone and aniline.
Bromine derivative from conden-
sation product of 1.41 dinitro
anthraquinone and para-tolui-
dine.

page_text: With reference to the nomenclature adopted in this Specification by 1.11 dinitro
anthraquinone I mean the body which corresponds to chrysazine, and by 1.3
dinitro anthraquinone I mean the body which corresponds to xanthopurpurine.
In the next Examples I illustrate the production of green colouring matters by
treating the halogen derivatives of alphylated amido anthraquinone with primary
aromatic amines. In order to prepare these green colouring-matters, the halogen
derivative is first heated to a high temperature with about ten times the quantity
of the primary aromatic amine chosen as instances I mention aniline, toluidine,
napthylamine phenylene-diamine and benzidine. This treatment can be effected
in the presence, or absence, of condensing agents, such as chloride of zinc, aniline
hydrochlorate, boric acid and so on. The heating is continued until the colour of
the melt no longer changes. On cooling, the colouring matter separates out, usually
in the crystalline form. It is collected and dried. In this form the new green
colouring matters are not generally directly useable for dyeing, being insufficiently
soluble in water so that they have to be converted by sulphonating into the form
of soluble sulphoacids. This conversion is illustrated in Examples 8 and 9.
PRODUCTION OF NEW GREEN COLOURING MATTER FROM BROMINE DERIVAtive of the
ALPHYLATED AMIDO-ANTHRAQUINONE FROM 1.41 DINITRO ANTHRAQUINONE ANILINE.
Mix about ten parts of the said halogen derivative (which may have been obtained,
for instance, as described in the foregoing Example 2) with about one hundred parts
of aniline. Stir the mixture and heat it, whilst stirring, until it boils. The melt is
at first red, but changes slowly to violet, blue, and finally to green.
After boiling
for about four hours and when no further change in the colour of the melt
observable, allow the melt to cool. The colouring matters separates out in finely
crystalline form as a blue powder. In order to render it capable of use for dyeing,
it is converted into the form of its soluble sulphoacid.
In the above Example ten parts of aniline salt may be added to act as condensing
agent. The reaction then proceeds more quickly without altering the nature of
the product obtained.
In Example 1 the aniline can be replaced by para-toluidine and a similar product
obtained. In working up this product the melt, after it is cooled, may be warmed up
once more, in order that the para-toluidine may melt, so that the colouring matter
can be separated from it by filtering. If desired, the colouring matters can be pre-
cipitated from their melts by treatment with acids, but the products thus obtained
are somewhat less pure.
PRODUCTION OF A NEW COLOURING MATTER FROM THE BROMINE DERIVATIVE OF THE
ALPHYL-AMIDO ANTHRAQUINONE OBTAINED FROM 1.41 DINITRO-ANTHRAQUINONE
AND PARA-TOLUIDINE, BY CONDENSATION WITH PARA TOLUIDINE IN
THE PRESENCE OF A DILUENT.
Mix together about ten parts of the said halogen derivative and about thirty parts
of para-toluidine, and add the mixture to about two hundred parts of melted
naphthalene. Raise the temperature of the mixture until it boils. The formation
of colouring matter begins as can be seen from the change in colour of the melt from
red to blue, and finally to green. Allow the melt to cool and extract by means of
alcohol. In this way the colouring matter is separated from any excess of para
toluidine and from the naphthalene. The colouring matter thus obtained is in the
insoluble form, and must be sulphonated to convert it into the form readily applicable
for dyeing.

page_text: SULPHONATION OF THE PRODUCT OBTAINED WHEN USING PARA-TOLUIDINE IN EXAMPLE 5,
AND A MIXTURE OF FUMING SULPHURIC ACID AND BORACIC ACID.
Mix together about ten parts of the insoluble colouring matter obtained according
to Example 5, with about ten parts boracic acid and one hundred parts of fuming
sulphuric acid containing about 5% free anhydride SO₁. Heat the mixture
to a temperature of about 100° Centigrade until the colouring-matter is soluble
in water. Work up the colouring matter in the manner described in Example 4.
In the following Examples I describe the conversion of the alphylated amido-anthra-
quinone into useful colouring matters by sulphonation. If the conditions of sulphona-
tion be so chosen that only a moderate sulphonating action takes place, colouring
matters are obtained which dye wool violet red shades. These colouring matters can
readily be separated from their solutions by means of common salt. But if an
energetic sulphonation be effected by the use, say, of fuming. sulphuric acid, higher
sulpho-acids are obtained which cannot be precipitated from their solutions with

