CN103467487A - Method for preparing 2,5-dicarboxylic acid diethy-3,4-ethylenedioxythiophene under catalysis of crown ether type phase transfer catalyst - Google Patents
Method for preparing 2,5-dicarboxylic acid diethy-3,4-ethylenedioxythiophene under catalysis of crown ether type phase transfer catalyst Download PDFInfo
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Abstract
The invention discloses a method for preparing 2,5-dicarboxylic acid diethy-3,4-ethylenedioxythiophene under the catalysis of a crown ether type phase transfer catalyst and belongs to the catalyzed synthesis field. The method comprises the following steps of: sequentially adding a certain amount of 2,5-dicarboxylic acid diethy-3,4-dihydroxythiophene sodium, 1,2-dichloroethane, the crown ether type phase transfer catalyst and potassium iodide into a three-neck flask, agitating and heating to a certain temperature, reacting for a certain time, then cooling to room temperature, adding a proper amount of distilled water and fully agitating, separating liquid, distilling under reduced pressure, and performing vacuum drying to obtain the product. According to the method, the yield of the synthesized 2,5-dicarboxylic acid diethy-3,4-ethylenedioxythiophene is high up to 98.6%. The method is low in cost, mild in conditions, and suitable for industrial production.
Description
Technical field
The invention discloses and a kind ofly using crown ether-like phase transfer catalysts and potassiumiodide as catalyzer, catalyze and synthesize the method for 2,5-dicarboxylate-3,4-ethylene dioxythiophene, belong to the field of catalyzing and synthesizing.
Background technology
Poly-ethylenedioxy thiophene (PEDOT) is a kind of novel conductive polymer, research finds that the doping state of PEDOT has that specific conductivity is high, the environment Heat stability is good, be difficult for the easily characteristics such as preparation of oxidized and film, be the ideal material that is prepared with the electronicss such as OLED, solar cell, ultracapacitor, have application prospect widely.PEDOT adopts chemical oxidising polymerisation or electrochemical polymerization to obtain by monomer 3,4-ethylene dioxythiophene (EDOT).At present, monomer EDOT is mainly synthetic by " five-step approach ", take ethyl chloroacetate as starting raw material, by the five step reactions such as nucleophilic substitution, Claisen condensation, O-alkylation, hydrolysis and decarboxylation, obtains EDOT.
Wherein, the 3rd step O-alkylated reaction, prepare the process of 2,5-diformazan diethyl ester-3,4-ethylene dioxythiophene, long reaction time, and productive rate is low.2,5-diformazan diethyl ester-3,4-ethylene dioxythiophene is the important intermediate for preparing monomer EDOT, in organic synthesis, has a wide range of applications, and the exploration of its synthetic technological condition is had to important realistic meaning.At present, 2,5-dicarboxylate-3,4-ethylene dioxythiophene is mainly by 2,5-dicarboxylate-3, and 4-dihydroxyl thiophene reacts to prepare with dihalo-ethane, and this process is mainly usingd salt as phase-transfer catalyst.But above synthetic method production cost is high, temperature of reaction is high, long reaction time, and product yield is lower.
The present invention is improved for the synthetic method to 2,5-dicarboxylate-3,4-ethylene dioxythiophene, selects new catalyst system, with Reaction time shorten, improves the yield of product.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of catalysis to prepare the novel method of 2,5-dicarboxylate-3,4-ethylene dioxythiophene.The method is with crown ether-like phase transfer catalysts and synthetic 2, the 5-dicarboxylate-3,4-ethylene dioxythiophene of potassiumiodide co-catalysis, simple to operate, be swift in response, and productive rate is high, is applicable to suitability for industrialized production.
