prop-2-ynal

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

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

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

Procedure: A solution of 4,5-bis(4-fluorophenyl)-2-(1-methylethyl)-1H-imidazole (200 mg) and propiolaldehyde (75% solution in toluene, 0.15 ml) in dry THF (15 ml) were heated under reflux, under nitrogen for 24 h. The residue was dissolved in acetone and absorbed onto silica gel before purifying by CC eluting with petroleum ether (b.p. 40°-60°)/ethyl acetate (2:1) to give the title compound (84 mg) as a pale yellow solid, δ(CDCl3), 1.49 (d,J=7 Hz, Me2CH), 3.25 (septet, J=7 Hz, Me2CH), 5.67 (dd,J=15 Hz, 7 Hz,CH=CH.CHO), 6.95 and 7.10-7.60 (t,J=9 Hz and m, CH=CH.CHO and aromatic protons), 9.40 (d, J=7 Hz, CH=CH.CHO). under reflux, under nitrogen for 24 h absorbed onto silica gel before purifying by CC eluting with petroleum ether (b.p. 40°-60°)/ethyl acetate (2:1)

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

Procedure: To a solution of 4,5-bis(4-fluorophenyl)-2-(1-methylethyl)-1H-imidazole (492 mg) in dry THF under nitrogen was added propiolaldehyde (0.97 ml) and the reaction mixture heated to reflux. Further quantities of propiolaldehyde were added in portions (3×1.1 g) during successive 2 h periods. The reaction mixture was concentrated and the deep red residue was purified by FCC eluting with system A (1:4) to give the title product (398 mg) as an off-white solid and as a 1:1 mixture of geometric isomers. δ(CDCl3) 9.48 (d, 1H, J 7.5 Hz, cis CHO), 9.40 (d, 1H, J 7.5 Hz, trans CHO), 7.5 (d, 1H, J 15 Hz, trans CH=CHCHO), 7.45-6.85 (m, 17H, aromatic protons and cis CH=CHCHO), 5.98 (t,1H,J 7.5 Hz, cis CH=CHCHO), 5.63 (dd, 1H, J 15 and 7.5 Hz, trans CH=CH CHO), 3.25 (septet, 1H, J 7 Hz, CH(CH3)2 of trans isomer), 3.05 (septet, 1H, J 7 Hz, CH(CH3)2 of cis isomer). the reaction mixture heated to reflux The reaction mixture was concentrated the deep red residue was purified by FCC eluting with system A (1:4)

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

Procedure: To a solution of 4,5-bis(4-fluorophenyl)-2-(1-methylethyl)-1H-imidazole (492 mg) in dry THF under nitrogen was added propiolaldehyde (0.97 ml) and the reaction mixture heated to reflux. Further quantities of propiolaldehyde were added in portions (3×1.1 g) during successive 2 h periods. The reaction mixture was concentrated and the deep red residue was purified by FCC eluting with system A (1:4) to give the title product (398 mg) as an off-white solid and as a 1:1 mixture of geometric isomers. δ(CDCl3) 9.48 (d, 1H, J 7.5 Hz, cis CHO), 9.40 (d, 1H, J 7.5 Hz, trans CHO), 7.5 (d, 1H, J 15 Hz, trans CH=CHCHO), 7.45-6.85 (m, 17H, aromatic protons and cis CH=CHCHO), 5.98 (t,1H,J 7.5 Hz, cis CH=CHCHO), 5.63 (dd, 1H, J 15 and 7.5 Hz, trans CH=CH CHO), 3.25 (septet, 1H, J 7 Hz, CH(CH3)2 of trans isomer), 3.05 (septet, 1H, J 7 Hz, CH(CH3)2 of cis isomer). the reaction mixture heated to reflux The reaction mixture was concentrated the deep red residue was purified by FCC eluting with system A (1:4)

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

Procedure: To 13 mL of an N,N-dimethylformamide solution containing 3.6 g of methyl 1-benzyl-4-(((trifluoromethyl)sulfonyl)oxy)-1,2,5,6-tetrahydropyridine-3-carboxylate, 0.75 mL of 2-propine-1-al and 2.2 mL of N,N-diisopropylethylamine, 61 mg of copper(I) iodide, and 0.14 g of bis(triphenylphosphine)palladium(II) dichloride were added under a nitrogen atmosphere. The reaction mixture was stirred at room temperature for 30 minutes. Water and ethyl acetate were added thereto. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The organic layer and the extract were combined, the resultant solution was washed with an aqueous saturated sodium chloride solution and dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The residue thus obtained was purified by silica gel column chromatography [eluent; chloroform] to obtain 2.7 g of a brown oily substance, methyl 1-benzyl-4-(3-hydroxy-1-propin-1-yl)-1,2,5,6-tetrahydropyridine-3-carboxylate containing N,N-dimethylformamide. were added under a nitrogen atmosphere The organic layer was separated the aqueous layer was extracted with ethyl acetate the resultant solution was washed with an aqueous saturated sodium chloride solution dried over anhydrous magnesium sulfate the solvent was removed under reduced pressure The residue thus obtained was purified by silica gel column chromatography [eluent; chloroform]

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

Procedure: The procedure of Rimek and Zymalkowski (Arch. Pharm. 1961, 294, 759-765) was followed. Over a period of 1 hour, 40.9 g (0.757 mol) of freshly-distilled propiolaldehyde was added dropwise to a solution of 42.1 g (0.379 mol) of 3-amino-2-cyclohexenone in 1.5 1 of N,N-dimethylformamide (DMF). The solution was stirred at room temperature for 12 hours. The DMF was evaporated at reduced pressure. Vacuum distillation (bp 60°-65° C. at 0.025-0.050 mmHg) of the resultant black tars gave 30.2 g (54.2%) of 7,8-dihydro-5(6H)-quinolinone as a colorless liquid. The DMF was evaporated at reduced pressure Vacuum distillation (bp 60°-65° C. at 0.025-0.050 mmHg) of the resultant black tars

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

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

Procedure: To 13 mL of an N,N-dimethylformamide solution containing 3.6 g of methyl 1-benzyl-4-(((trifluoromethyl)sulfonyl)oxy)-1,2,5,6-tetrahydropyridine-3-carboxylate, 0.75 mL of 2-propine-1-al and 2.2 mL of N,N-diisopropylethylamine, 61 mg of copper(I) iodide, and 0.14 g of bis(triphenylphosphine)palladium(II) dichloride were added under a nitrogen atmosphere. The reaction mixture was stirred at room temperature for 30 minutes. Water and ethyl acetate were added thereto. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The organic layer and the extract were combined, the resultant solution was washed with an aqueous saturated sodium chloride solution and dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The residue thus obtained was purified by silica gel column chromatography [eluent; chloroform] to obtain 2.7 g of a brown oily substance, methyl 1-benzyl-4-(3-hydroxy-1-propin-1-yl)-1,2,5,6-tetrahydropyridine-3-carboxylate containing N,N-dimethylformamide. were added under a nitrogen atmosphere The organic layer was separated the aqueous layer was extracted with ethyl acetate the resultant solution was washed with an aqueous saturated sodium chloride solution dried over anhydrous magnesium sulfate the solvent was removed under reduced pressure The residue thus obtained was purified by silica gel column chromatography [eluent; chloroform]

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

Procedure: The procedure of Rimek and Zymalkowski (Arch. Pharm. 1961, 294, 759-765) was followed. Over a period of 1 hour, 40.9 g (0.757 mol) of freshly-distilled propiolaldehyde was added dropwise to a solution of 42.1 g (0.379 mol) of 3-amino-2-cyclohexenone in 1.5 1 of N,N-dimethylformamide (DMF). The solution was stirred at room temperature for 12 hours. The DMF was evaporated at reduced pressure. Vacuum distillation (bp 60°-65° C. at 0.025-0.050 mmHg) of the resultant black tars gave 30.2 g (54.2%) of 7,8-dihydro-5(6H)-quinolinone as a colorless liquid. The DMF was evaporated at reduced pressure Vacuum distillation (bp 60°-65° C. at 0.025-0.050 mmHg) of the resultant black tars

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

Procedure: To 13 mL of an N,N-dimethylformamide solution containing 3.6 g of methyl 1-benzyl-4-(((trifluoromethyl)sulfonyl)oxy)-1,2,5,6-tetrahydropyridine-3-carboxylate, 0.75 mL of 2-propine-1-al and 2.2 mL of N,N-diisopropylethylamine, 61 mg of copper(I) iodide, and 0.14 g of bis(triphenylphosphine)palladium(II) dichloride were added under a nitrogen atmosphere. The reaction mixture was stirred at room temperature for 30 minutes. Water and ethyl acetate were added thereto. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The organic layer and the extract were combined, the resultant solution was washed with an aqueous saturated sodium chloride solution and dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The residue thus obtained was purified by silica gel column chromatography [eluent; chloroform] to obtain 2.7 g of a brown oily substance, methyl 1-benzyl-4-(3-hydroxy-1-propin-1-yl)-1,2,5,6-tetrahydropyridine-3-carboxylate containing N,N-dimethylformamide. were added under a nitrogen atmosphere The organic layer was separated the aqueous layer was extracted with ethyl acetate the resultant solution was washed with an aqueous saturated sodium chloride solution dried over anhydrous magnesium sulfate the solvent was removed under reduced pressure The residue thus obtained was purified by silica gel column chromatography [eluent; chloroform]

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

Procedure: A solution of 4,5-bis(4-fluorophenyl)-2-(1-methylethyl)-1H-imidazole (200 mg) and propiolaldehyde (75% solution in toluene, 0.15 ml) in dry THF (15 ml) were heated under reflux, under nitrogen for 24 h. The residue was dissolved in acetone and absorbed onto silica gel before purifying by CC eluting with petroleum ether (b.p. 40°-60°)/ethyl acetate (2:1) to give the title compound (84 mg) as a pale yellow solid, δ(CDCl3), 1.49 (d, J=7 Hz, Me2CH), 3.25 (septet, J=7 Hz, Me2CH), 5.67 (dd, J=15 Hz, 7 Hz, CH=CH.CHO), 6.95 and 7.10-7.60 (t, J=9 Hz and m, CH=CH.CHO and aromatic protons), 9.40 (d, J=7 Hz, CH=CH.CHO). under reflux, under nitrogen for 24 h absorbed onto silica gel before purifying by CC eluting with petroleum ether (b.p. 40°-60°)/ethyl acetate (2:1)