Efficient Synthesis of Benzoselenazoles and Benzothiazoles by an Ullmann Coupling of Dihalobenzenes with Acyl Iso(seleno/thio) cyanate–Malononitrile Adducts

Abstract

We describe a simple and efficient method for the synthesis of various benzoselenazoles and benzothiazoles by the Ullman coupling reaction of dihalobenzenes with acyl iso(seleno/thio)cyanate–malononitrile adducts in the presence of a copper catalyst with K₂CO₃ as a base at room temperature, without the help of additional ligands. Notable features of this protocol include the use of mild copper-catalyzed reaction conditions, simple and readily available raw materials, easy purification with the help of a solvent, and the synthesis of 17 new benzoselenazole and benzothiazole compounds.

Key words

Ullmann coupling - benzoselenazoles - benzothiazoles - acyl isoselenocyanates - acyl isothiocyanates - malononitrile

• References and Notes

• 1 Gao X, Liu J, Zuo X, Feng X, Gao Y. Molecules 2020; 25: 1675
• 2 Liao C, Kim U.-J, Kannan K. Environ. Sci. Technol. 2018; 52: 5007
• 3 Banerjee S, Payra S, Saha A. Curr. Organocatal. 2017; 4: 164
• 4 Singh MK, Tilak R, Nath G, Awasthi SK, Agarwal A. Eur. J. Med. Chem. 2013; 63: 635
• 5 Hu P, Li W, Li Y, Su Y, Zhang B, Shen L. Catal. Lett. 2024; 154: 2396
• 6 Geisler K, Kunzler A, Below H, Bulka E, Pfeiffer W.-D, Langer P. Synlett 2003; 1195
• 7 Fujiwara S.-i, Asanuma Y, Shin-ike T, Kambe N. J. Org. Chem. 2007; 72: 8087
• 8 Kaname M, Minoura M, Sashida H. Tetrahedron Lett. 2011; 52: 505
• 9 Kobayashi K, Yokoi Y. Helv. Chim. Acta 2012; 95: 761
• 10 Časar Z, Majcen-Le Marécha A, Lorcy D. New J. Chem. 2003; 27: 1622
• 11 Su T, Xie S, Li B, Yian J, Huang L, Li X. Synlett 2015; 215
• 12 Redon S, Kabri Y, Crozet MD, Vanelle P. Tetrahedron Lett. 2014; 55: 5052
• 13 Schwartz Radatz C, Rampon DS, Balaguez RA, Alves D, Schneider PH. Eur. J. Org. Chem. 2014; 6945
• 14 Volkova KD, Kovalska VB, Losytskyy MY, Bento A, Reis LV, Santos PF, Almeida P, Yarmoluk SM. J. Fluoresc. 2008; 18: 877
• 15 Conley NR, Dragulescu-Andrasi A, Rao J, Moerner WE. Angew. Chem. Int. Ed. 2012; 51: 3350
• 16 Braga AL, Rodrigues OE. D, Paixão MW, Appelt HR, Silveira CC, Bottega DP. Synthesis 2002; 2338
• 17 Rambo RS, Schneider PH. Tetrahedron: Asymmetry 2010; 21: 2254
• 18 Braga AL, Vargas F, Sehnem JA, Braga RC. J. Org. Chem. 2005; 70: 9021
• 19 Braga AL, Paixão MW, Marin G. Synlett 2005; 1675
• 20 Freudendahl DM, Shahzad SA, Wirth T. Eur. J. Org. Chem. 2009; 1649
• 21 Santos PF, Reis LV, Almeida P, Serrano JP, Oliveira AS, Vieira Ferreira LF. J. Photochem. Photobiol., A 2004; 163: 267
• 22 Reis LV, Serrano JP. C, Almeida P, Santos PF. Synlett 2002; 1617
• 23 Gandin V, Khalkar P, Braude J, Fernandes AP. Free Radical Biol. Med. 2018; 127: 80
• 24 Yadav M, Singh VP. J. Org. Chem. 2023; 88: 16934
• 25 Bogert MT, Stull A. J. Am. Chem. Soc. 1927; 49: 2011
• 26 Balaguez RA, Betin ES, Barcellos E, Lenardao EJ, Alves D, Schumacher RF. New J. Chem. 2017; 41: 1483
• 27 Freeman F. Chem. Rev. 1969; 69: 591
• 28 Lin Z, Zhang W, Wang L, Yu H, Wu C. Toxicol. Mech. Methods 2003; 13: 241
