ethyl (E)-3-(3-bromophenyl)prop-2-enoate

Conditions: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Trans ethyl 3-bromocinnamate (8.4 g), ethylamine (6.7 g), methanol (18 ml) and 4A molecular sieves (1 g) were combined and heated at reflux for 1/2 hour. The mixture was cooled to about 45° C and sodium methylate (0.6 g) added. The mixture was then heated at reflux 11/2 hour and then cooled. It was acidified with concentrated hydrochloric acid (12 ml). The sieves were removed by filtration. Ice water was added to the filtrate to precipitate trans 3-bromo-N-ethylcinnamamide, m.p. 89°-90° C (after recrystallization from ethanol/water). heated at reflux for 1/2 hour The mixture was then heated at reflux 11/2 hour cooled The sieves were removed by filtration Ice water was added to the filtrate to precipitate trans 3-bromo-N-ethylcinnamamide, m.p. 89°-90° C (after recrystallization from ethanol/water)

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

Procedure: Trans m-bromocinnamic acid (14.8 g), ethanol (173 ml) and concentrated sulfuric acid (0.4 ml) were combined and heated at reflux for 15 hours. About 150 ml of the ethanol was distilled off, and the remaining solution was poured into ice/water (140 ml). The cold mixture was made strongly alkaline with 40% sodium hydroxide and extracted with methylene chloride (4 × 60 ml). The combined methylene chloride extract was dried over anhydrous potassium carbonate. The potassium carbonate was removed by filtration and the solvent stripped off under reduced pressure. Trans ethyl 3-bromocinnamate, was obtained as a partially solidified oil. (IR spectrum was consistent with this compound). heated at reflux for 15 hours About 150 ml of the ethanol was distilled off the remaining solution was poured into ice/water (140 ml) extracted with methylene chloride (4 × 60 ml) The combined methylene chloride extract was dried over anhydrous potassium carbonate The potassium carbonate was removed by filtration

Conditions: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Trans ethyl 3-bromocinnamate (8.4 g), ethylamine (6.7 g), methanol (18 ml) and 4A molecular sieves (1 g) were combined and heated at reflux for 1/2 hour. The mixture was cooled to about 45° C. and sodium methylate (0.6 g) added. The mixture was then heated at reflux 11/2 hour and then cooled. It was acidified with concentrated hydrochloric acid (12 ml). The sieves were removed by filtration. Ice water was added to the filtrate to precipitate trans 3-bromo-N-ethylcinnamamide, m.p. 89°-90° C. (after recrystallization from ethanol/water). heated at reflux for 1/2 hour The mixture was then heated at reflux 11/2 hour cooled The sieves were removed by filtration Ice water was added to the filtrate to precipitate trans 3-bromo-N-ethylcinnamamide, m.p. 89°-90° C. (after recrystallization from ethanol/water)

Conditions: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Trans ethyl 3-bromocinnamate (8.4 g), ethylamine (6.7 g), methanol (18 ml) and 4A molecular sieves (1 g) were combined and heated at reflux for 1/2 hour. The mixture was cooled to about 45° C. and sodium methylate (0.6 g) added. The mixture was then heated at reflux 11/2 hour and then cooled. It was acidified with concentrated hydrochloric acid (12 ml). The sieves were removed by filtration. Ice water was added to the filtrate to precipitate trans 3-bromo-N-ethylcinnamamide, m.p. 89°-90° C. (after recrystallization from ethanol/water). heated at reflux for 1/2 hour The mixture was then heated at reflux 11/2 hour cooled The sieves were removed by filtration Ice water was added to the filtrate to precipitate trans 3-bromo-N-ethylcinnamamide, m.p. 89°-90° C. (after recrystallization from ethanol/water)

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

Procedure: Trans m-bromocinnamic acid (14.8 g), ethanol (173 ml) and concentrated sulfuric acid (0.4 ml) were combined and heated at reflux for 15 hours. About 150 ml of the ethanol was distilled off, and the remaining solution was poured into ice/water (140 ml). The cold mixture was made strongly alkaline with 40% sodium hydroxide and extracted with methylene chloride (4 × 60 ml). The combined methylene chloride extract was dried over anhydrous potassium carbonate. The potassium carbonate was removed by filtration and the solvent stripped off under reduced pressure. Trans ethyl 3-bromocinnamate, was obtained as a partially solidified oil. (IR spectrum was consistent with this compound). heated at reflux for 15 hours About 150 ml of the ethanol was distilled off the remaining solution was poured into ice/water (140 ml) extracted with methylene chloride (4 × 60 ml) The combined methylene chloride extract was dried over anhydrous potassium carbonate The potassium carbonate was removed by filtration

