Efficient Synthesis of Conjugated 1,3,4-Thiadiazole Hybrids through Palladium-Catalyzed Cross-Coupling of 2,5-Bis(4-bromophenyl)-1,3,4-thiadiazole with Boronic Acids

Abstract

New derivatives of 2,5-bis(4-heteroarylphenyl)-1,3,4-thiadiazole were synthesized under Suzuki cross-coupling reactions from 2,5-bis(4-bromophenyl)-1,3,4-thiadiazole and commercially available boronic acids. Reactions were conducted in a two-phase solvent system in the presence of catalytic amounts of tetrakis(triphenylphosphine)palladium(0), cesium carbonate as a base, and tetrabutylammonium bromide playing a role of a phase-transfer catalyst.

Key words

heterocycles - cross-coupling - phase-transfer catalysis - palladium - catalysis

• References and Notes

• 1a Hu Y, Li C, Wang X, Yang Y, Zhu H. Chem. Rev. 2014; 114: 5572
• 1b Haider S, Alam MS, Hamid H. Eur. J. Med. Chem. 2015; 92: 156
• 1c Tambe SM, Tasaganva RG, Inamdar SR, Kariduraganavar MY. J. Appl. Polym. Sci. 2012; 125: 1049
• 2a Sharma B, Verma A, Prajapati S, Sharma UK. Int. J. Med. Chem. 2013; 1
• 2b Shrivastava K, Purohit S, Singhal S, Pradesh U, Pradesh M. Asian J. Biomed. Pharm. Sci. 2013; 3: 6
• 3a Kraft A, Grimsdale AC, Holmes AB. Angew. Chem. Int. Ed. 1998; 37: 402
• 3b Segura JL. Acta Polym. 1998; 49: 319
• 3c Mitschke U, Bauerle P. J. Mater. Chem. 2000; 10: 1471
• 4a Schulz B, Bruma M, Brehmer L. Adv. Mater. 1997; 9: 601
• 4b Thelakkat M, Schmidt HW. Polym. Adv. Technol. 1998; 9: 429
• 5a Adachi C, Tsutsui T, Saito S. Appl. Phys. Lett. 1989; 55: 1489
• 5b Adachi C, Tsutsui T, Saito S. Appl. Phys. Lett. 1990; 56: 799
• 6 Wang C, Jung GY, Hua Y, Pearson C, Bryce MR, Petty MC, Batsanov AS, Goeta AE, Howard JA. K. Chem. Mater. 2001; 13: 1167
• 7a Kim DU, Aminaka E, Tsutsui T, Saito S. Jpn. J. Appl. Phys., Part 1 1995; 34: 6255
• 7b Kim DU, Tsutsui T. Mol. Cryst., Liq. Cryst. Sci. Technol., Sect. A 1996; 280: 325
• 8 Grykien R, Luszczynska B, Glowacki I, Kurach E, Rybakiewicz R, Kotwica K, Zagorska M, Pron A, Tassini P, Maglione MG, Del Mauro AD. G, Fasolino T, Rega R, Pandolfi G, Minarini C, Aprano S. Opt. Mater. (Amsterdam, Neth.) 2014; 37: 193
• 9a Wang C, Jung GY, Batsanov AS, Bryce MR, Petty MC. J. Mater. Chem. 2002; 12: 173
• 9b Waskiewicz K, Gabański R, Żak J, Suwiński J. Electrochem. Solid-State Lett. 2005; 8: E24
• 9c Fuks-Janczarek I, Reshak AH, Kuźnik N, Kityk IV, Gabański R, Łapkowski M, Motyka R, Suwiński J. Spectrochim. Acta, Part A 2009; 72: 394
• 9d Łapkowski M, Motyka R, Suwiński J, Data P. Macromol. Chem. Phys. 2012; 231: 29
• 9e Data P, Łapkowski M, Motyka R, Suwiński J. Electrochem. Acta 2012; 59: 567
• 10a Schulz B, Orgzall I, Freydank A, Xii C. Adv. Colloid Interface Sci. 2005; 116: 143
• 10b Chen ZK, Meng H, Lai YH, Huang W. Macromolecules 1999; 32: 4351
• 10c Tamoto N, Adachi C, Nagai K. Chem. Mater. 1997; 9: 1077
• 10d Sinigersky V, Wegner G, Schopov I. Eur. Polym. J. 1993; 29: 617
• 11a Dimitrowa K, Hauschild J, Zaschke H, Schubert H. J. Prakt. Chem. (Leipzig) 1980; 322: 933
• 11b Lin K.-T, Kuo H.-M, Sheu H.-S, Lai CK. Tetrahedron 2013; 69: 9045
• 11c Morikawa H, Tomishima M, Kayakiri N, Araki T, Barrett D, Akamatsu S, Matsumoto S, Uchida S, Nakai T, Takeda S, Maki K. Bioorg. Med. Chem. Lett. 2014; 24: 1172