page_text: common salt, or with potassium chloride, or at any rate only with far greater
difficulty than can the lower sulphonated products. These higher sulpho-acids can
be isolated by conversion into their c.deium salts, and double decomposition of these
with sodium carbonate, whereby the sodium salts of the sulpho-acids are obtained.
These sulpho-acids dye wool from the acid bath more yellowish red shades.
PRODUCTION OF A VIOLET RED COLOURING MATTER BY SULPHONATING THE ALPHYLATED
AMIDO ANTHRAQUINONES OBTAINED FROM 1.4¹ DINITRO-ANTHRAQUINONE AND ANILINE.
Mix together one hundred parts of the said alphylated amido-anthraquinone and
one thousand parts of concentrated sulphuric acid (containing about .96%
HSO). Raise the temperature to about 80° to 100° Centigrade. Maintain this
temperature until a test portion of the product dissolves readily in hot water.
Add a little common salt to
Allow the melt to cool and pour it into water.
precipitate the colouring matter. Filter press and dry. The product thus obtained
is a chocolate brown powder, easily soluble in hot water, the solution being red.
The addition of sodium carbonate, or caustic soda, to this solution does not change
the colour. The colouring matter is soluble in alcohol and in warm aniline, the
solution being cherry red. The solution in concentrated sulphuric acid is a dirty-
brown. It yields violet red shades when dyed upon animal fibre.
PRODUCTION OF HIGHER SULPHOACID FROM THE ALPHYLATED AMIDO-ANTHRAQUINONE
OBTAINED FROM 1.4¹ DINITRO-ANTHRAQUINONE AND ANILINE.
Mix together about ten parts of the said alphylated product and one hundred
parts of fuming sulphuric acid (containing about 20% free anhydride).
Warm the melt to a temperature of from 30° to 350 Centigrade, and stir the
mixture at this temperature until a test portion is completely soluble in
water. Pour the melt into ice water. Neutralise the solution exactly with
Add sodium
milk of lime. Filter off the precipitated calcium sulphate.
carbonate to the filtrate to convert the calcium salt of the colouring matter
into the sodium salt. Filter off the chalk and evaporate the filtrate to dryness.
The sodium salt thus obtained is a dark coloured powder, which is easily soluble in
water the solution being yellow red, which becomes bluer on the addition of caustic
It
soda. The colouring matter dissolves in sulphuric acid the solution being red.
is practically insoluble in alcohol and aniline. When wool is dyed with these
colouring matters from the acid bath, fast shades of red are obtained. The analogous
alphylated anthraquinones obtained from other aromatic amines, or other dinitro
anthraquinones, can be sulphonated in a similar way and analogous products be
obtained.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.

page_text: Improvements in the Manufacture and Production of Colouring-
matters and Intermediate Products of the Anthracene Series.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Gentleman, do hereby declare the nature of this invention (which has been communi-
cated to me from abroad by The Badische Anilin & Soda Fabrik, of Ludwig-
shafen-on-Rhine, in the German Empire,) and in what manner the same is to be
performed to be particularly described and ascertained in and by the following
statement:
It is known that if 1.4-di-ortho-nitro-anthraquinone be boiled with aniline, a
product is obtained which crystallises in deep-red needles and dissolves in hot
alcohol, the solution, being purple (see Römer, Berichte of the German Chemical
Society, Volume 16, page 363).
If, on the one hand, other primary aromatic amines be used instead of aniline, or,
on the other hand, isomeric dinitro-anthraquinones be employed, analogous com-
pounds are obtained, and these appear to be chemically alphylated amido-
anthraquinones.
My foreign correspondents have discovered that the said alphylated di-amido-
anthraquinones can be converted into colouring-matters in several ways. If they be
suitably treated with bromine, or chlorine, halogen derivatives are obtained, and these,
on condensation with primary aromatic amines, yield green colouring matters, which
after sulphonation, are soluble in water, and dye uninordanted wool, or wool that has
been mordanted with chrome, valuable fast green shades.
Another way in which the said alphylated amido-anthraquinones can be converted
into useful colouring matters consists in treating them with sulphonating agents,
whereby they are converted into colouring-matters which fix themselves on animal
fibre, giving brilliant shades varying from bordeaux and red-violet to yellow-red.
In the following Examples I describe the manner in which the alphylated amido-
anthraquinones can be obtained and converted into the useful colouring-matters.
These will serve to further illustrate the nature of the invention as well as the
manner in which it can be performed but the invention is not confined to the
Examples. The parts are by weight.
.
QUINONE AND ANILINE.
Mix together about ten parts of 1.4' dinitro-anthraquinone and one hundred parts
of aniline, Heat the mixture for from three to four hours, so that it boils. A
vigorous reaction takes place at first, but the heating is continued until this ceases.
Allow the mixture to cool. The alphylated amido-anthraquinone crystallises out.
Work up in any suitable way.
Instead of using the pure 1.4-dinitro-anthraquinone in the above example, crude
dinitro-anthraquinone, obtained by nitrating anthraquinone, can be employed, and,

