Semiconductor behavior of 2,5-aromatic disubstituted pyrroles, viewed from an experimental and theoretical perspective

Fomina, Lioudmila; Galán, Gerardo Zaragoza; Bizarro, Monserrat; Sánchez, Jorge Godínez; Zaragoza, I.P.; Salcedo, Roberto

doi:10.1016/j.matchemphys.2010.06.028

Cited by 13 publications

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“…1,3-Diynes are important building blocks in organic synthesis. Here we show that 2,5-diarylpyrroles, which possess organic semiconductor behavior, can be easily accessed from unsymmetrical 1,4-diaryl-1,3-butadiynes (Scheme ) …”

Section: Resultsmentioning

confidence: 94%

Copper-Catalyzed Decarboxylative Coupling of Alkynyl Carboxylates with 1,1-Dibromo-1-alkenes

et al. 2013

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A copper-catalyzed decarboxylative coupling reaction of potassium alkynyl carboxylates with 1,1-dibromo-1-alkenes was developed for the synthesis of unsymmetrical 1,3-diyne and 1,3,5-triyne derivatives. Diverse aryl, alkenyl, alkynyl, and alkyl substituted 1,1-dibromo-1-alkenes can react smoothly with aryl and alkyl substituted propiolates to produce unsymmetrical 1,3-diynes and 1,3,5-triynes with high selectivity and good functional group compatibility.

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Section: Resultsmentioning

confidence: 94%

Copper-Catalyzed Decarboxylative Coupling of Alkynyl Carboxylates with 1,1-Dibromo-1-alkenes

et al. 2013

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“…This work belongs to a research in which our group has published some interesting results [7,8]. The new compounds can take orientations orto-, meta-and para-.…”

Section: Introductionmentioning

confidence: 99%

Novel Hyperbranched Molecules Containing Pyrrole Units from Diacetylene Compounds and their Electronic Properties

Fomina

Sánchez

Olivares³

et al. 2014

MRS Proc.

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Novel hyperbranched molecules containing pyrrole units were obtained from ortho-, metaand para-diaminodiphenyldiacetylenes, as AB 2 type monomers by one-step polymerization. Diacetylenic fragments reacted with terminal amino groups in the presence of copper chloride to give pyrrole units. Diaminodiphenyldiacetylene monomers have been synthesized from ethynilanilines in three steps. The novel monomers and hyperbranched molecules were characterized by NMR, IR and thermal analysis. Some conductivity proofs were also carried out and this behavior was assessed.The electronic behavior of some of these molecules was studied by means of theoretical methods. DFT optimization processes were carried out for three structures derived from the generation growing. There are at least two conformational isomers of the structure (meta-and para-) which show conductivity properties, the meta-isomer shows semiconductor nature but this species is hard to modeling because the steric hindrances cause optimization problems and indeed the third generation species was not achieved. In other context, the para-isomer allows the calculation of three generations and shows clearly a tendency to narrow the energy gap between the frontier orbitals but besides the behavior of the HOMO-1 seems reinforce the conductivity phenomenon.

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Copper(II)‐Promoted, One‐Pot Conversion of 1‐Alkynes with Anhydrides or Primary Amines to the Respective 2,5‐Disubstituted Furans or Pyrroles under Microwave Irradiation Conditions

Lee

Jun

2015

Adv Synth Catal

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Furans and pyrroles are preparedf rom 1-alkynes by using aC u(II)-promoted, one-pot, microwave irradiationm ethod.G laser coupling of 1-alkynes and cyclization of the resulting 1,3-diyne in the presence of an anhydride or ap rimary amine results in the formation of the respective 2,5-diarylor 2,5-dialkyl-substituted furans andpyrroles.Keywords: copper;c yclization;h eterocycles;m icrowave heating Five-memberedh eterocyclic compoundsh ave attracted much attention over manyy ears because of their importance as building blocks for pharmaceuticals, molecular sensors ands emiconductors.[1] Numerous transitionm etal-catalyzed methodsh aveb eend evised for the preparation of these substances.[2] However, transitionm etal-promoted processesp reviously developed for this purpose have some drawbacks associated with the use of 1,3-diyne as as tarting material [3] and expensive transitionm etals,s uch as Au, [4] Ru [5] and Rh, [6] as catalysts.I na ddition,m ost of the protocols generate 2,5-diaryl-substituted five-membered heterocycles. [7] In this investigation described below, we have developed an ovel, one-pot,m icrowave irradiation-promoted, Cu(II)-catalyzed method for the synthesiso f 2,5-disubstituted furans and pyrroles from 1-alkynes and the respective anhydrides and primary amines as heteroatom source.T he reactions proceedt hrough ap athwayi nvolving intermolecular homocoupling of the 1-alkyne ands ubsequent cyclization of the resulting 1,3-diyne with the heteroatom precursors.C ompared with previouslyr eported methods, which have focused on 2,5-diaryl-substitued targets, the new synthetic protocol is unique in that it can be utilized to produce alkyl-as well as aryl-substituted furans and pyrrolesi nahighly concise and efficient manner. To the best of our knowledge,t here has been no report on the one-pot direct synthesis of aliphatic disubstituted heterocyclic compoundsfrom 1-alkylalkynes.In as tudy aimed at optimizing the conditions for the newly developed process,1 -octyne (1a)w as chosen as the prototypical 1-alkyne substrate.T he results (Table 1) show that reactiono f1a with acetic anhydride (Ac 2 O, 2)a nd ammonium acetate (NH 4 OAc, 3)c arried out in the presenceo fC u(OAc) 2 ·H 2 O( 4, 1equiv.)a t1 50 8 8Cf or 10 min under microwave irradiation conditions generates 2,5-dihexylfuran (5a)i n a9 5% GC yield (entry 1). Ac 2 O( 2)a nd NH 4 OAc( 3) are important reagents for this process because reactions catalyzed by Cu(OAc) 2 ·H 2 O( 4,1equiv.) in the absence of either of these respective substances generate 5a in only 44% and 24% yields (entries2and 3) and when botho ft hese reagents are not useda4% yield of 5a is obtained (entry 4). Ther eactiono f1 -octyne (1a)u tilizingb enzoic anhydride (Bz 2 O) with NH 4 OAc( 3)g ives 5a in 19% yield (entry 5). In the case of using NH 4 Cl instead of NH 4 OAc( 3), the reaction of 1a with Ac 2 O( 2)g eneratesatrace amount of 5a (entry 6). Use of CuCl 2 or CuI instead of Cu(OAc) 2 ·H 2 O( 4)d oes not produce any observable amount of 5a (entries 7a nd 8). Intere...

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Semiconductor behavior of 2,5-aromatic disubstituted pyrroles, viewed from an experimental and theoretical perspective

Cited by 13 publications

References 48 publications

Copper-Catalyzed Decarboxylative Coupling of Alkynyl Carboxylates with 1,1-Dibromo-1-alkenes

Copper-Catalyzed Decarboxylative Coupling of Alkynyl Carboxylates with 1,1-Dibromo-1-alkenes

Novel Hyperbranched Molecules Containing Pyrrole Units from Diacetylene Compounds and their Electronic Properties

Copper(II)‐Promoted, One‐Pot Conversion of 1‐Alkynes with Anhydrides or Primary Amines to the Respective 2,5‐Disubstituted Furans or Pyrroles under Microwave Irradiation Conditions

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