СИНТЕТИЧНИЙ ПОТЕНЦІАЛ 9,10-АНТРАХІНОНІЛДІАЗОНІЄВИХ СОЛЕЙ
For the first time, the literature sources concerning the chemical transformations of diazonium salts of 1(2)-amino-9,10-anthracenediones are generalized and systematized. The potential of 9,10-dioxoanthracenyldiazonium salts as key substrates in the preparation of various linear-functionalized, acy...
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V.I.Vernadsky Institute of General and Inorganic Chemistry
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Ukrainian Chemistry Journal| _version_ | 1871465636356423680 |
|---|---|
| author | Stasevich, Maryna Zvarych, Viktor Novikov, Volodymyr Vovk, Mykhailo |
| author_facet | Stasevich, Maryna Zvarych, Viktor Novikov, Volodymyr Vovk, Mykhailo |
| author_institution_txt_mv | [
{
"author": "Maryna Stasevich",
"institution": "Національний університет \"Львівська політехніка\""
},
{
"author": "Viktor Zvarych",
"institution": null
},
{
"author": "Volodymyr Novikov",
"institution": null
},
{
"author": "Mykhailo Vovk",
"institution": null
}
] |
| author_sort | Stasevich, Maryna |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:44Z |
| description | For the first time, the literature sources concerning the chemical transformations of diazonium salts of 1(2)-amino-9,10-anthracenediones are generalized and systematized. The potential of 9,10-dioxoanthracenyldiazonium salts as key substrates in the preparation of various linear-functionalized, acyclic and heterocyclic derivatives has been determined. The main synthetic transformations of diazonium salts of amino-9,10-anthracenediones, which are  realized without preserving the azo function lead to the formation of reaction products of Sandmeyer, Meerwein, and Gomberg–Bachmann–Hay, are analyzed. The use of 9,10-dioxoanthracenyldiazonium salts or products of their transformations for obtaining heteryl-containing condensed and functionalized derivatives is presented. |
| doi_str_mv | 10.33609/2708-129X.86.9.2020.55-72 |
| first_indexed | 2025-09-24T17:43:35Z |
| format | Article |
| fulltext |
55
UDC 547.673.+547-304.4 doi: 10.33609/2708-129X.86.9.2020.55-72
SYNTHETIC POTENTIAL OF 9,10-ANTHRAQUINONYLDIAZONIUM
SALTS
М. V. Stasevych1*, V. І. Zvarych1, V. P. Novikov1, М. V. Vovk2
1 Lviv Polytechnic National University, S. Bandera Str. 12, Lviv, 79013, Ukraine
2 Institute of Organic Chemistry of National Academy of Sciences of Ukraine, Murmanska Str. 5,
Kyiv 02660, Ukraine
*е-mail: maryna.v.stasevych@gmail.com
For the first time, the literature sources concerning the chemical transformations of diazonium salts
of 1(2)-amino-9,10-anthracenediones are generalized and systematized. The potential of 9,10-dioxoan-
thracenyldiazonium salts as key substrates in the preparation of various linear-functionalized, acyclic
and heterocyclic derivatives has been determined. The main synthetic transformations of diazonium
salts of amino-9,10-anthracenediones, which are realized without preserving the azo function lead
to the formation of reaction products of Sandmeyer, Meerwein, and Gomberg–Bachmann–Hay, are
analyzed. The use of 9,10-dioxoanthracenyldiazonium salts or products of their transformations for
obtaining heteryl-containing condensed and functionalized derivatives is presented.
Key words: diazonium salts of 1(2)-amino-9,10-anthracenedione, dediazonation, azo coupling, an-
nulation, heterylfunctionalization.
INTRODUCTION. In modern organic syn-
thesis diazonium salts belong to the impor-
tant classes of compounds with a powerful
synthetic potential, which have not lost their
relevance and importance to this day due to
their easy accessibility and pronounced reac-
tivity. Their use in various synthetic transfor-
mations opens access to new types of organic
compounds. In this context, diazonium salts
of amino-9,10-anthracenediones play an im-
portant role in developing approaches to the
synthesis of new substances with potential bio-
logical effects. At the same time, despite the di-
versity of the products of the arendiazonation
reaction, a relatively little arsenal of derivatives
was obtained on the basis of diazonium salts of
amino-9,10-anthracenediones, among which
diazo compounds and the products of the
Sandmeyer and Meerwein reactions should be
noted.
The formation of 9,10-anthracenediazoni-
um salts occurs only in solutions of concen-
trated acids, which is due to the decreased
basicity of the amino group of amino-9,10-an-
thracenediones [1]. Usually, 9,10-dioxoan-
thracenyldiazonium chloride is obtained in
the presence of concentrated HCl in organic
solvents [1, 2]. However, most often in diazoti-
zation reactions, hydrosulfate and tetrafluoro
borate salts 3–8 are obtained, which are more
ORGANIC CHEMISTRY SYNTHETIC POTENTIAL OF 9,10-ANTHRAQUINONYLDIAZONIUM SALTS
56 ISSN 2708-129X. Укр. хім. журн., 2020
stable during storage and convenient in use.
Diazonium hydrosulfates 3, 4 are easily formed
in concentrated H2SO4 under the action of so-
dium nitrite or nitrosyl sulfuric acid [3]. When
the latter interact with sodium tetrafluorobo-
rate, they give the corresponding salts 5 and
6 [1]. In recent years, t-BuONO is used as an
effective diazotizing agent, which makes it pos-
sible to obtain salts 7, 8.
Due to the high electrophilicity of the di-
azonium center, which is enhanced by quinoid
conjugation, salts 3–8 easily interact with nu-
cleophilic reagents, which allows the introduc-
tion of new substituents into the anthracene-
dione ring and to obtain both dediazonation
products and azo group derivatives.
This review focuses on the generalization
and systematization of the results of original
studies related to the transformation of diazo-
nium salts of amino-9,10-anthracenediones,
and the uses of diazonation reaction products
to obtain various derivatives of 9,10-anthra-
cenedione are presented.
