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Sustainable Triazine-Based Dehydro-Condensation Agents for Amide Synthesis

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Sustainable Triazine-Based Dehydro-Condensation Agents for Amide Synthesis molecules Article Sustainable Triazine-Based Dehydro-Condensation Agents for Amide Synthesis Roberto Sole 1 , Vanessa Gatto 2 , Silvia Conca 1 , Noemi Bardella 1, Andrea Morandini 1 and Valentina Beghetto 1,2,* 1 Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca’ Foscari di Venezia, Via Torino 155, 30172 Venezia, Italy; [email protected] (R.S.); [email protected] (S.C.); [email protected] (N.B.); [email protected] (A.M.) 2 Crossing srl, Viale della Repubblica 193/b, 31100 Treviso, Italy; [email protected] * Correspondence: [email protected]; Tel.: +39-041-2348928 Abstract: Conventional methods employed today for the synthesis of amides often lack of economic and environmental sustainability. Triazine-derived quaternary ammonium salts, e.g., 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM(Cl)), emerged as promising dehydro-condensation agents for amide synthesis, although suffering of limited stability and high costs. In the present work, a simple protocol for the synthesis of amides mediated by 2-chloro-4,6-dimethoxy-1,3,5-triazine (CDMT) and a tert-amine has been described and data are compared to DMTMM(Cl) and other CDMT-derived quaternary ammonium salts (DMT-Ams(X), X: − − Cl or ClO4 ). Different tert-amines (Ams) were tested for the synthesis of various DMT-Ams(Cl), but only DMTMM(Cl) could be isolated and employed for dehydro-condensation reactions, while all CDMT/tert-amine systems tested were efficient as dehydro-condensation agents. Interestingly, in best reaction conditions, CDMT and 1,4-dimethylpiperazine gave N-phenethyl benzamide in 93% yield in 15 min, with up to half the amount of tert-amine consumption. The efficiency of CDMT/tert-amine was further compared to more stable triazine quaternary ammonium salts having a perchlorate Citation: Sole, R.; Gatto, V.; Conca, S.; counter anion (DMT-Ams(ClO4)). Overall CDMT/tert-amine systems appear to be a viable and more Bardella, N.; Morandini, A.; Beghetto, V. economical alternative to most dehydro-condensation agents employed today. Sustainable Triazine-Based Dehydro-Condensation Agents Keywords: CDMT; triazines; amide synthesis; sustainable dehydro-condensation agents for Amide Synthesis. Molecules 2021, 26, 191. https://doi.org/ 10.3390/molecules26010191 Academic Editor: Narciso M. Garrido 1. Introduction Received: 8 December 2020 The synthesis of amides is among the most important reactions in organic chemistry and Accepted: 29 December 2020 biochemistry because of the widespread occurrence of amides in pharmaceuticals, peptides, Published: 2 January 2021 biologically active compounds, industrial polymers, detergents, and lubricants [1–6]. Conse- quently, many different physical [7] and chemical protocols have been developed for the Publisher’s Note: MDPI stays neu- synthesis of amides by dehydro-condensation of a carboxylic acid and an amine [8–13]. tral with regard to jurisdictional clai- Catalytic routes for the preparation of amides have also been reported with the intent to ms in published maps and institutio- increase atom efficiency of the process [2,14]. An alternative metal-free synthetic route nal affiliations. for the formation of amides has been recently proposed by Zhang et al. [15] by coupling reaction of formamide with different carboxylic acids. Albeit the strategic importance of this class of compounds, most methods commonly Copyright: © 2021 by the authors. Li- employed for the synthesis of amides still lack both in economic and environmental censee MDPI, Basel, Switzerland. sustainability, have low atom efficiency, generate large quantities of hazardous waste This article is an open access article products, and require complicated purification steps [16–18]. distributed under the terms and con- In this frame, dehydro-condensation reactions are a well-known and consolidated ditions of the Creative Commons At- protocol for the synthesis of amides, although toxic dehydro-condensation agents are often tribution (CC BY) license (https:// used to promote the reaction [17,19]. For example, carbodiimides such as dicyclohexyl- creativecommons.org/licenses/by/ carbodiimide (DCC) or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide chlorohydrate 4.0/). Molecules 2021, 26, 191. https://doi.org/10.3390/molecules26010191 https://www.mdpi.com/journal/molecules Molecules 2021, 26, 191 2 of 15 Molecules 2021, 26, x FOR PEER REVIEW 2 of 15 (EDC)(EDC) employed employed in in combination combination with withN-hydroxysuccinimide N-hydroxysuccinimide (NHS), (NHS), have have frequently frequently been employedbeen employed for the for scope the scope (Figure (Figure1)[20– 1)23 ].