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Synlett 2017; 28(15): 2036-2040
DOI: 10.1055/s-0036-1588844
DOI: 10.1055/s-0036-1588844
letter
Synthesis of (E)-4,5-Dihydro-1H-Pyrazoles via Tandem Intermolecular Addition–Cyclization of N-Propargylic Sulfonylhydrazones
We are grateful to the National Natural Science Foundation of China (No. 21272190) and NFFTBS (No. J1310024).Further Information
Publication History
Received: 30 March 2017
Accepted after revision: 30 April 2017
Publication Date:
31 May 2017 (online)
Abstract
A new strategy for the synthesis of (E)-4-benzylidene-4,5-dihydro-1H-pyrazoles through tandem intermolecular addition–intramolecular cyclization of N-propargylic sulfonylhydrazones has been developed. In this study, we firstly report that N-propargylic sulfonylhydrazones react with electrophilic reagents to afford 4-substituted pyrazole derivatives.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1588844.
- Supporting Information
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- 14 Representative Procedure for the Preparation of (E)-4-Benzylidene-4,5-dihydro-1H-pyrazoles 2 To a solution of N-propargylic sulfonylhydrazone 1 (0.5 mmol) and acetals 3 (1 mmol) in DBE (5 mL), FeCl3 (0.1 mmol) was added, and the mixture was stirred at 80 °C. When the reaction was completed (monitored by TLC), water was added to the mixture. The aqueous phase was extracted with CH2Cl2 (3 × 10 mL). The combined organic layers were washed with brine and dried over Na2SO4. The solvent was removed under vacuum, and then the residue was further purified by silica gel column chromatography (PE and EtOAc) to afford product 2.
- 15 Representative Analytical Data of (E)-4-Benzylidene-3-phenyl-1-tosyl-4,5-dihydro-1H-pyrazole (2a) White solid (mp 149–150 °C). 1H NMR (500 MHz, CDCl3): δ = 2.43 (s, 3 H), 4.81 (s, 2 H), 6.74–6.80 (m, 1 H), 7.25 (d, 2 H, J = 7.3 Hz), 7.32–7.38 (m, 3 H), 7.41–7.52 (m, 5 H), 7.60 (d, 2 H, J = 7.1 Hz), 7.88(d, 2 H, J = 8.0 Hz). 13C NMR (125 MHz, CDCl3): δ = 21.6, 54.2, 126.3, 128.6, 128.7, 128.8, 128.8, 128.9, 129.7, 129.8, 130.1, 132.0, 133.9, 135.3, 144.5, 160.1. ESI-HRMS: m/z calcd for C23H20N2O2S [M + H]+: 389.1318; found: 389.1322.