• 29 Jain AK, Sharma S, Vaidya A, Ravichandran V, Agrawal RK. Chem. Biol. Drug. Des. 2013; 81: 557
• 30 Junek H, Hamböck H. Mikrochim. Acta 1966; 54: 522
• 31 Junek H, Hamböck H, Sterk H. Monatsh. Chem. 1968; 99: 1028
• 32 Hassan SS. J. - Assoc. Off. Anal. Chem. 1981; 64: 611
• 33 Hornum M, Kongsted J, Reinholdt P. Phys. Chem. Chem. Phys. 2021; 23: 9139
• 34 Ullmann F, Sponagel P. Ber. Dtsch. Chem. Ges. 1905; 38: 2211
• 35 Evano G, Blanchard N, Toumi M. Chem. Rev. 2008; 108: 3054
• 36 Correa A, Carril M, Bolm C. Angew. Chem. Int. Ed. 2008; 47: 2880
• 37 Beletskaya IP, Ananikov VP. Chem. Rev. 2022; 122: 16110
• 38 Didehban K, Vessally E, Hosseinian A, Edjlali L, Saedi Khosroshahi E. RSC Adv. 2018; 8: 291
• 39 Zhang Y, Ngeow KC, Ying JY. Org. Lett. 2007; 9: 3495
• 40 Zhu W, Ma D. J. Org. Chem. 2005; 70: 2696
• 41 Hassan J, Sévignon M, Gozzi C, Schulz E, Lemaire M. Chem. Rev. 2002; 102: 1359
• 42 Nematpour M, Jahani M, Tabatabai SA. J. Iran. Chem. Soc. 2019; 16: 603
• 43 Yavari I, Nematpour M. Mol. Diversity 2015; 19: 703
• 44 Yavari I, Nematpour M. Helv. Chim. Acta 2014; 97: 1132
• 45 Yavari I, Nematpour M, Damghani T. Tetrahedron Lett. 2014; 55: 1323
• 46 Nematpour M. ChemistrySelect 2024; 9: e202400871
• 47 Nematpour M. Tetrahedron 2024; 163: 134145
• 48 Seyed-Talebi SM, Kazeminezhad I, Nematpour M. J. Catal. 2018; 361: 339
• 49 (3-Benzoyl-1,3-benzoselenazol-2(3H)-ylidene)malononitrile (7a); Typical Procedure A mixture of KSeCN (2; 1.5 mmol), and BzCl (1a; 1.5 mmol) in acetone (1 mL) was stirred for 10 min. The resulting acyl isoselenocyanate 5a, malononitrile (3; 1.0 mmol), and NaH (1.0 mmol) were dissolved in THF (3 mL), and the mixture was stirred for 15 min. A mixture of ortho-diiodobenzene (4a, 1.5 mmol), CuI (0.1 mmol), and K₂CO₃ (2.0 mmol) in THF (2 mL) was slowly added, and the resulting mixture was stirred for 4 h at r.t. until the reaction was complete [TLC (EtOAc–hexane, 1:6)]. The mixture was then diluted with CH₂Cl₂ (2 mL) and aq NH₄Cl (3 mL), and stirred for 10 min. The layers were separated and the aqueous layer was extracted with CH₂Cl₂. The combined organic fractions were dried (Na₂SO₄) and concentrated under reduced pressure, and the residue was washed with 3:1 hexane–EtOAc to remove impurities, giving a white powder; yield: 0.30 g (85%); mp 125–127 °C. IR (KBr): 2251, 2232, 1689, 1549, 1312, 965 cm^–1. ¹H NMR (500 MHz, CDCl3): δ = 7.07 (t, ³ J = 7.8 Hz, 1 H, Ar), 7.18 (d, ³ J = 7.6 Hz, 1 H, Ar), 7.21 (t, ³ J = 7.6 Hz, 1 H, Ar), 7.30 (t, ³ J = 7.6 Hz, 1 H, Ar), 7.62 (t, ³ J= 7.8 Hz, Ar, 2 H), 7.73 (d, ³ J = 7.6 Hz, 1 H, Ar), 8.05 (d, ³ J = 7.8 Hz, 2 H, Ar). ¹³C NMR (125.7 MHz, CDCl3): δ = 70.2 (C), 115.7 (CN), 117.2 (CN), 125.1 (CH), 126.1 (CH), 127.4 (2 CH), 127.8 (CH), 128.0 (CH), 128.9 (2 CH), 129.9 (CH), 133.9 (C), 135.7 (C), 142.3 (C), 167.3 (C=O), 180.2 (C). MS (EI-MS): m/z (%) = 350 (11) [M⁺; C₁₇H₉N₃OSe], 286 (21) [C₁₄H₉NOSe], 273 (100) [C₁₁H₄N₃OSe], 245 (52) [C₁₀H₄N₃Se], 105 (23) [C₇H₅O], 77 (64) [C₃N₂]. Anal. Calcd for C₁₇H₉N₃OSe (350.23): C, 58.30; H, 2.59; N, 12.00. Found: C, 58.32; H, 2.54; N, 12.04.