- Optimisation of substitution at the 2- and 5- positions of 3,4-dialkoxythiophenes via the Mannich reaction: The influences of steric crowding, electrophile reactivity and temperature
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A number of 3,4-dialkoxythiophene compounds have been synthesised and their reactivities assessed via the Mannich reaction with secondary amines. These reactions surprisingly gave the bis-Mannich bases substituted at the 2- and 5-positions as well as the expected mono-Mannich bases substituted at the 2-position. Conditions were optimised to give symmetrical bis-2,5-Mannich bases in one step and asymmetrical bis-2,5-Mannich bases in two steps. Several bis(thien-2-ylmethyl)amines derived from 3,4-dialkoxythiophenes are reported, their synthesis being performed under both normal and high dilution conditions. Some syntheses also afforded the (thien-2-ylmethyl)amine oligomers. Further substitution of the bis(thien-2-ylmethyl)amines at the 5-position via the Mannich reaction also proved successful. The factors affecting the yields and substitution patterns are discussed, together with molecular modelling of the spatial requirements.
- Halfpenny,Rooney,Sloman
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- Poly(thieno[3,4- b ]-1,4-oxathiane): Medium effect on electropolymerization and electrochromic performance
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The asymmetrical sulfur analog of 3,4-ethylenedioxythiophene (EDOT), thieno[3,4-b]-1,4-oxathiane (EOTT), was synthesized, and its electropolymerization was comparatively investigated by employing different solvent-electrolyte systems (room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF6), CH2Cl2-Bu4NPF6, and CH2Cl2-BmimPF6). Further, the effect of solvents and supporting electrolytes on the structure, morphology, electrochemical, electronic, and optical properties and electrochromic performance of the obtained poly(thieno[3,4-b]-1,4-oxathiane) (PEOTT) films were minutely studied. PEOTT film with a band gap (Eg) of about 1.6 eV could be facilely electrodeposited in all the solvent-electrolytes and displayed excellent electroactivity, outstanding redox stability in a wide potential window, and improved thermal stability. Cyclic voltammetry showed that EOTT could be electropolymerized at a lower oxidation potential in BmimPF6 (~1.0 V vs Ag/AgCl) due to several advantanges of RTIL BmimPF6 itself, such as high intrinsic conductivity and mild chemical conditions, etc., and the resulting PEOTT film exhibited compact morphology with better electroactivity and stability and higher electrical conductivity. On the other hand, PEOTT films from all the sovent-electrolytes also showed the electrochromic nature by color changing from gray blue to green, and further kinetic studies revealed that PEOTT had decent contrast ratios (36%), higher coloration efficiencies (212 cm2/C in BmimPF6), low switching voltages, moderate response time (1.2 s), excellent stability, and color persistence. From these results, PEOTT provides more plentiful electrochromic colors and holds promise for display applications.
- Wang, Zhipeng,Xu, Jingkun,Lu, Baoyang,Zhang, Shimin,Qin, Leiqiang,Mo, Daize,Zhen, Shijie
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Read Online
- Method for synthesizing 3,4-dimethoxythiophene
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The invention relates to a method for synthesizing 3,4-dimethoxythiophene. The method comprises steps as follows: S1, 2,5-dimethyl dicarboxylate-3,4-sodium thiophene diol and dimethyl sulfate are subjected to a heating reaction in an organic solvent, and 3,4-dimethoxythiophene-2,5-dimethyl dicarboxylate is obtained; S2, 3,4-dimethoxythiophene-2,5-dimethyl dicarboxylate is subjected to the heatingreaction with strong base in an alkylbenzene organic solvent with the boiling point not lower than 200 DEG C, then strong acid is added for acidification, and 3,4-dimethoxythiophene-2-formic acid is obtained; S3, 3,4-dimethoxythiophene-2-formic acid is subjected to a reduced-pressure heating reaction in a long-chain amine organic solvent with the boiling point not lower than 300 DEG C, and 3,4-dimethoxythiophene is obtained. The method is low in production cost, low in energy consumption and high in product yield, the organic solvents can be recycled, particularly, no catalyst is used in the step of decarboxylation, so that the cost is greatly reduced, and environmental pollution is reduced.
