Condensation of 1,2dicarbonyl compounds, such as glyoxal or biacetal, with thiodiglycolic esters in the presence of base gives the diacid directly from aqueous alcohol, or the diester from absolute alcohol section 3. Previously, we reported a dppft4 polymer with molecular weight up to 30 kda. Gemcitabines chemotherapeutic properties stem from its 2. Synthesis of new thiophene derivatives and their use as photostabilizers for rigid polyvinyl chloride january 2015. The chemistry of conducting polythiophenes by richard d. Furans and thiophenes ryan shenvi baran group meeting 091504 synthesis of thiophenes cho sh cn nh o cn snh2 o n h cn liebigs ann. Chemistry of thiophene 1,1dioxides university of texas. The aim of present study was the uses of 4 methyl cyanoacetanilide 1 in the synthesis of pyridine, pyran, thiophene, thi azole, pyrimidine, chromen derivatives together with their antitumor evaluations.
We report the synthesis of various thiophene phenylene co. Synthesis and characterization of polyacetylene with sidechain thiophene functionality. Monocyclic thiophene dioxides and benzob thiophene dioxides serve as a 2. A practical synthesis of 5functionalized thieno2,3d. Recent advances in the synthesis of thiophene derivatives. Thiopheneexpanded guanosine analogues of gemcitabine. The interaction between elemental sulfur and naotbu enables a facile singlestep protocol for the synthesis of thiophene derivatives from 1,3diynes. Synthesis and applications of thiophene derivatives as. Synthesis of nearinfrared absorbing and fluorescing thiophene fused bodipy dyes with strong electrondonating groups and their application in dyesensitised solar cells yasuhiro kubota, a kosei kimura, a jiye jin, b kazuhiro manseki, a kazumasa funabiki a and masaki matsui a. The interaction between elemental sulfur and naotbu enables a facile single step protocol for the synthesis of thiophene derivatives from 1,3diynes. Planar heptathienoacenes based on unsymmetric dithieno3,2. A notable feature of this protocol is that the thienannulation thiophene annulation proceeds with high regioselectivity via the sequential alkyne insertion, c. As unsaturated sulfones, many of them are thermally labile.
General properties, structure and reactivity of pyrroles, furans and thiophenes. In the reactions of 2, 5disubstituted thiophenes elimination of. Supporting information synthesis of thiophenebased tak. Thiophenefused bodipy dyes with two diethylaminophenyl groups as strong donors demonstrated nearinfrared nir absorption. Dietrich school of arts and sciences in partial fulfillment. Copperi thiophene 2carboxylate or cutc is a thiophene and a reagent in organic chemistry that especially promotes the ullmann reaction between aryl halides. A plausible mechanism based on epr experiments revealed that the trisulfur radical anion acts as a key intermediate of this process. The synthesis of 5hydroxymethyl, 5acetoxymethyl, 5formyl and 5cyanothieno2,3dpyrimidines, the methyl5carboxylate, and the respective amide functionality was accomplished by building up the functionalized molecule starting from appropriately substituted thiophene precursors. The analytical and spectral data of the latter product are consistent with their respective structures. Comparison of the 2 and 3positions of thiophene with benzene is provided. The classical approaches to substituted thiophenes are mainly based on condensationlike reactions or on subsequent functionalization of the. Thiophene nucleus is one of the most important potential entities in the largely growing chemical world of heterocyclic compounds exhibiting remarkable. Synthesis of 2 aminobenzobthiophenes from 42haloaryl1,2,3thiadiazoles article pdf available in russian journal of general chemistry 8412.
Synthesis, properties and biological activity of thiophene. Thiophenecontaining natural products furancontaining natural products or pharmaceuticals furancontaining syntheses r1 o hs s s s s s s s s r3 o r2 co2me r2 br co2me br cl co2me r2 cn r3 r2 cl r3 r2 h r3 cl r2 or4 r2 br r3 o r2 co2me oh r1 r2 r2 r3 o r1 oh h r2 r1 r2 oh o r1 r3 nh2 r2 o r1 r3 r2 o r1 r1 3r 4 r2 r r3 r2 fiesselmann thiophene synthesis. Pdf synthesis of pyran, pyridine, thiophene, pyrimidine. This chapter covers aspects of the most recent developments in the synthesis and application of thiophene oligomers and polymers for use in a wide range of fields, from very efficient organic solar cells 2015nc10085 to fluorophores specifically binding amyloid fibrils formed inside neural cells in alzheimers and other neurodegenerative diseases.
Thus, the reaction of either of compound3s a, 3b or 3c with elemental sulfur and malononitrile4 gave the thiophene derivatives 7ac, respectively. Moreover, thiophene derivatives find large application in material science 515 and in coordination chemistry 16,17, and as intermediate in organic synthesis 18,19. Synthesis of nearinfrared absorbing and fluorescing. Thiophene belongs to a class of heterocyclic compounds containing a five membered ring made up of one sulphur as heteroatom with the formula c4h4s. Synthesis of arylsubstituted thieno3,2bthiophene derivatives and.
