ChemInform Abstract: ADDITION REACTIONS OF THE NITROSO GROUP. XVI. DIFFERENCES IN THE REGIOSPECIFICITY OF THE E Z ISOMERS- PRODUCTS AND KINETICS OF THE DIELS-ALDER REACTION OF 1,2-DIARYLBUTADIENES AND NITROSOBENZENES

The kinetics of the Diels-Alder reaction of cyclopentadiene with bis(2-ethylhexyl) maleate has been studied at temperatures between 25 and 100 °C and at atmospheric pressure. The influence of temperature on the kinetic constants was determined by fitting the results to the Arrhenius equation. As a result, fitting line similar with the linear curve of the Arrhenius equation at 25, 30 and 40 °C. However, the fitting curve, at 60, 80 and 100 °C, tended towards the outside of the curve in the form of Arrhenius equation. The ratio of endo/exo was a slight change from increase of the reaction temperature.

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Reply to Comment on “Kinetics of a Diels−Alder Reaction of Maleic Anhydride and Isoprene in Supercritical CO2”

The Journal of Physical Chemistry A ◽

10.1021/jp030232v ◽

2003 ◽

Vol 107 (43) ◽

pp. 9249-9249 ◽

Cited By ~ 1

Author(s):

Evgeni M. Glebov ◽

Larisa G. Krishtopa ◽

Victor Stepanov ◽

Lev N. Krasnoperov

Keyword(s):

Maleic Anhydride ◽

Supercritical Co2 ◽

Alder Reaction ◽

Diels Alder ◽

Diels Alder Reaction ◽

Kinetics Of

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Kinetics of a Diels—Alder Reaction in Supercritical Propane

Innovations in Supercritical Fluids - ACS Symposium Series ◽

10.1021/bk-1995-0608.ch011 ◽

1995 ◽

pp. 166-178 ◽

Cited By ~ 7

Author(s):

Barbara L. Knutson ◽

Angela K. Dillow ◽

Charles L. Liotta ◽

Charles A. Eckert

Keyword(s):

Alder Reaction ◽

Diels Alder ◽

Diels Alder Reaction ◽

Kinetics Of

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Heterogeneous Intramolecular Electric Field as a Descriptor of Diels-Alder Reactivity

10.26434/chemrxiv.13266704.v1 ◽

2020 ◽

Author(s):

Matthew Hennefarth ◽

Anastassia N. Alexandrova

Keyword(s):

Electric Field ◽

Electron Density ◽

Electric Fields ◽

Alder Reaction ◽

Diels Alder ◽

Charge Movement ◽

External Electric Fields ◽

Topological Features ◽

Diels Alder Reaction ◽

Kinetics Of

<div> <div> <div> <p>External electric fields have proven to be an effective tool in catalysis, on par with pressure and temperature, affecting the thermodynamics and kinetics of a reaction. However, fields in molecules are complicated heterogeneous vector objects, and there is no universal recipe for grasping the exact features of these fields that implicate reactivity. Herein, we demonstrate that topological features of the heterogeneous electric field within the reactant state, as well as of the quantum mechanical electron density – a scalar reporter on the field experienced by the system – can be identified as rigorous descriptors of the reactivity to follow. We scrutinize specifically the Diels-Alder reaction. Its 3-D nature and the lack of a singular directionality of charge movement upon barrier crossing makes the effect of the electric field not obvious. We show that the electric field topology around the dienophile double bond, and the associated changes in the topology of the electron density in this bond are predictors of the reaction barrier. They are also the metrics by which to rationalize and predict how the external field would inhibit or enhance the reaction. The findings pave the way toward designing external fields for catalysis, as well as reading the reactivity without an explicit mechanistic interrogation, for a variety of reactions. </p> </div> </div> </div>

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Direct Diels-Alder reaction of chitin derived 3-acetamido-5-acetylfuran

10.26434/chemrxiv-2022-rf825 ◽

2022 ◽

Author(s):

