New Convenient Synthesis of Fluorescent 1,8-Naphthyridines and the Metal-Sensing Properties of the Dyes

Abstract

A new and efficient approach to a series of highly fluorescent non-aggregating donor–acceptor 1,8-naphthyridines is described. Examination of the photophysical properties of the 1,8-naphthyridines revealed that the presence of donor–acceptor functionality leads to bright green fluorescence with solvatochromism in solvents of differing polarities. The application of these molecules in metal sensing was also explored.

Key words

1,8-naphthyridines - lactones - non-aggregating - solvatochromism - metal sensing

• References and Notes

• 1a You Q.-D, Li Z.-Y, Huang C.-H, Yang Q, Wang X.-J, Guo QL, Chen X.-G, He X.-G, Li T.-K, Chern J.-W. J. Med. Chem. 2009; 52: 5649
• 1b Lv K, Liu M.-L, Feng L.-S, Sun L.-Y, Sun Y.-X, Wei Z.-Q, Guo H.-Q. Eur. J. Med. Chem. 2012; 47: 619
• 2a Nakatani K, Sando S, Saito I. J. Am. Chem. Soc. 2000; 122: 2172
• 2b Lu S.-H, Selvi S, Fang J.-M. J. Org. Chem. 2007; 72: 117
• 3a Chen Y, Li J.-L, Tong GS. M, Lu W, Fu W.-F, Lai S.-W, Che CM. Chem. Sci. 2011; 2: 1509
• 3b Borzsonyi G, Alsbaiee A, Beingessner RL, Fenniri H. J. Org. Chem. 2010; 75: 7233
• 4a Li Z, Yu M, Zhang L, Yu M, Liu J, Wei L, Zhang H. Chem. Commun. 2010; 46: 7169
• 4b Yu M.-M, Li Z.-X, Wei L.-H, Wei D.-H, Tang MS. Org. Lett. 2008; 10: 5115
• 5 Kukrek A, Wang D, Hou Y, Zong R, Thummel R. Inorg. Chem. 2006; 45: 10131
• 6 Wormell P, Lacey AR. Chem. Phys. 1987; 118: 71
• 7a Sadhukhan N, Bera JK. Inorg. Chem. 2009; 48: 978
• 7b Koizumi T, Tanaka K. Inorg. Chim. Acta 2004; 357: 3666
• 7c Chen Y, Zhao X.-J, Gan X, Fu W.-F. Inorg. Chim. Acta 2008; 361: 2335
• 8 Goel A, Chaurasia S, Dixit M, Kumar V, Prakash S, Jena B, Verma JK, Jain M, Anand RS, Manoharan SS. Org. Lett. 2009; 11: 1289
• 9 Goel A, Kumar V, Chaurasia S, Rawat M, Prasad R, Anand RS. J. Org. Chem. 2010; 75: 3656
• 10 Goel A, Kumar V, Nag P, Bajpai V, Kumar B, Singh C, Prakash S, Anand RS. J. Org. Chem. 2011; 76: 7474
• 11 Goel A, Kumar V, Singh SP, Sharma A, Prakash S, Singh C, Anand RS. J. Mater. Chem. 2012; 22: 14880
• 12 Goel A, Sharma A, Kathuria M, Bhattacharjee A, Verma A, Mishra PR, Nazir A, Mitra K. Org. Lett. 2014; 16: 756
• 13 Marco-Contelles J, Pérez-Mayoral E, Samadi A, Do Carmo Carreiras M, Soriano E. Chem. Rev. 2009; 109: 2652
• 14 Suárez-Ortiz GA, Sharma P, Amézquita-Valencia M, Arellano I, Cabrera A, Rosas N. Tetrahedron Lett. 2011; 52: 1641
• 15 Tominaga Y, Ushirogouchi A, Matsuda Y, Kobayashi G. Chem. Pharm. Bull. 1984; 32: 3384
• 16a Goel A, Dixit M, Chaurasia S, Kumar A, Raghunandan R, Maulik PR, Anand RS. Org. Lett. 2008; 10: 2553
• 16b Goel A, Verma D, Dixit M, Raghunandan R, Maulik PR. J. Org. Chem. 2006; 71: 804
• 16c Goel A, Singh SP, Kumar A, Kant R, Maulik PR. Org. Lett. 2009; 11: 5122
• 17 Reddy KV, Mogilaiah K, Sreenivasulu B. J. Indian Chem. Soc. 1986; 63: 443
