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Synthesis of Thieno[3,2-b]thiophenes from 2,5-Dicarbonyl 3-Nitrothiophenes via Nucleophilic Aromatic Substitution of the Nitro Group with Thiolates

Roman A. Irgashev, Nikita A. Kazin

Organics · pp. 507–519 · Published 7 Nov 2024

10.3390/org5040027

Abstract

In this study, we developed an efficient strategy for constructing thieno[3,2-b]thiophene molecules from 3-nitrothiophenes, containing carbonyl fragments at the C-2 and C-5 atoms, by nucleophilic aromatic substitution of the nitro group in these substrates. It was shown that the reaction of 3-nitrothiophene-2,5-dicarboxylates with thiophenols, thioglycolates and 2-mercaptoacetone in the presence of K2CO3 proceeds rapidly via nucleophilic displacement of the nitro group with the formation of 3-sulfenylthiophene-2,5-dicarboxylates. Further treatment of the resulting thiophene-2,5-dicarboxylates, which have -SCH2CO2Alk or -SCH2COMe moiety at C-3 atom, with sodium alcoholates afford obtaining 2,3,5-trisubstituted thieno[3,2-b]thiophene derivatives according to the Dieckman condensation. In turn, the reaction of methyl 5-formyl-4-nitrothiophene-2-carboxylate with methyl thioglycolate or 2-mercaptoacetone in the presence of K2CO3 proceeds to directly form 2,5-disubstituted thieno[3,2-b]thiophenes.

Nitro Nucleophilic substitution Substitution (logic) Nucleophilic aromatic substitution Chemistry Group (periodic table) Stereochemistry Electrophilic aromatic substitution

References (60)

