N,N,2-三甲基氮丙啶-1-羧酰胺

反应条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Pyrazole (20 mg), trans-N,N′-dimethylcyclohexane-1,2-diamine (24 μl), copper iodide (14 mg), and cesium carbonate (73 mg) were added to an N,N-dimethylpropyleneurea (2 ml) solution containing 3-iodo-7-nitroquinoline (45 mg), followed by stirring at 70° C. for 2.5 hours in a nitrogen atmosphere. Water was added to the reaction solution, an insoluble precipitate was purified by silica gel chromatography (n-hexane:ethyl acetate=1:0 to 0:1), and a light yellow solid of 7-nitro-3-(1H-pyrazol-1-yl)quinoline (36 mg) was thus obtained. an insoluble precipitate was purified by silica gel chromatography (n-hexane:ethyl acetate=1:0 to 0:1)

反应条件: temp:-100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of n-butyllithium (0.1 mol) in 65 ml of hexane is added to a mixture of 4"-propyl-2,3-difluoro-p-terphenyl (0.1 mol), potassium t-butylate (0.1 mol) and 200 ml of THF at -100° C. After stirring 5 minutes at -100° C. a mixture of brompentane (0.1 mol) and N,N-dimethylpropylene urea (0.1 mol, DMPU) is added. After warming-up to -30° C. and usual work-up 4"-propyl-4-pentyl-2,3-difluoro-p-terphenyl is obtained. is added After warming-up to -30° C.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of lithium diisopropylamide (0.02 mol) in THF/hexane, prepared from 0.02 mol of diisopropylamine in 25 ml of THF and 12.5 ml of a 1.6-molar solution of n-butyllithium in hexane, is added dropwise at 25° C. to a mixture of 0.02 mol of 1-(4'-pentylbiphenyl-4-yl)-2-(3,5-difluorophenyl)ethane, 0.02 mol of N,N-dimethylpropyleneurea, 0.02 mol of 1-iodopropane and 25 ml of THF. After stirring at room temperature for 1.5 hours, the reaction mixture is poured into water, the phases are separated, and the aqueous phase is extracted with 2×50 ml of methylene chloride. Drying over magnesium sulfate, evaporation of the solvent and chromatography give the pure product. the phases are separated the aqueous phase is extracted with 2×50 ml of methylene chloride Drying over magnesium sulfate, evaporation of the solvent and chromatography give the pure product

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of lithium diisopropylamide (0.02 mol) in THF/hexane, prepared from 0.02 mol of diisopropylamine in 25 ml of THF and 12.5 ml of a 1.6-molar solution of n-butyllithium in hexane, is added dropwise at 25° C. to a mixture of 0.02 mol of 1-(4'-pentylbiphenyl-4-yl)-2-(3,5-difluorophenyl)ethane, 0.02 mol of N,N-dimethylpropyleneurea, 0.02 mol of 1-iodopropane and 25 ml of THF. After stirring at room temperature for 1.5 hours, the reaction mixture is poured into water, the phases are separated, and the aqueous phase is extracted with 2×50 ml of methylene chloride. Drying over magnesium sulfate, evaporation of the solvent and chromatography give the pure product. the phases are separated the aqueous phase is extracted with 2×50 ml of methylene chloride Drying over magnesium sulfate, evaporation of the solvent and chromatography give the pure product

反应条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of 0.16 g of 10-[(6-chloro-3-pyridinyl)carbonyl]-10,11-dihydro-5H-pyrrolo[2,1-c][1,4]benzodiazepine, 40 mg of pyridine and 2 ml of 2-methylpropylamine is stirred and heated at 100° C. in a sealed vessel for 1 hour. To the mixture is added 0.2 ml of N,N-dimethylpropyleneurea and the mixture is heated at 110° C. for 7 hours. The volatiles are removed under vacuum and 10 ml of 0.5N NaOH is added to the residue. The mixture is filtered and the solid washed with water and then hexane. The solid is dissolved in ethyl acetate and the solution washed with 0.5N NaOH, brine and dried (Na2SO4). The solution is filtered through a thin pad of hydrous magnesium silicate and the filtrate concentrated to dryness. The residue is triturated with diisopropylether-hexane to give 0.18 g of white solid; mass spectrum (CI) 361 (M+H). the mixture is heated at 110° C. for 7 hours The volatiles are removed under vacuum and 10 ml of 0.5N NaOH is added to the residue The mixture is filtered the solid washed with water The solid is dissolved in ethyl acetate the solution washed with 0.5N NaOH, brine dried (Na2SO4) The solution is filtered through a thin pad of hydrous magnesium silicate the filtrate concentrated to dryness The residue is triturated with diisopropylether-hexane

反应条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Pyrazole (20 mg), trans-N,N′-dimethylcyclohexane-1,2-diamine (24 μl), copper iodide (14 mg), and cesium carbonate (73 mg) were added to an N,N-dimethylpropyleneurea (2 ml) solution containing 3-iodo-7-nitroquinoline (45 mg), followed by stirring at 70° C. for 2.5 hours in a nitrogen atmosphere. Water was added to the reaction solution, an insoluble precipitate was purified by silica gel chromatography (n-hexane:ethyl acetate=1:0 to 0:1), and a light yellow solid of 7-nitro-3-(1H-pyrazol-1-yl)quinoline (36 mg) was thus obtained. an insoluble precipitate was purified by silica gel chromatography (n-hexane:ethyl acetate=1:0 to 0:1)

