A Synthesis of Spirocyclic Oxazinoisoquinolines and Oxazinoquinolines Bearing Thiazolopyrimidine Moieties

Issa Yavari; Mahniya Hojati; Leila Azad; Mohammad R. Halvagar

doi:10.1055/s-0037-1609302

Synlett, Table of Contents

Synlett 2018; 29(08): 1024-1027
DOI: 10.1055/s-0037-1609302

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A Synthesis of Spirocyclic Oxazinoisoquinolines and Oxazinoquinolines Bearing Thiazolopyrimidine Moieties

Issa Yavari*

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

,

Mahniya Hojati

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

,

Leila Azad

^bDepartment of Chemistry, Islamic Azad University, Khodabandeh Branch, Khodabandeh, Zanjan, Iran

,

Mohammad R. Halvagar

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

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Abstract

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Abstract

The reaction of isoquinoline or quinoline with dialkyl acetylenedicarboxylates in the presence of alkyl 2-{3,5-dioxo-5H-thiazolo[3,2-a]pyrimidin-2(3H)-ylidene}acetates (generated in situ from acetylenedicarboxylates and 2-thiouracils) led to dialkyl 2-(2-alkoxy-2-oxoethylidene)-5-oxo-2H,5H,11b′H-spiro{thiazolo[3,2-a]pyrimidine-3,2′-[1,3]oxazino[2,3-a]isoquinoline}-3′,4′-dicarboxylates or dialkyl 2-(2-alkoxy-2-oxoethylidene)-5-oxo-2H,4a′H,5H-spiro{thiazolo[3,2-a]pyrimidine-3,2′-[1,3]oxazino[3,2-a]quinoline}-1′,2′-dicarboxylates in good yields. The structure of the target compounds was confirmed by X-ray diffraction study.

Key words

Huisgen’s 1,4-dipole - N-heterocycles - acetylenic esters - spiro compounds - thiouracil

