(4-bromophenyl)-trimethylsilane

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: The title compound was prepared from rac-[(3,4-dichloro-phenyl)-(methoxy-methyl-carbamoyl)-methyl]-carbamic acid tert-butyl ester (Intermediate 9) and 1-bromo-4-(trimethylsilyl)benzene with tert-butyl-lithium instead of n-butyllithium in analogy to Example 1a): MS (ISP): 452.0 and 454.0 (M+H)+.

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-phenyl-2,5-difluoroaniline (12 mmol), 4-bromo-trimethylsilylbenzene (10 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.15 mmol), (±)-2,2′-bis(diphenylphosphine)-1,1′-binaphthalene (0.3 mmol) and sodium tert-butoxie (14 mmol) are put in a two-neck round-bottom flask and dissolved in toluene (30 mL). Subsequently, the resulting solution is stirred in a bath under a temperature of about 100° C. for 24 hours. After completion of the reaction, toluene is removed. The reaction mixture is extracted with dichloromethane and water, and then being distilled under reduced pressure. The resulting residence is filtered by silica gel column and distilled under reduced pressure again. Next, by re-crystallizing and filtering with dichloromethane and petroleum ether, 4-phenyl-2,5-difluoro-N-(4-trimethylsilylphenyl)benzenamine (2.6 g) is yielded. is removed The reaction mixture is extracted with dichloromethane and water being distilled under reduced pressure The resulting residence is filtered by silica gel column distilled under reduced pressure again Next, by re-crystallizing filtering with dichloromethane and petroleum ether

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of dibenzofuran-4-yl-boronic acid (20.0 g, 94.3 mmol), (4-bromo-phenyl)-trimethyl-silane (21.62 g, 94.3 mmol), K2CO3 (39.1 g, 3 equiv., 283 mmol) in toluene (100 mL), ethanol (60 mL) and water (30 mL) was purged with nitrogen for 5 min (bubbled into solution) and treated with Pd(PPh3)4 (3.59 g, 2.9 mmol). After heating to 80° C. for 4 h, the solution was cooled to room temperature, poured into water (300 mL) and extracted with ethyl acetate (300 mL). The organic phase was washed with sat'd aq NaCl, dried over anhydrous MgSO4, filtered and concentrated in vacuo. Purification by flash column chromatography (5-20% ethyl acetate in heptane) afforded (4-dibenzofuran-4-yl-phenyl)-trimethyl-silane as a colorless oil (28.9 g, 96%). (bubbled into solution) the solution was cooled to room temperature extracted with ethyl acetate (300 mL) The organic phase was washed with sat'd aq NaCl dried over anhydrous MgSO4 filtered concentrated in vacuo Purification by flash column chromatography (5-20% ethyl acetate in heptane)

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

Procedure: Under a flow of argon, in a 1 L-recovery flask, 35 g of 1-bromo-4-(trimethylsilyl)benzene, 22.6 g of acetamide, 5.8 g of copper(I)iodide, 42.2 g of potassium carbonate, and 380 mL of xylene were placed. After stirring, 6.6 mL of N,N′-dimethylethylenediamine was added. The resultant was heated and stirred at reflux for 18 hours. The resultant was heated stirred at reflux for 18 hours

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

Procedure: Under a flow of argon, in a 1 L-recovery flask, 35 g of 1-bromo-4-(trimethylsilyl)benzene, 22.6 g of acetamide, 5.8 g of copper(I)iodide, 42.2 g of potassium carbonate, and 380 mL of xylene were placed. After stirring, 6.6 mL of N,N′-dimethylethylenediamine was added. The resultant was heated and stirred at reflux for 18 hours. The resultant was heated stirred at reflux for 18 hours