  1. 1 Wang, 2012, Semiconducting π-conjugated systems in field-effect transistors: A material odyssey of organic electronics [DOI]
  2. 2 Cinar, 2015, Thienothiophenes, dithienothiophenes, and thienoacenes: Syntheses, oligomers, polymers, and properties [DOI]
  3. 3 Tang, 2007, Conjugated copolymers based on fluorene-thieno[3,2-b]thiophene for light-emitting diodes and photovoltaic cells [DOI]
  4. 4 Mishra, 2010, Highly Air-stable thieno[3,2-b]thiophene-thiophene-thiazolo[5,4-d]thiazole-based polymers for light-emitting diodes [DOI]
  5. 5 Turkoglu, 2016, novel organoboron compounds derived from thieno[3,2-b]thiophene and triphenylamine units for oled devices [DOI]
  6. 6 Ito, 2013, Synthesis and properties of thieno[3,2-b]thiophene derivatives for application of ofet active layer [DOI]
  7. 7 Lim, 2017, A systematic study on molecular planarity and D–A conformation in thiazolothiazole- and thienylenevinylene-based copolymers for organic field-effect transistors [DOI]
  8. 8 Malov, 2019, Hole mobility in thieno[3,2-b]thiophene oligomers [DOI]
  9. 9 Chao, 2015, Biaxially extended conjugated polymers with thieno[3,2-b]thiophene building block for high performance field-effect transistor applications [DOI]
  10. 10 Amna, 2022, High-Performance, Low-Voltage Organic Field-Effect Transistors Using Thieno[3,2-b]Thiophene and Benzothiadiazole Co-Polymers [DOI]
  11. 11 Lee, 2009, Synthesis and characterization of 2,1,3-benzothiadiazole-thieno[3,2-b]thiophene-based charge transferred-type polymers for photovoltaic application [DOI]
  12. 12 Biniek, 2010, Impact of the alkyl side chains on the optoelectronic properties of a series of photovoltaic low-band-gap copolymers [DOI]
  13. 13 Chen, 2011, Crystalline conjugated polymer containing fused 2,5-di(thiophen-2-yl)thieno[2,3-b]thiophene and thieno[3,4-c]pyrrole-4,6-dione units for bulk heterojunction solar cells [DOI]
  14. 14 Li, 2013, Synthesis and photovoltaic properties of D-π-A copolymers based on thieno[3,2-b]thiophene bridge unit [DOI]
  15. 15 Kim, 2014, Thieno[3,2-b]thiophene-substituted benzo[1,2-b:4,5-b′]dithiophene as a promising building block for low bandgap semiconducting polymers for high-performance single and tandem organic photovoltaic cells [DOI]
  16. 16 Dang, 2014, Improved photovoltaic performance of two-dimensional low band-gap conjugated polymers with thieno[3,2-b]thiophene and diketopyrrolopyrrole units by altering pendent position of conjugated side chain [DOI]
  17. 17 Ha, 2020, Highly efficient and photostable ternary organic solar cells enabled by the combination of non-fullerene and fullerene acceptors with thienopyrrolodione-based polymer donors [DOI]
  18. 18 Zhang, 2015, A Solution-processed high performance organic solar cell using a small molecule with the thieno[3,2-b]thiophene central unit [DOI]
  19. 19 Wang, 2018, Two thieno[3,2-b]thiophene-based small molecules as bifunctional photoactive materials for organic solar cells [DOI]
  20. 20 Ye, 2018, High-performance organic solar cells based on a small molecule with thieno[3,2-b]thiophene as π-bridge [DOI]
  21. 21 Liao, 2019, Fused selenophene-thieno[3,2-b]thiophene–selenophene (ST)-based narrow-bandgap electron acceptor for efficient organic solar cells with small voltage loss [DOI]
  22. 22 Wang, 2020, An efficient star-shaped fused-ring electron acceptor with c 3h -symmetric core via thieno[3,2-b]thiophene extending conjugation strategy [DOI]
  23. 23 Li, 2024, Small molecule donor third component incorporating thieno[3,2-b]thiophene unit enables 19.18% efficiency ternary organic solar cells with improved operational stability [DOI]
  24. 24 Zimmermann, 2020, Tetrasubstituted thieno[3,2-b]thiophenes as hole-transporting materials for perovskite solar cells [DOI]
  25. 25 Isci, R., Unal, M., Yesil, T., Ekici, A., Sütay, B., Zafer, C., and Ozturk, T. (2023). Thieno[3,2-b]thiophene and triphenylamine-based hole transport materials for perovskite solar cells. Front. Mater., 10. [DOI]
  26. 26 Zhang, 2023, Thieno[3,2-b]thiophene-based linear dopant-free hole transport materials for efficient perovskite solar cells [DOI]
  27. 27 Rafiq, 2023, Recent synthetic approaches towards thienothiophenes: A potential template for biologically active compounds [DOI]
  28. 28 Kukolja, 1985, Orally absorbable cephalosporin antibiotics. 2.1 structure-activity studies of bicyclic glycine derivatives of 7-aminodeacetoxycephalosporanic acid [DOI]
