Patent Application
20070282111
Into a 10 mL Schrenk tube, a stirrer was put, and the tube was flushed with nitrogen. Then, 45 mg (0.049 mmol) of dipalladium(0) tris(dibenzylideneacetone), 66 mg (0.32 mmol) of tri-tert-butylphosphine and 1 mL of o-xylene were added, and this solution was stirred for 20 minutes at 60° C. in a nitrogen atmosphere to obtain a catalyst solution. A 100 mL three necked round bottomed flask was flushed with nitrogen, 0.79 g (5.0 mmol) of bromobenzene, 1.66 g (9.9 mmol) of carbazole, 1.37 g (9.9 mmol) of potassium carbonate, 39 mg (0.15 mmol) of 18-crown-6 and 30 mL of o-xylene were added. At room temperature, to this solution, the previous catalyst solution was added by a syringe, and the reaction solution was heated to 120° C. Two hours later, the heating was terminated, and the reaction solution was left to cool to room temperature. This reaction solution was extracted with 100 g of toluene, and the obtained organic layer was dried over anhydrous magnesium sulfate. This organic layer was subjected to a gas chromatography quantitative analysis using triphenylamine as an internal standard substance, whereby N-phenyl carbazole was 1.21 g (yield: 99%).
Into a 10 mL Schrenk tube, a stirrer was put, and the tube was flushed with nitrogen. Then, 45 mg (0.049 mmol) of dipalladium(0) tris(dibenzylideneacetone), 66 mg (0.32 mmol) of tri-tert-butylphosphine and 1 mL of o-xylene were added, and this solution was stirred for 20 minutes at 60° C. in a nitrogen atmosphere to obtain a catalyst solution. A 100 mL three necked round bottomed flask was flushed with nitrogen, and 1.00 g (5.0 mmol) of p-bromonitrobenzene, 1.66 g (9.9 mmol) of carbazole, 1.37 g (9.9 mmol) of potassium carbonate, 39 mg (0.15 mmol) of 18-crown-6 and 30 mL of o-xylene were added. At room temperature, to this solution, the previous catalyst solution was added by a syringe, and the reaction solution was heated to 120° C. Seven hours later, the heating was terminated, and the reaction solution was left to cool to room temperature. This reaction solution was extracted with 100 g of toluene, and the obtained organic layer was dried over anhydrous magnesium sulfate. This organic layer was subjected to a gas chromatography quantitative analysis using triphenylamine as an internal standard substance, whereby N-(4-nitrophenyl)carbazole was 1.14 g (yield: 80%).
Into a 10 mL Schrenk tube, a stirrer was put, and the tube was flushed with nitrogen. Then, 45 mg (0.049 mmol) of dipalladium(0) tris(dibenzylideneacetone), 66 mg (0.32 mmol) of tri-tert-butylphosphine and 1 mL of o-xylene were added, and this solution was stirred for 20 minutes at 60° C. in a nitrogen atmosphere to obtain a catalyst solution. A 100 mL three necked round bottomed flask was flushed with nitrogen, and 0.94 g (5.0 mmol) of p-bromoanisole, 1.66 g (9.9 mmol) of carbazole, 1.37 g (9.9 mmol) of potassium carbonate, 39 mg (0.15 mmol) of 18-crown-6 and 30 mL of o-xylene were added. At room temperature, to this solution, the previous catalyst solution was added by a syringe, and the reaction solution was heated to 120° C. Five hours later, the heating was terminated, and the reaction solution was left to cool to room temperature. This reaction solution was extracted with 100 g of toluene, and the obtained organic layer was dried over anhydrous magnesium sulfate. This organic layer was subjected to a gas chromatography quantitative analysis using triphenylamine as an internal standard substance, whereby N-(4-methoxyphenyl)carbazole was 0.87 g (yield: 71%).
