Synlett 2018; 29(20): 2638-2642
DOI: 10.1055/s-0037-1611022
letter
© Georg Thieme Verlag Stuttgart · New York

A Straightforward Synthesis to Novel 1,10-Phenanthrolines with Fused Thiophene Structure

Maike Tünnermann
,
Pia Rehsies
,
Ulrich Flörke
,
Paderborn University, Department of Chemistry, Warburger Strasse 100, 33098 Paderborn, Germany   Email: [email protected]
› Author Affiliations
M. Tünnermann thanks the Deutsche Bundesstiftung Umwelt (DBU) for a Ph.D. scholarship. The German ministry of research and education is acknowledged for funding in frame of project TrExHigh.
Further Information

Publication History

Received: 15 August 2018

Accepted after revision: 24 September 2018

Publication Date:
24 October 2018 (online)


Abstract

We report here a straightforward synthesis for a series of new structures with fused 1,10-phenanthroline-thiophene connection. They are synthesized with a modified Hinsberg thiophene procedure, followed by successive modification to yield several 5,7-disubstituted thieno[3,4-f][1,10]phenanthrolines, most notable thiophene-substituted compounds that could be potentially of use for organic electronics ­applications. For some selected examples, crystal structures were ­obtained, showing a nearly coplanar arrangement around the fused connection, also beneficial for an effective electron transfer in organic electronics or solar cells.

Supporting Information

 
  • References and Notes

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  • 14 The reaction was conducted under inert atmosphere. Compd 5 (0.04 g, 0.1 mmol, 1 equiv) and 13 (0.10 g, 0.2 mmol, 2 equiv) were added to a Schlenk flask with dry and oxygen-free toluene (2 mL) and DMF (0.5 mL). Pd(PPh3)4 (0.01 g, 8.7 μmol, 0.1 equiv) was added in counterflow to the mixture, and the reaction was stirred at 105 °C for 72 h. The mixture was allowed to cool down to ambient temperature while a white solid precipitated. The solvent was filtered off, and the solid was washed with toluene. The powder was dried under vacuum and identified as the desired product 15; yield 0.04 g (69 %). 1H NMR (500 MHz, CDCl3): δ = 2.62 (s, 6 H), 2.78 (s, 6 H), 7.10 (d, 3 J HH = 7.72 Hz, 2 H), 7.22 (d, 3 J HH = 3.65 Hz, 2 H), 7.33 (d, 3 J HH = 3.65 Hz, 2 H), 7.34 (d, 3 J HH = 4.43 Hz, 2 H), 7.70 (d, 3 J HH = 7.85 Hz, 2 H), 8.37 (dd, 3 J HH = 8.35 Hz, 4 J HH = 1.60 Hz, 2 H), 9.00 (dd, 3 J HH = 4.43 Hz, 4 J HH = 1.60 Hz, 2 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 24.1 (CH3), 24.3 (CH3), 121.1 (CH), 123.1 (CH), 125.7 (Cq), 127.9 (CH), 130.0 (CH), 130.0 (Cq), 131.0 (Cq), 132.6 (CH), 135.0 (Cq), 138.3 (CH), 144.7 (Cq), 147.1 (Cq), 149.8 (CH), 155.3 (Cq), 157.7 (Cq). 15N NMR (50.7 MHz, CDCl3): δ = 305.9 (s), 313.1 (s) ppm. MS-ESI (pos): m/z = 633.12 [M + Na]+, 611.14 [M + H]+, 306.07 [M + 2H]2+. Anal. Calcd for CHN4S3: N, 9.17; C, 70.79; H, 4.29; S, 15.75. Found: N, 8.76; C, 69.69; H, 4.67; S, 14.5.
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