• 12a Thomsen I, Pedersen U, Rasmussen PB, Yde B, Andersen TP, Lawesson S.-O. Chem. Lett. 1983; 12: 809
• 12b Deng H, Bernier SG, Doyle E, Lorusso J, Morgan BA, Westlin WF, Evindar G. ACS Med. Chem. Lett. 2013; 4: 942
• 12c Deokar H, Chaskar J, Chaskar A. J. Heterocycl. Chem. 2014; 51: 719
• 13a Linganna N, Lokanatha Rai KM. Synth. Commun. 1998; 28: 461
• 13b Swapna M, Premakumari C, Reddy SN, Padmaja A, Padmavathi V, Kondaiah P, Krishna NS. Chem. Pharm. Bull. 2013; 61: 722
• 13c Muralikrishna A, Mallikarjuna Reddy G, Lavanya G, Padmavathi V, Padmaja A. J. Heterocycl. Chem. 2014; 51: 179
• 14a Yella R, Khatun N, Rout SK, Patel BK. Org. Biomol. Chem. 2011; 9: 3235
• 14b Kashtoh H, Hussain S, Khan A, Saad SM, Khan JA. J, Khan KM, Perveen S, Choudhary MI. Bioorg. Med. Chem. 2014; 22: 5454
• 15a Remers WA, Gibs GJ, Weiss MJ. J. Heterocycl. Chem. 1969; 6: 835
• 15b Yu P, Hu J, Wan R, Li X, Zheng S, Xu Y. J. Chem. Res. 2014; 38: 347
• 15c Abdel-Aziem A. J. Heterocycl. Chem. 2015; 52: 251
• 16 Kudelko A, Wróblowska M. Tetrahedron Lett. 2014; 55: 3252
• 17a Kudelko A, Jasiak K. Synthesis 2013; 45: 1950
• 17b Kudelko A, Jasiak K, Ejsmont K. Monatsh. Chem. 2015; 146: 303
• 18a Suzuki A. Metal-Catalyzed Cross-Coupling Reactions. Diederich F, Stang PJ. Wiley-VCH; Weinheim: 1998. Chap. 2
• 18b Suzuki A. J. Organomet. Chem. 2002; 653: 83
• 19 Kudelko A, Wróblowska M, Jarosz T, Łaba K, Łapkowski M. ARKIVOC 2015; (v): 287
• 20 Siegrist AE, Maeder E, Dunnenberger M, Liechti P. GB 899842, 1962 ; Chem. Abstr. 1962, 57, 13767
• 21 Representative Procedure for Suzuki Coupling 2,5-Bis(4-bromophenyl)-1,3,4-thiadiazole (3, 0.40 g, 1.00 mmol), the appropriate boronic acid (2.50 mmol), tetrakis(triphenylphosphine)palladium(0) (0.06 g, 0.05 mmol), TBAB (0.03 g, 0.10 mmol), and Cs₂CO₃ (3.26 g, 10.00 mmol) were treated with a combination of toluene (10 mL), H₂O (6 mL), and EtOH (3 mL). The mixture was heated to 80 °C (oil bath) for 2–6 h (TLC monitoring). After cooling, CHCl₃ (200 mL) was added and the mixture filtered through silica gel (20 mL). The filtrate was separated, the organic layer was dried over MgSO₄ and then concentrated on a rotary evaporator. The residue was treated with a mixture of benzene–EtOAc (3:1). The solid precipitate was filtered off, washed with benzene–EtOAc (3:1) and air-dried to give the pure 2,5-disubstituted 1,3,4-thiadiazole. 3,5-Bis(4-biphenylyl)-1,3,4-thiadiazole (5a) White-pearl solid (0.34 g, 92% yield); mp 296–298 °C (lit.¹⁶ 294–296 °C). ¹H NMR (400 MHz, CDCl₃): δ = 7.41 (t, J = 7.6 Hz, 1 H), 7.49 (t, J = 7.6 Hz, 2 H), 7.66 (d, J = 7.6 Hz, 2 H), 7.74 (d, J = 8.4 Hz, 2 H), 8.11 (d, J = 8.4 Hz, 2 H). ¹³C NMR (400 MHz, CDCl₃): δ = 124.4, 127.1, 127.8, 128.1, 128.4, 129.0, 139.9, 143.9, 167.8. UV/Vis: λ_max (CHCl₃) 335.0 nm (ε · 10^–3 60.3 cm^–1 M^–1). IR (ATR): ν = 3060, 3037, 2162, 1946, 1821, 1675, 1604, 1561, 1488, 1451, 1432, 1420, 1401, 1316, 1253, 1185, 1170, 1100, 1040, 1027, 1005, 997, 988, 910, 838, 760,718, 684 cm^–1. Anal. Calcd for C₂₆H₁₈N₂S: C, 79.97; H, 4.65; N, 7.17. Found: C, 79.99; H, 4.63; N, 7.21. HRMS: m/z calcd for [C₂₆H₁₈N₂S + H⁺]: 391.1269; found: 391.1267.