双(三甲基硫化硅)

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

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

实验步骤: To 1,1,1,3,3,3-hexamethyldisilathiane (0.157 g, 0.9 mmol) in dimethylformamide (4 mL) was added sodium methoxide (0.049 g, 0.9 mmol) and the resulting mixture was sonicated to provide a homogeneous blue colored solution. This resulting solution was added to the solution of 1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-(1,3-dithiolan-2-yl)-5-(methylamino)-1H-pyrazole-3-carbonitrile (0.08 g, 0.2 mmol) in dimethylformamide (5 mL) at room temperature under nitrogen. This mixture was stirred at room temperature for one and half hour. It was then diluted with ether (30 mL) and water (30 mL). The layers were separated and the aqueous layer was extracted with ether. The ethereal layers were combined and washed twice with water (2×20 mL), dried (Na2SO4), and concentrated to provide a yellow solid. Upon chromatographic purification via silica gel eluting with heptane:ethyl acetate (4:1 to 2:1), a yellow solid (0.048 g, 55%) was obtained. 19F-NMR: −63.634. the resulting mixture was sonicated to provide a homogeneous blue colored solution The layers were separated the aqueous layer was extracted with ether washed twice with water (2×20 mL) dried (Na2SO4) concentrated to provide a yellow solid Upon chromatographic purification via silica gel eluting with heptane:ethyl acetate (4:1 to 2:1)

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

实验步骤: Preparation of 4-oxo-4,5-dihydro-3H-benzo[b][1,4]diazepin-2-yl]-thiobenzamides (according to Pen-Yuan Lin et al. Synthesis 1992, 1219]: To a solution of hexamethyldisilthiane (1.45 g, 8.0 mmol) in 1,3-dimethyl-2-imidazolidinone (8 mL) was added at 23° C. sodium methoxide (0.31 g, 6.8 mmol). The mixture was stirred for 5 min. and the blue solution formed was then added to a solution of 3-[7-(4-fluoro-phenyl)-4-oxo-4,5-dihydro-3H-benzo[b][1,4]diazepin-2-yl]-benzonitrile (Example 57) (1.42 g, 4 mmol) in 1,3-dimethyl-2-imidazolidinone (12 mL). The mixture was stirred for 3 h at 23° C. and then poured into water (100 mL). Stirring was continued for 0.5 h and the precipitate was isolated by filtration and triturated with ethyl acetate (50 mL) to give the title compound as light yellow solid (1.38 g). the blue solution formed The mixture was stirred for 3 h at 23° C. Stirring was continued for 0.5 h the precipitate was isolated by filtration triturated with ethyl acetate (50 mL)

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

实验步骤: Preparation of 4-oxo-4,5-dihydro-3H-benzo[b][1,4]diazepin-2-yl]-thiobenzamides (according to Pen-Yuan Lin et al. Synthesis 1992, 1219]: To a solution of hexamethyldisilthiane (1.45 g, 8.0 mmol) in 1,3-dimethyl-2-imidazolidinone (8 mL) was added at 23° C. sodium methoxide (0.31 g, 6.8 mmol). The mixture was stirred for 5 min. and the blue solution formed was then added to a solution of 3-[7-(4-fluoro-phenyl)-4-oxo-4,5-dihydro-3H-benzo[b][1,4]diazepin-2-yl]-benzonitrile (Example 57) (1.42 g, 4 mmol) in 1,3-dimethyl-2-imidazolidinone (12 mL). The mixture was stirred for 3 h at 23° C. and then poured into water (100 mL). Stirring was continued for 0.5 h and the precipitate was isolated by filtration and triturated with ethyl acetate (50 mL) to give the title compound as light yellow solid (1.38 g). the blue solution formed The mixture was stirred for 3 h at 23° C. Stirring was continued for 0.5 h the precipitate was isolated by filtration triturated with ethyl acetate (50 mL)

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

实验步骤: Preparation of 4-oxo-4,5-dihydro-3H-benzo[b][1,4]diazepin-2-yl]-thiobenzamides (according to Pen-Yuan Lin et al. Synthesis 1992, 1219]: To a solution of hexamethyldisilthiane (1.45 g, 8.0 mmol) in 1,3-dimethyl-2-imidazolidinone (8 mL) was added at 23° C. sodium methoxide (0.31 g, 6.8 mmol). The mixture was stirred for 5 min. and the blue solution formed was then added to a solution of 3-[7-(4-fluoro-phenyl)-4-oxo-4,5-dihydro-3H-benzo[b][1,4]diazepin-2-yl]-benzonitrile (Example 57) (1.42 g, 4 mmol) in 1,3-dimethyl-2-imidazolidinone (12 mL). The mixture was stirred for 3 h at 23° C. and then poured into water (100 mL). Stirring was continued for 0.5 h and the precipitate was isolated by filtration and triturated with ethyl acetate (50 mL) to give the title compound as light yellow solid (1.38 g). the blue solution formed The mixture was stirred for 3 h at 23° C. Stirring was continued for 0.5 h the precipitate was isolated by filtration triturated with ethyl acetate (50 mL)

