Synthesis of Pyrroles and Thiazolanes Promoted by N-Methylimidazole in Water

Abstract

A convenient and efficient approach to the synthesis of substituted pyrroles is reported based on three-component reaction of primary amines and alkyl propiolates in the presence of N-methyl­imidazole in water. A water-accelerated synthesis of thiazolane derivatives has also been established by employing the three-component reaction of primary amines, alkyl propiolates, and isothiocyanates in the presence of N-methylimidazole.

Key words

N-methylimidazole - pyrrole - thiazolane - three-component reaction

• References and Notes

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• 32 General Procedure for the Preparation of Compounds 13 To a magnetically stirred mixture of acetylene 1 (2 mmol) and N-methylimidazole (3, 5 mol%) in H₂O (5 mL) was added a mixture of isothiocyanate 12 and primary amine 2 (2 mmol) in H₂O (5mL) at r.t. The reaction mixture was then stirred. After the completion of the reaction (6 h; TLC; EtOAc–hexane = 1:7), the solid residue was filtered and washed with cold Et₂O to afforded pure compounds 13. Methyl 2-(Methylimino)-1,3-thiazolane-5-dicarboxylate (13a) Yellow powder, mp 164–166 °C, yield 0.26 g (75%). IR (KBr) ν_max = 1738, 1567, 1456, 1385, 1257 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 3.24 (3 H, s, NMe), 3.75 (3 H, s, MeO), 3.87 (1 H, dd, ² J _HH = 16 Hz, ³ J _HH = 7 Hz, CH), 4.12 (1 H, dd, ² J _HH =16 Hz, ³ J _HH = 3 Hz, CH), 4.78 (1 H, dd, ³ J _HH = 7 Hz ³ J _HH = 3 Hz, CH), 6.14 (1 H, br, NH) ppm. ¹³C NMR (125.7 MHz, CDCl₃): δ = 35.8 (NMe), 39.4 (CH), 47.5 (CH₂), 52.4 (MeO), 163.2 (C=N), 172.5 (C=O) ppm. MS: m/z (%) = 174 (15) [M⁺], 143 (84), 31 (100). Anal. Calcd (%) for C₆H₁₀N₂O₂S (174.22): C, 41.36; H, 5.79; N, 16.08. Found: C, 41.24; H, 5.62; N, 15.96.
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