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Centrohexaindan, the First Hydrocarbon with Topologically presence of only three signals in the 'H-NMR spectrum ser, H.-P. Krimmer, S. Fischer, M. C. Bohm, H. J. Lindner, Angew. and of six signals in the I3C-NMR spectrum (Table 1) is Chem. 98 (1986) 646; Angew. Chem. Int. Ed. Engl. 25 (1986) 630; E. consistent with a molecular structure with DZhsymmetry Heilbronner, Z.-Z. Yang, ibid. 99 (1987) 369 and 26 (1987) 360; J. D. Dunitz, C. Kriiger, H. Irngartinger, E. F. Maverick, Y. Wang, M. Nix- dorf, ibid. I00 (1988) 415 and 27 (1988) 387. 131 A. Toyota, Bull. Chem. Soc. Jpn. 48 (1975) 1152. Table I. Spectroscopic data of 4, 9, and 10. 'H-NMR (CDCI,, 300 MHz), [4] K. Hafner, G. F. Thiele, Tetrahedron Lett. 26 (1985) 2567. "C-NMR (CDCI,, 75.47 MHz), UV (n-hexane). 151 All the compounds gave correct elemental analyses. 161 R. Y. Levina, N. N. Mezentsova, 0. V. Lebeda, Zh. Obshch. Khim. 29 4: 'H-NMR: 6=1.14-1.28 (m,ISH, tBu), 2.48-3.02 (m, 8H, CHI), 5.75-6.26 (1955) 1079; B. F. Hallam, P. L. Pauson, J. Chem. SOC.1958, 646; K. (m, 4H, olefin-H); UV: A,,,,,(lg&)=253 nm (3.83) Alder, H.-J. Ache, F. H. Flock, Chem. Ber. 93 (1960) 1888; C. F. Wilcox, 9: 'H-NMR: 6=1.16 (s, ISH, tBu), 2.39, 2.86 (2 br. s, 4H, CH2), 5.65 (d, Jr., R. R Craig, J. Am. Chem. SOC.83 (1961) 3866; H. L. Lentzner, W. E. J=2.2 Hz, 2H, 1/8-H), 6.15 (s, 2H, 3/6-H), 6.52 (s, 2H, 9/10-H); UV: Watts, Tetrahedron 27 (1971) 4343. 1,,,(1g&)=228 (3.88) sh, 262 (3.47) sh, 327 (4.17) sh, 344 (4.40) sh, 358 (4.52), 171 T. Kauffmann, J. Ennen, H. Lhotak, A. Rensing, F. Steinseifer, A. Wol- 376 (4.40), 458 nm (2 78) termann, Angew. Chem. 92 (1980) 321; Angew. Chem. Int. Ed. Engl. 19 (1980) 328. 10: 'H-NMR: S= 1.33 (s, ISH, tBu), 6.84 (s, 4H, 1/3/6/8-H), 7.27 (s, 4H, [81 The unsubstituted can also be obtained 4/5/9/10-H); "C-NMR: 6=30.22 (4, C(CH3)3), 32.85 (s, C(CH,),), 124.90 1,2-dicyclopentadienylethane from sodium cyclopentadienide using this method (colorless crystals, (d, C-l/3/6/8), 126.15 (d, C-4/5/9/10), 139.30 (s, C-3a/5a/Sa/lOa), 160.87 m.p. IOT, yield 41%). (s, C-217); UV. Lm,,(lg&)=217 (4.19), 324 (4.88) sh, 335 (5.02), 413 (3.51) sh, 191 H. Sauter, H. Prinzbach, Angew. Chem. 84 (1972) 297; Angew. Chem. Inf. 425 (3.54) sh, 435 (3.59), 460 (3.53), 923 (1.99), 1015 (1.93) sh, 1064 (1.91) sh, Ed. Engl. 11 (1972) 296; H. Sauter, B. Gallenkamp, H. Prinzbach, Chem. 1375 nm (1.64) sh Ber. I10 (1977) 1382. [lo] Crystal data for 10: triclinic, Pi, Z= I, a=955.2(4), b=866.4(4), c=621.2(3) pm,a= 105.39(l)o,g=95.82(l)", y= 115.21(1)0. MoK, radia- tion, 1991 independent reflections, 1741 observed (1>20(1)), 141 pa- and delocalized n-electron system. This is confirmed by rameters refined, R=0.062, R,.=0.053. Further details of the crystal the X-ray structure analysis,"" which reveals a planar ring structure investigation are available on request from the Fachinforma- system with inversion center for 10 (Fig. 1). The maximum tionszentrum Energie, Physik, Mathematik GmbH, D-7514 Eggenstein- Leopoldshafen 2 (FRG) on quoting the depository number CSD-53098, distance of the ring-C atoms from the mean plane is k 1.5 the names of the authors, and the journal citation. We thank Prof. Dr. H. pm. The perimeter of the molecule, with CC bond lengths J. Lindner and Dr. H. Paulus for the X-ray structure analysis. of about 140 pm, exhibits substantial bond equivalency, [I I] K:P. Zeller in Houben- Weyl-Miiller: Methoden der oryanischen Chemie, whereas the two bridges are noticeably longer (149 pm). Vol. 5/2c, Thieme, Stuttgart 1985, p. 127, and references cited therein. [I21 T. Sugimoto, M. Shibata, S. Yoneda, Z. Yoshida, Y. Kai, K. Miki, N. Thus, the bridging bonds have predominantly single-bond Kasai, T. Kobayashi, J. Am. Chem. Sac. 108 (1986) 7032; M. Oda, Pure character, as in azulene." 'I Appl. Chem. 58 (1986) 7. Y z Centrohexaindan, The First Hydrocarbon with Topologically Non-Planar Molecular Structure** By Dietmar Kuck* and Andreas Schuster Herein we report on the synthesis of centrohexaindan 1 (hexabenzohexacyclo[5.5.2.24~10.1 1~7.04.'7.0'0~i7]heptadec- ane) and some properties of this unique hydrocarbon. Fig 1 Crystal structure of 10 (ORTEP, vibration ellipsoids at the 50% prob- ability level) at room temperature with selected bond lengths [pm] 1 The analogy to azulene also extends to the electronic spectrum of 10, which like that of azulene consists of three structural band systems whose extinctions decrease with Like dodecahedrane 2['.21among the spherically anne- increasing wavelength. Their positions compared to those lated polyquinanes, the "C1,-hexaquinane"[31 3 is the most of the bands of azulene, however, are strongly batho- fascinating member of the centrally annelated so-called chromically shifted, so that the longest wavelength absorp- centrop~lyquinanes.