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CAS No. : | 925-47-3 | MDL No. : | MFCD00087932 |
Formula : | C8H14O4S | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | TVCSSJHLVLMADJ-UHFFFAOYSA-N |
M.W : | 206.26 | Pubchem ID : | 70216 |
Synonyms : |
|
Num. heavy atoms : | 13 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.75 |
Num. rotatable bonds : | 8 |
Num. H-bond acceptors : | 4.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 50.73 |
TPSA : | 77.9 Ų |
GI absorption : | High |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -6.53 cm/s |
Log Po/w (iLOGP) : | 2.44 |
Log Po/w (XLOGP3) : | 1.45 |
Log Po/w (WLOGP) : | 0.85 |
Log Po/w (MLOGP) : | 0.93 |
Log Po/w (SILICOS-IT) : | 1.36 |
Consensus Log Po/w : | 1.4 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -1.5 |
Solubility : | 6.46 mg/ml ; 0.0313 mol/l |
Class : | Very soluble |
Log S (Ali) : | -2.69 |
Solubility : | 0.419 mg/ml ; 0.00203 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -1.77 |
Solubility : | 3.51 mg/ml ; 0.017 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 3.05 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P301+P312-P302+P352-P304+P340-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76.9% | With sodium ethanolate In ethanol at 68℃; for 1 h; Microwave irradiation | General procedure: Example B1 10.3 g of Example A6's product and 10.96 g of diethyl oxylate (Acros, Belgime) were mixed and then put in water bath at a temperature of 0 - 10°C. Sodium ethoxide (Acros, Belgime) in ethanol solution was dropwise added to the mixture and sufficiently stirred the solution. The solution was then moved into a microwave reactor and heated by a 2.45 GHz microwave of a power of 100 W for 60 minutes. The reaction temperature was maintained at 68°C. Next, the solution was added with HCl (Scharlau, Australia) to adjust pH value to 7.0 - 7.5 in order to stop the reaction, and then evaporated to remove ethanol. The dried mixture was added with HCl to adjust pH value to 2.5 - 3.0 and then added with 400 mL of deionized water to precipitate product. After filtering, the obtained product was dried in an oven to obtain 8.58 g product of 2,5-diethoxycarbonyl-3,4-dihydroxythiophene. The yield was 65.3percent. |
60% | With sodium ethanolate In ethanol at 0℃; Heating / reflux | 2) Synthesis of diethyl 3,4-dihydroxythiophene-2,5-dicarboxylate; [0080] In a 2 L two-necked flask equipped with a reflux condenser 175 g (2.57 mol) of sodium ethoxide was dissolved in 1200 mL anhydrous ethanol The reaction was cooled to 0 C and a solution of 106 g (0.514 mol) diethylthioglycolate and 188 g (1.28 mol) diethyl oxalate in ethanol was added dropwise. Upon completion of the addition, the cooling bath was removed and the reaction heated to reflux overnight. The reaction was then cooled to room temperature and filtered The resulting yellow solid was washed with ethanol and allowed to dry. The solid was split into two portions and each was added to a large Erlenmeyer flask with water to make a suspension upon stirring. Acidification with HCl provided a white solid. The solid was filtered and allowed to dry under vacuum to give 80g (60percent yield) of product as a white powder. Further mateπal can be isolated by cooling the mother liquor and subsequent filtration. Structure and puπty were confirmed by Η/13C NMR and LC-MS. |
44.9 g | Stage #1: With sodium ethanolate In ethanol at 5℃; for 2 h; Inert atmosphere; Reflux Stage #2: With hydrogenchloride In water at 5 - 10℃; Inert atmosphere |
