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Volumn , Issue 12, 1996, Pages 2019-2028

Chemical reactions of the stable carbene 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene

Author keywords

Betaines; Cycloaddition; Insertion; Nucleophilic carbene; Spiro compounds; Stable carbene; Triazolium salts

Indexed keywords


EID: 33748954621     PISSN: 09473440     EISSN: None     Source Type: Journal    
DOI: 10.1002/jlac.199619961212     Document Type: Article
Times cited : (149)

References (50)
  • 1
    • 0003906159 scopus 로고
    • VCH, Weinheim
    • For a brief historical essay on the clearly attempts to isolate carbenes see: W. Kirmse, Carbene, Carbenoide and Carbenanaloga, VCH, Weinheim 1969, p. 6.
    • (1969) Carbene, Carbenoide and Carbenanaloga , pp. 6
    • Kirmse, W.1
  • 12
    • 0000081750 scopus 로고    scopus 로고
    • For a comprehensive and well-written survey of the chemistry of stable carbenes including the Arduengo carbenes see: M. Regitz, Angew. Chem. 1996, 108, 791;
    • (1996) Angew. Chem. , vol.108 , pp. 791
    • Regitz, M.1
  • 20
    • 33748962018 scopus 로고    scopus 로고
    • note
    • The alkylthiotriazoline 4 proved to be unstable in the presence of oxygen, decomposing to a mixture of triazolinone 5 and triazolinthione 6. This reaction possibly takes place via a free-radical pathway with the intermediate formation of the corresponding hydroperoxides.
  • 26
    • 84980899326 scopus 로고
    • The insertion of Wanzlick carbenes into the C-H bonds of nitromethane and cyclopentanone has been reported: H.-W. Wanzlick, E. Schikora. Chem. Ber. 1961, 94, 2389.
    • (1961) Chem. Ber. , vol.94 , pp. 2389
    • Wanzlick, H.-W.1    Schikora, E.2
  • 31
    • 0000428842 scopus 로고
    • Nuclear Magnetic Resonance Spectroscopy of Boron Compounds
    • (Eds.: P. Diehl, E. Fluck, R. Kosfeld), Springer, Berlin
    • H. Nöth, B. Wrackmeyer, Nuclear Magnetic Resonance Spectroscopy of Boron Compounds, in NMR, Grundlagen und Fortschritte (Eds.: P. Diehl, E. Fluck, R. Kosfeld), vol. 14, Springer, Berlin, 1978.
    • (1978) NMR, Grundlagen und Fortschritte , vol.14
    • Nöth, H.1    Wrackmeyer, B.2
  • 33
    • 33748966489 scopus 로고    scopus 로고
    • note
    • 3 as the aci-nitro tautomer. This can be explained with the extensive double bond conjugation in this form.
  • 34
    • 0003845932 scopus 로고
    • QCPE 455 Indiana University, Bloomington, IN, USA
    • MOPAC, Version 6.0, J. J. P. Stewart, QCPE 455 (1990), Indiana University, Bloomington, IN, USA.
    • (1990) MOPAC, Version 6.0
    • Stewart, J.J.P.1
  • 35
    • 33748984451 scopus 로고
    • Ph. D. Thesis, University of Kaiserslautern
    • Similar products were obtained by Regitz and Nikolaus in the scope of a very comprehensive study of the reactivity of Wanzlick carbenes and electron-rich olefines with electron-deficient olefines and alkynes: D. Nikolaus, Ph. D. Thesis, University of Kaiserslautern, 1982. We are indebted to Prof. Regitz for providing us with a copy of the thesis.
    • (1982)
    • Nikolaus, D.1
  • 36
    • 0012345342 scopus 로고
    • Brumistrov et al. reported the formation and isolation of a cyclopropane from an imidazolidin-ylidene and N-phenylmaleic imide: S. E. Kondrateva, S. I. Burmistrov, Zh. Org. Khim. 1975, 11, 197. However, since no conclusive spectroscopic data with regard to the existence of the cyclopropane system are given and in the light of our findings we suppose that the isolated compound described in the publication is the corresponding open-chain methyleneimidazolidine.
    • (1975) Zh. Org. Khim. , vol.11 , pp. 197
    • Kondrateva, S.E.1    Burmistrov, S.I.2
  • 37
    • 33748966852 scopus 로고    scopus 로고
    • note
    • AM1 calculations carried out on simpler model systems for the reaction leading to methylenetriazoline 11a (i.e. the phenyl rings on the triazol moiety were omitted) suggest that the cyclopropane system is considerably more stable than the dipole (for the ring opening of the cyclopropane yielding the dipole a reaction enthalpy ΔH = +48 kJ/mol was found), which could be taken as some kind of evidence for the intermediate formation of the cyclopropane. However, more elaborate calculations including the search for the respective transition states are necessary to give a more detailed picture.
  • 38
    • 0342577977 scopus 로고
    • Spectroscopic evidence for the existence of a similar intermediate spirocyclic system was reported for the addition of cyclopropenylidene to methyl fumarate: W. M. Jones, M. E. Stowe, E. E. Wells, Jr., E. W. Lester, J. Am. Chem. Soc. 1968, 90, 1849.
    • (1968) J. Am. Chem. Soc. , vol.90 , pp. 1849
    • Jones, W.M.1    Stowe, M.E.2    Wells Jr., E.E.3    Lester, E.W.4
  • 39
    • 84981940246 scopus 로고
    • Extremely low rotational barriers were previously reported for similar systems: H. Kessler, Chem. Ber. 1970, 103, 973.
    • (1970) Chem. Ber. , vol.103 , pp. 973
    • Kessler, H.1
  • 40
    • 33748952838 scopus 로고    scopus 로고
    • note
    • AM1 calculations carried out for the methylenetriazoline 11a give a barrier of 45 kJ/mol for the rotation round the C = C bond. Analysis of the charge distribution and bond orders in the transition state show that the positive charge is efficiently delocalized in the triazol moiety, whereas the negative charge is involved in an enolate-type resonance with the adjacent ester group.
  • 41
    • 33748963239 scopus 로고    scopus 로고
    • note
    • 2.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.