Products formed at intermediate stages of electrochemical perfluorination of propionyl and n-butyryl chlorides. Further evidence in support of NiF3 mediated free radical pathway

Rangarajan, T. M.; Sathyamoorthi, Shyam; Velayutham, D.; Noel, M.; Singh, Rajpal; Brahma, Raju

doi:10.1016/j.jfluchem.2010.12.004

Cited by 10 publications

(8 citation statements)

References 16 publications

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“…Further, the corresponding olefinic protons appeared at 7.18 and 7.63 ppm for E and Z isomers, respectively. The existence of 17 ( E/Z) has been confirmed by using a combination 1–2D NMR spectroscopy, and the data are consistent with literature reports for methyl ester of 17 ( E/Z) , (Figures S29–S33). Along the same line, the presence of 13 was established by a combination of 1–2D NMR spectroscopy and literature precedence …”

Section: Results and Discussionsupporting

confidence: 90%

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Reactivity of Difunctional Polar Monomers and Ethylene Copolymerization: A Comprehensive Account

Gaikwad¹,

Deshmukh²,

Koshti³

et al. 2017

Macromolecules

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A comprehensive picture of insertion of 1,1disubstituted difunctional olefins, their ability to double the functional group density at the same level of incorporation as that of monofunctional olefin, and copolymerization with ethylene has been demonstrated. Exposure of a palladium complex [{P∧O}PdMe(L)] (P∧O = κ 2 -P,O−Ar 2 PC 6 H 4 SO 2 O with Ar = 2-MeOC 6 H 4 ; L = C 2 H 6 OS) to methyl 2acetamidoacrylate (MAAA) revealed slight preference for 1,2insertion over 2,1-insertion (1.0:0.7). In contrast, insertion of electron-deficient 2-(trifluoromethyl)acrylic acid (TFMAA) unveiled selective 2,1-insertion {via [(P∧O)PdC 5 H 6 F 3 O 2 ] (11)}. The unstable intermediate 11 undergoes β-hydride and β-fluoride elimination to produce subsequent insertion and elimination products. The identity of elimination products (E/Z)-2-trifluoromethyl)but-2-enoic acid [17(E/Z)] and 2-(difluoromethylene)butanoic acid (13) was fully established by 1−2D NMR spectroscopy. These insertion experiments, taken together with insertion rates, suggest that MAAA and TFMAA are amenable to insertion. Polymerization of ethylene with MAAA, TFMAA, acetamidoacrylic acid, 2-bromoacrylic acid, dimethyl allylmalonate, and allylmalonic acid was catalyzed by [{P∧O}PdMe(L)] (L = C 2 H 3 N) (5.ACN), and the highest incorporation of 11.8% was observed for dimethyl allylmalonate (DMAM). The changes in the surface properties of the copolymers after incorporation of difunctional olefins were evaluated by measuring the water contact angle. Copolymer with highest (11.8% of DMAM) incorporation revealed a reduced water contact angle of 76°. These findings demonstrate that 1,1-disubstituted difunctional olefins are amenable to polymerization, and incorporation of difunctional olefins in polyethylene backbone leads to the production of relatively hydrophilic polyethylene copolymers.

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Section: Results and Discussionsupporting

confidence: 90%

“…The mass analysis was further supported by NMR spectroscopy which revealed the presence of elimination product 13 and 17 ( E / Z ). The existence of 17 ( E / Z ) and 13 was fully established by a combination of spectroscopic and analytical methods, and the observed characteristic features comply with known literature data for 17 . , …”

Section: Methodssupporting

confidence: 75%

Reactivity of Difunctional Polar Monomers and Ethylene Copolymerization: A Comprehensive Account

Gaikwad¹,

Deshmukh²,

Koshti³

et al. 2017

Macromolecules

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“…An enormous amount of effort has gone into elucidating the mechanism of the electrochemical fluorination (ECF) of organic compounds in anhydrous HF since its development about 70 years ago. − This work has been aimed at explaining the complexity of the mixtures normally produced when the ECF process is used. Most relevant to the structures of the components identified in the commercial mixtures studied here is that intermediate free radicals formed during the production of PFECHS may have played two key roles.…”

Section: Resultsmentioning

confidence: 99%

Characterization of Nine Isomers in Commercial Samples of Perfluoroethylcyclohexanesulfonate and of Some Minor Components Including PFOS Isomers

Stefanac¹,

McCrindle

McAlees³

et al. 2018

Environ. Sci. Technol.

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Electrochemical fluorination of 4-ethylbenzenesulfonyl halides produces a mixture of compounds that has found extensive use as an erosion inhibitor in aircraft hydraulic fluids. This paper reports a study of the composition of commercial samples of this material from two industrial scale manufacturers in terms of the structures and relative concentrations of their components, the major of which is perfluoroethylcyclohexanesulfonate (PFECHS). Fractionation of one of these mixtures by column chromatography produced fractions in which all significant components were of sufficient purity to allow assignment of their structures by F NMR spectroscopy. Assessment of the relevant signals in theF NMR spectra of the commercial mixtures by integration revealed the presence of 14 constituents at levels ≥0.5% in terms of molar contributions. Ten of these involve five pairs of geometric isomers, including cis- and trans-PFECHS which accounted for between 55% and 60% of the components present. Three constituents were determined to be isomers of perfluorooctanesulfonate (PFOS), two branched and the other linear PFOS itself. The availability of samples of the various components also allowed us to identify the compounds responsible for the peaks observed when the commercial samples were analyzed by LC/MS using either C or perfluorophenyl stationary phases.

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“…2,17 The reason for the formation of these species and the mechanism of the Simons process are still under debate. [1][2][3]17,23,31 In principle, two mechanisms have been proposed: (I) either the uorination proceeds via the electrochemical oxidation of the substrate and consecutive reaction with HF following the EC b EC N mechanism (explanation in ref. 32; Fig.…”

mentioning

confidence: 99%

“…1, right). 1,2,4,17,[24][25][26][27][28][29][30][31] Both mechanisms have been investigated in the last decades, while indications were found for both of them. 1,3,23,31,33,34 The presence of cationic intermediates as proposed for the EC b EC N mechanism is supported by the observation of products that are typical of cationic isomerization processes.…”

mentioning

confidence: 99%

Unravelling highly oxidized nickel centers in the anodic black film formed during the Simons process by in situ X-ray absorption near edge structure spectroscopy

Senges,

Buzanich,

Lindič

et al. 2024

Chem. Sci.

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Products formed at intermediate stages of electrochemical perfluorination of propionyl and n-butyryl chlorides. Further evidence in support of NiF3 mediated free radical pathway

Cited by 10 publications

References 16 publications

Reactivity of Difunctional Polar Monomers and Ethylene Copolymerization: A Comprehensive Account

Reactivity of Difunctional Polar Monomers and Ethylene Copolymerization: A Comprehensive Account

Characterization of Nine Isomers in Commercial Samples of Perfluoroethylcyclohexanesulfonate and of Some Minor Components Including PFOS Isomers

Unravelling highly oxidized nickel centers in the anodic black film formed during the Simons process by in situ X-ray absorption near edge structure spectroscopy

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