2-hydroxy-3-iodo-4-methoxybenzaldehyde

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To the mixture of 1.5 g (5.4 mmol) of 2-hydroxy-3-iodo-4-methoxybenzaldehyde, 3.1 mL (20.6 mmol) of ethyl trifluoromethylcrotonate, and 4.2 g(12.9 mmol) of cesium carbonate was added 8 mL of anhydrous N,N-dimethylformamide. The mixture was heated to 90° C. overnight. After cooling to room temperature, to the reaction was added 150 mL of ethyl acetate. The organic solution was filtered, washed with brine and dried over anhydrous magnesium sulfate. After removing the volatiles, the residue was purified by silica chromatography with ethyl acetate/hexane (2:8) to give 0.3 g (14%) a light yellow solid: 1H NMR(CDCl3/400 MHz) 7.65(s, 1H), 7.17(d, J=8.4 Hz, 1H), 6.50(d, J=8.4 Hz, 1H), 5.80(q, J=6.8 Hz,1H), 4.30(m, 2H), 3.92(s, 3H), 1.33(t, J=7.6 Hz, 3H). MS (ESI+) 429.0(M+1, 100). HRMS (EI+) m/z calcd for (C14H12F3O4) 427.9732, found 427.9715. After cooling to room temperature, to the reaction The organic solution was filtered washed with brine dried over anhydrous magnesium sulfate After removing the volatiles the residue was purified by silica chromatography with ethyl acetate/hexane (2:8)

反応条件: temp:68.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 4.0 g (26.3 mmol) of 2-hydroxyl-4-methoxybenzaldehyde in 30 mL of ethanol was added 1.87 g (7.4 mmol) of iodine, followed by addition of a solution of 6 g (26.3 mmol) of periodic acid in 10 mL of water. The resulting dark yellow solution was heated to 68° C. for two h. After cooling to room temperature, the reaction was added to 300 mL of ethyl acetate. The resulting organic solution was washed with saturated aqueous solution of sodium sulfite, washed with brine and dried over anhydrous magnesium sulfate. After removing the volatiles, the crude products were purified by silica chromatography to afford 1.8 g (49%) of a light yellow solid: 1H NMR(CDCl3/400 MHz,) 12.18(s, 1H), 9.63(s, 1H), 7.53(d, J=8.4 Hz, 1H), 6.56(d, J=8.4 Hz, 1H), 3.99(s, 3H). 13C NMR (CDCl3/400 MHz) 194.2, 165.3, 163.0, 136.3, 116.1, 103.6, 57.2. MS (ESI+) 278.9(M+1, 100). After cooling to room temperature The resulting organic solution was washed with saturated aqueous solution of sodium sulfite washed with brine dried over anhydrous magnesium sulfate After removing the volatiles the crude products were purified by silica chromatography

反応条件: temp:68.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 4.0 g (26.3 mmol) of 2-hydroxyl-4-methoxybenzaldehyde in 30 mL of ethanol was added 1.87 g (7.4 mmol) of iodine, followed by addition of a solution of 6 g (26.3 mmol) of periodic acid in 10 mL of water. The resulting dark yellow solution was heated to 68° C. for two h. After cooling to room temperature, the reaction was added to 300 mL of ethyl acetate. The resulting organic solution was washed with saturated aqueous solution of sodium sulfite, washed with brine and dried over anhydrous magnesium sulfate. After removing the volatiles, the crude products were purified by silica chromatography to afford 1.8 g (49%) of a light yellow solid: 1H NMR(CDCl3/400 MHz,) 12.18(s, 1H), 9.63(s, 1H), 7.53(d, J=8.4 Hz, 1H), 6.56(d, J=8.4 Hz, 1H), 3.99(s, 3H). 13C NMR (CDCl3/400 MHz) 194.2, 165.3, 163.0, 136.3, 116.1, 103.6, 57.2. MS (ESI+) 278.9(M+1, 100). After cooling to room temperature The resulting organic solution was washed with saturated aqueous solution of sodium sulfite washed with brine dried over anhydrous magnesium sulfate After removing the volatiles the crude products were purified by silica chromatography

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Methylation of the phenolic --OH group in (12) with MeI-K2CO3 in refluxing acetone proceed smoothly to give 2,4-dimethoxy-3-iodobenzaldehyde (13), m.p. 103.3° C. [1H-NMR: (90 MHz, CDCl3, δ): 3.90 (overlapping s, 2×3H, C2 and C4-OCH3), 6.62 and 7.78 (pair of doublets. Jab=8Hz, C5-H and C6-H), 10.12 (s, 1H, HC=O).]

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To the mixture of 1.5 g (5.4 mmol) of 2-hydroxy-3-iodo-4-methoxybenzaldehyde, 3.1 mL (20.6 mmol) of ethyl trifluoromethylcrotonate, and 4.2 g(12.9 mmol) of cesium carbonate was added 8 mL of anhydrous N,N-dimethylformamide. The mixture was heated to 90° C. overnight. After cooling to room temperature, to the reaction was added 150 mL of ethyl acetate. The organic solution was filtered, washed with brine and dried over anhydrous magnesium sulfate. After removing the volatiles, the residue was purified by silica chromatography with ethyl acetate/hexane (2:8) to give 0.3 g (14%) a light yellow solid: 1H NMR(CDCl3/400 MHz) 7.65(s, 1H), 7.17(d, J=8.4 Hz, 1H), 6.50(d, J=8.4 Hz, 1H), 5.80(q, J=6.8 Hz,1H), 4.30(m, 2H), 3.92(s, 3H), 1.33(t, J=7.6 Hz, 3H). MS (ESI+) 429.0(M+1, 100). HRMS (EI+) m/z calcd for (C14H12F3O4) 427.9732, found 427.9715. After cooling to room temperature, to the reaction The organic solution was filtered washed with brine dried over anhydrous magnesium sulfate After removing the volatiles the residue was purified by silica chromatography with ethyl acetate/hexane (2:8)

反応条件: temp:68.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 4.0 g (26.3 mmol) of 2-hydroxyl-4-methoxybenzaldehyde in 30 mL of ethanol was added 1.87 g (7.4 mmol) of iodine, followed by addition of a solution of 6 g (26.3 mmol) of periodic acid in 10 mL of water. The resulting dark yellow solution was heated to 68° C. for two h. After cooling to room temperature, the reaction was added to 300 mL of ethyl acetate. The resulting organic solution was washed with saturated aqueous solution of sodium sulfite, washed with brine and dried over anhydrous magnesium sulfate. After removing the volatiles, the crude products were purified by silica chromatography to afford 1.8 g (49%) of a light yellow solid: 1H NMR(CDCl3/400 MHz,) 12.18(s, 1H), 9.63(s, 1H), 7.53(d, J=8.4 Hz, 1H), 6.56(d, J=8.4 Hz, 1H), 3.99(s, 3H). 13C NMR (CDCl3/400 MHz) 194.2, 165.3, 163.0, 136.3, 116.1, 103.6, 57.2. MS (ESI+) 278.9(M+1, 100). After cooling to room temperature The resulting organic solution was washed with saturated aqueous solution of sodium sulfite washed with brine dried over anhydrous magnesium sulfate After removing the volatiles the crude products were purified by silica chromatography