A new method for the reaction of cross-coupling: preparation of 5,5′-bi(1,10-phenanthroline)
-
Mehmet Salih Ağırtaş
Abstract
Synthesis and characterization of 5,5′-bi(1,10-phenanthroline) (3) are described. Compound 3 was obtained by treatment of 5-chloro-1,10-phenanthroline (1) with 4-hydroxy- phthalonitrile (2) in the presence of K2CO3 as a base in DMF at room temperature for 25 h.
Introduction
1,10-Phenanthroline and its derivatives are valuable compounds for metal complexation, due to their high coordination numbers and flexible coordination modes [1], [2]. This class of compounds has found extensive utility as chelating ligands in coordination chemistry and as building blocks in supramolecular chemistry [3]. Metal complexes of phenanthroline and its derivatives have also found interesting biological applications, in particular, as agents for recognition and cleavage of DNA [4], [5] and as inhibitors of telomerase [6]. We report here the synthesis and characterization of 5,5′-bi(1,10-phenanthroline) (3 in Scheme 1) using a new method that is an alternative to Suzuki-Miyaura cross-coupling reactions. To the best of our knowledge, compound 3 has not been described previously [7], [8].
5-Chloro-1,10-phenanthroline (1) was allowed to react with 4-hydroxyphthalonitrile (2) in the presence of K2CO3 in dry DMF under nitrogen atmosphere at room temperature for 25 h. Product 3 was obtained by using a conventional workup that did not involve chromatography. Currently, we are studying the scope and limitations of this new methodology that is more convenient and uses less expensive reagents than the classical Suzuki-Miyaura approach.
The reaction of Suzuki-Miyaura cross-coupling of phenylboronic acid and bromoaryl substrates requires the use of palladium complexes [9], [10], [11], [12], [13] that are difficult to prepare and handle. By contrast, the preparation of 4-hydroxyphthalonitrile is easy, and it is a commercial reagent.
A mechanism for this new cross-coupling reaction is suggested in Figure 1. As can be seen, the initial step involves the oxidative addition of 1 to 2. In the final step product 3 is formed with a concomitant release of substrate 2. As a result, compound 2 acts as a catalyst.
Catalytic cycle for cross-coupling of phenanthroline 1 (Ar-X) and 4-hydroxyphthalonitrile 2 (4HPN).
Experimental
5-Chloro-1,10-phenanthroline, K2CO3, CH2Cl2, THF, DMF and 4-hydroxyphthalonitrile were purchased from Merck (Istanbul, Turkey) and Sigma (Interlab A.S., Istanbul, Turkey). Solvents were purified according to standard procedures [14] and stored over 4Å molecular sieves. Melting point was measured on an electrothermal apparatus. IR spectrum was recorded on a Thermo Scientific FT-IR spectrophotometer, Waltham, MA, USA. 1H NMR spectrum was recorded on a Bruker 300 spectrometer (Bruker, Karlsruhe, Germany) with tetramethylsilane as the internal standard. Mass spectrum was recorded on a Bruker Microflex LT instrument (Bruker, Karlsruhe, Germany) using MALDI and 2,5-dihydroxybenzoic acid as the matrix.
Synthesis of 5,5′-bi(1,10-phenanthroline)
A mixture of 5-chloro-1,10-phenanthroline (1, 1 g, 4.66 mmol) and 4-hydroxyphthalonitrile (2, 0.67 g, 4.66 mmol) in N,N-dimethylformamide (DMF, 25 mL) was stirred at room temperature under nitrogen atmosphere. After stirring for 15 min, K2CO3 (2.5 g, 18 mmol) was added portion-wise to the mixture over a period of 2 h. After stirring the reaction mixture for an additional 25 h, the mixture was poured into water (150 mL) and extracted with dichloromethane. The extract was washed with 10% NaHCO3 and then with water, dried over anhydrous sodium sulfate and concentrated to give analytically pure product 3: yield 1.0 g (60%); mp 129–132°C; 1H NMR (300 MHz, DMSO-d6): δ 9.18 (dd, J=1.7 Hz and 4.3 Hz, 2H), 9.10 (dd, J=1.7 Hz and 4.3 Hz, 2H), 8.65 (dd, J=1.7 Hz and 8.4 Hz, 2H), 8.46 (dd, J=1.7 Hz and 8.1 Hz, 2H), 8.25 (s, 2H), 7.90 (dd, J=4.3 Hz and 8.4 Hz, 2H), 7.78 (dd, J=4.3 Hz and 8.1 Hz, 2H); IR: υmax 3020, 1589, 1554, 1481, 1400, 1373, 1284, 1037, 933, 906, 794, 736 cm−1; MS: m/z 358.10 [M]+. Anal. Calcd for C24H14N4: C, 80.43; H, 3.94; N, 15.63. Found: C, 80.61; H, 4.03; N, 15.56. Compound 3 is soluble in acetonitrile, dichloromethane, chloroform and DMF.