In a 1-liter four-necked flask, 82.8 g (0.24 mol) of 20percent sodium ethoxide (Wako Pure Chemical Industries, reagent grade 1) was charged under a nitrogen atmosphere and cooled to 5 ° C. To this, a solution obtained by adding 20.6 g (0.10 mol) of diethyl thioglycolate obtained in a) and 17.2 g (0.12 mol) of diethyl oxalate (manufactured by Wako Pure Chemical Industries, special grade) to ethanol 18.8 g was added dropwise over 1 hour. Further, the mixture was heated under reflux for 1.0 hour. After the completion of the reaction, the reaction solution was concentrated at 60 ° C/16 to 20 mmHg, and 515.2 g of water was added, cooled to 5 ° C, and 38.1 g (0.37 mol) of 35percent hydrochloric acid was added dropwise at 5 to 10 ° C to obtain a white precipitate. The obtained precipitate was filtered, dispersed in water, washed and filtered, and then dried at 60 ° C/1 mmHg for 4 hours to obtain 23.8 g of a white powder. In the same manner, 44.9 g of a white powder was obtained. These powders were single peaks by gas chromatography analysis and when 1 H-NMR and 13 C-NMR were measured, it was confirmed that they were 3,4-dihydroxy-2,5-dicarboxylic acid thiophene diethyl ester. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With sulfuric acid;Heating / reflux; | Example A:; [0078] Synthesis of 3,4-ethylenedioxythiophene methanol is adapted from the publication "Electropolymerization of and 3,4-ethylenedioxythiophene methanol in the presence of dodecylbenzenesulfonate", Lima A, Schottland P, Sadki A, Chevrot C; Synth. Met. 1998, 93, 33-41.; 1) Synthesis of diethyl thiodiglycolate; [0079] In a 2-necked round bottom flask equipped with a reflux condenser and an equilibrium addition funnel 100 g (0.667 mol) thiodiglycolic acid was dissolved in 500 mL refluxing ethanol. The equilibrium addition funnel was charged with 40 mL concentrated sulfuric acid. The acid was added dropwise EPO <DP n="24"/>and the reaction refluxed overnight. Upon cooling the reaction to room temperature it was carefully poured into 600 mL water. The product was extracted with diethyl ether until the ether wash no longer contained the desired product. The organic extracts were washed with a saturated sodium bicarbonate solution three times. Upon drying with magnesium sulfate and solvent removal under reduced pressure a colorless oil was isolated (131 3 g, 95% yield). Structure and pu?ty were confirmed by 1YU13C NMR and GC-MS. |
95.1% | With sulfuric acid; at 86℃; for 0.333333h;Microwave irradiation; | General procedure: Example A1 15.015 g of 2,2'-thiodiacetic acid (Acros, Belgium), 55.284 g of ethanol (ECHO, Taiwan), and 4.9 g of sulfuric acid (Sigma-Aldrich, Switzerland) were added into 20 g of toluene (ECHO, Taiwan) and then stirred for mixing and dissolving the reagents above. The obtained solution was moved into a microwave reactor and heated by a 2.45 GHz microwave at a power of 500 W for 30 minutes. A Dean-Stark receiver was installed outside the microwave reactor for dehydrating. The temperature of the heated solution was 86 - 87 C and refluxed. The solution was cooled down after the reaction, and then its pH value was adjusted to 7.0 - 7.5 by adding NaOH(aq) in order to stop esterification. The solution was then extracted by ethyl acetate/ n-hexane (9/1) and saturated salt water for three times. The obtained organic layer was dried by anhydrous magnesium sulfate, filtered, evaporated to remove solvent, and then vacuumed under a reduced pressure to obtain 17.1 g diethyl thioglycolate. The yield is 83.0%. |