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

实验步骤: Preparation of 4-oxo-4,5-dihydro-3H-benzo[b][1,4]diazepin-2-yl]-thiobenzamides (according to Pen-Yuan Lin et al. Synthesis 1992, 1219]: To a solution of hexamethyldisilthiane (1.45 g, 8.0 mmol) in 1,3-dimethyl-2-imidazolidinone (8 mL) was added at 23° C. sodium methoxide (0.31 g, 6.8 mmol). The mixture was stirred for 5 min. and the blue solution formed was then added to a solution of 3-[7-(4-fluoro-phenyl)-4-oxo-4,5-dihydro-3H-benzo[b][1,4]diazepin-2-yl]-benzonitrile (Example 57) (1.42 g, 4 mmol) in 1,3-dimethyl-2-imidazolidinone (12 mL). The mixture was stirred for 3 h at 23° C. and then poured into water (100 mL). Stirring was continued for 0.5 h and the precipitate was isolated by filtration and triturated with ethyl acetate (50 mL) to give the title compound as light yellow solid (1.38 g). the blue solution formed The mixture was stirred for 3 h at 23° C. Stirring was continued for 0.5 h the precipitate was isolated by filtration triturated with ethyl acetate (50 mL)

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

实验步骤: To 1,1,1,3,3,3-hexamethyldisilathiane (0.157 g, 0.9 mmol) in dimethylformamide (4 mL) was added sodium methoxide (0.049 g, 0.9 mmol) and the resulting mixture was sonicated to provide a homogeneous blue colored solution. This resulting solution was added to the solution of 1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-(1,3-dithiolan-2-yl)-5-(methylamino)-1H-pyrazole-3-carbonitrile (0.08 g, 0.2 mmol) in dimethylformamide (5 mL) at room temperature under nitrogen. This mixture was stirred at room temperature for one and half hour. It was then diluted with ether (30 mL) and water (30 mL). The layers were separated and the aqueous layer was extracted with ether. The ethereal layers were combined and washed twice with water (2×20 mL), dried (Na2SO4), and concentrated to provide a yellow solid. Upon chromatographic purification via silica gel eluting with heptane:ethyl acetate (4:1 to 2:1), a yellow solid (0.048 g, 55%) was obtained. 19F-NMR: −63.634. the resulting mixture was sonicated to provide a homogeneous blue colored solution The layers were separated the aqueous layer was extracted with ether washed twice with water (2×20 mL) dried (Na2SO4) concentrated to provide a yellow solid Upon chromatographic purification via silica gel eluting with heptane:ethyl acetate (4:1 to 2:1)

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

实验步骤: To 1,1,1,3,3,3-hexamethyldisilathiane (0.157 g, 0.9 mmol) in dimethylformamide (4 mL) was added sodium methoxide (0.049 g, 0.9 mmol) and the resulting mixture was sonicated to provide a homogeneous blue colored solution. This resulting solution was added to the solution of 1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-(1,3-dithiolan-2-yl)-5-(methylamino)-1H-pyrazole-3-carbonitrile (0.08 g, 0.2 mmol) in dimethylformamide (5 mL) at room temperature under nitrogen. This mixture was stirred at room temperature for one and half hour. It was then diluted with ether (30 mL) and water (30 mL). The layers were separated and the aqueous layer was extracted with ether. The ethereal layers were combined and washed twice with water (2×20 mL), dried (Na2SO4), and concentrated to provide a yellow solid. Upon chromatographic purification via silica gel eluting with heptane:ethyl acetate (4:1 to 2:1), a yellow solid (0.048 g, 55%) was obtained. 19F-NMR: −63.634. the resulting mixture was sonicated to provide a homogeneous blue colored solution The layers were separated the aqueous layer was extracted with ether washed twice with water (2×20 mL) dried (Na2SO4) concentrated to provide a yellow solid Upon chromatographic purification via silica gel eluting with heptane:ethyl acetate (4:1 to 2:1)

反应条件: temp:0.00; pressure:0.00; stir:

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

实验步骤: R. Detty et al. in J. Org. Chem. 1982, 47, 1354-1356 reiterated the above statement about the substantial nonreactivity of lithium sulfide and chlorotrimethylsilane and indicated that commercially available dilithium sulfide and chlorotrimethylsilane, when refluxed for seventy-two hours in tetrahydrofuran, gave only a 45% yield of hexamethyldisilthiane, also called "bis(trimethylsilyl)sulfide.

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

实验步骤: Preparation of 4-oxo-4,5-dihydro-3H-benzo[b][1,4]diazepin-2-yl]-thiobenzamides (according to Pen-Yuan Lin et al. Synthesis 1992, 1219]: To a solution of hexamethyldisilthiane (1.45 g, 8.0 mmol) in 1,3-dimethyl-2-imidazolidinone (8 mL) was added at 23° C. sodium methoxide (0.31 g, 6.8 mmol). The mixture was stirred for 5 min. and the blue solution formed was then added to a solution of 3-[7-(4-fluoro-phenyl)-4-oxo-4,5-dihydro-3H-benzo[b][1,4]diazepin-2-yl]-benzonitrile (Example 57) (1.42 g, 4 mmol) in 1,3-dimethyl-2-imidazolidinone (12 mL). The mixture was stirred for 3 h at 23° C. and then poured into water (100 mL). Stirring was continued for 0.5 h and the precipitate was isolated by filtration and triturated with ethyl acetate (50 mL) to give the title compound as light yellow solid (1.38 g). the blue solution formed The mixture was stirred for 3 h at 23° C. Stirring was continued for 0.5 h the precipitate was isolated by filtration triturated with ethyl acetate (50 mL)