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CAS No. : | 204905-77-1 | MDL No. : | MFCD01651766 |
Formula : | C7H6O3S | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | GNVXYRDVJKJZTO-UHFFFAOYSA-N |
M.W : | 170.18 | Pubchem ID : | 3540090 |
Synonyms : |
|
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H332-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 |
---|---|---|
86.3% | With bis(trichloromethyl) carbonate; In dichloromethane; at 0 - 35℃; for 1h; | To a mixture of EDOT (15.0 g, 0.1 mol) and DMF (11.0 g, 0.15 mol), BTC (11.9 g, 0.04 mol) dissolved in dry CH2Cl2 (80 mL) was added dropwise at 0C. The mixture was heated to 35C and stirred for 1 h, then cooled and poured into ice water (250 mL). The pH of the aqueous phase was adjusted to 7-8 with 10% sodium hydroxide and the organic phase was separated. The aqueous phase was extracted with CH2Cl2 for three times. The organic phase was combined and dried with anhydrous magnesium sulfate. After removing the solvent under reduced pressure, the crude product was recrystallized in 95% ethanol to yield white needle crystals 1 (15.5 g, 86.3% yield). 1H NMR (400 MHz) delta/ppm: 9.90 (s, 1H), 6.79 (s, 1H), 4.38-4.25 (m, 4H). |
83% | With trichlorophosphate; at -10 - 20℃; for 4h;Cooling with ice; | 3,4-Ethylenedioxythiophene (2 mL, 18 mmol) was dissolved in dry N N-Dimethylformamide(DMF) (10 mL, 126 mmol), the mixture was cooled to -10 C and POCl3 (1.76 mL, 18 mmol)was added slowly dropwise over min. The reaction mixture was then allowed to reach roomtemperature then stirred for an additional hour. The reaction was poured into an ice bath andneutralized using a basic aqueous solution. The product, in the form of white needles, wasfiltered and dried, yielding a quantitative yield (3.06 g). 1H NMR (300 MHz, CDCl3 , deltappm ):9.83 (s, 1H), 6.74 (s, 1H), 4.31 (d, 2H), 4.21 (d, 2H). 13C NMR (75 MHz, CDCl3 , deltappm ):180.0, 141.7, 110.8, 110.7, 65.2, 64.3. |
67% | With trichlorophosphate; at 0 - 20℃; for 8h;Inert atmosphere; | 5g (35.21 mmol) of 3,4-ethylenedioxythiophene was dissolved in 70 mL of N,N-dimethylformamide (DMF) in a two-necked flask, magnetically stirred and argon gas was introduced, the reaction system was lowered to 0 C, and 10.8 g (70.42 mmol) of phosphorus oxychloride was added dropwise to the system, and the reaction system was slowly returned to room temperature for 8 h overnight. After the reaction is completed, a rotary evaporator was used to spin dried DMF, the system was reduced to 0 C, 50 mL of saturated sodium bicarbonate solution was added to quench the excess phosphorus oxychloride, extracted and separated with 3*50 mL of dichloromethane and organic phase was spin dried, the sample was mixed with silica gel, and 4g of product was obtained by column chromatography, yield was 67%. The structure of the intermediate is resolved as follows: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With N-Bromosuccinimide; In acetonitrile; at 0 - 20℃; for 60h;Inert atmosphere; | Compound 1 (4.04 g, 23.7 mmol) was suspended in dry acetonitrile (100 mL) and cooled to0 C. NBS (4.36 g, 26.0 mmol), 1.1 equiv, was added and the mixture was stirred for 60 h atroom temperature, shielded from light and under nitrogen. The color changed from yellow topurple. The mixture was transferred with 150 mL of ethyl acetate to a separation funnel,washed with 10% aqueous Na2CO3 (2×200 mL), saturated Na2S2O3 (2×200 mL) and water(2×200 mL), dried with MgSO4, and evaporated in vacuo. Recrystallization twice from ethanol (60 mL) yielded 5.35 g (91%) of the bromide as yellow needles. 1H NMR (300 MHz,CDCl3 delta ppm ): 9.83 (s, 1H), 4.36 (m, 4H); 13C NMR (75 MHz, CDCl3 delta ppm):179.0, 147.9,140.4, 118.8, 102.0, 65.5, 65.1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With N-iodo-succinimide; toluene-4-sulfonic acid; In ethanol; at 25℃; for 0.166667h;Green chemistry; | General procedure: The thiophene derivative (1 mmol, 1 equiv) was dissolved in EtOH (2mL) at the temperature indicated in Tables 1-5. Then, NIS (1 or 1.1 equiv, see Tables 1-5) was added followed by PTSA (10% mol). The mixture was stirred for 10 min, then sat. Na2S2O3 (2 mL) was added. The mixture was diluted with EtOAc (3 mL). After phase separation, the organic phase was washed with 1 M Na2CO3 solution, dried (MgSO4), filtered through cotton, and evaporated to give the iodinated thiophene derivative. |
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