2-bromobut-2-ene

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A reaction flask was charged with 0.5 g (2.27 mmol) of 5-(4,4,5,5-tetramethyl-[1,3,2]dioxa borolan-2-yl)-pyridin-2-ylamine, 0.31 g (2.50 mmol) of 2-bromo-but-2-ene, 1.48 g (4.54 mmol) of Cs2CO3 and 52 mg (0.045 mmol) of tetrakis(triphenylphosphine)palladium under nitrogen atmosphere. The solids were dissolved in a degassed toluene/ethanol mixture (20 mL, 1/1) and the reaction heated to 90° C. for 7 h. The reaction was quenched with water (5 mL) and TBME (5 mL). The reaction mixture was filtered. The filtrate was extracted with TBME (20 mL). The organic extract was washed with brine and concentrated under reduced pressure. The residue was purified twice by column chromatography (silica, eluent DCM, 0-50% ethyl acetate) to afford 134 mg of 5-(1-methyl-propenyl)-pyridin-2-ylamine. ES−MS: m/z 149 [M+H+]; The reaction was quenched with water (5 mL) and TBME (5 mL) The reaction mixture was filtered The filtrate was extracted with TBME (20 mL) The organic extract was washed with brine concentrated under reduced pressure The residue was purified twice by column chromatography (silica, eluent DCM, 0-50% ethyl acetate)

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

Procedure: 2-Bromo-but-2-ene was reacted with o-nitrophenol to yield 2-but-1-en-oxynitrobenzene; which was reduced to the corresponding aniline; then reacted with N-chloromethyl-2-pyrrolidone to form the corresponding N-methylene-2-pyrrolidonyl derivative.

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

Procedure: To a solution of 5.0 g (28.9 mmol) of 3-phenyl-isoxazole-5-aldehyde in 40 ml of tetrahydrofuran, was added dropwise at -30° C. a solution of 1.5 g of metallic magnesium and 10.1 g (74.8 mmol) of 2-bromo-2-butene in 80 ml of tetrahydrofuran. After they were reacted at the same temperature for 30 minutes, the temperature of the reaction mixture was allowed to rise to room temperature and a saturated aqueous solution of ammonium chloride was added to terminate the reaction. Water was added, followed by extraction with ethyl ether. The organic layer was successively washed with water and saturated saline and then dried over anhydrous sodium sulfate. After ethyl ether was distilled off, the residue was purified by chromatography on a silica gel column (eluent: 9:1 hexane/ethyl acetate) so that 3-phenyl-5-(1-hydroxy-2-methyl-2-butenyl)isoxazole was obtained as oil. After they were reacted at the same temperature for 30 minutes to rise to room temperature to terminate the reaction followed by extraction with ethyl ether The organic layer was successively washed with water and saturated saline dried over anhydrous sodium sulfate After ethyl ether was distilled off the residue was purified by chromatography on a silica gel column (eluent: 9:1 hexane/ethyl acetate) so that 3-phenyl-5-(1-hydroxy-2-methyl-2-butenyl)isoxazole was obtained as oil

Conditions: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Analogously to example I, 2-lithium-2-butene was prepared from 2-bromo-2-butene (15.0 g; 0.11 mol) and lithium (2.8 g; 0.26 mol). To the product obtained, ethyl 4-bromobutanoate (11.0 g; 0.056 mol) was added dropwise and with reflux at -40-20° C., followed by stirring for 30 minutes at -20° C. Water (200 ml) and subsequently pentane (100 ml) were slowly added dropwise at -20° C. After separation of the layers the water layer was washed two times with 100 ml of pentane/ether (1/1, v/v), after which the combined organic layers were washed with water (50 ml). The organic layer was dried (K2CO3), filtered and evaporated. The yield was 14.0 g (96%). To the product obtained After separation of the layers the water layer was washed two times with 100 ml of pentane/ether (1/1 v/v), after which the combined organic layers were washed with water (50 ml) The organic layer was dried (K2CO3) filtered evaporated

