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Synlett 2018; 29(02): 243-245
DOI: 10.1055/s-0036-1590910
letter
© Georg Thieme Verlag Stuttgart · New York

A Synthesis of Functionalized 2-Indolizin-3-yl-1,3-benzothiazoles from 1-(1,3-Benzothiazol-2-ylmethyl)pyridinium Iodide and ­Acetylenic Esters

Issa Yavari*
a   Department of Chemistry, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran   Email: yavarisa@modares.ac.ir
,
Kiyana Ghafouri
a   Department of Chemistry, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran   Email: yavarisa@modares.ac.ir
,
Maryam Naeimabadi
a   Department of Chemistry, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran   Email: yavarisa@modares.ac.ir
,
Mohammad Reza Halvagar
b   Department of Inorganic Chemistry, Chemistry and Chemical Engineering Research Center of Iran, PO Box 14335-186, Tehran, Iran
› Author Affiliations
Further Information

Publication History

Received: 05 August 2017

Accepted after revision: 29 August 2017

Publication Date:
20 October 2017 (online)

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Abstract

Functionalized 2-indolizin-3-yl-1,3-benzothiazoles were obtained in moderate yields from the reaction between 1-(1,3-benzothiazol-2-ylmethyl)pyridinium iodide and acetylenic esters in acetonitrile. When isoquinoline was used under similar conditions, dialkyl 3-(1,3-benzothiazol-2-yl)pyrrolo[2,1-a]isoquinoline-1,2-dicarboxylates were obtained. The structures of these products have been confirmed by ­X-ray diffractometry.

Key words

indolizinylbenzothiazoles - alkynoate esters - ylide - benzothiazolylpyrroloisoquinolines

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1590910.
  • Supporting Information
 