Catalysis prepares the novel method of 2,5-dicarboxylate-3,4-ethylene dioxythiophene and carries out according to following step:
Add successively 2 in the four-hole boiling flask with driven stirring rod and thermometer, 5-dicarboxylate-3, 4-dihydroxyl sodium thiophene, a certain amount of 1, the 2-ethylene dichloride, 18-hat-6(or 15-hat-5 or dicyclohexyl-18-are preced with-6) and potassiumiodide, stir and be heated to certain temperature, be cooled to room temperature after reaction for some time, add distilled water stir about 0.5h, the add-on of distilled water is: by every 0.1mol 2, 5-dicarboxylate-3, 4-dihydroxyl sodium thiophene adds 500ml distilled water, be placed in separating funnel standing, separatory, organic phase is carried out to underpressure distillation, recovery distill 1, the 2-ethylene dichloride, the solid vacuum-drying that distillation is obtained, obtain white or micro-yellow crystals shape 2, 5-dicarboxylate-3, the 4-ethylenedioxy thiophene.
Wherein said 1,2-ethylene dichloride and 2,5-dicarboxylate-3, the mol ratio of 4-dihydroxyl sodium thiophene is 75:1-200:1.
Wherein said 18-hat-6(or 15-hat-5 or dicyclohexyl-18-hat-6) with 2,5-dicarboxylate-3, the mol ratio of 4-dihydroxyl sodium thiophene is 1:5-1:50.
Wherein said potassiumiodide and 2,5-dicarboxylate-3, the mol ratio of 4-dihydroxyl sodium thiophene is 1:1-1:10.
Wherein said temperature of reaction is 50-83 ℃, and the reaction times is 1-9h.
The present invention compares and has the following advantages with the preparation method who has 2,5-dicarboxylate-3,4-ethylene dioxythiophene now:
There is good catalytic activity while 1, selecting crown ether-like phase transfer catalysts catalysis solid-liquid two phase reaction, when especially the salt such as sodium, potassium solid is as reaction raw materials, crown ether can be combined with sodium, potassium plasma fast, makes the exposed organic phase that enters of organic negative ion participate in reaction.
2, add a small amount of potassiumiodide as promotor, concerted catalysis O-alkylated reaction.Crown ether-like phase transfer catalysts can be combined with potassium ion fast, make the iodine negative ion enter liquid phase when in and 1, the higher iodic ether of 2-ethylene dichloride generation substitution reaction formation reaction activity, iodic ether participates in the O-alkylated reaction again, further shorten the reaction times, improved reaction conversion ratio.
Embodiment
Embodiment 1
30.4g(0.1mol) 2, 5-dicarboxylate-3, 4-dihydroxyl sodium thiophene, 600ml(7.5mol) 1, in 2-ethylene dichloride and 0.002mol 18-hat-6 four-hole boiling flasks that add successively with driven stirring rod and thermometer, start to stir, be warming up to 60 ℃, reaction 9h, stop heating, be cooled to room temperature, add 500ml distilled water in flask, stir about 0.5h, be placed in separating funnel standing, separatory, organic phase is carried out to underpressure distillation, recovery distill 1, the 2-ethylene dichloride, the solid vacuum-drying that distillation is obtained, obtain product 2, 5-dicarboxylate-3, the 4-ethylenedioxy thiophene.Obtain product quality 12.8g, product purity 99%, yield 44.8%.
Embodiment 2
30.4g(0.1mol) 2, 5-dicarboxylate-3, 4-dihydroxyl sodium thiophene, 1000ml(12.5mol) 1, in 2-ethylene dichloride and 0.02mol 18-hat-6 four-hole boiling flasks that add successively with driven stirring rod and thermometer, start to stir, be warming up to 83 ℃, reaction 5h, stop heating, be cooled to room temperature, add 500ml distilled water in flask, stir about 0.5h, be placed in separating funnel standing, separatory, organic phase is carried out to underpressure distillation, recovery distill 1, the 2-ethylene dichloride, the solid vacuum-drying that distillation is obtained, obtain product 2, 5-dicarboxylate-3, the 4-ethylenedioxy thiophene.Obtain product quality 21.9g, product purity 99%, yield 76.7%.
