Synthesis and Reactivity of 5-Heterotruxenes Containing Sulfur or Nitrogen as the Heteroatom

Abstract

This paper presents an alternative path for the synthesis of 5-thiatruxene and the synthetic approach for 5-azatruxene not known so far. A new method for 5-thiatruxene improves the overall reaction yield from 17.5 to 22.6%, diminishes the synthesis time and costs by reducing synthetic steps from 5 to 2, and simplifies the isolation of intermediate and final products. The overall reaction yield for 5azatruxene is 32.4%. The typical reactivity of both aromatic systems is also demonstrated. Recent research results suggest the use of 5thiatruxene as the acceptor subunit of soluble blue emitters.

Influence of the heteroatom introduction on the physicochemical properties of 5-heterotruxenes containing nitrogen, oxygen and sulfur atom

“…Compound CCC was synthesized according to known literature procedures, 56 and OCC, SCC, (OS)CC, and (O2S)CC were obtained using synthetic routes published by our group. 57,58 Herein we describe an alternative synthetic pathway, improving on the initial approach, to access azatruxene derivative NCC, which we very recently reported for the rst time. 58 2-(Indan-1ylidene)indan-1-one 1, which is a product of the acid promoted, silicon mediated aldol cross-condensation of indan-1-one, turned out to be a valuable building block in the synthesis of OCC and SCC.…”

“…57,58 Herein we describe an alternative synthetic pathway, improving on the initial approach, to access azatruxene derivative NCC, which we very recently reported for the rst time. 58 2-(Indan-1ylidene)indan-1-one 1, which is a product of the acid promoted, silicon mediated aldol cross-condensation of indan-1-one, turned out to be a valuable building block in the synthesis of OCC and SCC. Moreover, 1 is a promising precursor for the synthesis of other 5-heterotruxenes, containing different p-block heteroatom The acid promoted aldol crosscondensation between a,b-unsaturated ketone 1 and acetophenone 2 leads to the phenyl derivative of 7,12-dihydroindeno [1,2-a]uorene 5, Scheme 1.…”

“…Overall NCC reaction yield is $60%, which is about two times higher than previously reported method. 58 The presented synthetic approach is an alternative to photocyclization, which allows the efficient synthesis of soluble derivatives of 5-heterotruxenes 57,58 and 5,10-diheterotruxenes. 65 The further development of this methodology may lead to new synthetic approaches of 5-heterotruxenes, as well as to explore the chemistry of unknown class of aromatic systems, namely 7,12-dihydroindeno[1,2-a]uorenes.…”

“…Studied compounds were synthesized according to literature procedures: CCC, 76 OCC, 57 SCC, (OS)CC and (O 2 S)CC. 58 All data considering CCC and OCC was taken from the work of Górski et al 57 A detailed protocol for obtaining NCC is available via the SI le. Optimization of the structures, energy levels calculation, and orbital visualization was realized by Gaussian 09 Rev.…”

Toward Soluble 5,10-Diheterotruxenes: Synthesis and Reactivity of 5,10-Dioxatruxenes, 5,10-Dithiatruxenes, and 5,10-Diazatruxenes

“…In addition, the nitrene insertion, successfully used in the synthesis of the 5-azatruxene core, in this case, leads to a complicated mixture of products. 55 In the presence of strong protic acid, ninhydrin 14 undergoes condensation with indole derivative 15c , leading to ketone 13c . In contrast to the previously discussed carbonyl compound 13b , ketone 13c has two ethyl groups as a solubilizing agent, allowing Wolff–Kizhner reduction.…”