Acknowledgements
The author thanks the Yüzüncü Yıl University Office of Scientific Research Projects for the financial support to his research laboratory.
References
[1] Irina, A. D.; Matthew, C.; Nataliya, M. S.; Vyacheslav V. S. Convenient synthesis of 5-aryl(alkyl)sulfanyl-1,10-phenanthrolines from 5,6-epoxy-5,6-dihydro-1,10-phenanthroline, and their activity towards fungal β-D-glycosidases. Tetrahedron Lett. 2011, 67, 7470–7478.10.1016/j.tet.2011.07.058Search in Google Scholar
[2] Luman, C. R.; Castellano, F. N. Phenanthroline Ligands; McCleverty, J. A. M., Thomas, J., Eds.; Compr. Coord. Chem. II; Elsevier: Oxford, UK, 2004, vol. 1, 25–39.10.1016/B0-08-043748-6/01202-0Search in Google Scholar
[3] Chelucci, G.; Thummel, R. P. Chiral 2,2′-bipyridines, 1,10-phenanthrolines, and 2,2′:6′,2″-terpyridines: syntheses and applications in asymmetric homogeneous catalysis. Chem. Rev.2002, 102, 3129–3170.10.1021/cr0101914Search in Google Scholar PubMed
[4] Kao, H.-C.; Hsu, C.-J.; Hsu, C.-W.; Lin, C.-H.; Wang, W.-J. Aza-bridged bis-1, 10-phenanthroline acyclic derivatives: synthesis, structure, and regioselective alkylation. Tetrahedron Lett.2010, 51, 3743–3747.10.1016/j.tetlet.2010.05.039Search in Google Scholar
[5] Bencini, A.; Lippolis, V. 1, 10-Phenanthroline: a versatile building block for the construction of ligands for various purposes. Coord. Chem. Rev.2010, 254, 2096–2180.10.1016/j.ccr.2010.04.008Search in Google Scholar
[6] Krapcho, A. P.; Sparapani, S.; Leenstra, A.; Seitz, J. D. Displacement reactions of 2-chloro- and 2,9-dichloro-1,10-phenanthroline: synthesis of a sulfur-bridged bis-1,10-phenanthroline macrocycle and a 2,20-amino-substituted-bis-1,10-phenanthroline, Tetrahedron Lett. 2009, 50, 3195–3197.10.1016/j.tetlet.2009.01.138Search in Google Scholar
[7] Toyota, S.; Woods, C. R.; Benaglia, M.; Siegel, J. S. Synthesis of unsymmetrical 2,8- and 2,9-dihalo-l,10-phenanthrolines and derivatives. Tetrahedron Lett. 1998, 39, 2697–2700.10.1016/S0040-4039(98)00409-2Search in Google Scholar
[8] Rice, C. R.; Anderson, K. M. A new synthesis of a potentially versatile ligand 2,2′-bi-(1,10- phenanthroline): crystal structure and complexation chemistry. Polyhedron2000, 19, 495–498.10.1016/S0277-5387(00)00292-8Search in Google Scholar
[9] Ratniyom, J.; Chaiprasert, T.; Pramjit, S.; Yotphan, S.; Sangtrirutnugul, P.; Srisuratsiri, P.; Kongsaeree, P.; Supavadee Kiatisevi, S. Air-stable imidazole-imine palladium complexes for Suzukie Miyaura coupling: toward an efficient, green synthesis of biaryl compounds. J. Organomet. Chem. 2014, 752, 161–170.10.1016/j.jorganchem.2013.12.015Search in Google Scholar
[10] Kotha, S.; Lahiri, K.; Kashinath, D. Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis. Tetrahedron2002, 58, 9633–9695.10.1016/S0040-4020(02)01188-2Search in Google Scholar
[11] Huang, F.; Batey, R. A. Cross-coupling of organoboronic acids and sulfinate salts using catalytic copper (II) acetate and 1, 10-phenanthroline: synthesis of aryl and alkenylsulfones. Tetrahedron2007, 63, 7667–7672.10.1016/j.tet.2007.05.029Search in Google Scholar
[12] Chen, L.; Gao, Z.; Li, Y. Immobilization of Pd (II) on MOFs as a highly active heterogeneouscatalyst for Suzuki–Miyaura and Ullmann-type coupling reactions. Catal. Today2015, 245, 122–128.10.1016/j.cattod.2014.03.074Search in Google Scholar
