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CAS No. : | 133831-28-4 | MDL No. : | MFCD00216479 |
Formula : | C11H9NO3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | KRDRROJESQUFMJ-UHFFFAOYSA-N |
M.W : | 203.19 | Pubchem ID : | 735867 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | 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 |
---|---|---|
86% | To DMF (20.9 g, 285.4 mmol, 22.0 mL, 1.0 eq) in a three-necked flask equipped with a stirrer, a thermometer at 0 C, was slowly added dropwise POCl3 (43.8 g, 285.4 mmol, 26.5 mL, 1.0 eq). After the addition, the mixture was stirred for 1 h at 0 C. Then methyl 1H-indole-6- carboxylate (50.0 g, 285.4 mmol, 1.0 eq) in DMF (600 mL) was added to the reaction mixture dropwise at 0 C. The mixture was allowed to warm to room temperature and stirred for 3 h with solid precipitating out. Then H2O (200 mL) was added to the mixture and the solution was basified with NaOH to pH=8~9. The basified solution was stirred at 100 C for additional 2 h. Water (2 L) was added to the mixture, and the resulting suspension was stirred for 0.5 h, and filtered. The filter cake was washed with H2O (200 mL) and dried under reduced pressure to give methyl 03-1-1 (50.0 g, 86%).1H NMR (DMSO, 400 MHz): δ 12.43 (br. s., 1H), 10.05-9.92 (m, 1H), 8.56-8.43 (m, 1H), 8.23-8.09 (m, 2H), 7.87-7.79 (m, 1H), 3.97-3.77 (m, 3H). | |
52% | With trichlorophosphate; at 20℃;Cooling with ice; | Methyl 1H-indole-6-carboxylate (65 mg, 0.37 mmol) was dissolved in 10 mL of N,N-dimethylformamide under stirring, and phosphorus oxychloride (86 mg, 0.56 mmol) was added under ice bath, and the addition was completed, naturally warmed to room temperature and reacted overnight. TLC detected all the disappearance of the raw materials, quenched by adding 5 mL of water under ice bath, extracted with ethyl acetate (20 mL*3), The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated, and the residue was purified by silica gel column chromatography (PE:EA=3:1) to obtain 39 mg of pale yellow solid, yield: 52%. |
27% | With trichlorophosphate; at 0 - 20℃; for 0.5h; | To a stirred solution of compound 26 (2.5 g, 14.28 mmol) in DMF (30 mL) at 0 C, POd3 (5.47 g, 35.7 mmol) was added and stirred at RT for 30 mm. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was quenched with ice cold water (100 mL); the obtained solid was filtered and dried in vacuo. The crude compound waspurified by silica gel column chromatography using 10% EtOAc/hexane to afford compound 27 (0.78 g, 27%) as an off-white solid. TLC: 30% EtOAc/Hexane (Rf: 0.4); ‘H NMR (400 MHz, DMSO-d6): ? 12.42 (s, 1H), 9.98 (s, 1H), 8.50 (s, 1H), 8.21 - 8.04 (m, 2H), 7.84 (d, J= 8.4 Hz, 1H), 3.88 (s, 3H), LCMS Observed (m/z): 203.95 (M+1). |
7% | With trichlorophosphate; at 0 - 20℃; for 2h;Inert atmosphere; | General procedure: To a solution of 1a (5.00 g,28.57 mmol) in dry DMF (20 ml) was added POCl3 (3.62 ml, 38.86 mol) at 0 C under N2 and then stirred at room temperature for 2 h. The reaction was quenched with H2O (60 ml) at 0 C and adjusted the pH to 7-8 with 2 M NaOH. The resulting solution was heated to 70 C and stirred for 30 min. After cooling to room temperature, the precipitate was filtered and washed with MeOH to give 2a as a light pink solid (5.22 g, 90%), |
With trichlorophosphate; at 0 - 80℃; for 17h; | POCb (5.25 g, 34.25 mmol, 3.18 mL, 1.5 eq) was added to DMF (15 mL) dropwise and stirred at 0 C for 1 h. Then a solution of methyl l//-indole-6-carboxylate (4 g, 22.83 mmol, 1 eq) in DMF (25 mL) was added to the mixture. The mixture was stirred at 80 C for 16 h. The reaction mixture was quenched by addition 0 (100 mL) at 0 C and stirred for 30 min at 25 C. The reaction mixture was filtered and the filter cake was concentrated to yield a residue which was added MeOH (35 mL) and stirred at 25 C for 1 h. The slurry was filtered and the filter cake was washed with MeOH (20 mL x 2). The filter cake was concerned to yield methyl 3-formyl-lH-indole-6-carboxylate (3.15 g, 13.95 mmol, 61.1% yield, 90.0% purity) as a light yellow solid. NMR (500 MHz, DMSO-rfd) d ppm 12.44 (s, 1H), 10.10-9.85 (m, 1H), 8.50 (s, 1H), 8.23-8.07 (m, 2H), 7.94-7.68 (m, 1H), 3.90-3.84 (m, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With water; iodine; In N,N-dimethyl-formamide; at 150℃; under 5171.62 Torr; for 0.133333h;Flow reactor; | General procedure: The continuous flow reactor system consisted of the dual pump (KP-22-13, SS), PTFE tubing (length: 16 m, ID: 1 mm), T-junction (1.25 mm thru-hole), back pressure regulator (40, 75, 100, 250 psi), oil bath and hot plate. In this experiment, we used BOLA PTFE tubing to experiment at high temperature. In order to react stably at the temperature above the boiling point of water, looked for the maximum temperature conditions according to the pressure of the back pressure regulator in which the bubble does not occur. The reaction started in the concentration of indole (1.0 mmol), HMTA (2.0 mmol) and I 2 (1.0 mmol) in solvent (10 mL). Since this reaction proceeds in a single phase of liquid, the reaction time was set by the inner volume of tubing and the flow rate in the continuous flow reactor. After the reaction is over, the product was quantified using 1 H NMR and the NMR yield was obtained. |