(Benzo[h])quinolinyl-substituted monoazatriphenylenes: Synthesis and photophysical properties

Article abstract of DOI:10.1007/s10593-014-1540-1

We propose a method for the synthesis of quinolinyl- and benzo[h]quinolinylmonoazatriphenylenes through 1,2,4-triazine intermediates with subsequent transformations in aza-Diels-Alder reaction. The photophysical properties of these new compounds were examined, and the effects due to additional fused aromatic rings were explored.

Full text of DOI:10.1007/s10593-014-1540-1

Chemistry of Heterocyclic Compounds, Vol. 50, No. 6, September, 2014 (Russian Original Vol. 50, No. 6, June, 2014)
(BENZO[h])QUINOLINYL-SUBSTITUTED
MONOAZATRIPHENYLENES: SYNTHESIS
AND PHOTOPHYSICAL PROPERTIES
D. S. Kopchuk1,2, A. F. Khasanov1, I. S. Kovalev1, G. A. Kim1,2,
1,2
1,2
I. L. Nikonov1, G. V. Zyryanov1,2 , V. L. Rusinov , and O. N. Chupakhin
*
We propose a method for the synthesis of quinolinyl- and benzo[h]quinolinylmonoazatriphenylenes
through 1,2,4-triazine intermediates with subsequent transformations in aza-Diels–Alder reaction. The
photophysical properties of these new compounds were examined, and the effects due to additional
fused aromatic rings were explored.
Keywords: monoazatriphenylene, phenanthrenequinone, aza-Diels–Alder reaction, heterocyclization,
luminescence.
Azatriphenylene derivatives attract significant interest due to their promising photophysical properties, in
particular the prolonged lifetime of fluorescent excited state, bathochromic shift of the absorption and emission
maxima compared to triphenylene, and the chemical reactivity with respect to the formation of coordination
compounds. Azatriphenylenes are widely used for the preparation of photoluminescent N,N'-metallated [1] and
cyclometallated [2] complexes. From biochemical point of view, azatriphenylenes represent interest as neutral
intercalating ligands for the structural study of DNA [3, 4]. The presence of 2-azatriphenylene fragments in certain
natural compounds [5-7] motivate the search for such compounds with biological activity, as potential anti-
inflammatory, antitumor, etc. agents. In the field of materials science, azatriphenylenes offer promise for the
design of discotic liquid crystals [8] and supramolecular architectures [9], as well as chemosensors for visual
(photoluminescent) detection of aliphatic and aromatic nitro compounds, such as explosives [10].
A particular interest has been attracted by pyridyl-substituted azatriphenylenes, which are 2,2'-bipyridine
ligands having annelated polyarene rings, with a wide range of possibilities for further functionalization, but
only one method is currently known for the synthesis of these compounds [11]. The possibility of tuning the
photophysical properties (the bathochromic shift of absorption and luminescence maxima, and the quantum
yield of luminescence) was previously demonstrated in the series of 2,2'-bipyridines by introducing various
_______
*To whom correspondence should be addressed, e-mail: gvzyryanov@gmail.com.
1Ural Federal University named after the First President of Russia B. N. Yeltsin, 19 Mir St., Yekaterinburg
620002, Russia.
2I. Ya. Postovskii Institute of Organic Synthesis, 22 S. Kovalevskoi St./20 Akademicheskaya St., Yekaterinburg
620219, Russia; ꢀ-mail: chupakhin@ios.uran.ru.
_________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 936-942, June, 2014. Original
article submitted February 19, 2014; revision submitted March 31, 2014.
864
0009-3122/14/5006-0864©2014 Springer Science+Business Media New York

aromatic substituents in the pyridine ring, including the possibility of annelation with additional aromatic rings
[12-15], that increased the practical potential of such bipyridines. Besides, the expansion of the conjugated
system increases the intermolecular ꢁ–ꢁ interactions, which are necessary for a range of processes (for example,
intermolecular migration of exciton after photoexcitation), while the change of geometry of the key pyridine
ligand enables selective binding of certain metal cations (for example, preferential complex formation with Zn2+
and Ca2+ cations in the presence of Cd2+ or selective binding of Am3+ cations from solutions of lantanoid ions
[16]). In this article, we propose a method for the synthesis of 2,2'-bipyridine type ligands of
monoazatriphenylene series with extended conjugated systems involving pyridine rings, namely, containing
2-quinoline and 2-benzo[h]quinoline fragments.