REACTIONS OF DEDIAZONIZATION OF
9,10-ANTHRACENYL DIAZONIUM SALTS
The authors of [3] found that the diazotiza-
tion of 1(2)-aminoanthracene-9,10-diones 9
and 10 in dioxane using the NaNO2-HCl sys-
tem leads to the products of the replacement
of the diazonium group with hydrogen atom
11 and OH-group 12. The formation of the
latter derivative is explained by the peri-effect
of diazo and hydroxy groups, which causes the
reduction process.
Deaminated methyl derivative 14 and pyra-
zoloanylelated compound 15 are the products
of the conversion of diazonium hydrosulfate of
1-amino-2-methyl-9,10-anthracenedione 13
in methanol and dioxane [4].
The treatment of 9,10-dioxoanthracenyl
diazonium 16 chlorides with zinc dust in etha-
nol solution was a convenient approach to the
synthesis of reduction products 17 [4].
-
-
UCJ № 9 / Vol. 86М. V. Stasevych, V. І. Zvarych, V. P. Novikov, М. V. Vovk
57https://ucj.org.ua
It should be noted that the introduction of
the hydroxyl group, halogen atom, azide, ni-
trile, sulfur- and phosphorus-containing sub-
stituents by replacing the diazonium group of
9,10-anthracenedione is widely used in syn-
thetic practice since the early XX century [1].
Hydroxyderivatives are easily obtained by
the hydrolysis of diazonium salts of amino-
anthracene-9,10-diones [3, 5, 6]. The inter-
action of the corresponding diazonium salt
with potassium iodide at room temperature
is used to obtain 1(2)-iodo-9,10-dioxoanthra-
cene [7]. The one-step interaction of 1(2)-ami-
no-9,10-dioxoanthracene with the diazotizing
NaNO2–HI system in dimethyl sulfoxide me-
dium allows one to obtain the target prod-
uct with higher yield [8]. The corresponding
1,8-difluoro derivative 19 was obtained under
the conditions of the Baltz-Schiman reaction
from bis-tetrafluoroborate 9,10-dioxoanthra-
cenyl diazonium 18.
Nitrile-containing 9,10-dioxoanthracenes
are usually obtained under the conditions of the
Sandmeyer reaction in the presence of an aque-
ous solution of a complex salt of copper (I) cya-
nide and potassium/sodium cyanide [1, 9].
The formation of 1(2)-azido derivatives of
9,10-anthracenedione easily occurs when the
corresponding diazonium salts interact with
sodium azide in an aqueous medium [10-12].
The synthesis of 1-mercapto-9,10-anthra-
cenedione involves a two-stage process, in
which the first stage is carried out by the thi-
ocyanation of the diazonium salt with potas-
sium rhodanide, and the second stage involves
alkaline hydrolysis in an aqueous-ethanolic
solution [1]. An alternative method of ob-
taining such a compound is the interaction of
9,10-dioxoanthracenyldiazonium hydrosulfate
with potassium dithiocarbonate in an aqueous
medium followed by hydrolysis [13].
Thiocyanate derivatives were obtained by
the diazotization of 1-amino- and 1,4-diami-
no-9,10-dioxoanthracene with sodium nitrite
in sulfuric acid, followed by the action of po-
tassium thiocyanate [14, 15].
Several studies on the synthesis of 1(2)-
thio-containing 9,10-anthracenediones by the
S-arylation of thioglycolic acid with diazoni-
um salts have been described in the literature
[14, 16]. 9,10-Dihydro-9,10-dioxoanthracene-
2-ylsulfonyl chloride was obtained from the
corresponding diazonium chloride and sul-
fur (IV) oxide in the presence of copper (II)
chloride [17]. Phosphorus-containing deriv-
atives based on diazonium tetrafluoroborates
of 9,10-anthracenedione are represented by
(9,10-dioxo-9,10-dihydroanthracene-1(2)-yl)
phosphonic acids 20, 21, which are formed
by the interaction of salts 5, 6 with phospho-
rus (III) chloride in the presence of a salt of
-
-
ORGANIC CHEMISTRY SYNTHETIC POTENTIAL OF 9,10-ANTHRAQUINONYLDIAZONIUM SALTS
58 ISSN 2708-129X. Укр. хім. журн., 2020
copper (I) and can be easily converted into am-
monium salts [18, 19].
The authors of [20] proposed an effective
variant for obtaining 9,10-dioxo-anthrace-
nyldithiocarbamates under the conditions
of “green” chemistry based on 9,10-dioxoan-
thracenyldiazonium salts. The reaction of
noncatalytic arylation with freshly obtained,
neutralized with sodium carbonate, diazoni-
um hydrosulfate salts of 1(2)-amino-9,10-an-
thracenediones 1, 2, 22–28 and a series of in
situ generated dithiocarbamic acids with frag-
ments of diethylamine, pyrrolidine, piperidine
and morpholine in an aqueous medium under
mild temperature conditions led to the prepa-
ration of carbodithioates 29a-v.
UCJ № 9 / Vol. 86М. V. Stasevych, V. І. Zvarych, V. P. Novikov, М. V. Vovk
59https://ucj.org.ua
9,10-Dioxoanthracenyl-2-diazonium tetra
fluoroborate 5 is a convenient reagent in
the synthesis of (N-Boc-3-pyrrolyl)anthra-
cene-1-yl-9,10-dioxoanthracene 30 under the
conditions of Pd-catalyzed arylation of N-(tert-
butoxycarbonyl) -3-pyrroline salt 5 [21].
The authors of [22-28] described the use of
diazonium salt 7 to obtain functional deriva-
tives 31 in the presence of copper (II) salts.
The influence of electron-donor substitu-
ents in the fourth position of the 9,10-diox-
oanthracene nucleus on the cyclization process
of alkynyl-containing hydrosulfate diazonium
salts 32, 35 was determined [29].
The presence of such substituents not only
stabilizes the latter, but also allows the nucleop-
hilic substitution of the diazo group with the
azide anion and the conversion of compounds
33, 36 to isoxazoles 34, 37 without involving
acetylene function.
Azidoderivatives 39 under heating above
110° C were converted to compounds of isoxa
zole type 40, which reacted with sulfoxide to
give sulfanylideneaminoanthracene-9,10-di-
ones 41 [30].
Isoxazole derivatives 40 can also be used to
prepare phosphoamides 42 and iminophos-
phoranes 43 [30].
