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Related Concept Videos

Preparation of 1° Amines: Azide Synthesis01:22

Preparation of 1° Amines: Azide Synthesis

Direct alkylation of ammonia produces polyalkylated amines, along with a quaternary ammonium salt. To exclusively prepare primary amines, the azide synthesis method can be used.
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
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Cycloaddition Reactions: MO Requirements for Thermal Activation

Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
Acid-Catalyzed Ring-Opening of Epoxides02:24

Acid-Catalyzed Ring-Opening of Epoxides

Epoxides that are three-membered ring systems are more reactive than other cyclic and acyclic ethers. The high reactivity of epoxides originates from the strain present in the ring. This ring strain acts as a driving force for epoxides to undergo ring-opening reactions either with halogen acids or weak nucleophiles in the presence of mild acid. The acid catalyst converts the epoxide oxygen, a poor leaving group, into an oxonium ion, a better leaving group, making the reaction feasible. The...
Aryldiazonium Salts to Azo Dyes: Diazo Coupling01:11

Aryldiazonium Salts to Azo Dyes: Diazo Coupling

The reaction of weakly electrophilic aryldiazonium (also called arenediazonium) salts with highly activated aromatic compounds leads to the formation of products with an —N=N— link, called an azo linkage. This reaction, presented in Figure 1, is known as diazo coupling and occurs without the loss of the nitrogen atoms of the aryldiazonium salt. Highly activated aromatic compounds such as phenols or arylamines favor the diazo coupling reaction. The coupling generally occurs at the para position.
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH301:11

ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3

All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
Cycloaddition Reactions: Overview01:16

Cycloaddition Reactions: Overview

Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.

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Updated: Jun 4, 2026

Preparation of Contiguous Bisaziridines for Regioselective Ring-Opening Reactions
04:38

Preparation of Contiguous Bisaziridines for Regioselective Ring-Opening Reactions

Published on: July 28, 2022

Computational studies on azaphosphiridines, or how to effect ring-opening processes through selective bond

Arturo Espinosa1, Rainer Streubel

  • 1Departamento de Química Orgánica, Facultad de Química, Universidad de Murcia, Campus de Espinardo, 30100 Murcia, Spain. artuesp@um.es

Chemistry (Weinheim an Der Bergstrasse, Germany)
|February 11, 2011
PubMed
Summary

This study investigates azaphosphiridine stability and reactivity, finding P-oxidation increases ring strain and TiCl3 selectively activates C-N bonds. Metal chlorides show limited P-N bond activation in these heterocyclic compounds.

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Synthesis and Purification of Iodoaziridines Involving Quantitative Selection of the Optimal Stationary Phase for Chromatography
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Synthesis and Purification of Iodoaziridines Involving Quantitative Selection of the Optimal Stationary Phase for Chromatography

Published on: May 16, 2014

Area of Science:

  • Computational Chemistry
  • Organophosphorus Chemistry
  • Heterocyclic Chemistry

Background:

  • Azaphosphiridines are strained three-membered heterocyclic compounds containing phosphorus and nitrogen.
  • Understanding their stability and reactivity is crucial for developing new synthetic methodologies.

Purpose of the Study:

  • To investigate the relative energies, ring stability, and ring strain of azaphosphiridine and its isomers.
  • To study the kinetics and thermodynamics of ring-opening reactions for P(III) and P(V) azaphosphiridine derivatives.
  • To explore the efficacy of various reagents in activating bonds within the azaphosphiridine ring.

Main Methods:

  • High-level theoretical calculations, including Coupled Cluster with Singles and Doubles and a Perturbative Triples correction (CCSD(T)).
  • Density Functional Theory (DFT) methods (e.g., BP86/def2-TZVP) for geometry optimization.
  • Analysis of bond strength parameters: electron density at bond critical points, Wiberg bond index, and relaxed force constants.

Main Results:

  • P-oxidation of azaphosphiridine increases ring strain and the barrier to nitrogen inversion.
  • Phosphorus in P(III) azaphosphiridines is a configurationally stable center.
  • N-protonation readily cleaves the P-N bond, while most metal chlorides show limited activation.
  • Titanium trichloride (TiCl3) selectively activates the C-N bond, with stronger activation for P(V) than P(III) derivatives.
  • Ring-expanding rearrangement is favored for heavier chalcogenide P(V) azaphosphiridines.

Conclusions:

  • Azaphosphiridine stability is influenced by phosphorus oxidation state and substituents.
  • Selective C-N bond activation by TiCl3 offers a potential synthetic route.
  • Comparative analysis of bond strength parameters provides insights into bond activation mechanisms.