Thermal Reactions of Pyrrolidine at Elevated Temperatures. Studies with a Single-Pulse Shock Tube

Article abstract of DOI:10.1021/j100307a045

The thermal decomposition of pyrrolidine was studied behind reflected shocks in a single-pulse shock tube over the temperature range 900-1400 K and overall densities of ca. 3 x 1E-5 mol/cm³.Under these conditions the following reaction products were found in the postshock mixtures: H2, CH4, C2H4, C2H6, C2H2, C3H6, CH2=C=CH2, CH3C<*>CH, CH2=CHCH2CH3, HCN, CH3CN, CH2=CHCN, C2H5CN, and small quantities of pyrrole and butadiene.Studies with a mixture of pyrrolidine and pyrrolidine-d9 show that C2H4 and C3H6 are produced by direct ring cleavage with the following rate parameters: pyrrolidine -> C2H4 + (CH2)2-NH, k = 3.42 x 1E16 exp(-75.2 x 1E3/RT) s^-1 and pyrrolidine -> C3H6 + CH2=NH, k = 1.35 x 1E16 exp(-80.4 x 1E3/RT) s^-1, where R is expressed in units of cal/(K mol).Hydrogen cyanide has the highest concentration among the nitrogen-containing products, followed by acetonitrile.No reaction products resulting from pyrrolidine isomerization were observed.