The Manufacture or Production of New Alizarin Dye Stuffs.
Year: 1893

page_text: Date of Application, 7th Apr., 1893
Complete Specification Left, 6th Jan., 1894-Accepted, 10th Feb., 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of New Alizarin Dye Stuffs.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
My foreign correspondents have found that alpha amido alizarin and its analogues
(such as amidoflavopurpurine, amidoanthrapurpurine, and the like) can be converted
with the greatest ease in alkyl derivatives (containing the alkyl groups bound to
nitrogen), for instance, by heating the said amido products with halogen alkyls.
The resulting alkylated coloring matters yield, with the aid of mordants, shades
considerably bluer than those produced by the original (non-alkylated) products.
Whilst, for example, alpha amido alizarin yields, with the aid of alumina mordants,
garnet-red shades, ethylised alpha amido alizarine produces, on alumina mordants,
bordeaux-like shades, shewing a strong bluish hue.
The process for producing these new coloring matters in general, consists in
heating the above amido products with halogen, alkyls or other alkylating
agents, with the addition of the respective alcohols, for some time, at elevated
temperatures.
One of the methods for producing ethylised alpha amido alizarin is illustrated by
the following example the parts being he weight
PRODUCTION OF ETHYLISED ALPHA AMIDO ALIZARIN.
10 parts of dried alpha amido alizarin are mixed with 10 parts of ethylbromide
and 100 parts of ethylalcohol. The resulting mixture is heated in a closed vessel
(autoclave) for five hours, at 150 degrees centigrade.
The alcohol in excess is then distilled off, and the residue is dissolved in diluted
soda lye. This alkaline solution, whilst heated to boiling, is decomposed by the
addition of an acid, and the separated dye stuff is filtered off and washed out with
water, in order to remove the acid.
The new coloring matter thus obtained forms a dark violet paste soluble in
alkalies, with a color which is bluer than that of the alkaline solutions of alpha
amido alizarin. Its solution in concentrated sulphuric acid shows a color which is
somewhat more yellowish than the color of the solution of alpha amido alizarin in
concentrated sulphuric acid. It easily dissolves in hot concentrated hydrochloric
acid with a yellow color, and, on cooling, the hydrochlorate partly separates in
crystalline form. Its shades produced by means of alumina mordants are bordeaux-
like, with a strong bluish hue.
In a manner similar to that described in the above example, the corresponding
products from alpha amido flavopurpurine, alpha amido anthrapurpurine, and other
amido hydroxy anthraquinones, are obtained.
The ethylbromide employed in the above example can be replaced by
ethylchloride, ethylsulphuric salts, or the like ethylating agents.
The process also is carried out in the same manner, if, in place of the ethylating
agents, the corresponding methyl products, propyl compounds, amylderivatives,
benzyl products, or other alkylating agents, are employed.

