CN101570542B - Synthetic process of 3, 4-ethylenedjoxythiophene - Google Patents
Synthetic process of 3, 4-ethylenedjoxythiophene Download PDFInfo
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- CN101570542B CN101570542B CN2009101040382A CN200910104038A CN101570542B CN 101570542 B CN101570542 B CN 101570542B CN 2009101040382 A CN2009101040382 A CN 2009101040382A CN 200910104038 A CN200910104038 A CN 200910104038A CN 101570542 B CN101570542 B CN 101570542B
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- ethylene glycol
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- enedioxy thiophene
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- ZUDCKLVMBAXBIF-UHFFFAOYSA-N COc1c[s]cc1OC Chemical compound COc1c[s]cc1OC ZUDCKLVMBAXBIF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a synthetic process of 3, 4-ethylenedjoxythiophene. 3, 4-dibromothiophene and disodium ethylene glycol are taken as raw materials to synthesize 3, 4-ethylenedjoxythiophene in the presence of catalyst, the reaction conditions are as follows: the temperature is 50-150 DEG C, the reaction time is 5-24 hours; the catalyst is halogenated kupfer, or compound of cupric oxide and halogenated potassium. Compared with the prior art, the invention has the superiorities of short line and high yield.
Description
Technical field
The present invention relates to a kind of technology of chemical synthetic drug, specifically, is a kind of 3, the synthesis technique of 4-enedioxy thiophene.
Background technology
3,4-enedioxy thiophene, English name: 3,4-ethylene dioxythiophene (EDOT), the EDOT monomer obtains poly-enedioxy thiophene (PEDOT) by chemical polymerization or electrochemical polymerization, PEDOT is a kind of novel organic conductive luminescent material of German Bayer company exploitation, advantage such as have specific conductivity height, luminous efficiency height, environmental stability is good, film is easily made and the transparency is good is used to prepare electronicss such as macromolecular solid body capacitance, Organic Light Emitting Diode (OLED), solar cell, anti-static coating, printed circuit board (PCB).Present 3,4-enedioxy thiophene synthesis technique mainly contains following several:
1, with the ethyl chloroacetate is raw material, synthesizes 3 by reactions such as sulphur replacement, Claisen condensation, O-alkylation and decarboxylations, 4-enedioxy thiophene.Synthetic route is as follows:
2, be raw material with thiophene and liquid bromine, by bromo, reduction, alkoxylate and the synthetic target product of ether exchange four-step reaction.Synthetic route is as follows:
3, with 2, the 3-dimethyl diketone is through methoxylation, and Cheng Huan obtains target product by ether exchange reaction at last again.Synthetic route is as follows:
Article one, the route reaction route is long, and final step decarboxylic reaction yield is on the low side; Second and the 3rd route are all through 3, and 4-dimethoxy-thiophene and ethylene glycol generation ether exchange reaction obtain final product.This reaction owing to carry out under acidic conditions in step, and the instability of product under acidic conditions, therefore influenced the yield and the quality of product greatly.
Summary of the invention
Technical problem to be solved by this invention is to provide that a kind of circuit is short, yield is high 3,4-enedioxy thiophene synthesis technique.
In order to address the above problem, the technical solution adopted in the present invention is: with 3,4-dibromo thiophene and ethylene glycol disodium are raw material, synthesize 3 in the presence of catalyzer, 4-enedioxy thiophene, and reaction conditions is: 50～150 ℃ of temperature, 5～24 hours time; Described catalyzer is a cuprous halide, or the mixture of cupric oxide and potassium halide.Synthetic route is as follows:
In technique scheme, 3,4-dibromo thiophene and ethylene glycol disodium react in organic solvent, and this organic solvent is N, wherein a kind of of dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) or more than one mixture.
In technique scheme, 3, after 4-dibromo thiophene and the reaction of ethylene glycol disodium finish, reaction solution is added in the entry, to use and the immiscible organic solvent extraction of water, extraction gets 3 with the organic phase evaporate to dryness, 4-enedioxy thiophene product after finishing.
As the preferred embodiment of technique scheme, the ratio of the mole number of described cupric oxide and potassium halide is 1: 0.01～0.05.
In technique scheme, the ethylene glycol disodium is pressed the preparation of row method: ethylene glycol and excessive sodium hydrate are dissolved in the toluene, back flow reaction 1～2 hour, reaction finishes the back distillation and removes toluene and water, vacuumize again and further remove toluene and water, then the dry ethylene glycol disodium that gets under 120～140 ℃ of conditions.The ethylene glycol disodium also can adopt common process to make.
Compared with prior art, of the present invention having the following advantages:
(1) synthetic thread is short out, and the present invention has simplified synthetic route with the synthetic step preparation of original two-step reaction EDOT.
(2) total recovery is higher than prior art, and synthetic route total recovery of the present invention reaches more than 78%.
Embodiment
Synthetic route is as follows:
Embodiment 1
1, the preparation of ethylene glycol disodium
31 gram (0.5 mole) ethylene glycol and 40 gram (1.0 moles) sodium hydroxide are dissolved in 500 milliliters of toluene, back flow reaction 1.5 hours, reaction finish the back distillation and remove toluene and water, vacuumize and further remove toluene and water, under 130 ℃ of conditions dry 0.5 hour then, the ethylene glycol disodium.
2,3, the preparation of 4-enedioxy thiophene
53 gram ethylene glycol bisthioglycolate sodium cooling to 50 that step 1 is obtained ℃ add N, 500 milliliters of dinethylformamides successively in reaction vessel, 3,4-dibromo thiophene 109 grams (0.45 mole), cuprous bromide 13 grams (0.09 mole), be warming up to 110 ℃, reaction is 5 hours under this temperature.Reaction is poured reaction solution in 2 premium on currency into after finishing, and product extracts with toluene; After extraction finishes, toluene solution is distilled to dried, obtains 3,4-enedioxy thiophene product 50 grams, yield 78%.