ORGANIC CHEMISTRY SYNTHETIC POTENTIAL OF 9,10-ANTHRAQUINONYLDIAZONIUM SALTS
60 ISSN 2708-129X. Укр. хім. журн., 2020
Anthra[1,9-cd:5,10-c’d’]diisoxazole 46 re-
acts similarly with triphenylphosphine, di-
methyl(diethyl, diphenyl)sulfoxides and tri-
alkyl(aryl)oxyphosphines with the disclosure
of both isoxazole cycles and the formation of
corresponding bisproducts 47–49 [30].
The behavior of the azides of 9,10-an-
thracenedione 50, 51 in the reaction of Cu-
catalyzed 1,3-dipolar cycloaddition (CuAAC)
with a number of substituted alkynes was
investigated [31]. It was found that the use
of systems such as CuI-L-proline in DMSO,
CuSO4-potassium ascorbate in a mixture of
DMF-H2O and CuI-TEA in chloroform led to
a positive result with obtaining 1,2,3-triazole
derivatives 52 only in the case of the latter op-
tion [31].
The Gomberg – Bachmann – Hay and
Meerwein reactions play an important role
in the transformation of the diazonium salts
of 9,10-anthracenediones, since the acylation
and Friedel – Crafts alkylation processes are
not characteristic of 9,10-dioxoanthracene de-
rivatives due to the effect of quinoid conjuga-
tion [32].
It was determined that the formation of
the products of this reaction, aryl-9,10-dioxo
anthracenes 53–60, occurs quite easily and in
high yields (40–60%). The arylation of tolu-
ene leads to the formation of 1(2)-isomers at
the ortho- and para-positions to CH3-groups
57, 59 (in the case of 9,10-dioxoanthra-
cene-1-yldiazonium) and mixtures 58, 60 (in
the case of 9,10-dioxoanthracene-2-yldiazoni-
um) [33].
UCJ № 9 / Vol. 86М. V. Stasevych, V. І. Zvarych, V. P. Novikov, М. V. Vovk
61https://ucj.org.ua
Studies of C-arylation of pyridine by diazo-
nium salts of anthracenediones under the con-
ditions of a modified Gomberg-Bachmann-
Hay reaction at a temperature of -10 °C to 70 °C
in the absence of catalyst and Cu-catalysis have
shown that a mixture of ortho-, meta- and pa-
ra-products of arylation of pyridine 61-66 was
the result of the interaction [34].
The use of Meyerwein reaction taking di-
azonium salts of 9,10-dioxoanthracene as an
example is represented by coupling reactions
with such unsaturated compounds as 1,1-di-
chloroethene, 1,1,2-trichloroethene, acrylic
acid esters, nitrile methacrylic acid, 2,4-dicy-
ano-1-butene in the presence of copper salts
[35]. 2- (9,10-Dioxo-9,10-dihydroanthracene-
1-yl)acetic acid 67 and its esters 68 were pre-
pared by the Cu-catalyzed coupling of diazoni-
um salt 3 with 1,1-dichloroethene under mild
conditions [36].
Under similar conditions, 2-(9,10-di-
oxo-9,10-dihydroanthracene-1-yl)chloroacet-
ic acid 69 was obtained in high yield from
1,1,2-trichloroethene and diazonium hydro-
gen sulfate 3 in acetate acid [35].
The authors of [35] suggested using meth-
acrylonitrile in the presence of copper(I)
chloride to obtain 1-(2-oxopropyl)anthra-
cene-9,10-dione 70, which was converted by
alkaline hydrolysis to 2-hydroxy-7H-ben-
zo[de]anthracene-7-one 71.
ORGANIC CHEMISTRY SYNTHETIC POTENTIAL OF 9,10-ANTHRAQUINONYLDIAZONIUM SALTS
62 ISSN 2708-129X. Укр. хім. журн., 2020
The Cu-catalyzed arylation of 2,4-dicy-
ano-1-butene in methanol leads to the for-
mation of a mixture of cyanohydrin 72, cya-
noketone 73, and 9,10-dioxoanthracene 74 as
a dediazonation product. 5-(9,10-Dioxo-9,10-
dihydroanthracene-1-yl) -4-oxopentanoic acid
76 was synthesized by an acid hydrolysis of
derivative 73. When methanol was replaced
by acetonitrile, the formation of 2-chloro-2-
[(9,10-dioxo-9,10-dihydroanthracene-1-yl)
methyl]pentanedinitrile 75 was observed as
the main product [35].
The authors of [2] observed the formation
of C-C coupling products 77-82 in the study
of the arylation of methyl esters of acrylic and
methacrylic acids, acrylamide and 1,4-benzo-
quinone by 9,10-anthracenedione-1-diazoni-
um tetrafluoroborate under the conditions of
Meerwein reaction.
Functionalized with a methylfuran frag-
ment, 9,10-anthracenedione derivative 83 was
obtained under the conditions of Meerwein
reaction by the arylation of diethyl 2-methyl-
enepentanedioate in the presence of copper(I)
chloride in methanol [35].
The behavior of 9,10-anthracenedione-1-di-
azonium chloride 84 was also studied under
the conditions of the Meerwein reaction in the
presence of CuCl2 in an acetone medium [37],
and it was found that the product of this inter-
action is tetrachlorocuprate (II) 85.
UCJ № 9 / Vol. 86М. V. Stasevych, V. І. Zvarych, V. P. Novikov, М. V. Vovk
63https://ucj.org.ua
The dediazonation of tetrachlorocuprate
(II) 85 in polar solvents at room tempera-
ture led to 1-chloro-9,10-anthracenediones.
Instead, 9,10-anthracenedione chloro- and
hydroxypropionates 86 were obtained in the
presence of acrylate esters [37].
The replacement of CuCl by FeSO4 leads to
the formation of a mixture of ketones 87 and
88, the yield of which is significantly affected
by the sequence of addition of reagents [32].
Annelated derivatives of 9,10-dioxoan-
thracene prepared on the basis of diazonium
salts are presented in the literature by a limited
number of examples. In particular, a conven-
ient method was proposed for the preparation
of benzofuran-dioxoanthracene compounds
90 by heating 4-hydroxy-9,10-dioxo-2-ary-
loxy-9,10-dihydroanthracene-1-diazonium
salts 89 [38].
