3,4-Ethylenedioxythiophene

Light yellow liquid

A solution of 3, 4-ethylenedioxy-2, 5-dicarboxylate thiophene (209 g, 0.73 mol) was dissolved in dimethylsulfoxide and water (Volume ratio of 4: 1, 1.5L), sodium chloride (128 g, 2.19 mol) was added and heated to 120 ° C for 4 hours. After the completion of the reaction, the dimethyl sulfoxide, , By-product ethyl formate and product 3, 4-ethylenedioxythiophene (EDOT), EDOT 86g, yield 83percent, product EDOT colorless liquidThe following production was carried out using 3, 4-dimethoxythiophene prepared by the same production method as in described above. This also applies to Examples 5 to 9 and Comparative Examples 3 to 9 described below.First, 10.1 g of 3, 4-dimethoxythiophene, 6.74 g of ethylene glycol, 1.1 g of p-toluenesulfonic acid monohydrate and 76.6 g of toluene were placed in a 100 ml four-necked flask, and the mixture was heated and stirred in an argon atmosphere.And heated to 100 DEG C while distilling methanol at 95 deg. At 100 , the methanol flow terminated and toluene reflux started.The compositional change in the reaction solution was followed by gas chromatography using N, N-dimethylformamide as an internal standard. As a result, 3, 4-dimethoxythiophene was found to be below the detection limit at the reflux time of 3 hours. Table 1 summarizes the relationship between the time from the start of reflux of toluene and the concentration of each component.The EDOT, DMEOT, mono- and di-substituents in Table 1 are3, 4-ethylenedioxythiophene, 3, 4-dimethoxythiophene, One in which one methoxy group of 3, 4-dimethoxythiophene is substituted with ethylene glycol, And methoxy groups of 3, 4-dimethoxythiophene were replaced with ethylene glycol The conversion (percent) in the table is theoretically 3, 4-ethylenedioxythiophene when N, N-dimethoxyformamide is measured by gas chromatography as an internal standard, Represents the ratio of the amount of 4-ethylenedioxythiophene.The residual ratio (percent) likewise represents the ratio of the actual amount of 3, 4-dimethoxythiophene in the reaction solution to the amount of 3, 4-dimethoxythiophene in theory.The reaction mixture was diluted with water, the insoluble material was removed by filtration, the crude product was extracted from toluene, the toluene layer was washed with water, washed with aqueous sodium hydrogencarbonate solution, and then dried with magnesium sulfate.After the magnesium sulfate was removed by filtration, the toluene layer was concentrated on a rotary evaporator to obtain a crude product.The yield of the crude product was 6.78 g (68.1percent) and the purity was 98.69percent by gas chromatography.The crude product was subjected to vacuum distillation to obtain 4.65 g (yield: 46.7percent) of 3, 4-ethylenedioxythiophene. The purity of its 3, 4-ethylenedioxythiophene was 99.64percent by gas chromatography.[0032] 3, 4-Ethylenedioxy-2, 5-thiophenedicarboxylic acid (460 g) and a copper powder (69 g) were added to ethylene glycol (1400 g) at room temperature. The reaction mixture was stirred under air for 30 minutes at room temperature, and air was continuously introduced into the reaction mixture. The reaction mixture was then heated at 140° C. for 8 hours. After the reaction was complete, the reaction mixture was purified using the same process as described in to obtain 3, 4-ethylenedioxythiophene (281 g, purity: 98percent).General procedure: Example E1 A mixed molten salt composed of 15 times the amount of potassium nitrate, sodium nitrate and sodium nitrite (of which potassium nitrate, sodium nitrate: nitriteAcid 5: 4: 1) was used as a dispersant, and the reaction was carried out at 250 ° C for 4.5 hours under the condition of introduction of CO2, and thieno [3, 4-b] -1, 4-dioxa-5, 7-dicarboxylic acid was directly decarboxylated to give 3, 4-ethylenedioxythiophene in a yield of 95percent.[Example 1] Decarboxylation using DBu/CuBr as a catalyst; [34] A 3, 4-ethylenedioxy-2, 5-thiophenedicarboxylic acid of 23g, l, 8-Diazabicyclo[5.4.0]undec-7-ene (DBU) of 3g, and CuBr of 2g were added to polyethylene glycol (PEG 400) of 60ml and mixed together. After the mixture was stirred at 15OGeneral procedure: A mixture 3, 4-dialcoxythiophene-2, 5-dicarboxylic acid (0.5 mmol), Ag2CO3 (0.20mmol, 55.15 mg) in DMSO (1.0 mL) was magnetically stirred. After 5 minutes, AcOH (1 mmol, 56 μl) was added, the microwave tube was closed and the mixture was heated using the microwaves reactor. The reaction was carried out during 30min when the temperature of the experiments reached 120 the 2, 5-dicarboxylic acid -34-ethylene dioxy thiophene 110.3g into the flask, add 40g catalyst, 1L ionic liquid is used as a solvent, the temperature is increased to 180 °C, reaction 20h; to room temperature after the reaction, distilled