Large polycyclic aromatic hydrocarbons have become useful materials and have necessitated synthetic methods to prepare them. Additionally, dimers of polycyclic aromatic hydrocarbons have become useful materials and have necessitated improved methods for preparing them. Finally, indenoperylenes and diindenoperylenes have become useful materials and have necessitated synthetic methods for preparing them. In the following publications synthetic details have been provided for preparing indenoperylenes: (a) Schlichting, P.; Rohr, U.; Müllen, K. Liebigs Ann./Reculeil 1997, 395-407. (b) Feiler, L.; Langhals, H.; Polborn, K. Liebigs Ann. 1995, 1229-1244. (c) Debad, J. D.; Morris, J. C.; Lynch, V.; Magnus, P.; Bard, A. J. Am. Chem. Soc. 1996, 118, 2374-2379. (d) Anotn, U.; Göltner, C.; Müllen, K. Chem. Ber. 1992, 125, 2325-2330. (e) Wehmeier, M.; Wagner, M.; Müllen, K. Chem. Eur. J., 2001, 2197-2205 (f) Bard, A. J.; Magnus, P.; Morris, J. C.; Debad, J. D. J. Org. Chem. 1997, 62, 530-537. Further disclosures describing their utility in OLED applications are found in Patents and applications EP 1,148,109 A2; EP 1,182,244 A1; EP 1,235,466 A2, U.S. Pat. No. 6,004,685, 82452US, 84436US, 84435US, JP 2001-338764-A, JP 2003-104916-A, JP 2002-110353-A; JP 2002-110355-A; JP 2002-110356-A; JP 1998-30295-A; JP 2002-025772-A; JP 2000-86549-A; JP 2002-025773-A; JP 2000-48958-A.
Manz et al report preparations of periflanthene using sodium amide to dimerize and oxidatively cyclodehydrogenate from fluoranthene to give periflanthene.
Bard et al described the preparation of dibenzo{[f,f′]-4,4′,7,7′-tetraphenyl}-diindeno[1,2,3-cd:1′,2′,3′-lm]perylene(A) from 7,12-diphenylbenzo[k]fluoranthene. The critical oxidizing reagent used to achieve the oxidative cyclodehydrogenation to form A was cobalt(III)fluoride. Additionally, Bard, et. al. have demonstrated that the cyclizations can be performed on a small scale using electrochemical techniques.
Müellen et al have used iron(III)chloride to prepare similar indenoperylenes. Mitsui Chemical also reports a similar approach.
Quinones have been reported as organic oxidants with diphenyl disulfides, but only polymeric materials have been isolated (E. Tsuchida, K. Yamamoto, M. Jikei, H. Hiroyuki, Macromolecules, 1990, 930-934). Triarylaminium oxidants have been used (F. Ciminale, L. Lopez, G. Farinola, S. Sportelli, A. Nacci, Eur. J. Org. Chem., 2002, 3850-3854; F. Ciminale, L. Lopez, V. Paradiso, A. Nacci, Tetrahedron, 1996, 13971-13980), but not to form aryl-aryl bonds. Hypervalent iodine compounds have been used to form aryl-aryl bonds (T. Kitamura, Y. Fujiwara, Organic Preparations and Procedures International, 1997, 409-458; A. Varvoglis, Tetrahedron, 1997, 1179-1255), but these processes have been limited to activated arenas.
Most recently TDK has reported the use of a Yamamoto (nickel) coupling strategy to bring on the dimerization of a fluoranthene and subsequent cyclization to an indenoperylene.
Because of the utility of these materials, there is a need to provide a process for preparing these materials in higher yields and with improved purity.
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