page_text: in an analogous manner, the isolated isomeric dinitro-anthraquinones can be used, the
corresponding alphylated amido-anthraquinones being obtained.
Instead of aniline, in the foregoing example, other primary aromatic amines can
be used, the corresponding alphylated amido-anthraquinones being obtained.
In the next Examples I illustrate the production of the halogen derivatives of the
alphylated amido-anthraquinones. The general process by which they are obtained
may be described as consisting in treating alphylated amido-anthraquinones in a
suitable solvent with an excess of bromine, or of chlorine.
QUINONE OBTAINED FROM 1.4-DINITRO-ANTHRAQUINONE AND ANILINE.
Dissolve about ten parts of the alphylated amido-ant braquinone obtained according
to Example 1 in about six hundred parts of carbon bisulphide. Heat the mixture to
facilitate solution. Then add about thirty parts of bromine, and boil the mixture
till no further evolution of hydro-bromic acid is observable. Distil off the carbon
bisulphide until only about one hundred and fifty, parts remain, and dilute the residue
with about five hundred parts of alcohol. The new bromine derivative separates out
as a crystalline precipitate. Filter and dry.
Suspend about ten parts of the aforesaid alphylated amido-anthraquinone in about
one hundred parts of glacial acetic acid, and add at the ordinary temperature thirty
parts of bromine. Stir the mixture thoroughly and warm gently for some time.
Allow to cool. The bromine derivative separates out. Collect by filtering.
IRODUCTION OF NEW CHLORINE DERIVATIVES OF THE ALPHYLATED AMIDO-ANTHRAQUINONE
FROM 1.4-DINITRO-ANTHRAQUINONE AND ANILINE.
Make a suspension of about ten parts of the aforesaid alphylated amido-anthra-
quinone, in about one hundred parts of glacial acetic acid, and treat the mixture at
the ordinary temperature with gaseous chlorine until the evolution of hydrochloric
acid ceases. Allow the mixture to stand for about twelve hours. A portion of the
product of reaction (which I term Product A) separates out; this generally contains
some unchanged alphylated product. The solution that remains contains higher
chlorinated derivatives of the alphylated product, (which I term Product B). Collect
the separated chlorinated product by filtering and to the filtrate add water to pre-
cipitate the higher chlorinated product. Collect this in the usual way.
In the following table I state the properties of various halogen derivatives obtained
by treating the various alphylated amido-anthraquinones herein indicated in the
manner described in the foregoing Examples. These are all mixtures of various
highly substituted halogen derivatives. They all possess the characteristic property
that on treatment with aromatic amines they are converted into valuable colouring-
matters, which, in the form of their sulpho acids, dye unmordanted, or chrome-
mordauted, wool, valuable green shades.

page_text: Bromine derivative from conden-
sation product of 1.1'-dinitro-
anthraquinone and aniline.
Bromine derivative from conden-
sation product of 1.4'-dinitro-
anthraquinone and para-tolui-
dine.

page_text: Bromine derivative from conden-
sation product of 1.4'-dinitro-
anthraquinone and alpha-naph-
thylamine.

