In-depth characterization of self-healing polymers based on π–π interactions

• Josefine Meurer,
• Julian Hniopek,
• Johannes Ahner,
• Michael Schmitt,
• Jürgen Popp,
• Stefan Zechel,
• Kalina Peneva and
• Martin D. Hager

Beilstein J. Org. Chem. 2021, 17, 2496–2504, doi:10.3762/bjoc.17.166

• synthesized utilizing a polycondensation of a perylene tetracarboxylic dianhydride with polyether-based diamines and the resulting materials were investigated using various analytical techniques. Thus, the molecular structure of the polymers could be correlated with the ability for self-healing. Moreover, the

Chemical syntheses and salient features of azulene-containing homo- and copolymers

• Vijayendra S. Shetti

Beilstein J. Org. Chem. 2021, 17, 2164–2185, doi:10.3762/bjoc.17.139

• dehalogenative polycondensation reaction of 1,3-dibromoazulene (4) by an organonickel catalyst (Yamamoto protocol) yielded 1,3-polyazulene 5. The polymer was partially soluble in many organic solvents such as chloroform, THF, xylenes, DMF, N-methylpyrrolidone (NMP), and also in Brønsted acids like TFA and conc

Progress and challenges in the synthesis of sequence controlled polysaccharides

• Giulio Fittolani,
• Theodore Tyrikos-Ergas,
• Denisa Vargová,
• Manishkumar A. Chaube and
• Martina Delbianco

Beilstein J. Org. Chem. 2021, 17, 1981–2025, doi:10.3762/bjoc.17.129

• enzymes cannot distinguish between acceptors with different lengths in the reaction mixture. Chemical polymerization is often performed by ring-opening of the respective anhydrosugar (Figure 1B) or polycondensation reactions. This approach is highly valuable to generate long chains in short time, allowing

Recent advances in the application of isoindigo derivatives in materials chemistry

• Andrei V. Bogdanov and
• Vladimir F. Mironov

Beilstein J. Org. Chem. 2021, 17, 1533–1564, doi:10.3762/bjoc.17.111

• polymers in which aromatic fragments are linked by a single bond, a number of homopolymers 53 was obtained by the aldol polycondensation reaction [97]. These compounds have rigid and almost planar structures with a wide absorption range, high electron affinity, good solubility, and ambient stability

Valorisation of plastic waste via metal-catalysed depolymerisation

• Francesca Liguori,
• Carmen Moreno-Marrodán and
• Pierluigi Barbaro

Beilstein J. Org. Chem. 2021, 17, 589–621, doi:10.3762/bjoc.17.53

• chloride) compounds [243]. One-pot depolymerisation–polycondensation reactions were developed to produce random copolyesters poly(ethylene terephthalate-co-adipate) from PET in the presence of EG and adipic acid [244]. The depolymerisation step was carried out using a zinc acetate catalyst (1 wt %), with

Ugi reaction-derived prolyl peptide catalysts grafted on the renewable polymer polyfurfuryl alcohol for applications in heterogeneous enamine catalysis

• Alexander F. de la Torre,
• Gabriel S. Scatena,
• Oscar Valdés,
• Daniel G. Rivera and
• Márcio W. Paixão

Beilstein J. Org. Chem. 2019, 15, 1210–1216, doi:10.3762/bjoc.15.118

• -supported catalysts amenable for continuous-flow asymmetric enamine catalysis [9][10]. The acid-catalyzed polymerization of furfuryl alcohol renders a dark polymer featuring a complex cross-linked polyunsaturated scaffold derived from polycondensation and Diels–Alder reactions [11][12]. Worldwide, there is

Mechanochemistry of supramolecules

• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2019, 15, 881–900, doi:10.3762/bjoc.15.86

• stabilities by exhibiting a decomposition temperature up to 320 °C. In 2013, Severin and co-workers reported the mechanochemical synthesis of large macrocycles with borasiloxane and imine links using a ball mill (Figure 12). In a polycondensation reaction using diamines, 4-formylbenzeneboronic acid and t