Rafael Gomes ◽

Juliana Pereira ◽

João Ravasco ◽

João Vale ◽

Fausto Queda

Keyword(s):

Alder Reaction ◽

Diels Alder ◽

Fine Tuning ◽

Reduced Form ◽

Partial Hydrolysis ◽

Reaction Conditions ◽

Diels Alder Reaction ◽

Direct Use ◽

Kinetics Of ◽

Hydrolysis Of

The Diels-Alder (DA) reaction of biomass derived furans is an emerging technology for the preparation of new molecular entities and “drop-in” commodity chemicals. In this work we address the challenge of the direct use of electron-poor furanic platforms as dienes through the use of an unexplored chitin derived furan, 3-acetamido-5-acetylfuran (3A5AF). The 3-acetamido group promoted a remarkable increase in the kinetics of the DA allowing for the preparation of 7-oxanorbornenes (7-ONB) at 50 ºC. Partial hydrolysis of the enamide to hemi-acylaminals was possible upon fine tuning of the reaction conditions, disabling retro-DA processes. Finally, DA reaction of the reduced form of 3A5AF allowed quantitative formation of 7-ONB in aqueous condition after 10 minutes. Certanly these are the first steps for expanding the toolbox of chitin derived 3A5AF as diene.

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On the opposite effect of guanidinium chloride and guanidinium sulphate on the kinetics of the Diels-Alder reaction

Journal of Molecular Liquids ◽

10.1016/j.molliq.2018.11.054 ◽

2019 ◽

Vol 275 ◽

pp. 100-104 ◽

Cited By ~ 3

Author(s):

Giuseppe Graziano

Keyword(s):

Opposite Effect ◽

Alder Reaction ◽

Diels Alder ◽

Guanidinium Chloride ◽

Diels Alder Reaction ◽

Kinetics Of

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Design and synthesis of tetraazachlorins, tetraazabacteriochlorins and tetraazaisobacteriochlorins

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424609000310 ◽

2009 ◽

Vol 13 (02) ◽

pp. 188-202 ◽

Cited By ~ 14

Author(s):

Elena A. Makarova ◽

Evgeny A. Lukyanets

Keyword(s):

Dicarboxylic Acids ◽

Alder Reaction ◽

Diels Alder ◽

Azomethine Ylides ◽

Addition Reactions ◽

Dipolar Cycloadditions ◽

Design And Synthesis ◽

Diels Alder Reaction ◽

Oxidation Resistant ◽

Derivatives Of

Three approaches to the synthesis of reduced derivatives of tetraazaporphine such as tetraazachlorin, tetraazabacteriochlorin, and tetraazaisobacteriochlorin are reviewed. The first synthesis of alkyl-substituted tetraazachlorins was achieved by the catalytic hydrogenation of magnesium complexes of tetraazaporphines. Two other synthesis approaches for reduced tetraazaporphines based on the mixed condensation of the precursors with different hydrogenation levels and β–β addition reactions have been developed in the last decade. The use of tetramethylsuccinonitrile as the saturated component in the mixed condensation with derivatives of aromatic and heteroaromatic dicarboxylic acids enable the synthesis of oxidation-resistant benzo-; 1,2- and 2,3-naphtho-; pyrazino-; 2,3- and 3,4-pyridino-fused tetraazachlorins, tetraazabacteriochlorins, and tetraazaisobacteriochlorins. Fullerene conjugates of reduced tetraazaporphine derivatives were obtained using 1,2-dicyanofullerene as the source of the hydrogenated sites. Tetraazaporphine can act as dienophile in Diels-Alder reaction with dienes of the anthracene and cyclopentadiene series and also as dipolarophile in 1,3-dipolar cycloadditions with azomethine ylides and nitrones. In addition, the effect of the reduction of peripheral double bonds in tetraazaporphine macrocycle alone, and in combination with annelation of benzene or heterocyclic rings on the absorption spectra is discussed.

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