CN103467485A - Preparation method of 2,5-diethyl dioctyl phthalate-3,4-ethylenedioxythiophene - Google Patents
Preparation method of 2,5-diethyl dioctyl phthalate-3,4-ethylenedioxythiophene Download PDFInfo
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- dicarboxylate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 36
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims abstract description 27
- DPPYVKXVOFYYKT-UHFFFAOYSA-N sodium;thiophene Chemical compound [Na].C=1C=CSC=1 DPPYVKXVOFYYKT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012153 distilled water Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims abstract description 9
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 238000004821 distillation Methods 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- -1 2,5-Dimethyldiethyl-3,4-ethylenedioxythiophene Chemical compound 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
本发明公开了一种合成2,5-二甲酸二乙酯-3,4-乙烯二氧噻吩的制备方法，包括以下步骤：向三口烧瓶中依次加入2,5-二甲酸二乙酯-3,4-二酚钠噻吩、1,2-二氯乙烷、聚乙二醇400/600/2000和碘化钾，搅拌，升温，反应温度60-83℃（回流温度），反应时间2-10h，然后冷却至室温，加入蒸馏水充分搅拌，分液，减压蒸馏，真空干燥得产品。本发明方法合成2,5-二甲酸二乙酯-3,4-乙烯二氧噻吩的收率可高达98.3%。本发明方法成本低、条件温和、操作简单且对环境污染小，适合大规模制备。The invention discloses a preparation method for synthesizing diethyl 2,5-dicarboxylate-3,4-ethylenedioxythiophene, which comprises the following steps: sequentially adding 2,5-diethyl dicarboxylate-3 , 4-diphenol sodium thiophene, 1,2-dichloroethane, polyethylene glycol 400/600/2000 and potassium iodide, stirring, heating up, reaction temperature 60-83°C (reflux temperature), reaction time 2-10h, Then cool to room temperature, add distilled water and stir thoroughly, separate liquid, distill under reduced pressure, and dry in vacuum to obtain the product. The yield of synthesizing diethyl 2,5-dicarboxylate-3,4-ethylenedioxythiophene by the method of the invention can be as high as 98.3%. The method of the invention has low cost, mild conditions, simple operation and little environmental pollution, and is suitable for large-scale preparation.
Description
技术领域 technical field
本发明的目的是公开一种以聚乙二醇和碘化钾作为一个催化剂体系，催化合成2,5-二甲酸二乙酯-3,4-乙烯二氧噻吩的方法，属于有机合成领域。 The purpose of the invention is to disclose a method for catalytically synthesizing 2,5-diethyl dicarboxylate-3,4-ethylenedioxythiophene by using polyethylene glycol and potassium iodide as a catalyst system, which belongs to the field of organic synthesis.
背景技术 Background technique
自从发现聚乙炔具有高电导率以来，导电聚合物这个领域就引起了科学家们的广泛关注。在20世纪80年代，德国拜尔公司成功地开发了聚乙撑二氧噻吩（PEDOT）。研究发现PEDOT的掺杂态具有电导率高、环境热稳定性好、不易被氧化且薄膜易制备等特点，拥有广泛的应用前景。PEDOT是由单体3,4-乙撑二氧噻吩（EDOT）采用化学氧化聚合或电化学聚合得到的。由于PEDOT 在工业领域的应用不断深入，极大的促进了 EDOT新合成工艺的开发，力求低成本、高收率的工业化生产路线。 Since the discovery of polyacetylene's high electrical conductivity, the field of conducting polymers has attracted widespread attention from scientists. In the 1980s, the German company Bayer successfully developed polyethylenedioxythiophene (PEDOT). The study found that the doped state of PEDOT has the characteristics of high electrical conductivity, good thermal stability in the environment, not easy to be oxidized, and easy to prepare thin films, which has a wide range of application prospects. PEDOT is obtained by chemical oxidation polymerization or electrochemical polymerization of monomer 3,4-ethylenedioxythiophene (EDOT). Due to the continuous deepening of the application of PEDOT in the industrial field, the development of a new synthesis process for EDOT has been greatly promoted, and an industrial production route with low cost and high yield has been strived for.
