The extension of conjugated system in pyridyl-substituted monoazatriphenylenes for the tuning of photophysical properties

Article abstract of DOI:10.1007/s10593-014-1541-0

We propose a method for the synthesis of diaryl-substituted pyridylmonoazatriphenylenes by the heterocyclization reaction of dihalosubstituted phenanthrenequinones with pyridine-2-carboxylic acid amidrazone, followed by aza-Diels-Alder reaction and Suzuki cross coupling. The obtained compounds showed more promising photophysical properties, compared to non-arylated analogs.

Full text of DOI:10.1007/s10593-014-1541-0

Chemistry of Heterocyclic Compounds, Vol. 50, No. 6, September, 2014 (Russian Original Vol. 50, No. 6, June, 2014)
THE EXTENSION OF CONJUGATED SYSTEM IN
PYRIDYL-SUBSTITUTED MONOAZATRIPHENYLENES
FOR THE TUNING OF PHOTOPHYSICAL PROPERTIES
D. S. Kopchuk1,2, A. F. Khasanov1, I. S. Kovalev1, G. V. Zyryanov1,2
,
*
G. A. Kim1,2, I. L. Nikonov1, V. L. Rusinov1,2, and O. N. Chupakhin1,2
We propose a method for the synthesis of diaryl-substituted pyridylmonoazatriphenylenes by the
heterocyclization reaction of dihalosubstituted phenanthrenequinones with pyridine-2-carboxylic acid
amidrazone, followed by aza-Diels–Alder reaction and Suzuki cross coupling. The obtained compounds
showed more promising photophysical properties, compared to non-arylated analogs.
Keywords: monoazatriphenylene, phenanthrenequinone, aza-Diels–Alder reaction, cross coupling,
heterocyclization, luminescence, Suzuki reaction.
Azatriphenylene (dibenzo[f,h]quinoline) structures, which are of interest due to their remarkable
photophysical and coordination properties [1], have been found in several natural compounds [2, 3].
Azatriphenylenes and their annelated derivatives are used in the inorganic biochemistry as intercalating ligands
– components of luminescent metal complexes – for the study of DNA structure and its defragmentation [4, 5].
Azatriphenylenes are also promising luminescent sensors for organic anions and nitroaromatic compounds [6].
Of particular interest are pyridyl-substituted azatriphenylenes, which are polycyclic 2,2'-bipyridine
ligands with broad possibilities for further functionalization. It has been previously shown that extending the
conjugated system of 2,2'-bipyridines [7, 8], 1,10-phenanthrolines [9, 10], and 2,2':6',2''-terpyridines [11, 12]
may be used for the tuning of photophysical characteristics of these compounds. For example, the absorption
and luminescence maxima may be shifted to the longer wavelengths, and the quantum yield of luminescence
may be increased, improving the potential for practical applications of these compounds. These properties of
pyridylmonoazatriphenylenes currently remain unexplored, as only very few chemical structures of this type
have been synthesized so far. In this article, we propose a method for the synthesis of 2,2'-bipyridine ligands
with extended conjugated system by introducing additional aromatic substituents in the monoazatriphenylene
system.
_______
*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; е-mail: chupakhin@ios.uran.ru.
_________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 943-952, June, 2014. Original
article submitted February 19, 2014; revision submitted March 31, 2014.
0009-3122/14/5006-0871©2014 Springer Science+Business Media New York
871

The most frequently used methods for the preparation of azatriphenylenes are the Skraup synthesis
[13-16], various heterocyclization reactions [17-19], and cross-coupling reactions [20]. Another method
involves the cycloaddition of difficult to obtain alkenes or arylacetylenes with aromatic substrates, which is
catalyzed by transition metal salts [21]. These methods often require the use of forcing conditions or scarce
reagents. In addition, we should note the preparation of monoazatriphenylenes through their 1,2,4-triazine
analogs (this method often allows to prepare various substituted pyridines, unavailable by other methods
[22-24]). Such a method is applicable to the monoazatriphenylene series in cases of intramolecular Diels–Alder
reactions of the corresponding triazatriphenylenes with acetylene moieties [25]. Besides that, we recently
described the synthesis of pyridylmonoazatriphenylenes by preparing their 1,2,4-triazine analogs with further
aza-Diels–Alder reaction with enamines [26], relying on the use of commercially available reagents. The scope
of our work includes the development of this direction.
One of the starting compounds for the preparation of target structures in this case was 9,10-phen-
anthrene quinone (1), with a range of methods currently known for its functionalization. Thus, its various
derivatives may be used in the heterocyclization reaction with amidrazones, leading to 1,2,4-triazine analogs of
functionalized azatriphenylenes.
For example, the bromination of phenanthrenequinone with N-bromosuccinimide (NBS) in sulfuric acid
may produce 2,7-dibromophenanthrenequinone 2а [27]. The iodination of phenanthrenequinone with
N-iodosuccinimide (NIS) in sulfuric acid allows to synthesize 2,7-diiodophenanthrenequinone 2c (this method
of iodination [28] was earlier proposed for fluorenone, but has not been used for the preparation of compound
2c). It should be noted that halogenation at positions 2 and 7 occurs with a high degree of selectivity, according
to the electrophilic substitution rules in aromatic systems. An alternative method for the preparation of
compound 2c [29] by using molecular iodine under oxidative conditions (experiments with potassium
permanganate and manganese dioxide were performed), contrary to literature data about the formation of
2,7-diiodophenanthrenequinone 2с under these conditions, unexpectedly gave the 2-iodophenanthrenequinone
2d, also of interest as a starting material for the synthesis of azatriphenylenes. The structure of compound 2d
was established by mass spectrometry data, and also by comparing its 1Н NMR spectrum with the literature data
[30].