under reduced pressure to obtain 3, 4-ethylene dioxy thiophene 70.5g, The above-mentioned the resulting 2, 5-dicarboxylic acid -3, 4 ethylene dioxy thiophene with the catalyst, in order to ion liquid as the reaction solvent, under the protection of nitrogen reaction, cooling after the reaction, the solution is distilled under reduced pressure to obtain 3, 4-ethylene dioxy thiophene.To 10L flask, 3, 4-ethoxy thiophene 218g (1.27mmol), p- toluene sulfonic acid 24.1g (0.12mol, 9.4mol against DET1mol), hydroquinone 7.0g (0.06mol, DET1mol against 4.7mol), after the ethylene glycol 617g (10.9mmol, the 8.6mol) and o- xylene 4.36kg (20 parts by weight with respect to DET1 parts by weight) to DET1mol was added under a nitrogen atmosphere, xylene reflux, and reacted for 4 hours (xylene reflux temperature = 137-142 ° C). After cooling, 10percent sodium bicarbonate, add water 3L, the organic layer was extracted. Further, once more, to obtain a EDOT-containing solution Repeat experiments. The resulting EDOT-containing solution, gas chromatography analysis results, it was found to contain 310.5g (yield = 86molpercent) and EDOT. After concentrating the organic layer, using die casting Industry Co., Sulzer pack packed distillation column (10 stages), distillation was carried out of EDOT at a reflux ratio = 10 (110 ° C / 10mmHg). As a result, the purity = 99.92percent of EDOT 260.8g (distillation yield = 84percent) was isolated. 3, 4-diethoxy-thiophene of the raw material was not detected.To 30cc reaction tube that has been replaced with nitrogen, 3, 4-dibromothiophene 0.48g (2.0mmol), ethylene glycol 0.14g (2.2mmol), 19mg copper iodide (0.10mmol), 8-hydroxyquinoline 58mg (0.20mmol), potassium phosphate anhydride 1.7g (8.0mmol), N, N-dimethylformamide 9.6 g, was reacted for 24 hours at 120 °C. The reaction mixture was allowed to cool, after dissolving the residual base is added to water and diluted with toluene. Subsequently, subjected to filtration to give a brown transparent organic layer. Analysis of the present organic layer by gas chromatography quantitative analysis cyclododecane as an internal standard, 3, 4-ethylenedioxythiophene (EDOT) is 15percent yield of (3, 4-dibromo-thiophene basis) generated by the percentage, of the intermediate 3-bromo-4-(1-hydroxy-alkyloxy)thiophene is at the same time, was produced at a rate of 43percent yield (3, 4 dibromothiophene criteria).General procedure: The following production was carried out using 3, 4-dimethoxythiophene prepared by the same production method as in described above. This also applies to Examples 5 to 9 and Comparative Examples 3 to 9 described below.First, 10.1 g of 3, 4-dimethoxythiophene, 6.74 g of ethylene glycol, 1.1 g of p-toluenesulfonic acid monohydrate and 76.6 g of toluene were placed in a 100 ml four-necked flask, and the mixture was heated and stirred in an argon atmosphere.And heated to 100 DEG C while distilling methanol at 95 deg. At 100 , the methanol flow terminated and toluene reflux started.The compositional change in the reaction solution was followed by gas chromatography using N, N-dimethylformamide as an internal standard. As a result, 3, 4-dimethoxythiophene was found to be below the detection limit at the reflux time of 3 hours. Table 1 summarizes the relationship between the time from the start of reflux of toluene and the concentration of each component.The EDOT, DMEOT, mono- and di-substituents in Table 1 are3, 4-ethylenedioxythiophene, 3, 4-dimethoxythiophene, One in which one methoxy group of 3, 4-dimethoxythiophene is substituted with ethylene glycol, And methoxy groups of 3, 4-dimethoxythiophene were replaced with ethylene glycol The conversion (percent) in the table is theoretically 3, 4-ethylenedioxythiophene when N, N-dimethoxyformamide is measured by gas chromatography as an internal standard, Represents the ratio of the amount of 4-ethylenedioxythiophene.The residual ratio (percent) likewise represents the ratio of the actual amount of 3, 4-dimethoxythiophene in the reaction solution to the amount of 3, 4-dimethoxythiophene in theory.The reaction mixture was diluted with water, the insoluble material was removed by filtration, the crude product was extracted from toluene, the toluene layer was washed with water, washed with aqueous sodium hydrogencarbonate solution, and then dried with magnesium sulfate.After the magnesium sulfate was removed by filtration, the toluene layer was concentrated on a rotary evaporator to obtain a crude product.The yield of the crude product was 6.78 g (68.1percent) and the purity was 98.69percent by gas chromatography.The crude product was subjected to vacuum distillation to obtain 4.65 g (yield: 46.7percent) of 3, 4-ethylenedioxythiophene. The purity of its 3, 4-ethylenedioxythiophene