2,5-二甲二乙酯-3,4-乙烯二氧噻吩是制备单体EDOT的重要中间体，在有机合成中有着广泛的应用，对其合成工艺条件的探索有重要的现实意义。目前，2,5-二甲酸二乙酯-3,4-乙烯二氧噻吩主要是通过2,5-二甲酸二乙酯-3,4-二酚钠噻吩与二卤乙烷反应来制备。普遍采用的催化剂为：（1）正四丁基溴化铵和无水碳酸钾体系；（2）三乙胺。以上合成方法生产成本高，反应时间长，产品收率较低。 2,5-Dimethyldiethyl-3,4-ethylenedioxythiophene is an important intermediate for the preparation of monomer EDOT, which is widely used in organic synthesis, and the exploration of its synthesis process conditions has important practical significance. At present, diethyl 2,5-dicarboxylate-3,4-ethylenedioxythiophene is mainly prepared by reacting diethyl 2,5-dicarboxylate-3,4-diphenolate sodium thiophene with dihaloethane. Commonly used catalysts are: (1) n-tetrabutylammonium bromide and anhydrous potassium carbonate system; (2) triethylamine. Above synthetic method production cost is high, and reaction time is long, and product yield is lower.
本发明旨在对2,5-二甲酸二乙酯-3,4-乙烯二氧噻吩的合成方法进行改进和优化，缩短反应时间，提高产品的收率。 The invention aims at improving and optimizing the synthesis method of 2,5-diethyl dicarboxylate-3,4-ethylenedioxythiophene, shortening the reaction time and increasing the yield of the product.
发明内容 Contents of the invention
本发明的目的为了克服现有技术的不足，提供一种新的2,5-二甲酸二乙酯-3,4-乙烯二氧噻吩的制备方法，该方法反应时间短，产率高，操作简单，适合于工业化生产。 The purpose of the present invention is in order to overcome the deficiencies in the prior art, provide a kind of new preparation method of 2,5-dicarboxylate-3,4-ethylenedioxythiophene, the method reaction time is short, productive rate is high, easy to operate Simple and suitable for industrialized production.
为实现上述目的，按照下述步骤进行： To achieve the above purpose, follow the steps below:
向三口烧瓶中依次加入2,5-二甲酸二乙酯-3,4-二酚钠噻吩、一定量的1,2-二氯乙烷、聚乙二醇400/600/2000和碘化钾，搅拌，加热到一定温度，反应一段时间，然后冷却至室温，加入蒸馏水充分搅拌，蒸馏水的量为：按上述每60.8g 2,5-二甲酸二乙酯-3,4-二酚钠噻吩加入600ml蒸馏水，分液，减压蒸馏，回收1,2-二氯乙烷，把得到的固体真空干燥，可得白色或微黄色产品，即为2,5-二甲酸二乙酯-3,4-乙烯二氧噻吩。 Add diethyl 2,5-dicarboxylate-3,4-diphenol sodium thiophene, a certain amount of 1,2-dichloroethane, polyethylene glycol 400/600/2000 and potassium iodide successively into the three-necked flask, and stir , heated to a certain temperature, reacted for a period of time, then cooled to room temperature, added distilled water and stirred thoroughly, the amount of distilled water is: add 600ml per 60.8g of diethyl 2,5-dicarboxylate-3,4-diphenol sodium thiophene as above Distill water, separate liquid, distill under reduced pressure, recover 1,2-dichloroethane, and dry the obtained solid in vacuum to obtain a white or slightly yellow product, which is diethyl 2,5-dicarboxylate-3,4- Ethylenedioxythiophene.
其中所述的1,2-二氯乙烷与2,5-二甲酸二乙酯-3,4-二酚钠噻吩的摩尔比为12.5:1-125:1。 The molar ratio of 1,2-dichloroethane to 2,5-dicarboxylate-3,4-diphenol sodium thiophene is 12.5:1-125:1.
其中所述的聚乙二醇400/600/2000与2,5-二甲酸二乙酯-3,4-二酚钠噻吩的摩尔比均为1:5-1:40。 The molar ratios of polyethylene glycol 400/600/2000 and 2,5-diethyl dicarboxylate-3,4-diphenol sodium thiophene are all 1:5-1:40.
其中所述的碘化钾与2,5-二甲酸二乙酯-3,4-二酚钠噻吩的摩尔比为1:4-1:20。 The molar ratio of potassium iodide to diethyl 2,5-dicarboxylate-3,4-diphenol sodium thiophene is 1:4-1:20.