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References

References and Notes
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16 General Procedure for the Preparation of Compounds 4 and 6 To a stirred solution of 2 (2 mmol) and 3 (1 mmol) in toluene (10 mL) at reflux was added dropwise a solution of isoquinoline or quinoline (0.286 g, 1 mmol) in toluene (4 mL). After completion of the reaction as evidenced by TLC, the solvent was evaporated and the residue was recrystallized from AcOEt/n-hexane (1:3) to afford the pure product. Dimethyl 2-(2-Methoxy-2-oxoethylidene)-5-oxo-2H,5H,11b′H-spiro[thiazolo[3,2-a]pyrimidine-3,2′-[1,3]oxazino[2,3-a]isoquinoline]-3′,4′-dicarboxylate (4a) Yellow crystals; mp 88–90 °C; yield 0.43 g (85%). IR (KBr): ν_max = 1748 (C=O), 1711 (C=O), 1628 (C=O) cm^–1. ¹H NMR: δ = 3.63 (3 H, s, MeO), 3.77 (3 H, s, MeO), 3.96 (3 H, s, MeO), 5.95 (1 H, d, ³J = 7.8 Hz, CH), 6.13 (1 H, s, CH), 6.25 (1 H, d, ³ J = 6.5 Hz, CH), 6.45 (1 H, d, ³ J = 7.7 Hz, CH), 7.16 (1 H, d, ³ J = 7.6 Hz, CH), 7.30 (1 H, d, ³ J = 7.6 Hz, CH), 7.34–742 (2 H, m, CH), 7.51 (1 H, s, CH), 7.84 (1 H, d, ³ J = 6.5 Hz, CH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 52.5 (MeO), 52.6 (MeO), 54.1 (MeO), 83.3 (CH), 95.9 (C), 107.0 (CH), 108.9 (C), 112.4 (CH), 113.1 (CH), 123.5 (CH), 125.8 (C), 126.0 (CH), 128.0 (CH), 128.5 (CH), 129.4 (C), 130.4 (CH), 146.1 (C), 153.9 (CH), 154.3 (C), 161.4, 162.8, 162.9, 163.2, 166.7 (5 C, C=O and C=N). MS (EI, 70 eV): m/z (%) = 509 (15) [M⁺], 386 (27), 321 (100), 294 (20), 281 (17), 254 (50), 226 (36), 129 (80). Anal. Calcd for C₂₄H₁₉N₃O₈S (509.49): C, 56.58; H, 3.76; N, 8.25%. Found: C, 56.42; H, 3.78; N, 8.27%. Dimethyl 2-(2-Methoxy-2-oxoethylidene)-5-oxo-2H,4a′H,5H-spiro{thiazolo[3,2-a]pyrimidine-3,3′-[1,3]oxazino[3,2-a]quinoline}-1′,2′-dicarboxylate (6a) Yellow crystals; mp 75–77 °C; yield 0.44 g (87%). IR (KBr): ν_max = 1735 (C=O), 1717 (C=O), 1689 (C=O) cm^–1. ¹H NMR (500.1 MHz, CDCl₃): δ = 3.65 (3 H, s, MeO), 3.70 (3 H, s, MeO), 3.92 (3 H, s, MeO), 5.99 (1 H, s, CH), 5.99 (1 H, dd, ³ J = 9.9, 4.3 Hz, CH), 6.22 (1 H, d, ³ J = 6.7 Hz, CH), 6.80 (1 H, d, ³ J = 4.3 Hz, CH), 6.89 (1 H, d, ³ J = 9.8 Hz, CH), 6.99 (1 H, d, ³ J = 8.1 Hz, CH), 7.09 (1 H, t, ³ J = 7.4 Hz, CH), 7.28 (1 H, d, ³ J = 8.1 Hz, CH), 7.33 (1 H, t, ³ J = 7.4 Hz, CH), 7.80 (1 H, d, ³ J = 6.7 Hz, CH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 52.5 (MeO), 52.6 (MeO), 54.1 (MeO), 83.3 (CH), 95.9 (C), 107.0 (CH), 108.9 (C), 112.4 (CH), 113.1 (CH), 123.5 (CH), 125.8 (C), 126.0 (CH), 128.0 (CH), 128.5 (CH), 129.4 (C), 130.4 (CH), 146.1 (C), 153.9 (CH), 154.3 (C), 161.4, 162.8, 162.9, 163.2, 166.7 (5 C, C=O and C=N). MS (EI, 70 eV): m/z (%) = 509 (15) [M⁺], 386 (27), 321 (100), 294 (20), 281 (17), 254 (50), 226 (36), 129 (80). Anal. Calcd for C₂₄H₁₉N₃O₈S (509.49): C, 56.58; H, 3.76; N, 8.25%. Found: C, 56.37; H, 3.75; N, 8.22%.
17 X-ray Crystal-Structure Determination of 4b and 6d The X-ray diffraction measurements were carried out on a STOE IPDS 2T diffractometer with graphite-monochromated Mo Kα radiation. All single crystals were obtained from AcOEt/n-hexane solutions and mounted on a glass fiber for data collection. Cell constants and orientation matrixes for data collection were obtained by least-square refinement of the diffraction data from 7475 and 5215 for 4b and 6d, respectively. Diffraction data were collected in a series of ω scans in 1° oscillations and integrated using the STOE X-AREA software package (see ref.²²). Multi-Scan absorption corrections were applied using WinGX-2013.3 software. The structures were solved by direct methods and subsequent difference Fourier maps and then refined on F2 by a full-matrix least-squares procedure using anisotropic displacement parameters. Atomic factors are from the International Tables for X-ray Crystallography. All nonhydrogen atoms were refined with anisotropic displacement parameters. Hydrogen atoms were placed in ideal positions and refined as riding atoms with relative isotropic displacement parameters. All refinements were performed using the X-STEP32, SHELXL-2014, and WinGX-2013.3 programs (see ref.²³).
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