CN107880014A - A kind of synthetic method of 3,4 dimethoxy-thiophene - Google Patents
A kind of synthetic method of 3,4 dimethoxy-thiophene Download PDFInfo
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- CN107880014A CN107880014A CN201711047689.3A CN201711047689A CN107880014A CN 107880014 A CN107880014 A CN 107880014A CN 201711047689 A CN201711047689 A CN 201711047689A CN 107880014 A CN107880014 A CN 107880014A
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- dimethoxy
- thiophenes
- ester
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- dimethylformamide
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- ZUDCKLVMBAXBIF-UHFFFAOYSA-N 3,4-dimethoxythiophene Chemical compound COC1=CSC=C1OC ZUDCKLVMBAXBIF-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000010189 synthetic method Methods 0.000 title claims abstract description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 14
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000009413 insulation Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- -1 formyl amine Chemical class 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- 235000019253 formic acid Nutrition 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 21
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000007127 saponification reaction Methods 0.000 abstract description 6
- 239000012267 brine Substances 0.000 abstract description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract description 5
- 238000012805 post-processing Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- JBOAELCPSXBGSR-UHFFFAOYSA-N 2,3-dimethoxythiophene Chemical compound COC=1C=CSC=1OC JBOAELCPSXBGSR-UHFFFAOYSA-N 0.000 abstract 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000003987 high-resolution gas chromatography Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940006460 bromide ion Drugs 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 101150041968 CDC13 gene Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- DPPYVKXVOFYYKT-UHFFFAOYSA-N sodium;thiophene Chemical compound [Na].C=1C=CSC=1 DPPYVKXVOFYYKT-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/32—Oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a kind of synthetic method of 3,4 dimethoxy-thiophenes, this method is by 2, the dimethoxy-thiophene of 5 dicarboxylic acid dimethyl ester 3,4 is dissolved in dimethylformamide in water, adds de- ester catalyst, it it is 130 180 DEG C in temperature, pressure is 0 10 kg/cm2After 5 18h are reacted under (table), filtered, rectification under vacuum obtains 3,4 dimethoxy-thiophenes, wherein, filtering and rectification under vacuum are carried out under heat-insulation pressure keeping state.This method is eliminated the intermediate links such as saponification, acidifying, shortens synthetic route, reduced the consumption of raw material using de- ester technology, the generation of spent brine solution is especially the reduction of, reduces integrated cost, simplifies postprocessing working procedures, whole piece synthetic route is more environmentally friendly, safer, more efficient.
Description
Technical field
The present invention relates to a kind of synthetic method of heterocyclic compound, and in particular to the synthesis of one kind 3,4- dimethoxy-thiophenes
Method.
Background technology
The polymer of 3,4- dimethoxy-thiophenes is mainly for the production of solid capacitor, organic thin film solar cell material
Material, OLED material, electrochromic material, antistatic material etc., there is the strong transparency, electrical conductivity height, stability is good, is easy to add
A variety of advantages such as work, in the high science and technology market field such as new energy, demand is very powerful.
Had early in 2006《One-pot synthesis of 3,4-dimethoxy thiophene》Report, its process route mainly pass through thiophene
Fen bromination, selective reduction, o-alkylation obtain target product.The deadly defect of the technique is using the extremely strong bromine of corrosivity
Element, not only course of reaction is extremely unfriendly to environment, corrosion resistance to equipment requires very high；And bromide ion remains in its product
Height, directly affect product quality；And in mother liquor, in product and in postprocessing working procedures, every solution containing bromide ion, even
Low concentration, also there is strong corrosivity to relevant device, operation difficulty is big, and production environment is poor, production equipment and scene
Auxiliary equipment seriously corroded, safeguard and maintenance difficult, sewage disposal expense is very high, belongs to superseded chemical production technology.
Domestic classical industrialized production route is for initiation material, through four with 2,5- dicarboxylic acid methyl ester -3,4- diphenol sodium thiophene at present
Footwork sintetics 3,4- dimethoxy-thiophenes.But process route is longer, technology falls behind, and total recovery is relatively low, only 72.2
~80.3%, particularly in first step saponification, second step acidization, first add excessive NaOH and carry out saponification, reacted
Excessive H is added after2SO4Carry out acidifying neutralization, then by centrifugal filtration, plus water washing remove byproduct sulfate and
Other organic matters, isolated intermediate products 2,5- dioctyl phthalate -3,4- dimethoxy-thiophenes, decarboxylation are gone again after drying water removal.
