CN101062927B - Preparation method of 3,4-ethene dioxythiophene - Google Patents
Preparation method of 3,4-ethene dioxythiophene Download PDFInfo
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- CN101062927B CN101062927B CN200610040091A CN200610040091A CN101062927B CN 101062927 B CN101062927 B CN 101062927B CN 200610040091 A CN200610040091 A CN 200610040091A CN 200610040091 A CN200610040091 A CN 200610040091A CN 101062927 B CN101062927 B CN 101062927B
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- 238000002360 preparation method Methods 0.000 title claims description 28
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 24
- 235000009508 confectionery Nutrition 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 18
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical class COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- 239000003444 phase transfer catalyst Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 229930192474 thiophene Natural products 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 229960002798 cetrimide Drugs 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- -1 YLENE Chemical compound 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006959 Williamson synthesis reaction Methods 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000005977 Ethylene Substances 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000013065 commercial product Substances 0.000 abstract 1
- 230000000911 decarboxylating effect Effects 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 abstract 1
- 229950006389 thiodiglycol Drugs 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 6
- 239000007859 condensation product Substances 0.000 description 5
- 239000000413 hydrolysate Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 4
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 4
- 229960001826 dimethylphthalate Drugs 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a preparing method of 3, 4-ethylene dioxide thiofuran (EDOT), which comprises the following steps: adopting reasonable processing line; choosing thiodiglycol as initial raw material; esterifying; condensing; Williamson; hydrolyzing; decarboxylating; getting the end product. This invention possesses simple craft, low cost and high receiving rate, which is fit for commercial product.
Description
Technical field
The present invention relates to a kind of compound method of organic cpds, particularly a kind of method of preparation 3,4-ethene dioxythiophene.
Background technology
3,4-ethene dioxythiophene (EDOT), outward appearance are colourless or light yellow transparent liquid, Cas126213-50-1,10.5 ℃ of fusing points, 225 ℃ of boiling points (101.3kpa).It is to be used for preparing polyethylene dioxythiophene (PEDOT) as a kind of electron chemistry articles for use.Polyethylene dioxythiophene is a kind of novel organic conductive luminescent material; Having high conductivity, good environmental stability, film and be prone to advantages such as system and the transparency are good, is the ideal material of electronicss such as the demonstration of preparation organic electroluminescence, solar cell, ultracapacitor plastics antistatic coating, illumination film coating, transmitter, corrosion protection.Because its unique electricity and optical characteristics and wide application field, polyethylene dioxythiophene will cause the extensive concern of novel industry and related industries.
At present, domestic still do not have preparation 3, a 4-ethene dioxythiophene monomeric reported in literature.Foreign literature has been reported with 3; 4-dibromo thiophene is that raw material carries out Ullmann reaction and makes 3,4-ethene dioxythiophene, because the required raw material 3 of this method; 4-dibromo thiophene costs an arm and a leg; And severe reaction conditions, cost are high, product yield is low, cause this method can only be applied to the laboratory, and can not carry out suitability for industrialized production.
