New fluorinated 1,2-diaminoarenes, quinoxalines, 2,1,3-arenothia(selena) diazoles and related compounds

Article abstract of DOI:10.1016/j.jfluchem.2014.06.019

5,6,7,8-Tetrafluoroquinoxaline (1) and its previously unknown derivatives (2-8) were synthesized from glyoxal and polyfluorinated 1,2-diaminoarenes (10-17) obtained by reduction of corresponding 2,1,3-arenothiadiazoles (including new ones 21 and 22). The

Full text of DOI:10.1016/j.jfluchem.2014.06.019

Journal of Fluorine Chemistry 165 (2014) 123–131
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
New fluorinated 1,2-diaminoarenes, quinoxalines,
2,1,3-arenothia(selena)diazoles and related compounds§
Arkady G. Makarov a,b, Natalia Yu. Selikhova b, Alexander Yu. Makarov a,b
,
Victor S. Malkov b, Irina Yu. Bagryanskaya a,c, Yuri V. Gatilov a,c, Alexey S. Knyazev b,
b,**
*
a,b,d,
Yuri G. Slizhov
, Andrey V. Zibarev
a Institute of Organic Chemistry, Russian Academy of Sciences, 630090 Novosibirsk, Russia
b Department of Chemistry, National Research University – Tomsk State University, 634050 Tomsk, Russia
c Department of Natural Sciences, National Research University – Novosibirsk State University, 630090 Novosibirsk, Russia
d Department of Physics, National Research University – Novosibirsk State University, 630090 Novosibirsk, Russia
A R T I C L E I N F O
A B S T R A C T
Article history:
5,6,7,8-Tetrafluoroquinoxaline (1) and its previously unknown derivatives (2–8) were synthesized from
glyoxal and polyfluorinated 1,2-diaminoarenes (10–17) obtained by reduction of corresponding 2,1,3-
arenothiadiazoles (including new ones 21 and 22). The thiadiazoles were prepared from polyfluorinated
Ar–NH2 via Ar–N55S55N–SiMe3 (34–37) and their fluoride-induced nucleophilic ortho-cyclization. New
approaches to Ar–N55S55N–SiMe3 based on interaction between polyfluorinated Ar–N55SCl2 (32) and
LiN(SiMe3)2, and between ArN(SiMe3)Li and Me3Si–N55S55O, were tried together with our previous
synthetic method based on reaction of Ar–N55S55O with Me3SnLiN(SiMe3)2. New polyfluorinated 2,1,3-
arenoselenadiazoles (26–28) were prepared from corresponding diamines and SeO2 and 26 also from the
diamine and SeCl4. Compounds synthesized were characterized by multinuclear NMR (particularly 1H,
19F, 77Se), compounds 1, 2, 4, 7, 8, 16 (salt with 2 HCl), 19, 26, 28 and 32 by single-crystal X-ray
diffraction, and quinoxalines 1–8, thiadiazole 22 and selenadiazoles 27 and 28 by UV-vis and
fluorescence techniques.
Received 23 May 2014
Received in revised form 20 June 2014
Accepted 21 June 2014
Available online 30 June 2014
Keywords:
1,2-Diaminoarenes
Organofluorine
Quinoxalines
Selenadiazoles
Synthesis
Thiadiazoles
ß 2014 Elsevier B.V. All rights reserved.
1. Introduction
materials and pharmaceuticals [2], and preparation of low-
fluorinated quinoxalines attracted considerable attention [3]. In
Aza-analogs of naphthalene, 10
p
-electron 6-6-bicyclic aromat-
this context it is rather astonishing that described polyfluorinated
quinoxalines cover only 2,3,5,6,7,8-hexafluoroquinoxaline, 5,6,7,8-
tetrafluoroquinoxaline (1, Chart 1) and a few 2,3-R2 derivatives of
the latter, and their properties are poor studied [4–6].
Polyfluorinated 2,1,3-benzochalcogenadiazoles (chalcogen: S,
Se, Te), 10p-electron 5-6-bicyclic hetero analogs of (octafluoro)
naphthalene, also received very limited attention [7,8] despite of
the fact that the chemistry and numerous applications of their
hydrocarbon congeners are extensively studied [9,10]. Only
recently, persistent radical anions of polyfluorinated 2,1,3-
benzochalcogenadiazoles were recognized as candidate building
blocks for magnetically-active molecule-based functional
materials [10a–c].
ic compound, play essentially important roles in many fields of
chemistry, chemical technology and related disciplines. In
particular, quinoxaline (benzopyrazine) and its derivatives repre-
sent one of the most significant groups of aza-aromatics for
fundamental organic chemistry and its applications to biomedicine
and materials science [1]. It is well known that in many cases
hydrogen substitution by fluorine improves properties of both
§
This work was performed under Agreement no. 79/12 between Institute of
Organic Chemistry, Russian Academy of Sciences, Novosibirsk, and National
Research University – Tomsk State University, Tomsk, and within Joint Laboratory
of the University and the Academy.
It should be noted that quinoxalines and 2,1,3-benzothia(se-
lena)diazoles (structurally connected by mutual substitution of the
C55C bond and S or Se atom) are closely related compounds since
*
Corresponding author at: Institute of Organic Chemistry, Russian Academy of
Sciences, 630090 Novosibirsk, Russia. Fax: +7 383 330 9752.
**
Corresponding author.at: National Research University, Tomsk State University,
634050 Tomsk, Russia. Fax: +7 3822 423 944.
E-mail addresses: decan@xf.tsu.ru (Y.G. Slizhov),
zibarev@nioch.nsc.ru (A.V. Zibarev).
they have very similar
p-electronic structure manifesting in
similarity of their UV–vis [11] and HeI PES [12] spectra and spin
http://dx.doi.org/10.1016/j.jfluchem.2014.06.019
0022-1139/ß 2014 Elsevier B.V. All rights reserved.

124
A.G. Makarov et al. / Journal of Fluorine Chemistry 165 (2014) 123–131
density distribution in triplet state [13]. 2,1,3-Benzotelluradiazoles
also fit the analogy [14].
was synthesized and isomeric thiadiazoles 25a,b were observed in
the reaction mixtures as minor components. Neither quinoxaline 9
nor diamine 18 and compound 38 (Chart 1) were prepared.
In this work we report on atom-efficient one-step synthesis of
compound 1 and its congeners 2–8 (Chart 1) from glyoxal and
corresponding 1,2-diaminoarenes (10–17, Chart 1). The latter,
including previously unknown 12–14 and 16, were obtained by
reduction of 4,5,6,7-tetrafluoro-2,1,3-benzothiadiazole [7a] and its
easily accessible derivatives (19–24, Chart 1). The thiadiazoles
were synthesized from polyfluorinated Ar–NH2 via Ar–N55S55N–
SiMe3 (34–37) and their fluoride-induced nucleophilic ortho-
cyclization. Two new approaches to polyfluorinated Ar–N55S55N–
SiMe3 compounds based on interaction between polyfluorinated
Ar–N55SCl2 (32, Chart 1) and LiN(SiMe3)2, and between ArN(Si-
Me3)Li and Me3Si–N55S55O, were tried additionally to our previous
synthetic method based on reaction of Ar–N55S55O with Me3Sn-
LiN(SiMe3)2. Besides quinoxalines, 1,2-diaminoarenes 13, 14 and
17 were converted into polyfluorinated 2,1,3-arenoselenadiazoles
(26–28, Chart 1) in the reaction with selenium dioxide and 13 also
with selenium tetrachloride. Compounds synthesized were
characterized by multinuclear NMR (particularly 1H, 19F, 77Se),
and compounds 1, 2, 4, 7, 8, 16 (salt with 2 HCl), 19, 26, 28 and 31
by single-crystal X-ray diffraction (XRD; Table S1, Supporting
Information). Additionally, fluorescence of quinoxalines 1–8 and
chalcogenadiazoles 22, 27 and 28 was measured to clarify
applicability of optically-detected EPR (OD-EPR) technique to
detecting their radical anions in the future work [15].
2. Results and discussion
In the hydrocarbon series, a classical approach to the synthesis
of quinoxalines is condensation of aromatic 1,2-diamines with 1,2-
diones (the Koerner-Hinsberg reaction) [16]. To the best of our
knowledge, in the fluorocarbon series this approach was used only
twice, namely, for preparing 2,3-R2 derivatives of 1 [5] some of
which are of interest as molecular tweezers.
The present work expands the discussed approach onto the
synthesis of polyfluorinated quinoxalines via reaction between
polyfluorinated 1,2-diaminoarenes and glyoxal. Previously, it was
shown that polyfluorinated 1,2-diaminoarenes are easily accessi-
ble by reduction of corresponding 2,1,3-arenothiadiazoles [7]. The
general synthetic route to those is based on transformation of
fluorinated Ar–NH2 into Ar–N55S55N–SiMe3 and intramolecular
cyclization of the latter by means of nucleophilic substitution of
ortho-F atom under the action of CsF in MeCN [7,17].
In this work, three related approaches (Scheme 1) were used to
convert polyfluorinated Ar–NH2 into compounds Ar–N55S55N–SiMe3
(33–38) based on transformation of the amines into: 1) Ar–N55S55O
(29–31) by the Michaelis reaction followed by their interaction with
Me3SiN(SiMe3)2 (compounds 35 and 36) or LiN(SiMe3)2 (cf. [7a,18]);
2) Ar–N55SCl2 (32; via N55S55O derivative 29) followed by their
reaction with LiN(SiMe3)2 (compound 35); and 3) Ar–N(SiMe3)Li
followed by their reaction with Me3Si–N55S55O (compound 34).
In the case of polyfluorinated 5-aminoindane, attempts to carry
out the aforementioned functionalizations were unsuccessful for
the reasons which are not entirely clear. Only N-sulfinylamine 31
Chart 1. Compounds 1–38 (for chemical names see Table S2, Supporting Information).

A.G. Makarov et al. / Journal of Fluorine Chemistry 165 (2014) 123–131
125
Me3SnN(SiMe3)2
Ar-N=S=N-SiMe3
35, 36
SOCl2
Ar-N=S=O
29-31
LiN(SiMe3)2
PCl5
Ar-N=SCl2
Ar-N=S=N-SiMe3
- Ar-N=PCl3
32
35
Ar-NH2
33
BuLi;
Me3SiCl
Me3Si-N=S=O
Ar-N(SiMe3)2Li
Ar-N=S=N-SiMe3
34
Scheme 1. Synthesis of compounds 29–36.
Previously approaches based on R–N55SCl2 (R55t-Bu, Ar, ArSO2) [19]
and Me3Si–N55S55O [20] derivatives were known only with a few
examples in the hydrocarbon series.
N=S=N-SiMe3
N
N
CsF / MeCN
R
R
F
F
S
It should be noted that all approaches tried have some
limitations. Particularly, compound 38 was not prepared from
compound 31 and LiN(SiMe3)2 in hexane/THF or Me3SnN(SiMe3)2
in MeCN. Instead, a mixture of corresponding ArNH–SiMe3 and
isomeric thiadiazoles 25a,b was observed (1H and 19F NMR,
GC–MS) in the first case, and a complex mixture (1H and 19F NMR)
of unidentified compounds in the second one. Synthesis of
compound 32 was accompanied by formation of compound 33
(Scheme 1) isolated even in higher yield than the target 32. The
structure of the latter was defined by XRD (Fig. 1; Table S1,
Supporting Information) for the first time for Ar–N55SCl2 deriva-
tives in both fluorocarbon and hydrocarbon series.
35, 36
21, 22
Scheme 2. Synthesis of compounds 21 and 22.
Diamines 13, 14 and 17 were also converted into corresponding
polyfluorinated selenadiazoles 26–28 by reaction with selenium
dioxide which is widely used for this purpose in the hydrocarbon
series. Additionally, selenadiazole 26 was synthesized from
diamine 13 and selenium tetrachloride using approach suggested
in [7a] (Scheme 5). Structure of 26 was confirmed by XRD (Fig. 5;
Table S1, Supporting Information).
Compounds Ar–N55S55N–SiMe3 were converted into corre-
sponding thiadiazoles including previously undescribed deriva-
tives 21 and 22 (Scheme 2) by the action of CsF in MeCN (cf. [7,17]).
Structure of 19 (prepared earlier in the similar way [7a]) was
confirmed by XRD (Fig. 2; Table S1, Supporting Information).
The polyfluorinared 2,1,3-arenothiadiazoles (both known 19,
20, 24 [7] and newly prepared 21 and 22) were reduced into new
1,2-diaminoarenes (Scheme 3). Compound 16 was obtained by
reduction of 4,5,6-trifluoro-2-nitro-1,3-phenylenediamine (39,
Scheme 3) and its structure was confirmed by XRD in the form
of salt with 2 HCl (Fig. 3; Table S1, Supporting Information).
The diamines synthesized together with some known deriva-
tives [7] reacted with glyoxal taken as aqueous solution or solid
hydrate to give polyfluorinated quinoxalines 1–8 (Scheme 4).
Structures of compounds 1, 2, 4, 7 and 8 were confirmed by XRD
(Fig. 4; Fig. S1 and Table S1, Supporting Information).
3. Conclusions
Conceptually/technically related synthetic protocols for prepa-
ration of new (poly) fluorinated quinoxalines, as well as 2,1,3-
arenothia(selena)diazoles, 1,2-diaminoarenes and some other
derivatives, are elaborated, in all cases with corresponding anilines
as starting materials. The compounds synthesized, including –
N55S55X (X55O, NSiMe3, Cl2) derivatives [22], are of obvious interest
to organofluorine, aromatic and heterocyclic chemistry. For
example, polyfluorinated 1,2-diaminoarenes, besides synthetic
applications, are candidate analytical reagents for the GC-ECD
determination of selenium including environmental [23]. Particu-
larly, redox properties of polyfluorinated 2,1,3-arenothia(selena)-
diazoles and quinoxalines, especially their ability to form long-
lived radical anions (cf. [6,10]) and serve as electron acceptors for
charge-transfer complexes (cf. [24]), are worth of special study.
Fig. 2. XRD molecular structure of compound 19 (displacement ellipsoids at 30%).
´
˚
Selected bond lengths (A) and bond angles (8) (two crystallographically
Fig. 1. XRD molecular structure of compound 32 (displacement ellipsoids at 30%).
independent molecules): N1–S2 1.617(2)/1.614(2), S2–N3 1.620(2)/1.622(2),
N3–C3a 1.346(3)/1.339(3), C3a–C7a 1.432(4)/1.430(4), C7a–N1 1.340(3)/
1.338(3); C7a–N1–S2 106.4(2)/106.6(2), N1–S2–N3 100.9(1)/100.5 (1), S2–N3–
C3a 106.0(2)/106.3(2), N3–C3a–C7a 113.3(2)/113.4(2), C3a–C7a–N1 113.3(2)/
113.3(2).
´
˚
Selected bond lengths (A), dihedral and torsion angles (8): C1–N1 1.402(1), N1–S1
1.501(1), S1–Cl1 2.0953(5), S1–Cl2 2.1244(5); C2–C1–N1 121.57(10), C1–N1–S1
129.29(8), N1–S1–Cl1 109.99(4), N1–S1–Cl2 111.59(4), Cl1–S1–Cl2 93.83(2);
C2–C1–N1–S1 À92.72(13), C1–N1–S1–Cl1 À42.91(12), C1–N1–S1–Cl2 59.82(11).

126
A.G. Makarov et al. / Journal of Fluorine Chemistry 165 (2014) 123–131
NH2
NH2
N
N
High-resolution mass-spectra (EI, 70 eV) were taken with a
Thermo Electron Corporation DFS mass-spectrometer. Gas-chro-
matography–mass-spectrometry experiments were performed
with Hewlett-Packard G1800A instrument.
UV–vis and fluorescent (FL) spectra were collected with Varian
Cary 5000 and Varian Cary Eclipse instruments for heptane
solutions, respectively, unless otherwise indicated.
Glioxal (40% aqueous solution and solid hydrate) was received
from Novokhim Co. Ltd., Tomsk, Russia, and (Me3Si)2NH, SOCl2,
BuLi, Me3SiCl and LiN(SiMe3)2 from Aldrich. Starting compounds
Me3SnN(SiMe3)2 [18], Me3Si–N55S55O (0.56 M solution in
(Me3Si)2O [26]), and Ar–NH2 (Ar = 5-C9F9 [27a], 4-HC6F4 [27b,c],
4-F3CC6F4 [27d,e], 2,4-Cl2C6F3 [27f]) were prepared by known
methods.
[H]
F
R
S
R
F
19-22, 24
11-14, 17
F
F
F
NH2
NO2
F
F
NH2
NH2
SnCl2 / HCl
F
NH2
NH2
39
16
Scheme 3. Synthesis of compounds 11–14, 16 and 17.
Tables 1–3 contain physical, analytical and NMR data of the
compounds synthesized. Compounds 1 [4a], 10, 11, 13, 15, 19, 23
[7a], 20 [7c], 24 [7b], 29, 31 and 37 [18] were known before. They
present in the Tables in the cases they were prepared by new/
improved approaches, or/and additionally characterized in this work.
Importantly, the chalcogenadiazoles and quinoxalines synthesized
can be functionalized further at the C–F centers via nucleophilic
substitution, and the quinoxalines also at the C–H centers via
electrophilic substitution. N-Oxidation of these compounds is also
of interest [10a].
4.2. X-ray diffraction
The XRD structure of compound 32 provides the first example
for Ar–N55SCl2 derivatives in both fluorocarbon and hydrocarbon
series.
The XRD data (Table S1, Supporting Information) were collected
on a Bruker Kappa Apex II CCD diffractometer using
˚
a (l = 0.71073 A) radiation with a
w,v-scans of
Previously, it was shown that bicyclic aromatics and aza-
aromatics with only one polyfluorinated ring create new possibili-
ties for crystal engineering of organic solids [25]. In further work
crystal structures of compounds 1–8, 19, 26 and 28 will be studied
in detail and results will be published elsewhere.
narrow (0.58) frames with Mo K
graphite monochromator. Absorption corrections were applied
using the empirical multi-scan method with the SADABS program
[28]. The structures were solved by direct methods and refined by
full-matrix least-squares method against all F2 in anisotropic
approximation using the SHELX-97 programs set [29]. For 1, 2, 4, 8
and 19, the H atom positions were calculated with a riding model
and those for NH2 groups in 7 and 16 were located from difference
Fourier maps and refined in isotropic approximation. The obtained
structures were analyzed for exposing shortened contacts between
nonbonded atoms with the programs PLATON [30] and MERCURY
[31]. The bond lengths and bond angles of all compounds are
typical [32].
4. Experimental
4.1. General
1H NMR spectra were measured with Bruker AV-300 and Bruker
AV-400 spectrometers at the frequencies of 300.1 and 400.1 MHz,
respectively, and 19F NMR spectra with
a Bruker AV-300
Atomic coordinates, thermal parameters, bond lengths and
bond angles have been deposited at the Cambridge Crystallo-
graphic Data Center as CCDC – 994919 (1), – 994920 (2), – 994921
(4), –994922 (7), –994923 (8), –994924 (16Á2HCl), –994925 (19), –
994926 (26), –996836 (28), –994927 (32). These data can be
obtained free of charge via http://www.ccdc.cam.ac.uk/cgi-bin/
catreq.cgi, or from the Cambridge Crystallographic Data Center, 12
Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336 033; or
deposit@ccdc.cam.ac.uk
spectrometer at the frequency of 282.4 MHz; the standards were
TMS and C6F6
(
d19F = À162.9 ppm with respect to CFCl3),
respectively. The 31P NMR spectra were taken with Bruker AV-
300 machine at the frequency of 121.5 MHz, the standard was 85%
H3PO4. The 77Se NMR spectra were recorded with a Bruker AM-400
instrument at the frequency of 76.31 MHz, and a Bruker AV-600 at
the frequency of 114.5 MHz; the standard was Me2Se. The NMR
spectra were obtained for solutions in CDCl3 unless otherwise
indicated.
´
˚
Fig. 3. XRD molecular (left, displacement ellipsoids at 30%) and crystal (right) structure of 16Á2HCl. Selected bond lengths (A) and bond angles (8) (crystallographic numbering
used): C1–N1 1.357(2), C2–N2 1.451(2), C1–C2 1.408(2), C2–C3 1.389(2), N1–C1–C2 121.55(8), C1–C2–N2 120.3(1). Cations and anions are connected by N–H. . .Cl contacts
˚
˚
featuring shortened H. . .Cl distances (A): H1. . .Cl1 2.46(2), H2. . .Cl1 2.36(1), H3. . .Cl1 2.30(2). Note, that normal H. . .Cl contact is 2.86 A [21].

A.G. Makarov et al. / Journal of Fluorine Chemistry 165 (2014) 123–131
127
O
O
H
H
(Me3Si)2O were subsequently added, with 30-min periods
between them, to a stirred solution of 5.00 g (30 mmol) of 4-
HC6F4–NH2 in 120 ml of Et2O. The reaction mixture was
warmed-up to À25 8C and kept at this temperature for 2 h.
Then 3.30 (30 mmol) of Me3SiCl was added, the reaction
mixture warmed-up to 25 8C, filtered, the solvents were
evaporated, and the residue was distilled under reduced
pressure. Compound 34 [18] was obtained in the form of
orange liquid.
N
N
NH2
NH2
R
F
F
R
10-17
1-8
Scheme 4. Synthesis of compounds 1–8.
(b) Stirred mixture of 4.86 g (0.015 mol) of Me3SnN(SiMe3)2, 30 ml
of MeCN and 0.015 mol of 29 or 30 was refluxed for 15 min. The
solvent and volatile by-products were distilled off under
reduced pressure, and the residue was distilled in vacuo.
Compounds 35 and 36 were obtained in the form of orange-red
oils.
(c) At À60 8C and under argon, solution of 1.41 g (4.7 mmol) of 32
in 15 ml of Et2O was added dropwise to a stirred solution of
0.80 g (4.8 mmol) of LiN(SiMe3)2 in 30 ml of the same solvent
during 15 min. Reaction mixture was warmed-up to ambient
temperature during 2 h, filtered, the solvent was distilled off
under reduced pressure, and the residue distilled in vacuo.
Compound 35 was obtained in the yield of 0.83 g (56%).
(d) Compound 38 was not synthesized from compound 31 and
LiN(SiMe3)2 in hexane/THF; instead, a mixture of correspond-
ing ArNH–SiMe3 and isomeric thiadiazoles 25a,b was observed
(1H and 19F NMR, GC–MS). The 5: 1 mixture of 25a: 25b was
separated from the ArNH–SiMe3 by column chromatography
(silica/hexane).
4.3. Preparations
4.3.1. N-Sulfinylarylamines 29–31 and their precursors
(a) 4-HOC6F4–NO2 [33] was treated with SOCl2 in DMF to give 4-
ClC6F4–NO2 (40) [34], 52%, b. p. 91–92 8C/18 mm, m. p. 33–
34 8C. 19F NMR: 25.7, 16.6. MS, M+ m/z, found (calculated):
228.9552 (228.9554, 35Cl).
(b) A mixture of 5.30 g (23 mmol) of 40, 18.40 g (82 mmol) of
SnCl2Á2H2O and 20 ml of concentrated HCl was refluxed for 5 h,
neutralized with saturated solution of Na2CO3 to pH ꢀ 8, and
extracted with 5 Â 30 ml of methyl-tert-buthyl ether. Organic
layer was dried with MgSO4, solvent distilled off under reduced
pressure, and the residue sublimed at 45 8C/1 mm and
recrystallized from hexane. 4-ClC6F4–NH2 [35] was obtained
in the form of white crystals, 2.99 g (65%), m.p. 55–56 8C (54.3–
55.4 8C [35b]). 1H NMR: 3.94. 19F NMR: 17.9, 0.9. MS, M+ m/z,
found (calculated): 198.9825 (198.9812, 35Cl).
19F NMR: 25a: 53.6 (4F), 43.4 (2F), 30.4 (2F); 25b: 55.4 (2F),
54.9 (2F), 33.2 (2F), 29.7 (1F), 17.7 (1F).
(c) Corresponding Ar–NH2 [27a,f] (25 mmol) was refluxed with
excess of SOCl2 (3 ml) until evaluation of HCl ceased, the
solvent was distilled off, and the residue was distilled under
reduced pressure (29, 31) or crystallized from hexane at À20 8C
(30). Compound 29 [18b] was obtained in the form of yellow
liquid solidified upon cooling to room temperature, crystalli-
zation of the product from hexane gave yellow crystals;
compound 30 was obtained in the form of bright-yellow
crystals and compound 31 in the form of orange-yellow liquid.
Interaction of 31 with Me3SnN(SiMe3)2 under conditions
described above gave a complex mixture (1H and 19F NMR) of
unidentified compounds.
4.3.3. 2,1,3-Arenothiadiazoles 21 and 22
(a) A solution of 3.16 g (0.01 mol) of 29 in 30 ml of MeCN was
added dropwise during 2 h to refluxed and stirred suspension
of 1.52 g (0.01 mol) of freshly calcinated CsF in 200 ml of MeCN.
After additional 0.5 h, the reaction mixture was cooled to 20 8C
and filtered. The solvent was distilled off under reduced
pressure and the residue was chromatographed on alumina
column (hexane – Et2O 3:1) and sublimed in vacuo. Compound
21 was obtained in the form of colorless crystals.
4.3.2. 1-Aryl-3-trimethylsilyl-1,3-diaza-2-thiaallenes 34–36,
attempted synthesis of compound 38, and thiadiazoles 25a,b
(a) At À60 8C and under argon, 12 ml of 2.5 M solution of n-BuLi in
hexanes, 3.30 g (30 mmol) of Me3SiCl, the same portion of n-
BuLi, and 8.05 g of 56% solution of Me3SiNSO (30 mmol) in
Fig. 4. XRD molecular structures (displacement ellipsoids at 30%) of compounds 1 and 8 (for compounds 2, 4 and 7 see Fig. S1, Supporting Information). Selected bond lengths
´
˚
(A) and angles (8): 1: N1–C2 1.312(2), C2–C3 1.414(2), C3–N4 1.311(2), N4–C4a 1.365(2), C4a–C8a 1.416(2), C8a–N1 1.361(2); C8a–N1–C2 115.7(1), N1–C2–C3 122.8(1), C2–
C3–N4 123.0(1), C3–N4–C4a 115.6(1), N4–C4a–C8a 121.3(1); C4a–C8a–N1 121.6(1). 8: N1–C2 1.320(2), C2–C3 1.403(2), C3–N4 1.315(2), N4–C4a 1.354(2), C4a–C10b
1.412(2), C10b–N1 1.358(2); C10b–N1–C2 116.8(1), N1–C2–C3 122.7(2), C2–C3–N4 122.0(2), C3–N4–C4a 116.3(2), N4–C4a–C10b 122.3(1); C4a–C10b–N1 119.8(1).

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A.G. Makarov et al. / Journal of Fluorine Chemistry 165 (2014) 123–131
N
Free 16 was obtained by treatment of 16Á2HCl with aqueous
Na2CO3 followed by extraction with Et2O. The filtrate was
neutralized with 5.27 g of Na2CO3 and extracted with Et2O
(20 Â 15 ml). Combined ether extract was dried over MgSO4,
evaporated to dryness and the residue was sublimed at 90 8C/
1 mm. Compound 16 was obtained in the form of colorless
crystals.
SeO2
SeCl4
R
R
F
Se
Se
N
NH2
NH2
26-28
R
F
N
N
F
13, 14, 17
(d) (modified procedure [7b]) A mixture of 227 mg (0.0008 mol) of
24, 503 mg (0.008 mol) of Zn dust, 1.5 ml (0.018 mol) of
hydrochloric acid and 2.7 ml of ethanol was refluxed for 4 h.
After cooling to 20 8C, 15 ml of water was added, the precipitate
of was filtered off. The filtrate was evaporated to dryness and
the residue sublimed at 120 8C/1 mm. Combined product was
crystallized from ethanol. Compound 17 was obtained in the
form of white crystals.
26
Scheme 5. Synthesis of compounds 26–28.
(b) A solution of 1.36 g (4.1 mmol) of 36 in 30 ml of MeCN was
added dropwise during 2 h to refluxed and stirred suspension
of 0.71 g (4.7 mmol) of freshly calcinated CsF in 200 ml of
MeCN. After additional 0.5 h, the reaction mixture was cooled
to 20 8C and filtered. The solvent was distilled off under
reduced pressure and the residue was extracted with hexane
(5 Â 10 ml), the extract was evaporated and the residue
sublimed in vacuo (110 8C/1 mm). Compound 22 was obtained
4.3.5. Quinoxalines 1–8
in the form of light-yellow crystals. UV–vis,
216 (4.15, sh.), 232 (4.25), 304 (4.07), 311 (4.05), 317 (3.14),
344 (3.49, sh.). FL, lmax exc), nm: 406 (316).
lmax, nm, (log e):
(a) A mixture of 250 mg (1.4 mmol) of 10, 116 mg (1.7 mol) of
crystalline glyoxal (a), or 241 mg (1.7 mol) of 40% aqueous
glyoxal (b), and 6 ml of ethanol was refluxed for 4 h. The
solvent was distilled off at reduced pressure, and the residue
was sublimed at 50 8C/1 mm and crystallized from hexane.
Compound 1 [4a] was obtained in the form of colorless crystals
(
l
4.3.4. 1,2-Diaminoarenes 12–14, 16 and 17
suitable to XRD. UV–vis (EtOH),
lmax, nm, (log e): 236 (4.49),
311 (3.58). FL, lmax exc), nm: 410 (310).
(
l
(a) A mixture of 285 mg (ꢀ0.002 mol) of 20, 275 mg (ꢀ0.006 mol)
of NaBH4, 78 mg (0.0003 mol) of Co(OAc)2Á4H2O and 5 ml of
ethanol was refluxed for 9 h. After cooling to 20 8C, the reaction
mixture was diluted with water, and precipitate was filtered off
and washed with ether. The filtrate was extracted with ether
(4 Â 25 ml). The combined ether solution was dried over
MgSO4 and evaporated. Concentrated HCl (0.1 ml) was added
to the residue, and the mixture was extracted with toluene
(3 Â 7 ml). Aqueous solution was neutralized with 353 mg of
Na2CO3, evaporated to dryness and the residue sublimed at
75 8C/1 mm. Compound 12 was obtained in the form of
colorless crystals.
(b) A mixture of 3.5 mmol of 11 or 12 and 514 mg (3.5 mmol) of
40% aqueous glyoxal in 15 ml of ethanol was refluxed for 5 h,
the solvent was distilled off under reduced pressure, and the
residue sublimed at 80 8C/1 mm.
Compound 2 was obtained in the form of white crystals.
Single crystals suitable to XRD were obtained by crystallization
from ethanol. UV–vis,
FL, lmax exc), nm: 388 (310).
Compound 3 was obtained in the form of white crystals.
UV–vis, max, nm, (log ): 234 (4.46), 313 (3.60). FL, lmax exc),
nm: 409 (310).
lmax, nm, (log e): 239 (4.57), 310 (3.42).
(
l
l
e
(l
(c) A solution of 380 mg (2.6 mmol) of 40% aqueous glyoxal in
10 ml of ethanol was added during 2 h to refluxed solution of
2.6 mmol of 13, or 14, or 15 in 10 ml of the same solvent. The
reaction mixture was refluxed for 3 h, the solvent was distilled
off under reduced pressure, and the residue sublimed at 70 8C/
1 mm and crystallized from hexane.
(b) Compounds 13 and 14 were prepared by reduction of 21 and 22
by SnCl2/HCl under conditions [35] similar to described above
(item 4.3.1), and purified by sublimation in vacuo and
crystallized from hexane. Compounds 13 and 14 were obtained
in the form of colorless crystals.
(c) A mixture of 840 mg (ꢀ4 mmol) of 39 [36], 3.05 g (ꢀ14 mmol)
of SnCl2Á2H2O and of 4 ml (ꢀ50 mmol) of concentrated HCl was
refluxed for 0.5 h. After cooling to room temperature, crystals
of 16Á2HCl (0.133 g) were filtered off being suitable to XRD.
Compound 4 was obtained in form of yellowish crystals.
UV–vis,
nm: 382 (318).
l
max, nm, (log
e
): 242 (4.67), 318 (3.57). FL, lmax (lexc),
´
˚
Fig. 5. XRD molecular structure (displacement ellipsoids at 30%) of 26 (Cl atoms are 0.60: 0.40(1) disordered over two positions) and 28. Selected bond lengths (A) and bond
angles (8): 26: Se2–N1 1.791(6), Se2–N3 1.798(6), N1–C7a 1.327(9), N3–C3a 1.323(9), C3a–C7a 1.440(10); N1–Se2–N3 93.4(3), Se2–N1–C7a 107.2(4), Se2–N3–C3a 106.8(5),
N1–C7a–C3a 116.0(6), N3–C3a–C7a 116.5(6). 28: Se2–N1 1.788(6), Se2–N3 1.803(7), N1–C9b 1.322(9), N3–C3a 1.311(11), C3a–C9b 1.431(11); N1–Se2–N3 92.9(3), Se2–N1–
C9b 107.1(5), Se2–N3–C3a 107.1(5), N3–C3a–C9b 116.4(7), N1–C9b–C3a 116.4(7).

A.G. Makarov et al. / Journal of Fluorine Chemistry 165 (2014) 123–131
129
Table 1
Isolated yields, melting (boiling) points and MS data for compounds.
Compound
Yield %
M. p. 8C, b. p. 8C/mm
MS, m/z, found/calc.
1
59 (a), 64 (b)
95–97 8C
115–117
85–86
202.0145/202.0149
184.0239/184.0243
166.0335/166.0337
217.9857/217.9853
233.9552/233.9558
252.0114/252.0117
199.0355/199.0352
288.0115/288.0117
144.0493/144.0494
196.0018/196.0015, 35Cl
211.9718/211.9714
177.0504/177.0508
–
2
89
3
74
4
77
94–95
5
84
107–108
81–82
6
88
7
35
158–159
162–163
60–61
8
66
12
13
14
16
17
21
22
26
27
28
29
30
31
32
33
34
35
36
44
86
139–140
143–144
143–145
137–139
36–37
90
39
65
82
223.9419/223.9423, 35Cl
239.9126/239.9122
82
59–61
92 (a), 88 (b)
181–182 (sealed capillary)
178–179
197–198
52–53, 105–106/20
47–48
271.8903/271.8867, 35Cl, 80Se
64
95
96
80
90
23
44
83
38
62
283.8590/283.8593 76Se
339.9140/339.9133, 78Se
–
–
103–104/1
41–42
–
–
93–94
332.8451/332.8453, 35Cl
–
91–93/1
85–86/2
80–82/0.2
315.9877/315.9880, 35Cl
331.9582/331.9579
and the residue sublimed at 75 8C/1 mm. Compound 7 was
Compound 5 was obtained in form of yellowish crystals.
UV–vis, max, nm, (log ): 245 (4.63), 321 (3.71). FL, lmax exc),
nm: 393 (320).
Compound 6 was obtained in form of white crystals. UV–vis,
max, nm, (log ): 240 (4.60), 289 (3.30), 325 (3.32). FL, lmax
exc), nm: 399 (325).
obtained in the form of yellow crystals. UV–vis,
(log ): 262 (4.47), 324 (3.01), 384 (3.21). FL, lmax
491 (385).
l
max, nm,
l
e
(l
e
(lexc), nm:
Crystals suitable to XRD were obtained by crystallization
from 1: 1 mixture of hexane and CH2Cl2.
l
e
(
l
(e) A mixture of 60 mg (0.2 mmol) of 17, 40 mg (0.3 mmol) of 40%
aqueous glyoxal and 2 ml of ethanol was refluxed for 2 h. After
cooling to 20 8C, the crystalline precipitate was filtered off and
sublimed at 120 8C/1 mm. Compound 8 was obtained in the
(d) A mixture of 100 mg (ꢀ0.5 mmol) of 16 in 1.5 ml of water,
105 mg (ꢀ0.6 mmol) of Na2S2O5 in 0.5 ml of water and 79 mg
(ꢀ0.5 mmol) of 40% aqueous glyoxal was refluxed for 3 h. After
cooling, the solution was made basic with 20% NaOH and
extracted with chloroform (9 Â 7 ml). The combined chloro-
form solution was dried over MgSO4, evaporated to dryness
form of colorless crystals suitable to XRD. UV–vis (EtOH), lmax
nm, (log ): 226 (4.60), 269 (4.26), 350 (3.80), 366 (3.82). FL,
exc), nm: 409 (365).
,
e
lmax (l
Table 2
Analytical data for compounds.a,b
4.3.6. 2,1,3-Arenoselenadiazoles 26–28
Compound
Found/calculated %
C
H
N
F
2
3
52.05/52.19
57.87/57.84
44.05/43.96
41.04/40.88
42.43/42.88
47.97/48.25
50.40/50.02
50.09/50.00
36.68/36.66
34.10/33.83
40.41/40.69
32.14/32.09
30.07/29.90
26.50/26.54
25.02/25.03
34.88/35.21
27.88/27.50
23.80/23.98
21.23/21.52
1.61/1.64
14.97/15.21
16.87/16.86
12.88/12.82
11.68/11.92
11.09/11.11
20.81/21.10
9.71/9.72
30.85/30.96
22.80/22.87
26.22/26.08
16.19/16.17
45.32/45.21
28.38/28.62
39.46/39.56
26.28/26.36
29.74/29.00
17.61/17.84
31.88/32.18
25.83/25.38
15.40/15.76
20.94/20.99
13.18/13.20
33.32/33.42
21.90/21.75
25.46/25.29
22.86/22.69
(a) At 0 8C and under argon, a solution of 0.66 g (3 mmol) of SeCl4
in 5 ml of monoglyme was added to a stirred solution of 0.59 g
(3 mmol) of 13 and 0.95 g (12 mmol) of pyridine in 15 ml of the
same solvent. After additional 1 h at 20 8C, the reaction
mixture was filtered, the solvent distilled off under reduced
pressure, the residue crystallized from EtOH and sublimed in
vacuo. Compound 26 was obtained in the form of yellow
crystals.
(b) Mixture of 0.18 g (0.9 mmol) of 13, 0.11 g (1.0 mmol) SeO2 and
10 ml of EtOH was refluxed for 2 h, evaporated to dryness, and
the residue was sublimed at 90 8C/1 mm and crystallized from
hexane Compound 26 was obtained in the form of yellow
crystals. Crystals suitable for XRD were obtained by crystalli-
zation from EtOH.
2.47/2.43
4
1.03/0.92
5
1.10/0.86
6
0.86/0.80
7
2.07/2.02
8
0.61/0.70
12
13
14
16
21
22
26
27
28
30
32
33
4.30/4.20
19.36/19.44
13.77/14.25
13.05/13.15
23.53/23.72
12.05/12.47
11.26/11.62
10.31/10.32
9.58/9.73
2.07/2.05
1.90/1.89
3.47/3.41
–
–
–
–
–
–
–
–
8.21/8.21
5.41/5.35
4.59/4.66
(c) Mixture of 139 mg (0.7 mmol) of 14, 99 mg (0.9 mmol)
SeO2 and 20 ml of EtOH was refluxed for 1.5 h, evaporated
to dryness, and crystallized from hexane. Compound 27
was obtained in form of light-yellow crystals. UV–vis,
4.34/4.18
a
S: 29, 13.32/13.06; 32, 10.41/10.67. Cl: 13, 19.72/18.04; 22, 29.00/29.42; 26,
12.92/13.06; 27, 24.40/24.63; 30, 26.62/27.06; 32, 35.09/35.40; 33, 42.06/42.35. Se:
28, 23.40/23.15. P: 33, 9.51/9.25.
l
max, nm, (log e): 223 (3.97), 251 (3.64, sh.), 328 (4.14),
b
Vacuum distillation gave compound 36 with purity of ꢀ92–94% only according
334 (4.19), 340 (4.19), 371 (3.41, sh.). FL, lmax (lexc), nm:
to the data of elemental analysis for C, H, Cl, F and N. The sample was characterized
370 (334).
by MS and NMR (Tables 1 and 3) and used in the synthesis of compound 22.

130
A.G. Makarov et al. / Journal of Fluorine Chemistry 165 (2014) 123–131
Table 3
NMR chemical shifts,
d
, for compounds.
1H
8.99
Compound
19F
1a
2
10.0 (4F)
8.96, 8.91, 7.42
36.4, 30.9, 7.5
3
8.86, 8.84, 7.87, 7.62
28.5, 11.7
4
8.95, 8.94
34.5, 28.6, 9.7
5
9.02, 8.95
55.1, 39.1
6
9.08, 9.03
105.7, 38.3, 25.9, 10.2
7
8.86, 8.71, 4.6 (NH2)
8.0, 6.0,–3.7
8
9.07 (t), 9.02 (d)
26.1, 21.9 (Jperi =70.8 Hz), 17.9 (Jperi = 70.8 Hz), 11.4, 11.2, 9.2
12
13
14
16
21
22
26b
27b
28b
29
31
32
33c
34
35
36
6.30 (1H), 6.40 (1H), 3.56 (2H)
12.8, 3.5
3.45
21.3, 11.5, 0.1
3.6 (s, D1/2 240 Hz)
3.23
36.0, 26.3
À4.8 (2F), À11.0 (1F)
–
40.2, 26.9, 14.1
–
52.3, 43.4
–
39.5, 20.9, 13.3
–
51.6, 44.3
–
25.4, 19.4 (Jperi =71 Hz), 18.2 (Jperi = 71 Hz), 15.8, 11.7, 9.9
–
22.9 (2F), 21.9 (2F)
–
55.3 (2F), 55.1 (2F), 45.0 (1F), 39.0 (1F), 32.6 (2F), 22.8 (1F)
–
22.2, 17.5
–
Two groups of signals: at 22.3, 17.8 (minor); and at 19.0, 12.6 (major)
6.84, 0.18
0.20
22.1, 17.4
20.0 (2F), 18.8 (2F)
44.3, 25.0, 20.9
0.20
a
The 19F NMR spectra are solvent-dependent, and for EtOH solution d1H are 10.5 (2F) and 9.0 (2F) (this work) whereas for acetone solution 15.4 and 13.7 [4a].
d77Se: 26: 1592; 27: 1550; 28: 1554.
b
c
d31P: Two singlets: at 10.7 (minor), and at À29.9 (major).
(d) A solution of 111 mg of SeO2 (1.0 mmol) in 0.3 ml of water was
added to refluxing solution of 266 mg of 17 (1.0 mmol) in 6 ml
of EtOH. After 20 min, the reaction mixture was cooled to room
temperature, and the precipitate was filtered off, washed with
EtOH and dried. Compound 28 was obtained in the form of
pale-yellow crystalline powder.
References
[1] Relevant literature is too abundant to be cited completely. Selected references:
(a) M.P. Cabal, in: J. Alvarez-Builla, J.J. Vaquero, J. Barluengo (Eds.), Modern
Heterocyclic Chemistry, vol. 3, Wiley-VCH, Weinheim, 2011, pp. 1683–1776;
(b) N. Sato, in: A.R. Katritzky, C.W. Rees, E.F.V. Scriven (Eds.), Comprehen-
sive Heterocyclic Chemistry II, vol. 6, Pergamon Press, Oxford, 1996, pp.
233–278;
UV–vis (EtOH), lmax, nm, (log e): 224 (4.49), 253 (3.90), 281
(4.05), 331 (3.70), 364 (4.11), 381 (4.07). FL, lmax (lexc), nm:
406 (363).
(c) A.E.A. Porter, in: A.R. Katritzky, C.W. Rees (Eds.), Comprehensive Het-
erocyclic Chemistry, vol. 3, Pergamon Press, Oxford, 1984, pp. 157–198;
(d) A.S. Patidar, M. Jeykandan, A.K. Mobiya, G. Selvam, Int. J. PharmaTech
Res. 3 (2011) 386–392;
(e) R.M. Rajurkar, V.A. Agrawal, S.S. Thonte, R.G. Ingale, Pharmacophore 1
(2010) 65–76;
(f) G.K. Dutta, S. Patil, Org. Electron. 13 (2012) 1266–1276;
(g) J.Y. Lee, W.S. Shin, J.R. Haw, D.K. Moon, J. Mater. Chem. 19 (2009) 4938–4945.
[2] Relevant literature is too abundant to be cited completely. Selected recent books
and review articles:
4.3.7. Reaction of compound 29 with PCl5. Compounds 32 and 33
At ambient temperature, solution of 6.14 g (25 mmol) of 29 in
9 ml of CCl4 was added to a stirred suspension of finely powdered
5.25 g (25 mmol) of PCl5 in 3 ml of the same solvent. Reaction
mixture was heated to 60 8C and kept at this temperature until true
solution formed (ꢀ30 min). The solvent was distilled off under
reduced pressure, and the residue washed on a glass filter with 2 ml
of hexane. Compound 33 was obtained in the form of white crystals.
Filtrate was evaporated under reduced pressure and the residue
sublimed at 60 8C/1 mm and crystallized from hexane. Compound
32 was obtained in the form of yellow crystals suitable to XRD.
(a) V. Gouverneur, K. Mueller (Eds.), Molecular Medicine and Medicinal Chemis-
try. Vol. 6: Fluorine in Pharmaceuticals and Medicinal Chemistry: From Biophysi-
cal Aspects to Clinical Applications, World Scientific, London, 2012;
(b) M.L. Tang, Z. Bao, Chem. Mater. 23 (2011) 446–453;
(c) D. O’Hagan, J. Fluor. Chem. 131 (2010) 1071–1081;
(d) S. Purser, P.R. Moore, S. Swallow, V. Gouverneur, Chem. Soc. Rev. 37 (2008)
320–330;
(e) W.K. Hagmann, J. Med. Chem. 51 (2008) 4359–4369;
(f) F. Babudri, G.M. Farinola, F. Naso, R. Ragni, Chem. Commun. (2007)
1003–1022;
(g) K.L. Kirk, J. Fluor. Chem. 127 (2006) 1013–1029;
(h) J.-P. Begue, D. Bonnet-Delpon, J. Fluor. Chem. 127 (2006) 992–1012;
(i) C. Isanbor, D. O’Hagan, J. Fluor. Chem. 127 (2006) 303–319.
[3] With the Chemical Abstracts Plus and Reaxys databases, ꢀ1000 low-fluorinated
quinoxalines were retrieved being mostly 6-F and 6,7-F2 derivatives bearing
various other functions. Selected recent references:
Acknowledgments
The authors are grateful to Dr. Eugeny V. Malykhin for his
generous gift of some starring materials, and to the former
Collective Chemical Service Center of Siberian Branch of the
Russian Academy of Sciences for instrumental facilities. Financial
support from the Ministry of Education and Science of the Russian
Federation (project of Joint Laboratories of Siberian Branch of the
Russian Academy of Sciences and National Research Universities)
is gratefully acknowledged.
(a) E.V. Nosova, T.V. Trashakhova, V.S. Ustyugov, N.N. Mochulskaya, M.S. Valova,
G.N. Lipunova, V.N. Charushin, Russ. Chem. Bull. 60 (2011) 942–947;
(b) N.N. Mochulskaya, E.N. Nagibina, Yu.S. Volchenkova, L.P. Sidorova, V.N.
Charushin, Russ. J. Org. Chem. 41 (2005) 1694–1701;
(c) V.N. Charushin, G.A. Mokrushina, A.V. Tkachev, J. Fluor. Chem. 107 (2001)
71–80.
[4] (a) C.G. Allison, R.D. Chambers, J.A.H. MacBride, W.K.R. Musgrave, J. Fluor. Chem.
1 (1971/1972) 59–67;
(b) R.D. Chambers, C.W. Hall, J. Hutchinson, R.W. Millar, J. Chem. Soc. Perkin
Trans. 1 (1998) 1705–1713;
(c) A. Costa, M. Tato, R.S. Matthews, Magn. Reson. Chem. 24 (1986) 547–548.
[5] (a) M. Etzkorn, J.C. Timmerman, M.D. Brooker, X. Yu, M. Gerken, Beilstein J. Org.
Chem. 6 (2010), http://dx.doi.org/10.3762/bjoc.6.39;
Appendix A. Supplementary data
(b) A. Heaton, M. Hill, F. Drake, J. Fluor. Chem. 81 (1997) 133–138.
[6] D.M.V. van den Ham, G.F.S. Harrison, A. Spaans, D. van der Meer, Rec. Trav. Chim.
94 (1975) 168–173.
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.jfluchem.2014.06.019.

A.G. Makarov et al. / Journal of Fluorine Chemistry 165 (2014) 123–131
131
[7] (a) A.V. Zibarev, A.O. Miller, J. Fluor. Chem. 50 (1990) 359–363;
(b) I.Yu. Bagryanskaya, Yu.V. Gatilov, A.O. Miller, M.M. Shakirov, A.V. Zibarev,
Heteroatom Chem. 5 (1994) 561–565;
(c) A.Yu. Makarov, I.Yu. Bagryanskaya, Yu.V. Gatilov, T.V. Mikhalina, M.M. Sha-
kirov, L.N. Shchegoleva, A.V. Zibarev, Heteroatom Chem. 12 (2001) 563–576.
[20] (a) O.J. Scherer, G. Wolmershaeuser, R. Jotter, Z. Naturforsch.
432–436;
B 37 (1982)
(c) A.Yu. Makarov, I.Yu. Bagryanskaya, F. Blockhuys, C. Van Alsenoy, Yu.V. Gatilov,
V.V. Knyazev, A.M. Maksimov, T.V. Mikhalina, V.E. Platonov, M.M. Shakirov, A.V.
Zibarev, Eur. J. Inorg. Chem. 2003 (2003) 77–88.
(b) A.W. Cordes, M. Hojo, H. Koenig, M.C. Noble, R.T. Oakley, W.T. Pennington,
Inorg. Chem. 25 (1986) 1137–1145.
[8] (a) J. Fajer, B.H.J. Bielski, R.H. Felton, J. Phys. Chem. 72 (1968) 1281–1288;
(b) V.N. Kovtonyuk, A.Yu. Makarov, M.M. Shakirov, A.V. Zibarev, J. Chem. Soc.
Chem. Commun. (1996) 1991–1992;
[21] R.S. Rowland, R. Taylor, J. Phys. Chem. 100 (1996) 7384–7391.
[22] The heteroatom chemistry of –N5S5O and –N5S5N– functions is very rich.
Selected books and review articles:
(c) A.F. Cozzolino, P.S. Whitfield, I. Vargas-Baca, J. Am. Chem. Soc. 132 (2010)
17265–17270.
(a) R. Bussas, G. Kresze, H. Muensterer, A. Schwoebel, Sulfur Rep. 2 (1983) 215–
377;
[9] Selected recent review articles and book chapters:
(a) B.A.D. Neto, A.A.M. Lapis, E.N. da Silva Junior, J. Dupont, Eur. J. Org. Chem. 2013
(2013) 228–255;
(b) S. Bleisch, R. Mayer, Methoden der Organischen Chemie (Houben-Weyl),
Thieme, Stuttgart, 1985, E11/1;
(c) A.V. Zibarev, G.G. Yakobson, Usp. Khim. (Russ. Chem. Rev.) 54 (1985) 1706–
1737 (in Russian);
(d) T. Chivers, A Guide to Chalcogen-Nitrogen Chemistry, World Scientific,
Singapore, 2005;
(e) T. Chivers, R.S. Laitinen, in: F. Devillanova (Ed.), Handbook of Chalcogen
Chemistry. New Perspectives in Sulfur, Selenium and Tellurium, RSC Press, Cam-
bridge, 2007.
(b) A.F. Cozzolino, P.J.W. Elder, I. Vargas-Baca, Coord. Chem. Rev. 225 (2011)
1426–1438;
(c) S. Yamazaki, in: A.R. Katritzky, C.W. Rees, E.F.V. Scriven, R.J.H. Taylor (Eds.),
Comprehensive Heterocyclic Chemistry III, vol. 6, Wiley, New York, 2008, pp.
518–581;
(d) P.A. Koutentis, Sci. Synth. 13 (2004) 297–348;
(e) R.A. Aitken, Sci. Synth. 13 (2004) 777–822;
(f) S. Grivas, Curr. Org. Chem. 4 (2000) 707–726;
(g) Shinkai I., Reider P., in: A.R. Katritzky, C.W. Rees, E.F.V. Scriven (Eds.),
Comprehensive Heterocyclic Chemistry II, vol. 4, Pergamon Press, Oxford,
1996, pp. 355–377.
[23] V.L. Salenko, M.M. Troshkov, A.V. Zibarev, J. Chromatogr. 549 (1991) 429–433.
[24] N.A. Pushkarevsky, A.V. Lonchakov, N.A. Semenov, E. Lork, L.I. Buravov, L.S.
Konstantinova, T.G. Silber, N. Robertson, N.P. Gritsan, O.A. Rakitin, J.D. Woollins,
E.B. Yagubskii, A.V. Zibarev, Synth. Met. 162 (2012) 2267–2276.
[25] (a) I.Yu. Bagryanskaya, Yu.V. Gatilov, A.M. Maksimov, V.E. Platonov, A.V. Zibarev,
J. Fluor. Chem. 126 (2005) 1281–1287;
[10] (a) A.V. Lonchakov, O.A. Rakitin, N.P. Gritsan, A.V. Zibarev, Molecules 18 (2013)
9850–9900;
(b) F. Cozzi, S. Bacchi, G. Filippini, T. Pilati, A. Gavezzotti, Chem. Eur. J. 13 (2007)
7177–7184;
(b) A.V. Zibarev, R. Mews, in: J.D. Woollins, R.S. Laitinen (Eds.), Selenium and
Tellurium Chemistry: From Small Molecules to Biomolecules and Materials,
Springer, Berlin, 2011, pp. 123–149;
(c) N.V. Vasilieva, I.G. Irtegova, N.P. Gritsan, A.V. Lonchakov, A.Yu. Makarov, L.A.
Shundrin, A.V. Zibarev, J. Phys. Org. Chem. 23 (2010) 536–543;
(d) S.N. Konchenko, N.P. Gritsan, A.V. Lonchakov, U. Radius, A.V. Zibarev, Men-
deleev Commun. 19 (2009) 7–9;
(c) I.Yu. Bargyanskaya, M.A. Grishina, L.Yu. Safina, G.A. Selivanova, V.A. Potemkin,
Yu.V. Gatilov, Zh. Strukt. Khim. 49 (2008) 933–941 (in Russian).
[26] J.D. Davis, L.D. Spicer, Inorg. Chem. 19 (1980) 2191–2192.
[27] (a) G.G. Furin, N.G. Malyuta, V.E. Platonov, G.G. Yakobson, Zh. Org. Khim. 10
(1974) 830–838 (in Russian);
(b) T.A. Vaganova, S.Z. Kusov, V.I. Rodionov, I.K. Shundrina, E.V. Malykhin, Russ.
Chem. Bull. 56 (2007) 2239–2246;
(c) G.A. Selivanova, L.Yu. Gurskaya, L.M. Pokrovskii, V.F. Kollegov, V.D. Shtein-
garts, J. Fluor. Chem. 125 (2004) 1829–1834;
(d) G.A. Selivanova, T.V. Chuikova, A.A. Shtark, V.D. Shteingarts, Zh. Org. Khim. 24
(1988) 2513–2518 (in Russian);
(e) A.O. Miller, G.G. Furin, J. Fluor. Chem. 36 (1987) 247–272;
(f) G.A. Selivanova, L.M. Pokrovskii, V.D. Shteingarts, Russ. J. Org. Chem. 38 (2002)
1023–1029.
(e) R.T. Boere, T.L. Roemmele, Coord. Chem. Rev. 210 (2000) 369–445;
(f) C.L. Kwan, M. Carmack, J.K. Kochi, J. Phys. Chem. 80 (1976) 1786–1792.
[11] (a) V.G. Pesin, Khim. Geterotsikl. Soed. (1969) 235–242 (in Russian);
(b) E. Sawicki, B. Chastein, H. Bryant, A. Carr, J. Org. Chem. 22 (1957) 625–629.
[12] (a) R.A.W. Johnstone, F.A. Mellon, J. Chem. Soc. Faraday Trans. (1973) 1155–1163;
(b) M.H. Palmer, S.M.F. Kennedy, J. Mol. Struct. 43 (1978) 33–48;
(c) N.E. Petrachenko, V.I. Vovna, A.V. Zibarev, G.G. Furin, Khim. Geterotsikl. Soed.
(1991) 563–567 (in Russian).
[13] T.S. Lin, Chem. Phys. Lett. 43 (1976) 338–343.
[14] A.F. Cozzolino, N.E. Gruhn, D.L. Lichtenberer, I. Vargas-Baca, Inorg. Chem. 47
(2008) 6220–6226.
[28] SADABS, Version 2008-1, Bruker AXS, Madison, WI, 2008.
[29] G.M. Sheldrick, Acta Crystallogr. A 64 (2008) 122–127.
[30] (a) A.L. Spek, PLATON:
A Multipurpose Crystallographic Tool, Version 10M,
[15] According to preliminary data, under CVA conditions compound 1 reduces into
persistent radical anion detectable at ambient temperature by conventional EPR.
However, it was not the case for compound 8 whose radical anion was detected
only by OD-EPR (on this technique applied to radical anions of polyfluorinated
aromatics, see, for example, M.M. Barlukova, I.V. Beregovaya, V.P. Vysotsky,
L.N. Snchegoleva, V.A. Bagryansky, Yu.N. Molin, J. Phys. Chem. A 109 (2005)
4404–4409.)
Utrecht University, The Netherlands, 2003;
(b) A.L. Spek, J. Appl. Crystallogr. 36 (2003) 7–13.
[31] C.F. Macrae, P.R. Edgington, P. McCane, E. Pidcock, G.P. Shields, R. Taylor, M.
Towler, J. van de Stree, J. Appl. Crystallogr. 39 (2006) 453–457.
[32] F.H. Allen, O. Kenard, D.G. Watson, L. Bramer, A.G. Orpen, R. Taylor, J. Chem. Soc.
Perkin Trans. II (1987) S1–S19213.
[33] (a) A.O. Miller, G.G. Furin, Zh. Org. Khim. 25 (1989) 355–357 (in Russian);
(b) A.G. Budnik, N.V. Kalinichenko, V.D. Shteingarts, Zh. Org. Khim. 10 (1974)
1923–1927 (in Russian).
[16] Y.T. Pratt, in: R.C. Elderfield (Ed.), Heterocyclic Compounds, vol. 6, Wiley, New
York, 1957, pp. 377–409.
[17] E. Lork, R. Mews, M.M. Shakirov, P.G. Watson, A.V. Zibarev, Eur. J. Inorg. Chem.
2001 (2001) 2123–2134.
[34] A.A. Shtark, V.D. Shteingarts, Izv. Sib. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk.
(1976) 123–128 (in Russian).
[18] (a) A.V. Zibarev, A.O. Miller, Yu.V. Gatilov, G.G. Furin, Heteroatom Chem. 1 (1990)
443–453;
[35] (a) G.A. Selivanova, L.M. Pokrovskii, V.D. Shteingarts, Russ. J. Org. Chem. 37
(2001) 404–409;
(b) A.O. Miller, A.V. Zibarev, M.A. Fedotov, G.G. Furin, Zh. Obshch. Khim. 59 (1989)
586–590 (in Russian).
(b) H. Kobayashi, T. Sonoda, K. Takuma, N. Honda, T. Nakata, J. Fluor. Chem. 27
(1985) 1–22;
[19] (a) O.J. Scherer, G. Wolmershaeuser, Angew. Chem. Int. Ed. Engl. 14 (1975)
485–486;
(c) G.M. Brooke, R.D. Chambers, J. Heyes, W.K.R. Musgrave, Proc. Chem. Soc.
(1963) 213.
(b) R. Lux, G. Kresze, Liebig’s Ann. Chem. (1989) 605–606;
[36] G.M. Brooke, J. Burdon, J.C. Tatlow, J. Chem. Soc. (1961) 802–807.