Zinc Chloride Catalyzed, Dipolar Aprotic Solvent-Mediated, One-Pot Synthesis of 2-[(Benzo[d]thiazol-2-ylamino)(phenyl)methyl]phenols

^◊ Both the authors contributed equally.

Abstract

A three-component one-pot method has been developed for the synthesis of 2-[(benzo[d]thiazol-2-ylamino)(phenyl)methyl]phenols from a variety of aldehydes, 2-amino-1,3-benzothiazoles, and phenols. Phenol, substituted phenols, and polyhydroxybenzenes participated well, providing the corresponding derivatives in good yields. In the case of polyhydroxybenzenes, for which the formation of positional isomers or dimers might have been possible, the sterically less hindered positional isomer was formed exclusively via the ortho-quinone methide.

Key words

Betti bases - benzothiazoles - phenols - aldehydes - quinone methides

• References and Notes

• 1a Betti M. Gazz. Chim. Ital. 1900; 30: 301
• 1b Betti M. Gazz. Chim. Ital. 1900; 30: 310
• 2a Szatmári I, Sillanpää R, Fülöp F. Tetrahedron: Asymmetry 2008; 19: 612
• 2b Radosevich AT, Chan VS, Shih H.-W, Toste FD. Angew. Chem. Int. Ed. 2008; 47: 3755
• 3a Periasamy M, Reddy MN, Anwar S. Tetrahedron: Asymmetry 2004; 15: 1809