In addition to 2,7-dihalo-substituted quinones, the isomeric 3,6-dibromoquinone 2b may be obtained in the
reaction of phenanthrenequinone 1 with bromine in nitrobenzene in the presence of benzoyl peroxide [31].
R1
R
(For 2a): NBS, H2SO4, 20°C, 3 h
(For 2b): Br2, PhNO2, (PhCOO)2,
O
O
O
O
110°C, 16 h
(For 2c): NIS, H2SO4, 0–20°C, 24 h
(For 2d): I2, KMnO4, Ac2O, AcOH,
H2SO4, 35°C, 1 h
2a R = H, R1 = R2 = Br
2b R = Br, R1 = R2 = H
2c R = H, R1 = R2 = I
2d R = H, R1 = I, R2 = H
R
R2
1
It is obvious that after heterocyclization and aza-Diels–Alder reaction the halogen atoms in the molecule
of monoazatriphenylene may be substituted in various ways, in order to tune the properties of target compounds.
It should also be noted that dibenzo[f,h]quinolines with halogen atoms at positions 6 and 11 may be used as
monomer units for the synthesis of various polymers. Monoiodo derivative in such a case presents interest as the
capping monomer for obtaining polymers of limited chain length.
Despite the availability of halogenated phenanthrenequinones, only in few cases these compounds have
been used for the preparation of the respective triazatriphenylenes [32-34], while no examples are known in the
literature for obtaining similar monoazatriphenylenes in aza-Diels–Alder reactions.
872

The synthesis of triazatriphenylenes (3-(2-pyridyl)phenanthro[9,10-e][1,2,4]triazines) 3a-c by the
reactions of phenanthrenequinone derivatives 2a-c with amidrazone 4 [35] is relatively smooth:
heterocyclization occurs upon refluxing in ethanol. The reaction products may be easily isolated from the
reaction mixture on account of their lower solubility in comparison to the starting materials, and the yields reach
64%. In the case of 2-iodophenanthrenequinone 2d, the formation of two isomers 5a and 5b is observed in this
reaction, in a ratio close to 1:1. The separation of these isomers is not considered necessary, taking into account
the possible use of similar compounds as capping agents for polymers.
R1
R1
H2N
HN
NH
R
N
N
N
N
N
N
4
N
2a–d
or
N
N
EtOH, , 10 h
R
3a–c
(from 2a–c)
5a,b
(from 2d)
R1
R
3 a R = H, R1 = Br; b R = Br, R1 = H; c R = H, R1 = I; 5 a R = I, R1 = H; b R = H, R1 = I
The further aza-Diels–Alder reaction using the previously described [36, 37] efficient procedure
(interaction of 1,2,4-triazine with 1-morpholinocyclopentene at 200°С under inert atmosphere without solvent)
was used for obtaining monoazatriphenylenes annelated with a cyclopentane ring – 10-(2-pyridyl)-12,13-
dihydro-11H-dibenzo[f,h]cyclopenta[c]quinolines 6a-c. Such compounds are potentially more useful, due to
better solubility compared to non-annelated analogs. In the case of dibromo-substituted triazatriphenylenes
3а,b, this procedure allowed to successfully obtain the target monoazatriphenylenes 6a,b in up to 82% yields.
Different results were obtained with the analogous iodo derivatives. A complex mixture of products was
obtained when reacting a mixture of compounds 5а and 5b, as well as compound 3c with enamine under the
conditions described above. This was probably linked to the partial exchange of iodine atoms for amine
fragments. Performing the reaction in high-boiling solvents (1,2-dichlorobenzene, о-xylene) also did not allow
to obtain the desired iodo-containing cyclopentenomonoazatriphenylene. For example, prolonged refluxing in
o-xylene resulted in the isolation of unchanged starting materials. In particular, in the case of iodo-containing
triazatriphenylenes, significant difficulties are encountered when attempting the synthesis of 2,2'-bipyridine
analogs annelated with cyclopentane ring. The preparation of the monoazatriphenylene diiodo derivative 6с was
eventually possible only by performing the aza-Diels–Alder reaction with 2,5-norbornadiene. This compound was
deemed to have less practical potential, as its solubility is lower. Thus, if triazatriphenylene iodo derivatives are used,
it is probably advantageous to substitute the labile iodine atoms for other functional groups prior to performing the
aza-Diels–Alder reaction.
R1
R
(For 6a,b)
(CH2)n
N
1-morpholinocyclopentene
200°С, 3 h
3a–c
(For 6c)
2,5-norbornadiene
1,2-Cl2C6H4, , 35 h
N
6 a R = H, R1 = Br, n = 3
b R = Br, R1 = H, n = 3
c R = H, R1 = I, n = 0
R
R1
6a–c
873

The 1Н NMR spectra of the obtained compounds featured signals of azatriphenylene АВХ systems (and
also AB system signals in the case of compound 6с), pyridine ring signals, but in the case of the
monoazatriphenylenes 6a,b also aliphatic proton signals due to the cyclopentene fragment.
