Synthesis of an asymmetric heterotriptycene

Abstract

This paper describes the synthesis of an unsubstituted heterocyclic asymmetric triptycene, 5,12-dihydro-5,12-[2',3'-6]thienonaphthacene (8). The choice of the starting materials in this synthesis, naphtho [2,3-6]thiophene (5) and 1,4-epoxy-l,4-dihydronaphthalene (6), is based in part on Hückel molecular orbital computations and in part on experimental data.Triptycene (l)1,a has a rigid "propeller" structure and Csh symmetry. Triptycenes are asymmetric when every one of the three aromatic rings is unlike the other two. This asymmetry can be achieved by attaching substituents at appropriate positions, as done by Ogura (2),3,4 or by having every ring inherently different from the other two. An example of

Thienoacene‐Based Organic Semiconductors

“…Among various thienoacenes, linearly fused acenedithiophenes (AcDTs), including benzodithiophene (BDT, 17 ) [ 53 ] and anthradithiophene (ADT, 3 ) ( Figure 12 ), [ 13 ] the isoelectronic analogues of anthracene and pentacene, respectively, are key building blocks that have been most widely used for the development of organic semiconductors applicable to, for example, vaporor solution-processable molecular semiconductors [ 54 ] and mono mer units for conjugated semiconducting polymers. [ 55 ] In addition to linear-fused systems, angular-fused AcDTs have also been developed.…”

Novel dialkoxy-substituted benzodithienothiophenes for high-performance organic field-effect transistors

“…16 Moreover, AcDTs with bulky substituents at the peri positions tend to give a high mobility of up to 1.5 cm 2 V À1 s À1 , 17 which is correlated with their herringbone-like packing structures, realizing efficient twodimensional carrier transport. 4,5,11,17,[20][21][22][23][24][25] In this work, we designed and synthesized new-type AcDT analogues, namely, benzodithieno[3,2-b]thiophene (BDTT) derivatives with angular-shaped cores. 6 Thereafter, Anthony and co-workers developed a number of ADTs, including the first solution-processable small-molecule materials (TES-ADT) for OFETs, which gave high mobility exceeding 1 cm 2 V À1 s À1 , 18 followed by the development of tetracenodithiophenes (TDTs) and pentacenodithiophenes (PDTs) modified with trialkylsilylethynyl substituents.…”

Synthesis of Benzo[1,2‐b:4,5‐b’]dithiophene and Benzocondensed Thiaheterocycles

“…The reaction of aldehydes 3 b‐d produced the thiaheterocyles 7 b , 7 c and the new polycondensed BDT 7 d with yields comparable to that of the parent BDT 7 a . Aldehydes 3 e and 3 f also gave the expected intermediates 4 e and 4 f , but the subsequent cyclization failed, leading to a complex crude reaction mixture.…”

“…The reaction of aldehydes 3 b-d produced the thiaheterocyles 7 b, [12] 7 c [13] and the new polycondensed BDT 7 d with yields comparable to that of the parent BDT 7 a. Aldehydes 3 e and 3 f also gave the expected intermediates 4 e and 4 f, but the subsequent cyclization failed, leading to a complex crude reaction mixture. In the case of the pyrrole derivative 4 e, after column chromatography, only traces of the expected compound 7 e were detected by mass spectra, while in the case of 4 f only a small amount (19%) of the intermediate 2-(phenylmethyl)-3-thiophene carboxaldehyde (9) [14] was isolated after chromatographic purification.…”