Moreover, benzofuran- 93 and benzothio-
phene-condensed derivatives 94 of 9,10-an-
thracenedione were obtained by the photocycli-
zation of 1-aryloxy(arylthio)-9,10-dioxoanthra-
cenyldiazonium chlorides 91 and 92 in dioxane
or in a mixture of acetate acid with dioxane [39].
The preparation of condensed tetrahy-
drodipyranium derivatives 95 was described
in [39], where bis(hydrosulfatediazoni-
um)9,10-dioxoanthracene 44 was used in cou-
pling reactions with unsaturated compounds
(nitriles of acrylic and methacrylic acids, me-
thyl and ethyl esters of acrylic acid, styrene and
methylstyrene) in the presence of copper(I)
salts in a dimethylphosphite medium.
ORGANIC CHEMISTRY SYNTHETIC POTENTIAL OF 9,10-ANTHRAQUINONYLDIAZONIUM SALTS
64 ISSN 2708-129X. Укр. хім. журн., 2020
REACTIONS OF DIAZONIUM SALTS OF
AMINO-9,10-ANTHRACENEDIONES WITH
PRESERVATION OF THE AZO FUNCTION
The azo coupling reaction of diazonium
salts of 9,10-dioxoanthracene is one of the key
reactions and is widely used in the production
of azo dyes [40]. The property of diazotized
amino-9,10-anthracenediones to form color-
ed azo coupling products has also been used
in analytical methods, in particular for the de-
termination of ascorbic acid [41] and isonia-
zid [42].
A number of α- and β-carbonyl-containing
compounds were successfully used in the mod-
ified Jappa-Klingemann reaction with 9,10-di-
oxoanthracenyldiazonium hydrosulfates 3 and
96 to obtain hydrazone derivatives 97 and 98,
in which acyl and/or alkoxycarbonyl groups
are present in the ylidene part of the hydrazone
fragment [43]. Products 97 and 98 were easily
formed with good yields in an aqueous medi-
um by the arylation of carbonyl reagents with
freshly prepared diazonium hydrosulfates 3
and 96 under mild temperature and non-base
conditions.
The authors in [44] proposed a method
for the synthesis of indazolone derivative 99,
which consisted in a sequential two-stage in-
teraction of aminoanthracenedione 1 with
3-hydroxybenzoic acid and p-toluidine.
The formation of phenolic and naphthalene
derivatives containing the 9,10-dioxoanthra-
cene diazo component occurs quite easily un-
der the conditions of azo coupling of diazoni-
um salts with an aromatic component [45–47].
For the products of azo coupling of diazonium
salts 100 with β-naphthol 101 in solutions of
dimethyl sulfoxide or chloroform, a tenden-
cy to azo-hydrazone tautomerism was found
as a result of the peri-effect of the carbonyl
group [48].
In the above mentioned work, a number of
1-arylazo-9,10-anthracenedione derivatives 103
with aminoalkyl, aminocarbocyclic and hetero-
cyclic moieties at the position 4 were prepared in
sequential reactions of azo coupling of salt 102
and nucleophilic substitution in compounds
UCJ № 9 / Vol. 86М. V. Stasevych, V. І. Zvarych, V. P. Novikov, М. V. Vovk
65https://ucj.org.ua
103 in a medium of N,N-dimethylacetamide
at 50–60 °C or N,N-dimethylformamide in the
temperature range of 60-80 °C.
As noted above, the Cu(I)-catalyzed aryla-
tion of phenylacetylene by 9,10-dioxoanthra-
cenyldiazonium tetrafluoroborate 5 has its own
specificity and can occur with the formation of
various reaction products [33]. In particular,
it was established that in aqueous acetone azo
couplings are realized with the formation of
hydrazones of derivative 105. Instead, isomer-
ic 1-[(2-oxo-2-phenylethyl) diazenyl]anthra-
cene-9,10-dione 106 is formed in the medium
of acetic acid or dimethyl sulfoxide.
In contrast to the products of a similar reac-
tion in DMSO [32], the arylation of styrene un-
der conditions of a catalytic amount of iron(II)
sulfate in dioxane leads to the formation of azo
product 107 [33].
A convenient way of obtaining hybrid
structures with 1,3-oxazepinedione 110 and
benzo[1,3]oxazepinedione 111 cycles based on
the successive transformations of azo coupling
product 108 obtained with 9,10-dioxoanthra-
cene-1-yldiazonium 84 and salicylic aldehyde
has been proposed in [49].
A series of 9,10-anthracenedione triazene
derivatives 113 and 115 was obtained by the
arylation of the corresponding arylamines and
hydroxylamine substituted by salts 112 in the
presence of catalytic amounts of AcONa in a
DMF medium. The synthesized compounds
ORGANIC CHEMISTRY SYNTHETIC POTENTIAL OF 9,10-ANTHRAQUINONYLDIAZONIUM SALTS
66 ISSN 2708-129X. Укр. хім. журн., 2020
were found to be capable of azo-hydrazone
tautomerism [48].
Triazene derivatives with N-aminoalkyl
fragments 117 were obtained in high yields
by the azo coupling of diazonium salt 5 with a
number of aliphatic amines [10, 50, 51].
The work [48] describes the synthesis of
1-(aryltriazen)-4-substituted-9,10-dioxoan-
thracenes 118, which were cyclized to triazo-
lo-anelated derivatives 119 in dimethyl sul-
foxide in the presence of catalytic amounts of
potassium carbonate.
The diazotization of acetylene-containing
1-amino-9,10-anthracenediones 120 in the
presence of hydrochloric acid leads to the for-
mation of a mixture of annelated pyrazole de-
rivatives 121 and 122.
In turn, diazonium sulfates 123 intramo-
lecularly condense under the action of sulfuric
acid into naphtho[2,3-h]cinoline-4,7,12- (1H)-
triones 124 [52, 53].
