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Synlett 2025; 36(02): 129-136
DOI: 10.1055/s-0043-1774862
letter

Triton B Catalyzed Rapid and Mild Synthetic Protocol for both Henry Reaction of Isatin and Michael Reaction of Chalcone with Nitroalkane

Mrinal Talukdar
,
Nasreen Islam
,
Akanksha Mishra
,
Alpa Y Dave
,
Eeshwaraiah Begari∗
E. B thanks the DST-SERB (File No: EEQ/2017/000764), Department of Science and Technology, India, for financial support. The authors M. T, N. I, A. M, A. D and E. B, thank the Vice-Chancellor, CUG Gandhinagar, for providing the Central Instrumentation facilities. M. T thanks UGC-India for the fellowship.
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Abstract

A highly efficient and general synthetic protocol for both Henry and Michael reactions was developed using metal-free catalyst Triton B (benzyltrimethylammonium hydroxide) and isatins and chalcones, respectively. This methodology is inexpensive, the reagents are easy to handle, and the approach offers wide functional group tolerance of isatins and chalcones. The base catalyst Triton B is less toxic, recyclable, and reusable. This efficient method reduces reaction times, minimizes reagent excess, avoids chromatography, and is aligned with sustainable chemistry principles, offering eco-friendly applications in diverse industries.

Keywords

phase-transfer catalyst - Triton B (benzyltrimethylammonium hydroxide) - Henry reaction - Michael addition - rapid synthesis

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0043-1774862.
  • Supporting Information


Publication History

Received: 03 January 2024

Accepted after revision: 06 April 2024

Article published online:
23 April 2024

© 2024. Thieme. All rights reserved

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    • 50a Synthesis of Compounds 3a–l and 5a–n; General Procedure: A mixture of nitroalkane 2 (1.5 mmol), substituted isatin 1 (1 mmol) or substituted chalcone 4 (1 mmol) and Triton B (40% solution in methanol, 1 mL) were stirred at ambient temperature for 2–3 minutes. The progress of the reaction was monitored by TLC (thin-layer chromatography). After complete conversion of the starting materials, the reaction mixture was extracted with diethyl ether (4 × 10 mL). Removal of the solvent under reduced pressure gave the analytically pure products 3 or 5 without column chromatography.
    • 50b Characterization Data for Compound 3a: Yield: 98%; light-brown solid; mp 135–140 °C; Rf = 0.40 (40% EtOAc/hexane). 1H NMR (500 MHz, DMSO-d 6): δ = 10.58 (s, 1 H, NH), 7.41 (d, J = 7.3 Hz, 1 H, ArH), 7.28 (td, J = 7.7, 1.1 Hz, 1 H, ArH), 7.00 (td, 1 H, ArH), 6.86 (d, J = 7.7 Hz, 1 H, ArH), 6.78 (s, 1 H, OH), 5.02 (q, 2 H, CH2NO2). 13C NMR (126 MHz, DMSO-d 6): δ = 176.38, 143.03, 130.74, 128.37, 125.16, 122.30, 110.52, 78.92, 73.27. HRMS (ESI+): m/z calcd for [C9H8N2O4 + H]+: 209.0562; found: 209.0544.
    • 50c Characterization Data for Compound 3b: Yield: 95%; off-white solid; mp 169–174 °C; Rf = 0.38 (40% EtOAc/hexane). 1H NMR (500 MHz, DMSO-d 6): δ = 10.73 (s, 1 H, NH), 7.65 (d, J = 2.0 Hz, 1 H, ArH), 7.47 (dd, J = 8.3, 2.1 Hz, 1 H, ArH), 6.90 (s, 1 H, OH), 6.83 (d, J = 8.3 Hz, 1 H, ArH), 5.09 (q, 2 H, CH2NO2). 13C NMR (126 MHz, DMSO-d 6): δ = 175.99, 142.45, 133.34, 130.99, 128.16, 113.89, 112.52, 78.33, 73.09. HRMS (ESI+): m/z calcd for [C9H7BrN2O4 + H]+: 286.9667; found: 286.9641.
    • 50d Characterization Data for Compound 5a: Yield: 98%; colorless solid; mp 87–90 °C; Rf = 0.36 (15% EtOAc/hexane). 1H NMR (500 MHz, DMSO-d 6): δ = 7.94 (d, J = 7.2 Hz, 2 H, ArH), 7.64 (t, J = 7.4 Hz, 1 H, ArH), 7.52 (t, J = 7.7 Hz, 2 H, ArH), 7.38 (d, J = 7.3 Hz, 2 H, ArH), 7.30 (t, J = 7.6 Hz, 2 H, ArH), 7.23 (t, J = 7.3 Hz, 1 H, ArH), 4.99 (dd, J = 12.9, 5.6 Hz, 1 H, CHNO2), 4.87 (dd, J = 12.9, 9.8 Hz, 1 H, CHNO2), 4.05 (dq, J = 9.7, 6.8 Hz, 1 H, CH), 3.55 (qd, J = 18.0, 7.0 Hz, 2 H, CH2). 13C NMR (126 MHz, DMSO-d 6): δ = 197.91, 140.49, 136.86, 133.88, 129.20, 128.95, 128.39, 128.26, 127.68, 80.15, 41.61, 39.71. HRMS (ESI+): m/z calcd for [C16H15NO3 + H]+: 270.1130; found: 270.1160.
    • 50e Characterization Data for Compound 5b: Yield: 98%; off-white solid; mp 45–48 °C; Rf = 0.38 (15% EtOAc/hexane). 1H NMR (500 MHz, DMSO-d 6): δ = 7.93 (d, 2 H, ArH), 7.65 (t, J = 7.4 Hz, 1 H, ArH), 7.53 (t, J = 7.7 Hz, 2 H, ArH), 7.43 (d, J = 8.5 Hz, 2 H, ArH), 7.37 (d, 2 H, ArH), 5.00 (dd, J = 13.0, 5.5 Hz, 1 H, CHNO2), 4.87 (dd, J = 13.0, 9.8 Hz, 1 H, CHNO2), 4.05 (dq, 1 H, CH), 3.56 (qd, 2 H, CH2). 13C NMR (126 MHz, DMSO-d 6): δ = 197.75, 139.57, 136.77, 133.94, 132.30, 130.27, 129.23, 128.89, 128.39, 79.92, 41.42, 39.11. HRMS (ESI+): m/z calcd for [C16H14ClNO3 + H]+: 304.0740; found: 304.0733.