反应条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Pyrazole (20 mg), trans-N,N′-dimethylcyclohexane-1,2-diamine (24 μl), copper iodide (14 mg), and cesium carbonate (73 mg) were added to an N,N-dimethylpropyleneurea (2 ml) solution containing 3-iodo-7-nitroquinoline (45 mg), followed by stirring at 70° C. for 2.5 hours in a nitrogen atmosphere. Water was added to the reaction solution, an insoluble precipitate was purified by silica gel chromatography (n-hexane:ethyl acetate=1:0 to 0:1), and a light yellow solid of 7-nitro-3-(1H-pyrazol-1-yl)quinoline (36 mg) was thus obtained. an insoluble precipitate was purified by silica gel chromatography (n-hexane:ethyl acetate=1:0 to 0:1)

反应条件: temp:-100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of n-butyllithium (0.1 mol) in 65 ml of hexane is added to a mixture of 4"-propyl-2,3-difluoro-p-terphenyl (0.1 mol), potassium t-butylate (0.1 mol) and 200 ml of THF at -100° C. After stirring 5 minutes at -100° C. a mixture of brompentane (0.1 mol) and N,N-dimethylpropylene urea (0.1 mol, DMPU) is added. After warming-up to -30° C. and usual work-up 4"-propyl-4-pentyl-2,3-difluoro-p-terphenyl is obtained. is added After warming-up to -30° C.

反应条件: temp:-100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of n-butyllithium (0.1 mol) in 65 ml of hexane is added to a mixture of 4"-propyl-2,3-difluoro-p-terphenyl (0.1 mol), potassium t-butylate (0.1 mol) and 200 ml of THF at -100° C. After stirring 5 minutes at -100° C. a mixture of brompentane (0.1 mol) and N,N-dimethylpropylene urea (0.1 mol, DMPU) is added. After warming-up to -30° C. and usual work-up 4"-propyl-4-pentyl-2,3-difluoro-p-terphenyl is obtained. is added After warming-up to -30° C.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of lithium diisopropylamide (0.02 mol) in THF/hexane, prepared from 0.02 mol of diisopropylamine in 25 ml of THF and 12.5 ml of a 1.6-molar solution of n-butyllithium in hexane, is added dropwise at 25° C. to a mixture of 0.02 mol of 1-(4'-pentylbiphenyl-4-yl)-2-(3,5-difluorophenyl)ethane, 0.02 mol of N,N-dimethylpropyleneurea, 0.02 mol of 1-iodopropane and 25 ml of THF. After stirring at room temperature for 1.5 hours, the reaction mixture is poured into water, the phases are separated, and the aqueous phase is extracted with 2×50 ml of methylene chloride. Drying over magnesium sulfate, evaporation of the solvent and chromatography give the pure product. the phases are separated the aqueous phase is extracted with 2×50 ml of methylene chloride Drying over magnesium sulfate, evaporation of the solvent and chromatography give the pure product

反应条件: temp:2.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Add a solution of t-butyl methylmalonate (129 g, 0.75 mol) in THF (385 mL) to a slurry of LiH (14.9 g, 1.875 mol) in THF (900 mL) and N,N-dimethylpropylene urea (DMPU, 155 g, 1.2 mol) over 30 minutes while maintaining the temperature at 0-5° C. Heat the reaction mixture to 65° C. and add a solution of cis-1,4-dichloro-2-butene (95%, 100 g, 0.8 mol, 1.08 eq) in THF (100 mL) over 5.5 hours, maintaining the temperature at 63-67° C. Stir the reaction for 4 hours at 65° C. A water/MTBE work-up of the reaction mixture yields 1-(methoxycarbonyl)-1-(tert-butoxycarbonyl)cyclopent-3-ene. Heat the reaction mixture to 65° C. maintaining the temperature at 63-67° C the reaction for 4 hours at 65° C

反应条件: temp:2.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Add a solution of t-butyl methylmalonate (129 g, 0.75 mol) in THF (385 mL) to a slurry of LiH (14.9 g, 1.875 mol) in THF (900 mL) and N,N-dimethylpropylene urea (DMPU, 155 g, 1.2 mol) over 30 minutes while maintaining the temperature at 0-5° C. Heat the reaction mixture to 65° C. and add a solution of cis-1,4-dichloro-2-butene (95%, 100 g, 0.8 mol, 1.08 eq) in THF (100 mL) over 5.5 hours, maintaining the temperature at 63-67° C. Stir the reaction for 4 hours at 65° C. A water/MTBE work-up of the reaction mixture yields 1-(methoxycarbonyl)-1-(tert-butoxycarbonyl)cyclopent-3-ene. Heat the reaction mixture to 65° C. maintaining the temperature at 63-67° C the reaction for 4 hours at 65° C