Synlett 2007(13): 2053-2056  
DOI: 10.1055/s-2007-984897
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Simple and Versatile Synthesis of 1,2-Diarylacenaphthylenes via Suzuki-Miyaura Coupling, and its Application in the Synthesis of a New ­Acenaphthylene-1,2-bis(p-quinone methide) Derivative

Hiroyuki Kurata*, Yuko Takehara, Sang Kim, Kanae Sakai, Kouzou Matsumoto, Takeshi Kawase, Masaji Oda
Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka, 560-0043, Japan
Fax: +81(6)68505387; e-Mail: kurata@chem.sci.osaka-u.ac.jp;
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Publikationsverlauf

Received 18 May 2007
Publikationsdatum:
12. Juli 2007 (online)

Abstract

1,2-Diaryl-substituted acenaphthylene derivatives were prepared simply via Suzuki-Miyaura coupling in good or excellent yields. By applying this method, acenaphthylene-1,2-bis(p-quinone methide) with two 3,5-di-tert-butyl-4-oxocyclohexadienylidene units, which is a stable deep purple crystalline substance with a very broad absorption in the whole visible region and relatively low ­reduction potential, was prepared and characterized.

9

In agreement with literature reports, [3c] [7] 1H NMR spectra of 1e and 1f show the presence of 1:1 mixtures of rotational isomers.

12

Crystallographic data of 3: C40H46O2, M = 558.80, monoclinic, P21/c, a = 21.040 (9), b = 13.717 (6), c = 24.053 (10) Å, β = 103.24 (4)°, V = 6757 (17) Å3, Z = 8, D c = 1.098 g cm-3, 64264 reflections measured, 15373 unique (R int = 0.145) used in refinement. R1 = 0.058 [I > 2σ(I)], wR = 0.155 (all data). T = 200 K. X-ray data have been deposited at the Cambridge Crystallographic Data Centre (CCDC-649872). Copies of the data can be obtained free of charge at www.ccdc.cam.uk/data_request/cif or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ [fax: +44 (1223)336033; e-mail: deposit@ccdc.cam.ac.uk].

13

Variable-temperature NMR measurement of 3 was performed in a bromobenzene-d 5 solution. The coalescence temperature of the tert-butyl signals was 78 ± 3 °C.

14

Measurements were carried out in DMF solution at r.t. using a glassy carbon electrode with tetrabutylammonium perchlorate as the supporting electrolyte.