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Chemoenzymatic polycondensation of para-benzylamino phenol

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Abstract

para-Benzylamine substituted oligophenol was synthesized via enzymatic oxidative polycondensation of 4-(benzylamino)phenol (BAP). Polymerization involved only the phenolic moiety without oxidizing the sec-amine (benzylamine) group. Chemoselective polycondensation of BAP monomer using HRP enzyme yielded oligophenol with sec-amine functionality on the side-chain. Effects of various factors including solvent system, reaction pH and temperature on the polycondensation were studied. Optimum polymerization process with the highest yield (63 %) and molecular weight (Mn = 5000, degree of polymerization ≈ 25) was achieved using the EtOH/ buffer (pH 5.0; 1: 1 vol. ratio) at 25°C in 24 h under air. Characterization of the oligomer was accomplished by 1H NMR and 13C NMR, Fourier transform infrared spectroscopy (FT-IR), gel permeation chromatography (GPC), ultraviolet-visible spectroscopy (UV-Vis), cyclic voltammetry (CV) and thermogravimetric analysis (TGA). The polymerization process involved the elimination of hydrogen from BAP, and phenolic-OH end groups of the oligo(BAP), confirmed using 1H NMR and FT-IR analyses. The oligomer backbone possessed phenylene and oxyphenylene repeat units, and the resulting oligomer was highly soluble in common organic solvents such as acetone, CHCl3, 1,4-dioxane, N,N-dimethylformamide (DMF), tetrahydrofurane (THF) and dimethylsulfoxide (DMSO). Oligo(BAP) was thermally stable and exhibited 5 % and 50 % mass loss determined by thermogravimetric analysis at 247°C and 852°C, respectively.

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Authors and Affiliations

  1. Department of Chemistry, Nigde University, 51240 Nigde, Turkey

    Pinar Yildirim & Ersen Turac

  2. Department of Chemistry, Mustafa Kemal University, 31001 Hatay, Turkey

    Ersen Gokturk

  3. Department of Chemistry, Kahramanmaras Sutcu Imam University, 46100, Kahramanmaras, Turkey

    Haci O. Demir

  4. Department of Chemistry, M. Çikrikçioğlu Vocational College, Erciyes University, 38039, Kayseri, Turkey

    Ertugrul Sahmetlioglu

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  1. Pinar Yildirim
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  2. Ersen Gokturk
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  3. Ersen Turac
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  4. Haci O. Demir
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  5. Ertugrul Sahmetlioglu
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Correspondence to Ertugrul Sahmetlioglu.

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Yildirim, P., Gokturk, E., Turac, E. et al. Chemoenzymatic polycondensation of para-benzylamino phenol. Chem. Pap. 70, 610–619 (2016). https://doi.org/10.1515/chempap-2015-0242

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