The monoazatriphenylene dibromo derivatives 6а,b were used as starting compounds for obtaining the
target molecules 7а-d with an extended conjugated system. The synthesis was performed by Suzuki cross-
coupling reaction with the arylboronic acids 8a,b in a mixture of water, toluene, and ethanol. Potassium
carbonate was used as base, the cross-coupling products were obtained in high yields and were purified by
recrystallization from toluene.
R1
R
Ar–B(OH)2
7a R = H; R1 = Ph
8a,b
b R = H, R1 = 3,4,5-(MeO)3C6H2
c R = Ph; R1 = H
6a,b
PdCl2(PPh3)2, PPh3
K2CO3, toluene, H2O
EtOH, 85°C, 7 h
N
N
d R = 3,4,5-(MeO)3C6H2; R1 = H
R
8a Ar = Ph,
b Ar = 3,4,5-(MeO)3C6H2
R1
7a–d
The photophysical properties of the obtained pyridylmonoazatriphenylenes were studied in comparison
to our previously described unsubstituted 10-(2-pyridyl)-12,13-dihydro-11Н-dibenzo[f,h]cyclopenta[c]-
quinoline (7е) [26]. The luminescence spectra are presented in Figure 1, results are given in Table 1.
Fig. 1. Luminescence spectra of the pyridylmonoazatriphenylenes 7a-e in acetonitrile at room temperature.
The study of photophysical properties indicated a shift of absorption and emission maxima towards the
longer wavelengths due to the extension of the conjugated system. In the case of compounds 7а,с (with phenyl
substituents), the overall shape of luminescence spectrum remained practically unchanged, except that a
bathochromic shift of emission maxima was noted. For compounds 7b,d (with trimethoxyphenyl substituents),
874

TABLE 1. Photophysical Characteristics of Compounds 7a-e
Com-
pound
Absorption maxima
in acetonitrile, nm
Luminescence maximum
in acetonitrile, nm
Quantum yield
of luminescence*
289, 318
200, 294, 323
193, 281, 325, 368
207, 284, 328, 370
263, 313, 339, 357
379, 398
475
379, 396, 423 (sh)
481
364, 381, 403 (sh)
0.207
0.139
0.146
0.216
0.213
7a
7b
7c
7d
7e
_______
*The quantum yields of all compounds were measured relative to quinine
sulfate (Ф = 0.546 in 0.1 N aqueous Н2SO4 solution [38]).
substantial changes in the character of emission spectrum were observed, along with a larger bathochromic shift
of emission maximum, which likely could be explained by the more substantial changes in chromophore
structure. The quantum yields were somewhat lower in the case of compounds 7b,c, while for the two other new
monoazatriphenylenes the quantum yields remained practically unchanged.
Thus, we propose convenient methods for the preparation of previously unreported monoaza-
triphenylene diaryl derivatives of practical interest, based on the use of commercially available starting
materials. These compounds were obtained by halogenation of 9,10-phenanthrenequinone followed by a
heterocyclization reaction, aza-Diels–Alder reaction, and Suzuki cross coupling. Limitations for using iodine
derivatives as intermediates were identified, and the advantages of bromine derivatives were demonstrated. The
photophysical properties of the obtained compounds were examined in comparison to our previously reported
unsubstituted analog. The more promising photophysical properties of aryl derivatives were demonstrated,
manifested as bathochromic shifts of absorption and emission maxima, due to the extended conjugated system
in these monoazatriphenylenes.
EXPERIMENTAL
1H and 13С NMR spectra were acquired on a Bruker Avance II instrument (400 and 100 MHz,
respectively) in CDCl3 (compounds 6a,b, 7a-d) and in DMSO-d6 (the rest of the compounds), internal standard
was TMS. Absorption spectra were recorded on a Shimadzu UV-2401PC spectrophotometer in acetonitrile.
Luminescence spectra were recorded on a Varian Cary Eclipse fluorimeter in acetonitrile. Mass spectra were
recorded on a Bruker Daltonics MicrOTOF-Q II mass spectrometer under chemical ionization conditions at
atmospheric pressure (compounds 2c,d) or electrospray ionization (the rest of the compounds). Elemental
analysis was performed on a PerkinElmer РЕ 2400 series II CHN-analyzer. Melting points were determined
with a Boetius apparatus. The TLC analysis was performed on Merck silica gel 60F254 plates, eluent EtOAc,
visualization under UV light.
9,10-Phenanthrenequinone (1) was purchased from Sigma-Aldrich. 2,7-Dibromo-9,10-phenanthrene-
quinone (2a) [27], 3,6-dibromo-9,10-phenanthrenequinone (2b) [31], and pyridine-2-carboxamide hydrazone
(4) [35] were obtained according to published methods.
2,7-Diiodo-9,10-phenanthrenequinone (2c). N-iodosuccinimide (6.48 g, 28.82 mmol) was added to
cold (0°C) 98% H2SO4 (90 ml), and the mixture was stirred for 25 min at 0°C. Then 9,10-phenanthrenequinone
(1) (1.50 g, 7.20 mmol) was added, and the mixture was stirred for 24 h at room temperature. The mixture was
treated with ice-cold water (200 ml), the precipitate formed was filtered off, washed with water, and dried. The
reaction product was used in the next stage without additional purification. Yield 2.94 g (89%), dark-red
1
4
crystals, mp >250°C. H NMR spectrum, δ, ppm (J, Hz): 8.03-8.06 (4H, m, H-3,4,5,6); 8.26 (2H, d, J = 1.2,
875

H-1,8). Mass spectrum, m/z (Irel, %): 461 [M+H]+ (100). Found, %: C 36.83; H 1.03. C14H6I2О2. Calculated, %:
C 36.55; H 1.31.
