Organometallic Chemistry. IX. The Metalation of Benzocyclobutene with Sodium and Potassium Alkyls<sup>1,2</sup>

Finnegan, R.A.

doi:10.1021/jo01015a562

Cited by 40 publications

(16 citation statements)

References 2 publications

(2 reference statements)

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“…32,33 In turn, the electronegativity of the R-carbon is also increased. In the case of these polymers, this corresponds to the 2-position of the thiophene heterocycle.…”

Section: Resultsmentioning

confidence: 99%

Theoretical and Electrochemical Analysis of Poly(3,4-alkylenedioxythiophenes): Electron-Donating Effects and Onset of p-Doped Conductivity

et al. 2010

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Conducting polymers have widespread industrial applications owing to a unique combination of mechanical, optical, and electronic properties. Specifically, the family of poly(alkylenedioxythiophene) derivatives has received much attention due to its inherently high conductivity, environmental stability, and tunability. However, although the electron-donating characteristics of the alkoxy moieties are well-known, the source of the differences among these substitutions has been limited to speculative arguments based on bulk properties. To address these issues, a combined electrochemical and density functional theory (DFT) study was undertaken that reveals the significant electronic and geometric characteristics responsible for the comparative properties of these materials. It was found that the geometry of the alkylenedioxy backbone substitution modulates the π-donating character of the oxygen and that this directly influences the onset of p-doped conductivity. These studies also indicate that this framework equally applies to several other heterocyclic polymer systems. An improved theory for these materials is expected to provide the insight and knowledge base for new conducting polymers with enhanced stability and optoelectronic properties.

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“…32,33 In turn, the electronegativity of the R-carbon is also increased. In the case of these polymers, this corresponds to the 2-position of the thiophene heterocycle.…”

Section: Resultsmentioning

confidence: 99%

Theoretical and Electrochemical Analysis of Poly(3,4-alkylenedioxythiophenes): Electron-Donating Effects and Onset of p-Doped Conductivity

et al. 2010

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“…Benson (1947) reported that compounds of the type R-N(NO)-NH-C(R')= NH, where R' is cyano or 2,4-dibromophenyl, yield substituted tetrazoles by elimination of a water molecule. Boyer & Canter (1955) 1-(4-CHLOROBENZYL)-I -NITROSO-2-(4,5-DIHYDRO-2-IMIDAZOLYL)HYDRAZINE However, Finnegan & Henry (1965) found that compounds of the type R-N(NO)-NH-C(NH2)= NH were surprisingly stable, and all attempts to effect ring closure were unsuccessful. They found that in some cases carbamyl azide, N3.…”

Section: Introductionmentioning

confidence: 99%

“…It was decided that an X-ray crystal structure determination would aid in explaining the chemistry of the various N-nitroso compounds prepared by Finnegan & Henry (1965). Therefore, a determination of the unit cell and space group was made for a number of derivatives.…”

Section: Introductionmentioning

confidence: 99%

The structure of 1-(4-chlorobenzyl)-1-nitroso-2-(4,5-dihydro-2-imidazolyl)hydrazine monohydrate

Palenik¹

1965

Acta Cryst

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“…Originally regarded" as simply polyenes of peculiar topology, the suggestion has been made recently" that stability alternation (albeit strongly attenuated) might be observed when [4n]-radialenes are compared with their [4n + 2] vinylogs similar to the aromatic-antiaromatic alternance noted in the annulenes." Prior to our work, of the parent radialenes only [3]_52 and [4]-radialene'3 were known, in addition to several substituted derivatives" including alkylated [6]radialenes.f'" The parent compounds have been shown to be extremely air sensitive, unstable compounds and it is of interest, particularly in the light of the recent theoretical work," to compare the "cyclobutadienoid" [4]-radialene with the "benzenoid" [6]-radialene. The sensitivity and chemical reactivity of 3, in addition to its spectral features, suggest that, at least within the limits of detection, 3 does not enjoy special electronic stability in comparison to the other radialenes.…”

Section: R 1 • R 2-brmentioning

confidence: 99%

Unusual Rearrangements in the C₁₂H₁₂‐Manifold 1,5,9‐Cyclododecatriyne, 1,2:3,4:5,6‐Tricyclobutabenzene, Hexaradialene

Barkovich

Strauss

Vollhardt

1980

Israel Journal of Chemistry

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1,5,9‐Cyclododecatriyne has been synthesized by a bromination‐dehydrobromination sequence starting from all‐cis‐1,5,9‐cyclododecatriene. Its physical properties point to substantial interaction of the acetylenic groups through space and through bond although this effect does not result in significant homoaromatic stabilization. Attempts to convert the triyne to isolable 1,2:3,4:S,6‐tricyclobutabenzene failed, but condensed phase thermolysis in the presence of dimethylmaleate led to the isolation of a formal triadduct. Flash pyrolysis resulted in the formation of hexaradialene. The latter is an extremely air sensitive, polymerizable molecule, devoid of detectable aromatic stabilization, in accord with theoretical treatments. Thermochemical estimates are presented which indicate the exothermicity of the 1,5,9‐cyclododecatriyne → hexaradialene interconversion. The most likely intermediate in this transformation is 1,2:3,4:5,6‐tricyclobutabenzene, also in accord with group equivalent calculations, although other pathways cannot be.ruled out rigorously.

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Organometallic Chemistry. IX. The Metalation of Benzocyclobutene with Sodium and Potassium Alkyls^1,2

Cited by 40 publications

References 2 publications

Theoretical and Electrochemical Analysis of Poly(3,4-alkylenedioxythiophenes): Electron-Donating Effects and Onset of p-Doped Conductivity

Theoretical and Electrochemical Analysis of Poly(3,4-alkylenedioxythiophenes): Electron-Donating Effects and Onset of p-Doped Conductivity

The structure of 1-(4-chlorobenzyl)-1-nitroso-2-(4,5-dihydro-2-imidazolyl)hydrazine monohydrate

Unusual Rearrangements in the C₁₂H₁₂‐Manifold 1,5,9‐Cyclododecatriyne, 1,2:3,4:5,6‐Tricyclobutabenzene, Hexaradialene

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Organometallic Chemistry. IX. The Metalation of Benzocyclobutene with Sodium and Potassium Alkyls1,2

Cited by 40 publications

References 2 publications

Theoretical and Electrochemical Analysis of Poly(3,4-alkylenedioxythiophenes): Electron-Donating Effects and Onset of p-Doped Conductivity

Theoretical and Electrochemical Analysis of Poly(3,4-alkylenedioxythiophenes): Electron-Donating Effects and Onset of p-Doped Conductivity

The structure of 1-(4-chlorobenzyl)-1-nitroso-2-(4,5-dihydro-2-imidazolyl)hydrazine monohydrate

Unusual Rearrangements in the C12H12‐Manifold 1,5,9‐Cyclododecatriyne, 1,2:3,4:5,6‐Tricyclobutabenzene, Hexaradialene

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Organometallic Chemistry. IX. The Metalation of Benzocyclobutene with Sodium and Potassium Alkyls^1,2

Unusual Rearrangements in the C₁₂H₁₂‐Manifold 1,5,9‐Cyclododecatriyne, 1,2:3,4:5,6‐Tricyclobutabenzene, Hexaradialene