The results of measurements of thermal explosions for mixtures of methyl isocyanide with ethyl isocyanide, diethylmercury and di-t-butyl peroxide in spherical vessels near 350 "C are reported. Although the linear mixture rule holds quite well with ethyl isocyanide, it appears to fail mildly for diethylmercury; in the case of di-t-butyl peroxide too much reaction occurs in the inlet to the reaction vessel for a test of the rule to be made. Approximate measurements of the thermal conductivities for ethyl isocyanide and diethylmercury are reported.

No abstract

The thermal isomerisation of allyl isocyanide to allyl cyanide has been studied in the gas phase over the temperature range 130–200 °C. The reaction is homogeneous and first order, and at high pressure (20 Torr) has an activation energy of 40.8 ± 0.6 (2sdm) kcal mol−1; the corresponding range of frequency factor is 1014.77±0.30 s−1.

An exploratory study has been made of the gas-phase reactions of methylene radicals, generated by the photolysis of ketene near 3000 Å, with methyl, ethyl, and allyl isocyanides at room temperature.With methyl isocyanide, the principal product at low pressure is ethyl cyanide, together with a few percent of methyl cyanide; ethyl isocyanide is also formed, increasingly so as the total pressure is increased. Reaction appears to take place through a vibrationally excited ethyl isocyanide intermediate, and approximate rate constants for each reaction pathway are derived. Isotopic studies suggest that the methylene radicals insert in the H3C—NC bond of the methyl isocyanide.

Das durch Photolyse von Keten erzeugte Carben reagiert mit Me‐NC unter Einschiebung in die C‐N‐ Bindung zum schwingungsangeregten Ethylisocyanid, das sich hauptsächlich zu ET‐CN stabilisiert.