Summary of the invention
What the present invention solved is exactly the problem that the method raw materials cost is high, product yield is low of existing preparation 3,4-ethene dioxythiophene, and the preparation method of 3,4-ethene dioxythiophene that a kind of technology is simple, with low cost, yield is higher is provided.It is to be starting raw material with sulfo-two sweet acid, makes through esterification, condensation, etherificate, hydrolysis, decarboxylation five steps reaction, and reaction formula is:
The present invention is to realize through such technical scheme for reaching above purpose, is that starting raw material comprises the steps: with sulfo-two sweet acid
(a) esterification:
With sulfo-two sweet acid, methyl alcohol, catalyst mix; After reaction finishes, after neutralization, SX, drying,, promptly obtain carboxylate sulfo-two sweet dimethyl phthalates again through underpressure distillation;
(b) condensation reaction:
Above-mentioned carboxylate is added in the methanol solution of sodium methylate, add oxalic acid diethyl ester; After reaction finishes, after acidifying, filtration, drying, obtain condensation product 2,5-dioctyl phthalate dimethyl ester-3,4-dihydroxyl thiophene;
(c) Williamson reaction:
With above-mentioned condensation product, 1,2-dihalo-ethane, K
2CO
3, phase-transfer catalyst adds in the solvent; After reaction finishes, reclaim solvent, add water after the cooling, carry out successively obtaining etherificate product 2,5-dioctyl phthalate dimethyl ester-3,4-ethene dioxythiophene after suction filtration, washing, the drying;
(d) hydrolysis reaction:
With the aqueous solution of above-mentioned etherificate product, NaOH, after reaction finishes, carry out acidifying, after suction filtration, washing, drying, obtain hydrolysate 2,5-dioctyl phthalate-3,4-ethene dioxythiophene;
(e) decarboxylic reaction
With said hydrolyzed product, catalyzer, solvent, reaction under nitrogen protection; After reaction finished, through cooling, filtration, solution carried out underpressure distillation, collects the cut of 75～77 ℃ (1.33kpa), promptly gets 3,4-ethene dioxythiophene.
As improvement, step (a) is in the esterification, and the mass ratio of sulfo-two sweet acid, methyl alcohol, catalyzer is 1:2～10:0.1～0.5.Under reflux state, react, by the yield of the synthetic sulfo-two sweet dimethyl phthalates of sulfo-two sweet acid near 95%.
As improvement, step (b) is in the condensation reaction, and the mol ratio of sulfo-two sweet dimethyl phthalates, sodium methylate, oxalic acid diethyl ester is 1:2～5:1～3; This reaction must guarantee anhydrous state; Because of being exothermic process in the reaction process, therefore, must under lower temperature, carry out (0～40 ℃); Operating process is prone to slowly add oxalic acid diethyl ester.The condensation product yield is more than 90%.
As improvement, step (c) is in the etherification reaction, and the mol ratio of sulfo-two sweet dimethyl phthalates, sodium methylate, oxalic acid diethyl ester is 1:2～5:1～3.Solvent is benzene,toluene,xylene, chlorobenzene, ethanol, THF (THF), DMSO organic solvents such as (DMSO 99.8MIN.s).Phase-transfer catalyst is a quaternary ammonium salt-type phase transfer catalyst, like CETRIMIDE POWDER, tetrabutylammonium chloride, tetramethyl ammonium chloride, 4 bromide, Tetrabutyl amonium bromide, tetrabutylammonium iodide, benzyl tributyl brometo de amonio.The quality of phase-transfer catalyst is 2,5-dioctyl phthalate dimethyl ester-3,4-dihydroxyl thiophene, 1,2-dihalo-ethane and K
2CO
30.5～10% of three's quality sum.60～150 ℃ of temperature controls, the actual recovery of etherificate product can reach 65～70%.
As improvement, step (d) is in the hydrolysis reaction, and the mol ratio of 2,5-dioctyl phthalate dimethyl ester-3,4-ethene dioxythiophene, NaOH is 1:2～6, and the concentration of aqueous solution of NaOH is the best with 5%～30%.At 50～100 ℃ of reaction 3～8h, acidifying PH=1～2, the hydrolysate that after filtration, drying, obtains, its yield can reach more than 90%.
As improvement, step (e) is in the decarboxylic reaction, and solvent is meant toluene, YLENE, DMSO (DMSO 99.8MIN.), quinoline, Witcizer 300 etc.; The quality of solvent is 2～10 times of 2,5-dioctyl phthalate-3,4-ethene dioxythiophene quality.Catalyzer is verditer, verditer or their mixture, and catalyst levels is 1%～20% of 2,5-dioctyl phthalate-3,4-ethene dioxythiophene and a solvent quality sum.Hydrolysate is reaction 10～15h under 80～200 ℃, and the product yield after the purification can reach 65～70%.