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Paragraph 0030; 0037; 0044; 0051; 0058; 0062; 0065
(2018/05/16)
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- A 3, 4 - dimethoxy synthetic method of thiophene (by machine translation)
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The invention discloses a 3, 4 - dimethoxy thiophene synthesis method, the method will be 2, 5 - dicarboxylic acid dimethyl ester - 3, 4 - dimethoxy thiophene dissolved in dimethyl formamide in aqueous solution, then adding the pectins catalyst, at a temperature of 130 - 180 °C, pressure is 0 - 10 kg/cm2 Reaction (table) 5 - 18 h after, filtered, pressure reducing rectification to get 3, 4 - dimethoxy thiophene, wherein filtering and rectification are in thermal insulation a pressure maintaining state. The method utilizes the pectins technology, has eliminated saponification, acidified and other intermediate links, shortens the synthetic route, reduces the consumption of raw materials, in particular reduces the production of waste aqueous solution, reduces the integrated cost, simplify the post-processing procedure, the whole synthetic route more environment-friendly, safer, more efficient. (by machine translation)
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Paragraph 0015; 0022-0029
(2018/04/26)
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- BLUE ELECTROCHROMIC COMPOUND, PREPARATION METHOD AND SUBASSEMBLY THEREOF
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One class of blue thiophene electrochromic compounds include 3,4-(2,2-bis(2-oxo-3-phenylpropyl))propylenedioxythiophene, 3,4-(2,2-bis(2-oxo-3-phenylbutyl))propylenedioxythiophene, and 3,4-(2,2-bis(2-oxo-3-phenylamyl))propylenedioxythiophene. The thiophene electrochromic compounds can change color between blue and transparency. The thiophene compounds can be electropolymerized on the surface of the ITO glass to form a film. The film has characteristics of low driving voltage (within ±1V), fast response time, and large transmittance difference between colored-state and bleached-state (up to 77.5%). The thiophene electrochromic compounds can be used in the electrochromic window, rearview mirror, electrochomeric display, and the like.
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Paragraph 0058; 0061
(2016/10/04)
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- Synthesis of 4,4′-dimethoxy-3,3′-bithiophene
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Abstract Reaction between 3,3′-dibromothiophene and sodium methylate/methanol in the presence of KI/CuO afforded 3-bromo-4-methoxythiophene as a major product. It was transformed into 4,4′-dimethoxy-3,3′-bithiophene by using Pd(OAc)2 as a catalyst and agarose as a ligand. The conditions of the reaction were mild with an acceptable yield of 20 %. The product was characterized by MS, 1H NMR, and its spectra of UV-Vis and cyclic voltammetry were given. Graphical Abstract: 4,4′-dimethoxy-3,3′-bithiophene was synthesized from 3-bromo-4-methyloxy thiophene in the homogeneous system formed by water and agarose.[Figure not available: see fulltext.]
- Zuo, Hujin,Huang, Rui,Zhang, Qisong,Li, Meijiang,Wang, Chengyun,Shen, Yongjia
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p. 6385 - 6391
(2015/08/18)
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- Process for production of thiophene derivative
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[Purpose] thiophene for preparing derivatives method, among other things, purity thiophene derivatives obtained in high yield by provides a method. [Constitution] halogenated thiophene and an alkali metal alkoxide seed alcohol solvent during is a process, alcohol solvent is regulated so as to have reaction outflow by including for a manipulation type well. , dialkoxy thiophene which comprises the step of obtaining an, oxygen atoms and thiophene dialkoxy said including compound or the like, an evacuating product caused by reaction while type well. outflow reaction to reaction step of reacting a carboxylic acid component characterized by including, of thiophene derivatives is manufacturing method. (by machine translation)
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Paragraph 0184-0190
(2017/01/02)
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- Electrochemical sensor based on f-SWCNT and carboxylic group functionalized PEDOT for the sensitive determination of bisphenol A
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A simple, sensitive, and reliable method for the voltammetric determination of bisphenol A (BPA) by using carboxylic group functionalized single-walled carbon nanotubes (f-SWCNT)/carboxylic-functionalized poly(3,4- ethylenedioxythiophene) (PC4) complex modified glassy carbon electrode (GCE) has been successfully developed. The electrochemical behavior of BPA at the surface of the modified electrode is investigated by electrochemical techniques. The cyclic voltammetry results show that the as-prepared electrode exhibits strong catalytic activity toward the oxidation of BPA with a well-defined anodic peak at 0.623 V in PBS (0.1 mol/L, pH 7.0). The surface morphology of the 3D network of composite film is beneficial for the adsorption of analytes. Under the optimized conditions, the oxidation peak current is proportional to BPA concentration in the range between 0.099 and 5.794 μmol/L (R2 = 0.9989), with a limit of detection of 0.032 μmol/L (S/N = 3). The enhanced performance of the sensor can be attributed to the excellent electrocatalytic property of f-SWCNT and the extraordinary conductivity of PC4. Furthermore, the proposed modified electrode displays high stability and good reproducibility. The good result on the voltammetric determination of BPA also indicates that the as-fabricated modified electrode will be a good candidate for the electrochemical determination and analysis of BPA.
