C_3v‐Symmetrical Tribenzotriquinacenes Bearing Six Benzylic Tentacle Groups at the Molecular Periphery

Abstract

The synthesis and characterization of several C3v‐symmetrically extended tribenzotriquinacenes (TBTQs) bearing six benzylic C1‐tentacular functional groups at the arene periphery were reported. A new C3v‐symmetrical hexakis(chloromethyl)‐substituted TBTQ derivative was used as the key intermediate, and other derivatives were synthesized with high efficiency by either sixfold nucleophilic substitution reactions with phenols or sixfold Friedel–Crafts alkylation reactions with various arenes.

Tris(tetraceno)triquinacenes: Synthesis and Photophysical Properties of Threefold Linearly Extended Tribenzotriquinacenes

“…In view of the poor solubility of some extended TBTQ derivatives,17a the sixfold chloromethylated 4b,8b,12b‐tripropyl‐12d‐methyl congener 3 was chosen as a starting point (Scheme ) 25c. According to a procedure reported previously,25a treatment of 3 with sodium sulfide under phase‐transfer catalysis (PTC) conditions furnished the corresponding threefold thioether 4 in moderate yield.…”

“…5b‐Methyl‐4b,9b,14b‐tri‐ n ‐propyl‐4b,6,8,9b,11,13,14b,15b‐octahydro‐1 H ,3 H ‐[2]benzothieno[5′,6′:5,6]thieno[3′′,4′′:5′,6′]indeno‐[1′,2′,3′:3,4]pentaleno[1,2‐ f ][2]benzothiophene (4) : A solution of the sixfold benzyl chloride 3 25c (500 mg, 0.710 mmol) and hexadecyltrimethylammonium bromide (193 mg, 0.532 mmol) in anhydrous dichloromethane (50 mL) was stirred under argon while a solution of sodium sulfide nonahydrate (768 mg, 3.20 mmol) in demineralized water (50 mL) was added dropwise through a dropping funnel. The resulting milky mixture was vigorously stirred in the dark at ambient temperature for 24 h. The organic layer was separated and the aqueous layer was extracted with dichloromethane (3×25 mL).…”

“…[20,21] Different from triptycenes bearing three acene wings oriented perpendicular to a common plane and mutually at 120 8, [22] TBTQ-based acenes would stretch out into the three-dimensional space at about 90 8 to each other, with obvious consequences for the so-called internal free volume (IFV) generated. [22,23] Whereas various successful directed extensions of the three aromatic wings of the TBTQ system have been reported, [17,18,[24][25][26][27] threefold (''linear'') extension with acene units has not been achieved yet. By contrast, single-wing extension was feasible by Diels-Alder methodology involving in situ-generated TBTQ-based monoaryne and monoisobenzofuran analogues at low temperature for trapping with vari-Keywords: acenes · photophysics · polycyclic compounds · quinones · UV/Vis spectroscopy Abstract: The linear extension of the rigid, C 3v -symmetrical carbon framework of tribenzotriquinacene (TBTQ) along its three wings is reported.…”

Versatile Syntheses of Hemi‐Cryptophanes and a Metallo‐Cryptophane from a Hexa‐Functionalized C3v‐Symmetrical Tribenzotriquinacene (TBTQ) Derivative

“…[14][15][16] Derivatives of TBTQ belong to the centropolyindane family and have ah ighly (C 3v -) symmetrical aromatic carbon framework with three indane wings oriented orthogonally to each other (Figure 1). [17] It was therefore envisaged that properly multi-functionalized TBTQ derivatives, such as the 2,3,6,7,10,11-hexakis(chloromethyl)-TBTQ derivatives 2a [18] or 2b [19] can be versatile synthetic intermediates for the formation of different types of cage molecules. We previously reported that compounds 2a or 2b underwents ix-fold substitution reactions with different nucleophiles to form six-fold TBTQ derivatives, such as 3a-3d.…”

Tribenzotriquinacene‐Based Triscyclophanes: Intra‐ and Inter‐Wing C3v‐Symmetrical Extension of the Bowl‐Shaped Tribenzotriquinacene Core

“…The C 3 v ‐symmetrical, bowl‐shaped structure11,12 and the “Cartesian” geometry1b of the TBTQ scaffold and the diverse and well controllable chemical reactivity of the TBTQ hydrocarbons [1,4,11,13,14] enables a large range of intriguing extensions, which may lead to novel applications as nanoscaled building blocks and supramolecular hosts. [1a,3a,3c,15–18] In recent years, extension of the TBTQ skeleton has mainly been focused on the elongation and enlargement of the three indane wings 19–21. For example, threefold linear extension of the three independent aromatic π‐electron systems by using various condensation [4a,13a,13c,13g,15–18,19] and Diels–Alder methodologies20,21 have been pursued to enlarge the convex‐concave surface of the TBTQ core.…”