The preparation method of 3,4-ethene dioxythiophene according to the invention has following characteristics:
(1) yield of product 3,4-ethene dioxythiophene is higher, and total recovery can reach more than 32%.
(2) adopt the high vacuum underpressure distillation, 3, the 4-ethene dioxythiophene product purity that obtains is high, color and luster is attractive in appearance.
(3) technology is simple in the reaction process, does not need HTHP in the reaction.
(4) used solvent can recycle and reuse in the reaction.
(5) required catalyst levels is few, price is low, easy preparation.
(6) synthesis technique of the present invention is simple, production cost is low, product yield is high, clean process is free from environmental pollution, is fit to commercialization production.
Embodiment
Below in conjunction with embodiment the present invention is described further.
The preparation of sulfo-two sweet dimethyl phthalates
Embodiment 1:
With the two sweet acid of 338g (2.25mol) sulfo-, 2560ml methyl alcohol, 135g sulfuric acid (catalyzer) mixes; Stir, be warming up to backflow, reaction times 6～8h, normal pressure steamed methyl alcohol after reaction finished; Cooling, the alkali lye of adding 5% is transferred PH=7～7.5, ether (3*300ml) extraction, anhydrous sodium sulfate drying.Normal pressure concentrates ether, underpressure distillation again, and collecting boiling point is the cut of 172～176 ℃/1.33kPa, promptly obtaining outward appearance is the carboxylate sulfo-two sweet dimethyl phthalate 382.8g of nearly colourless transparent liquid, content 99.3%, yield 94.8%.
Catalyst type and consumption are changed, and other is with embodiment 1, and its result sees table 1.
Table 1
| Embodiment | Catalyzer | Catalyst levels (g) | Sulfo-two sweet dimethyl phthalate amounts (g) | Content (%) | Yield (%) |
| 2 | Sulfuric acid | 35 | 323.7 | 99.1 | 80.0 |
| 3 | Sulfuric acid | 105 | 370.2 | 99.0 | 91.4 |
| 4 | Phosphoric acid | 150 | 226.5 | 99.5 | 56.2 |
| 5 | Tosic acid | 35 | 311.3 | 99.7 | 77.4 |
| 6 | Tosic acid | 168 | 376 | 99.8 | 93.6 |
Methanol usage is changed, and other is with embodiment 1, and its result sees table 2.
Table 2
| Embodiment | Methanol usage (ml) | Sulfo-two sweet dimethyl phthalate amounts (g) | Content (%) | Yield (%) |
| 7 | 855 | 324 | 99.5 | 80.4 |
| 8 | 1700 | 3.59 | 99.0 | 88.7 |
| 9 | 2130 | 372.4 | 99.6 | 92.5 |
| 10 | 3410 | 367.8 | 99.2 | 91.0 |
| 11 | 4250 | 357 | 99.3 | 88.4 |
Temperature of reaction is changed, and other is with embodiment 1, and its result sees table 3.
Table 3
| Embodiment | Temperature of reaction (℃) | Sulfo-two sweet dimethyl phthalate amounts (g) | Content (%) | Yield (%) |
| 12 | 30 | 222 | 99.3 | 55 |
| 13 | 40 | 271.3 | 99.6 | 67.4 |
| 14 | 50 | 329.7 | 99.1 | 81.5 |
| 15 | 60 | 380 | 99.2 | 94.0 |
| 16 | 70 | 380.4 | 99.3 | 94.2 |
The preparation of 2,5-dioctyl phthalate dimethyl ester-3,4-dihydroxyl thiophene
Embodiment 17:
To add by the carboxylate 380g (2.13mol) that embodiment 1 makes in the 2475ml methanol solution of 460g (8.52mol) sodium methylate, drip 772g (5.33mol) oxalic acid diethyl ester, 0～10 ℃ of temperature control down in stirring; Be warming up to backflow after dropwising, reaction times 3～5h is after question response finishes; Reclaim methyl alcohol, add 1L water, use hcl acidifying; After filtration, drying, obtain condensation product 2,5-dioctyl phthalate dimethyl ester-3,4-dihydroxyl thiophene 455g of off-white color pressed powder; Content 99.4%, yield 92%.
