- 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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- An improved procedure for the synthesis of 3,4-ethylenedioxythiophene
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An improved procedure for the synthesis of 3,4-ethylenedioxythiophene is reported starting from ethyl chloroacetate. Reaction with sodium sulfide gave diethyl thiodiglycolate which was then reacted with diethyl oxalate, and then 1,2-dibromoethane to give 2,5-dicarbethoxy-3,4-ethylenedioxythiophene. Hydrolysis, and decarboxylation gave 3,4-ethylenedioxythiophene in 16% overall yield. The structures of the key intermediates in synthetic routes were confirmed, and every step was optimised, to give a procedure suitable for large-scale industrial production.
- Zhang, Hua,Qian, Chao,Chen, Xin-Zhi
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- The first direct experimental comparison between the hugely contrasting properties of PEDOT and the all-sulfur analogue PEDTT by analogy with well-defined EDTT-EDOT copolymers
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The structures of poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-ethylenedithiathiophene) (PEDTT) vary only in the substituent chalcogen atoms, yet the electronic properties of the materials are surprisingly dissimilar. The difference in electronic band gaps is approximately 0.8 eV and the polymers behave very differently upon p-doping. Two new terthiophenes have been synthesised using Negishi coupling methods. The X-ray crystal structures of EDOT-EDTT-EDOT (OSO) and EDTT-EDOT-EDTT (SOS) show strong intramolecular chalcogen-chalcogen contacts which are responsible for persistent conformers in solution and solid state, although significant interchain interactions should also influence the properties of the materials. SOS and OSO can be polymerised by electrochemical oxidation to give the corresponding, well-defined poly(terthiophenes) PSOS and POSO. Spectroelectrochemical studies on all four polymers reveal strong similarities between PEDTT and PSOS, and between PEDOT and POSO. Together with independent electrochemical and absorption studies, the results indicate that the unique properties of PEDOT are influenced more by conformational effects (intrachain S...O contacts) than substituent effects. The Royal Society of Chemistry 2005.
- Spencer, Howard J.,Skabara, Peter J.,Giles, Mark,McCulloch, Iain,Coles, Simon J.,Hursthouse, Michael B.
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- Two-step synthesis of 3,4-ethylenedioxythiophene (EDOT) from 2,3-butanedione
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3,4-Ethylenedioxythiophene (EDOT) was synthesized from commercially available 2,3-butanedione in only a two-step procedure including ketalization and thiophene formation.
- Hachiya, Iwao,Yamamoto, Toshihiro,Inagaki, Tatsuhiko,Matsumoto, Tomohiro,Takahashi, Atsushi,Mizota, Isao,Shimizu, Makoto
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- 3,4-ethylenedioxythiophene and 3,4-ethylenedioxyselenophene: Synthesis and reactivity of Cα-Si bond
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(Figure Presented) A synthetic approach to synthesize EDOT and EDOS from a common precursor 5 is reported. The method involves zirconocene dichloride mediated reaction of a common diyne 5 followed by treatment with disulfur dichloride (S2Cl2) and in situ prepared selenium dichloride (SeCl2). The higher lability of α-trimethylsilyl group in EDOS compared to EDOT is explained using DFT calculations.
- Das, Soumyajit,Dutta, Pradip Kumar,Panda, Snigdha,Zade, Sanjio S.
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- Radical-Cascade Avenue for 3,4-Fused-Ring-Substituted Thiophenes
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A single-step intramolecular radical cascade reaction of diynes and thioacetic acid in the presence of a catalytic amount of azobis(isobutyronitrile) as a radical initiator has been developed to synthesize thiophenes. This method allows easy and effective construction of a thiophene scaffold having 3,4-fused-ring substitution and unsubstituted 2,5-positions for further functionalization and polymerization. Using this method, derivatives of cyclopenta[c]thiophene, 3,4-ethylenedioxythiophene, and thiophene-containing spirocyclic compound have been synthesized.
- Agrawal, Abhijeet R.,Kumar, Neha Rani,Debnath, Sashi,Das, Sarasija,Kumar, Chandan,Zade, Sanjio S.
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- Synthesis process of 3, 4-ethylenedioxythiophene
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The invention discloses a synthesis process of 3, 4-ethylene dioxythiophene, which comprises the following steps: by using diethyl 2, 5-dicarboxylate-3, 4-ethylene dioxythiophene as a raw material anda dimethylformamide water solution as a solvent, heating to 110-120 DEG C in the presence of a catalyst, reacting for 2-4 hours, filtering, and carrying out vacuum distillation to obtain 3, 4-ethylene dioxythiophene, wherein the catalyst is a mixture of copper oxide and zinc oxide. Copper oxide and zinc oxide are used as catalysts, one-step degreasing is achieved, the steps are simple, the synergistic effect of copper oxide and zinc oxide can be fully achieved, the reaction temperature is reduced, the reaction time is shortened, the reaction selectivity is improved, by-products are reduced, and the yield and purity of a target product are improved.
