Improvements in the Production of Alpha-nitro-alpha-amido and Alpha-quinoline-compounds of Alizarine and the Anthra- and Flavo-purpurines.
Year: 1892

page_text: Date of Application, 15th Aug., 1892
Complete Specification Left, 15th May, 1893-Accepted, 1st July, 1893
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBWERKE VORMALS MEISTER LUCIUS
AND BRUNING, of Hoechst / Main, in the Empire of Germany, Chemical
Manufacturers.]
Improvements in the Production of Alpha-nitro-alpha-amido and
Alpha-quinoline-compounds of Alizarine and the Anthra- and
Flavo-purpurines.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, in the County of London,
Chartered Patent Agent, do hereby declare the nature of this invention to be as
follows:-
My foreign correspondents have discovered that the benzoyl compounds of
alizarine, anthra and flavo purpurines are by nitration with nitro sulphuric acid
and subsequent saponification, sinoothly converted into the alpha nitro compounds
and then by quiuolisation into the alpha quinoline compounds of alizarine and the
anthra and flavo purpurines, which latter bodies are very valuable green coloring
matters.
As raw materials may be used the di- or tri-benzoylised alizarines and anthra and
flavo purpurines or also the monobenzoylised compounds, which latter can be easily
produced by heating molecular quantities of the respective alizarines and benzoyl-
chloride.
The production of alpba nitro-alizarine is for example carried out as follows:
6 parts of dibenzoylalizarine in powder are mixed by degrees with a mixture,
well cooled with ice and salt, of 11 parts of nitric acid of 43° Bé. and 16 parts of
sulphuric acid of 66° Bé., care being taken that the temperature never rises
above 45° C.
At first the alizarine deliquesces into a paste, seemingly without previously
dissolving and afterwards gradually transforms into a finely divided light yellow
solid mass.
The reaction mixture is kept agitated at from 20° to 25° C. and as
soon as a sample in alcoholic alkaline dissolution no longer shows the alizarine
spectrum it is poured into glacial water.
The light yellow nitro body which separates, is filtered off and washed neutrally.
In order to isolate the free nitro compound, the dibenzoyl-alpha-nitro alizarine
is dissolved in hot soda lye, precipitated by means of acid, filtered and the benzoic
acid removed by washing with hot water. The benzoic acid can be recovered from
the filtrates.
The production and isolation of the alpha-nitro-anthra-purpurine and of the
alpha-nitro flavo purpurine can be carried out in the same manner as described for
the alpha nitro alizarine.
In regard to their exterior appearance and behaviour the alpha nitro anthra-
purpurine and the alpha nitro flavopurpurine very nearly resemble alpha nitro
alizarine.
The two nitro bodies dissolve in alkalies and in concentrated sulphuric acid,
showing bluish to yellow red coloration; the nitro flavopurpurine in the respective
solutions always showing a yellower shade than the nitro anthrapurpurine.
The alpha amido anthra and flavo purpurines, like alpha amido alizarine, are
easily obtained from the corresponding nitro compounds by means of reducing
agents.
It will be found advantageous to work in hot alkaline solutions with the suitable
quantity of one or the other of the usual reducing agents, such as tin chloride,
sulphide of sodium or glucose. By acidulation the free amido body can be
precipitated from the reduction mixture.

