Mannich reaction involving calix[4]resorcinarenes and aminoacetals

Vagapova, L. I.; Бурилов, А. Р.; Pudovik, M. A.

doi:10.1134/s1070363210030187

Cited by 4 publications

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“…The mixture of (0.5 g; 1.5 mmol) bicyclic phosphonate 1, (0.27 g; 3 mmol) morpholine 4b, and (0.09 g; 3 mmol) paraformaldehyde in 20 mL benzene was kept under reflux with the Dean-Stark adapter for 12 h (until the evolution of water stops). Yield: 0.23 g (27% 3,8 .0 10,15 ]-heptadeca-3,5,7,10,12,14-hexaene 1-oxide (7) The mixture of (0.3 g; 1.0 mmol) bicyclic phosphonate 2, (0.35 g; 4.0 mmol) morpholine 4b, and (0.12 g; 4.0 mmol) paraformaldehyde in 20 mL benzene was kept under reflux with the Dean-Stark adapter for 16 h (until the evolution of water stops). The formed precipitate was filtered and dried in vacuum up to a constant weight.…”

Section: Resultsmentioning

confidence: 99%

“…The solvent was removed, and residue was recrystallized from isopropyl alcohol under reflux. Yield: 0.21 g (30% (8) 0.5 g (1.7 mmol) bicyclic phosphonate 2 in the mixture of 9 mL ethanol and 3 mL water was stirred until complete dissolution; after that, 0.59 g (6.8 mmol) morpholine 4b and 0.2 g (6.8 mmol) paraformaldehyde were added. [7.7.1.0 3,8 .0 10,15 ]-heptadeca-3,5,7,10,12,14hexaene 1-oxide (6) The mixture of (0.5 g; 1.7 mmol) bicyclic phosphonate 2, (0.3 g; 3.4 mmol) morpholine 4b, and (0.10 g; 3.4 mmol) paraformaldehyde in 20 mL benzene was kept under reflux with the Dean-Stark adapter for 16 h (until the evolution of water stops).…”

Section: Resultsmentioning

confidence: 99%

“…Many studies have been devoted to understanding of the Mannich reaction [1][2][3]. The Mannich reaction is one of the most available methods of the synthesis of new macrocyclic structures [4,5], involving calix [4] resorcinols [6][7][8][9]. The Mannich reaction is one of the most available methods of the synthesis of new macrocyclic structures [4,5], involving calix [4] resorcinols [6][7][8][9].…”

Section: Introductionmentioning

confidence: 99%

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Modification of Bicyclic Phosphonates Based on Resorcinols and Its Derivatives via the Mannich Reaction

et al. 2015

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Amino‐containing derivatives of various structures have been obtained via the Mannich reaction in a series of bicyclic phosphonates based on 2‐methylresorcinol, resorcinol, and pyrogallol with paraformaldehyde and secondary amines via the Mannich reaction. The structure and composition of the obtained compounds have been determined using 31Р and 1Н NMR spectroscopy, IR spectroscopy, mass spectrometry (MALDI‐TOF), and X‐ray analysis.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Modification of Bicyclic Phosphonates Based on Resorcinols and Its Derivatives via the Mannich Reaction

et al. 2015

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“…Thus obtained macromolecules are used as the supramolecular catalysts, extractants, and precursors in the synthesis of new macromolecular compounds [1,[6][7][8].In the present work we investigated the possibility of modifying calix[4]resorcinol with γ-aminobutyric acid by the Mannich reaction. γ-Aminobutyric acid and its derivatives are used as neurotransmitters in the central nervous system [9].…”

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confidence: 99%

“…Thus obtained macromolecules are used as the supramolecular catalysts, extractants, and precursors in the synthesis of new macromolecular compounds [1,[6][7][8].…”

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confidence: 99%

Calix[4]resorcinols modified with γ-aminobutyric acid fragments

et al. 2015

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The Mannich reaction involving amines, amino alcohols, aminoacetals, aminophosphonates, and aminophosphine oxides is one of the most convenient methods of functionalization of calix[4]resorcinols [1][2][3][4][5]. Thus obtained macromolecules are used as the supramolecular catalysts, extractants, and precursors in the synthesis of new macromolecular compounds [1,[6][7][8].In the present work we investigated the possibility of modifying calix[4]resorcinol with γ-aminobutyric acid by the Mannich reaction. γ-Aminobutyric acid and its derivatives are used as neurotransmitters in the central nervous system [9]. Recently it was shown that the complex based on 5,11,17,23-tetra-tert-butyl-25,27-bis[carboxymethoxy]-26,28-dihydroxycalix[4]arene with γ-aminobutyric acid has prolonged anticonvulsant activity [10]. Furthermore, amino acid molecules are often used as additional pharmacophore groups and are key intermediates in the synthesis of many biologically important molecules [11].Interaction of calix[4]resorcinol I with formaldehyde and γ-aminobutyric acid II in aqueous ethanol medium at a ratio of the initial reactants of 1 : 4 : 4 led to the formation of the products of incomplete substitution of the macrocycle. In the ESI mass spectrum of the precipitate obtained there were the signals of m/z 716, 831, 946, indicating the presence of mono-, di-, and trisubstituted calixarene macrocycles, respectively.We found that the optimal solution for the reaction performing was ethanol-water-DMSO mixture allowing to obtain calix[4]resorcinol comprising four amino acid III fragments at the upper rim of the molecule in a yield of 68%.The reaction of calix[4]resorcinol I with formaldehyde and γ-aminobutyric acid II in a ratio of 1 : 8 : 4 under reflux led to the formation of oxazine derivative IV in a high yield (Scheme 1).Structure and composition of the synthesized compounds III and IV were confirmed by IR, NMR 1 H and 13 C spectroscopy, mass spectrometry (ESI) and elemental analysis data. 23-dodecaene (III). A solution of 0.35 g (3.34 mmol) of amino acid II in 5 mL of water, 0.28 g (3.34 mmol) of 37% aqueous solution of formaldehyde and 20 mL of dimethyl sulfoxide were added successively to a mixture of 0.5 g (0.83 mmol) of calix[4]resorcinol I in 5 mL of ethanol. The reaction mixture was stirred at room temperature for 8 h. The solvent was distilled off in vacuum. The residue was re-precipitated from chloroform to hexane, washed with water and dried in vacuum to constant weight. Yield 0.68 g (68%), mp 177-178°C. IR spectrum, ν, cm -1 : 1610 m (С=С Ar ), 1716 m, 1733 (C=O), 2734 br (NH + ), 3422 br (OH). 1 H NMR spectrum (CDCl 3 ), δ, ppm: 0.94 t (12H, 4CH 3 CH 2 , 3 J HH 7.0 Hz), 1.99 br.s (8H, 4NCH 2 CH 2 ), 2.23-2.27 m (8H, 4CH 2 СН 3 ), 2.33 br.s (8Н,

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