79% | sulfuric acid; for 12h;Heating / reflux; | Carboxylic acid EDOT monomer can be synthesized, as shown in Scheme 1. Products formed and reacted are designated by Arabic numerals. First thiodiglycolic acid (1 , 25 g, 0.17 mol) is refluxed with 10 ml sulfuric acid in 100 ml ethanol for 12 hours. The solution is cooled, diluted with 150 ml of water, and the product is extracted into diethyl ether three times. The organic layer is then washed three times with Na2CO3ZH2O, dried with MgSO4 and the solvent is removed to produce 27.06 g of diethyl thiodiglycolate (2, 79% yield ). Diethyl thioglycolate (27.06 g, 0.13 mol) is then added dropwise with diethyl oxalate (50 g, 0.34 mol) to 250 ml of sodium ethoxide (0.58 mol) at 0 C. After complete addition the solution is refluxed for 1 hour to form diethyl 3,4- dihydroxythiophene-2,5-dicarboxylate disodium salt (3). After filtration, (3) is acidified using hydrochloric acid, and the precipitate is filtered and washed with water. The product, diethyl 3,4-dihydroxythiophene-2,5-dicarboxylate (4), is dried and recrystallized in methanol to produce a yield of 27.02 g (80 %). Next, (4) (8.75g, 0.034 mol) is added to 200 ml of boiling ethanol. Epibromohydrin (3.75 ml, 0.045 mol) and K2CO3 (0.94 g in 50 ml water) are added to the reaction. After 30 minutes, more epibromohydrin (6.5 ml, 0.079 mol) and K2CO3 (0.5 g) are added and the solution is refluxed for 60 hours. The product is diluted with 150 ml of acidified water (5 % HCI) and extracted two times with chloroform. The organic layer is then washed with 5 % aqueous KCI, dried with MgSO4, and the solvent is evaporated. The product, diethyl 2-(hydroxymethyl)-2,3- dihydrothieno[3,4-b] [1 ,4]dioxin-5,7-dicarboxylate (5) is purified by precipitation in diethyl ether. The by-product, diethyl 2-hydroxy-2,3-dihydrothieno[3,4- b][1 ,4]dioxin-5,7-dicarboxylate, is also present with (5) but this compound cannot react in the next step so it is not separated from (5). Oxidation of the hydroxyl group on (5) is achieved by adding a catalytic amount of pyridinium chlorochromate (0.18 g, 0.8 mmol) and (5) (8.54 g, mixture with by-product) to a cooled solution (0 0C) of periodic acid (15 g, 0.066 mol) in 240 ml of acetonitrile. The solution is stirred for 3 hours as it warms to room temperature. After the reaction, the solution is diluted with 300 ml of ethyl acetate, washed with a 1 :1 solution of brine:water, and the product is extracted into a solution of sodium bicarbonate and water. The aqueous later is then acidified with HCI and the <n="11"/>product is extracted into ethyl acetate. The organic layer is then dried with MgSO4 and the solvent is removed. The product, diethyl 2-(carboxylic acid)-2,' - dihydrothieno[3,4-b] [1 ,4] dioxin-5,7 dicarboxylate (6), is recrystallized in xylenes to produce a 26 % yield from compound (4) to compound (6). Compound (6) (2,8g) is then reacted with KOH (3g, 0.05 mol) in 75 ml of water and 30 ml of ethanol for 1 hour at 60 C. After the reaction the solvent is removed and the product is washed with ethanol. The product is then filtered, dissolved in 150 ml of water and acidified with HCI. The product, diethyl 2-(carboxylic acid)-2,3- dihydrothieno[3,4-b] [1 ,4]dioxin-5,7-dicarboxylic acid (7), is recovered as a white precipitate after stirring in acidified water for 3 hours in -100% yield (2.36 g, 8.6 mmol). Compound (7) (2.36 g) is decarboxylated by refluxing with copper chromite catalyst (0.24 g, 0.76 mmol) in 14 ml of freshly distilled quinoline at 160 - 170 C for 2 hours. The solution is diluted with ethyl acetate and filtered to remove catalyst. The product is then washed with 5 % HCI three times, NaCI/water twice and extracted into 2 % KOH. The aqueous layer is then acidified with HCI and the product is extracted into ethyl acetate, dried with MgSO4 and the solvent is removed to produce 1.17 g (75% yield) of the final product, 2,3-dihydrothieno[3,4-b][1 ,4]dioxin-2-carboxylic acid i.e. carboxylic acid EDOT (8). This reaction scheme results in a total yield from compound 1 to compound 8 of 12%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With selenium(IV) oxide; dihydrogen peroxide; In methanol; at 20℃; for 2h; | To a stirred solution of <strong>[925-47-3]diethyl 2,2'-thiodiacetate</strong>, 2 (1.0 mol) in methanol (20 mL), a pinch of selenium dioxide, 30% H2O2 (10 mL)was added drop wise and stirring continued while maintaining the temperature of the reaction mixture at 20 C for about 2 h. The contents were extracted with dichloromethane (3 25 mL) andremoval of the solvent afforded diethyl 2,2'-sulfonyldiacetate 3 as athick oil.Yield: 88%; 1H NMR (300 MHz, CDCl3): d 1.36 (t, 6H, eOCH2CH3),4.32 (q, 4H, eOCH2CH3), 4.39 (s, 4H, CH2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92.9% | With sodium sulfide; In ethanol; at 50℃; for 1h;Inert atmosphere; | under the protection of nitrogen, the 80g sodium sulfide, 500 ml anhydrous ethanol, 0.5g the crown in the flask, normal temperature next adds by drops 122.5g (1mol) chloro ethyl acetate, completion of the dropping temperature to 50 C, thermal insulation 1h, sampling GC tracking, ? 2% chloroacetic acid ethyl ester content, reaction finishes; filtering, with 30 ml anhydrous ethanol washing two times to combining the filtrate 705g, GC content 27.1%, folding thiophosphoro b Ganong ester 191.4g, molar yield 92.9%. |
90% | With sodium sulfide; sodium hydroxide; sodium dihydrogenphosphate;methyl tributylammonium chloride; In water; toluene; at 30 - 35℃; for 5h;pH 6.0; | EXAMPLE 6In a 1 ltr. jacketed glass reactor, 35.8 g of sodium dihydrogenphosphate dihydrate were dissolved in 168.4 g of water (pH=3.9) and adjusted to pH=6.0 with 12.2 g of sodium hydroxide solution (32%). The buffer solution was warmed to 33 C. and admixed with 13.0 g of tributylmethylammonium chloride solution (75% in water) and 40.0 g of ethyl chloroacetate. Simultaneously, 611.2 g of sodium sulphide solution (16% in water) and 275.3 g of ethyl chloroacetate were metered in at 30-35 C. within 2 h. Subsequently, a further 19.3 g of sodium sulphide solution (16% in water) were metered in and the mixture was stirred at 33 C. for a further 1 h. Subsequently, a further 19.3 g of sodium sulphide solution (16% in water) were metered in and the mixture was stirred at 33 C. for a further 2 h. The reaction solution was admixed with 130 ml of toluene and stirred vigorously. Subsequently, the lower phase was removed. After the toluene had been distilled off at approx. 300 mbar, 277.2 g of a clear liquid comprising 90% diethyl thiodiglycolate and 9% toluene were obtained. This corresponds to a yield of 95% of theory. |
70% | With sodium sulfide; In water; for 1h;Reflux; | To a refluxing alcoholic solution of ethyl chloroacetate, 1(2.0 mol), solution of sodium sulfide (1.0 mol) in water was added and the mixture was refluxed for an hour. The course of the reaction was monitored by TLC. After completion of the reaction, the solvent was removed in vacuo. Then the residue was treated with cold water and neutralized with dil. HCl. The separated oily product was extracted with dichloromethane (3 25 mL) and on evaporation of the solvent afforded diethyl 2,2'-thiodiacetate (2) as a thick oil in 70% yield; it answered positive test for sulphur. |
With sodium sulfide; In acetone; at 20℃; for 6h; | Ethyl chloroacetate (245.2 g, 2.0 mol) Was added dropwise to a solution of sodium sulfide (78 g, 1.0 mol) In acetone solution (2 L), stirred at room temperature for 2 hours, To produce diethyl thioacetate; after completion of the monitoring reaction, Directly filtered, evaporated to dryness to give crude 323 g, which was used directly in the next step without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76.9% | With sodium ethanolate; In ethanol; at 68℃; for 1h;Microwave irradiation; | General procedure: Example B1 10.3 g of Example A6's product and 10.96 g of diethyl oxylate (Acros, Belgime) were mixed and then put in water bath at a temperature of 0 - 10C. Sodium ethoxide (Acros, Belgime) in ethanol solution was