- Zhang, Long,Wen, Yang-Ping,Yao, Yuan-Yuan,Wang, Zi-Fei,Duan, Xue-Min,Xu, Jing-Kun
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p. 517 - 522
(2014/05/06)
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- Electrochromic enhancement of poly(3,4-ethylenedioxythiophene) films functionalized with hydroxymethyl and ethylene oxide
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2-((2,3-Dihydrothieno[3,4-b]dioxin-2-yl)methoxy)methyl oxirane (EDOT-MO) was successfully synthesized by the reaction of epichlorohydrin with hydroxymethylated-3,4-ethylenedioxylthiophene (EDOT-MeOH), which was synthesized via a simple four-step sequence. Poly(hydroxymethylated-3,4- ethylenedioxylthiophene) (PEDOT-MeOH) and poly(2-((2,3-dihydrothieno[3,4-b] dioxin-2-yl)methoxy)methyl oxirane) (PEDOT-MO) were electrosynthesized through electropolymerization of EDOT-MeOH and EDOT-MO, respectively. Structural, electrochemical, optical, and thermal properties of as-formed polymers were investigated by FTIR, cyclic voltammetry, UV-vis, and thermogravimetry. Spectroelectrochemistry studies demonstrated that PEDOT-MeOH and PEDOT-MO could be reversibly oxidized and reduced accompany with obvious color changes. Further kinetic studies demonstrated that the introduction of hydroxymethyl or ethylene oxide group significantly improved electrochromic properties of 3,4-ethylenedioxythiophene (PEDOT) and resulted in high contrast ratios (57.3% at 585 nm) and coloration efficiencies (338.5 cm2 C-1), low switching voltages, and fast response time.
- Zhang, Shimin,Xu, Jingkun,Lu, Baoyang,Qin, Leiqiang,Zhang, Long,Zhen, Shijie,Mo, Daize
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p. 1989 - 1999
(2014/06/24)
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- Systematic study on chemical oxidative and solid-state polymerization of poly(3,4-ethylenedithiathiophene)
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Systematic research on the synthesis, chemical oxidative polymerization of 3,4-ethylenedithiathiophene (EDTT) in the presence of surfactants or not, and solid-state polymerization of 2,5-dibromo-3,4-ethylenedithiathiophene (DBEDTT) and 2,5-diiodo-3,4-ethylenedithiathiophene (DIEDTT) under solventless and oxidant-free conditions has been investigated. Effects of oxidants (Fe 3+ salts, persulfate salts, peroxides, and Ce4+ salts), solvents (H2O, CH3CN/H2O, and CH 3CN), surfactants, and so forth on polymerization reactions and properties of poly(3,4-ethylenedithiathiophene) (PEDTT) were discussed. Characterizations indicated that FeCl3 was more suitable oxidant for oxidative polymerization of EDTT, while CH3CN was a better solvent to form PEDTT powders with higher yields and electrical conductivities. Dispersing these powders in aqueous polystyrene sulfonic acid (PSSH) solution showed better stability and film-forming property than sodium dodecylsulfate and sodium dodecyl benzene sulfonate. Oxidative polymerization of EDTT in aqueous PSSH solutions formed the solution processable PEDTT dispersions with good storing stability and film-forming performance. Solvent treatment showed indistinctive effect on electrical conductivity of free-standing PEDTT films. As-formed PEDTT synthesized from solid-state polymerization showed similar electrical conductivity, poorer stability, but better thermoelectric property than oxidative polymerization. Contrastingly, PEDTT synthesized from DIEDTT showed higher electrical conductivity (0.18 S cm-1) than DBEDTT which showed better thermoelectric property with higher power factor value (6.7 × 10-9 W m-1 K-2).