Embodiment 3
30.4g(0.1mol) 2, 5-dicarboxylate-3, 4-dihydroxyl sodium thiophene, 1600ml(20mol) 1, the 2-ethylene dichloride, 0.01mol 18-hat-6 and 0.06mol potassiumiodide add in the four-hole boiling flask with driven stirring rod and thermometer successively, start to stir, be warming up to 75 ℃, reaction 4h, stop heating, be cooled to room temperature, add 500ml distilled water in flask, stir about 0.5h, be placed in separating funnel standing, separatory, organic phase is carried out to underpressure distillation, recovery distill 1, the 2-ethylene dichloride, the solid vacuum-drying that distillation is obtained, obtain product 2, 5-dicarboxylate-3, the 4-ethylenedioxy thiophene.Obtain product quality 27.1g, product purity 99%, yield 94.8%.
Embodiment 4
30.4g(0.1mol) 2, 5-dicarboxylate-3, 4-dihydroxyl sodium thiophene, 800ml(10mol) 1, in 2-ethylene dichloride and 0.002mol 15-hat-5 four-hole boiling flasks that add successively with driven stirring rod and thermometer, start to stir, be warming up to 70 ℃, reaction 7h, stop heating, be cooled to room temperature, add 500ml distilled water in flask, stir about 0.5h, be placed in separating funnel standing, separatory, organic phase is carried out to underpressure distillation, recovery distill 1, the 2-ethylene dichloride, the solid vacuum-drying that distillation is obtained, obtain product 2, 5-dicarboxylate-3, the 4-ethylenedioxy thiophene.Obtain product quality 14.6g, product purity 99%, yield 50.9%.
Embodiment 5
30.4g(0.1mol) 2, 5-dicarboxylate-3, 4-dihydroxyl sodium thiophene, 600ml(7.5mol) 1, the 2-ethylene dichloride, 0.01mol 15-hat-5 and 0.01mol potassiumiodide add in the four-hole boiling flask with driven stirring rod and thermometer successively, start to stir, be warming up to 83 ℃, reaction 1h, stop heating, be cooled to room temperature, add 500ml distilled water in flask, stir about 0.5h, be placed in separating funnel standing, separatory, organic phase is carried out to underpressure distillation, recovery distill 1, the 2-ethylene dichloride, the solid vacuum-drying that distillation is obtained, obtain product 2, 5-dicarboxylate-3, the 4-ethylenedioxy thiophene.Obtain product quality 18.1g, product purity 99%, yield 63.3%.
Embodiment 6
30.4g(0.1mol) 2, 5-dicarboxylate-3, 4-dihydroxyl sodium thiophene, 1200ml(15mol) 1, the 2-ethylene dichloride, 0.02mol 15-hat-5 and 0.1mol potassiumiodide add in the four-hole boiling flask with driven stirring rod and thermometer successively, start to stir, be warming up to 60 ℃, reaction 4h, stop heating, be cooled to room temperature, add 500ml distilled water in flask, stir about 0.5h, be placed in separating funnel standing, separatory, organic phase is carried out to underpressure distillation, recovery distill 1, the 2-ethylene dichloride, the solid vacuum-drying that distillation is obtained, obtain product 2, 5-dicarboxylate-3, the 4-ethylenedioxy thiophene.Obtain product quality 24.5g, product purity 99%, yield 85.5%.
Embodiment 7
30.4g(0.1mol) 2, 5-dicarboxylate-3, 4-dihydroxyl sodium thiophene, 600ml(7.5mol) 1, the 2-ethylene dichloride, 0.01mol 15-hat-5 and 0.06mol potassiumiodide add in the four-hole boiling flask with driven stirring rod and thermometer successively, start to stir, be warming up to 83 ℃, reaction 3h, stop heating, be cooled to room temperature, add 500ml distilled water in flask, stir about 0.5h, be placed in separating funnel standing, separatory, organic phase is carried out to underpressure distillation, recovery distill 1, the 2-ethylene dichloride, the solid vacuum-drying that distillation is obtained, obtain product 2, 5-dicarboxylate-3, the 4-ethylenedioxy thiophene.Obtain product quality 28.2g, product purity 99%, yield 98.6%.
