The effects on the character and yield of liquid products synthesized directly from calcium carbide under elevated pressures, of the species of gases, pressure, and temperature have been summarized. It has been found that the yield of liquid products increases with increasing total pressure of the system up to about 100 atmospheres and then decreases with further increase in the pressure. The apparent characteristics of the products in carbon monoxide (or water gas) system seem different from the others, and an explanation for this has been given. As in the low pressure runs, carbon monoxide has rather harmful effects while, on the other hand, carbon dioxide has beneficial effects on the yield of liquid products. There have been found slight differences in the yields and the properties of the products under elevated and ordinary pressures, and these differences have been explained as due rather to the effects of the time of contact and temperature than to any change in the mechanism of the polymerization reaction. The limitations and the significance of the synthesis of hydrocarbon liquids directly from calcium carbide and several unique properties of the carbide which may be useful in organic syntheses have been pointed out and discussed.
The synthesis of isobutyl alcohol in the presence of calcium carbide and a methanol catalyst has been made in liquid paraffin. It has been found that the reaction proceeds more smoothly, though not necessarily more effectively, than in dry system. The effect of thorium on the catalytic activity of methanol catalyst has been investigated briefly. It has been found that 0.05 to 0.2 mole of it will increase the total yield of liquid products, but will not affect appreciably that of methanol. The preponderate formations of ethylene, propane, and butane and the absence of ethane, even in the presence of excess ethylene and hyrogen, have been qualitatively explained.
Following compounds were obtained in crystals: 2,3,5,6-Diacetone-l-mannofuranose, m.p., 122–122.5° and [α]D=−27° (in acetone). Bis-phenylhydrazone of l-lyxo-trihydroxy-glutaric dialdehyde, m.p., 165–165.5° and [α]D=+73° (in pyridine). Bis-p-nitro-phenyl-hydrazone of l-lyxotrihydroxy-glutaric dialdehyde, m.p., 203.5–204°. Potassium diacetone-l-mannonate, [α]D10=+32.2° (in water). And diacetone-l-mannopolactone, m.p. 124–124.5°.