was 99.64percent by gas chromatography. ((+) - 10-camphistsulfonic acid monohydrate of the same substance amount (mol number) was used in place of the cuedemen sulphonic acid monohydrate of Example 5, the compositional change in the reaction solution was evaluated by N, N-dimethylformamide was traced by gas chromatography as an internal standard. Table 7 summarizes the relationship between the time from the start of reflux of toluene and the concentration of each component.General procedure: The following production was carried out using 3, 4-dimethoxythiophene prepared by the same production method as in described above. This also applies to Examples 5 to 9 and Comparative Examples 3 to 9 described below.First, 10.1 g of 3, 4-dimethoxythiophene, 6.74 g of ethylene glycol, 1.1 g of p-toluenesulfonic acid monohydrate and 76.6 g of toluene were placed in a 100 ml four-necked flask, and the mixture was heated and stirred in an argon atmosphere.And heated to 100 DEG C while distilling methanol at 95 deg. At 100 , the methanol flow terminated and toluene reflux started.The compositional change in the reaction solution was followed by gas chromatography using N, N-dimethylformamide as an internal standard. As a result, 3, 4-dimethoxythiophene was found to be below the detection limit at the reflux time of 3 hours. Table 1 summarizes the relationship between the time from the start of reflux of toluene and the concentration of each component.The EDOT, DMEOT, mono- and di-substituents in Table 1 are3, 4-ethylenedioxythiophene, 3, 4-dimethoxythiophene, One in which one methoxy group of 3, 4-dimethoxythiophene is substituted with ethylene glycol, And methoxy groups of 3, 4-dimethoxythiophene were replaced with ethylene glycol The conversion (percent) in the table is theoretically 3, 4-ethylenedioxythiophene when N, N-dimethoxyformamide is measured by gas chromatography as an internal standard, Represents the ratio of the amount of 4-ethylenedioxythiophene.The residual ratio (percent) likewise represents the ratio of the actual amount of 3, 4-dimethoxythiophene in the reaction solution to the amount of 3, 4-dimethoxythiophene in theory.The reaction mixture was diluted with water, the insoluble material was removed by filtration, the crude product was extracted from toluene, the toluene layer was washed with water, washed with aqueous sodium hydrogencarbonate solution, and then dried with magnesium sulfate.After the magnesium sulfate was removed by filtration, the toluene layer was concentrated on a rotary evaporator to obtain a crude product.The yield of the crude product was 6.78 g (68.1percent) and the purity was 98.69percent by gas chromatography.The crude product was subjected to vacuum distillation to obtain 4.65 g (yield: 46.7percent) of 3, 4-ethylenedioxythiophene. The purity of its 3, 4-ethylenedioxythiophene was 99.64percent by gas chromatography. Except that 2-amino-1-naphthalenesulfonic acid monohydrate of the same substance (mol number) was used instead of the cuedemen sulphonic acid monohydrate of Example 5, and the compositional change in the reaction solution was evaluated by N, N-dimethylformamide was traced by gas chromatography as an internal standard. The relationship between the time from the start of reflux of toluene and the concentration of each component is summarized in Table 8.The following production was carried out using 3, 4-dimethoxythiophene prepared by the same production method as in described above. This also applies to Examples 5 to 9 and Comparative Examples 3 to 9 described below.First, 10.1 g of 3, 4-dimethoxythiophene, 6.74 g of ethylene glycol, 1.1 g of p-toluenesulfonic acid monohydrate and 76.6 g of toluene were placed in a 100 ml four-necked flask, and the mixture was heated and stirred in an argon atmosphere.And heated to 100 DEG C while distilling methanol at 95 deg. At 100 , the methanol flow terminated and toluene reflux started.The compositional change in the reaction solution was followed by gas chromatography using N, N-dimethylformamide as an internal standard. As a result, 3, 4-dimethoxythiophene was found to be below the detection limit at the reflux time of 3 hours. Table 1 summarizes the relationship between the time from the start of reflux of toluene and the concentration of each component.The EDOT, DMEOT, mono- and di-substituents in Table 1 are3, 4-ethylenedioxythiophene, 3, 4-dimethoxythiophene, One in which one methoxy group of 3, 4-dimethoxythiophene is substituted with ethylene glycol, And methoxy groups of 3, 4-dimethoxythiophene were replaced with ethylene glycol The conversion (percent) in the table is theoretically 3, 4-ethylenedioxythiophene when N, N-dimethoxyformamide is measured by gas chromatography as an internal standard, Represents the ratio