dropwise added to the mixture and sufficiently stirred the solution. The solution was then moved into a microwave reactor and heated by a 2.45 GHz microwave of a power of 100 W for 60 minutes. The reaction temperature was maintained at 68C. Next, the solution was added with HCl (Scharlau, Australia) to adjust pH value to 7.0 - 7.5 in order to stop the reaction, and then evaporated to remove ethanol. The dried mixture was added with HCl to adjust pH value to 2.5 - 3.0 and then added with 400 mL of deionized water to precipitate product. After filtering, the obtained product was dried in an oven to obtain 8.58 g product of 2,5-diethoxycarbonyl-3,4-dihydroxythiophene. The yield was 65.3%. |
60% | With sodium ethanolate; In ethanol; at 0℃;Heating / reflux; | 2) Synthesis of diethyl 3,4-dihydroxythiophene-2,5-dicarboxylate; [0080] In a 2 L two-necked flask equipped with a reflux condenser 175 g (2.57 mol) of sodium ethoxide was dissolved in 1200 mL anhydrous ethanol The reaction was cooled to 0 C and a solution of 106 g (0.514 mol) diethylthioglycolate and 188 g (1.28 mol) diethyl oxalate in ethanol was added dropwise. Upon completion of the addition, the cooling bath was removed and the reaction heated to reflux overnight. The reaction was then cooled to room temperature and filtered The resulting yellow solid was washed with ethanol and allowed to dry. The solid was split into two portions and each was added to a large Erlenmeyer flask with water to make a suspension upon stirring. Acidification with HCl provided a white solid. The solid was filtered and allowed to dry under vacuum to give 80g (60% yield) of product as a white powder. Further mate?al can be isolated by cooling the mother liquor and subsequent filtration. Structure and pu?ty were confirmed by Eta/13C NMR and LC-MS. |
44.9 g | In a 1-liter four-necked flask, 82.8 g (0.24 mol) of 20% sodium ethoxide (Wako Pure Chemical Industries, reagent grade 1) was charged under a nitrogen atmosphere and cooled to 5 C. To this, a solution obtained by adding 20.6 g (0.10 mol) of <strong>[925-47-3]diethyl thioglycolate</strong> obtained in a) and 17.2 g (0.12 mol) of diethyl oxalate (manufactured by Wako Pure Chemical Industries, special grade) to ethanol 18.8 g was added dropwise over 1 hour. Further, the mixture was heated under reflux for 1.0 hour. After the completion of the reaction, the reaction solution was concentrated at 60 C/16 to 20 mmHg, and 515.2 g of water was added, cooled to 5 C, and 38.1 g (0.37 mol) of 35% hydrochloric acid was added dropwise at 5 to 10 C to obtain a white precipitate. The obtained precipitate was filtered, dispersed in water, washed and filtered, and then dried at 60 C/1 mmHg for 4 hours to obtain 23.8 g of a white powder. In the same manner, 44.9 g of a white powder was obtained. These powders were single peaks by gas chromatography analysis and when 1 H-NMR and 13 C-NMR were measured, it was confirmed that they were 3,4-dihydroxy-2,5-dicarboxylic acid thiophene diethyl ester. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83 g | With sodiumsulfide nonahydrate; In water; at 10 - 25℃; for 19h;Inert atmosphere; | In a 1-liter four-necked flask, 167.1 g (1.0 mol) of ethyl bromoacetate (Tokyo Chemical Industry, Reagent 1 grade) and 339.0 g of water were charged under a nitrogen atmosphere and cooled to 10 C.While maintaining the temperature at 10 C., 132.9 g (0.55 mol) of sodium sulfide 9-hydrate (special grade, manufactured by Kishida Chemical Co., Ltd., a special grade) dissolved in 163.2 g of water was added dropwise over 1 hour and further stirred at 25 C. The reaction was carried out for 18 hours.The reaction solution was extracted with ethyl acetate and washed with water, and 20.3 g of anhydrous magnesium sulfate (manufactured by Kanto Kagaku Co., Ltd., reagent deer special grade) was added thereto, dehydrated, and concentrated at 90 C./16 to 20 mmHg to obtain 83.0 g of concentrated liquid Was obtained |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium methylate; In methanol; at 0 - 60℃; for 4.5h;Product distribution / selectivity; | [80] Example 1[81] A IL 3-neck flask was equipped with an impeller stirrer, a reflux condenser and a dropping funnel and was then flame-dried with a nitrogen purge.