Synlett 2016; 27(14): 2085-2090
DOI: 10.1055/s-0035-1561478
cluster
© Georg Thieme Verlag Stuttgart · New York

Fulvalene Derivatives Containing a Tetrabenzofluorene Unit: New Nonplanar Fulvalenes with High Electron Affinity

Kenta Yamada
a   Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280, Japan   Email: kawase@eng.u-hyogo.ac.jp
,
Hiroshi Shibamoto
a   Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280, Japan   Email: kawase@eng.u-hyogo.ac.jp
,
Yusuke Tanigawa
a   Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280, Japan   Email: kawase@eng.u-hyogo.ac.jp
,
Hiroyuki Ishikawa
a   Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280, Japan   Email: kawase@eng.u-hyogo.ac.jp
,
Jun-ichi Nishida
a   Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280, Japan   Email: kawase@eng.u-hyogo.ac.jp
,
Chitoshi Kitamura
b   Graduate School of Engineering, University of Shiga Prefecture, 2500, Hassaka-cho, Hikone, Shiga 522-8533, Japan
,
Hiroyuki Kurata
c   Department of Environmental and Food Science, Faculty of Environmental and Information Science, Fukui University of Technology, Gakuen 3-6-1, Fukui 910-8505, Japan
,
Takeshi Kawase*
a   Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280, Japan   Email: kawase@eng.u-hyogo.ac.jp
› Author Affiliations
Further Information

Publication History

Received: 18 April 2016

Accepted after revision: 21 May 2016

Publication Date:
21 June 2016 (online)


Abstract

17H-Tetrabenzo[a,c,g,i]fluoren-17-one possessing a nonplanar, helicene-like structure was efficiently prepared by aerial oxidation of 17H-tetrabenzo[a,c,g,i]fluorene under mild basic conditions. A quinone methide and an unsymmetrical fulvalene containing a tetrabenzofluorene unit were synthesized from the ketone. Treatment of 17-bromotetrabenzo[a,c,g,i]fluorene with a base afforded a symmetric fulvalene as an air-sensitive blue solid. Electrochemical analyses revealed that these compounds have high electron affinities.

Supporting Information

 
  • References and Notes

    • 1a Hopf H. Classics in Hydrocarbon Chemistry: Syntheses, Concepts, Perspectives. Wiley-VCH; Weinheim: 2000
    • 1b Cross Conjugation: Modern Dendralene, Radialene and Fulvene Chemistry. Hopf H, Sherburn MS. Wiley-VCH; Weinheim: 2016
  • 2 Brunetti FG, Gong X, Tong M, Heeger AJ, Wudl F. Angew. Chem. Int. Ed. 2010; 49: 532
  • 3 De Ridder R, Martin RH. Bull. Soc. Chim. Belg. 1960; 69: 534
  • 4 Schröder K, Haase D, Saak W, Lützen A, Beckhaus R, Wichmann S, Schellenberg J. Organometallics 2006; 25: 3824
  • 5 Kitamura C, Tanigawa Y, Kurata H, Kobayashi T, Naito H, Kawase T. Tetrahedron 2012; 68: 1688
  • 6 Ueda Y, Tanigawa Y, Kitamura C, Ikeda H, Yoshimoto Y, Tanaka M, Mizuno K, Kurata H, Kawase T. Chem. Asian J. 2013; 8: 392

    • A fulvene derivative containing a TBF unit has been reported; see:
    • 7a Ramage R, Gilles R. Tetrahedron Lett. 1992; 33: 385
    • 7b Brown AR, Irving SL, Ramage R, Gilles R. Tetrahedron 1995; 51: 11815