其中所述的反应温度为60-83℃，反应时间为2-10h。 The reaction temperature described therein is 60-83° C., and the reaction time is 2-10 h.
本发明与现有2,5-二甲酸二乙酯-3,4-乙烯二氧噻吩的制备方法相比具有以下优点： Compared with the preparation method of the existing diethyl 2,5-dicarboxylate-3,4-ethylenedioxythiophene, the present invention has the following advantages:
1、直接使用2,5-二甲酸二乙酯-3,4-二酚钠噻吩作为原料，不需要再加入大量碱催化剂无水碳酸钾，减少了操作步骤，降低了工艺成本。 1. Directly use diethyl 2,5-dicarboxylate-3,4-diphenol sodium thiophene as a raw material, without adding a large amount of alkali catalyst anhydrous potassium carbonate, which reduces operating steps and process costs.
2、首次选择聚乙二醇类作为相转移催化剂，该类催化剂在固液两相反应中具有优良的催化活性且对环境无污染；同时，采用少量碘化钾作为助催化剂，协同催化O-烷基化反应。该方法避免了碘离子与鎓盐类相转移催化剂共同使用而出现催化剂中毒的情况，进一步缩短了反应时间，提高了产品收率。 2. For the first time, polyethylene glycol was selected as a phase transfer catalyst. This type of catalyst has excellent catalytic activity in solid-liquid two-phase reaction and has no pollution to the environment; at the same time, a small amount of potassium iodide is used as a cocatalyst to synergistically catalyze O-alkyl reaction. The method avoids catalyst poisoning caused by the joint use of iodide ions and onium salt phase transfer catalysts, further shortens the reaction time and improves the product yield.
具体实施方案 specific implementation plan
实施例1 Example 1
向三口烧瓶中依次加入2,5-二甲酸二乙酯-3,4-二酚钠噻吩60.8g（0.2mol）、1,2-二氯乙烷200ml（2.5mol)和聚乙二醇400, 0.005mol，搅拌升温至60℃，反应10h，反应完毕后冷却至室温，向其中加入600ml蒸馏水，搅拌0.5h，分液，将有机相减压蒸馏，回收试剂1,2-二氯乙烷，将蒸馏得到的固体置于真空干燥箱干燥。得产物2,5-二甲酸二乙酯-3,4-乙烯二氧噻吩24.5g，纯度99%，收率42.8%。 Add 60.8 g (0.2 mol) of diethyl 2,5-dicarboxylate-3,4-diphenolate sodium thiophene, 200 ml (2.5 mol) of 1,2-dichloroethane and polyethylene glycol 400 into the three-necked flask in sequence. , 0.005mol, stir and heat up to 60°C, react for 10h, cool to room temperature after the reaction is complete, add 600ml of distilled water, stir for 0.5h, separate liquids, distill the organic phase under reduced pressure, and recover the reagent 1,2-dichloroethane , and the solid obtained by distillation was dried in a vacuum oven. 24.5 g of the product 2,5-diethyl dicarboxylate-3,4-ethylenedioxythiophene was obtained, with a purity of 99% and a yield of 42.8%.
实施例2 Example 2
向三口烧瓶中依次加入2,5-二甲酸二乙酯-3,4-二酚钠噻吩60.8g（0.2mol）、1,2-二氯乙烷800ml（10mol)和聚乙二醇400, 0.02mol，搅拌升温至70℃，反应6h，反应完毕后冷却至室温，向其中加入600ml蒸馏水，搅拌0.5h，分液，将有机相减压蒸馏，回收试剂1,2-二氯乙烷，将蒸馏得到的固体置于真空干燥箱干燥。得产物2,5-二甲酸二乙酯-3,4-乙烯二氧噻吩32.9g，纯度99%，收率57.5%。 Add 60.8 g (0.2 mol) of diethyl 2,5-dicarboxylate-3,4-diphenolate sodium thiophene, 800 ml (10 mol) of 1,2-dichloroethane and polyethylene glycol 400 in sequence to the three-necked flask, 0.02mol, stirred and heated to 70°C, reacted for 6h, cooled to room temperature after the reaction, added 600ml of distilled water, stirred for 0.5h, separated liquids, and distilled the organic phase under reduced pressure to recover the reagent 1,2-dichloroethane, The solid obtained by distillation was dried in a vacuum oven. 32.9 g of the product 2,5-diethyl dicarboxylate-3,4-ethylenedioxythiophene was obtained, with a purity of 99% and a yield of 57.5%.
