Ethyl Aminomalonate

A mixture of 100 g. (0.52 mole) of ethyl isonitrosomalonate (p. 156), 150 ml. of absolute ethanol, and 15 g. of Raney nickel catalyst [iOrg. Syntheses, 21, 15 (1940)] is placed in a low-pressure hydrogenation apparatus [Org. Syntheses Coll. Vol. 1, 61 (1941)] and agitated at 40-50° and a hydrogen pressure of 18-50 lb. per sq. in. until absorption of hydrogen is complete (about 8 hours). The catalyst is removed by filtration, and the filtrate is distilled to give 60 g. (65%) of ethyl aminomalonate boiling at 83-87°/3-4 mm. The product should be used as soon as possible, since it is unstable. 

---

Methylimidazole HCI 2-Amino-5-chloro-2 -fluoro-benzophenone Ethyl aminomalonate hydrochloride... 

IB) 1-(2-Amino-5-chlorophenyl)-1-(2-fluorophenyl)-3,3-bis-(ethoxycarbonyl)-2-a2a-prop-1-ene A mixture of 88 g of the product obtained above, 300 g of ethyl aminomalonate hydrochloride and 60 ml of acetic acid in 2.3 liters of absolute ethanol is heated to the reflux temperature for 6 hours. The alcohol and the acetic acid are evaporated in vacuo and the residue is taken up in ether. The solution is washed with a dilute sodium bicarbonate solution and... 

A mixture of 58 g. (0.32 mole) of ethyl aminomalonate (p. 144), 50 ml. of pyridine, and 250 ml. of water is stirred while 48.5 g. (0.35 mole) of benzoyl chloride is added at such a rate that the temperature of the reaction mixture remains below 50°. The mixture is cooled to room temperature, and the white crystalline precipitate is collected by filtration and dried. The solid is recrystallized by dissolving in the minimum amount of hot benzene and slowly adding six times the volume of petroleum ether. There is obtained 92.4 g. (90%) of ethyl benzamidomalonate melting at 73-74°. 

Bart reaction, 55, 81, 231 Benzoin condensation, 122, 169 Benzoylation of ethyl aminomalonate, 145... 

---