Video Experimental Relacionado

Updated: Jul 10, 2026

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides (CHIPS)

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides (CHIPS)

Published on: June 20, 2014

El trípeto de 1,3-difenilpropinilideno (Ph-C-C-C-Ph) también se utiliza

Jeffrey T DePinto¹, Wendy A deProphetis, Jessica L Menke

¹Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706-1396, USA.

Journal of the American Chemical Society

|February 7, 2007

Resumen

La fotólisis de la 1,3-difenildiazopropina genera el triplete de 1,3-difenilpropinilideno, un radical diradical 1,3-alenico. Este diradical se somete a la ciclización fotoquímica al difenilciclopropenilideno, lo que demuestra la química reversible de los carbenos.

Área de la Ciencia:

La fotoquímica es la fotoquímica.
Química orgánica es la química orgánica.
La espectroscopia es una técnica de espectroscopia.

Sus antecedentes:

Los carbenos son reactivos intermedios cruciales en la síntesis orgánica.
Comprender la estructura y la reactividad de los carbenos alénicos es clave para avanzar en la química de los carbenos.
La 1,3-difenildiazopropina sirve como precursor para generar especies específicas de carbenos.

Objetivo del estudio:

Para caracterizar el triplet generado fotoquímicamente 1,3-difenilpropinilideno.
Para investigar los isómeros conformacionales y la geometría de equilibrio de esta dirradical alénica.
Para explorar la reactividad fotoquímica y el comportamiento de captura del triplete 1,3-difenilpropinilideno.

Principales métodos:

Fotólisis de 1,3-difenildiazopropina en matrices de baja temperatura.
Caracterización espectroscópica mediante espectroscopia IR, UV/vis y EPR.
Cálculos de la teoría funcional de la densidad (DFT).
Experimentos de captura química con oxígeno molecular (O2).

Principales resultados:

Se generó y caracterizó el triplet 1,3-difenilpropinilideno, que existe en dos isómeros conformacionales distinguibles.
Se determinó que la geometría de equilibrio era un diradical allenico D2d altamente simétrico, no un carbeno acetilenico localizado en el enlace.
El atrapamiento químico produjo óxido de carbonilo, cetona y dioxirano, productos típicos de atrapamiento de carbenos.
La irradiación fotoquímica condujo a la ciclización reversible a la difenilaciclopropenilideno.

Conclusiones:

El trípeto 1,3-difenilpropinilideno adopta una estructura diradical alénica.
Su comportamiento fotoquímico incluye la ciclización al difenilciclopropenilideno, mostrando transformaciones reversibles de carbenos.
El estudio proporciona información sobre la estructura, la espectroscopia y la reactividad de los diradicales allenicos.

Más Videos Relacionados

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphos^Ph Complexes

Published on: April 10, 2015

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex

Published on: July 27, 2022

Videos de Conceptos Relacionados

Hybridization of Atomic Orbitals II

Hybridization of Atomic Orbitals II

sp3d and sp3d 2 Hybridization

Conformations of Ethane and Propane

Conformations of Ethane and Propane

In an organic molecule, free rotation about the carbon-carbon single bond results in energetically different conformers of the molecule. Due to this rotation, called the internal rotation, ethane has two major conformations — staggered and eclipsed.
Staggered conformation is a low energy and more stable conformation with the C-H bonds on the front carbon placed at 60°dihedral angles relative to the C-H bonds on the back carbon, leading to a reduced torsional strain. In staggered ethane, the...

Chirality at Nitrogen, Phosphorus, and Sulfur

Chirality at Nitrogen, Phosphorus, and Sulfur

Chirality is most prevalent in carbon-based tetrahedral compounds, but this important facet of molecular symmetry extends to sp3-hybridized nitrogen, phosphorus and sulfur centers, including trivalent molecules with lone pairs. Here, the lone pair behaves as a functional group in addition to the other three substituents to form an analogous tetrahedral center that can be chiral.
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...

Prochirality

Prochirality

The concept of prochirality leads to the nomenclature of the individual faces of a molecule and plays a crucial role in the enantioselective reaction. It is a concept where two or more achiral molecules react to produce chiral products. A typical process is the reaction of an achiral ketone to generate a chiral alcohol. Here, the achiral reactant reacts with an achiral reducing agent, sodium borohydride, to generate an equimolar mixture of the chiral enantiomers of the product. For example, an...

[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement

[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement

The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.

[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement

[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement

The Claisen rearrangement is a [3,3] sigmatropic rearrangement of allyl vinyl ethers to unsaturated carbonyl compounds. The rearrangement is a concerted pericyclic reaction proceeding via a chair-like transition state.