page_text: With reference to the nomenclature adopted in this Specification, by 1.1-dinitro-
anthraquinone I mean the body which corresponds to chrysazine, and by 1: 3-
dinitro-anthraquinone I mean the body which corresponds to xanthopurpurine.
In the next Examples I illustrate the production of green-colouring matters by
treating the halogen derivatives of alphylated-amido-anthraquinone with primary
aromatic amines. In order to prepare these green colouring-matters, the halogen
derivative is first heated, to a high temperature, with about ten times the quantity
of the primary aromatic amine chosen, as instances I mention aniline, toluidine,
naphthylamine, phenylenediamine, and benzidine. This treatment can be effected
in the presence, or absence, of condensing agents, such as chloride of zinc, aniline-
hydrochlorate, boracic-acid, and so on. The heating is continued until the colour of
the melt no longer changes. On cooling, the colouring matter separates out, usually
in the crystalline form. It is collected and dried. In this form the new green
colouring matters are not generally directly useable for dyeing, being insufficiently
soluble in water so that they have to be converted by sulphonating into the con-
dition of soluble sulphoacids. This conversion is illustrated in Examples 8 and 9.
PRODUCTION OF NEW GREEN COLOURING MATTER FROM THE BROMINE DERIVATIVE
THE ALPHYLATED AMIDO-ANTHRAQUINONE FROM 1.41-DINITRO-ANTHRAQUINONE AND
ANILINE.
OF
Mix about ten parts of the said halogen derivative (which may have been obtained,
for instance, as described in the foregoing Example 2) with about one hundred parts
of aniline. Stir the mixture and heat it, whilst stirring, until it boils. The melt is
at first red, but changes slowly to violet, blue, and finally to green. After boiling
for about four hours, and when no further change in the colour of the melt is
observable, allow the melt to cool. The colouring-matter separates out in a finely
crystalline form as a blue powder. In order to render it capable of use for dyeing,
it is converted into the condition of its soluble sulphoacid.
In the above Example, ten parts of aniline salt may be added to act as condensing
agent. The reaction then proceeds more quickly, without altering the nature of
the product obtained.
In this Example the aniline can be replaced by para-toluidine and a similar product
be obtained. In working up this product the melt, after it is cooled, may be again
warmed up, in order that the para-toluidine may melt, so that the colouring-matter
can be separated from it by filtering. If desired the colouring-matters can be pre-
cipitated from their melts by treatment with acids, but the products thus obtained
are somewhat less pure.
PRODUCTION OF A NEW COLOURING-MATTER FROM THE BROMINE DERIVATIVE OF THE
ALPHYL-AMIDO-ANTHRAQUINONE OBTAINED FROM 1.41-DINITRO-ANTHRAQUINONE
AND PARA-TOLUIDINE, BY CONDENSATION WITH PARA-TOLUIDINE IN
THE PRESENCE OF A DILUENT.
Mix together about ten parts of the said halogen derivative and about thirty parts
of para-toluidine, and add the mixture to about two hundred parts of melted
naphthalene. Raise the temperature of the mixture until it boils. The formation
of colouring-matter begins as can be seen from the change in colour of the melt from
red to blue and finally to green. Allow the melt to cool and extract by means of
alcohol. In this way the colouring-matter is separated from any excess of para-
toluidine and from the naphthalene. The colouring-matter thus obtained is in the
insoluble form, and must be sulphonated to convert it into the form readily applicable
for dyeing.

page_text: Mix about ten parts of the product obtained according to Example 5, in the con-
dition of dry powder, with one hundred parts of monohydrate sulphuric acid. Stir
the mixture from time to time and maintain the temperature at about forty degrees
Centigrade. Continue this treatment till a test portion is completely soluble in water.
Pour the melt into water, and precipitate the colouring-matter by means of common
salt, or chloride of potash. The new colouring-matter, in the form thus obtained, is
readily soluble in hot water, the solution being green which is hardly changed by the
addition of alkali..
EXAMPLE 9.
SULPHONATION OF THE PRODUCT OBTAINED WHEN USING PARA-TOLUIDINE IN EXAMPLE 5,
AND A MIXTURE OF FUMING SULPHURIC ACID AND BORACIC ACID.
Mix together about ten parts of the insoluble colouring-matter obtained according
to Example 5, with about ten parts boracic acid, and one hundred parts of fuming
sulphuric acid, containing about five per cent. free anhydride SO₂. Heat the mixture
to a temperature of about one hundred degrees Centigrade until the colouring-
matter is soluble in water.
Work up the colouring-matter in the manner described
in Example 8.
In the following Examples I describe the conversion of the alphylated amido-anthra-
quinone into useful colouring-matters by sulphonation. If the conditions of sulphona-
tion be so chosen that only a moderate sulphonating action takes place, colouring
matters are obtained which dye wool violet-red shades. These colouring-matters can
readily be separated from their solutions by means of common salt. But if an
energetic sulphonation be effected, by the use, say, of fuming sulphuric acid, higher
sulpho-acids are obtained which cannot be precipitated from their solutions with