The sodium methylate consumption is changed, and other is with embodiment 17, and its result sees table 4.
Table 4
| Embodiment | Sodium methylate consumption (g) | 2,5-dioctyl phthalate dimethyl ester-3,4-dihydroxyl thiophene amount (g) | Content (%) | Yield (%) |
| 18 | 230 | 436.6 | 99.0 | 87.4 |
| 19 | 345 | 449.3 | 99.3 | 90.2 |
| 20 | 518 | 457.8 | 99.5 | 92.1 |
| 21 | 575 | 460.3 | 99.4 | 92.5 |
The oxalic acid diethyl ester consumption is changed, and other is with embodiment 17, and its result sees table 5.
Table 5
| Embodiment | Oxalic acid diethyl ester consumption (g) | 2,5-dioctyl phthalate dimethyl ester-3,4-dihydroxyl thiophene amount (g) | Content (%) | Yield (%) |
| 22 | 308.9 | 418 | 99.4 | 80.4 |
| 23 | 463.3 | 423.4 | 99.4 | 85.1 |
| 24 | 617.7 | 450.9 | 99.6 | 90.8 |
| 25 | 926.6 | 459.3 | 99.5 | 92.4 |
The preparation of 2,5-dioctyl phthalate dimethyl ester-3,4-ethene dioxythiophene
Embodiment 26:
Condensation product 440g (1.9mol), 1198g (6.38mol) 1,2-ethylene dibromide, 503g (3.65mol) K that will make by embodiment 17
2CO
3, 105g CETRIMIDE POWDER (phase-transfer catalyst) adds in the 4500ml toluene (solvent), stir and heat up 90 ℃ of temperature controls; Reaction times 10～15h reclaims solvent and unreacted 1,2-ethylene dibromide with the material concentrating under reduced pressure after question response finishes; Cooling back adds 5L water, stirring at normal temperature 30min, carry out successively after suction filtration, washing, the drying the etherificate product 2 of off-white color to gray solid powder; 5-dioctyl phthalate methyl esters-3; 4-ethene dioxythiophene 319g, content 98.5%, yield 64%.
1,2-ethylene dibromide consumption is changed, and other is with embodiment 26, and its result sees table 6.
Table 6
| Embodiment | 1,2-ethylene dibromide consumption (g) | 2,5-dioctyl phthalate dimethyl ester-3,4-ethene dioxythiophene amount (g) | Content (%) | Yield (%) |
| 27 | 357 | 242.8 | 98.0 | 48.5 |
| 28 | 714 | 274.6 | 97.9 | 54.8 |
| 29 | 1428 | 322.2 | 98.2 | 64.5 |
| 30 | 1606.5 | 321.8 | 98.5 | 64.6 |
| 31 | 1785 | 324.1 | 98.1 | 64.8 |
With K
2CO
3Consumption changes, and other is with embodiment 26, and its result sees table 7.
Table 7
| Embodiment | K 2CO 3Consumption (g) | 2,5-dioctyl phthalate dimethyl ester-3,4-ethene dioxythiophene amount (g) | Content (%) | Yield (%) |
| 32 | 262.2 | 238.1 | 98.5 | 47.8 |
| 33 | 393.3 | 284.6 | 98.6 | 57.2 |
| 34 | 786.6 | 321.9 | 98.3 | 64.5 |
| 35 | 1048.8 | 323.4 | 98.3 | 64.8 |
Phase-transfer catalyst kind and consumption are changed, and other is with embodiment 26, and its result sees table 8.