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Paragraph 0029-0044
(2021/01/24)
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- Decarboxylation method of thieno[3,4-b]-1,4-dioxa-5,7-dicarboxylic acid
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The invention discloses a decarboxylation method of thieno[3,4-b]-1,4-dioxa-5,7-dicarboxylic acid. According to the method provided by the invention, a fused salt type compound is used as a dispersant and a decarboxylation reaction is carried out at 100 DEG C to 300 DEG C; in a reaction process, a catalyst does not need to be added. The method is simple, high in product yield and low in raw material cost and is very suitable for industrial production; the adding amount of an anti-color-changing agent used in the decarboxylation method is less, an adding method is simple and the cost is low, so that the decarboxylation method is very suitable for the industrial production.
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Paragraph 0023; 0024; 0025
(2017/02/28)
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- Polymer material monomer 3, 4 - ethylene dioxy thiophene preparation method
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The invention relates to a method for preparing polymer monomer 3,4-ethylenedioxythiophene. The method includes firstly dissolving ethyl chloroacetate and sodium sulphide in acetone to react to obtain diethyl thioglycolate; secondly, dissolving the diethyl thioglycolate to ethanol, adding sodium ethoxide and diethyl oxalate into the ethanol, heating and reflowing to obtain ethanol solution of 2,5-dioctyl phthalate ethyl ester-3,4-thiophene glycol sodium; thirdly, adding dichloroethane and tetrabutylammonium bromide into the ethanol solution of the 2,5-dioctyl phthalate ethyl ester-3,4-thiophene glycol sodium, heating and reflowing to obtain 3,4-ethylenedioxy-2,5-dioctyl phthalate ethyl ester thiophene; fourthly, dissolving the 3,4-ethylenedioxy-2,5-dioctyl phthalate ethyl ester thiophene in mixed solvent, adding sodium chloride, heating and reacting, and finally reducing pressure and rectifying. The method for preparing polymer monomer 3,4-ethylenedioxythiophene is few in procedures, low in cost, safe and reliable in technique, simple and fast in post-treatment method, and products are high in yield and purity.
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Paragraph 0021; 0087-0088
(2017/08/26)
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- Preparation method of 3,4-ethylene dioxy thiophene
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The invention relates to a preparation method of organic matter, in particular to a preparation method of 3,4-ethylene dioxy thiophene.With chloracetate as the initial raw material, 3,4-ethylene dioxy thiophene is preparated through vulcanization reaction, condensation, etherification, saponification and decarboxylic reaction.The method is easy to operate, low in cost, safe, environmentally friendly, high and stable in product yield, good in product color and luster, simple in process during reaction, not strict in reaction condition and quite suitable for industrial production.
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Paragraph 0015
(2016/12/01)
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- A foam metal micro-reactor continuous process for the decarboxylation (by machine translation)
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The invention discloses a foam metal micro-reactor continuous process for the decarboxylation, dibasic carboxylic acid is dissolved in the dispersing agent, and then continuously through the foam metal micro-reactor to achieve compared with the prior art continuous decarboxylation, the invention realizes continuous process for the decarboxylation, improving the production efficiency, the production cost is reduced. (by machine translation)
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Paragraph 0021-0025; 0028; 0033
(2018/02/04)
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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 0240-0243
(2017/01/02)
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- 3, 4-ethylene dioxythiophene manufacturing method
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PROBLEM TO BE SOLVED: To provide a method for economically producing 3,4-ethylenedioxythiophene at high yield.SOLUTION: The objective 3,4-ethylenedioxythiophene can be efficiently synthesized by reacting 3,4-dialkoxythiophene represented by general formula (1) (wherein R is a 2-4C alkyl group) with ethylene glycol in an organic solvent in the coexistence of an organic sulfonic acid catalyst and a quinone-based compound.