-
UCJ № 9 / Vol. 86М. V. Stasevych, V. І. Zvarych, V. P. Novikov, М. V. Vovk
67https://ucj.org.ua
It was found that compounds 125 with the
simultaneous presence of an acetyl fragment at
the position 4 of the anthracenedione nucleus
and of electron-donating substituents in the
alkynyl fragment form cyclic derivatives 126
in excellent yields (up to 89%) [29].
3-Phenyl-1H-naphtho[2,3-g]indazole-6,11-
dione 128 was formed in a fairly high yield
from 1-diazonium-2-benzyl-9,10-anthracene-
dione sulfate 127 in ethanol [54].
An efficient synthetic approach [55] for the
preparation of a number condensed deriva-
tives of 9,10-anthracenediones, namely an-
thra[1,2-d][1,2,3]triazine-4,7,12(3H)-triones
130, was proposed via the conditions of diazo-
tization intramolecular cyclization reaction of
1-amino-9,10-dioxoanthracene-2-carboxam-
ides 129.
CONCLUSIONS. Thus, the presented gene
ralized literature data on the known reactions
of diazonium salts of 9,10-anthracenedione
show their pronounced synthetic potential.
Moreover, the preparation of derivatives ac-
cording to the dediazonation scheme under
the conditions of the Sandmeyer, Meerwein,
Gomberg – Bachmann – Hay or azo coupling
reactions is presented in most of the published
works. In turn, the approach associated with
the arylation of S-nucleophiles is less studied
and is limited to the synthesis of only some
of their representatives. The works devoted to
the arylation of aryl alkynes, arylamines, and
carbonyl-containing compounds by diazo-
nium salts with the formation of hydrazone
derivatives deserve special attention. The use
of 9,10-anthracenyldiazonium salts is no less
synthetically significant in the reactions of an-
nelation of triazole, pyrazole, pyridazine and
triazinone nucleus.
-
-
-
ORGANIC CHEMISTRY SYNTHETIC POTENTIAL OF 9,10-ANTHRAQUINONYLDIAZONIUM SALTS
68 ISSN 2708-129X. Укр. хім. журн., 2020
СИНТЕТИЧНИЙ ПОТЕНЦІАЛ
9,10-АНТРАХІНОНІЛДІАЗОНІЄВИХ СОЛЕЙ
М. В. Стасевич1*, В. І. Зварич1,
В. П. Новіков1, М. В. Вовк2
1 Національний університет «Львівська
політехніка», вул. С. Бандери, 12, Львів
79013, Україна
2 Інститут органічної хімії НАН Укра
їни, вул. Мурманська, 5, Київ 02660, Україна
*е-mail: maryna.v.stasevych@gmail.com
Вперше узагальнено та систематизо-
вано літературні джерела, які стосуються
хімічних перетворень діазонієвих солей
1(2)-аміно-9,10-антрацендіонів. Розкрито
потенціал солей 9,10-діоксоантраценілдіа-
зонію як ключових субстратів у процесах
одержання різноманітних лінійно-функ
ціоналізованих, ациклічних та гетероци-
клічних похідних. Проаналізовано основ-
ні синтетичні перетворення діазонієвих
солей аміно-9,10-антрацендіонів, які ре-
алізуються без збереження азофункції і
призводять до утворення продуктів реак-
цій Зандмеєра, Меєрвейна та Гомберга –
Бахмана – Хея. Висвітлено використання
солей 9,10-діоксоантраценілдіазонію або
продуктів їхніх трансформацій для одер-
жання гетерилвмісних конденсованих та
функціоналізованих похідних.
Ключові слова: діазонієві солі 1(2)-амі-
но-9,10-антрацендіонів, дедіазоніювання,
азосполучення, анелювання, гетерилфунк-
ціоналізація
СИНТЕТИЧЕСКИЙ ПОТЕНЦИАЛ
9,10-АНТРАХИНОНИЛДИАЗОНИЕВЫХ СОЛЕЙ
М. В. Стасевич1*, В. І. Зварич1,
В. П. Новиков1, М. В. Вовк2
1 Национальный университет «Львивська
политэхника», ул. С. Бандеры, 12, Львов
79013, Украина
2 Институт органической химии НАН Ук
раины, ул. Мурманская, 5, Киев 02660, Украина
*е-mail: maryna.v.stasevych@gmail.com
Впервые обобщены и систематизирова-
ны литературные источники, касающиеся
химических превращений диазониевих со-
лей 1(2)-амино-9,10-антрацендионов. Рас
крыт потенциал солей 9,10-диоксоантра
ценилдиазония как ключевых субстратов
в процессах получения различных линей-
но-функционализированных, ацикличе-
ских и гетероциклических производных.
Проанализированы основные синтетиче-
ские преобразования диазониевих солей
амино-9,10-антрацендионов, которые ре-
ализуются без сохранения азофункции и
приводят к образованию продуктов реак-
ций Зандмейера, Меервейна и Гомберга –
Бахмана – Хэя. Освещено использование
солей 9,10-диоксоантраценилдиазония или
продуктов их трансформации для получе-
ния гетерилсодержащих конденсирован-
ных и функционализированных произво-
дных.
Ключевые слова: диазониевые соли 1(2)-
амино-9,10-антрацендионов, дедиазониро-
вание, азосочетание, аннелирование, гете-
рилфункционализация
UCJ № 9 / Vol. 86М. V. Stasevych, V. І. Zvarych, V. P. Novikov, М. V. Vovk
69https://ucj.org.ua
REFERENCES
1. Gorelik М.V. Chemistry of Anthraquinones
and Their Derivatives. (Moscow: Che
mistry, 1983. [in Russian].
2. Sweidan K., Zalloum H., Sabbah D. A.,
Idris G., Abudosh K., Mubarak M.S. Syn
thesis, characterization, and anticancer
evaluation of some new N1-(anthraquinon-
2-yl)amidrazone derivatives. Canadian
Journal of Chemistry. 2018. 96: 1123.
3. Denisov V.Ya., Tkachenko T.B. Investigation
of the reactions of anthraquinonyl diazo-
nium salts. Izvestiya Vysshikh Uchebnykh
Zavedenii, Seriya “Khimiya I Khimicheskaya
Tekhnologiya”. 2005. 48: 99.