Embodiment 8
30.4g(0.1mol) 2, 5-dicarboxylate-3, 4-dihydroxyl sodium thiophene, 800ml(10mol) 1, in 2-ethylene dichloride and 0.02mol dicyclohexyl-18-hat-6 four-hole boiling flasks that add successively with driven stirring rod and thermometer, start to stir, be warming up to 83 ℃, reaction 9h, stop heating, be cooled to room temperature, add 500ml distilled water in flask, stir about 0.5h, be placed in separating funnel standing, separatory, organic phase is carried out to underpressure distillation, recovery distill 1, the 2-ethylene dichloride, the solid vacuum-drying that distillation is obtained, obtain product 2, 5-dicarboxylate-3, the 4-ethylenedioxy thiophene.Obtain product quality 22.8g, product purity 99%, yield 79.8%.
Embodiment 9
30.4g(0.1mol) 2, 5-dicarboxylate-3, 4-dihydroxyl sodium thiophene, 1400ml(17.5mol) 1, the 2-ethylene dichloride, 0.002mol dicyclohexyl-18-hat-6 and 0.1mol potassiumiodide add in the four-hole boiling flask with driven stirring rod and thermometer successively, start to stir, be warming up to 50 ℃, reaction 6h, stop heating, be cooled to room temperature, add 500ml distilled water in flask, stir about 0.5h, be placed in separating funnel standing, separatory, organic phase is carried out to underpressure distillation, recovery distill 1, the 2-ethylene dichloride, the solid vacuum-drying that distillation is obtained, obtain product 2, 5-dicarboxylate-3, the 4-ethylenedioxy thiophene.Obtain product quality 20.2g, product purity 99%, yield 70.5%.
Embodiment 10
30.4g(0.1mol) 2, 5-dicarboxylate-3, 4-dihydroxyl sodium thiophene, 1000ml(12.5mol) 1, the 2-ethylene dichloride, 0.01mol dicyclohexyl-18-hat-6 and 0.08mol potassiumiodide add in the four-hole boiling flask with driven stirring rod and thermometer successively, start to stir, be warming up to 75 ℃, reaction 4h, stop heating, be cooled to room temperature, add 500ml distilled water in flask, stir about 0.5h, be placed in separating funnel standing, separatory, organic phase is carried out to underpressure distillation, recovery distill 1, the 2-ethylene dichloride, the solid vacuum-drying that distillation is obtained, obtain product 2, 5-dicarboxylate-3, the 4-ethylenedioxy thiophene.Obtain product quality 26.8g, product purity 99%, yield 93.7%.
Claims (6)
1. a crown ether-like phase transfer catalysts catalysis prepares 2, 5-dicarboxylate-3, the method of 4-ethylenedioxy thiophene, it is characterized in that carrying out in the steps below: in the four-hole boiling flask with driven stirring rod and thermometer, add successively 2, 5-dicarboxylate-3, 4-dihydroxyl sodium thiophene, a certain amount of 1, the 2-ethylene dichloride, 18-hat-6 or 15-hat-5 or dicyclohexyl-18-hat-6 and potassiumiodide, stir and be heated to certain temperature, be cooled to room temperature after reaction for some time, add distilled water stir about 0.5h, the add-on of distilled water is: by every 0.1mol 2, 5-dicarboxylate-3, 4-dihydroxyl sodium thiophene adds 500ml distilled water, be placed in separating funnel standing, separatory, organic phase is carried out to underpressure distillation, recovery distill 1, the 2-ethylene dichloride, the solid vacuum-drying that distillation is obtained, obtain white or micro-yellow crystals shape 2, 5-dicarboxylate-3, the 4-ethylenedioxy thiophene.