2-Iodo-9,10-phenanthrenequinone (2d). A mixture of KMnO4 (1.45 g, 9.18 mmol), AcOH (18 ml),
Ас2О (10.5 ml), and I2 (2.33 g, 9.18 mmol) was cooled to 5°C, and 98% H2SO4 (12 ml) was added dropwise at a
temperature not exceeding 10°C. Then 9,10-phenanthrenequinone (1) (0.83 g, 3.99 mmol) was added and the
mixture was stirred for 1 h at 35°C. The reaction mixture was treated with ice-cold water (100 ml) containing
previously dissolved Na2SO3 and K2CO3. The precipitate formed was filtered off, washed with water, and dried.
1
Yield 0.73 g (55%), dark-red crystals, mp 222-224°C. H NMR spectrum, δ, ppm (J, Hz): 7.51-7.55 (1H, m);
3
4
7.74-7.78 (1H, m); 8.00-8.09 (3H, m); 8.22 (1H, d, J = 8.0, H-4); 8.28 (1H, d, J = 1.6, H 1). Mass spectrum,
m/z (Irel, %): 335 [M+H]+ (100). Found, %: C 50.08; H 2.02. C14H7IО2. Calculated, %: C 50.33; H 2.11.
Triazatriphenylenes 3а-с, 5a,b (General Method). Amidrazone of pyridine-2-carboxylic acid (4)
(0.68 g, 5 mmol) was added to a suspension of phenanthrenequinone 2a-d (5 mmol) in EtOH (500 ml). The
mixture was refluxed for 10 h. The reaction mixture was filtered while hot, the obtained precipitate was washed
with EtOH and dried. Analytical reference sample was recrystallized from EtOH.
6,11-Dibromo-3-(2-pyridyl)phenanthro[9,10-e][1,2,4]triazine (3a). Yield 1.40 g (60%), light-yellow
1
crystals, mp 279-281°C. H NMR spectrum, δ, ppm (J, Hz): 7.63-7.67 (1H, m, H-5 Py); 8.07-8.13 (3Н, m,
3
4
Н 7,10, H-4 Py); 8.77-8.83 (3Н, m, H-8,9, H-3 Py); 8.94 (1Н, dd, J = 4.9, J = 1.8, Н-6 Py); 9.45 (1Н, d,
4J = 1.8, Н-5); 9.51 (1Н, d, 4J = 1.8, Н-12). Mass spectrum, m/z (Irel, %): 467 [М+Н]+ (100). Found, %: C 51.22;
H 2.01; N 11.73. C20H10Br2N4. Calculated, %: C 51.53; H 2.16; N 12.02.
7,10-Dibromo-3-(2-pyridyl)phenanthro[9,10-e][1,2,4]triazine (3b). Yield 1.49 g (64%), light-yellow
crystals, mp >250°C. 1H NMR spectrum, δ, ppm (J, Hz): 7.66-7.70 (1H, m, H-5 Py); 8.08-8.15 (3Н, m, H-6,11,
H-4 Py); 8.79 (1Н, dd, 3J = 7.5, 4J = 1.2, Н-3 Py); 8.93 (1Н, dd, 3J = 4.9, 4J = 1.8, Н-6 Py); 9.23 (1Н, d, 4J = 1.4,
4
H-8); 9.24 (1Н, d, J = 1.4, H-9); 9.27 (1Н, d, 3J = 8.8, Н-5); 9.31 (1Н, d, 3J = 8.6, Н-12). Mass spectrum, m/z
(Irel, %): 467 [М+Н]+ (100). Found, %: C 51.19; H 1.98; N 11.81. C20H10Br2N4. Calculated, %: C 51.53; H 2.16;
N 12.02.
6,11-Diiodo-3-(2-pyridyl)phenanthro[9,10-e][1,2,4]triazine (3с). Yield 1.26 g (45%), light-yellow
1
3
crystals, mp >250°C. H NMR spectrum, δ, ppm (J, Hz): 7.66-7.80 (1H, m, H-5 Py); 8.14 (1Н, ddd, J = 7.5,
3J = 7.5, 4J = 1.8, Н-4 Py); 8.25 (1Н, dd, 3J = 8.8, 4J = 1.7, Н-7); 8.30 (1Н, dd, 3J = 8.8, 4J = 1.7, Н-10); 8.61-
8.67 (2Н, m, Н-8,9); 8.79 (1Н, dd, J = 7.5, J = 1.2, Н-3 Py); 8.95 (1Н, dd, J = 4.9, J = 1.8, Н-6 Py); 9.59
(1Н, d, 4J = 1.8, Н-5); 9.67 (1Н, d, 4J = 1.8, Н-12). Mass spectrum, m/z (Irel, %): 561 [М+Н]+ (100). Found, %:
C 42.79; H 1.65; N 9.71. C20H10I2N4. Calculated, %: C 42.89; H 1.80; N 10.00.