      For recent studies on direct oxidation of fluorene to fluorenone, see:
    • 8a Artamkina GA, Grinfel’d AA, Beletskaya IP. Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.) 1983; 32: 345
    • 8b Noureldin NA, Zhao D, Lee DG. J. Org. Chem. 1997; 62: 8767
    • 8c Zheng G, Liu C, Wang Q, Wang M, Yang G. Adv. Synth. Catal. 2009; 351: 2638
    • 8d Jacques M. Synth. Commun. 1989; 19: 2061
    • 8e Gershonov E, Katz E, Karton Y, Zafrani Y. Tetrahedron 2007; 63: 3762
  • 9 17H-Tetrabenzo[a,c,g,i]fluoren-17-one (4) Dark-red prisms; yield: 256 mg (70%); mp 284.0–286 °C (Lit.2 295 °C). IR (KBr): 3072w, 3057w, 1697s, 1425m, 1095m, 748s, 729s, 718s cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.64–7.84 (m, 8 H), 8.31 (d, J = 8.2 Hz, 2 H), 8.69 (d, J = 7.9 Hz, 2 H), 8.78 (d, J = 8.6 Hz, 2 H), 9.23 (d, J = 8.6 Hz, 2 H). 13C NMR (125.8 MHz, CDCl3): δ = 122.75, 123.95, 124.85, 125.88, 126.46, 126.58, 126.95, 127.63, 128.46, 128.55, 128.94, 131.60, 134.71, 146.93, 197.44. MS (EI): m/z (%): 380 [M+] (100), 352 [M–CO]+ (35), 350 (38). UV/Vis (CH2Cl2): λmax (ε, M−1·cm−1) = 321 (29500), 336 (33500), 423 (2320), 530 (900) nm. 3,5-Di-tert-butyl-4-(17H-tetrabenzo[a,c,g,i]fluoren-17-ylidene)cyclohexa-2,5-dien-1-one (5) Black-red prisms; yield: 15 mg (10%); mp 293–294 °C. FT-IR (KBr): 719s, 747s, 870m, 1256m, 1364m, 1456w, 1620s (C=O), 2859w, 2947m, 3077w cm–1. 1H NMR (500 MHz, CDCl3): δ = 1.18 (s, 18 H), 7.61–7.66 (m, 6 H), 7.73 (t, J = 7.8 Hz, 2 H), 7.90 (s, 2 H), 8.22 (t, J = 8.3 Hz, 2 H), 8.48 (d, J = 8.3 Hz, 2 H), 8.74 (t, J = 8.3 Hz, 2 H), 8.77 (d, J = 8.3 Hz, 2 H). MS (EI): m/z (%): 570 [M + 2]+ (100), 569 [M + 1]+ (10), 568 [M+] (20). HRMS (ESI): m/z [M + 1]+ calcd for C43H37O: 569.2839; found: 569.2851. UV/Vis (CH2Cl2): λ (ε, M−1·cm−1) = 301 (26500), 358 (27000), 452 (20500), 529 (6300) nm. 13C NMR spectra for 57 could not be recorded because of the low solubilities of these compounds. 17-(9H-Fluoren-9-ylidene)-17H-tetrabenzo[a,c,g,i]fluorene (6) Black-violet prisms; yield: 7 mg (5%); mp >300 °C. FT-IR (KBr): 733s, 1429w, 1447m, 3034w, 3064w cm–1. 1H NMR (500 MHz, CDCl3): δ = 6.90 (t, J = 7.2 Hz, 2 H), 7.09 (t, J = 7.2 Hz, 2 H), 7.15 (t, J = 7.6 Hz, 2 H), 7.38 (t, J = 7.6 Hz, 2 H), 7.42 (d, J = 7.6 Hz, 2 H), 7.56 (t, J = 7.6 Hz, 2 H), 7.65 (d, J = 7.7 Hz, 2 H), 7.69 (t, J = 7.6 Hz, 2 H), 7.93 (d, J = 8.3 Hz, 2 H), 8.33 (d, J = 8.3 Hz, 2 H), 8.59 (d, J = 8.1 Hz, 2 H), 8.68 (d, J = 8.1 Hz, 2 H). HRMS (ESI): m/z [M+] calcd for C42H24: 528.1881; found: 528.1873. UV/Vis (CH2Cl2): λ (ε, M−1·cm−1) = 303 (29600), 342 (13100), 359 (12100), 545 (13600) nm. 17-Bromo-17H-tetrabenzo[a,c,g,i]fluorene (12) Dark-red prisms; yield: 267 mg (60%); mp 255–256 °C. FT-IR (KBr): 1125, 1157, 1435, 1447, 3069 cm–1. 1H NMR (270 MHz, CDCl3): δ = 6.58 (s, 1 H), 7.62–7.81 (m, 4 H), 8.43 (d, J = 7.6 Hz, 4 H), 8.64 (d, J = 7.9 Hz, 4 H), 8.81 (t, J = 7.6 Hz, 4 H). 13C NMR (125.8 MHz, CDCl3): δ = 44.35, 123.35, 123.78, 124.81, 125.48, 126.80 (2C), 127.01, 127.71, 127.79, 128.05, 131.00, 132.48, 136.40, 140.04. The structure was confirmed by the X-ray crystallographic analysis; see Figure S3 in the Supporting Information. 17,17′-Bi(17H-tetrabenzo[a,c,g,i]fluorenylidene) (7) Dark-blue leaflets; yield: 40 mg (50%); mp >300 °C. IR (KBr): 1495, 1564, 1607, 2851, 2920, 2957, 3038, 3073 cm–1. 1H NMR (500 MHz, CDCl3): δ = 6.72 (t, J = 7.7 Hz, 4 H), 7.64–7.71 (m, 12 H), 7.96 (d, J = 8.2 Hz, 4 H), 8.42 (d, J = 8.2 Hz, 4 H), 8.49 (d, J = 7.9 Hz, 4 H), 8.63 (d, J = 7.9 Hz, 4 H). MS (EI): m/z 728. HRMS (ESI): m/z [M+] calcd for C58H32: 728.2499; found: 728.2505. UV/Vis (CH2Cl2): λ (ε, M−1·cm−1) = 312 (29500), 370 (17400), 495 (3300), 641 (14800) nm.
  • 10 CCDC 950544 (12) contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
  • 11 Kurata H, Tanaka T, Sauchi T, Kawase T, Oda M. Chem. Lett. 1997; 26: 947
  • 12 Oota A, Imai T, Yamazaki A, Oba T, Karikomi M, Minabe M. Bull. Chem. Soc. Jpn. 2006; 79: 333
  • 13 Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA. Jr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ. Gaussian 09, Revision A.02. Gaussian, Inc; Wallingford: 2009
  • 14 Although the energy barriers between the twist and butterfly conformations of 6 and 7 are unknown, 1H NMR spectra (Figures S16 and S17) indicated that they exist as single isomers in CDCl3 solution.
  • 15 Potter RG, Hughes TS. J. Org. Chem. 2008; 73: 2995
  • 16 For a previous report on CV data for 4, see: Eakins GL, Alford JS, Tiegs BJ, Breyfogle BE, Stearman CJ. J. Phys. Org. Chem. 2011; 24: 1119
    • 17a Hünig S, Schwarz H. Justus Liebigs Ann. Chem. 1957; 599: 131
    • 17b Takahashi K, Sakae T, Takase K. Chem. Lett. 1978; 237
    • 17c Stezowski JJ, Biedermann PU, Hildenbrand T, Dorsch JA, Eckhardt CJ, Agranat I. J. Chem. Soc., Chem. Commun. 1993; 213