2-(4-氯苯基)-1-苯乙胺

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of oxime geometric isomers 7 (840 mg, 3.23 mmol) in 30 ml dry THF (freshly distilled from sodium/benzophenone ketyl) under nitrogen was added borane-tetrahydrofuran complex (1.0 M in THF, 16.2 ml, 16.2 mmol) by syringe at room temperature. The resulting pale yellow solution was refluxed overnight, and cooled in an ice bath. Water (25 ml) was carefully added to quench, followed by 20% NaOH (25 ml). The resulting bi-phasic solution was refluxed with vigorous magnetic stirring overnight. After cooling to room temperature, hexanes (40 ml) were added, and the layers were separated. The aqueous portion was extracted with hexanes (1×40 ml). The combined organic portions were dried over potassium carbonate and concentrated in vacuo to a cloudy, pale yellow syrup. This syrup was purified by column chromatography on 18 g neutral alumina (activity I) using chloroform as eluant to afford the amine as 455.6 mg of a colorless, slightly cloudy syrup (61% yield): Rf 0.36 (5% Et2NH/CHCl3); IR (CDCl3) 3376 (w), 3316 (w), 3031 (w), 2928 (m), 2856 (w), 1602 (m), 1493 (m), 1451 (m); 1H NMR (CDCl3) δ7.38-7.28 (m, 5H), 7.26 (d, J=8.3 Hz, 2H), 7.09 (d, J=8.3 Hz, 2H), 4.18 (dd, J=8.3, 5.4 Hz, 1H), 2.98 (dd, J=13.4, 5.4 Hz, 1H), 2.84 (dd, J=13.4, 8.4 Hz), 1.50 (br s, 2H); low resolution mass spec. 232 (M+, 22), 215 (37), 125 (54), 106 (100), 89 (49), 79 (100). The resulting pale yellow solution was refluxed overnight cooled in an ice bath to quench The resulting bi-phasic solution was refluxed with vigorous hexanes (40 ml) were added the layers were separated The aqueous portion was extracted with hexanes (1×40 ml) The combined organic portions were dried over potassium carbonate concentrated in vacuo to a cloudy, pale yellow syrup This syrup was purified by column chromatography on 18 g neutral alumina (activity I)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of oxime geometric isomers 7 (840 mg, 3.23 mmol) in 30 ml dry THF (freshly distilled from sodium/benzophenone ketyl) under nitrogen was added borane-tetrahydrofuran complex (1.0M in THF, 16.2 ml, 16.2 mmol) by syringe at room temperature. The resulting pale yellow solution was refluxed overnight, and cooled in an ice bath. Water (25 ml) was carefully added to quench, followed by 20% NaOH (25 ml). The resulting bi-phasic solution was refluxed with vigorous magnetic stirring overnight. After cooling to room temperature, hexanes (40 ml) were added, and the layers were separated. The aqueous portion was extracted with hexanes (1×40 ml). The combined organic portions were dried over potassium carbonate and concentrated in vacuo to a cloudy, pale yellow syrup. This syrup was purified by column chromatography on 18 g neutral alumina (activity I) using chloroform as eluant to afford the amine as 455.6 mg of a colorless, slightly cloudy syrup (61% yield): Rf 0.36 (5% ET2 NH/CHCl3); IR (CDCl3) 3376 (w), 3316 (w), 3031 (w), 2928 (m), 2856 (w), 1602 (m), 1493 (m), 1451 (m); 1H NMR (CDCl3) δ7.38-7.28 (m, 5H), 7.26 (d, J=8.3 Hz, 2H), 7.09 (d, J=8.3 Hz, 2H), 4.18 (dd, J=8.3, 5.4 Hz, 1H), 2.98 (dd, J=13.4, 5.4 Hz, 1H), 2.84 (dd, J=13.4, 8.4 Hz), 1.50 (br s, 2H); low resolution mass spec. 232 (M+, 22), 215 (37), 125 (54), 106 (100), 89 (49), 79 (100). The resulting pale yellow solution was refluxed overnight cooled in an ice bath to quench The resulting bi-phasic solution was refluxed with vigorous hexanes (40 ml) were added the layers were separated The aqueous portion was extracted with hexanes (1×40 ml) The combined organic portions were dried over potassium carbonate concentrated in vacuo to a cloudy, pale yellow syrup This syrup was purified by column chromatography on 18 g neutral alumina (activity I)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of oxime geometric isomers 7 (840 mg, 3.23 mmol) in 30 ml dry THF (freshly distilled from sodium/benzophenone ketyl) under nitrogen was added borane-tetrahydrofuran complex (1.0M in THF, 16.2 ml, 16.2 mmol) by syringe at room temperature. The resulting pale yellow solution was refluxed overnight, and cooled in an ice bath. Water (25 ml) was carefully added to quench, followed by 20% NaOH (25 ml). The resulting bi-phasic solution was refluxed with vigorous magnetic stirring overnight. After cooling to room temperature, hexanes (40 ml) were added, and the layers were separated. The aqueous portion was extracted with hexanes (1×40 ml). The combined organic