3
4
3
4
A Mixture of 6-Iodo-3-(2-pyridyl)phenanthro[9,10-e][1,2,4]triazine (5a) and 11-Iodo-3-(2-pyri-
1
dyl)phenanthro[9,10-e][1,2,4]triazine (5b). Yield 1.19 g (55%), light-yellow crystals. H NMR spectrum, δ,
ppm (J, Hz): 7.61-7.65 (1H, m, H-5 Py); 7.85-8.02 (2Н, m); 8.07-8.11 (1H, m, Н-4 Py); 8.21 (0.5Н, dd, 3J = 8.4,
4J = 1.6) and 8.26 (0.5Н, dd, 3J = 8.4, 4J = 1.6, H-7 (5a), H-10 (5b)); 8.59 (0.5 H, d, 3J = 8.4) and 8.62 (0.5H, d,
3J = 8.4, H-8 (5a), H-9 (5b)); 8.76-8.82 (2Н, m); 8.90 (0.5Н, dd, 3J = 4.9, 4J = 1.8) and 8.93 (0.5Н, dd, 3J = 4.9,
4
4
4J = 1.8, Н-6 Py); 9.39-9.46 (1Н, m, H-12 (5a), H-5 (5b)); 9.65 (0.5H, d, J = 1.6) and 9.73 (0.5H, d, J = 1.6,
H-5 (5a), H-12 (5b)). Mass spectrum, m/z (Irel, %): 435 [М+Н]+ (100). Found, %: C 55.04; H 2.29; N 12.56.
C20H11IN4. Calculated, %: C 55.32; H 2.55; N 12.90.
Preparation of Monoazatriphenylenes 6a,b (General Method). A mixture of triazatriphenylene 3a,b
(2.50 mmol) and 1-morpholinocyclopentene (2 ml, 12.50 mmol) was stirred under argon atmosphere for 2 h at
200°C, treated with 1-morpholinocyclopentene (1 ml, 6.25 mmol), and stirred for another 1 h under the same
conditions. The reaction mixture was cooled to room temperature, and MeCN (30 ml) was added. The obtained
mixture was refluxed for 15 min and then maintained for 3 h at room temperature. The precipitate formed was
filtered off, washed with MeCN, and dried. Analytical reference sample was obtained by recrystallization from
MeCN.
876

2,7-Dibromo-10-(2-pyridyl)-12,13-dihydro-11Н-dibenzo[f,h]cyclopenta[c]quinoline (6a). Yield
1.00 g (80%), colorless crystals, mp 242-244°C. 1H NMR spectrum, δ, ppm (J, Hz): 2.22-2.26 (2Н, m, 12-CH2);
3
3.59-3.63 (4Н, m, 11,13-CH2); 7.34-7.38 (1H, m, H-5 Рy); 7.71-7.75 (2Н, m, Н-3,6); 7.94 (1Н, ddd, J = 7.5,
4
3
3
3
3J = 7.5, J = 1.8, Н-4 Рy); 8.28 (1Н, d, J = 8.8, Н-4); 8.38 (1Н, d, J = 8.8, Н-5); 8.59 (1Н, dd, J = 7.5,
4J = 1.2, Н-3 Рy); 8.68 (1Н, d, J = 1.8, Н-1); 8.75 (1Н, dd, J = 4.9, J = 1.8, Н-6 Py); 9.49 (1Н, d, J = 1.8,
Н-8). Mass spectrum, m/z (Irel, %): 505 [М+Н]+ (50). Found, %: C 59.44; H 2.97; N 5.50. C25H16Br2N2.
Calculated, %: C 59.55; H 3.20; N 5.56.
4
3
4
4
3,6-Dibromo-10-(2-pyridyl)-12,13-dihydro-11Н-dibenzo[f,h]cyclopenta[c]quinoline (6b). Yield
1.03 g (82%), colorless crystals, mp 202-204°C. 1H NMR spectrum, δ, ppm (J, Hz): 2.23-2.27 (2Н, m, 12-CH2);
3
4
3.60-3.64 (4Н, m, 11,13-CH2); 7.34-7.38 (1H, m, H-5 Рy); 7.74 (1Н, dd, J = 8.8, J = 1.6, Н-2); 7.79 (1Н, dd,
4
3J = 8.8, J = 1.6, Н-7); 7.92 (1Н, ddd, 3J = 7.5, 3J = 7.5, 4J = 1.8, Н-4 Рy); 8.45 (1Н, dd, 3J = 7.5, 4J = 1.2, Н-3
Рy); 8.56-8.62 (2Н, m, Н-1,4); 8.66 (1Н, d, 4J = 1.6, Н-5); 8.75 (1Н, dd, 3J = 4.9, 4J = 1.8, Н-6 Рy); 9.30 (1Н, d,
3J = 8.8, Н-8). 13С NMR spectrum, δ, ppm: 25.7; 33.3; 37.2; 121.8; 122.1; 123.1 (2С); 123.6; 125.0; 126.0;
127.9; 128.9; 129.0; 130.0; 130.5; 130.7; 130.8; 131.1; 136.4; 139.5; 143.8; 148.6; 150.4; 151.7; 158.4. Mass
spectrum, m/z (Irel, %): 505 [М+Н]+ (50). Found, %: C 59.51; H 3.01; N 5.43. C25H16Br2N2. Calculated, %:
C 59.55; H 3.20; N 5.56.
