diethyl 2-benzylidenepropanedioate

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:

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:

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: 120 g of benzalmalonic acid diethyl ester, 33.6 g of potassium cyanide, 1600 cc of ethanol and 160 cc of water are stirred at a bath temperature of 60° for 12 to 14 hours. The reaction mixture is then cooled with ice water, the potassium bicarbonate which crystallizes is filtered off, the filtrate is made neutral with about 15 cc of 1 N hydrochloric acid, air is passed through the solution with a water jet vacuum pump for 1 hour, the solvent is distilled off on a rotary evaporator, 100 cc of water are added to the oily residue, and extraction is effected 6 times with 250 cc amounts of ether. The 3-cyano-3-phenyl-propionic acid ethyl ester, obtained after distilling off the ether, is purified by vacuum distillation. B.P. 125°-130°/0.15 mm Hg. the potassium bicarbonate which crystallizes is filtered off the solvent is distilled off on a rotary evaporator, 100 cc of water are added to the oily residue, and extraction

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

実験手順: One mole of a correspondingly substituted benzaldehyde is heated on a water trap with 160 g. (1 mole) of diethyl malonate, 30 ml. of glacial acetic acid, and 3 ml. of piperidine in 1 liter of benzene until 1 mole of water has been split off. The benzenic solution is worked up as usual.

反応条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 50 g of benzylidenemalonic acid, diethyl ester, (E. H. Kroeker, et al., J. Am. Chem. Soc., 56, 1171-3 (1934)) and 10 ml of 10% aqueous sodium bicarbonate were mixed with 100 ml of ethanol. 42 ml of 30% hydrogen peroxide was added dropwise over a 5-hour period at 70° C. Then 30 ml of 30% hydrogen peroxide was added over a one-hour period at 60° C. 100 ml of ethanol was added and the mixture was stirred for 8 hours at 60° C. The solvent was evaporated and the residue was extracted with methylene chloride. The solvent was evaporated from the separated extract and the residue was distilled to give ethyl 2-(ethoxycarbonyl)-3-phenyloxiranecarboxylate (6A), as a fraction boiling at 178°-180° C. at 0.05 Torr. The solvent was evaporated the residue was extracted with methylene chloride The solvent was evaporated from the separated extract the residue was distilled

反応条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 64 g (257.8 mmol) of diethyl benzylidenepropanedioate and 17 g (261 mmol) of potassium cyanide in 750 mL of EtOH and 75 mL of water is heated for 18 hours at 60° C. The medium is then concentrated under reduced pressure and taken up in 500 mL of brine and then extracted with Et2O (2×500 mL). The organic phases are dried over Na2SO4, filtered and then concentrated under reduced pressure. 43.5 g of ethyl 3-cyano-3-phenylpropanoate are obtained in the form of a solid, which is used without further purification in the following step. The medium is then concentrated under reduced pressure extracted with Et2O (2×500 mL) The organic phases are dried over Na2SO4 filtered concentrated under reduced pressure

反応条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 50 g of benzylidenemalonic acid, diethyl ester, (E. H. Kroeker, et al., J. Am. Chem. Soc., 56, 1171-3 (1934)) and 10 ml of 10% aqueous sodium bicarbonate were mixed with 100 ml of ethanol. 42 ml of 30% hydrogen peroxide was added dropwise over a 5-hour period at 70° C. Then 30 ml of 30% hydrogen peroxide was added over a one-hour period at 60° C. 100 ml of ethanol was added and the mixture was stirred for 8 hours at 60° C. The solvent was evaporated and the residue was extracted with methylene chloride. The solvent was evaporated from the separated extract and the residue was distilled to give ethyl 2-(ethoxycarbonyl)-3-phenyloxiranecarboxylate (6A), as a fraction boiling at 178°-180° C. at 0.05 Torr. The solvent was evaporated the residue was extracted with methylene chloride The solvent was evaporated from the separated extract the residue was distilled