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Volumn 10, Issue 22, 2008, Pages 5139-5142

A facile synthesis of elusive alkoxy-substituted hexa-peri- hexabenzocoronene

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; ALKOXY RADICAL; FLUORENE; FLUORENE DERIVATIVE; HEXA PERI HEXABENZOCORONENE; HEXA-PERI-HEXABENZOCORONENE; POLYCYCLIC HYDROCARBON; UNCLASSIFIED DRUG; WATER;

EID: 58149177443     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol8020429     Document Type: Article
Times cited : (69)

References (38)
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    • A hydrogenation of 7b (4) in ethyl acetate using Pd/C as a catalyst did not afford the corresponding hydroquinone 5 but a reduced indenofluorene derivative containing cyclohexanone moieties; see the Supporting Information.
    • A hydrogenation of 7b (4) in ethyl acetate using Pd/C as a catalyst did not afford the corresponding hydroquinone 5 but a reduced indenofluorene derivative containing cyclohexanone moieties; see the Supporting Information.
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    • For a discussion of the arenium ion versus cation-radical mechanisms in various organic transfromations, see: (a) Rathore, R.; Kochi, J. K. Acta Chem. Scand. 1998, 52, 114-130.
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    • The ECEC mechanism is also applicable to other (oxidative) biaryl syntheses; see: (a) Ronlan, A.; Hammerich, O.; Parker, V. D. J. Am. Chem. Soc. 1973, 95, 7132-7138.
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    • Rathore, R.; Kochi, J. K. J. Org. Chem. 1995, 60, 7479-7490. The electron-tranfer or cation-radical mechanisms proposed in Schemes 2 and 3 may alternatively be considered to be occurring via carbocation intermediates. For example, an intramolecular attack of the protonated anisyl moiety on the adjecent anisyl group will result into a dearomatized intermediate which can then undergo oxidative aromatization. Although we strongly favor a cation-radical mechanism for the Scholl reactions (such as in Scheme 3), the carbocation pathways can not be easily ruled out.
    • (b) Rathore, R.; Kochi, J. K. J. Org. Chem. 1995, 60, 7479-7490. The electron-tranfer or cation-radical mechanisms proposed in Schemes 2 and 3 may alternatively be considered to be occurring via carbocation intermediates. For example, an intramolecular attack of the protonated anisyl moiety on the adjecent anisyl group will result into a dearomatized intermediate which can then undergo oxidative aromatization. Although we strongly favor a cation-radical mechanism for the Scholl reactions (such as in Scheme 3), the carbocation pathways can not be easily ruled out.
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    • (a) The distonic radical cations have ample literature precedent in the syntheses of a variety of biaryls; see: Hammerich, O.; Parker, V. D. Adv. Phys. Org. Chem. 1984, 20, 55-190, and references cited therein.
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    • Cyclohexadienyl-type radicals are known to undergo oxidation at ∼0 V (vs SCE); see: Haddon, R. C.; Wudl, F.; Kaplan, M. L.; Marshall, J. H.; Cais, R. E.; Bramwell, F. B. J. Am. Chem. Soc. 1978, 100, 7629-7633.
    • Cyclohexadienyl-type radicals are known to undergo oxidation at ∼0 V (vs SCE); see: Haddon, R. C.; Wudl, F.; Kaplan, M. L.; Marshall, J. H.; Cais, R. E.; Bramwell, F. B. J. Am. Chem. Soc. 1978, 100, 7629-7633.
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    • 13C NMR spectra were broad at 22 °C but, however, were sharpened at higher temperatures (90 °C); see Figure S5 in the Supporting Information.
    • 13C NMR spectra were broad at 22 °C but, however, were sharpened at higher temperatures (90 °C); see Figure S5 in the Supporting Information.
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    • A detailed evaluation of the liquid crystalline properties of 2 and its derivatives with varying chain lengths will be undertaken, and the results will be reported in due course
    • A detailed evaluation of the liquid crystalline properties of 2 and its derivatives with varying chain lengths will be undertaken, and the results will be reported in due course.


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