Not only process route is added equipment investment and energy resource consumption, is also increased operation difficulty and manpower consumption by meaningless extension, also
Substantial amounts of effluent brine is generated, causes wastewater treatment process operations difficult, integrated cost rises.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide the synthesis side of one kind 3,4- dimethoxy-thiophenes
Method, this method are eliminated the intermediate links such as saponification, acidifying, shorten synthetic route, reduced disappearing for raw material using de- ester technology
Consumption, is especially the reduction of the generation of spent brine solution, reduces integrated cost, simplifies postprocessing working procedures, whole piece synthetic route is more
Environmental protection, it is safer, it is more efficient.
To solve prior art problem, the technical scheme that the present invention takes is：
The synthetic method of one kind 3,4- dimethoxy-thiophenes, 2,5- dicarboxylic acid dimethyl ester -3,4- dimethoxy-thiophenes is molten
In dimethylformamide in water, de- ester catalyst is added, is 130-180 DEG C in temperature, gauge 0-10kg/
cm2After lower reaction 5-18h, filtered, rectification under vacuum obtains 3,4- dimethoxy-thiophenes, wherein, filtering and rectification under vacuum are being protected
Carried out under warm packing state.
It is 2,5- dicarboxylic acid dimethyl esters -3,4- dimethoxy-thiophene and dimethyl formamide solution as improved
Mass ratio be 1:2-5.
It is 2,5- dicarboxylic acid dimethyl esters -3,4- dimethoxy-thiophene and dimethyl formamide solution as improved
Mass ratio be 1:3.
It is that the mass ratio of dimethylformamide and water is 5-8 in the dimethylformamide in water as improved:
1。
It is that the mass ratio of dimethylformamide and water is 7 in the dimethylformamide in water as improved:1.
It is that the de- ester catalyst is cupric oxide as improved.
It is that the quality of the de- ester catalyst is 2,5- dicarboxylic acid dimethyl ester -3,4- dimethoxy-thiophenes as improved
1-9% times.
It is that the quality of the de- ester catalyst is 2,5- dicarboxylic acid dimethyl ester -3,4- dimethoxy-thiophenes as improved
3% times.
Reaction scheme is as follows：
Compared with prior art, innovative point of the invention resides in reduced product " production stage ", eliminate " unnecessary "
Production process, while the consumption of the public work such as raw and auxiliary material and water power vapour is reduced, decrease equipment investment and manually disappear
Consumption；Even more important meaning is, eliminates the generation for the inorganic salt waste for being difficult to handle.Because a large amount of inorganic salts enter waste water
Afterwards, many strains that can make to cultivate in sewage disposal system are poisoned, and cause systemic breakdown.So the salt of this this by-product can not enter
Enter sewage disposal system, it is necessary to separately build set of device, recycled.This not only wastes substantial amounts of human and material resources, simultaneously
Substantial amounts of solid waste is also produced, it is necessary to which spending a large amount of expenses to be sent to qualified unit goes burning disposal.With following advantage：
1st, " saponification, acidifying, filtering, washing, drying, decarboxylation " process in classical technique is improved to directly remove by the present invention
Ester group.By yield from 75% or so, 89.6~94.8% are brought up to；Eliminate caustic soda consumption, acid that saponification process needs to add
The sulfuric acid consumption added during change, process route is shortened, is especially a cancellation the generation of spent brine solution in classical process,
Integrated cost reduces, and postprocessing working procedures simplify, and the process route of whole product is more safe and environment-friendly, efficient；
2nd, after the mixed solvent of DMF and the water composition added in the present invention separates with product rectifying, it can directly cover and use down
In a batch of synthetic reaction, convenient post-treatment is quick, meets the requirement of national green environmental protection；
3rd, product purity produced by the invention is up to 98~99%, no any processing of needs, can be directly used for downstream electronic
The production of product, meet the increasingly powerful market demand.
Brief description of the drawings
Fig. 1 is the route map that prior art synthesizes 3,4- dimethoxy-thiophenes.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various replacements or modification to the present invention, but these are replaced or modification is each fallen within protection scope of the present invention.
