Abstract
Owing to the directional H-bonding, coordination and π-stacking abilities, terpyridines have been widely used as supramolecular tectons in molecular architectures, skeletons in molecular devices and metallopolymers, and are gaining importance in medicinal chemistry. In this paper, we have synthesized, characterized and applied deep eutectic ionic liquids (DEILs) based on 1,4-diazabicyclo[2.2.2]octane; triethylenediamine (DABCO)-derived quaternary ammonium salts for the preparation of terpyridines. These DEILs were synthesized through N-alkylation of DABCO with haloalkanes (1-bromopentane or 1-bromoheptane) followed by mixing and heating with methanol or polyethylene glycol as a hydrogen bond donor. The synthesized DEILs were structurally characterized by IR and NMR. The formation of deep eutectic solvent was confirmed by freezing point depression, it composition was investigated through phase diagram, and its thermal stability was determined through differential scanning calorimetry, derivative thermogravimetry and thermal gravimetric analysis studies. Further, these DEILs were investigated for their effectiveness towards synthesis of 2,2′:6′,2″-terpyridine, 3,2′:6′,3″-terpyridineand 4,2′:6′,4″-terpyridine derivatives through Kröhnke reaction. The results show that these three types of terpyridines can be obtained in reasonable yields (80%–97%) by the one-pot reaction of 2-, 3- or 4-acetylpyridine with a variety of aromatic aldehydes in the presence of DEIL as a reaction medium, sodium hydroxide as a base and ammonium acetate as a cyclizing agent. This methodology is highly efficient and cost-effective for synthesis of symmetrical as well as unsymmetrical terpyridines. Importantly, these DEILs can be reused several times without an obvious loss of activity and are non-toxic, low-volatile, biodegradable and highly thermally stable. Therefore, these DEILs as a non-conventional reaction medium for the synthesis of terpyridines provides appealing opportunities to be investigated in the domain of green synthesis.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Dhar P C, Mohanty P. Synthesis and photophysical application of functionalized 2,2′:6′,2″-terpyridine metal complexes. ChemInform, 2016, 47(24): 1–10
Husson J, Knorr M. 2,2′:6′,2″-Terpyridines functionalized with thienyl substituents: Synthesis and applications. Journal of Heterocyclic Chemistry, 2012, 49(3): 453–478
Constable E C. 2,2′:6′,2″-Terpyridines: From chemical obscurity to common supramolecular motifs. Chemical Society Reviews, 2007, 36(2): 246–253
Hofmeier H, Schubert U S. Recent developments in the supramolecular chemistry of terpyridine-metal complexes. Chemical Society Reviews, 2004, 33(6): 373–399
Halcrow M A. The synthesis and coordination chemistry of 2,6-bis (pyrazolyl) pyridines and related ligands—versatile terpyridine analogues. Coordination Chemistry Reviews, 2005, 249(24): 2880–2908
Wild A, Winter A, Schluetter F, Schubert U S. Advances in the field of π-conjugated 2,2′:6′,2″-terpyridines. Chemical Society Reviews, 2011, 40(3): 1459–1511
Rotas G, Sandanayaka A S, Tagmatarchis N, Ichihashi T, Yudasaka M, Iijima S, Ito O. (Terpyridine) copper (II)-carbon nanohorns: Metallo-nanocomplexes for photoinduced charge separation. Journal of the American Chemical Society, 2008, 130(14): 4725–4731
Hayami S, Komatsu Y, Shimizu T, Kamihata H, Lee Y H. Spin-crossover in cobalt (II) compounds containing terpyridine and its derivatives. Coordination Chemistry Reviews, 2011, 255(17–18): 1981–1990
