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Basicity of Heterocyclic Aromatic Amines01:25

Basicity of Heterocyclic Aromatic Amines

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Heterocyclic amines, where the N atom is a part of an alicyclic system, are similar in basicity to alkylamines. Interestingly, the heterocyclic amine having a nitrogen atom as part of an aromatic ring has much less basicity than its corresponding alicyclic counterpart. For this reason, as presented in Figure 1, piperidine (pKb = 2.8) is significantly more basic than pyridine (pKb = 8.8).
5.9K
Aryldiazonium Salts to Azo Dyes: Diazo Coupling01:11

Aryldiazonium Salts to Azo Dyes: Diazo Coupling

2.9K
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...
2.9K
Alkyl Halides02:45

Alkyl Halides

16.5K
Structural Properties
Alkyl halides are halogen-substituted alkanes wherein one or more hydrogen atoms of an alkane is replaced by a halogen atom such as fluorine, chlorine, bromine, or iodine. The carbon atom in an alkyl halide is bonded to the halogen atom, which is sp3-hybridized and exhibits a tetrahedral shape.
Unlike alkyl halides, compounds in which a halogen atom is bonded to an sp2 -hybridized carbon atom of a carbon-carbon double bond (C=C) are called vinyl halides. Whereas aryl...
16.5K
¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

1.7K
The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene...
1.7K
Intermolecular Forces03:13

Intermolecular Forces

58.2K
Atoms and molecules interact through bonds (or forces): intramolecular and intermolecular. The forces are electrostatic as they arise from interactions (attractive or repulsive) between charged species (permanent, partial, or temporary charges) and exist with varying strengths between ions, polar, nonpolar, and neutral molecules. The different types of intermolecular forces are ion–dipole, dipole–dipole, hydrogen bonds, and dispersion; among these, dipole–dipole, hydrogen...
58.2K
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH301:11

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

6.0K
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...
6.0K

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Updated: Jun 25, 2025

Synthesis of pH Dependent Pyrazole, Imidazole, and Isoindolone Dipyrrinone Fluorophores using a Claisen-Schmidt Condensation Approach
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Synthesis of pH Dependent Pyrazole, Imidazole, and Isoindolone Dipyrrinone Fluorophores using a Claisen-Schmidt Condensation Approach

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The Cohesive Interactions in Phenylimidazoles.

José C S Costa1, Ana I M C Lobo Ferreira1, Carlos F R A C Lima1

  • 1CIQUP, Institute of Molecular Sciences (IMS), Department of Chemistry and Biochemistry, Faculty of Science, University of Porto, Rua do Campo Alegre s/n, Porto P4169-007, Portugal.

The Journal of Physical Chemistry. A
|May 30, 2024
PubMed
Summary

This study reveals how adding phenyl groups to imidazole affects its solid-state thermodynamics and structure. Phenyl group addition shows additive effects on properties like heat capacity and sublimation.

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Area of Science:

  • Physical Chemistry
  • Materials Science
  • Crystallography

Background:

  • Understanding the solid-state thermodynamics of organic molecules is crucial for materials design.
  • Phenylimidazole derivatives are important in various chemical applications.
  • Structure-property relationships in substituted imidazoles require further investigation.

Purpose of the Study:

  • To investigate the thermodynamic properties of phenylimidazole solid phases.
  • To explore the influence of phenyl group substitution on imidazole thermodynamics and supramolecular behavior.
  • To establish structure-property correlations for phenylimidazole derivatives.

Main Methods:

  • Experimental measurements of heat capacity, volatility, and thermal behavior.
  • UV-vis spectroscopy and quantum chemical calculations.
  • Analysis of solid-liquid and solid-gas equilibria.

Main Results:

  • Additive effects of phenyl group introduction on thermodynamic properties were observed.
  • A correlation was found between sublimation thermodynamics and unit cell molar volume for specific phenylimidazoles.
  • 4-Phenylimidazole showed higher cohesive energy and disrupted coplanarity due to stronger intermolecular interactions compared to 2-phenylimidazole.

Conclusions:

  • Phenyl group substitution significantly impacts the solid-state thermodynamics and supramolecular structure of imidazoles.
  • Intermolecular interactions, particularly N-H···N hydrogen bonding, play a key role in determining molecular packing and properties.
  • Crystalline lattice order influences phase transition entropies in phenylimidazole derivatives.