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; Kiyana Ghafouri; Maryam Naeimabadi; Mohammad Reza Halvagar

doi:10.1055/s-0036-1590910

Synlett, Table of Contents

Synlett 2018; 29(02): 243-245
DOI: 10.1055/s-0036-1590910

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

Authors

Issa Yavari*

^aDepartment of Chemistry, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran Email: yavarisa@modares.ac.ir
Kiyana Ghafouri

^aDepartment of Chemistry, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran Email: yavarisa@modares.ac.ir
Maryam Naeimabadi

^aDepartment of Chemistry, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran Email: yavarisa@modares.ac.ir
Mohammad Reza Halvagar

^bDepartment of Inorganic Chemistry, Chemistry and Chemical Engineering Research Center of Iran, PO Box 14335-186, Tehran, Iran

Abstract

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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

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References

References and Notes
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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.

For details, see:

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

Authors

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