portions were dried over potassium carbonate and concentrated in vacuo to a cloudy, pale yellow syrup. This syrup was purified by column chromatography on 18 g neutral alumina (activity I) using chloroform as eluant to afford the amine as 455.6 mg of a colorless, slightly cloudy syrup (61% yield): Rf 0.36 (5% ET2 NH/CHCl3); IR (CDCl3) 3376 (w), 3316 (w), 3031 (w), 2928 (m), 2856 (w), 1602 (m), 1493 (m), 1451 (m); 1H NMR (CDCl3) δ7.38-7.28 (m, 5H), 7.26 (d, J=8.3 Hz, 2H), 7.09 (d, J=8.3 Hz, 2H), 4.18 (dd, J=8.3, 5.4 Hz, 1H), 2.98 (dd, J=13.4, 5.4 Hz, 1H), 2.84 (dd, J=13.4, 8.4 Hz), 1.50 (br s, 2H); low resolution mass spec. 232 (M+, 22), 215 (37), 125 (54), 106 (100), 89 (49), 79 (100). The resulting pale yellow solution was refluxed overnight cooled in an ice bath to quench The resulting bi-phasic solution was refluxed with vigorous hexanes (40 ml) were added the layers were separated The aqueous portion was extracted with hexanes (1×40 ml) The combined organic portions were dried over potassium carbonate concentrated in vacuo to a cloudy, pale yellow syrup This syrup was purified by column chromatography on 18 g neutral alumina (activity I)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A stirred solution of 1-phenyl-2-(4-chlorophenyl)ethylamine (6.00 gm, 2.6×10-2 mol), propargyl bromide (80% in toluene, 4.82 gm, 3.2×10-2 mol), and diisopropylethylamine (5.04 gm, 3.9×10-2 mol) in 50 ml of anhydrous tetrahydrofuran was refluxed at 90° C. under a dry nitrogen atmosphere for four hours. Then, an additional portion of propargyl bromide (0.48 gm, 3.9×10-3 mol) was added, and reflux was continued to another two hours. The reaction mixture was cooled to room temperature, and the resulting white precipitate was removed by filtration. The mother liquor was concentrated on a rotary evaporator, the residue was diluted with 100 ml of diethyl ether, and the resulting white precipitate was again removed by filtration. The etheral mother liquor was quickly extracted with two 50 ml portions of 2N aqueous HCl. Upon standing, the combined aqueous layers yielded the desired intermediate, N-propargyl-1-phenyl-2-(4-chlorophenyl)ethylamine hydrochloride, as an off-white precipitate, which was washed with diethyl ether (4.53 gm, 57%), mp=191°-193°. reflux the resulting white precipitate was removed by filtration The mother liquor was concentrated on a rotary evaporator the residue was diluted with 100 ml of diethyl ether the resulting white precipitate was again removed by filtration The etheral mother liquor was quickly extracted with two 50 ml portions of 2N aqueous HCl

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of oxime geometric isomers 7 (840 mg, 3.23 mmol) in 30 ml dry THF (freshly distilled from sodium/benzophenone ketyl) under nitrogen was added borane-tetrahydrofuran complex (1.0 M in THF, 16.2 ml, 16.2 mmol) by syringe at room temperature. The resulting pale yellow solution was refluxed overnight, and cooled in an ice bath. Water (25 ml) was carefully added to quench, followed by 20% NaOH (25 ml). The resulting bi-phasic solution was refluxed with vigorous magnetic stirring overnight. After cooling to room temperature, hexanes (40 ml) were added, and the layers were separated. The aqueous portion was extracted with hexanes (1×40 ml). The combined organic portions were dried over potassium carbonate and concentrated in vacuo to a cloudy, pale yellow syrup. This syrup was purified by column chromatography on 18 g neutral alumina (activity I) using chloroform as eluant to afford the amine as 455.6 mg of a colorless, slightly cloudy syrup (61% yield): Rf 0.36 (5% Et2NH/CHCl3); IR (CDCl3) 3376 (w), 3316 (w), 3031 (w), 2928 (m), 2856 (w), 1602 (m), 1493 (m), 1451 (m); 1H NMR (CDCl3) δ7.38-7.28 (m, 5H), 7.26 (d, J=8.3 Hz, 2H), 7.09 (d, J=8.3 Hz, 2H), 4.18 (dd, J=8.3, 5.4 Hz, 1H), 2.98 (dd, J=13.4, 5.4 Hz, 1H), 2.84 (dd, J=13.4, 8.4 Hz), 1.50 (br s, 2H); low resolution mass spec. 232 (M+, 22), 215 (37), 125 (54), 106 (100), 89 (49), 79 (100). The resulting pale yellow solution was refluxed overnight cooled in an ice bath to quench The resulting bi-phasic solution was refluxed with vigorous hexanes (40 ml) were added the layers were separated The aqueous portion was extracted with hexanes (1×40 ml) The combined organic portions were dried over potassium carbonate concentrated in vacuo to a cloudy, pale yellow syrup This syrup was purified by column chromatography on 18 g neutral alumina (activity I)