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Valence-Bond Isomers of Aromatic Systems
Prof. Dr. E. E. van Tamelen,
Prof. Dr. E. E. van Tamelen
Department of Chemistry, Stanford University, Stanford, California, U.S.A.
Search for more papers by this authorProf. Dr. E. E. van Tamelen,
Prof. Dr. E. E. van Tamelen
Department of Chemistry, Stanford University, Stanford, California, U.S.A.
Search for more papers by this authorAbstract
The prefix xn is proposed for the classification of valence-bond isomers of aromatic systems, where n is the change in the number of rings or in the number of π-bonds on isomerization. Representatives of the x1-series are Dewar benzene and 9, 10-dihydronaphthalene. Benzvalene and prismane belong to the x2 and x3 series, respectively. Various derivatives of such valence-bond isomers have recently become known.
References
- 1(a) C. K. Ingold, J. chem. Soc. (London) 121, 1133 (1922); (b) W. Baker, Chemistry in Britain 1, 191 (1965).
- 2 G. Wheland: Advanced Organic Chemistry. Wiley, New York 1960, pp. 117–118.
- 3 Gr. ξύξλoς = ring or circle.
- 4 Inclusion of a given example carries no implication as to lifetime or isolability.
- 5 H. G. Viehe, R. Merényi, J. F. M. Oth, J. R. Senders, and P. Valange, Angew. Chem. 76, 922 (1964); Angew. Chem. internat. Edit. 3, 755 (1964); H. G. Viehe, Angew. Chem. 77, 768 (1965); Angew. Chem. internat. Edit. 4, 746 (1965).
- 6 C. E. Berkoff, R. C. Cookson, J. Hudec, and R. O. Williams, Proc. chem. Soc. (London) 1961, 312.
- 7 C. M. Sharts and J. D. Roberts, J. Amer. chem. Soc. 83, 871 (1961).
- 8 K. L. Wierzchowski, D. Shugar, and A. R. Katritzky, J. Amer. chem. Soc. 85, 827 (1963).
- 9 R. Breslow in P. de Mayo: Molecular Rearrangements, Part I. Interscience, New York-London 1963, pp. 243–245.
- 10 E. E. van Tamelen and S. P. Pappas, J. Amer. chem. Soc. 84, 3789 (1962).
- 11 E. E. van Tamelen and S. P. Pappas, Abstract. 18th National Organic Symposium, Columbus, Ohio (U.S.A.), June 1963; J. Amer. chem. Soc. 85, 3297 (1963).
- 11aFor a review, cf. S. Hünig, H. R. Müller, and W. Thier, Angew. Chem. 77, 368 (1965); Angew. Chem. internat. Edit. 4, 271 (1965).
- 12 D. E. Applequist and R. Searle, J. Amer. chem. Soc. 86, 1389 (1964).
- 13 R. Criegee and F. Zanker, Angew. Chem. 76, 716 (1964); Angew. Chem. internat. Edit. 3, 695 (1964).
- 14 E. M. Arnett and J. M. Bollinger, Tetrahedron Letters 1964, 3803.
- 15a E. C. Taylor, W. W. Paudler, and I. Kuntz, Jr., J. Amer. chem. Soc. 83, 2967 (1961).
- 15b E. C. Taylor, R. O. Kan, and W. W. Paudler, J. Amer. chem. Soc. 83, 4484 (1961).
- 16 D. Seebach, Angew. Chem. 77, 119 (1965); Angew. Chem. internat. Edit. 4, 124 (1965).
- 17 Personal communications.
- 18 E. Vogel, Liebigs Ann. Chem. 615, 14 (1958).
- 19 R. Criegee and K. Noll, Liebigs Ann. Chem. 627, 1 (1959).
- 20 L. J. Oosterhoff, as quoted in E. Havinga and J. L. M. A. Schlatmann, Tetrahedron 16, 151 (1961).
- 21 R. B. Woodward and R. Hoffmann, J. Amer. chem. Soc. 87, 395 (1965).
- 22 H. C. Longuet-Higgins and E. W. Abrahamson, J. Amer. chem. Soc. 87, 2045 (1965).
- 23 K. Kirk, Ph. D. Thesis, University of Wisconsin, 1963.
- 24 After learning about our prior results (personal communication), A. W. Burgstahler and P.-L. Chien published independently their confirmatory observations: J. Amer. chem. Soc. 86, 2940 (1964).
- 25 K. E. Wilzbach and L. Kaplan, J. Amer. chem. Soc. 86, 2307 (1964).
- 26 L. Kaplan, K. E. Wilzbach, W. G. Brown, and S. S. Yang, J. Amer. chem. Soc. 87, 675 (1965).
- 27 R. Srinivasan, J. Amer. chem. Soc. 85, 4045 (1963).