Table 8
| Embodiment | Phase-transfer catalyst | Phase-transfer catalyst consumption (g) | 2,5-dioctyl phthalate dimethyl ester-3,4-ethene dioxythiophene amount (g) | Content (%) | Yield (%) |
| 36 | Tetrabutylammonium chloride | 25 | 191.1 | 98.6 | 38.4 |
| 37 | Tetrabutylammonium chloride | 250 | 247.8 | 98.2 | 49.6 |
| 38 | Tetrabutyl amonium bromide | 25 | 213.6 | 98.3 | 42.8 |
| 39 | Tetrabutyl amonium bromide | 250 | 266.7 | 98.4 | 53.5 |
| 40 | Tetrabutylammonium iodide | 25 | 224.3 | 98.0 | 44.8 |
| 41 | Tetrabutylammonium iodide | 250 | 274.8 | 98.0 | 54.9 |
| 42 | CETRIMIDE POWDER | 25 | 248.6 | 97.9 | 49.6 |
| 43 | CETRIMIDE POWDER | 50 | 281.6 | 98.6 | 56.6 |
| 44 | CETRIMIDE POWDER | 150 | 319.1 | 98.7 | 64.2 |
| 45 | CETRIMIDE POWDER | 250 | 322.1 | 98.7 | 64.8 |
Solvent species and consumption are changed, and other is with embodiment 26, and its result sees table 9.
Table 9
| Embodiment | Solvent | Solvent load (ml) | 2,5-dioctyl phthalate dimethyl ester-3,4-ethene dioxythiophene amount (g) | Content (%) | Yield (%) |
| 46 | THF | 2000 | 146 | 95.8 | 28.5 |
| 47 | THF | 4000 | 167.8 | 96.2 | 32.9 |
| 48 | Benzene | 2000 | 231.9 | 96.9 | 45.8 |
| 49 | Benzene | 4000 | 259.4 | 97.4 | 51.5 |
| 50 | Ethanol | 2000 | 196.3 | 97.2 | 38.9 |
| 51 | Ethanol | 4000 | 212.1 | 96.0 | 41.5 |
| 52 | Toluene | 2000 | 263.3 | 98.0 | 52.6 |
| 53 | Toluene | 3500 | 291.4 | 98.0 | 58.2 |
| 54 | Toluene | 5500 | 321.9 | 98.3 | 64.5 |
Temperature of reaction is changed, and other is with embodiment 26, and its result sees table 10.
Table 10
| Embodiment | Temperature of reaction (℃) | 2,5-dioctyl phthalate dimethyl ester-3,4-ethene dioxythiophene amount (g) | Content (%) | Yield (%) |
| 55 | 60 | 211.7 | 98.5 | 42.5 |
| 56 | 70 | 262.5 | 98.3 | 52.6 |
| 57 | 80 | 293.3 | 98.2 | 58.7 |
| 58 | 100 | 311.6 | 98.1 | 62.3 |
| 59 | 110 | 303.3 | 97.2 | 60.1 |
| 60 | 150 | 209.5 | 96.5 | 41.2 |
The preparation of 2,5-dioctyl phthalate-3,4-ethene dioxythiophene
Embodiment 61:
To stir, be warming up to backflow after mixing by etherificate product 310g (1.18mol), 198.5g (4.96mol) NaOH, the 2L water that embodiment 26 makes, reaction times 3～5h reduces to room temperature and carries out acidifying adjusting PH=1～2 with dilute sulphuric acid after question response finishes; Separate out gray precipitate; Obtain hydrolysate 2,5-dioctyl phthalate-3,4-ethene dioxythiophene 257g of gray solid powder after suction filtration, a small amount of washing, the drying; Content 99.4%, yield 94.6%.
The NaOH consumption is changed, and other is with embodiment 61, and its result sees table 11.