of the amount of 4-ethylenedioxythiophene.The residual ratio (percent) likewise represents the ratio of the actual amount of 3, 4-dimethoxythiophene in the reaction solution to the amount of 3, 4-dimethoxythiophene in theory.The reaction mixture was diluted with water, the insoluble material was removed by filtration, the crude product was extracted from toluene, the toluene layer was washed with water, washed with aqueous sodium hydrogencarbonate solution, and then dried with magnesium sulfate.After the magnesium sulfate was removed by filtration, the toluene layer was concentrated on a rotary evaporator to obtain a crude product.The yield of the crude product was 6.78 g (68.1percent) and the purity was 98.69percent by gas chromatography.The crude product was subjected to vacuum distillation to obtain 4.65 g (yield: 46.7percent) of 3, 4-ethylenedioxythiophene. The purity of its 3, 4-ethylenedioxythiophene was 99.64percent by gas chromatography. The same procedure as in Example 5 was repeated except that dodecylbenzene sulfonic acid monohydrate (moles) was used in place of the cuedemen sulphonic acid monohydrate in Example 5 to change the composition in the reaction solution to N, N-dimethylform The amide was traced by gas chromatography as an internal standard. The relationship between the time from the start of reflux of toluene and the concentration of each component is summarized in Table 5The following production was carried out using 3, 4-dimethoxythiophene prepared by the same production method as in described above. This also applies to Examples 5 to 9 and Comparative Examples 3 to 9 described below.First, 10.1 g of 3, 4-dimethoxythiophene, 6.74 g of ethylene glycol, 1.1 g of p-toluenesulfonic acid monohydrate and 76.6 g of toluene were placed in a 100 ml four-necked flask, and the mixture was heated and stirred in an argon atmosphere.And heated to 100 DEG C while distilling methanol at 95 deg. At 100 , the methanol flow terminated and toluene reflux started.The compositional change in the reaction solution was followed by gas chromatography using N, N-dimethylformamide as an internal standard. As a result, 3, 4-dimethoxythiophene was found to be below the detection limit at the reflux time of 3 hours. Table 1 summarizes the relationship between the time from the start of reflux of toluene and the concentration of each component.The EDOT, DMEOT, mono- and di-substituents in Table 1 are3, 4-ethylenedioxythiophene, 3, 4-dimethoxythiophene, One in which one methoxy group of 3, 4-dimethoxythiophene is substituted with ethylene glycol, And methoxy groups of 3, 4-dimethoxythiophene were replaced with ethylene glycol The conversion (percent) in the table is theoretically 3, 4-ethylenedioxythiophene when N, N-dimethoxyformamide is measured by gas chromatography as an internal standard, Represents the ratio of the amount of 4-ethylenedioxythiophene.The residual ratio (percent) likewise represents the ratio of the actual amount of 3, 4-dimethoxythiophene in the reaction solution to the amount of 3, 4-dimethoxythiophene in theory.The reaction mixture was diluted with water, the insoluble material was removed by filtration, the crude product was extracted from toluene, the toluene layer was washed with water, washed with aqueous sodium hydrogencarbonate solution, and then dried with magnesium sulfate.After the magnesium sulfate was removed by filtration, the toluene layer was concentrated on a rotary evaporator to obtain a crude product.The yield of the crude product was 6.78 g (68.1percent) and the purity was 98.69percent by gas chromatography.The crude product was subjected to vacuum distillation to obtain 4.65 g (yield: 46.7percent) of 3, 4-ethylenedioxythiophene. The purity of its 3, 4-ethylenedioxythiophene was 99.64percent by gas chromatography. (Number of moles) of cadmium sulfonic acid monohydrate of Example 52-naphthalene sulfonic acidMonohydrate was used, and the compositional change in the reaction solution was followed by gas chromatography using N, N-dimethylformamide as an internal standard. The relationship between the time from the start of reflux of toluene and the concentration of each component is summarized in Table 5

Mainly used in the synthesis of conductive polymer PEDT, widely used in modern electronics industry. It is used as a reducing agent in synthetic gold nanoparticles; as the starting material for palladium-catalyzed arylation reactions; for synthesizing coupling polymers and co-polymers, and as a synthetic conductive polymer PEDT.

Molecular Weight:142.18
XLogP3:1.3
Hydrogen Bond Acceptor Count:3
Exact Mass:142.00885060
Monoisotopic Mass:142.00885060
Topological Polar Surface Area:46.7
Heavy Atom Count:9
Complexity:95.2
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes