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1.
Vladimir D. Kiselev Ilzida I. Shakirova Dmitry A. Kornilov Helen A. Kashaeva Lubov N. Potapova Alexander I. Konovalov 《Journal of Physical Organic Chemistry》2013,26(1):47-53
Solvent, temperature, and high pressure influence on the rate constant of homo‐Diels–Alder cycloaddition reactions of the very active hetero‐dienophile, 4‐phenyl‐1,2,4‐triazolin‐3,5‐dione (1), with the very inactive unconjugated diene, bicyclo[2,2,1]hepta‐2,5‐diene (2), and of 1 with some substituted anthracenes have been studied. The rate constants change amounts to about seven orders of magnitude: from 3.95.10?3 for reaction (1+2) to 12200 L mol?1 s?1 for reaction of 1 with 9,10‐dimethylanthracene (4e) in toluene solution at 298 K. A comparison of the reactivity (ln k2) and the heat of reactions (?r‐nH) of maleic anhydride, tetracyanoethylene and of 1 with several dienes has been performed. The heat of reaction (1+2) is ?218 ± 2 kJ mol?1, of 1 with 9,10‐dimethylanthracene ?117.8 ± 0.7 kJ mol?1, and of 1 with 9,10‐dimethoxyanthracene ?91.6 ±0.2 kJ mol?1. From these data, it follows that the exothermicity of reaction (1+2) is higher than that with 1,3‐butadiene. However, the heat of reaction of 9,10‐dimethylanthracene with 1 (?117.8 kJ mol?1) is nearly the same as that found for the reaction with the structural C=C counterpart, N‐phenylmaleimide (?117.0 kJ mol?1). Since the energy of the N=N bond is considerably lower (418 kJ/bond) than that of the C=C bond (611 kJ/bond), it was proposed that this difference in the bond energy can generate a lower barrier of activation in the Diels–Alder cycloaddition reaction with 1. Linear correlation (R = 0.94) of the solvent effect on the rate constants of reaction (1+2) and on the heat of solution of 1 has been observed. The ratio of the volume of activation (?V≠) and the volume of reaction (?Vr‐n) of the homo‐Diels–Alder reaction (1+2) is considered as “normal”: ?V≠/?Vr‐n = ?25.1/?30.95 = 0.81. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
2.
The reaction mechanisms as well as substituted effect and solvent effect of the enyne–allenes are investigated by Density Functional Theory (DFT) method and compared with the Myers–Saito and Schmittel reactions. The Myers–Saito reaction of non‐substituted enyne–allenes is kinetically and thermodynamically favored as compared to the Schmittel reaction; while the concerted [4 + 2] cycloaddition is only 1.32 kcal/mol higher than the C2? C7 cyclization and more exothermic (ΔRE = ?69.38 kcal/mol). For R1 = CH3 and t‐Bu, the increasing barrier of the C2? C7 cyclization is higher than that for the C2? C6 cyclization because of the steric effect, so the increased barrier of the [4 + 2] cycloaddition is affected by such substituted electron‐releasing group. Moreover, the strong steric effect of R1 = t‐Bu would shift the C2? C7 cyclization to the [4 + 2] cycloaddition. On the other hand, for R1 = Ph, NH2, O?, NO2, and CN substituents, the barrier of the C2? C6 cyclization would be more diminished than the C2? C7 cyclization due to strong mesomeric effect; the reaction path of C2? C7 cyclization would also shift to the [4 + 2] cycloaddition. The solvation does not lead to significant changes in the potential‐energy surface of the reaction except for the more polar surrounding solvent such as dimethyl sulfoxide (DMSO), or water. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
3.
Surfactant‐assisted specific‐acid catalysis (SASAC) for Diels–Alder reactions of dienophiles 1 and 4 with cyclopentadiene 2 in aqueous media at 32 °C was studied. This study showed that acidified anionic surfactants (pH 2) such as sodium dodecyl sulfate (SDS) and linear alkylbenzene sulfonic acid (LAS) accelerate Diels—Alder reactions. Conversely, under similar reaction conditions (pH 2) these reactions are inhibited by (acidified) cationic surfactants such as dodecyltrimethylammonium bromide (DTAB), dodecyldimethylammonium bromide (DDAB), and dodecylmethylammonium bromide (DMAB). A modest rate acceleration resulting from the surfactant hydrogen‐bonding capacity is also recorded for the Diels–Alder reaction of naphthoquinones ( 6 ) with cyclopentadiene ( 2 ) in aqueous media at 32 °C. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
4.
Substituent effects in the Diels–Alder reactions of butadienes,cyclopentadienes, furans and pyroles with maleic anhydride
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Yongge Qiu 《Journal of Physical Organic Chemistry》2015,28(5):370-376
In this study, activation energies in the Diels–Alder reactions of a series of substituted butadienes, cyclopentadienes, furans and pyroles with maleic anhydride were calculated by the M06‐2X/6‐31G(d) method. The substituent effects on the reactivity and the endo–exo selectivity have been examined. The strength of reactivity effect has an order of pyroles > furans > cyclopentadienes > butadienes, which is highly correlated with the lowest unoccupied molecular orbital energy, the electronic chemical potential and the electrophilicity of parent diene but relatively less correlated with the highest occupied molecular orbital energy and chemical hardness. The trend that an increase of necleophilicity caused by an electron‐donating group on the diene favors the endo TS is effective with C2 substitution. With C1 substitution, the trend is ambiguous or even opposite. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
5.
The Diels–Alder (DA) reaction is one of the most important reactions in organic chemistry. The controversy surrounding this reaction as to whether it follows a concerted or stepwise mechanism has existed for a long time. The reaction of 1,3‐butadiene and ethylene is the paradigmatic example of the DA reaction. We have reinvestigated the mechanism of this reaction using density functional theory. The theoretical study considered all types of possible pathways for the reaction of 1,3‐butadiene and ethylene using six functionals at different rungs of Jacob's ladder. Therefore, a complete picture is given for a thorough understanding of the iconic DA reaction, and a new stationary point during the reaction processes has been reported for the first time. The calculated results indicated that three functionals, ωB97X‐D, M06‐2X, and B2‐PLYP, of the fourth and fifth rungs of Jacob's ladder performed well in the investigation of the mechanism of this reaction and that the reliable basis set should be larger than 6‐311+G(2d,p). The cis‐1,3‐butadiene more easily reacted with ethylene compared with 1,3‐butadiene in the trans conformation. The concerted mechanism was found to be energetically favorable, whose energy barrier is around 10 kcal/mol lower than that of the stepwise mechanism. Two investigated solvents, toluene and CH3CN, had little impact on this simple DA reaction. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
6.
Regioselectivity and stereoselectivity of Diels–Alder reaction: a DFT study on the functionalization of organic semiconductor crystals
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Diels–Alder (DA) reaction is one of the most commonly tools in functionalizing organic semiconductor crystals. The DA reactions of two organic semiconductors, i.e. tetracene ( 1 ) and rubrene ( 2 ), to several dienophiles ( 3 to 7 ) were performed experimentally recently. But the kinetics and mechanism of stereoselectivity and regioselectivity remain unknown. In the current study, all related 20 DA reactions (totally 32 possible pathways) were investigated by density functional theory. It was found that the reaction of 7 and a–b position of 1 is the most favorable one. The c–d position of 2 is more reactive than its a–b position when 2 combines with 3 , but is less reactive when combines with 4 to 7 . The endo and exo pathways have similar activation barriers in each reaction. The rate coefficients were calculated using the canonical variational transition state theory and their Arrhenius expressions were fitted. The theoretical conclusion agrees with the experimental observations and is of general importance for similar reactions. Solvent has a slight effect on these reactions. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
7.
Investigation of the relative reactivity of bonds in fullerenes will provide fundamental theory for the design of fullerene‐based materials. We have theoretically investigated the reactivity of the Diels–Alder (DA) cycloaddition of cis‐1,3‐butadiene to all types of bonds in C60 and C70 using the M06‐2X hybrid density functional theory (DFT) calculations (J. Phys. Org. Chem. 2012, 25 850–855) and have pointed out that the DA cycloadditions of cis and trans forms of 1,3‐butadiene to ethylene have a specially intimate relationship (J. Phys. Org. Chem. 2014, 27 652–660). For the aim of telling a whole story of the DA cycloaddition concerning C60 and C70, the DA cycloadditions of trans‐1,3‐butadiene to all types of bonds in C60 and C70 were explored at the same theoretical level as those of the cis‐1,3‐butadiene. The calculated results related with the trans‐ and cis‐1,3‐butadienes were compared. The potential energy curves of DA cycloadditions of trans‐ and cis‐1,3‐butadiene to C60 and C70 were discussed. The distortion–interaction energy model was employed to elucidate the origin of different reactivity of all kinds of C?C bonds. The solvent effects were examined using the continuum solvent model. These current results, along with our previous research, will help to obtain an overall view of the DA cycloadditions of 1,3‐butadiene to C60 and C70. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
8.
Kinetics and thermochemistry of the unusual [2π + 2σ + 2σ]‐cycloaddition of quadricyclane with some dienophiles
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Vladimir D. Kiselev Dmitry A. Kornilov Oleg V. Anikin Igor A. Sedov Alexander I. Konovalov 《Journal of Physical Organic Chemistry》2018,31(1)
Kinetic parameters of the unusual [2π + 2σ + 2σ]‐cycloaddition reactions of quadricyclane ( 1 ) with tetracyanoethylene ( 2 ), 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione ( 3 ), N‐phenylmaleimide ( 4 ), and diethyl azodicarboxylate ( 5 ) are determined experimentally. Additionally, the enthalpies of 1 + 2 reaction in 1,4‐dioxane solution (?236.6 ± 1.0 kJ mol?1) and 1 + 3 reaction in toluene (?255.0 ± 2.8 kJ mol?1) are determined calorimetrically and shown to be the largest in absolute magnitude among all known cycloaddition reactions involving these dienophiles. Solvent effect on the rate of 1 + 3 reaction in 11 solvents is studied and found to be moderate and similar to that of the conventional Diels‐Alder and ene reactions. The difference in the reaction rate constants of 1 with different dienophiles can be up to 9 orders of magnitude and is mainly caused by the difference in activation enthalpies. This difference is not correlated with the standard enthalpies of reactions and is likely the result of high sensitivity of the [2π + 2σ + 2σ] reaction rates to the energy of donor‐acceptor interactions between the reactants. 相似文献
9.
Himani Sharma Dinesh C. Agarwal A. K. Shukla D. K. Avasthi V. D. Vankar 《Journal of Raman spectroscopy : JRS》2013,44(1):12-20
Multiwalled carbon nanotubes (MWCNTs) are grafted with gold (Au) nanoparticles of different sizes (1–12 and 1–20 nm) to form Au–MWCNT hybrids. The Au nanoparticles pile up at defect sites on the edges of MWCNTs in the form of chains. The micro‐Raman scattering studies of these hybrids were carried using visible to infrared wavelengths (514.5 and 1064 nm). Enhanced Raman scattering and fluorescence is observed at an excitation wavelength of 514.5 nm. It is found that the graphitic (G) mode intensity enhances by 10 times and down shifts by approximately 3 cm−1 for Au–MWCNT hybrids in comparison with pristine carbon nanotubes. This enhancement in G mode due to surface‐enhanced Raman scattering effect is related to the interaction of MWCNTs with Au nanoparticles. The enhancement in Raman scattering and fluorescence for large size nanoparticles for Au–MWCNTs hybrids is corroborated with localized surface plasmon polaritons. The peak position of localized surface plasmons of Au nanoparticles shifts with the change in environment. Further, no enhancement in G mode was observed at an excitation wavelength of 1064 nm. However, the defect mode (D) mode intensity enhances, and peak position is shifted by approximately 40 cm−1 to lower side at the same wavelength. The enhanced intensity of D mode at 1064 nm excitation wavelength is related to the double resonance phenomenon and shift in the particular mode occurs due to more electron phonon interactions near Fermi level. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
10.
Vladimir D. Kiselev Dmitry A. Kornilov Helen A. Kashaeva Lyubov N. Potapova Alexander I. Konovalov 《Journal of Physical Organic Chemistry》2014,27(5):401-406
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. 相似文献
11.
Ana Vidiš Ernst Küsters Gottfried Sedelmeier Paul J. Dyson 《Journal of Physical Organic Chemistry》2008,21(4):264-270
The Diels–Alder reaction has been examined in room temperature ionic liquids with high molar concentrations of Lewis acids under various conditions. A molar ratio of 10% catalyst gave a large increase in the selectivity and the yield of the reaction. The effect of catalysts on reaction rates was also examined under 100 MPa of pressure which leads to modest improvements in reaction rates. Ultrasound and microwave dielectric heating were also shown to improve the rate and, to a minor extent, selectivity of the examined reactions. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
12.