6,11-Diiodo-2-(2-pyridyl)phenanthro[9,10-b]pyridine (6c). Triazatriphenylene 3c (0.5 g, 0.89 mmol) was
suspended in 1,2-dichlorobenzene (40 ml). 2,5-Norbornadiene (0.27 ml, 2.67 mmol) was added, and the mixture was
refluxed for 35 h while adding 2,5-norbornadiene (0.27 ml, 2.67 mmol) every 8 h. The solvent was removed by
distillation under vacuum, the residue was purified by column chromatography (eluent 3:1 CH2Cl2–EtOAc, Rf 0.2).
1
Yield 200 mg (40%), light-yellow crystals, mp >250°C. H NMR spectrum, δ, ppm (J, Hz): 7.51-7.55 (1H, m,
3
4
H-5 Рy); 8.05-8.09 (3Н, m); 8.56-8.60 (2Н, m); 8.75-8.79 (3Н, m); 9.15 (1Н, dd, J = 4.9, J = 1.8, Н-6 Рy);
9.31 (1Н, d, 3J = 8.8, Н-4); 9.70 (1Н, d, 4J = 1.8, Н-12). Mass spectrum, m/z (Irel, %): 559 [М+Н]+ (100). Found,
%: C 47.01; H 1.93; N 4.87. C22H12I2N2. Calculated, %: C 47.34; H 2.17; N 5.02.
Preparation of Monoazatriphenylene Aryl Derivatives 7a-d (General Method). A solution of
dibromomonoazatriphenylene 6a,b (0.50 mmol) in toluene (25 ml) was treated with the boronic acid 8a,b
(1.05 mmol), PdCl2(PPh3)2 complex (18 mg, 25 µmol), and PPh3 (13 mg, 50 µmol). Separately a solution of
K2CO3 (1.38 g, 10.00 mmol) in distilled water (20 ml) was prepared and added to the reaction mixture. Ethanol
(10 ml) was added, and the mixture was stirred under argon atmosphere at 85°C for 7 h. The organic phase was
separated, washed with K2CO3 and NH4Cl solutions, then dried over anhydrous Na2SO4. The solvents were
removed by distillation under vacuum, and the residue was recrystallized from toluene.
2,7-Diphenyl-10-(2-pyridyl)-12,13-dihydro-11Н-dibenzo[f,h]cyclopenta[c]quinoline (7а). Yield 180
1
mg (72%), colorless crystals, mp 270-272°C. H NMR spectrum, δ, ppm (J, Hz): 2.24-2.28 (2Н, m, 12-CH2);
3
3
3.64 (2Н, t, J = 7.5, 11-CH2); 3.78 (2Н, t, J = 7.5, 13-CH2); 7.32-7.36 (1H, m, H-5 Py); 7.41-7.45 (2H, m,
3
H Ph); 7.51-7.57 (4H, m); 7.77-7.81 (2H, m); 7.86-7.97 (5H, m); 8.63 (1Н, d, J = 8.8, Н-4); 8.65 (1Н, dd,
3J = 7.5, J = 1.2, Н-3 Рy); 8.72 (1Н, d, J = 8.8, Н-5); 8.75 (1Н, dd, J = 4.9, J = 1.8, Н-6 Рy); 8.85 (1Н, d,
4
3
3
4
4J = 1.6, Н-1); 9.71 (1Н, d, J = 2.0, Н-8). 13С NMR spectrum, δ, ppm: 26.0; 33.3; 37.4; 122.7; 122.9; 123.4;
4
123.6; 123.8; 124.3; 126.0; 126.2; 127.2 (2C); 127.3; 127.4; 128.8; 129.0; 129.6; 130.0; 130.5; 132.1; 132.3;
136.3; 139.1; 139.2; 139.8; 141.1; 141.4; 145.2; 148.4; 150.4; 151.8; 158.9. Mass spectrum, m/z (Irel, %): 499
[М+Н]+ (100). Found, %: C 88.97; H 5.11; N 5.43. C37H26N2. Calculated, %: C 89.13; H 5.26; N 5.62.
2,7-Bis(3,4,5-trimethoxyphenyl)-10-(2-pyridyl)-12,13-dihydro-11Н-dibenzo[f,h]cyclopenta[c]quino-
line (7b). Yield 230 mg (68%), colorless crystals, mp 236-238°C. 1H NMR spectrum, δ, ppm (J, Hz): 2.27-2.31
(2Н, m, 12-CH2); 3.67 (2Н, t, 3J = 7.5, 11-CH2); 3.82 (2Н, t, 3J = 7.5, 13-CH2); 3.95 (3H, s, OCH3); 3.96 (3H, s,
OCH3); 4.01 (6H, s, 2OCH3); 4.02 (6H, s, 2OCH3); 6.99 (2H, s, Н Ar); 7.08 (2H, s, Н Ar); 7.33-7.37 (1H, m,
H-5 Py); 7.85-7.96 (3H, m, H-3,6, H-4 Py); 8.65 (1Н, d, 3J = 8.5, Н-4); 8.69 (1Н, dd, 3J = 7.5, 4J = 1.2, Н-3 Py);
8.73-8.77 (2H, m, Н-5, Н-6 Py); 8.85 (1Н, d, 4J = 1.6, Н-1); 9.72 (1Н, d, 4J = 2.0, Н-8). 13С NMR spectrum, δ,
ppm: 26.2; 33.3; 37.4; 53.7; 56.3; 56.4; 61.0; 104.8; 104.9; 123.0; 123.4; 123.5; 123.8; 124.3; 125.3; 126.1;
126.3; 127.3; 129.6; 130.0; 130.5; 132.0; 135.3; 136.3; 137.0; 137.2; 138.0; 138.2; 139.3; 139.4; 140.0; 145.1;
877

147.6; 148.5; 150.5; 151.9; 153.7; 153.8; 158.7. Mass spectrum, m/z (Irel, %): 679 [М+Н]+ (100). Found, %:
C 75.93; H 5.48; N 3.89. C43H38N2О6. Calculated, %: C 76.09; H 5.64; N 4.13.
