Base-Promoted Ecofriendly Synthesis of Trisubstituted Pyrazoles from α,β-Alkynyl N-Tosylhydrazones under Metal- and Solvent-Free Conditions

Ning Li; Baoguo Li; Shufeng Chen

doi:10.1055/s-0035-1561853

Synlett, Table of Contents

Synlett 2016; 27(10): 1597-1601
DOI: 10.1055/s-0035-1561853

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Base-Promoted Ecofriendly Synthesis of Trisubstituted Pyrazoles from α,β-Alkynyl N-Tosylhydrazones under Metal- and Solvent-Free Conditions

Ning Li

Inner Mongolia Key Laboratory of Fine Organic Synthesis, Department of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, P. R. of China Email: shufengchen@imu.edu.cn

,

Baoguo Li

Inner Mongolia Key Laboratory of Fine Organic Synthesis, Department of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, P. R. of China Email: shufengchen@imu.edu.cn

,

Shufeng Chen*

Inner Mongolia Key Laboratory of Fine Organic Synthesis, Department of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, P. R. of China Email: shufengchen@imu.edu.cn

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Abstract

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Abstract

A simple and green method is described for the synthesis of trisubstituted pyrazoles from α,β-alkynyl N-tosylhydrazones under metal- and solvent-free conditions. Notably, only diisopropylamine is required as a promoter, and the reaction can be easily performed at room temperature and on a gram scale.

Keywords

hydrazones - green chemistry - pyrazoles - cyclizations

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References

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18 Pyrazoles 2; General Procedure i-Pr₂NH (0.6 mmol) and the appropriate N-tosylhydrazone 1 (0.3 mmol) were thoroughly ground with a pestle and mortar for 30 min. When the reaction was complete, the mixture was purified by crystallization from CH₂Cl₂ or by column chromatography (silica gel, EtOAc–PE) to give the pure pyrazole product 2. 3,5-Diphenyl-1-tosyl-1H-pyrazole (2a) White solid; yield: 103 mg (92%; gram scale: 81%); mp 122–124 °C. IR (KBr): 3029, 2921, 2855, 1594, 1558, 1459, 1382, 1195, 1177, 761, 660, 598 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 2.35 (s, 3 H), 6.60 (s, 1 H), 7.19 (d, J = 8.0 Hz, 2 H), 7.35–7.45 (m, 8 H), 7.62 (d, J = 8.0 Hz, 2 H), 7.84 (d, J = 7.0 Hz, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 21.69, 109.54, 126.48, 127.84, 128.04, 128.72, 129.33, 129.49, 129.62, 129.67, 130.02, 131.37, 134.88, 145.35, 149.48, 155.21. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₂H₁₉N₂O₂S: 375.1167; found: 375.1161.

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