4. Baqi Y., Müller C.E. Efficient and mild
deamination procedure for 1-aminoan-
thraquinones yielding a diverse library of
novel derivatives with potential biological
activity. Tetrahedron Letters. 2012. 53: 6739.
5. Rochlin E., Rappoport Z. Stable simple
enols. resolution of chiral 1-[9‘-(2‘-fluoro-
anthryl)]-2,2-dimesitylethenol. A different
racemization mechanism for the enol and
its acetate. Journal of Organic Chemistry.
2003. 68: 216.
6. Proctor C.J., Kralj B., Larka E.A., Porter C.J.,
Maquestiau A., Beynon J.H. Studies of con-
secutive reactions of quinones in a reversed
geometry mass spectrometer. Organic Mass
Spectrometry. 1981. 16: 312.
7. Shao M., Chen G., Zhao Y. Synthesis and
electronic properties of a conjugated ttfaq
trimer and donor-acceptor ensembles of
TTFAQ and anthraquinone. Synlett. 2008.
3: 371.
8. Baik W., Luan W.Q., Lee H.J., Yoon C.H.,
Koo S., Kim B.H. Efficient one-pot transfor-
mation of aminoarenes to haloarenes using
halodimethylisulfonium halides generat-
ed in situ. Canadian Journal of Chemistry.
2005. 83: 213.
9. Willem F., van der Schalk U. Über anthra-
chinon-carbonsäure. Chemische Berichte.
1911. 44: 128.
10. Iden H., Fontaine F.-G., Morin J.-F. Syn
thesis and complexation study of new
ExTTF-based hosts for fullerenes. Organic
& Biomolecular Chemistry. 2014. 12: 4117.
11. Dyall L.K. Pyrolysis of aryl azides. IV.
Neighbouring group effects by ortho
carbonyl groups. Australian Journal of
Chemistry. 1977. 30: 2669.
12. Mullock E.B., Suschitzky H. Syntheses
of heterocyclic compounds, part XXI.
Oxazoles from pyrolysis of aryl and het-
erocyclic azides in a mixture of acetic
and polyphosphoric acid. Journal of the
Chemical Society C: Organic. 1968. 0: 1937.
13. Verfahren zur darstellung von mercapta-
nen der anthrachinonreibe. German Patent
DE241985, December 6, 1908.
14. Gattermann L. Die mercaptane des anthra-
chinons. Justus Liebigs Annalen der Chemie.
1912. 393: 113.
15. Shah M.K., Shah M.K., Shah K.H. Thio
cyanation of 1-aminoanthraquinones.
Indian Journal of Chemistry. 1976. 14B (8):
625.
16. Reid E.E., Mackall C.M., Miller G.E.
Derivatives of anthraquinone. Aliphatic
thio-ethers, dithio-ethers, and thio-ether
sulfonic acids. Journal of the American
Chemical Society. 1921. 43: 2104.
17. Ikemoto N., Liu J.C., Brands K.M.J.,
McNamara J.M., Reider P.J. Practical routes
to the triarylsulfonyl chloride interme-
diate of a β3 adrenergic receptor agonist.
Tetrahedron. 2003. 59: 1317.
ORGANIC CHEMISTRY SYNTHETIC POTENTIAL OF 9,10-ANTHRAQUINONYLDIAZONIUM SALTS
70 ISSN 2708-129X. Укр. хім. журн., 2020
18. Lukin A.M., Petrova G.S. On the synthesis
of anthraquinone-1-arsonic 1-phosphonic
acids by the diazomethod. Zhurnal obsh-
chey khimii. 1957, 27, 2171.
19. Sabadakh O.P., Rev’yuk A.R., Taras T.M.,
Bolіbrukh L.D. Synthesis of Antrachi
nonphosphonic Acids. Visnyk Natsio
nal'noho universytetu «L'vivs'ka politekhni-
ka», seriya Khimiya, tekhnolohiya rechovyn
ta yikh zastosuvannya. 2008. 609: 145.
20. Zvarych V., Stasevych M., Lunin V., Deniz
N.G., Sayil C., Ozyurek M., Guclu K., Vovk
M., Novikov V. Synthesis and investigation
of antioxidant activity of the dithiocarba-
mates derivatives of 9,10-anthracenedione.
Monatshefte für Chemie. 2016. 147: 2093.
21. Antonio C.B., de Oca M., Correia, C.R.D.
Synthesis of aryl pyrrolizidines from end-
ocyclic enecarbamates. Novel applications
of the Heck arylation of 3-pyrrolines us-
ing diazonium salts. ARKIVOC. 2003, x:
390.
22. Haeupler B., Burges R., Janoschka T.,
Jaehnert T., Wild A., Schubert U.S.
PolyTCAQ in organic batteries: enhanced
capacity at constant cell potential using
two-electron-redox-reactions. Journal of
Materials Chemistry A. 2014. 2: 8999.
23. Coleman R.S., Mortensen M.A. Stereo
controlled synthesis of anthracene β-C-ri-
bosides: fluorescent probes for photophys-
ical studies of DNA. Tetrahedron Letters.
2003. 44: 1215.
24. Phanstiel O. IV. Fluorescent cytotoxic com-
pounds specific for the cellular polyamine
transport system. U.S. Patent 8,410,311,
April 2, 2013.
25. Lee K.-H., Kim M.-K., Yang G.-S. Con
densed-cyclic compound and organic light
emitting diode having organic layer includ-
ing the same. U.S. Patent 20110031484,
February 10, 2011.
26. Nomura H., Kawakami S., Ohsawa N.,
Suzuki T. Anthracene derivatives and
light-emitting devices using the anthra-
cene derivatives. U.S. Patent 2009004506,
January 1, 2009.
27. Crisostomo F.P., Martin T., Carrillo R. As
corbic acid as an initiator for the direct
C–H arylation of (hetero)arenes with ani-
lines nitrosated in situ. Angewandte Chemie
International Edition. 2014. 53: 2181.
28. Crisostomo F.P., Martin T., Carrillo R.
Ascorbic acid as an initiator for the di-
rect C–H arylation of (hetero)arenes with
anilines nitrosated in situ. Angewandte
Chemie. 2014. 126: 2213.
