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Volumn 64, Issue 12, 1999, Pages 4247-4254

Synthesis of peri-cyclobutarenes by thermolysis of [methoxy(trimethylsilyl)methyl]arenes

Author keywords

[No Author keywords available]

Indexed keywords

NAPHTHALENE DERIVATIVE; TRIMETHYLSILYL DERIVATIVE;

EID: 0033546255     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo981104j     Document Type: Article
Times cited : (14)

References (53)
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    • 6b These transformations as yet, however, are not usable preparatively.
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    • 7b-e Such Wittig rearrangements are retarded at low temperatures by TMEDA.
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    • 2b In the present investigation, piptopyrolysis of 5H-(1-naphthyl)tetrazole at 600 °C/0.05-0.1 mm in a quartz tube packed with quartz chips yields naphthalene-1-carbonitrile and hydrogen cyanide essentially totally.
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    • A particular advantage of the present method is that 13 is a low-melting solid (mp 40.5-43.0 °C) and with slight heating can be conveniently admitted at low pressure into the pyrolysis equipment as a liquid or by simple distillation.
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    • Sekiguchi, A.; Ando, W. Tetrahedron Lett. 1979, 4077. Sekiguchi, A.; Ando, W. J. Org. Chem. 1980, 45, 5286. These authors report that substituted phenyl(trimethylsilyl)methanols eliminate trimethylsilanol at ∼500 °C to give products of the phenylcarbenes generated.
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    • In other studies from this laboratory, loss of carbon atoms from arylcarbene precursors become major processes at temperatures above 650 °C.
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    • Carbon-carbon rearrangements of arylcarbenes were initially reported by (a) Vander Stouw, G. G. Ph.D. Dissertation, The Ohio State University, Columbus, Ohio, 1964; Dissertation Abstracts, Ann Arbor, Michigan, 1965. (b) Joines, R. C.; Turna, A. B.; Jones, W. J. Am. Chem. Soc. 1969, 91, 7754. (c) Crow, W. D.; Wentrup, C. Chem. Commun. 1969, 1387. (d) Schissel, P.; Kent, M. E.; McAdoo, D. J.; Hedeya, E. J. Am. Chem. Soc. 1970, 92, 2147. (e) Baron, W. J.; Jones, M., Jr.; Gaspar, P. P. J. Am. Chem. Soc. 1970, 92, 4739. (f) For excellent summaries and discussion of arylcarbene rearrangements, see: Gaspar, P. P.; Hsu, J.-P.; Chari, S.; Jones, M., Jr. Tetrahedron 1985, 41, 1479 and ref 2b.
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    • Carbon-carbon rearrangements of arylcarbenes were initially reported by (a) Vander Stouw, G. G. Ph.D. Dissertation, The Ohio State University, Columbus, Ohio, 1964; Dissertation Abstracts, Ann Arbor, Michigan, 1965. (b) Joines, R. C.; Turna, A. B.; Jones, W. J. Am. Chem. Soc. 1969, 91, 7754. (c) Crow, W. D.; Wentrup, C. Chem. Commun. 1969, 1387. (d) Schissel, P.; Kent, M. E.; McAdoo, D. J.; Hedeya, E. J. Am. Chem. Soc. 1970, 92, 2147. (e) Baron, W. J.; Jones, M., Jr.; Gaspar, P. P. J. Am. Chem. Soc. 1970, 92, 4739. (f) For excellent summaries and discussion of arylcarbene rearrangements, see: Gaspar, P. P.; Hsu, J.-P.; Chari, S.; Jones, M., Jr. Tetrahedron 1985, 41, 1479 and ref 2b.
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    • -1 mm each yield 53 and 54 in ∼7% and 1% yields; phenanthrene, 9-methylphenanthrene and 9-phenanthrenecarbonitrile are also formed.
  • 53
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    • Sadtler Research Laboratories, Inc., Philadelphia, PA
    • 1H NMR Spectrum 2349M. Sadtler Research Laboratories, Inc., Philadelphia, PA.
    • 1H NMR Spectrum 2349M


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