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Volumn 62, Issue 23, 1997, Pages 8091-8094

The Direct Alkylation of π-Rich, Acid-Sensitive Heterocyclic Compounds via Essentially Free Carbocations

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EID: 0000140026     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo971081t     Document Type: Article
Times cited : (30)

References (51)
  • 1
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    • Publication no. 56 in a series on alkane diazonium ion-pairs and deamination. Preceding publication: White, E. H. et al. J. Org. Chem. 1996, 61, 7986.
    • (1996) J. Org. Chem. , vol.61 , pp. 7986
    • White, E.H.1
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    • 4b
    • 4b
  • 8
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    • note
    • 2b,4b
  • 10
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    • Ph.D. Thesis of Ron W. Darbeau, The Johns Hopkins University, Baltimore, Maryland
    • (b) From the Ph.D. Thesis of Ron W. Darbeau, The Johns Hopkins University, Baltimore, Maryland, 1996.
    • (1996)
  • 11
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    • note
    • 4b
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    • Muller, E., Ed., (Houben-Weyl), Georg Thieme Verlag: Stuttgart
    • (h) Soll, H. Methoden der Organischen Chemie; Muller, E., Ed., (Houben-Weyl), Georg Thieme Verlag: Stuttgart, 1958; Vol. 11, Part 2, p 133.
    • (1958) Methoden der Organischen Chemie , vol.11 , Issue.PART 2 , pp. 133
    • Soll, H.1
  • 24
    • 1542497337 scopus 로고
    • (c) N-Alkylpyrroles, however, are readily prepared by reaction of pyrryl salts with iodoalkanes (Candy, C. F.; Jones, A. R. J. Org. Chem. 1971, 36, 3990 and Hobbs, C. F. et al. J. Am. Chem. Soc., 1962, 84, 43).
    • (1971) J. Org. Chem. , vol.36 , pp. 3990
    • Candy, C.F.1    Jones, A.R.2
  • 25
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    • (c) N-Alkylpyrroles, however, are readily prepared by reaction of pyrryl salts with iodoalkanes (Candy, C. F.; Jones, A. R. J. Org. Chem. 1971, 36, 3990 and Hobbs, C. F. et al. J. Am. Chem. Soc., 1962, 84, 43).
    • (1962) J. Am. Chem. Soc. , vol.84 , pp. 43
    • Hobbs, C.F.1
  • 26
    • 1542602026 scopus 로고    scopus 로고
    • Half-lives were determined by measuring the changes in the integral of the benzyl signal as a function of time at a constant temperature in the NMR probe
    • (a) Half-lives were determined by measuring the changes in the integral of the benzyl signal as a function of time at a constant temperature in the NMR probe.
  • 27
    • 85086528304 scopus 로고    scopus 로고
    • note
    • 4b benzylation would be faster.
  • 28
    • 85086527405 scopus 로고    scopus 로고
    • note
    • 1H NMR or GC and by GC, respectively (see ref 2e for comparison).
  • 30
    • 0344898021 scopus 로고
    • 8b and 6.4 (Friedrich, E. C.; Vartanian, P. F. J. Organomet. Chem. 1976, 110, 159). Since oxygen is more electronegative than nitrogen it would be expected to deshield the benzylic protons to a greater extent than would nitrogen (Silverstein, R. M.; Bassler, G. C.; Morrill, T. C. Spectrometric Identification of Organic Compounds, 4th ed.; John Wiley and Sons: New York, 1981; p 220).
    • (1976) J. Organomet. Chem. , vol.110 , pp. 159
    • Friedrich, E.C.1    Vartanian, P.F.2
  • 31
    • 0003520774 scopus 로고
    • John Wiley and Sons: New York
    • 8b and 6.4 (Friedrich, E. C.; Vartanian, P. F. J. Organomet. Chem. 1976, 110, 159). Since oxygen is more electronegative than nitrogen it would be expected to deshield the benzylic protons to a greater extent than would nitrogen (Silverstein, R. M.; Bassler, G. C.; Morrill, T. C. Spectrometric Identification of Organic Compounds, 4th ed.; John Wiley and Sons: New York, 1981; p 220).
    • (1981) Spectrometric Identification of Organic Compounds, 4th Ed. , pp. 220
    • Silverstein, R.M.1    Bassler, G.C.2    Morrill, T.C.3
  • 32
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    • note
    • 4a,13
  • 34
    • 1542707035 scopus 로고    scopus 로고
    • note
    • (a) Ideal data would be obtained by decomposing the same precursor (e.g., 1a) at the same temperature in a medium comprised of the solvent under study dissolved in a large excess (∼90%) of an inert diluent.
  • 35
    • 85086526446 scopus 로고    scopus 로고
    • 2c
    • 2c
  • 38
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    • 4b
    • 4b
  • 41
    • 1542392460 scopus 로고    scopus 로고
    • note
    • 4e Thus it would appear that phenyldiazomethane on general acid protonation leads directly to the corresponding intimate ion-pair and eventually into the nitrogen-separated ion-pair (eqs 1 and 4) which is the active alkylating agent in these deaminations. Ion-pair formation is likely to be facilitated in more polar solvents such as acetone and methanol.
  • 45
    • 0002624810 scopus 로고
    • Chemical Carcinogenesis
    • Searle, C., Ed., ACS Monograph No. 182, American Chemical Society, Washington, DC
    • (b) Preussman, R.; Stewart, B. W. Chemical Carcinogenesis; Searle, C., Ed., ACS Monograph No. 182, American Chemical Society, Washington, DC, 1984; pp 643-828.
    • (1984) ACS Monograph No. 182 , vol.182 , pp. 643-828
    • Preussman, R.1    Stewart, B.W.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.