The synthesis of polyarene-modified 5-phenyl-2,2'-bipyridines via the methodology and aza-Diels-Alder reaction

Article abstract of DOI:10.1016/j.mencom.2014.03.018

Nucleophilic substitution of hydrogen () in 6-phenyl-3-(2-pyridyl)-1,2,4- triazine under the action of lithium derivatives of polynuclear arenes followed by aza-Diels-Alder reaction with norbornadiene or morpholinocyclopentene gives the novel polyarenemodified photoluminescent 5-phenyl-2,2'-bipyridine ligands.

Full text of DOI:10.1016/j.mencom.2014.03.018

Mendeleev
Communications
Mendeleev Commun., 2014, 24, 117–118
The synthesis of polyarene-modified 5-phenyl-2,2'-bipyridines
H
via the S methodology and aza-Diels–Alder reaction
N
Igor S. Kovalev, Dmitry S. Kopchuk,* Albert F. Khasanov,a
a
a,b
a,b
a,b
a,b
Grigory V. Zyryanov, Vladimir L. Rusinov and Oleg N. Chupakhin
a
b
Department of Organic Chemistry, Ural Federal University, 620002 Ekaterinburg, Russian Federation
I. Ya. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences,
6
20990 Ekaterinburg, Russian Federation. Fax: +7 343 374 1189; e-mail: dkopchuk@mail.ru
DOI: 10.1016/j.mencom.2014.03.018
H
Nucleophilic substitution of hydrogen (S ) in 6-phenyl-3-(2-pyridyl)-1,2,4-triazine under the action of lithium derivatives of poly-
N
nuclear arenes followed by aza-Diels–Alder reaction with norbornadiene or morpholinocyclopentene gives the novel polyarene-
modified photoluminescent 5-phenyl-2,2'-bipyridine ligands.
i, ii or iii
iv
The polyarene-modified (pyrene, anthracene, naphthalene, etc.)
,2'-bipyridines (bipy) and 2,2':6',2''-terpyridines due to their
Ar–H
Ar–Br
Ar–Li
2
3
a–c
2a–c
1
rich photophysical properties, as well as their binding ability to
metal cations and DNA, are of wide use as promising components
Ph
N
Ph
Ar
N
N
2
3
N
v
for photochemotherapeutic agents, components for solar cells,
Ar–Li
N
4
N
chemosensors for various analytes, for instance oxygene or
metal cations. In addition, the electrochemical properties of
polyaromatic oligopyridines are also of practical interest. The
N
N
H
5
H
6
1
4a–c
most common synthetic routes to construct the polyarene-modified
7,8
(CH2)n
oligopyridines are the cross-coupling reactions, Knoevenagel
Ph
Ar
N
N
vi or vii
Ph
Ar
9
condensation, a non-direct attachment of polyaromatic chromo-
N
phores to the oligopyridine core, for instance, via the alkyl bridges
N
N
N
10
by the alkylation reactions, and heterocyclization of substituted
11
5a–c
polyarenes. Finally, 2,2'-bypyridines bearing polyaromatic sub-
stituents can be prepared as a mixture of two isomers by the inverse
aza-Diels–Alder reaction between 3-(2-pyridyl)-1,2,4-triazines
and polyaromatic acetylenes.12 Most of these methods are often
limited by the availability of the starting compounds.
6a–d
a–c n = 0, method vi
d n = 3, method vii
a,d Ar = pyren-1-yl (method i)
b Ar = phenanthren-9-yl (method ii)
c Ar = triphenylen-2-yl (method iii)
On the other hand, reactions of nucleophilic substitution of
H 13
hydrogen (SN) are known as a versatile tool for the direct
Scheme 1 Reagents and conditions: i, N-bromosuccinimide, CH Cl , 20°C,
2 h; ii, Br , CCl , 77°C, 2 h; iii, Br , CH Cl , 20°C, 1 week; iv, Bu Li, dry
THF–dry toluene (1:1), –78°C®20°C, overnight; v, DDQ, CH Cl , 20°C,
30 min; vi, 2,5-norbornadiene, o-xylene, 143°C, 18 h; vii, 1-morpholino-
cyclopentene, o-xylene, 143°C, 10 h.