Table 11
| Embodiment | NaOH consumption (g) | 2,5-dioctyl phthalate-3,4-ethene dioxythiophene amount (g) | Content (%) | Yield (%) |
| 62 | 94.4 | 242.3 | 99.1 | 88.4 |
| 63 | 141.6 | 250.5 | 99.2 | 91.5 |
| 64 | 236 | 258.2 | 99.6 | 94.7 |
| 65 | 283.2 | 259 | 99.4 | 94.8 |
The water yield that adds in the reaction is changed, and other is with embodiment 61, and its result sees table 12.
Table 12
| Embodiment | Water consumption (L) | 2,5-dioctyl phthalate-3,4-ethene dioxythiophene amount (g) | Content (%) | Yield (%) |
| 66 | 0.48 | 188.5 | 99.0 | 68.7 |
| 67 | 1.1 | 226.9 | 99.1 | 82.8 |
| 68 | 2.5 | 254.1 | 99.2 | 92.8 |
| 69 | 3.7 | 237.9 | 99.2 | 86.9 |
Temperature of reaction is changed, and other is with embodiment 61, and its result sees table 13.
Table 13
| Embodiment | Temperature of reaction (℃) | 2,5-dioctyl phthalate-3,4-ethene dioxythiophene amount (g) | Content (%) | Yield (%) |
| 70 | 50 | 203.3 | 99.0 | 74.1 |
| 71 | 70 | 225.3 | 99.2 | 82.3 |
| 72 | 80 | 237.7 | 99.3 | 86.9 |
| 73 | 90 | 247.2 | 99.0 | 90.1 |
The preparation of 3,4-ethene dioxythiophene
Embodiment 74:
To under nitrogen protection, stir intensification, 160 ℃ of temperature controls, reaction times 10～12h by hydrolysate 255g (1.1mol), 100g verditer (catalyzer), the 1250ml quinoline (solvent) that embodiment 61 makes.React the postcooling that finishes, leach catalyzer, solution carries out underpressure distillation, and the cut of collecting 75～77 ℃/1.33kpa promptly gets decarboxylate 3,4-ethene dioxythiophene 103g of nearly colourless transparent liquid, yield 65.9%, content 99.5%.
Catalyst type and consumption are changed, and other is with embodiment 74, and its result sees table 14.
Table 14
Solvent species and consumption are changed, and other is with embodiment 74, and its result sees table 15.
Table 15
| Embodiment | Solvent | Solvent load (ml) | 3,4-ethene dioxythiophene amount (g) | Content (%) | Yield (%) |
| 89 | YLENE | 1250 | 53 | 98.5 | 33.4 |
| 90 | YLENE | 2250 | 60.6 | 98.3 | 38.1 |
| 91 | Quinoline | 550 | 82.7 | 99.1 | 52.4 |
| 92 | Quinoline | 900 | 92.3 | 99.0 | 58.4 |
| 93 | Quinoline | 2000 | 103.7 | 99.2 | 65.8 |
| 94 | Witcizer 300 | 550 | 65.8 | 98.6 | 41.5 |
| 95 | Witcizer 300 | 900 | 79.6 | 98.4 | 50.1 |
| 96 | Witcizer 300 | 1800 | 85.1 | 98.1 | 53.4 |
Temperature of reaction is changed, and other is with embodiment 74, and its result sees table 16.
