Enamine Chemistry. III. A New Carboxyethylation Method.

Enamines as Intermediates

“…After removal of the toluene at atmospheric pressure, the product is obtained by distillation at reduced pressure, bp 118-120°/10 mm, ni 5 1.5122-1.5129, in about 75% yield. The flask is fitted with a water separator and a condenser and is brought to reflux (mantle).…”

“…2-KETOCYCLOHEXANEPROPIONI C ACI D (5) Ο A mixture of 100 g (0.6 mole) of 1-morpholino-l -cyclohexene, 28.8 g (0.4 mole) of j8-propiolactone, and 100 ml of chlorobenzene is placed in a 500-ml round-bottom flask fitted with a condenser (drying tube). The mixture is refluxed for 4 hours.…”

Novel synthesis of 8-Aza Steroids

“…The spectral data of 15 showed that it was the enol ether of 13. The strong Bohlmann bands observed in the infrared spectrum of 15 provided evidence for the trans-anti stereochemistry for the 9,13, and 14 positions.…”

“…The immonium bond of 14 would be expected to undergo reduction to give 15, the enol ether of 13. Treatment of 14 with hydrogen over palladium gave no reaction; however, reaction of 14 with sodium borohydride gave two products, 15 and 16. The spectral data of 15 showed that it was the enol ether of 13.…”

“…The reaction of a limited number of enamines with ßpropiolactone was reported to give the substituted propioamide. 14 This suggested that the alkylation of 5c would occur with subsequent cyclization to form the desired intermediate 6c. Reaction did not occur at the reflux temperature of benzene or toluene; however, with chlorobenzene as solvent 5c gave a moderate yield of 6c.…”