A 3-l., three-necked, round-bottomed flask is equipped with a glass paddle stirrer, a condenser containing a mixture of acetone and solid carbon dioxide, and a gas inlet tube. The outlet of the condenser is protected from the atmosphere by a T-tube through which a slow stream of nitrogen is passed. The flask is purged with nitrogen, and about 1.5 l. of anhydrous liquid ammonia is either poured or distilled into the flask. A small crushed crystal of ferric nitrate nonahydrate is added, followed by 23 g. (1 g. atom) of freshly cut sodium in small pieces (Note 1).

Methylacetylene (44–48 g., 1.1–1.2 mole) (Note 2) is bubbled in through the gas inlet tube with rapid stirring. Sodium methylacetylide precipitates as a flocculent gray solid. The solid carbon dioxide is removed from the condenser, and the ammonia is evaporated overnight under a slow stream of nitrogen. A hot water bath may be used to drive off residual ammonia. One liter of dry tetrahydrofuran (Note 3) and 500 ml. of anhydrous ether are added, and with rapid stirring a slow stream of anhydrous carbon dioxide from a cylinder is passed into the mixture (Note 4). After 8 hours the rate of absorption of carbon dioxide is very slow. Any solid caked on the inside walls of the flask should be scraped off with the glass paddle stirrer. A very slow flow of carbon dioxide is continued overnight (Note 5).

The solvent is removed as completely as possible by distillation on a steam bath under water-pump vacuum. Two hundred milliliters of water is added, and the solid is dissolved by swirling the flask (Note 6). The solution is filtered if suspended solid is present. The aqueous solution is extracted twice with 100-ml. portions of ether. The aqueous layer in a 1-l. Erlenmeyer flask is then cooled in ice, and a mixture of 70 ml. of concentrated hydrochloric acid and 200 g. of ice is added slowly with swirling. The acidified solution is continuously extracted with 200 ml. (or more) of ether for 24–36 hours. The extract is evaporated in a stream of air or nitrogen to give tetrolic acid in the form of a mushy tan solid that is further dried in a vacuum desiccator over concentrated sulfuric acid for 2 days (Note 7). The product is a tan crystalline solid weighing 58–60 g. (69–71% based on sodium) and melting at 71–75°. It is purified further by addition to 700 ml. of boiling hexane. As soon as the tetrolic acid has dissolved, about 1 g. of activated carbon is added, and the solution is filtered through a heated funnel (Note 8). The filtrate is refrigerated (5°) overnight and 42–50 g. (50–59%) (Note 9) of tetrolic acid is collected in the form of white needles, m.p. 76–77°. A second recrystallization from hexane gives tetrolic acid melting at 76.5–77° (Note 10).