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Stage #1: at -40℃; for 1 h; Stage #2: With ammonium chloride In tetrahydrofuran; water at -40 - 20℃;
A 1.0 M solution of vinylmagnesium bromide in TηF (0.13 L, 130 mmol) is added slowly to 10 g (43 mmol) of 3-bromo-4-chloro-nitrobenzene in 140 mL of TηF at -40 °C. The mixture is stirred at -40 C for an additional hour when aqueous NH4Cl is added. The mixture is allowed to warm to rt, and then is extracted with EtOAc. The extract is washed with brine, dried over MgSO4, filtered, concentrated, and purified twice by chromatography (33percent EtOAc in hexanes) to provide 0.95 g (9.7percent) of 4-bromo-5-chloro-lH-indole and 0.77 g (7.9percent) of 6- bromo-5-chloro-lH-indole. Each of the indole products is separately treated with 1.1 equivalents of BoC2O and 0.2 equivalents of DMAP in MeCN. The mixtures are <n="128"/>concentrated and the residues chromatographed (10percent EtOAc in hexanes) to provide 1-011 (32percent) and 1-012 (48percent).
unde nitrogen stream 2-bromo-1-chloro-4-nitrobenzene (25g, 0.107mol) in THF (250 ml) , vinylmagnesium bromoide (1M in THF, 321 ml, 0.321mol) is slowly added ,1 hour stirring time in -40 °C . NH4Cl then completion aqueous solution, visitor is checked through a elevated temperature room temperature. After, ethyl which has organic layer which is then subjected to reverse phase, MgSO4in organic layer to the second interlayer, filters the concentrated within, column chromatography for purifying the 6-bromo-5-chloro-1H-indole (7.89g, yield: 32percent) is obtained.
A 1.0 M solution of vinylmagnesium bromide in TetaF (0.13 L, 130 mmol) is added slowly to 10 g (43 mmol) of 3-bromo-4-chloro-nitrobenzene in 140 mL of TetaF at -40 C. The mixture is stirred at -40 C for an additional hour when aqueous NH4Cl is added. The mixture is allowed to warm to rt, and then is extracted with EtOAc. The extract is washed with brine, dried over MgSO4, filtered, concentrated, and purified twice by chromatography (33% EtOAc in hexanes) to provide 0.95 g (9.7%) of 4-bromo-5-chloro-lH-indole and 0.77 g (7.9%) of 6- bromo-5-chloro-lH-indole. Each of the indole products is separately treated with 1.1 equivalents of BoC2O and 0.2 equivalents of DMAP in MeCN. The mixtures are <n="128"/>concentrated and the residues chromatographed (10% EtOAc in hexanes) to provide 1-011 (32%) and 1-012 (48%).
A 1.0 M solution of vinylmagnesium bromide in TetaF (0.13 L, 130 mmol) is added slowly to 10 g (43 mmol) of 3-bromo-4-chloro-nitrobenzene in 140 mL of TetaF at -40 C. The mixture is stirred at -40 C for an additional hour when aqueous NH4Cl is added. The mixture is allowed to warm to rt, and then is extracted with EtOAc. The extract is washed with brine, dried over MgSO4, filtered, concentrated, and purified twice by chromatography (33% EtOAc in hexanes) to provide 0.95 g (9.7%) of 4-bromo-5-chloro-lH-indole and 0.77 g (7.9%) of 6- bromo-5-chloro-lH-indole. Each of the indole products is separately treated with 1.1 equivalents of BoC2O and 0.2 equivalents of DMAP in MeCN. The mixtures are <n="128"/>concentrated and the residues chromatographed (10% EtOAc in hexanes) to provide 1-011 (32%) and 1-012 (48%).
5-chloro-6-(1-methyl-1H-pyrazol-4-yl)-1H-indole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
76%
With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In 1,2-dimethoxyethane; water; at 120℃; for 12.0h;Inert atmosphere;
To a solution of <strong>[1191028-50-8]6-bromo-5-chloro-1H-indole</strong> (500 mg, 2.17 mmol), l-methyl-4-(4,4,5,5- tetramethyl-l,3,2-dioxaborolan-2-yl)-IH-pyrazole (0.54 g, 2.60 rnrnol) and Na2CO3 (0.69 g, 6.51 mmol) in DME/1120 (10 mL, 4: 1) was added bis(triphenylphosphine)palladium(II) dichloride (140 mg, 0.22 mmol). The mixture was heated to 120 C for 12 h under a nitrogenatmosphere. After cooling the reaction to room temperature, water (10 mL) was added and the mixture was extracted with EtOAc (10 mL x 3). The combined organic layers were washed with sat. aq. NaHCO3 (10 mL x 3), dried over anhydrous Na2SO4 and concentrated in vacuo. The crude residue was purified by silica gel chromatography (petroleum ether / EtOAc3: 1) to give the title compound (0.38 g, 76%) as a light yellow solid.
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 85℃; for 4.0h;Inert atmosphere;
under nitrogen <strong>[1191028-50-8]6-bromo-5-chloro-1H-indole</strong> (7.89g, 34.3mmol) in THF/H2O (80 ml/20 ml) , 2-Nitrophenylboronic acid (5.71g, 34.3mmol), and K2CO3(14.2g, 0.103mol) , Pd (PPh3)4(1.98g, 1.71mmol) are added , stirring 4 hours in 85 C . After, after cooled to room temperature, was of concentrating the THF. Furthermore, ethyl which has organic layer which is then subjected to reverse phase, MgSO4in organic layer to the second interlayer, filters the concentrated within, column chromatography for purifying the 5-chloro-6 -(2-nitrophenyl) -1H-indole (6.72g, yield: 72%) is obtained.
In tetrahydrofuran; at -40℃; for 1h;Inert atmosphere;
unde nitrogen stream 2-bromo-1-chloro-4-nitrobenzene (25g, 0.107mol) in THF (250 ml) , vinylmagnesium bromoide (1M in THF, 321 ml, 0.321mol) is slowly added ,1 hour stirring time in -40 C . NH4Cl then completion aqueous solution, visitor is checked through a elevated temperature room temperature. After, ethyl which has organic layer which is then subjected to reverse phase, MgSO4in organic layer to the second interlayer, filters the concentrated within, column chromatography for purifying the 6-bromo-5-chloro-1H-indole (7.89g, yield: 32%) is obtained.
2-(5-chloro-6-bromo-1H-indol-3-yl)-2-oxoacetyl chloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
47 g
With aluminum (III) chloride; In dichloromethane; for 2.0h;Reflux;
40 g of 5-chloro-6-bromoanthraquinone was added to 450 ml of anhydrous dichloromethane.Add 15g of aluminum trichloride,Then add 60g oxalyl chloride,Heated to reflux for 2 hours,Cool to room temperature, add water,Liquid separation, drying, concentration,The residue is separated on the column 47 g of 2-(5-chloro-6-bromo-1H-indol-3-yl)-2-oxoacetyl chloride