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Volumn 121, Issue 45, 1999, Pages 10496-10503

Photoequilibration of 1-naphthylcarbene and 4,5- benzobicyclo[4.1.0]hepta-2,4,6-triene

Author keywords

[No Author keywords available]

Indexed keywords

ARGON; BICYCLO COMPOUND; CYCLOALKENE; METHANE; NAPHTHYL GROUP;

EID: 0033579178     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9920157     Document Type: Article
Times cited : (19)

References (73)
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    • (a) Jones, W. M.; Brinker, U. H. In Pericyclic Reactions; Marchand, A. P., Lehr, R. E., Eds.; Academic Press: New York, 1977; Vol. 1, Chapter 3.
    • (1977) Pericyclic Reactions , vol.1
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    • Abramovitch, R. A., Ed.; Plenum Press: New York, Chapter 4
    • (c) Wentrup, C. In Reactive Intermediates; Abramovitch, R. A., Ed.; Plenum Press: New York, 1980; Vol. 1, Chapter 4.
    • (1980) Reactive Intermediates , vol.1
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    • Regitz, M., Ed.; G. Thieme Verlag: Stuttgart
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    • (1989) Methoden der Organische Chemie (Houben-Weyl) , vol.E19B , pp. 824-976
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  • 16
    • 13044259877 scopus 로고    scopus 로고
    • Ph.D. Dissertation, University of California, Los Angeles, 1981
    • (c) West, P. R. Ph.D. Dissertation, University of California, Los Angeles, 1981.
    • West, P.R.1
  • 17
    • 33845183891 scopus 로고
    • A review of strained cyclic allenes is given in the following: Johnson, R. P. Chem. Rev. 1989, 89, 1111-1124.
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    • Johnson, R.P.1
  • 33
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    • Reference 1a, pp 123-136
    • (e) Reference 1a, pp 123-136.
  • 41
    • 13044267386 scopus 로고    scopus 로고
    • note
    • In this experiment, cyclobuta[de]naphthalene (4) is detectable only by UV/visible spectroscopy (Figure 2). The concentration of 4 in the matrix remains constant throughout subsequent photolyses.
  • 42
    • 13044251499 scopus 로고    scopus 로고
    • note
    • Information available as Supporting Information.
  • 45
    • 13044295684 scopus 로고    scopus 로고
    • note
    • max 343 nm) is consistent with Horn's description.
  • 47
    • 0000448891 scopus 로고    scopus 로고
    • Reference 1e, p 311
    • For leading references, see: (a) McMahon, R. J.; Chapman, O. L.; Hayes, R. A.; Hess, T. C.; Krimmer, H. P. J. Am. Chem. Soc. 1985, 107, 7597-7606. (b) Reference 1e, p 311.
  • 50
    • 13044270662 scopus 로고    scopus 로고
    • note
    • The ratio of s-E:s-Z rotamers remains constant as observed by ESR spectroscopy. Additionally, all infrared bands attributed to 1 appear and disappear at the same rate.
  • 51
    • 13044305546 scopus 로고    scopus 로고
    • note
    • max resulting from the overlapping absorption spectra of the two conformers. We attempted the analogous experiment with our system (λ = 356 ± 10 nm). In this instance, however, the ratio of s-E:s-Z isomers of carbene 1 did not change.
  • 53
    • 13044295685 scopus 로고    scopus 로고
    • note
    • The subtle spectral changes are difficult to observe by infrared spectroscopy. Very few bands can be distinguished from the baseline and only the steady disappearance of 4 can be tracked with certainty.
  • 54
    • 13044293685 scopus 로고    scopus 로고
    • note
    • Because cyclobuta[de]naphthalene (4) was prepared by flash vacuum pyrolysis of 1-naphthyldiazirine (12), we speculated that a trace amount of diazirine contaminant in the matrix could be responsible for the ESR signal observed on photolysis of 4. However, extended photolysis (λ = 396 ± 10 nm) of 4 under conditions where diazirine 12 is known to afford triplet 1-naphthylcarbene (1) failed to produce the triplet ESR signal of carbene 1.
  • 55
    • 13044290313 scopus 로고    scopus 로고
    • note
    • max 484, 416, 327, 316, 298, 284 nm). Further irradiation (λ > 200, λ = 290 ± 10 or λ > 300 nm) produces no discernible change. The spectroscopic bands do not decay in the dark at 10 K, even over several hours. Full arc irradiation (λ > 200 nm) of 4 followed by broad-band photolysis (λ > 497 nm) results in complete disappearance of the 912 G ESR signal as well as the expected disappearance of carbene 1. The 912 G signal can be partially regenerated by photolyzing at λ = 290 ± 10 nm or completely regenerated by full arc irradiation. The intensity of the other ESR signals (648, 1456, 1670 G) does not change under any of the photochemical conditions.
  • 57
    • 13044254467 scopus 로고    scopus 로고
    • note
    • 6
  • 59
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    • and references therein
    • (b) Cramer, C. J.; Smith, B. A. J. Phys. Chem. 1996, 100, 9664-9670 and references therein.
    • (1996) J. Phys. Chem. , vol.100 , pp. 9664-9670
    • Cramer, C.J.1    Smith, B.A.2
  • 64
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    • note
    • 2〉 = 0.
  • 68
    • 13044287037 scopus 로고    scopus 로고
    • note
    • The ratio of matrix to sample is always approximately 500:1.
  • 72
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    • Ph.D. Dissertation, Ohio State University, 1983
    • Wright, B. Ph.D. Dissertation, Ohio State University, 1983.
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  • 73
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    • note
    • NMR and mass spectral characterization are complicated by the compound's insolubility in a wide variety of solvents.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.