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

Kenta Yamada; Hiroshi Shibamoto; Yusuke Tanigawa; Hiroyuki Ishikawa; Jun-ichi Nishida; Chitoshi Kitamura; Hiroyuki Kurata; Takeshi Kawase

doi:10.1055/s-0035-1561478

Synlett, Inhaltsverzeichnis

Synlett 2016; 27(14): 2085-2090
DOI: 10.1055/s-0035-1561478

cluster

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

Kenta Yamada

^aGraduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280, Japan eMail: kawase@eng.u-hyogo.ac.jp

,

Hiroshi Shibamoto

^aGraduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280, Japan eMail: kawase@eng.u-hyogo.ac.jp

,

Yusuke Tanigawa

^aGraduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280, Japan eMail: kawase@eng.u-hyogo.ac.jp

,

Hiroyuki Ishikawa

^aGraduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280, Japan eMail: kawase@eng.u-hyogo.ac.jp

,

Jun-ichi Nishida

^aGraduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280, Japan eMail: kawase@eng.u-hyogo.ac.jp

,

Chitoshi Kitamura

^bGraduate School of Engineering, University of Shiga Prefecture, 2500, Hassaka-cho, Hikone, Shiga 522-8533, Japan

,

Hiroyuki Kurata

^cDepartment 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*

^aGraduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280, Japan eMail: kawase@eng.u-hyogo.ac.jp

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Abstract

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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.

Key words

conjugation - nonplanar π-systems - tetrabenzofluorenes - fulvalenes - electron acceptors - polycycles

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Referenzen

References and Notes

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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): λ_max (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 5–7 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.
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Zusatzmaterial

Supporting Information