[82] 57.7 g (0.30 mol) of a 28% sodium methoxide solution and 25 g of methanol were placed and stirred in the 3-neck flask.[83] A mixture of 30.7 g (0.15 mol) of 98% <strong>[925-47-3]diethyl thioglycolate</strong> and 25.18 g (0.15 mol) of diethyl oxalate was placed in the dropping funnel and was then added dropwise at a temperature of 0 to 50C over 30 min.[84] The mixture was stirred at room temperature for 1 hour and then stirred at 6O0C under reflux for another 3 hours to complete the reaction.[85] When it begins to form a yellow diethyl-3,4-dihydroxythiophene-2,5-dicarboxylate disodium salt, the solvent is refluxed by the exothermic reaction.[86] After the reaction was complete, the reactants were cooled to room temperature and washed three times with 60 mL of methanol, followed by drying at a temperature of 60 to 7O0C under vacuum.[87] 82 g (0.27 mol) of the thus-dried dialkyl-3,4-dihydroxythiophene-2,5-dicarboxylate disodium salt and 550 g of ethanol were placed in a 2L reaction vessel having a plane ground joint and equipped with an impeller stirrer, a reflux condenser, a thermometer and a dropping funnel, and 50.55 g (0.27 mol) of 1,2-dichlorotetramethyldisilane and 50 g of ethanol were placed in the dropping funnel and were then added dropwise at 5O0C.[88] Next, the reaction mixture was stirred at 8O0C under reflux for 2 hours, and the reaction vessel was cooled to room temperature and 600 mL of an aqueous 5% HCl solution was then gradually added thereto via the dropping funnel.[89] The reaction mixture was extracted three times with 500 mL of chloroform and dried over magnesium sulfate, followed by removal of the solvent under vacuum.[90] 800 mL of an aqueous potassium hydroxide (84 g, 1.50 mol) solution was added dropwise to the thus-obtained white solids, and the mixture was stirred at 7O0C under reflux for 2 hours, such that the mixture is completely dissolved.[91] The solution of the reaction vessel was concentrated under vacuum to a total volume of 400 mL, and then 168 mL of cone. HCl was gradually added dropwise at O0C to thereby give white solids with completion of the reaction.[92] After stirring for another 2 hours at room temperature, the resulting 3,4-tetramethyldisilylenedioxythiophene carboxylic acid was dried under vacuum. [93] 1200 mL of tetramethylene sulfone was introduced into the flask under stirring, and 240 g (0.75 mol) of 3,4-tetramethyldisilylenedioxythiophene carboxylic acid was then added thereto. The resulting mixture was heated to 950C under pressure of 0.35 mbar over 2 hours.[94] When the reaction was complete, the reactants were cooled to room temperature and 3,4-tetramethyldisilylenedioxythiophene was distilled under vacuum (0.3 mbar) to thereby afford 27.65 g (0.12 mol) of a desired product (yield: 80%).[95] Table 1[96]. [97] Example 2 [98] A IL 3-neck flask was equipped with an impeller stirrer, a reflux condenser and a dropping funnel and was then flame-dried with a nitrogen purge.[99] 69.23 g (0.36 mol) of a 28% sodium methoxide solution and 25 g of methanol were placed and stirred in the 3-neck flask. [100] A mixture of 37.13 g (0.18 mol) of 98% <strong>[925-47-3]diethyl thioglycolate</strong> and 26.30 g (0.18 mol) of diethyl oxalate was placed in the dropping funnel and was then added dropwise at a temperature of 0 to 50C over 30 min.