Embodiment 2
1, the preparation of ethylene glycol disodium
With ethylene glycol and sodium is raw material, makes by prior art.
2,3, the preparation of 4-enedioxy thiophene
The 53 gram ethylene glycol disodiums that step 1 obtains are put into reaction vessel, add 500 milliliters of N-Methyl pyrrolidone successively, 3,4-dibromo thiophene 109 grams (0.45 mole), cupric oxide 36 grams (0.45 mole) and potassiumiodide 0.82 gram (0.005 mole), be warming up to 50 ℃, reaction is 24 hours under this temperature.Reaction is poured reaction solution in 2 premium on currency into after finishing, and product extracts with toluene; After extraction finishes,, obtain product 55 grams, yield 86% with the toluene solution distillation.
Embodiment 3
1, the preparation of ethylene glycol disodium
The preparation method is identical with embodiment 1.
2,3, the preparation of 4-enedioxy thiophene
53 gram ethylene glycol bisthioglycolate sodium cooling to 50 that step 1 is obtained ℃ add 500 milliliters of N-Methyl pyrrolidone, 3 successively in reaction vessel, 4-dibromo thiophene 109 grams (0.45 mole), cuprous iodide 17.14 grams (0.09 mole) are warming up to 150 ℃, and reaction is 5 hours under this temperature.Reaction is poured reaction solution in 2 premium on currency into after finishing, and product extracts with toluene; After extraction finishes,, obtain product 51 grams, yield 80% with the toluene solution distillation.
Embodiment 4
1, the preparation of ethylene glycol disodium
The preparation method is identical with embodiment 1.
2,3, the preparation of 4-enedioxy thiophene
53 gram ethylene glycol bisthioglycolate sodium cooling to 50 that step 1 is obtained ℃, in reaction vessel, add N successively, 500 milliliters of N-N,N-DIMETHYLACETAMIDEs, 3,4-dibromo thiophene 109 grams (0.45 mole), cupric oxide 36 grams (0.45 mole) and Potassium Bromide 2.38 grams (0.02 mole) are warming up to 90 ℃, and reaction is 18 hours under this temperature.Reaction is poured reaction solution in 2 premium on currency into after finishing, and product extracts with toluene; After extraction finishes,, obtain product 54 grams, yield 84% with the toluene solution distillation.
Embodiment 5
1, the preparation of ethylene glycol disodium
The preparation method is identical with embodiment 1.
2,3, the preparation of 4-enedioxy thiophene
53 gram ethylene glycol bisthioglycolate sodium cooling to 50 that step 1 is obtained ℃, in reaction vessel, add N-Methyl pyrrolidone and N successively, 500 milliliters of the mixed solutions of dinethylformamide, 3,4-dibromo thiophene 109 grams (0.45 mole), cuprous chloride 8.9 grams (0.09 mole) are warming up to 100 ℃, and reaction is 20 hours under this temperature.Reaction is poured reaction solution in 2 premium on currency into after finishing, and product extracts with toluene; After extraction finishes,, obtain product 50 grams, yield 79% with the toluene solution distillation.
Claims (5)
1. one kind 3, the synthesis technique of 4-enedioxy thiophene is characterized in that: with 3,4-dibromo thiophene and ethylene glycol disodium are raw material, synthesize 3 in the presence of catalyzer, 4-enedioxy thiophene, and reaction conditions is: 50～150 ℃ of temperature, 5～24 hours time; Described catalyzer is a cuprous halide, or the mixture of cupric oxide and potassium halide.
2. according to claim 13, the synthesis technique of 4-enedioxy thiophene, it is characterized in that: 3,4-dibromo thiophene and ethylene glycol disodium react in organic solvent, this organic solvent is N, wherein more than one of dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO).
3. according to claim 1 and 23, the synthesis technique of 4-enedioxy thiophene, it is characterized in that: 3, after 4-dibromo thiophene and the reaction of ethylene glycol disodium finish, reaction solution is added in the entry, use and the immiscible organic solvent extraction of water, after extraction finishes, the organic phase evaporate to dryness is got 3,4-enedioxy thiophene product.
4. according to claim 13, the synthesis technique of 4-enedioxy thiophene is characterized in that: the ratio of the mole number of described cupric oxide and potassium halide is 1: 0.01～0.05.
5. according to claim 13, the synthesis technique of 4-enedioxy thiophene, it is characterized in that: the preparation method of described ethylene glycol disodium is: ethylene glycol and excessive sodium hydrate are dissolved in the toluene, back flow reaction 1～2 hour, reaction finishes the back distillation and removes toluene and water, vacuumize again and further remove toluene and water, then the dry ethylene glycol disodium that gets under 120～140 ℃ of conditions.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5663871B2 (en) * | 2009-12-24 | 2015-02-04 | 東ソー株式会社 | Method for producing thiophenes |
| CN102532160A (en) * | 2011-11-28 | 2012-07-04 | 中国科学技术大学 | Catalytic synthesis method of conductive polymer monomer |
| CN102659812A (en) * | 2012-05-17 | 2012-09-12 | 陈群 | Simple method for preparing 3,4-ethylenedioxythiophene |
| 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 |
| CN110183465A (en) * | 2019-06-26 | 2019-08-30 | 福建博鸿新能源科技有限公司 | The preparation method of (2,3- dihydro-thiophene simultaneously [3,4-B] [1,4] dioxane hex- 2- yl) methanol |
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