In order to obtain pyridylmonoazatriphenylenes, we previously used a method based on the preparation of
their 1,2,4-triazine analogs and subsequent aza-Diels–Alder reaction with enamines. This is a well-known
method for the synthesis of various pyridine derivatives [17-19], but rarely applied to quinolinylpyridines [20],
and no such examples of benzo[h]quinolinylpyridine preparation are known. Previous approaches to the
synthesis of 3-(quinolin-2-yl)-1,2,4-triazines include the cyclization of isonitrosoacetophenone hydrazones with
quinoline-2-carbaldehyde [20], the interaction of quinoline-2-carboxylic acid hydrazide with 1,2-diones
followed by reaction with ammonia [21], as well as the interaction of 1,2-diones with quinoline-
2-carboxyamidrazone [22]. Besides, the preparation of 3-(quinolin-2-yl)-1,2,4-triazin-5-ones by cyclization of
quinoline-2-carboxyamidrazone and glyoxylic acid derivatives is also known [23]. No 3-(benzo[h]quinolin-2-yl)-
1,2,4-triazines have been described in the literature, and only few methods are known for the preparation of
2-(benzo[h]quinolin-2-yl)pyridines. For example, the Friedlander condensation [24], Krönke method [25], as well
as the condensation of ꢂ-naphthisatin with acetylpyridine derivatives, have been proposed for this purpose [26, 27].
We used the interaction of 9,10-phenanthrenequinone (1) and the corresponding amidrazones for the
preparation of the necessary 1,2,4-triazine precursors of the target structures. The starting materials for the
synthesis of the necessary amidrazones were quinoline N-oxide (2ꢀ) and benzo[h]quinoline N-oxide (2b) [28].
The cyanation reaction of the N-oxides 2a,b was performed by a modified literature procedure [29]
using trimethylsilyl cyanide and dimethylcarbamoyl chloride. We substituted the dichloromethane solvent
reported in the literature [29] with 1,2-dichloroethane. This change of solvent was found to result in a complete
conversion of the starting N-oxides 2a,b into the nitriles 3a,b, unlike in the previously proposed example.
Besides that, we investigated an alternative approach to the preparation of cyano derivatives 3a,b, by
using KCN and trimethylsilyl chloride in DMF, with triethylamine (in situ preparation of Me3SiCN). It should be
noted that these reagents are considerably more affordable than trimethylsilyl cyanide and dimethylcarbamoyl
chloride, while the yields of compounds 3a,b were comparable in both cases.
Quinoline-2-carboxyamidrazone 4ꢀ was obtained according to a published method [22]. The
corresponding benzo[h]quinoline amidrazone 4b has not been previously described. The method for its
synthesis is significantly different from that for 2-cyanopyridine or 2-cyanoquinoline, because the exceedingly
slow progress of this reaction requires treatment of 2-cyanobenzo[h]quinoline with excess hydrazine hydrate for
many days at room temperature. The reaction was performed in a 1:1 mixture of ethanol and THF due to the low
solubility of the starting material in ethanol.
The heterocyclization reactions were performed by refluxing a mixture of 9,10-phenanthrenequinone (1)
and the amidrazones 4a,b in ethanol. Precipitation of compounds 5a,b was observed upon cooling of the
reaction mixture, which provided for a convenient isolation of these products.
The aza-Diels–Alder reaction using 1-morpholinocyclꢃpentene as dienophile allowed to prepare the
2,2'-bipyridine type ligands 6a,b, annelated with a cyclꢃpentane ring. The reaction was performed according to an
efficient previously described method (heating of 1,2,4-triazine with enamine at 200°C without solvent [30]).
Treatment of the reaction mixture with acetonitrile led to the precipitation of compounds 6a,b, which obviated the
need for purification by column chromatography. The preparation of monoazatriphenylenes lacking an annelated
cyclꢃpentane ring was possible by using 2,5-norbornadiene as dienophile (involving in situ formation of aza-Diels–
Alder product and subsequent retro process with the elimination of a nitrogen molecule), and was accomplished by
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refluxing for many hours in 1,2-dichlorobenzene as a high-boiling solvent. When using the lower-boiling ꢀ-xylene,
the yield of compound 6ꢁ did not exceed 5% even after prolonged refluxing.
