Search results for "isomerization"

Competition between decarboxylation and isomerization in the C3H5O 2+ energy surface. Justification of the experimental results by molecular orbital …

1994

In constrast with recent molecular orbital calculations on the decarboxylation of O-protonated 2-oxetanone, this experimental work indicates that no decarboxylation of this cation occurs in sulphuric acid solution up to 150°C, but instead a clean isomerization to protonated acrylic acid takes place. Parallel theoretical work shows that the gas-phase model is too crude to account successfully for the experimental facts obtained in acidic media. However, the latter are well reproduced when the effect of the solvent is taken into account. The present findings do not necessarily invalidate the reaction mechanism currently accepted to explain the rate enhancement and change of stereochemistry ac…

On the Mechanism of Xylene Isomerization and its Limitations as Reaction Test for Solid Acid Catalysts

1993

The kinetics of the gas-phase isomerization of m-xylene, over a series of ultraestable Y zeolites, has been studied in a fixed-bed flow reactor under initial conditions. Using deuterated p-xylene as reactant it has been seen that more than 20% of the m- and o-xylene obtained, are formed via a bimolecular mechanism. The relative proportion of uni- to bimolecular mechanism depends on the zeolite composition. The relation between the turnover number, calculated from the kinetic rate constant for the unimolecular mechanism, and the framework Al content of the zeolite, was coincident with the topological zeolite model. Besides, the values of the adsorption constants indicate that dealumination h…

ChemInform Abstract: Differential Reactivity of Fluorinated Homopropargylic Amino Esters vs Gold(I) Salts. The Role of the Nitrogen Protecting Group.

2015

The gold(I)-catalyzed hydroarylation/isomerization reaction of N-protected homopropargyl amino esters (III) gives quinoline derivatives of type (IV).

ChemInform Abstract: Gold-Catalyzed Intramolecular Hydroamination of o-Alkynylbenzyl Carbamates: A Route to Chiral Fluorinated Isoindoline and Isoqui…

2013

Title compounds are prepared in enantiomerically pure form by the diastereoselective addition of fluorinated nucleophiles to N-(tert-butanesulfinyl)imines (I) followed by a sequence of Sonogashira cross-coupling/gold(I)-catalyzed cycloisomerization of the corresponding carbamate.

ChemInform Abstract: Regio- and Stereoselective Synthesis of Spiropyrrolizidines and Piperazines Through Azomethine Ylide Cycloaddition Reaction.

2016

A series of original spiropyrrolizidine derivatives has been prepared by a one-pot three-component [3 + 2] cycloaddition reaction of (E)-3-arylidene-1-phenyl-pyrrolidine-2,5-diones, l-proline, and the cyclic ketones 1H-indole-2,3-dione (isatin), indenoquinoxaline-11-one and acenaphthenequinone. We disclose an unprecedented isomerization of some spiroadducts leading to a new family of spirooxindolepyrrolizidines. Furthermore, these cycloadducts underwent retro-1,3-dipolar cycloaddition yielding unexpected regioisomers. Upon treatment of the dipolarophiles with in situ generated azomethine ylides from l-proline or acenaphthenequinone, formation of spiroadducts and unusual polycyclic fused pip…

Photochemical isomerization of aryl hydrazones of 1,2,4-oxadiazole derivatives into the corresponding triazoles

2012

The photochemical version of the Boulton-Katritzky reaction has been studied, examining the behaviour of the arylhydrazones of 3-benzoyl-5-X-1,2,4-oxadiazoles. The effect of several modifications of the substrates structure (the E and/or Z structures of arylhydrazones, the possible presence of substituents in the arylhydrazono moiety, and the nature of substituents at C-5 of the 1,2,4-oxadiazole ring) on the course of the photochemical rearrangement has been examined.

Competing Ring-Photoisomerization Pathways in the 1,2,4-Oxadiazole Series. An Unprecedented Ring-Degenerate Photoisomerization

2002

The irradiation of some 5-alkyl-3-amino-1,2,4-oxadiazoles at lambda = 254 nm in methanol in the presence of triethylamine (TEA) gave ring-photoisomerization both into 2-alkyl-5-amino-1,3,4-oxadiazoles and, unprecedently, into the ring-degenerate 3-alkyl-5-amino-1,2,4-oxadiazoles. The competing ring contraction-ring expansion route and the internal cyclization-isomerization mechanism explain the results.

ISomerization of xylene: MINDO/3 study of the cyclization of benzenium cation into bicyclo[3.1.0]hexenyl cation

1989

Abstract A MINDO/3 study of thermal electrocyclic closing of the benzenium cation to form a bicyclo[3.1.0]hexenyl cation is presented. The calculated mechanism discusses the possibility of cyclization of xylenium cations on a silica catalyst or in superacid media. The structure and energy of the transition state, the enthalpies of isomerization and barriers of activation were calculated for the following processes: isomerization of 2,6-dimethylbenzenium cation into 2,6-dimethylbicyclo[3.1.0]hexenyl cation, isomerization of 2,4-dimethylbenzenium cation into 2,4-dimethylbicyclo[3.1.0]-hexenyl cation, and isomerization of benzenium cation into bicyclo[3.1.0]-hexenyl cation. Equilibrium and kin…

Corrigendum to “Light-induced, site-selective isomerization of glyoxylic acid in solid xenon” [Chem. Phys. Lett. 616–617 (2014) 91–97]

2015

The Chemistry of the [1,2,3]Triazolo[1,5-a]pyridines: An Update

2010

Publisher Summary This chapter discusses the recent advancement in the chemistry of [1,2,3] triazolo[1,5-a]pyridines. It describes new discoveries in the physical properties and theoretical chemistry, focusing on synthesis of [1,2,3]triazolo[1,5-a]pyridine system, synthesis of novel aryltriazolopyridines, chiral ligands from [1,2,3]triazolo[1,5-a]pyridines, pyridylcarbene formation from triazolopyridines, ring-chain isomerization on [1,2,3]triazolo[1,5-a]pyridines, and novel pyridylcarbonylpyridines. All triazolopyridines have interesting ligand properties to form polynuclear complexes with different metal ions. X-ray single-crystal studies, magnetic, photo-magnetic, and colorimetric measur…