实施例3 Example 3
向三口烧瓶中依次加入2,5-二甲酸二乙酯-3,4-二酚钠噻吩60.8g（0.2mol）、1,2-二氯乙烷1200ml（15mol)、聚乙二醇400, 0.04mol和碘化钾0.03mol，搅拌升温至83℃，反应4 h，反应完毕后冷却至室温，向其中加入600ml蒸馏水，搅拌0.5h，分液，将有机相减压蒸馏，回收试剂1,2-二氯乙烷，将蒸馏得到的固体置于真空干燥箱干燥。得产物2,5-二甲酸二乙酯-3,4-乙烯二氧噻吩55.3g，纯度99%，收率96.7%。 Add 60.8 g (0.2 mol) of diethyl 2,5-dicarboxylate-3,4-diphenol sodium thiophene, 1,200 ml (15 mol) of 1,2-dichloroethane, polyethylene glycol 400, 0.04mol and potassium iodide 0.03mol, stirred and heated to 83°C, reacted for 4 hours, cooled to room temperature after the reaction, added 600ml of distilled water, stirred for 0.5h, separated, and the organic phase was distilled under reduced pressure to recover reagent 1,2- Dichloroethane, and the solid obtained by distillation was dried in a vacuum oven. 55.3 g of the product 2,5-dicarboxylate-3,4-ethylenedioxythiophene was obtained, with a purity of 99% and a yield of 96.7%.
实施例4 Example 4
向三口烧瓶中依次加入2,5-二甲酸二乙酯-3,4-二酚钠噻吩60.8g（0.2mol）、1,2-二氯乙烷600ml（7.5mol)和聚乙二醇600, 0.005mol，搅拌升温至70℃，反应8h，反应完毕后冷却至室温，向其中加入600ml蒸馏水，搅拌0.5h，分液，将有机相减压蒸馏，回收试剂1,2-二氯乙烷，将蒸馏得到的固体置于真空干燥箱干燥。得产物2,5-二甲酸二乙酯-3,4-乙烯二氧噻吩32.1g，纯度99%，收率56.1%。 Add 60.8 g (0.2 mol) of diethyl 2,5-dicarboxylate-3,4-diphenolate sodium thiophene, 600 ml (7.5 mol) of 1,2-dichloroethane and polyethylene glycol 600 into the three-necked flask in sequence , 0.005mol, stir and heat up to 70°C, react for 8h, cool to room temperature after the reaction, add 600ml of distilled water, stir for 0.5h, separate liquids, distill the organic phase under reduced pressure, and recover the reagent 1,2-dichloroethane , and the solid obtained by distillation was dried in a vacuum oven. 32.1 g of the product 2,5-dicarboxylate-3,4-ethylenedioxythiophene was obtained, with a purity of 99% and a yield of 56.1%.
实施例5 Example 5
向三口烧瓶中依次加入2,5-二甲酸二乙酯-3,4-二酚钠噻吩60.8g（0.2mol）、1,2-二氯乙烷2000ml（25mol)和聚乙二醇600, 0.04mol，搅拌升温至83℃，反应4h，反应完毕后冷却至室温，向其中加入600ml蒸馏水，搅拌0.5h，分液，将有机相减压蒸馏，回收试剂1,2-二氯乙烷，将蒸馏得到的固体置于真空干燥箱干燥。得产物2,5-二甲酸二乙酯-3,4-乙烯二氧噻吩40.5g，纯度99%，收率70.8%。 Add 60.8 g (0.2 mol) of diethyl 2,5-dicarboxylate-3,4-diphenolate sodium thiophene, 2000 ml (25 mol) of 1,2-dichloroethane and polyethylene glycol 600 in sequence to the three-necked flask, 0.04mol, stirred and heated to 83°C, reacted for 4h, cooled to room temperature after the reaction was completed, added 600ml of distilled water, stirred for 0.5h, separated liquids, distilled the organic phase under reduced pressure, and recovered the reagent 1,2-dichloroethane, The solid obtained by distillation was dried in a vacuum oven. 40.5 g of the product 2,5-dicarboxylate-3,4-ethylenedioxythiophene was obtained, with a purity of 99% and a yield of 70.8%.