[101] The mixture was stirred at room temperature for 1 hour and then stirred at 6O0C under reflux for another 3 hours to complete the reaction. [102] When it begins to form a yellow diethyl-3,4-dihydroxythiophene-2,5-dicarboxylate disodium salt, the solvent is refluxed by the exothermic reaction. [103] After the reaction was complete, the reactants were cooled to room temperature and washed three times with 60 mL of methanol, followed by drying at a temperature of 60 to 700C under vacuum.[104] 50 g (0.16 mol) of the thus-dried dialkyl-3,4-dihydroxythiophene-2,5-dicarboxylate disodium salt and 550 g of ethanol were placed in a 2L reaction vessel having a plane ground joint and equipped with an impeller stirrer, a reflux condenser, a thermometer and a dropping funnel, and 32.51 g (0.16 mol) of l,3-dichloro-l,l,3,3-tetramethyldisiloxane and 50 g of ethanol were placed in the dropping funnel and were then added dropwise at 500C.[105] Next, the reaction mixture was stirred at 800C under reflux for 2 hours, and the reaction vessel was cooled to room temperature and 600 mL of an aqueous 5% HCl solution was gradually added thereto via the dropping funnel.[106] The reaction mixture was extracted three times with 500 mL of chloroform and dried over magnesium sulfate, followed by removal of the solvent under vacuum.[107] 500 mL of an aqueous potassium hydroxide (50 g, 0.99 mol) solution was added dropwise to the thus-obtained white solids, and the mixture was stirred at 700C under reflux for 2 hours, such that the mixture is complet... | |
With sodium ethanolate; In ethanol; for 4h;Reflux; | The previous step (323 g) was dissolved in ethanol (2 L) Sodium ethoxide (136 g, 2 mol) was added in portions at room temperature, Diethyl oxalate (146 g, 1 mol) was slowly added and the temperature was refluxed for 4 hours, After monitoring the reaction, To obtain an ethanol solution of sodium 2,5-dicarboxylate-3,4-thienylene glycol, The solution can be used directly in the next reaction, Without any purification | |
With sodium ethanolate; In ethanol; at 0℃; for 1h;Heating / reflux; | Carboxylic acid EDOT monomer can be synthesized, as shown in Scheme 1. Products formed and reacted are designated by Arabic numerals. First thiodiglycolic acid (1 , 25 g, 0.17 mol) is refluxed with 10 ml sulfuric acid in 100 ml ethanol for 12 hours. The solution is cooled, diluted with 150 ml of water, and the product is extracted into diethyl ether three times. The organic layer is then washed three times with Na2CO3ZH2O, dried with MgSO4 and the solvent is removed to produce 27.06 g of <strong>[925-47-3]diethyl thiodiglycolate</strong> (2, 79% yield ). Diethyl thioglycolate (27.06 g, 0.13 mol) is then added dropwise with diethyl oxalate (50 g, 0.34 mol) to 250 ml of sodium ethoxide (0.58 mol) at 0 C. After complete addition the solution is refluxed for 1 hour to form diethyl 3,4- dihydroxythiophene-2,5-dicarboxylate disodium salt (3). After filtration, (3) is acidified using hydrochloric acid, and the precipitate is filtered and washed with water. The product, diethyl 3,4-dihydroxythiophene-2,5-dicarboxylate (4), is dried and recrystallized in methanol to produce a yield of 27.02 g (80 %). Next, (4) (8.75g, 0.034 mol) is added to 200 ml of boiling ethanol. Epibromohydrin (3.75 ml, 0.045 mol) and K2CO3 (0.94 g in 50 ml water) are added to the reaction. After 30 minutes, more epibromohydrin (6.5 ml, 0.079 mol) and K2CO3 (0.5 g) are added and the solution is refluxed for 60 hours. The product is diluted with 150 ml of acidified water (5 % HCI) and extracted two times with chloroform. The organic layer is then washed with 5 % aqueous KCI, dried with MgSO4, and the solvent is evaporated. The product, diethyl 