For a review on Betti bases, see:
• 3b Cardellicchio C, Capozzi MA. M, Naso F. Tetrahedron: Asymmetry 2010; 21: 507
• 4a Kantevari S, Yempala T, Yogeeswari P, Sriram D, Sridhar B. Bioorg. Med. Chem. Lett. 2011; 21: 4316
• 4b Kalavagunta PK, Bagul PK, Jallapally A, Kantevari S, Banerjee SK, Ravirala N. Eur. J. Med. Chem. 2014; 83: 344
• 4c Kalavagunta PK, Pala R, Pathipati UR, Ravirala N. J. Agric. Food Chem. 2014; 62: 6571
• 4d Serrao E, Debnath B, Otake H, Kuang Y, Christ F, Debyser Z, Neamati N. J. Med. Chem. 2013; 56: 2311
• 4e Khandarkar KM, Shanti MD, Ahmed M, Meshram JS. J. Chem. Sci. (Berlin, Ger.) 2013; 125: 1573
• 4f Venugopala KN, Krishnappa M, Nayak SK, Subrahmanya BK, Vaderapura JP, Chalannavar RK, Gleiser RM, Odhav B. Eur. J. Med. Chem. 2013; 65: 295
• 5a Adrom B, Maghsoodlou MT, Hazeri N, Lashkari M. Res. Chem. Intermed. 2015; 41: 7553
• 5b Gudipati SR, Srinivas B, Ramachandraiah A. Mol. Cryst. Liq. Cryst. 2014; 605: 225
• 5c Tayebee R, Amini MM, Akbari M, Aliakbari A. Dalton Trans. 2015; 44: 9596
• 5d Tayebee R, Amini MM, Rostamian H, Aliakbari A. Dalton Trans. 2014; 43: 1550
• 5e Sahu PK, Sahu PK, Agarwal DD. RSC Adv. 2015; 5: 69143
• 5f Sahu PK, Sahu PK, Thavaselvam D, Alafeefy AM, Agarwal DD. Med. Chem. Res. 2015; 24: 725
• 6 Cherkadu V, Kalavagunta PK, Ningegowda M, Shivananju NS, Madegowda M, Priya BS. Synlett 2016; 27: 1116
• 7a Taghrir H, Ghashang M, Biregan MN. Chin. Chem. Lett. 2016; 27: 119
• 7b Kantevari S, Yempala T, Vuppalapati SV. N. Synthesis 2010; 959
• 8 Olyaei A, Zarnegar M, Sadeghpour M, Rezaei M. Lett. Org. Chem. 2012; 9: 451
• 9a Emmadi NR, Atmakur K, Chennapuram M, Nanubolu JB. RSC Adv. 2014; 4: 14501
• 9b Karami B, Farahi M, Farmani N, Tanuraghaj HM. New J. Chem. 2016; 40: 1715
• 10a Salgado-Escobar O, Chavelas-Hernández L, Domínguez-Mendoza BE, Linzaga-Elizalde I, Ordoñez M. Molecules. 2015; 20: 13794
• 10b Moosavi-Zare AR, Zolfigol MA, Daraei M. Synlett 2014; 25: 1173
• 10c Jameel AA, Padusha MS. A, Ibrahim KS. S. Asian J. Chem. 2011; 23: 1269
• 10d Jameel AA, Padusha MS. A. Asian J. Chem. 2010; 22: 3422
• 10e Barroso S, Abreu AM, Araújo AC, Coelho AM, Maulide N, Martins AM. Synlett 2010; 2425
• 10f Shaabani A, Rahmati A, Farhangi E. Tetrahedron Lett. 2007; 48: 7291
• 10g Jurd L. J. Heterocycl. Chem. 1997; 34: 601
• 10h Mulla SA. R, Salama TA, Pathan MY, Inamdar SM, Chavan SS. Tetrahedron Lett. 2013; 54: 672
• 11a Zagol-Ikapitte I, Amarnath V, Bala M, Roberts LJ. II, Oates JA, Boutaud O. Chem. Res. Toxicol. 2010; 23: 240
• 11b Lu X, Rodríguez M, Gu W, Silverman RB. Bioorg. Med. Chem. 2003; 11: 4423
• 11c Goodwin BL, Ruthven CR. J, Sandler M. Xenobiotica. 1994; 24: 129
• 11d Meek AR, Simms GA, Weaver DF. Can. J. Chem. 2012; 90: 865
• 12a Szucova L, Zatloukal M, Spichal L, Voller J, Dolezal K, Strnad M, Massino FJ. US 2009170879, 2009
• 12b Uksova K, Havlicek L, Krystof V, Lenobel R, Strnad M. WO 2004018473, 2004
• 12c Shi J, Zhang J, Yue Z, Li M, Zhu C, Zhang Y, Zi J, Wang Y, Fan X, Xu R, Lin S, Li Y, Yang Y, Sheng L. EP 2511283, 2012
• 12d Dolezal K, Popa I, Zatloukal M, Lenobel R, Hradecká D, Vojtesek B, Uldrijan S, Mlejnek P, Werbrouck S, Strnad M. WO 2004058791, 2004
• 12e Shi J, Zhang J, Yue Z, Li M, Zhu C, Zhang Y, Zi J, Wang Y, Fan X, Xu R, Lin S, Li Y, Yang Y, Sheng L. US 2013045942, 2013
• 13a Agliardi S, Del Sordo S, Mailland F, Legora M. WO 2011080265, 2011
• 13b Agliardi S, Del Sordo S, Mailland F, Legora M. EP 2345642, 2011
• 14a Zhao Z, Wolkenberg SE, Lu M, Munshi V, Moyer G, Feng M, Carella AV, Ecto LT, Gabryelski LJ, Lai M.-T, Prasad SG, Yan Y, McGaughey GB, Miller MD, Lindsley CW, Hartman GD, Vacca JP, Williams TM. Bioorg. Med. Chem. Lett. 2008; 18: 554
• 14b Wolkenberg SE, Zhao Z, Lindsley C. WO 2007002368, 2007
• 15a Silverman RB, Xue F. US 2012088798, 2012