Table 16
| Embodiment | Temperature of reaction (℃) | 3,4-ethene dioxythiophene amount (g) | Content (%) | Yield (%) |
| 97 | 80 | 64.9 | 99.1 | 41.1 |
| 98 | 100 | 85.0 | 99.7 | 54.2 |
| 99 | 150 | 96.2 | 99.2 | 61.5 |
| 100 | 180 | 98.8 | 99.4 | 62.8 |
| 101 | 200 | 84.3 | 99.5 | 53.6 |
Claims (14)
1.3 the preparation method of 4-ethene dioxythiophene is characterized in that, comprises the steps:
(a) esterification:
With sulfo-two sweet acid, methyl alcohol, catalyst mix; After reaction finishes, after neutralization, SX, drying,, promptly obtain sulfo-two sweet dimethyl phthalates again through underpressure distillation;
(b) condensation reaction:
Above-mentioned gained sulfo-two sweet dimethyl phthalates are added in the methanol solution of sodium methylate, add oxalic acid diethyl ester; After reaction finishes, after acidifying, filtration, drying, obtain 2,5-dioctyl phthalate dimethyl ester-3,4-dihydroxyl thiophene;
(c) Williamson reaction:
With above-mentioned gained 2,5-dioctyl phthalate dimethyl ester-3,4-dihydroxyl thiophene, 1,2-dihalo-ethane, K
2CO
3, phase-transfer catalyst adds in the solvent; After reaction finishes, reclaim solvent, add water after the cooling, carry out obtaining 2 after suction filtration, washing, the drying 5-dioctyl phthalate dimethyl ester-3,4-ethene dioxythiophene successively;
(d) hydrolysis reaction:
With above-mentioned gained 2,5-dioctyl phthalate dimethyl ester-3, the aqueous solution of 4-ethene dioxythiophene, NaOH after reaction finishes, is carried out acidifying, after suction filtration, washing, drying, obtains 2,5-dioctyl phthalate-3,4-ethene dioxythiophene;
(e) decarboxylic reaction
With above-mentioned gained 2,5-dioctyl phthalate-3,4-ethene dioxythiophene, catalyzer, solvent, reaction under nitrogen protection; After reaction finished, through cooling, filtration, solution carried out underpressure distillation, collects the cut of 75～77 ℃/1.33kpa, promptly gets 3, the 4-ethene dioxythiophene;
Phase-transfer catalyst described in the step (c) is CETRIMIDE POWDER, tetrabutylammonium chloride, tetramethyl ammonium chloride, 4 bromide, Tetrabutyl amonium bromide, tetrabutylammonium iodide, benzyl tributyl brometo de amonio; The quality of phase-transfer catalyst is 2; 5-dioctyl phthalate dimethyl ester-3; 4-dihydroxyl thiophene, 1,2-dihalo-ethane and K
2CO
30.5～10% of three's quality sum;
The mass ratio of the two sweet acid of sulfo-described in the step (a), methyl alcohol, catalyzer is 1: 2～10: 0.1～0.5, and catalyzer is meant phosphoric acid, sulfuric acid, hydrochloric acid, tosic acid.
2. said 3 according to claim 1, the preparation method of 4-ethene dioxythiophene is characterized in that the temperature of reaction in the step (a) is 30～80 ℃.
3. according to claim 1 said 3; The preparation method of 4-ethene dioxythiophene; The mol ratio that it is characterized in that the sulfo-two sweet dimethyl phthalates described in the step (b), sodium methylate, oxalic acid diethyl ester is 1: 2～5: 1～3, and the concentration of described sodium methylate in methanol solution is 10%～30%.
4. said 3 according to claim 1, the preparation method of 4-ethene dioxythiophene is characterized in that 2 described in the step (c), 5-dioctyl phthalate dimethyl ester-3,4-dihydroxyl thiophene, 1,2-dihalo-ethane, K
2CO
3Mol ratio be 1: 1～5: 1～4.
5. said 3 according to claim 1, the preparation method of 4-ethene dioxythiophene is characterized in that 1 described in the step (c), and the halo group is iodine, bromine or chlorine in the 2-dihalo-ethane.
6. said 3 according to claim 1, the preparation method of 4-ethene dioxythiophene is characterized in that the solvent described in the step (c) is benzene,toluene,xylene, chlorobenzene, ethanol, THF, DMSO 99.8MIN..
7. said 3 according to claim 1, the preparation method of 4-ethene dioxythiophene is characterized in that the temperature of reaction in the step (c) is 60～150 ℃.