[20–23]. FigureFigure 1.1. ChemicalChemical structuresstructures ofof variousvarious dehydro-condensationdehydro-condensation agents. agents. HydroxybenzotriazoleHydroxybenzotriazole (HOBt) (HOBt) [24 [24–26],–26], 1-hydroxy-7-azabenzotriazole 1-hydroxy-7-azabenzotriazole (HOAt) (HOAt) [27 –[27–29], and29], uroniumand uronium or guanidinium or guanidinium salt derivatives salt derivatives such as, such e.g., hexafluorophosphateas, e.g., hexafluorophosphate azaben- zotriazoleazabenzotriazole tetramethyl tetramethyl uronium uronium (HATU), (HATU), hexafluorophosphate hexafluorophosphate benzotriazole benzotriazole tetramethyl tet- uroniumramethyl (HBTU), uronium hexafluorophosphate (HBTU), hexafluorophos chlorobenzotriazolephate chlorobenzotriazole tetramethyl uronium tetramethyl (HCTU), anduronium 1-cyano-2-ethoxy-2-oxoethylidenaminooxy)-dimethylamino-morpholino-carbenium (HCTU), and 1-cyano-2-ethoxy-2-oxoethylidenaminooxy)-dimethylamino-mor- hexafluorophosphatepholino-carbenium hexafluorophosphate (COMU) (Figure1) have(COMU) also (Figure been efficiently 1) have also used been to promoteefficiently carbodiimide-mediatedused to promote carbodiimide-mediated peptide coupling reactions peptide [18coupling,30], although reactions with [18,30], scarce although environ- mentalwith scarce and economicenvironmental sustainability and economic [9,10,31 sust]. Inainability fact, DCC [9,10,31]. and EDC In lead fact, to DCC the formation and EDC of toxic by-products [17], while uronium derivatives may contain highly harmful hydrazide lead to the formation of toxic by-products [17], while uronium derivatives may contain impurities [19]. highly harmful hydrazide impurities [19]. More stringent rules regulating the use and disposal of organic solvents and increas- More stringent rules regulating the use and disposal of organic solvents and increas- ingly restrictive EU directives on hazardous substances make the quest for greener and ingly restrictive EU directives on hazardous substances make the quest for greener and more efficient products and processes increasingly important [17,18]. more efficient products and processes increasingly important [17,18]. In this prospective, quaternary ammonium salts of 2-halo-4,6-dialkoxy-1,3,5-triazines, In this prospective, quaternary ammonium salts of 2-halo-4,6-dialkoxy-1,3,5-tria- e.g., 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM(Cl)), zines, e.g., 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (see Figure2), represent a valid alternative for the formation of amide bonds both in or- (DMTMM(Cl)), (see Figure 2), represent a valid alternative for the formation of amide ganic and water solvent [20,21,32–39]. In the last years, DMTMM(Cl), commonly known as bonds both in organic and water solvent [20,21,32–39]. In the last years, DMTMM(Cl), DMTMM, has found many applications as dehydro-condensation agent for the synthesis of commonly known as DMTMM, has found many applications as dehydro-condensation amides and esters [36,40], collagen cross-linking [7,21,38], preparation of carboxymethylcel- luloseagent basedfor the films synthesis [39], amine of amides grafting and onesters hyaluronan [36,40], collagen [20,40,41 cross-linking], and peptide [7,21,38], synthesis prep- [42]. Additionally,aration of carboxymethylcellulose the synthesis of a library based of 2-(4,6-dimethoxy-1,3,5-triazinyl)trialkyl films [39], amine grafting on hyaluronan ammo- [20,40,41], and peptide synthesis− [42]. Addition− ally, the synthesis of a library of 2-(4,6- nium salts (DMT-Ams(X), X: Cl or ClO4 ) and their activity as dehydro-condensation - - agentsdimethoxy-1,3,5-triazinyl)trialkyl for the synthesis of amides, ammonium has been reported salts (DMT-Ams(X), by Kunishima X: et al.Cl [ 43or] (FigureClO4 ) and2). Thistheir work activity is a as milestone dehydro-condensation in the understanding agents of for triazine the synthesis based-condensation of amides, has agents been and re- theirported application by Kunishima in various et al. fields[43] (Figure of chemistry. 2). This Further work is interesting a milestone feature in the is understanding that DMTMM andof triazine DMT-Ams(X) based-condensation all degrade forming agents and 2,4-dimethoxy-6-hydroxy-1,3,5-triazine their application in various fields of (DMTOH)chemistry. andFurther the correspondinginteresting feature tertiary is that amine DMTMM hydrochloric and DMT-Ams(X) salt, which areall degrade nontoxic. forming Moreover, 2,4- DMTOHdimethoxy-6-hydroxy-1,3,5-triazine can be recovered and recycled (DMTOH) to produce and 2-chloro-4,6-dimethoxy-1,3,5-triazinethe corresponding tertiary amine hy- (CDMT)drochloric or salt, DMTMM which (Figure are nontoxic.2)[ 37]. Moreover, To date, one DMTOH of the main can limitationsbe recovered to and large-scale recycled use to ofproduce DMTMM 2-chloro-4,6-dimethoxy-1,3,5-triazine and DMT-Ams(X)
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