Schubert U S, Eschbaumer C. Macromolecules containing bipyridine and terpyridine metal complexes: Towards metallosupramolecular polymers. Angewandte Chemie International Edition, 2002, 41(16): 2892–2926
Khatyr A, Ziessel R. Chiral bipyridine and terpyridine ligands grafted with l-tyrosinefragments. Synthesis, 2001, 2001(11): 1665–1670
Poupart S, Boudou C, Peixoto P, Massonneau M, Renard P Y, Romieu A. Aminopropargyl derivative of terpyridine-bis (methylenamine) tetraacetic acid chelate of europium (Eu (TMT)-AP 3): A new reagent for fluorescent labelling of proteins and peptides. Organic & Biomolecular Chemistry, 2006, 4(22): 4165–4177
Zhao L X, Kim T S, Ahn S H, Kim T H, Kim E K, Cho W J, Choi H, Lee C S, Kim J A, Jeong T C, et al. Synthesis, topoisomerase I inhibition and antitumor cytotoxicity of 2,2′:6′,2″-, 2,2′:6′,3″-and 2,2′:6′,4″-terpyridine derivatives. Bioorganic & Medicinal Chemistry Letters, 2001, 11(19): 2659–2662
Son J K, Zhao L X, Basnet A, Thapa P, Karki R, Na Y, Jahng Y, Jeong T C, Jeong B S, Lee C S, Lee E S. Synthesis of 2,6-diaryl-substituted pyridines and their antitumor activities. European Journal of Medicinal Chemistry, 2008, 43(4): 675–682
Anthonysamy A, Balasubramanian S, Shanmugaiah V, Mathivanan N. Synthesis, characterization and electrochemistry of 4′-functionalized 2,2′:6′,2″-terpyridine ruthenium (II) complexes and their biological activity. Dalton Transactions (Cambridge, England), 2008, (16): 2136–2143
Chelucci G, Saba A, Vignola D, Solinas C. New chiral 2,2′:6′,2″-terpyridines as ligands for asymmetric catalysis: Cyclopropanation and hydrosilylation reactions. Tetrahedron, 2001, 57(6): 1099–1104
Lehn J M, Sanders J K. Supramolecular chemistry: Concepts and perspectives. Angewandte Chemie-English Edition, 1995, 34(22): 2563
Potts K T, Cipullo M J, Ralli P, Theodoridis G. Synthesis of 2,6-disubstituted pyridines, polypyridinyls, and annulated pyridines. Journal of Organic Chemistry, 1982, 47(16): 3027–3038
Kröhnke F. The specific synthesis of pyridines and oligopyridines. Synthesis, 1976, 1976(1): 1–24
Schubert U S, Eschbaumer C. New synthetic strategy toward pyridine-based ligands for supramolecular chemistry utilizing 2,6-bis (trimethyltin) pyridine as the central building block. Organic Letters, 1999, 1(7): 1027–1029
Handy S T, Zhang X. Organic synthesis in ionic liquids: The stille coupling. Organic Letters, 2001, 3(2): 233–236
Heller M, Schubert U S. Multi-functionalized 2,2′:6′,2″-terpyridines. Synlett, 2002, 2002(5): 751–754
Tu S, Li T, Shi F, Wang Q, Zhang J, Xu J, Zhu X, Zhang X, Zhu S, Shi D. A convenient one-pot synthesis of 4′-aryl-2,2′:6′,2″-terpyridines and 2,4,6-triarylpyridines under microwave irradiation. Synthesis, 2005, 2005(18): 3045–3050
Cave G W, Raston C L. Toward benign syntheses of pyridines involving sequential solvent free aldol and michael addition reactions. Chemical Communications, 2000, 22: 2199–2200
Raston C L, Cave G W. Green chemistry laboratory: Benign synthesis of 4,6-diphenyl [2,2′] bipyridine via sequential solventless aldol and Michael addition reactions. Journal of Chemical Education, 2005, 82(3): 468
Faisal M, Larik F A, Saeed A. A highly promising approach for the one-pot synthesis of biscoumarins using HY zeolite as recyclable and green catalyst. Journal of Porous Materials, 2018
Constable E C, Handel R, Housecroft C E, Neuburger M, Schofield E R, Zehnder M. Efficient syntheses of 4′-(2-thienyl)-and 4′-(3-thienyl)-2,2′:6′,2″-terpyridine: Preparation and characterization of Fe (II), Ru (II), Os (II) and Co (II) complexes. Polyhedron, 2004, 23 (1): 135–143
