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CAS No. : | 165250-69-1 | MDL No. : | MFCD11035915 |
Formula : | C9H8N2O2 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | XRJNLFAXLSBIDS-UHFFFAOYSA-N |
M.W : | 176.17 | Pubchem ID : | 15453462 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | |
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 |
---|---|---|
In methanol; dichloromethane; | D. 4-Methyl-5-nitroindole To a suspension of 4-methyl-5-nitroindoline (4.767 g, 0.0268 mol) in 100 mL of methanol was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (6.697 g, 0.0295 at room temperature for 1 h. The reaction mixture was then evaporated and the residue was taken up in dichloromethane. This solution was then washed with saturated aqueous NaHCO3 (*4), dried (Na2 SO4) and evaporated to give a solid. Crystallization of this material from ethyl acetate-hexane (-20 C.) afforded 4.161 g of the title compound as greenish-gold needles, mp 179-180 C. Chromatography of the mother liquor (SiO2 /ethyl acetate-hexane, 1:1) gave an additional 0.417 g of the pure product. Total yield=4.578 g (97%): IR (KBr) 3318, 1604, 1585 cm-; 1 H NMR (DMSO-d6, 200 MHz) delta 11.72 (br s, 1H), 7.81 (d, J=9.0 Hz, 1H), 7.56 (t, J=2.8 Hz, 1H), 7.39 (d, J=8.9 Hz, 1H), 6.79 (m, 1H), 2.75 (s, 3H). Anal. Calcd for C 9 H8 N2 O2: C, 61.35; H, 4.58; N, 15.90. Found: C, 61.32; H, 4.40; N, 15.96. | |
In methanol; dichloromethane; | D. 4-Methyl-5-nitroindole To a suspension of 4-methyl-5-nitroindoline (4.767 g, 0.0268 mol) in 100 mL of methanol was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (6.697 g, 0.0295 mol) all at once and the resulting mixture was stirred at room temperature for 1 h. The reaction mixture was then evaporated and the residue was taken up in dichloromethane. This solution was then washed with saturated aqueous NaHCO3 (*4), dried (Na2 SO4) and evaporated to give a solid. Crystallization of this material from ethyl acetate-hexane (-20 C.) afforded 4.161 g of the title compound as greenish-gold needles, mp 179-180 C. Chromatography of the mother liquor (SiO2 /ethyl acetate-hexane, 1:1) gave an additional 0.417 g of the pure product. Total yield=4.578 g (97%): IR (KBr) 3318, 1604, 1585 cm-1; 1 H NMR (DMSO-d6, 200 MHz) delta11.72 (br s, 1H), 7.81 (d, J=9.0 Hz, 1H), 7.56 (t, J=2.8 Hz, 1H), 7.39 (d, J=8.9 Hz, 1H), 6.79 (m, 1H), 2.75 (s, 3H). Anal. Calcd for C9 H8 N2 O2: C, 61.35; H, 4.58; N, 15.90. Found: C, 61.32; H, 4.40; N, 15.96. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With formaldehyd; In acetonitrile; | 5-(4-Methyl-5-nitroindol-3-ylmethyl)-2,2-dimethyl-1,3-dioxane-4,6-dione An adaption of the procedure of Flaugh was used. Thus, a solution of <strong>[165250-69-1]4-methyl-5-nitroindole</strong> (0.880 g, 5.00 mmol), Meldrum's acid (0.864 g, 6.00 mmol), 37% aqueous formaldehyde (0.5 mL, 6.0 mmol) and D,L-proline (0.029 g, 0.25 mmol) in 25 mL of acetonitrile was stirred at room temperature for 72 h. The resulting yellow slurry was stored at -20 C. and then the cold mixture was filtered. The filtercake was washed with cold acetonitrile and ether, and then it was dried in vacuo to give the title compound (1.055 g, 64%) as a canary-yellow solid, mp 196-198 C. (dec): IR (KBr) 3338, 1782, 1742 cm-1; 1 H NMR (DMSO-d6, 200 MHz) delta 11.46 (br s, 1H), 7.61 (d, J=8.9 Hz, 1H), 7.32 (d, J=8.9 Hz, 1H), 7.25 (d, J= 2.4 Hz, 1H), 4.74 (t, J=5.0 Hz, 1H), 3.64 (d, J=4.9 Hz, 1H), 2.80 (s, 3H), 1.84 (s, 3H), 1.69 (s, 3H). Anal. Calcd for C16 H16 N2 O6: C, 57.83; H, 4.85; N, 8.43. Found: C, 57.42; H, 4.68; N, 8.52. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | palladium-carbon; In methanol; | 4-Methyl-5-aminoindole A solution of <strong>[165250-69-1]4-methyl-5-nitroindole</strong> (0.72 g, 4.1 mmol) in 50 mL of methanol was stirred with 50 mg of 10% Pd/C under H2 for 12 h. Reaction mixture was filtered and concentrated in vacuo to provide an oil (0.61 g, >95%) which was characterized as the desired product by NMR analysis and subjected to a following reaction without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.72 g (4.1 mmol, 80%) | With methylmagnesium bromide; chloranil; In tetrahydrofuran; | 4-Methyl-5-nitroindole To a solution of 5-nitroindole (from Aldrich, 0.82 g, 5.1 mmol) in 20 mL of dry THF was added 5.0 mL (15 mmol) of methylmagnesium bromide for 0.5 h period and the resulting reaction mixture was stirred for 1 h at 25 C. Reaction was the quenched by adding a THF solution of tetrachloro-1,4-benzoquinone (1.2 g, 4.9 mmol). Reaction mixture was concentrated in vacuo, yielding a dark solid which was subjected to column chromatography (30% EtOAc/n-Hexane) to yield 0.72 g (4.1 mmol, 80%) of the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With borane-THF; In tetrahydrofuran; at 20 - 50℃; for 1.75h;Cooling with ice; Inert atmosphere; | General procedure: [Reference Example 151] (0733) (0734) To the solution of 200 mg of 6-fluoro-5-nitro-1H-indole-2,3-dione in 4 mL of tetrahydrofuran, 2.2 mL of a 1.1 mol/L borane-tetrahydrofuran solution was added dropwise under ice-cooling and a nitrogen atmosphere, and the resultant was stirred at room temperature for one hour and 30 minutes and then stirred at 50C for 15 minutes. After cooling the reaction mixture to room temperature, water and 1 mL of 1 mol/L hydrochloric acid were added thereto dropwise, and the solvent was distilled off under reduced pressure. After adding ethyl acetate and water, the organic layer was separated, washed with a saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to give 172 mg of 6-fluoro-5-nitro-1H-indole as a yellow brown solid. 1H-NMR (DMSO-d6) delta: 6.71 (1H, s), 7.47 (1H, d, J = 11.9 Hz), 7.60 (1H, s), 8.48 (1H, d, J = 7.3 Hz), 11.82 (1H, s). MS (ESI, m/z): 179 (M-H)-. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | To a cooled solution (ice-water bath) of <strong>[165250-69-1]4-methyl-5-nitroindole</strong> (1.76 g, 10 mmol) in DMF (30 mL) was added KOH pellets (0.78 g, 14 mmol). The cooling bath was removed, and the mixture was stirred at rt for 10 min. Iodine (2.79 g, 11 mmol) was added, and the stirring was continued for 5 h at room temperature. To this mixture was added potassium carbonate (3.17 g, 23 mmol) and methyl iodide (3.1 mL, 50 mmol), and stirring was continued at room temperature for 16 h. The mixture was diluted with water (150 mL), and treated with solid NaHSO3 with stirring until all excess iodine was quenched. The crude product was collected by filtration, washed with plenty of water, and dried. |
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