- Chen, Shuai,Lu, Baoyang,Duan, Xuemin,Xu, Jingkun
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experimental part
p. 1967 - 1978
(2012/07/17)
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- Robust PEDOT films by covalent bonding to substrates using in tandem sol-gel, surface initiated free-radical and redox polymerization
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Poly(3,4-ethylenedioxythiophene), PEDOT, films are used as antistatic coatings on electrically insulating substrates such as plastic and glass. A novel method for the synthesis of conducting PEDOT films on insulators relies on sol-gel chemistry to attach a di-Si(OEt)3 functionalized free radical initiator (AIBN) on oxidized surfaces, followed by: (a) attachment of 3,4-(vinylenedioxy)thiophene (VDOT: an analogue to EDOT susceptible to radical addition through its vinylenedioxy group); and, (b) oxidative (with FeCl 3) co-polymerization of surface-confined VDOT with 3,4-ethylenedioxythiophene (EDOT). In conjunction with classical photolithography, the method yields thin (~150 nm) yet dense, pinhole-free (confirmed electrochemically), hard (>6H), extremely adhesive (5B), patterned, highly conducting (52 mho cm-1) films. The process is applied mainly on glass but it works equally well on oxidized metal surfaces (aluminum, steel, Pt). Control studies related to "grafting from" with surface-confined AIBN were conducted by growing inexpensive poly(styrene) and poly(methylmethacrylate) films.
- Sadekar, Anand G.,Mohite, Dhairyashil,Mulik, Sudhir,Chandrasekaran, Naveen,Sotiriou-Leventis, Chariklia,Leventis, Nicholas
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p. 100 - 108
(2013/01/12)
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- Synthesis, electropolymerization and characterization of a cross-linked PEDOT derivative
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The synthesis of a novel electropolymerizable monomer, 2,2′,3, 3′-tetrahydro-2,2′-bithieno[3,4-b][1,4]dioxine (THBTD), based on two 3,4-ethylenedioxythiophene (EDOT) moieties connected through the ethylenedioxy bridge is reported. The new monomer paves the way for the development of cross-linked networks based on the EDOT moiety. Polymer films were electrogenerated from monomeric solutions by consecutive potential sweeps or by flow of constant anodic currents and the polymer structure was studied using FTIR. The relationship between the mass of the electrogenerated polymer (after reduction) and the polymerization charge gives the productivity of the consumed charge (mg C-1) while the charge stored and delivered by the films was determined by cyclic voltammetry getting the specific charge (C g -1). Simultaneously with the electroinitiated polymerization a chemical polymerization occurs around the electrode by monomer protonation giving protonated and no electroactive polymer chains. This chemical polymerization was followed in solution by UV-Vis spectroscopy using different conditions. Productivities and specific charges change with the conditions of synthesis in opposite directions. The voltammetric control presents a main redox couple (0.54/0.50 V) and a strong reduction process at -2.89 V that only can be reoxidized at more anodic potentials than 0.3 V as usual for charge trapping effects. EQCM studies indicate a remarkable difference between PEDOT and poly(THBTD). While poly(THBTD) shows a predominantly reversible anionic exchange during oxidation from the neutral state, the parent pristine PEDOT presents a mixed anionic and cationic exchange. Electrochromic color changes from an intense blue color of the oxidized film to a clear orange color in the reduced films as observed by in situ UV-Vis spectroscopy. Interestingly, the electrochromic changes in poly(THBTD) are opposed to those of PEDOT. Both thiophene derivative polymers present a similar thermal degradation at 305 and 314 °C, respectively.
- Arias-Pardilla, Joaquin,Gimenez-Gomez, Pablo A.,De La Pena, Alejandro,Segura, Jose L.,Otero, Toribio F.
