An intramolecular acetylene transfer between anthracene and 5,6,7,8-tetrafluorobenzobarrelene. A novel synthesis of janusene and dibenzobarrelene

Cantrell, Gary L.; Filler, Robert

doi:10.1021/jo00192a038

Cited by 8 publications

(5 citation statements)

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“…The parent compounds were synthesized by Prof. R. Filler's group at the Illinois Institute of Technology. , The NMR spectra taken to confirm their structure indicated that the compounds were 99% pure, except for the sample of 1,2,3,4-tetrafluoroanthracene, which is a 7/1 molar ratio of itself with its photodimer 9,10-dehydrodi(1,2,3,4-tetrafluoroanthracene). All radicals were generated in situ using a two-electrode electrochemical cell (Wilmad WG-810) placed within the EPR cavity.…”

Section: Methodsmentioning

confidence: 99%

Fluorine Hyperfine Splittings in the Electron Spin Resonance (ESR) Spectra of Aromatic Radicals. An Experimental and Theoretical Investigation

2003

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This article reports our experimental and theoretical investigations of fluorine hyperfine coupling constants (hfcc's) in the anion and cation radicals of a number of fluorinated benzenes, naphthalenes, and anthracenes. We have obtained electron spin resonance (ESR) spectra and hfcc's for the electrolytically generated anion radicals of 1,2,3,4-tetrafluoronaphthalene, 1,2,3,4-tetrafluoroanthracene, and 9,10-perfluoroanthraquinone. The experimental values of the hfcc's of these radicals, along with the hfcc's of several cation radicals of fluorinated benzenes and naphthalenes currently available in the literature, have been compared to our theoretical predictions using the UB3LYP density functional method in conjunction with a variety of basis sets. The EPR-III basis set usually gave the best agreement between theory and experiment for the fluorine splittings with an average relative error of 15%. We also find that it is possible to correlate the experimental fluorine hfcc's with the calculated π-and total electron spin populations F on the fluorine atom, the adjacent carbon atom, and the carbon-fluorine bond, thus providing some chemical insight into the origin of the interactions. The best correlation is obtained with a two-parameter equation of the formThe fit to 21 fluorine splittings using the EPR-III basis set and Mulliken π-electron spin populations gives an average error of only 9%. The average error obtained with EPR-II and NBO π-electron spin populations is 8%. Roughly 80% of the fluorine hfcc can be attributed to π-electron spin population on the fluorine atom. Our results indicate that conjugation of the fluorine atom with the ring is the primary source of the unpaired electron density on fluorine and that the often-assumed separability of σ-and π-electrons in aromatic systems is justified in these radicals as well.

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Section: Methodsmentioning

confidence: 99%

Fluorine Hyperfine Splittings in the Electron Spin Resonance (ESR) Spectra of Aromatic Radicals. An Experimental and Theoretical Investigation

2003

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“…[8][9][10][11][12] These interactions have a pivotal influence on the electronic properties, and consequently on the reactivity of such systems. 13,14 Janusene (1), C 30 H 22 , named in allusion to the roman god Janus, was first synthesized by Cristol in 1967 by the [4p+2p] cycloaddition reaction between anthracene and dibenzobarrelene, and its synthesis was later optimized by Cantrell and Filler 15,16 (Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

Janusene as a silver ion scavenger: insights from computation

et al. 2022

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“…Among acetylene equivalents used for dibenzobarrelene preparation are (E)-1-phenylsulfonyl-2-trimethylsilylethylene devised by Paquette [7], 1-benzenesulfonyl-2-trimethylsilylacetylene developed by Williams [8], (Z) and (E)-1,2-bis(phenylsulfonyl)ethylene used by Künzer [9] and De Lucchi [10], 1,4-benzodithiin-1,1,4,4-tetraoxide, in fact cyclic variant of (Z)-1,2bis(phenylsulfonyl)ethylene reported by Wenkert [11] and maleic anhydride used by Warrener [12]. Synthetically more elegant is intramolecular acetylene transfer via addition-reversion route from tetrafluorobenzobarrelene (one-pot) was reported by Filler [13].…”

Section: Introductionmentioning

confidence: 99%

One-Step Synthesis of 5a,11a-Janusene Imide Employing 2,3-Dibromo-N-methylmaleimide as Acetylene Equivalent

Štrbac

Margetić

2020

The 24th International Electronic Conference on Synthetic Organic Chemistry

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Synthesis of janusene (5,5a,6,11,11a,12-hexahydro-5,12:6,11-di-o-benzenonaphthacene) requires several reaction steps starting from anthracene. In this account, one-pot, three steps synthesis of janusene N-methyl-5a,11a-dicarboximide employing 2,3-dibromo-N-methylmaleimide as acetylene equivalent is described. This thermal reaction is simple synthetic procedure in comparison to sequential-multi step [4+2] cycloaddition routes. Here 2,3-dibromo-Nmethylmaleimide acts effectively as 'molecular glue' bridging two anthracene molecules together.

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An intramolecular acetylene transfer between anthracene and 5,6,7,8-tetrafluorobenzobarrelene. A novel synthesis of janusene and dibenzobarrelene

Cited by 8 publications

References 0 publications

Fluorine Hyperfine Splittings in the Electron Spin Resonance (ESR) Spectra of Aromatic Radicals. An Experimental and Theoretical Investigation

Fluorine Hyperfine Splittings in the Electron Spin Resonance (ESR) Spectra of Aromatic Radicals. An Experimental and Theoretical Investigation

Janusene as a silver ion scavenger: insights from computation

One-Step Synthesis of 5a,11a-Janusene Imide Employing 2,3-Dibromo-N-methylmaleimide as Acetylene Equivalent

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