3,6-Diphenyl-10-(2-pyridyl)-12,13-dihydro-11Н-dibenzo[f,h]cyclopenta[c]quinoline (7c). Yield 160
1
mg (64%), colorless crystals, mp 185-187°C. H NMR spectrum, δ, ppm (J, Hz): 2.24-2.28 (2Н, m, 12-CH2);
3
3
3.64 (2Н, t, J = 7.5, 11-CH2); 3.73 (2Н, t, J = 7.5, 13-CH2); 7.32-7.36 (1H, m, H-5 Py); 7.42-7.46 (2H, m,
3
H Ph); 7.53-7.57 (4H, m); 7.80-7.84 (4H, m); 7.85-7.97 (3H, m); 8.70 (1Н, d, J = 8.2, Н-1); 8.75 (1Н, dd,
3J = 4.9, J = 1.8, Н-6 Py); 8.82 (1Н, d, J = 1.2, Н-4); 8.93 (1Н, d, J = 1.2, Н-5); 9.55 (1H, d, J = 8.5, H-8).
13С NMR spectrum, δ, ppm: 26.0; 33.2; 37.3; 120.9; 121.6; 122.9; 123.7; 125.6; 126.6; 126.7; 127.5 (2C);
127.6; 127.7; 128.2; 128.9; 129.0; 129.4; 130.9; 131.0; 131.3; 136.4; 139.0; 139.6; 141.0; 141.5; 144.7; 148.5;
150.3; 151.8; 158.8. Mass spectrum, m/z (Irel, %): 499 [М+Н]+ (100). Found, %: C 89.00; H 5.13; N 5.39.
C37H26N2. Calculated, %: C 89.13; H 5.26; N 5.62.
4
3
3
3
3,6-Bis(3,4,5-trimethoxyphenyl)-10-(2-pyridyl)-12,13-dihydro-11Н-dibenzo[f,h]cyclopenta[c]quino-
1
line (7d). Yield 240 mg (71%), colorless crystals, mp 123-125°C. H NMR spectrum, δ, ppm (J, Hz): 2.27-2.31
(2Н, m, 12-CH2); 3.66 (2Н, t, 3J = 7.5, 11-CH2); 3.76 (2Н, t, 3J = 7.5, 13-CH2); 3.94 (3H, s, OСН3); 3.95 (3H, s,
OСН3); 3.99 (6H, s, OСН3); 4.00 (6H, s, OСН3); 6.98 (2H, s, Н Ar); 6.99 (2H, s, Н Ar); 7.33-7.37 (1H, m, H-5
Py); 7.86 (1H, dd, 3J = 8.6, 4J = 1.8, Н-2); 7.89-7.95 (2H, m, H-7, H-4 Py); 8.69 (1Н, dd, 3J = 7.5, 4J = 1.2, Н-3
3
4
Py); 8.73 (1H, d, J = 8.6, H-1); 8.74-8.78 (2H, m, H-4, H-6 Py); 8.88 (1H, d, J = 1.8, H-5); 9.57 (1H, d,
3J = 8.6, H-8). 13С NMR spectrum, δ, ppm: 26.1; 33.2; 37.3; 56.4; 61.1; 104.9; 105.0; 120.7; 121.5; 123.0;
123.1; 123.7; 125.9; 126.8; 126.9; 128.3; 129.4; 130.1; 131.1; 131.2; 136.7; 137.0; 137.5; 138.0; 138.1; 139.1;
140.0; 141.3; 144.8; 148.3; 150.1; 151.9; 153.7; 153.8; 158.4. Mass spectrum, m/z (Irel, %): 679 [М+Н]+ (100).
Found, %: C 75.91; H 5.44; N 3.91. C43H38N2О6. Calculated, %: C 76.09; H 5.64; N 4.13.
The work was performed with support from the Ministry of Education and Science of the Russian
Federation (state contract 8430), Grants Council of the President of Russian Federation (grant
MK 1511.2013.3), as well as the Program 211 of the Government of the Russian Federation (contract
No. 02.А03.21.0006).
REFERENCES
1.
2.
B. H. Bakker, M. Goes, N. Hoebe, H. J. van Ramesdonk, J. W. Verhoeven, M. H. V. Werts, and
J. W. Hofstraat, Coord. Chem. Rev., 208, 3 (2000).
T. R. Govindachari, N. Viswanathan, J. Radhakrishnan, R. Charubala, N. Nityanandra Rao, and
B. R. Pai, Indian J. Chem., 11, 1215 (1973).
3.
4.
T. R. Govindachari, B. R. Pai, and K. Nagarajan, J. Chem. Soc., 2801 (1954).
C. W. Lim, O. Tissot, A. Mattison, M. W. Hooper, J. M. Brown, A. R. Cowley, D. I. Hulmes, and
A. J. Blacker, Org. Process Res. Dev., 7, 379 (2003).
5.
