Ene reaction of triazolinediones with alkenes. 2. Kinetics and substituent effects

Ohashi, Shigeru; Butler, George B.

doi:10.1021/jo01305a021

Cited by 46 publications

(40 citation statements)

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“…Similar activation of dienophiles in H ‐donor solvents is well known for other types of reactions. Previously, the solvent effect on the rate of the number of reactions involving dienophile 1 has been considered, which makes it possible to compare the solvent effect on the rate of the studied ene reactions 1 + 2 → 3 and 1 + 4 → 5 with regard to the [2π+2σ+2σ]‐cycloaddition reaction of 1 with quadricyclane ( 7 ), ene reaction with 2‐methylbutene‐2 ( 14 ), [2π+2π]‐cycloaddition reaction of 1 with 2‐chloroethylvinyl ether ( 15 ), ene reaction between 1 and norbornene ( 9 ) with Wagner‐Meerwein rearrangement, ene reaction of 1 with trans ‐hexene‐3 ( 16 ), [4π+2π]‐cycloaddition reaction of 1 with anthracene ( 17 ), and [2π+2π]‐cycloaddition reaction of 1 with bisadamantylidene ( 10 ) (Equations ):

\begin{matrix} true \\ right \ln k ((), bold1 + bold2) & = & left ((), 1.04 \pm 0.03) \cdot \ln k ((), bold1 + bold4) - ((), 0.65 \pm 0.07); \\ left R^{2} = 0.9939, N = 9 \end{matrix}

\begin{matrix} true \\ right \ln k ((), bold1 + bold7) & = & left ((), 0.82 \pm 0.14) \cdot \ln k ((), bold1 + bold4) + ((), 0.13 \pm 0.29); \\ left R^{2} = 0.8515, N = 8 \end{matrix}

\begin{matrix} true \\ right \ln k ((), bold1 + bold15) & = & left ((), 0.52 \pm 0.03) \cdot \ln k ((), bold1 + bold4) + ((), 2.65 \pm 0.08); \\ left R^{2} = 0.9869, N = 5 \end{matrix}

\begin{matrix} true \\ right \ln k ((), bold1 + bold9) & = & left \end{matrix}

…”

Section: Resultsmentioning

confidence: 99%

Kinetics of the ene reactions of 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione with β‐pinene and 2‐carene: Temperature, high pressure, and solvent effects

Kiselev

Kornilov

Anikin

et al. 2018

Int J of Chemical Kinetics

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The data on temperature, solvent, and high hydrostatic pressure influence on the rate of the ene reactions of 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione (1) with 2‐carene (2), and β‐pinene (4) have been obtained. Ene reactions 1+2 and 1+4 have high heat effects: ∆Hr‐n (1+2) −158.4, ∆Hr‐n(1+4) −159.2 kJ mol−1, 25°C, 1,2‐dichloroethane. The comparison of the activation volume (∆V≠(1+2) −29.9 cm3 mol−1, toluene; ∆V≠(1+4) −36.0 cm3 mol−1, ethyl acetate) and reaction volume values (∆Vr‐n(1+2) −24.0 cm3 mol−1, toluene; ∆Vr‐n(1+4) −30.4 cm3 mol−1, ethyl acetate) reveals more compact cyclic transition states in comparison with the acyclic reaction products 3 and 5. In the series of nine solvents, the reaction rate of 1+2 increases 260‐fold and 1+4 increases 200‐fold, respectively, but not due to the solvent polarity.

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\begin{matrix} true \\ right \ln k ((), bold1 + bold2) & = & left ((), 1.04 \pm 0.03) \cdot \ln k ((), bold1 + bold4) - ((), 0.65 \pm 0.07); \\ left R^{2} = 0.9939, N = 9 \end{matrix}

\begin{matrix} true \\ right \ln k ((), bold1 + bold7) & = & left ((), 0.82 \pm 0.14) \cdot \ln k ((), bold1 + bold4) + ((), 0.13 \pm 0.29); \\ left R^{2} = 0.8515, N = 8 \end{matrix}

\begin{matrix} true \\ right \ln k ((), bold1 + bold15) & = & left ((), 0.52 \pm 0.03) \cdot \ln k ((), bold1 + bold4) + ((), 2.65 \pm 0.08); \\ left R^{2} = 0.9869, N = 5 \end{matrix}

\begin{matrix} true \\ right \ln k ((), bold1 + bold9) & = & left \end{matrix}

…”

Section: Resultsmentioning

confidence: 99%

Kinetics of the ene reactions of 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione with β‐pinene and 2‐carene: Temperature, high pressure, and solvent effects

Kiselev

Kornilov

Anikin

et al. 2018

Int J of Chemical Kinetics

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“…This suggests that the volume of the activated complex of reactions 1 + 4 → 5 and 1 + 6 → 7 in toluene is smaller by 16% than that of the products 5 and 7 . The data available, showing the weak influence of the solvent polarity on the reaction rate, allow to exclude the solvent electrostriction in the solvation shell of the activated complex as the main cause resulting in this ratio: ∆ V ≠ corr /∆ V r − n > 1. This “abnormal” ratio (∆ V ≠ corr /∆ V r − n > 1) in the isopolar DARs was explained by different possibilities of the solvent molecules to fit the large steric hindered structures of the cyclic activated complex and cyclic adducts .…”

Section: Resultsmentioning

confidence: 99%

“…An extensive study of the products structure, the reaction rate and the solvent effect on the reaction of [4 + 2]‐cycloaddition of 1 with various 1,3‐dienes was presented . Practically, at the same time, the ene synthesis of 1 with various alkenes was initiated . N ‐allylurazole derivatives, the ene reaction products, are usually formed when the allyl hydrogen atom is present in alkene as well as α‐shift of the double bond in the product is possible …”

Section: Introductionmentioning

confidence: 99%

4‐Phenyl‐1,2,4‐triazoline‐3,5‐dione in the ene reactions with cyclohexene, 1‐hexene and 2,3‐dimethyl‐2‐butene. The heat of reaction and the influence of temperature and pressure on the reaction rate

Kiselev

Kornilov

Kashaeva

et al. 2014

J of Physical Organic Chem

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The values of the enthalpy (53.3; 51.3; 20.0 kJ mol−1), entropy (−106; −122; −144 J mol−1K−1), and volume of activation (−29.1; −31.0; −cm3 mol−1), the reaction volume (−25.0; −26.6; −cm3 mol−1) and reaction enthalpy (−155.9; −158.2; −150.2 kJ mol−1) have been obtained for the first time for the ene reactions of 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione 1, with cyclohexene 4, 1‐hexene 6, and with 2,3‐dimethyl‐2‐butene 8, respectively. The ratio of the values of the activation volume to the reaction volume (∆V≠corr/ΔVr − n) in the ene reactions under study, 1 + 4→5 and 1 + 6→7, appeared to be the same, namely 1.16. The large negative values of the entropy and the volume of activation of studied reactions 1 + 4→ 5 and 1 + 6→7 better correspond to the cyclic structure of the activated complex at the stage determining the reaction rate. The equilibrium constants of these ene reactions can be estimated as exceeding 1018 L mol−1, and these reactions can be considered irreversible. Copyright © 2014 John Wiley & Sons, Ltd.

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“…We observed only small variations of the ratio of products 3 and 4 with increase in solvent polarity for reactions carried out in diethyl ether, CHCl 3 , C 6 H 6 , CH 3 EXPERIMENTAL NMR spectra were recorded using a Varian Gemini BP spectrometer, UV spectra were recorded on a Specord spectrometer (Carl Zeiss Jena) using 10 mm cells.…”

Section: Introductionmentioning

confidence: 99%

“…Butler [3] carried out kinetic measurements for the reaction of 4-substituted -1,2,4-triazoline-3,5-diones including PTAD with different olefins.…”

Section: Introductionmentioning

confidence: 99%

Effect of Solvent on Rate of Reactions of Different Olefins With 4-Phenyl-1,2,4-Triazoline-3,5-Dione

Kinart

2003

Physics and Chemistry of Liquids

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Ene reaction of triazolinediones with alkenes. 2. Kinetics and substituent effects

Cited by 46 publications

References 0 publications

Kinetics of the ene reactions of 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione with β‐pinene and 2‐carene: Temperature, high pressure, and solvent effects

Kinetics of the ene reactions of 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione with β‐pinene and 2‐carene: Temperature, high pressure, and solvent effects

4‐Phenyl‐1,2,4‐triazoline‐3,5‐dione in the ene reactions with cyclohexene, 1‐hexene and 2,3‐dimethyl‐2‐butene. The heat of reaction and the influence of temperature and pressure on the reaction rate

Effect of Solvent on Rate of Reactions of Different Olefins With 4-Phenyl-1,2,4-Triazoline-3,5-Dione

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