ethoxy(trimethyl)silane

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 10 mL round bottom flask were added 6-tert-butyl-8-fluoro-2H-phthalazin-1-one 101h (640 mg, 2.9 mmol), 2-chloro-6-fluorobenzaldehyde (506 mg, 3.2 mmol), and cesium carbonate (488 mg, 1.5 mmol). The flask was evacuated and backfilled with nitrogen three times then ethoxytrimethylsilane (684 mg, 5.8 mmol) and DMF (5 mL) were added to the reaction flask. The resulting mixture was heated to 60° C. After 4 h of stirring, the solution was allowed to cool down to ambient temperature and the reaction was quenched by addition of 2 mL of H2O drop-wise. The desired product started to precipitate from the DMF and water mixture. The solid was collected by filtration after cooling down to 5° C., and washed with DMF/water (2/1, 2 mL, pre-cooled to 6° C.) and H2O (2 mL). The filter cake was dried under vacuum oven at 65° C. for overnight to afford 519 mg (52%) of 101i as a yellow solid. MS: [M+H]+: 359 The flask was evacuated to cool down to ambient temperature the reaction was quenched by addition of 2 mL of H2O drop-wise to precipitate from the DMF and water mixture The solid was collected by filtration after cooling down to 5° C. washed with DMF/water (2/1, 2 mL, pre-cooled to 6° C.) and H2O (2 mL) The filter cake was dried under vacuum oven at 65° C. for overnight

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 10 mL round bottom flask were added 6-tert-butyl-8-fluoro-2H-phthalazin-1-one 101h (640 mg, 2.9 mmol), 2-chloro-6-fluorobenzaldehyde (506 mg, 3.2 mmol), and cesium carbonate (488 mg, 1.5 mmol). The flask was evacuated and backfilled with nitrogen three times then ethoxytrimethylsilane (684 mg, 5.8 mmol) and DMF (5 mL) were added to the reaction flask. The resulting mixture was heated to 60° C. After 4 h of stirring, the solution was allowed to cool down to ambient temperature and the reaction was quenched by addition of 2 mL of H2O drop-wise. The desired product started to precipitate from the DMF and water mixture. The solid was collected by filtration after cooling down to 5° C., and washed with DMF/water (2/1, 2 mL, pre-cooled to 6° C.) and H2O (2 mL). The filter cake was dried under vacuum oven at 65° C. for overnight to afford 519 mg (52%) of 101i as a yellow solid. MS: [M+H]+: 359 The flask was evacuated to cool down to ambient temperature the reaction was quenched by addition of 2 mL of H2O drop-wise to precipitate from the DMF and water mixture The solid was collected by filtration after cooling down to 5° C. washed with DMF/water (2/1, 2 mL, pre-cooled to 6° C.) and H2O (2 mL) The filter cake was dried under vacuum oven at 65° C. for overnight

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 3 L round bottom flask were added 6-tert-butyl-8-fluoro-2H-phthalazin-1-one (132.3 g, 0.6 mol), 2-chloro-6-fluorobenzaldehyde (104.8 g, 0.66 mol) and cesium carbonate (117.4 g, 0.36 mol). The flask was evacuated and backfilled with Nitrogen three times. Then, ethoxytrimethylsilane (142 g, 1.2 mol) and DMF (1.6 L) were added to the reaction flask, and the resulting mixture was heated to 60° C. After 4 h stirring, the solution was allowed to cool down to ambient temperature and the reaction was quenched by addition of 800 mL of H2O dropwise. The desired product started to precipitate from DMF and water mixture. The solid was collected by filtration after cooling down to 5° C., and washed with DMF/water (2/1, 750 mL, pre-cooled to 6° C.) and H2O (400 mL). The filter cake was dried under vacuum oven at 65° C. overnight to afford 147 g of the title compound (68.2% isolated yield) as a yellow solid. MS (ESI) 358, 360 (M+H)−. The flask was evacuated to cool down to ambient temperature the reaction was quenched by addition of 800 mL of H2O dropwise to precipitate from DMF and water mixture The solid was collected by filtration after cooling down to 5° C. washed with DMF/water (2/1, 750 mL, pre-cooled to 6° C.) and H2O (400 mL) The filter cake was dried under vacuum oven at 65° C. overnight