Embodiment 1
The synthetic method of one kind 3,4- dimethoxy-thiophenes, reacted in volume 1000ml, pressure-resistant 3MPa stainless steel lab scale
In kettle, 2,5- dicarboxylic acid methyl ester -3,4- dimethoxy-thiophene 100g (purity 98.6%) are added, are dissolved in dimethylformamide DMF
The quality of the aqueous solution, wherein dimethylformamide is 265g, water 35g, adds CuO 3g, capping kettle and in stirring
Lower heating, reaction temperature is kept at 170 ± 5 DEG C, control reaction pressure is in 6 ± 0.5kg/cm2(table), it is anti-under heat-insulation pressure keeping state
Answer 8.5 hours.After completion of the reaction, filter while hot, filter residue adds a small amount of DMF to wash, and its cleaning solution merges decompression essence with filtered fluid
Evaporate, obtain product 3,4- dimethoxy-thiophene 52.37g, purity 98.9%, yield 94.8%.The DMF solution that rectifying goes out can follow
Ring uses.
The product of embodiment 1 is detected, the data obtained is as shown in the table.
Embodiment 2
The synthetic method of one kind 3,4- dimethoxy-thiophenes, reacted in volume 1000ml, pressure-resistant 3MPa stainless steel lab scale
In kettle, 2,5- dicarboxylic acid methyl ester -3,4- dimethoxy-thiophene 100g (purity 98.6%) are added, are dissolved in dimethylformamide DMF
In the aqueous solution, wherein the quality of dimethylformamide is 430g, water 70g, adds CuO 8.9g, and capping kettle is simultaneously stirring
Being heated under state, 130 DEG C start to react and (have a small amount of bubble to produce) in observing response kettle, persistently overheating up to 160 ± 5 DEG C,
Reaction pressure is controlled in 5.5 ± 0.5kg/cm2(table), react 5 hours under heat-insulation pressure keeping state.After completion of the reaction, mistake while hot
Filter, filter residue add a small amount of DMF to wash, and its cleaning solution merges rectification under vacuum with filtered fluid, obtains product 3,4- dimethoxy-thiophenes
48.95g, purity 99.1%, yield 89.6%.The DMF solution that rectifying goes out can be recycled.
Embodiment 3
The synthetic method of one kind 3,4- dimethoxy-thiophenes, reacted in volume 1000ml, pressure-resistant 3MPa stainless steel lab scale
In kettle, 2,5- dicarboxylic acid methyl ester -3,4- dimethoxy-thiophene 100g (purity 98.6%) are added, are dissolved in dimethylformamide DMF
In the aqueous solution, wherein, DMF 175g, water 35g, CuO 1g are added, capping kettle simultaneously heats under stirring, keeps anti-
Temperature is answered at 175 ± 5 DEG C, control reaction pressure is in 9.5 ± 0.5kg/cm2(table), react 18 hours under heat-insulation pressure keeping state.Instead
After answering, heat filtering is remained, filter residue adds a small amount of DMF to wash, and its cleaning solution merges rectification under vacuum with filtered fluid, obtains product 3,
4- dimethoxy-thiophene 49.92g, purity 98.6%, yield 90.1%.The DMF solution that rectifying goes out can be recycled.
Embodiment 1-3 product is detected,
Below by proton nmr spectra, mass spectrum, the compound 3 that high resolution gas chromatography synthesizes to the present invention, 4- dimethoxies
Base thiophene is characterized.
(1) hydrogen nuclear magnetic resonance modal data is as follows：
H-NMR (400MHz, CDC13):δ=3.80 (s, 6H, 2-OCH3), 6.08 (s, 2H, thiphene ring hydrogen), nuclear magnetic resonance
Measurement result is 3,4- dimethoxy-thiophenes.
(2) mass spectrograph determination data is as follows：
ESI-MS (m/z, %) 145.The compound molecular weight is 144, and it is I [M+H] to occur 145 in spectrogram+Signal, matter
Spectrum measurement result is defined as 3,4- dimethoxy-thiophenes.
(3) high resolution gas chromatography：
Purity is 98~99%.
