The Manufacture or Production of Derivatives of Hydroxy- anthraquinones.
Year: 1893

page_text: Date of Application, 7th Feb., 1893
Complete Specification Left, 6th Nov., 1893-Accepted, 9th Dec., 1893
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRIich
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of Derivatives of Hydroxy-
anthraquinones.
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:-
It is known that betanitroalizarine cannot be efficiently produced by treating
alizarine dissolved in concentrated sulphuric acid with nitric acid or salts thereof,
as the chief product formed in this reaction is the nitropurpurine first described as
nitrohydroxyalizarine by Strecker in the Zeitschrift für Chemie, 1868, page 264.
My foreign correspondents have found that, by nitrating the boric acid ether of
alizarine (for instance, in concentrated sulphuric acid), betanitroalizarine is formed
conveniently and in theoretical amount; that the boric acid ethers of the "analogues
of alizarine," when treated with nitrating agents, yield with ease the corresponding
betanitro derivatives of the hydroxyanthraquinones employed, but that the arsenic
acid ethers of alizarine and its analogues are converted by nitration into the
isomeric alphanitro derivatives of alizarine or its analogues.
According to the researches of my foreign correspondents, the boric acid ether of
alizarine is, for example, easily obtained by introducing solid boric acid into a
solution of alizarine in concentrated sulphuric acid. The formation of the boric
acid ether, which instantly commences, is complete when a test portion poured into
concentrated sulphuric acid dissolves with a violet red color, instead of with the
brownish red color of alizarine. A sample poured into cold water dissolves with
difficulty in soda lye, with dull brown color, unlike the alizarine, which dissolves in
alkali with a beautiful violet color. The boric acid ether produced in this or
a similar manner, is separated with very great ease into its components, by heating or
boiling with water or diluted acids. The other boric acid ethers derived from the
"analogues of alizarine," can be obtained in the aforesaid manner, and show a
chemical behaviour similar to that of the boric acid ether of alizarine.
In order to illustrate this new process for obtaining betanitro-derivatives of
hydroxyanthraquinones by means of boric acid ethers, the following example is
given The parts are by weight

page_text: My foreign correspondents have ascertained (as above mentioned) that the
arsenic, acid ethers of alizarine and the analogues thereof, show a different behaviour
when treated with nitrating agents, as the said arsenic acid ethers are transformed
with the same ease into alphanitro derivatives.
Arsenic acid ethers of flavo purpurine, anthrapurpurine, hydroxy flavopurpurine,
hydroxyanthrapurpurine, have already been mentioned by my foreign corre-
spondents in the Specification of the application for Letters Patent No. 12580,
dated 7th July 1892. The arsenic acid ethers of alizarine and the other analogues
thereof, can be obtained in the same manner as described in the said Specification.
These arsenic acid.ethers in general possess similar properties. The arsenic acid
ether of alizarine only differs from the arsenic acid ethers of the analogous products
by a somewhat greater stability.
This new
process for producing alphanitro derivatives of hydroxyanthra-
quinones by means of arsenic acid ethers, is illustrated by the following example,
the parts being by weight.
PRODUCTION OF ALPHANITROALIZARINE.
10 parts of alizarine are dissolved in 200 parts of sulphuric acid at 66 degrees
Baumé and 10 parts of solid arsenic acid are stirred into this solution. The
mixture is well cooled, and then 3 litres (in case the parts are kilos. by weight) of
nitric acid, at 42 degrees Baumé, are gradually added thereto, whilst the
temperature chiefly is kept below 0 degrees centigrade. After standing for some
hours, the liquid is poured into cold water. The precipitate thus separated is
filtered of, redissolved in soda lye, and the resulting alkaline solution, whilst
heated to boiling, is decomposed with an excess of sulphuric acid. Boiling is con-
tinued until the arsenic acid ether of alpha nitro alizarine first produced, is perfectly
decomposed. The decomposition is complete as soon as a sample dissolves in soda
lye with the beautiful violet color of alphauitroalizarine. The dye-stuff precipitated
is filtered off and washed.
My foreign correspondents have described in the foregoing examples two
methods, the one for producing beta nitro alizarine by means of the boric acid ether
of alizarine, the other for obtaining alpha nitro alizarine by means of the arsenic
acid ether of alizarine.
If, in the said examples, alizarine is replaced by the corresponding quantities of
the "analogues of alizarine," the nitro derivatives of the latter compounds result
in a similar manner, that is to say, the beta nitro derivatives are obtained from the
boric acid ethers, whilst the isomeric alpha nitro products result from the arsenic
acid ethers, supposing the formation of the isomeric nitro products to be theoretically
possible.
By "analogues of alizarine" my foreign correspondents understand not only
mono, di, or polyhydroxyanthraquinones (such as alpha or beta monohydroxy-
anthraquinone, purpuroxanthine, quinizarine, anthraflavinic acid, isoanthraflavinic
acid, anthrarufine, chrysazine, and the like, purpurine, flavopurpurine, anthra-
purpurine, anthragallol, hydroxychrysazine, alizarine bordeaux, purpurinbordeaux,
Hlavopurpurinbordeaux, anthrapurpurin bordeaux, anthrachryson, alizarinpenta-
cyanine, rufigallic acid, alizarinhexacyanine, hexahydroxyanthraquinone and the
like), but also the products derived from the last named or similar hydroxyanthra-
quinones, chiefly those compounds employed by my foreign correspondents as
original products, or obtained by them as intermediate or end products, as described
in the Specifications of Letters Patents No. 8725 of 1890, 12715 of 1890, 17712 of
1890, 18637 of 1890, 18729 of 1890, 1883 of 1891, 4871 of 1891, 8702 of 1891, and
in the Specifications of Applications Nos. 13677 of 1891, 21717 of 1891, 1657 of
1892, 12580 of 1892, and 12579 of 1892.
In the employment of such or similar compounds, beta or alpha nitro products