Into a 10 mL Schrenk tube, a stirrer was put, and the tube was flushed with nitrogen. Then, 45 mg (0.049 mmol) of dipalladium(0) tris(dibenzylideneacetone), 66 mg (0.32 mmol) of tri-tert-butylphosphine and 1 mL of benzene were added, and this solution was stirred for 20 minutes at 60° C. in a nitrogen atmosphere to obtain a catalyst solution. A 100 mL three necked round bottomed flask was flushed with nitrogen, and 1.08 g (5.0 mmol) of methyl 4-bromobenzoate, 1.66 g (9.9 mmol) of carbazole, 1.37 g (9.9 mmol) of potassium carbonate, 39 mg (0.15 mmol) of 18-crown-6 and 30 mL of benzene were added. At room temperature, to this solution, the previous catalyst solution was added by a syringe, and the reaction solution was heated to 90° C. Seven hours later, the heating was terminated, and the reaction solution was left to cool to room temperature. This reaction solution was extracted with 100 g of toluene, and the obtained organic layer was dried over anhydrous magnesium sulfate. This organic layer was subjected to a gas chromatography quantitative analysis using triphenylamine as an internal standard substance, whereby N-(4-methyl benzoate)carbazole was 1.50 g (yield: 99%).
The same operation as in Example 1 was carried out except that no 18-crown-6 was added, whereby 0.34 g (yield: 28%) of N-phenylcarbazole was obtained.
The same operation as in Example 1 was carried out except that no 18-crown-6 was added, and the reaction time was changed to 31 hours, whereby 0.90 g (yield: 74%) of N-phenylcarbazole was obtained.
The same operation as in Example 2 was carried out except that no 18-crown-6 was added, whereby 0.20 g (yield: 14%) of N-(4-nitrophenyl)carbazole was obtained.
The same operation as in Example 2 was carried out except that no 18-crown-6 was added, and the reaction time was changed to 28 hours, whereby 0.65 g (yield: 45%) of N-(4-nitrophenyl)carbazole was obtained.
The same operation as in Example 3 was carried out except that no 18-crown-6 was added, whereby 0.23 g (yield: 19%) of N-(4-methoxyphenyl)carbazole was obtained.
The same operation as in Example 3 was carried out except that no 18-crown-6 was added, and the reaction time was changed to 31 hours, whereby 0.43 g (yield: 31%) of N-(4-methoxyphenyl)carbazole was obtained.
The same operation as in Example 4 was carried out except that no 18-crown-6 was added, whereby 0.47 g (yield: 31%) of N-(4-methyl benzoate)carbazole was obtained.
The same operation as in Example 4 was carried out except that no 18-crown-6 was added, and the reaction time was changed to 22 hours, whereby 0.83 g (yield: 55%) of N-(4-methyl benzoate)carbazole was obtained.
Into a 10 mL Schrenk tube, a stirrer was put, and the tube was flushed with nitrogen. Then, 45 mg (0.049 mmol) of dipalladium(0) tris(dibenzylideneacetone), 66 mg (0.32 mmol) of tri-tert-butylphosphine and 1 mL of o-xylene were added, and this solution was stirred for 20 minutes at 60° C. in a nitrogen atmosphere to obtain a catalyst solution. A 100 mL three necked round bottomed flask was flushed with nitrogen, and 0.79 g (5.0 mmol) of bromobenzene, 1.69 g (10.0 mmol) of diphenylamine, 2.12 g (10.0 mmol) of potassium phosphate, 39 mg (0.15 mmol) of 18-crown-6 and 30 mL of o-xylene were added. At room temperature, to this solution, the previous catalyst solution was added by a syringe, and the reaction solution was heated to 120° C. Ten hours later, the heating was terminated, and the reaction solution was left to cool to room temperature. This reaction solution was extracted with 100 g of toluene, and the obtained organic layer was dried over anhydrous magnesium sulfate. This organic layer was subjected to a gas chromatography quantitative analysis using 2-bromonaphthalene as an internal standard substance, whereby triphenylamine was 0.86 g (yield: 70%).
The same operation as in Example 5 was carried out except that no 18-crown-6 was added, whereby 0.25 g (yield: 20%) of triphenylamine was obtained.
The same operation as in Example 5 was carried out except that no 18-crown-6 was added, and the reaction time was changed to 23 hours, whereby 0.66 g (yield: 54%) of triphenylamine was obtained.
The entire disclosure of Japanese Patent Application No. 2006-156919 filed on Jun. 6, 2006 including specification, claims and summary is incorporated herein by reference in its entirety.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2006-156919 | Jun 2006 | JP | national |
