Synlett 2019; 30(01): 30-43
DOI: 10.1055/s-0037-1610269
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© Georg Thieme Verlag Stuttgart · New York

Synthesis of Functional Carbo-benzenes with Functional Properties: The C2 Tether Key

a  CNRS, LCC (Laboratoire de Chimie de Coordination), 205 Route de Narbonne, BP44099, 31077 Toulouse Cedex 4, France   Email: valerie.maraval@lcc-toulouse.fr   Email: remi.chauvin@lcc-toulouse.fr
b  Université de Toulouse, UPS, ICT-FR 2599, 31062 Toulouse Cedex 9, France
,
Cécile Barthes
a  CNRS, LCC (Laboratoire de Chimie de Coordination), 205 Route de Narbonne, BP44099, 31077 Toulouse Cedex 4, France   Email: valerie.maraval@lcc-toulouse.fr   Email: remi.chauvin@lcc-toulouse.fr
b  Université de Toulouse, UPS, ICT-FR 2599, 31062 Toulouse Cedex 9, France
,
Arnaud Rives
a  CNRS, LCC (Laboratoire de Chimie de Coordination), 205 Route de Narbonne, BP44099, 31077 Toulouse Cedex 4, France   Email: valerie.maraval@lcc-toulouse.fr   Email: remi.chauvin@lcc-toulouse.fr
b  Université de Toulouse, UPS, ICT-FR 2599, 31062 Toulouse Cedex 9, France
,
a  CNRS, LCC (Laboratoire de Chimie de Coordination), 205 Route de Narbonne, BP44099, 31077 Toulouse Cedex 4, France   Email: valerie.maraval@lcc-toulouse.fr   Email: remi.chauvin@lcc-toulouse.fr
b  Université de Toulouse, UPS, ICT-FR 2599, 31062 Toulouse Cedex 9, France
,
a  CNRS, LCC (Laboratoire de Chimie de Coordination), 205 Route de Narbonne, BP44099, 31077 Toulouse Cedex 4, France   Email: valerie.maraval@lcc-toulouse.fr   Email: remi.chauvin@lcc-toulouse.fr
b  Université de Toulouse, UPS, ICT-FR 2599, 31062 Toulouse Cedex 9, France
› Author Affiliations

The reported results have been obtained with fundings from the following sources: Agence Nationale de la Recherche (ANR-11-BS07-016-01), the Centre National de la Recherche Scientifique (CNRS prematuration program, October 2016-November 2017, PHOTOH2 project), and the Toulouse IDEX program 2015-2017 (CARBO-DEVICE project).
Further Information

Publication History

Received: 11 July 2018

Accepted after revision: 13 August 2018

Publication Date:
12 October 2018 (online)


Abstract

Beyond demonstration of conceptual relevance and synthetic feasibility of aryl/alkyl-substituted representatives, carbo-benzene molecules started to gain prospects of broader impact through the emergence of alkynyl derivatives. This is first illustrated by examples of di- and hexaalkynyl-carbo-benzenes, a carbo-naphthalene, a carbo-biphenyl, and two carbo-terphenyls. A focus is then given to dialkynyl derivatives by reference to the peripherally C2-extruded parents. In the centro­symmetric quadrupolar series, the C2 expansion or ethynylogation effect is more particularly considered for 9H-fluoren-2-yl, tris(O-n-­alkyl)pyrogallyl, indol-3-yl, 4-anilinyl, and tetraphenyl-carbo-phenyl substituents on the following respective properties: two-photon absorption, chemical stability, columnar mesogenicity, on-surface photo­induced charge separation vs single-molecule conductance, and reduction potential. Topical results and prospects of application are discussed on the basis of crystallographic, spectroscopic, and electrochemical analyses vs DFT-calculated nuclear and electronic structures. For the sake of the discussion consistency, complementary experimental and computational results are disclosed in the dianilinyl series. Overall, it is shown that combined advances in strategy, protocols, and substrate scope of acetylenic synthesis remain crucial for the development of yet poorly explored but promising types of molecular materials.

