2,3-dimethylbutane-2,3-diamine

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: A 3.1 ml (5.0 mmole) of n-butyllithium.hexane solution was added dropwise to 1.51 g (5.0 mmole) of 1-benzyl-2,3,4,5-tetramethoxy-6-methylbenzene and 0.83 ml (5×1.1 mmole) of 1,1,2,2-tetramethylethylenediamine dissolved in anhydrous tetrahydrofuran (15 ml), under an atmosphere of argon at -5° C. over the period of 5 minutes, followed by stirring at -5° to 0° C. for 25 minutes. Then, a solution of 0.96 g (5.0 mmole) of 4-chlorobutanol.tetrahydropyranyl ether in tetrahydrofuran (5 ml) was added to the mixed solution over the period of 5 minutes, followed by stirring for further 15 minutes under ice-cooling. Subsequently, the cooling bath was removed, and stirring was effected at room temperature for 20 minutes. The reaction solution was cooled with ice, and made acid by adding a 10% aqueous phosphoric acid solution, and the product was extracted with isopropyl ether. The organic layer was separated out, washed with aqueous sodium chloride solution, dried (magnesium sulfate). The solvent was distilled off and the residue was dissolved in methanol (15 ml), followed by addition of 48 mg (5×1/20 mmole) of p-toluenesulfonic acid and stirring at 70° C. for 15 minutes. After cooling by standing at room temperature, the mixed solution was neutralized by adding an aqueous sodium hydrogen-carbonate solution, and the solvent was distilled off. Isopropyl ether and water were added to the residue to effect extraction. The isopropyl ether layer was washed with aqueous sodium chloride solution, dried (magnesium sulfate) and evaporated. The residual solution was chromatographed on a silica gel column to perform purification (elution with isopropyl ether) to thereby give 1.29 g (69%) of 5-(2,3,4,5-tetramethoxy-6-methylphenyl)-5-phenylpentane-1-ol. Its typical physical properties and nuclear magnetic resonance spectrum data are shown in Table 14. by stirring for further 15 minutes under ice- cooling Subsequently, the cooling bath was removed stirring was effected at room temperature for 20 minutes The reaction solution was cooled with ice by adding a 10% aqueous phosphoric acid solution the product was extracted with isopropyl ether The organic layer was separated out washed with aqueous sodium chloride solution dried (magnesium sulfate) The solvent was distilled off the residue was dissolved in methanol (15 ml) stirring at 70° C. for 15 minutes After cooling by standing at room temperature the solvent was distilled off Isopropyl ether and water were added to the residue extraction The isopropyl ether layer was washed with aqueous sodium chloride solution dried (magnesium sulfate) evaporated The residual solution was chromatographed on a silica gel column purification (elution with isopropyl ether)

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

実験手順: A 3.1 ml (5.0 mmole) portion of n-butyllithium.hexane solution was added dropwise to 1.35 g (5.0 mmole) of 1-benzyl-2,5-dimethoxy-3,4,6-trimethylbenzene and 0.83 ml (5×1.1 mmole) of 1,1,2,2-tetramethylethylenediamine dissolved in anhydrous tetrahydrofuran (15 ml), under an atmosphere of argon at 50° C. over the period of 5 miniutes, followed by stirring at 50° to 55° C. for 25 minutes. Then, a solution of 0.83 g (5.0 mmole) of n-hexyl bromide in tetrahydrofuran (5 ml) was added dropwise to the mixed solution over the period of 5 minutes, followed by stirring at 50° C. for further 10 minutes. The reaction solution was cooled with ice and made acid by adding a 10% aqueous phosphoric acid solution, and the product was extracted with isopropyl ether. The organic layer was separated out, washed with aqueous sodium chloride solution, dried (magnesium sulfate) and evaporated. The residual solution was chromatographed on a silica gel column to effect purification (elution with hexane/isopropyl ether) to thereby give 1.37 g (77%) of 7-(2,5-dimethoxy-3,4,6-trimethylphenyl)-7-phenylheptane. Its typical physical properties and nuclear magnetic resonance specrum data are shown in Table 14. by stirring at 50° C. for further 10 minutes The reaction solution was cooled with ice the product was extracted with isopropyl ether The organic layer was separated out washed with aqueous sodium chloride solution dried (magnesium sulfate) evaporated The residual solution was chromatographed on a silica gel column to effect purification (elution with hexane/isopropyl ether)