page_text: common salt, or with potassium chloride, or at any rate only with far greater
difficulty than can the lower sulphonated products. These higher sulphoacids can
be isolated by conversion into their calcium salts, and double decomposition of these
with sodium carbonate; whereby the sodium salts of the sulphoacids are obtained.
These sulphoacids dye wool from the acid bath, yellower red shades.
PRODUCTION OF A VIOLET-RED COLOURING-MATTER BY SULPHONATING THE ALPHYLATED
AMIDO-ANTHRAQUINONES OBTAINED FROM 1.4'-DINITRO-ANTHRAQUINONE AND ANILINE.
Mix together one hundred parts of the said alphylated amido-anthraquinone and
one thousand parts of concentrated sulphuric acid (containing about 96 per cent.
H2SO4). Raise the temperature to between about eighty degrees and one hundred
degrees Centigrade. Maintain this temperature until a test portion of the product
dissolves readily in hot water. Allow the melt to cool and pour it into water.
Add a little common salt to precipitate the colouring-matter. Filter, press,
and dry. The product thus obtained is a chocolate-brown powder, easily
soluble in hot water, the solution being red. The addition of sodium
carbonate, or caustic soda, to this solution does not change the colour. The colouring-
matter is soluble in alcohol and in warm aniline, the solution being cherry-red. The
solution in concentrated sulphuric acid is a dirty-brown. It yields violet-red shades,
when dyed upon animal fibre.
PRODUCTION OF HIGHER SULPHOACID FROM THE ALPHYLATED AMIDO-ANTHRAQUINONE
OBTAINED FROM 1.4¹-DINITRO-ANTHRAQUINONE AND ANILINE.
Mix together about ten parts of the said alphylated product, and one hundred
parts of fuming sulphuric acid, (containing about 20 per cent. free anhydride).
Warm the melt to a temperature of from thirty degrees to thirty five degrees
Centigrade, and stir the mixture, at this temperature, until a test portion is
completely soluble in water. Pour the melt into ice water. Neutralise the solution
exactly with milk of lime. Filter off the precipitated calcium sulphate. Add
sodium carbonate to the filtrate to convert the calcium salt of the colouring-matter
into the sodium salt. Filter off the chalk, and evaporate the filtrate to dryness.
The sodium salt thus obtained is a dark coloured powder, which is easily soluble in
water, the solution being yellow-red, which becomes bluer on the addition of caustic
It
soda. The colouring-matter dissolves in sulphuric acid the solution being red.
is practically insoluble in alcohol and aniline. When wool is dyed with these
colouring-matters from the acid bath, fast shades of red are obtained. The analogous
alphylated anthraquinones obtained from other aromatic amines, or other dinitro-
anthraquinones, can be sulphonated in a similar way and analogous products be
obtained.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same. is to be performed, I declare that what I
claim is
1. The production of halogen derivatives of alphylated amido-anthraquinones by
treating an alphylated amido-anthraquinone with chlorine, or with bromine.
2. The production of colouring-matters by treating the halogen derivatives of
alpbylated amido-anthraquinones, such as can be obtained in the manner claimed in
the preceding claiming clause, with primary aromatic amines; with, or without, the
presence of a condensing agent.
3. The production of colouring-matters by treating alphylated amido-anthraqui-
nones with the sulphonating agents hereinbefore defined.

page_text: 4. The manufacture of halogen derivatives of alphylated amido-anthraquinones and
colouring-matters therefrom as described in the foregoing examples thereof.
5. The manufacture of colouring-matters by sulphonating alphylated amido-
anthraquinones as described in the foregoing examples thereof.
6. As new products the halogen derivatives of alphylated amido-anthraquinones
and colouring-matters therefrom such as can be obtained substantially as herein-
before described.
7. As new products, the colouring-matters such as can be obtained by sulphonating
alphylated amido-anthraquinones substantially as hereinbefore described.
Dated thin 11th day of January 1800
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.