An Efficient Aromatization of 2-Amino-4,5,6,7-tetrahydrobenzo-[b]thiophene-3-carboxylates in Dimethyl Sulfoxide Catalyzed by p-Toluenesulfonic Acid

Mehdi Adib; Mehd Soheilizad; Saideh Rajai-daryasaraei; Peiman Mirzaei

doi:10.1055/s-0034-1379998

Synlett, Table of Contents

Synlett 2015; 26(08): 1101-1105
DOI: 10.1055/s-0034-1379998

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An Efficient Aromatization of 2-Amino-4,5,6,7-tetrahydrobenzo-[b]thiophene-3-carboxylates in Dimethyl Sulfoxide Catalyzed by p-Toluenesulfonic Acid

Mehdi Adib*

^aSchool of Chemistry, College of Science, University of Tehran, P. O. Box 14155-6455, Tehran, Iran Email: madib@khayam.ut.ac.ir

,

Mehd Soheilizad

^aSchool of Chemistry, College of Science, University of Tehran, P. O. Box 14155-6455, Tehran, Iran Email: madib@khayam.ut.ac.ir

,

Saideh Rajai-daryasaraei

^aSchool of Chemistry, College of Science, University of Tehran, P. O. Box 14155-6455, Tehran, Iran Email: madib@khayam.ut.ac.ir

,

Peiman Mirzaei

^bDepartment of Chemistry, Shahid Beheshti University, Tehran, Iran

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Abstract

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Abstract

A novel oxidation–aromatization of alkyl 2-amino-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylates is reported. The Gewald product, obtained from three-component condensation reaction between a cyclohexanone, an alkyl cyanoacetate, and sulfur, underwent an oxidation reaction in dimethyl sulfoxide in the presence of a catalytic amount of p-toluenesulfonic acid to give the corresponding alkyl 2-aminobenzo[b]thiophene-3-carboxylate in excellent yield.

Key words

2-aminobenzo[b]thiophene-3-carboxylates - Gewald reaction - oxidation–aromatization - dimethyl sulfoxide - p-toluenesulfonic acid

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References

References and Notes
1 Abreu AS, Ferreira PM. T, Monteiro LS, Queiroz MJ. R. P, Ferreira IC. F. R, Calhelha RC, Estevinho LM. Tetrahedron 2004; 60: 11821
2 Raga MM, Moreno-Mañas M, Cuberes MR, Palacín C, Castelló JM, Ortiz JA. Arzneim. Forsch. 1992; 42: 691
3 Mourey RJ, Burnette BL, Brustkern SJ, Daniels JS, Hirsch JL, Hood WF, Meyers MJ, Mnich SJ, Pierce BS, Saabye MJ, Schindler JF, South SA, Webb EG, Zhang J, Anderson DR. J. Pharmacol. Exp. Ther. 2010; 333: 797
4 Black LJ, Jones CD, Falcone JF. Life Sci. 1983; 32: 1031

5a Chen Z, Mocharla VP, Farmer JM, Pettit GR, Hamel E, Pinney KG. J. Org. Chem. 2000; 65: 8811
5b Flynn BL, Flynn GP, Hamel E, Jung MK. Bioorg. Med. Chem. Lett. 2001; 11: 2341

6 Markwell RE, Smith SA, Ward RW. US 4548948 (A), 1985
7 Burkart SE, Davis SG, Lutomski KA, Meier GA, Phillips RB, Roush DM. US 5073564 (A), 1991
8 Tao ZF, Hasvold LA, Leverson JD, Han EK, Guan R, Johnson EF, Stoll VS, Stewart KD, Stamper G, Soni N, Bouska JJ, Luo Y, Sowin TJ, Lin NH, Giranda VS, Rosenberg SH, Penning TD. J. Med. Chem. 2009; 52: 6621
9 Laporte MG, Lessen TA, Leister L, Cebzanov D, Amparo E, Faust C, Ortlip D, Bailey TR, Nitz TJ, Chunduru SK, Young DC, Burns CJ. Bioorg. Med. Chem. Lett. 2006; 16: 100

10a Arndt HD. Angew. Chem. 2006; 118: 4664
10b Kellen JA. In Vivo 2001; 15: 459
10c Jordan VC. J. Med. Chem. 2003; 46: 1081
10d Detre S, Riddler S, Salter J, A’Hern R, Dowsett M, Johnston SR. D. Cancer Res. 2003; 63: 6516
10e Rossi A, Pergola C, Koeberle A, Hoffmann M, Dehm F, Bramanti P, Cuzzocrea S, Werz O, Sautebin L. Br. J. Pharmacol. 2010; 161: 555
10f Qin Z, Kastrati I, Chandrasena RE. P, Liu H, Yao P, Petukhov PA, Bolton JL, Thatcher GR. J. J. Med. Chem. 2007; 50: 2682
10g Liu H, Liu J, van Breemen RB, Thatcher GR, Bolton JL. Chem. Res. Toxicol. 2005; 18: 162

11a Fouad I, Mechbal Z, Chane-Ching KI, Adenier A, Maurel F, Aaron JJ, Vodicka P, Cernovska K, Kozmik V, Svoboda J. J. Mater. Chem. 2004; 14: 1711
11b Jung KH, Kim KH, Lee DH, Jung DS, Park CE, Choi DH. Org. Electron. 2010; 11: 1584

12a Tietze LF, Lohmann JK, Stadler C. Synlett 2004; 1113
12b Tietze LF, Thede K, Schimpf R, Sannicolo F. Chem. Commun. 2000; 583

13 Nakamaya J In Comprehensive Heterocyclic Chemistry II . Vol. 2. Katritzky AR, Rees CW, Scriven EF. V. Chapt. 11 Pergamon Press; London: 1996: 607-677 ; and references cited therein
14 Sato O, Nakayama J In Comprehensive Heterocyclic Chemistry III . Vol 3. Katritzky AR, Ramsden CA, Scriven EF. V, Taylor RJ. K. Chapt. 11 Elsevier Science; Oxford: 2008: 843-922 ; and references cited therein

15a Kim S, Dahal N, Kesharwani T. Tetrahedron Lett. 2013; 54: 4373
15b Teplyakov FS, Vasileva TG, Petrov ML, Androsov DA. Org. Lett. 2013; 15: 4038
15c Romagnoli R, Baraldi PG, Lopez-Cara C, Preti D, Aghazadeh Tabrizi M, Balzarini J, Bassetto M, Brancale A, Fu XH, Gao Y, Li J, Zhang SZ, Hamel E, Bortolozzi R, Basso G, Viola G. J. Med. Chem. 2013; 56: 9296
15d Lyapunova AG, Androsov DA, Petrov ML. Tetrahedron Lett. 2013; 54: 3427
15e Hari DP, Hering T, König B. Org. Lett. 2012; 14: 5334
15f Han J, Wang Q, Chang X, Liu Y, Wang Y, Meng J. Tetrahedron 2011; 67: 8865
15g Mésangeau C, Fraise M, Delagrange P, Caignard DH, Boutin JA, Berthelot P, Yous S. Eur. J. Med. Chem. 2011; 46: 1835
15h Duan Z, Ranjit S, Liu X. Org. Lett. 2010; 12: 2430
15i Isloor AM, Kalluraya B, Pai KS. Eur. J. Med. Chem. 2010; 45: 825
15j Kobayashi K, Horiuchi M, Fukamachi S, Konishi H. Tetrahedron 2009; 65: 2430
15k Pradhan TK, De A. Tetrahedron Lett. 2005; 46: 1493

16 Zhang X, Zhou X, Kisliuk RL, Piraino J, Cody V, Gangjee A. Bioorg. Med. Chem. 2011; 19: 3585
17 Seio K, Tanaka H, Kohara T, Hashimoto K, Fujimura M, Horiuchi H, Yasumatsu Y, Kimura K. US 6271225 (B1), 2001
18 Eiden F, Felbermeir G. Arch. Pharm. 1984; 317: 675
19 Gewald N, Neumann G, Böttcher H. Z. Chem. 1966; 6: 261

20a Adib M, Sheikhi E, Haghshenas P, Rajai-Daryasarei S, Bijanzadeh HR. Zhu L. G. Tetrahedron Lett. 2014; 55: 4983
20b Adib M, Sheikhi E, Bagheri M, Bijanzadeh HR, Amanlou M. Tetrahedron 2012; 68: 3237
20c Adib M, Sheikhi E, Rezaei N. Tetrahedron Lett. 2011; 52: 3191
20d Adib M, Ansari S, Bijanzadeh HR. Synlett 2011; 619
20e Adib M, Karimzadeh M, Mahdavi M, Sheikhi E, Mirzaei P. Synlett 2011; 834

21 Adib M, Bayanati M, Soheilizad M, Janatian Ghazvini H, Tajbakhsh M, Amanlou M. Synlett 2014; 25: 2918
22 General Procedure for the Preparation of Methyl 2-Aminobenzo[b]thiophene-3-carboxylate (7a) A mixture of cyclohexanone (0.196 g, 2.0 mmol), methyl cyanoacetate (0.198 g, 2.0 mmol), elemental sulfur (0.064 g, 2.0 mmol), and morpholine (0.174 g, 2.0 mmol) was heated at 75 °C for 1 h. After nearly complete conversion into the corresponding 2-aminothiophene, as was indicated by TLC monitoring, the reaction mixture was cooled to r.t., and the solid residue was recrystallized from EtOH to afford methyl 2-amino-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylate (6a ). Then a solution of 6a (0.211 g, 1 mmol) and TsOH (0.052 g, 0.3 mmol) in DMSO (1 mL) was heated at 190 °C for 45 min in a silicone oil bath. Progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was cooled to r.t., H₂O (4 mL) was added to the mixture, which then was extracted with CH₂Cl₂ (3 × 5 mL). The extract was dried with Na₂SO₄, and the solvent was removed. The residue was crystallized from n-hexane–EtOAc (5:1) to afford the pure product as pale yellow crystals, mp 126–128 °C, yield 0.203 g, 98% (on the basis of 6a). IR (KBr): ν_max = 3395, 3280 and 3167 (NH), 1647 (C=O), 1591, 1493, 1464, 1431, 1372, 1275, 1231, 1146, 1011, 779, 741, 662 cm^–1. MS: m/z (%) = 207 (95) [M⁺], 175 (100), 147 (40), 121 (37), 103 (8), 77 (9), 69 (6). ¹H NMR (500.1 MHz, CDCl₃): δ = 3.97 (s, 3 H, CH₃), 6.55 (br s, 2 H, NH₂), 7.16 (td, J = 7.6, 1.2 Hz, 1 H, CH), 7.34 (td, J = 7.8, 1.2 Hz, 1 H, CH), 7.52 (d, J = 8.0 Hz, 1 H, CH), 8.10 (d, J = 8.0 Hz, 1 H, CH). ¹³C NMR (100.6 MHz, CDCl₃): δ = 51.1 (OCH₃), 99.7 (CCO₂), 121.4, 122.4, 122.5 and 125.5 (4 × CH), 128.8 and 137.3 (2 × C), 164.5 (SCN), 166.7 (C=O).