Carbon-chain isomerization during the electrochemical fluorination in anhydrous hydrogen fluoride—a mechanistic study

Ignat’ev, Nikolai; Welz‐Biermann, Urs; Heider, U.; Kucheryna, Andriy; Ahsen, Stefan von; Habel, Wolfgang; Sartori, Peter; Willner, Helge

doi:10.1016/s0022-1139(03)00174-x

Cited by 29 publications

(48 citation statements)

References 62 publications

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“…Purity of the PFBSF was checked by Gas Chromatography and 19 F NMR spectra (>99%). The analytical data are found to be in conformity with 19 F NMR data reported in the literature [31].…”

Section: Preparation Of Potassium Nonaflate (Knfo)supporting

confidence: 87%

Electrochemical behaviour of tetra-n-butylammonium nonaflate as an ionic liquid and as a supporting electrolyte in aprotic solvents: A comparative study

Manivel

Velayutham

Noel

2011

Journal of Electroanalytical Chemistry

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“…Purity of the PFBSF was checked by Gas Chromatography and 19 F NMR spectra (>99%). The analytical data are found to be in conformity with 19 F NMR data reported in the literature [31].…”

Section: Preparation Of Potassium Nonaflate (Knfo)supporting

confidence: 87%

Electrochemical behaviour of tetra-n-butylammonium nonaflate as an ionic liquid and as a supporting electrolyte in aprotic solvents: A comparative study

Manivel

Velayutham

Noel

2011

Journal of Electroanalytical Chemistry

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“…(C 2 F 5 ) 3 PF 2 is produced on a technical scale by the electrochemical fluorination of triethylphosphane in anhydrous HF and was generously provided by Merck (Darmstadt, Germany). [13] (C 2 F 5 ) 3 PF 2 adds aqueous HF to form the strong acid [14] which hydrolyzes at 130 8C to afford (C 2 F 5 ) 2 P(O)OH. [15] The chlorinating reagent PhPCl 4 transforms this acid into the corresponding phosphinic acid chloride, (C 2 F 5 ) 2 P(O)Cl.…”

Section: Resultsmentioning

confidence: 99%

Chlorobis(pentafluoroethyl)phosphane: Improved Synthesis and Molecular Structure in the Gas Phase

Hayes

Berger

Mitzel

et al. 2011

Chemistry A European J

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(C(2)F(5))(2)PCl is now accessible through a significantly improved synthesis protocol starting from the technical product (C(2)F(5))(3)PF(2). (C(2)F(5))(3)PF(2) was reduced in the first step with NaBH(4) in a solvent-free reaction at 120 °C. The product, P(C(2)F(5))(3), was treated with an excess of an aqueous sodium hydroxide solution to afford the corresponding phosphinite salt Na(+)(C(2)F(5))(2)PO(-) selectively under liberation of pentafluoroethane. Subsequent chlorination with PhPCl(4) resulted in the selective formation of (C(2)F(5))(2)PCl, which was isolated by fractional condensation in an overall yield of 66 %. The gas electron diffraction (GED) pattern for (C(2)F(5))(2)PCl was recorded and found to be described by a two-conformer model. A quantum chemical investigation of the potential-energy surface revealed the possible existence of many low-energy conformers, each with a number of low-frequency vibrational modes and therefore large-amplitude motions. The conformer calculated to be most stable was also found to be most abundant by GED and comprised 61(5) % of the total. The molecular structure parameters determined by GED were in good agreement with those calculated at the MP2/TZVPP level of theory; the only significant difference was a discrepancy of about 3° in the C-P-C angle, which, for the lowest-energy conformer, was refined to 98.2(4)° and was calculated to be 94.9°.

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“…Recently a mechanistic scheme for carbon chain isomerisation during the electrochemical fluorination of alkane sulfonyl fluoride was proposed [29]. We have extended this study to n-butyryl, iso-butyryl and pivaloyl chlorides and explained the cause for higher conversion from iso-alkane carboxylic acid to n-alkane carboxylic acid during electrochemical fluorination [30].…”

Section: Introductionmentioning

confidence: 84%

“…Both perfluoro-n-alkanes and perfluoro-iso-alkanes are obtained (compound [21][22][23][24][25][26][27][28][29][30][31][32][33]. For all the five acid chlorides, the perfluoro-n-alkane content was found to be in the range 38-44%.…”

Section: Product Distribution In Alkali Insoluble Fractionmentioning

confidence: 99%

Effect of alkyl chain length on the electrochemical perfluorination of n-alkane (C6–C10) carboxylic acid chlorides

et al. 2007

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Carbon-chain isomerization during the electrochemical fluorination in anhydrous hydrogen fluoride—a mechanistic study

Cited by 29 publications

References 62 publications

Electrochemical behaviour of tetra-n-butylammonium nonaflate as an ionic liquid and as a supporting electrolyte in aprotic solvents: A comparative study

Electrochemical behaviour of tetra-n-butylammonium nonaflate as an ionic liquid and as a supporting electrolyte in aprotic solvents: A comparative study

Chlorobis(pentafluoroethyl)phosphane: Improved Synthesis and Molecular Structure in the Gas Phase

Effect of alkyl chain length on the electrochemical perfluorination of n-alkane (C6–C10) carboxylic acid chlorides

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