CN102241691A - Decarboxylation method of 3,4-ethylenedioxy thiophene - Google Patents
Decarboxylation method of 3,4-ethylenedioxy thiophene Download PDFInfo
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- CN102241691A CN102241691A CN2011101944967A CN201110194496A CN102241691A CN 102241691 A CN102241691 A CN 102241691A CN 2011101944967 A CN2011101944967 A CN 2011101944967A CN 201110194496 A CN201110194496 A CN 201110194496A CN 102241691 A CN102241691 A CN 102241691A
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- enedioxy thiophene
- decarboxylation
- thiophene
- ethylenedioxy thiophene
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Abstract
The invention discloses a decarboxylation method of 3,4-ethylenedioxy thiophene. The method comprises the following step of: decarboxylating 2,5-dicarboxylic acid-3,4-ethylenedioxy thiophene by taking metal phthalocyanine with the structure shown as a general formula (I) as a catalyst to obtain 3,4-ethylenedioxy thiophene, wherein M refers to Mg, Mn, Fe, Co, Ni, Cu, Ag or Zn; and R is independently selected from -H, -Et, -OH, -OCH3, -COOH, -COOEt, -NH2, -NO2, -CN, -F, -Cl, -Br, -I and -Ph. The yield of the 3,4-ethylenedioxy thiophene is high, a solvent used in a reaction is environmentally-friendly and low-cost water, and the catalyst is reusable. The method has the advantages of simple process, low cost, high yield and environmental friendliness, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of decarboxylation legal system and be equipped with 3, the method for 4-enedioxy thiophene belongs to technical field of organic synthesis.
Background technology
3,4-enedioxy thiophene (EDOT), English is called 3,4-ethylene dioxythiophene, outward appearance is colourless or light yellow transparent liquid, CAS: 126213-50-1,10.5 ℃ of fusing points, 225 ℃ of boiling points.At first be found as medicine intermediate in the latter half eighties 20th century, afterwards, German Bayer AG has successfully developed poly-(3,4-enedioxy thiophene), i.e. PEDOT.Subsequently, adopt a kind of water miscible polymer electrolyte polystyrolsulfon acid (being called for short PSS) to mix and solved the processing problems of PEDOT, the PSS/PEDOT film that obtains has high conductivity, high mechanical strength, high visible light transmissivity and superior stability, is the ideal material of antistatic coating, solid electrolyte capacitators, the plating of through hole wiring board, PLED, solar cell, ultracapacitor, electromagnetic interference shield, selective permeation film, electrochromism device, camouflage, naval vessel anticorrosion and antifouling, absorbing material, superconducting material and information storage material etc.
Relevant 3, the report of the synthetic method of 4-enedioxy thiophene is less, EDOT synthetic " five-step approach " technology be stenger in 1998 propose.Chinese invention patent application CN101062927A also discloses a kind of " five-step approach " preparation method, the final step of this method is 2,5-dicarboxylic acid-3,4-enedioxy thiophene obtains 3 through decarboxylation, 4-enedioxy thiophene, it, reacts in high boiling point organic amine solvents such as quinoline as catalyzer with Cu powder or copper oxide.But solvent cost height, separation used in should reacting are difficult, bring very big difficulty to production.Though Chinese invention patent application CN101104619A will merge into a step in two steps of back, but still not avoid the use of high boiling point organic amine solvents such as quinoline.
Chinese invention patent application CN101519409A adopts comparatively cheap DMF to make solvent, decarboxylation under the Cu-series catalyst effect, but this reaction system will be introduced the decarboxylation smoothly of oxygen ability, has caused certain restriction to industrialization.
Chinese invention patent application CN1759119A discloses a kind of decarboxylation method used, and under condition of no solvent, solid material carries out in the presence of fluidized bed body, and product is discharged with the form of gas.Though this reaction system is easy to industrialization, productive rate is lower, big to equipment requirements height, energy consumption, still is unsuitable for suitability for industrialized production 3,4-enedioxy thiophene.