Conditions: temp:2.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 1-Boc-piperidone (2.39 g, 12 mmol) and ethoxytrimethylsilane (3.75 mL, 24 mmol) in 80 mL of CCl4 under stirring at 0° C. was added trimethylsilyl trifluoromethylsulfonate (217 μL, 1.2 mmol) and trimethyl-(2-methylene-4-trimethylsilyloxybutyl)silane (E. I. Marko et al., Journal of Organic Chemistry 1992, 57, 2211-2213) dissolved in in 23 mL of CCl4. After stirring at 0-5° C. for 6 h and overnight resting at 0° C., the reaction mixture was washed with water, dried on Na2SO4, filtered and the solvent was evaporated to dryness in vacuo. The residual 6.5 g of colourless oil was purified by means of automated flash chromatography (SP1®TM-Biotage; Petroleum Ether-EtOAc gradient from 99:1 to 85:15) to give 3.2 g of the title compound as colourless oil. Yield: 1000% resting at 0° C. the reaction mixture was washed with water dried on Na2SO4 filtered the solvent was evaporated to dryness in vacuo The residual 6.5 g of colourless oil was purified by means of automated flash chromatography (SP1®TM-Biotage; Petroleum Ether-EtOAc gradient from 99:1 to 85:15)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 500 ml polymerizer equipped with an agitating element was charged with 142 ml of decane, 100 ml of octene-1 and 8 ml of 7-methyl-1,6-octadiene. Into this solution elevated in temperature to 50° C. were introduced continuously hydrogen and nitrogen at rates of 1 liter and 50 liters per hour, respectively. The polymerizer was then charged with 0.625 mmol of triisobutylaluminum, 0.21 mmol of trimethylethoxysilane and 0.0125 mmol, in terms of titanium atom, of the solid titanium catalyst component [A] to initiate polymerization. After a thirty-minute polymerization at 50° C., the polymerization was stopped by the addition of small amounts of isobutyl alcohol to the system, and the resulting polymer solution was then poured in large amounts of methanol to separate out a copolymer. The copolymer was recovered and dried at 120° C. under reduced pressure overnight to give 12.4 g of octene-1/7-methyl-1,6-octadiene copolymer. The intrinsic viscosity [η], as measured in decahydronaphthalene at 135° C., of the thus obtained copolymer was 6.4 dl/g, and the content of 7-methyl-1,6-octadiene in the copolymer was 6.6 mol %. A 500 ml polymerizer equipped with an agitating element elevated in temperature to 50° C. polymerization After a thirty-minute polymerization at 50° C. to separate out a copolymer The copolymer was recovered dried at 120° C. under reduced pressure overnight

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 10 mL round bottom flask were added 6-tert-butyl-8-fluoro-2H-phthalazin-1-one 101h (640 mg, 2.9 mmol), 2-chloro-6-fluorobenzaldehyde (506 mg, 3.2 mmol), and cesium carbonate (488 mg, 1.5 mmol). The flask was evacuated and backfilled with nitrogen three times then ethoxytrimethylsilane (684 mg, 5.8 mmol) and DMF (5 mL) were added to the reaction flask. The resulting mixture was heated to 60° C. After 4 h of stirring, the solution was allowed to cool down to ambient temperature and the reaction was quenched by addition of 2 mL of H2O drop-wise. The desired product started to precipitate from the DMF and water mixture. The solid was collected by filtration after cooling down to 5° C., and washed with DMF/water (2/1, 2 mL, pre-cooled to 6° C.) and H2O (2 mL). The filter cake was dried under vacuum oven at 65° C. for overnight to afford 519 mg (52%) of 101i as a yellow solid. MS: [M+H]+: 359 The flask was evacuated to cool down to ambient temperature the reaction was quenched by addition of 2 mL of H2O drop-wise to precipitate from the DMF and water mixture The solid was collected by filtration after cooling down to 5° C. washed with DMF/water (2/1, 2 mL, pre-cooled to 6° C.) and H2O (2 mL) The filter cake was dried under vacuum oven at 65° C. for overnight

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 10 mL round bottom flask were added 6-tert-butyl-8-fluoro-2H-phthalazin-1-one 101h (640 mg, 2.9 mmol), 2-chloro-6-fluorobenzaldehyde (506 mg, 3.2 mmol), and cesium carbonate (488 mg, 1.5 mmol). The flask was evacuated and backfilled with nitrogen three times then ethoxytrimethylsilane (684 mg, 5.8 mmol) and DMF (5 mL) were added to the reaction flask. The resulting mixture was heated to 60° C. After 4 h of stirring, the solution was allowed to cool down to ambient temperature and the reaction was quenched by addition of 2 mL of H2O drop-wise. The desired product started to precipitate from the DMF and water mixture. The solid was collected by filtration after cooling down to 5° C., and washed with DMF/water (2/1, 2 mL, pre-cooled to 6° C.) and H2O (2 mL). The filter cake was dried under vacuum oven at 65° C. for overnight to afford 519 mg (52%) of 101i as a yellow solid. MS: [M+H]+: 359 The flask was evacuated to cool down to ambient temperature the reaction was quenched by addition of 2 mL of H2O drop-wise to precipitate from the DMF and water mixture The solid was collected by filtration after cooling down to 5° C. washed with DMF/water (2/1, 2 mL, pre-cooled to 6° C.) and H2O (2 mL) The filter cake was dried under vacuum oven at 65° C. for overnight