• 18 Naphthyridines 6a–e and 8a–e; General Procedure A mixture of the appropriate carbonitrile 4a–e (1 mmol) with 1-(2-methyl-1,8-naphthyridin-3-yl)ethanone (5; 1.2 mmol) or 8,9-dihydrobenzo[b]-1,8-naphthyridin-6(7H)-one (7; 1.2 mmol) and KOH (1.5 mmol) in anhyd DMF (5 mL) was stirred at r.t. under N₂ for 25–30 min. When the reaction was complete (TLC), the mixture was poured onto crushed ice with vigorous stirring then neutralized with 10% aq HCl. The resulting precipitate was collected by filtration and purified by column chromatography (silica gel, CHCl₃–MeOH). 3-(2-Methyl-1,8-naphthyridin-3-yl)-5-piperidin-1-yl-biphenyl-4-carbonitrile (6a) Yellow solid; yield: 262 mg (65%); mp 130–132 °C (CHCl₃–MeOH); R_f  = 0.54 (CHCl₃–MeOH, 24:1); IR (KBr): 2932 (s), 2852 (s), 2213 (s), 1656 (m), 1591 (m), 1553 (m) cm^–1; ¹H NMR (300 MHz, CDCl₃, TMS): δ = 1.52–1.96 (m, 6 H), 2.74 (s, 3 H), 3.19–3.42 (m, 4 H), 7.03–7.71 (m, 8 H), 7.98–8.30 (m, 2 H), 9.03–9.23 (m, 1 H); ¹³C NMR (75.5 MHz, CDCl₃): δ = 24.0, 24.4, 26.1, 53.4, 105.0, 116.9, 117.1, 120.8, 121.3, 121.9, 127.2, 128.8, 129.0, 133.9, 136.8, 137.4, 139.4, 144.8, 146.3, 153.8, 155.5, 158.2, 160.9; MS (ESI): m/z = 405 [M + H]⁺; HRMS: m/z [M + H]⁺ calcd for C₂₇H₂₅N₄: 405.2079; found: 405.2130. 4-Phenyl-2-piperidin-1-yl-5,6-dihydronaphtho[2,1-b]-1,8-naphthyridine-1-carbonitrile (8a) Yellow solid; yield: 257 mg (62%); mp 194–196 °C (CHCl₃–MeOH); R_f  = 0.60 (CHCl₃–MeOH, 24:1); IR (KBr): 2939 (s), 2850 (w) 2214 (s), 1584 (s), 1443 (m) cm^–1; ¹H NMR (300 MHz, CDCl₃,TMS): δ = 1.48–1.72 (m, 2 H), 1.74–2.01 (m, 4 H), 2.67–3.02 (m, 2 H), 3.03–3.41 (m, 6 H), 7.00 (s, 1 H), 7.10–7.65 (m, 6 H), 8.31 (d, J = 6.2 Hz, 1 H), 8.90–9.25 (m, 2 H); ¹³C NMR (75.5 MHz, CDCl₃): δ = 23.9, 25.9, 26.1, 33.4, 53.8, 102.8, 119.1, 120.5, 121.7, 121.9, 127.0, 128.1, 128.5, 128.8, 130.7, 135.1, 137.5, 137.8, 139.9, 146.4, 153.8, 155.2, 157.7, 163.9; MS (ESI): m/z = 417 [M + H]⁺; HRMS: m/z [M + H]⁺ calcd for C₂₈H₂₅N₄: 417.2079; found: 417.2085.
• 19 Wu J, Liu W, Ge J, Zhang H, Wang P. Chem. Soc. Rev. 2011; 40: 3483
• 20 Majewicz TG, Caluwe P. J. Org. Chem. 1975; 40: 3407
• 21a Hirano T, Kikuchi K, Urano Y, Higuchi T, Nagano T. Angew. Chem. Int. Ed. 2000; 39: 1052
• 21b Nolan EM, Lippard SJ. Acc. Chem. Res. 2009; 42: 193
• 21c Tamanini E, Katewa A, Sedger LM, Todd MH, Watkinson M. Inorg. Chem. 2009; 48: 319
• 21d Xu Z, Yoon J, Spring DR. Chem. Soc. Rev. 2010; 39: 1996
• 21e Lau YH, Rutledge PJ, Watkinson M, Todd MH. Chem. Soc. Rev. 2011; 40: 2848
• 22 Neupane LN, Park J.-Y, Park JH, Lee K.-H. Org. Lett. 2013; 15: 254
• 23a Obare SO, Murphy CJ. New J. Chem. 2001; 25: 1600
• 23b Obare SO, Murphy CJ. Inorg. Chem. 2001; 40: 6080
• 23c Fahrni CJ, O’Halloran TV. J. Am. Chem. Soc. 1999; 121: 11448
• 23d Buccella DJ, Horowitz A, Lippard SJ. J. Am. Chem. Soc. 2011; 133: 4101
• 24a Shortreed M, Kopelman R, Kuhn M, Hoyland B. Anal. Chem. 1996; 68: 1414
• 24b Wang H, Xue L, Jiang H. Org. Lett. 2011; 13: 3844
• 24c Xu Z, Xiao Y, Qian X, Cui J, Cui D. Org. Lett. 2005; 7: 889
• 24d Shen L, Lu X, Tian H, Zhu W. Macromolecules 2011; 44: 5612