Olefin metathesis in multiblock copolymer synthesis

• Maria L. Gringolts,
• Yulia I. Denisova,
• Eugene Sh. Finkelshtein and
• Yaroslav V. Kudryavtsev

Beilstein J. Org. Chem. 2019, 15, 218–235, doi:10.3762/bjoc.15.21

• multiblock copolymers with respect to self-assembly. In recent years, it was demonstrated that such polymers can be prepared with many of the available techniques, including polycondensation [28], chain-shuttling polymerization [29], copper-mediated radical polymerization [30][31][32], reversible addition

Synthesis and supramolecular properties of regioisomers of mononaphthylallyl derivatives of γ-cyclodextrin

• Markéta Bláhová,
• Sergey K. Filippov,
• Lubomír Kováčik,
• Jiří Horský,
• Simona Hybelbauerová,
• Zdenka Syrová,
• Tomáš Křížek and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2017, 13, 2509–2520, doi:10.3762/bjoc.13.248

• binding constant and NA-γ-CD concentration (see Supporting Information, File 1). Number average and weight average degrees of polymerization (nn and nw) are given by standard relations derived for polycondensation [40] The values of nn and nw calculated from ITC results for 10 mM solutions of NA-γ-CD are

Sugar-based micro/mesoporous hypercross-linked polymers with in situ embedded silver nanoparticles for catalytic reduction

• Qing Yin,
• Qi Chen,
• Li-Can Lu and
• Bao-Hang Han

Beilstein J. Org. Chem. 2017, 13, 1212–1221, doi:10.3762/bjoc.13.120

• -linkers [4], and self-polycondensation of small molecular monomers [5]. Since the Tan group proposed the new synthetic strategy that "knits" low functionality rigid aromatic compounds with formaldehyde dimethyl acetal (FDA) as an external cross-linking agent through a Friedel–Crafts reaction to synthesize

Dynamics and interactions of ibuprofen in cyclodextrin nanosponges by solid-state NMR spectroscopy

• Monica Ferro,
• Franca Castiglione,
• Nadia Pastori,
• Carlo Punta,
• Lucio Melone,
• Walter Panzeri,
• Barbara Rossi,
• Francesco Trotta and
• Andrea Mele

Beilstein J. Org. Chem. 2017, 13, 182–194, doi:10.3762/bjoc.13.21

• of Chemistry, University of Torino, Via Pietro Giuria 7, 10125 Torino, Italy 10.3762/bjoc.13.21 Abstract Two different formulations of cyclodextrin nanosponges (CDNS), obtained by polycondensation of β-cyclodextrin with ethylenediaminetetraacetic acid dianhydride (EDTAn), were treated with aqueous

• chiral selectors for the enantioseparation of racemic ibuprofen [32]. In our case, the primary OH groups of CD units react with EDTA dianhydride to form a cross-linked polyester. As a matter of fact, this type of polycondensation makes the CD cavity less available compared to the former case. The overall

• result is that the guest molecules are mainly confined in the pores formed by the polycondensation process rather than forming a genuine inclusion complex with the single CD units. From a practical point of view, our class of polymerized cyclodextrins can be conveniently exploited as sorbent or scaffold

Extrusion – back to the future: Using an established technique to reform automated chemical synthesis

• Deborah E. Crawford

Beilstein J. Org. Chem. 2017, 13, 65–75, doi:10.3762/bjoc.13.9

• the extrusion of two or more compatible polymer blends, leading to the formation of a polymer–polymer complex [13]. Bulk polymerisation involves several common organic transformations, including living polymerisation, polyaddition, radical and polycondensation polymerisation. Living polymerisation