29. Stepanov A.A., Gornostaev L.M., Vasi
levsky S.F., Arnold E.V., Mamatyuk V.I.,
Fadeev D.S., Gold B., Alabugin I.V. Cha
meleonic reactivity of vicinal diazonium
salt of acetylenyl-9,10-anthraquinones:
synthetic application toward two heterocy-
clic targets. Journal of Organic Chemistry.
2011. 76: 8737.
30. Sutter P., Weis C.D. Ring opening reactions
of 6H-anthra[1,9-cd]isoxazol-6‐ones and
related compounds. Journal of Heterocyclic
Chemistry. 1982. 19: 997.
31. Stasevych M., Zvarych V., Lunin V.,
Vovk M., Novikov V. The new 1,2,3-triazo
lylantracene-9,10-diones: synthesis and
computer bioactivity screening. Chemistry
& Chemical Technology. 2017. 11: 1.
32. Tkachenko TB, Stepanova E.Yu. Inves
tigation of the interaction of 1-anthraqui-
nonyldiazonium salts with phenylacetylene
and styrene. Vestnik Kemerovskogo gosu-
darstvennogo universiteta. 2008. 2: 227.
33. Tkachenko T.B. The reactions of aminoan-
UCJ № 9 / Vol. 86М. V. Stasevych, V. І. Zvarych, V. P. Novikov, М. V. Vovk
71https://ucj.org.ua
thraquinones of anthraquinonyl diazoni-
um salts, accompanied by a complication of
the carbon skeleton. Abstract of the disser-
tation for the degree of candidate of chem-
ical sciences: specialty 02.00.03 “Organic
chemistry”. Kemerovo State University,
Tomsk, 2005.
34. Stasevych M.V., Zvarych V.I., Lunin V.V.,
Kopak N.A., Novikov V.P., Chernobaev I.I.,
Vovk M.V. Arylation of pyridine with
9,10-dioxoanthracenyl-1(2)-diazonium
hydrosulfates. Russian Journal of General
Chemistry. 2018. 88: 836.
35. Weis C.D. Meerwein arylation reactions
of olefins with anthraquinone diazonium
hydrogen sulfates: formation of new car-
bon bonds at the carbon atoms C-1 and at
C-1,5 of the anthraquinone system. Dyes
and Pigments. 1988. 9(1): 1.
36. Ribaldone G., Borsotti G. Process for pre-
paring antraquinone-1-acetic acid and es-
ters thereof. U.S. Patent 3,891,650, June 24,
1975.
37. Obushak N.D., Lyakhovich M.B., Fedo
rovich I.S., Ganushchak N.I. 1-Anthra
quinonediazonium tetrachlorocuprate(II)
and its dediazotization. Russian Journal of
Organic Chemistry. 1997. 33: 345.
38. Gornostaev L. M., Arnold E.V., Lykova E.
V., Sadoschenko M.V. Synthesis and func-
tionalization of 7-hydroxyanthra[2,1-b]
benzo[d]furan-8,13-diones. Chemistry of
Heterocyclic Compounds. 2010. 6: 665.
39. Klimenko L.S., Mainagashev I.Ya., Fo
kin E.P. Photochemical and thermal trans-
formations of diazo derivatives of 1-ary-
loxy- and 1-arylthio-2-aminoanthraqui-
nones. Bulletin of the Russian Academy of
Sciences, Division of chemical science. 1992.
41: 459.
40. Bien H.-S., Stawitz J., Wunderlich K. An
thraquinone Dyes and Intermediates.
In Ullmann’s Encyclopedia of Industrial
Chemistry, 6th ed., Ed. Kellersohn T.
(Weinheim, Germany: Wiley-VCH Verlag
Gmbh, 2003).
41. de Pieri Troiani E., Faria R.C. Cathodically
pretreated poly(1-aminoanthraquinone)-
modified electrode for determination of
ascorbic acid, dopamine, and uric acid.
Journal of Applied Electrochemistry. 2013.
43: 919.
42. Mahfouz N.M.A., Emara K.M. Colorimetric
determination of isoniazid and its pharma-
ceutical formulations. Talanta. 1993. 40:
1023.
43. Stasevych M., Zvarych V., Lunin V., Ko
pak N., Komarovska-Porokhnyavets O.,
Deniz N.G., Sayil C., Ozyurek, M.,
Guclu, K., Vovk M., Novikov V. Synthesis,
investigation of antimicrobial and antioxi-
dant activity of anthraquinonylhydrazones.
Monatshefte für Chemie. 2018. 149: 1111.
44. Brass K., Albrecht F. Zur Kenntnis der
Diazide des Anthrachinons. Chemische
Berichte. 1928. 61: 983.
45. Hai-Ying L., Liang-Cai L. The synthe-
sis and structure characteristics of two
novel azo-quinone derivatives. Synthetic
Communications. 2001. 31: 155.
46. Saika T., Iyoda T., Honda K., Shimidzu T.
Multi-mode chemical transducers. Part 2.
Electrochromic and photochromic proper-
ties of azoquinone compounds. Journal of
the Chemical Society, Perkin Transactions 2.
1993. 6: 1181.
47. Sakilidi V.T., Bulgakova N.A., Gornostaev
L.M., Taigunova V.S. Structure of diazo
coupling products of anthraquinone-1-di-
azonium salts with 2,6-di-tert-butylphenol
ORGANIC CHEMISTRY SYNTHETIC POTENTIAL OF 9,10-ANTHRAQUINONYLDIAZONIUM SALTS
72 ISSN 2708-129X. Укр. хім. журн., 2020
and β-naphthol. Russian Journal of Organic
Chemistry. 2000. 36: 1485.
48. Bulgakova N. A. Synthesis, structure and
properties of some derivatives of 9,10-an-
thraquinone containing a nitrogen-nitro-
gen bond. Abstract of the dissertation for
the degree of candidate of chemical scienc-
es: specialty 02.00.03 “Organic Chemistry”,
Krasnoyarsk State Pedagogical University,
Krasnoyarsk, 2002.
49. Khan A.K., Raoof I.B., Essa H. J. Synthesis,
characterization of some new azo com-
pounds containing 1,3-oxazepine, anth-
raquinone moieties and studying their ac-
tivity against pathogenic bacteria. Journal of
Natural Sciences Research. 2015. 5(22): 69.