page_text: My foreign correspondents do not limit themselves to the directions given in the
above example, for the proportions given therein, the temperature employed
therein, and the other conditions mentioned therein, can be varied to a greater or
less extent.
Dated 1 1
COMPLETE SPECIFICATION.
The Manufacture or Production of New Alizarin Dye Stuffs.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, do hereby declare the
nature of this invention and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement :-
My foreign correspondents have found that alpha-amido alizarin and its
analogues (such as alpha-amido flavo purpurin, alpha amido anthra purpurin, and
the like) can be very readily converted into alkyl derivatives, in which the alkyl
groups are combined with nitrogen, for instance, by heating the said amido products
with alkyl haloids. The resulting alkylated colouring matters yield shades, with
mordants, which are considerably bluer than those produced by the original non-
alkylated products. For example, whereas, on using alumina mordants, alpha-
amido-alizarin yields garnet-red shades, ethylated alpha-amido alizarin produces
bordeaux-like shades, exhibiting a strong bluish hue.
The process for producing these new colouring matters, in general, consists in
heating the afore-mentioned amido products for some time, at elevated temperatures,
with an alkyl haloid or other alkylating agent, a quantity of the corresponding
alcohol being advantageously added.
One of the methods of producing ethylated alpha amido alizarin is illustrated
by the following example, the parts being by weight.
EXAMPLE.
PRODUCTION OF ETHYLISED ALPHA-AMIDO ALIZARIN.
10 parts of dried alpha-amido alizarin are mixed with 10 parts of ethyl bromide
and 100 parts of ethyl alcohol, and the mixture is heated in a closed vessel
(autoclave) for five hours at 150 degrees centigrade.
The excess of alcohol is then distilled off; the residue is dissolved in diluted
soda lye, and the alkaline solution, having been heated to boiling, is decomposed
by the addition of an acid; the separated dye-stuff is filtered off and washed with
water to remove the adhering acid.
The new colouring matter thus obtained is a dark violet paste, which dissolves
in alkalies, affording a solution which is bluer in colour than an alkaline solution of
alpha-amido-alizarin. The colour of its solution in concentrated sulphuric acid
is somewhat more yellowish than the colour of the solution of alpha amido
alizarin- in this solvent. It easily dissolves in hot concentrated muriatic acid,
affording a yellow coloured liquid, on cooling which, the hydrochloride partly
separates in a crystalline form.. The shades produced 'with it, by means of alumina
mordants, are bordeaux-like, and exhibit a strong bluish hue.
The corresponding products are obtained in a similar. manner from alpha amido
flavo purpurin, alpha amido. anthrapurpurin, and other amido hydroxyanthra-
quinones. Such alkylated amido hydroxyanthraquinones; in general, exhibit
properties similar to those possessed by the aforesaid ethylated alpha amido alizarin.
The shades obtainable for instance by means of methylated alpha amido alizarin,
:

page_text: ethylated alpha amido anthrapurpurin, and ethylated alpha amido flavo purpurin,
and alumina mordants, are a so-called "bordeaux red" of a bluish hue, methylated
alpha-amido-anthrapurpurin, and methylated alpha amido flavo purpurin yielding
claret red shades with alumina mordants.
Instead of ethyl bromide, ethylchloride, ethyliodide, or the like ethylating
agents, can be used.
The process is also carried out in a manner analogous to that described in the
above given example, if, in place of the aforesaid ethylating agents, the corre-
sponding methyl, propyl, or amyl derivatives, or other alkylating agents, are used.
My foreign correspondents do not limit themselves to the directions given in
the above example, as the proportions therein mentioned, the temperature therein
stated, and the other conditions therein mentioned, can be varied to a greater or
less extent.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed, as communicated to me
by my foreign correspondents, I declare that what I claim is :-
1. The production of new colouring matters, which are alkylated amido-
hydroxyanthraquinones containing alkyl groups in place of the bydrogen atoms
of the amido groups, by alkylating alpha amido hydroxyanthraquinones in a
suitable manner.
2. The process for producing methylated alpha amido alizarin, methylated alpha
amido anthrapurpurin, or methylated alpha-amido flavopurpurio, which process
consists in heating alpha amido alizarin, alpha amido anthrapurpurin, or alpba
amido favopurpurin, respectively, with methyl haloids, or other suitable
methylating agents, and, if desirable, a solvent or diluent, and subsequently
isolating the new dye stuffs in a suitable manner.
3. The process for producing ethylated alpha amido alizarin, ethylated alpha,
amido anthra purpurin, or ethylated alpha amido flavopurpurin, which process
consists in heating alpha amido alizarin, alpha amido anthrapurpurin, or alpha
amido flavopurpurin, respectively, with ethylhaloids, or other suitable ethylating
agents, and, if desirable, a solvent or diluent, and subsequently isolating the new
colouring matters in a suitable manner.
4. As new products of manufacture, the new alkylated amido hydroxyanthra-
quinone dye-stuffs, such as methylated or ethylated alpha amido alizarin,
methylated or ethylated alpha amido anthrapurpurin, and methylated or ethylated
alpha amido flavopurpurin, produced by the process hereinbefore defined, or by
any other means affording the same result.
Dated thin and 1 of Innu 1801
NEWTON & SON,
Agents for the Applicant.