Synthesis 2019; 51(03): 677-682
DOI: 10.1055/s-0037-1611368
feature
© Georg Thieme Verlag Stuttgart · New York

Scalable Synthesis of Naphthothiophene and Benzodithiophene Scaffolds as π-Conjugated Synthons for Organic Materials

Andrea Nitti*
a  Department of Chemistry and INSTM Research Unit, University of Pavia, Viale Taramelli 10, 27100 Pavia, Italy   Email: andrea.nitti01@universitadipavia.it   Email: dario.pasini@unipv.it
,
Gabriele Bianchi
b  Research Center for Renewable Energies and Environment, Istituto Donegani, Eni Spa, Via Fauser 4, 28100 Novara, Italy
,
Riccardo Po
b  Research Center for Renewable Energies and Environment, Istituto Donegani, Eni Spa, Via Fauser 4, 28100 Novara, Italy
,
a  Department of Chemistry and INSTM Research Unit, University of Pavia, Viale Taramelli 10, 27100 Pavia, Italy   Email: andrea.nitti01@universitadipavia.it   Email: dario.pasini@unipv.it
› Author Affiliations
We thank Eni S.p.A. through its University contact branch Eni Corporate University (contract with the University of Pavia No. C49/09/13), and for research contracts through the INSTM consortium, and the University of Pavia for a Postdoctoral Fellowship to AN
Further Information

Publication History

Received: 13 October 2018

Accepted: 05 November 2018

Publication Date:
13 December 2018 (online)


Abstract

The synthesis on a gram-scale and the full characterization of naphtho[1,2-b]thiophene and benzo[1,2-b:6,5-b']dithiophene 4-carboxylate esters bearing 2-octyldodecyl side chains, and their stannylated and brominated derivatives, suitable for their insertion into π-conjugated polymers is described. The fully soluble and processable synthons are obtained through a cascade sequence of reactions, namely direct arylation and cross aldol condensation, which create an effective pathway for the annulation and π-extension of suitable, commercially available reagents. The newly reported synthesis are compared, whenever possible, using ‘green chemistry metrics’ with literature synthesis, showing dramatic improvements.

Supporting Information

 
  • References

  • 1 Chatzisideris MD, Laurent A, Christoforidis GC, Krebs FC. Appl. Energy 2017; 208: 471
  • 2 Li H, Xiao H, Ding L, Wang J. Sci. Bull. 2018; 63: 340
  • 3 Meng L, Zhang Y, Wan X, Li C, Zhang X, Wang Y, Ke X, Xiao Z, Ding L, Xia R, Yip H.-L, Cao Y, Chen Y. Science 2018; 361: 1094
  • 4 Chen J, Liao Q, Wang G, Yan Z, Wang H, Wang Y, Zhang X, Tang Y, Facchetti A, Marks TJ, Guo X. Macromolecules 2018; 51: 3874
  • 5 Baran D, Ashraf RS, Hanifi DA, Abdelsamie M, Gasparini N, Röhr JA, Holliday S, Wadsworth A, Lockett S, Neophytou M, Emmott CJ. M, Nelson J, Brabec CJ, Amassian A, Salleo A, Kirchartz T, Durrant JR, McCulloch I. Nat. Mat. 2017; 16: 363
  • 6 Punzi A, Operamolla A, Omar OH, Brunetti F, Scaccabarozzi AD, Farinola GM, Stingelin N. Chem. Mater. 2018; 30: 2213
  • 7 Kan B, Feng H, Wan X, Liu F, Ke X, Wang Y, Zhang H, Li C, Hou J, Chen Y. J. Am. Chem. Soc. 2017; 139: 4929
  • 8 Po R, Bianchi G, Carbonera C, Pellegrino A. Macromolecules 2015; 48: 453
  • 9 Po R, Roncali J. J. Mater. Chem. C 2016; 4: 3677
  • 10 Sheldon RA. Green Chem. 2017; 19: 18
    • 11a Søndergaard R, Manceau M, Jørgensen M, Krebs FC. Adv. Energy Mater. 2012; 2: 415
    • 11b Manceau M, Bundgaard E, Carlé JE, Hagemann O, Helgesen M, Søndergaard R, Jørgensen M, Krebs FC. J. Mater. Chem. 2011; 21: 4132
    • 12a Tanaka K, Osuga H, Tsujiuchi N, Hisamoto M, Sakaki Y. Bull. Chem. Soc. Jpn 2002; 75: 551
    • 12b Kaisha CK, Yamada N, Kamatani J, Saitoh A. Patent PCT Int. Appl. WO2011132623A1, 2011
  • 13 Irfan A, Muhammad S, Chaudhry AR, Al-Sehemi AG, Jin R. Optik 2017; 149: 321
    • 14a Pala SK, Sahua T, Misraa T, Gangulya T, Pradhanb TK, De A. J. Photochem. Photobiol. A: Chem. 2015; 174: 138
    • 14b Welker M, Turbiez MG. R, Chebotareva N, Kirner HJ. Patent PCT Int. Appl. WO 2014086722, 2014
    • 15a Yamamoto Y, Matsui K, Shibuya M. Chem. Eur. J. 2015; 21: 7245
    • 15b Mamane V, Hannen P, Fürstner A. Chem. Eur. J. 2004; 10: 4556
    • 16a Boufroura H, Souibgui A, Gaucher A, Marrot J, Pieters G, Aloui F, Ben Hassine B, Clavierd G, Prim D. Org. Biomol. Chem. 2015; 13: 10844
    • 16b Sarkar P, Dechambenoit P, Durola F, Bock H. Asian. J. Org. Chem. 2012; 1: 366
    • 17a Campos-Gómez E, Campos PJ, González HF, Rodríguez MA. Tetrahedron 2012; 68: 4292
    • 17b Song K, Wu L.-Z, Yang C.-H, Tung C.-H. Tetrahedron Lett. 2000; 41: 1951
    • 18a Murai M, Hosokawa N, Roy D, Takai K. Org. Lett. 2014; 16: 4134
    • 18b Wakabayashi R, Kurahashi T, Matsubara S. Synlett 2013; 24: 2297
    • 19a Sankar E, Raju P, Karunakaran J, Mohanakrishnan AK. J. Org. Chem. 2017; 82: 13583
    • 19b Zhu C, Qiu L, Xu G, Li J, Sun J. Chem. Eur. J. 2015; 21: 12871
    • 20a Nitti A, Bianchi G, Po R, Pasini D. Molecules 2017; 22: 821
    • 20b Nitti A, Debattista F, Abbondanza L, Bianchi G, Po R, Pasini D. J. Polym. Sci., Part A: Polym. Chem. 2017; 55: 1601
    • 21a Monari M, Montroni E, Nitti A, Lombardo M, Trombini C, Quintavalla A. Chem. Eur. J. 2015; 21: 11038
    • 21b Ball CJ, Willis MC. Eur. J. Org. Chem. 2013; 425
    • 22a Nitti A, Bianchi G, Po R, Swager TM, Pasini D. J. Am. Chem. Soc. 2017; 139: 8788
    • 22b Nitti A, Signorile M, Boiocchi M, Bianchi G, Po R, Pasini D. J. Org. Chem. 2016; 81: 11035