Synthesis of 1,2,3,4-tetrafluoro- and 1,2,3,4,5,6,7,8-octafluoroanthracenes via cycloaddition-reversion

Cantrell, Gary L.; Filler, Robert

doi:10.1016/s0022-1139(00)85106-4

Cited by 10 publications

(5 citation statements)

References 13 publications

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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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“…[22] Oxidative deamination of adduct 5: [20] A stirred solution of crude adduct 5 (0.280 g, % 1 mmol) in CHCl 3 (5 mL), cooled to 0 8C, was treated with 3-chloroperbenzoic acid (70 %, 0.500 g, 2 mmol). The solution turned colourless in about 15 min and after another 15 min a white precipitate formed.…”

Section: Synthesismentioning

confidence: 99%

Synthesis, X‐ray Diffraction and Computational Study of the Crystal Packing of Polycyclic Hydrocarbons Featuring Aromatic and Perfluoroaromatic Rings Condensed in the Same Molecule: 1,2,3,4‐Tetrafluoronaphthalene, ‐anthracene and ‐phenanthrene

Cozzi

Bacchi

Filippini

et al. 2007

Chemistry A European J

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We have synthesised some planar polycyclic compounds, in which unsubstituted aromatic rings are condensed with perfluorinated aromatic rings, and have carried out a combined X-ray diffraction and computational study to analyse their self-recognition behaviour in crystalline phases. We compare our results with the parent hydrocarbons and with other compounds that have a variable degree of fluorination. Whereas the molecular planes in crystals of hydrocarbons with mono- or difluorinated aromatic rings or of perfluorinated compounds arrange themselves in V-shaped configurations, our present results show that perfluorinated rings tend to stack over unsubstituted rings even when these two moieties coexist in a condensed system, producing crystalline materials with parallel molecular layers with the arene-perfluoroarene recognition pattern. Our analysis shows that the packing energy of all these crystals is dispersion-dominated and that coulombic terms are selective rather than quantitatively predominant in crystals with arene-perfluoroarene interactions. No compelling proof of a special role of C-H...F interactions has been found.

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“…1,2,3,4-Tetrafluoro- and 2,3-bis(trifluoromethyl)-9,10-dihydro-9,10-ethenoanthracene-11,12-dicarboxylic acid dimethyl esters were obtained similarly from the corresponding substituted anthracenes (1,2,3,4-tetrafluoroanthracene and 2,3-bis(trifluoromethyl)anthracene). 1,2,3,4-Tetrafluoroanthracene was prepared according to Cantrell's method . 2,3-Bis(trifluoromethyl)anthracene was synthesized from 2,3-bis(trifluoromethyl)-9,10-dihydro-9,10-ethenoanthracene, which was obtained from the Diels−Alder reaction of 2,3-dimethylene-1,4-dihydro-1,4-ethenonaphthalene and hexafluoro-2-butyne, followed by dehydrogenation with DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) …”

Section: Resultsmentioning

confidence: 99%

Orbital Unsymmetrization Affects Facial Selectivities of Diels−Alder Dienophiles

1996

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We investigated the Diels-Alder reactions of maleic anhydrides embedded in a dibenzobicyclo[2.2.2]octatriene motif as a nonsterically biased dienophile. Substituents on a benzene ring in these dienophiles are far from the reaction center, providing a sterically equivalent pi-face. Instead substituents can unsymmetrize the dienophilic pi face through pi (anhydride)-pi (aromatic) orbital interactions. Electron-withdrawing substituents affect the facial bias and relative rates of these cycloadditions. The preference of the cycloadditions is opposite in direction to those observed in nucleophilic additions of 2-substituted-9,10-dihydro-9,10-ethanoanthracen-11-ones (dibenzobicyclo[2.2.2]octadienones) and in electrophilic additions of 2-substituted 9,10-dihydro-9,10-ethenoanthracenes (dibenzobicyclo[2.2.2]octatrienes), though all of them have related dibenzobicyclic systems.

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Synthesis of 1,2,3,4-tetrafluoro- and 1,2,3,4,5,6,7,8-octafluoroanthracenes via cycloaddition-reversion

Cited by 10 publications

References 13 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

Synthesis, X‐ray Diffraction and Computational Study of the Crystal Packing of Polycyclic Hydrocarbons Featuring Aromatic and Perfluoroaromatic Rings Condensed in the Same Molecule: 1,2,3,4‐Tetrafluoronaphthalene, ‐anthracene and ‐phenanthrene

Orbital Unsymmetrization Affects Facial Selectivities of Diels−Alder Dienophiles

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