8. according to claim 1 said 3; The preparation method of 4-ethene dioxythiophene is characterized in that 2 described in the step (d), 5-dioctyl phthalate dimethyl ester-3; The mol ratio of 4-ethene dioxythiophene, NaOH is 1: 2～6, and the concentration of aqueous solution of described NaOH is 5%～30%.
9. said 3 according to claim 1, the preparation method of 4-ethene dioxythiophene is characterized in that the temperature of reaction in the step (d) is 50～100 ℃.
10. said 3 according to claim 1, the preparation method of 4-ethene dioxythiophene is characterized in that the catalyzer described in the step (e) is verditer, verditer or their mixture.
11. said 3 according to claim 1, the preparation method of 4-ethene dioxythiophene is characterized in that the catalyst levels described in the step (e) is 2,5-dioctyl phthalate-3,1%～20% of 4-ethene dioxythiophene and solvent quality sum.
12. said 3 according to claim 1, the preparation method of 4-ethene dioxythiophene is characterized in that the solvent described in the step (e) is meant toluene, YLENE, DMSO 99.8MIN., quinoline, Witcizer 300.
13. said 3 according to claim 1, the preparation method of 4-ethene dioxythiophene, the quality that it is characterized in that the solvent in the step (e) is 2,5-dioctyl phthalate-3,2～10 times of 4-ethene dioxythiophene quality.
14. said 3 according to claim 1, the preparation method of 4-ethene dioxythiophene is characterized in that the temperature of reaction in the step (e) is 80～200 ℃.
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| CN101591345B (en) * | 2008-05-27 | 2011-11-23 | 台氟科技股份有限公司 | Synthesizing method of conductive high polymer monomer |
| CN102002057B (en) * | 2010-11-24 | 2012-08-01 | 三门峡奥科化工有限公司 | Preparation method for 3,4-ethylene dioxythiophene-2,5-dicarboxylic acid dimethyl ester |
| CN102477044A (en) * | 2010-11-26 | 2012-05-30 | 苏州凯达生物医药技术有限公司 | Synthetic method of monomer 3,4-ethylenedioxythiophene (EDOT) of conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) |
| CN102558195A (en) * | 2011-03-30 | 2012-07-11 | 贝利医药原料(苏州)有限公司 | Process for preparing 2,5-dimethyl isophthalate-3,4-ethylenedioxythiophene |
| CN102241691B (en) * | 2011-07-13 | 2014-03-26 | 西北大学 | Decarboxylation method of 3,4-ethylenedioxy thiophene |
| CN102924471B (en) * | 2011-08-09 | 2015-04-15 | 远东新世纪股份有限公司 | 3,4-ethylenedioxythiophene preparation method |
| CN102382122A (en) * | 2011-09-19 | 2012-03-21 | 武汉市祥德科技发展有限公司 | Preparation technology of 2,5-dioctyl phthalate-3,4-ethylenedioxy thiophene |
| JP2014201545A (en) * | 2013-04-04 | 2014-10-27 | 東ソー株式会社 | METHOD OF MANUFACTURING 2-HYDROXYMETHYL-2,3-DIHYDRO-THIENO[3,4-b][1,4]DIOXIN-5,7-DICARBOXYLIC ACID DIALKYL ESTER |
| JP6260385B2 (en) * | 2014-03-24 | 2018-01-17 | 東ソー株式会社 | Method for producing 2-hydroxymethyl-2,3-dihydro-thieno [3,4-b] [1,4] dioxin-5,7-dicarboxylic acid dialkyl ester |
| CN104016999A (en) * | 2014-06-27 | 2014-09-03 | 江西科技师范大学 | Method for preparing 3,4-alkylenedioxyfuran compound |
| CN104497006A (en) * | 2014-11-26 | 2015-04-08 | 千辉药业（安徽）有限责任公司 | Preparation method for 3,4-ethylenedioxythiophene |
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