page_text: The alpha-amido anthrapurpurine is of a dark brown red, the alpha amido flavo
purpurine, of a lighter red brown colour. The colour of the solutions in alkalies is
blue red to yellow red and also in this form the flavo-purpurine compounds show a
yellower coloration than the anthrapurpurine compounds.
With concentrated hydrochloric acid the two amido bodies form brownish
yellow nearly insoluble salts which are decomposed already by a small quantity of
water.
In concentrated sulphuric acid, the amido anthrapurpurine dissolves with red
colour the amidoflavopurpurine with yellow color.
The alpha quinoline-compounds of alizarine, as well as those of the anthra- and
flavo-purpurines can be obtained from the respective alpha amido-compounds by
the well known methods of quinolising, thus for example by heating with
concentrated hydrochloric acid, chloride of zinc and glycerine or in sulphuric
solution with glycerine and an oxidising agent such as for example nitrobenzene.
With the last named agents the operation is carried out for example as
follows.
1 part of the amido compound in powder is dissolved in from 7 to 8 parts of
sulphuric acid of 66° Bé. and admixed with part of glycerine and part of
nitrobenzene. The mass is slowly heated to 110° C., is kept at this temperature
for 3 hours and is then poured into water. There separates a black mass which is
filtered off and washed.
For further purification the quinolines may be recrystallised from diluted hot
sulphuric acid and be precipitated from the obtained sulphuric solution by a
copious quantity of water. Also, the purification may be carried out with equally
good effect by boiling the sodium-salts of the quinolines (which are soluble with
difficulty) with diluted soda-lye.
The alizarine alpha quinoline is nearly insoluble in water, of greenish blue-black
colour and forms blue salts with small quantities of soda- or potash-lye, but green
salts with large quantities of lye. The ammonia salt is blue. The compounds
with acids which are coloured deep-red, are decomposed again by water.
The anthrapurpurine-alpha quinoline is blueish-black. The ammonia salt is dark
green-blue and like the blueish-green sodium salt, of very difficult solubility even
in hot water.
The flavo-purpurine alpha quinoline is greenish black; mixed with water it
forms with a small excess of soda-lye, a nearly insoluble salt, which even on being
boiled remains grey-violet. A larger excess of lye produces a blue, and a further
quantity a green-blue body. With ammonia is produced a dark brownish red
compound. Strong solutions of mineral acids produce red salts decomposable by
water.
The bisulphite compounds of alizarine-and also of the flavo- and anthra-
purpurine-alpha quinolines are easily soluble in water and are obtained by
treating the free quinoline in form of a paste with concentrated solutions of alkali-
bisulphites, for example bisulphite of sodium, at average temperatures for a few
days.
The beautiful carmine-red solutions thus obtained can be filtered, precipitated by
means of common salt and the bisulphite compounds be used in the form of pastes
or powder for dyeing and printing.
The bisulphite compounds are split up into their components by boiling with
water or more easily by the addition of acids or alkalies.
Dated this 15th day of August 1892.
ABEL & IMRAY,
Agents for the Applicant.

page_text: COMPLETE SPECIFICATION.
Improvements in the Production of Alpha-nitro-alpha-amido and
Alpha-quinoline-compounds of Alizarine and the Anthra- and
Flavo-purpurines.
1, OLIVER IMRAY of No. 28 Southampton Buildings, in the County of London,
Chartered 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 discovered that the benzoyl compounds of
alizarine, anthra- and flavo-purpurines are, by nitration with nitro sulphuric acid
and subsequent saponification, smoothly converted into the alpha nitro compounds,
and then, by quinolisation, into the alpha quinoline compounds of alizarine and the
anthra- and flavo-purpurines, which latter bodies are very valuable green colouring
matters.
As raw materials may be used the di- or tri-benzoylised alizarines and anthra-
aud flavo-purpurines, or also the monobenzoylised compounds, which latter can be
easily produced by heating molecular quantities of the respective alizarines and
benzoylchloride.
The production of alpha-nitro-alizarine is, for example, carried out as follows:
6 parts of dibenzoylalizarine in powder are mixed by degrees with a mixture,
well cooled with ice and salt, of 11 parts of nitric acid of 43° Bé. and 16 parts of
sulphuric acid of 66° Bé., care being taken that the temperature never rises
above 45° C.
At first the alizarine deliquesces into a paste, seemingly without previously
dissolving and afterwards gradually transforms into a finely divided light yellow
solid mass.
The reaction mixture is kept agitated at from 20° to 25° C. and, as
soon as a sample in alcoholic alkaline solution no longer shows the alizarine
spectrum, it is poured into glacial water.
The light yellow nitro body which separates is filtered off and washed neutrally.
In order to isolate the free nitro compound, the dibenzoyl-alpha-nitro alizarine is
dissolved in hot soda lye, precipitated by means of acid, filtered, and the benzoic
acid removed by washing with hot water. The benzoic acid can be recovered from
the filtrates.
The production and isolation of the alpha-nitro-anthra-purpurine and of the
alpha-nitro-flavo-purpurine can be carried out in the same manner as described for
the alpha-nitro-alizarine.
In regard to their exterior appearance and behaviour, the alpha-nitro-anthra-
purpurine and the alpha-nitro-flavo-purpurine very nearly resemble alpha-nitro-
alizarine.
The two nitro bodies dissolve in alkalies and in concentrated sulphuric acid,
showing bluish to yellow red coloration; the nitro-flavo-purpurine in the respective
solutions always showing a yellower shade than the nitro-anthra-purpurine.
The alpha-amido-anthra- and flavo purpurines, like alpha-amido-alizarine, are
easily obtained from the corresponding nitro compounds by means of reducing
agents.
It will be found advantageous to work in hot alkaline solutions with the suitable
quantity of one or the other of the usual reducing agents, such as tin chloride,
sulphide of sodium or glucose. By acidulation the free amido body can be
precipitated from the reduction mixture.
The alpha-amido-anthra-purpurine is of a dark brown red, the alpha-amido-flavo-
purpurine, of a lighter red brown colour. The colour of the solutions in alkalies is
blue red to yellow red and also in this form the flavo-purpurine compounds shew a
yellower coloration than the anthrapurpurine compounds.