- 28 W. G. Dauben and F. G. Willey, Tetrahedron Letters 1962, 893.
- 29 C. Hoogzand and W. Hübel, Tetrahedron Letters 1961, 637.
- 30 E. J. Forbes, J. chem. Soc. (London) 1955, 3864.
- 31 P. D. Gardner, R. L. Brandon, and G. R. Haynes, J. Amer. chem. Soc. 79, 6334 (1957).
- 32 O. L. Chapman, H. G. Smith, and R. W. King, J. Amer. chem. Soc. 85, 803 (1963).
- 33 O. L. Chapman and D. J. Pasto, J. Amer. chem. Soc. 80, 6685 (1958); J. Amer. chem. Soc. 82, 3642 (1960).
- 34 P. R. Story and S. R. Fahrenholtz, J. Amer. chem. Soc. 87, 1623 (1965).
- 35 E. J. Corey and J. Streith, J. Amer. chem. Soc. 86, 950 (1964).
- 36 V. Prelog, Perspectives in Organic Chemistry, edited by A. Todd. Interscience, New York 1956, p. 127.
- 37 Consideration should be given two hypothetical cyclodecapentaenes: The all-cis and the cis-cis-trans-cis-trans isomers.
- 38 C. D. Nenitzescu, M. Avram, and E. Marica, Chem. Ber. 90, 1857 (1957).
- 39 R. Cookson, J. Hudecz, and M. Marsden, Chem. and Ind. 1961, 21.
- 40 B. C. T. Pappas, Ph. D. Thesis, University of Wisconsin, 1963.
- 41 C. G. Krespan, B. C. McKusick, and T. L. Cairns, J. Amer. chem. Soc. 82, 1515 (1960); J. Amer. chem. Soc. 83, 3428 (1961).
- 42 H. E. Zimmerman and G. L. Grunewald, J. Amer. chem. Soc. 86, 1434 (1964).
- 43 H. Winicov, Ph. D. Thesis, University of Wisconsin, 1960.
- 44 O. Diels and K. Alder, Liebigs Ann. Chem. 498, 16 (1932); Liebigs Ann. Chem. 505, 103 (1933); Liebigs Ann. Chem. 510, 87 (1934).
- 45 E. E. van Tamelen, P. E. Aldrich, P. Bender, and G. Miller, Proc. chem. Soc. 1959, 309. See also R. M. Acheson and G. A. Taylor, Proc. chem. Soc. 1959, 186.
- 46 E. E. van Tamelen and B. Pappas, J. Amer. chem. Soc. 85, 3296 (1963).
- 47 For review and discussion, see [20].
- 48 A. C. Cope, A. C. Haven, F. L. Rampand, and E. R. Trumball, J. Amer. chem. Soc. 74, 4867 (1952).
- 49
E. Vogel,
H. Kiefer, and
W. R. Roth,
Angew. Chem.
76, 432
(1964);
10.1002/ange.19640761008 Google ScholarAngew. Chem. internat. Edit. 3, 442 (1964).
- 50 K. Mislow, J. chem. Physics 20, 1489 (1952).
- 51
E. Vogel,
W. Meckel, and
W. Grimme,
Angew. Chem.
76, 786
(1964);
Angew. Chem. internat. Edit.
3, 643
(1964).
10.1002/anie.196406431 Google Scholar
- 52 The novel formation of 1,2-diester (92) may involve isomerization of (89) – by one of several alternative pathways – to diester (73), known to be a progenitor of naphthalene-1, 2-dicarboxylic ester at the temperature involved [42].
- 53 E. Vogel and H. D. Roth, Angew. Chem. 76, 145 (1964); Angew. Chem. internat. Edit. 3, 228 (1964).
- 54 E. Vogel, M. Biskup, W. Pretzer, and W. A. Böll, Angew. Chem. 76, 785; Angew. Chem. internat. Edit. 3, 642 (1964).
- 55 F. Sondheimer and A. Shani, J. Amer. chem. Soc. 86, 3168 (1964).
- 56 E. Vogel and W. A. Böll, Angew. Chem. 76, 784 (1964), Angew. Chem. internat. Edit. 3, 642 (1964).
- 57 T. J. Katz and P. J. Garratt, J. Amer. chem. Soc. 85, 2852 (1963).
- 58 E. A. LaLancette and R. E. Benson, J. Amer. chem. Soc. 85, 2853 (1963).
- 59 Alternatively, a pathway involving valence-bond isomerization of a radical [(97a) → (97b)] can be visualized.
- 60 H.-R. Blattmann, D. Meuche, E. Heibronner, R. J. Molyneux, and V. Boekelheide, J. Amer. chem. Soc. 87, 130 (1965).
- 61 E. F. Ullmann and J. E. Milks, J. Amer. chem. Soc. 84, 1315 (1962).