[~~In contrast to 1, however, centro- tions already lie in the near IR. hexacyclic hydrocarbons like the centrohexaquinane 3 10 not only belongs to the few hydrocarbons with a pla- and the corresponding hexaene 4 have not yet been syn- nar eight-membered but, in addition, it is also a thesized, even though they are of considerable interest re- completely planar 14 n-electron system which has no fur- garding their special ring co~pling.[~-~] ther cyclic conjugated subunits apart from the 14 n perim- eter. The molecular structure and spectroscopic properties justify the classification of 10 as a non-benzenoid aromatic hydrocarbon. Received: April 28, 1988 [Z 2727 IE] German version: Angew. Chem. 100 (1988) 1213 2 3 + 5 [I] D. Lloyd: Non-benzenoid Conjugated Carbocyclic Compounds, Elsevier, Amsterdam 1984, and references cited therein. [2] K. Hafner, Anyew Chem. 75 (1963) 1041 ; Angew. Chem. Inr. Ed. Engl. 3 [*] Dr. D. Kuck, DipLChem. A. Schuster (1964) 165; Pure Appl. Chem. Suppl. 2 (1971) 1; K. Hafner, H.-P. Knm- Fakultat fur Chemie der Universitat mer, Angew. Chem 92 (1980) 202; Angew. Chem. Int. Ed. Engl. 19 (1980) Universitatsstrasse 25, D-4800 Bielefeld 1 (FRG) 199; K. Hafner, Pure Appl. Chem. 54 (1982) 939; K. Hafner, B. Stowas- [**I Benzoannelated Centropolyquinanes, Part 5.-Part 4, see [13b]. 1192 0 VCH Verlagsgesellschaji mbH. 0-6940 Weinheim. 1988 0570-0833/88/0909-1192 $ 02.50/0 Angew. Chem. Int. Ed. Engl. 27 (1988) No. 9 The only centrohexacyclic compound known so far is the double 1,3-interaction in 7 leads to a conformation the triether 5, which was synthesized simultaneously by with S4 symmetry which is static on the NMR time scale Simmons et a1.@]and Paquette et al.[91Attempts to prepare (Scheme 1). Therefore, different to the case of 6,[14]no 3 via a route similar to that used for the synthesis of 5 AA'BB' system is observed in the 300-MHz 'H-NMR spec- have thus far As the hexabenzo derivative of 4, trum for the four aromatic rings, but instead an ABCX sys- compound 1 is the first hydrocarbon with centrohexacy- tem, whereby an ortho-proton is in each case strongly de- clic molecular structure. shielded by the neighboring benzene ring.["] The fascination of the centrohexaquinane structure of 1 lies in the annelation of six cyclopentane rings around a central C atom common to all rings.l4]The central neopen- tane skeleton is bridged by six o-phenylene groups corre- sponding to the six edges of a regular tetrahedron, such that the central, quaternary C atom is surrounded by four further, equivalent quaternary sp3-C atoms1''] and there- fore should exhibit ideal tetrahedral coordination.['" Fur- thermore, in the ground state l should have prefect Td Scheme 1. Conformers of 7 symmetry, in analogy to the hexaene 4 calculated by Erm- When 7 is heated together with four equivalents of er.f61 Centrohexaindan 1 combines a number of known lower AlBr3 in benzene, fourfold C-C coupling takes place with benzoannelated centropolyquinane moieties (centropolyin- formation of the centrohexaindan 1 in 50yo overall yield! dans). Thus, in 1, three 2,2'-spirobiindans are fused along During the reaction, salt-like intermediates are formed the three space axes to give a three-dimensional cross, whose structural elucidation should provide interesting de- tribenzotriquinacenel'*l and tri~tindan"~'(sym-tribenzo- tails about the hitherto unknown fenestrane ions with car- [3.3.3]propellane) are condensed with each other four- benium centers at the bridgeheads. fold degenerate, and, finally, 1 contains three fenestranes (tetrabenzo[5.5.5.S]fenestranes, "fenestrindans") 6.II4' It is Table 1. Spectroscopic data of centrohexaindan 1 thus the first fenestrane substituted with carbon on all four MS (EI, 70 ev): m/z=516 (Mso, loo%), 515 (12), 439 (3). 258 (M2s, 4) bridgehead^."^] IR (KBr): V=3070 (m), 3020 (m), 1470 (s), 755,751 (s), 700 cm-' (m) 'H-NMR (300 MHz, CDC13): 6=7.27, 7.79 (AA'BB') I3C-NMR (75.8 MHz, CD2CI,): 6573.5 (S, Ca),95.4 (S, Cc'"""), 124.5 (d, cortho), 129.1 (d, Cme''), 148.6 (C"") UV (n-heptane, r=4.
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