Synthesis of Tailored Perfluoro Unsaturated Monomers for Potential Applications in Proton Exchange Membrane Preparation
Abstract
:1. Introduction
2. Results
2.1. Planning the Synthetic Strategy
2.1.1. The Heck-Type Coupling Reaction
2.1.2. The Nucleophilic Displacement Approach
2.1.3. Carbanion Approach: The Wittig–Horner Reaction
2.2. Thin Film Membrane Deposition by Low-Pressure Plasma
3. Materials and Methods
3.1. General Remarks
3.2. Deposition and Characterization of Thin Film Membranes by PECVD
3.3. General Procedures for the Synthesis of Perfluorinated Monomers
3.3.1. Procedure for the Heck Coupling in Table 1: Synthesis of Perfluorosulfonic Ester 14
3.3.2. Procedure for the Synthesis of Fluorinated Carboxylic Esters 16 and 19 (Scheme 4, Equations (1) and (2))
3.3.3. Procedure for the Oxidative Heck Coupling: Synthesis of Perfluorinated Phosphonyl Ester 22 (Scheme 4, Equation (3))
3.3.4. Procedures for the Nucleophilic Substitution: Synthesis of Perfluorinated Sulfonic Esters 25 and 27
3.3.5. Procedures for Wittig–Horner Reaction: Synthesis of Perfluorinated Sulfonic Esters 29 and 30
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Run | Vinyl Sulfonate | Arf-X | Catalyst | Solvent | Base | Product | Yield (%) |
---|---|---|---|---|---|---|---|
1 | 1 | 5 | Pd(OAc)2/PPh3 | NMP | K2CO3 | | traces |
2 | 1 | 5 | Pdcolloids | DMF | K2CO3 | traces | |
3 | 2 | 5 | Pd(OAc)2/PPh3 | DMF | K2CO3 | | 5 |
4 | 2 | 5 | Pdcolloids | DMF | K2CO3 | traces | |
5 | 3 | 5 | Pdcolloids | H2O | TBAOH | | 17–50 b |
6 | 3 | 6 | Pdcolloids | H2O | TBAOH | | 13–45 b |
7 | 4 | 5 | Pdcolloids | H2O | TBAOH | | traces |
8 | 1 | 7 | Pd(OAc)2/PPh3 | DMF | K2CO3 | | 5 |
9 | 2 | 7 | Pd(OAc)2/PPh3 | DMF | K2CO3 | | 65 c |
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Monopoli, A.; Casiello, M.; Cotugno, P.; Milella, A.; Palumbo, F.; Fracassi, F.; Nacci, A. Synthesis of Tailored Perfluoro Unsaturated Monomers for Potential Applications in Proton Exchange Membrane Preparation. Molecules 2021, 26, 5592. https://doi.org/10.3390/molecules26185592
Monopoli A, Casiello M, Cotugno P, Milella A, Palumbo F, Fracassi F, Nacci A. Synthesis of Tailored Perfluoro Unsaturated Monomers for Potential Applications in Proton Exchange Membrane Preparation. Molecules. 2021; 26(18):5592. https://doi.org/10.3390/molecules26185592
Chicago/Turabian StyleMonopoli, Antonio, Michele Casiello, Pietro Cotugno, Antonella Milella, Fabio Palumbo, Francesco Fracassi, and Angelo Nacci. 2021. "Synthesis of Tailored Perfluoro Unsaturated Monomers for Potential Applications in Proton Exchange Membrane Preparation" Molecules 26, no. 18: 5592. https://doi.org/10.3390/molecules26185592