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scheme or table
p. 4944 - 4952
(2012/06/18)
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- Synthesis and characterization of monomeric and polymeric Cu(II) complexes of 3,4-ethylenedioxythiophene-functionalized with cyclam ligand
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A functionalized EDOT derivative with 1,4,8,11-tetraazacyclotetradecane (cyclam) ligand pendant to the ethylene bridge (4) and its complexes [M(4)(BF4)2], where M(II) = Cu(II), was prepared and characterized. Their electrochemical copolymerization with EDOT was studied. The electro-co-polymerized films were characterized by electrochemical methods, X-ray photoelectron spectroscopy and by X-ray fluorescence spectroscopy. The co-polymerization method was found to afford a good control of the metal concentration in the polymer matrix and represents a good technique for preparing electronically conductive polymers containing redox-active metal complexes.
- Velauthamurty, Kuhamoorthy,Higgins, Simon J.,Rajapakse, R.M. Gamini,Bandara,Shimomura, Masaru
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experimental part
p. 326 - 332
(2011/03/17)
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- First triazole-bridged unsymmetrical porphyrin dyad via click chemistry
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(Chemical Equation Presented) Click chemistry has been successfully applied in the synthesis of the first example of a triazole-bridged porphyrin dyad containing N2S2 porphyrin and N4 or ZnN 4 porphyrin subunits, and fluorescence study indicated a possibility of singlet-singlet energy transfer from the N4 or ZnN4 porphyrin subunit to the N2S2 porphyrin subunit.
- Punidha, Sokkalingam,Sinha, Jasmine,Kumar, Anil,Ravikanth, Mangalampalli
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p. 323 - 326
(2008/09/17)
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- DERIVATIZED 3,4-ALKYLENEDIOXYTHIOPHENE MONOMERS, METHODS OF MAKING THEM, AND USE THEREOF
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The present invention relates to methods of making derivatized 3,4-alkylenedioxythiophene monomers and methods of using the 3,4-alkylenedioxythiophene monomers.
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Page/Page column 24
(2008/06/13)
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- Synthesis and crystal structures of 2,3,12,13-tetraalkoxy-21,23- dithiaporphyrins and 2,3-dialkoxy-21-monothiaporphyrins
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The tetraalkoxy and dialkoxy substituted 21,23-dithiaporphyrins and 21-monothiaporphyrins, respectively, having methoxy, butoxy, octyloxy and dodecyloxy substituents at β-thiophene carbons were synthesized and characterized. The X-ray structure was solved for tetrabutoxy substituted 21,23-dithiaporphyrin and it exhibited a more planar structure compared with unsubstituted S2TPP, whereas the dimethoxy substituted 21-monothiaporphyrin showed a saddle shaped structure similar to unsubstituted STPPH. A series of 21,23-dithia and 21-monothiaporphyrins having methoxy, butoxy, octyloxy and dodecyloxy substituents at β-thiophene carbons were synthesized and characterized.
- Agarwal, Neeraj,Hung,Ravikanth, Mangalampalli
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p. 10671 - 10680
(2007/10/03)
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- Simple one-step synthesis of 3,4-dimethoxythiophene and its conversion into 3,4-ethylenedioxythiophene (EDOT)
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3,4-Dimethoxythiophene (2) was synthesized in one-step from readily available bulk chemicals via a ring closure reaction, and was then trans-etherified with ethylene glycol to give 3,4-ethylenedioxythiophene (3) (EDOT).
- Von Kieseritzky, Fredrik,Allared, Fredrik,Dahlstedt, Emma,Hellberg, Jonas
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p. 6049 - 6050
(2007/10/03)
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- Processes for preparing of 3,4-alkylenedioxythiophenes and 3,4-dialkoxythiophenes
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The present invention relates to a process for preparing 3,4-dialkoxythiophenes or 3,4-alkylenedioxythiophenes in high yield via the rapid decarboxylation of 3,4-dialkoxythiophenedicarboxylic acid or 3,4-aklylenedioxythiophenedicarboxylic acid in a water-miscible polar solvent in the presence of copper catalyst under an oxygen atmosphere.
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- Process for the alkylation of 3,4-dihydroxythiophene-2,5-dicarboxylic esters
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The invention relates to a process for the alkylation of 3,4-dihydroxythiophene-2, 5-dicarboxylic esters or their alkali metal or alkaline earth metal salts with alkylating agents in a polar diluent in the presence of quaternary onium salts.
