4-bromobutoxy-tert-butyl-dimethylsilane

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

Procedure: 7-Methoxyquinoxalin-2(1H)-one (synthesized with reference to WO2009/1126; 400 mg, 2.27 mmol) was dissolved in N,N-dimethylformamide (8 ml). The solution was cooled in an ice bath, lithium hydride (purity 90%, 26 mg, 2.95 mmol) was then added thereto and the mixture was stirred at room temperature for 40 minutes. The reaction solution was cooled in an ice bath again, (4-bromobutoxy)(tert-butyl)dimethylsilane (synthesized with reference to Journal of Medicinal Chemistry, 2008, vol. 51, No. 18, pages 5690-5701; 580 mg, 2.17 mmol) and sodium iodide (442 mg, 2.95 mmol) were added thereto, and the mixture was stirred overnight at room temperature. The reaction mixture was diluted with ethyl acetate, washed sequentially with saturated sodium chloride solution (×2), water and saturated sodium chloride solution, dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure. The obtained residue was purified by silica gel column chromatography (n-hexane/ethyl acetate) to yield 363 mg (44%) of the title compound in the form of a light yellow syrup. The solution was cooled in an ice bath The reaction solution was cooled in an ice bath again the mixture was stirred overnight at room temperature washed sequentially with saturated sodium chloride solution (×2), water and saturated sodium chloride solution dried over anhydrous magnesium sulfate the solvent was removed under reduced pressure The obtained residue was purified by silica gel column chromatography (n-hexane/ethyl acetate)

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

Procedure: In a manner similar to that of Example 2a, by reacting 260 mg of ethyl 4″-(acetylethylamino)-3″-tert-butyl-4′-hydroxy[1,1′;3′,1″]terphenyl-4-carboxylate (0.56 mmol) in 12 mL of dimethylformamide with 225 mg of caesium carbonate and 0.16 mL of 1-bromo-4-(tert-butyldimethylsilanyloxy)butane, 310 mg of ethyl 4″-(acetylethylamino)-3″-tert-butyl-4′-[4-(tert-butyldimethylsilanyloxy)butoxy]-[1,1′;3′,1″]terphenyl-4-carboxylate (yield=99%) are obtained in the form of an oil.

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

Procedure: In a manner similar to that of Example 2a, by reacting 123 mg of ethyl 3″-tert-butyl-4′-hydroxy-4″-pyrrolidin-1-yl[1,1′;3′,1″]terphenyl-4-carboxylate (0.27 mmol) with 110 mg (0.34 mmol) of caesium carbonate and 80 μL of 1-bromo-4-(tert-butyldimethylsilanyloxy)butane (0.30 mmol), 170 mg of ethyl 3″-tert-butyl-4′-[4-(tert-butyldimethylsilanyloxy)butoxy]-4″-pyrrolidin-1-yl[1,1′;3′,1″]terphenyl-4-carboxylate are obtained (yield=97%) in the form of an oil. are obtained (yield=97%) in the form of an oil

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

Procedure: In a manner similar to that of Example 2a, by reacting 260 mg of ethyl 4″-(acetylethylamino)-3″-tert-butyl-4′-hydroxy[1,1′;3′,1″]terphenyl-4-carboxylate (0.56 mmol) in 12 mL of dimethylformamide with 225 mg of caesium carbonate and 0.16 mL of 1-bromo-4-(tert-butyldimethylsilanyloxy)butane, 310 mg of ethyl 4″-(acetylethylamino)-3″-tert-butyl-4′-[4-(tert-butyldimethylsilanyloxy)butoxy]-[1,1′;3′,1″]terphenyl-4-carboxylate (yield=99%) are obtained in the form of an oil.

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

Procedure: In a manner similar to that of Example 2a, by reacting 260 mg of ethyl 4″-(acetylethylamino)-3″-tert-butyl-4′-hydroxy[1,1′;3′,1″]terphenyl-4-carboxylate (0.56 mmol) in 12 mL of dimethylformamide with 225 mg of caesium carbonate and 0.16 mL of 1-bromo-4-(tert-butyldimethylsilanyloxy)butane, 310 mg of ethyl 4″-(acetylethylamino)-3″-tert-butyl-4′-[4-(tert-butyldimethylsilanyloxy)butoxy]-[1,1′;3′,1″]terphenyl-4-carboxylate (yield=99%) are obtained in the form of an oil.

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

Procedure: 1 g of ethyl 3″-tert-butyl-4″-diethylamino-4′-hydroxy[1,1′;3′,1″]terphenyl-4-carboxylate obtained in Example 1d (2.2 mmol) are dissolved in 20 mL of dimethylformamide under a nitrogen atmosphere. 880 mg (2.7 mmol) of caesium carbonate are added. The reaction medium stirred at room temperature turns yellow. 0.64 mL of 1-bromo-4-(tert-butyldimethylsilanyloxy)butane (2.4 mmol) is then added and the reaction medium is heated at 80° C. for 18 hours. The reaction medium is then cooled to room temperature and then filtered. The solvents are evaporated off and the residue obtained is purified by chromatography on silica gel (eluent: 70/30 heptane/ethyl acetate). the reaction medium is heated at 80° C. for 18 hours The reaction medium is then cooled to room temperature filtered The solvents are evaporated off the residue obtained is purified by chromatography on silica gel (eluent: 70/30 heptane/ethyl acetate)