• molecular weight at moderate temperatures of 60 °C [25]. Polycondensation polymerisation Finally, another important example of organic synthesis in the production of polymers is the polycondensation reaction to produce polymers such as polyamides. There are numerous patents on this application of polymer

• depicts the screw configuration employed and each reaction. Adapted from [16]. Proposed mechanism for the branching of polylactide. Adapted from [23]. Chemical reaction between isocyanate and an alcohol to form polyurethane. Generic polycondensation reaction to produce polyamides. Synthesis of HKUST-1

Isosorbide and dimethyl carbonate: a green match

• Fabio Aricò and
• Pietro Tundo

Beilstein J. Org. Chem. 2016, 12, 2256–2266, doi:10.3762/bjoc.12.218

• derivatives [82][83]. On another hand, a greener synthetic methodology to bio-based polymers is to first synthesize a more reactive derivative of isosorbide and then perform the polycondensation reaction (Scheme 4). In this prospect a good candidate is the dicarboxymethyl isosorbide (DCI). In fact

• homopolymer preparation, DCI was synthesised by reacting isosorbide, DMC and Li(acac) at 98 °C. The polycondensation was then achieved employing an high vacuum and increasing the temperature to 240 °C. The so-formed poly(isosorbide carbonate) had a molecular weight (Mn) of 28,800 g/mol. The conversion of

• isosorbide was almost quantitative (95.2%). Similarly poly(aliphaticdiol-co-isosorbide carbonate)s were prepared via melt polycondensation of DMC with isosorbide and several aliphatic diols employing Li(acac) and the TiO2/SiO2-based catalyst (Scheme 4) [85]. High-molecular-weight (Mw = 32,600) and optically

3,6-Carbazole vs 2,7-carbazole: A comparative study of hole-transporting polymeric materials for inorganic–organic hybrid perovskite solar cells

• Wei Li,
• Munechika Otsuka,
• Takehito Kato,
• Yang Wang,
• Takehiko Mori and
• Tsuyoshi Michinobu

Beilstein J. Org. Chem. 2016, 12, 1401–1409, doi:10.3762/bjoc.12.134

• -Cbz-EDOT, by Stille polycondensation. Despite the same chemical composition, 3,6-Cbz-EDOT and 2,7-Cbz-EDOT displayed different optical and electrochemical properties due to the different connectivity mode of the carbazole unit. Therefore, their performances as hole-transporting polymeric materials in

• ; hole transport; perovskite solar cell; polycondensation; Introduction Inorganic–organic hybrid perovskite solar cells (PSCs) have recently received significant attention due to their remarkably high power convention efficiencies (PCEs). After the seminal study reported by Miyasaka et al. in 2009 with

• the electron-donating properties, the carbazole monomers were copolymerized with the electron-rich 3,4-ethylenedioxythiophene (EDOT) unit by Stille polycondensation. The energy levels and hole mobilities of the resulting carbazole copolymers, namely 3,6-Cbz-EDOT and 2,7-Cbz-EDOT, were estimated from

Convenient preparation of high molecular weight poly(dimethylsiloxane) using thermally latent NHC-catalysis: a structure-activity correlation

• Stefan Naumann,
• Johannes Klein,
• Dongren Wang and
• Michael R. Buchmeiser

Beilstein J. Org. Chem. 2015, 11, 2261–2266, doi:10.3762/bjoc.11.246

• found that steric hindrance of the NHC shut down polymerization activity. Finally, a report on the polycondensation of α,ω-disilanols describes the efficient polycondensation via NHCs in spite of the generation of water during the reaction, finding that the most basic NHC in the small study delivered

Dicarboxylic esters: Useful tools for the biocatalyzed synthesis of hybrid compounds and polymers

• Ivan Bassanini,
• Karl Hult and
• Sergio Riva

Beilstein J. Org. Chem. 2015, 11, 1583–1595, doi:10.3762/bjoc.11.174

• for example Zang et al. [49], Kobayashi and Makino [50], Gross et al. [51]). Nowadays lipases are not only used to achieve simple polycondensation reactions, but are exploited due to their chemo-, stereo- and enantioselectivity. In addition, they are seen as environmentally friendly alternative to