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

Procedure: To a 1L 3-neck flask equipped with a mechanical stir arm was added 14.5 g (65.1 mmol) of 1-bromo-4-trimethylsilylbenzene, 9.2 g (78.1 mmol) of benzimidazole, 9.1 g (143 mmol) of copper power, 31.4 g (228 mmol) of potassium carbonate, and 1.7 g (6.5 mmol) of 18-crown-6. These chemicals were stirred vigorously in 400 mL tetrahydronaphthalene at 180° C. under N2 atmosphere. After 20 hours of heating, the mixture was filtered warm. The solids on the funnel were repeatedly washed with dichloromethane to remove all organic products as filtrate. The mother liquor was then evaporated in vacuo and pooled with a small batch of crude material from a previous reaction. This residue was purified by distilling on a Kugelrohr apparatus twice. At 160° C., the removal of organic impurities was evidenced. At 200° C. the product distilled. Purification gave 14.2 g N-(p-trimethylsilylphenyl)benzimidazole as a white solid. After 20 hours of heating the mixture was filtered warm The solids on the funnel were repeatedly washed with dichloromethane to remove all organic products as filtrate The mother liquor was then evaporated in vacuo pooled with a small batch of crude material from a previous reaction This residue was purified by distilling on a Kugelrohr apparatus twice At 160° C., the removal of organic impurities At 200° C. the product distilled Purification

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

Procedure: The title compound was prepared from rac-[(3,4-dichloro-phenyl)-(methoxy-methyl-carbamoyl)-methyl]-carbamic acid tert-butyl ester (Intermediate 9) and 1-bromo-4-(trimethylsilyl)benzene with tert-butyl-lithium instead of n-butyllithium in analogy to Example 1a): MS (ISP): 452.0 and 454.0 (M+H)+.

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

Procedure: Under argon, 94.4 g of p-dibromobenzene is cooled to -20° C. in 400 ml of absolute ether. To the solution is added dropwise 255 ml of 15% butyllithium in hexane so that the temperature does not rise above -10° C. Then the mixture is agitated for one hour at room temperature. After a negative Gilman test (H. Gilman, J. Swiss, J. Amer. Chem. Soc. 62: 1847 [1940]), the mixture is again cooled to -20° C. and 46 ml of trimethylchlorosilane in 200 ml of absolute ether is added dropwise thereto so that the temperature does not exceed -10° C. After the addition step is finished, the mixture is stirred for 16 hours at room temperature and another hour under reflux. The thus-formed precipitate is suctioned off and thoroughly washed with ether. The resultant filtrate is concentrated and then distilled with a water-jet aspirator, thus producing 65.52 g of p-bromotrimethylsilylbenzene, bp (16 torr) 103°-110° C. does not rise above -10° C After a negative Gilman test (H. Gilman, J. Swiss, J. Amer. Chem. Soc. 62: 1847 [1940]), the mixture is again cooled to -20° C. does not exceed -10° C After the addition step the mixture is stirred for 16 hours at room temperature and another hour under reflux thoroughly washed with ether The resultant filtrate is concentrated distilled with a water-jet aspirator

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Bromo-4-(trimethylsilyl)benzene (1.15 g, 5 mmol) was dissolved in THF (30 ml) and cooled to −78° C. Under argon a 1.6 M solution of n-butyl lithium in hexane (3.13 ml, 5 mmol) was added dropwise keeping the temperature below −70° C. The clear colorless solution was stirred at −78° C. for 15 min and DMF (1.156 ml, 15 mmol) was added quickly. The reaction temperature increased to −68° C. The reaction was stirred for additional 15 min at −78° C., quenched with 1N aqueous hydrogen chloride solution and extracted twice with diethyl ether. The combined organic layers were washed twice with water and once with saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered and the solvent was evaporated to leave the product as a colorless oil (920 mg, 100%). The product was pure enough to be used directly in the next step. MS (ISP) 179.2 (M+H+). 1H NMR (CDCl3, 300 MHz): δ 10.02 (s, 1H) 7.84 (d, 2H), 7.69 (d, 2H), 0.31 (s, 9H). the temperature below −70° C The reaction temperature increased to −68° C The reaction was stirred for additional 15 min at −78° C. quenched with 1N aqueous hydrogen chloride solution extracted twice with diethyl ether The combined organic layers were washed twice with water and once with saturated aqueous sodium chloride solution dried over sodium sulfate filtered the solvent was evaporated

Conditions: temp:0.00; pressure:0.00; stir: