European Journal of Organic Chemistry
10.1002/ejoc.201900961
ARTICLE
[
20]
employed. A method suggested in ref.
oxidation potential values.
was used for calculation of
Acknowledgements
This work was supported by Russian Science Foundation
(Project number 19-13-00094). We would like to acknowledge
Thermo Fisher Scientific Inc., MS Analytica (Moscow, Russia),
and personally to Prof. Alexander Makarov for providing mass
spectrometry equipment for this work.
Gas phase optimizations and spin density distributions in radical II were
[
37]
calculated in ORCA 4.1.1 quantum chemistry package
using PBE
-
8
functional and cc-pVDZ basis set. A threshold of 1·10 Hartree was used
-
6
-5
for SCF convergence; thresholds of 1·10 Hartree and 3·10 Hartree
-
1
Bohr on energy and RMS gradient, respectively, were employed in
optimization procedures.
Keywords: stable nitroxide • radicals, • oxidation potentials, •
density functional calculations, • cathodic materials
Phenothiazine and 3,7-di-tert-butyl-phenothiazine were synthesized as
[
38]
[25]
described in refs.
and , respectively.
[
1]
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Synthesis of 3,7-di-tert-butyl-10H-phenothiazine 5,5-dioxide (I): To a
solution of 5 g (25 mmol) of 3,7-di-tert-butyl-phenothiazine in 50 ml of
glacial acetic acid and 10 ml of CH
peroxide solution (75 mmol) was added. The mixture was kept at 80-
5°C for 5 h. After it returned to room temperature, it was diluted with 50
2
Cl
2
, 6.1 mL of 37% hydrogen
[2]
9105.
8
[
[
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mL of distilled water and the resulting mixture was stirred for 5 h. Then it
was filtered and the resulting brown precipitate was recrystallized from a
minimal amount of methanol (about 15 ml). The methanol filtrate was
evaporated under reduced pressure and the solid residue was
recrystallized from a minimal amount of toluene (about 15 ml). The
combined fractions were dried under reduced pressure yielding 2.6 g
[5]
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6]
(50%) of orange crystals.
+
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Lett. 2011, 2, 449–453.
ESI-(+)MS: m/z
=
344.1678 ([M+H] , 344.1684 calculated for
+
[
[
8]
9]
C
C
20
H
26NO
2
S),
S).
366.1499
([M+Na] ,
366.1504
calculated
for
20
H25NNaO
2
1
4
H NMR (400 MHz, CDCl
3
) δ, ppm: 8.00 (br. s, 1H, NH), 7.97 (d, J = 2.2
Hz, 2H-5), 7.34 (dd, J = 8.7, J = 2.2 Hz, 2H-3), 6.78 (d, J = 8.7 Hz, 2H-
H. Karoui, F. L. Moigne, O. Ouari, P. Tordo in Stable
Radicals:Fundamentals and Applied Aspects of Odd-Electron
Compounds (Eds.: R. Hicks), Wiley, Chichester, 2010.
G. I. Likhtenshtein, J. Yamauchi, S. Nakatsuji, A. I. Smirnov, R.
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Materials Science, WILEY-VCH Verlag GmbH & Co. KGaA,
Weinheim, 2008.
3
4
3
2), 1.29 (s, 18H, t-Bu).
13
[10]
C NMR (100 MHz, CDCl
3
) δ, ppm: 145.08 (C-4), 135.83 (C-1), 130.90
C-3), 120.24 (C-6), 118.69 (C-5), 116.34 (C-2), 34.78 (C-7), 31.31 (CH ).
(
3
For atoms numeration, see SI.
[
[
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12]
13]
O. A. Levitskiy, V. V Sentyurin, A. V Bogdanov, T. V Magdesieva,
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-
1
IR (KBr, cm ): 3307, 3188, 3089, 2962, 2868, 1678, 1616, 1576, 1522,
1
8
495, 1400, 1363, 1342, 1265, 1240, 1203, 1130, 1059, 955, 910, 885,
22, 783, 729, 685, 636, 577.
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A. Bogdanov, O. Levitskiy, A. Vorobiev, T. Magdesieva,
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Synthesis of 3,7-di-tert-butyl-10H-phenothiazine-N-oxyl 5,5-dioxide (II):
00 mg (0.58 mmol) of I was dissolved in 10 ml of benzene and the
mixture was heated to 80°C. Then 18 mg (0.03 mmol) of cobalt(II)
stearate was added. The color of the solution immediately changed to
dark blue. Afterwards, t-BuOOH (120 μL, 1.25 mmol) was dissolved in
2
[14]
[
[
[
[
[
[
[
15]
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20]
21]
R. Imachi, T. Ishida, M. Suzuki, M. Yasui, F. Iwasaki, T. Nogami,
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2
.9 ml of heated benzene and the resulted solution was added to the
reaction mixture successively in 3 portions each 20 min. The color of the
solution immediately changed to dark brown. The reaction mixture was
stirred at 80°C for 30 min, cooled to room temperature and the solvent
was evaporated under reduced pressure. The residue was dissolved in
M. Nakagawa, T. Ishida, M. Suzuki, D. Hashizume, M. Yasui, F.
Iwasaki, T. Nogami, Chem. Phys. Lett. 1999, 302, 125–131.
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2 2
minimal amount of eluent (CH Cl /hexane 7:6) and the resulted solution
1
215.
R. Suzuki, R. Tada, Y. Miura, N. Yoshioka, J. Mol. Struct. 2016,
106, 399–406.
was fractionated using column chromatography (Silica gel 40–63 μm,
Merk). The first colored fraction (red) was collected and evaporated
yielding 50 mg (24%) of the nitroxide II as a yellow- brownish solid.
1
T. V Magdesieva, O. A. Levitskiy, Russ. Chem. Rev. 2018, 87, 707–
725.
̶
ESI-(-)MS: m/z = 358.1481 (M , 358.1477 calculated for C20
3
H24NO S)
O. A. Levitskiy, T. V. Magdesieva, Mendeleev Commun. 2018, 28,
ESR (toluene solution): g = 2.0056; a
= 0.78 G (2H), a = 0.59 G (2H).
N H
= 7.95 G (2N), a = 2.16 G (2H),
187–189.
a
H
H
R. Suzuki, R. Tada, Y. Miura, N. Yoshioka, J. Mol. Struct. 2016,
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