2-(hydroxymethyl)-2,3- dihydrothieno[3,4-b] [1 ,4]dioxin-5,7-dicarboxylate (5) is purified by precipitation in diethyl ether. The by-product, diethyl 2-hydroxy-2,3-dihydrothieno[3,4- b][1 ,4]dioxin-5,7-dicarboxylate, is also present with (5) but this compound cannot react in the next step so it is not separated from (5). Oxidation of the hydroxyl group on (5) is achieved by adding a catalytic amount of pyridinium chlorochromate (0.18 g, 0.8 mmol) and (5) (8.54 g, mixture with by-product) to a cooled solution (0 0C) of periodic acid (15 g, 0.066 mol) in 240 ml of acetonitrile. The solution is stirred for 3 hours as it warms to room temperature. After the reaction, the solution is diluted with 300 ml of ethyl acetate, washed with a 1 :1 solution of brine:water, and the product is extracted into a solution of sodium bicarbonate and water. The aqueous later is then acidified with HCI and the <n="11"/>product is extracted into ethyl acetate. The organic layer is then dried with MgSO4 and the solvent is removed. The product, diethyl 2-(carboxylic acid)-2,' - dihydrothieno[3,4-b] [1 ,4] dioxin-5,7 dicarboxylate (6), is recrystallized in xylenes to produce a 26 % yield from compound (4) to compound (6). Compound (6) (2,8g) is then reacted with KOH (3g, 0.05 mol) in 75 ml of water and 30 ml of ethanol for 1 hour at 60 C. After the reaction the solvent is removed and the product is washed with ethanol. The product is then filtered, dissolved in 150 ml of water and acidified with HCI. The product, diethyl 2-(carboxylic acid)-2,3- dihydrothieno[3,4-b] [1 ,4]dioxin-5,7-dicarboxylic acid (7), is recovered as a white precipitate after stirring in acidified water for 3 hours in -100% yield (2.36 g, 8.6 mmol). Compound (7) (2.36 g) is decarboxylated by refluxing with copper chromite catalyst (0.24 g, 0.76 mmol) in 14 ml of freshly distilled quinoline at 160 - 170 C for 2 hours. The solution is diluted with ethyl acetate and filtered to remove catalyst. The product is then washed with 5 % HCI three times, NaCI/water twice and extracted into 2 % KOH. The aqueous layer is then acidified with HCI and the product is extracted into ethyl acetate, dried with MgSO4 and the solvent is removed to produce 1.17 g (75% yield) of the final product, 2,3-dihydrothieno[3,4-b][1 ,4]dioxin-2-carboxylic acid i.e. carboxylic acid EDOT (8). This reaction scheme results in a total yield from compound 1 to compound 8 of 12%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ethanol; sodium ethanolate; In tetrahydrofuran; at 65℃; for 2.5h; | The title compound was prepared using the methods disclosed in US 6,559,993 and US 2004/0147765. Accordingly, the thioether 25 (10.8, 52.4 mmol) and 2,3- butanedione (2.25 g, 26.2 mmol) were dissolved in dry THF (20 mL) under argon. A solution of NaOEt in ethanol (20 %, m/v; 1.5 eq) was added dropwise, and the mixture was heated at 65 0C for 2.5 h and cooled to rt. After aqueous work up the product was dried over Na2SO4 and purified on silica gel to give of 2.5 g of 5- (ethoxycarbonyl)-3,4-dimethylthiophene-2-carboxylic acid, which was dissolved in chinoline. Coppper (0.30 g) was added, and the mixture was aerated for 30 min at rt followed by heating overnight at 140 0C. After aqueous work up the product was dried and purified on silica gel. Compound 26: 1H NMR (CDCl3): delta 7.08 (IH, s); 4.33 (2H, q, J 7.2); 2.47 (3H, s); 2.18 (3H, s); 1.38 (3H, t, J 7.2). ESI-TOF-MS [M+H]+: calc. for C9HnO2S+ 185.06, found 185.07 |
Tags: 925-47-3 synthesis path| 925-47-3 SDS| 925-47-3 COA| 925-47-3 purity| 925-47-3 application| 925-47-3 NMR| 925-47-3 COA| 925-47-3 structure
[ 127846-80-4 ]
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[ 127846-80-4 ]
Ethyl 2-[(2-methoxy-2-oxoethyl)sulfanyl]acetate
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