Conditions: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Trans ethyl 3-bromocinnamate (8.4 g), ethylamine (6.7 g), methanol (18 ml) and 4A molecular sieves (1 g) were combined and heated at reflux for 1/2 hour. The mixture was cooled to about 45° C and sodium methylate (0.6 g) added. The mixture was then heated at reflux 11/2 hour and then cooled. It was acidified with concentrated hydrochloric acid (12 ml). The sieves were removed by filtration. Ice water was added to the filtrate to precipitate trans 3-bromo-N-ethylcinnamamide, m.p. 89°-90° C (after recrystallization from ethanol/water). heated at reflux for 1/2 hour The mixture was then heated at reflux 11/2 hour cooled The sieves were removed by filtration Ice water was added to the filtrate to precipitate trans 3-bromo-N-ethylcinnamamide, m.p. 89°-90° C (after recrystallization from ethanol/water)

Conditions: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Trans ethyl 3-bromocinnamate (8.4 g), ethylamine (6.7 g), methanol (18 ml) and 4A molecular sieves (1 g) were combined and heated at reflux for 1/2 hour. The mixture was cooled to about 45° C and sodium methylate (0.6 g) added. The mixture was then heated at reflux 11/2 hour and then cooled. It was acidified with concentrated hydrochloric acid (12 ml). The sieves were removed by filtration. Ice water was added to the filtrate to precipitate trans 3-bromo-N-ethylcinnamamide, m.p. 89°-90° C (after recrystallization from ethanol/water). heated at reflux for 1/2 hour The mixture was then heated at reflux 11/2 hour cooled The sieves were removed by filtration Ice water was added to the filtrate to precipitate trans 3-bromo-N-ethylcinnamamide, m.p. 89°-90° C (after recrystallization from ethanol/water)

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

Procedure: Trans m-bromocinnamic acid (14.8 g), ethanol (173 ml) and concentrated sulfuric acid (0.4 ml) were combined and heated at reflux for 15 hours. About 150 ml of the ethanol was distilled off, and the remaining solution was poured into ice/water (140 ml). The cold mixture was made strongly alkaline with 40% sodium hydroxide and extracted with methylene chloride (4 × 60 ml). The combined methylene chloride extract was dried over anhydrous potassium carbonate. The potassium carbonate was removed by filtration and the solvent stripped off under reduced pressure. Trans ethyl 3-bromocinnamate, was obtained as a partially solidified oil. (IR spectrum was consistent with this compound). heated at reflux for 15 hours About 150 ml of the ethanol was distilled off the remaining solution was poured into ice/water (140 ml) extracted with methylene chloride (4 × 60 ml) The combined methylene chloride extract was dried over anhydrous potassium carbonate The potassium carbonate was removed by filtration

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A vigorously stirred solution of ethyl trans-3-(3-bromophenyl)-2-propenoate (26.71 g, 0.105 mol) in dry toluene (150 ml) at -5° C. (ice-EtOH) under nitrogen was treated with lithium aluminium hydride (3.98 g, 0.105 mol) in one portion. The reaction temperature was allowed to gradually warm to room temperature over 30 min., at 25° C. the reaction became quite exothermic (25°-40° C.) with the formation of a grey gelatinous precipitate. Stirring was continued for 1 h, after which the reaction was carefully quenched with water (300 ml) and ice (200 g) then allowed to stand at 25° C. for 30 min. The mixture was filtered through Celite (Registered Trade Mark) and the residue was washed with ethyl acetate (2×200 ml). The filtrate was extracted with the organic washings, the combined organic phases were washed with brine (3×300 ml), water (300 ml), dried (Na2SO4) and evaporated to give the title compound as a pale yellow oil (21.42 g, 96%). Distillation at 120° C. at 0.05 mmHg. gave a colourless oil. (Found C, 50.73; H, 4.12; Br, 37.53. C9H9BrO requires C, 50.73; H, 4.26; Br, 37.50%); νmax (thin film)/cm-1 3325.5 (br. OH), 2862.0, 1653.0, 1591.0, 1562.5; δH (270 MHz) 2.15 (1H, bs, 1-OH), 4.30 (2H, dd, 2×1-H, 3J1,2 =5.5, 4J1,3 1.5 Hz), 6.33 (1H, dt, 2-H, 3J2,3 =15.8, 3J2,1 =5.3 Hz), 6.53 (1H, dt, 3-H, 3J3,2 =16.2, 4J3,1 =1.3 Hz), 7.15 (1H, t, 5'-H, Jo =7.8 Hz), 7.26 (1H, dt, 6'-H, Jo =7.6, Jm =1.3 Hz), 7.35 (1H, dt, 4'-H, Jo =7.9, Jm =1.6 Hz), 7.50 (1H, t, 2'-H, Jm =1.6 Hz). δC (67.8 MHz) 63.2 (1-C), 122.7 (3'-C), 125.0 (2-C), 129.2 (5'-H), 138.8 (1'-C). The remaining signals fall in the narrow range 130.0 to 130.4 ppm; m/z 214.1, 212.1 (44.86,49.78, M+), 196.0, 194.0 (1.47, 1.03), 185.0, 183.0 (10.81, 12.19), 172.0, 170.0 (46.47, 49.07), 158.0, 156.0 (15.47, 15.80), 133.1, 131.1 (36.29, 25.66), 104.1 (100). (25°-40° C.) after which the reaction was carefully quenched with water (300 ml) and ice (200 g) to stand at 25° C. for 30 min The mixture was filtered through Celite (Registered Trade Mark) the residue was washed with ethyl acetate (2×200 ml) The filtrate was extracted with the organic washings the combined organic phases were washed with brine (3×300 ml), water (300 ml) dried (Na2SO4) evaporated