Method A:
(For 4ꢀ)
R
O
R
N+
R
Me3SiCN, Me2NCOCl
N2H4·H2O, EtOH
R
NC
N
ClCH2CH2Cl, 60°ꢄ, 15 h
20°ꢄ, 10 h
Method B:
(For 4b)
KCN, Me3SiCl, Et3N
N2H4·H2O
2a,b
3a,b
DMF, 50°C, 16 h
EtOH–THF
20°ꢄ, 1 week
O
O
H2N
HN
R
NH
N
N
R
N
N
R
1
R
N
EtOH, ꢀ, 12 h
4a,b
5a,b
(For 6a,b)
2–5 a R = H, b R+R = benzo-
(CH2)n
N
1-morpholinocyclopentene
200°ꢄ, 3 h
R
R
(For 6c)
2,5-norbornadiene
1,2-Cl2C6H4, ꢀ, 20 h
6 a R = H, n = 3,
N
b R+R = benzo-, n = 3,
c R+R = benzo-, n = 0
6a–c
Thus, the application of 1-morpholinocyclꢃpentene as a dienophile is preferred, in particular because
monoazatriphenylenes with annelated cycloalkane rings typically have a better solubility compared to
compounds lacking such a fragment, and therefore have more potential for practical applications.
1
The structures of the obtained compounds 5a,b, 6a-c were confirmed by ꢅ and 13ꢄ NMR data, mass
spectrometry, and elemental analysis.
Within the scope of this project we compared the photophysical characteristics of new mono-
azatriphenylenes to our previously described 10-(pyridin-2-yl)-12,13-dihydro-11ꢁ-dibenzo[f,h]cyclopenta-
[c]quinoline (6d) [11]. The luminescence spectra of compounds 6a-d are presented in Figure 1, and the
Fig. 1. The fluorescence spectra of monoazatriphenylenes 6a-d.
866

TABLE 1. Photophysical Characteristics of Compounds 6a-d
Com-
pound
Absorption maxima in
acetonitrile, nm
Luminescence maximum in
acetonitrile, nm
Quantum yield of
luminescence*
263, 330, 343, 361
253, 329, 348, 368
251, 332, 348, 368
263, 313, 339, 357
389
0.031
0.523
0.390
0.213
6a
6b
6c
6d
381, 397, 421 (sh)
377, 396, 418 (sh)
364, 381, 403 (sh)
_______
*The quantum yields were determined relative to quinine sulfate
(ꢂ = 0.546 in 0.1 N aquous ꢅ SO4 solution [28]) for compounds 6a,b,d
2
and 2-aminopyridine (ꢂ = 0.60 0.005 in 1 N aqueous ꢅ SO4 solution
2
[32]) for compound 6ꢁ.
results are listed in Table 1. The annelation of additional aromatic rings to the pyridine fragment led in all
cases to a bathochromic shift of absorption and emission maxima. At the same time, the quantum yield of
luminescence for compounds 6b,c was significantly increased, compared to the azatriphenylene 6d, especially in
the case of product 6b. The low quantum yield of compound 6ꢀ was apparently linked to a significant contribution
from the non-radiative nꢆꢁ* transition in the excited state, which resulted in a low intensity of photoluminescence
[31].
Thus, in the current work we propose convenient methods for the preparation of previously unknown,
potentially useful 2,2'-bipyridine type ligands – monoazatriphenylenes, containing quinoline and benzo[h]-
quinoline fragments at position 2. The extended conjugated system of these compounds may allow the tuning of
their properties.
EXPERIMENTAL
Absorption spectra were recorded on a Shimadzu UV-2401PC spectrometer in acetonitrile. Luminescence
spectra were recorded on a Varian Cary Eclipse fluorimeter in acetonitrile. 1H and 13ꢄ NMR spectra were acquired
on a Bruker Avance II spectrometer (400 and 100 MHz, respectively) in ꢄDCl3, the internal standard was TMS.
Mass spectra were recorded on a Bruker Daltonics MicrOTOF-Q II mass spectrometer with electrospray ionization.
Elemental analysis was performed with a PerkinElmer PE 2400 II CHN-analyzer. Melting points were determined
with a Boetius apparatus. Merck silica gel 60F254 plates were used for TLC, with visualization under UV light.
Quinoline N-oxide (2ꢀ) was purchased from Sigma-Aldrich. Benzo[h]quinoline N-oxide (2b) [28] and
quinoline-2-carboxamide hydrazone 4ꢀ [22] were obtained by literature methods.