modification of various p-deficient heterocycles, in particular,
2
2
s
1
1
4
2 4 2 2 2
1
S
,2,4-triazines, by the residues of electron-rich species. This
2
2
H
methodology comprising the aza-Diels–Alder reaction was
N
shown to be a promising strategy for the synthesis of 2,2'-bi-
pyridines and 2,2':6',2''-terpyridines via their 6-Nu-1,2,4-tri-
azine precursors. However, it was limited to activated forms of
the parent arenes 3a,b. The procedure for the preparation of
2
0
1
,2,4-triazines, e.g. 1,2,4-triazine-4-oxides, and strong nucleo-
2-bromotriphenylene 2c was slightly modified: the mono-
brominated product was obtained only after the prolonged stirring
of triphenylene 3c with bromine in dichloromethane at ambient
temperature. Treatment of as-triazine 1 with aryllithium com-
pounds gave the corresponding stable s-adducts 4 in up to 96%
yields. The most practical ratio for 1:ArLi was 0.8:1, which
caused full consumption of triazine 1, while the excess of ArLi
upon work-up was converted back to the arenes 3 easily separable
philes, e.g. in situ formed cyanide anion, lithium acetylides,
15
lithiumcarboranes. Here we report a versatile synthetic strategy
towards novel photoluminescent 5-phenyl-2,2'-bipyridine ligands
bearing 6-positioned polyaromatic substituents based on sequence
H
of S reaction between lithium salts of polyarenes and 6-phenyl-
N
3
-(2-pyridyl)-1,2,4-triazine 1 followed by the aza-Diels–Alder
†
reaction of the resulted 5-aryl-1,2,4-triazines (Scheme 1).
s
The starting 6-phenyl-3-(2-pyridyl)-1,2,4-triazine 1 was pre-
by flash chromatography. The Bu Li was more effective compared
to BuLi which gave admixtures of N-butylated 1,2,4-triazines
(ESI-MS data).
1
6
pared as described. 1,2,4-Triazine moiety is highly p-deficient
and is susceptible to form s-adducts with nucleophiles which
can be further aromatized.17 In this study, aryllithium compounds
obtained in situ from the corresponding bromoarenes 2 were
The structure of compounds 4 was confirmed by ESI-MS,
1
13
1
H and C NMR and elemental analysis data. H NMR spectra
1
8
3
used as nucleophiles (see Scheme 1). 1-Bromopyrene 2a and
of compounds 4 contained signals of protons next to the sp -
hybridized carbon atom as a one-proton singlet at 6.22–7.00 ppm
and the sp -hybridized carbon atoms appear in the C NMR
9
-bromophenanthrene 2b19 were synthesized by bromination of
3
13
†
For procedures and characteristics of compounds, see Online Supple-
spectrum as a resonance peaks at 54.9–57.7 ppm, along with the
1
mentary Materials.
resonances of the NH protons as singlets in the H NMR spectrum.
©
2014 Mendeleev Communications. All rights reserved.
– 117 –

Mendeleev Commun., 2014, 24, 117–118
A. B. Dobrynin, T. P. Gerasimova, S. A. Katsyuba, O. G. Sinyashin and
For the aromatization of s-adducts 4, 2,3-dichloro-5,6-dicyano-
The products 5 were
easily separable by the column chromatography on alumina in
D. G. Yakhvarov, Mendeleev Commun., 2013, 23, 135.
benzoquinone (DDQ) is effective.1
7(a),21
6
(a) C. Goze, C. Sabatini, A. Barbieri, F. Barigelletti and R. Ziessel, Eur.
J. Inorg. Chem., 2008, 1293; (b) H.-C. Lin, D. A. Straus, V. A. Johnson,
J. E. Lu, L. Lopez and R. H. Terrill, Electrochim. Acta, 2012, 62, 140.
7 (a) A. L. Rodriguez, G. Peron, C. Duprat, M. Vallier, E. Fouquet and
F. Fages, Tetrahedron Lett., 1998, 39, 1179; (b) M. Beinhoff, W. Weigel,
M. Jurczok, W. Rettig, C. Modrakowski, I. Brüdgam, H. Hartl and A. D.
Schlüter, Eur. J. Org. Chem, 2001, 3819.
