Chemoselective nucleophilic additions to perfluorocyclopentene: An efficient building block to highly fluorinated molecules

Alvino, Ernest L.; Lochmaier, Emeline C.; Iacono, Scott T.; Jennings, Abby R.

doi:10.1016/j.jfluchem.2020.109454

Cited by 4 publications

(5 citation statements)

References 35 publications

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“…[33] To date, few articles focusing on the hydrosilylation of eugenol and its O-substituted derivatives have been published. These examples involve reactions with different silylating agents, including chlorosilanes, [34] 1,1,3,3-tetramethyldisiloxane, [35] 1,1,1,3,5,5,5-heptamethyl-trisiloxane, [36] polysiloxanes, [37] silane dendrimers [38] and silsesquioxanes. [39] However, to the best of our knowledge, the addition of readily hydrolysable silanes across an eugenol C=C bond, leading to the precursor of coupling agents, is limited to 3 examples.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Bio‐Based Silane Coupling Agents by the Modification of Eugenol

et al. 2021

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A simple method for the synthesis of new bio-based silane coupling agents (SCAs) with a terpene aromatic core by the functionalization of cheap, natural eugenol and its sulfur derivatives using the hydrosilylation of the C=C bonds with HSi(OEt) 3 , followed by nucleophilic substitution reactions of OH/SH groups is presented. The obtained alkoxysilanes possess different polymerreactive functionalities (alkenyl, epoxide, thiirane, thiocarbamoyl, thioester, thioether moieties). This new group of biogenic SCAs was fully characterized using 1 H, 13 C, 29 Si NMR, FT-IR, GC-MS, and HRMS or elemental analysis. Examples of their application as additives to tire rubbers and their influence on several factors are also discussed.

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Section: Introductionmentioning

confidence: 99%

Synthesis of Bio‐Based Silane Coupling Agents by the Modification of Eugenol

et al. 2021

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“…[4][5][6] With its commercial availability and known reactivity, especially towards various nucleophiles, perfluorocyclopentene (PFCP) is one such fluorinated cyclic compound that has been utilized for this purpose. [7][8][9] Although the first reports of using PFCP to obtain fluorinated polymers involves employing plasma polymerization techniques, the utilization of PFCP to obtain fluoropolymers has evolved to include chemically transforming PFCP into a polymerizable monomer or reacting PFCP directly with di-nucleophiles. 10,11 In the former case, one of the first known reports of generating a polymerizable monomer from PFCP was presented by Kim et al In this publication, the authors prepared a PFCP monomer that was terminated with methyl methacrylate (Fig.…”

Section: Introductionmentioning

confidence: 99%

“…Additionally, there are numerous reports on preparing fluoropolymers using step‐growth and polycondensation techniques from fluorinated monomers 4–6 . With its commercial availability and known reactivity, especially towards various nucleophiles, perfluorocyclopentene (PFCP) is one such fluorinated cyclic compound that has been utilized for this purpose 7–9 …”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of perfluorocyclopentene‐thioether polymers

Bishop,

Balmaceda,

Iacono

et al. 2024

Polymer International

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Due to their unique properties and use in high performance materials, the ability to obtain fluorinated polymers utilizing straightforward synthetic methods remains of interest. In this study, we report the facile synthesis of new fluoropolymers via nucleophilic addition of a di‐thiol to perfluorocyclopentene. Initially, model studies were completed with perfluorocyclopentene and benzenethiol and TMS‐protected benzenethiol to identify the optimal reaction conditions for the polymerization. These reaction conditions were then utilized to prepare perfluorocyclopentene‐thioether polymers from perfluorocyclopentene and 4, 4′‐thiobisbenzenethiol. The isolated polymers had molecular weight distributions consistent with step‐growth polymers and 19F NMR spectroscopy revealed that the addition of the nucleophile to perfluorocyclopentene was controlled. Analysis by differential scanning calorimetry showed that the polymers were amorphous with glass transition temperatures around 65 °C. Thermogravimetric analysis in both air and nitrogen showed an initial degradation temperature around 370 °C, while the air analysis produced an additional plateau with a degradation temperature near 592 °C. This is the first known report of utilizing perfluorocyclopentene for the preparation of perfluorinated‐thioether polymers.This article is protected by copyright. All rights reserved.

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“…An electrophilic fluoroolefin, a naphthyl-derivatized perfluorocylopentene ( Np-PFCP) , was analyzed for its ability to react with sulfur with and without the K-DTC catalyst. While known to undergo reaction with various nucleophiles under moderate conditions, there have been no known reports of its reactivity with radical species . Attempts by co-workers to polymerize PFCP by thiol–ene click chemistry have also been unsuccessful, indicating its significantly improved reactivity under two-electron conditions.…”

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confidence: 99%

“…While known to undergo reaction with various nucleophiles under moderate conditions, there have been no known reports of its reactivity with radical species. 42 Attempts by co-workers to polymerize PFCP by thiol−ene click chemistry have also been unsuccessful, indicating its significantly improved reactivity under two-electron conditions. When assessed for its reactivity with sulfur, Np-PFCP was found only to react when a catalyst was present.…”

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confidence: 99%

The Role of Dithiocarbamate Catalysts in the Diversification of Sulfur Speciation Towards Anionic Sulfur

Lauer,

Godman,

Iacono

2023

ACS Macro Lett.

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Recently, there has been growing interest in the implementation of various "catalysts" to further diversify the substrate scope for inverse vulcanization reactions. While there have been several proposals on the mechanism of how these catalysts work, the speciation of sulfur in these mixtures has remained elusive. As a key component to understanding when and if these catalysts are appropriate, we sought to elucidate the role of dithiocarbamate species in inverse vulcanization reactions by attempting to characterize the speciation of sulfur. The reaction efficacy for various substrates containing different functional groups with sulfur, either with or without a metal dithiocarbamate, potassium diethyldithiocarbamate (K-DTC), suggests the formation of a rapidly fluctuating sulfur speciation and, most importantly, the presence of anionic sulf ur. The work concludes with some suggestions on best practices for the utilization of dithiocarbamate catalysts based on our results.

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Chemoselective nucleophilic additions to perfluorocyclopentene: An efficient building block to highly fluorinated molecules

Cited by 4 publications

References 35 publications

Synthesis of Bio‐Based Silane Coupling Agents by the Modification of Eugenol

Synthesis of Bio‐Based Silane Coupling Agents by the Modification of Eugenol

Synthesis and characterization of perfluorocyclopentene‐thioether polymers

The Role of Dithiocarbamate Catalysts in the Diversification of Sulfur Speciation Towards Anionic Sulfur

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