2‐Triphenylmethyldicyclohept[ cd,g ]indene: A Novel cata‐peri Condensed Nonalternant Hydrocarbon
1991; Wiley; Volume: 30; Issue: 9 Linguagem: Inglês
10.1002/anie.199111741
ISSN1521-3773
AutoresYoshikazu Sugihara, Junji Saito, Ichiro Murata,
Tópico(s)Molecular spectroscopy and chirality
ResumoAngewandte Chemie International Edition in EnglishVolume 30, Issue 9 p. 1174-1176 Communication 2-Triphenylmethyldicyclohept[cd,g]indene: A Novel cata-peri Condensed Nonalternant Hydrocarbon† Dr. Yoshikazu Sugihara, Corresponding Author Dr. Yoshikazu Sugihara Department of Chemistry, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan)Department of Chemistry, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan)Search for more papers by this authorJunji Saito, Junji Saito Department of Chemistry, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan)Search for more papers by this authorProf. Dr. Ichiro Murata, Corresponding Author Prof. Dr. Ichiro Murata Department of Chemistry, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan)Department of Chemistry, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan)Search for more papers by this author Dr. Yoshikazu Sugihara, Corresponding Author Dr. Yoshikazu Sugihara Department of Chemistry, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan)Department of Chemistry, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan)Search for more papers by this authorJunji Saito, Junji Saito Department of Chemistry, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan)Search for more papers by this authorProf. Dr. Ichiro Murata, Corresponding Author Prof. Dr. Ichiro Murata Department of Chemistry, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan)Department of Chemistry, Faculty of Science Osaka University Toyonaka, Osaka 560 (Japan)Search for more papers by this author First published: September 1991 https://doi.org/10.1002/anie.199111741Citations: 10 † This work was supported by a Grant-in-Aid for Scientific Research on Priority Areas (No. 02230103) from the Ministry of Education, Science and Culture, Japan. AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Graphical Abstract The electronic structure of the title compound 1/1′ is best described in terms of two Kekulé structures of the previously unknown dicyclohepta[a, d]benzene. The stretched π-electron system should be distorted very little by the triphenylmethyl-substituted “external” double bond. 1/1′ can be synthesized in a few steps from 4-methylazulene, whereby an electrocyclic reaction with participation of 14 π electrons is of central importance. References 1 R. Zahradnik, J. Michl, Collect. Czech. Chem. Commun. 30 (1965) 520– 536; B. A. Hess, Jr., L. J. Schaad, J. Org. Chem. 36 (1971) 3418– 3423. 2 Y. Sugihara, H. Yamamoto, K. Mizoue, I. Murata, Angew. Chem. 99 (1987) 1283– 1285; Angew. Chem. Int. Ed. Engl. 26 (1987) 1247– 1249. 3 Y. Sugihara, H. Fujita, I. Murata, J. Chem. Soc. Chem. Commun. 1986, 1130– 1131. 4 Y. Aoki, A. Imamura, I. Murata, Tetrahedron 46 (1990) 6659– 6672. 5 K. Hafner, H. Weldes, Justus Liebigs Ann. Chem. 606 (1957) 90– 99. We thank Prof. K. Hafner for a generous gift of azulene. 6For a similar procedure see: M. Müller, S. Braun, K. Hafner, Angew. Chem. 92 (1980) 633– 635; Angew. Chem. Int. Ed. Engl. 19 (1980) 621– 623. 7 H. Prinzbach, H. Bingmann, D. Hunkler, Tetrahedron Lett. 1978, 649– 652; H. Prinzbach, H. Bingmann, A. Beck, D. Hunkler, E. Sauter, E. Hädicke, Chem. Ber. 114 (1981) 1697– 1722; H. Prinzbach, L. Knothe, Pure Appl. Chem. 58 (1986) 25– 37. 8 Generally, hydride abstraction from a tertiary center as in 10 is an unfavorable process under normal conditions and therefore the hydrogen to be eliminated has to be moved thermally or photochemically. In the present case, attempts to migrate a hydrogen atom in 10 resulted in the formation of a tarry material. 9 K. Hafner, A. Stephan, C. Bernhard, Justus Liebigs Ann. Chem. 650 (1961) 42– 62. 10 For the conversion 10 → 3a, we examined dehydrogenation with either p-chloranil or 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. An unstable greenish product was obtained which showed a similar UV/VIS spectrum to that of 3b; however, its structure could not be characterized due to the low yield. 11 All the new compounds were fully characterized by spectral data together with satisfactory elemental analyses. 12 K. Komatsu, M. Fujimori, K. Okamoto, Tetrahedron 33 (1977) 2791– 2797; K. Komatsu, private communication. 13(a) W. K. Schenk, R. Kyburz, M. Neuenschwander, Helv. Chim. Acta 58 (1975) 1099– 1119. (b) H. Prinzbach, H.-W. Schneider, Angew. Chem. 85 (1973) 1112– 1114; Angew. Chem. Int. Ed. Engl. 12 (1973) 1007– 1009. 14For theoretical studies see: R. Zahradnik, J. Michl, J. Kopecky, Collect. Czech. Chem. Commun. 31 (1966) 640– 648; Collect. Czech. Chem. Commun. 29 (1964) 1932– 1944; R. Zahradnik, J. Michl, Collect. Czech. Chem. Commun. 30 (1965) 3550– 3559; T. Nakajima, Pure Appl. Chem. 28 (1971) 219– 238; A. Toyota, Bull. Chem. Soc. Jpn. 48 (1975) 1152– 1156; Z. Zhou, R. G. Parr, J. Am. Chem. Soc. 111 (1989) 7371– 7379. For an attempted synthesis see: J. Beeby, P. J. Garratt, J. Org. Chem. 38 (1973) 3051– 3052. 15 HMO π-bond orders for 3a: p1,2 = 0.6957,p2,2a = 0.5681,p2a,3 = 0.5236, p3,4 = 0.7236, p4,5 = 0.5589, p5,6 = 0.7362, p6.6a = 0.4941, p6a,7 = 0.6033, p7,7a = 0.5974, p7a,8 = 0.5346, p8,9 = 0.6960, p9,10 = 0.6059, p10,11 = 0.6617, p11,12 = 0.6344, p12,12a= 0.6118, p12a,12b= 0.4737, p1,12b = 0.5623, P2a,2b = 0.4839, p2b,12b = 0.5379, p2b,6a = 0.5096, p7a,12a = 0.4709. 16 Measured against SCE in CH3CN with 0.1 M nBu4NClO, as supporting electrolyte at room temperature, Pt working electrode, n = 200 mVs−1. The peak separations are 50, 100, and 60 mV for the first and second oxidation and first reduction waves, respectively. 17For amphoteric hydrocarbons see: K. Nakasuji, K. Yoshida, I. Murata, J. Am. Chem. Soc. 104 (1982) 1432– 1433; J. Am. Chem. Soc. 105 (1983) 5136– 5137; Chem. Lett. 1982, 969– 970; S. Sasaki, K.-U. Klabunde, I. Murata, J. Toyoda, K. Nakasuji, Angew. Chem. 103 (1991) 198– 199; Angew. Chem. Int. Ed. Engl. 30 (1991) 172– 173. 18 Attempts to convert 3b into 3a through protonation and detriphenylmethylation were unsuccessful. Citing Literature Volume30, Issue9September 1991Pages 1174-1176 ReferencesRelatedInformation
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