methyl 4-(4-oxobutyl)benzoate

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To mixture of 4.19 g (1.5 eq) of pyridinium chlorochromate and 1.76 g (1.0 eq) of sodium acetate in 100 mL of dry methylene chloride are added, under nitrogen and with stirring, 2.70 g 1.0 eq) of methyl 4-(4-hydroxybutyl)benzoate in 50 mL of dry methylene chloride. The reaction mixture is stirred 12 hours, diluted with diethyl ether, and filtered. After concentration at reduced pressure, the residue is distilled under vacuum to yield 4-(4-carbomethoxyphenyl)-butanal as an oil, b.p. 131° C. at <1 torr; IR (film) νmax 2950, 2720, 1722, 1612, 1285, and 1110 cm-1 ; 1H NMR (CDCl3) delta 9.77 (m, 1H, --CHO), 7.98 (d, J=9 Hz, 2H, Ar), 7.24 (d, J=8.2 Hz, 2H, Ar), 3.90 (s, 3H, --CH3), 2.72 (t, 2H, benzyl), 2.47 (mm, 2H, --CH2CHO), 1.95 (m, 2H, --CH2). are added, under nitrogen The reaction mixture is stirred 12 hours filtered After concentration at reduced pressure the residue is distilled under vacuum

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of 4.97 g (23 mmol) of pyridinium chlorochromate and 1.23 g (15 mmol) of sodium acetate in 100 mL of dry methylene chloride was added 3.2 g (15.3 mmol) of methyl 4-(4-hydroxybutyl)benzoate in 50 mL of methylene chloride at room temperature. The resulting mixture was stirred at room temperature for 3 hours, diluted with 150 mL of ethyl ether, filtered through a silica gel pad, and concentrated. The residue was purified by column chromatography (silica gel/hexane:ethyl acetate=4:1) to give 2.85 g (90%) of 4-(4-methoxycarbonylphenyl)butyraldehyde as a light yellow oil: 1H NMR (CDCl3) δ 2.15-2.40 (2H, m), 2.72 (2H, t, J=6.6 Hz), 2.96 (2H, t, J=7.2 Hz), 4.15 (3H, s), 7.50 (2H, d, J=8.1 Hz), 8.21 (2H, d, J=8.1 Hz), 10.01 (1H. s); MS m/z 206 (M+), 175, 162, 131,103, 91, 63. filtered through a silica gel pad concentrated The residue was purified by column chromatography (silica gel/hexane:ethyl acetate=4:1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To mixture of 4.19 g (1.5 eq) of pyridinium chlorochromate and 1.76 g (1.0 eq) of sodium acetate in 100 mL of dry methylene chloride are added, under nitrogen and with stirring, 2.70 g 1.0 eq) of methyl 4-(4-hydroxybutyl)benzoate in 50 mL of dry methylene chloride. The reaction mixture is stirred 12 hours, diluted with diethyl ether, and filtered. After concentration at reduced pressure, the residue is distilled under vacuum to yield 4-(4-carbomethoxyphenyl)-butanal as an oil, b.p. 131° C. at <1 torr; IR (film) νmax 2950, 2720, 1722, 1612, 1285, and 1110 cm-1 ; 1H NMR (CDCl3) delta 9.77 (m, 1H, --CHO), 7.98 (d, J=9 Hz, 2H, Ar), 7.24 (d, J=8.2 Hz, 2H, Ar), 3.90 (s, 3H, --CH3), 2.72 (t, 2H, benzyl), 2.47 (mm, 2H, --CH2CHO), 1.95 (m, 2H, --CH2). are added, under nitrogen The reaction mixture is stirred 12 hours filtered After concentration at reduced pressure the residue is distilled under vacuum

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To mixture of 4.19 g (1.5 eq) of pyridinium chlorochromate and 1.76 g (1.0 eq) of sodium acetate in 100 mL of dry methylene chloride are added, under nitrogen and with stirring, 2.70 g 1.0 eq) of methyl 4-(4-hydroxybutyl)benzoate in 50 mL of dry methylene chloride. The reaction mixture is stirred 12 hours, diluted with diethyl ether, and filtered. After concentration at reduced pressure, the residue is distilled under vacuum to yield 4-(4-carbomethoxyphenyl)-butanal as an oil, b.p. 131° C. at <1 torr; IR (film) νmax 2950, 2720, 1722, 1612, 1285, and 1110 cm-1 ; 1H NMR (CDCl3) delta 9.77 (m, 1H, --CHO), 7.98 (d, J=9 Hz, 2H, Ar), 7.24 (d, J=8.2 Hz, 2H, Ar), 3.90 (s, 3H, --CH3), 2.72 (t, 2H, benzyl), 2.47 (mm, 2H, --CH2CHO), 1.95 (m, 2H, --CH2). are added, under nitrogen The reaction mixture is stirred 12 hours filtered After concentration at reduced pressure the residue is distilled under vacuum

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of 4.19 g (1.5 eq) of pyridinium chlorochromate and 1.76 g (1.0 eq) of sodium acetate in 100 mL of dry methylene chloride are added, under nitrogen and with stirring, 2.70 g (1.0 eq) of methyl 4-(4-hydroxybutyl)benzoate in 50 mL of dry methylene chloride. The reaction mixture is stirred 12 hours, diluted with diethyl ether, and filtered. After concentration at reduced pressure, the residue is distilled under vacuum to yield 4-(4-carbomethoxyphenyl)butanal as an oil, b.p. 131° C. at <1 torr; IR (film) ν max 2950, 2720, 1722, 1612, 1285, and 1110 cm-1 ; 1H NMR (CDC13) delta 9.77 (m, 1H, --CHO), 7.98 (d, J=9 Hz, 2H, Ar), 7.24 (d, J=8.2 Hz, 2H, Ar), 3.90 (s, 3H, --CH3), 2.72 (t, 2H, benzyl), 2.47 (m, 2H, --CH2CHO), 1.95 (m, 2H, --CH2). are added, under nitrogen The reaction mixture is stirred 12 hours filtered After concentration at reduced pressure the residue is distilled under vacuum

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of 4.19 g (1.5 eq) of pyridinium chlorochromate and 1.76 g (1.0 eq) of sodium acetate in 100 mL of dry methylene chloride are added, under nitrogen and with stirring, 2.70 g (1.0 eq) of methyl 4-(4-hydroxybutyl)benzoate in 50 mL of dry methylene chloride. The reaction mixture is stirred 12 hours, diluted with diethyl ether, and filtered. After concentration at reduced pressure, the residue is distilled under vacuum to yield 4-(4-carbomethoxyphenyl)butanal as an oil, b.p. 131° C. at <1 torr; IR (film) ν max 2950, 2720, 1722, 1612, 1285, and 1110 cm-1 ; 1H NMR (CDC13) delta 9.77 (m, 1H, --CHO), 7.98 (d, J=9 Hz, 2H, Ar), 7.24 (d, J=8.2 Hz, 2H, Ar), 3.90 (s, 3H, --CH3), 2.72 (t, 2H, benzyl), 2.47 (m, 2H, --CH2CHO), 1.95 (m, 2H, --CH2). are added, under nitrogen The reaction mixture is stirred 12 hours filtered After concentration at reduced pressure the residue is distilled under vacuum

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 3.36 g (1.0 eq) of 4-(4-carbomethoxyphenyl)butanal, 1.29 g (1.2 eq) of malononitrile, 0.05 g of D,L-alanine, 1 mL of glacial acetic acid, and 60 mL of benzene is refluxed with azeotropic removal of water. After 3 hours, about 85% of the theoretical amount of water should be formed and removed. The mixture then is cooled to room temperature and poured into water. The aqueous layer is extracted twice with benzene and the combined organic layers are dried over sodium sulfate, filtered and concentrated under reduced pressure. Chromatography with 1:1 ethyl acetate:hexanes and concentration of the eluant yield methyl 4-(5,5-dicyanopentyl)benzoate as an oil. IR (film) max ν max 2240, 1718, 1615, 1280, and 1110 cm-1 ; 1H NMR (CDCl3) delta 7.99 (d, J=8.1 Hz, 2H, Ar), 7.24-7.29 (m, 3H, Ar, vinyl), 3.90 (s, 3H, --CH3), 2.79 (t, J=7.4 Hz, 2H, benzyl), 2.60-2.64 (m, 2H, --CH2C=C), 1.94-1.97 (m, 2H, --CH2 --). removed poured into water The aqueous layer is extracted twice with benzene the combined organic layers are dried over sodium sulfate filtered concentrated under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 3.36 g (1.0 eq) of 4-(4-carbomethoxyphenyl)butanal, 1.29 g (1.2 eq) of malononitrile, 0.05 g of D,L-alanine, 1 mL of glacial acetic acid, and 60 mL of benzene is refluxed with azeotropic removal of water. After 3 hours, about 85% of the theoretical amount of water should be formed and removed. The mixture then is cooled to room temperature and poured into water. The aqueous layer is extracted twice with benzene and the combined organic layers are dried over sodium sulfate, filtered and concentrated under reduced pressure. Chromatography with 1:1 ethyl acetate:hexanes and concentration of the eluant yield methyl 4-(5,5-dicyanopentyl)benzoate as an oil. IR (film) max ν max 2240, 1718, 1615, 1280, and 1110 cm-1 ; 1H NMR (CDCl3) delta 7.99 (d, J=8.1 Hz, 2H, Ar), 7.24-7.29 (m, 3H, Ar, vinyl), 3.90 (s, 3H, --CH3), 2.79 (t, J=7.4 Hz, 2H, benzyl), 2.60-2.64 (m, 2H, --CH2C=C), 1.94-1.97 (m, 2H, --CH2 --). removed poured into water The aqueous layer is extracted twice with benzene the combined organic layers are dried over sodium sulfate filtered concentrated under reduced pressure