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- Process for the preparation of dialkylthiophenes and alkylenedioxythiophenes
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A process for the preparation of dialkoxythiophenes and alkylene-dioxythiophenes in high purity and very good yields by decarboxylation of dialkoxythiophene-dicarboxylic acids or alkylenedioxythiophenedicarboxylic acids, respectively, in solvents that have a higher boiling point than the product and contain no nitrogen bases.
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Page column 5
(2008/06/13)
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- On the origin of optical activity in polythiophenes
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Optically active substituents attached as sidechain to π-conjugated polymers provide a particularly interesting and revealing tool to study the nanoscopic and mesoscopic supramolecular organization of π-conjugated polymers in general. Chiral substituents allow the properties of these polymers to be studied with circularly polarized light in both absorption and emission. Here we describe a comprehensive investigation on the structure and optical properties of poly{3,4-bis[(S)-2-methylbutoxy]thiophene} (PBMBT) as an example to elucidate the molecular origin of the chiroptical effects in chiral conjugated polymers. The chiral side chains of PBMBT induce very strong bisignate circular dichroism (CD) effects in the π-π* absorption when the polymer is in an aggregated phase. The anisotropy factor in absorption (g(abs)) is as high as 8 x 10-2. The photoluminescence of PBMBT aggregates is characterized by a very small stokes shift (90 meV) and exhibits circular polarization (CPL). The chiroptical properties in absorption and emission of PBMBT are associated with a high degree of intrachain and interchain order as they are present in aggregated phases but absent when the polymer chains are molecularly dissolved or in a melt. The observed CD and CPL effects are consistent with an exciton splitting between transition dipole moments in the excited state on different polymer chains. The strong optical activity associated with the π-π* transition of PBMBT is attributed to originate from a helical packing of predominantly planar chains, rather than from a helical intrachain conformation. As a result a detailed molecular description of the polythiophene morphology is obtained. (C) 2000 Elsevier Science B.V.
- Langeveld-Voss,Janssen,Meijer
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p. 285 - 301
(2007/10/03)
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- Convenient synthesis of 3,4-bis(alkylthio) thiophenes
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A variety of symetrically substituted 3,4dithioether-thiophenes were prepared by the acid catalyzed nucleophilic substitution of 3,4- di(methoxy)thiophene with the appropriate thiol.
- Goldoni, Francesca,Langeveld-Voss, Bea M. W.,Meijer
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p. 2237 - 2244
(2007/10/03)
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- A facile synthesis of 3,4-dialkoxythiophenes
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Dialkylation of diethyl 3,4-dihydroxythiophenedicarboxylate followed by ester hydrolysis and acid decarboxylation provides a general route to 3,4-dialkoxythiophenes.
- Coffey,McKellar,Reinhardt,Nijakowski,Feld
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p. 2205 - 2212
(2007/10/03)
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- Copper(I) Halide Catalysed Synthesis of Alkyl Aryl and Alkyl Heteroaryl Ethers
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A number of alkyl aryl and alkyl heteroaryl ethers have been prepared from (hetero) aryl halides (mainly bromides) and sodium alkoxides, using copper(I)bromide as a catalyst.The influence of the main solvent, the halogen atom, reaction temperature and the presence of oxygen upon the rate and selectivity has been studied.Furthermore the decomposition of the catalyst and the reduction of the aryl halide are studied.
- Keegstra, Menno A.,Peters, Theo H. A.,Brandsma, Lambert
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p. 3633 - 3652
(2007/10/02)
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- Thiophene derivatives and their preparation
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Thiophene derivatives of the formula STR1 WHEREIN Rx is --S-CHR5 -COOH or -S-CH2 -CH2 -OH, Ry is 1-2 of halogen alkoxy of 1-6 carbon atoms, aralkyl of 7-10 carbon atoms, phenyl, halophenyl or alkylcarbonyl of 1-6 carbon atoms in the alkyl group, and R5 is a hydrogen atom, when Ry is a halogen atom, when R5 is alkyl, their enantiomers, and their pharmacologically acceptable salts thereof with bases, possess antilipolytic activity.
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