• traditional polymerization methods [52]. Binns et al. summarized the attempts to scale up synthesis of polyesters by enzyme catalyzed polycondensation of adipic acid and hexane-1,6-diol in a very well-worth reading article [53]. They discussed the very slow progress in achieving high molecular weight polymers

• telechelics in a one-pot polycondensation. The backbone of the telechelics was built from ethylene glycol and divinyl adipate. Specific degrees of polymerisation (4, 8 and 13) were reached by terminating the process with the addition of 2-hydroxyethyl methacrylate. Well-defined telechelics with more than 90

Synthesis and chemosensing properties of cinnoline-containing poly(arylene ethynylene)s

• Natalia A. Danilkina,
• Petr S. Vlasov,
• Semen M. Vodianik,
• Andrey A. Kruchinin,
• Yuri G. Vlasov and
• Irina A. Balova

Beilstein J. Org. Chem. 2015, 11, 373–384, doi:10.3762/bjoc.11.43

• and a sila-Sonogashira coupling as the polycondensation technique. The fluorescence of the cinnoline-containing polymers in THF was highly sensitive to quenching by Pd2+ ions. Keywords: cinnolines; fluorescence quenching; Pd2+ detection; poly(arylene ethynylene)s; Sonogashira coupling; Introduction

• ). These experiments revealed that both bromine atoms at pyridazine and benzene rings are highly reactive in the Sonogashira coupling due to the strong activation of the electron deficient nature of the heterocycle. Having starting compounds 5a,b in hand, we were ready to carry out the polycondensation

• with 1,4-diiodo-2,5-bis(octyloxy)benzene (9). There are two main reactions of polycondensation that have been reported as synthetic approaches towards PAEs: the acyclic diyne metathesis polymerization (ADIMET) [55] and the Sonogashira coupling [56]. Both of them have their own advantages and drawbacks

Synthetic strategies for the fluorescent labeling of epichlorohydrin-branched cyclodextrin polymers

• Milo Malanga,
• Mihály Bálint,
• István Puskás,
• Kata Tuza,
• Tamás Sohajda,
• László Jicsinszky,
• Lajos Szente and
• Éva Fenyvesi

Beilstein J. Org. Chem. 2014, 10, 3007–3018, doi:10.3762/bjoc.10.319

• review has been recently published [11]. Cationic and anionic cyclodextrin polymers were synthesized by simultaneous modification and branching from β-CD, epichlorohydrin and choline chloride (for cationic polymer) or chloroacetic acid (for anionic polymer) in an one-step polycondensation process and

Anomalous diffusion of Ibuprofen in cyclodextrin nanosponge hydrogels: an HRMAS NMR study

• Monica Ferro,
• Franca Castiglione,
• Carlo Punta,
• Lucio Melone,
• Walter Panzeri,
• Barbara Rossi,
• Francesco Trotta and
• Andrea Mele

Beilstein J. Org. Chem. 2014, 10, 2715–2723, doi:10.3762/bjoc.10.286

• growth of the polycondensation products leads to a statistic three-dimensional network characterized by different types of cavities, namely the apolar cavity of the CD units and the pores of the growing polymer. As previously stressed, CDNS are, in the majority of cases, completely – or almost completely

Synthesis and characterization of a hyper-branched water-soluble β-cyclodextrin polymer

• Francesco Trotta,
• Fabrizio Caldera,
• Roberta Cavalli,
• Andrea Mele,
• Carlo Punta,
• Lucio Melone,
• Franca Castiglione,
• Barbara Rossi,
• Monica Ferro,
• Vincenza Crupi,
• Domenico Majolino,
• Valentina Venuti and
• Dominique Scalarone