Constable E C, Harverson P, Smith D R, Whall L. The coordination chemistry of 4′-(4-tert-butylphenyl)-2,2′:6′,2″-terpyridine—a solubilising oligopyridine. Polyhedron, 1997, 16(20): 3615–3623
Anastas P T, Warner J C. Green Chemistry: Theory and Practice. Oxford: Oxford University Press, 2000, 30–40
Anastas P T, Williamson T C, eds. Green Chemistry: Frontiers in Benign Chemical Syntheses and Processes. Oxford: Oxford University Press, 1998, 132–150
Ali Ghumro S, Alharthy R D, Al-Rashida M, Ahmed S, Malik M I, Hameed A. N-Alkylated 1,4-diazabicyclo [2.2.2] octane-polyethylene glycol melt as deep eutectic solvent for the synthesis of fisher indoles and 1 H-tetrazoles. ACS Omega, 2017, 2(6): 2891–2900
Faisal M, Shahid S, Ghumro S A, Saeed A, Larik F A, Shaheen Z, Channar P A, Fattah T A, Rasheed S, Mahesar P A. DABCO-PEG ionic liquid-based synthesis of acridine analogous and its inhibitory activity on alkaline phosphatase. Synthetic Communications, 2018, 48(4): 462–472
Smith E L, Abbott A P, Ryder K S. Deep eutectic solvents (DESs) and their applications. Chemical Reviews, 2014, 114(21): 11060–11082
Parnham E R, Drylie E A, Wheatley P S, Slawin A M, Morris R E. Ionothermal materials synthesis using unstable deep-eutectic solvents as template-delivery agents. Angewandte Chemie, 2006, 118(30): 5084–5088
Smith E L, Abbott A P, Ryder K S. Deep eutectic solvents (DESs) and their applications. Chemical Reviews, 2014, 114(21): 11060–11082
Zhang Q, Vigier K D, Royer S, Jerome F. Deep eutectic solvents: Syntheses, properties and applications. Chemical Society Reviews, 2012, 41(21): 7108–7146
Faisal M, Saeed A, Shahzad D, Fattah T A, Lal B, Channar P A, Mahar J, Saeed S, Mahesar P A, Larik F A. Enzyme inhibitory activities an insight into the structure-activity relationship of biscoumarin derivatives. European Journal of Medicinal Chemistry, 2017, 141: 386–403
Li J J. Named Reactions: A Collection of Detailed Mechanisms and Synthetic Applications. Heidelberg: Springer Science & Business Media, 2010, 86–92
Faisal M, Shahzad D, Saeed A, Lal B, Saeed S, Larik F A, Channar P A, Mahesar P A, Mahar J. Review on asymmetric synthetic methodologies for chiral isoquinuclidines; 2008 to date. Tetrahedron, Asymmetry, 2017, 11: 1445–1461
Mundy B P, Ellerd M G, Favaloro F G Jr. Name reactions and reagents in organic synthesis. John Wiley & Sons, 2005, 203–205
Smith C B, Raston C L, Sobolev A N. Poly(ethyleneglycol)(PEG): A versatile reaction medium in gaining access to 4′-(pyridyl)-terpyridines. Green Chemistry, 2005, 7(9): 650–654
Smith E L, Abbott A P, Ryder K S. Deep eutectic solvents (DESs) and their applications. Chemical Reviews, 2014, 114(21): 11060–11082
Garcia G, Aparicio S, Ullah R, Atilhan M. Deep eutectic solvents: Physicochemical properties and gas separation applications. Energy & Fuels, 2015, 29(4): 2616–2644
Kareem M A, Mjalli F S, Hashim M A, Alnashef I M. Phosphonium-based ionic liquids analogues and their physical properties. Journal of Chemical & Engineering Data, 2010, 55(11): 4632–4637
Faisal M, Shahzad D, Larik F A, Dar P. Synthetic approaches to access acortatarins, shensongines and pollenopyrroside; potent antioxidative spiro-alkaloids with a naturally rare morpholine moiety. Fitoterapia, 2018, 129: 366–382
Thomas P A, Marvey B B. Room temperature ionic liquids as green solvent alternatives in the metathesis of oleochemical feedstocks. Molecules (Basel, Switzerland), 2016, 21(2): 184