Ricardo Salazar P. A. Navarrete‐Encina J. A. Squella C. Camargo Luis J. Nú?ez‐Vergara 《Journal of Physical Organic Chemistry》2009,22(6):569-577
Reactivity of two new C4‐indolyl substituted 1,4‐dihydropyridines (1,4‐DHPs) toward superoxide anion (O2? ) in dimethylsulfoxide (DMSO) is reported. Reactivity was followed by electrochemical and spectroscopic techniques. Gas chromatography‐mass spectrometry (GC–MS) was used to identify the final products of the reaction. C4 indolyl‐substituted‐1,4‐DHPs reacted toward O2? at significant rates, according to the calculated kinetic rate constants. Results are compared with 4‐phenyl‐DHP and the commercial 1,4‐DHPs, nimodipine, nisoldipine, and amlodipine. Indolyl‐substituted 1,4‐DHPs were more reactive than the commercial derivatives. The direct participation of proton of the 1‐position of the secondary amine in the quenching of O2? was demonstrated. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
13.
Margarida S. Miranda Luís Pinto da Silva Joaquim C. G. Esteves da Silva 《Journal of Physical Organic Chemistry》2014,27(1):47-56
2‐Ethylhexyl 4‐methoxycinnamate (EHMC) is a very commonly used UVB filter that is known to isomerize from the (E) to the (Z) isomer in the presence of light. In this study, we have performed high level quantum chemical calculations using density functional theory (DFT) with the B3LYP density functional and extended basis sets to study the gas‐phase molecular structure of EHMC and its energetic stability. Calculations were also performed for related smaller molecules cinnamic acid and 4‐methoxycinnamic acid. Charge delocalization has been analyzed using natural charges and Wiberg bond indexes within the natural bond orbital analysis and using nucleus independent chemical shifts. Density functional theory calculations reveal that the (E) isomer of EHMC is more stable than the (Z) by about 20 kJ mol?1 in both the gas and aqueous phases. The enthalpy of formation in the gas phase of (E)‐EHMC was derived from an isodesmic bond separation reaction. Long‐range corrected DFT calculations in implicit water were made in order to understand the excited state properties of the (E) and (Z) isomers of EHMC. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
14.
Jorge Soto‐Delgado Luis R. Domingo Ramiro Araya‐Maturana Renato Contreras 《Journal of Physical Organic Chemistry》2009,22(6):578-584
The polar Diels–Alder (DA) reactions of 2‐acetyl‐1,4‐benzoquinone (acBQ) with methyl substituted 1,3‐butadienes have been studied using DFT methods at the B3LYP/6‐31G(d) level of theory. These reactions are characterized by a nucleophilic attack of the unsubstituted ends of the 1,3‐dienes to the β conjugated position of the acBQ followed by ring‐closure. The reactions present a total regioselectivity and large endo selectivity. The analysis based on the global electrophilicity of the reagents at the ground state, and the natural bond orbital (NBO) population analysis at the transition states correctly explain the polar nature of these cycloadditions. The large electrophilic character of acBQ is responsible for the acceleration observed in these polar DA reactions. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
15.
Margarida S. Miranda José E. Rodríguez‐Borges Joaquim C. G. Esteves da Silva Xerardo García‐Mera 《Journal of Physical Organic Chemistry》2012,25(6):515-522
The cycloaddition between glyoxylate imines possessing two chiral auxiliaries, N‐(R)‐ or N‐(S)‐1‐phenylethyl and 8‐phenylmenthyl or 8‐phenylneomenthyl, and cyclopentadiene is described. Computational calculations using density functional theory with the Becke, three‐parameter, Lee–Yang–Parr functional and the 6‐31G(d) basis set were performed to better understand the highly diastereoselective mechanism and the exo‐selectivity observed experimentally for these ionic aza‐Diels–Alder reactions. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
16.
Evaluation of the UFXC32k photon‐counting detector for pump–probe experiments using synchrotron radiation
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Anna Koziol Michel Bordessoule Alessandra Ciavardini Arkadiusz Dawiec Paulo Da Silva Kewin Desjardins Pawel Grybos Brahim Kanoute Claire Laulhe Piotr Maj Claude Menneglier Pascal Mercere Fabienne Orsini Robert Szczygiel 《Journal of synchrotron radiation》2018,25(2):413-418
This paper presents the performance of a single‐photon‐counting hybrid pixel X‐ray detector with synchrotron radiation. The camera was evaluated with respect to time‐resolved experiments, namely pump–probe–probe experiments held at SOLEIL. The UFXC camera shows very good energy resolution of around 1.5 keV and allows the minimum threshold setting to be as low as 3 keV keeping the high‐count‐rate capabilities. Measurements of a synchrotron characteristic filling mode prove the proper separation of an isolated bunch of photons and the usability of the detector in time‐resolved experiments. 相似文献