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Carbon-13 Isotope Fractionation in the decarboxylation of Phenylpropiolic Acid (PPA) Below and Above Its melting Point and in the Decarboxylation of PPA in Phenylacetylene Medium

Zieliński M., Zielińska A., Papiernik-Zielińska H.

Polish Journal of Chemistry

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2000

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Vol. 74, nr 8

1143-1148

EN

C-13 isitipe fractionation in the decarboxylation of pure phenylpropiolic acid (PPA) below and above its melting point and the decarboxylation of PPA in phenylacetylene solutions has been investigated in sealed under vacuum reaction vessels.

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Carbon-13 isotope effect for decarboxylation of phenylpropiolic acid (PPA) in concentrated phosphoric acids

Zieliński M., Zielińska A., Papiernik-Zielińska H., Ogrinc N., Kobal I.

Nukleonika

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2000

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Vol. 45, nr 2

121-124

EN

13C isotope effects on the decarboxylation of phenylpropiolic acid (PPA) in 93–97% H3PO4 and in 23% diphosphoric acid in orthophosphoric acid have been investigated from 293 to 353 K. The initial 13C fractionations in all three systems are in agreement with the 13C decarboxylation fractionations expected assuming the loss of the one carbon-carbon bond in the transition state. In 100% H3PO4 and in 23% diphosphoric acid in orthophosphoric acid later fractions of carbon dioxide are depleted in carbon-13 to a greater degree than expected, probably due to isotopic preequilibria between stable and decarboxylating forms of PPA. At 353 K and higher temperature strong deviations of the experimental rate constants and of the experimental 13C fractionations from the values extrapolated from lower temperature are observed. A tentative decarboxylation scheme operating in concentrated phosphoric acid media is proposed.

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Carbon-13 isotope effect for decarboxylation of phenylpropiolic acid (PPA) in orthophosphoric acid

Zielińska A., Zieliński M., Zielińska-Papiernik H.

Nukleonika

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1999

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Vol. 44, nr 3

403-410

EN

The carbon-13 isotope effect accompanying decarboxylation of phenylpropiolic acid in 85% orthophosphoric acid has been studied in the temperature range 323-353 K. The first fraction of CO2 was found to be generated at 323 K in 85% H3PO4 with the carbon-13 isotope effect, k[indeks dolny]12/k[indeks dolny]13, equal to 1.011-1.015. The subsequent fractions of carbon dioxide produced in the temperature range 323-353 K have shown none but about 0.2% per cent kinetic isotope effect (KIE). It has been suggested that the initial larger carbon-13 fractionation, accompanying the decarboxylation of PPA in 85% orthophosphoric acid, is caused by isotopic equilibra linking decarboxylating monomeric species of PPA with dimeric and larger units formed during solvation and dissolving of solid PPA in orthophosphoric acid. The solvated PPA molecules are decarboxylated in the homogeneous solution with a negligible carbon-13 KIE. The triple bond of phenylpropiolic acid is attacked by the hydrated protons, H3O⊕aq, and formation of the Calpha-H bond is the rate determining step. The bond rupture between the alpha carbon and the carboxyl group is the next fast reaction step. The enthalpy of activation, ΔH[indeks górny]≠ = 123.4 kJ/mol, and the positive entropy of activation, ΔS≠ = +30 e.u.(SI), exclude the chelate like structure of the transition state. This suggests a flexible structure of the transition state complex which must be less solvated than in the initial state. Some further studies of the carbon-13 KIEs in phosphoric acid environment are suggested.

PL

Zbadano efekt izotopowy 13C w reakcji dekarboksylacji kwasu fenylopropiolowego (PPA) w 85% H3PO4 w 323-373 K. Delta (PDB) pierwszej porcji dwutlenku węgla, przy stopniach dekarboksylacji około f= 0.1, wskazuje na jej początkowe wzbogacenie w 13C o około 1,0-1,5%. Spowodowane jest to prawdopodobnie procesami równowagowymi, zachodzącymi między ulegającymi dekarboksylacji monomerami PPA a większymi agregatami, powstającymi w wyniku oddziaływania kryształów PPA z uwodnionymi cząsteczkami kwasu ortofosforowego. Dalsza dekarboksylacja PPA przebiega w roztworze homogenicznym bez wyraźnego rozfrakcjonowania izotopów węgla. Przyłączenie protonów do wiązania potrójnego i tworzenie wiązania Calfa-H zachodzi w etapie krytycznym reakcji, poprzedzającym właściwą dekarboksylację, tj. utratę cząsteczki dwutlenku węgla przez kwas fenylopropiolowy. Entalpia aktywacji ΔH[indeks górny]≠ = 123,4 kJ/mol i dodatnia entropia aktywacji ΔS[indeks górny]≠ = +30 e.u.(SI) sugerują niecykliczny, swobodny, stan przejściowy kompleksów reakcji dekarboksylacji PPA w 85% kwasie ortofosforowym. Zaproponowano dalsze badania efektu izotopowego 13C w środowisku kwasów fosforowych.

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(13)C kinetic isotope effects in the decarboxylation of phenylpropiolic acid (PPA) assisted with formic acid and (13)C KIE in the decarbonylation of formic acid in the presence of PPA

Zieliński M., Zielińska A., Paul H., Papiernik-Zielińska H.

Polish Journal of Chemistry

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1998

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Vol. 72, nr 12

2551-2555

EN

Carbon-13 kinetic isotope effects, (13)C-KIE, in the decarboxylation of phenylpropiolic acid (carboxyl C-13) in formic acid medium and (13)C KIE in the decarbonylation of liquid formic acid assisted with PPA and acetophenone have been studied in the 70-100 degree C temperature interval. The kinetic and isotope results have been discussed and interpreted as indicating that the formation of C alpha-H bond, preceded by the protonation of acetylenic bond of PPA, is the rate determining step followed by carbon dioxide splitting. The (13)CO-KIE in the carbon monoxide generation assisted with PPA is much larger than the (13)CO-KIE observed in the generation of CO in the presence of phenylacetylene. Thus the decaeboxylation of PPA and decarbonylation of formic acid are interrelated processes proceeding in the reaction cage.