The above-mentioned proton nmr spectra of comprehensive analysis, mass spectrum, high resolution gas chromatography, show that the compound that the present invention synthesizes is 3,
4- dimethoxy-thiophenes.Its structural formula is：
Total recovery of the present invention reaches 89.6~94.8%.
The present invention is by raw material 2,5- dicarboxylic acid dimethyl ester -3,4- dimethoxy-thiophenes, in specific mixed solvent and catalysis
Under the conditions of agent, certain temperature and pressure are kept, prepares purpose product 3,4- dimethoxy-thiophenes through single step reaction, and pass through nuclear-magnetism
Resonate hydrogen spectrum, mass spectrum, and high resolution gas chromatography carries out data characterization.Present invention process route is ingenious to make use of directly de- ester technology,
Process route is short, and production efficiency is high, and integrated cost is low, and discharge of wastewater is few, and that particularly generally acknowledges at present in environmental protection is reluctant
Brine waste is eliminated, and convenient post-treatment is quick.Product yield of the present invention be up to 89.6~94.8%, high purity 98~
99%.
In addition, the invention is not restricted to above-mentioned embodiment, as long as in without departing from the scope of the present invention, can take various
Mode implements the present invention.
Claims (8)
1. one kind 3, the synthetic method of 4- dimethoxy-thiophenes, it is characterised in that by 2,5- dicarboxylic acid dimethyl ester -3,4- dimethoxies
Base thiophene is dissolved in dimethylformamide in water, adds de- ester catalyst, is 130-180 DEG C in temperature, gauge is
0-10 kg/cm2After lower reaction 5-18h, filtered, rectification under vacuum obtains 3,4- dimethoxy-thiophenes, wherein, filtering and decompression essence
Evaporate and carried out under heat-insulation pressure keeping state.
A kind of 2. synthetic method of 3,4- dimethoxy-thiophenes according to claim 1, it is characterised in that 2, the 5- bis-
The mass ratio of formic acid dimethyl ester -3,4- dimethoxy-thiophenes and dimethyl formamide solution is 1:2-5.
A kind of 3. synthetic method of 3,4- dimethoxy-thiophenes according to claim 2, it is characterised in that 2, the 5- bis-
The mass ratio of formic acid dimethyl ester -3,4- dimethoxy-thiophenes and dimethyl formamide solution is 1:3.
A kind of 4. synthetic method of 3,4- dimethoxy-thiophenes according to claim 1, it is characterised in that the dimethyl
The mass ratio of dimethylformamide and water is 5-8 in formyl amine aqueous solution:1.
A kind of 5. synthetic method of 3,4- dimethoxy-thiophenes according to claim 4, it is characterised in that the dimethyl
The mass ratio of dimethylformamide and water is 7 in formyl amine aqueous solution:1.
6. the synthetic method of a kind of 3,4- dimethoxy-thiophenes according to claim 1, it is characterised in that the de- ester is urged
Agent is cupric oxide.
7. the synthetic method of a kind of 3,4- dimethoxy-thiophenes according to claim 1, it is characterised in that the de- ester is urged
The quality of agent is 1-9% times of 2,5- dicarboxylic acid dimethyl ester -3,4- dimethoxy-thiophenes.
8. the synthetic method of a kind of 3,4- dimethoxy-thiophenes according to claim 7, it is characterised in that the de- ester is urged
The quality of agent is 3% times of 2,5- dicarboxylic acid dimethyl ester -3,4- dimethoxy-thiophenes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112209945A (en) * | 2020-11-10 | 2021-01-12 | 湖北吉和昌化工科技有限公司 | Synthesis process of 3, 4-ethylenedioxythiophene |
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| CN103254169A (en) * | 2013-04-18 | 2013-08-21 | 青岛和成医药化工有限公司 | Process for synthesizing 3, 4-dimethoxythiophene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103254169A (en) * | 2013-04-18 | 2013-08-21 | 青岛和成医药化工有限公司 | Process for synthesizing 3, 4-dimethoxythiophene |
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| FALL M等: "《Revisiting the electropolymerization of 3,4-dimethoxythiophene in organic and micellar media》", 《SYNTHETIC METALS》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112209945A (en) * | 2020-11-10 | 2021-01-12 | 湖北吉和昌化工科技有限公司 | Synthesis process of 3, 4-ethylenedioxythiophene |
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