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Synlett 2024; 35(07): 816-820
DOI: 10.1055/s-0042-1751623
letter

[Pyridine–SO3H]ZnCl3: A Multipurpose Catalyst for A3 Coupling Synthesis of Propargylamines under Mild Conditions

Ahmad Reza Moosavi-Zare∗
a   Department of Chemical Engineering, Hamedan University of Technology, Hamedan, 65155, Iran
b   Chemistry Department, College of Sciences, Shiraz University, Shiraz 71946-84795, Iran
,
Mohammad Rezaei-Gohar
c   Department of Chemistry, K. N. Toosi University of Technology, P.O. BOX 15875 - 4416, Tehran, Iran
,
Mahsa Tavasoli
d   Faculty of Chemistry, Bu-Ali Sina University, Hamedan, 6517838683, Iran
,
Hamid Goudarziafshar
a   Department of Chemical Engineering, Hamedan University of Technology, Hamedan, 65155, Iran
› Author AffiliationsHamedan University of Technology
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Abstract

N-Sulfopyridin-1-ium monozinc(II) trichloride ([NSPy]ZnCl3) was prepared and used as a multipurpose catalyst for the synthesis of propargylamines by the A3 coupling reaction of aromatic aldehydes, alkynes, and secondary amines under mild conditions. In this reaction, the carbonyl group in the aldehyde was activated by the acidic part in the catalyst, and the C–H activation of phenylacetylene was carried out by zinc.

Key words

A3 coupling reaction - C–H bond activation - propargylamines - ionic liquid catalysis - amines - multicomponent reaction

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0042-1751623.
  • Supporting Information


Publication History

Received: 07 June 2023

Accepted after revision: 08 September 2023

Article published online:
25 October 2023

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  • 43 Procedure for the preparation of [Pyridine–SO3H]Cl. A solution of pyridine (0.395 g, 5 mmol) in CH2Cl2 (40 mL) was added dropwise to a stirring solution of chlorosulfonic acid (0.58 g, 5 mmol) in dry CH2Cl2 (40 mL) over a period of 10 min at 0 °C. After the addition was completed, the reaction mixture was stirred for 20 min, stand for 5 min, and the CH2Cl2 was decanted. Afterward, the liquid residue was triturated with CH2Cl2 (3×10 mL) and dried under powerful vacuum at 90 °C to give [Pyridine–SO3H]Cl as a viscous colorless oil in 95 % yield (0.929 g) [7].
  • 44 Procedure for the preparation of [NSPy]ZnCl3 . To a round-bottomed flask (50 mL) containing [Pyridine–SO3H]Cl (0.975 g, 5 mmol), Zinc chloride (0.682 g, 5 mmol) was added over a period of 10 minutes at 85 °C and then stirred for 2 hours at 80 °C to give [NSPy]ZnCl3.
  • 45 Propargylamines 1–9; General ProcedureA round-bottomed flask (25 mL) equipped with a reflux condenser was charged with CHCl3 (10 mL). The appropriate aromatic aldehyde (1 mmol), phenylacetylene (1 mmol), amine (1 mmol), and [NSPy]ZnCl3 (15 mol%) were added, and the mixture was stirred for the appropriate time at r.t. When the reaction was complete (TLC), the solvent was removed, and the product was purified by plate chromatography.4-[1-(4-Chlorophenyl)-3-phenylprop-2-yn-1-yl]morpholine (1)Pale yellow oil; yield: 92%. 1H NMR (250 MHz, CDCl3): δ = 2.61 (t, J = 6.8 Hz, 4 H), 3.72 (t, J = 6.8 Hz, 4 H), 4.77 (s, 1 H), 7.34 (d, J = 4.75 Hz, 5 H), 7.50 (s, 1 H), 7.58 (d, J = 7.75 Hz, 3 H). 13C NMR (62.5 MHz, CDCl3): δ = 49.7, 61.3, 67.0, 84.3, 88.8, 122.6, 128.3, 129.8, 131.7, 133.5, 136.4.4-[1-(3-Nitrophenyl)-3-phenylprop-2-yn-1-yl]morpholine (2)Pale yellow oil; yield: 91%. 1H NMR (250 MHz, DMSO-d 6): δ = 2.46 (s, 2 H), 2.58 (d, J = 10.50 Hz, 2 H), 3.58 (s, 4 H), 5.15 (s, 1 H), 7.40 (s, 3 H), 7.51 (s, 2 H), 7.68 (t, J = 8.00 Hz, 1 H), 8.00 (d, J = 7.50 Hz, 1 H), 8.16 (d, J = 8.00 Hz, 1 H), 8.36 (s, 1 H). 13C NMR (62.5 MHz, DMSO-d 6): δ = 49.7, 60.4, 66.6, 84.5, 89.2, 122.2, 123.1, 123.2, 129.1, 129.3, 130.3, 132.0, 135.2, 140.5, 148.2. 4-[1-(2,5-Dimethoxyphenyl)-3-phenylprop-2-yn-1-yl]morpholine (5)Pale yellow oil; yield: 84%. 1H NMR (250 MHz, DMSO-d 6): δ = 2.52 (t, J = 4.50 Hz, 4 H), 3.39–3.53 (m, 4 H), 3.68 (s, 3 H), 3.74 (s, 3 H), 5.00 (s, 1 H), 6.86 (d, J = 8.75 Hz, 1 H), 6.95 (d, J = 8.75 Hz, 1 H), 7.08 (s, 1 H), 7.34 (s, 3 H), 7.43 (s, 2 H). 13C NMR (62.5 MHz, DMSO-d 6): δ = 50.3, 55.0, 55.7, 56.9, 66.6, 86.6, 87.0, 113.4, 113.6, 116.1, 122.7, 127.1, 129.0, 131.8, 151.5, 153.3.