page_text: in general are obtained, according as the corresponding boric or arsenic acid ethers
are treated with nitrating agents.
Of course, my foreign correspondents do not limit themselves to the methods
described in the above two examples. The processes illustrated thereby can be
varied, and all methods of nitration employed in chemistry can be used. Such
modifications do not alter the nature of this invention, as the latter merely relates
to the production of beta or alpha nitro derivatives of alizarine or its analogues
hereinbefore defined, by means of boric acid ethers or arsenic acid ethers.
Dated this 7th day of February 1893.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Derivatives of Hydroxy-
anthraquinones.
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 :-
It is known that beta nitroalizarin cannot be efficiently produced by adding to
alizarin dissolved in concentrated sulphuric acid, nitric acid, or salts thereof, the
chief product formed in such case being the nitro purpurine first described as nitro
hydroxyalizarin by Strecker in the Zeitschrift für Chemie, 1868, page 264.
My foreign correspondents have found that beta nitroalizarin is readily formed in
theoretical amount by nitrating a solution of the boric acid ether of alizarin in
concentrated sulphuric acid, and that, when treated with nitrating agents, the boric
acid ethers of the "analogues of alizarin” also readily yield the corresponding beta
nitro derivatives of the hydroxyanthraquinones employed, but that the arsenic acid
ethers of alizarin and its analogues are converted by nitration into the isomeric alpha
nitro derivatives of alizarin or its analogues.
According to the researches of my foreign correspondents, the boric acids ether
of alizarin is easily obtained, for example, by introducing crystallised boric acid
into a solution of alizarin in concentrated sulphuric acid. The formation of the
boric acid ether, which proceeds very quickly, is complete when, on forming a test
portion into concentrated sulphuric acid, it dissolves, forming a violet red coloured
liquid, instead of a brownish-red, as in the case of alizarin. The substance
precipitated by pouring a sample into cold water, dissolves with difficulty in soda
ye, a dull brown coloured solution being obtained, unlike that afforded by alizarin,
which, when dissolved in alkali, affords a beautiful violet coloured liquid. The
boric acid ether produced in this or a similar manner, is hydrolysed with very great
ease, by heating or boiling with water or diluted acids. The other boric acid
ethers derived from the "analogues of alizarin," can be obtained in the aforesaid
manner, and their chemical behaviour is similar to that of the boric acid ether of
alizarin.
In order to illustrate this new process of obtaining beta nitro-derivatives of
hydroxyanthraquinones by means of boric acid ethers, the following example is
given. The parts are by weight.
FIRST EXAMPLE.
CONVERSION OF ALIZARIN INTO BETA NITRO ALIZARIN.
10 parts of crystallised boric acid are stirred into a solution prepared by
dissolving 10 parts of alizarin in 200 parts of sulphuric acid (at 66 degrees Baumé).
The resulting mixture is rendered cold and then three litres (in case the parts are