1 Introduction

2 Hexaalkynyl-carbo-benzene

3 ortho-Dialkynyl-carbo-benzene

4 para-Dialkynyl-carbo-benzenes

4.1 Bistrimethylsilylethynyl-carbo-benzene

4.2 Bisfluorenylethynyl-carbo-benzene

4.3 Bistrialkoxyarylethynyl-carbo-benzenes

4.4 Bisindolylethynyl-carbo-benzene

4.5 Bisanilinylethynyl-carbo-benzene

5 Carbo-oligo(phenyleneethynylene)s

6 Conclusions

Supporting Information

 
  • References and Notes


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  • 31 Experimental Procedure and Characterization of 27b First StepBis(benzonitrile)palladium(II)chloride (41.3 mg, 0.107 mmol) and CuI (9.6 mg, 0.074 mmol) were placed into a Schlenk tube under argon and dissolved in 4 mL of dry 1,4-dioxane. The mixture was then treated with tri-tert-butylphosphine (0.22 mL, 1 M solution in toluene, 0.22 mmol) at r.t. After the solution turned black, distilled diisopropylamine (0.65 mL, 4.99 mmol), 4-bromo-N,N-bis(trimethylsilyl)aniline (1.0 mL, 3.54 mmol) and trimethylsilylacetylene (0.65 mL, 4.60 mmol) were added. The resulting mixture was heated at 50 °C for 2 h, and then cooled down to r.t. before addition of EtOAc, filtering through Celite®, and concentration under reduced pressure to afford 29 as a black sticky liquid (1.42 g), which was used without further purification.Second StepA solution of the crude product 29 (1.42 g) in methanol (20 mL) was cooled down to 0 °C, before treatment with K2CO3 (884 mg, 6.40 mmol). The resulting mixture was stirred for 1 h at 0 °C before addition of distilled water (20 mL). Then, the methanol was removed under reduced pressure. The remaining aqueous layer was extracted with Et2O, and the combined organic layers were washed with brine, dried over anhydrous MgSO4, and concentrated under reduced pressure to afford 27b as a spectroscopically pure brown viscous liquid (920 mg, 3.50 mmol, 98% yield over 2 steps). Analytical Data 1H NMR (400 MHz, 298 K, (CD3)2CO): δ = 0.10 (s, 18 H, -Si(CH3)3), 3.7 (s, 1 H, ≡CH) 6.96 (d, 3 J HH = 8.0 Hz, 2 H, o-C6H4–), 7.39 (d, 3 J HH = 8.0 Hz, 2 H, m-C6H4–) ppm. 13C{1H} NMR (100 MHz, 298 K, (CD3)2CO): δ = 1 .31 (–Si(CH3)3), 77.66 (–C≡C–H), 83.37 (–C≡C–H), 117.54 (ipso-C6H4), 130.28 (o-C6H4), 132.77 (m-C6H4), 149.08 (p-C 6H4) ppm.
  • 32 Experimental Preparation and Characterization of 1p First StepA solution of 27b (638 mg, 2 .44 mmol) in dry THF (15 mL) was treated at –78 °C with lithium bis(trimethylsilyl)amide (2.8 mL, 1 M solution in THF, 2.8 mmol). The resulting mixture was stirred for 1 h at –78 °C before dropwise addition of a solution of 16 (706 mg, 1.04 mmol) in dry THF (60 mL) at the same temperature. The resulting mixture was allowed to warm up to r.t. under stirring over 18 h. After treatment with a saturated aqueous solution of NH4Cl and extractions of the aqueous layer with Et2O, the combined organic layers were washed with brine, dried over anhydrous MgSO4, and concentrated under reduced pressure to afford the diol 28b as an orange solid (1.48 g), which was used without further purification.Second StepA solution of the crude 28b (1.48 g) in dry DCM (330 mL) was treated at –78 °C with SnCl2 (2.43 g, 12.8 mmol) and HCl·Et2O (12.4 mL, 2 M solution in Et2O, 24.8 mmol). The resulting mixture was allowed to warm up to –15 °C under stirring over 3.5 h, and then kept for 10 min. at r.t. before addition of NaOH (25 mL, 2 M aqueous solution, 50 mmol). The resulting mixture was stirred at r.t. for 16 h. After treatment with a saturated aqueous solution of Na2CO3 and extractions of the aqueous layer with DCM, the combined organic layers were dried over anhydrous MgSO4 before filtration through Celite® and concentration under reduced pressure. Washings of the crude solid with pentane and Et2O afforded the expected carbo-benzene 1p as a dark violet solid (160 mg, 0.21 mmol, 20% yield over 2 steps).Analytical Data 1H NMR (400 MHz, 298 K, (D8-THF)): δ = 5.38 (br s, 4 H, –NH2), 6.83 (3 J HH = 8.0 Hz, 4 H, m-C6 H 4–NH2), 7.70 (t, 3 J HH = 8.0 Hz, 4 H, p-C6H5), 7,80 (d, 3 J HH = 8.0 Hz, 4 H, o-C6 H 4–NH2), 7.98 (t, 3 J HH = 8.0 Hz, 8 H, m-C6H5), 9.47 (t, 3 J HH = 8.0 Hz, 8 H, o-C6H5) ppm. 13C{1H} NMR (100 MHz, 298 K, (D8-THF)): δ = 87.00–113.90 (–C≡C– and >C≡C≡C≡C<), 115,16 (m-C6H4–NH2), 119,85, 120,81 (>C(C6H4–NH2)– and >C(C6H5)–), 130.00–130.84 (o, m, p-C6H5), 134.85 (o-C6H4–NH2), 140.33, 152.07 (p-C6H4–NH2 and p-C6H5) ppm. MS (MALDI-TOF/DCTB): m/z (%) = 756.2 (100) [M]+.HRMS (MALDI-TOF/DCTB): m/z [M]+ calcd for C58H32N2: 756.2565; found: 756.2602; [M + Na]+ calcd for C58H32N2Na: 779.2463; found: 779.2437. UV-vis (THF): λmax(ε) = 493 nm (131000 L/mol/cm). Voltammetry: reduction: E (V/SCE) = –0.67 (rev), –1.09 (rev), –1.56 (irrev), oxidation: 0.74 (irrev).
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