实施例6 Example 6
向三口烧瓶中依次加入2,5-二甲酸二乙酯-3,4-二酚钠噻吩60.8g（0.2mol）、1,2-二氯乙烷1000ml（12.5mol)、聚乙二醇600 , 0.01mol和碘化钾0.01mol，搅拌升温至70℃，反应6h，反应完毕后冷却至室温，向其中加入600ml蒸馏水，搅拌0.5h，分液，将有机相减压蒸馏，回收试剂1,2-二氯乙烷，将蒸馏得到的固体置于真空干燥箱干燥。得产物2,5-二甲酸二乙酯-3,4-乙烯二氧噻吩50.7g，纯度99%，收率88.7%。 Add 60.8 g (0.2 mol) of diethyl 2,5-dicarboxylate-3,4-diphenol sodium thiophene, 1,000 ml (12.5 mol) of 1,2-dichloroethane, polyethylene glycol 600 , 0.01mol and potassium iodide 0.01mol, stir and heat up to 70°C, react for 6h, cool to room temperature after the reaction, add 600ml of distilled water, stir for 0.5h, separate the liquids, distill the organic phase under reduced pressure, and recover the reagent 1,2- Dichloroethane, and the solid obtained by distillation was dried in a vacuum oven. 50.7 g of the product 2,5-dicarboxylate-3,4-ethylenedioxythiophene was obtained, with a purity of 99% and a yield of 88.7%.
实施例7 Example 7
向三口烧瓶中依次加入2,5-二甲酸二乙酯-3,4-二酚钠噻吩60.8g（0.2mol）、1,2-二氯乙烷1000ml（12.5mol)、聚乙二醇600, 0.03mol和碘化钾0.03mol，搅拌升温至83℃，反应3h，反应完毕后冷却至室温，向其中加入600ml蒸馏水，搅拌0.5h，分液，将有机相减压蒸馏，回收试剂1,2-二氯乙烷，将蒸馏得到的固体置于真空干燥箱干燥。得产物2,5-二甲酸二乙酯-3,4-乙烯二氧噻吩56.2g，纯度99%，收率98.3%。 Add 60.8 g (0.2 mol) of diethyl 2,5-dicarboxylate-3,4-diphenol sodium thiophene, 1,000 ml (12.5 mol) of 1,2-dichloroethane, polyethylene glycol 600 , 0.03 mol and potassium iodide 0.03 mol, stirred and heated to 83°C, reacted for 3 hours, cooled to room temperature after the reaction, added 600ml of distilled water to it, stirred for 0.5 hours, separated the liquid, distilled the organic phase under reduced pressure, and recovered the reagent 1,2- Dichloroethane, and the solid obtained by distillation was dried in a vacuum oven. 56.2 g of the product 2,5-dicarboxylate-3,4-ethylenedioxythiophene was obtained, with a purity of 99% and a yield of 98.3%.
实施例8 Example 8
向三口烧瓶中依次加入2,5-二甲酸二乙酯-3,4-二酚钠噻吩60.8g（0.2mol）、1,2-二氯乙烷1600ml（20mol)和聚乙二醇2000, 0.04mol，搅拌升温至83℃，反应2h，反应完毕后冷却至室温，向其中加入600ml蒸馏水，搅拌0.5h，分液，将有机相减压蒸馏，回收试剂1,2-二氯乙烷，将蒸馏得到的固体置于真空干燥箱干燥。得产物2,5-二甲酸二乙酯-3,4-乙烯二氧噻吩30.7g，纯度99%，收率53.6%。 Add 60.8 g (0.2 mol) of diethyl 2,5-dicarboxylate-3,4-diphenolate sodium thiophene, 1,600 ml (20 mol) of 1,2-dichloroethane and polyethylene glycol 2000 to the three-necked flask, 0.04mol, stir and heat up to 83°C, react for 2h, cool to room temperature after the reaction, add 600ml of distilled water to it, stir for 0.5h, separate the liquids, distill the organic phase under reduced pressure, and recover the reagent 1,2-dichloroethane, The solid obtained by distillation was dried in a vacuum oven. 30.7 g of the product 2,5-dicarboxylate-3,4-ethylenedioxythiophene was obtained, with a purity of 99% and a yield of 53.6%.