Preparation of the Nitriles 3a,b (General Method). ꢇ. The N-oxide 2a,b (7.0 mmol) was dissolved in
1,2-dichloroethane (50 ml). Trimethylsilyl cyanide (0.96 ml, 7.7 mmol) and dimethylcarbamoyl chloride (0.65 ml,
7.0 mmol) were added, and the mixture was stirred for 15 h at 60°C. The reaction mixture was cooled, washed
with Na2CO3 solution, then with ꢅ ꢈ, and extracted with CH2Cl2 (3×50 ml). The extract was dried over
2
anhydrous Na2SO4, the solvents were removed under vacuum. The residue was treated with Et2O, the precipitate
was filtered off and dried. The obtained nitriles 3a,b were used in the next stage without additional purification.
B. The N-oxide 2a,b (7.0 mmol) was dissolved in anhydrous DMF (50 ml). Triethylamine (1.07 ml,
7.7 mmol) and KCN (1.37 g, 21.0 mmol) were added, followed by dropwise addition of Me3SiCl (3.55 ml,
28.0 mmol). The obtained mixture was stirred for 8 h at 50°C. Another portion of KCN (0.91 g, 14.0 mmol) was
added, followed by dropwise addition of Me3SiCl (2.37 ml, 18.7 mmol), the obtained mixture was stirred for
another 8 h at 50°C, cooled to room temperature, treated with water (100 ml), and stirred for 1 h. The precipitate
formed was filtered off, washed with water, and dried. The obtained nitriles 3a,b were used in the next stage
without additional purification.
867

Quinoline-2-carbonitrile (3a). Yield 0.98 g (91%, method ꢇ), 0.82 g (76%, method B), colorless
crystals, mp 91-93°C (mp 88-91°C [33]). The spectral data matched the data from the literature [33].
Benzo[h]quinoline-2-carbonitrile (3b). Yield 1.21 g (85%, method ꢇ), 1.01 g (71%, method B),
colorless crystals, mp 162-164°C. 1H NMR spectrum, ꢉ, ppm (J, Hz): 7.72 (1ꢅ, d, 3J = 8.4, H-6); 7.78-7.82 (2ꢅ,
3
3
m); 7.85 (1ꢅ, d, J = 8.4, ꢅ-5); 7.92-7.97 (2ꢅ, m); 8.29 (1ꢅ, d, J = 7.9, ꢅ-3); 9.28-9.32 (1ꢅ, m, ꢅ-4). Mass
spectrum, m/z (Irel, %): 205 [M+H]+ (100). Found, %: C 82.16; H 3.87; N 13.55. C14H8N2. Calculated, %:
C 82.34; H 3.95; N 13.72.
Benzo[h]quinoline-2-carboxamide Hydrazone (4b). The nitrile 3b (0.50 g, 2.45 mmol) was dissolved
in a 1:1 mixture of EtOH and THF (100 ml). Hydrazine hydrate (1.19 ml, 24.5 mmol) was added, and the
obtained mixture was maintained for 1 week at room temperature. The solvents were removed under vacuum,
the residue was treated with ether, and the precipitate was filtered off. The compound was used in the next stage
1
without additional purification. Yield 0.52 g (90%). H NMR spectrum, ꢉ, ppm (J, Hz): 5.54 (2ꢅ, br. s, NH2);
3
7.68-7.78 (3ꢅ, m); 7.83 (1ꢅ, d, J = 8.8); 7.91-7.95 (1ꢅ, m); 8.18 (1ꢅ, d, 3J = 8.4, ꢅ-5); 8.27 (1ꢅ, d, 3J = 8.4,
ꢅ-6); 9.29-9.31 (1ꢅ, m, ꢅ-4). Mass spectrum, m/z (Irel, %): 237 [ꢊ+ꢅ]+ (100). Found, %: C 70.92; H 4.89;
N 23.49. C14H12N4. Calculated, %: C 71.17; H 5.12; N 23.71.
Preparation of Triazatriphenylenes 5a,b (General Method). 9,10-Phenanthrenequinone (1) (0.25 g,
1.2 mmol) was dissolved in EtOH (50 ml). A solution of the amidrazone 4a,b (1.44 mmol) in EtOH (30 ml) was
added, the mixture was stirred at reflux for 12 h and cooled to room temperature. The precipitate was filtered off,
washed with EtOH, and dried.