Beilstein J. Org. Chem. 2014, 10, 2586–2593, doi:10.3762/bjoc.10.271

• demanding task considering the high number of functional groups per CD unit. To synthesize soluble CD polymers different routes can be followed: 1) grafting of CDs on pre-synthesized polymers [8] 2) polycondensation of difunctionalized CD monomers obtained by selective modification of the CD secondary

Atherton–Todd reaction: mechanism, scope and applications

• Stéphanie S. Le Corre,
• Mathieu Berchel,
• Hélène Couthon-Gourvès,
• Jean-Pierre Haelters and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2014, 10, 1166–1196, doi:10.3762/bjoc.10.117

Controlled synthesis of poly(3-hexylthiophene) in continuous flow

• Helga Seyler,
• Jegadesan Subbiah,
• David J. Jones,
• Andrew B. Holmes and
• Wallace W. H. Wong

Beilstein J. Org. Chem. 2013, 9, 1492–1500, doi:10.3762/bjoc.9.170

• P3HT gave comparable performance. Results and Discussion The most widely used synthetic route to regioregular P3HT is the Kumada catalyst transfer polycondensation (KCTP) developed by the McCullough group [6] and the Yokozawa group [7]. In a representative experiment for the preparation of P3HT, the

New enzymatically polymerized copolymers from 4-tert-butylphenol and 4-ferrocenylphenol and their modification and inclusion complexes with β-cyclodextrin

• Adam Mondrzyk,
• Beate Mondrzik,
• Sabrina Gingter and
• Helmut Ritter

Beilstein J. Org. Chem. 2012, 8, 2118–2123, doi:10.3762/bjoc.8.238

• ]. Several oxido-reductases and their catalytic mechanisms are well-studied; the most common are soybean peroxidase, bilirubin peroxidase, laccase and horse radish peroxidase (HRP) [8][9][10][11][12]. Taking the latter case, horse radish peroxidase catalyzes the oxidative polycondensation of electron-rich

Synthesis and characterization of low-molecular-weight π-conjugated polymers covered by persilylated β-cyclodextrin

• Aurica Farcas,
• Ana-Maria Resmerita,
• Andreea Stefanache,
• Mihaela Balan and
• Valeria Harabagiu

Beilstein J. Org. Chem. 2012, 8, 1505–1514, doi:10.3762/bjoc.8.170

• illustrated in Scheme 1. In order to analyse the influence of end-capping reagents on the photophysical properties we changed the termination of the growing chains to 3T instead of bromobenzene, as in previously reported results [12]. A noncomplexed PDOF-BT copolymer was also synthesized by polycondensation

Synthesis and characterization of a novel carboxyl group containing (co)polyimide with sulfur in the polymer backbone

• Miroslav Mrsevic,
• David Düsselberg and
• Claudia Staudt

Beilstein J. Org. Chem. 2012, 8, 776–786, doi:10.3762/bjoc.8.88

• fluorinated sulfur- and carboxylic acid groups consisting of 4,4′-(hexafluoroisopropylidene)di(phthalic anhydride) (6FDA), 3,5-diaminobenzoic acid (DABA), 4,4′-diaminodiphenylsulfide (4,4′-SDA) and 3,3′-diaminodiphenylsulfone (3,3′-DDS) were synthesized in a two-step polycondensation reaction. The synthesized

• Preparation of (co)polyimides The syntheses of the polyimides and (co)polyimides were performed in a two-step polycondensation reaction as shown in Scheme 1, analogous to that of Sroog et al. [23] and that previously described by our group [17]. In this work, chemical imidization was used exclusively, because

• polycondensation reactions from a commercially available fluorinated dianhydride 6FDA, two sulfur-containing diamines (4,4′-SDA and 3,3′-DDS) and one diamine with a carboxylic acid (DABA). The structures of all polymers were verified by 1H NMR spectroscopy, FTIR spectroscopy and GPC measurements, with molecular