  29. 29 Prugh, 1991, New isomeric classes of topically active ocular hypotensive carbonic anhydrase inhibitors: 5-substituted thieno[2,3-b]thiophene-2-sulfonamides and 5-substituted thieno[3,2-b]thiophene-2-sulfonamides [DOI]
  30. 30 Kaizerman, 2003, DNA binding ligands targeting drug-resistant bacteria: Structure, activity, and pharmacology [DOI]
  31. 31 Deng, 2011, Discovery of 2-(4-methylfuran-2(5h)-ylidene)malononitrile and thieno[3,2-b]thiophene-2-carboxylic acid derivatives as g protein-coupled receptor 35 (gpr35) agonists [DOI]
  32. 32 Faull, 1981, Some reactions of ethyl 2-anilino-4-oxo-4,5-dihydrothiophen-3-carboxylate [DOI]
  33. 33 Fuller, 1997, Thienothiophenes. Part 2.1 Synthesis, metallation and bromine→lithium exchange reactions of thieno[3,2-b]thiophene and its polybromo derivatives [DOI]
  34. 34 Krayushkin, 2001, Photochromic dihetarylethenes. 6. photochromic derivatives of thieno[3,2-b]thiophene [DOI]
  35. 35 Zhang, 2004, Alkyl-Substituted Thieno[3,2-b]thiophene polymers and their dimeric subunits [DOI]
  36. 36 Tietz, 2012, Novel 5-(4-alkoxyphenyl)thieno[3,2-b]thiophene-2-carboxylate esters: Highly efficient synthesis and mesogenic evaluation of a new class of materials exhibiting the smectic c phase [DOI]
  37. 37 Sun, 2014, Synthetically controlling the optoelectronic properties of dithieno[2,3-d:2′,3′-d′]benzo[1,2-b:4,5-b′]dithiophene-alt-diketopyrrolopyrrole-conjugated polymers for efficient solar cells [DOI]
  38. 38 Tietz, 2012, Preparation of brominated 2-alkoxythiophenes via oxidation and etherification of 2-thienyltrifluoroborate salts [DOI]
  39. 39 Rudebusch, 2014, Quinoidal diindenothienoacenes: Synthesis and properties of new functional organic materials [DOI]
  40. 40 Demina, 2019, Synthesis of aryl-substituted thieno[3,2-b]thiophene derivatives and their use for n,s-heterotetracene construction [DOI]
  41. 41 Roncali, 2011, Efficient Synthesis of 3,6-dialkoxythieno[3,2-b]thiophenes as precursors of electrogenerated conjugated polymers [DOI]
  42. 42 Abramenko, 1976, Synthesis of 2-methylthieno[3,2-b]thieno[2,3-d]thiazole [DOI]
  43. 43 Rutherford, 1992, Poly(2,5-ethynylenethiophenediylethynylenes), related heteroaromatic analogues, and poly(thieno[3,2-b]thiophenes). synthesis and thermal and electrical properties [DOI]
  44. 44 Prim, 1994, Synthesis of new 2-arylthieno[3,2-b]thiophenes [DOI]
  45. 45 Capan, 2012, Concise syntheses, polymers, and properties of 3-arylthieno[3,2-b]thiophenes [DOI]
  46. 46 Schroth, 1997, 1,2-Dithiins and precursors, xvii: Synthesis and properties of thieno anellated 1,2-dithiins, structural influence on colour [DOI]
  47. 47 Henssler, 2009, Facile and scalable synthesis of the fused-ring heterocycles thieno[3,2-b]thiophene and thieno[3,2-b]furan [DOI]
  48. 48 Zoltewicz, J.A. (2006). New directions in aromatic nucleophilic substitution. Organic Syntheses, Springer.
  49. 49 Pietra, 1972, Nucleophilic aromatic substitution of the nitro-group [DOI]
  50. 50 Beck, 1978, Nucleophilic displacement of aromatic nitro groups [DOI]
  51. 51 Kolasa, 1993, Practical synthesis of 2-acetylbenzo[b]thiophene [DOI]
  52. 52 Valderrama, 2009, Synthesis and antitumor evaluation of thiophene analogs of kigelinone [DOI]
  53. 53 Boivin, 2021, Biosourced vanillin-based building blocks for organic electronic materials [DOI]
  54. 54 Beck, 1973, Synthesis of Methyl 3-Hydroxybenzo[b]thiophene-2-carboxylate esters by nitro displacement [DOI]
  55. 55 Beck, 1972, A Direct Synthesis of benzo[b]thiophene-2-carboxylate esters involving nitro displacement [DOI]
  56. 56 Nomoto, 1991, Studies on cardiotonic agents. VI. Synthesis of novel 4,5-dihydro-3(2H)-pyridazinone derivatives carrying some benzoheterocycles at the 6-position [DOI]
  57. 57 Dalinger, 2000, Regioselectivity of the substitution for the nitro group in 2,4,6-trinitrobenzonitrile under the action of thiols. The synthesis of 4,6-dinitroderivatives of benzoannelated sulfur-containing heterocycles [DOI]
  58. 58 Xue, 2015, Crystal engineering of cadmium coordination polymers decorated with nitro-functionalized thiophene-2,5-dicarboxylate and structurally related bis(imidazole) ligands with varying flexibility [DOI]
  59. 59 Morrison, 2017, Targeting bacillosamine biosynthesis in bacterial pathogens: Development of inhibitors to a bacterial amino-sugar acetyltransferase from Campylobacter Jejuni [DOI]
  60. 60 Colburn, 1977, Condensed Thiophen Ring Systems. Part 20. Synthesis of 5-arylthieno[3,2-b]pyrroles and 5-arylthieno[3,2-c]pyrazoles [DOI]

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