3-(Quinolin-2-yl)phenanthro[9,10-e][1,2,4]triazine (5a). Yield 0.25 g (58%), light-yellow crystals,
1
mp >250°C. H NMR spectrum, ꢉ, ppm (J, Hz): 7.65-7.69 (1ꢅ, m); 7.81-7.99 (6H, m); 8.46-8.50 (2ꢅ, m);
8.64-8.68 (2ꢅ, m); 8.99 (1ꢅ, d, 3J = 8.8, ꢅ-4 quinoline); 9.58-9.62 (2ꢅ, m, ꢅ-1,9). 13C NMR spectrum, ꢉ, ppm:
121.1; 123.1; 125.4; 127.1; 127.2; 127.6; 127.9; 128.2; 128.7; 128.8; 129.1; 130.0; 130.6; 131.0; 131.1; 131.5;
132.5; 132.6; 134.0; 137.2; 148.6; 153.6; 160.7; 161.2. Mass spectrum, m/z (Irel, %): 359 [ꢊ+ꢅ]+ (100). Found,
%: C 80.22; H 3.83; N 15.29. C24H14N4. Calculated, %: C 80.43; H 3.94; N 15.63.
3-(Benzo[h]quinolin-2-yl)phenanthro[9,10-e][1,2,4]triazine (5b). Yield 0.32 g (66%), light-yellow
1
3
crystals, mp 255-257°C. H NMR spectrum, ꢉ, ppm (J, Hz): 7.74-7.98 (9H, m); 8.44 (1ꢅ, d, J = 8.4, ꢅ-6
benzoquinoline); 8.61-8.65 (2ꢅ, m); 9.10 (1ꢅ, d, 3J = 8.4, ꢅ-5 benzoquinoline); 9.58-9.62 (2ꢅ, m, ꢅ-1,8); 9.73
(1ꢅ, d, J = 8.0, ꢅ-4 benzoquinoline). 13C NMR spectrum, ꢉ, ppm: 122.1; 123.2; 123.3; 125.2; 125.4; 125.5;
3
127.2; 127.5; 127.6; 127.7; 128.0; 128.2; 128.4; 128.8; 128.9; 129.5; 131.2; 131.6; 132.1; 132.7; 134.0; 134.1;
137.0; 143.6; 145.6; 147.1; 152.0; 161.2. Mass spectrum, m/z (Irel, %): 409 [ꢊ+ꢅ]+ (100). Found, %: C 82.11;
H 3.81; N 13.49. C28H16N4. Calculated, %: C 82.34; H 3.95; N 13.72.
Preparation of Monoazatriphenylenes 6a,b (General Method). A mixture of triazatriphenylene 5a,b
(0.70 mmol) and 1-morpholinocyclꢃpentene (0.56 ml, 3.50 mmol) was stirred for 2 h at 200°C under argon
atmosphere. Another portion of 1-morpholinocyclꢃpentene (0.28 ml, 1.75 mmol) was then added, and stirred for
1 h under the same conditions. The reaction mixture was cooled to room temperature and acetonitrile (15 ml)
was added. The obtained mixture was refluxed for 10 min, the precipitate formed was filtered off, washed with
acetonitrile, and dried. A sample for analysis was prepared by recrystallization from acetonitrile.
10-(Quinolin-2-yl)-12,13-dihydro-11ꢀ-dibenzo[f,h]cyclꢂpenta[c]quinoline (6a). Yield 0.24 g (87%),
light-colored crystals, mp 190-192°C. 1H NMR spectrum, ꢉ, ppm (J, Hz): 2.28-2.32 (2ꢅ, m, 12-ꢄꢅ ); 3.78 (2ꢅ,
2
3
3
t, J = 7.2, 11-ꢄꢅ ); 3.85 (2ꢅ, t, J = 7.2, 13-ꢄꢅ ); 7.88-7.92 (1ꢅ, m); 8.19-8.23 (1ꢅ, m); 8.34-8.38 (1ꢅ, m);
2
2
8.60-8.64 (1ꢅ, m); 8.67-8.75 (2ꢅ, m); 8.89 (1ꢅ, d, 3J = 8.4, ꢅ-4 quinoline); 9.56-9.60 (1ꢅ, m, ꢅ-8). 13C NMR
spectrum, ꢉ, ppm: 26.0; 33.6; 37.4; 121.3; 122.4; 123.3; 123.4; 126.1; 126.6; 126.7; 127.2; 127.3; 127.6; 127.7;
127.8; 128.3; 129.2; 129.9; 130.1; 130.8; 131.1; 131.8; 136.0; 139.7; 144.9; 147.7; 150.1; 152.0; 158.6. Mass
spectrum, m/z (Irel, %): 397 [ꢊ+ꢅ]+ (100). Found, %: C 87.81; H 4.94; N 6.87. C29H20N2. Calculated, %:
C 87.85; H 5.08; N 7.07.