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A vigorously stirred solution of ethyl trans-3-(3-bromophenyl)-2-propenoate (26.71 g, 0.105 mol) in dry toluene (150 ml) at -5° C. (ice-EtOH) under nitrogen was treated with lithium aluminium hydride (3.98 g, 0.105 mol) in one portion. The reaction temperature was allowed to gradually warm to room temperature over 30 min., at 25° C. the reaction became quite exothermic (25°-40° C.) with the formation of a grey gelatinous precipitate. Stirring was continued for 1 h, after which the reaction was carefully quenched with water (300 ml) and ice (200 g) then allowed to stand at 25° C. for 30 min. The mixture was filtered through Celite (Registered Trade Mark) and the residue was washed with ethyl acetate (2×200 ml). The filtrate was extracted with the organic washings, the combined organic phases were washed with brine (3×300 ml), water (300 ml), dried (Na2SO4) and evaporated to give the title compound as a pale yellow oil (21.42 g, 96%). Distillation at 120° C. at 0.05 mmHg. gave a colourless oil. (Found C, 50.73; H, 4.12; Br, 37.53. C9H9BrO requires C, 50.73; H, 4.26; Br, 37.50%); νmax (thin film)/cm-1 3325.5 (br. OH), 2862.0, 1653.0, 1591.0, 1562.5; δH (270 MHz) 2.15 (1H, bs, 1-OH), 4.30 (2H, dd, 2×1-H, 3J1,2 =5.5, 4J1,3 1.5 Hz), 6.33 (1H, dt, 2-H, 3J2,3 =15.8, 3J2,1 =5.3 Hz), 6.53 (1H, dt, 3-H, 3J3,2 =16.2, 4J3,1 =1.3 Hz), 7.15 (1H, t, 5'-H, Jo =7.8 Hz), 7.26 (1H, dt, 6'-H, Jo =7.6, Jm =1.3 Hz), 7.35 (1H, dt, 4'-H, Jo =7.9, Jm =1.6 Hz), 7.50 (1H, t, 2'-H, Jm =1.6 Hz). δC (67.8 MHz) 63.2 (1-C), 122.7 (3'-C), 125.0 (2-C), 129.2 (5'-H), 138.8 (1'-C). The remaining signals fall in the narrow range 130.0 to 130.4 ppm; m/z 214.1, 212.1 (44.86,49.78, M+), 196.0, 194.0 (1.47, 1.03), 185.0, 183.0 (10.81, 12.19), 172.0, 170.0 (46.47, 49.07), 158.0, 156.0 (15.47, 15.80), 133.1, 131.1 (36.29, 25.66), 104.1 (100). (25°-40° C.) after which the reaction was carefully quenched with water (300 ml) and ice (200 g) to stand at 25° C. for 30 min The mixture was filtered through Celite (Registered Trade Mark) the residue was washed with ethyl acetate (2×200 ml) The filtrate was extracted with the organic washings the combined organic phases were washed with brine (3×300 ml), water (300 ml) dried (Na2SO4) evaporated