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

Procedure: 2-bromo-2-butene (108 g; 0.800 mol) was added to 10.0 g of lithium (1.43 mol) in diethyl ether (300 ml) in about 30 minutes with reflux. After stirring overnight (17 hours), ethyl-3-(N,N-dimethylamino)propionate (52.0 g; 0.359 mol) was added to the reaction mixture in about 15 minutes. After stirring for 30 minutes at room temperature 200 ml of water was added dropwise. After separation the water phase was extracted two times with 50 ml of CH2Cl2. The organic phase was reduced by evaporation and the residue was distilled at reduced pressure. The yield was 51.0 g (67%). with reflux was added to the reaction mixture in about 15 minutes was added dropwise After separation the water phase was extracted two times with 50 ml of CH2Cl2 The organic phase was reduced by evaporation the residue was distilled at reduced pressure

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

Procedure: To a solution of 5.0 g (28.9 mmol) of 3-phenylisoxazole-5-aldehyde in 40 ml of tetrahydrofuran, was added dropwise at -30° C. a solution of 1.5 g of metallic magnesium and 10.1 g (74.8 mmol) of 2-bromo-2-butene in 80 ml of tetrahydrofuran. After they were reacted at the same temperature for 30 minutes, the temperature of the reaction mixture was allowed to rise to room temperature and a saturated aqueous solution of ammonium chloride was added to terminate the reaction. Water was added, followed by extraction with ethyl ether. The organic layer was successively washed with water and saturated saline and then dried over anhydrous sodium sulfate. After ethyl ether was distilled off, the residue was purified by chromatography on a silica gel column (eluent: 9:1 hexane/ethyl acetate) so that 3-phenyl-5-(1-hydroxy-2-methyl-2-butenyl)isoxazole was obtained as oil. After they were reacted at the same temperature for 30 minutes to rise to room temperature to terminate the reaction followed by extraction with ethyl ether The organic layer was successively washed with water and saturated saline dried over anhydrous sodium sulfate After ethyl ether was distilled off the residue was purified by chromatography on a silica gel column (eluent: 9:1 hexane/ethyl acetate) so that 3-phenyl-5-(1-hydroxy-2-methyl-2-butenyl)isoxazole was obtained as oil

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

Procedure: To a solution of 5.0 g (28.9 mmol) of 3-phenyl-isoxazole-5-aldehyde in 40 ml of tetrahydrofuran, was added dropwise at -30° C. a solution of 1.5 g of metallic magnesium and 10.1 g (74.8 mmol) of 2-bromo-2-butene in 80 ml of tetrahydrofuran. After they were reacted at the same temperature for 30 minutes, the temperature of the reaction mixture was allowed to rise to room temperature and a saturated aqueous solution of ammonium chloride was added to terminate the reaction. Water was added, followed by extraction with ethyl ether. The organic layer was successively washed with water and saturated saline and then dried over anhydrous sodium sulfate. After ethyl ether was distilled off, the residue was purified by chromatography on a silica gel column (eluent: 9:1 hexane/ethyl acetate) so that 3-phenyl-5-(1-hydroxy-2-methyl-2-butenyl)isoxazole was obtained as oil. After they were reacted at the same temperature for 30 minutes to rise to room temperature to terminate the reaction followed by extraction with ethyl ether The organic layer was successively washed with water and saturated saline dried over anhydrous sodium sulfate After ethyl ether was distilled off the residue was purified by chromatography on a silica gel column (eluent: 9:1 hexane/ethyl acetate) so that 3-phenyl-5-(1-hydroxy-2-methyl-2-butenyl)isoxazole was obtained as oil

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

Procedure: 2-Bromo-but-2-ene was reacted with o-nitrophenol to yield 2-but-1-en-oxynitrobenzene; which was reduced to the corresponding aniline; then reacted with N-methylol-2-pyrrolidone to form the corresponding N-methylene-2-pyrrolidonyl derivative.

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

Procedure: 2-Bromo-but-2-ene was reacted with o-nitrophenol to yield 2-but-1-en-oxynitrobenzene; which was reduced to the corresponding aniline; then reacted with N-chloromethyl-2-pyrrolidone to form the corresponding N-methylene-2-pyrrolidonyl derivative.