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Structure of Benzene: Kekulé Model01:07

Structure of Benzene: Kekulé Model

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In 1865, August Kekule suggested the structure of benzene according to the structural theory of organic chemistry based on the three assertions—formula of benzene is C6H6, all the hydrogens of benzene are equivalent, and each carbon must have four bonds due to its tetravalency.
He proposed that benzene has a cyclic structure of six carbon atoms attached to one hydrogen atom each, with three alternating pi bonds.
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NMR Spectroscopy of Benzene Derivatives01:34

NMR Spectroscopy of Benzene Derivatives

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Simple unsubstituted benzene has six aromatic protons, all chemically equivalent. Therefore, benzene exhibits only a singlet peak at δ 7.3 ppm in the 1H NMR spectrum. The observed shift is far downfield because the aromatic ring current strongly deshields the protons. Any substitution on the benzene ring makes the aromatic protons nonequivalent, and the protons split each other. The peak is, therefore, no longer a singlet and the splitting pattern and their associated coupling...
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Structure of Benzene: Molecular Orbital Model01:18

Structure of Benzene: Molecular Orbital Model

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According to the molecular orbital (MO) model, benzene has a planar structure with a regular hexagon of six sp2 hybridized carbons. As shown in Figure 1, each carbon is bonded to three other atoms with C–C–C and H–C–C bond angles of 120°. The C–H bond length is 109 pm, and the C–C bond length is 139 pm which is midway between the single bond length of sp3 hybridized carbons (154 pm) and sp2 hybridized carbons (133 pm).
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Aromatic Compounds: Overview01:25

Aromatic Compounds: Overview

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In general, the term ‘aromatic’ indicates a pleasant smell or fragrance from fresh flowers, freshly prepared coffee, etc. In the early history of organic chemistry, many benzene derivatives were isolated from the pleasant odor oils of the plants. For example, vanillin was isolated from the oil of vanilla, methyl salicylate from the oil of wintergreen, and cinnamaldehyde from the oil of cinnamon. They all had a pleasant odor; hence the name aromatic was given.
In 1825, Faraday...
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Anxiolytic Drugs: Benzodiazepines and Buspirone01:29

Anxiolytic Drugs: Benzodiazepines and Buspirone

1.5K
Benzodiazepines are a class of anxiolytic drugs known for their rapid efficacy and high therapeutic-to-lethal dose ratio, but with a potential risk of drug dependence. These drugs are lipophilic, allowing for rapid absorption after oral administration, eventually reaching the central nervous system (CNS). Once in the CNS, benzodiazepines bind to the allosteric site of the GABAA receptor. This binding enhances the inhibitory effects of the neurotransmitter GABA. By doing so, they prevent...
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Nomenclature of Aromatic Compounds with a Single Substituent01:23

Nomenclature of Aromatic Compounds with a Single Substituent

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Benzene is the simplest aromatic hydrocarbon or arene. The IUPAC names for simple monosubstituted benzene derivatives are derived by adding the substituent's name as a prefix to the parent benzene. For example, halobenzene, where the halogen could be fluoro (F), chloro (Cl), bromo (Br), and iodo (I).
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Updated: Oct 6, 2025

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
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Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Published on: July 30, 2017

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Benzvalyne: Real or imaginary?

Kimberley N Poland1, Brent R Westbrook1, David H Magers2

  • 1Department of Chemistry and Biochemistry, University of Mississippi, University, Mississippi 38655, USA.

The Journal of Chemical Physics
|January 16, 2022
PubMed
Summary
This summary is machine-generated.

Benzvalyne, a strained bicyclic isomer of o-benzyne, is confirmed as a true minimum on the potential energy surface by advanced computational methods. Its high strain energy and predicted dipole moment suggest potential detectability in interstellar space.

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Efficient Synthesis of Polyfunctionalized Benzenes in Water via Persulfate-promoted Benzannulation of α,β-Unsaturated Compounds and Alkynes
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Area of Science:

  • Computational Chemistry
  • Astrochemistry
  • Organic Chemistry

Background:

  • Benzvalyne is a bicyclic structural isomer of o-benzyne.
  • Its existence as a minimum on the potential energy surface (PES) is debated across different theoretical levels.
  • Related o-benzyne has been recently observed in TMC-1 via radio astronomy.

Purpose of the Study:

  • To computationally determine the stability of benzvalyne as a minimum on the potential energy surface.
  • To investigate the structural and energetic properties of benzvalyne.
  • To assess the potential detectability of benzvalyne in interstellar environments.

Main Methods:

  • Utilized various levels of theory including MCSCF, MP2, coupled-cluster (CCSDT-1b, CCSDT-2), and density functional theory (B3LYP-D3, B2PLYP-D3, M06-D3).
  • Analyzed harmonic frequencies to identify normal modes and assess molecular stability.
  • Calculated the strain energy and dipole moment of the benzvalyne molecule.

Main Results:

  • Multiple computational methods confirm benzvalyne as a C2v minimum on the PES, despite some methods yielding an imaginary frequency.
  • Benzvalyne exhibits a highly strained structure with a C-C≡C bond angle of 108° and a total strain energy of 159 kcal/mol.
  • The molecule possesses a significant predicted dipole moment (2.6 D) and vibrational modes suggesting potential C≡C bond dissociation.

Conclusions:

  • Advanced computational methods, particularly those with higher electron correlation (CCSDT-1b, CCSDT-2), support benzvalyne as a true, albeit strained, minimum.
  • The high strain energy and unique structural features, including the strained triple bond, are key characteristics of benzvalyne.
  • The predicted dipole moment suggests benzvalyne could be detectable in interstellar clouds like TMC-1, similar to o-benzyne.