page_text: TRODUCTION
OT
After
10 parts of alizarin are dissolved in 200 parts of sulphuric acid (66 degrees
Baumé), and 10 parts of solid arsenic acid are stirred into this solution. The
mixture is well cooled, and then 3 litres (in case the parts are kilos. by weight) of
nitric acid (42 degrees Baumé) are gradually added thereto, the temperature being,
as far as possible, prevented from rising above 0 degrees centigrade.
standing during several hours, the liquid is poured into cold water. The precipitate
which separates is filtered off, redissolved in soda-lye, and the resulting alkaline
solution is heated to boiling, and decomposed with an excess of sulphuric acid.
Boiling is continued until the whole of the arsenic acid ether of alpha nitro alizarin
initially produced, is decomposed. The decomposition is complete as soon as a
sample dissolves in soda lye, affording the beautiful violet colour characteristic of
alphanitroalizarin. The precipitated dye-stuff is filtered off and washed.
My foreign correspondents have described in the foregoing examples, two methods,.
one, that of producing beta nitro alizarin by means of the boric acid ether of
alizarin; the other, that of obtaining alpha nitroalizarin by means of the arsenic acid
ether of alizarin.
The production of the analogues, alpha nitrohydroxyanthraquinones, and beta
nitrohydroxyanthraquinones can also be effected in the manner illustrated by the
above examples, which are typical, though my foreign correspondents do not limit
themselves to the directions given therein.
If, in the said examples, alizarin is replaced by the corresponding quantities of
the "analogues of alizarin," the nitro derivatives of the latter compounds are
formed in a similar manner, that is to say, the beta nitro derivatives are obtained
from the boric acid ethers, whilst the isomeric alpha nitro products are formed from
the arsenic acid ethers, in cases in which the formation of isomeric nitro products
is theoretically possible.
My foreign correspondents have prepared in the manner hereinbefore defined; for
instance, beta nitro flavopurpurin, betanitro anthra purpurin, and beta nitro alizarin
bordeaux, viz., by treating with nitric acid, solutions of the boric acid ethers of
flavopurpurin, anthra purpurin, and alizarin bordeaux, respectively, in concentrated
sulphuric acid. The last named beta nitro compounds have already been otherwise
prepared, while of the corresponding alpha nitro products which my foreign corre-
spondents have produced by subjecting the arsenic acid ethers of flavopurpurin,

page_text: anthra purpurin, and alizarin bordeaux, respectively, to the above process, the ampua.
nitro alizarin bordeaux has not hitherto been described.
Having now particularly described and ascertained the nature of the said
invention 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 alpha nitrohydroxyanthraquinones from arsenic acid ethers.
of hydroxyanthraquinones.
2. The manufacture of beta nitrohydroxyanthraquinones from boric acid ethers.
of hydroxyanthraquinones.
3. The process for producing alpha nitroalizarin, alpha nitro flavopurpuriu, alpha
nitro anthra purpurin, or alpha nitro alizarin bordeaux, which process consists in
nitrating sulphuric acid solutions of the arsenic acid ethers of alizarin, flavopurpurin,
anthrapurpurin, or alizarin bordeaux, respectively; hydrolysing the resulting nitro
compounds of the ethers employed; and subsequently isolating the aforesaid alpha.
nitro hydroxyanthraquinones in a suitable manner.
4. The process for producing beta nitroalizarin, heta nitroflavopurpurin, beta
nitro anthrapurpurin, or beta nitro alizarin bordeaux, by nitrating sulphuric acid
solutions of the boric acid ethers of alizarin, flavo purpurin, anthrapurpurin, or
alizarin bordeaux, respectively; hydrolysing the resulting nitro compounds of the
ethers employed; and subsequently isolating, in a suitable manner, the said beta--
nitrohydroxyanthraquinones.
5. As new product of manufacture, alpha nitro alizarin bordeaux produced by the
process herein before defined, or by any other way affording the same result.
Dated this 6th day of November 1893.
NEWTON & SON,
Agents for the Applicant.