6.
B. A. Sweetman, H. Muller-Bunz, and P. J. Guiry, Tetrahedron Lett., 46, 4643 (2005).
D. S. Kopchuk, I. N. Egorov, T. A. Tseitler, A. F. Khasanov, I. S. Kovalev, G. V. Zyryanov,
V. L. Rusinov, and O. N. Chupakhin, Khim. Geterotsikl. Soedin., 538 (2013). [Chem. Heterocycl.
Compd., 49, 503 (2013).]
V. N. Kozhevnikov, O. V. Shabunina, D. S. Kopchuk, M. M. Ustinova, B. Koenig, and
D. N. Kozhevnikov, Tetrahedron, 64, 8963 (2008).
7.
8.
9.
10.
11.
A. H. Younes, L. Zhang, R. J. Clark, and L. Zhu, J. Org. Chem., 74, 8761 (2009).
H. S. Joshi, R. Jamshidi, and Y. Tor, Angew. Chem., Int. Ed., 38, 2722 (1999).
J. C. Loren and J. S. Siegel, Angew. Chem., Int. Ed., 40, 754 (2001).
G. Albano, V. Balzani, E. C. Constable, M. Maestri, and D. R. Smith, Inorg. Chim. Acta, 277, 225
(1998).
878

12.
13.
14.
15.
16.
17.
18.
19.
W. Goodall and J. A. G. Williams, Chem. Commun., 2514 (2001).
F. Hershnann, Ber. Dtsch. Chem. Ges., 41, 1998 (1908).
M. Krueger and E. Mosettig, J. Org. Chem., 5, 313 (1940).
N. P. Buu-Hoi, J. Org. Chem., 19, 721 (1954).
W. Marckwald, Justus Liebigs Ann. Chem., 274, 331 (1893).
P. J. Campos, E. Anon, M. C. Malo, and M. A. Rodriguez, Tetrahedron, 54, 14113 (1998).
O. Bilgic and D. W. Young, J. Chem. Soc., Perkin Trans. 1, 1233 (1980).
D. N. Nicolaides, K. E. Litinas, G. K. Papageorgiou, and J. Stephanidou-Stephanatou, J. Heterocycl.
Chem., 28, 139 (1991).
20.
21.
22.
23.
24.
I. Nagao, M. Shimizu, and T. Hiyama, Angew. Chem., Int. Ed., 48, 7573 (2009).
A. McIver, D. D. Young, and A. Deiters, Chem. Commun., 4750 (2008).
G. R. Pabst, O. C. Pfüller, and J. Sauer, Tetrahedron, 55, 8045 (1999).
A. Rykowski, D. Branowska, and J. Kielak, Tetrahedron Lett., 41, 3657 (2000).
D. S. Kopchuk, A. F. Khasanov, I. S. Kovalev, G. V. Zyryanov, V. L. Rusinov, and O. N. Chupakhin,
Mendeleev Commun., 23, 209 (2013).
25.
26.
E. C. Taylor, J. E. Macor, and J. L. Pont, Tetrahedron, 43, 5145 (1987).
D. S. Kopchuk, G. V. Zyryanov, I. S. Kovalev, A. F. Khasanov, A. S. Medvedevskikh, V. L. Rusinov,
and O. N. Chupakhin, Khim. Geterotsikl. Soedin., 535 (2013). [Chem. Heterocycl. Compd., 49, 500
(2013).]
E. K. Unver, S. Tarkuc, C. Tanyeli, L. Toppare, and Y. A. Udum, J. Polym. Sci., Part A: Polym. Chem.,
48, 1714 (2010).
F. Dewhurst and P. K. J. Shah, J. Chem. Soc. C, 1503 (1969).
P. Luliński and L. Skulski, Bull. Chem. Soc. Jpn., 72, 115 (1999).
D. Chaudhuri, K. J. van Schooten, S. Liu, J. M. Lupton, H. Wettach, E. Sigmund, and S. Höger, Angew.
Chem., Int. Ed., 49, 7714 (2010).
K. Brunner, A. van Dijken, H. Börner, J. J. A. M. Bastiaansen, N. M. M. Kiggen, and
B. M. W. Langeveld, J. Am. Chem. Soc., 126, 6035 (2004).
S. C. De, Q. J. Indian Chem. Soc., 4, 183 (1927).
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
J. Schmidt and H. Bürkert, Ber. Dtsch. Chem. Ges., 1356 (1927).
S. C. De, J. Indian Chem. Soc., 7, 361 (1930).
F. H. Case, J. Org. Chem., 30, 931 (1965).
V. N. Kozhevnikov, M. M. Ustinova, P. A. Slepukhin, A. Santoro, D. W. Bruce, and
D. N. Kozhevnikov, Tetrahedron Lett., 49, 4096 (2008).
37.
D. S. Kopchuk, A. F. Khasanov, I. S. Kovalev, G. A. Kim, I. L. Nikonov, G. V. Zyryanov,
V. L. Rusinov, and O. N. Chupakhin, Khim. Geterotsikl. Soedin., 936 (2014). [Chem. Heterocycl.
Compd., 50, 864 (2014).]
38.
S. Parker, Photoluminescence of Solutions [Russian translation], Mir, Moscow (1972), p. 251.
879