Wasserscheid P, Welton T, eds. Ionic Liquids in Synthesis. New York: John Wiley & Sons, 2008, 110–130
Zhao H. Current studies on some physical properties of ionic liquids. Physics and Chemistry of Liquids, 2003, 41(6): 545–557
Earle M J, Seddon K R. Ionic liquids: Green solvents for the future. Pure and Applied Chemistry, 2000, 72(7): 1391–1398
Zhao L X, Kim T S, Ahn S H, Kim T H, Kim E K, Cho W J, Choi H, Lee C S, Kim J A, Jeong T C, et al. Synthesis, topoisomerase I inhibition and antitumor cytotoxicity of 2,2′:6′,2″-, 2,2′:6′,3″- and 2,2′:6′,4″-terpyridine derivatives. Bioorganic & Medicinal Chemistry Letters, 2001, 11(19): 2659–2662
Wang J, Hanan G S. A facile route to sterically hindered and non-hindered 4′-aryl-2,2′:6′,2″-terpyridines. Synlett, 2005, 2005(08): 1251–1254
Patel M N, Gandhi D S, Parmar P A. Effect of substituent of terpyridines on the DNA-interaction of polypyridyl ruthenium (II) complexes. Spectrochimica Acta. Part A: Molecular and Biomolecular Spectroscopy, 2011, 84(1): 243–248
Matias T A, Mangoni A P, Toma S H, Rein F N, Rocha R C, Toma H E, Araki K. Catalytic water-oxidation activity of a weakly coupled binuclear ruthenium polypyridyl complex. European Journal of Inorganic Chemistry, 2017, 2017(4): 768
Ma Y, Zhang S, Wei H, Dong Y, Shen L, Liu S, Zhao Q, Liu L, Wong W Y. Enhanced singlet oxygen generation of a soft salt through efficient energy transfer between two ionic metal complexes. Dalton Transactions (Cambridge, England), 2018, 47(16): 5582–5588
Cave G W, Raston C L. Efficient synthesis of pyridines via a sequential solventless aldol condensation and michael addition. Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry, 2001, (24): 3258–3264
Tu S, Jia R, Jiang B, Zhang J, Zhang Y, Yao C, Ji S. Kröhnke reaction in aqueous media: One-pot clean synthesis of 4′-aryl-2,2′:6′,2″-terpyridines. Tetrahedron, 2007, 63(2): 381–388
Kulangiappar K, Anbukulandainathan M, Raju T. Synthetic communications: An international journal for rapid communication of synthetic organic chemistry. Synthetic Communications, 2014, 1 (44): 2494–5202
Smith C B, Raston C L, Sobolev A N. Poly(ethyleneglycol)(PEG): A versatile reaction medium in gaining access to 4′-(pyridyl)-terpyridines. Green Chemistry, 2005, 7(9): 650–654
Al Mousawi A, Dumur F, Garra P, Toufaily J, Hamieh T, Goubard F, Bui T T, Graff B, Gigmes D, Pierre Fouassier J, et al. Azahelicenes as visible light photoinitiators for cationic and radical polymerization: Preparation of photoluminescent polymers and use in high performance LED projector 3D printing resins. Journal of Polymer Science. Part A, Polymer Chemistry, 2017, 55(7): 1189–1199
Acknowledgements
This study was funded by Higher Education Commission (HEC), Islamabad.
Author information
Authors and Affiliations
Corresponding authors
Electronic supplementary material
11705_2018_1788_MOESM1_ESM.pdf
Deep eutectic ionic liquids based on DABCO-derived quaternary ammonium salts: A promising reaction medium in gaining access to terpyridines
Rights and permissions
About this article
Cite this article
Faisal, M., Haider, A., ul Aein, Q. et al. Deep eutectic ionic liquids based on DABCO-derived quaternary ammonium salts: A promising reaction medium in gaining access to terpyridines. Front. Chem. Sci. Eng. 13, 586–598 (2019). https://doi.org/10.1007/s11705-018-1788-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11705-018-1788-6