• 15b Labby KJ, Xue F, Kraus JM, Ji H, Mataka J, Li H, Martásek P, Roman LJ, Poulos TL, Silverman RB. Bioorg. Med. Chem. 2012; 20: 2435
• 15c Calderone V, Fiamingo FL, Amato G, Giorgi I, Livi O, Martelli A, Martinotti E. Eur. J. Med. Chem. 2008; 43: 2618
• 15d Pajouhesh H, Kaul R, Grimwood M, Tan J, Zhou Y. US 2009298834, 2009
• 15e Kuehnert S, Merla B, Bahrenberg G, Schroeder W. US 2010234429, 2010
• 15f Harris RN. III, Repke DB, Walker KA. M. US 2012157494, 2012
• 16a Tripathi RP, Saxena N, Tiwari VK, Verma SS, Chaturvedi V, Manju YK, Srivastva AK, Gaikwad A, Sinha S. Bioorg. Med. Chem. 2006; 14: 8186
• 16b Qiao C, Wilson DJ, Bennett EM, Aldrich CC. J. Am. Chem. Soc. 2007; 129: 6350
• 16c Somu RV, Boshoff H, Qiao C, Bennett EM, Barry CE, Aldrich CC. J. Med. Chem. 2006; 49: 31
• 16d Dobrikov GM, Valcheva V, Stoilova-Disheva M, Momekov G, Tzvetkova P, Chimov A, Dimitrov V. Eur. J. Med. Chem. 2012; 48: 45
• 17 Jorda R, Sacerdoti-Sierra N, Voller J, Havlíček L, Kráčalíková K, Nowicki MW, Nasereddin A, Kryštof V, Strnad M, Walkinshaw MD, Jaffe CL. Bioorg. Med. Chem. Lett. 2011; 21: 4233
• 18a Frost AE, Freedman HH, Westerback SJ, Martell AE. J. Am. Chem. Soc. 1958; 80: 530
• 18b Kerber E, Morcos A. WO 2005120232, 2005
• 18c Sritharan M, Asuthkar S. Indian J. Med. Microbiol. 2004; 22: 92
• 18d Madhyastha S. US 2005049181, 2005
• 19 Nimmrich V, Barghorn S, Ebert U, Hillen H, Gross G, Draguhn A, Bruehl C, Grimm C, Krantz C. WO 2008104386, 2008
• 20 Collins SJ, Si J. US 2008255244, 2008
• 21 Lee W.-H, Chen P.-L, Zhou L, Zhu J. WO 2007120726, 2007
• 22 Tiollier J, Sicard H, Bonnafous C. WO 2008059052, 2008
• 23a Shen H, Kannari K, Yamato H, Arai A, Matsunaga M. Tohoku J. Exp. Med. 2003; 199: 149
• 23b Ryan M, Slevin JT. Am. J. Health-Syst. Pharm. 2006; 63: 1599
• 24 Kumar KP, Satyanarayana S, Reddy PL, Narasimhulu G, Ravirala N, Reddy BV. S. Tetrahedron Lett. 2012; 53: 1738
• 25 Chinta RR, Harikrishna V, Tulam VK, Mainkar PS, Dubey PK. Asian J. Chem. 2016; 28: 899
• 26 Redlich C, Beckett WS, Sparer J, Barwick KW, Riely CA, Miller H, Sigal SL, Shalat SL, Cullen MR. Ann. Intern. Med. 1988; 108: 680
• 27 Kerton FK. Alternative Solvents for Green Chemistry . RSC; Cambridge: 2009. Chap. 1 14
• 28 Vinci D, Donaldson M, Hallett JP, John EA, Pollet P, Thomas CA, Grilly JD, Jessop PG, Liotta CL, Eckert CA. Chem. Commun. 2007; 1427
• 29a Gunasekaran P, Prasanna P, Perumal S, Almansour AI. Tetrahedron Lett. 2013; 54: 3248
• 29b Rahman MA, Karim MR, Arifuzzaman M, Siddiquee TA, Mirza AH. Tetrahedron Lett. 2014; 55: 3267
• 30 CCDC 1469602 contains the supplementary crystallographic data for compound 4f. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
• 31 2-[(Benzo[d]thiazol-2-ylamino)(4-methoxyphenyl)methyl]-4-chlorophenol (4e); Typical Procedure ZnCl₂ (14 mg, 0.1 mmol, 0.1 equiv) was added to a solution of p-anisaldehyde (136 mg, 1 mmol, 1 equiv), 4-chlorophenol (128 mg, 1 mmol, 1 equiv), and 2-aminobenzothiazole (135 mg, 0.9 mmol, 0.9 equiv) in DMSO (1 mL), and the mixture was heated at 110 °C for 3 h. The mixture was then cooled and extracted with EtOAc (3 × 10 mL). The combined extracts were washed sequentially with H₂O (5 mL) and brine (5 mL) then dried (MgSO₄) and filtered. The organic layer was concentrated under reduced pressure, and the crude product was purified by column chromatography (silica gel, hexane–EtOAc) and washed with pentane to give a brownish-yellow solid; yield: 233 mg (65%); mp 194 °C. ¹H NMR (300 MHz, DMSO-d ₆): δ = 9.97–9.84 (br s, 1 H), 8.43 (d, J = 7.6 Hz, 1 H), 7.48 (d, J = 7.6 Hz, 1 H), 7.31 (d, J = 7.9 Hz, 1 H), 7.25–7.08 (m, 4 H), 7.00–6.89 (m, 2 H), 6.82–6.72 (m, 3 H), 6.35 (d, J = 6.6 Hz, 1 H), 3.68 (s, 3 H). HRMS: m/z calcd for C₂₁H₁₈ClN₂O₂S = 397.0772; found: 397.0746.