N-(4-bromophenyl)-3-methylbut-2-enamide

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

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

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

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

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

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 6.7 g (26.02 mmol) of molten N-(4-bromophenyl)3,3dimethylacrylamide (Compound 92) (heated to 135 degrees C.) was added 4.15 g (31.09) of aluminum chloride over 25 min. The reaction mixture was stirred at 130 degrees C. for 16 h and then treated with a further 1 g (7.5 mmol) of aluminum chloride. The reaction mixture was heated at 130 degrees C. for a further 9 h and then cooled to room temperature: The reaction was then quenched by the slow addition of 100 ml of ice cold water with slight warming of flask to facilitate mixing. The mixture was extracted with 1×100 ml and 4×50 ml of ether. The organic extracts were combined and washed with 25 ml of saturated NaCl solution and then dried (MgSO4). The solvent was removed in vacuo and the residue purified by flash chromatography (silica; 30% ethyl acetate in hexanes) to give the title compound as a pale yellow solid. PMR (CDCl3): & 1.37 (6H, s), 2.53 (2H, s), 6.85 (1H, d, J~8.4 Hz), 7.32 (1H, dd, J~8.4 Hz, 2.1 Hz), 7.43 (1H, d, J~2.1 Hz), 10.12 (1H, broad s). The reaction mixture was heated at 130 degrees C for a further 9 h cooled to room temperature The reaction was then quenched by the slow addition of 100 ml of ice cold water with slight warming of flask to facilitate mixing The mixture was extracted with 1×100 ml and 4×50 ml of ether washed with 25 ml of saturated NaCl solution dried (MgSO4) The solvent was removed in vacuo the residue purified by flash chromatography (silica; 30% ethyl acetate in hexanes)

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

Procedure: To a solution of 9.48 g (80 mmol) of 3,3-dimethylacryloyl chloride in 200 ml of dry THF was added with vigorous shaking a solution of 13.76 g (80 mmol) of 4-bromoaniline in 300 ml of dry THF. The mixture was stood at room temperature for 2 h and then treated with 80 g of ice followed by 200 ml of hexane. The organic layer was separated and the aqueous layer was extracted with 2×50 ml of hexanes. The organic layers were combined and washed successively with 30 ml of water and 2×30 ml of saturated NaCl solution and then dried (MgSO4). The solvent was removed in vacuo and the residue purified by recrystallization from an ethyl acetate and hexanes mixture to give the title compound as colorless crystals. PMR (CDCl3): & 1.91 (3H, s), 2.23 (3H, s), 5.73 (1H, broad s), 7.38-7.55 (5H, m). The organic layer was separated the aqueous layer was extracted with 2×50 ml of hexanes washed successively with 30 ml of water and 2×30 ml of saturated NaCl solution dried (MgSO4) The solvent was removed in vacuo the residue purified by recrystallization from an ethyl acetate and hexanes mixture

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

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 6.7 g (26.02 mmol) of molten N-(4-bromophenyl)3,3-dimethylacrylamide (Compound 92) (heated to 135 degrees C.) was added 4.15 g (31.09) of aluminum chloride over 25 min. The reaction mixture was stirred at 130 degrees C. for 16 h and then treated with a further 1 g (7.5 mmol) of aluminum chloride. The reaction mixture was heated at 130 degrees C. for a further 9 h and then cooled to room temperature: The reaction was then quenched by the slow addition of 100 ml of ice cold water with slight warming of flask to facilitate mixing. The mixture was extracted with 1×100 ml and 4×50 ml of ether. The organic extracts were combined and washed with 25 ml of saturated NaCl solution and then dried (MgSO4). The solvent was removed in vacuo and the residue purified by flash chromatography (silica; 30% ethyl acetate in hexanes) to give the title compound as a pale yellow solid. PMR (CDCl3): & 1.37 (6H, s), 2.53 (2H, s), 6.85 (1H, d, J~8.4 Hz), 7.32 (1H, dd, J~8.4 Hz, 2.1 Hz), 7.43 (1H, d, J~2.1 Hz), 10.12 (1H, broad s). The reaction mixture was heated at 130 degrees C for a further 9 h cooled to room temperature The reaction was then quenched by the slow addition of 100 ml of ice cold water with slight warming of flask to facilitate mixing The mixture was extracted with 1×100 ml and 4×50 ml of ether washed with 25 ml of saturated NaCl solution dried (MgSO4) The solvent was removed in vacuo the residue purified by flash chromatography (silica; 30% ethyl acetate in hexanes)