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

実験手順: A 3.1 ml (5.0 mmole) of n-butyllithium.hexane solution was added dropwise to 1.51 g (5.0 mmole) of 1-benzyl-2,3,4,5-tetramethoxy-6-methylbenzene and 0.83 ml (5×1.1 mmole) of 1,1,2,2-tetramethylethylenediamine dissolved in anhydrous tetrahydrofuran (15 ml), under an atmosphere of argon at -5° C. over the period of 5 minutes, followed by stirring at -5° to 0° C. for 25 minutes. Then, a solution of 0.96 g (5.0 mmole) of 4-chlorobutanol.tetrahydropyranyl ether in tetrahydrofuran (5 ml) was added to the mixed solution over the period of 5 minutes, followed by stirring for further 15 minutes under ice-cooling. Subsequently, the cooling bath was removed, and stirring was effected at room temperature for 20 minutes. The reaction solution was cooled with ice, and made acid by adding a 10% aqueous phosphoric acid solution, and the product was extracted with isopropyl ether. The organic layer was separated out, washed with aqueous sodium chloride solution, dried (magnesium sulfate). The solvent was distilled off and the residue was dissolved in methanol (15 ml), followed by addition of 48 mg (5×1/20 mmole) of p-toluenesulfonic acid and stirring at 70° C. for 15 minutes. After cooling by standing at room temperature, the mixed solution was neutralized by adding an aqueous sodium hydrogen-carbonate solution, and the solvent was distilled off. Isopropyl ether and water were added to the residue to effect extraction. The isopropyl ether layer was washed with aqueous sodium chloride solution, dried (magnesium sulfate) and evaporated. The residual solution was chromatographed on a silica gel column to perform purification (elution with isopropyl ether) to thereby give 1.29 g (69%) of 5-(2,3,4,5-tetramethoxy-6-methylphenyl)-5-phenylpentane-1-ol. Its typical physical properties and nuclear magnetic resonance spectrum data are shown in Table 14. by stirring for further 15 minutes under ice- cooling Subsequently, the cooling bath was removed stirring was effected at room temperature for 20 minutes The reaction solution was cooled with ice by adding a 10% aqueous phosphoric acid solution the product was extracted with isopropyl ether The organic layer was separated out washed with aqueous sodium chloride solution dried (magnesium sulfate) The solvent was distilled off the residue was dissolved in methanol (15 ml) stirring at 70° C. for 15 minutes After cooling by standing at room temperature the solvent was distilled off Isopropyl ether and water were added to the residue extraction The isopropyl ether layer was washed with aqueous sodium chloride solution dried (magnesium sulfate) evaporated The residual solution was chromatographed on a silica gel column purification (elution with isopropyl ether)

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

実験手順: A 3.1 ml (5.0 mmole) portion of n-butyllithium.hexane solution was added dropwise to 1.35 g (5.0 mmole) of 1-benzyl-2,5-dimethoxy-3,4,6-trimethylbenzene and 0.83 ml (5×1.1 mmole) of 1,1,2,2-tetramethylethylenediamine dissolved in anhydrous tetrahydrofuran (15 ml), under an atmosphere of argon at 50° C. over the period of 5 minutes, followed by stirring at 50° to 55° C. for 25 minutes. Then, a solution of 0.83 (5.0 mmole) of n-hexyl bromide in tetrahydrofuran (5 ml) was added dropwise to the mixed solution over the period of 5 minutes, followed by stirring at 50° C. for further 10 minutes. The reaction solution was cooled with ice and made acid by adding a 10% aqueous phosphoric acid solution, and the product was extracted with isopropyl ether. The organic layer was separated out, washed with aqueous sodium chloride solution, dried (magnesium sulfate) and evaporated. The residual solution was chromatographed on a silica gel column to effect purification (elution with hexane/isopropyl ether) to thereby give 1.37 g (77%) of 7-(2,5-dimethoxy-3,4,6-trimethylphenyl)-7-phenylheptane. Its typical physical properties and nuclear magnetic resonance specrum data are shown in Table 14. by stirring at 50° C. for further 10 minutes The reaction solution was cooled with ice the product was extracted with isopropyl ether The organic layer was separated out washed with aqueous sodium chloride solution dried (magnesium sulfate) evaporated The residual solution was chromatographed on a silica gel column to effect purification (elution with hexane/isopropyl ether)

反応条件: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To dioxane (10 mL) was added 5-bromo-3-methylpyridin-2-amine (2 g, 10.6 mmol), sodium iodide (3.2 g, 21.4 mmoL), copper iodide (0.190 g, 1.06 mmol) and the solution degassed followed by addition of tetramethylethane-1,2-diamine (0.803 mL, 1.06 mmol) this mixture heated at 110° C. overnight. After cooling water was added and extracted the crude product with ethyl acetate. The residue was purified by column chromatography to give 5-iodo-3-methylpyridin-2-amine as a beige solid (2.3 g, 93%). the solution degassed was added extracted the crude product with ethyl acetate The residue was purified by column chromatography