(2-bromo-1-phenylethenyl)benzene

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

Procedure: n-Butyllithium in hexane (2.5 M, 20 mL) was added slowly under nitrogen to a stirred solution of 2,2-diphenylvinyl bromide (6.50 g, 25.1 mmol) in THF (40 mL) at −78° C. and then the mixture was stirred further for 1 h. n-Butyl borate (15 mL, 55.5 mmol) was added at −78° C. before the mixture was warmed slowly to room temperature and stirred overnight. Water (50 mL) was added, followed by conc. HCl (100 mL) to acidify the mixture, which was then stirred for 3 h. The reaction mixture was extracted with EtOAc and the combined organic phases were dried over MgSO4. Concentration under reduced pressure gave 2,2-diphenylvinyl boronic acid, which, without further purification, was reacted with pinacol (4.25 g, 36.0 mmol) in toluene under reflux for 2 h to effect condensation by the azeotropic removal of the water formed. The mixture was concentrated under reduced pressure and the residue was purified by column chromatography (hexanes/CH2Cl2=1/1) to afford C (4.10 g, 53%) as transparent liquid. was added at −78° C. before the mixture was then stirred for 3 h The reaction mixture was extracted with EtOAc the combined organic phases were dried over MgSO4 Concentration under reduced pressure

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

Procedure: 20 g (111 mmoles) of 1,1-diphenylethylene was dissolved in 70 ml of cyclohexane, to which was then added dropwise 35 g (222 mmoles) of bromine at room temperature. The mixture was stirred at the same temperature for 20 hours and further heated under reflux for one hour. After cooling, the reaction mixture was washed with a sodium thiosulfate aqueous solution and saturated salt water, and an organic phase was separated by liquid separation. The organic phase was concentrated and subjected to Kugel distillation (at 145 to 148° C./0.6 Torr) to obtain 24 g (yield: 86%) of desired 1,1-diphenyl-2-bromoethylene. 4.8 g (18 mmoles) of 1,1-diphenyl-2-bromoethylene, 0.486 g (20 mmoles) of Mg, a small piece of iodine, and 100 mL of THF were added to a 300 ml eggplant type flask to prepare a Grignard reagent. The reaction mixture was cooled to −78° C., to which trimethoxyborane was then added dropwise while maintaining the same temperature. The mixture was stirred at room temperature for 2 hours, to which 2N hydrochloric acid was then added. An organic phase was treated to isolate desired 1,1-diphenylvinylboronic acid as a white powder in a yield of 35%. The same procedures as in Synthesis Example 4 were followed, except for using 3.28 g of 1,1-diphenylvinylboronic acid in place of the 4-biphenylylboronic acid, to obtain 3.77 g (yield: 72%) of the desired compound. further heated under reflux for one hour After cooling the reaction mixture was washed with a sodium thiosulfate aqueous solution and saturated salt water an organic phase was separated by liquid separation The organic phase was concentrated subjected to Kugel distillation (at 145 to 148° C./0.6 Torr)

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

Procedure: Into a reactor were introduced 110 g (0.60 mol) of the 1,1-diphenylethylene and 1,098 g of carbon tetrachloride under a nitrogen atmosphere. A solution prepared by mixing 95.9 g (0.60 mol) of bromine with 288 g of carbon tetrachloride was added dropwise thereto over 1 hour with cooling with ice. After completion of the addition, the reaction mixture was stirred at that temperature for 7 hours and then concentrated. To the residue were added 119 g of pyridine and 500 mL of toluene. This mixture was refluxed for 3 hours. After being cooled, the reaction mixture was washed with 5% hydrochloric acid and water, subsequently dried with anhydrous sodium sulfate, and then concentrated under reduced pressure. The resultant concentrate was distilled and then recrystallized from methanol to obtain 126 g (81%) of the target compound as white crystals. A solution prepared was added dropwise over 1 hour with cooling with ice After completion of the addition concentrated To the residue were added 119 g of pyridine and 500 mL of toluene This mixture was refluxed for 3 hours After being cooled the reaction mixture was washed with 5% hydrochloric acid and water subsequently dried with anhydrous sodium sulfate concentrated under reduced pressure The resultant concentrate was distilled recrystallized from methanol

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

Procedure: n-Butyllithium in hexane (2.5 M, 20 mL) was added slowly under nitrogen to a stirred solution of 2,2-diphenylvinyl bromide (6.50 g, 25.1 mmol) in THF (40 mL) at −78° C. and then the mixture was stirred further for 1 h. n-Butyl borate (15 mL, 55.5 mmol) was added at −78° C. before the mixture was warmed slowly to room temperature and stirred overnight. Water (50 mL) was added, followed by conc. HCl (100 mL) to acidify the mixture, which was then stirred for 3 h. The reaction mixture was extracted with EtOAc and the combined organic phases were dried over MgSO4. Concentration under reduced pressure gave 2,2-diphenylvinyl boronic acid, which, without further purification, was reacted with pinacol (4.25 g, 36.0 mmol) in toluene under reflux for 2 h to effect condensation by the azeotropic removal of the water formed. The mixture was concentrated under reduced pressure and the residue was purified by column chromatography (hexanes/CH2Cl2=1/1) to afford C (4.10 g, 53%) as transparent liquid. was added at −78° C. before the mixture was then stirred for 3 h The reaction mixture was extracted with EtOAc the combined organic phases were dried over MgSO4 Concentration under reduced pressure

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

Procedure: 20 g (111 mmoles) of 1,1-diphenylethylene was dissolved in 70 ml of cyclohexane, to which was then added dropwise 35 g (222 mmoles) of bromine at room temperature. The mixture was stirred at the same temperature for 20 hours and further heated under reflux for one hour. After cooling, the reaction mixture was washed with a sodium thiosulfate aqueous solution and saturated salt water, and an organic phase was separated by liquid separation. The organic phase was concentrated and subjected to Kugel distillation (at 145 to 148° C./0.6 Torr) to obtain 24 g (yield: 86%) of desired 1,1-diphenyl-2-bromoethylene. 4.8 g (18 mmoles) of 1,1-diphenyl-2-bromoethylene, 0.486 g (20 mmoles) of Mg, a small piece of iodine, and 100 mL of THF were added to a 300 ml eggplant type flask to prepare a Grignard reagent. The reaction mixture was cooled to −78° C., to which trimethoxyborane was then added dropwise while maintaining the same temperature. The mixture was stirred at room temperature for 2 hours, to which 2N hydrochloric acid was then added. An organic phase was treated to isolate desired 1,1-diphenylvinylboronic acid as a white powder in a yield of 35%. The same procedures as in Synthesis Example 4 were followed, except for using 3.28 g of 1,1-diphenylvinylboronic acid in place of the 4-biphenylylboronic acid, to obtain 3.77 g (yield: 72%) of the desired compound. further heated under reflux for one hour After cooling the reaction mixture was washed with a sodium thiosulfate aqueous solution and saturated salt water an organic phase was separated by liquid separation The organic phase was concentrated subjected to Kugel distillation (at 145 to 148° C./0.6 Torr)