50. Sabadakh O.P., Moklyak M.G., Luchkevich
E.R., Taras T.M., Bolibrukh L.D., Gubitska
I.I. Selection of conditions for the synthe-
sis of triazines of the anthraquinone se-
ries. Visnyk Natsional'noho universytetu
«L'vivs'ka politekhnika», seriya Khimiya,
tekhnolohiya rechovyn ta yikh zastosuvann-
ya. 2014. 787: 249.
51. Sabadakh O.P., Taras T.N., Luchkevich
E.R., Novikov V.P. Synthesis of triazene de-
rivatives of 9,10-anthraquinone. Russian
Journal of Organic Chemistry. 2015. 51:
277.
52. Fedenok L.G., Barabanov I.I., Zolniko
va N.A., Bashurova V.S., Bogdanchikov
G.A. Mechanism and synthesis potentiali-
ties of the cyclization of vic-(alkynyl)aren-
ediazonium salts. Chemistry for Sustainable
Development. 2011. 19: 647.
53. Fedenok L.G., Barabanov I.I., Bashu
rova V.S., Bogdanchikov G.A. Mechanism
of the heterocyclization of vic-alkynylan-
thra- and vic-alkynylnaphthoquinone di-
azonium salts. Tetrahedron. 2004. 60: 2137.
54. Denisov V. Ya., Tkachenko TB Studies of
reactions of salts of anthraquinonyl di-
azonium. Izvestiya Vysshikh Uchebnykh
Zavedenii, Seriya “Khimiya I Khimicheskaya
Tekhnologiya”. 2005. 48: 99.
55. Zvarych V., Stasevych M., Novikov V., Ru
sanov E., Vovk M., Szweda P., Grecka K.,
Milewski S. Anthra[1,2-d][1,2,3]triazine-
4,7,12(3H)-triones as a new class of anti-
staphylococcal agents: synthesis and bi-
ological evaluation. Molecules. 2019. 24:
4581.
Стаття надійшла 22.07.20
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-234 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:05:11Z |
| publishDate | 2020 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/cf/e3073f3e2eba7ce439187af67a10e6cf.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-2342026-07-22T08:23:44Z SYNTHETIC POTENTIAL OF 9,10-ANTHRAQUINONYLDIAZONIUM SALTS СИНТЕТИЧЕСКИЙ ПОТЕНЦИАЛ 9,10-АНТРАХИНОНИЛДИАЗОНИЕВЫХ СОЛЕЙ СИНТЕТИЧНИЙ ПОТЕНЦІАЛ 9,10-АНТРАХІНОНІЛДІАЗОНІЄВИХ СОЛЕЙ Stasevich, Maryna Zvarych, Viktor Novikov, Volodymyr Vovk, Mykhailo diazonium salts of 1(2)-amino-9,10-anthracenedione, dediazonation, azo coupling, annulation, heterylfunctionalization. For the first time, the literature sources concerning the chemical transformations of diazonium salts of 1(2)-amino-9,10-anthracenediones are generalized and systematized. The potential of 9,10-dioxoanthracenyldiazonium salts as key substrates in the preparation of various linear-functionalized, acyclic and heterocyclic derivatives has been determined. The main synthetic transformations of diazonium salts of amino-9,10-anthracenediones, which are  realized without preserving the azo function lead to the formation of reaction products of Sandmeyer, Meerwein, and Gomberg–Bachmann–Hay, are analyzed. The use of 9,10-dioxoanthracenyldiazonium salts or products of their transformations for obtaining heteryl-containing condensed and functionalized derivatives is presented. V.I.Vernadsky Institute of General and Inorganic Chemistry 2020-10-20 Article Article Organic chemistry Органическая xимия Органічна xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/234 10.33609/2708-129X.86.9.2020.55-72 Ukrainian Chemistry Journal; Vol. 86 No. 9 (2020): Ukrainian Chemistry Journal; 55-72 Украинский химический журнал; ##issue.vol## 86 ##issue.no## 9 (2020): Украинский химический журнал; 55-72 Український хімічний журнал; Том 86 № 9 (2020): Український хімічний журнал; 55-72 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/234/128 Copyright (c) 2020 Maryna Stasevich, Viktor Zvarych, Volodymyr Novikov, Mykhailo Vovk https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Stasevich, Maryna Zvarych, Viktor Novikov, Volodymyr Vovk, Mykhailo СИНТЕТИЧНИЙ ПОТЕНЦІАЛ 9,10-АНТРАХІНОНІЛДІАЗОНІЄВИХ СОЛЕЙ |
| title | СИНТЕТИЧНИЙ ПОТЕНЦІАЛ 9,10-АНТРАХІНОНІЛДІАЗОНІЄВИХ СОЛЕЙ |
| title_alt | SYNTHETIC POTENTIAL OF 9,10-ANTHRAQUINONYLDIAZONIUM SALTS СИНТЕТИЧЕСКИЙ ПОТЕНЦИАЛ 9,10-АНТРАХИНОНИЛДИАЗОНИЕВЫХ СОЛЕЙ |
| title_full | СИНТЕТИЧНИЙ ПОТЕНЦІАЛ 9,10-АНТРАХІНОНІЛДІАЗОНІЄВИХ СОЛЕЙ |
| title_fullStr | СИНТЕТИЧНИЙ ПОТЕНЦІАЛ 9,10-АНТРАХІНОНІЛДІАЗОНІЄВИХ СОЛЕЙ |
| title_full_unstemmed | СИНТЕТИЧНИЙ ПОТЕНЦІАЛ 9,10-АНТРАХІНОНІЛДІАЗОНІЄВИХ СОЛЕЙ |
| title_short | СИНТЕТИЧНИЙ ПОТЕНЦІАЛ 9,10-АНТРАХІНОНІЛДІАЗОНІЄВИХ СОЛЕЙ |
| title_sort | синтетичний потенціал 9,10-антрахінонілдіазонієвих солей |
| topic_facet | diazonium salts of 1(2)-amino-9,10-anthracenedione dediazonation azo coupling annulation heterylfunctionalization. |
| url | https://ucj.org.ua/index.php/journal/article/view/234 |
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