Dissociation constants for polyfluoro acids of phosphorus in various media

Матвеева, А. Г.; Kudryavtsev, I. Yu.; Grigor'eva, A. A.; Matrosov, E. I.; Kuznetsova, E.; Zakharov, L. S.; Кабачник, М. И.

doi:10.1007/bf00954148

Cited by 4 publications

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“…[c] --1.29 [90] 6.37 [92] ---Cl 2 CHCO 2 H 1363.8 [c] 6.36 [93] 15.8 [82] 1.29 [94] 7.3 [82] 6.3 [82] 7.55…”

Section: Protic Molecules In Molecular Liquidsmentioning

confidence: 99%

“…For example, the dielectric constant of (aprotic) 1-methylimidazole indicates it is a polar liquid, even if its value is frequency dependent (e.g., e = 21.5 at 5.8 GHz and 32.3 at 2.45 GHz). [123] Addition of HX (X = Cl À , Br À ) does not lead to sol- [73] 25.9 [73] 1.99 [71] --17.2 [73] -CH 3 OH 1606.4 [c] 29.0 [1] À2.4 [74] 15.5 [1] -% 16.5 [30] --CH 3 [15] 12.3 [1] 23.51 [2] 4.75 [33] 10.3 [78] 9.52 [79] 13.5 [80] -ClCH 2 CO 2 H 1408 [18] 9.00 [81] 18.8 [82] 2.81 [82] 8.3 [82] 7.8 [82] 10.1 [82] -C 6 H 5 CO 2 H 1400 [c] 11.0 [83] 20.7 [83] 4.2 [83] 10.25 [84] 9.4 [85] 12.3 [83] 4.20 [86] HCl 1396 [15] 1.8 [1] 8.9 [2] À8 [33] 2.08 [87] 1.23 [88] 3.55 [ [90] 6.37 [92] ---Cl 2 CHCO 2 H 1363.8 [c] 6.36 [93] 15.8 [82] 1.29 [94] 7.3…”

Section: Protic Molecules In Molecular Liquidsmentioning

confidence: 99%

See 1 more Smart Citation

Brønsted Acidity and the Medium: Fundamentals with a Focus on Ionic Liquids

2011

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Fundamental aspects of Brønsted acidity in ionic liquid systems, in relation to those of simple protic molecules in the gas phase, pure protic molecules in the condensed phase and solutions of protic molecules in molecular systems, are presented. The variety of acidities possible, beyond those observed in aqueous systems, is emphasised and discussed in terms of differences of solvent levelling, ionisation, dissociation, homo-/hetero-conjugate ion speciation and the stabilisation of proton-transfer products from solvent to solvent. It is argued that data regarding aqueous systems do not necessarily explain acid/base behaviour in other liquids satisfactorily. Methods of measuring acidity are reviewed, particularly by spectrophotometry and electrochemistry and recommendations proffered for estimating speciation and acidity of ionic liquids of various complexities.

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“…[c] --1.29 [90] 6.37 [92] ---Cl 2 CHCO 2 H 1363.8 [c] 6.36 [93] 15.8 [82] 1.29 [94] 7.3 [82] 6.3 [82] 7.55…”

Section: Protic Molecules In Molecular Liquidsmentioning

confidence: 99%

Section: Protic Molecules In Molecular Liquidsmentioning

confidence: 99%

Brønsted Acidity and the Medium: Fundamentals with a Focus on Ionic Liquids

2011

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“…Lower reactivity of the phosphorochloridates with larger fluorocarbon chains is unlikely to be due to an electronic effect, as increasing the fluorocarbon chain length barely affects the charge on phosphorus; the pK a values for phosphoric acids [H(CF 2 ) 2 CH 2 O] 2 P(O)OH and [H(CF 2 ) 4 CH 2 O] 2 P(O)OH are essentially the same within experimental error[12] and pK a studies on the diacids H(CF 2 ) n CH 2 OP(O)(OH) 2 indicate that the charge on phosphorus is similar when n = 2 or 4[13].…”

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confidence: 72%

Fluorinated phosphorus compounds

Timperley

Bird

Waters

2005

Journal of Fluorine Chemistry

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Twenty nine bis(fluoroalkyl) phosphates (R F O) 2 P(O)OR were prepared in 18-75% yield by treating phosphorochloridates (R F O) 2 P(O)Cl, where R F was HCF C with methanol, ethanol, propanol and isopropanol in diethyl ether in the presence of triethylamine. The bulky chloridate [(CH 3 ) 2 CF 3 CO] 2 P(O)Cl reacted with methanol, ethanol and propanol, but not with isopropanol -even on heating in the presence of the catalyst 4-dimethylaminopyridinedue to steric hindrance at phosphorus. The relative reactivities of three of the chloridates decreased in the order [(CF 3 ) 2 CHO] 2-P(O)Cl > [(FCH 2 ) 2 CHO] 2 P(O)Cl > [(CH 3 ) 2 CF 3 CO] 2 P(O)Cl. Also described is the synthesis of phosphates (CF 3 CH 2 O) 2 P(O)OCH 2 R, where R = CH 2 Br, CH 2 Cl, CH 2 F and CHF 2 , and diphosphates [H(CF 2 ) n CH 2 O] 2 P(O)OCH 2 (CF 2 ) 2 CH 2 OP(O)[OCH 2 (CF 2 ) n H] 2 , where n = 1, 2 and 4. Crown

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“…20 With an effective synthetic protocol in hand, we evaluated the activity of aryl phosphinic acid-phosphoric acid 11a as a Brønsted acid catalyst to demonstrate the efficacy of the design. For this purpose, we initially chose the hetero-Diels-Alder reaction of phenylglyoxal hydrate (13a) with Danishefsky's diene 12 21 (Table 2) due to these expected noteworthy advantages: (1) adequate acidity 22 from the phosphinic acid-phosphoric acid combination that directly generates a non-hydrate form of glyoxal, as a beneficial consequence, 13a could exert a prominent electrophile without arduous distillation and manipulation; 7 (2) exquisite acidity from the phosphinic acid-phosphoric acid combination that could accommodate the use of acid-susceptible dienes such as Danishefsky's dienes without decomposition during the reaction. We found that the hetero-Diels-Alder reaction of 13a with 12, 11a (5 mol%), and 4 Å molecular sieves in toluene at À20 1C for 48 h gave rise to product 14a in 82% yield (entry 1).…”

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confidence: 99%