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A vigorously stirred solution of ethyl trans-3-(3-bromophenyl)-2-propenoate (26.71 g, 0.105 mol) in dry toluene (150 ml) at -5° C. (ice-EtOH) under nitrogen was treated with lithium aluminium hydride (3.98 g, 0.105 mol) in one portion. The reaction temperature was allowed to gradually warm to room temperature over 30 min., at 25° C. the reaction became quite exothermic (25°-40° C.) with the formation of a grey gelatinous precipitate. Stirring was continued for 1 h, after which the reaction was carefully quenched with water (300 ml) and ice (200 g) then allowed to stand at 25° C. for 30 min. The mixture was filtered through Celite (Registered Trade Mark) and the residue was washed with ethyl acetate (2×200 ml). The filtrate was extracted with the organic washings, the combined organic phases were washed with brine (3×300 ml), water (300 ml), dried (Na2SO4) and evaporated to give the title compound as a pale yellow oil (21.42 g, 96%). Distillation at 120° C. at 0.05 mmHg. gave a colourless oil. (Found C, 50.73; H, 4.12; Br, 37.53. C9H9BrO requires C, 50.73; H, 4.26; Br, 37.50%); νmax (thin film)/cm-1 3325.5 (br. OH), 2862.0, 1653.0, 1591.0, 1562.5; δH (270 MHz) 2.15 (1H, bs, 1-OH), 4.30 (2H, dd, 2×1-H, 3J1,2 =5.5, 4J1,3 1.5 Hz), 6.33 (1H, dt, 2-H, 3J2,3 =15.8, 3J2,1 =5.3 Hz), 6.53 (1H, dt, 3-H, 3J3,2 =16.2, 4J3,1 =1.3 Hz), 7.15 (1H, t, 5'-H, Jo =7.8 Hz), 7.26 (1H, dt, 6'-H, Jo =7.6, Jm =1.3 Hz), 7.35 (1H, dt, 4'-H, Jo =7.9, Jm =1.6 Hz), 7.50 (1H, t, 2'-H, Jm =1.6 Hz). δC (67.8 MHz) 63.2 (1-C), 122.7 (3'-C), 125.0 (2-C), 129.2 (5'-H), 138.8 (1'-C). The remaining signals fall in the narrow range 130.0 to 130.4 ppm; m/z 214.1, 212.1 (44.86,49.78, M+), 196.0, 194.0 (1.47, 1.03), 185.0, 183.0 (10.81, 12.19), 172.0, 170.0 (46.47, 49.07), 158.0, 156.0 (15.47, 15.80), 133.1, 131.1 (36.29, 25.66), 104.1 (100). (25°-40° C.) after which the reaction was carefully quenched with water (300 ml) and ice (200 g) to stand at 25° C. for 30 min The mixture was filtered through Celite (Registered Trade Mark) the residue was washed with ethyl acetate (2×200 ml) The filtrate was extracted with the organic washings the combined organic phases were washed with brine (3×300 ml), water (300 ml) dried (Na2SO4) evaporated

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

Procedure: To a solution of ethyl (2E)-3-(3-bromophenyl)prop-2-enoate and ethyl (2Z)-3-(5-bromopyridin-3-yl)prop-2-enoate (4:1 ratio of isomers, 332 mg, 1.30 mmol) in methanol (10 mL) and water (2.5 mL) was added copper (I) chloride (257 mg, 2.59 mmol) and sodium borohydride (98 mg, 2.59 mmol). After 15 minutes, the reaction was diluted with ethyl acetate and filtered through CELITE. The filtrate was washed with water, dried over magnesium sulfate, filtered and concentrated in vacuo. The residue was purified by silica gel chromatography to afford ethyl 3-(5-bromopyridin-3-yl)propanoate. MS ESI calc'd. for C10H13BrNO2 [M+H]+ 258 and 260. found 258 and 260. 1H NMR (500 MHz, DMSO-d6) δ 8.52 (d, J=2.2 Hz, 1H), 8.44 (d, J=1.8 Hz, 1H), 7.96 (t, J=2.0 Hz, 1H), 4.02 (q, J=7.1 Hz, 2H), 2.84 (t, J=7.5 Hz, 2H), 2.67 (t, J=7.5 Hz, 2H), 1.12 (t, J=7.1 Hz, 3H). filtered through CELITE The filtrate was washed with water dried over magnesium sulfate filtered concentrated in vacuo The residue was purified by silica gel chromatography