10-(Benzo[h]quinolin-2-yl)-12,13-dihydro-11ꢀ-dibenzo[f,h]cyclꢂpenta[c]quinoline (6b). Yield 0.27 g
(85%), light-colored crystals, mp 235-237°C. H NMR spectrum, ꢉ, ppm (J, Hz): 2.36-2.40 (2ꢅ, m, 12-ꢄꢅ );
1
2
868

3.81 (2ꢅ, t, 3J = 7.2, 11-ꢄꢅ ); 4.05 (2ꢅ, t, 3J = 7.2, 13-ꢄꢅ ); 7.65-7.88 (8H, m); 7.93-7.97 (1ꢅ, m); 8.38 (1ꢅ, d,
2
2
3J = 8.6, ꢅ-6 benzoquinoline); 8.61-8.65 (1ꢅ, m); 8.69-8.73 (2ꢅ, m); 9.12 (1ꢅ, d, J = 8.6, ꢅ-5 benzo-
quinoline); 9.44 (1ꢅ, d, 3J = 8.0, ꢅ-4 benzoquinoline); 9.60-9.62 (1ꢅ, m, ꢅ-8). 13C NMR spectrum, ꢉ, ppm: 26.3;
34.4; 37.4; 121.8; 122.4; 123.2; 123.3; 124.9; 125.4; 125.8; 126.2; 126.6; 127.0; 127.2; 127.4; 127.8; 127.9;
128.0; 128.3; 130.2; 130.9; 131.2; 131.9; 132.2; 133.9; 136.0; 139.4; 144.9; 145.7; 147.3; 150.1; 152.1; 157.1.
Mass spectrum, m/z (Irel, %): 447 [ꢊ+ꢅ]+ (100). Found, %: C 88.55; H 4.79; N 6.03. C33H22N2. Calculated, %:
C 88.76; H 4.97; N 6.27.
3
2-(Benzo[h]quinolin-2-yl)dibenzo[f,h]quinoline (6c). The triazatriphenylene 5a (0.13 g, 0.31 mmol)
was suspended in 1,2-dichlorobenzene (30 ml). 2,5-Norbornadiene (0.16 ml, 1.53 mmol) was added, and the
mixture was refluxed for 20 h with the addition of 2,5-norbornadiene in portions (0.16 ml, 1.53 mmol) every
5 h. The reaction mixture was cooled to room temperature, the precipitate formed was filtered off, washed with
EtOH, and dried. A sample for analysis was obtained by recrystallization from ꢀ-xylene. Yield 0.27 g (85%),
light-colored crystals, mp 273-275°C. 1H NMR spectrum, ꢉ, ppm (J, Hz): 7.71-7.90 (8H, m); 7.94-7.98 (1ꢅ, m);
8.40 (1ꢅ, d, 3J = 8.4, ꢅ-6 benzoquinoline); 8.65-8.74 (3ꢅ, m); 9.10 (1ꢅ, d, 3J = 8.8, ꢅ-3); 9.17 (1ꢅ, d, 3J = 8.4,
ꢅ-5 benzoquinoline); 9.23 (1ꢅ, d, 3J = 8.8, ꢅ-4); 9.60 (1ꢅ, d, 3J = 8.0, ꢅ-4 benzoquinoline); 9.62-9.66 (1ꢅ, m,
H-12). Mass spectrum, m/z (Irel, %): 407 [ꢊ+ꢅ]+ (100). Found, %: C 88.52; H 4.28; N 6.71. C30H18N2.
Calculated, %: C 88.65; H 4.46; N 6.89.
This work received financial support from the Ministry of Education and Science of the Russian
Federation (state contract 8430), the Grants Council of the President of the Russian Federation (grant MK-
1511.2013.3), as well as the program 211 of the Government of the Russian Federation (contract No.
02.ꢇ03.21.0006).
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