page_text: With concentrated hydrochloric acid the two amido bodies form yellow nearly
insoluble salts which are decomposed already by a small quantity of water.
In concentrated sulphuric acid, the amido-anthra-purpurine
colour, the amido-flavo-purpurine with yellow colour.
dissolves with red
The alpha-quinoline compounds of alizarine, as well as those of the authra- and
flavo-purpurines, can be obtained from the respective alpha-amido-compounds by
the well known methods of quinolising, thus, for example, by heating with
concentrated hydrochloric acid, chloride of zinc and glycerine or in sulphuric
solution with glycerine and an oxidising agent, such as, for example, nitro-
benzene.
With the last named agents the operation is carried out, for example, as
follows:
1 part of the amido compound in powder is dissolved in from 7 to 8 parts of
sulphuric acid of 66° Bé. and admixed with part of glycerine and part of
nitrobenzene. The mass slowly heated to 110° C, is kept at this temperature for
3 hours and is then poured into water. There separates a black mass which is
filtered off' and washed. For further purification the quinolines may be recrystallised
from diluted hot sulphuric acid and be precipitated from the obtained sulphuric
solution by a copious quantity of water. Also, the purification may be carried out
with equally good effect by boiling the sodium-salts of the quinolines (which are
soluble with difficulty) with diluted soda-lye.
The alizarine alpha quinoline is nearly insoluble in water, of greenish blue-black
colour and forms blue salts with small quantities of soda- or potash-lye, but green
salts with large quantities of lye.
The ammonia salt is blue. The compounds with acids which are coloured deep-
red, are decomposed again by water.
The anthrapurpurine-alpha quinoline is bluish black. The ammonia salt is dark
green-blue and like the bluish-green sodium salt of very difficult solubility even in
hot water.
The flavo-purpurine alpha quinoline is greenish black, mixed with water it forms
with a small excess of soda-lye, a nearly insoluble salt, which even on being boiled
remains grey-violet.
A larger excess of lye produces a blue, and a further quantity, a green-blue body.
With ammonia is produced a dark brownish red compound.
Strong solutions of mineral acids produce red salts decomposable by water.
The bisulphite compounds of alizarine and also of the flavo- and anthra-
purpurine-alpha-quinolines are easily soluble in water and are obtained by treating
the free quinoline in form of a paste with concentrated solutions of alkali-
bisulphites, for example bisulphite of sodium, at average temperatures for a
few days.
The beautiful carmine-red solutions thus obtained can be filtered, precipitated by
means of common salt, and the bisulphite compounds can be used in the form of
pastes or powder for dyeing and printing.
The bisulphite compounds are split up into their components by boiling with
water or, more easily, by the addition of acids or alkalies.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed 1 declare that what I
claim is:
1-The production of alpha nitro compounds of alizarine, anthrapurpurine and
flavopurpurine by nitrating benzoylised alizarine or anthra- and flavo-purpurines
with nitro sulphuric acid at temperatures between 0° and 50° C. and saponifying
with alkalies the benzoylised nitro alizarine or the nitro-anthra- and nitro-favo
purpurines thus obtained.
2-The production of alpha-amido-anthra- and alpha-amido-flavo-purpurines, by
reducing in alkaline solution alpha-nitro authra-purpurine or alpha-nitro-flavo-
purpurine.

page_text: 3-The production of alizarine-alpha-quinoline, anthra-purpurine-alpha-quinoline
and flavo-purpurine-alpha quinoline, by heating alpha-amido-alizarine, alpha-amido-
anthrapurpurine or alpha-amido flavo-purpurine with glycerine, sulphuric acid
and an oxidising agent such as nitrobenzene, at temperatures between 100° and
130° C.
4 The production of easily soluble bisulphite compounds of the alpha quinolines
of alizarine, anthrapurpurine and flavo-purpurine, by treating the free quinolines
with concentrated solutions of alkali-bisulphite compounds at temperatures
below 50° C.
5-The alpha-nitro-anthra-purpurine
The alpha-nitro-flavo-purpurine
alpha-amido-anthra-purpurine
alpha-amido-flavo-purpurine
The
The
The anthra-purpurine-alpha quinoline
The flavo-purpurine-alpha quinoline
The alizarine-alpha quinoline
and the bisulphite compounds of the three alpha quinolines produced as set forth
in Claims 1, 2, 3 and 4.
ABEL & IMRAY,
Agents for the Applicant.