(a) A. C. Benniston, A. Harriman, D. J. Lawrie and S. A. Rostron,
Tetrahedron Lett., 2004, 45, 2503; (b) M. Hissler, A. Harriman, A. Khatyr
and R. Ziessel, Chem. Eur. J., 1999, 5, 3366; (c) D. V. Kozlov, D. S. Tyson,
C. Goze, R. Ziessel and F. N. Castellano, Inorg. Chem., 2004, 43, 6083.
J. J. Gu, J. Chen and R. H. Schmehl, J. Am. Chem. Soc., 2010, 132, 7338.
up to 91% yields. The structure of 5 was confirmed by ESI-MS,
1
13
H and C NMR and elemental analysis data.
1
,2,4-Triazine derivatives 5 were converted into pyridines
22
according to the general strategy (see Scheme 1). Their Diels–
Alder reaction with 2,5-norbornadiene or 1-morpholinocyclo-
pentene was performed by the prolonged refluxing of the reactants
in xylene. Products 6a–c were purified by column chromato-
graphy, poorly soluble compound 6d was purified by recrystal-
lization. The structures of compounds 6a–d were confirmed by
8
9
1
1
0 (a) A. Bilyk and M. M. Harding, J. Chem. Soc., Dalton Trans., 1994, 77;
1
13
‡
ESI-MS, H and C NMR and elemental analysis data. It is
worth to mention that due to the pronounced low solubility of
pyrene-substituted bipy ligands1 the use of enamine counter-
parts seems the good means to enhance the solubility of the target
pyrene-substituted oligopyridines and their metal complexes.
In summary, the effective synthetic route towards polyarene-
modified 5-phenyl-2,2'-bipyridines is developed. Replacement
of pyridine ring in oligopyridine systems by an aryl affords com-
pounds suitable for the preparation of ortho-metallated tridentate
(
b) A. Le Goff, K. Gorgy, M. Holzinger, R. Haddad, M. Zimmerman and
S. Cosnier, Chem. Eur. J., 2011, 17, 10216.
(b)
1 (a) S. Ji, W. Wu, W. Wu, H. Guo, Q. Yang, Q. Wang, X. Zhang and
Y. Wu, Front. Chem. China, 2010, 5, 193; (b) L. Chouai, F. Wu, Y. Jang
and R. P. Thummel, Eur. J. Inorg. Chem., 2003, 2774; (c) M. Barboiu,
L. Prodi, M. Montalti, N. Zaccheroni, N. Kyritsakas and J.-M. Lehn,
Chem. Eur. J., 2004, 10, 2953; (d) N. M. Cox, L. P. Harding, J. E. Jones,
S. J. A. Pope, C. R. Rice and H. Adams, Dalton Trans., 2012, 41, 1568;
(
e) J. G. Cordaro, J. K. McCusker and R. G. Bergman, Chem. Commun.,
002, 1496.
12 S. Diring, P. Retailleau and R. Ziessel, Tetrahedron Lett., 2007, 48, 8069.
2
2
3
(
C^N^N)-ligands. Being formally anionic, these ligands form
6
8
1
1
1
3 O. N. Chupakhin, V. N. Charushin and H. van der Plas, Nucleophilic
Aromatic Substitution of Hydrogen, Academic Press, San Diego, 1994.
4 D. N. Kozhevnikov, V. L. Rusinov and O. N. Chupakhin, Adv. Heterocycl.
Chem., 2002, 82, 261.
5 (a)V. N. Kozhevnikov, D. N. Kozhevnikov, T. V. Nikitina, V. L. Rusinov,
O. N. Chupakhin, M. Zabel and B. Köenig, J. Org. Chem., 2003, 68,
2882; (b) D. N. Kozhevnikov, V. N. Kozhevnikov, A. M. Prokhorov,
M. M. Ustinova, V. L. Rusinov, O. N. Chupakhin, G. G. Aleksandrov
and B. Köenig, Tetrahedron Lett., 2006, 47, 869; (c) A. M. Prokhorov,
D. N. Kozhevnikov, V. L. Rusinov, O. N. Chupakhin, I. V. Glukhov,
M. Yu. Antipin, O. N. Kazheva, A. N. Chekhlov and O. A. Dyachenko,
Organometallics, 2006, 25, 2972.
stable photoluminescent complexes with d and d transition
ii 12,24
metals, for instance the cyclometallated complexes of Pt ,
ii 25
iii 26
Pd , and Ir .