Summary of the invention
It is a kind of 3 that the object of the invention provides, and the synthetic method of 4-enedioxy thiophene is to solve in the prior art 2,5-dicarboxylic acid-3,4-enedioxy thiophene decarboxylation cost height, the deficiency that environment is unfriendly, operational requirement is high, yield is low.
In order to reach above purpose, the technical solution used in the present invention is:
A kind of 3,4-enedioxy thiophene decarboxylation method used is catalyzer with the metal phthalocyanine, 2, and 5-dicarboxylic acid-3, the decarboxylation of 4-enedioxy thiophene obtains 3,4-enedioxy thiophene.
Described metal phthalocyanine structure shown in general formula (I),
M is Mg, Mn, Fe, Co, Ni, Cu, Ag or Zn;
R is independently selected from-H ,-Et ,-OH ,-OCH
3,-COOH ,-COOEt ,-NH
2,-NO
2,-CN ,-F ,-Cl ,-Br ,-I ,-Ph.
Specifically, be catalyzer with the metal phthalocyanine, water is solvent, normal pressure refluxes down, and 2,5-dicarboxylic acid-3,4-enedioxy thiophene gets final product decarboxylation, use that oily-water seperating equipment is continuable tells 3 of generation, 4-enedioxy thiophene, drying, underpressure distillation, collect the cut of 122 ℃/7kPa, get 3,4-enedioxy thiophene, yield is greater than 90%.
Advantage of the present invention and positively effect: (1) adopts the inventive method, products obtained therefrom 3, and the yield height of 4-enedioxy thiophene, purity height, color and luster is attractive in appearance, and total recovery can reach more than 90%; (2) reaction uses green cheap water to be solvent, and reusable edible, and catalyzer can reuse; (3) technology of the present invention is simple, cost is low, productive rate is high, environmentally friendly, production equipment is easy to purchase, technical process is continuous, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is equipped with 3, the reaction formula of 4-enedioxy thiophene for the decarboxylation legal system;
Fig. 2 is 3, the IR collection of illustrative plates of 4-enedioxy thiophene;
Fig. 3 is 3,4-enedioxy thiophene
1H NMR collection of illustrative plates;
Fig. 4 is 3, the MS collection of illustrative plates of 4-enedioxy thiophene.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1:
As shown in Figure 1, take by weighing 23g 2,5-dicarboxylic acid-3,4-enedioxy thiophene and 0.2 g CuPc are (shown in Figure 2, R=H M=Cu), adds in the 250mL reaction flask, adds 100mL water, water-and-oil separator is installed, and reflux promptly has oily matter to tell in the reaction process.With the oily matter drying of telling, underpressure distillation gets 3,4-enedioxy thiophene 13.0g(productive rate 92%).The product characterization result shown in Fig. 2-4, GC-MS:m/z=142,127,116,95,69,58,45;
1H NMR (CDCl
3) δ (ppm): 6.320 (s, 2H, ArH), 4.193 (s, 4H, OCH
2); IR (KBr) ν: 3111,2980,2923,2872,1487,1450,1423,1366,1185,1057,891,761 cm
-1
Similar to Example 1, adopt the different metal phthalocyanine as catalyzer, the result is as shown in the table.
Claims (4)
1. one kind 3,4-enedioxy thiophene decarboxylation method used is characterized in that: with the metal phthalocyanine catalyzer, and 2,5-dicarboxylic acid-3, the decarboxylation of 4-enedioxy thiophene obtains 3,4-enedioxy thiophene.
2. according to claim 13,4-enedioxy thiophene decarboxylation method used is characterized in that: the metal phthalocyanine structure shown in general formula (I),
M is Mg, Mn, Fe, Co, Ni, Cu, Ag or Zn;
R is independently selected from-H ,-Et ,-OH ,-OCH
3,-COOH ,-COOEt ,-NH
2,-NO
2,-CN ,-F ,-Cl ,-Br ,-I ,-Ph.