It is challenging to realize both a fully conjugated rigid polymer backbone and high molecular weight at the same time. Fiesselmann thiophene synthesis was applied for the convenient construction of thieno3,2b thiophene derivatives. These metrics are regularly updated to reflect usage leading up to the last few days. Using ilbutane, the sulfur first effects dehydrogenation and then interacts with the unsaturated. University of groningen tuning of the luminescence in poly. Pdf a simple method for the synthesis of fused thiophenes. Introduction in the late 1970s, conjugated polymers were proclaimed as futuristic new materials that would lead to the next generation of electronic and optical devices. All intermediates and aimed heptathienoacenes were fully characterized by 1h nmr, c nmr, and hrms. A similar strategy starting from the pyrimidine precursor and subsequent direct functionalization.
Thiophenes are classically prepared by the reaction of 1,4di ketones, diesters, or dicarboxylates with sulfidizing reagents such as p 4 s 10 such as in the paalknorr thiophene synthesis. Here, we report the successful synthesis of a conjugated semiconducting polymer with tunable molecular weight over a wide range. The thiophene ring is a common building block for novel oligomeric and polymeric materials. Tris4nitrophenyl amine was reduced using snhcl to obtain tris4aminophenyl amine. New method for the synthesis of 2thiophenecarboxylic acids in the presence of v, fe, or mo containing catalysts. Pdf synthesis of new thiophene derivatives and their use. Various synthetic approaches to the construction of thiophene and substituted thiophene have been efficiently developed. Thiophene is an essential precursor to synthesize a wide range of conjugated organosulfur moieties, sulfurcontaining polycyclic aromatic hydrocarbons, macrocycles, and pharmaceutical compounds. Thiophene oxidation and reduction chemistry 231 was developed 21. Pdf synthesis and characterization of polyacetylene with.
Synthesis and properties of soluble fused thiophene. A read is counted each time someone views a publication summary such as the title, abstract, and list of authors, clicks on a figure, or views or downloads the fulltext. Pdf thiophene nucleus has been established as the potential entity in the largely growing chemical world of heterocyclic compounds. The synthesis of thiophene carboxylic acids from 1,2. Pdf synthesis, properties and biological activity of thiophene. The chemistry of thiophene soxides1 and related compounds thies thiemann,a david j. Methods and strategies for the synthesis of fivemembered heteroaromatics. New method for the synthesis of 2thiophenecarboxylic. Syntheses, xray structures, and chiroptical properties. Figure 3 sem images of polythiophene prepared by 57 mmol of cetyltrimethylammonium. Baran, richter essentials of heterocyclic chemistryi.
Synthesis and extraction of methyl thiophene aldehyde were carried out following established procedure 26. Thiophene is a naturally occurring substance found in coal tar and petroleum. Issue 5th eurasian conference on heterocyclic chemistry arkivoc 2009 ix 961 issn 15517012 page 96 arkat usa, inc. Thiophene2carboxylic acid an overview sciencedirect. A new design and synthesis was required to overcome this limitation. Hinsberg thiophene synthesis major reference works. Through molecular design and synthesis control, our new polymer can be selectively prepared with numberaveraged molecular weight mn ranging from approximately 20 to 100 kda, realizing both high molecular weight and high solubility at the same time. Baran, richter essentials of heterocyclic chemistryi heterocyclic chemistry o s n n h n h n h o o n o n s n n h n n h hn n h n n h n n h h o n n h o h s n s s h n n n o o n n h h n n n n ss n n n s n n o n n n h nn s furan pk a. However, chlorination with nchlorosuccinimide in hexane at reflux temperature gave a mixture of 2,5dichloro. They occur in coal tar distillates the discovery of thiophene in coaltar benzene provides one of the classic anecdotes of organic chemistry. The first synthesis of thiophene by meyer, reported the same year that he made his discovery, involves acetylene and elemental sulfur. Recent advances and applications of reductive desulfurization in organic synthesis jana rentner, marko kljajic, lisa offner. Additionally, anthelmintic and insecticidal activities have been ascribed to appropriately functionalized thiophene derivatives. The classical approaches to substituted thiophenes are mainly based on condensationlike reactions or on subsequent functionalization of the thiophene ring 2030.
View enhanced pdf access article on wiley online library html view download pdf for offline viewing. Baran group meeting furans and thiophenes 091504 furans. As part of our ongoing program to investigate the synthesis of thiophene derivatives with potential biological activity, we became interested in the preparation of the various thienopyridinols. When ethanol was used, sulfoxides were general ly obtained in. Thiophene ring can be constructed from nonheterocyclic precursors by two reaction pathways 5. Feacac 3 and moco6 proved to be most efficient in this reaction.
Thus, new 5 or 6aryl3hydroxythieno3,2b thiophene 2carboxylates were obtained by condensation of 5 or 4aryl3chlorothiophene2carboxylates, respectively, with methyl thioglycolate in the presence of potassium tert. Synthesis of metalcontaining poly thiophene methines. Issue 5 the chemistry of thiophene soxides1 and related. The hinsberg reaction is most useful for synthesis of thiophene 2,5dicarboxylic acids or esters equation 28. Electronic supporting information files are available without a subscription to acs web editions. Condensation reaction of thioglycolic acid derivatives with. Fiesselmann thiophene synthesis the fiesselmann thiophene synthesis involves the condensation reaction of thioglycolic acid derivatives with acetylenic esters, which upon treatment with base results in the formation of 3hydroxy2thiophenecarboxylic acid derivatives. The simple thiophenes are stable liquids that closely resemble the corresponding benzene compounds in. Chlorination of thiophene with sulfuryl chloride gives a mixture of 2chloro and 2,5dichlorothiophenes.