This work was supported by the Russian Ministry of Educa-
tion and Science (state contract no. 8430), the Russian Foundation
for Basic Research (grant no. 12-03-31726), the Council for
grants of the President of the Russian Federation (grant no. MK-
511.2013.3) and Act #211 of the Russian Federation Govern-
ment (no. 02.A03.21.0006).
1
1
6 V. N. Kozhevnikov, D. N. Kozhevnikov, O. V. Shabunina, V. L. Rusinov
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.mencom.2014.02.018.
and O. N. Chupakhin, Tetrahedron Lett., 2005, 46, 1791.
17 (a) I. A. Utepova, A. E. Lakhina, M. V. Varaksin, I. S. Kovalev, V. L.
Rusinov, P. A. Slepukhin, M. I. Kodess and O. N. Chupakhin, Russ.
Chem. Bull., Int. Ed., 2008, 57, 2156 (Izv. Akad. Nauk, Ser. Khim., 2008,
2
116); (b) D. N. Kozhevnikov, N. N. Kataeva, V. L. Rusinov and O. N.
References
Chupakhin, Russ. Chem. Bull., Int. Ed., 2004, 53, 1295 (Izv. Akad. Nauk, Ser.
Khim., 2004, 1243); (c) I.A. Utepova,A.A. Misikhina, O. N. Chupakhin
and P.A. Slepukhin, Organometallics, 2011, 30, 3047; (d)O. N. Chupakhin,
I. A. Utepova, M. V. Varaksin, E. V. Tretyakov, G. V. Romanenko, D. V.
Stass and V. I. Ovcharenko, J. Org. Chem., 2009, 74, 2870.
1
(a) E. C. Constable, M. Neuburger, P. Rösel, G. E. Schneider, J. A.
Zampese, C. E. Housecroft, F. Monti, N. Armaroli, R. D. Costa and
E. Orti, Inorg. Chem., 2013, 52, 885; (b) C. Goze, D. V. Kozlov, D. S.
Tyson, R. Ziessel and F. N. Casellano, New J. Chem., 2003, 27, 1679;
(
c) S. Leroy-Lhez and F. Fages, Eur. J. Org. Chem., 2005, 2684.
18 R. H. Mitchell, Y.-H. Lai and R. V. Williams, J. Org. Chem., 1979, 44, 4733
.
2
(a) S. Roy, S. Roy, S. Saha, R. Majumdar, R. R. Dighe, E. D. Jemmis and
A. R. Chakravarty, Dalton Trans., 2011, 40, 1233; (b) U. Basu, I. Khan,
D. Koley, S. Saha, P. Kondaiah and A. R. Chakravarty, J. Inorg. Biochem.,
19 C.A. Dornfeld, J. E. Callen, G. H. Coleman, R. E. Carnahan and H.Adkins,
Org. Synth., 1948, 28, 19.
20 N.Yamada, J. Kamatani and A. Saitoh, Patent WO2012/86366 A1 (Chem.
Abstr., 2012, 157, 150376).
2
012, 116, 77.
M. Hussain, A. El-Shafei, A. Islam and L. Han, Phys. Chem. Chem. Phys.,
013, 15, 8401.
3
4
5
21 O. N. Chupakhin, I. A. Utepova, I. S. Kovalev, V. L. Rusinov and Z. A.
2
Starikova, Eur. J. Org. Chem., 2007, 857.
S. Ji, W. Wu, W. Wu, P. Song, K. Han, Z. Wang, S. Liu, H. Guo and
J. Zhao, J. Mater. Chem., 2010, 20, 1953.
(a) A. C. Benniston, A. Harriman, D. J. Lawrie, M. Mehrabi and O. D.