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Paragraph 0044
(2016/12/12)
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- Method of manufacturing thiophens
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PROBLEM TO BE SOLVED: To provide a method for producing 3,4-alkylenedioxythiophenes extremely useful as a raw material or an intermediate for a functional material, and 3-halogeno-4-(1-hydroxyalkyloxy)thiophenes being intermediates thereof. SOLUTION: A thiophene is reacted with a diol in the presence of a catalyst containing a copper compound and 8-hydroxyquinoline and a base in an aprotic polar solvent to give a 3,4-alkylenedioxythiophene and a 3-halogeno-4-(1-hydroxyalkyloxy)thiophene represented by formula (4) (wherein X and Y are each independently a halogen atom: R1and R2are each independently a hydrogen atom, linear, branched or cyclic alkyl which may contain a substituent, aryl which may contain a substituent, heteroaryl which may contain a substituent, hydroxy, carboxy, ester, formyl, cyano, amino or nitro; R3to R6are each independently a hydrogen atom, linear, branched or cyclic alkyl which may contain a substituent; m is an integer of 0-4). COPYRIGHT: (C)2011,JPOandINPIT
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Paragraph 0049; 0052
(2016/12/16)
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- Diprotodecarboxylation reactions of 3,4-dialkoxythiophene-2,5-dicarboxylic acids mediated by AG2CO3 and microwaves
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An efficient and rapid method is reported to obtain 3,4-dialkoxythiophenes from 3,4-dialkoxythiophene-2,5-dicarboxylic acids through a diprotodecarboxylation reaction with Ag2CO3/AcOH as a catalytic system and microwave heating in dimethylsulfoxide (DMSO) as solvent. This methodology lets us obtain for the first time good performance with thiophenes bearing strong electron-donating groups such as alkoxides. This methodology eliminates the usage of harmful quinoline as solvent, as well as the long reaction times typically used (12-18 h) to obtain the 3,4-dialkoxythiophenes. The reaction of 7 diacids showed good yields (60-89%) following 20 min of microwave heating in a temperature range of 120-150 °C. [Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications for the following free supplemental resource(s): Full experimental and spectral details.]
- Cisneros-Perez, Pablo A.,Martinez-Otero, Diego,Cuevas-Yanez, Erick,Uribe-Frontana, Bernardo A.
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supporting information
p. 222 - 230
(2013/12/04)
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- Preparation method of 3,4-ethylenedioxythiophene
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A method of preparing 3,4-ethylenedioxythiophene is provided. The preparation is performed by microwave heating to greatly increase the yield and decrease the reaction time, energy consumption, solvent usage, and environmental damage.
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Paragraph 0096-0102
(2013/03/26)
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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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scheme or table
p. 1967 - 1978
(2012/07/17)
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- PROCESS FOR PREPARATION OF DIALKOXYTHIOPHENES AND ALKYLENEDIOXYTHIOPHENES
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Provided is a process for preparing 3,4-substituted thiophenes by reacting a thiophenedicarboxylic acid derivative in an aprotic polar solvent at the presence of a catalyst mixture of 1,8-Diazabicyclo[5,4,0]undec-7-ene and a copper salt. The 3,4-substituted thiophenes according to the present invention is prepared to have high purity and a high yield and has a benefit that a reaction is efficiently generated at 100 to 180℃, which is a lower temperature than that of the related art, by using a catalyst containing 1,8-Diazabicyclo[5,4,0]undec-7-ene (DBU) and a copper salt.
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Page/Page column 4
(2010/11/04)
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- Synthesis of 3,4-Ethylenedioxythiophene (EDOT) from (Z)-but-2-ene-1,4-diol or but-2-yne-1,4-diol
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3,4-Ethylenedioxythiophene (EDOT) was synthesized from commercially available (Z)-but-2-ene-1,4-diol or but-2-yne-1,4-diol using epoxidation, etherification, and thiophene formation. The Japan Institute of Heterocyclic Chemistry.
- Hachiya, Iwao,Matsumoto, Tomohiro,Inagaki, Tatsuhiko,Takahashi, Atsushi,Shimizu, Makoto
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p. 449 - 460
(2011/04/24)
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- Process for the purification of thiophenes
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Purification of an optionally 3- and 3,4-substituted thiophene (I) comprises precipitating (I), which is liquid at room temperature, as solid from a solution in a solvent or solvent mixture by cooling introducing it into a cooled solvent (mixture) or cooled solution of the same (I) at a temperature below the melting point of (I) and separation. Purification of an optionally 3- and 3,4-substituted thiophene of formula (I) comprises precipitating (I), which is liquid at room temperature, as solid from a solution in a solvent or solvent mixture by cooling introducing it into a cooled solvent (mixture) or cooled solution of the same (I) at a temperature below the melting point of (I) and separation: [Image] R 1>, R 2>H, optionally substituted 1-20C (oxy)alkyl, optionally with 1-5 O and/or S atoms in the chain, or together an optionally substituted 1-20C dioxyalkylene or 1-20 C dioxyarylene group. Independent claims are included for: (1) purified (I) with a purity of not less than 99.50%; (2) (I) with a purity of not less than 99.50%.
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(2008/06/13)
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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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- METHOD FOR THE DECARBOXYLATION OF DICARBOXYLIC ACIDS
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The invention relates to a method for the thermal decarboxylation of dicarboxylic acids, in particular to 3,4-ethylene dioxythiophene-2,5-dicarboxylic acid as an educt. According to said method the educt is used in solid form and/or the reaction is carried out in the presence of a plurality of fluidised bed bodies. No solvents are used in the reaction and the decarboxylation product that is formed during the reaction is carried away from the reaction zone in gaseous form.
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Page/Page column 8-9
(2008/06/13)
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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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(2008/06/13)
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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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- 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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