Syntheses of fluorous quaternary ammonium salts and their application as phase transfer catalysts for halide substitution reactions in extremely nonpolar fluorous solvents

This study outlines the influence of a series of reaction conditions on the yield and reactivity of the glycidyl etherification reaction of the bark extractive-based bioepoxy monomer (E-epoxy). To maximize the yield and epoxy content, the glycidylation reaction was examined with various substrates, solvents, catalysts, time periods, reaction temperatures, and sodium hydroxide/hydroxyl (NaOH/OHV) ratios. Spray-dried bark extractives were used as substrates due to their higher hydroxyl group content and lower molecular weight compared to the oven-dried bark extractives. A dioxane/water combination was selected from among four solvents based on the yield and epoxy equivalent weights of the final product, and tetrabutylammonium hydroxide was chosen as a ring-opening catalyst due to its effect of suppressing hydrolysis. Furthermore, a response surface methodology was applied to find the optimal reaction time, reaction temperature, and NaOH/OHV ratio of the E-epoxy monomer. The maximum extent of conversion with minimum epoxy equivalent weight was achieved after 4.5 h with an NaOH/OHV ratio of 3.4 at 80 °C. This work identifies the effects of reaction parameters on the yield and reactivity of E-epoxy and sheds new light on the glycidylation reaction between epichlorohydrin and renewable biomass.

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“…13 C NMR spectra of E-epoxy monomers synthesized in various solvent systems.Scheme 2. Mechanism of Glycidyl Etherification Catalyzed by TBAH14,41…”

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confidence: 99%

Effects of Reaction Parameters on the Glycidyl Etherification of Bark Extractives during Bioepoxy Resin Synthesis

Kuo

Barros

Sain

et al. 2016

ACS Sustainable Chem. Eng.

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“…As was strikingly visible also from the statistical analysis, the invention of the biphasic fluorous systems induced many new ideas in different sectors of chemical sciences. We demonstrate this tendency by citing a few characteristic references from three leading scientists in the field, who showed also high betweenness centrality scores in Table (Dennis P. Curran ,− and Gianluca Pozzi − ) and in Table (John A. Gladysz − ).…”

Section: Main Communities Of the Network Using Fastgreedy Algorithmmentioning

confidence: 73%

Impact of the Discovery of Fluorous Biphasic Systems on Chemistry: A Statistical and Network Analysis

Barabás

Fülöp

Molontay

et al. 2017

ACS Sustainable Chem. Eng.

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Fluorous chemistry has been in the focus of research interests since the end of the last century. One of the most important contributions in the field was the article Facile Catalyst Separation Without Water: Fluorous Biphase Hydroformylation of Olef ins by Istvań T. Horvath and Joźsef Rabai. It has had great impact on academic chemical research. According to Web of Science (downloaded on 31 January 2017), in more than two decades, 2384 researchers have cited this work in 1077 scientific documents. In the present paper, we illustrate and analyze the co-authorship network determined by these citing documents. We studied the statistical features of these publications, as well as the macro-and micro-characteristics of the network using standard social network analysis techniques. We also interpret the results from a chemical point of view.

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Fluoroponytailed Crown Ethers and Quaternary Ammonium Salts as Solid-Liquid Phase Transfer Catalysts in Organic Synthesis

Pozzi

Fish

2011

Topics in Current Chemistry

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Fluorous derivatives of dibenzo-18-crown-6 ether were prepared, and then successfully applied in representative solid-liquid phase transfer catalysis reactions, which were performed in standard organic solvents, such as chlorobenzene and toluene, as well as in fluorous solvents, such as perfluoro-1,3-dimethylcyclohexane. It was clearly shown that properly designed fluoroponytailed crown ethers could promote the disintegration of the crystal lattice of alkali salts, and transfer anions from the solid surface into an apolar, non-coordinating perfluorocarbon phase, for phase transfer catalysis reactions in organic synthesis. Furthermore, 3,5-bis(perfluorooctyl)benzyl bromide and triethylamine were reacted under mild conditions to provide an analogue of the versatile phase transfer catalyst, benzyltriethylammonium chloride, containing two fluoroponytails. This fluoroponytailed quaternary ammonium salt was also successfully employed as a catalyst in a variety of organic reactions conducted under solid-liquid phase transfer catalysis conditions, without a perfluorocarbon phase. Thus, being both hydrophobic and lipophobic, fluorous crown ethers and ammonium salts, could be rapidly recovered in quantitative yields, and reused without loss of activity, over several reaction cycles.

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Syntheses of fluorous quaternary ammonium salts and their application as phase transfer catalysts for halide substitution reactions in extremely nonpolar fluorous solvents

Cited by 9 publications

References 54 publications

Effects of Reaction Parameters on the Glycidyl Etherification of Bark Extractives during Bioepoxy Resin Synthesis

Effects of Reaction Parameters on the Glycidyl Etherification of Bark Extractives during Bioepoxy Resin Synthesis

Impact of the Discovery of Fluorous Biphasic Systems on Chemistry: A Statistical and Network Analysis

Fluoroponytailed Crown Ethers and Quaternary Ammonium Salts as Solid-Liquid Phase Transfer Catalysts in Organic Synthesis

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