Russel, Inorg. Chim. Acta, 2005, 358, 3483; (b) X. Peng, Y. Xu, S. Sun,
Y. Wu and J. Fan, Org. Biomol. Chem., 2007, 5, 226; (c) E. A. Trofimova,
22 (a) D. L. Boger, Tetrahedron, 1983, 39, 2869; (b) G. R. Pabst, O. C.
Pfüller and J. Sauer, Tetrahedron, 1999, 55, 8045; (c) A. Rykowski,
D. Branowska and J. Kielak, Tetrahedron Lett., 2000, 41, 3657; (d) V. N.
Kozhevnikov, O. V. Shabunina, D. S. Kopchuk, M. M. Ustinova, B. König
and D. N. Kozhevnikov, Tetrahedron, 2008, 64, 8963; (e) D. S. Kopchuk,
I. S. Kovalev, A. F. Khasanov, G. V. Zyryanov, P. A. Slepukhin, V. L.
Rusinov and O. N. Chupakhin, Mendeleev Commun., 2013, 23, 142;
‡
5
-Phenyl-6-(pyren-1-yl)-2,2'-bipyridine 6a. Yield 270 mg (0.63 mmol,
(
f) D. S. Kopchuk, A. F. Khasanov, I. S. Kovalev, G. V. Zyryanov, V. L.
1
7
9%), mp 214–216°C. H NMR (CDCl ) d: 7.02 (m, 3H, Ph), 7.09–7.14
3
Rusinov and O. N. Chupakhin, Mendeleev Commun., 2013, 23, 209.
3
(
m, 2H, Ph), 7.31 (m, 1H, 5-H ), 7.75 (ddd, 1H, 4-H , J 7.8 and 7.8 Hz,
J 1.6 Hz), 7.82 (d, 1H, 3-HPyrene
th
Py
Py
23 F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, 5 edn.,
4
3
,
J 8.0 Hz), 7.96–8.10 (m, 6H,
Wiley, New York, 1988.
3
-HPy(center),pyrene), 8.12–8.17 (m, 2H, pyrene), 8.19 (d, 4-HPy(center),
24 (a) C. W. Chan, L. K. Cheng and C. M. Che, Coord. Chem. Rev., 1994,
132, 87; (b) M. Hissler, J. E. McGarrah, W. B. Connick, D. K. Geiger,
S. D. Cummings and R. Eisenberg, Coord. Chem. Rev., 2000, 208, 115.
25 (a) W. Lu, B.-X. Mi, M. C. W. Chan, Z. Hui, C.-M. Che, N. Zhu and
S.-T. Lee, J. Am. Chem. Soc., 2004, 126, 4958; (b) W. Lu, M. C. W. Chan,
N. Zhu, C.-M. Che, C. Li and Z. Hui, J. Am. Chem. Soc., 2004, 126, 7639.
26 M. Baldo, D. F. O’Brien, A. Shoustikov, S. Sibley, M. E. Thompson and
S. R. Forrest, Nature, 1998, 395, 151.
3
3
4
J 7.8 Hz), 8.49 (dd, 1H, 3-H , J 7.8 Hz, J 1.6 Hz), 8.62 (d, 1H,
Py
3
3
4
13
2
-HPyrene, J 8.0 Hz), 8.74 (dd, 1H, 6-H , J 4.8 Hz, J 1.6 Hz). C NMR
Py
(
CDCl ): 119.7, 121.7, 123.8, 124.4, 124.8, 125.0, 125.2, 125.5, 125.9,
3
1
1
27.1, 127.4, 127.5, 127.6, 128.1, 128.5, 129.3, 129.4, 131.0, 131.1, 131.3,
35.8, 136.9, 138.1, 139.2, 139.3, 139.4, 149.2, 154.6, 156.1, 156.8.
+
ESI-MS, m/z: 433.17 [M+H] (calc., m/z: 433.17). Found (%): C, 88.58;
H, 4.41; N, 6.27. Calc. for C H N (%): C, 88.86; H, 4.66; N, 6.48.
32
20
2
For characteristics of compounds 6b–d, see Online Supplementary
Materials.
Received: 10th September 2013; Com. 13/4201
–
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