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Volumn 70, Issue 10, 2005, Pages 4013-4021

Isolation, X-ray structures, and electronic spectra of reactive intermediates in Friedel-Crafts acylations

Author keywords

[No Author keywords available]

Indexed keywords

ACYLATION; AROMATIC COMPOUNDS; CARBOXYLIC ACIDS; CHLORINE COMPOUNDS; ELECTRON SPECTROSCOPY; GALLIUM COMPOUNDS; POSITIVE IONS; TITANIUM COMPOUNDS; X RAY CRYSTALLOGRAPHY; ZIRCONIUM COMPOUNDS;

EID: 18744410671     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo0501588     Document Type: Article
Times cited : (23)

References (75)
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  • 10
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    • note
    • Insofar as X-ray structural parameters reflect molecular electron-density distributions.
  • 12
    • 18744408278 scopus 로고    scopus 로고
    • note
    • When a number of reactive intermediates are extant in solution, especially under equilibrium control, those which are isolated in crystal form generally depend on their solvation energy, crystal-lattice energy, molecular symmetry, etc., and not necessarily on their abundance (importance).
  • 14
    • 0000670569 scopus 로고
    • For previous X-ray studies of analogous structures, mostly carried out at higher (room) temperature and lower precision, see: (a) Chevrier, B.; Le Carpentier, J.-H.; Weiss, R. Acta Crystallogr. 1972, B28, 2659, 2667.
    • (1972) Acta Crystallogr. , vol.B28 , pp. 2659
    • Chevrier, B.1    Le Carpentier, J.-H.2    Weiss, R.3
  • 20
    • 33947330030 scopus 로고
    • For X-ray diffraction studies at room temperature, see: (a) Boer, F. P. J. Am. Chem. Soc. 1988, 90, 6706.
    • (1988) J. Am. Chem. Soc. , vol.90 , pp. 6706
    • Boer, F.P.1
  • 29
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    • See also Olah et al. in ref 14
    • (c) Olah, G. A.; Lin, H. C.; Germain, A. Synthesis 1974, 12, 895. See also Olah et al. in ref 14.
    • (1974) Synthesis , vol.12 , pp. 895
    • Olah, G.A.1    Lin, H.C.2    Germain, A.3
  • 30
    • 18744414334 scopus 로고    scopus 로고
    • note
    • (a) We were limited in our mechanistic objectives (vide infra) to these difficult (low-temperature) experimental problems, so it is important to emphasize the caveat that the GC-MS analyses in Table S2 (and Table S3) were not required to be highly reproducible. The semiquantitative results are thus primarily intended to convey the relative trends in arene conversions to Friedel-Crafts ketones, as well as arene recovery and byproduct formation under low-temperature conditions.
  • 31
    • 18744392934 scopus 로고    scopus 로고
    • note
    • (b) For the synthetic utility of acylium salts, see the extensive studies of Olah et al. cited in ref 15.
  • 42
    • 18744374298 scopus 로고    scopus 로고
    • note
    • + also have similar absorptions in this region but are generally blue-shifted by about 5-10 nm.
  • 46
    • 18744391225 scopus 로고    scopus 로고
    • note
    • (a) The relative acceptor properties of the carbocations can be judged by differences in their reduction potentials.
  • 50
    • 18744403820 scopus 로고    scopus 로고
    • note
    • 10,12 was limited to 1-1.5 pm (largely owing to thermal motion) in contrast to 0.3-0.5 pm from our low-temperature data.
  • 51
    • 3242850248 scopus 로고
    • (b) The bond lengths for C=O and C-Cl of 1.181 and 1.804 Å that were determined in hydrocinnamoyl chloride at -150 °C generally fall in the range (1.16-1.21 and 1.75-1.83 Å) of those in other acid chlorides typically reported by: Leser, J.; Rabinovich, D. Acta Crystallogr. 1978, B34, 2253, 2257, 2260, 2264.
    • (1978) Acta Crystallogr. , vol.B34 , pp. 2253
    • Leser, J.1    Rabinovich, D.2
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  • 55
    • 18744410230 scopus 로고    scopus 로고
    • note
    • 1 = 1.48 Å and K = 0.50, which includes the correction for the change in covalent radius with hybridization.
  • 56
    • 18744389276 scopus 로고    scopus 로고
    • note
    • 26b is possible, particularly with regard to solvation of the oxygen nonbonded electron pairs to induce acylium bending (vide infra). Unfortunately, the X-ray results do not address this possibility.
  • 59
    • 18744391790 scopus 로고    scopus 로고
    • note
    • Relative to the bond length of 1.07 Å estimated for a C=O triple bond as described by Davlieva et al. in ref 11 (footnote 18).
  • 62
    • 0003970635 scopus 로고
    • Cambridge University Press: Cambridge, UK
    • (a) Schofield, K. Aromatic nitration; Cambridge University Press: Cambridge, UK, 1980.
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  • 66
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    • Unpublished results
    • (a) Gwaltney, S. R. Unpublished results.
    • Gwaltney, S.R.1
  • 67
    • 18744371694 scopus 로고    scopus 로고
    • note
    • 29 following Mulliken's theoretical classification of intermolecular interactions.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.