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 6.7 g (26.02 mmol) of molten N-(4-bromophenyl)3,3-dimethylacrylamide (Compound 92) (heated to 135 degrees C.) was added 4.15 g (31.09) of aluminum chloride over 25 min. The reaction mixture was stirred at 130 degrees C. for 16 h and then treated with a further 1 g (7.5 mmol) of aluminum chloride. The reaction mixture was heated at 130 degrees C. for a further 9 h and then cooled to room temperature: The reaction was then quenched by the slow addition of 100 ml of ice cold water with slight warming of flask to facilitate mixing. The mixture was extracted with 1×100 ml and 4×50 ml of ether. The organic extracts were combined and washed with 25 ml of saturated NaCl solution and then dried (MgSO4). The solvent was removed in vacuo and the residue purified by flash chromatography (silica; 30% ethyl acetate in hexanes) to give the title compound as a pale yellow solid. PMR (CDCl3): & 1.37 (6H, s), 2.53 (2H, s), 6.85 (1H, d, J~8.4 Hz), 7.32 (1H, dd, J~8.4 Hz, 2.1 Hz), 7.43 (1H, d, J~2.1 Hz), 10.12 (1H, broad s). The reaction mixture was heated at 130 degrees C for a further 9 h cooled to room temperature The reaction was then quenched by the slow addition of 100 ml of ice cold water with slight warming of flask to facilitate mixing The mixture was extracted with 1×100 ml and 4×50 ml of ether washed with 25 ml of saturated NaCl solution dried (MgSO4) The solvent was removed in vacuo the residue purified by flash chromatography (silica; 30% ethyl acetate in hexanes)

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

Procedure: To a solution of 9.48 g (80 mmol) of 3,3-dimethylacryloyl chloride in 200 ml of dry THF was added with vigorous shaking a solution of 13.76 g (80 mmol) of 4-bromoaniline in 300 ml of dry THF. The mixture was stood at room temperature for 2 h and then treated with 80 g of ice followed by 200 ml of hexane. The organic layer was separated and the aqueous layer was extracted with 2×50 ml of hexanes. The organic layers were combined and washed successively with 30 ml of water and 2×30 ml of saturated NaCl solution and then dried (MgSO4). The solvent was removed in vacuo and the residue purified by recrystallization from an ethyl acetate and hexanes mixture to give the title compound as colorless crystals. PMR (CDCl3): & 1.91 (3H, s), 2.23 (3H, s), 5.73 (1H, broad s), 7.38-7.55 (5H, m). The organic layer was separated the aqueous layer was extracted with 2×50 ml of hexanes washed successively with 30 ml of water and 2×30 ml of saturated NaCl solution dried (MgSO4) The solvent was removed in vacuo the residue purified by recrystallization from an ethyl acetate and hexanes mixture

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 6.7 g (26.02 mmol) of molten N-(4-bromophenyl)3,3dimethylacrylamide (Compound 92) (heated to 135 degrees C.) was added 4.15 g (31.09) of aluminum chloride over 25 min. The reaction mixture was stirred at 130 degrees C. for 16 h and then treated with a further 1 g (7.5 mmol) of aluminum chloride. The reaction mixture was heated at 130 degrees C. for a further 9 h and then cooled to room temperature: The reaction was then quenched by the slow addition of 100 ml of ice cold water with slight warming of flask to facilitate mixing. The mixture was extracted with 1×100 ml and 4×50 ml of ether. The organic extracts were combined and washed with 25 ml of saturated NaCl solution and then dried (MgSO4). The solvent was removed in vacuo and the residue purified by flash chromatography (silica; 30% ethyl acetate in hexanes) to give the title compound as a pale yellow solid. PMR (CDCl3): & 1.37 (6H, s), 2.53 (2H, s), 6.85 (1H, d, J~8.4 Hz), 7.32 (1H, dd, J~8.4 Hz, 2.1 Hz), 7.43 (1H, d, J~2.1 Hz), 10.12 (1H, broad s). The reaction mixture was heated at 130 degrees C for a further 9 h cooled to room temperature The reaction was then quenched by the slow addition of 100 ml of ice cold water with slight warming of flask to facilitate mixing The mixture was extracted with 1×100 ml and 4×50 ml of ether washed with 25 ml of saturated NaCl solution dried (MgSO4) The solvent was removed in vacuo the residue purified by flash chromatography (silica; 30% ethyl acetate in hexanes)