  • References and Notes

  • 1 Aiello S. Wells G. Stone EL. Kadri H. Bazzi R. Bell DR. Stevens MF. G. Matthews CS. Bradshaw TD. Westwell AD. J. Med. Chem. 2008; 51: 5135
    CrossrefSearch in Google Scholar
  • 2 Wang K. Guengerich FP. Chem. Res. Toxicol. 2012; 25: 1740
    CrossrefPubMedSearch in Google Scholar
  • 3 Huang Q. Mao J. Wan B. Wang Y. Brun R. Franzblau SG. Kozikowski AP. J. Med. Chem. 2009; 52: 6757
    CrossrefPubMedSearch in Google Scholar
  • 4 Huang S.-T. Hsei I.-J. Chen C. Bioorg. Med. Chem. 2006; 14: 6106
    CrossrefPubMedSearch in Google Scholar
  • 5 Singh M. Singh SK. Gangwar M. Nath G. Singh SK. RSC Adv. 2014; 4: 19013
    CrossrefSearch in Google Scholar
  • 6 Akhtar T. Hameed S. Al-Masoudi N. Loddo R. La Colla P. Acta Pharm. (Zagreb, Croatia) 2008; 58: 135
    PubMedSearch in Google Scholar
  • 7 Mortimer CG. Wells G. Crochard J.-P. Stone EL. Bradshaw TD. Stevens MF. G. Westwell AD. J. Med. Chem. 2006; 49: 179
    CrossrefSearch in Google Scholar
  • 8 Siddiqui N. Alam M. Siddiqui AA. Asian J. Chem. 2004; 16: 1005
    Search in Google Scholar
  • 9 Ghinet A. Abuhaie C.-M. Gautret P. Benoit R. Dubois J. Farce A. Belei D. Bîcu E. Eur. J. Med. Chem. 2015; 89: 115
    CrossrefPubMedSearch in Google Scholar
  • 10 Gupta SP. Mathur AN. Nagappa AN. Kumar D. Kumaran S. Eur. J. Med. Chem. 2003; 38: 867
    CrossrefPubMedSearch in Google Scholar
  • 11 Huang W. Zuo T. Jin H. Liu Z. Yang Z. Yu X. Zhang L. Zhang L. Mol. Diversity 2013; 17: 221
    CrossrefPubMedSearch in Google Scholar
  • 12 Kapat A. Nyfeler E. Giuffredi GT. Renaud P. J. Am. Chem. Soc. 2009; 131: 17746
    CrossrefPubMedSearch in Google Scholar
  • 13 Kostik EI. Abiko A. Oku A. J. Org. Chem. 2001; 66: 2618
    CrossrefPubMedSearch in Google Scholar
  • 14 Basavaiah D. Devendar B. Lenin DV. Satyanarayana T. Synlett 2009; 411
    Thieme Connect
  • 15 Rotaru AV. Druta ID. Oeser T. Müller TJ. J. Helv. Chim. Acta 2005; 88: 1798
    CrossrefSearch in Google Scholar
  • 16 Yavari I. Hosseinpour R. Skoulika S. Synlett 2015; 26: 380
    Thieme ConnectSearch in Google Scholar
  • 17 Yavari I. Naeimabadi M. Halvagar MR. Tetrahedron Lett. 2016; 57: 3718
    CrossrefSearch in Google Scholar
  • 18 Yavari I. Naeimabadi M. Hosseinpour R. Halvagar MR. Synlett 2016; 27: 2601
    Thieme ConnectSearch in Google Scholar
  • 19 3-(1,3-Benzothiazol-2-yl)indolizine-1-carboxylate Esters 4; General Procedure A mixture of 2-methyl-1,3-benzothiazole (1; 1 mmol), pyridine (2.5 mmol), and I2 (0.256 g, 1 mmol) in MeCN (3 mL) was heated at 70 °C for 12 h. Then, a solution of i-Pr2NEt (0.258 g, 2 mmol) and ester 3 (1 mmol) in MeCN (2 mL) was added and the mixture was stirred at r.t. for 3 h, then kept in a freezer for 5 h. The precipitate was collected by filtration and crystallized from hexane–EtOAc (1:7). Products 6a and 6b were similarly prepared by using isoquinoline (5) instead of pyridine. Dimethyl 3-(1,3-Benzothiazol-2-yl)indolizine-1,2-dicarboxylate (4a) Yellow crystals; yield: 0.31 g (77%); mp 156–157 °C. IR (KBr): 2941, 1727, 1696, 1511, 1380, 1219 cm–1. 1H NMR (500 MHz, CDCl3): δ = 3.98 (s, 3 H, MeO), 4.10 (s, 3 H, MeO), 7.30 (t, 3 J = 7.2 Hz, 1 H), 7.40 (t, 3 J = 7.3 Hz, 1 H), 7.56 (t, 3 J = 7.1 Hz, 1 H), 7.70 (t, 3 J = 7.3 Hz, 1 H), 7.81 (d, 3 J = 9.0 Hz, 1 H), 8.07 (d, 3 J = 9.0 Hz, 1 H), 8.35 (d, 3 J = 7.2 Hz, 1 H), 10.14 (d, 3 J = 6.7 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 52.1 (MeO), 53.2 (MeO), 115.1 (CH), 119.9 (CH), 120.3 (CH), 120.4 (C), 122.8 (CH), 125.2 (CH), 125.3 (C), 125.4 (CH), 126.2 (CH), 126.5 (CH), 128.3 (C), 133.8 (C), 137.1 (C), 152.9 (C), 156.9 (C), 163.6 (C=O), 166.8 (C=O). Anal. Calcd for C19H14N2O4S (366.39): C, 62.29; H, 3.58; N, 7.65. Found: C, 62.05; H, 3.55; N, 7.71. Dimethyl 3-(1,3-Benzothiazol-2-yl)pyrrolo[2,1-a]isoquinoline-1,2-dicarboxylate (6a) Yellow crystals; yield: 0.33 g (88%); mp 174.7–175.8 °C. IR (KBr): 2947, 1712, 1445, 1200, 758 cm–1. 1H NMR (500 MHz, CDCl3): δ = 3.97 (s, 3 H, MeO), 4.01 (s, 3 H, MeO), 7.12 (d, 3 J = 7.6 Hz, 1 H), 7.45 (t, 3 J = 7.1 Hz, 1 H), 7.53 (t, 3 J = 7.5 Hz, 1 H), 7.69 (t, 3 J = 7.8 Hz, 1 H), 7.7 (t, 3 J = 7.5 Hz, 1 H), 7.94 (d, 3 J = 7.8 Hz, 1 H), 8.14 (d, 3 J = 8.1 Hz, 1 H), 8.36 (d, 3 J = 8.4 Hz, 1 H), 9.05 (d, 3 J = 8.9 Hz, 1 H), 9.33 (d, 3 J = 9.9 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 52.7 (MeO), 52.8 (MeO), 109.5 (C), 115.4 (C), 119.0 (CH), 121.4 (CH), 122.9 (CH), 123.3 (CH), 123.3 (CH), 123.6 (CH), 123.7 (CH), 124.5 (CH), 124.6 (CH), 125.6 (CH), 126.3 (C), 127.3 (C), 129.4 (C), 131.9 (CH), 135.0 (C), 152.8 (C), 156.6 (CN), 165.8 (C=O), 167.8 (C=O). Anal. Calcd for C23H16N2O4S (416.45): C, 66.34; H, 3.87; N, 6.73. Found: C, 66.12; H, 3.90; N, 6.78.
  • 20 X-ray structure determination and refinement data for 4a and 6a: The X-ray diffraction (XRD) measurements were carried out on STOE IPDS-2T diffractometers with graphite-monochromated Mo(Kα) radiation. Each single crystal was mounted on a glass fiber and used for data collection. Yellow single crystals of compounds 4a and 6a, suitable for single-crystal XRD measurements were obtained by recrystallization from hexane–EtOAc. The structures were solved by direct methods and refined by full matrix least-squares calculations based on F2 to final R1 = 0.0395 and wR2 (all data) = 0.1104 for 4a and F2 to final R1 = 0.0464 and wR2 (all data) = 0.1186 for 6a by using SHELXL-2014 and WinGX-2013.3 programs.21 Product 4a: formula, C19H14N2O4S: monoclinic, space group P21/c, a = 10.409(2), b = 22.788(5), c = 7.3592(15) Å; β = 107.92(3)°, Z = 4, V = 1660.9(6) Å3, 5684 independent reflections. Product 12a: formula, C23H16N2O4S: monoclinic, space group P21/c, a = 12.489(3), b = 7.2745(15), c = 22.191(4) Å; β = 105.68(3)°, V = 105.68(3) Å3, 4658 independent reflections.
  • 21 CCDC 1555570 and 1555571 contain the crystallographic data for 4a and 6a, respectively. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/data_request/cif.