[13] Thathonga, Y.; Jitchatia, R.; Wongkhan, K. Air-stable anthracene-phosphine oxide adduct ligand in Pd catalysed Suzuki-Miyaura reactions. APCBEE Procedia2012, 3, 154–160.10.1016/j.apcbee.2012.06.062Search in Google Scholar
[14] Armarego, W. L. F.; Chai, C. L. L. Purification of laboratory chemicals, 7th ed., Butterwordh-Heinemann, Oxford, 2013.10.1016/B978-0-12-382161-4.00004-2Search in Google Scholar
©2017 Walter de Gruyter GmbH, Berlin/Boston
This article is distributed under the terms of the Creative Commons Attribution Non-Commercial License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.
Articles in the same Issue
- Frontmatter
- Preliminary Communications
- Tandem hetero-Diels–Alder-hemiacetal reaction in the synthesis of new chromeno[4′,3′:4,5]thiopyrano[2,3-d]thiazoles
- A new method for the reaction of cross-coupling: preparation of 5,5′-bi(1,10-phenanthroline)
- Design and synthesis of 4,5-diaryl/heteroarylthiophene-2-carboxylic acid derivatives and evaluation of their biological activities
- Research Articles
- Synthesis and properties of dicarbazolyltriphenylethylene-substituted fluorene derivatives exhibiting aggregation-induced emission enhancement
- Synthesis of a new polycyclic heterocyclic ring system. Part III. Benzo[b]imidazo[1,5-d][1,4]oxazepine-1,4(2H,5H)-diones
- Br2- or HBr-catalyzed synthesis of asymmetric 3,3-di(indolyl)indolin-2-ones
- Mono- and bis-dipicolinic acid heterocyclic derivatives – thiosemicarbazides, triazoles, oxadiazoles and thiazolidinones as antifungal and antioxidant agents
- Synthesis and antimicrobial activity of new piperazine-based heterocyclic compounds
- Synthesis and evaluation of chromene-based compounds containing pyrazole moiety as antimicrobial agents
- Ultrasonic synthesis, characterization, and antibacterial evaluation of novel heterocycles containing hexahydroquinoline and pyrrole moieties
Articles in the same Issue
- Frontmatter
- Preliminary Communications
- Tandem hetero-Diels–Alder-hemiacetal reaction in the synthesis of new chromeno[4′,3′:4,5]thiopyrano[2,3-d]thiazoles
- A new method for the reaction of cross-coupling: preparation of 5,5′-bi(1,10-phenanthroline)
- Design and synthesis of 4,5-diaryl/heteroarylthiophene-2-carboxylic acid derivatives and evaluation of their biological activities
- Research Articles
- Synthesis and properties of dicarbazolyltriphenylethylene-substituted fluorene derivatives exhibiting aggregation-induced emission enhancement
- Synthesis of a new polycyclic heterocyclic ring system. Part III. Benzo[b]imidazo[1,5-d][1,4]oxazepine-1,4(2H,5H)-diones
- Br2- or HBr-catalyzed synthesis of asymmetric 3,3-di(indolyl)indolin-2-ones
- Mono- and bis-dipicolinic acid heterocyclic derivatives – thiosemicarbazides, triazoles, oxadiazoles and thiazolidinones as antifungal and antioxidant agents
- Synthesis and antimicrobial activity of new piperazine-based heterocyclic compounds
- Synthesis and evaluation of chromene-based compounds containing pyrazole moiety as antimicrobial agents
- Ultrasonic synthesis, characterization, and antibacterial evaluation of novel heterocycles containing hexahydroquinoline and pyrrole moieties