2. crown ether-like phase transfer catalysts catalysis according to claim 1 prepares the method for 2,5-dicarboxylate-3,4-ethylene dioxythiophene, it is characterized in that wherein said 1,2-ethylene dichloride and 2,5-dicarboxylate-3, the mol ratio of 4-dihydroxyl sodium thiophene is 75:1-200:1.
3. crown ether-like phase transfer catalysts catalysis according to claim 1 prepares 2,5-dicarboxylate-3, the method of 4-ethylenedioxy thiophene, it is characterized in that wherein said 18-hat-6 or 15-hat-5 or dicyclohexyl-18-hat-6 and 2,5-dicarboxylate-3, the mol ratio of 4-dihydroxyl sodium thiophene is 1:5-1:50.
4. crown ether-like phase transfer catalysts catalysis according to claim 1 prepares 2, the method of 5-dicarboxylate-3,4-ethylene dioxythiophene, is characterized in that wherein said potassiumiodide and 2,5-dicarboxylate-3, the mol ratio of 4-dihydroxyl sodium thiophene is 1:1-1:10.
5. crown ether-like phase transfer catalysts catalysis according to claim 1 prepares the method for 2,5-dicarboxylate-3,4-ethylene dioxythiophene, it is characterized in that wherein said temperature of reaction is 50-83 ℃, and the reaction times is 1-9h.
6. a crown ether-like phase transfer catalysts catalysis prepares 2, 5-dicarboxylate-3, the method of 4-ethylenedioxy thiophene, it is characterized in that carrying out in the steps below: in the four-hole boiling flask with driven stirring rod and thermometer, add successively 2, 5-dicarboxylate-3, 4-dihydroxyl sodium thiophene, a certain amount of 1, the 2-ethylene dichloride, 18-hat-6 or 15-hat-5 or dicyclohexyl-18-hat-6, stir and be heated to certain temperature, be cooled to room temperature after reaction for some time, add distilled water stir about 0.5h, the add-on of distilled water is: by every 0.1mol 2, 5-dicarboxylate-3, 4-dihydroxyl sodium thiophene adds 500ml distilled water, be placed in separating funnel standing, separatory, organic phase is carried out to underpressure distillation, recovery distill 1, the 2-ethylene dichloride, the solid vacuum-drying that distillation is obtained, obtain white or micro-yellow crystals shape 2, 5-dicarboxylate-3, the 4-ethylenedioxy thiophene.
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| CN104592249A (en) * | 2015-01-15 | 2015-05-06 | 新发药业有限公司 | Low-cost simple method for preparing clopidogrel free alkali |
| CN110615799A (en) * | 2019-09-17 | 2019-12-27 | 苏州亚科科技股份有限公司 | Preparation method of EDOT intermediate |
| CN111303050A (en) * | 2020-04-07 | 2020-06-19 | 西安近代化学研究所 | Synthesis method of bupirimate |
| CN114015358A (en) * | 2021-11-26 | 2022-02-08 | 上海华谊涂料有限公司 | Water-based oxidation type cross-linked resin drier and preparation method thereof |
| CN114149381A (en) * | 2021-12-22 | 2022-03-08 | 欧阳瑞知 | Preparation method of 2, 3-dihydro-5-methyl-2-oxo-1, 3, 4-oxadiazole-3-acetone |
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| CN114015358A (en) * | 2021-11-26 | 2022-02-08 | 上海华谊涂料有限公司 | Water-based oxidation type cross-linked resin drier and preparation method thereof |
| CN114149381A (en) * | 2021-12-22 | 2022-03-08 | 欧阳瑞知 | Preparation method of 2, 3-dihydro-5-methyl-2-oxo-1, 3, 4-oxadiazole-3-acetone |
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