3. according to claim 13,4-enedioxy thiophene decarboxylation method used, it is characterized in that: be catalyzer with the metal phthalocyanine, water is solvent, atmospheric pressure reflux, 2,5-dicarboxylic acid-3,4-enedioxy thiophene can decarboxylation obtain 3,4-enedioxy thiophene.
4. according to claim 33,4-enedioxy thiophene decarboxylation method used is characterized in that: use oily-water seperating equipment to tell 3 of generation continuously, 4-enedioxy thiophene, drying, underpressure distillation, the cut of 122 ℃/7kPa of collection, get 3,4-enedioxy thiophene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110194496.7A CN102241691B (en) | 2011-07-13 | 2011-07-13 | Decarboxylation method of 3,4-ethylenedioxy thiophene |
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| CN201110194496.7A CN102241691B (en) | 2011-07-13 | 2011-07-13 | Decarboxylation method of 3,4-ethylenedioxy thiophene |
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| CN102241691B CN102241691B (en) | 2014-03-26 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633811A (en) * | 2012-05-04 | 2012-08-15 | 苏州大学 | Purification method for preparing high-purity 3,4-ethylenedioxythiophene |
| CN104926713A (en) * | 2015-05-24 | 2015-09-23 | 西北大学 | Synthetic method of polysubstitution 1,2,5,6-tetrahydropyridine compound |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010034453A1 (en) * | 2000-04-04 | 2001-10-25 | Gunter Rauchschwalbe | Process for the preparation of dialkylthiophenes and alkylenedioxythiophenes |
| CN1759119A (en) * | 2002-12-16 | 2006-04-12 | 兰爱克谢斯德国有限责任公司 | Method for the decarboxylation of dicarboxylic acids |
| CN101062927A (en) * | 2006-04-30 | 2007-10-31 | 贝利医药原料(苏州)有限公司 | Preparation method of 3,4-ethene dioxythiophene |
| CN101104619A (en) * | 2007-07-24 | 2008-01-16 | 陕西科技大学 | Decarboxylation preparation technique for ethylene dioxythiophene |
| CN101519409A (en) * | 2008-02-27 | 2009-09-02 | 成都丽凯手性技术有限公司 | Method for preparing 3, 4-ethylenedioxythiophene |
-
2011
- 2011-07-13 CN CN201110194496.7A patent/CN102241691B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010034453A1 (en) * | 2000-04-04 | 2001-10-25 | Gunter Rauchschwalbe | Process for the preparation of dialkylthiophenes and alkylenedioxythiophenes |
| CN1759119A (en) * | 2002-12-16 | 2006-04-12 | 兰爱克谢斯德国有限责任公司 | Method for the decarboxylation of dicarboxylic acids |
| CN101062927A (en) * | 2006-04-30 | 2007-10-31 | 贝利医药原料(苏州)有限公司 | Preparation method of 3,4-ethene dioxythiophene |
| CN101104619A (en) * | 2007-07-24 | 2008-01-16 | 陕西科技大学 | Decarboxylation preparation technique for ethylene dioxythiophene |
| CN101519409A (en) * | 2008-02-27 | 2009-09-02 | 成都丽凯手性技术有限公司 | Method for preparing 3, 4-ethylenedioxythiophene |
Non-Patent Citations (1)
| Title |
|---|
| A.B.KORZHENEVSKII，等: "Influence of the Structure of the Macroheterocyclic Ligand on the Catalytic Properties of Metal Tetraarenoporphyrazine Complexes:III.Oxidative Decarboxylation of Oxalic Acid", 《RUSSIAN JOURNAL OF GENERAL CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633811A (en) * | 2012-05-04 | 2012-08-15 | 苏州大学 | Purification method for preparing high-purity 3,4-ethylenedioxythiophene |
| CN104926713A (en) * | 2015-05-24 | 2015-09-23 | 西北大学 | Synthetic method of polysubstitution 1,2,5,6-tetrahydropyridine compound |
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| CN102241691B (en) | 2014-03-26 |
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