实施例9 Example 9
向三口烧瓶中依次加入2,5-二甲酸二乙酯-3,4-二酚钠噻吩60.8g（0.2mol）、1,2-二氯乙烷800ml（10mol)、聚乙二醇2000, 0.02mol和碘化钾0.01mol，搅拌升温至70℃，反应5h，反应完毕后冷却至室温，向其中加入600ml蒸馏水，搅拌0.5h，分液，将有机相减压蒸馏，回收试剂1,2-二氯乙烷，将蒸馏得到的固体置于真空干燥箱干燥。得产物2,5-二甲酸二乙酯-3,4-乙烯二氧噻吩52.3g，纯度99%，收率91.4%。 Add 60.8 g (0.2 mol) of diethyl 2,5-dicarboxylate-3,4-diphenol sodium thiophene, 800 ml (10 mol) of 1,2-dichloroethane, polyethylene glycol 2000, 0.02 mol and 0.01 mol of potassium iodide, stirred and heated to 70°C, reacted for 5 hours, cooled to room temperature after the reaction, added 600ml of distilled water, stirred for 0.5 hours, separated, and the organic phase was distilled under reduced pressure to recover the reagent 1,2-di Chloroethane, the solid obtained by distillation was dried in a vacuum oven. 52.3 g of the product 2,5-diethyl dicarboxylate-3,4-ethylenedioxythiophene was obtained, with a purity of 99% and a yield of 91.4%.
实施例10 Example 10
向三口烧瓶中依次加入2,5-二甲酸二乙酯-3,4-二酚钠噻吩60.8g（0.2mol）、1,2-二氯乙烷600ml（7.5mol)、聚乙二醇2000, 0.005mol和碘化钾0.05mol，搅拌升温至60℃，反应8h，反应完毕后冷却至室温，向其中加入600ml蒸馏水，搅拌0.5h，分液，将有机相减压蒸馏，回收试剂1,2-二氯乙烷，将蒸馏得到的固体置于真空干燥箱干燥。得产物2,5-二甲酸二乙酯-3,4-乙烯二氧噻吩47.6g，纯度99%，收率83.2%。 Add 60.8 g (0.2 mol) of diethyl 2,5-dicarboxylate-3,4-diphenol sodium thiophene, 600 ml (7.5 mol) of 1,2-dichloroethane, polyethylene glycol 2000 , 0.005mol and potassium iodide 0.05mol, stirred and heated to 60°C, reacted for 8h, cooled to room temperature after the reaction, added 600ml of distilled water to it, stirred for 0.5h, separated the liquid, distilled the organic phase under reduced pressure, and recovered the reagent 1,2- Dichloroethane, and the solid obtained by distillation was dried in a vacuum oven. 47.6 g of the product 2,5-dicarboxylate-3,4-ethylenedioxythiophene was obtained, with a purity of 99% and a yield of 83.2%.
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| CN101570541A (en) * | 2008-04-28 | 2009-11-04 | 大丰市天生药业有限公司 | Preparation method of 3, 4-ethylenedioxythiophene |
| CN102180887A (en) * | 2011-03-15 | 2011-09-14 | 江苏大学 | Method for synthesizing 2,5-diethyl phthalate-3,4-ethylene dioxythiophene |
| CN102731524A (en) * | 2012-07-09 | 2012-10-17 | 张家港市贝利化学品有限公司 | Synthesis method of 3,4-ethylenedioxythiophene (EDOT) as novel conductive high polymer monomer |
| EP2548875A1 (en) * | 2011-07-19 | 2013-01-23 | Far Eastern New Century Corporation | Preparation method of 3,4-ethylenedioxythiophene |
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| CN101570541A (en) * | 2008-04-28 | 2009-11-04 | 大丰市天生药业有限公司 | Preparation method of 3, 4-ethylenedioxythiophene |
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| EP2548875A1 (en) * | 2011-07-19 | 2013-01-23 | Far Eastern New Century Corporation | Preparation method of 3,4-ethylenedioxythiophene |
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